Chemistry 12th 1

CBSE 2025
CHEMISTRY
Including Case Based Questions
CLASS 12
Chapter-wise Question Bank

Based on Previous 20 Years 63 Papers
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CBSE Chemistry Question Bank Class 12
Edition July 2024
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CONTENTS
Exam 2024 Solved Paper 5-14
CHAP 1. Solution 15-81
CHAP 2. Electrochemistry 82-147
CHAP 3. Chemical Kinetics 148-206
CHAP 4. The d and f-block Elements 207-244
CHAP 5. Coordination Compounds 245-287
CHAP 6. Haloalkanes and Haloarenes 288-330
CHAP 7. Alcohols, Phenols and Ethers 331-381
CHAP 8. Aldehydes, Ketones and Carboxylic Acids 382-435
CHAP 9. Amines 436-477
CHAP 10. Biomolecules 478-515
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Page 5 Exam 2024 Solved Paper CBSE Chemistry Class 12
Exam 2024 Solved Paper

Class XII 2023-24
Chemistry
Time: 3 Hours Max. Marks: 70
General Instructions:
1. There are 33 questions in this question paper with internal choice.
2. SECTION A consists of 16 multiple-choice questions carrying 1 mark each.
3. SECTION B consists of 5 very short answer questions carrying 2 marks each.
4. SECTION C consists of 7 short answer questions carrying 3 marks each.
5. SECTION D consists of 2 case-based questions carrying 4 marks each.
6. SECTION E consists of 3 long answer questions carrying 5 marks each.
7. All questions are compulsory.
8. Use of log tables and calculators is not allowed.
3. Isotonic solutions have the same

SECTION-A (a) Density
(b) Refractive index
(c) Osmotic pressure
Directions (Q. Nos. 1-16) : The following questions are
multiple-choice questions with one correct answer. Each (d) Volume
question carries 1 mark. There is no internal choice in this Ans : (c) Osmotic pressure
section.
Isotonic solutions have same osmotic pressure at a
given temperature.
1. Which of the following species can act as the
strongest base?
(a) OH- (b) C 6 H 5 O- 4. The specific sequence in which amino acids are
arranged in a protein is called its
(a) Primary structure
(c) RO- (d) (b) Secondary structure
(c) Tertiary structure
(d) Quaternary structure
Ans : (c) RO-
An alkoxide ion is a better proton acceptor than Ans : (a) Primary structure
hydroxide ion. Hence, alkoxides are stronger bases. Each polypeptide in a protein has amino acids
linked with each other in a specific sequence of
2. Auto-oxidation of chloroform in air and light amino acids, called primary structure of protein.
produces a poisonous gas known as
(a) Phosphine (b) Mustard gas 5. Transition metals are known to make interstitial
(c) Phosgene (d) Tear gas compounds. Formation of interstitial compounds
makes the transition metal
Ans : (c) Phosgene (a) More hard
Chloroform is slowly oxidised by air in the presence (b) More soft
of light to an extremely poisonous gas, carbonyl (c) More ductile
chloride, also known as phosgene
(d) More metallic
Ans : (a) More hard
Interstitial compounds are very hard, some borides
approach diamond in hardness.
6. The correct name of the given reaction is 9. Dilution affects both molar conductivity as well as
conductivity. Effect of dilution on both is
(a) Molar conductivity decreases whereas
conductivity increases on dilution
(a) Hoffmann Bromamide degradation reaction (b) Molar conductivity increases whereas
(b) Gabriel Phthalimide synthesis conductivity decreases on dilution
(c) Carbyl amine reaction (c) Both decrease with dilution
(d) Gatterman reaction (d) Both increase with dilutionss
Ans : (d) Gatterman reaction Ans : (b) Molar conductivity increases whereas
conductivity decreases on dilution
Upon dilution, conductivity decreases, due to
decrease in concentration of ions.
Upon dilution, due to increase in total number of
ions in weak electrolytes and in strong electrolytes
mobility increases. Hence, molar conductivity
Gatterman reaction is used for obtaining increases.
chlorobenzene or bromobenzene from benzene
diazonium chloride by treating it with Cu/HCl or 10. Which of the following cell is used in inverter?
Cu/HBr respectively. (a) Fuel cell
(b) Mercury cell
7. Visha took 4 test-tubes namely A, B, C & D (c) Lead storage cell
containing CH 3 CH = CH 2 , CH 3 CH 2 CH = CH 2, (d) Dry cell
CH 3 CH = CH - CH 3 , and ^CH 3h2 C = CH 2
respectively and tried to convert them into tert- Ans : (c) Lead storage cell
butyl alcohol. She carried out acid catalysed Lead storage cell is used in inverter.
hydration reaction on every alkene. Out of the four
test-tubes, the one which will give desired result is 11. In which of the following molecules, C atom marked
(a) A (b) B with asterisk is chiral?
(c) C (d) D
Ans : (d) D
In the presence of few drops of conc. H2SO4, alkenes

react with water to form alcohol in accordance with
the Markovnikov rule.
(a) I, II, III
8. Van’t Hoff factor for KCl solution assuming the
complete dissociation is (b) II, III, IV
(a) 1 (b) 2 (c) I, II, III, IV
(c) 0.5 (d) 1.5 (d) I, III, IV
Ans : (b) 2 Ans : (b) II, III, IV

Upon complete dissociation, The chiral carbon atom is the one which is bonded
KCl K+ + Cl- to four different atoms/groups.
van’t Hoff factor = ‘n’ for strong electrolytes
n=2
(c) Assertion (A) is true, but Reason (R) is false.

(d) Assertion (A) is false, but Reason (R) is true.
Ans : None of the option is correct.
p-methoxyphenol is weaker acid as compared to
p-nitrophenol due to the reason that the conjugate
base formed in p-nitrophenol is stabilised by the –M
effect of nitro group.
Also, methoxy group shows –I and +M effect which
makes both Assertion (A) and Reason (R) are false.
14. Assertion (A) : Inversion of configuration is observed

in S N 2 reaction.
Reason (R) : The reaction proceeds with the
12. For the reaction A + 2B C + D . The order of formation of carbocation.
the reaction is (a) Both Assertion (A) and Reason (R) are true
(a) 1 with respect to A and Reason (R) is the correct explanation of
(b) 2 with respect to B the Assertion (A).
(c) Can’t be predicted as order is determined (b) Both Assertion (A) and Reason (R) are true,
experimentally but Reason (R) is not the correct explanation
(d) 3 of Assertion (A).
(c) Assertion (A) is true, but Reason (R) is false.
Ans : (c) Can’t be predicted as order is determined
(d) Assertion (A) is false, but Reason (R) is true.
experimentally
Order of a reaction is an experimental quantity, Ans : (c) Assertion (A) is true, but Reason (R)
which cannot determined theoretically. is false.
A + 2B C+D Assertion saying inversion of configuration is
The order of the above reaction can’t be predicted observed in S N 2 reaction is correct. As attack of
as order is determined experimentally. nucleophile takes place from backside.
S N 2 reaction proceeds with the formation of
transition state, no intermediate is formed in the
Directions (Q. Nos. 13-16) : Each of the following questions reaction, making the reason a false statement. (A)
consists of two statements, one is Assertion and the other is true and (R) is false.
is Reason. Give answer :
15. Assertion (A) : The units of rate constant of a zero
13. Assertion (A) : p-methoxyphenol is a stronger acid order reaction and rate of reaction are the same.
than p-nitrophenol. Reason (R) : In zero order reaction, the rate of
Reason (R) : Methoxy group shows +I effect reaction is independent of the concentration of
whereas nitro group shows –I effect. reactants.
(a) Both Assertion (A) and Reason (R) are true (a) Both Assertion (A) and Reason (R) are true
and Reason (R) is the correct explanation of and Reason (R) is the correct explanation of
the Assertion (A). the Assertion (A).
(b) Both Assertion (A) and Reason (R) are true, (b) Both Assertion (A) and Reason (R) are true,
but Reason (R) is not the correct explanation but Reason (R) is not the correct explanation
of Assertion (A). of Assertion (A).
(c) Assertion (A) is true, but Reason (R) is false. liberated by the same quantity of electricity
(d) Assertion (A) is false, but Reason (R) is true. passing through the electrolytic solution are
proportional to their chemical equivalent weights.
Ans : (a) Both Assertion (A) and Reason (R) (b) The coating of surfaces of metallic objects
are true and Reason (R) is the correct with oxides or other salts of the metal is called
explanation of the Assertion (A). corrosion.
A Products Some examples of corrosion are rusting of iron,
tarnishing of silver and development of green
Rate \ 6A@n coating on copper and bronze.
Rate = k 6A@n n = order of reaction
For zero order, n=0 18. Resistance of a conductivity cell filled with
0.2 mol L-1 KCl solution is 200 W . If the resistance
Rate = k
of the same cell when filled with 0.05 mol L-1 KCl
So, units of rate is same as that of rate constant for
solution is 620 W , calculate the conductivity and
zero order reaction i.e., mol L-1 s-1 and this is due
molar conductivity of 0.05 mol L-1 KCl solution.
to rate of reaction is independent of concentration
The conductivity of 0.2 mol L-1 KCl solution is
of reactants. Assertion (A) is true and Reason (R)
0.0248 S cm-1 .
is true and Reason (R) is correct explanation of
Assertion (A). Ans :
As cell is same, then cell constant is same i.e. , of
A
16. Assertion (A) : Zr and Hf are of almost similar both the solution is same.
atomic radii.
Reason (R) : This is due to Lanthanoid contraction. k 1 # R1 = , = k 2 # R2
A
(a) Both Assertion (A) and Reason (R) are true k 1 = Conductivity of 0.2 mol L-1 KCl solution
and Reason (R) is the correct explanation of = 0.0248 S cm-1
the Assertion (A). R1 = Resistance of 0.2 mol L-1 KCl solution = 200 W
(b) Both Assertion (A) and Reason (R) are true,
but Reason (R) is not the correct explanation k 2 = Conductivity of 0.05 mol L-1 KCl solution (We
of Assertion (A). have to calculate)
(c) Assertion (A) is true, but Reason (R) is false. R2 = Resistance of 0.05 mol L-1 KCl solution
= 620 W
(d) Assertion (A) is false, but Reason (R) is true. 0.0248 S cm-1 # 200 W = k 2 # 620 W
Ans : (a) Both Assertion (A) and Reason (R)
k 2 = 0.0248 # 200 S cm-1
are true and Reason (R) is the correct 620
explanation of the Assertion (A). k 2 = 0.008 S cm-1
[Zr(160 pm); Hf (159 pm)] Molar conductivity is given by
-1
Zr and Hf are of almost similar atomic radii despite
/ m = 0.008 S cm-1
of having a difference in principal quantum number. 0.05 mol L
This is due to the lanthanoid contraction which
/ m = 0.16 S cm-1 dm3 mol-1
compensates this increasing size.
/ m = 0.16 # 103 S cm2 mol-1
(1 dm = 10 cm)
SECTION-B / m = 160 S cm mol-1
2
Directions (Q. Nos. 17-21) : This section contains 5 19. Show that in case of a first order reaction, the time
questions with internal choice in one question. The taken for completion of 99% reaction is twice the
following questions are very short answer type and carry time required for 90% completion of the reaction.
2 marks each. (log 10 = 1)
17. Define the following terms: Ans :
(a) Faraday’s second law of electrolysis
(b) Corrosion As we know that,
Time required for the completion of 99% reaction
Ans :
6R0@
t99% = 2.303 log
(a) According to the Faraday’s second law of k 6R@
electrolysis the amount of different substances
At t99% , if 6R0@ = 100 , 6R@ = 1 Dimethyl amine is secondary amine and do

not show this reaction.
t99% = 2.303 log 100 = 2 # 2.303 ..(i) (ii) Iodobenzene is formed along with KCl and
k k
Similarly N2.
6R0@
t90% = 2.303 log
k 6R@
t90% = 2.303 log 100 = 2.303 ...(ii)
k 10 k
After dividing eqn. (i) and (ii) we get
t99% 2 # 2.303/k
= =2 21. Classify the following sugars into monosaccharides
t90% 2.303/k
and disaccharides :
Hence t99% = 2 # t90% Fructose, Lactose, Glucose, Maltose
Ans :
20. (a) Carry out the following conversions :
(i) Nitrobenzene to Aniline Monosaccharides are Glucose and Fructose.
(ii) Aniline to Phenol Disaccharides are Lactose and Maltose.
or
(b) (i) Write a chemical test to distinguish between
Dimethyl amine and Ethanamine.
(ii) Write the product formed when benzene
SECTION-C
diazonium chloride is treated with KI. Directions (Q. Nos. 22-28) : This section contains 7
Ans : questions with internal choice in one question. The
following questions are short answer type and carry 3
marks each.
22. Give the structure of the major product expected

from the following reactions:
(a) Reaction of Ethanal with methyl-magnesium
bromide followed by hydrolysis.
(b) Hydration of But-1-ene in the presence of dilute
sulphuric acid.
(c) Reaction of phenol with bromine water.
Ans :
or
(b) (i) Carbylamine reaction can distinguish
between Dimethyl amine and Ethanamine.
Ethanamine reacts with CHCl 3 and
ethanolic KOH to form isocyanides which
is foul smelling substance.
Heat
CH 3 CH 2 - NH 2 + CHCl 3 + 3KOH
CH 3 CH 2 NC + 3KCl + 3H 2 O
23. A compound ‘X’ with molecular formula C3H9N Ans :

reacts with C6H5SO2Cl to give a solid, insoluble in IUPAC names of the given compounds are
alkali. Identify ‘X’ and give the IUPAC name of the (a) Potassium hexacyanidoferrate (III)
product. Write the reaction involved. (b) Dichloridobis (ethane-1,2-diamine) platinum
Ans : (IV)
Compound 'X' = CH 3 CH 2 - NH - CH 3 (c) Tetraamminechloridonitrito-O-cobalt (III)
(secondary amine) chloride
IUPAC name : N-Ethyl-N-methylbenzene (d) Tetrahydroxidozincate (II)
sulphonamide (Product)
Reaction with aryl sulphonyl chloride 26. Draw the structures of major product(s) in each of
the following reactions :
24. The rate constant of a reaction quadruples when

the temperature changes from 300 K to 320 K.
Calculate the activation energy for this reaction.
[log 2 = 0.30, log 4 = 0.60,
2.303R = 19.15 J K-1 mol-1@
Ans :
Given, T1 = 300 K , T2 = 320 K
As we know that
log kl = Ea ; 1 - 1 E Ans :
k 2.303R T1 T2
log b 4k l = Ea ; 1 - 1 E
k 2.303R 300 320
log 4 = Ea
;
320 - 300 E
2.303R 96000
0.60 = Ea ; 20 E
19.15 96000
0.6 # 19.15 # 9600 = E
a
2
Ea = 55152 J/mol
Ea = 55.152 kJ/mol
25. Write IUPAC names of the following coordination

compounds : (any three)
(a) K 3 6Fe ^CNh6@
(b) 6Pt ênh2 Cl 2@ 2+
(c) 6Co ^NH 3h4 Cl ÔNOh@Cl
(d) 6Zn ÔHh4@ 2-
SECTION-D
case-based questions. Each question has an internal choice
and carries 4 marks each. Read the passage carefully and
answer the questions that follow.
29. Certain organic compounds are required in small

amounts in our diet but their deficiency causes specific
disease. These compounds are called vitamins.
27. Calculate the emf of the following cell : Most of the vitamins cannot be synthesized in our
body but plants can synthesize almost all of them.
Ni ^ s h + 2Ag+ ^0.01 Mh Ni2+ ^0.1 Mh + 2Ag ^ s h
o So they are considered as essential food factors.
Given that E cell = 1.05 V , log 10 = 1
However, the bacteria of the gut can produce some
Ans : of the vitamins required by us. All the vitamins are
For the given cell generally available in our diet. The term ‘vitamin’
was coined from the words vital + amine, since
Ni ^ s h + 2Ag+ ^0.01 Mh Ni2+ ^0.1 Mh + 2Ag ^ s h
the earlier identified compounds had amino group.
6Ni2+@
o
E cell = E cell - 0.059 log Vitamins are classified into two groups depending
2 7Ag A
+ 2
upon their solubility in water or fat namely-fat
-1 soluble vitamins and water soluble vitamins.
= 1.05 - 0.059 log 10-2 2
2 ^10 h Answer the following questions :
(a) What is the other name of vitamin B6?
= 1.05 - 0.059 log 103 (b) Name the vitamin whose deficiency causes
2
increased blood clotting time.
= 1.05 - 0.059 # 3 (c) Xerophthalmia is caused by the deficiency
2 of which vitamin? Give two sources of this
= 1.05 - 0.09 = 0.96 volt vitamin.
or
28. Account for the following : (c) Why can’t vitamin C be stored in our body?
(a) Haloalkanes react with NaCN to form both Name the disease caused by the deficiency of
cyanides and isocyanides. this vitamin.
(b) Haloarenes do not undergo nucleophilic Ans :
substitution reaction easily.
(c) Benzyl chloride gives S N 1 reaction. (a) Pyridoxine is the other name of vitamin B6.
(b) Deficiency of vitamin K causes increased blood
Ans : clotting time.
(a) Haloalkane react with NaCN to form cyanides (c) Xerophthalmia is caused by the deficiency of
(major product) and isocyanides (minor vitamin A.
product) because CN- is an ambidentate Two sources of vitamin A are:
ligand and it can attack either by C centre or (1) Fish liver oil
N centre. (2) Carrots
(b) C – Cl bond acquires a partial double bond or
character due to resonance, so haloarenes do (c) Vitamin C is water soluble vitamin so it is
not undergo nucleophilic substitution reaction readily excreted in urine and cannot be stored
easily. in our body. Scurvy disease is caused by the
(c) Benzyl chloride gives S N 1 reaction because deficiency of vitamin C.
the carbocation formed gets stabilised through
resonance. 30. The oxidation number of the central atom in a
complex is defined as the charge it would carry if all
the ligands are removed along with the electron pairs
that are shared with the central atom. Similarly the
charge on the complex is the sum of the charges of
the constituent parts i.e. the sum of the charges on
the central metal ion and its surrounding ligands. (ii) Write the reaction of compound (A) with
Based on this, the complex is called neutral if the (1) 2, 4-Dinitrophenyl hydrazine and
sum of the charges of the constituents is equal to (2) Fehling solution
zero. However, for an anion or cationic complex, the (iii) Write the equation of compound (A) when
sum of the charges of the constituents is equal to it undergoes Cannizzaro reaction.
the charge on the coordination sphere. or
Based on the above information, answer the (b) (i) Account for the following :
following questions : (1) The alpha (a )-hydrogens of aldehydes
(a) Define ambidentate ligand with an example. and ketones are acidic in nature.
(b) What type of isomerism is shown by (2) Oxidation of aldehydes is easier than
[Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl? ketones.
(c) Define Chelate effect. How it affects the (ii) Arrange the following in :
stability of complex? (1) Decreasing reactivity towards
or nucleophilic addition reaction propanal,
(c) Find the coordination number and oxidation acetone, benzaldehyde.
state of chromium in Na3[Cr(C2O4)3]. (2) Increasing order of boiling point :
Ans : Propane, Ethanol, Dimethylether,
Propanal
(a) Ligand which has two different donor atoms (iii) Give simple chemical test to distinguish
and either of the two ligetes in the complex is between Benzoic acid and Benzaldehyde.
called ambidentate ligand.
Example : NO -2 and SCN- ion Ans :
NO -2 ion can coordinate either through nitrogen
or through oxygen to a central metal atom/ion
(b) [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl show
ionisation isomerism.
(c) When bidentate or polydentate ligand
coordinate with the central metal ion by ring
formation, this effect is known as chelate effect.
When a ligand attaches to the metal ion in
a manner which leads to the formation of 5–
or 6– membered ring. Then the metal-ligand
association is found to be more stable.
or
(c) Coordination number of chromium in
Na3[Cr(C2O4)3] is 6 because C 2 O 2- 4 ligand is
bidentate ligand.
Oxidation number of chromium in
Na3[Cr(C2O4)3] is + 3 + x + 3 ^- 2h = 0; x = + 3
SECTION-E
long answer type and carry 5 marks each. Two questions
have an internal choice.
31. (a) An organic compound (A) with the molecular

formula C9H10O forms 2, 4-DNP derivative,
reduces Fehling solution and undergoes
Cannizzaro reaction. On vigorous oxidation, it
gives 1, 2-benzene dicarboxylic acid.
(i) Identify the compound (A) and write its
IUPAC name.
or Zn has lowest enthalpy of atomisation due to

(b) (i) (1) The acidity of a -hydrogen atoms absence of number of unpaired electrons.
of carbonyl compounds is due to Zn has weaker interatomic interaction and
strong electron withdrawing effect hence weak bonding exist between zinc atoms
of the carbonyl group and resonance resulting in lowest enthalpy of atomisation.
stabilization of the conjugate base. (d) When sodium chromate is acidified with
(2) Aldehydes have H attached to carbonyl sulphuric acid, then orange coloured sodium
C, so aldehydes can be oxidised by mild dichromate ^Na 2 Cr2 O 7 : 2H 2 Oh is formed.
oxidising agent. Oxidation of ketones
involves C – C bond cleavage. 2Na 2 CrO 4 + 2H+ Na 2 Cr2 O 7 + 2Na+ + H 2 O
(ii) (1) Propanal > Benzaldehyde > Acetone
(e) Zn, Cd and Hg are soft metals because they
Aldehydes are generally more reactive
have completely filled d-orbitals.
towards nucleophilic addition reaction.
Due to absence of unpaired electrons, weak
(2) Propane < Dimethylether < Propanal
metallic bonding takes place.
< Ethanol
Outer E.C. of Zn = 3d 10 4s2
(iii) Tollen’s test
Benzaldehyde gives Tollen’s test Outer E.C. of Cd = 4d10 5s2
Outer E.C. of Hg = 5d 10 6s2
(f) MnO -4 (permanganate) titration is not carried
out in the presence of HCl.
MnO -4 is a strong oxidising agent which will
convert Cl- and Cl 2 . Some of the MnO -4 is
used for the conversion of Cl- to Cl 2 which will
not give exact result of titration.
Benzoic acid does not give Tollens’ test.
Hence, we cannot use HCl with MnO -4 for
quantitative estimation.
32. Attempt any five of the following :
(g) In lower oxidation state of transition metals,
(a) Ce(III) is easily oxidised to Ce(IV). Comment.
some of the valence electrons of the metal atom
(b) E°(Mn2+/Mn) is –1.18 V. Why is this value
are not involved in bonding.
highly negative in comparison to neighbouring
Hence, in lower oxides, metal can donate
d block elements?
electrons and behave as base.
(c) Which element of 3d series has lowest enthalpy
While in higher oxides of transition metals,
of atomisation and why?
valence electrons are involved in bonding and
(d) What happens when sodium chromate is acidified?
are not available for donation of electrons. In
(e) Zn, Cd and Hg are soft metals. Why?
higher oxides, effective nuclear charge of metal
(f) Why is permanganate titration not carried out
is also high, which allow the metal ion to accept
in the presence of HCl?
the electrons and behave as acid.
(g) The lower oxides of transition metals are basic
whereas the highest are amphoteric/acidic. 33. (a) (i) Ishan’s automobile radiator is filled with
Give reason. 1.0 kg of water. How many grams of
Ans : ethylene glycol (Molar mass = 62 g mol-1)
must Ishan add to get the freezing point
(a) Ce(III) is easily oxidised to Ce(IV) because
of the solution lowered to - 2.8cC . K f for
formation of Ce(IV) is favoured by its noble
water is 1.86 K kg mol-1 .
gas configuration, i.e., 6Xe@4f 0 .
(ii) What type of deviation from Raoult’s law
Hence, Ce(III) changes its E.C. 6Xe@4f 1 to
is shown by ethanol and acetone mixture?
Ce(IV) 6Xe@4f 0 .
o Give reason.
(b) E Mn /Mn is highly negative in comparison to
2+
or
neighbouring d-block elements, i.e., (Cr and Fe).
o o (b) (i) Boiling point of water at 750 mm Hg
E Mn /Mn = - 1.18 V , E Cr /Cr = - 0.91 ,
2+ 2+
o pressure is 99.68ºC. How much sucrose

E Fe /Fe = - 0.44 V
(Molar mass = 342 g mol-1 ) is to be added
2+
o
The highly negative E Mn /Mn is determined on
2+
to 500 g of water such that it boils at ? (Kb
the basis of summation of Ta H o , D i H 1o , T i H 2o
for water = 0.52 K kg mol-1 ).
and D hyd H o of particular metal
(c) Zinc has lowest enthalpy of atomisation in (ii) State Henry’s law and write its any one
3d series. The D a H o (kJ mol–1) of Zn is 126. application.
Ans :
(a) (i) As we know that
DTf = K f m
Let x g of ethylene glycol is added to
radiator
Now,
DTf = K f x
62 # 1
62 DTf
x= = 62 # 2.8
Kf 1.86
x = 93.33
(ii) Mixture of ethanol and acetone shows
positive deviation from Raoult’s law.
In pure ethanol, molecules are hydrogen
bonded. On adding acetone, its molecules
get in between the host molecules and
break some of the hydrogen bonds between
them. Due to weakening of interactions,
the solution shows positive deviation from
Raoult’s Law.
or
(b) (i) Here
DTb = 100c - 99.68c = 0.32cC
DTb = Kb m
Let x g of sucrose is added
DTb = Kb # x # 1000
342 # 500
x = DTb # 342 # 500

Kb # 1000
x = 0.32 # 342 # 500 = 105.2 g

0.52 # 1000
Mass of sucrose added = 105.2 g
(ii) Henry’s law states that, the partial
pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas
(x) in the solution.
p = KH x [KH is Henry’s law constant]
Application of Henry’s law: To increase
the solubility of CO2 in soft drinks and
soda water, the bottle is sealed under high
pressure.

Chap 1 Solution Page 15
CHAPTER 1
Solution
SUMMARY 5. Normality (N) : Number of gram equivalents of

solute present per litre of the solution.
N = wB # 1000
Eq. mass of solute # VS (in cc)
1. SOLUTION
A solution is a homogeneous mixture of two or more 6. Mole fraction (x) : Ratio of the number of moles
substances whose composition can be changed within of solute or solvent to the total number of moles
certain fixed limits. Binary solution consists of two of the solution.
components as given below: xA = nA
nA + nB
1. Solute : The component of the solution present in
small proportion. It is generally denoted by B . and xB = nB ; xA + xB = 1
nA + nB
2. Solvent : The component of solution present in
large proportion. It is generally denoted by A. 7. Parts per million (ppm) : Number of the parts by
weight of solute in one million parts by weight of
2. CONCENTRATION OF SOLUTION the solution.
The concentration of a solution may be expressed in ppmB = wB # 106
wS
different ways as:
1. Mass percentage : Mass of the solute (in g) 8 Formality (F) : Number of gram formula masses
present in 100 g of a solution. of solute present in one litre of the solution.
For example: 20% H 2 SO 4 solution by mass means wB # 1000
F =
-E Formula mass of B # VS (in cc)
wB = 20 g , wA = 80 g and wS = 100 g
NOTE :
(wS = weight of solution) 1. Normality = Molarity # Basicity
Mass percentage of B = wB 100 (For acids)
wA + wB #
2. Normality = Molarity # Acidity
2. Volume percentage : Volume of the solute (in cc) (For bases)
present in 100 cc of the solution. 3. Normality equation : N1 V1 = N2 V2
Volume percentage of B = VB # 100 4. Molarity equation : M1 V1 = M2 V2
VA + VB
3. Molarity (M) : Number of moles of solute present The molarity equation for reaction between two
per litre of the solution. reactants in solution is
M1 V1 = M2 V2
M = wB # 1000 n1 n2
MB # VS (in cc)
wB = Mass of solute Where n1 = Number of moles reactant 1,
MB = Molecular mass of solute n2 = Number of moles of reactant 2
4. Molality (m) : Number of moles of solute present 5. Molarity equation of mixture of solutions:
in one kg of solvent. M1 V1 + M2 V2 = N3 (V1 + V2)
m = wB # 1000 6. Normality equation of mixture of solutions:
MB # wA (in g)
N1 V1 + N2 V2 = N3 (V1 + V2)
wA = Mass of solvent in gram
Page 16 Solution Chap 1
7. Equivalent mass of : 1. Nature of the solute and solvent : Like dissolves

like. Polar solute is soluble in polar solvent and a
Acid = Molecular Mass non-polar, one in a non-polar solvent.
Basicity
2. Temperature of the solution :
Base = Molecular Mass
Acidity For endothermic process,
Salt = Molecular Mass Solubility ? Temperature
Total + ve valency of metal ion
For exothermic process,
Ion = Formula Mass of ion 1
Charge Solubility ?
8. Normality of an acid = Molarity # Basicity Temperature
9. Normality of a base = Molarity # Acidity
10. Oxidising and reducing agent 5. VAPOUR PRESSURE
= Molecular mass or at mass The pressure exerted by the vapour of a liquid in

Number of e- s lost or gained by one equilibrium with the liquid at particular temperature
molecule of subs tance is called its vapour pressure. It depends upon:
(a) Nature of liquid.
3. SOLUBILITY OF GASES IN LIQUIDS
(b) Temperature.
Solubility of a gas in liquid is the volume of gas in But, if we add a non-volatile solute in the solution,
cc (measured at STP) which dissolves in one litre of the vapour pressure decreases.
the liquid to form a saturated solution at a particular
temperature. It depends: 6. RAOULT’S LAW
1. Nature of gas : Gases like H 2 , O 2 , N 2 are less
1. For volatile solute : In a solution, the V.P. of a
soluble in water, while NH 3 , CO 2 are more soluble.
component at a given temperature is equal to the
2. Nature of the liquid. (like dissolves like) mole fraction of that component in the solution
3. Temperature of the solution. multiplied by the V.P. of that component in the
Solubility \ 1 pure state.
Temperature
PA = PcA xA ,
dissolution of gas in liquid is an exothermic process
PB = PcB xB
4. Pressure of the gas over solution : The solubility of
a gas in a liquid at a given temperature is directly 2. For non-volatile solutes : According to this law,
proportional to the partial pressure of the gas “the vapour pressure of a solution containing a
over the solution (Henry’s law). Mathematically, non-volatile solute is directly proportional to the
mole fraction of solvent”.
m ? p or m = Kp
Where K is a constant of proportionality. PS ? xA
Expressing solubility in terms of mole fraction, or
Henery’s Law can be written as “This relative lowering of vapour pressure of a
x ? p or x = Klp solution having non-volatile solute is equal to the
mole fraction of solute.”
or p = KHx
Pc - PS
= xB
Where p is partial pressure of the gas and K H is Pc
called Henry’s constant.
7. IDEAL SOLUTIONS
Hence, KH = 1
Kl
Thus, Henry’s law can be defined as - “Partial The solutions in which the intermolecular interaction
pressure of a gas in vapour phase (p) is directly between the two components (A ) B) is of the same
proportional to mole fraction (x) of gas in solution”. magnitude as the intermolecular interaction between
pure components A ) A and B ) B are called ideal
4. SOLUBILITY OF SOLIDS IN LIQUIDS solutions.
Solubility of a solid in a liquid is the maximum Examples : Benzene and Toluene, Hexane and Heptane.
amount of the solid (in g) which dissolves in 100 g of The characteristics of an ideal solution are:
the liquid to form a saturated solution at a particular 1. It must obey Raoult’s law
temperature. It depends upon: 2. TH mixing = 0
3. TVmixing = 0 (a) PA < PAcxA and PB < PBcxB

In such solutions, PA = PAcxA , PB = PBcxB (b) TH mixing < 0
(c) TVmixing < 0
8. NON-IDEAL SOLUTIONS
The solutions in which the intermolecular interactions
between the two components (A ) B) are of different
magnitude as the intermolecular interactions between
pure components A ) A and B ) B are called non-
ideal solutions.
The characteristics of non-ideal solution are:
1. It does not obey the Raoult’s law
2. TH mixing ! 0
3. TVmixing ! 0
They are of two types:
1. Non-ideal solution showing positive deviations :
Those solutions in which (A ) B) interactions
are weaker than A ) A and B ) B interactions
are called non-ideal solutions showing positive Vapour pressure diagram showing negative deviation
deviations.
Examples : Benzene and acetone, acetone and
ethylalcohol. The characteristics of these solutions 9. COLLIGATIVE PROPERTIES
are: Those properties of a solution which depend on the
(a) PA > PcA xA and PcB xB number of solute particles only but not on the nature
(b) TH mixing > 0 of the solute are called colligative properties. There
are four colligative properties of a solution. These are:
(c) TVmixing > 0
1. Relative lowering in vapour pressure : The
relative lowering of vapour pressure of a solution
is equal to the mole fraction of the solute.
Pc - PS
= xB
Pc
For very dilute solutions
Pc - PS
= nB
Pc nA
wB
Pc - PS MB
= wA
Pc MA
wB
Pc - PS MB
Also,
PS
= wA (If solution is not dilute)
MA
2. Elevation in boiling point : For a dilute solution,

the elevation in boiling point is directly
proportional to the molality of the solution.
TTb ? m
Vapour pressure diagram showing positive deviation
TTb = K b m
2. Non-ideal solution showing negative deviation :
Those solutions in which (A ) B) interactions TTb = K b # wB # 1000
MB wA
are stronger than A ) A and B ) B interactions
Where K b = molal elevation constant.
are called non-ideal solutions showing negative
deviations. 3. Depression in freezing point : For a dilute solution,
Examples : Acetone and chloroform and aniline. the depression in freezing point is directly
The characteristics of these solutions are proportional to the molality of the solution.
TTf ? m 14. DEGREE OF ASSOCIATION

TTf = K f m It is defined as the fraction of total number of moles
of the substance which associate in solution at
TTf = K f # wB # 1000 equilibrium.
MB wA
Where K f = molal depression constant. m (i - 1)
a = moles,
1-m
4. Osmotic pressure : The pressure which must be Where m = number of moles associated.
applied to the solution side to just prevent the
passage of pure solvent into it through a semi 15. DEGREE OF DISSOCIATION
permeable membrane
It is defined as the fraction of total number of moles
p = CRT
of the electrolyte which dissociate into ions in solution
or p = nB RT at equilibrium.
V
a = i-1
p = wB RT m-1
MB $ V
Where, m = number of moles dissociated.
10. ISOTONIC SOLUTIONS
16. MODIFIED COLLIGATIVE PROPERTIES
Those solutions which have the same osmotic pressure
The inclusion of Van’t hoff factor modifies the
at the same temperature are called isotonic solutions.
equations for the colligative properties as follows:
p1 = p 2
Pc - PS
1. = i $ xB
Pc
11. REVERSE OSMOSIS
2. TTb = iK b m
If a pressure more than osmotic pressure is applied 3. TTf = iK f $ m
on the solution side, the solvent will flow from the
solution side to solvent side through a semi permeable 4. p = i CRT
membrane. This phenomenon is called reverse osmosis.
Example : Desalination of sea water. ***********
12. ABNORMAL MOLECULAR MASSES OBJECTIVE QUESTIONS

Sometimes the observed molecular mass of a substance
determined with the help of colligative properties is 1. Value of Henry’s constant KH
quite different from the normal molecular mass. This (a) increases with decrease in temperature.
is called abnormal molecular mass.
(b) decreases with increase in temperature.
It is mainly due to the dissociation or association
of the solute particles in the solution. (c) increases with increase in temperature.
(d) remains constant.
13. VAN’T HOFF FACTOR Ans : OD 2020
It is defined as “the ratio of normal molecular mass to KH increases as temperature increases and vice versa.
the observed molecular mass.” Thus (c) is correct option.
or 2. The Van’t Hoff’s factor of 0.1 M Ba ^NO 3h2 solution is
“The ratio of observed colligative property to the 2.74. The degree of association is –
normal or calculated colligative property.” (a) 91.3% (b) 87%
i = Normal molecular mass (c) 100% (d) 74%
Obsrved molecular mass
Ans : SQP 2018
Observed colligative property
or i =
Normal colligative property Ba ^NO 3h2 ) Ba + 2NO
2+ -
3
If i = 1 (Neither association nor dissociation)

Initial 0.1 M 0 0
For dissociation i > 1, For association, i < 1
At eq. ^0.1 - ah M aM aM
^0.1 - ah + a + 2a 4. Which of the following aqueous solution should have

i =
0.1 the highest boiling point?
= 0 . 1 + 2a = 2.74 (a) 1.0 M NaOH (b) 1.0 M Na 2 SO 4
0.1
(c) 1.0 M NH 4 NO 3 (d) 1.0 M KNO 3
On solving a = 0.087
Ans : DELHI 2017
So, a% = 0.087 # 100 = 87% As we know greater value of Van’t Hoff factor higher
0.1
Thus (b) is correct option. will be the elevation in boiling point and hence higher
will be the boiling point of solution Since value of i for
3. A 5% solution of cane sugar (Mol. Wt = 342) is Na 2 SO 4 is highest.
isotonic with 1% solution of substance X . The
molecular weight of X is – Solution Vant’t off factor (i)
(a) 68.4 (b) 34.2 1.0M Na 2 SO 4 3
(c) 171.2 (d) 136.2 1.0M NH 4 NO 3 2
Ans : COMP 2018, SQP 2012
1.0M KNO 3 2
Strength ]C g of 5% cane sugar solution
= 5 gm/100 ml Hence, 1.0M Na 2 SO 4 has highest boiling point.
= 50 gms/litre Thus (b) is correct option.
A solution has an osmotic pressure of 0.0821 atm. at
= 50 moles/litre
5.
342 300 K. Its concentration would be :
(mol. wt. of sugar = 342 ) (a) 0.66 M (b) 0.32 M
So, osmotic pressure of 5% cane sugar (c) 0.066 M (d) 0.033 M
Solution p 1 = C # R # T Ans : FOREIGN 2017
where, C = Concentration of solution in moles/ Given, p = 0.0821
litre t = 300k
T = Temp. in degrees kelvin We know that,
-1 -1
R = 0.0821 litre atoms K mol p = CRT
p 1 = 50 # 0.0821 # T ...(1) or C = p
342 RT
Concentration of 1% sol. of substance X R = 0.0821 L atm K-1 mol-1
= 1 gm/100 ml T = 300K
= 10 gm/liter 0.0821 atm
C =
(0.0821 Latm K-1 mol-1) # 300K
= 10 moles/liter
M = 0.3 # 10-2 mol L-1
Where, M = molecular mass of substances X = 0.0033 M
So, p 2 (osmotic pressure of 1% solution of substance Thus (d) is correct option.
X)
6. Azeotropic mixture of HCl and H 2 O has:
= 10 # 0.0821 # T ...(2) (a) 48% HCl (b) 22.2% HCl
M
As both solution are isotonic, so p 1 = p 2 (c) 36% HCl (d) 20.2% HCl
50 0.0821 # T = 10 # 0.0821 # T Ans : OD 2017
342 # M
The Volume of water that must be added to a mixture
M (mo. wt. of X ) = 342 = 68.4 of 250 ml of 0.6 M HCl and 750 ml of 0.2 M HCl to
5
obtain 0.25 M solution of HCl is 20.2%.
Thus (a) is correct option.
Thus (d) is correct option.
7. If 2 gm of NaOH is present in 200 ml of its solution, 10. Which one of the following will produce maximum
its molarity will be : depression of freezing point?
(a) 0.25 (b) 0.5 (a) K2 SO4 (b) NaCl
(c) 5 (d) 10 (c) Urea (d) Glucose
Ans : SQP 2015, COMP 2013 Ans : OD 2013, SQP 2009
We know that Depression in freezing point is a collegative property.

moles of solution (n) It depends on the number of solute particles in the
Molarity ^C h = solution.
volume of solutionV (mL)
w (moles of solute) Number of solution particles the solution \ collegative
And n = property.
m (molar mass of solute)
Molar mass of NaOH = 23 + 16 + 1 = 40 (a) For, K 2 SO 4 $ 2K+ + SO 24-
Number of particles = 2 + 1 = 3
^C h = MB # 1000
Or, W
B V (in ml) (b) For, NaCl $ Na + Cl-
Hence, C = 2 # 1000 Number of particles = 1 + 1 = 2
40 # 200
(c) For, Urea $ No, dissociation
Molarity of solution = 0.25 M Number of particles = 1
Thus (a) is correct option. (d) For, Glucose $ No, dissociation
8. Volume of one mole of any gas at NTP is : Number of particles = 1
(a) 11.2 litre (b) 22.4 litre Thus (a) is correct option.
(c) 10.2 litre (d) 22.8 litre 11. 234.2 gm of sugar syrup contains 342 gm of sugar.
What is the molal concentration of the solution?
Ans : DELHI 2015
(a) 0.1 (b) 0.5
One mole of any gas at NTP (normal temperature
and pressure) occupies 22.4 litre (by volume) of space. (c) 5.5 (d) 55
We know that for ideal gas: Ans : COMP 2011
PV = nRT , Given,
Weight of sugar syrup = 234.2 gm
Where, P = Pressure of gas = ^1 atmh
Weight of sugar in the syrup = 34.2 gm
V = Volume of gas
Hence, Weight of water in the syrup,
n = moles of gas (n = 1)
WA = 234.2 - 34.2 = 200 gm
R = Gas constant ^= 0.0821h Molar weight of Sugar,
T = Temperature ^= 273 k - capitalh C 12 H 22 O 11 = (12 # 12) + (22 # 1) + (16 # 11)
Hence, V = nRT = 342
P
Molal Concentration
= 1 # 0.0821 # 273
1 i.e., Molality = Moles of solute
Mass of solvent in kg
V = 22.4.L (for one mole of gas)
Hence, Molal concentration ^mh
Thus (b) is correct option.
= 34.2 # 1000
9. Avogadro’s number ^N h is equal to : 342 # 200
(a) 6.023 # 1024 (b) 6.023 # 1023 = 34200 = 0.5
68400
(c) 6.023 # 10-23 (d) 11.2
Ans : FOREIGN 2015
12. Which of the following is not a colligative property?
One mole of any substance contain 6.023 # 1023
number of particles is known as Avogadro’s number (a) Depression in freezing point
(N). In other words, 6.023 # 1023 number of any (b) Optical activity
particle is known as one mole. (c) Gas dispersed in gas
(d) Elevation of boiling point
Ans : DELHI 2010

Since molality does not include the volume term, it is
The property which depends on the relative quantity independent of temperature.
of solute and solvent but not on the nature of solute, Thus (d) is correct option.
and termed as collegative property.
15. Isotonic solutions have same:
Optical-property depends on the nature of compound.
Thus is not a collegative-property. All other given (a) Molar concentration (b) Molality
options belongs to collegative property. (c) Normality (d) None of these
Thus (b) is correct option. Ans : SQP 2015, 2009
Isonotic solutions have same molar concentration at
13. Statement I : Van’t Hoff factor for KCI is 2 whereas
given temperature provided the Van’t Hoff factor (i)
it is 1.45 for CH 3 COOH .
is same.
Statement II : CH 3 COOH is completely ionized.
(a) Both the statements are true and Statement II is
the correct explanation of Statement I. 16. The vapour pressure of two liquids P and Q are 80
and 60 torr, respectively. The total vapour pressure of
(b) Both the statements are true, but Statement II is solution obtained by mixing 3 mole of P and 2 mole
not the correct explanation of Statement I. of Q would be:
(c) Statement I is true, but Statement II is false. (a) 72 torr (b) 140 torr
(d) Statement I is false, but Statement II is true. (c) 68 torr (d) 20 torr
Ans : FOREIGN 2014 Ans : COMP 2011, 2009
Van’t Hoff factor (or i factor) is defined as the ratio Given,
of the observed colligative property to the calculated
V.PP = 80 torr
colligative property.
Observed colligative property V.PQ = 60 torr
i =
Calculated colligative property Ptotal = V.PP # XP + V.Pq # XQ
Each KCl (K+ and Cl- ) ionize to gives 2 ions thus
Van’t Hoff factor for KCl is 2. = b80 + 3 + 60 # 2 l
5 5
Acetic acid (CH 3 COOH) is a weak acid and ionizes as = 16 # 3 + 12 # 2
CH 3 COOH ? CH 3 COO- + H+
Ptotal = 48 + 24 = 72 torr
Hence, CH 3 COO- (i) < 2 , thus
The Van’t Hoff factor will lie in between 1 and 2 i.e.
1.45. 17. When mercuric iodide is added to the aqueous
solutions of potassium iodide then:
Thus (c) is correct option.
(a) freezing point is raised.
14. Which of the following concentration unit is (b) freezing point is lowered.
independent of temperature?
(c) freezing point does not change.
(a) Normality (b) Molarity
(d) boiling point does not change.
(c) Formality (d) Molality
Ans : DELHI 2007
Ans : OD 2009
Added Hgl 2 from a complex with KI in the solutions
Volume is temperature dependent, hence expression as follows:
involving volume term (normality, molarity and
2KI + HgI 2 " K 2 [HgI 4]
formality) varies with temperature.
geq. of solute As a result, number of particles decreases and so DTf
Normality = increases.
vol. of solution in L
Molarity = moles of solute
vol. of solution in L 18. An ideal solution is formed when its components:
Formality = formula mass (a) have no volume change on mixing
vol. of solution in L
moles of solute (b) have no enthalpy change on mixing
Molality =
mass of solvent in Kg (c) have both the above characteristics
(d) have high solubility
Ans : FOREIGN 2003

For isotonic solution
For ideal solution,
p1 = p 2
DVmixing = 0
= 10 # 0.821 # T
and DH mixing = 0 60
Thus (c) is correct option. = 50 # 0.821 # T
M
19. Colligative properties of the solution depend on:
M = 300 gm mol-1
(a) Nature of solute
(b) Nature of solvent
22. The Van’t Hoff factor i for a compound which
(c) Number of particles present in the solution
undergoes dissociation in one solvent and association
(d) Number of moles of solvent only in other solvent is respectively:
Ans : OD 2011 (a) less than one and greater than one.
Colligative properties of dilute solution containing non (b) less than one and less than one.
volatile solute depends upon the number of particles
(c) greater than one and less than one.
of the solute present in the solution.
(d) greater than one and greater than one.
Ans : DELHI 2016
20. Which is not colligative property? If compound dissociates in solvent i > 1 and on
(a) Freezing Point association i < 1.
(b) Lowering of vapour pressure Thus (c) is correct option.
(c) Depression of freezing point 23. All from ideal solution except:
(d) Elevation of boiling point (a) C 6 H 6 and C 6 H 5 CH 3
Ans : SQP 2016 (b) C 2 H 6 and C 2 H 5 I
Colligative property is strictly true only for dilute (c) C 6 H 5 Cl and C 6 H 5 Br
solutions which behaves as nearly ideal solution.
These properties are: lowering of vapour pressure of (d) C 2 H 5 I and C 2 H 5 OH
the solvent, elevation in boiling point of the solvent, Ans : FOREIGN 2009, OD 2007
depression in freezing point of the solvent. C 2 H 5 I and C 2 H 5 OH form non-ideal solution.
Thus (a) is correct option. Thus (d) is correct option.
21. A solution containing 10g per dm3 of urea (molecular 24. A solution of acetone in ethanol:
mass = 60 g mol-1 ) is isotonic with a 5% solution (a) shows a positive deviation from Raoult’s law
of a non-volatile solute. The molecular mass of this (b) behaves like a non ideal solution
non- volatile solute is:
(c) obeys Raoult’s law
(a) 300 g mol-1 (b) 350 g mol-1
(d) shows a negative deviation from Raoult’s law
(c) 200 g mol-1 (d) 250 g mol-1
Ans : OD 2001, SQP 2005
Ans : COMP 2013
A solution of acetone in ethanol shows positive
Osmotic pressure of urea from the formula. deviation from Raoult’s law. It is because ethanol
pV = nRT molecules are strongly hydrogen bonded. When
acetone is added, these molecules break the hydrogen
p = nRT bonds and ethanol becomes more volatile. Therefore
V
10 is vapour pressure is increased.
= 0.821 # T [1dm3 = 1litre]
60 # Thus (a) is correct option.
5% solutions means 25. By increasing the temperature, the vapour pressure
100 ml = 5 gm of substance:
1000 ml = 50 g/L (a) always increases
(b) does not depend on temperature
Osmotic pressure of solution having non-volatile solute
(c) always decreases
p 2 = 50 # 0.821 # T
M (d) partially depends on temperature
Ans : COMP 2008

29. Pressure cooker reduces cooking time because:
By increasing the temperature the vapour pressure (a) the heat is more easily distributed
of a substance always increases because more vapour
will be formed at higher temperature. (b) the higher pressure tenderizes the food
Thus (a) is correct option. (c) the boiling point of the water inside is elevated
(d) a larger flame is used
26. Which one of the following salts will have the same
value of van’t Hoff factor (i) as that of K 4 [Fe (CN) 6]: Ans : SQP 2014, DELHI 2009
(a) Al 2 (SO 4) 3 (b) NaCl The boiling point of water inside the cooker increases
beyond 100 o C due to accumulation of steam and
(c) Al (NO 3) 3 (d) Na 2 SO 4 increase in pressure. Thus making it possible to cook
Ans : DELHI 2001 food faster.
K 4 [Fe (CN) 6] and Al 2 (SO 4) 3 both dissociates to give Thus (c) is correct option.
6 ions or i = 5
30. During osmosis, flow of water through a semi-
K 4 [Fe (CN) 6] 4K+ + [Fe (CN) 6] permeable membrane is:
and Al 2 (SO 4) 3 2Al3+ + 3SO 4-- (a) from both sides of semi-permeable with equal flow
rates
(b) from both sides of semi-permeable membrane
27. For a dilute solution, Raoult’s law that: with unequal flow rates
(a) the lowering of vapour pressure is equal to the (c) from solution having lower concentration only
mole fraction of the solute
(d) from solution having higher concentration only
(b) the relative lowering of vapour pressure is equal
Ans : COMP 2006
to the mole fraction of the solute
During osmosis water flows through semi-permeable
(c) the relative lowering of vapour pressure is
membrane from lower concentration to higher
proportional to the amount of solute in solution
concentration.
(d) the vapour pressure of the solution is equal to the Thus (c) is correct option.
mole fraction of the solvent
Ans : FOREIGN 2000
31. Which one is a colligative property?
According to Raoult’s Law. (a) boiling point (b) vapour pressure
Relative lowering of vapour pressure (c) osmotic pressure (d) freezing point
po - p Ans : DELHI 2002
=
po Osmotic pressure is a colligative property.
= n solute Thus (c) is correct option.
n solute + N solvent
= xsolute 32. Which of the following aqueous solution has minimum
freezing point?
(a) 0.01 m NaCl (b) 0.005 m C 2 H 5 OH
28. The osmotic pressure of equimolar solution of (c) 0.005 m Mgl 2 (d) 0.005 m MgSO 4
BaCl 2, NaCl and sucrose will be in the order:
Ans : FOREIGN 2015
(a) Sucrose > NaCl > BaCl 2
As we know that,
(b) Sucrose > BaCl 2 > NaCl
TTf = i # K f # m
(c) NaCl > BaCl 2 > Sucrose
Van’t Hoff factor, i = 2 for NaCl
(d) BaCl 2 > NaCl > Sucrose
Hence TTf = 0.02 K f
Ans : OD 2015
which is maximum in the present case.
The number of mole particles of BaCl 2 , NaCl and
sucrose in the solution are 3, 2 and 1 respectively. Hence TTf is maximum or freezing point is minimum.
Thus (d) is correct option. Thus (a) is correct option.
33. A solution contains non-volatile solute of molecular Ans : FOREIGN 2013
mass M2 . Which of the following can be used to In solution containing A and B component showing
calculate the molecular mass of solute in terms of negative A - A and B - B interactions are weaker
osmotic pressure? than that of A - B interactions. For Such solutions.
(a) M2 = 9m2 C VRT (b) M2 = 9m2 C RT DH = - ve
p V p
and DV = - ve
(c) M2 = 9m2 C pRT (d) M2 = 9m2 C p Thus (d) is correct option.
V V RT
Ans : OD 2001 37. Which of the following liquid pairs shows a positive
pV = nRT deviation from Raoult’s law?
(a) Water-nitric acid
= m RT
M (b) Benzene-methanol
or M2 = 9m2 C RT (c) Water-hydrochloric acid
V p
Thus (b) is correct option. (d) Acetone-chloroform
34. Camphor is often used in molecular mass determination Ans : OD 2008
because: Positive deviations are shown by such solutions in

(a) it is readily available. which solvent-solvent and solute-solute interactions are
stronger than the solvent interactions. In such solution,
(b) it has a very high cryoscopic constant. the interactions among molecules becomes weaker.
(c) it is volatile. Therefore their escape tendency increases which results
(d) it is solvent for organic substances. in the increase in their partial vapour pressures.
Ans : SQP 2010, COMP 2015
In a solutions of benzene and methanol there exists
Solvent having high cryoscopic constant can be used in inter molecular H - bonding.
determination of molecular mass by cryoscopic method.
35. The mole fraction of the solute in one molal aqueous
solution is: In this solution benzene molecules come between
ethanol molecules which weaken intermolecular forces.
(a) 0.009 (b) 0.018
This results in increase in vapour pressure.
(c) 0.027 (d) 0.036
Ans : DELHI 2015
38. Equimolar solution in the same solvent have:
One molal solution means one solute present in 1 kg
(1000 g) Solvent i.e., (a) Different boiling and different freezing points
Mole of solute = 1 (b) Same boiling and same freezing points
1000 g (c) Same freezing point but different boiling points
Mole of solvent ^H 2 Oh = = 1000
18 g 18 (d) Same boiling point but different freezing points
Mole fraction of solute = 1 Ans : SQP 2002
61 + 1000
18 @
Equimolar solutions of normal solutes in the same
= 18 = 0.018 solvent will have the same boiling points and same
1018
freezing points.
36. In mixture A and B components show –ve deviation
as: 39. The molecular weight of benzoic acid in benzene as
determined by depression in freezing point method
(a) DVmix > 0
corresponds to:
(b) D H mix > 0 (a) ionization of benzoic acid.
(c) A - B interaction is weaker than A - A and (b) dimerization of benzoic acid.
B - B interaction.
(c) trimerizatin of benzoic acid.
(d) A - B interaction is stronger than A - A and
B - B interaction. (d) solvationof benzoic acid.
Ans : COMP 2001 Ans : SQP 2015
Benzoic acid exists as dimer in benzene. According to Boyle-van’t Hoff Law,

Thus (b) is correct option. p \ c (at constant temp)
40. As a result of osmosis, the volume of the solution: Thus (a) is correct option.
(a) gradually decreases 44. For an electrolyte, elevation of B.P. is directly
(b) gradually increases proportional to:
(a) molarity (b) molality
(c) is not affected
(c) mole fraction (d) all of these
(d) suddenly increases
Ans : COMP 2011, DELHI 2013
Ans : DELHI 2004
Thus (b) is correct option. TTb = Kb # i # molality

Where TTb = elevation in boiling
41. If A contains 2% NaCl and is separated by a
semipermeable membrane from B Which contains i = van’t Hoff factor
10% NaCl, then which event will occur? TTb \ Molality
(a) NaCl will flow from A to B. Thus (b) is correct option.
(b) NaCl will flow from B to A. 45. For an electrolyte, elevation of B.P. is directly
(c) Water will net flow from A to B. proportional to:
(d) Water will net flow from B to A. 1. Pure solvent " separated solvent molecules, TH1
Ans : FOREIGN 2014, 2008 2. Pure solute " separated solute molecules, TH2
Solvent net flow from low concentration solution to 3. Separated solvent &solute molecules " solution,
high concentration solution. TH3 . Solution so formed will be ideal if.
Thus (c) is correct option. (a) TH so ln = TH3 - TH1 - TH2
(b) TH so ln = TH1 + TH2 + TH3
42. Which of the following pairs of solution are isotonic at
the same temperature? (c) TH so ln = TH1 + TH2 - TH3
(a) 0.1 M Ca (NO 3) and 0.1 M Na 2 SO 4 (d) TH so ln = TH1 - TH2 - TH3
(b) 0.1 M NaCl and 0.1 M Na 2 SO 4 Ans : FOREIGN 2016
(c) 0.1 M urea and 0.1 M MgCl 2 For an ideal solution
(d) 0.2 M urea and 0.1 M NaCl TH mixing = 0
Ans : OD 2016 TH = TH1 + TH2 + TH3

The solution which provide same number of ions are (According to Hess’s law)
isotonic. i.e. for ideal solutions there is no change in magnitude
Ca ^NO 3h2 $ Ca2+ + 2NO 3- of the attractive forces in the two components present.
Total ions produced = 3
46. Which of the following colligative property can provide
Na 2 SO 4 $ 2Na+ + SO 42- molar mass of proteins (or polymers or colloids) with
Total ions produced = 3 greatest precision?
0.1 MCa ^NO 3h2 and 0.1 M (a) Osmotic pressure.
Na 2 SO 4 are isotonic. (b) Elevation of boiling point.

Thus (a) is correct option. (c) depression of freezing point.
(d) Relative lowering of vapour pressure.
43. Osmotic pressure of a solution at a given temperature:
Ans : SQP 2012
(a) increases with concentration
Molecular masses of polymers are best determined
(b) decreases with concentration by osmotic pressure method. Firstly because other
(c) remains same colligative properties gives so low values that
(d) initially increases and then decreases they cannot be measured accurately and secondly,
osmotic pressure measurements can be made at room Freezing point of solution,

temperature and do not require heating which may T = 271.95 K
change the nature of polymer.
Molal depression constant or cryoscopic constant,
K f = 1.86 K mole-1
47. Which one of the following is not correct for an ideal
solution? Molar mass of solute,
(a) It must obey Raoult’s law 1000 # K f # w
m =
^T0 - T h # W
(b) TH = 0
= 1000 # 1.86 # 1.25
(c) TC = 0 ^273 - 271.94h # 20
(d) TH = 0TV ! 0
= 50 # 1.86 # 1.25 = 109.67
Ans : OD 2004 1.06
For an ideal solution Thus (a) is correct option.
TH = 0 51. The relative lowering of the vapour pressure is equal
to the ration between the number of:
TV = 0
(a) solute molecules to the solvent molecules in the
Thus (d) is correct option. solution
48. The normality of 10% (weight/volume) acetic acid is: (b) solute molecules to the total molecules in the
(a) 1 N (b) 10 N solution
(c) 1.7 N (d) 0.83 N (c) solvent molecules to the total molecules in the
Ans : SQP 2003 solution
As we know that, (d) solvent molecules to the total number of ions of
the solute.
Mol. mass of CH 3 COOH = 60
Ans : DELHI 2013, 2007
Normality = 10 # 1000 = 1.7 ;
60 # 100 According to Raoult’s law, the relative lowering in
Thus (c) is correct option. vapour pressure of a dilute solution is equal to the
mole fraction of the solute present in the solution.
49. Osmotic pressure of a sugar solution at 24 o C is 2.5
atmosphere. The concentration of the solution in gm p0 - p
= mole fraction of solute
mole per litre is: p
(a) 10.25 (b) 1.025 = n
n+N
(c) 102.5 (d) 0.1025 Thus (b) is correct option.
Ans : SQP 2006
52. A solution is obtained by dissolving 12 gm of urea
C = p = 2.5 (mol. wt. 60) in a litre of water. Another solution is
RT 0.082 # 297
obtained by dissolving 68.4 gm of cane sugar (mol. wt.
= 0.1025 mol litre-1 342) in a litre of water at the same temperature. The
Thus (d) is correct option. lowering of vapour pressure in the first solution is:
50. The freezing point of a solution prepared from 1.25 gm (a) same as that of 2nd solution
of a non electrolyte and 20 gm of water is 271.94 K. If (b) nearly one fifth of the 2nd solution
Kf is 1.86 Kmol-1 . Then the molar mass of the solute (c) double that of 2nd solution
will be nearly:
(d) nearly five times that of 2nd solution
(a) 109 (b) 106
Ans : FOREIGN 2011, OD 2008
(c) 115 (d) 93
Given, In the Ist solution,
Ans :
Weight of urea ^wu h = 12 g
COMP 2015
Weight of solute or non-electrolyte,

w = 1.25 gm Mu = 60
Weight of solvent or water, Vw = 1 litre

W = 20 gm and In second solution,
wc = 68.4 gm Ans : DELHI 2006
As both the solutions are isotonic hence there is no net

Mc = 342
movement of the solvent through the semi-permeable
We know that according to Ist solution, membrane between two solutions.
Number of the moles of urea Thus (a) is correct option.
nu = wu = 68.4 = 0.2 56. At 25 o C , the highest osmotic pressure is exhibited by
Mu 342
0.1 M solution of:
According IInd solution,
(a) CaCl 2 (b) KCl
Number of the moles of cane sugar
(c) Glucose (d) Urea
nc = wc = 68.4 = 0.2 Ans :
Mc 342 FOREIGN 2007
We know that lowering in vapour pressure depends on Conc. of particles in CaCl 2 sol. will be max. as
the number of solute. Since both solutions have same i = 3 is max.
number of moles, therefore, lowering in vapour point
will be same.
Thus (a) is correct option. 57. Vapour pressure of benzene at 30 o C is 121.8 mm.
When 15 g of a non-volatile solute is dissolved in 250 g
53. The 5.85 g of NaCl and one kg of water is added to benzene its vapour pressure decreased to 120.2 mm.
prepare a solution. What is the strength of NaCl in The molecular weight of the solute.
this solution? (Molecular weight of NaCl = 58.5 )
(Mo wt. of solvent = 78 )
(a) 0.1 Normal (b) 0.1 Molal
(a) 356.2 (b) 45.8
(c) 0.1 Molar (d) 0.1 Formal
(c) 530.1 (d) 656.7
Ans : SQP 2001
Ans : OD 2016
Molality = mol kg-1 Give, vapour pressure of pure solute
= 5.85 = 0.1 P0 = 121.8 mm ;
58.5
Thus (b) is correct option. Weight of solute w = 15 g
54. Blood cells retain their normal shape in solution Weight of solvent W = 250 g
which are: Vapour pressure of pure solvent
(a) hypotonic to blood P = 120.2 mm
(b) isotonic to blood and Molecular weight of Solvent
(c) hypertonic to blood M = 78
(d) equinormal to blood 0
From Raoult’s law = P -0 P = w # M
Ans : COMP 2007, DELHI 2002 P m W
Blood cells neither swell nor shrink in isotonic solution. = 121.8 - 120.2
As isotonic solutions have equal concentration 121.8
therefore there is no flow of solvent is found and hence = 15 # 78
solvent neither enters nor flow out of the blood cells. m 250
Thus (b) is correct option. m = # # 121.8
15 78
250 1.6
55. If 0.1 M solution of glucose and 0.1 M solution of
= 356.2
urea are placed on two sides of the semi-permeable
membrane to equal heights, then it will be correct to Thus (a) is correct option.
say that: 58. A solution of urea (mol. mass 56 g mol-1 ) boils at
(a) there will be no net movement across the 100.18 o C at the atmospheric pressure. If K f and Kb
membrane for water are 1.86 and 0.512 K Kg mol-1 respectively,
(b) glucose will flow towards urea solution the above solution will freeze at:
(c) urea will flow towards glucose solution (a) 0.654 o C (b) - 0.654 o C
(d) water will flow from urea solution to glucose (c) 6.54 o C (d) - 6.54 o C
Ans : SQP 2009

C 6 H 12 O 6 and C 12 H 22 O 11 are not ionised so they have
As TTf = K f m single particle.
TTb = Kb m $
Hence, Al 2 (SO 4) 3 have maximum value of depression
in F.P or lowest F.P.
TTf
Now, m = = TTb Thus (a) is correct option.
Kf Kb
K 61. Which of the following statements, regarding the mole
TTf = TTb f fraction ^x h of a component in solution, in incorrect?
Kb
[TTb = 100.18 - 100 = 0.18 o C] (a) 0 # x # 1
As the freezing point of pure water is 0 o C (b) x # 1
TTf = 0 - Tf (c) x is always non-negative
0.654 = 0 - T (d) - 2 # x # 2
Tf = - 0.654 Ans : DELHI 2010, FOREIGN 2007
Mole fraction of any component A

Thus the freezing point of solution will be - 0.654 o C .
Thus (b) is correct option. x = No. of moles of A
Total No.of Moles
59. The vapour pressure at a given temperature of an As total no. of moles > no. of moles of A thus x can
ideal solution containing 0.2 mol of a non-volatile never be equal to one on zero.
solute and 0.8 mol of solvent is 60 mm of Hg. The Thus (a) is correct option.
vapour pressure of the pure solvent at the same
temperature is: 62. Molarity of liquid HCl will be, if density of solution
is 1.17 gm/cc.
(a) 150 mm of Hg (b) 60 mm of Hg
(a) 36.5 (b) 32.05
(c) 75 mm of Hg (d) 120 mm of Hg
(c) 18.25 (d) 42.10
Ans : OD 2015
Ans : OD 2014
According to Raoult’s law
Density = 1.17 gm/cc (Given)
P0 - P = X
d = Mass
B
P0 As
R V Volume
SXB = Mole fraction of solute = .2 = 1 W Volume = 1cc
S .2 + . 8 5 W
SP = 60 mm of Hg W Mass = d = 1.17 g
T X
P0 - P = 1 Now, molarity = No. of moles
P0 5 Volume in litre
= 11.7 # 1000 = 1170
0
or 4P = (P) # 5
36.5 # 1 36.5
P0 = 60 # 5 = 75 mm of Hg = 32.05 M
4
Thus (c) is correct option. Thus (b) is correct option.
60. Which of the following 0.10 m aqueous solutions will 63. 1 M, 2.5 litre NaOH solution is mixed with another
have the lowest freezing point? 0.5 M, 3 litre NaOH solution. Then find out the
(a) Al 2 (SO 4) 3 (b) C 6 H 12 O 6 molarity of resultant solution.
(c) KCl (d) C 12 H 22 O 11 (a) 0.80 M (b) 1.0 M
Ans : COMP 2002

(c) 0.73 M (d) 0.50 M
Depression in F.P. \ No. of particles. Ans : SQP 2003
Al 2 ^SO 4h3 provides five ions on ionisation From molarity equation,

M1 V1 + M2 V2 = MV
Al 2 ^SO 4h3 $ 2Al3 + 3SO 24-
1 # 2.5 + 0.5 # 3 = M # 5.5
While KCl provides two ions
KCl K+ + Cl- M = 4 = 0.73 M
5.5
64. 1.00 g of non-electrolyte solute (molar mass = 1.86 # 1000 # 68.5 = 0.372
250 g mol-1 ) was dissolved in 51.2 g of benzene. If the 342 # 1000
freezing point depression constant, K f of benzene is Tf = - 0.372 o C
5.12 K Kg mol-1 , the freezing point of benzene will Thus (a) is correct option.
be lowered by:
68. 25.3 g of sodium carbonate, Na 2 CO 3 is dissolved in
(a) 0.3 K (b) 0.5 K
enough water to make 250 mL of solution. If sodium
(c) 0.4 K (d) 0.2 K carbonate dissociates completely, molar concentration
Ans : COMP 2015 of sodium ion,
TT = K f m Na+ and carbonate ions, CO 2-
3 are respectively (Molar
mass of Na 2 CO 3 = 106 g mol-1 )
= 5.12 # 1 # 1000 = 0.4 K
250 51.2 (a) 0.955 M and 1.910 M
(b) 1.910 M and 0.955 M
65. A 0.0020 m aqueous solution of an ionic compound
(c) 1.90 M and 1.910 M
Co (NH 3) 5 (NO 2) Cl freezes at 0.00732 o C . Number of
moles of ions which 1 mol of ionic compound produces (d) 0.477 M and 0.477 M
on being dissolved in water will be (K f = - 1.86 o C/m) : Ans : FOREIGN 2011
(a) 3 (b) 4 Concentration of
(c) 1 (d) 2 Na 2 CO 3 = 25.3 # 1000 = 0.955 M
106 250
Ans : SQP 2007
6Na @ = 2 # 0.955 = 1.91 M
+
TTf = i # K f # m
6CO 3 @ = 0.955 M
2-
TTf
i =
Kf # m Thus (b) is correct option.
= 0.00732 =2 69. The freezing point depression constant for water is
1.86 # 0.002 - 1.86 o C m-1 . If 5.00 g Na 2 SO 4 is dissolved in 45.0
Thus (d) is correct option. g H 2 O, the freezing point is changed by - 3.82 o C.
66. An aqueous solution is 1.00 molal in KI. Which Calculate the van’t hoff factor for Na 2 SO 4 .
change will cause the vapour pressure of the solution (a) 2.05 (b) 2.63
to increase? (c) 3.11 (d) 0.381
(a) Addition of NaCl
Ans : OD 2014, DELHI 2012
(b) Addition of Na 2 SO4 o -1
Given, K f = - 1.86 cm
(c) Addition of 1.00 molal KI
mass of solute = 5.00 g
(d) Addition of water
mass of solvent = 45.0 g
Ans : DELHI 2005
When the aqueous solution of one molal KI is diluted TTf = i # K f m

with water, concentration decreases, therefore the 3.82 = i # 1.86 # 5 # 1000
vapour pressure of the resulting solution increases. 142 # 45
Thus (d) is correct option. i = 2.63
67.
-1
A solution of sucrose (molar mass = 342 g mol ) has (Molecular mass of Na 2 SO 4 = 142 )
been prepared by dissolving 68.5 g of sucrose in 1000 Thus (b) is correct option.
g of water. The freezing point of the solution obtained 70. Mole fraction of the solute in a 1.00 molal aqueous
will be (K f for water = 1.86 K kg mol-1 ): solution is:
(a) - 0.372 o C (b) - 0.520 o C (a) 0.1770 (b) 0.0177
(c) + 0.372 o C (d) - 0.570 o C (c) 0.0344 (d) 1.7700
Ans : SQP 2002 Ans : SQP 2013
TTf = K f 1000W2 1 molal solution means 1 mole of solute dissolved in

M2 W1 1000 gm solvent.
n solute = 1 Tbo = boiling point of solvent

wsolvent = 1000 g or Tb = Tbo + TTb
n solvent = 1000 = 55.56 Elevation in boiling point is a colligative property,

18 which depends upon the no. of particles. Thus greater
X solute = 1 = 0.0177 the number of particles, greater is it elevation and
1 + 55.56 hence greater will be its boiling point.
Na 2 SO 4 2Na + SO 4
71. 200 mL of an aqueous solution of a protein contains
Since Na 2 SO 4 has maximum number of particles (c)
its 1.26 g. The osmotic pressure of this solution at
hence has maximum boiling point.
300 K is found to be 2.57 # 10-3 bar. The molar mass
of protein will be:
( R = 0.083 L bar mol-1 K-1 ) 74. 0.5 molal aqueous solution of a weak acid (HX) is
(a) 51022 g mol-1 (b) 122044 g mol-1 20% ionised. If K f for water is 1.86 K kg mol-1 , the
lowering in freezing point of the solution is:
(c) 31011 g mol-1 (d) 61038 g mol-1
(a) 0.56 K (b) 1.12 K
Ans : COMP 2011
(c) –0.56 K (d) –1.12 K
(p) = CRT Osmotic pressure
Ans : OD 2009, SQP 2007
(p) = wt # 1000 RT
Molecular mass # V As TTf = iK f m
= 2.57 # 10-3 For
1.26 # 1000 HX H + + X-
= 0.083 # 300
Mol. mass # 200 # t=0 1 0 0
Molecular mass = 61038 g ^1 - 0.20h 0.20 0.20
Thus (d) is correct option. Total no. of moles = 1 - 0.20 + 0.20 + 0.20
o
72. Freezing point of an aqueous solution is (0.186) C. = 1 + 0.20 = 1.2
Elevation of boiling point of the same solution is
TTf = 1.2 # 1.86 # 0.5
Kb = 0.512 o C , K f = 1.86 o C , find the increase in
boiling point. = 1.1160 . 1.12 K
(a) 0.186 o C (b) 0.0512 o C Thus (b) is correct option.
o o
(c) 0.092 C (d) 0.2372 C 75. An X molal solution of a compound in benzene has
Ans : DELHI 2017 mole fraction of solute equal to 0.2. The value of X is:
WB (a) 14 (b) 3.2
TTb = Kb 1000 ;
MB # WA # (c) 1.4 (d) 2
TTf = K f WB 1000; Ans : COMP 2012
MB # WA #
Relation between molality and mole fractions.
TTb = Kb = TTb
TTf Kf - 0.186 m = 1000 # x2
x1 M1
= 0 . 512 = 0.512 o C
1.86 = 1000 # .2 = 3.2
Thus (b) is correct option. .8 # 78
73. Which one of the following aqueous solutions will
exhibit highest boiling point? 76. A binary liquid solution is prepared by mixing n
(a) 0.015 M urea (b) 0.01 MKNO3 -heptane and ethanol. Which one of the following
statements is correct regarding the behaviour of the
(c) 0.01 MNa 2 SO4 (d) 0.015 M glucose solution?
Ans : FOREIGN 2006 (a) The solution is non-ideal, showing - ve deviation
o
TT = Tb - T
b b
o from Raoult’s Law.
Where, Tb = boiling point of solution (b) The solution is non-ideal, showing + ve deviation
from Raoult’s Law.
(c) n -heptane shows + ve deviation while ethanol 79. The rise in the boiling point of a solution containing
shows-ve deviation from Raoult’s Law. 1.8 g of glucose in 100 g of solvent is 0.1 o C . The molal
(d) The solution formed is an ideal solution. elevation constant of the liquid is:
(a) 0.01 K/m (b) 0.1 K/m
Ans : SQP 2016
For this solution intermolecular interactions between- (c) 1 K/m (d) 10 Km

n -heptance and ethanol are weaker than n -heptance- Ans : FOREIGN 2016
n heptance & ethanol-ethanol interactions hence the
Kb = 0.1 # 180 # 100 = 1 K/m
solution of n -heptane and ethanol is non-ideal and 1.8 # 1000
shows positive deviation from Raoult’s law. Thus (c) is correct option.
Thus (b) is correct option. 80. A 0.5 molal solution of ethylene glycol in water is used
77. The vapour pressure of a solvent decreased by 10 mm as coolant in a car. If the freezing point constant of
of mercury when a non-volatile solute was added to water be 1.86 o C per mole, the mixture shall freeze at:
the solvent. The mole fraction of the solute in the (a) 0.93 o C (b) - 0.93 o C
solution is 0.2. What should be the mole fraction of (c) 1.86 o C (d) - 1.86 o C
the solvent if the decrease in the vapour pressure is to
Ans : OD 2009
be 20 mm of mercury?
(a) 0.8 (b) 0.6 TTf = K f # m
(c) 0.4 (d) 0.2 = 1.86 # 0.5 = 0.93 ;
Ans : COMP 2013 Tf = 0.93 o C
According to Raoult’s law. Thus (b) is correct option.
Tp
= n (Mole fraction of solute) 81. The relationship between osmotic pressure at 273 K
p0 n+N
when 10g glucose (P1) 10 10 g urea ^P2h , and 10 g
10 = 0.2 sucrose (P3) are dissolved in 250 ml of water is:
p0
(a) P1 > P2 > P3 (b) P3 > P1 > P2
p0 = 50 mm
(c) P2 > P1 > P3 (d) P2 > P3 > P1
For other solution of same solvent
20 = n (Mole fraction of solute)
p0 n+N Moles of glucose 10 = 0.05
180
Mole fraction of solute = 20
5 Urea = 10 = 0.16
60
Mole fraction of solute = 0.4
As mole fraction of solute + mole traction of solvent Sucrose = 10 = 0.029
342
=1 Hence, osmotic pressure P2 > P1 > P3 (p ? c)
Hence, mole fraction of solvent = 1 - 0.4 = 0.6 Thus (c) is correct option.
82. The relationship between the values of osmotic pressure
78. What is the lowering of vapour pressure due to the of 0.1 M solutions of KNO 3 (P1) and CH 3 COOH (P2) is:
solute in a 2 molal aqueous solution at 100 o C ? P1 = P2
(a) (b) P1 > P2
(a) 0.018 atm (b) 0.036 atm P1 + P2 P1 + P2
(c) 0.18 atm (d) 0.36 atm (c) P2 > P1 (d) P1 = P2
Ans : DELHI 2011 Ans : DELHI 2017
Relative lowering in vapour pressure KNO 3 is strong electrolyte which dissociates into two
ions. Therefore, its vant Hoff factor is 2. Acetic acid
= m # MA = 2 # 18 = 0.036 (CH 3 COOH) is a weak electrolyte, it does not dissociate.
1000 1000
Relative lowering in vapour pressure = cB So, its vant Hoff factor is less than that of KNO 3
Osmotic pressure of 0.1 M KNO 3 > Osmotic pressure
c B = 0.036
of 0.1 MCH 3 COOH .
0
P - P = TP = c B # 1 = 0.036 atm or P1 > P2
Thus (b) is correct option. Thus (b) is correct option.
83. Which has the minimum freezing point? Ans : COMP 2001, DELHI 2004
(a) One molal NaCl aq. solution If H 2 O = x mol = 18x g

(b) One molal CaCl 2 aq. solution then urea x mol = 60x g
(c) one molal KCl aq. solution Total mass of the solution
(d) one molal urea aq. solution = 18x + 60x = 78x g
Ans : FOREIGN 2011 Mass % urea = 60x # 100
78x
Among the given option, CaCl 2 solution will produce
maximum (three) ions per molecule, so it will show = 76.92%
minimum freezing point. Thus (c) is correct option.
Thus (b) is correct option. 87. The vapour pressure of pure benzene at 25 o C is
84. The vapour pressure of pure liquid A is 0.80 atm. 640mm Hg and that of solution of solute A is 630mm
When a non volatile B is added to A, its vapour Hg. The molarity of solution is:
pressure drops to 0.60 atm. The mole fraction of B in (a) 0.2 M (b) 0.4 M
the solution is:
(c) 0.5 M (d) 0.1 M
(a) 0.125 (b) 0.25
Ans : FOREIGN 2005
(c) 0.5 (d) 0.75
Tp
= nB
Ans : OD 2008 p0 nA
Mole fraction (c B) of B (solute) in a solution is given nB = 640 - 630 = 0.0156
by the reaction. nA 640 1
p - p3 or 1 mole i.e. 78 g benzene contains solute
cB =
p
= 0.0156 mol
[p = V.P. of liquid A (solvent); ps = V.P. of solution]
3
Given, Molarity of solution = 0.0156 # 10 = 0.2 M
78
p = 0.80 atm; Thus (a) is correct option.
ps = 0.60 atm
Substituting the given values, we get
c B = 0.80 - 0.60
0.80 ASSERTION AND REASON
= 0.20 = 0.25
0.80
DIRECTION : Given below are two statements labelled as
Assertion and Reason. Select the most appropriate answer
85. The freezing point of equimolal aqueous solutions will from the options given below:
be highest for:
(a) C 6 H 5 NH 3 Cl (aniline hydrochloride) 88. Assertion : Osmotic pressure is a colligative property.
Reason : Osmotic pressure is proportional to the
(b) Ca (NO 3) 2
molarity.
(c) La (NO 3) 3 (a) Both Assertion and Reason are true and Reason
(d) C 6 H 12 O 6 (glucose) is the correct explanation of Assertion
Ans : SQP 2006 (b) Both Assertion and Reason are true, but Reason
The salt that ionises to least extent will have highest is not the correct explanation of Assertion.
freezing point (i.e., minimum TTf ] (c) Assertion is true, but Reason is false.
Thus (d) is correct option. (d) Assertion is false, but Reason is true.
86. Equal moles of water and urea are taken in a flask. Ans : OD 2013
What is mass percentage of urea in the solution?
p = CRT (C = concentration or molarity) For a dilute
(a) 7.692% (b) 769.2% aqueous solution, molarity is equal to molality.
(c) 76.92% (d) 0.7692% Thus (a) is correct option.
89. Assertion : If a liquid solute more volatile then the 92. Assertion : Lowering of vapour pressure is directly
solvent is added to the solvent, the vapour pressure of proportional to osmotic pressure of the solution.
the solution may increase i.e., ps > p0 Reason : Osmotic pressure is a colligative property.
Reason : In the presence of a more volatile liquid (a) Both Assertion and Reason are correct and
solute, only the solute will form the vapours and Reason is a correct explanation of the Assertion.
solvent will not.
(b) Both Assertion and Reason are correct but Reason
(a) Both Assertion and Reason are correct and is not the a correct explanation of the Assertion.
Reason is a correct explanation of the Assertion.
(c) Assertion is correct but Reason is incorrect.
is not the a correct explanation of the Assertion. (d) Both the Assertion and Reason are incorrect.
(c) Assertion is correct but Reason is incorrect. Ans : SQP 2020
The relationship between lowering of vapour pressure

(d) Both the Assertion and Reason are incorrect.
and osmotic pressure can be derived as follows:
Ans : COMP 2020, OD 2005
Van’t Hoff equation for dilute solutions is
Both the solute and solvent will form the vapours but
vapour phase will become richer in the more volatile p = n RT ...(1)
V
component. In case of a dilute solution, the volume of solution
Thus (c) is correct option. can be taken as equal to that of solvent. If N is the
90. Assertion : If red blood cells were removed from the number of moles of solvent of molecular weight M
body and placed in pure water, pressure inside the and density r , the volume V is given by
cells increases. V = NM ...(2)
r
Reason : The concentration of salt content in the cells
increases. or n = pM ...(3)
N r.R.T.
(a) Both Assertion and Reason are correct and
From Raoult’s law,
P0 - P = n ...(4)
(b) Both Assertion and Reason are correct but Reason N
P0
is not the a correct explanation of the Assertion.
P0 - P = nM [From (3) and (4)]
(c) Assertion is correct but Reason is incorrect. P0 rRT
(d) Both the Assertion and Reason are incorrect. or (P0 - P) = pM # P0
rRT
Ans : OD 2007 MP 0
The factor rRT is constant at constant temperature.
Pressure inside the cell increases due to osmosis. Water
enters the cell because concentration is higher inside (P0 - P) ap
the cell. This results in lowering of concentration of or lowering of V.P. a osmotic pressure.
medium inside the cell. Osmotic pressure is a colligative property is correct.
Thus (c) is correct option. Thus (a) is correct option.
91. Assertion : Molecular mass of benzoic acid when 93. Assertion : The water pouch of instant cold pack for
determined by colligative properties is fond high treating athletic injuries breaks when squeezed and
Reason : Dimerisation of benzoic acid. NH 4 NO 3 dissolves lowering the temperature.
(a) Both Assertion and Reason are correct and Reason : Addition of non-volatile solute into solvent
Reason is a correct explanation of the Assertion. results into depression of freezing point of the solvent.
(b) Both Assertion and Reason are correct but Reason (a) Both Assertion and Reason are correct and
is not the a correct explanation of the Assertion. Reason is a correct explanation of the Assertion.
(c) Assertion is correct but Reason is incorrect. (b) Both Assertion and Reason are correct but Reason
Ans : DELHI 2017
A molecular mass of benzoic acid is found high because (d) Both the Assertion and Reason are incorrect.
of dimerisation of benzoic acid. Ans : FOREIGN 2015
Thus (a) is correct option. Thus (a) is correct option.

94. Assertion : The molecular weight of acetic acid 98. Define cryoscopic constant.
determined by depression in freezing point method in Ans : FOREIGN 2013
benzene and water was found to be different. It is the depression in freezing point produced on
Reason : Water is polar and benzene is non-polar. dissolving one mole of a substance in 1000 g or 1 kg
(a) Both Assertion and Reason are correct and of the solvent.
Reason is a correct explanation of the Assertion. 99. Which is colligative property among the following?
(b) Both Assertion and Reason are correct but Reason Polysaccharide, osmotic pressure, aldol condensation,
is not the a correct explanation of the Assertion. polarimeter?
(c) Assertion is correct but Reason is incorrect. Ans : OD 2013
Osmotic pressure is a colligative property.

Ans : COMP 2019
100. Correct the following statement by changing the
underlined part of the sentence.
In polar solvent, acetic acid will dissociate leading to
greater depression in freezing point. Water boils below 100°C by the addition of NaCl.
Thus (a) is correct option. Ans : COMP 2008
Water boils above 100c C by the addition of NaCl. It is

because, NaCl is a strong electrolyte and it dissociates
into 2 ions, therefore its van’t Hoff value, i is 2 and
VERY SHORT ANSWER QUESTIONS the elevation of boiling point DTb , is proportional to i .
101. Correct the given statement :
95. Why the freezing point depression ^DTf h of 0.4 M
“Osmotic pressure and boiling point are colligative
NaCl solution is nearly twice than that of 0.4 M
properties.”
glucose solution?
Ans : DELHI 2004
Ans : SQP 2017
Osmotic pressure and elevation in boiling point are
Depression in freezing point is a colligative property colligative properties.
which depends on the number of particles. Glucose is
a molecular compound, it remains as a single molecule 102. Correct the following statement.
in solution. “Molarity of a solution is independent of temperature”.
NaCl ionises in solution to give two particles (ions) Ans : FOREIGN 2005
NaCl $ Na+ + Cl- “Molarity of a solution depends on temperature”.

103. Correct the given statement.
Thus, depression in freezing point ( DTf ) of 0.4 M
“Addition of sodium chloride lowers the boiling point
NaCl is greater than 0.4 M glucose solution.
and freezing point of water.”
96. What is the unit of molal depression constant? Ans : OD 2003, 2005
Ans : COMP 2014, DELHI 2010 Addition of sodium chloride increases the boiling
The unit of molal depression constant is K kg mol-1 . point and decreases the freezing point of water.
97. Define Raoult’s law for the elevation in boiling point 104. Correct the given statement.
of a solution. “Freezing point of a solution is directly proportional
Ans : DELHI 2014 to its molality.”
Raoult’s law states that relative lowering of vapour Ans : SQP 2001
pressure is directly proportional to the mole fraction Depression in freezing point of a solvent is directly
of the solute particles. The elevation in boiling point proportional to its molality.
( DTb ) is directly proportional to the lowering in i.e. DTf \ m
vapour pressure ( Dp ). 105. The osmotic pressure of 0.25 M urea solution is 2.67
DTb \ Dp atm. What will be the osmotic pressure of a 0.25 M
Dp solution of potassium sulphate?
and = w M (Raoult’s law)
pc M lW Ans : COMP 2010
or Dp \ w and DTb \ w Osmotic pressure, p = iCRT where, i is van’t Hoff

M lW M lW factor.
Value of i for urea is 1 (one) while i for potassium = ^120 mm Hg # 0.5h + ^160 mm Hg # 0.5h
sulphate is 3(strong electrolyte). Also, molarity, M for
Ps = 60 + 80 mm Hg.
the two solutions is same (0.25 M).
Ps = 140 mm Hg.
p ^K SO
2 4 soutionh = i # p urea
= 3 # 2.67 = 8.01 atm 109. Why does vapour pressure of a liquid decrease with
addition of a non volatile solid solute?
âs p urea = 2.67 atmh
Ans : SQP 2018
106. 0.1 M urea solution shows less depression in freezing In a solution containing non-volatile solute, the
point than 0.1 M MgCl 2 solution. Explain. surface of solution contains both volatile solvent
Ans : DELHI 2011 molecules and non-volatile solute molecules. As the
Depression in freezing point is a colligative property solute is non-volatile, the number of molecules that
which depends on the number of particles. Urea is a escapes from the liquid surface as vapours, decreases.
molecular compound, it remains as a single molecule. This results, less number of molecules are now in the
In solution magnesium chloride is an ionic compound, vapour state at a given temperature and results the
it ionises as follows to give three particles. decrease in vapour pressure of the solvent.
MgCl 2 $ Mg2+ + 2Cl- More the amount of non-volatile solute added, more
the lowering in vapour pressure.
Thus, 0.1 M urea solution shows less depression in
freezing point than 0.1 M MgCl2 solution. 110. How molarity of a solution different from molality?
107. The elevation in boiling point produced by dilute Ans : COMP 2015, OD 2008
equimolar solution of three substances are in the Molarity ^M h

order A > glucose > B. Suggest a reason for this Molarity is defined as the number of moles of solute
observation. dissolved in one litre or one cubic decimetre of the
Ans : FOREIGN 2010 solution.
Elevation in boiling point is a colligative property Moles of solute
Molarity =
which depends upon number of particles of non- Volume of solution (L)
volatile solute present in the solution. Larger the Molality ^m h
molecular mass of the solute, smaller is the value of It is defined as the number of moles of the solute per
elevation in boiling point. kilogram of the solvent.
On dissociation, molecular mass of the solute decreases Moles of solute
while elevation in boiling point rises and vice- Molality =
versa. Thus, the reason for the given observation in Thus, Molarity is the number of moles of solute per
substance A dissociates while substance B associates litre of solution while molality is the number of moles
in the solution. of solute per kilogram of the solvent.
111. Discuss Raoult’s law of relative lowering of vapour
pressure.
SHORT ANSWER QUESTIONS Ans : DELHI 2015
When a non-volatile solute is added to a solvent, the

vapour pressure is lowered. So, vapour pressure of a
108. The vapour pressure of pure liquid X and pure
solution (p) is always less than the vapour pressure of
liquid Y at 25°C are 120 mm Hg and 160 mm Hg
pure solvent (pc) at the given temperature. (pc - p)
respectively. If equal mole of X and Y are mixed to
is called the lowering in vapour pressure and the ratio
form an ideal solution, calculate the vapour pressure
` pc j is known as the relative lowering in vapour
pc - p
of the solution.
pressure. According to Raoult’s law, the relative
Ans : OD 2023
lowering in vapour pressure of a dilute solution is
Consider we have 1 mole of both X and Y in the equal to the mole fraction of the solute present in the
solution. Then, the mole fraction of X is 0.5 and the solution. i.e.,
mole fraction of Y is also 0.5. According to Raoult’s
pc - p
law, = cB
pc
Ps = PcX XX + PcY XY Where, c B = mole fraction of solute
112. What do you mean by mole fraction? Explain it ? mole fraction of the gas ^ch in the solution.
Ans : FOREIGN 2014 p = KH $ c
Mole fraction is the relation of moles of solvent or
Here, K H = Henry’s law constant.
solute to that of total number of moles in the solution.
It is demoted by (x). Different gases have different K H values at the same
temperature.
Let,
Number of moles of solute = n 116. State the main advantage of molality over molarity as
the unit of concentration.
Number of moles of solvent = N
Ans : DELHI 2005
Then,
Molality does not change with change in temperature
Mole-fraction (of solute) =n (= say x ) while molarity decreases with rise in temperature.
A
n+N
117. What is meant by molality of the solution ?
and Mole-fraction (solvent) = N (= say xB)
n+N Ans : FOREIGN 2001
Then, xA + xB = 1 Molality is defined as the number of moles of the
solute per kilogram of the solvent. It is represented
113. What is reverse osmosis? by m .
Ans : OD 2010 Molality (m) = Number of moles of solute
The direction of osmosis can be reversed if a pressure Mass of solvent (in kg)
larger than the osmotic pressure is applied to the 118. Explain Raoult’s Law.
solution side. The pure solvent flows out of the Ans : OD 2014, 2012
solution through semipermeable membrane towards
Raoult’s law for the solutions of liquids in liquids:
the pure solvent (or less concentrated solution) side.
“The equilibrium vapour pressure of a volatile solute
This phenomenon is called reverse osmosis. This
is linearly proportional to the mole fraction of that
method is used in desalination to get salt free-water
component in liquid phase”.
from sea water as shown in figure.
pA = XA pAc and pB = XB pBc

where, A and B are volatile solute and solvent
respectively.
PcA and PcB are the vapour pressures in pure state.
If XA and XB are the mole fraction of the components
A and B respectively in the vapour phase then,
PA = XA .p total
The pressure required for the reverse osmosis is quite
high. A workable porous membrane is a film of cellulose PB = XB .p total
acetate placed over a suitable support. Cellulose Raoult’s law for solutions of solids in liquid i.e., for
acetate is permeable to water but impermeable to non-volatile solutes,
impurities and ions present in sea water. p solution = X solvent pc solvent
114. Define osmotic pressure. Why does osmotic pressure
become abnormal? 119. Define the term mole fraction.
Ans : SQP 2009, FOREIGN 2004 Ans : SQP 2004
Osmotic pressure may be defined as the excess The mole fraction of a component is the ratio of the
pressure which must be applied to solution in order to number of moles of the component to the total number
prevent flow of solvent into the solution through the of moles of all the components present in the solution.
semi-permeable membrance It is denoted by p . Mole fraction of a component
Explain the Henry’s law about dissolution of a gas in Number of moles of the component
115. =
Total number of moles of all the components
a liquid.
Ans : COMP 2002 For a binary solution, mole fraction of component A,
Henry’s law states that, the partial pressure of the c A = nA
gas in vapour phase (p) is directly Proportional to the nA + nB
Similarly, for B , cB = nB diluted with less soluble helium gas is used as

nA + nB breathing gas.
and cA + cB =1 123. What do you mean by saturated and unsaturated
120. Differentiate between molarity and molality of a solution?
solution. How can we change molality value of a Ans : OD 2018, 2014
solution into molarity value? Saturated solution : A solution in which no more
Ans : COMP 2008 solute can be dissolved at the same temperature and
Molarity is defined as the number of moles of the pressure is called a saturated solution.
solute per kilogram of the solvent. It is represented Unsaturated solution : A solution in which more
by m . solute can be dissolved at the same temperature and
pressure is called an unsaturated solution.
Molality (m) = Number of moles of solute # 1000
Mass of solvent (in g)
124. Define solubility. Name the factors on which solubility
It does not change with change with in temperature.
of a solute in a solvent depends.
Molarity is defined as the number of moles of solute
Ans : SQP 2002
dissolved in one litre or one cubic decimetre of the
solution. The concentration of solute in a saturated solution at
given temperature is called its solubility.
Molality (m) = Number of moles of solute # 1000 Solubility of a solute in a solvent depends upon
Volume of solution (in mL)
It decreases with increase in temperature (as V ? T ). 1. nature of solute and solvent
We can change molality value of a solution into 2. temperature
molarity value by using following relation: 3. pressure.
Molality (m) = M # 1000 125. What is the effect of temperature on solubility of a

(1000 # d) - (M # M2) gas in a liquid?
Where, M is the molarity and M2 is the molar mass Ans : COMP 2004
of component 2 (generally solute) and d is the density
Solubility of a gas in a liquid decreases with increases
of solution (in g cm-3).
in temperature. This is because dissolution of a gas
121. Explain why aquatic species are more comfortable in in a liquid is an exothermic process (i.e. TH is - ve ).
cold water rather than in warm water.
126. Why do the gases always tend to be less soluble in
Ans : DELHI 2010
liquids as the temperature is raised?
Increases in temperature decreases the solubility of
Ans : DELHI 2007
oxygen in water.
Dissolution of gases in liquids is exothermic process
The amount of oxygen dissolved in water decreases
at higher temperature. As a result, it becomes more Gas + Liquid Solution + Heat
difficult to breathe less oxygen. Hence, the aquatic
or Gas + Liquid Solution, TH = - ve
species are not comfortable in warm water.
Therefore, in accordance with Le chatelier’s principle,
122. Write two important applications of Henry’s law.
an increase in temperature will shifts the equilibrium
Ans : FOREIGN 2010
towards left i.e. the solubility of gas in liquid will
Henry’s law states that, the partial pressure of the decrease.
gas in vapour phase (p) is directly Proportional to the
Suggest the most important intermolecular interaction
mole fraction of the gas ^ch in the solution.
127.
in the following pairs:
p = KH $ c 1. n-hexane and n-octane
Here, K H = Henry’s law constant. 2. I 2 and CCl 4
Different gases have different K H values at the same 3. NaClO 4 and water
temperature. 4. Methanol and acetone
Application of Henry’s Law 5. Acetonitrile (CH 3 CN) and acetone (C 3 H 6 O)
1. To increase the solubility of CO 2 in sot drinks and Ans : FOREIGN 2011
soda water, the bottle is sealed under high pressure. 1. Both n-hexane and n-octane are non-polar
2. To minimise the painful effects of bends or molecules. Hence intermolecular interaction
decompression sickness in deep sea divers. oxygen between them will be London Dispersion Forces.
2. Both I 2 and CCl 4 are non-polar molecules. Hence p ?X

intermolecular interaction between them will be
p = pcX
London Dispersion Forces.
3. NaClO 4 is an ionic compound which will where, pc is the vapour pressure of pure component
dissociate, when dissolved in water, to give Na+ and x is the mole fraction of that component.
and ClO 4- ions. The interaction between these 132. Will the molarity of a solution at 50cC be same, less
ions and polar water molecules will be Ion-Dipole or more than molarity at 25cC ?
interactions. Ans : FOREIGN 2007
4. Both methanol and acetone are polar molecules. Molarity at 50cC of a solution will be less than that
Hence interaction between them will be Dipole-
at 25cC because molarity with temperature. This is
Dipole interactions.
because volume of the solution increases with increases
5. Both acetonitrile and acetone are polar molecules. in temperature but number of mole of solute remains
Hence intermolecular interactions between them the same.
will be Dipole-Dipole interactions.
133. Which aqueous solution has higher concentration : 1
128. Briefly explain the effects of temperature on the
molar or 1 molal solution of the same solute. Give
solubility of solids in liquids.
reason.
Ans : OD 2002
Ans : OD 2010
The solubility of a solid in a liquid can be represented
1 Molar solution has higher concentration than 1
by the following equilibrium equation.
molar solution. A molar solution contains one mole of
Solid + liquid solution solute in one litre of solution while a one molal solution
This equilibrium follows Le Chatelier’s principle. contains one mole of solute in 1000 g of solvent. If
If the dissolution process is exoterhmic i.e. THc < 0 density of water is one, then one mole of solute is
the solubility should decrease with rise in temperature present in 1000 ml of water in 1 molal solution while
e.g. in case of NaOH, Na 2 CO 3 etc. But if the one mole of solute is present in less than 100 ml of
dissolution process is endothermic i.e., THc > 0 , the water in 1 molar solution (100 ml solution = amount
solubility should increase with rise in temperature e.g. of solute + amount of solvent). Thus, 1 molar solution
in NH 4 Cl , NaCl etc. is more concentrated.
129. Define Vapour pressure. 134. The molecular weights of sodium chloride and glucose
are determined by the depression of freezing point
Ans : SQP 2002
method. Compared to their theoretical molecular
Vapour Pressure of a liquid (or solution) is the
weight, what will be their observed molecular weights
pressure exerted by its vapour in equilibrium with the
when determined by the above method? Justify your
liquid (or solution) at a particular temperature.
answer.
130. Define ideal solution. Ans : SP 2007
Ans : COMP 2012, DELHI 2010 Observed molecular mass of sodium chloride will be
The solutions which obey Raoult’s law over the half of its theoretical mass.
entire range of concentration are known as ideal This is because depression in freezing point method is
solutions. For ideal solutions, TH (mixing) = 0 n and a colligative property which depends upon the number
TV (mixing) = 0 , e.g. solution of n -hexane and n of solute particles present in solution.
-hepane, bromoethane and chloroethane, etc. One molecule of sodium chloride furnishes two
In these solution (binary solutions), A - B type (i.e. particle, Na+ and Cl- in aqueous solution as it is a
solute-solvet) interactions. strong electrolyte.
131. State Raoult’s law in its general form in reference to NaCl $ Na+ + Cl-1
solutions.
According to van’t Hoff factor, observed molecular
Ans : DELHI 2005
mass
Raoult’s law For a solution of volatile liquids, the Normal molecular mass
partial vapour pressure of each component of the =
Number of particles formed per molecule
solution is directly proportional to its mole fraction Observed molecular mass of glucose as determined by
present in solution. Thus, for any component, partial the depression of freezing point method will be same
vapour pressure, as its theoretical molecular mass. It is because glucose
neither shows association nor dissociation in aqueous 2. If the solute particles associate or dissociate.
solution as it is a weak electrolyte. 3. When the solute-solvent interactions are different
135. Why does soda water fizz when the bottle is opened? from the solute-solute and solvent-solvent
Name the law that explains this phenomenon. interaction.
Ans : DELHI 2009 141. Mixture of methyl alcohol and chloroform shows a
Soda water is prepared by dissolving CO2 in water positive deviation from Raoult’s law. Explain.
under a pressure of 5 to 10 atm. The bottle is tightly Ans : OD 2015
capped to prevent the escape of CO2. When the Methyl alcohol molecules are bonded together through
bottle is opened, the pressure reduced and most of hydrogen bounding. When chloroform is added to
the dissolved CO2 gas escapes from the solution in methyl alcohol, the molecules of chloroform try to
the form of fizz or effervescence. This phenomenon is get in between the molecules of methyl alcohol and
based upon Henry’s law of solubility of gases. This law break the hydrogen bonds. This reduces the methyl
states that, ‘at constant temperature, the solubility of alcohol-methyl alcohol intermolecular attraction and
gas in a liquid is directly proportional to the pressure the volume gets increased i.e. T Mix V is positive. Since
of the gas.’ some energy is used up in breaking the hydrogen
136. What is a colligative property? Give two examples. bounds, T Mix H is positive.
Ans : OD 2007 142. Mixture of chloroform and acetone shows a negative
The properties of dilute solutions which depend only deviation from Raoult’s law. Explain.
on the number of solute particles but not upon their Ans : SQP 2003
nature are called colligative properties. Both chloroform and acetone cannot take part in
Two colligative properties of solutions are hydrogen bonding when present alone. But when
(i) Relative lowering of vapour pressure chloroform and acetone are mixed, the hydrogen
bonding takes place between the two as shown below:
(ii) Elevation in boiling point.
137. Which out of molarity or molality will change in
temperature why?
Ans : SQP 2003
Molarity changes with rise in temperature. Volume

of a solution increases with rise in temperature and
this causes change in molarity because it is related as
moles of solute in a given volume of solution. T Mix V is negative, T Mix H is negative.
138. How is the molality of a solution different from its Due to hydrogen bonding escaping tendencies of both
molarity? the liquids become less an as such the mixture shows
Ans : COMP 2011
a negative deviation from Raoult’s law.
Molarity is the number of moles of solute per litre of 143. What are colligative properties? Name four such
the solution while molality is the number of moles of properties.
solute per kilogram of the solvent. Ans : COMP 2009
139. The dissolution of ammonium chloride in water is The properties of solution which depend only on the
endothermic process. What is the effect of temperature number of particles of the solute and do not depend on
on its solubility? the nature of solute are called colligative properties.
Ans : DELHI 2009, OD 2007 Examples of colligative properties are:
Since dissolution of NH 4 Cl in water is endothermic 1. Relative lowering of vapour pressure
process, its solubility increases with rise in temperature 2. Osmotic pressure
(Le-Chatelier principle). 3. Elevation of boiling point
140. What are limitations of Raoult’s law? 4. Depression of freezing point
Ans : FOREIGN 2009 144. What role does the molecular interaction play in
The limitations of Raoult’s law are as follows : solution of alcohol and water?
1. When the solution is not dilute there are significant Ans : DELHI 2003
interactions between solute and solvent molecules. Alcohol is a polar compound. It can form H-bond
As a result Raoult’s law in not applicable. with water molecules, so alcohols are miscible with
water in all proportion. They also have dipole- Ans : FOREIGN 2010
dipole interactions due to which there is the force of Vapour pressure is the pressure of the vapour at
attraction between alcohol and water molecules. equilibrium state when rate of evaporation becomes
equal to rate of condensation. Equilibrium constant
145. Why are aquatic species more comfortable in cold does not change at a particular temperature and,
water in comparison to warm water? therefore, vapour pressure remains constant.
Ans : FOREIGN 2015
151. Can we separate the components of azeotropic mixture
Cold water has more dissolved oxygen than warm
by distillation?
water because solubility of gas in liquid decreases with
Ans : OD 2011
increase in temperature.
No, we cannot separate the components of an
146. Why do gases always tend to be less soluble in liquids azeotropic mixture by distillation because at a
as the temperature is raised? particular composition, both the components boil at
Ans : OD 2006 the same temperature.
Gases have weak forces of attraction which the liquids. 152. Define boiling point.
Mostly, dissolution of gases in liquid is an exothermic
Ans : SQP 2012
process. When temperature is raised, the force of
Boiling point of a liquid is that temperature at which its
attraction between gas molecules and liquid molecules
vapour pressure is equal to the atmospheric pressure.
decreases, therefore, solubility decreases on increasing
For example water boils as 373.15 K (100cC) because
temperature.
at this temperature the vapour pressure of water is
147. Amongst the following compounds, identify which 1.013 bar (1 atmosphere).
are insoluble, partially soluble and highly soluble in
153. Define freezing point?
water?
Ans : COMP 2016
1. phenol, 2. toluene, 3. formic acid, 4. ethylene glycol,
5. chloroform, 6. pentanol. Freezing point of a substance is that temperature
at which the vapour pressure of the substance in its
Ans : SQP 2007, DELHI 2005
liquid phase is equal to its vapour pressure in the solid
1. Phenol is partially soluble in water.
phase.
2. Toluene is insoluble in water.
154. Why is the timed saved when cooking is done in a
3. Formic acid is highly soluble in water.
pressure cooker ?
4. Ethylene glycol is highly soluble in water.
Ans : DELHI 2011
5. Chloroform is insoluble in water.
At higher pressure over the liquid (due to weight of
6. Pentanol is partially soluble in water.
the pressure cooker lid), the liquid boils at higher
148. Why is the vapour pressure of an aqueous solution of temperature. Therefore, cooking occurs faster.
glucose lower than that of water?
155. Why NaCl solution freezes at lower temperature than
Ans : COMP 2005
water but boils at higher temperature than water?
It is because in glucose solution, the surface of
liquid consists of both solute and solvent molecules, Ans : OD 2017
therefore, the fraction of surface covered by the solvent When a solute is dissolved in a solvent, the vapour
molecules gets reduced. Hence, escaping tendency of pressure decreases. As a result, the solution boils at
solvent molecules into vapours also gets reduced, thus, a higher temperature while solvent freezes at a lower
vapour pressure of glucose solution decreases. temperature.
149. How does sprinkling of salt help in clearing snow 156. Based on solute-solvent interactions, arrange the
covered roads in hilly areas? Explain the phenomenon following in order of increasing solubility in n =octane
involved in the process. and explain: Cyclohexane, KCl, CH 3 OH , CH 3 CN .
Ans : DELHI 2016 Ans : FOREIGN 2001
When salt is spread over snow covered roads, snow KCl < CH 3 OH < CH 3 CN < Cyclohexane
starts melting from the surface because of the KCl is an ionic compound, least soluble in n -octane.
depression in freezing point of water and it helps in Cyclohexane is non-polar, therefore, most soluble in
clearing the roads. n -octane.
150. Why is the vapour pressure of a liquid constant at a CH 3 OH is more polar than CH 3 / N , therefore, less
constant temperature? soluble in non-polar solvent i.e., n -octane.
157. What is meant by ‘reverse osmosis’ ? 161. Give important application of Osmosis.
Ans : SQP 2000 Ans : OD 2005
If extra pressure is applied on the solution side and Applications of Osmosis:

exceeds the osmotic pressure, the osmosis can be 1. Desalination of sea water
reversed. That is, pure water can be forced out of the 2. Water purification (water treatment)
solution to pass through the pores of the membrane in 3. Food processing
the opposite direction. This is called reverse osmosis.
162. What is abnormal molecular mass? Give its causes.
158. What is de-icing agent? How does it work? Ans : SQP 2011, 2009
or When the molecular mass of a substance determined
CaCl 2 is used to clear snow in cold countries. Explain. by study of any of the colligative properties comes out
Ans : COMP 2019, DELHI 2007 to be different than theoretical expected value, the
substance is said to show abnormal molecular mass.
Common salt (NaCl) and CaCl 2 are called de-icing
Abnormal molecular masses are obtained when.
agents because they lowers the freezing point of water
to such extent that it does not freeze to form ice. 1. The solute undergoes dissociation or association
Hence, they are used to clear snow from roads. in solution.
2. The solution is non-ideal.
159. Why osmotic pressure technique is preferred over
other methods to find out molar mass of solutes. 163. Define Ebullioscopic constant or molal elevation
Ans : DELHI 2001
constant.
For the determination of molar masses of proteins, Ans : COMP 2012
polymers and other macromolecules, it is one of the Molal Elevation Constant (Ebullioscopic Constant) :
most suitable methods because of the following reasons: It is equal to elevation in boiling point of 1 molal
1. As the molar masses of macro-molecules are of the solution, i.e. 1 mole of solute is dissolved in 1 kg of
order of 106 g mol-1 the molality of the solution solvent. It is also called ebullioscopic constant. The
taken is very low. For such solutions methods like units of Kb is K/m or cC/m of K kg mol-1 , where 'm'
elevation in boiling point, depression in freezing is molality.
point etc. cannot be used because changes
164. Some liquids on mixing form azeotropes. What are
measured in these properties are very small and
thus cannot be accurately measured. In osmotic azeotropes?
pressure method molarity of the solution is used. or
As compared to other colligative properties Define the term azeotrope.
magnitude of osmotic pressure is large even for Ans : DELHI 2001
very dilute solution.
Azeotropes are binary mixture having the same
2. Elevation in boiling point method for biomolecules composition in liquid and vapour phase and boil at
is not suitable because these molecules are not
constant temperatures.
stable at higher temperature, the advantage of
the osmotic pressure is that it can be measured at 165. State the formula relating pressure of a gas with its
room temperature. mole fraction in liquid solution in contact with it.
160. What are isotonic, hypertonic and hypotonic solution? Ans : FOREIGN 2001
Ans : FOREIGN 2003

The pressure of a gas over a solution in which the gas
is dissolved is proportional to the mole fraction of the
Isotonic solution : Two solution having same osmotic
gas dissolved in the solution i.e.,
pressure at a given temperature are called isotonic
solutions. p\x
Hypotonic solution : A solution is called hypertonic if p = KHx
its osmotic pressure is lower than that of the solution
(where K H is Henry’s law constant)
separating it by a semi-permeable membrane.
Hypertonic solution : A solution is called hypertonic if 166. What is anti-freeze?
its osmotic pressure is higher than that of the solution Ans : OD 2006
separating it by a semipermeable membrane, the flow Anti-freeze is a substance which is added to solvent to
of solvent due to osmosis, will be into the hypertonic lower its freezing point. It is used in car radiators to
solution from hypotonic solution. lower the freezing point of water, e.g. ethylene glycol.
167. Define osmotic pressure. When the bottle is opened at room temperature under
Ans : SQP 2003 normal atmosphere conditions, the pressure inside the
It is the extra pressure which must be applied on bottle decreases to atmospheric pressure and excess
solution side so as to prevent the flow of solvent CO 2 fizzes out.
molecules from solution through semi-permeable 173. Which colligative property is preferred for the molar
membrane. mas determination of macromolecules ?
168. Why is osmotic pressure considered as a colligative Ans : SQP 2006
property? Osmotic pressure measurement is preferred over all

Ans : COMP 2001 other colligative properties because
Osmotic pressure depends upon the number of 1. even in dilute solutions, the osmotic pressure
particles of solute and not on the nature of solute, values are appreciably high and can be measured
therefore, it is considered as colligative property. accurately.
2. osmotic pressure can be measured at room
169. State Raoult’s law for a solution containing volatile temperature. On the other hand, elevation in
components. How does Raoult’s law become a special boiling point is measured at high temperature
case of Henry’s law? where the solute may decompose. The depression
Ans : DELHI 2016 in freezing point is measured at low temperatures.
Raoult’s law for volatile components : It states 174. How can you remove the hard calcium carbonate
that vapour pressrue of each component is directly layer of the egg without damaging its semi-permeable
proportional to its mole fraction. membrane? Can this egg be inserted into a bottle with
pA = pAcxA a narrow neck without distorting its shape? Explain
the process involved.
In solution of gas in liquid, one of the component is so
volatile that it exists as gas and its solubility is given Ans : COMP 2015
by Henry’s law, p = K H .x 1. Place an egg in dil. HCl or dil. H 2 SO 4 solution.
Only difference between Raoult’s law and Henry’s law 2. After sometime, outer shell of egg dissolves.
is K H differs from pcA . thus, Raoult’s law becomes a 3. The egg with only semopermeable membrane is
special case of henry’s law in which K H becomes equal now removed and placed in hypertonic solution.
to pcA . 4. After sometime, the size of the egg gets reduced
170. How is vapour pressure of solvent affected when a non due to osmosis.
volatile solute is dissolved in it? 5. The egg is then placed in bottle with narrow neck.
Ans : FOREIGN 2010 6. Add hypotonic solution in the bottle containing
When a non-volatile solute is added to solvent, the egg.
vapour pressure of solution decreases because surface 7. The egg regains its shape due to osmosis.
molecules consist of both solute and solvent molecules
so escaping tendency of solvent molecules into vapours 175. 1. Out of 1 M glucose and 2 M glucose, which one
decreases. has a higher boiling point and why?
2. What happens when the external pressure applied
171. The depression in freezing point of water observed
becomes more than the osmotic pressure of
for the same amount of acetic acid, trichloroacetic
solution?
acid and increases in the order given above. Explain
briefly. Ans : DELHI 2011, OD 2005
1. The elevation in boiling point is a colligative
Ans : OD 2013
property and depends upon the number of
It is because trifluoracetic acid is stronger acid than moles of solute added. Higher the concentration
trichloroacetic acid, whereas acetic acid is the weakest of solute added, higher will be the elevation in
acid. Stronger acid produces more number of ions, boiling point. Thus, 2M glucose solution has
therefore, has more TTf , hence lower freezing point. higher boiling point than 1M glucose solution.
172. Why soda water bottle kept at room discomfort in 2. When the external pressure applied becomes more
breathing at high altitude. than the osmotic pressure of the solution, then the
Ans : DELHI 2007 solvent molecules form the solution pass through
the semipermeable membrane to the solvent side.
To increase the solubility of CO 2 in soft drinks, the
This process is called reverse osmosis.
soda water bottles are sealed under high pressure.
176. Outer hard shells of two eggs are removed. One of the 181. When dehydrated fruits and vegetables are placed in
eggs is placed in pure water and the other is placed water, they slowly swell and return to original form.
in saturated solution of sodium chloride. What will be Why? Would a temperature increase accelerate the
observed and why? process? Explain.
Ans : FOREIGN 2015 Ans : FOREIGN 2000
The egg placed in water will swell due to osmosis of The cell walls of fruits and vegetables are
pure water into the egg. On the other hand, the egg semipermeable. The liquid inside the cells in the dried
placed in saturated solution of NaCl will shrink due fruits and vegetables is more concentrated. When
to osmosis of water out of the egg. This is because these dried fruits and vegetables are placed in water,
osmosis always occurs from higher concentration of water enters the fruits and vegetables due to osmosis
solvent to lower concentration of solvent. and they swell and return to their original form. Since
the increase in temperature increase the osmotic
177. Will the depression in freezing point be same or pressure (p ? T), hence the process gets accelerated
different if 0.1 mole of glucose is dissolved in one litre by increase in temperature.
of water?
182. What is ‘semipermeable’ membrane?
Ans : OD 2015
Ans : OD 2015, 2013
The depression in freezing point will be same in both It is the membrane which has sub-microscopic pores
the solutions because both are non-electrolytes and through which small solvent molecules like water can
give same number of solute particles. pass but bigger solute particles cannot pass.
178. Are equimolar solutions of sodium chloride and urea 183. Why is great care taken in intravenous injection to
isotonic? Why? have comparable concentration of solutions to be
Ans : SQP 2014, OD 2010 injected to that of blood plasma ?
Sodium chloride gets dissociated to two ions (Na+ and Ans : SQP 2011
Cl- ) and exerts almost double osmotic pressure than During intravenous injections, the concentrations of
urea (which is non-electrolyte). the solution to be injected should be comparable to
179. Blood cells are isotonic with 0.9% sodium chloride blood plasma. If the solution is less concentrated, its
solution. What happens if we place blood cells in a osmotic pressure will be low. The water will try to
solution containing move into the red blood cells through the cell walls.
1. 1.2% sodium chloride solution? As a result, cells will swell and burst. On the other
2. 0.4% sodium chloride solution? hand, if the solution is more concentrated, the water
in the cells will try to move outside the cell to the
Ans : COMP 2006
more concentrated solution by osmosis. This causes
1. 1.2% sodium chloride solution is hypertonic with
cells to shrink and consequently cease to function.
respect to 0.9% sodium chloride solution or blood
cells, when blood cells are placed in this solution, 184. Sodium chloride solution freezes at lower temperature
water flows out of the cells and they shrink due to than water but boils at higher temperature than
loss of water by osmosis. water, Explain.
2. 0.4% sodium chloride solution is hypotonic with Ans : COMP 2013
respect to 0.9% sodium chloride solution or blood
cells, When blood cells are placed in this solution, Freezing point of a liquid depresses on the addition
water flows into the cells and they swell. of a non-volatile solute and therefore, a solution of
sodium chloride freezes at lower temperature than
180. Will the elevation in boiling point be same if 0.1 mole freezing point of water. On the other hand, there is
of sodium chloride or 0.1 mole of sugar is dissolved in elevation in boiling point on the addition of a non-
1 L of water? volatile solute and consequently boiling point of
Ans : DELHI 2001
sodium chloride solution is more than that of water.
The elevation in boiling point of 0.1 mole of NaCl and
0.1 mole of sugar dissolved in water will not be same. 185. What is de-icing agent? How does it function?
Elevation in boiling point is a colligative property and Ans : DELHI 2010
depends upon the number of solute particles. NaCl Common salt acts as a de-icing agent because it lowers
is ionic and give more number of particles due to the freezing point of water to such an extent that it
ionisation than sugar which consists of molecules. does not freeze to form ice. Hence, it is used to clear
snow from roads.
186. Why is camphor preferred as a solvent for measuring 190. A doctor advised a person suffering from high blood
the molecular mass of naphthalene by Rast method? pressure to take less quantity of common salt. Explain.
Ans : FOREIGN 2012 Ans : DELHI 2008, 2002
Camphor has a large K f value (39.8%) and therefore, This is because higher quantity of common salt (NaCl)
causes large depression in melting point of solution will increase number of Na+ and Cl- ions in the body
with very small amount of solute (naphthalene). fluid which can increase the osmotic pressure of the
body fluid i.e. higher blood pressure of a person.
187. When mercuric iodide is added to tan aqueous solution
of KI the freezing point is raised, Why? 191. Arrange the following solutions in increasing order of
Van’t Hoff factor:
Ans : OD 2005
0.1 M CaCl 2 , 0.1 M KCl , 0.1 M Al 2 (SO 4) 3 ,
HgI 2 forms a complex with KI and therefore, the
0.1 M C 12 H 22 O 11
number of particles in solution decreases.
Ans : FOREIGN 2003
HgI 2 + 2KI $ K 2 6HgI 4@
0.1 M C 12 H 22 O 11 < 0.1 M KCl ,
As a result, the depression in freezing point is less and < 0.1 M CaCl 2 < 0.1 M Al 2 (SO 4) 3
hence the freezing point increases.
192. What role does the molecular interactions play in
188. Under what conditions Vant Hoff’s factor 'i' is solution of alcohol and water?
1. equal to unity Ans : OD 2009
2. less than 1 and There are strong hydrogen bonding in alcohol
3. greater than 1 molecules as well as water molecules. On mixing
Explain the answer. alcohol and water, the molecular interactions become
Ans : SQP 2016
weak. Therefore, they show positive deviation from
ideal behaviour. As a result, the solution will have
1. When the solute does not undergo any dissociation
or association in the solution i.e., for non- higher vapour pressure and lower boiling point than
electrolyte solutes. that of alcohol and water.
2. When the solute undergo association in the 193. Why do gases always tend to be less soluble in liquids
solution. as the temperature is raised?
3. When the solute undergoes dissociation in the Ans : SQP 2016
solution. The dissolution of a gas in a liquid is exothermic
189. Given below is the sketch of a plant for carrying out process. Therefore, in accordance with Le-Chatelier’s
a process. principle, with increase in temperature, the
equilibrium shifts in the backward direction.
Liquid + Gas Dissolved gas TH = - ve
Therefore, the solubility of gas in solution decreases
with rise in temperature.
194. What do you mean by relative lowering of vapour
pressure?
Ans : OD 2011, SQP 2014
The relative lowering of vapour pressure of a liquid is

1. Name the process occurring in the above plant. the pressure of the vapour which is directly proportion
2. To which container does the net flow of solvent to the mole fraction of solute i.e. relative lowering in
3. Name one SPM which can be used in this plant. V.P.
4. Give one practical use of the plant. Where
Ans : COMP 2017 TP = difference in vapour pressure
1. Reverse osmosis Pc = V.P. of pure liquid
2. To fresh water container
x B = mole fraction of solute
3. Film of cellulose acetate
4. This can be used as desalination plants to meet TP ? x ,
B
Pc
potable water requirements. TP
Pc
is known as relative lowering n vapour pressure.
195. State Rault’s law. How is it applicable in determining 197. Differentiate between Osmosis and diffusion. How
the molecular weight of non-electrolyte solute? is osmotic pressure determined by Barklay-Hartlay
Ans : SQP 2011 method?
Rault’s Law- According to this law, The pressure of Ans : DELHI 2016, FOREIGN 2014
any volatile constituent of a solution at a constant The difference between osmosis and diffusion are as
temperature is equal to the vapour pressure of pure follows :
constituent multiplied by the mole fraction of that Osmosis Diffusion
constituent in the solution. Raoult’s law is applicable
in determining the molecular weight of non electrolite 1. The process of osmosis No semi-permeable
solute because unsaturated solute is solvent is pure takes place through membrane is needed
solute than its boiling point is elevated. Hence we a semipermiable for the diffusion
membrane. process.
determine the molecular weight of non electrolite
solute. 2. The osmosis involves In diffusion both the
3 P = XB P o the movement of the solute and the solvent
A
solvent molecules only. molecules can move.
3 P = P Ao - PA
3. Osmosis is limited to Diffusion is common
solutions only. in gases as well as in
liquids
4. Osmosis can be It cannot be stopped
stopped or reversed or reversed.
by applying additional
pressure on the higher
concentration side.
LONG ANSWER QUESTIONS Osmotic-pressure determination by barkeley hartley

method : A porcelain tube having copper ferrocyanide
196. (a) What do you mean by the term ‘Depression of membrane in its walls is enclosed in a metallic jacket.
freezing point’ ? The porcelain tube is fitted with a reservoir of pure
(b) State Raoult’s Law of depression of freezing point. solvent at one end and a capillary tube at the other
How is it useful in determining the molecular end. There is an arrangement in a metallic jacket for
weight of non-volatile and non-electrolyte solute? applying external pressure which can be measured
Ans : COMP 2012
with the help of pressure gauge.
(a) We know that, freezing point of a liquid is the The concentration of the solution does not change as
temperature at which, its solid and liquid phases the flow of solvent is not permitted into the solution.
have the same vapour pressure. The freezing point Note : As osmotic-pressure is balance by the external
of pure liquid is fixed. But if we add a non-volatile pressure, there is no strain on the membrane, thus is
solute, in the pure liquid, the freezing point of does not burst.
the liquid is lowered the vapour pressure of the
liquid is descreated due to presense of non-volatile
solution particles at the surface of liquid.
TTF = F.P.of solvent - F.P.of solution
Where, F.P = Freezing point
(b) The depression of freezing point of solvent
by dissolving a non-volatile solute is directly
proportional to the molal concentration of the
dissolved solute.
TTF \ Cm
or TTF = K f # Cm (K f is the molal depression 198. What do you mean by vapour pressure? What
constant. Thus molal depression constant (K f ) happens to the vapour pressure, when 1. volatile
may be defined as the depression in freezing point solute is dissolved in solution. 2. non-volatile solute is
which would be produced by dissolving one mole dissolved in solution?
of non-volatile solute in 1000g of solvent.
Ans : COMP 2014

vapour pressure in the pure state, then according
Vapour Pressure : The pressure exerted by the to Raoult’s law,
vapours of a liquid which are in equilibrium with it at
p1 \ x1 and p1 = x1 p1c
a given temperature is called vapour pressure.
The proportionally constant is equal to the vapour
1. When volatile solute is dissolved in solution : Let pressure of pure solvent, pc
1 .
two volatile liquids 1 and 2 have mole fractions as
x1 and x2 , respectively. If p1 and p2 are vapour 199. What do you mean by the term ‘elevation of boiling
pressure of these components in the solution, point’ ?
then according to Raoult’s law
Ans : DELHI 2016
For component 1, p1 \ x1 and p1 = p1c x1
Similarly, for component 2, p2 = p2c x2 Elevation in boiling point : The boiling point of a
where pc 1 is the vapour pressure of pure liquid is that temperature at which its vapour pressure
component 1 and pc 2 is the vapour pressure of becomes equal to the atmospheric pressure. When a
pure component 2 at same temperature. non-volatile solute is added to a solvent the boiling
According to Dalton’s law of partial pressure, the point of the solution is always higher than that of
total pressure (p total) over the solution phase in the pure solvent. For example, A solution of 1 mole of
container will be the sum of the partial pressures sucrose in 1000 g of water boils at 373.52 K at 1
of the components of the solution and is given as, atm pressure. This difference in the boiling points of
p total = p1 + p2 the solution wt and pure solvent (Tb c) is called the
elevation of boiling point (TTb) Elevation in boiling
So, p total = p 1° x1 + p 2° x2 point depends on the number of solute molecules
As we know, x1 + x2 = 1 or x1 = 1 - x2 rather than their nature.
So, elevation in boiling point is given by
Then, p = p1c (1 - x2) + pc2 x2
TTb = Tb - Tb c
= p1c (pc2 - p1c ) x2
From this equation, following conclusions can be For dilute solution, the elevation in boiling point is
drawn directly proportional to the molal concentration of the
solute in a solution.
(i) The total vapour pressure over the solution
Thus, TTb \ m (molal concentration of solution)
can be related to the mole fraction of any one
component. TTb = K b m
(ii) Total vapour pressure over the solution varies where m (molality) is the number of moles of solute
linearly with the mole fraction of component dissolved.
2. 200. State Raoult’s law. How is it useful in determining the
(iii) The total vapour pressure over the solution molecular weight of non-electrolyte solute?
increases or decreases with increase in mole Ans : SQP 2015
fraction of component 1, depending upon the
State Raoult’s law, states that, At a given temperature,
vapour pressures of the pure components 1
for a solution of volatile liquids, the partial vapour
and 2.
pressure of each component of the solution is directly
2. When Non-volatile solute is dissolved in solution proportional to its mole fraction.
: The vapour pressure of the solution of a non-
Let two volatile liquids 1 and 2 have mole fractions
volatile solute at a given temperature is lower
as x1 and x2 , respectively. If p1 and p2 are vapour
than the vapour pressure of the pure solvent at
the same temperature. This decrease in vapour pressure of these components in the solutions, then
pressure occurs because in solid-liquid solution, according to Raoult’s law
the surface has both solute and solvent molecules, For component 1, p1 \ x1 and p1 = pc1 x1
so the fraction of the surface covered by solvent Similarly, for component 2, p2 = pc2 x2
molecules gets reduced, so the number of solvent Where pc1 is the vapour pressure of pure component
molecules escaping from the surface is reduced 1 and pc is the vapour pressure of pure component 2
2
resulting in lowering the vapour pressure. at same temperature.
In a binary solution (when solute is non-volatile
Usefulness of Determination of Molecular-Weight of
and non-electrolyte, only the solvent molecules
Non-electrolyte Solute : Solute particles in a solution
are present in the vapour phase and contribute
may go for association or dissociation , thus their
to vapour pressure), if p1 is the vapour pressure
of the solvent, x1 is its mole fraction and p 10 is its molecular mass may changes. Thus to determine the
molecular-mass of an abnormal solute, colligative Types of Solution

properties are very useful, as they only depends on
the number not on the nature of solute. Types of Solute Solvent Common Examples
solution
201. Define osmotic pressure. Prove that osmotic pressure
is a molecular property. G a s e o u s Gas Gas Mixture of Oxygen
Solution an Nitrogen gas
Liquid Gas Chloroform mixed
The excess pressure which must be applied to a solution with nitrogen gas
to prevent the passage of solvent into it through a Solid Gas Camphor in nitrogen
semipermeable membrane is called osmotic pressure. gas
It is shown in figure. It is a colligative property as it
depends on the number of solute molecules (C ) of the Liquid Gas Liquid Oxygen dissolved in
Solutions water
solution at a given temperature T . Thus,
Liquid Liquid Ethanol dissolved in
water
Solid Liquid Glucose dissolved in
water
Solid Gas Solid Solution of hydrogen
Solution in palladium
Liquid Solid Amalgam of mercury
with sodium
Solid Solid Copper dissolved in
gold.
p ?C
203. Define the following terms:
p = CRT 1. Mole fraction
where, p = osmotic pressure 2. Molality
and R = gas constant 3. Molarity
4. Normality
But, C =n 5. Percentage
V
6. ppm
and n =W
M Ans : FOREIGN 2006, OD 2011
where, n is the number of moles of solute dissolved in 1. Mole fraction (x) : The fraction obtained by
V liter of solution, W is the weight of solute and M dividing number of moles of a component by
is its molar mass. the total number of moles of all the component
present in the solution is called Mole Fraction.
Therefore, p = WRT Mole fraction of a component
VM
WRT Number of moles of Component
M2 = =
Vp Total number of moles of all the component
For example, in a binary mixture, if the number
202. Define the term solution. How many types of solutions of moles of A and B are nA and nB respectively,
are formed? Write briefly about each type with an the mole fraction of A will be
example
xA = nA
nA + nB
Solutions are homogeneous mixture of two or more nB
Mole fraction of B , xB =
than two components. The component that is nA + nB
present in the largest quantity is known as solvent, it nA + nB
determines the Physical state in which solution exists. xA + xB = =1
nA + nB nA + nB
One or more components present in the solution other Sum of the mole fraction of all the components present
than solvent are called solutes. in a solution is unity. Mole fraction is independent of
Binary solution consist of two components solvent temperature as it is a mass/mass relationship.
and solute.
2. Molality (m) : Molality is the number of moles 6. Parts per million (ppm) : When a solute is present
of the solute present in per kilogram (kg) of the into traces quantities it is convenient to express
solvent. concentration in parts per million (ppm). Mass of
Moles of solute the solute present in one million (106) parts by
Molality (m) = mass of the solution is called parts per million.
Units of molaltiy is m or mol kg-1 . It is Number of parts of component 6
ppm = # 10
independent of temperature as it is a mass/mass Total number of parts of
relationship. all components of the solution
3. Molarity (M) : Molarity is the number of moles of
solute dissolved in one litre (or 1 cubic decimeter) 204. Why do we get abnormal molecular masses from
of solution. colligative properties? What is van’t Hoff factor? How
Molarity = Moles of solute will you explain cases of association and dissociation
Volume of solution in litre of solute in such cases?
Units of molarity is M or mol L-1 . Molarity Ans : DELHI 2016
decreases with rise in temperature as it is a mass/ The solute undergoes association or dissociation
volume relationship and volume increases with therefore we get abnormal molecular masses.
increases in temperature.
For example acetic acid when dissolved in benzene
4. Normality (N) : Normality is the number of gram exist as double associated molecule in benzene due to
equivalents of the solute dissolved in one litre
hydrogen bonding which may be represented as
(1 dm3) of solution.
Number of gram equivalent of solute
Normality =
Volume of the solution in litre
Normality = Mass of solute 1000

Eq. mass of the value # V (ml)
Units of Normality is N or gm eq. mol-1 . Normality We get molecular mass of acetic acid 120 in place of
decrease with rise in temperature as it is a gm 60 by colligative properties. To calculate the extent of
eq/volume relationship and volume increases with association or dissociation Van’t Hoff factor ‘i’ is used
increase in temperature. Van’t Hoff Factor
5. Percentage : The percentage of a solution is The ratio of the observed value of the colligative
usually expressed either as Mass percentage or property to the theoretical value of colligative property
volume percentage or Mass by volume percentage. is called Van’t Hoff factor (i).
(a) Mass Percentage (w/w) Observed Value of Colligative Property
i =
Mass % of a component Theoretical Value of Colligative Property
Mass of component in the solution Since colligative properties are inversely proportional
= # 100
Total mass of the solution to molecular mass of the solute, it follows that
For example, if a solution is described by 10% Normal or calculated molecular mass (MC )
i =
glucose in water by mass, it means that 10 g Observed molecular mass (M0)
glucose is dissolved in 90 g of water resulting if i > 1 there is dissociation of solute particle
in a 100 g solution. if i < 1 there is association of solute particle
(b) Volume percentage (v/v) For example the value of i for aqeous KCl solution
Volume % of a component is 2, while the value for acetic acid (ethanoic acid) in
Volume of the component benzene is nearly 0.5.
= 100
Total volume of the solution # Inclusion of Van’t Hoff factor modifies the equation
for colligative properties as follows:
For example 10% (V/V) ethanol solution in
water means that 10 ml of ethanol is dissolved Relative lowering of vapour pressure of solvent
in water such that the total volume of the pc - ps
=
solution is 100 ml. pc
(c) Mass by volume percentage (w/v) n
=i 2
ni
Mass/Volume % of a component
Elevation of Boiling point,
Mass of the component in the solution
= 100
Total volume of the solution in ml # TTb = i Kb m
Depression of Freezing point T mix H = - ve in case of negative deviation because

TTf = i K f m it is an exothermic process as new forces A - B are
stronger than A - A and B - B .
Osmotic pressure of solution
p = i CRT
205. What is meant by positive and negative deviation

from Raoult’s law and how is the sign of T mix H related
to positive and negative deviation from Raoult’s law?
Ans : DELHI 2013
Positive Deviation from Raoult’s Law : Those non-ideal

solutions, in which partial pressure of each component
A and B is higher than that calculated from Raoult’s
law show positive deviation from Raoult’s law show
positive deviation from Raoult’s law, as shown in
figure, e.g. water and ethanol, chloroform and water,
ethanol and CCl 4 , methanol and chloroform, benzene
and methanol, acetic acid and toluene, acetone and
ethanol, methanol and H 2 O , etc.
T mix H = + ve in case of positive deviation because it
is endothermic process because new forces A - B are 206. State the Explain :
weaker than A - A and B - B . 1. Raoult’s law for volatile solute.
2. Raoult’s law for non-volatile solute.
Ans : COMP 2005
1. Raoult’s law for volatile solute :
In a solution, the vapour pressure of a component at a
given temperature is directly proportional to its mole
fraction. For example, if we have two miscible liquids
A and B then
Negative Deviation form Raoult’s Law : The partial

vapour pressure of component 'A' is found to be less
than that calculated form Raoult’s law on adding the
second component 'B' and when A is added to B , the
partial vapour pressure of component 'B' is found to
be less than that calculated from Raoult’s law. The
total vapour pressure of solution is less than that of PA ? xA or PA = PcA # xA
ideal solution of same composition. Boiling point of PB ? xB or PB = PcB # xB
such a solution is relatively higher than the boiling Where xA and xB are mole fractions of A and B
point of A and B respectively. This type of deviation respectively, PcA and PcB are vapour pressure of A
from ideal behaviour is known as negative deviation and B respectively in pure state.
from Raoult’s law, as shown in figure. For example,
If PS is total vapour pressure of the solution at some
Chloroform and acetone, chloroform and methyl
temperature then according to Dalton’s Law of partial
acetate, H 2 O and HCl, H 2 O and HNO 3 , acetic acid
pressure.
and pyridine, chloroform and benzene, etc.
Ps = PA + PB 3. Each components They do not obey

Ps = PcA xA + PcB xB obey Raoult’s law at Raoult’s law. They
all temperature and show positive or
= PcA (1 - xB) + PcB xB concentrations i.e., negative deviations
= PcA + (PcB - PcA) xB PA = xA PcA from Raoult’s law i.e.,
PB = xB PcB PA ! xA PcA
A plot of PA and PB against xA or xB for a solution
is a straight line (line I and line II) and total vapour PB ! xB PcB
pressure of solution is shown by line III. 4. They do not form They form azetropes
2. Raoult’s law for non-volatile solute : azeotropes eg. eg. Methyl alcohol +
If the solute B is non-volatile it will not contribute Benzene + Toluene chloroform
to total vapour pressure of the solution. Therefore, n-Hexane + chloroform + Acetone
vapour pressure of solution = vapour pressure of the n-Heptane
solvent, A in solution Bromoethane +
Chloroethane
Ps = xA # Pc ...(1)
Where ps is vapour pressure of solution, xA is mole 208. State Henry’s Law an mention some important
fraction of solvent in solution and pc is the vapour applications.
pressure of the pure solvent. A plot between vapour or
pressure and mole fraction of solvent at constant
Define Henry’s law. Give its one importance.
temperature is a straight line eq (1) can be written as
Ans : FOREIGN 2010
ps
= xA (here xA = nA ) The partial pressure of the gas in vapour phase (p) is
pc nA + nB
ps n directly proportional to the mole fraction of the gas
= A
pc nA + nB (x) in the solution, p = K H x
Subtracting each side from 1, we get Here K H is the Henry’s law constant.
p If we draw a graph between partial pressure of the
1 - s = 1 - nA
pc nA + nB gas versus mole fraction of the gas in solution, then
pc - ps nB we should get a plot of the type as shown (for the
or c pc = nA + nB m solubility of HCl gas in cyclohexane at 29.3 K). The
The relative lowering of vapour pressure of solution slope of the line is the Henry’s law constant K H .
containing a non volatile solute is equal to the mole Different gases have different K H values at the same
fraction of the solute in the solution. temperature. This suggests that K H is a function of
the nature of the gas. Higher the value of K H at a
207. Give the difference between ideal and non-ideal given pressure, the lower is the solubility of the gas
solutions. in the liquid.
Ans : SQP 2012
The difference between ideal and non-ideal solutions

are as follows:
Ideal Solutions Non-ideal Solutions

1. The interaction The interactions
between the between the
components are components are
similar to those in different from those of
the pure components. the pure components.
2. There is no volume TV ! O , TH ! O
change and enthaply on mixing the
change on mixing the components.
components (TV = O Application of Henry’s Law are as follows :
, TH = O) 1. To increase the solubility of CO 2 in soft drinks
and soda water, the bottle sealed under high
pressure.
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2. To minimise the painful effects accompanying the equal to atmospheric pressure increases, hence the
decompression of deep sea divers, oxygen diluted boiling point of the solution increases. The elevation
with less soluble helium gas is use as breathing of boiling point is represented as TTb .
gas.
TTb = Tb - T cb
3. In lungs, where oxygen is present in air with high
partial, haemoglobin combines with oxygen to from Where, Tb = Boiling point of solution
oxyhaemoglobin. In tissues where partial pressure Tbc = Boiling point of pure solvent
of oxygen is low, Oxyhaemoglobin releases oxygen
for utilization in cellular activities.
209. Give the difference between solutions showing positive

deviation and negative deviation from ideal behaviour
Ans : OD 2010, SQP 2015
The difference between solutions showing positive

deviation and negative deviation from ideal behaviour
are as follows :
Solution showing Solution showing

positive deviation negative deviation
1 The interaction The interaction
between the between the
components are less components greater
than in the pure than the pure
components. components.
For dilute solutions elevation in boiling point (TTb) is
2. TVMix = + ve TVMix = - ve
directly proportional to the molality of the solution,
3. THMix = + ve THMix = - ve m
TTb = Kb # m
4. pA > xA pcA , pA < xA pcA ,
pB > xB pcB Here, m (molality) is the number of moles of solute
pB < xB pcB dissolved in 1 kg of solvent and the constant of
5. Form minimum boiling From maximum proportionality. Kb is called Boiling point elevation
azeotropes eg. Methyl boiling azeotropes. constant or molal elevation constant (Ebullioscopic
alcohol and chloroform eg. Chloroform and constant). The unit of Kb is K kg mol-1 . Kb is defined
acetone. as the elevation of boiling point when the molality of
solution is unity. If w2 gram of solute of molar mass
M2 is dissolved in w1 gram of solvent, then molality, m
of the solution is given by the expression,
w2
M2
m = w1
1000
= 1000 # w2
M2 # w1
TTb = Kb # 1000 # w2
M2 # w1
M2 = 1000 # w2 # Kb
210. What is the relationship between boiling point TTb # w1
elevation and molality of a solute in a dilute solution. From the above equation, molecular mass of solute
Show that it is a colligative property. can be calculated by knowing the values of other
Ans : COMP 2006, DELHI 2002 quantities.
When a non-volatile solute is added to the solvent As elevation of boiling point depends upon the
the vapour pressure of the solution decreases. As such number of solute present per kg of solvent and not on
the temperature at which vapour pressure becomes the nature of the solute, it is a colligative property.
211. What is depression of freezing point? How can you As depression of freezing point depends upon the
calculate molecular mass of a solute using it? Show number of solute present per kg of solvent and not on
that it is a colligative property. the nature of solute, it is a colligative property.
Ans : FOREIGN 2013
212. What is osmosis and osmotic pressure and show that
The addition of non-volatile solute to pure solvent
osmotic pressure is a colligative property?
lowers its vapour pressure, so the freezing point of
Ans : OD 2014
a solution is expected to be less than that of pure
solvent. This is known as depression of freezing point The spontaneous flow of the solvent molecules from
is represented as TTf . the solvent to the solution or from a less concentrated
solution to a more concentrated solution through
TTf = Tf - T cf a semipermeable membrane is called osmosis.
Tfc = freezing point of pure solvent Semipermeable membrane is a membrane which allows
the solvent molecules to pass through but not the solute
Tf = freezing point of solution
particles. These membranes are of two types:
Depression of freezing point (TTf ) for dilute solution 1. Natural semipermeable membrane - eg. vegetable
is directly proportional to molality (m) of the solution membrane and animal membrane (eg. pig’s bladder)
Thus, TTf \ m 2. Artifical semipermeable membrane eg. parchment
or TTf = K f m paper, cellophane.
When the membrane permits the solvent molecules to
K f is called freezing point Depression constant or
come out through the molecules to come out through
molal Depression constant or Cryoscopic constant.
the membrane, it is called exosmosis eg. If we put grapes
The unit of K f is K kg mol-1 .
in a concentrated solution of NaCl, the graphs shrink.
K f is defined as the depression of freezing point when
the molality of solution is unity.
If w2 gram of the solute having molar mass as M2
present in w1 gram of solvent, then molality (m) of the
solution is given by the expression.
When the membrane permits the solvent molecules

to enter inside, it is called endosmosis. eg. If we put
kismis or grapes into pure water, they swell Osmotic
pressure. The minimum excess pressure that has to
be applied on the solution to prevent the entry of
the solvent into the solution through semipermeable
membrane is called the osmotic pressure.
w2
M2
m = w1
1000
= 100 # w2
M2 # w1
K f # w2 # 1000
TTf =
M2 # w1
K f # w2 # 1000
M2 =
TTf # w1
From the above equation, molecular mass of solute
can be calculated by knowing the values of other
quantities.
Osmotic pressure (p) of a solution is formed to be Again, Van’t Hoff factor (i) = 1 + a
directly proportional to the molar concentration (C) 1
of the solution and its temperature (T) 1.0753 = 1 + a
p \ C and p \ T a = 1.0753 - 1 = 0.0753
p\C\T Degree of Dissociation = 0.0753
or p = CRT 214. If 11 g of oxalic acid are dissolved in 500 mL of solution
R is a constant, which is same as gas constant. (density = 1.1 g mL-1 ), what is the mass % of oxalic
acid in solution?
Now, C =n Ans :
V OD 2012
11 g of oxalic acid are present in 500 mL of solution.

= Number of moles of solute
Volume of solution in litre Density of solution = 1.1 g mL-1
p = n RT Mass of solution = (500 mL) # (1.1 g mL-1)
V
or pV = nRT = 550 g
This equation is called Van’t Hoff-equation for dilute Mass of oxalic acid = 11 g
solution.
If w2 gms of solute is dissolved in V litres of solution Mass % of oxalic acid = 11 # 100 = 2%
550
and M2 is the molecular mass of solute then:
215. 2.46 g of sodium hydroxide (molar mass = 40 ) are

R is a constant, which is same as gas constant:
dissolved in water and the solution is made to 100 cm3
pV = w2 RT in a volumetric flask. Calculate the molarity of the
M2
solution.
w
M2 = 2 RT
p V Ans : SQP 2002
As osmotic pressure is proportional to the number of Given,

moles of solute in the solution and does not depend Amount of NaOH = 2.46 g
upon nature of solute and hence it is a colligative Volume of solution = 100 cm3
property.
Moles of NaOH = Mass of NaOH
Molar mass
2.46 g
NUMERICAL QUESTIONS =
40 g mol-1
= 0.0615 mol
Molarity = Moles of NaOH # 1000

213. When 19.5 g of F—CH 2 —COOH (Molar mass = 78 g Volume of solution
mol-1), is dissolved in. 500 g of water, the depression
= 0.0615 mol # 1000 mL L-1
in freezing point is observed to be 1°C. Calculate the 100 mL
degree of dissociation of F—CH 2 —COOH . [Given : = 0.615 mol L-1
K f for water = 1.86 K kg mol-l]
= 0.615 M
Ans : FOREIGN 2023
Given, WB = 19.5 g, WA = 500 g, DTf = 1ºC 216. Calculate the molality of a solution containing 20.7
g of potassium carbonate dissolved in 500 mL of
MB = 78 g mol-1,
solution (assume density of solution = 1 g mL-1 )
K f = 1.86 K kg mol-1 Ans : COMP 2018, SQP 2010
We know Given,
DTf = i # K f # WB # 1000 Mass of K 2 CO 3 = 20.7 g
MB # WA
Molar mass of K 2 CO 3 = 138 g mol-1
i = 1 # 78 # 500
19.5 # 1000 # 1.86 20.7 g
Moles of K 2 CO 3 =
138 g mol-1
i = 1 = 1.0753
0.93 = 0.15 mol
Mass of solution = (500 mL) # (1 g mL-1) Ans : SQP 2011
Given,
= 500 g
Mass of oxalic acid = 31.5 g
Amount of water = 500 - 20.7 = 479.3 g
Equivalents of oxalic acid = 31.5
Moles of solute 63
Molality = 1000
Mass of solvent in gram # = 0.5 (Eq. wt. 126
2 = 63 )
= 0.15 mol # 1000 g kg-1 Volume of solution = 1250 mL

479.3 g
= 0.313 mol kg-1 or = 0.313 m Normality = 0.5 # 1000
1250
= 0.4 N
217. 2.5 g of ethanoic acid (CH 3 COOH) is dissolved in 75 g
of benzene. Calculate the molality of the solution. 220. 2.82 g glucose (molar mass = 180) are dissolved in
Ans : DELHI 2015
30 g of water. Calculate (a) the molality, (b) mole
fraction of glucose and water.
Molar mass of CH 3 COOH
Ans : COMP 2012
= 2 # 12 + 4 # 1 + 2 # 16 (a) Calculation of molality of solution.
= 60 g mol-1 Mass of glucose = 2.82 g
2.5 g
Moles of CH 3 COOH = = 0.0417 mol Moles of glucose = 2.82 (Molar mass = 180 )
60 g mol-1 180
Mass of benzene = 75 g Mass of water = 30 g
Molality of CH 3 COOH = Moles of CH 3 COOH # 1000 Molality =

Moles of glu cos e
1000
Mass of benzene (in g) Mass of water #
= 0.0417 mol # 1000 = 2.82 # 1000
75 180 # 30
= 0.556 m = 0.522 m
218. Calculate the mole fraction of ethylene glycol (b) Calculation of mole fraction
(C 2 H 6 O 2) in a solution containing 20% of C 2 H 6 O 2 Moles of glucose = 2.82 = 0.0157
by mass. 180
Ans : FOREIGN 2005, OD 2010 Moles of water = 30 = 1.67
18
20% ethylene glycol solution means that 20 g of 0.0157
ethylene glycol is present in 100 g of solution or 20 g Mole fraction of glucose =
0.0157 + 1.67
of ethylene glycol is present in 80 g of water. = 0.009
20 g 1.67
Molar mass of C 2 H 6 O 2 = Mole fraction of water =
62 g mol-1 0.0157 + 1.67
= 0.322 mol = 0.991
80 g
Moles of water = 221. If the density of the water = 1 g mL-1 . Find out the
18 g mol-1
molarity of pure water?
= 4.444 mol
Ans : DELHI 2018
Moles of C 2 H 6 O 2
x glycol = Given,
Moles of C 2 H 6 O 2 + Moles of H 2 O
0.322 Density of water = 1 g mL-1
= = 0.068
0.322 + 4.444 Mass of 1000 mL of water = Volume # Density
= 4.444 = 0.932
x water = 1000 # 1 = 1000 g
0.322 + 4.444
or x water = 1 - 0.068 = 0.932 Moles of water = 1000 = 55.55 mol
18
Now, 55.55 moles of H 2 O are present in 1000 ml or
219. Calculate the normality of solution containing 31.5 g
1 L of water
of hydrated oxalic acid (H 2 C 2 O 4 .2H 2 O) in 1250 mL
of solution. Hence, molarity = 55.55 M
222. Calculate the mass percentage of aspirin (C 9 H 8 O 4) Moles of sugar = 34.2 = 0.1
in acetonitrile (CH 3 CN) when 6.5 g of C 9 H 8 O 4 is 342
dissolved in 450 g of CH 3 CN . (Molar mass = 342)
Ans : FOREIGN 2009, DELHI 2004
Molality = 0.1 # 1000
Given, 180
= 0.56 m
Mass of aspirin (C 9 H 8 O 4) = 6.5 g
Mass of acetonitrile (CH 3 CN) = 450 g 2. Moles of sugar = 34.2 = 0.1
342
Total mass of solution = 450 + 6.5 = 456.5 g Moles of water = 180 = 10
18
Mass % aspirin = 6.5 # 100
465.5 Moles fraction of sugar = 0.1
10 + 0.1
= 1.424%
= 0.0099
223. A solution is 25 % water, 25% ethanol and 50% acetic
225. Calculate the moles of methanol in 5 litres of its 2 m
acid by mass. Calculate the mole fraction of each
solution, if the density of the solution is 0.981 kg L-1
component.
(Molar mass of methanol = 32.0 g mol-1 )
Ans : OD 2000
Ans : COMP 2001
Let the total mass of solution = 100 g
Mass of 5 L solution = 5L # 0.981 kg L-1
Mass of water = 25 g
= 4.905 kg = 4905 g
Mass of ethanol = 25 g
Mass of 2 m solution = 1000 g + 2 moles of methanol
Mass of acetic acid = 50 g
= 1000 + 2 # 32
Moles of water = 25 = 1.388
18 = 1000 + 64 = 1064 g
(Molar mass of H 2 O = 18 )
Now 1064 g of solution contains methanol
Moles of ethanol = 25 = 0.543 = 2 mol
46
(Molar mass of C 2 H 5 OH = 46 ) 4905 g of solution contains methanol
Moles of acetic acid = 50 = 0.833 = 2 # 4905 = 9.22 mol

60 1064
(Molar mass of CH 3 COOH = 60 ) 226. What is the mole fraction of the solute in 2.5 m
aqueous solution?
Total number of moles = 1.388 + 0.543 + 0.833
Ans : DELHI 2005, 2004
= 2.764 2.5 m aqueous solution means that 2.5 moles of solute
Mole fraction of water = 1.388 = 0.502 are present in 1000 g of water. Thus,
2.764
Moles of solute = 2.5
Mole fraction of ethanol = 0.543 = 0.196
2.764 Moles of water = 1000 = 55.6
18
Mole fraction of acetic acid = 0.833 = 0.302 Mole fraction of solute = 2.5 = 0.043
2.764 2.5 + 55.6
224. A sugar syrup of weight 214.2 g contains 34.2 g of
sugar (C 12 H 22 O 11). Calculate : 227. Calculate the volume of 80% H 2 SO 4 by weight (density
1. Molal concentration and = 1.80 g mL-1 ) required to prepare 1L of 0.2 MH 2 SO 4
2. Mole fraction of sugar in the syrup. Ans : FOREIGN 2015
Ans : SQP 2012

80% H 2 SO 4 solution means that 80 g of H 2 SO 4 are
present in 100 g of solution in water.
1. Given,
Weight of sugar syrup = 214.2 g Moles of H 2 SO 4 present = 80 mol
98
Weight of sugar in syrup = 34.2 g Volume of solution = Mass
Density
Weight of water in syrup = 214.2 - 34.2
100 g
= 180.0 g = = 55.5 mL
1.8 g mL-1
Molarity of solution = 80 # 1000 = 14.7 M 1. Calculation of molarity of solution

98 # 55.5 Weight of H 2 SO 4 per 100 g of solution = 15 g
To calculate the volume of 14.7 M H 2 SO 4 required to
Gram moles of H 2 SO 4 = 15 mol
prepare, 1 L of 0.2 M H 2 SO 4 , we can apply molarity 98
equation :
Volume of solution = Mass
M 1 V1 = M 2 V2 Density
100 g
14.7 # V1 = 0.2 # 1000 = = 90.9 mL
1.10
Hence, V1 = 0.2 # 1000 Hence, Molarity of H 2 SO 4
14.7
= Moles of H 2 SO 4
= 13.60 mL # 1000
Volume of solution (mL)
Volume of 14.7 M H 2 SO 4 required = 13.60 mL
= 15 # 1000 = 1.68 M
98 # 90.9
228. A solution of glucose (molar mass = 180 g mol-1 ) in 2. Calculation of normality
water is labelled as 10% by mass. What would be
the molality an molarity of the solution? (Density of Equivalent mass H 2 SO 4 = Molar mass
2
solution = 1.2 g mL-1 ) 98
= = 49
Ans : OD 2016 2
10% (by mass) solution of glucose means that 10 g Gram equivalents of H 2 SO 4 = Mass of H 2 SO 4
of glucose is present in 100 g of solution or in 90 g of Equivalent mass
water. = 15
49
1. Calculation of molality
Gram equivalent of H 2 SO 4
Mass of glucose = 10 g Normality = # 1000
Volume of solution (mL)
Moles of glucose = 10 = 0.0556 = 15 # 1000 = 3.36 N
180 49 # 90.9
(Molar of water = 180 ) 3. Calculation of molality
Mass of water = 90 g Water of water in solution = 100 - 15 = 85 g
Hence, Molality =
Mass of glu cos e
100 Moles of H 2 SO 4 = 15
Mass of water # 98
Moles of H 2 SO 4
= 0.0556 # 1000 = 0.618 m Molality =
Wt. of solvent in gram #
1000
90
2. Calculation of molarity = 15 # 1000 = 1.8 m
98 # 85
Moles of glucose = 0.0556
230. An antifreeze solution is prepared from 222.6 g of
Volume of solution = Mass ethylene glycol, C 2 H 4 (OH) 2 and 200 g of water.
Density
Calculate the molality of the solution. If the density
= 100 = 83.3 mL of this solution be 1.072 g mL-1 , what will be the
1.20
molarity of the solution?
Moles of glu cos e
Molarity = 1000 Ans :
Vol. of soluiton # COMP 2017, OD 2013
= 0.0556 # 1000 = 0.667 M Given,
83.3
229. A commercially available sample of sulphuric acid Mass of ethylene glycol = 222.6 g
is 15% H 2 SO 4 by weight (density = 1.10 g mL-1 ). Molar mass of ethylene glycol
Calculate = 2 # At. mass of C + 6 # At. mass of H +
1. Molarity 2 # At.mass of O
2. Normality and = 2 # 12 + 6 # 1 + 2 # 16 = 62
3. Molality of the solution
Ans : SQP 2002 Moles of ethylene glycol = 222.6 = 3.59 mol
62
15% H 2 SO 4 solution means that 15 g of H 2 SO 4 are Mass of water = 200 g
present in 100 g of solution in water.
Moles of ethylene glycol 1. Express this is percent by mass.

Molality = # 1000
Mass of water 2. Determine the molality of chloroform in the water
= 3.59 # 1000 = 17.95 m sample.
200 Ans : OD 2018
2. Calculation of molarity
15 ppm (by mass) means 15 g of CHCl 3 is present in
Given, 106 g of solution.
Moles of ethylene glycol = 3.59 mol 1. Percent by mass
Mass of solution = 200 + 222.6 = Mass of chloroform # 100
Total mass
= 422.6 g
= 156 # 100 = 1.5 # 10-3 %
Volume of solution = Mass 10
Density
= 422.6 Mass of CHCl 3 = 15 g
1.072
= 394.22 mL
Moles of CHCl 3 = 15
119.5
Moles of ethylene glycol
Molarity = # 1000 (Molar mass of CHCl 3 = 119.5 )
Vol. of solution
= 3.59 # 1000 = 9.11 M = 0.1255 mol
394.22
Mass of water = 106 - 15 = 106
231. The mole fraction of benzene in a solution with
toluene is 0.50. Calculate the mass percent of benzene Molality = Moles of CHCl 3 # 1000
Mass of water
in the solution.
Ans : DELHI 2000, FOREIGN 2009 = 0.1255 # 1000
106
Let mass percentage of benzene in solution is x . This = 1.255 # 10-4 m
means 100 g of solution contains x g benzene and
(100 - x) g of toluene. Note : If we use mass of water as 106 - 15 = 9999085 g,
Mass of benzene = x g even than molality comes out to be 1.255 # 10-4 m
Moles of benzene = x 233. The mole fraction of water in a sulphuric acid solution
78
is 0.85. Calculate the molality of the solution.
(Mol. mass of C 6 H 6 = 78 )
Ans : SQP 2012
Mass of toluene = (100 - x) g
Mole fraction of water in solution = 0.85
Moles of toluene = 100 - x Mole fraction of H 2 SO 4 in solution = 1 - 0.85 = 0.15 .
92
(Mol. mass of C 6 H 5 CH 3 = 92 ) If n1 is the number of moles of water and n2 is the
number of moles H 2 SO 4 in the solution, then
Now, mole fraction of benzene = 0.5
Mole of benzene Mole fraction of H 2 SO 4 = n2 = 0.15
= 0.5 n1 + n2
Moles of benzene + Moles of toluene Molality of H 2 SO 4 solution means the number of
x
78
= 0.5 moles of H 2 SO 4 present in 1000 g of H 2 O . Thus, we
100 - x
x
78 + 92 have,
x 78 # 92 w1 = 1000 g
78 # ; 92x + 78 (100 - x)E
= 0.5
or n1 = 1000 = 55.55 ,
92x = 45x + 3900 - 39x 18
85x = 39000 n2 = ?
x = 45.9 n2 = 0.15
55.55 + n2
Mass percent benzene = 45.9 wt%
n2 = 0.15 n2 + 8.3325
232. A sample of drinking water was found to be severely
contaminated with chloroform (CHCl 3), supposed to or n2 = 9.8
be carcinogen. The level of contamination was 15 ppm Hence, Molality = 9.8 m
(by mass).
Alternatively, 1 mol of NaHCO 3 will react with 0.00526 mol of HCl.

If n1 and n2 are the number of moles of water and Total mols of HCl required to react with mixture of
H 2 SO 4 respectively, then NaHCO 3 and Na 2 CO 3
= 2 # 0.00526 + 0.00526
x water = n1 = 0.85 ...(1)
n1 + n2
= 0.01578 mol
xH SO = n2 = 0.85 To calculated volume of 0.1 M HCl corresponding to
2 4
n1 + n2
0.01578 mol, we have
= 1 - 0.85 = 0.15 ...(2)
0.1 mol of 0.1 M HCl is present in 1000 mL
Dividing equation (2) by equation (1),
n2 = 0.15 0.01578 mol of 0.1 M HCl is present in 1000 # 0.01578
0.1
n1 0.85
235. A 6.90 M solution of KOH in water contains 30%
Now, n1 = 1000 = 55.55 by mass of KOH. Calculate the density of the KOH
18
solution. (Molar mass of KOH = 56 g mol-1 )
n2 = 0.15 # 55.55 Ans : DELHI 2010
0.85
6.90 M solution of KOH contains 6.90 moles of KOH
= 9.8 moles
in 1000 mL of solution.
Hence, molality of solution = 9.8 m
Weight of KOH in solution = 6.90 # 56
234. How many mL of a 0.1 M HCl are required to react = 386.4 g
completely with 1 g mixture of Na 2 CO 3 and NaHCO 3 Weight of KOH in 1000 mL solution = 386.4 g
containing equimolar amounts of two?
Since the solution is 30% by weight, it means that
Ans : COMP 2012 30 g of KOH are present in 100 g of solution.
Let the amount of Na 2 CO 3 be x in the mixture. Hence, 386.4 g of KOH is present in
Amount of NaHCO 3 = 1 - x = 100 # 386.4 = 1288 g of solution
30
Moles of Na 2 CO 3 = x Weight
106
Density =
(Molar mass of Na 2 CO 3 = 106 ) Volume
= 1288 = 1.288 g mL-1
Moles of NaHCO 3 = 1 - x 1000
84
(Molar mass of NaHCO 3 = 84 ) 236. The Henry’s law constant for oxygen dissolved
Since number of moles of both are equal in water is 4.34 # 10 4 atm at 25cC . If the partial
x = 1-x pressure of oxygen in air is 0.2 atm, under atomspheric
106 84 conditions, calculate the concentration (in moles per
84x = 106 - 106x litre) of dissolved oxygen in water in equilibrium with
190x = 106 air at 25cC .
x = 0.558
According to Henry’s law
Hence, Moles of Na 2 CO 3 = 0.558 = 0.00526 p = KHx
106
Moles of NaHCO 3 = 1 - 0.558 = 0.00526 K H = 4.34 # 10 4 atm,
84
pO = K H xO
(Moles are equal) 2 2
Now, HCl reacts with Na 2 CO 3 as: p

or xO = O 2
2
KH
Na 2 CO 3 + 2HCl $ 2NaCl + H 2 O + CO 2
0.2
= = 4.6 # 10-6
NaHCO 3 + HCl $ NaCl + H 2 O + CO 2 4.34 # 10 4
According to the reactions, 1 mol of NaCO 3 will Changing mole fraction into molarity
react with 2 mol of HCl and therefore, 0.00526 mol Moles of water = 1000 = 55.5 mol
of Na 2 CO 3 will react with 2 # 0.00526 mol of HCl. 18
Similarly, Since nO is very small in comparison to n H O
2 2
nO + n H O = n H O pN 0.79
2 2 2
xN = 2
=
2
KN 8.54 # 10 4
nO 2
xO = 2
= 9.25 # 10-6
2
nH O
2
xO # n H O = nO pO 0.21
2 2 2
xO = 2
=
-6
2
KO 4.56 # 10 4
4.6 # 10 # 55.5 = nO
2
2
= 4.60 # 10-6
nO = 2.55 # 10-4 mol
Proportion of N 2 and O 2
2
-4
Since 2.55 # 10 mol are present in 1000 mL of = 9.25 # 10-6 : 4.6 # 10-6
solution,
= 2 :1
Molarity = 2.55 # 10-4 M
239. The vapour pressure of ethyl alcohol at 298 K is 40
237. If N 2 gas is bubbled through water at 293 K, how mm of Hg. Its mole fraction in a solution with methyl
many millimoles of N 2 gas would dissolve in 1 litre alcohol is 0.80. What is its vapour pressure in solution
of water. Assume that N 2 exerts a partial pressure if the mixture obeys Raoult’s law?
of 0.987 bar. The K H for N 2 at 293 K is 76.48 k bar. Ans : COMP 2014
Ans : OD 2015 According to Raoult’s law,
The solubility of gas is related to its mole fraction in pA = pA cxA
aqueous solution.
Vapour pressure of pure ethyl
The mole fraction of the gas in solution,
alcohol (pAc) = 40 mm of Hg
p
xN = N = 0.987 bar 2
KH 2
76480 bar Mole fraction of ethyl alcohol
-5
= 1.29 # 10 xA = 0.80
If n is the number of moles of N 2 in solution and 1 Vapour pressure of ethyl alcohol
litre of water contains 55.5 mol, then In solution pA = 40 # 0.80
xN = n . n
n + 55.5
2
55.6 = 32 mm of Hg.
= 1.29 # 10-5 240. An aqueous solution of glucose is made by dissolving
(n in the denominator is neglected because it is 10 g of glucose (C 6 H 12 O 6) in 90 g of water at 303 K.
<< 55.5 ) If the vapour pressure of pure water at 303 K be
Hence, n = 55.5 # 1.29 # 10-5 32.8 mm Hg, what would be the vapour pressure of
the solution?
= 7.16 # 10-4 mol
Ans : DELHI 2010, FOREIGN 2009
or = 7.16 # 10-1 m mol According to Raoult’s law, vapour pressure of the
= 0.716 m mol solution,
pA = pA cxA
238. Dry air contains 79% N 2 and 21% O 2 . Determine the Where pAc = vapour pressure of pure water and xA is
proportion of N 2 and O 2 (in terms of mole fractions) the mole fraction of water. Since solute is non-volatile.
dissolved in water at 1 atm pressure. Henry’s law Vapour pressure of solution = pA = pA cxA
constant for N 2 and O 2 in H 2 O are 8.54 # 10 4 atm
and 4.56 # 10 4 atm respectively. pAc = 32.8 mm Hg
Ans : SQP 2017 Moles of water = 90 = 5.0
18
Total pressure of air over water = 1 atm partial
pressure of N 2 and O 2 are : Moles of glucose = 10 = 0.0556
180
p N = 1 # 79 = 0.79 atm Mole fraction of water, xA = 5.0
100 2
5.0 + 0.0556
pO = 1 # 21 = 0.21 atm = 0.989
100 2
Vapour pressure of solution = 32.8 # 0.989

Applying Henry’s law
= 32.44 mm
pN = K H $ x
2
241. At 298 K, the vapour pressure of pure benzene, C 6 H 6 Lowering of vapour pressure
is 0.256 bar and the vapour pressure of pure toluene (pAc- pA) = 0.061
C 6 H 5 CH 3 is 0.0925 bar. If the mole fraction of benzene
Hence, Relative lowering of vapour pressure,
in solution is 0.40.
pAc- pA
1. What is the total vapour pressure of the solution? = 0.061 = 0.00348
pAc 17.5
2. Calculate the composition of the vapour in terms
2. Calculation of vapour pressure of solution
of mole fraction.
Ans : OD 2015
p = Vapour pressure of solvent
1. Calculation of total vapour pressure - lowering in vapour pressure
According to Raoult’s law, = 17.5 - 0.061
Vapour pressure of a component
= 17.439 mm of Hg
= Vapour pressure of pure liquid # Mole fraction
3. Calculation of mole fraction of sugar and water
Mole fraction of benzene,
Mole fraction of sugar, xB (solute)
x benzene = 0.40 pAc- pA
= xB
Vapour pressure of pure benzene, pAc
pcbenzene = 0.256 bar pAc- pA
Here, = 0.00348
pAc
Partial vapour pressure of benzene,
Hence, Mole fraction of sugar,
p benzene = 0.256 # 0.40 = 0.1024 bar
xB = 0.00348
Mole fraction of toluene,
Mole fraction of water,
x toluene = 1 - 0.40 = 0.60
xA = 1 - xB = 1 - 0.00348
Vapour pressure of pure toluene,
= 0.9965
pctoluene = 0.0925 bar
243. Vapour pressure of chloroform (CHCl 3) and
Partial vapour pressure of toluene,
dichloromethane (CH 2 Cl 2) at 295 K are 200 mm Hg
p toluene = 0.0925 # 0.60 and 415 mm Hg respectively.
= 0.0555 bar 1. Calculate the vapour pressure of the solution
Total vapour pressure of solution, prepared by mixing 25.5 g of CHCl 3 and 40 g of
CH 2 Cl 2 at 290 K and
p total = p benzene + p toluene
2. Mole fraction of each component in solution.
= 0.1024 + 0.0555 = 0.158 bar Ans : DELHI 2013
2. Calculation of composition of vapour phase 1. Molar mass of CHCl 3
Mole fraction of benzene in vapour phase = 1 # 12 + 1 # 1 + 3 # 35.5
p
y benzene = benzene = 0.1024 = 0.648 = 119.5 g mol-1
p total 0.158
Mole fraction of toluene in vapour phase Molar mass of CH 2 Cl 2
= 1 # 12 + 2 # 1 + 2 # 35.5
y toluene = 0.0555 = 0.351
0.158 = 85 g mol-1
242. Vapour pressure of water at 20cC is 17.5 mm of Hg 25.5 g
Molar of CHCl 3 = = 0.213 mol
and lowering of vapour pressure of a sugar solution is 119.5 g mol-1
0.061 mm of Hg. Calculate 40 g
Moles of CH 2 Cl 2 = = 0.470 mol
1. relative lowering of vapour pressure 55 g mol-1
2. vapour pressure of the solution Total number of moles
3. mole fraction of sugar and water = 0.213 + 0.470 = 0.683 mol
xCHCl = 0.213 = 0.312
1. Calculation of relative lowering of vapour pressure
3
0.683
Vapour pressure of water xCH Cl = 1.0 - 0.312 = 0.688
2 2
(pAc) = 17.5 mm of Hg pCHCl = pcCHCl 3 # xCHCl 3

3
= 200 # 0.312 = 62.4 mm Hg Vapour pressure of pure component

pCH Cl = pcCH 2 Cl 2 # xCH 2 Cl 2
2 2
Y = 400 mm Hg
= 4.15 # 0.688 = 288.5 245. What would be the molar mass of compound if 6.21 g
p total = 62.4 + 288.5 = 347.9 mm Hg of it dissolved in 24.0 g of chloroform form a solution
that has a boiling point of 68.04cC . The boiling point
2. Mole fraction in vapour phase
of pure chloroform is 61.7cC and the boiling point
p
yCHCl = CHCl = 62.4 = 0.18
3
elevation constant, Kb for chloroform is 3.63cC/m .
3
p 347.9
Ans : SQP 2010
p
yCH Cl = CH Cl = 288.5 = 0.82
2 2
Elevation in boiling point
2 2
p 374.9
244. Two liquids X and Y on mixing form an ideal solution. TTb = 68.04 - 61.7
The vapour pressure of the solution containing 3 mol = 6.34cC
of X and 1 mol of Y is 550 mm of Hg. But when Mass of substance, wB = 6.21 g ,
4 mol of X and 1 mol of Y are mixed, the vapour
Mass of chloroform, wA = 24.0 g
pressure of the solution, thus, formed is 560 mm of
Hg. What will be the vapour pressure of the pure X Kb = 3.63cC/m
and pure Y at this temperature?
Kb = TTb # MB # wA
Ans : FOREIGN 2005, OD 2010 wB # 1000
Let the vapour pressure of X be p1c and of Y be p2c or MB = K b # wB # 1000
TTB # wA
and x1 and x2 be their mole fraction.
= 3 . 63 # 6.21 # 1000
Then according to Raoult’s law, the total pressure, p is 6.34 # 24
p = p1c.x1 + p1c.x2 = 148.15 g mol-1
In the first solution, 246. The vapour pressure of pure benzene at a certain
x1 = 3 = 0.75 temperature is 0.850 bar. A non-volatile, non-
3+1 electrolyte solid weighing 0.50 g is added to 39.0 g of
x2 = 1 = 0.25 benzene (molar mass 78 g mol-1 ). The vapour pressure
3+1 of the solution, then is 0.845 bar. What is the molar
Hence, p1c# 0.75 + p2c# 0.25 = 550 mm ...(1) mass of the solid substance ?
In the second solution, Ans : COMP 2000
According to Raolut’s law
x1 = 4 = 0.80
4+1 pAc- pA
= xB
pAc
x2 = 1 = 0.20
4+1
= wB # MA (for dilute solution)
Hence, p1c# 0.80 + p2c# 0.20 = 560 mm ...(2) MB # wA
Multiplying equation (1) by 4 and equation (2) by 5, wB = 0.50 g , wA = 39.0 g ,
we get pA = 0.845 bar ,
3p1c+ p2c = 2200 mm ...(3)
pAc = 0.850 bar
4p1c+ p2c = 2800 mm ...(4) 0.850 - 0.845 = 0.5 # 78
Subtracting - p1c = - 600 mm 0.850 39.0 # MB
0.005 = 0.5 # 78
Hence, p1c = 600 mm of Hg 0.850 39.0 # MB
Subtracting in equation (3) we get
or MB = 0.5 # 78 # 0.850
3 # 600 + p2c = 2200 0.005 # 39.0
= 170 g mol-1
p2c = 2200 - 1800
247. On dissolving 3.24 g of sulphur in 40 g of benzene,
= 400 mm Hg
boiling point of solution was higher than that of benzene
Vapour pressure of pure component by 0.81 K. Kb value for benzene is 2.53 K kg mol-1 .
X = 600 mm Hg What is the molecular formula of sulphur?
(Atomic mass of sulphur = 32 g mol-1 )
Ans : DELHI 2006 Ans : SQP 2010
Let us first calculate the molar mass of sulphur, wB = 30 g , wA = 90 g , pA = 2.8 kPa

MB = Kb # 1000 # wB According to Raoult’s law,
TTb # wA wB
pAc- pA
Kb = 2.53 K kg mol-1 , = xB . MB
. wB # M A
pAc wA
MA + Mw B
B
MB # wB
wB = 3.24 g ,wA = 40 g ,
pAc- 2.8
Hence = 30 # 18
TTb = 0.81 K pAc MB 90
Hence, MB = 2.53 # 1000 # 3.24 = 253 1 - 2.9 = 6

0.81 # 40 pAc MB
Let the molecular formula of sulphur = Sx 2.9 = 1 - 6 = MB - 6
pAc MB MB
Atomic mass of sulphur = 32 2.9 M - 6
= B ...(1)
Molecular mass = 32 # x pAc MB
Similarly, wB = 30 g , wA = 90 + 18 = 108 g ,
32x = 253
pA = 2.9 kPa
x = 7.91 . 8
pAc- 2.9
Hence, Molecular formula of sulphur = S8 Hence, = 30 # 18
pAc MB 108
248. Calculate the mass of a non-volatile solute (molecular 1 - 2.9 = 5
pAc MB
mass = 40 ), which should be dissolved in 114 g octane
to reduce its vapour pressure to 80% 2.9 = 1 - 5 = MB - 5
pAc MB MB
2.9 = MB - 5 ...(2)
The vapour pressure is reduced to 80% on the addition pAc MB
of a non-volatile solute so that Dividing equation (1) by equation (2) we get
pAc- pA
= 100 - 80 = 1 = 0.2 2.8 = MB - 6
pAc 100 5 2.9 MB - 5
Now, according to Raoult’s law 2.8 MB - 14 = 2.9 MB - 17.4
pAc- pA
= xB 2.9 MB - 2.8 MB = 17.4 - 14
pAc
Let mass of non-volatile solute to be added = x g 0.1 MB = 3.4
x
pAc- pA MB = 34 g mol-1
Hence, = 40
pAc 114
+ x
114 40
Substituting the value of MB in equation (1) we get
(Molar mass of octane = 114 ) 2.8 = 34 - 6 = 28
x
pAc 34 34
0.2 = 40
1 + 40x 28pAc = 2.8 # 34
0.2 a1 + x k = x pAc = 3.4 kPa
40 40
0.2 = x - 0.2x 250. Molal elevation constant for benzene is 2.52 K/m. A
40 40
solution of some organic substance in benzene boils at
0.2 = 0 . 8 x 0.126cC higher than benzene. What is the molality of
40 g
the solution?
x = 10 g Ans : COMP 2002
mass of solute to be added = 10 g The elevation in boiling point on dissolving a solute is
249. A solution containing 30 g of a non-volatile solute in TTb = Kb .m
90 g water has a vapour pressure of 2.8 kPa at 298 K. TTb = 0.126c, Kb = 2.52 K/m
Further 18 g of water is added to solution, the new
vapour pressure becomes 8.9 kPa at 298 K. Calculate: Hence, m = TTb = 0.126 = 0.05
Kb 2.52
1. Molecular mass of solute.
2. Vapour pressure of water at 298 K. Hence, Molality of solution = 0.05 m
251. The boiling point of benzene is 353.23 K. When 1.80 g 253. Calculate the vapour pressure of an aqueous solution
of a non-volatile solute was dissolved in 90 g of benzene, containing 5% by mass of urea (NH 2 CONH 2) at
the boiling point is raised to 354.11 K. Calculate the 298 K. The vapour pressure of water at 298 K is 23.75
molar mass of the solute. (Kb for benzene is 2.53 K mm Hg.
kg mol-1 ) Ans : DELHI 2007, FOREIGN 2013
Ans : OD 2015 A 5% aqueous solution of urea means that out of 100
Molar mass of a substance can be calculated as g solution, urea is 5g and water is 95 g.
MB = Kb # wB # 1000 Weight of solute (urea), wB = 5 g ;
mB # wA
Weight of solvent (water), wA = 95 g ;
Kb = 2.53 K kg mol-1
Molar mass of urea, MB = 60 ,
wB = 1.80 g ,
Molar mass of water, MA = 18 ,
wA = 90 g
Vapour pressure of water, pAc = 23.75 mm Hg
TTb = 354.11 - 353.23 = 0.88 K
Vapour pressure of solution, pA = ?
Hence, MB = 2.53 # 1.80 # 1000
90 # 0.88 pAc- pA
= wB M A
= 57.5 g mol -1 pAc wA MB
23.75 - pA
252. A solution containing 0.730 g of camphor (molar mass or = 5 # 18
23.75 95 # 60
= 152 ) in 36.8 g of acetone (b.p. 56.30cC ) boils at
56.55cC . A solution of 0.564 g of an unknown compound or 23.75 - pA = 5 # 18 # 23.75 = 0.375
95 # 60
in the same weight of solvent boils at 56.46cC . Calculate
or pA = 23.75 - 0.375 = 23.375
the molar mass of the unknown compound.
Hence, pressure of solution = 23.375 mm Hg
Ans : SQP 2016
254. A solution of glycerol (C 3 H 8 O 3) in water was prepared
In this problem, the value of Kb is not given. The first
by dissolving some glycerol in 500 g of water. This
data is used to calculate Kb which is used to calculate
solution has a boiling point of 100.42cC while pure
the molar mass from the second data.
water boils at 100cC What mass of glycerol was
1. Calculation of Kb for acetone
dissolved to make the solution?
Kb = TTb # MB # wA Ans : COMP 2014
wB # 1000
Elevation in boiling point
TTb = 56.55 - 56.30 = 0.25cC ,
Tb = Kb # 1000 # wB
MB = 152 wA # MB
wB = 0.730 g , wA = 36.8 g TTb = 100.42 - 100 = 0.42c,
wA = 500 g , wB = ? ,
Hence, Kb = 0.25 # 152 # 36.8
0.736 # 1000
Kb = 0.512 K kg mol-1
= 1.92 K m-1
MB = 3 # 12 + 8 # 1 + 3 # 16
2. Calculation of molar mass of unknown compound
= 92
MB = Kb # 1000 # wB
TTb # wA
042 = 0.512 # 1000 # wB
Kb = 1.92 Km-1 , 500 # 92
or wB = 0 . 42 # 500 # 92
TTb = 56.46 - 56.30 0.512 # 1000
= 0.16cC = 37.37 g
wB = 0.564 g , Mass of glycerol to be added = 37.73 g
wA = 36.8 g , 255. A solution prepared by dissolving 1.25 g of oil of winter
green (methyl salicylate) in 99.0 g if benzene has a
MB = 1.92 # 1000 # 0.564 boiling point of 80.31cC . Determine the molar mass of
0.16 # 36.8
this compound. (B.P. of pure benzene = 80.10cC and
= 183.9
Kb for benzene = 2.53cC kg mol-1 )
Ans : DELHI 2017

258. Addition of 0.643 g of a compound to 50 mL of benzene
Tb = Kb # 1000 # wB (density 0.879 g/mL) lowers the freezing point from
MB # wA 5.51cC to 5.03 cC . If K f for benzene is 5.12 K kg mol-1,
or MB = Kb # 1000 # wB Calculate the molar mass of the compound.
TTb # wA
Ans : COMP 2016
Kb = 2.53 cC kg mol-1 , The molar mass, MB is calculated as:
wA = 99.0 g , wB = 1.25 g K # wB # 1000
MB = f
wA # TTf
TTb = 80.31 - 80.10 = 0.21cC
wB = 0.643 g ,
MB = 2.53 # 1000 # 1.25
0.21 # 99.0 wA = (50 mL) # (0.879 g/mL)
-1
= 152.1 g mol = 43.95 g
256. 18 g of glucose, C 5 H 12 O 6 (molar mass = 180 g mol-1 ) K f = 5.12 K m-1
is dissolved in 1 kg of water in a saucepan. At what TTf = 5.51 - 5.03 = 0.48c
temperature will this solution boil?
(Kb for water = 0.52 K kg mol-1 , boiling point of pure MB = 5.12 # 0.643 # 1000
43.95 # 0.48
water = 373.1 K ).
= 156.06
259. The molal freezing point depression constant of benzene
T b = Kb # 1000 # wB (C 5 H 6) is 4.90 K kg mol-1 . Selenium exists as a polymer
wA # MB
wB = 18 g , wA = 1000 g , MB = 180 of the type Se x . When 3.26 g of selenium is dissolved in
226 g of benzene, the observed freezing point is 0.112 cC
Kb = 0.52 K m-1 lower than for pure benzene. Deduce the molecular
formula of selenium. (Atomic mass of Se = 78.8 g mol-1 .
Hence, Tb = 0.52 # 1000 # 18
1000 # 180
Ans : OD 2011
= 0.052 K The molar mass MB is calculated as:
Boiling point of solution K # wB # 1000
MB = f
= 373.15 + 0.052 = 373.202 K wA # TTf
TTf = 0.112c,
257. 45 g of ethylene glycol (C 2 H 6 O 2) is mixed with 600 g
of water. Calculate wA = 226 g ,
1. the freezing point depression wB = 3.26 g ,
2. the freezing point of the solution K f = 4.90 Km-1
(K f for water = 1.86 K kg ml-1 )
Ans : SQP 2009 MB = 4.90 # 3.26 # 1000
226 # 0.112
K # wB # 1000 = 632 g mol-1
1. Tf = f
wA # MB
Now, molecular mass of
wA = 600 g , wB = 45 g ,
Sex = x # 78.8
K f = 1.86 K kg mol-1
632 = x # 78.8
MB = 2 # 12 + 6 # 1 + 2 # 16
x = 632 = 8
= 62 mol-1 78.8
Hence, Molecular formula of selenium = Se8
Tf = 1.86 # 45 # 1000
600 # 62 260. 1.02 g of urea when dissolved in 98.5 g of certain
= 2.25 K solvent decreases its freezing point by 0.211 K. 160 g
of unknown compound when dissolved in 86.0 g of the
Hence, Freezing point depression = 2.25 K
same solvent depresses the freezing point by 0.34 K.
2. Freezing point of aqueous solution Calculate the molar mass of the unknown compound.
= 273.15 - 2.25 = 270.90 K (Molar mass of urea = 60 g mol-1 )

Since boiling point is higher than room temperature
Let us first calculate K f in summer, it is advisable to keep this substance in
K f # wB # 1000 the car radiator during summer.
TTf =
wA # MB
262. Two elements A and B form compounds having
For urea solution, molecular formula AB2 and AB 4 . When dissolved
wB = 1.02 g , wA = 98.5 g , in 20 g of benzene, 1 g of AB2 lowers the freezing
point by 2.3 K, whereas 1.0 g of AB 4 lowers it by
TTf = 0.211 K
1.3 K. The molar depression constant for benzene is
K f # 1.02 # 1000 5.1 K kg mol-1 . Calculate the atomic mass of A and
0.211 =
98.5 # 60 B.
Hence, K f = 0.211 # 98.5 # 60 Ans : SQP 2018
1.02 # 1000
Let us first calculate molar masses of AB2 and AB 4
= 1.22 Km-1
For AB2 compound
Now, molar mass of unknown compound can be K # wB # 1000
calculated as MB = f
wA # TTf
K # wB # 1000
TTf = f TTf = 2.3 K , wB = 1.0 g ,
wA # MB
K f # wB # 1000 wA = 20.0 g
or MB =
wA # TTf K f = 5.1 K kg mol-1
wB = 1.60 g , wA = 86.0 g ,
MB = 5.1 # 1.0 # 1000 = 11087
TTf = 0.34 K , K f = 1.22 Km -1 20.0 # 2.3
Hence, MAB = 110.87
MB = 1.22 # 1.60 # 1000
2
Hence,
86.0 # 0.34 For AB 4 compound
= 66.76 g mol-1 TTf = 1.3 K , wB = 1.0 g ,
-1
261. Ethylene glycol (molar mass = 62 g mol ) is a wA = 20.0 g
common automobile antifreeze. Calculate the freezing
point of a solution containing 12.4 g of this substance MB = 5.1 # 1.0 # 1000 = 196.5
20.0 # 1.3
in 100 g of water. Would it be advisable to keep this
Hence, MAB = 196.15
substance in car radiator during summer? 4
Let a is the atomic mass of A and b is the atomic

(K f for water = 1.86 Km-1 and Kb for water
mass of B, then
= 0.512 Km-1 )
Ans : COMP 2013, DELHI 2014 MAB = a + 2b = 110.87
2
...(1)
Moles of ethylene glycol MAB = a + 4b = 196.15
4
...(2)
= 12.4 = 0.2 mol Subtracting equation (2) from equation (1)
62
- 2b = - 85.28
Molality = .2 # 1000 = 2 m
0
100 Hence, b = 42.64
Freezing point depression Substituting the value of b in equation (1)
TTf = K f # m a + 2 # 42.64 = 110.87
= 1.86 # 2 = 3.72 K a = 110.87 - 85.28 = 25.59
Freezing point of aqueous solution Atomic mass of A = 25.59
= 273.15 - 3.72 = 269.43 K
Atomic mass of B = 42.64
Boiling point elevation of solution
TTf = Kb # m 263. 200 cm3 of an aqueous solution of a protein contains
1.26 g of the protein. The osmotic pressure of such
= 0.52 # 2 = 1.04 K a solution at 300 K is found to be 2.57 # 10-3 bar.
Boiling point of solution Calculate the molar mass of the protein.
= 373.15 + 1.04 = 374.19 K ( R = 0.083 L bar mol-1 - 1 )
Ans : FOREIGN 2015

c2 = 1.52 # 36 = 0.061 M
According to Van’t Hoff equation, 4.98 180
Hence, Concentration of second solution = 0.061 M
p = cRT = n RT = wB RT
V MB V
266. A solution prepared by dissolving 8.95 mg of a gene
Hence, MB = wB RT fragment in 35.0 mL of water has an osmotic pressure
pV
of 0.335 torr at 25cC . Assuming the gene fragment is
V = 200 cm3 = 0.20 L ,
a non-electrolyte, determine its molar mass.
wB = 1.26 g , T = 300 K Ans : DELHI 2003, FOREIGN 2012
R = 0.083 L bar K-1 mol-1 , Mass of gene fragment = 8.95 mg

-3
p = 2.57 # 10 bar = 8.95 # 10-3 g
1.26 g # 0.083 L bar K-1 mol-1 # 300 K Volume of water = 35.0 mL = 35.0 # 10-3 L
MB =
2.57 # 10-3 bar # 0.20L
Osmotic pressure, p = 0.335 torr
= 61039 g mol-1
= 0.335
264. If 1.71 g of sugar (molar mass = 342 ) are dissolved 760 atm
in 500 cm3 of a solution at 300 K , what will be its Temperature = 25cC = 273 + 25
osmotic pressure?
= 298 K
(R = 0.083 L bar K-1 mol-1 )
Ans : OD 2007 p = wB RT
MB # V
According to Van’t Hoff equation,
0.335 = 8.95 # 10-3 # 0.0821 # 298
p = cRT = n RT = wB RT 760 MB # 35.0 # 10-3
V MB V
-3
wB = 1.71 g , MB = 8.95 # 10 # 0.0821 # 298
-3
# 760
0.335 # 35.0 # 10
V = 500 L = 0.5 L = 14193.3 g mol-1
1000
T = 300 K and = 1.42 # 10 4 g mol-1
R = 0.083 L bar K-1 mol-1 267. Calculate the boiling point of solution when 2 g of
Na 2 SO 4 (M = 142 g mol6 - 1) was dissolved in 50 g
p = 1.71 # 0.083 # 300 of water, assuming Na 2 SO 4 undergoes complete
342 # 0.5
ionization. (Kb of water = 0.52 K kg mol-1 )
= 0.249 bar
Ans : OD 2012
36 g of glucose dissolved per litre of the solution
TTb = i # kb # wB # 1000
265.
has an osmotic pressure of 4.98 bar at 300 K. If the MB # wA
osmotic pressure of the solution is 1.52 bar at the Weight of solute, wB = 2g
same temperature, what would be its concentration?
Molar mass = 142 g mol-1
Given, Weight of solvent = 50 g
c1 = 36 M , p 1 = 4.98 bar Kb = 0.52 Km-1

180
Na 2 SO 4 undergoes complete ionization as:
and c2 = ? p 2 = 1.52 bar
Na 2 SO 4 2Na+ + SO 24-
According to Van’t Hoff equation,
One mole of Na 2 SO 4 gives 3 mole particles and
p = cRT
therefore,
4.98 bar = 36 RT ...(1) i =3
180
1.52 bar = c2 RT ...(2) Hence, TTb = 3 # 0.52 # 2 # 1000 = 0.439
142 # 50
Dividing equation (2) by equation (1), Boiling point of solution
c2 180 = 1.52
36 # 4.98 = 373 + 0.439 = 373.439 K
268. Calculate the amount of CaCl 2 (molar mass Ans : FOREIGN 2016
= 111 g mol-1 ) which must be added to 500 g of Molecular mass can be calculated from boiling point
water to lower its freezing point by 2 K, assuming data as:
CaCl 2 is completely dissociated. (K f for water MB = Kb # wB # 1000
= 1.86 K kg mol-1 ) TTb # wA
Ans : SQP 2011, COMP 2012 wB = 6.8 g , wA = 100 g ,
CaCl 2 undergoes complete dissociation as: Kb = 100.11 - 100 = 0.11,
2+ -
CaCl 2 Ca + 2Cl Kb = 0.52 K m-1
One mole of CaCl 2 will give 3 mole particles and
therefore, the value of 'i' will be equal to 3. Hence, MB = 0.52 # 6.8 # 1000 = 321.45
0.11 # 100
TTf = iK f # m Now, p = nRT , n = 6.8
V 321.45
i # K f # wB # 1000
= V = 100 g = 100 ml = 0.1 L
MB # wA
K f = 1.86 K kg mol-1 , R = 0.082 L atm mol-1 K-1
wA = 500 g , wB = ? , T = 298 K
TTf = 2 K , i = 3 , MB = 111 g mol-1 p = 6.8 # 0.082 # 298
321.45 # 0.1
2 = 3 # 1.86 # wB # 1000 = 5.17 atm
111 # 500
Hence, wB = 2 # 111 # 500 271. A solution containing 0.5 g of KCl dissolved in 100 g
3 # 1.86 # 1000 of water freezes at - 0.24cC . Calculate the percentage
= 19.89 g ionization of the salt. (K f for water = 1.86 Km-1 )
Ans : OD 2015
269. At 25cC , 3 g of solute A in 100 mL of an aqueous
Let us first calculate the observed molar mass as:
solution gave an osmotic pressure of 2.5 atmosphere.
What is the nature of solute (associated or dissociated) K # wB # 1000
MB = f
if its normal molar mass is 246? TTf # wA
wB = 0.5 g , wA = 100 g ,
Ans : DELHI 2014
Normal molar mass of solute = 246 TTf = 0 - (- 0.24) = 0.24c
The molar mass may be calculated as: K f = 1.86
p = cRT = nRT = wB RT Hence, MB = 1.86 # 0.5 # 1000 = 38.75

V MB V 0.24 # 100
Normal molar mass of KCl
or MB = wB RT
pV = 39 + 35.5 = 74.5
wB = 3.0 g , V = 100 ml = 0.1 L ,
Van’t Hoff factor, i = Normal molar mass
p = 2.5 atm , Observed molar mass
R = 0.082 L atm mol-1 K-1 = 74.5 = 1.92

38.75
KCl ionize as:
MB = 3 # 0.082 # 298 = 293
2.5 # 0.1 If a is the degree of ionization, then
This means that the solute has abnormal behaviour
KCl K+ + Cl-
in solution. Since observed molar mass is more than
the normal value (246) the solute exists as associated Initial moles 1 0 0
in solution.
Moles after dissociation 1-a a a
270. A solution of an organic compound was prepared
by dissolving 6.8 g in 100 g of water. Calculate the Total number of moles after dissociation
osmotic pressure of this solution at 298 K when = 1-a+a+a
boiling point of solution is 100.11cC . Given Kb for
water = 0.52 Km-1 and R = 0.082 litre atm K-1 mol-1 . = 1+a
i = Observed moles of solute 273. A solution containing 3.100 g of BaCl 2 in 250 g of water
Normal moles of solute boils at 100.083cC . Calculate the Van’t Hoff factor
= 1+a and molality of BaCl 2 in this solution. (Kb for water
1 = 0.52 Km-1 , molar mass of BaCl 2 = 208.3 g mol-1 )
Hence, 1 + a = 1.92 or 1 + a = 1.92 Ans : COMP 2002
1
Molality of the solution,
or a = 1.92 - 1 = 0.92
m = wB # 1000
Percentage ionization = 92% MB # wA
wB = 3.100 g , wA = 250 g , MB = 208.3
272. 2 g of benzoic acid (C 6 H 5 COOH) dissolved in 25 g
of benzene shows a depression in freezing point equal m = 3.100 # 1000 = 0.05952
208.3 # 250
to 1.62 K. Molar depression constant for benzene is
Now, let us calculate normal elevation in boiling point,
4.9 K kg mol-1 . What is the percentage association of
acid if it forms double molecules (dimer) in solution? TTb = Kb # m
Ans : SQP 2017 = 0.05952 # 0.52 = 0.03095
Let us first calculate observed molar mass,
Observed elevation in boiling point,
K # wB # 1000
MB = f TTb = 100.083 - 100 = 0.083cC
TTf # wA
wB = 2 g , wA = 25 g , TTf = 1.62 K i = Observed TTb = 0.083 = 2.68
Normal TTb 0.03095
K f = 4.9 K kg mol-1
274. The freezing point of a solution containing 0.3
MB = 4.9 # 2 # 1000 = 241.98 g mol-1 g of acetic acid in 30.0 g of benzene is lowered by
1.62 # 25 0.45c. Calculate Van’t Hoff factor. (Kb for benzene
Observed molar mass = 241.98 mol-1 = 5.12 K kg mol-1 )
Normal molar mass of C 6 H 5 COOH Ans : DELHI 2013, SQP 2011
= 7 # 12 + 6 # 1 + 2 # 16 Let us first calculate observed molar mass
= 122 g mol-1 K # wB # 1000
MB = f
Benzoic acid associates as: TTf # wA
wB = 0.3 g , wA = 30.0 g ,
2C 6 HCOOH (C 6 H 5 COOH) 2
TTf = 0.45c, K f = 5.12 K kg mol-1

If a is the degree of association
Hence, MB = 5.12 # 0.3 # 1000 = 113.8
initial moles 1 0 0.45 # 30
Moles after association 1-a a Normal molar mass = 60
2
Total moles after association Now i = Normal molar mass
Observed molar mass
= 1 - a + a2
= 60 = 0.527
= 1 - a2 113.8
i = Normal molar mass 275. A solution contains 0.8960 g of K 2 SO 4 in 500 mL

observed molar mass solution. Its osmotic pressure is found to be 0.690 atm
= 122 = 0.504 at 27cC . Calculate the value of Van’t Hoff factor. (At
241.98 mass K = 39.0 , O = 16 , R = 0.082 atm mol-1 K-1
1 - a2 Ans : FOREIGN 2000
Now i = = 0.504
1 Let us first calculate observed molar mass,
- a = 0.504 - 1 MB = wB # R # T
2
p#V
a
- = - 0.496
2 wB = 0.8960 g , V = 500 ml = 0.5 L
a = 0.496 # 2 = 0.992 R = 0.082 L atm mol-1 K-1 ,
Thus, degree of association of benzoic acid in benzene p = 0.690 atm , T = 300 K
= 99.2% .
MB = 0.8960 # 0.082 # 300 = 63.9 [CH 3 COO-] = mx

0.690 # 0.5
= 0.0106 # 0.041 = 4.35 # 10-4
Normal molar mass = 2 # 39 + 32 + 4 # 32 = 174
[H+] = mx = 4.35 # 10-4
Van’t Hoff factor, i = Normal molar mass
Observed molar mass [CH 3 COO-] [H+]
Ka =
[CH 3 COOH]
= 174 = 2.72
63.9 (4.35 # 10-4) (4.35 # 10-4)
=
0.0102
276. 0.6 mL of acetic acid (CH 3 COOH) having density
1.06 g mL-1 is dissolved in 1 litre of water. The = 1.86 # 10-5
depression in freezing point observed for this strength 277. Calculate the freezing point depression expected for
of acid was 0.0205cC . Calculate the Van’t Hoff factor 0.0711 m aqueous solution of Na 2 SO 4 . If this solution
and dissociation constant of the acid. actually freezes at - 0.320cC , what would be the value
Ans : OD 2000, SQP 2008 of Van’t Hoff factor? (K f for water is 1.86cC mol-1 )
0.6 mL # 1.06 g mL Ans : COMP 2010
Molar of acetic acid =
60 g mol
Freezing point depression,
= 0.016 mol
TTf = K f # m
6M (CH 3 COOH = 60@ K f = 1.86cC mol-1 , m = 0.0711
-1
Mass of water = 1000 mL # 1 g mL = 1000 g
TTf = 1.86 # 0.0711
Molality = 0.0106 # 1000 = 0.132c
1000 g
= 0.0106 mol kg-1 Observed freezing point
Now, TTf = K f # m = 0 - (- 0.320) = 0.320c

Observed freezing point
= 1.86 K kg mol-1 # 0.0106 mol kg-1 Van’t Hoff factor =
Calculated freezing point
= 0.0197 K
= 0.320 = 2.42
Observed freezing point depression 0.132
= 0.0205 K 278. Calculate the mass percentage of benzene (C 6 H 6)

and carbon tetrachloride (CCl 4) if 22 g of benzene is
Observed freezing point
Van’t Hoff factor = dissolved in 122 g of carbon tetrachloride.
Calculated freezing point
Ans : DELHI 2015
= 0.0205 K = 1.041
0.0197 K Total mass of solution = 22 + 122 = 144 g
Acetic acid dissociation as:
Mass % benzene = 22 # 100 = 15.28%
144
CH 3 OOH CH 3 COO- + H+
Mass % CCl 4 = 122 # 100 = 84.72%
144
Initial conc. m 0 0 279. Calculate the mole fraction of benzene in solution
Conc. after m (1 - x mol) mx mol mx mol containing 30% by mass in carbon tetrachloride.
dissociation Ans : FOREIGN 2011
Total moles of particles = m (1 - x + x + x) Mass of benzene = 30 g

= m (1 + x) Moles of benzene = 30 = 0.385
78
m (1 + x)
i = = 1.041 (Mol. mass of C 6 H 6 = 78 )
m
x = 0.041 Mass of CCl 4 = 70 g
Hence, Degree of dissociation = 0.041 Mass of CCl 4 = 70 = 0.454
154
[CH 3 COOH] = m (1 - x)
(Mol. mass of CCl 4 = 154 )
= 0.0106 # (1 - 0.041) 0.385
xC H = = 0.459
= 0.0102
6 6
0.385 + 0.454
280. A solution X is prepared by dissolving 3 moles (a) Molality = 0.120 # 1000

of glucose in one litre of water and a solution Y is 80
prepared by dissolving 1.5 moles of sodium chloride in = 1.5 m
one litre of water. Will the osmotic pressure of X be
(b) Volume of solution = 100 = 83.19 mL
higher, lower or equal to that of Y ? 1.202
Give a reason for your answer. Molarity = 0.120 # 1000
83.19
Ans : SQP 2012
Osmotic pressure is a colligative property which = 1.44 M
depends on the number of particles present in solution. (c) Moles of Kl = 0.120
Since, glucose is non-electrolyte.
Moles of H 2 O = 80 = 4.44
Value of van’t Hoff factor i for sodium chloride 18
= 1 and n = 3 mol xKl = 0.120
1.44 + 0.120
Value of van’t Hoff factor i for sodium chloride = 0.0263
= 2 and n =1.5 mol
283. Calculate the molarity of each of the following
Now for glucose, osmotic pressure,
solutions:
p = inRT 1. 30 g of Co (NO 3) 2 .6H 2 O in 4.3 L of solution.
V
2. 30 mL of 0.5 M H 2 SO 4 diluted to 500 mL
[Here, volume ^V h of water = 1000 mL]
= 1 # 3 RT/1000 = 3 RT/100
1. Molar mass of Co (NO 3) 2 .6H 2 O
For NaCl, osmotic pressure,
= 58.93 + 2 # 14 + 6 # 16 + 6 # 18
p = inRT
V = 290.93
= 2 # 1.5 RT/1000 = 3 RT/1000 Moles of Co (NO 3) 2 .6H 2 O
So, p is same for both the solution. = 30 = 0.103
290.93
281. Calculate the mass of urea (NH 2 CONH 2) required in Molarity = 0.103 = 0.024 M
4.3
making 2.5 kg of 0.25 molal aqueous solution.
Ans : OD 2009
2. M1 V1 = M2 V2
0.25 molal solution means 0.25 moles of urea in 1000 g 0.5 # 30 mL = M2 # 500 mL
of water
Hence, M2 = 0.5 # 30 = 0.03 M
Mass of urea = 0.25 # 60 = 15 g 500
Total mass of solution = 1000 + 15 = 1015 g
284. H 2 S a toxic gas with rotten egg like smell is used for
or = 1.015 kg
qualitative analysis. If the solubility of H 2 S in water
1.015 kg of solution contain urea = 15 g at STP is 0.195 m, calculate Henry’s law constant.
2.5 kg of solution will required urea Ans : FOREIGN 2005
= 15 # 2.5 = 36.94 g 0.195 m solution means that 0.195 moles of H 2 S is

1.015
dissolved in 1 kg of water.
282. Calculate (a) molality, (b) molarity and (c) mole
Moles of H 2 S = 0.195
fraction of Kl if density of 20% (mass/mass) aqueous
solution of Kl is 1.202 g mL-1 . Moles of water = 1000 = 55.55
18
Ans : SQP 2000
Moles fraction of H 2 S = 0.195 = 0.0035
20% solution of Kl means 20 g of Kl are present in 100 55.55 + 0.195
g of solution or 80 g of water.
Now, p = K H x2
Mass of Kl = 20 g
Pressure = 0.987 bar
Molar mass of Kl = 39 + 127 = 166
p
Moles of Kl = 20 = 0.120 or KH = = 0.987 bar = 282 bar
x2 0.0035
166
285. Henry’s law constant for CO 2 in water is 1.67 # 108 Pa The solution will boil at the temperature
at 298 K. Calculate the quantity of CO 2 in 500 mL of = 100 + 0.052
soda water when packed under 2.5 atm CO 2 pressure
at 298 K. = 100.052cC
Ans : OD 2009 287. The vapour pressure of pure liquid A and B are 450
8 and 700 mm Hg at 350 K respectively. Find out the
K H = 1.67 # 10 Pa
composition of the liquid mixture if total pressure
p = 2.5 atm is 600 mm Hg. Also find the composition of vapour
= 2.5 # 101.325 # 103 Pa phase.
Ans : SQP 2010, 2008
= 2.533 # 105 Pa
Let, mole fraction of liquid A in solution = xA
Now, p = K H x2 Mole fraction of liquid B is solution
p 5
or, x2 = = 2.533 # 108 Pa = xB = (1 - xA)
KH 1.67 # 10 Pa
p = pA + pB = xA pcA + xB pcB
= 1.517 # 10-3
Hence, 600 = xA # 450 + 700 - xA # 700
Moles of water = 500 = 27.78
18 250 xA = 100
x2 = n2 = n2
Hence, xA = 100 = 0.4
n1 + n2 27.78 + n2 250
= 1.517 # 10-3 xB = 1 - 0.4 = 0.6
n2 = 0.0419 + 0.0015 n2 Composition in vapour phase
or 0.9985 n2 = 0.0419 pA = xA pcA = 0.4 # 450 = 180 mm
n2 = 0.0420 pB = xB pcB = 0.6 # 700 = 420 mm
Amount of CO 2 dissolved Total pressure = 180 + 420 = 600 mm
= 0.0420 # 44 = 1.85 g Mole fraction of A in vapour phase,
286. 18 g of glucose ^C 6 H 12 O 6h was added to 1 kg water at yA = 180 = 0.3
1.013 bar atmospheric pressure in a vessel. At which 600
temperature will water boil? Kb for water is 0.52 Mole fraction of B in vapour phase,
K Kg mol-1 . yB = 420 = 0.7
Ans : OD 2012
600
Given, 288. Vapour pressure of pure water at 298 K is 23.8 mm
Mass of solute (glucose), Hg. 50 g of urea (NH 2 CONH 2) is dissolved in 850 g of
WB = 18 g water. Calculate the vapour pressure of water for this
solution and its relative lowering.
Hence, molar mass of glucose
Ans : COMP 2016
MB = 180
Moles of urea = 50 = 0.833
Mass of solvent, (WA) water i.e., 60
= 1 kg = (1000 g) Moles of water = 850 = 47.222
18
kb = 0.52 k.kg.mol-1
Mole fraction of urea = 0.833
0.833 + 47.222
Hence, TTb = kb . WB # 1
MB WA (kg) = 0.0173
where, TTb = elevation in boiling point. pcA - pA
= xB = 0.0173
TTb = 0.52 # 18 # 1 = 0.52 pcA
180 1 10 23.8 - pA
= 0.0173
Hence, TTb = 0.052 23.8
Since, Boiling point of pure water 23.8 - pA = 0.412
= 100cC pA = 23.39
289. Boiling point of water at 750 mm Hg is 99.63cC . How Hence, weight of solvent = 99 g (w)
much sugar is to be added to 500 g of water such that Molecular weight of aniline = ?
it boils at 100cC . Mole weight of ether = 74 ^mh
Ans : DELHI 2013 We known that,
TTb = 100 - 99.63 = 0.37c TP = P0 - Px = W # M = x
Pc P0 m#w ^ Bh
MB = Kb # 100 # WB
WA # TTb 0.007 = W # M a= x B k
m#w xA
342 = 0.522 # 1000 # WB [for dilute solution]
500 # 0.37
WB = 342 # 500 # 0.37 = 121.7 g Hence, m = W#M
0.522 # 1000 0.007 # w
290. Calculate the mass of ascorbic acid (Vitamin C, m = 1 # 74 = 106.78

0.007 # 99
C 6 H 8 O 6 ) to be dissolved in 75 g of acetic acid to
293. 46 g of ethyl alcohol is dissolved in 18 g of water.
lower its melting point by 1.5cC . K f = 3.9 K kg mol-1 .
Calculate the mole fraction of ethyl alcohol.
Ans : FOREIGN 2012, 2010
(Atomic weight of C = 12 , O = 16 and H = 1)
TTb = 1.5c
Ans : SQP2008
M = 6 # 12 + 1 # 8 + 6 # 16 Given, mass of ethyl alcohol (w) = 46 g,
= 176 Mass of water (W) = 18 g
K f # 1000 # WB We know that,
M = Molecular weight of ethyl alcohol (C2H5OH)
WA # TTf
176 = 3.9 # 1000 # WB = 2 # 12 + 5 # 1 + 16 + 1 = 46
75 # 1.5
Number of moles of ethyl alcohol in 46 g
WB = 176 # 75 # 1.5 = 5.08 g
Mass of ethyl alcohol
3.9 # 1000 = = 46 = 1 mol
Molar mass of ethyl alcohol 46
291. Calculate the osmotic pressure in Pascals exerted by Molecular weight of water (H2O)
a solution prepared by dissolving 1.0 g of polymer of
molar mass 185,000 in 450 mL of water at 37cC . = 2 # 1 + 16 = 18
Ans : OD 2005 Number of moles of water in
p = cRT = n RT 18 g = 18 = 1 mol
V 18
Mole fraction of ethyl alcohol
n = 1.0
185000 n
C 2 H 5 OH
= = 1 = 1 = 0.5
V = 450 mL C 2 H 5 OH + n H 2 O 1 + 1 2
n
294. If the molality of an aqueous solution of cane sugar is

T = 273 + 37 = 310 K
0.4445, what is the mole fraction of cane sugar?
R = 8.314 # 103 Pa L mol-1 K-1 Ans : SQP 2012
3 Given, molality of cane sugar solution
p = 1.0 # 8.314 # 10450# 310
185, 000 # 1000 = 0.4445 mol/kg
= 30.96 Pa That means, number of moles (n) of cane sugar
292. The relative lowering of vapour pressure of 1% solution present in 1 kg of water = 0.4445
of Aniline in Ether was 0.007. Calculate the molecular We know that, number of moles of water,
weight of Aniline.
^N h = 1000
18
= 55.5555
Ans : SQP 2012
Given, (Density of water = 1000 kg/m3 = 1 g/cm 3, molecular

Relative lowering of V.P = 0.007 weight of H2O =18 g mol–1)
1% solution of aniline, Thus, molarity = Number of moles of water
Volume ^L h
Weight of solute = 1 g (w)
1000/18
Weight of solution = 100 g = = 55.5555 M
1
Mole fraction of cane sugar = ws + wu

n solute ms m u
= = n
n solute + N solvent n + N n = 2 + 2
0.4445 342 60
= Number of moles of solvent (water),
0.4445 + 55.5555
= 0.4445 = 0.0079 N = 100
56 18
295. Calculate the mole fraction of water in a sodium 23.56 - p + 6022
hydroxide solution which has 80 g of NaOH and 54 g = 342

= 0.007
23.56 + 602 + 100
2
342 18
of H2O. (Relative atomic masses of Na = 23, O = 16 23.56 - p = 0.007 # 23.56 = 0.165
and H = 1)
Ans : OD 2008
p = 23.56 - 0.165
Molecular mass of NaOH = 23.395 torr
= 23 + 16 + 1 = 40 gmol -1
Hence, the vapour pressure of the solution is
Number of moles of NaOH in 80 g 23.395 torr
What is the mass of a non-volatile solute (molar mass
^n h = Mass of NaOH 297.
Molecular mass of NaOH 60) that needs to be dissolved in 100 g of water in
order to decrease the vapour pressure of water by
= 80 = 2 mol
40 25%? What will be the molality of the solution?
Molecular mass of water Ans : SQP2010
= 2 + 16 = 18 gmol-1 According to Raoult’s law,

Dp pc - p
Number of moles of water in 54 g, = = n
pc pc n+N
^N h = 18
54 = 3 mol
w/m
=
Total number of moles in solution w/m + W/M
= n+N Given, Dp = 25% (atm), i.e. pc = 100 (atm),
= 2 + 3 = 5 mol m = 60 , W = 100 g ,
Mole fraction of water in solution M = 18 (for water), w = ?

Number of moles of water 25 = w/60
=
Total number of moles present in solution 100 w/60 + 100/18
= N = 3 = 0.6 1 = w/60
n+N 5 4 18w + 60 # 100
296. A solution is prepared by dissolving 2.0 g of sucrose 18 # 60
and 2.0 g of urea in 100 g of water at 298 K. w = 111.11 g
Calculate the vapour pressure of the solution, if the Mass of solute required is 111.11 g.
vapour pressure of pure water at 298 K is 23.56 torr. Now, Molality (m)
(Molecular weight of urea = 60 and sucrose = 342)
Ans : FOREIGN 2008 = Number of moles of solute
The expression for Raoult’s law for the solution 111.11/60
containing non-volatile solute is = = 18.518
100/1000
Dp pc - p
= = n Hence, molality of the solution is 18.518 mol kg–1.
pc pc n+N
298. The osmotic pressure of blood is 7.65 atm at 27c C .
w/m
= How much glucose should be used per litre to prepare
w/m + W/M
an intravenous injection that has the same osmotic
Given that, pc = 23.56 torr pressure as blood?
Number of moles of solute, Ans : DELHI 2003, 2001
n = Number of moles of sucrose Let, the weight of glucose is wg .

+ Number of moles of urea If glucose solution has same osmotic pressure as blood.
Thus, p glu cos e = p blood = 7.65 atm
p = w#R#T Freezing point of solution,

M#V
Tfl = 276.8 K
Given : Volume of solution, V = 1 L
It is known that, DTf = i # K f # m
Gas constant, R = 0.0821 L atm mol-1 K-1
DTf
Temperature, T = 27c C = ^27 + 273h K Kf =
i#m
= 300 K Here, van’t Hoff factor, i for solute is considered as 1.
-1
Molecular weight of glucose, M = 180 g mol Depression in freezing point,
Thus, p = w # 0.0821 # 300 DTf = T fo = Tfl
180 # 1
7 . 65 = 278.8 - 276.8 K = 2 K
w = # 180
0.0821 # 300 2
Kf = = 8 K molal-1
= 55.9 g mol -1 1 # 0.25
301. Calculate osmotic pressure of a solution containing
299. 0.5 g of a non-volatile solute is dissolved in 100 g of 3.42 g of sucrose in 1 L of water at 400 K.
ethyl acetate at 20c C . The vapour pressure of the Ans : DELHI 2014
solution and pure ethyl acetate are 72.0 torr and Given that, weight of sucrose = 3.42 g
72.8 ton, respectively at - 28c C . Calculate molecular
Volume of solution = 1 L
weight of the solute.
Ans : SQP2006 T = 400 K
Given that, weight of solvent, w = 100 g Molecular weight of sucrose = 342 g mol-1
Vapour pressure of solution, p = 72.0 torr Gas constant, R = 0.0821 atm K-1 mol-1
Osmotic pressure ^p h of a solution is given by
Vapour pressure of solvent (ethyl acetate),
pc = 72.8 torr
p = w#R#T
Molecular weight of solvent = 88 g mol-1 mV
According to Raoult’s law, = 3.42 # 0.0821 # 400
342 # 1
pc - p
= n = 0.328 atm . 0.33 atm
pc N+n
But for dilute solutions, n <<< N 302. The cryoscopic constant of water is 1.86 K mol-1 kg-1
.An aqueous solution of cane sugar freezes at
pc - p
Thus, = n - 0.372c C . Calculate molality of the solution.
pc N
Ans : COMP 2007
72.8 - 72 = 0.5/m
72.8 100/88 Given : Cryoscopic constant,
K f = 1.86 K mol-1 kg-1
m = 0.5 # 88 # 72.8
0.8 100 Freezing point of solution,
= 40.04
Tfl = - 0.327c C
Hence, molecular weight of non-volatile solute is
40.04 g mol-1 . = 6273 + ^- 0.327h@ K
300. The freezing point of nitrobenzene is 278.8 K. A = 272.673 K

0.25 molal solution of a substance (molecular weight Freezing point of pure water,
= 120) in nitrobenzene has a freezing point of T fo = 0c C = 273 K
276.8 K. Calculate the molal depression constant of
nitrobenzene. Depression in freezing point,
Ans : COMP 2010, OD 2007 DTf = T fo - Tf l
Given that, T fo = 278.8 K = 273 - 272.673 K = 0.327 K
Molality of a solution, We know that, DTf = i # K f # m
m = 0.25 m Since, cane sugar is a non-electrolyte, thus i (van’t
w = 120 g mol -1 Hoff factor) is equal to 1.
0.327 = 1 # 1.86 # m
m = 0.327 305. A solution containing 0.5 g of KCl dissolves in 100 g

1.86 of water and freezes at - 0.24c C . Calculate the degree
= 0.17 molal . 0.2 molal of dissociation of the salt. (K f for water = 1.86c C ).
Hence, molality of solution is 0.2 molal. (Atomic weights of K = 39 , Cl = 35.5) .
Ans : SQP 2015
303. The elevation in boiling point when 0.30 g of acetic Given, Weight of KCl (solute) = 0.5 g
acid is dissolved in 100 g of benzene is 0.0633°C.
Calculate the molecular weight of acetic acid from Weight of solvent (water) = 100 g
this data. What conclusion can you draw about the Freezing point ^Tf h = - 0.24c C
molecular state of the solute in the solution? (Given
Kb for benzene = 2.53 K kg mol-1 , at. wt. of C = 12, K f = 1.86c C
H = 1, O = 16). Molecular mass of KCl = 39 + 35.5 = 74.5
Ans : SQP 2020 From depression in freezing point
Given, weight of solute ^wB h = 0.30 g Tf = i # K f # m
weight of solvent
0.24c C = i # 1.86c C # 0.5 # 1000
^WAh = 100 g 74.5 100
i = 1.92
DTb = 0.0633c C = 0.0633 K
For KCl, i = 1+a
Kb = 2.53 K kg mol-1
(where a is the degree of dissociation)
MB = Kb # wB # 1000 a = 1.92 - 1
WA # DTb
= 2. 53 # 1000 # 0.30 = 119.9 g/mol a = .92 or 92%
100 # 0.0633
306. If 1.71 g of sugar (molar mass = 342 g/mol) are
i = Normal molar mass dissolved in 500 mL of an aqueous solution at 300 K ,
Abnormal molar mass
60 = 0.5 what will be its osmotic pressure?
119.90 Ans : DELHI 2015
i <1
Given, Weight of sugar = 1.71 g
As i is less than 1, thus association will take place.
Molar mass of sugar = 342 g/mol
304. The molecular weight of an organic compound is Volume of solvent = 500 mL
58 g mol-1 . What will be the boiling point of a solution Temperature = 300 K
containing 48 g of the solute in 1200 g of water?
Osmotic pressure, p = CRT
Ans : SQP 2016, 2010
Given, C = 1.71 # 1000

342 500
Wa = Weight of H 2 O (solvent) = 1200 g p = 0.01 # 0.821 L atm/K/mol # 300 K
wb = Weight of organic compound = 48 g C = 0.01 mol/L , p = 0.2463 atm
o -1
T b = 100c C , Kb = 0.513c C kg mol 307. 0.70 g of an organic compound when dissolved in 32 g of
acetone produces an elevation of 0.25c C in the boiling
DTb = Kb # 1000 # wb
Mb # Wa point. Calculate the molecular mass of organic compound.
^0.513c C kg mol-1h # 100 # 48 g (Kb for acetone = 1.72 K kg mol-1 )
=
^58 g mol-1h # 1200 g Ans : COMP 2015
= 0.0353c C Given,
As we know that, DTb = 0.25c, or 0.25 K,
o
DTb = Tb - T b Kb = 1.72 kg mol-1
0.0353 = Tb - 100 DTb = Kb # m
Tb = 100 + 0.0353 0.25 = 1.72 # 0.70 1000
molecular weight # 32 g
= 100.0353c C = 373.1853 K
Molecular weight = 150.5 g
CASE BASED QUESTIONS (iii) The solution show positive deviation from
Raoult’s law.
308. Scuba divers when come towards the surface, the (iv) Pº A - Ps = x
B
Pº A
pressure gradually decreases resulting in the release
of dissolved gases leading to formation of bubbles of 310. Binary solutions can be of nine different types
nitrogen gas in the blood which blocks the capillaries depending upon the nature of the solute and solvent
and thus harmful effects are created. To avoid bends whether solid, liquid or gas. They may be further
and toxic effect of high concentration of nitrogen gas, classified as solid, liquid and gaseous solutions based
the air is diluted with helium. After reading the above on the component which acts as the solvent. However,
passage, answer the following questions : the liquid solutions are the most important. Both solids
(i) Which law is associated with this ? and gases dissolve in liquids resulting in homogeneous
(ii) Why is the condition of bends overcome by the mixtures, i.e. solutions. The solubility is governed by
use of Helium ? number of factors such as nature of solute and solvent,
(iii) Give one application of above mentioned law. temperature, pressure etc. The concentrations of the
(iv) Hydrogen is more soluble than helium in water at solutions can be expressed in different ways such as
a particular temperature. Why ? normality, molarity, molality, mole fraction etc. Out
Ans : of these, molality and mole fraction are better as they
do not change with the change in temperature.
(i) Henry’s law.
Based on the above passage, answer the .following
(ii) Because Helium is non-reactive gas.
questions:
(iii) Henry’s law is used to increase the solubility of
(i) Solubility curve of Na 2 SO 4 $ 10H 2 O in water with
CO 2 in soft drink.
temperature is given as:
(iv) Because helium has higher value of Henry’
constant ^K Hh as K H is inversily proportional to
the solubility of gas.
309. Solution which obey’s Raoult’s law at every range of
concentration are called ideal solution which do not
show any deviation while those solution which do
not obey’s Raoult’s law are called non-ideal solution.
Non-ideal solution show two types of deviation from
Raoult’s law called positive and negative deviation.
Azeotropes are the mixture of liquids which boils at
constant temperature like a pure liquid and possess
What do you infer about the temperature
same composition of components in liquid as well as
variation of curve with solubility process?
in vapour phase. Azeotropes arises due to very large
deviation from Rault’s law. (ii) On what factor does the maximum amount of a
solid solute that can be dissolved in a specified
(i) Azeotropic mixture distils without any change in
amount of a given liquid solvent not depend
composition. Why ?
upon?
(ii) Give two examples of non-ideal solution showing
negative deviation. (iii) What is the molality of a sulphuric acid solution
in which mole fraction of water is 0.85?
(iii) Two liquid ‘P’ and ‘Q’ are mixed and the resulting
solution becomes colder. What do you conclude (vi) How much amount of salt is contained in 1000 g
about deviation from Raoult’s law ? of a 4% solution of salt?
(iv) Give mathematical expression of Raoult’s law for Ans :
non-volatile solute in volatile solvent. (i) Solubility process is endothermic till 34°C and is
Ans : exothermic after —34°C.
(i) Azeotropic mixtures are constant boiling (ii) The maximum amount of a solid solute that can
mixture and cannot distils without any Chang in be dissolved in a specified amount of a given
composition. liquid solvent does not depend upon pressure.
(ii) (a) Chloroform and acetone. (iii) If n1 and n2 are the number of moles of water and
(b) Chloroform and benzene. H2SO4 respectively, then
X water = n1 = 0.85 ...(1) (c) Chloroform-Acetone

n1 + n2
Benzene-Toluene
X H SO = n2 = - 1 - 0.85
2 4
n1 + n2 (d) Ps 2 xA P A% + xB P B%
= 0.15 ...(2) Positive deviations
Dividing eq. (2) by eq. (1), Ps 1 xA P A% + xB P B%
n2 = 0.15 Negative deviations.
n1 0.85
1000 312. Elevation in boiling point is the increase in boiling
Now, n1 = = 55.55
18 point when a non volatile solute is added to the
solvent.
Hence, n2 = 0.15 # 55.55 = 9.8 moles
0.85 Addition of the solute lowers the vapour pressure
Hence, molality of solution = 9.8 of solvent, hence more heat is required to increase
(vi) Total weight of solution = 1000 g the vapour pressure upto the atmospheric pressure.
% of solute = 4% The addition of 3 g of a substance to 100 g CCl 4
(M = 154 g mol-1) raises the boiling point of CCl 4 by
Weight of solute (salt) = 4 # 1000 = 40 g 0.60°C. Kb (CCl 4) is 5.03 K kg mol-1 .
100
So, amount of salt = 40 g Given : K f (CCl 4) = 31.8 K kg mol-1 and r (solution)
311. In the 1880s, French chemist François-Marie Raoult = 1.64 g cm-3 .
discovered that when a substance is dissolved in a Answer the following questions :
solution, the vapor pressure of the solution will (a) Determine the relative lowering of vapour pressure
generally decrease. This observation depends on two of the solution.
variables: (b) Determine the molar mass of the substance.
(i) the mole fraction of the amount of dissolved solute (c) What will be the freezing point depression of the
present and solution ?
(ii) the original vapor pressure (pure solvent). (d) Define molal elevation constant for a solvent. Why
At any given temperature for a particular solid or is elevation of boiling point a colligative property
liquid, there is a pressure at which the vapor formed ?
above the substance is in dynamic equilibrium with its Ans :
liquid or solid form. This is the vapor pressure of the
substance at that temperature. At equilibrium, the (a)If M2 is the molar mass of the substance, then
rate at which the solid or liquid evaporates is equal to using the expression
the rate that the gas is condensing back to its original 3
TP = 250
= 0.01814
form. All solids and liquids have a vapor pressure, and Pc 100
+ 250
3
154
this pressure is constant regardless of how much of the
substance is present. (b) From the molality of the solution, we get
m2
# 1000
Answer the following questions : Molality = n2 # 1000 = M2
(a) What is the value of TH mixing and TVmixing for an m1 m1

ideal solution? Now, TTf = K f # m
TTf
(b) Do the intermolecular forces between A and B or m = = 3.793 = 0.12
are weaker or stronger than that between A - A Kf 31.8
and B - B in an non-ideal solution with positive 3
# 1000
M2
deviation ? 0.12 = ;
100
(c) Give an example of non-ideal solution with
M2 = 250
negative deviation. Give an example of ideal
solution. TTf K
(c) = f
TTb Kb
(d) Write the expression for the pressure of non ideal
solution with positive and negative deviations. Kf
TTf TT
Kb # b
Ans :
(a) TH mixing = 0 , TVmixing = 0 = 31.8 # 0.6 = 3.793°C
5.03
(b) Weaker
(d) Molal elevation constant may be defined as the (c) Substituting the value of p solvent
%
in (1) we get,
elevation in boiling point when the molality of (3.4 - 2.8)
the solution is unity (i.e., 1 mole of the solute is = 6
3.4 M2
dissolved in 1 kg (1000 g) of the solvent). The units 0.6
or = 6
of Kb are therefore, degree/molality i.e., K/m or 3.4 M2
°C/m or K kg mol-1 . Elevation of boiling point M2 = 34 g
is a colligative property because it depends on
(d) (i) Nature of liquid (intermolecular force)
number of solute particles present in a solution.
(ii) Temperature.
313. A solution containing 30 g of non-volatile solute
exactly in 90 g of water has a vapour pressure of 2.8 314. Many gases dissolve in water, Oxygen dissolves only
K Pa at 298 k Further 18 g of water is added to to small extent which sustains all aquatic life. NH3
this solution. The new vapour pressure becomes 2.9 and HCl are highly soluble in water. Solubility of
k Pa at 298 K When a non-volatile solute is added gases increases with increase in pressure and decreases
to a solvent, the surface has molecules of solute and with increase in temperature.
solvent both. Thus, the number of molecules of solvent
present in upper surface is less. The number of solvent
molecules escaping from the surface is reduced.
Answer the following questions :
(a) Write down the expression for relative lowering
of vapour pressure with the mole fraction of the
solute.
(b) Calculate the vapour pressure of water at 298 K.
(c) Find out the molecular mass of solute?
(d) Name two factors on which the vapour pressure of
the liquid depends.
Ans :
(a) The relative lowering of vapour pressure is given
by the following expression,
(p solvent
%
- psolution) n2
= Henry’s law states “The partial pressure of the gas in
p s%olvent (n1 + n2)
vapour phase (p) is proportional to the mole fraction
(b) For dilute solutions,
of the gas in the solution. p = KH x .”
n2 11 n1 , Where, KH is Henry’s law constant. If we draw a
Therefore, graph between partial pressure of the gas versus mole
(p solvent
%
- psolution) fraction of gas in solution, then we will get straight
= n2 line as shown in graph.
p solvent
% n1
(W2 # M1) Different gases have different KH values of the same
= temperature. This suggests, KH is a function of nature
(M2 # W1)
(p solvent
%
- 2.8) of gas.
= 6 ...(1)
p solvent
%
M2 Answer the following questions :
Similarly for Second case we get, (a) What is significance of KH ?
(p solvent
%
- 2.9) (30 # 18) (b) What is slope of the line given in graph?
= (c) (i) Why does solubility of gas in liquid decreases
p solvent
%
(M2 # 108)
(p solvent
%
- 2.9) with increase solution in cyclohexane in
= 5 ...(2) temperature?
p solvent
%
M2
On solving eq.(1) and (2), we get (ii) Why are cold drinks filled with CO2 at high
pressure?
(p solvent
%
- 2.8)
=6 (d) (i) What is cause of anoxia at high altitude?
(p solvent - 2.9)
%
5
(ii) Why do scuba divers take air diluted with
p solvent
%
= 3.4 k Pa
helium?
i.e., vapour pressure of water at 298 K is 3.4 kPa
Ans : = 135 mm
(a) Higher the value of KH , lower will be solubility of
p B = pc B x B
gas
(b) Slope of line = KH (Henry’s law constant). = pc B (1 - xA)
(c) (i) KH increases with increase in temperature, = 200 # 0.7
therefore, solubility decreases.
= 140 mm
(ii) It is because solubility of CO2 in cold drink
increases with increase in pressure. pA
yA =
pA + pB
(d) (i) Low concentration of oxygen in blood and
= 135
tissues at higher altitude causes people weak 135 + 140
and unable to think clearly due to anoxia.
(ii) To avoid bends (pains) as well as toxic effect = 135 = 0.49
275
of high concentration of N2 in blood as N2 is
more soluble in blood than Helium. 316. The vapour pressure of solvent is lowered by the
presence of non-volatile solute and this lowering of
315. Observe the table in which azeotropic mixtures are vapour pressure is governed by Raoult’s law, according
given along their boiling points of pure components to which ‘the relative lowering of vapour pressure of
and azeotropes. the solvent over a solution is equal to mole fraction
of solute present in the solution. However in a binary
Some Azeotropic Mixtures
solution if both components are volatile then another
A B Minimum A(in B Mixture form of Raoult’s law is used. The partial vapour
Boiling K) (in K) Azeot-
Azeotropes ropes pressure of each component is directly proportional to
their mole fractions and p total = p 10 x1 + p 20 x2 . Solutions
H2O C2H5OH 95.37% 373 351.3 351.15
H2O C3H7OH 71.69% 373 370.19 350.72 which obey Raoult’s law over the entire range of
CH3COCH3 CS2 67% 329 319.25 312.30 concentration are called ideal solutions. Two types of
H2O HCl 20.3% 373 188 383K deviations from Raoult’s law are observed, positive
and negative by non-ideal solution depending upon
H2O HNO3 68.0% 373 359 393.5K
interaction between the components. Azeotropes are
H2O HClO4 71.6% 373 383 476K
formed due to very large deviations from Raoult’s law.
Answer the following questions : Read the passage and answer the following questions:
(a) Why do ethanol and H2O show positive deviation (a) What type of solution is formed by ethanol and
from Raoult’s law ? water?
(b) Why do H2O and HCI form maximum boiling (b) What type of solution is formed by benzene and
azeotropes? toluene?
(c) (i) What are azeotropes ? (c) The vapour pressure of pure ‘A’ and ‘B’ are 450
(ii) How are azeotropes separated ? mm and 700 mm Hg respectively at 350 K. What
are the mole fraction of ‘A’ and ‘B’ in vapour
(d) If pc A = 450 mm, pc B = 200 mm, what is mole
phase, if total pressure on mixing is 600 mm.
fraction of A in vapour phase if xA = 0.3 in liquid
(d) Calculate the mass of solute (non-volatile) with
phase ?
molar mass 40 g/mol which must be dissolved
Ans :
in 114 g octane to reduce its vapour pressure to
(a) It is because force of attraction between ethanol- 80%.
water are less than ethanol-ethanol and H2O—
Ans :
H2O.
(a) They form non-ideal solution showing positive
(b) It is because force of attraction between H2O and
deviation. They form minimum boiling azeotropes.
HCl are more than HCl—HCl and H2O—H2O.
(b) They will form ideal solution.
(c) (i) Azeotropes are constant boiling mixtures
which distill out unchanged in their composition. (c) pc A xA + pc B (1 - xA) = 600 mn
(ii) They are separated by azeotropic distillation. 450xA + 700 (1 - xA) = 600
(d) p A = pc A x A 450xA - 700xA = 600 - 700 = - 100
= 450 # 0.3 - 250xA = - 100
xA = 0.4 , (c) KH = 4.27 # 105 mm Hg

xB = 0.6 in liquid phase p = 760 mm Hg
pA = pc A xA = 450 # 0.4 According to Henry’s law,
= 180 mm p = KH # xCH 4
pB = pc B xB = 700 # 0.6 p 760

xCH = =
= 420 mm
4
KH 4.27 # 105
pA = 1.78 # 10-3
yA =
pA + pB
(d) According to Henry’s law,
= 180 = 180
180 + 420 600 m = KH # p
pc A - p A 6.56 # 10-2 = KH # 1
(d) = xB
pc A KH = 6.56 # 10-2
WB
100 - 80 = MB For another case,
100 WB
+W A
MB M A
5 # 10-2 = 6.56 # 10-2 # p
WB
20 = 40 -2
100 WB
+ 114 p = 5 # 10 -2 = 0.762 bar
40 114 6.56 # 10
WB = 10 g
318. Assume that only solvent molecules can pass through
317. The solubility of gases increases with increase these semipermeable membranes. If this membrane is
of pressure. William Henry made a systematic placed between the solvent and solution the solvent
investigation of the solubility of a gas in a liquid. molecules will flow through the membrane from pure
According to Henry’s law “the mass of a gas dissolved solvent to the solution. This process of flow of the
per unit volume of the solvent at constant temperature solvent is called osmosis. The flow will continue till the
is directly proportional to the pressure of the gas in equilibrium is attained. The flow of the solvent from
equilibrium with the solution”. its s membrane solution side across a semipermeable
Dalton during the same period also concluded can be stopped if some extra pressure is applied on
independently that the solubility of a gas in a liquid the solution. This pressure that solution. The flow
solution depends upon the partial pressure of the gas. of solvent is called osmotic pressure of the solution.
If we use the mole fraction of gas in the solution as The flow of solvent from concentrated solution across
a measure of its solubility, then Henry’s law can be a semipermeable membrane is due to osmosis. The
modified as “the partial pressure of the gas in the important point to be kept in mind is that solvent
vapour phase is directly proportional to the mole molecules always flow from lower concentration to
fraction of the gas in the solution.” higher concentration of solution. The osmotic pressure
has been found to depend on the concentration of the
Read the above passage and answer the following
solution.
questions:
Answer the following questions ?
(a) What is the relation of KH with temperature ?
(i) What happens when a cell is placed in water
(b) Write expression for Henry’s law.
containing less than 0.9% (mass/volume) salt ?
(c) Calculate solubility of methane in benzene at 298
(ii) What is edema ?
K under 760 mm Hg. (Given Henry’s constant
(iii) Which colligative property is used for
= 4.27 # 105 mm Hg) ?
determination of molecular mass of proteins ?
(d) The partial pressure of ethane over a saturated
Ans :
solution containing 6.56 # 10-2 g of ethane is
1 bar. If the solution contains 5.00 # 10-2 g of (i) Blood cells collapse due to loss of water by
ethane then what will be the partial pressure (in osmosis.
bar) of the gas ? (ii) People taking a lot of salt or salty food experience
Ans : water retention in tissue cells and inter-cellular
spaces because of osmosis. The resulting puffiness
(a) KH , increases with temperature.
or swelling is called edema.
(b) p = KH # x (iii) Osmotic presure.
319. Some liquids on mixing, form azeotropes which are

binary mixtures having the same composition in liquid
and vapour phase and boil at a constant temperature.
In such cases, it is not possible to separate the
components by fractional distillation. There are two
types of azeotropes called minimum boiling azeotrope
and maximum boiling azeotrope. The solutions which
show a large positive deviation from Raoult’s law form
minimum boiling azeotrope at a specific composition.
The solutions that show large negative deviation from
Raoult’s law form maximum boiling azeotrope at a
specific composition.
(i) Give an example of maximum boiling azeotrope ?
(ii) What are the conditions for ideal solutions as per
Raoult’s Law ?
Ans :
(i) Nitric acid and water .
(ii) The enthalpy of mixing components to form the
solution is zero and the volume of mixing is also
zero, i.e.,
D mix H = 0, D mix V = 0
***********
Page 82 Electrochemistry Chap 2
CHAPTER 2
Electrochemistry
SUMMARY At cathode : H+ + e- $ H
H + H $ H2
At anode : Cl- - e- $ Cl
1. ELECTROLYTIC CELL
Cl + Cl $ Cl 2
It is a device in which electricity from outside source
The overall reaction is :
is used to carry out a reaction (electrolysis). The
device or cell used to carry out electrolysis is called 2H+ (aq) + 2Cl- (aq) $ H 2 (g) + Cl 2 (g)
electrolytic cell. The solution becomes basic in nature due to the
formation of NaOH.
2. ELECTROCHEMICAL CELL OR GALVANIC CELL
6. ELECTROLYSIS OF AQUEOUS CuSO 4
It is a device in which indirect redox reaction takes
place and decrease in energy during the reaction It consists of Cu2+ , H+ , SO 2- -
4 and OH ions.
appears in the form of electricity. On passing electricity, following reaction takes place :
3. ELECTROLYSIS OF MOLTEN NACL At cathode : Cu2+ + 2e- $ Cu

At anode : OH- - e- $ OH
In molten state, NaCl consists of Na+ consist Cl-
ions, On passing electricity, following reactions takes 4OH $ 2H 2 O + O 2
place : The overall reaction is :
At cathode : +
Na + e $ Na - 2Cu2+ (aq) + 4OH- (aq) $ 2Cu (s) + 2H 2 O (l) + O 2 (g)
At anode : Cl- - e- $ Cl The solution becomes acidic in nature due to the
formation of H 2 SO 4 .
Cl + Cl $ Cl 2
The over all reaction : 7. ELECTROLYSIS OF CuSO 4 USING Cu ELECTRODES
2Na+ (l) + 2Cl- (l) $ 2Na (s) + Cl 2 (g) It consists of Cu2+ , H+ , SO 2- -
4 and OH ions.
On passing electricity, following reactions takes

4. ELECTROLYSIS OF ACIDIFIED WATER
place :
It consists of H+ , OH- , SO 2-
4 ions. At cathode : Cu2+ + 2e- $ Cu
On passing electricity, following reactions takes place :
At anode : Cu $ Cu2+ + 2e-
+ -
At cathode : H +e $ H
8. FARADAY’S LAW OF ELECTROLYSIS
H + H $ H2
At anode : OH- - e- $ OH (a) The amount of substance deposited at any electrode
during electrolysis is directly proportional to the
4OH $ 2H 2 O + O 2 quantity of electricity passing i.e.,
The overall reaction is : W \Q
4H+ (aq) + 4OH- (aq) $ 2H 2 (g) + 2H 2 O (l) + O 2 (g)
W = zQ
5. ELECTROLYSIS OF CONCENTRATED AQUEOUS NACL or W = zIt
+ + -
It consists of Na , H , Cl and OH ions. -
Where, z = electrochemical equivalent,
On passing electricity, following reactions takes place : W = amount of the substance deposited (g),
Chap 2 Electrochemistry Page 83
I = Strength of current passed (amperes), 14. CELL CONSTANT

t = time (sec). It is defined as the ratio of distance between the
electrodes (l) to the area of the electrodes (a).
When I = 1 ampere, t = 1 sec, then W = z .
Thus, electrochemical equivalent of a substance Cell constant = l
a
may be defined as the mass of the substance -1
Its units are cm
deposited when a current of 1 ampere is passed
for one second. 15. CONDUCTIVITY (k) OR SPECIFIC CONDUCTANCE
(b) When the same quantity of electricity is passed
through solutions of different electrolytes It is reciprocal of resistivity.
connected in series, then the weights of the k (Kappa) = 1
substances deposited at the electrodes are directly r
proportional to their equivalent weights. So, Its units are ohm-1 cm-1 or S m-1 or W-1 m-1 .
wA = Eq.wt. of A
wB Eq. wt. of B 16. EQUIVALENT CONDUCTIVITY (/eq)
9. FARADAY It is defined as the conductance offered by all the

ions formed by dissolving one gram equivalent of the
The charge on one mole of electrons is called 1 electrolyte in solution.
Faraday. Thus,
1 Faraday (1F) = 96500 C Leq = k # 1000
Normality
So, charge on n mole of electrons will be equal to Its units are ohm-1 cm2 (g equiv) -1 or S m2 eq-1
Q =nF
17. MOLAR CONDUCTIVITY (Lm)
10. METALLIC CONDUCTORS It is defined as the conductance offered by all the
Those substance which allow the flow of current by ions formed by dissolving one mole of an electrolyte
movement of electrons are called metallic conductors. in solution.
Example : Cu, Ag, Fe etc. Lm = k # 1000
Molarity
11. ELECTROLYTIC CONDUCTOR Its units are ohm-1 cm2 mol-1 or S m2 mol-1
Those substances which conduct electricity with
18. KOHLRAUSCH’S LAW
the chemical decomposition are called electrolytic
conductors. According to this law, “the molar conductivity of a
Example : HCl, HNO 3 , NaOH etc. weak electrolyte at infinite dilution is the sum of the
ionic conductivities of all the ions at infinite dilution
12. CONDUCTANCE (C) each multiplied with the number of ions present in the
formula unit of the electrolyte.” So,
It is the reciprocal of resistance.
y+ x-
L3
m (Ax By ) = xL m (A ) + yL m (B )
3 3
C = 1
R
19. APPLICATION OF KOHLRAUSCH’S LAW
It units are ohm-1 (W-1) or siemens (S).
1. In the calculation of L3m for weak electrolyte
13. SPECIFIC RESISTANCE OR RESISTIVITY (r) 2. In the calculation of degree of dissociation

c
It is defined as the resistance of a conductor of 1 cm a = L3 m
Lm
length and having area of cross-section equal to 1 cm2 .
3. In the calculation of dissociation constant of weak
r = Ra electrolyte.
l
2
Its units are ohm cm or ohm m. k = Ca
1-a
l = Length of conductor in cm 4. In the calculation of solubility of weak electrolyte.
2
a = Area of cross-section in cm
Solubility = kl1000
Leq
3
20. REPRESENTATION OF ELECTROCHEMICAL CELL 25. APPLICATIONS OF NERNST EQUATION

The following conventions are used to represent the 1. Calculate of E.M.F. of a cell :
electrochemical cell. The Daniel cell is represented as For the cell reaction :
follow: ne-
aA + bB cC + dD
Zn (s) ; Zn2+ (C 1 M) z Cu2+ (C 2 M) ; Cu (s)
Salt
[Oxidised state]
- 2.303 RT log
Anode (Oxidation) Cathode (Reduction)
o
bridge E cell = E cell
nF [Reduced state]
21. STANDARD HYDROGEN ELECTRODE [Oxidised state]
E cell = E cell
o
- 0.0591 log at 298 K
n [Reduced state]
It is reference electrode and used to measure the
[Reduced state]
electrode potential of any metal electrode. It can act or E cell = E cell
o
+ 0.0591 log at 298 K
n [Oxidised state]
both as anode and cathode. Its electrode potential is
assumed to be zero. 2. Calculation of conc. of a solution of half-cell by
measuring E.M.F. of the cell using Nernst equation.
22. ELECTROCHEMICAL SERIES 3. Calculation of equilibrium constant Kc
The arrangement of different metal electrodes in the o
E cell = 2.303 RT log Kc
nF
increasing order of standard reduction potentials is
called electrochemical series. or o
E cell = 0.0591 log Kc
n
o
23. APPLICATIONS OF ELECTROCHEMICAL SERIES (at equilibrium, E cell = 0)
1. To compare the oxidising and reducing powers of 26. COMMERCIAL CELLS
electrodes:
There are two types of commercial cells
Oxidising power \ Reduction potential
1. Primary cells : In these cells, the electrode reactions
Reducing power \ 1
Reduction potential cannot be reversed by external electric source.
Example : Dry cell, mercury cell.
2. To compare the reactivity of a metal :
2. Secondary cells : In these cells, the electrode
Reaction of a metal \ 1 reactions can be reversed by an external source.
Reduction potential Examples : Lead storage battery, nickel cadmium
3. To calculate the standard of E.M.F. of a cell : storage cell.
o o o
E.M.F. of a cell (E cell) = E oxidn + E redn
27. DRY CELL
o o
= E cathode + E anode
This cell is based upon leclanche cell. In this cell
4. To predict the spontaneity of a reaction :
If the E.M.F. of the cell is positive, then the cell Zinc cylinder - acts an anode
reaction is spontaneous or possible. Graphite rod - acts as cathode
NH 4 Cl + ZnCl 2 - acts as electrolyte
24. NERNST EQUATION When the cell is working, the following reactions take
This equation gives a relation between electrode place :
potential and concentration of metal ions. At anode : Zn (s) $ Zn2+ + 2e-
For a general electrode reaction At cathode :
n+ -
M (aq) + ne $ M (s) 2MnO 2 (s) + 2NH 4 + (aq) + 2e- $ Zn2+ (aq) + Mn 2 O 3 (s) + 2NH 3 (g) + H 2 O (l)
The overall cell reaction is :

o
E cell = E cell - 2.303 RT log n+1
nF [M (aq)] Zn (s) + 2NH +4 (aq) + 2MnO 2 (s) $ Zn2+ (aq) + Mn 2 O 3 (s) + 2NH 3 (g) + H 2 O (l)
The NH 3 gas produced reacts with ZnCl 2 to form of

o
E cell = E cell - 0.0591 log n+1 at 298 K
n [M (aq)] complex for avoiding bursting.
2NH 2 + ZnCl 2 $ [Zn (NH 3) 2 Cl 2]
o
E cell = E cell + 0.0591 log 6M n+ (aq)@ at 298 K
n This cell does not work for a long time because acidic
NH 4 Cl corrodes the zinc vessel.
28. MERCURY CELL At anode : Cd (s) + 2OH- (aq) $ Cd (OH) 2 (s) + 2e-
In this cell : At cathode :
Zinc vessel - acts as anode NiO 2 (s) + 2H 2 O (l) + 2e- $ Ni (OH) 2 (s) + 2OH- (aq)
Mercury (II) oxide - acts as cathode The overall cell reaction is :
KOH + ZnO - acts as electrolyte
Cd (s) + NiO 2 (s) + 2H 2 O (l) $ Cd (OH) 2 (s) + Ni (OH) 2 (s)
When the cell is working, the following reactions take
place : So, KOH is used up during its working. At this time
cell needs recharging.
At anode :
During recharging : Electrical energy is supplied
Zn (s) + 2OH- (aq) $ ZnO (s) + H 2 O (l) + 2e-
to the cell from an external source. The following
At anode : reaction takes place during this process and the cell
HgO (s) + H 2 O (l) + 2e- $ Hg (l) + 2OH- becomes ready to work again :
The overall cell reaction is : Cd (OH) 2 (s) + Ni (OH) 2 $ Cd (s) + NiO 2 (s) + 2H 2 O (l)
Zn (s) + HgO (s) $ ZnO (s) + Hg (l) 31. H 2 - O 2 FUEL CELL

In this case, the overall cell reaction does not involve
In fuel cell, the energy produced during the combustion
any ion in solution whose conc. can change due to
of fuels is directly converted into electrical energy.
which this cell can work for a long time.
In this cell, H 2 and O 2 gases are bubbled through
29. LEAD STORAGE BATTERY OR CELL a porous carbon electrode into conc. aqueous KOH
or NaOH. Each electrode is coated with catalyst (Pt,
In this battery or cell :
Ag etc.). During the working of the cell, the following
Pb plates - act as anode reactions take place :
PbO 2 plates - acts as cathode At anode :
Conce. H 2 SO 4 (38%) - acts as electrode 2H 2 (g) + 4OH- (aq) $ 4H 2 O (l) + 4e-
When the batter works, the following reaction take At cathode :
place : (During discharging) O 2 (g) + 2H 2 O (l) + 4e- $ 4OH- (aq)
At anode : Pb (s) + SO 24- (aq) $ PbSO 4 (s) + 2e- The overall cell reaction is :
At cathode : 2H 2 (g) + O 2 (g) $ 2H 2 O (l)
PbO 2 (s) + SO 24- (aq) + 4H+ (aq) + 2e- $ 2PbSO 4 (s) Advantages of fuel cell :
The overall cell reaction is : 1. It is pollution free.
2. Its efficiency is high.
Pb (s) + PbO 2 (s) + 4H+ (aq) + 2SO 24- (aq) $ 2PbSO 4 (
3. It is light in weight.
So, H 2 SO 4 is used up during its working. At this time 4. It can work for a long time by the continuous
battery needs recharging. supply of H 2 and O 2 .
During recharging : Electrical energy is supplied to Disadvantages of fuel cell :
the batter from an external source. The following 1. High cost of catalyst used.
reaction takes place during this process and the
2. Problem to hold gaseous fuel at low temperature
battery becomes ready to work again : or high pressure.
2PbSO 4 (s) + 2H 2 O (l) $ Pb (s) + PbO 2 (s) + 4H+ (aq
32. CORROSION
30. NI-CD STORAGE CELL The process of slow conversion of a metal into
In this cell : unwanted materials by the reaction with moisture and
oxygen present in atmosphere is called corrosion.
Cd rods - acts as anode
Example : Rusting of iron.
NiO 2 rods - acts as cathode
33. ELECTROCHEMICAL THEORY OF RUSTING OF IRON
Dil. KOH - acts as electrolyte
When the cell works, the following reactions take Impure iron surface acts as electrochemical cell in the
place : presence of water called corrosion cell.
In these cell : NaF $ Na+ + F-

Pure iron - acts as anode H 2 O $ H+ + OH-
impure iron - acts as cathode (Fe 2 O 3 .xH 2 O) Reaction at Cathode
Water + moisture - act as electrolyte H+ and Na+ cations move towards the cathode but H+
are deposited. This is due to the fact that hydrogen
The following reactions take place at the surface of
is below sodium in the electrochemical series. So, has
iron :
lower discharge potential.
At anode : Fe $ Fe2+ + 2e-
H+ + e- $ H
At cathode : 2H+ + 1 O 2 + 2e- $ H 2 O H + H $ H 2 ^g h (Hydrogen)
2
The net reaction is : Reaction at Anode
OH- and F- ions migrate towards the anode but only
Fe + 2H+ + 1 O 2 $ Fe2+ + H 2 O OH- ions gets deposited at anode. The reason is same
2
At iron surface : i.e., OH- ions have lower discharge potential.
or
2Fe2+ + 1 O 2 + 2H 2 O $ Fe 2 O 3 + 4H+
2 4OH $ 2H 2 O + O 2 ^g h
Fe 2 O 3 + xH 2 O $ Fe 2 O 3 .x H 2 O Hence, product at cathode is hydrogen an product at
(Rust)
anode is oxygen.
34. PREVENTION OF CORROSION Thus (d) is correct option.
The rusting of iron can be prevented by the following 3. Fused NaCl on electrolysis gives ......... on cathode.
method : (a) chlorine (b) sodium
1. Barrier protection (c) sodium amalgam (d) hydrogen
2. Sacrificial protection
3. Cathodic protection
Fused NaCl contain Na+ and Cl- ions. On electrolysis
4. Using anti-rust solution
Na+ ions move towards negatively charged electrode
and changed as sodium [Na (s)] while Cl- ions move
*********** towards positively charged electrode and libirate
Cl 2 (g). Thus, Reduction success at cathode and
oxidation at anode are as follows:
OBJECTIVE QUESTIONS At Anode : 2Cl- (oxidation) Cl 2 (g) + 2e-
At Cathode : Na + (+ e) - $ Na (s)
1. Which of the following solutions of KCl will have the
highest value of molar conductivity?
(a) 0.01 M (b) 1 M 4.
(c) 0.5 M (d) 0.1 M

Ans : OD 2023
Molar conductivity increases with dilution. It means

lesser the concentration larger will be molar conductivity.
Thus (a) is correct option. Ec = 1.30 V
At pH = 2, Electrode potential is –
2. A dilute aqueous solution of sodium fluoride is
electrolysed; the products at the anode and cathode (a) 1.36 V (b) 1.30 V
are – (c) 1.42 V (d) 1.20 V
(a) F2 ,Na (b) F2 ,H 2 Ans : DELHI 2018
E = Ec - 0.059 log 6H+@2

(c) O 2 ,Na (d) O 2 ,H 2
2
Ans : SQP 2018
When a dilute aqueous solution of sodium fluoride is = 1.30 - .059 log ^10-2h2
0
2
electrolysed, the reaction is
= 1.30 + 0.236 8. If 96500 coulomb of electricity is passed through

2 CuSO 4 solution, it will liberate
= 1.418 V (a) 63.5 g Cu (b) 31.76 g Cu
. 1.42 V (c) 96500 g Cu (d) 100 g Cu
5. Faraday’s law of electrolysis is related to : Ans : DELHI 2017
(a) Atomic number of cation Molar mass of copper = 63.5

(b) Speed of cation As Copper (Cu) contain (+) 2 charge in CuSO 4, it
requires 2F (= 2 # 96500 C) charge to give one mole
(c) Speed of anion
i.e. 63.5 g of copper. Thus on giving 96500 C of
(d) Equivalent weight of element electricity, we get 632.5 = 31.76 g of copper.
Ans : FOREIGN 2016
According to Faraday’s law,
Mass of any element, w , \ Charge Q .
DIRECTION : For the following Question Nos. 9 to 11 a
i.e., for 1 mol of charge, if given to any element, 1 paragraph is given. Read carefully the passage and select the
equivalent weight of that substance is obtained. correct answer out of given four options.
Hence, Faraday’s law of electrolysis is related with the
equivalent weight of electrolytes. Fuel cell is an electrochemical cell which converts
chemical energy into electrical energy. The most
successful fuel cell is H 2 - O 2 fuel cell, which is known
6. Equivalent conductance of saturated BaSO 4 is as Bacon cell. It has been used to fulfil the electric
400 ohm-1 cm2 eq-1 and specific conductance is power required in Apollo mission. This fuel cell is
8 # 10-5 ohm-1 cm2 eq-1 . The Ksp of BaSO 4 is – pollution free.
(a) 4 # 10-8 M2 (b) 10-8 M2 9. The cell used in Apollo mission was
(c) 2 # 10-4 M2 (d) 10-4 M2 (a) Leclanche cell (b) Daniell cell
Ans : OD 2007
(c) Voltaic cell (d) Bacon cell
1000 # sp.conductance Ans : FOREIGN 2010
l 0 ^BaSO 4h =
conc. ^Normalityh The Bacon-fuel-cell is used in Apollo mission. It is a
-5 kind of H 2 - O 2 fuel cell.
Normality = 1000 # 8 # 10
400 Hence, (d) is the correct option.
Normality
Hence, Molarity = = 10-4 M 10. The fuel used in the cell used in Apollo mission was
2
(a) H 2 (b) H 2 - O 2
= Solubility
(c) CH 4 (d) O 2
Hence, Ksp = S 2 = 10-8 M2
Ans : OD 2009
Note: In Ksp , S is solubility in molL-1 (molarity)
Fuel cell made of H 2 - O 2 is used in Apollo-mission.
It is pollution free and has highest efficiency (about
7. When one Faraday of electric current is passed, the 70%). It is also less in weight.
mass deposited, equal to Thus (b) is correct option.
(a) One gram equivalent
11. Fuel cells are preferred to other energy producing
(b) One gram mole
devices in space because of
(c) Electrochemical equivalent
(a) high efficiency (b) pollution free
(d) Half gram equivalent
(c) less weight (d) all of these
The mass deposited is equal to one gram equivalent. Ans : SQP 2007
Because “Faraday” is not a measure of current. The Fuel cell is preferred over others cell due to:
ampere is the measure of current. The mass of metal 1. They are pollution free.
transferred in plating depends on the metal and the 2. They have high efficiency.
process. 3. They are of less mass.
12. The standard electrode potentials for the half cell (c) Statement I is true, but Statement II is false.
reactions are : (d) Statement I is false, but Statement II is true.
Zn $ Zn2+ + 2e ; E0 = + 0.76 V Ans : OD 2015, 2 SQP 012
2+
Fe $ Fe + 2e ; E = + 0.41V 0 The number of ions per unit volume carrying the
current decreases on dilation, so conductivity (i.e.,
The e.m.f. of the cell reaction Fe2+ + Zn $ Zn2+ + Fe specific conductance) always decrease with decreases
(a) - 0.35 V (b) + 0.35 V in concentration at infinite dilution, solutions of acetic
(c) - 1.17 V (d) + 1.17 V acid, hydrochloric acid and NaOH etc. all dissociate
Ans : COMP 2006
to ions which can move faster in water.
Given, Thus (b) is correct option.
According to values 16. Faraday’s second law at electrolysis is related to
E 0
= 0.76 V [act as anode i.e., (A)] (a) atomic number of the cation
Zn+2 /Zn
(b) equivalent weight of the electrolyte
E fe0 +2
/fe = 0.41 V [act as cathode i.e., (C)]
(c) atomic number of nation
In the given reaction Zn is oxidised to Zn2+ and Fe2+
is reduced to Fe. Hence (d) speed of nation
Since, E êmf h = E ]0Cg - E ]0Ag Ans : SQP 2009, DELHI 2007
Faradays second law state that, when some quantity

= - 0.41 - ^- 0.76h = + 0.35 V of charge is passed through different electrolytes, then
Thus (b) is correct option. the masses of different substances deposited at the
13. Electric conductance is the direct measure of , respective electrons are in the ratio of their equivalent
masses.
(a) resistance (b) current
(c) concentration (d) None
17. In electrolytic cell, cathode acts as an/a
Ans : DELHI 2013
(a) oxidising agent (b) reducing agent
We know that electric conductance is inversely
proportional to resistance. (c) either of the two (d) neither (a) nor (b)
Ans :
Electric conductance \ 1
COMP 2005
R In an electrolytic cell reducing occurs at cathode.
Thus (a) is correct option. Thus (b) is correct option.
14. Which of the following is a secondary cell?
(a) Leclanche cell (b) Lead storage battery 18. The cell reaction Cu + 2Ag+ " Cu+2 + Ag is best
represented by
(c) Concentration cell (d) all of these
(a) Cu (s) Cu+2 (aq) Ag+ (aq) Ag (s)
Ans : FOREIGN 2010
(b) Pt Cu+2 Ag+ (aq) Ag (s)
As recharging of a discharged lead storage cell/battery
is possible, it is a secondary cell. In the discharged (c) Cu+2 Cu Pt Ag
state, the lead (Pb) of the anode and lead dioxide (d) None to cathode through internal supply
(PbO 2) of the cathode are completely converted to
Ans : DELHI 2011
lead sulphate (PbSO 4). A discharged lead storage cell
however can be recharged by passing a direct current
through the storage cell. 19. In the electrolytic cell, flow of electrons is from
Thus (b) is correct option. (a) Cathode to anode in solution
15. Statement I : The specific conductance of an electrolyte (b) Cathode to anode through external supply
decreases dilution. (c) Cathode to anode through internal supply
Statement II : Ions move faster in dilute solution. (d) Anode to cathode through internal supply
(a) Both the statements are true and Statement II is
Ans : OD 2011
the correct explanation of Statement I.
In an electrolytic cell, electrons do not flow themselves.
(b) Both the statements are true, but Statement II is
It is the migration of ions toward oppositely charged
not the correct explanation of Statement I.
electrodes that indirectly constitutes the flow of electrons 23. Equivalent conductances of NaCl, HCl and
from cathode to anode through internal supply. CH 3 COONa at infinite dilution are 126.45, 426.16
Thus (c) is correct option. and 91 ohm-1 cm2 respectively. The equivalent
conductance of CH 3 COOH at infinite dilution would
20. For the galvanic cell
be
Zn Zn2+ (0.1M) Cu2+ (1.0M) Cu the cell potential (a) 101.38 ohm-1 cm2 (b) 253.62 ohm-1 cm2
increase if:
(a) [Zn2+] is increased (c) 390.71 ohm-1 cm2 (d) 678.90 ohm-1 cm2
(b) [Cu2+] is increased Ans : OD 2009
By Kohlraush’s law,
(c) [Cu2+] is decreased
/°eq NaCl = 126.45
(d) surface area of anode is increased
l 0Na + l Cl
+
0
= 126.45
- ...(i)
Ans : FOREIGN 2002
0 0
For the given cell l H+ +l Cl- = 426.16 ...(ii)
[Zn+ (aq)] 0
l CH 0
OO + l Na = 91 ...(iii)
E cell = Eccell - 0.059V log
- +
3
2 [Cu+ (aq)] on adding (ii) and (iii) then subtract (i) from it
The cell potential will decreases with increase with 0
l CH 0
OO + l Na = 517.16 - 126.45
3
- +
increase in [Zn+2 (aq)] and will increases with increase

in [Cu2+ (aq)] i.e. (c) / 0
(CH 3 COOH) = 390.71 ohm-1 cm2
Thus (b) is correct option. Thus (c) is correct option.
21. In a hydrogen-oxygen fuel cell, combustion of hydrogen 24. Which of the following is non-electrolyte?
occurs to (a) NaCl (b) CaCl 2
(a) produce high purity water
(c) C 12 H 22 O 11 (d) CH 3 COOH
(b) create potential difference between two electrodes
Ans : SQP 2015
(c) generate heat The compounds which when dissolved in water, do not
(d) remove absorbed oxygen from electrode surfaces produce ions, are called as non-electrolytes. Therefore,
Ans : COMP 2008, OD 2005
C 12 H 22 O 11 is non-electrolyte because it does not give
ions with water.
In H 2 - O 2 fuel cell, the combustion of H 2 occurs to
create potential difference between the two electrodes. Thus (c) is correct option.
Thus (b) is correct option. 25. Which of the following is the use of electrolysis?
22. The e.m.f. of a Daniell cell at 298 K is E 1 . (a) Electrorefining (b) Electroplating
ZnSO 4 CuSO 4 (c) Both (a) and (b) (d) None of these
Zn Cu
(0.01M) (1.0M) Ans : COMP 2013
When the concentration of ZnSO 4 is 1.0 M and that Electrorefining and electroplating are done by
of CuSO 4 is 0.01 M, the e.m.f. changed to E 2 . When electrolysis.
is the relationship between E1 and E ? Thus (c) is correct option.
(a) E 2 = 0 ! E 1 (b) E 1 > E 2 26. Several blocks of magnesium are fixed to the bottom
(c) E 1 < E 2 (d) E 1 = E 2 of a ship to
Ans : OD 2011 (a) make the ship lighter
Cell reaction is, (b) prevent action of water and salt
2+ 2+
Zn + Cu " Zn + Cu (c) prevent puncturing by under-sea rocks
[Zn ] 2+
(d) keep away the sharks
E cell = Eccell - RT ln
nF [Cu2+] Ans : DELHI 2008
Greater the factor 9 C , less is the EMF

(Zn2+)
(Cu2+)
Magnesium provides cathodic protection and prevent
rusting or corrosion.
Hence, E1 > E 2
27. The conductivity of strong electrolyte is Ans : COMP 2007
(a) Increase on dilution electrolyte is Higher the reduction potential, stronger is the
oxidizing agent.
(b) Decrease on dilution
(c) Does not change with dilution
31. Which of the following is an insulator?
(d) Depends upon density of electrolytes itself (a) Graphite (b) Aluminium
Ans : FOREIGN 2005
(c) Diamond (d) Silicon
We know that according to Debye Huckel rule, on
Ans : DELHI 2012
dilution the ionisation of strong acid increases due to
increasing volume. Since ionic mobility also increases. Diamond is an insulator.
Therefore the conductivity of strong electrolyte Thus (c) is correct option.
increases on dilution slightly. 32. The most durable metal plating on iron to protect
Thus (a) is correct option. against corrosion is
28. The unit of equivalent conductivity is (a) nickel plating (b) copper plating
(a) S cm-2 (c) tin plating (d) zinc plating
2
(b) ohm cm (g-equivalent) Ans : FOREIGN 2015, 2013
(c) ohm cm This is because zinc has higher oxidation potential than
Ni, Cu and Sn. The process of coating of iron surface
(d) ohm-1 cm2 ^g - equivalenth-1
with zinc is known as galvanization. Galvanized iron
Ans : SQP 2002 sheets maintain their lustre due to the formation of
The equivalent conductivity of a solution, protective layer of basic zinc carbonate.
/eq = 1000 # k Thus (d) is correct option.
C
33. Which organic compound is an electrolyte?
where, k = specific conductance
(a) CH 3 OH (b) CH 3-O-CH 3
= Unit ohm-1 cm-1
(c) C 6 H 12 O 6 (d) CH 3 COONa
eq
C = normality of the solution unit gm cm 3 Ans : OD 2000
Sodium acetate ionises in aqueous solution hence

Hence, the unit of / eq is Ohm-1 cm2 (gm equivalent) -1
(CH 3 COONa) it is an electrolyte.
29. The standard electrode potentials of four elements A,
B, C and D are –3.05, –1.66, –0.40 and +0.80. The 34. The most convenient method to protect the bottom of
highest chemical reactivity will be exhibited by: ship made of iron is
(a) A (b) B (a) Coating it with red lead oxide
(c) C (d) D (b) White tin plating
Ans : OD 2010
(c) Connecting it with Mg Block
Standard electrode potential i.e. reduction potential (d) Connecting it with Pb block
of A is minimum (–3.05 V) i.e. its oxidation potential Ans : SQP 2005
is maximum which implies ‘A’ is maximum reactive For bottom of ship to be protected it is connected
chemically. with more reactive metal than iron like magnesium.
Thus (a) is correct option. This technique is called cathodic protection.
30. The standard reduction potential at 25cC of Li+ /Li Thus (c) is correct option.
, Ba2+ /Ba , Na+ /Na and Mg2+ /Mg are –3.03, –2.73, 35. Which reaction is not feasible?
–2.71 and –2.37 volt respectively. Which one of the (a) 2KI + Br2 " 2KBr + I 2
following is the strongest oxidising agent?
(b) 2KBr + I 2 " 2KI + Br2
(a) Na+ (b) Li+
(c) 2KBr + CI 2 " 2KCI + Br2
(c) Ba2+ (d) Mg2+
(d) 2H 2 O + 2F2 " 4HF + O 2
reaction is not possible because Br ion is not oxidised At anode:

to Br2 with I 2 due to higher electrode (oxidation)
2OH- H2O + 1 O2
potential of I 2 than bromine. 2
36. An increase in equivalent conductance of a strong 40. The standard hydrogen electrode potential is zero,
electrolyte with dilution is mainly due to because
(a) increase in ionic mobility of ions (a) Hydrogen oxidized easily
(b) 100% ionisation of electrolyte at normal dilution (b) Electrode potential is considered as zero
(c) increase in both i.e. number of ions and ionic (c) Hydrogen atom has only one electron
mobility of ions (d) Hydrogen is a very light element
(d) increase in number of ions Ans : COMP 2009
Ans : DELHI 2011 Electrode potential is considered as zero.
Dilution of strong electrolytes increase ionisation, Thus (b) is correct option.
hence ionic mobility of ions which in turn increases
41. H 2 cannot be displaced by
equivalent conductance of the solution.
(a) Li+ (b) Sr2+
37. Standard electrode potential for Sn couple is +0.15V
4+
2+
(c) Al3+ (d) Ag+
Sn3+
and that for the CrCr couple is 0.74 V. These two Ans : OD 2006
couples in their standard state are connected to make Ag+ comes after H+ in the electrochemical series,
a cell. The cell potential will be hence it can’t displace H 2 .
(a) +1.19 V (b) +0.89 V Thus (d) is correct option.
(c) +0.18 V (d) +1.83 V 42. The aqueous solution of which of the following
Ans : FOREIGN 2001 decomposes on passing electric current
Given, (a) Cane sugar (b) Urea
E Sn +4
/Sn+2 = + 0.15 V (c) Methanol (d) Potassium iodide
E Cr +3
/Cr = - 0.74 V Ans : DELHI 2016
E°cell = E°cathode - E°anode Thus (d) is correct option.
= 0.15 - (- 0.74) 43. On passing C ampere of electricity through a

electrolyte solution for t second, m gram metal
= + 0.89 V deposits on cathode. The equivalent weight E of the
Thus (b) is correct option. metal is
38. Standard electrode potential of three metals X , Y (a) E = C # t (b) E = C # m
m # 96500 t # 96500
and Z are 1.2 V, +0.5 V and 3.0 V, respectively. The
(c) E = 96500 # m (d) E = # t # 96500
C
reducing power of these metals will be: C#t m
(a) Y > Z > X (b) X < Y < Z Ans : FOREIGN 2010
(c) Z > X > Y (d) X > Y > Z Thus (c) is correct option.
Ans : OD 2008 44. The best way to prevent rusting of iron is
As the value of standard reduction potential decreases (a) Making it cathode
the reducing power increases i.e.,
(b) putting in saline water
Z > X > Y
(- 3.0) (- 1.2) (+ 0.5) (c) both of these
Thus (c) is correct option. (d) none of these
39. On electrolysis of dilute sulphuric acid using platinum Ans : OD 2014, 2011
electrodes, the product obtained at the anode will be Cathodic protection is best method to prevent iron
(a) hydrogen (b) oxygen from rusting. In this method iron is made cathode by
(c) hydrogen sulphide (d) sulphur dioxide application of external current.
Saline water is highly conducting and hence accelerates Ans : DELHI 2008
the formation of rust. Given for the reaction

Thus (a) is correct option. Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq),
45. Two electrolytic cells, one containing acidified ferrous E° = + 1.10 V
chloride and another acidified ferric chloride, are At equilibrium,
connected in series. The ratio of iron deposited at
cathodes in the two cells will be Hence, E°cell = 0.0591 log 10 K eq
n
(a) 3 : 1 (b) 2 : 1 Here (n " number of exchange of electrons)
(c) 1 : 1 (d) 3 : 2 or 1.10 = 0.0591 log 10 K eq
2
Ans : SQP 2016
2.20 = log k = 37.22
At cathodes: 0.059 10 eq
Fe+ 2e- $ Fe ; or, K eq = 1.66 # 1037

Fe3+ + 3e- $ Fe Thus (d) is correct option.
The standard e.m.f. of a galvanic cell involving cell
(E Fe) 1 = At.wt. ;
48.
2 reaction with n = 2 is found to be 0.295 V at 25°C.
The equilibrium constant of the reaction would be
(E Fe) 2 = .wt.
At
3 (Given F = 96500 C mol-1 ; R = 8.314JK-1 mol-1 )
(E Fe) 1
Hence, =3 (a) 2.0 # 1011 (b) 4.0 # 1012
(E Fe) 2 2
(c) 1.0 # 102 (d) 1.0 # 1010
Ans : FOREIGN 2001
46. An electrochemical cell is set up as:
E° = 0.0591 log 10 K
Pt : H 2 (1 atm) HCl (0.1 M) CH 3 COOH (0.1 M) H 2 (1 atm) n
Pt : The e.m.f. of this cell will not be zero, because Here, n = 2,
(a) the temperature is constant E° = 0.295
(b) e.m.f. depends on molarities of acid used
Hence, log 10 K = 2 # 0.295 = 10
0.0591
(c) acids used in two compartments are different
K = 1010
(d) pH of 0.1 M CHl and 0.1 M CH 3 COOH is not
same Thus (d) is correct option.
Ans : COMP 2011 49. Standard potentials (E °) for some half-reactions are
For a concentration cell having different concentrations given below:
of ions. 1. Sn 4+ + 2e " Sn2+; E° = + 0.15 V
E = 0.0591 log c 1 2. 2Hg2+ + 2e " Hg 22+; E° = + 0.92 V

n c2
3. PbO 2 + 4H+ + 2e " Pb2 + 2H 2 O;
If all the concentrations are identical then obviously
the cell voltage is zero. But as the pH of 0.1 M HCl E° = + 1.45 V
(strong acid) & pH of 0.1M CH 3 COOH is (weak acid) Based on the above, which one of the following
not same, therefore the cell voltage is not zero. statements is correct?
Thus (d) is correct option. (a) Sn 4+ is a stronger oxidizing agent than Pb 4+ .
(b) Sn2+ is a stronger reducing agent than Hg 22+ .
47. E ° for the cell, Zn Zn2+ (aq) Cu2 + (aq) Cu is
1.10V at 25c C . The equilibrium constant for the cell (c) Hg2+ is a stronger oxidizing agent than Pb 4+ .
reaction. (d) Pb2+ is a stronger reducing agent than Sn2+ .
2+ 2+
Zn + Cu (aq) Cu + Zn (aq), is of the order of Ans : SQP 2012
(a) 10 -18
(b) 10 -37 In electrochemical series, Sn is above hydrogen and Hg
below hydrogen. Elements above hydrogen are reducing
(c) 1018 (d) 1037 in nature while below hydrogen are oxidising in nature.
50. The standard potential of the half cells are given 52. In the Silver plating of copper, K [Ag (CN) 2] is used
below instead of AgNO 3 . The reason is
Zn2+ + 2e- Zn; E = - 7.62V (a) A thin layer of Ag is formed on Cu
(b) More voltage is required
Fe2+ + 2e- Fe; E = - 7.81V
(c) Ag+ ions are completely removed from solution
2+ 2
The emf of the cell, Fe + Zn Zn + Fe is (d) Less availability of Ag+ ions, as Cu cannot displace
(a) 1.54 V (b) –1.54 V Ag from [Ag (CN) 2] - ion
(c) –0.19 V (d) +0.19 V Ans : DELHI 2011
Ans : OD 2015 In the silver plating of copper,

In the below reaction K [Ag (CN) 2] is used instead of AgNO 3 . Copper being
Zn+2 + 2e- $ Zn; more electropositive readily precipitate silver from
their salt solution
E 1 = - 7.62 V ...(i)
Cu + 2AgNO 3 $ Cu (NO 3) 2 + Ag
+2 -
Fe + 2e $ Fe;
Whereas in K [Ag (CN) 2] solution a complex anion
E 2 = - 7.81 V ...(ii) [Ag (CN) 2] - is formed and hence Ag+ are less available
On subtracting the equation (i) and (ii), in the solution and therefore copper cannot displace
Ag from its complex ion.
Fe++ + Zn $ Fe + Zn++
E = E 2 - E1
53. On heating one end of a piece of a metal and the other
= - 7.81 - (- 7.62) end becomes hot because of
E = - 0.19V (a) resistance of the metal.
Thus (c) is correct option. (b) mobility of atoms in the metal.
51. Aluminium displaces hydrogen from acids but copper (c) energized electrons moving to the other end.
Cu
does not. A galvanic cell prepared by combining Cu 2+ (d) minor perturbation in the energy of atoms.
and AlAl has an e.m.f of 2.0 V at 298°K . If the potential
3+
Ans : FOREIGN 2006
of copper electrode is +0.34 V, that of aluminium is
When one end of a metal is heated, the free electrons
(a) +1.66 (b) –1.66 are energized and move to the other end. It heats up
(c) +2.34 (d) –2.3 V the other end of the metal.
Ans : COMP 2017, SQP 2015 Thus (c) is correct option.
The given statement explains that Al is placed above 54. A hypothetical electrochemical cell is shown below
Cu in E.C.S. Hence it can reduce Cu from its salt +
6
solution (reduction). Thus Al acts as a reducing agent A A+ (xM) B+ (yM) B
now, The emf measured is +0.20 V. The cell reaction is
Given: electrode potential of copper (a) A+ + e- " A; B+ + e- " B
(E°cell) = + 0.34 V (b) The cell reaction cannot be predicated
e.m.f of cell = 2 V (c) A + B+ " A+ + B
We know that, (d) A+ + B " A + B+
emf of a galvanic cell (E°cell)
Ans : OD 2004
= Electrode potential of Cu (cathode) The cell reaction is as follow
– electrode potential of Al (anode)
2.0 = 0.34 - E°Al
E°Al = 0.34 - 2.00
= - 1.66 V
55. If 0.5 amp current is passed through acidified silver electrolyte depending on the nature of the other
nitrate solution for 100 minutes. The mass of silver ion of the electrolyte.
deposited on cathode is ( eq.wt. of silver nitrate=108) (c) infinite dilution, each ion makes definite
(a) 2.3523 g (b) 3.3575 g contribution to conductance of an electrolyte
(c) 5.3578 g (d) 6.3575 g whatever be the nature of the other ion of the
electrolyte.
Ans : SQP 2016
Given, (d) infinite dilution, each ion makes definite

contribution to equivalent conductance of an
Current, i = 0.5 amp ;
electrolyte, whatever be the nature of the other
Time, t = 100 minutes # 60 ion of the electrolyte.
= 6000 sec Ans : DELHI 2000
Equivalent weight of silver nitrate Kohlrausch’s Law states that at infinite dilution,
each ion migrates independently of its co-ion and
E = 108
contributes to the total equivalent conductance of an
According to Faraday’s first law of electrolysis electrolyte a definite share which depends only on its
W = Eit own nature.
96500 Thus (d) is correct option.
= 108 # 0.5 # 6000 58. What is the E° cell for the reaction
96500
= 3.3575 g Cu2+ (aq) + sn2+ (aq) Cu (s) + Sn 4+ (aq)
Thus (b) is correct option. at 25°C if the equilibrium constant for the reaction
is 1 # 106 ?
56. For the cell reaction.
(a) 0.5328 V (b) 0.3552 V
Cu2+ (C 1, aq) + Zn (s) " Zn2+ (C 2, aq) + Cu (s) of an
electrochemical cell, the change in free energy, TG at (c) 0.1773 V (d) 0.7104 V
a given temperature is a function of Ans : FOREIGN 2009 , OD 2007
(a) ln (C 1) (b) ln c C 2 m E°cell = 2.303RT log K eq

C1 nF
(c) l n (C 2) (d) l n (C 1 + C 2) . 0591
= log K eq
Ans : COMP 2010 n
TG = nE°F = .0591 log 106
2
For concentration cell,
= .0591 # 3 = 0.1773
E = RT ln C 2 Thus (c) is correct option.
nF C 1
In the above equation R,T, n and F are constant 59. If 0.01 M solution of an electrolyte has a resistance of
40 ohms in a cell having a cell constant of 0.4 cm-1 ,
So, E is based upon ln C 2
C1 then its molar conductance in ohm-1 cm2 mol-1 is
Now, TG = - nEF (a) 102 (b) 10 4
= - nF # RT ln C 2 (c) 10 (d) 103
nF C 1
Ans : OD 2003
= - RT ln C 2 Given,
C1
Thus (b) is correct option. Molarity = 0.01 M
57. Kohlrausch’s law states that at: Resistance = 40 ohm
(a) finite dilution, each ion makes definite contribution Cell constant, l = 0.4 cm-1
to equivalent conductance of an electrolyte, A
whatever be the nature of the other ion of the Cell conductivity, (k) = Cell constant
Resistance
electrolyte.
(b) infinite dilution each ion makes definite = 4
0 .
40
contribution to equivalent conductance of an = 0.01 ohm-1 cm-1
Molar conductance (/m) = 1000k 63. Cu+ (aq) is unstable in solution and undergoes
Molarity simultaneous oxidation and reduction according to
= 1000 # .01 the reaction:
.01
= 103 ohm-1 cm2 mol-1 2Cu+ (aq) Cu2+ (aq) + Cu (s)
Thus (d) is correct option. Choose correct E ° for above reaction if E°Cu 2+
/Cu
= 0.34 V and E°Cu /Cu = 0.15 V
2+ +
60. Without losing its concentration ZnCl2 solution cannot

be kept in contact with (a) –0.38 V (b) +0.49 V
(a) Au (b) Al (c) +0.38 V (d) –0.19 V
(c) Pb (d) Ag Ans : FOREIGN 2006
+ +2
Ans : SQP 2008 2Cu $ Cu + Cu
Without losing its concentration ZnCl 2 solution can 2e + Cu+2 $ Cu ;
-
not kept in contact with Al because Al is more reactive E°1 = 0.34 V ; ...(i)
than Zn due to electrode (reduction) potential. - +2 +
e + Cu $ Cu ;
E°2 = 0.15 V ; ...(ii)
61. Specific conductance of a 0.1 N KCl solution at 23°C
is 0.012 ohm-1 cm-1 . Resistance of cell containing the Cu+ + e- $ Cu;
solution at same temperature was found to be 55 ohm. E°3 = ? ...(iii)
The cell constant is
Now, TG°1 = - nFE°1 = - 2 # 0.34F
(a) 0.918 cm-1 (b) 0.66 cm-1
TG°2 = - 1 # 0.15F,
(c) 1.142 cm-1 (d) 1.12 cm-1
Ans : COMP 2003
TG°3 = - 1 # E°3 F
Given, Again, TG°1 = TG°2 + TG°3
specific conductance of the solution, - 0.68F = - 0.15F - E°3 F
k = 0.012 ohm-1 cm-1 . and
E° 3 = 0.68 - 0.15 = 0.53 V
resistance R = 55 ohm. + +2
E°cell = E°cathode c Cu
Cu
m - E°anode d Cu + n
We know that, Cu
cell constant = specific conductance # observed = 0.53 - 0.15 = 0.38 V
resistance Thus (c) is correct option.
+2
= 0.012 # 55 = 0.66 cm -1 64. Standard electrode potentials are : FeFe Ec = - 0.44 ;

Ec = + 0.77 ; If Fe+2, Fe+3 and Fe blocks are kept
+3
Fe
Thus (b) is correct option. Fe+2
together, then
62. The ionic conductance of Ba2+ and Cl- are (a) Fe+2 increase
respectively 127 and 76 ohm-1 cm2 at infinite dilution.
The equivalent conductance (in ohm-1 cm2 ) of BaCl 2 (b) Fe+3 decreases
+2
at infinite dilution will be (c) Fe+3 remains unchanged
(a) 139.5 (b) 203 Fe
(c) 279 (d) 101.5 (d) Fe+2 decreases
Ans : DELHI 2012 Ans : OD 2001
+2
The equivalent conductance of BaCl 2 at infinite Fe E° = - 0.44
dilution. Fe
Fe+3
/3 of BaCl 2 = 1 l 3 of Ba++ + l 3 of Cl- E° = 0.77
2 Fe+2
127 The metal having higher negative electrode potential
= + 76
2 can displaced metals having lower values of negative
= 139.5 ohm-1 cm2 electrode potential from their salt solutions.
65. In electrolysis of NaCl when Pt electrode is taken then Ans : DELHI 2005
H 2 is liberated at cathode while with Hg cathode it TG = - nEF

forms sodium amalgam. This is because For 1 mol of Al, n =3
(a) Hg is more inert than Pt. 4
Hence, for 3 mol of Al,
(b) More voltage is required to reduce H+ at Hg than
at Pt. n = 3# 4 = 4
3
(c) Na is dissolved in Hg while it does not dissolve in According to question,
Pt.
827 # 1000 = 4 # E # 96500
(d) Conc. of H+ ions is larger when Pt electrode is
taken. E = 827 # 1000 = 2.14 V
4 # 96500
Ans : SQP 2009 Thus (b) is correct option.
In electrolysis of NaCl when Pt electrode is taken 68. 4.5 g of aluminium (at. mass 27 amu) is deposited at
then H 2 liberated at cathode while with Hg cathode cathode from Al3+ solution by a certain quantity of
it forms sodium amalgam because more voltage is electric charge. The volume of hydrogen produced at
required to reduce H + at Hg that Pt. STP from H+ ions in solution by the same quantity of
Thus (b) is correct option. electric charge will be
66. On passing a current of 1.0 ampere for 16 min and 5 (a) 44.8 L (b) 22.4 L
sec through one litre solution of CuCl 2 , all copper of (c) 11.2 L (d) 5.6 L
the solution was deposited at cathode. The strength
Ans : FOREIGN 2008
of CuCl 2 solution was (Molar mass of Cu = 63.5 ;
No. of gram equivalent of
Faraday constant = 96, 500 Cmol-1 )
(a) 0.01 N (b) 0.01 M H+ = No. of gm eq. of
(c) 0.02 M (d) 0.2 M Al3+ = 4.5 = 0.5
9
Ans : COMP 2000 3+ 27
Eq wt. of Al = =9
By Faraday’s I st Law, 3
W = q Number of gm eq. of H+ = No. of mole of H+
E 96500 Mass of H+ = 0.5 # 1g = 0.5 g
(where q = it = charge of ion)
We know that, 2g H 2 at STP = 22.4 L
We know that,
Hence, 0.5 gH 2 at STP = 22.4 # 0.5 = 5.6 L
No of equivalent = W = it 2
E 96500 Thus (d) is correct option.
= 1 # 965 69. If E° Fe /Fe = - 0.441 V and E° Fe /Fe = + 771 V the
2+ 3+ 2+
96500
standard EMF of the reaction Fe + 2Fe3+ " 3Fe2+
= 1 will be
100
(a) 1.653 V (b) 1.212 V
(where i = A , t = 16 # 60 + 5 = 965 sec .)
Since, we know that (c) 0.111 V (d) 0.330 V
no. of equivalent Ans : OD 2002
Normality =
Volume (in litre)
1
= 100
1
67. On the basis of the information available from the E°cell = E°cathode - E°Anode
reaction 43 Al + O 2 $ 23 Al 2 O 3, TG = - 827kJ mol-1 = .771 - (- .441)
of O 2 the minimum e.m.f required to carry out an
electrolysis of Al 2 O 3 is (F = 96500 C mol-1 ) = .771 + .441
(a) 8.56 V (b) 2.14 V = 1.212 V
(c) 4.28 V (d) 6.42 V Thus (b) is correct option.
70. The equilibrium constant of the reaction (a) 8.1 # 10 4 g (b) 2.4 # 105 g
Cu (s) + 2Ag+ (aq) Cu2+ (aq) + 2Ag (s); E° = 0.46 V
(c) 1.3 # 10 4 g (d) 9.0 # 103 g
at 298 K is
Ans : DELHI 2016
(a) 2.0 # 1010 (b) 4.0 # 1010
As we know that, Q = i # t
(c) 4.0 # 1015 (d) 2.4 # 1010
After substituting the values we get,
Ans : SQP 2005
Q = 4.0 # 10 4 # 6 # 60 # 60 C
As E°cell = 0.0591 log K c
n = 8.64 # 108 C
0.46 = 0 . 0591 log K c Now, since 96500 C liberates 9 g of Al
2
8.64 # 108 C liberates = 9 # 8.64 # 108 g of Al
Hence, log K c = 2 # 0.46 96500
0.0591
= 8.1 # 10 4 g of Al
= 15.57
or, K c = Antilog 15.57 M
73. The equivalent conductance of 32 solution of a weak
15 15
= 3.7 # 10 . 4 # 10 monobasic acid is 8.0 mhos cm2 and at infinite
Thus (c) is correct option. dilution is 4000 mhos cm2 . The dissociation constant
of this acid is:
71. Given:
(a) 1.25 # 10-6 (b) 6.25 # 10-4
1. Cu2+ + 2e- " Cu, E° = 0.337 V
2. Cu2+ + e- " Cu+, E° = 0.153 V (c) 1.25 # 10-4 (d) 1.25 # 10-5
Electrode potential, E° for the reaction. Ans : FOREIGN 2009, DELHI 2005
Cu+ + e- " Cu , will be: Degree of dissociation
(a) 0.90 V (b) 0.30 V
a = /
(c) 0.38 V (d) 0.52 V /3
Ans : COMP 2007 = 8.0 = 2 # 10-2

400
2+ -
Cu + 2e $ Cu ; 2
K a = Ca = Ca2
TG° = - nE° F (1 - a)
= 2 # F # 0.337 = 1 # (2 # 10-2) 2
32
= - 0.674 F ...(i) = 1.25 # 10-5
Cu+ $ Cu2 + e- ; Thus (d) is correct option.
TG° = - nE°F 74. For the reduction of silver ions with copper metal, the
standard cell potential was found to be +0.46 V at
= - 1 # F # - 0.153
25°C . The value of standard Gibbs energy, TG° will
= 0.153 F ...(ii) be (F = 96500 C mol-1)
On adding eq. (i) and (ii), (a) -89.0 kJ (b) -89.0 kJ
Cu+ + e- $ Cu ; (c) -44.5 kJ (d) -98.0 kJ
TG° = - 0.521 F = - nE°F ; Ans : OD 2001
+ 2+
Here, n =1 Cu + 2Ag (aq) $ Cu (aq) + 2Ag (s)
E° = + 0.52 V Here, n =2
Thus (d) is correct option. E°cell = + 0.46 V

72. Al 2 O 3 is reduced by electrolysis at low potentials TG° = - nE°F
and high currents. If 4.0 # 10 4 amperes of current is
= - 2 # 0.46 # 96500 kJ
passed through molten Al 2 O 3 for 6 hours, what mass 1000
of aluminium is produced? (Assume 100% current = - 89kJ
efficiency. At mass of Al = 27 g mol-1 )
75. The electrode potentials for Cu2+ (aq) + e- $ Cu+ (aq) Ans : FOREIGN 2004
and Cu+ (aq) + e- $ Cu (s) are +0.15 V and + 0.50, Standard Gibbs free energy is given as
respectively. The value of E°Cu /Cu will be:
2+
TG° = - nE°F
(a) 0.500 V (b) 0.325 V If E° < 0 i.e. negative
(c) 0.650 V (d) 0.150 V
TG° > 0
Ans : SQP 2004
Further TG° - RT ln K eq
Cu2+ + 1e- " Cu+
TG° > 0
E1c= 0.15 V; DGc1 = - n1 E1cF
Cu+ + 1e- " Cu When K eq < 0
E2c= 0.50 V; DGc2 = - n2 Ec2 F Thus (d) is correct option.

2+ -
Cu + 2e " Cu 79. What will be the emf for the given cell
Pt H 2 (P1) H+ (aq) H 2 (P2) Pt
DGc = DG1c + DGc2
- nEcF = - 1n1 E1cF + (- 1) n2 E2cF (a) RT log e P1 (b) RT log e P1
F P2 2F P2
- nEcF = - 1 (n1 E1cF + n2 E2cF) (c) RT log e P2 (d) None of these
F P1
E° = n1 E 1° + n2 E 2° Ans : OD 2007
n
If P1 > P2 ,
= 0.15 # 1 + 0.50 # 1 = 0.325
2
Thus (b) is correct option. then E cell = 2.303 RT log P1
nF P2
76. Standard reduction electrode potentials of three Thus (b) is correct option.
metals A, B and C are respectively +0.5 V, –3.0 V 80. The E°M /M Values for Cr, Mn, Fe and Co are –0.41,
3+ 2+
and –1.2 V. the reducing powers of these metals are +1.57, +0.77 and +1.97 V respectively. For which one
(a) A > B > C (b) C > B > A of these metals the change in oxidation state from +2
(c) A > C > B (d) B > C > A to +3 is easiest?
(a) Fe (b) Mn
Ans : COMP 2009
(c) Cr (d) Co
A B C
+ 0.5V - 3.0 V - 1.2 V Ans : SQP 2010, OD 2008
The higher the negative value of reduction potential, The given values show that Cr has maximum
the more is the reducing power. Hence B > C > A . oxidation potential, therefore its oxidation will be
easiest. (Change the sign to get the oxidation values)
77. On the basis of the following E° values, the strongest
oxidizing agent is [Fe (CN) 6] 4- " [Fe (CN) 6] 3- + e-1; 81. A solution contains Fe2+ , Fe3+ and I- ions. this
3+
E° = - 0.35 V ; Fe2+ " Fe3+ + e-1 ; E° = - 0.77 V solution was treated with iodine at 35°C .E° for Fe
Fe
is 2+
+0.77 V and E° for 2II = 0.536 V

2
-
(a) [Fe (CN) 6] 4 (b) Fe2+

The favourable redox reaction is:
(c) Fe3+ (d) [Fe (CN) 6] 3- (a) I 2 will be reduced to I -
Ans : DELHI 2000 (b) There will be no redox reaction
From the given data we find Fe3+ is strongest oxidizing
(c) I - will be oxidised to I 2
agent. More the positive value of E° op , more is the
tendency to get oxidized. (d) Fe2+ will be oxidised to Fe3+
Thus (c) is correct option. Ans : COMP 2013
78. If the E °cell for a given reaction has a negative Given,

value, then which of the following gives the correct F+3
= + 0.77 V
relationships for the values of TG° and K eq ? Fe2+
(a) TG° > 0; K eq > 1 (b) TG° < 0; K eq > 1 I2 = 0.536 V
and
(c) TG° < 0; K eq < 1 (d) TG° > 0; K eq < 1 2I -
CLASS 12

CLASS 10

2 (e- + Fe+3 " Fe+2) Ec = 0.77 V 85. For the electrochemical cell, M M + X- X
+ -
2I - " I2 + 2e- Ec = - 0.536 V E° (M M) = 0.44 V E° (X X ) = 0.33 V
+3
2Fe + 2I " 2Fe + I2 - +2 (a) E ccell = - 0.77 V
Ec = EcOX + Ecred (b) M+ + X- " M + X is the spontaneous reaction
= 0.77 - 0.536 = 0.164 V (c) M + X " M+ + X- is the spontaneous reaction
So, reaction will taken place. (d) E ccell = 0.77 V
Thus (c) is correct option. Ans : SQP 2012, FOREIGN 2008
-
82. The highest electrical conductivity of the following Given, M X
aqueous solution is of M+ X
(a) 0.1 M difluoroacetic acid E (cX/X ) = 0.33 V
-
(b) 0.1 M fluoroacetic acid and E (cM +

/M) = 0.44 V
(c) 0.1 M chloroacetic acid The cell reaction is as follows
(d) 0.1 M acetic acid M+ $ M + X
X-
Ans : DELHI 2017
Difluoro acetic acid being strongest acid will furnish E ccell = E Cc - E cA

maximum number of ions showing highest electrical = 0.44 - (0.33) = 0.11 V
conductivity. Hence, E is positive, so the reaction is spontaneous.
c
cell
83. According to Nernst equation, which is not correct if The standard reduction potential of LiLi , Ba Na + 2+ +
86. Ba , Na and
Q = KC Mg2+
Mg are –3.05, –2.73, –2.17 and –2.37 volt respectively.

(a) E cell = 0 (b) RT In Q = E ccell Which one of the following is strongest oxidising agent?
nF
nFE° cell (a) Ba2+ (b) Mg2+
(c) KC = e RT (d) E cell = E ccell
(c) Na+ (d) Li+
Ans : FOREIGN 2003
Ans : FOREIGN 2011
E cell = E ccell - RT ln Q Higher the reduction potential strongest is the
nF
oxidizing agent. So, Mg2+ is strongest oxidizing agent
At equilibrium, E cell = 0 and Q = KC
among the given options.
E cell ! E ccell Thus (b) is correct option.
Thus (d) is correct option. 87. The equivalent conductances of two strong electrolytes
84.
2+
The emf of the cell Ni Ni (1.0M) Au (1.0M) Au is 3+ at infinite dilution in H 2 O (where ions move freely
through a solution) at 25°C are given below:
2+ 3+
;Given E°Ni = - 0.25 V and E°Au = + 1.5 VE 2
Ni Au / °CH 3 COONa = 91.0 S cm
equiv
(a) 2.00 (b) 1.25 V 2
/ ° HCl = 91.0 S cm
(c) -1.25 V (d) 1.75 V equiv
Ans : OD 2008 What additional information/quantity one needs to
Given Ni is anode and Au is cathode calculate / ° of an aqueous solution of acetic acid?
(a) / ° of chloro acetic acid (ClCH 2 COOH)
E cNi 2+
/Ni = - 0.25 V and
(b) / ° of NaCl
E c 3+
Au /Au = + 1.5 V
(c) / ° of CH 3 COOK
As we know that,
(d) The limiting equivalent conductance of H+ (l° H ) +
E ccell = E Cc - E cA
Ans : COMP 2016
= 1.5 - (- 0.25)
According to Kohlraush’s law, molar conductivity
= 1.5 + 0.25 = 1.75 V of weak electrolyte acetic acid (CH 3 COOH) can be
Thus (d) is correct option. calculated as follow:
/° CH COOH = (/° CH COOH + /° HCL) - /° NaCl Ans : COMP 2012

3 3
With increase in temperature, electrolytic conduction

Hence, Value of /° NaCl should also be known for
increases because dissociation increases but metallic
calculating value of /° CH COOH .
3
conduction decreases because kernels start vibrating
and hinder the flow of electrons.
88. The best conductor of electricity is a 1 M solution of Thus (b) is correct option.
(a) Boric acid (b) Acetic acid
93. Which one of the following will not conduct electricity?
(c) Sulphuric acid (d) Phosphoric acid (a) Crystalline NaCl
Ans : DELHI 2011 (b) Cu SO 4 solution
H 2 SO 4 being a strong electrolyte is the best conductor.
(c) Graphite
(d) NaCl crystal having defects
89. The conduction of electricity through metallic
conductor is due to the movement of
Crystalline NaCl does not conduct electricity.
(a) metal atoms (b) electrons
(c) ions (d) metallic kernels
94. The pH of aqueous KCl solution is 7.0. This solution
Ans : FOREIGN 2010
was electrolysed for a few second using Pt electrodes.
The conduction of electricity through a metal is due When of the following is correct?
to flow of electrons. (a) The pH of solution decreases
(b) The pH of solution increases
90. The conductance of 0.1 M HCl solution is greater (c) Cl2 is liberated at cathode
than that of 0.1 M NaCl. This is because
(d) The pH of solution remains the same
(a) HCl is more ionized than NaCl
Ans : OD 2001
(b) HCl is an acid whereas NaCl solution is neutral
KCl K+ + Cl-
(c) H+ ions have greater mobility than Na+ ions
(d) Interionic forces in HCl are weaker than those in H2O H+ + OH-
NaCl At cathode : 2H+ + 2e- $ H 2
Ans : OD 2001
At anode : 2Cl- $ Cl 2 + 2e-
Greater conductance of HCl is due to greater mobility The aqueous solution contains excess of OH- ions. So
of H+ ions. the pH of solution increases.
91. The flow of current in an electrolyte is due to 95. Which of the following is wrong about molar
movement of conductivity?
(a) electrons (b) protons (a) The solution contains Avogadro’s number of
(c) ions (d) molecules molecules of the electrolyte
Ans : SQP 2005 (b) It is the product of specific conductivity and
The flow of current in an electrolyte is due to flow of volume of solution in cc containing 1 mole of the
ions. electrolyte
Thus (c) is correct option. (c) Its units are ohm-1 cm2 mol-1
92. The effect of temperature increase on conduction is (d) Its value for 1 M NaCl solution is same as that of
as follow: 1 M glucose solution
(a) Metallic conduction increases, electrolytic Ans : SQP 2003
conduction decreases Glucose is a non electrolyte and hence a non conductor.
(b) Electrolytic conduction increases, metallic Thus (d) is correct option.
conduction decreases
96. The degree of ionization increases
(c) Both metallic and electrolytic conduction increase
(a) With increases in concentration of the solution
(d) Both metallic and electrolytic conduction decrease
(b) On addition of excess of water to the solution
(c) On decreasing the temperature of the solution Ans : SQP 2000
The increase in molar conductivity of any strong

(d) On stirring the solution vigorously
electrolyte with dilution is due decrease in the inter
Ans : COMP 2013 ionic forces.
Degree of ionisation increases with dilution. Thus (d) is correct option.
101. The electrolysis of a certain liquid resulted in the
97. Which one of the following solutions will have highest formation of H 2 at the cathode and Cl 2 at the anode.
conductivity? The liquid is
(a) 0.1 M CH 3 COOH (b) 0.1 M NaCl (a) pure water
(b) NaCl solution in water
(c) 0.1 M KNO 3 (d) 0.1 M HCl
(c) H 2 SO 4
Ans : DELHI 2017
(d) CuCl solution in water
NaCl, KNO 3 , HCl are strong electrolytes but the
size of H+ is smallest. Smaller the size of the ions, Ans : COMP 2010
greater is the conductance and hence greater is the NaCl Na+ + Cl-
conductivity.
Thus (d) is correct option. H2O H+ + OH-
At cathode : 2H+ + 2e- $ H 2
98. If x is the specific resistance of the solution and
At anode : 2Cl- $ Cl 2 + 2e-
N is the normality of the solution. The equivalent
conductivity of the solution is given by Thus (b) is correct option.
(a) 1000x (b) 1000 102. If the electrolysis of fused MgCl 2 , 3g of Mg is

N Nx deposited at the cathode. If 24.125 amperes of current
(c) 1000N (d) Nx was passing through in the electrolysis, the time of
x 1000 electrolysis is
Ans : FOREIGN 2009
(a) 600 minutes (b) 1000 minutes
Equivalent conductivity
(c) 1000 secs (d) 600 secs
1000 # Specific conductivity
= Ans : DELHI 2014, 2011
Normality
= 1000 W = ECt
Normality # Specific Resis tance 96500
= 1000 3 = 12 # 24.125 # t
Nx 96500
Thus (b) is correct option. Time, t = 96500 # 3 = 1000 sec
12 # 24.125
99. Which of the following solutions has the highest Thus (c) is correct option.
equivalent conductance? 103. Electrolysis of an aqueous solution of NaOH between
(a) 0.01 M NaCl (b) 0.050 M NaCl platinum electrodes yields
(c) 0.005 M NaCl (d) 0.02 M NaCl (a) H 2 at the cathode and O 2 at the anode
Ans : OD 2003 (b) H 2 at the anode and O 2 at the cathode
With dilution the equivalent conductance increases. So (c) Only H 2 at the cathode
0.005 M NaCl having highest equivalent conductance.
(d) Only O 2 at the anode
Ans : FOREIGN 2003
100. The increase in the molar conductivity of HCl with
NaOH Na+ + OH-
dilution is due to
(a) increase in the self ionisation of water H2O H+ + OH-
(b) hydrolysis of HCl At cathode : 2H+ + 2e- $ H 2
(c) decrease in the self ionisation of water At anode : 4OH- $ 2H 2 O + O 2 + 4e-
(d) decrease in the interionic forces Thus (a) is correct option.
104. The variation of Lm of acetic acid with concentration 107. When CuSO 4 solution is electrolysed by using Pt
is correctly represented by electrode substance formed at cathode is
(a) oxygen (b) hydrogen
(c) copper (d) SO 2
Ans : DELHI 2013
+2 -2
CuSO 4 Cu + SO 4
H2O H+ + OH-
At cathode : Cu+2 + 2e- $ Cu
108. The reaction amongst the following that takes place
at the anode when aqueous AgNO 3 solution is
electrolysed between Ag electrodes is (electrons are
Ans : OD 2007
emitted)
For weak electrolytes, Lm first increases slowly and (a) NO 3 " NO 3 (b) 4OH- " 2H 2 O + O 2
then rapidly with dilution but does not becomes (c) Ag " Ag+ (d) Ag+ " Ag
constant. Ans : FOREIGN 2001
Thus (c) is correct option. + -
At anode : Ag $ Ag + e
105. Which of the following plots represents correctly Thus (c) is correct option.
variation of equivalent conductance (L) with dilution
for a strong electrolyte? 109. When 48250 coulomb quantity of current is passed
through copper sulphate, the number of atoms of Cu
formed at the cathode are
(a) 0.25 (b) 3.01 # 1023
(c) 1.505 # 1023 (d) 0.5
Ans : OD 2010, 2007
W = ECt
96500
= .75 # 48250 = 31.75 gram
31
96500 2
No. of atom of Cu = 31.75 # 6.023 # 1023
2 # 63.5
= 1.505 # 1023
Ans : SQP 2015 Thus (c) is correct option.
Equivalent conductance increases with dilution and 110. Solubility of a sparingly soluble salt S , specific
ultimately becomes constant. conductance, K and the equivalent conductance L0
Thus (b) is correct option. are related as
106. On electrolysis of dilute H 2 SO 4 between Platinum (a) S = 1000L0 (b) S = KL0
K
electrodes, the gas evolved at the anode is
(a) SO 2 (b) SO 3 (c) S = K (d) S = 1000K
1000L0 L0
(c) O 2 (d) H 2 Ans : SQP 2016
Ans : COMP 2002 Thus (d) is correct option.

H 2 SO 4 2H+ + SO -4 2 111. The specific conductances of four electrolytes are
given below. Which one offers higher resistance to the
H2O H+ + OH- passage of electric current?
At anode : 4OH- $ 2H 2 O + O 2 + 4e- (a) 7.0 # 10-5 (b) 9.2 # 10-9
Thus (c) is correct option. (c) 6.0 # 10-7 (d) 4.0 # 10-8
Ans : COMP 2011

116. When one ampere current is passed through a Cu
K = 1 #1 wire for 10 seconds, the number of electrons passing
R a through it is
or R\ 1 (a) 1.6 # 10+19 (b) 1 # 10+35
K
Thus (b) is correct option. (c) 1 # 10+16 (d) 6.69 # 1019
Ans : COMP 2013
112. In which of the following processes of electrolysis,
23
Cu $ Cu2+ + 2e- reaction occurs at the anode 96500 coulombs = 6.023 # 10 electrons
(a) Aq CuSO 4 solution between graphite electrodes 23
10 coulombs = 6.23 # 10 # 10 = 6.69 # 1019
96500
(b) Fused CuSO 4 between Pt electrodes
(c) Aqueous CuSO 4 between Cu electrodes
117. When CuSO 4 solution is electrolysed, substance
(d) Aqueous CuSO 4 between Cu cathode and Ag formed at anode is
anode
(a) Cu (b) H 2
Ans : DELHI 2001
(c) O 2 (d) SO 2
+2 -
At anode : (Cu) : Cu $ Cu + 2e
Ans : DELHI 2000
Thus (c) is correct option. +2 -2
CuSO 4 Cu + SO 4
113. The amount of the substance deposited at the
electrode during electrolysis by the passage of one H2O H+ + OH-
coulomb of current is known as At anode : 4OH- " 2H 2 O + O 2 + 4e-
(a) Equivalent weight
(b) Chemical equivalent weight
118. The ratio of masses of H 2 (g) and Mg metal deposited
(c) Electro chemical equivalent weight
by the same quantity of current from H 2 SO 4 and
(d) Electro chemical atomic weight MgSO 4 is electrolysed
Ans : FOREIGN 2008 (a) 1 : 8 (b) 1 : 16
Electrochemical equivalent weight. (c) 1 : 32 (d) 1 : 12
Thus (c) is correct option. Ans : FOREIGN 2003
114. The weight in gms of O 2 formed at Pt anode during W1 = E1 = 1
the electrolysis of aq K 2 SO 4 Solution for the passage W2 E2 12
of one coulomb of electricity is
W1 : W2 = 1 : 12
(a) 16 (b) 8
96500 96500
(c) 32 (d) 64 119. In the electrolysis of H 2 O , 11.2 litres of H 2 is liberated
96500 96500
at the cathode at STP. The volume of O 2 at STP
Ans : OD 2010 liberated at the anode is
GEW of Oxygen 8 (a) 11.2 lit (b) 5.6 lit
ECE of O 2 = =
96500 96500
(c) 2.8 lit (d) 22.4 lit
Ans : OD 2009
115. During the electrolysis of aq HCl solution 1.008 g of
H 2 at the cathode and 35.5 g of Cl 2 at the anode are Wt of H 2 = 11.2 # 2 = 1 gram
22.4
liberated, the quantity of current passing through the
W1 = E1
cell is W2 E2
(a) 96500 coulombs (b) 48250 coulombs 1 =1
(c) 2412.5 coulombs (d) 0.5 coulombs W2 8
Ans : SQP 2016 W2 = 8 grams
One gram equivalent weight of the substance is Vol. of at STP = 8 # 22.4 = 5.6 litres
liberated by passing 96500 coulombs of electricity. 32
120. A certain quantity of current liberated 0.54 g of H 2 124. If a direct current deposited of 19.5 grams of potassium
in 5 hours, how many grams of copper is deposited (At. wt. 39) in one minute, the number of grams of
by the same current in the same time (at. wt of Cu aluminium (At. wt. 27) deposited by the same current
= 63.5 ) during the same time would be
(a) 12.7 g (b) 15.9 g (a) 27 grams (b) 31.5 grams
(c) 31.8 g (d) 63.5 g (c) 9 grams (d) 4.5 grams
Ans : SQP 2013 Ans : OD 2009
W1 = E1 As we know that,
W2 E2 W1 = E1
0.54 = 1.08 W2 E2
W2 63.5
2
19.5 = 39
We of Copper, W2 = 0 . 54 # 31.75 = 15.9 gram W2 27
3
1.08
Thus (b) is correct option. Weight of Al, W2 = .5 # 9
19
39
121. Two electrolysis cell containing aq solutions of CuSO 4 = 4.5 gram
and AgNO 3 respectively are connected in series and
electrolysis is carried out. If 0.54 g of Ag is deposited
in one of the cells, how much copper is deposited 125. The quantity of current required to oxidise one mole
in the other cell (At. wts of Cu, Ag are 63.54, 108 of water is (H 2 O " 2H+ + 2e- + 2O1 )
2
respectively) (a) 96500 coulomb

(a) 0.6354 g (b) 0.31779 g
(b) 1 # 96500 coulombs
2
(c) 6.345 g (d) 3.177 g
(c) 2 # 96500 coulombs
Ans : COMP 2015
(d) 4 # 96500 coulombs
W1 = E1
W2 E2 Ans : COMP 2010, OD 2006
0.54 = 108
W2 63.54 H 2 O " 2H+ + 2e- + 1 O 2
2
1 mole
Wt of Copper, W2 = 0.54 # 63.54 = 0.3177 gram 2 moles
108
1 moles of electrons = 96500 coulomb
122. The weights of metals of different valencies deposited 2 moles of electrons = 2 # 96500 coulomb
at the cathode during electrolysis are in the ratio of Thus (c) is correct option.
(a) Their chemical equivalent weights 126. Three Faradays of electricity was passed through an
(b) Their atomic weights aqueous solution of Iron (II) bromide. The weight of
Iron (at wt. = 56 ) deposited at the cathode is
(c) Their atomic numbers
(a) 56 grams (b) 84 grams
(d) Their densities
(c) 112 grams (d) 168 grams
Ans : DELHI 2006
Ans : OD 2003
Wt of Iron = 3 # Equivalent weight of Iron
123. Faraday’s laws of electrolysis are related to the
(a) Atomic number of the cation = 3 # 56
2
(b) Atomic number of anion = 84 gram
(c) Equivalent weight of electrolyte Thus (b) is correct option.
(d) Speed of cation 127. The weight of Silver that can be replaced by 0.01
Ans : FOREIGN 2013 gram equivalent of magnesium from silver nitrate
Faraday’s laws of electrolysis are related to the solution is?
Equivalent weight of electrolyte. (a) 1.08 gram (b) 10.8 gram
Thus (c) is correct option. (c) 54 gram (d) 5.4 gram
Ans : 2011, 2008

131. How many coulombs of electricity are required for
No of gram equivalents of Mg reduction of 1 mole of MnO -4 to Mn+2 ?
= No. of gram equivalent of Ag (a) 96500 (b) 1.93 # 105
Wt of Ag = 0.01 # 108 (c) 4.83 # 105 (d) 9.65 # 106
= 1.08 gram Ans : SQP 2003
- + - +2
Thus (a) is correct option. MnO + 8H + 5e " Mn + 4H 2 O
4
128. 96500 coulombs will liberate ........... litres of oxygen 1 mole 5 moles
at STP during electrolysis or acidulated water 1 moles of electrons = 96500 coulombs
(a) 22.4 (b) 11.2 5 moles of electrons = 5 # 96500 coulombs
(c) 33.6 (d) 5.6 = 482500 = 4.83 # 105
Ans : 2016
96500 Coulomb liberates 8 gram of O 2
132. The density of Cu is 8.94 gram/cc. The weight of
Vol of O 2 at STP = 8 # 22.4 litre the Cu required to plate area of 10 cm # 10 cm to a
32
thickness of 10-2 cm is
= 5.6 litre
(a) 5.2 gram (b) 8.94 gram
(c) 4.47 gram (d) 17.98 gram
129. How long has a current of 3 amperes to be applied Ans : COMP 2005
through a solution of silver nitrate to coat a metal
surface of 80 cm2 with 0.005 mm thick layer? (Density Wt. of Copper = Volume # density
of silver is 10.5 g/C.C) = 10 # 10 # 10-2 # 8.94
(a) 63.01 seconds (b) 125.09 seconds = 8.94 grams
(c) 250 seconds (d) None Thus (b) is correct option.
Ans : 2011
133. The cell reaction of the cell Cu ; Cu2+ < Ag+ ; Ag is
Weight of silver = 80 # 0.005 # 10.5 gram (a) Cu + 2Ag+ " Cu2+ + 2Ag
10
(b) 2Ag + Cu2+ " Cu + 2Ag+
W = Eit
96500 (c) Cu2+ + Ag+ " Cu + Ag
8 # 0.005 # 10.5 = 108 # 3 # t (d) Cu + Ag+ " Cu+ + Ag
96500
Ans :
t = 96500 # 8 # 0.005 # 10.5
DELHI 2000
108 # 3 Anode half reaction : Cu " Cu+2 + 2e-
Time = 125.09 sec Cathode half reaction : 2Ag+ + 2e- " 2Ag
Cell representation : Cu+ 2Ag+ " Cu+2 + 2Ag
130. If three faradays of electricity is passed through the Thus (a) is correct option.
solution of AgNO 3 , CuSO 4 and AuCl 3 , the molar
134. KCl is used in the construction of salt bridge because
ratio of cation deposited at the cathodes will be
(a) K+ , Cl- are isoelectronic
(a) 1 : 1 : 1 (b) 1 : 2 : 3
(b) KCl is an ionic substance
(c) 3 : 2 : 1 (d) 6 : 3 : 2
(c) K+ , Cl- have unit charges
Ans : DELHI 2014, SQP 2010
Molar ratio of cations (d) K+ , Cl- move with equal mobilities

Ans : FOREIGN 2005
= 3 moles : 3 moles : 3 moles K+ , Cl- ions move with equal mobilities.
2 3
= 3 : :1
2
135. The cell for which the cell reaction is
= 6 : 3 :2 H 2 + Cu+2 " 2H+ + Cu is, represented as
Thus (d) is correct option. (a) Cu ; Cu2+ < H+ ; H 2 (g)
(b) H 2 (g) ; H+ < Cu2+ ; Cu
(c) Pt, H 2 (1 atm), H+ < Cu2+ ; Cu 139. In the cell Zn ; Zn+2 (aq) < Cu2+ (aq) ; Cu
(d) Pt, H 2 (1 atm) ; H+ (aq) < Cu2+ (aq) ; Cu (a) Copper electrode is negative electrode
Ans : OD 2009 (b) Zinc electrode is a positive electrode
Oxidation half reaction : H 2 " 2H +
(c) Zinc reduces Cu2+ ions
Reduction half reaction : Cu+2 " Cu (d) Copper reduces Zn2+ ions
Cell representation :Pt, H 2 (1atm) ; H (+aq) < Cu (+aq2) ; Cu Ans : FOREIGN 2009
+2 +2
Thus (d) is correct option. Zn + Cu " Zn + Cu
136. The cell reaction of the hell Thus (c) is correct option.
Zn ; Zn2+ (aq) < Cu2+ (aq) ; Cu is
140. The cell reaction for the following cell is,
(a) Cu + Zn " Cu2 ++ + Zn2+
Ag : AgCl (s) ; KCl aq ; Hg 2 Cl 2 (s) : Hg
(b) Cu + Zn2+ (aq) " (aq) " Cu2+ (aq) + Zn (a) 2Hg + 2AgCl " 2Ag + Hg 2 Cl 2
(c) Zn + Cu2+ (aq) " Zn2+ (aq) + Cu (b) 2Hg + 2KCl " Hg 2 Cl 2 + 2K
(d) Cu2+ + Zn2+ " Cu + Zn (c) 2Ag + Hg 2 Cl 2 " 2Hg + 2AgCl
Ans : SQP 2000
(d) 2Ag + 2KCl " 2AgCl + 2K
Anode half reaction : Zn " Zn+2 + 2e-
Ans : OD 2000
+2 -
Cathode half reaction : Cu + 2e " Cu 2Ag " 2AgCl
+2 +2
Cell reaction : Zn + Cu (aq) " Zn (aq) + Cu Hg 2 Cl 2 " 2 Hg
Thus (c) is correct option. Cell reaction : 2Ag + H 2 Cl 2 " 2Hg + 2AgCl
137. The standard reduction potentials at 298cK for the Thus (c) is correct option.
following half reductions are given against each
141. The reaction, 1
H 2 (g) + AgCl (s) " H (+aq) + Cl (-aq) + Ag (s)
Zn (+aq2) + 2e- " Zn (s) - 0.762 2
occurs in the Galvanic cell

Cr (+aq2) + 3e- " Cr(s) - 0.740
(a) Ag ; AgCl (s) ; KCl (sol) ; AgNO 3 (sol) ; Ag
2H (+aq2) + 2e- " H 2(q) - 0.00
(b) Pt, H 2 (g) ; HCl (sol) ; AgNO 3 (sol) ; Ag
Fe (+aq3) + e- " Fe (+aq2) + 0.770 (c) Pt, H 2 (g) ; HCl (sol) + AgCl (s) ; Ag
Which is the strongest reducing agent?
(d) Pt, H 2 (g) ; KCl (sol) ; AgCl (s) ; Ag
(a) Zn (s) (b) Cr(s)
Ans : SQP 2003
(c) H 2 (g) (d) Fe (+aq2)
Anode half reaction : 1 H " H+
Ans : COMP 2013, SQP 2010 2 2
Zn contain lowest reduction potential. Hence it is Cathode half reaction : AgCl " Ag + Cl-
strongest reducing agent.
Thus (a) is correct option. Cell representation : Pt, H 2 (g) ; HCl (sol) + AgCl (s) ; Ag
138. The correct representation of the cell for which the
cell reaction is Ni + 2Ag+ " Ni+2 + 2Ag 142. In a simple electro chemical cell, which is in standard
(a) Ni ; Ni2+ (aq) < Ag+ (aq) ; Ag state. Half cell reactions with that appropriate
(b) Ag ; Ag+ (aq) < Ni+ (aq) ; Ni oxidation potentials are
(c) Ni2+ (aq) ; Ni < Ag+ (aq) ; Ag Pb (s) - 2e- " Pb (+aq2) Ec = - 0.3 volt
(d) Ni ; Ni2+ (aq) < 2Ag+ (aq) < Ag Ag (i) - e- " Ag (+aq) Ec = - 0.80 volt
Ans : DELHI 2016 Which of the following reactions takes place?
Oxidation half reaction : Ni " Ni +2
(aq)
(a) Pb (+aq2) + 2Ag (s) " 2Ag (+aq) + Pb (s)
Reduction half reaction : 2Ag +

+ 2e- " Ag (b) Pb (+aq2) + 2Ag (s) " 2Ag (+aq) + Pb (aq)
(aq)
(c) Ag (+aq) + Pb (s) " Ag (s) + Pb (+aq2)
Cell representation : Ni ; Ni (+aq2 ) < Ag (+aq) ; Ag
(d) Ag (+s) + Pb (aq) " Ag (s) + Pb (+aq2)
Ans : COMP 2000

(a) Zn will reduce Fe+2 (b) Zn will reduce Mg+2
Low oxidation potential electrode acts as anode and
(c) Mg oxidise Fe (d) Zn oxidise Fe
high oxidation potential electrode and high oxidation
potential electrode acts as cathode. Ans : OD 2016
2Ag " 2Ag+ + 2e- (Anode) The low reduction potential element reduce the high
reduction potential element. The high reduction
Pb+2 + 2e- " Pb (cathode) potential element oxidise the low reduction potential
Pb (2aq) + 2Ag (s) " 2Ag (+aq) + pb (s) element.
143. State which of the following is the strongest oxidising 146. The voltage of cell whose half cells are given below is
agent Mg+2 + 2e- " Mg E = - 2.37 V Cu+2 + 2e- " Cu
E = + 0.34 V
MnO -4 , E = + 1.52 V
M+2 (a) 3.78 volts (b) 1.71 volts
Fe+3 , E = + 0.76 V (c) -2.71 volts (d) 2.71 volts
Fe+2 Ans : COMP 2008
BrO -3 ,
E = - 1.50 V E cell = E cathode - E Anode
Br2
Cr2 O -7 2 = 0.34 - (- 2.37)
, E = + 1.33 V
Cr+3 = 2.71 volts
- +3
(a) MnO 4 (b) Fe Thus (d) is correct option.
- -2
(c) BrO 3 (d) Cr2 O 7
147. The standard reduction potential, Ec for the half
Ans : DELHI 2009
reaction are as
The highest reduction potential substance acts as
Zn " Zn+2 + 2e- , Ec = + 0.76 V
strong oxidising agent. So MnO -4 acts as the strongest
oxidising agent. Fe " Fe+2 + 2e- , Ec = + 0.41 V
Thus (a) is correct option. The emf of the cell reaction Fe+2 + Zn " Zn+2 + Fe is
144. The electrode potential are (a) -0.35 V (b) 0.35 V
Ag+ (c) +1.17 V (d) -1.17 V
= + 0.80 V
AgEc Ans : SQP 2011, 2008
Co+2 = - 0.28 V E cell = ECathode - E Anode
Co Ec
= - 0.41 + 0.76 = + 0.35 V
Cu+2 = + 0.34 V
CuEc Thus (b) is correct option.
Zn+2 = - 0.76 V
ZnEc 148. The depolariser used in dry cell is
The most reactive metal which displaces other metals (a) MnO 2 (b) NH 4 Cl
from their salts in solution is (c) Carbon (d) ZnCl 2
(a) Ag (b) CO Ans : DELHI 2015
(c) Cu (d) Zn Thus (a) is correct option.

Ans : FOREIGN 2012 149. Which is the following represents the Daniel cell ?
The lowest reduction potential element is more (a) Zn ; Zn+2 ; H+ ; H 2 , Pt
reactive and displaces other metals form their salt (b) Zn ; Zn+2 ; Cu ; Cu+2
solution.
(c) Zn < Zn+2 ; Cu+2 ; Cu
(d) Cu ; Cu+2 ; Zn+2 ; Zn
145. Observe the following values and pick up the correct
+2 Ans : FOREIGN 2017
statement Ec for Mg
+2
Mg is - 2.38 A , for Zn is – 0.76 V

Zn
Fe +2 Thus (c) is correct option.

and for Fe is –0.44 V
150. The reaction occurring at the anode during the (c) Neither anode nor cathode
recharging of lead storage battery is (d) Either anode or cathode depending upon its
(a) Pb + SO 24- " PbSO 4 + 2e- standard reduction potential
(b) Pb + PbO 2 + H 2 SO 4 " 2PbSO 4 + 2H 2 O Ans : SQP 2013
- 2-
(c) PbSO 4 + 2e " Pb + SO 4 Thus (a) is correct option.
(d) 2PbSO 4 + 2H 2 O " Pb + PbO 2 + 2H 2 SO 4 156. Galvanized iron sheets are coated with
Ans : OD 2007 (a) Nickel (b) Chromium
At anode : -
PbSO 4 + 2e " Pb + SO 2-
4 (c) Copper (d) Zinc
Thus (c) is correct option. Ans : COMP 2005
151. The reaction occurring at the anode during the Thus (d) is correct option.
recharging of lead storage battery is
(a) Pb + SO 24- " PbSO 4 + 2e-
(b) PbSO 4 + 2e- " Pb + SO 24- ASSERTION AND REASON
2- + -
(c) PbSO 4 + 2H 2 O " PbO 2 + SO + 4H + 2e
4
(d) Pb2+ + SO 24- " PbSO 4 DIRECTION : Given below are two statements labelled as
Ans : SQP 2012 Assertion and Reason. Select the most appropriate answer
At anode Pb + SO 24- " PbSO 4 + 2e- from the options given below.
Thus (a) is correct option. 157. Assertion : Conductivity decreases with decrease in
152. The device used to convert the chemical energy of H 2 concentration of electrolyte.
gas into electrical energy is called Reason : Number of ions per unit volume that carry
(a) Daniel cell (b) electrolytic cell the current in a solution decreases on dilution.
(c) fuel cell (d) storage cell (a) Both Assertion and Reason are true and Reason
is the correct explanation of Assertion
(b) Both Assertion and Reason are true, but Reason
is not the correct explanation of Assertion.
153. In H 2 - O 2 fuel cell the reaction occurring at cathode
(c) Assertion is true, but Reason is false.
is
(a) 2H 2 + O 2 " 2H 2 O (l) (d) Assertion is false, but Reason is true.
(b) H+ + OH- " H 2 O Ans : COMP 2020
1
(c) O 2 + 2H 2 O + 4e- " 4OH- Conductivity (k) \
dilution
(d) H+ + e- " 1 H 2 Thus (a) is correct option.
2
Ans : FOREIGN 2011 158. Assertion : If l0Na and l0Cl are molar limiting
+ -
Thus (c) is correct option. conductivity of sodium and chloride ions respectively,
154. When a lead storage battery is charged, it acts as then the limiting molar conductivity for sodium
(a) a primary cell chloride is given by the equation:
L0NaCl = l0Na + l0Cl
+ -
(b) an electrolytic cell
Reason : This is according to Kohlrausch law of
(c) a galvanic cell
independent migration of ions.
(d) a concentration cell (a) Both Assertion and Reason are correct and
Ans : OD 2016 Reason is a correct explanation of the Assertion.
Thus (b) is correct option. (b) Both Assertion and Reason are correct but Reason
155. According to electrochemical theory of corrosion, the is not the a correct explanation of the Assertion.
metal undergoing corrosion acts as (c) Assertion is correct but Reason is incorrect.
(a) Anode (d) Both the Assertion and Reason are incorrect.
(b) Cathode
Ans : OD 2019
161. Assertion : On increasing dilution, the specific
According to Kohlrausch law, “limiting molar conductance keep on increasing.
conductivity of an electrolyte can be represented as Reason : On increasing dilution, degree of ionisation
the sum of the individual contributions of the anion of weak electrolyte increases and molality of ions also
and cation of the electrolyte”. increases.
Thus (a) is correct option. (a) Both Assertion and Reason are correct and
159. Assertion : Copper metal gets readily corroded in an
acidic aqueous solution. (b) Both Assertion and Reason are correct but Reason
Reason : Free energy change for this process is positive. is not the a correct explanation of the Assertion.
(a) Both Assertion and Reason are correct and (c) Assertion is correct but Reason is incorrect.
Reason is a correct explanation of the Assertion. (d) Both the Assertion and Reason are incorrect.
(b) Both Assertion and Reason are correct but Reason Ans : SQP 2008
is not the a correct explanation of the Assertion. The specific conductivity decreases while equivalent
(c) Assertion is correct but Reason is incorrect. and molar conductivities increases with dilution.
(d) Both the Assertion and Reason are incorrect. Thus (d) is correct option.
Ans : DELHI 2015 162. Assertion : E0 for Mn3+ /Mn2+ is more positive than
Copper lies below hydrogen in electrochemical series Cr3 /Cr2+ .
so it cannot displace H2 from dilute acids. Hence it Reason : The third ionization energy of Mn is larger
is not easily corroded in acidic solutions. Further, than that of Cr.
corrosion is a spontaneous process for which free (a) Both Assertion and Reason are correct and
energy change must be negative. Reason is a correct explanation of the Assertion.
Thus (d) is correct option. (b) Both Assertion and Reason are correct but Reason
160. Assertion : For the Daniel cell, Zn y Zn2+ z Cu2+
Cu with, E cell = 1.1 V , the application of opposite (c) Assertion is correct but Reason is incorrect.
potential greater than 1.1 V results into flow of (d) Both the Assertion and Reason are incorrect.
electron from cathode to anode.
Ans : FOREIGN 2020
Reason : Zn is deposited at anode and Cu is deposited
Reduction potential of Mn3+ is more than Cr3+. So,
at cathode.
Mn3+ is easily reduced in comparison with Cr3+ or
(a) Both Assertion and Reason are correct and Cr2+ is easily oxidised than Mn2+ is more than Cr2+ .
Reason is a correct explanation of the Assertion. Both Assertion and Reason are true.
(b) Both Assertion and Reason are correct but Reason Thus (a) is correct option.
163. Assertion : Galvanised iron does not rust.
(c) Assertion is correct but Reason is incorrect. Reason : Zinc has a more negative electrode potential
(d) Both the Assertion and Reason are incorrect. than iron.
Ans : DELHI 2011 (a) Both Assertion and Reason are correct and
In a Daniel cell, Reason is a correct explanation of the Assertion.
Zn y Zn2+ z Cu2+ y Cu , E cell = 1.1 V (b) Both Assertion and Reason are correct but Reason
The oxidation half cell is Zn $ Zn2+ + 2e-
The reduction half cell is Cu2+ 2e- $ Cu (c) Assertion is correct but Reason is incorrect.
So, Zn + Cu2+ $ Zn2+ + Cu (d) Both the Assertion and Reason are incorrect.
Thus here Zn is oxidised and deposited at anode, Ans : SQP 2018
and Cu is reduced and deposited at cathode. If the Galvanised iron does not rust easily because zinc
opposite potential is greater than 1.1 V, then electrons (Which is present in the form of coating) has more
flow from cathode to anode. So both Assertion and negative electrode potential (- 0.76 V) than iron (-
Reason are correct. 0.41 V) i.e., Zn is less reactive than Fe.
164. Assertion : A small amount of acid or alkali is added 167. Assertion : The cell potential of mercury cell is 1.35 V,
before electrolysis of water. which remains constant.
Reason : Pure water is weak electrolyte. Reason : In mercury cell, the electrolyte is a paste of
(a) Both Assertion and Reason are correct and KOH and ZnO.
Reason is a correct explanation of the Assertion. (a) Both Assertion and Reason are correct and
(b) Both Assertion and Reason are correct but Reason Reason is a correct explanation of the Assertion.
is not the a correct explanation of the Assertion. (b) Both Assertion and Reason are correct but Reason
(c) Assertion is correct but Reason is incorrect. is not the a correct explanation of the Assertion.
(d) Both the Assertion and Reason are incorrect. (c) Assertion is correct but Reason is incorrect.
Ans : SQP 2015

Water is a covalent compound, hence pure water is Ans : COMP 2018
a weak electrolyte and feebly ionised and thus bad Zn (l) + HgO (s) $ Zn (s) + Hg (l)
conductor of electricity. However, addition of a small
The cell potential remains constant during its life
amount of acid or alkali increases ionisation of water
as the overall reaction does not involve any ion in
making at good conductor of electricity.
solution whose concentration changes during its life
Thus (a) is correct option. time.
165. Assertion : During electrolysis of CuSO4 (aq) using Thus (b) is correct option.
copper electrodes, copper is dissolved at anode and
deposited at cathode.
Reason : Oxidation takes place at anode and reduction VERY SHORT ANSWER QUESTIONS
at cathode.
(a) Both Assertion and Reason are correct and 168. Name the law or principle to which the following
Reason is a correct explanation of the Assertion. observations confirm:
(b) Both Assertion and Reason are correct but Reason When 96500 coulombs of electricity is passed through
is not the a correct explanation of the Assertion. a solution of copper sulphate, 3.175 g of copper is
(c) Assertion is correct but Reason is incorrect. deposited on the cathode (At. wt. of Cu = 63.5).
Faraday’s first law of electrolysis is confirmed from
Ans : DELHI 2009
the given statement which states that ‘the amount
At cathode : Cu2+ (aq) + 2e- $ Cu (s) (Reduction) of substance deposited at a particular electrode as a
At anode : Cu (s) $ Cu2+ (aq) + 2e- (Oxidation) result of electrolysis is directly proportional to the
Thus (a) is correct option. quantity of electricity passed’.
166. Assertion : On increasing dilution, the specific 169. How many hours does it take to reduce 3 moles of
conductance keep on increasing. Fe3+ to Fe2+ with 2.0 A current intensity?
Reason : On increasing dilution, degree of ionisation Ans : OD 2016
of weak electrolyte increase and molality of ions also Given, current = 2 A
increases.
Number of moles of iron = 3 mol
Reason is a correct explanation of the Assertion. From number of moles,
weight of iron = 3 # 55.8 = 168 g
is not the a correct explanation of the Assertion. From Faraday’s equation, w = ZIt
(c) Assertion is correct but Reason is incorrect. t = 168 # 96500
56 # 2 # 3600
t = 40.2 h
Ans : OD 2006
The specific conductivity decreases while equivalent 170. What happens when a nickel rod is dipped into a
and molar conductivities increase with dilution. copper sulphate solution? Justify your answer.
o o
Thus (d) is correct option. ( E Ni
2+
/Ni = - 0.25 V and E Cu /Cu = + 0.34 V ).
2+
or 174. What is standard hydrogen electrode?

Will nickel displace copper from a 1 M solution of Ans : SQP 2014
copper sulphate? Justify your answer. Standard Hydrogen Electrode (SHE) is an electrode
o
( E Ni
2+
o
/Ni = - 0.25 V , E Cu /Cu = + 0.34 V )
2+ in which H2 gas at one atmospheric pressure is passed
through a solution of H+ ions of 1 M concentration
at 25°C placed in contact with Pt foil. This electrode
Since, the standard electrode potential of Ni is less
is also called Normal Hydrogen Electrode (NHE). Its
than that of Cu and possesses greater reducing power.
potential is taken as zero.
So, nickel can displace copper from copper sulphate
solution. 175. Give a reason for the following.
Cu2+ âq h + Ni ^s h $ Ni2+ âq h + Cu ^s h Specific conductance decreases with dilution whereas
or equivalent conductance increases with dilution.
^- 0.25 Vh E ^+ 0.34 Vh Ans :
o o COMP 2007
Since, E Ni2+ /Ni Cu2+ /Cu
Specific conductance depends on number of ions per
Therefore, Ni possesses a greater reducing power. unit volume. On dilution, number of ions will decrease
Hence, Ni displaces Cu from CuSO4 solution. per unit volume.
171. Calculate the number of coulombs required to deposit Hence, specific conductance of the solution will
5.4 g of Al, when the electrode reaction is decrease.
Al3+ + 3e- $ Al Equivalent conductance is the product of specific
[Atomic weight of Al = 27g/mol] conductivity and volume of the solution containing
one gram equivalent of the electrolyte.
Ans : DELHI 2016
3+ -
As the decreasing value of specific conductivity is
Al + 3e $ Al
more than compensated by the increasing value of V,
For 27 g (1 mol) of Al required = 3 # 96500 C so the value of L eq increases with dilution.
1 g of Al required = 3 # 96500 C Correct the following statement.
27 176.
For a strong electrolyte, the plot of equivalent

5.4 g of Al required = 3 # 96500 # 5.4 = 57900 C
27 conductance versus concentration of the solution is a
Thus, the number of coulombs required to deposit straight line.
5.4 g Al is 57900 C. Ans : DELHI 2002
172. Correct the following statement. Copper displaces For a strong electrolyte, the plot of molar conductance
both zinc and silver from their solutions. versus square root of concentration of solution is a
Ans : FOREIGN 2000
straight line.
Zinc displaces both copper and silver from their 177. Correct the following statement.
solutions.
On dilution of a solution, its equivalent and specific
or conductance increases.
Copper displaces only silver from the solution not Ans : FOREIGN 2001
zinc. On dilution of a solution, its equivalent conductance
The reduction potential of three elements is in the increases and specific conductance decreases.
order Zn< Cu< Ag. Hence, zinc is more reactive.
178. Specific conductivity of 0.20 M solution of KCl at
173. The reduction potential of a metal X is - 0.76 V while
298 K is 0.025 S cm–1. Calculate its molar conductivity.
that of Y is - 2.38 V . Which of the two metals is
Ans : OD 2017
a stronger reducing agent? Give a reason for your
answer. Given, Specific conductivity ^ h = 0.025 S cm
k -1
Ans : OD 2010 Concentration (C ) = 0.20 M

Reduction potential of X ^- 0.76 Vh < Y ^- 2.38 Vh . Now, molar conductivity
Strong reducing agents have a large negative value. ^L mh = 1000 # k
Hence, metal Y is a stronger reducing agent than C
metal X. = 1000 # 0.025 = 125 S cm2 mol-1
0.2
179. Arrange Ag, Cr and Hg metals in the increasing order 183. Define electrode and electrode potential.
of reducing power. Ans : FOREIGN 2018
o o
Given : E Ag +
/Ag = + 0.80 V , E Cr 3+
/Cr = - 0.74 V (i) Electrode : An electrode is a solid electric
o conductor that allows the passage of electric
E Hg2+ /Hg = + 0.79 V
current through it self. Electrode are of two types,
Ans : SQP 2013 cathode (negative plate) and anode (positive
Since, the standard potential values are in the order of plate).
E Cr /Cr ^- 0.74 Vh < E Hg /Hg ^0.79 Vh < E Ag /Ag ^0.80 Vh
o o o
3+ 2+ + (ii) Electrode potential : It is the potential difference
i.e. arranged in the increasing order to gain electrons. developed between the electrodes and its
To lose electron or to act as reducing agent, the order electrolyte or it is the difference set up between
will be reverse, the metal and its ions in the solution. It is called
o o o electrode potential.
i.e. E Ag +
/Ag < E Hg 2+
/Hg < E Cr 3+
/Cr
184. Define specific conductance and equivalent
180. Two metallic elements A and B have the following conductance.
standard potentials: Ans : OD 2018
A = 0.40 V , B = 0.80 V , what would you expect if Specific Conductance : The reciprocal of specific
element A was added to an aqueous salt solution of resistance (resistivity) is called the specific conductance
element B? Give a reason for your answer. or conductivity.
Ans : COMP 2013, OD 2010
k =1
Standard potential of A < B. Hence, A has more r
reducing power than B. So, when A is added to an
k = 1$ l
aqueous salt solution of B, then B will form precipitate R A
and A will form the salt displacing B from its solution.
k = G$ l
A
where, l = distance between the electrodes
SHORT ANSWER QUESTIONS A = their cross-sectional area
Equivalent Conductance:
181. Give reasons ;
It is defined as the conducting power of all the ions
(i) Mercury cell delivers a constant potential during produced by dissolving one gram equivalent of an
its life time. electrolyte in solution.
(ii) In the experimental determination of electrolytic It is expressed as Le and is related to specific
conductance, Direct Current (DC) is not used. conductance as,
Ans : DELHI 2023
(i) Mercury cell delivers a constant potential during Le = k # 1000

C eq
its life time because net cell reaction does not where C eq is the concentration in gram equivalent per
involve ions. litre (or normality).
(ii) In the experimental determination of electrolytic
185. Give the name and chemical composition of important
conductance direct current (DC) is not used
ores of Aluminium and Copper.
because it will lead to electrolysis of the solution
Ans : SQP 2017
taken in the cell. So, AC current is used for this
measurement to prevent electrolysis. (a) Ore of aluminium
182. Define fuel cell with an example. What advantages = Bauxite (Al 2 O 3 + SiO 2 + TiO 2 + Fe 2 O 3)
do the fuel cells have over primary and secondary Cryalite = Na 3 AlF6
batteries.
(b) Copper = Copper pyrite CuFeS 2
Ans : DELHI 2023
Fuel cells : They are galvanic cells that are designed Malachite = CuCO 2 Cu (OH) 3
to convert the energy of combustion of fuels like 186. State and explain Faraday’s 2nd Law of electrolysis.
hydrogen, methane,methanol directly into electrical
Ans : COMP 2017
energy, e.g., hydrogen-oxygen fuel cell. The advantage
of fuel cell over the primary and secondary cell is that Faraday’s second law of electrolysis states that, when
they provide continual supply of fuel. the same quantity of electricity is passed through
several electrolytes, the mass of the substances W = ZQ

deposited are proportional to their respective chemical
equivalent or equivalent weight.
W = Zit 6a Q = it @
Where, r = current
187. Construct electric cells for the following reactions:
(i) Fe+ + Cu2+ $ Cu + Fe2+ t = time
(ii) 2Fe3+ + 2Cl- $ 2Fe2+ + Cl 2 190. Define Electrochemical equivalent.
Ans : DELHI 2018 Ans : OD 2016, SQP 2011
(i) Fe + Cu+2 $ Cu + Fe+2 Electrochemical equivalent or Faraday’s Constant :
Oxidation reaction, (for iron) It is defined as the amount of substance liberated at
the electrode when current of one ampere is passed
Fe ^ s h $ Fe+2 êq.h + 2e-
through the electrolyte for one second. Its value is
Reduction reaction, 96500 Cmol-1 .
Cu+2 + 2e- $ Cu ^ s h W = Zit
Hence, Cell reaction,
Z =W
Fe | Fe+2 || Cu+2 | Cu it
(ii) 2Fe+3 + 2Cl- $ 2 Fe+2 + Cl 2 W = 1 Kg

Oxidation reaction, i = 1A
- -
2 Cl $ Cl 2 + 2e and t = 1 sec .
and Reduction reaction, then, Z = 1, thus electrochemical equivalent will be
+3 -
2 Fe + 2e $ 2Fe +2 unity, if 1A of current is passed for 1 second and 1kg
of substance is deposited/liberated.
Hence, Cell reaction,
2 Cl- | Cl 2 || 2 Fe+3 | 2 Fe+2 191. What is salt bridge? What are its uses?
Ans : COMP 2014
188. What is specific conductance and molar conductance?
When two solution in an electrochemical cell are kept
Ans : FOREIGN 2017
apart through an arrangement, the arrangement is
Conductivity or specific conductance of an electrolyte called slat-bridge.
solution is a measure of its ability to conduct electricity.
Salt bridge carries out two important functions
SI Unit of specific conductance
1. It completes the circuit
= Slemers per meter (S/m) 2. It maintains the electrical neutrality of the
Conductivity is also temperature dependent. solution in the half cells.
The molar conductance is defined as the conductance
192. Define standard electrode potential.
of all the ions produced by ionization of 1 g mole of an
electrolyte when present in Vml of solution. Ans : DELHI 2016, FOREIGN 2014, OD 2013
Units of molar conductance The electrode potential under the conditions of unit
concentration of all the species in the half cell is called
= W-1 cm-2 mol-1 the standard electrode potential. According to the
189. State Faraday’s 1st law of electrolysis. IUPAC convention, standard reduction potential of
Ans : OD 2016, SQP 2011 a cell is now called the standard electrode potential.
The value of the oxidation potential of the same cell
Faraday’s 1st Law of electrolysis : Faraday’s First law
reaction will be the same with the sign reversed.
states that the amount of chemical reaction occurring
at an electrode by passing current is proportional In a Daniel or galvanic cell, the half cell in which
to the quantity of electricity passed through the oxidation takes place is called anode and the other half
electrolyte (in solution or in molten State).i.e. cell in which reduction takes place is called cathode.
The potential difference between the two half cells is
If W = Mass of substances
called the cell potential. It is the difference in standard
Q = Charge and reduction potential of cathode and standard reduction
Z = Electrochemical equivalent. potential of anode.
o o o
Then, W aQ E cell = E cathode - E anode
193. What are Faraday’s laws of electrolysis? Explain. Ans : FOREIGN 2005
Ans : SQP 2014

Metal Anode ; Metal ion (conc.) ; Metal ion (conc) ;
Metal Cathode
Faraday’s First Law : Faraday’s first law state that
the amount the chemical reaction occurring at an Salt Bridge
electrode by passing current is proportional to the Oxidation takes place at the anode while reduction
quantity of electricity passed through the electrolyte takes place at the cathode
(in solution or in molten state). Example : For the cell reaction
Faraday’s Second law : States that when the same
Zn (s) + Cu+2 (aq) " Zn2 (aq) + Cu (s)
quantity of electricity is passed through different
electrolytes, the amounts of different substances Cell representation is :
formed are proportional to their chemical equivalent Zn ; Zn2+ (C 1) < Cu2+ (C 2) ; Cu
weights (i.e., atomic mass of the metal divided by the
197. Arrange the following metals in the order in which
number of electrons required to reduce a cation of the
they displace each other from the solution of their
metal).
salts :
W1 = W2 = W3 = .......
E1 E2 E3 Al, Ag, Cu, Fe, Mg and Zn.
where, W is the mass of substance and E is its Ans : OD 2001
equivalent. Mg, Al, Zn, Fe, Cu, Ag

194. State colligative properties of dilute solution. Write 198. What is salt bridge ? Give its functions.
down the different types of colligative properties. or
Ans : COMP 2012 List the important uses of salt bridge.
There are four main colligative properties: Ans : SQP 2012, OD 2006
1. Relative lowering in Vapour pressure. A salt bridge is a U - shaped tube containing

2. Elevation is boiling point. concentrated solution of an inert electrolyte like KCl,
3. Depression in freezing point. KNO 3 , K 2 SO 4 , etc.
4. Osmotic pressure. (An inert electrolyte is one whose ions do not take
All the above said colligative properties (C.P) are part in the redox reaction and also do not react with
directly propositional to the concentration i.e. electrolyte used.)
Functions :
C.P. \ concentration.
1. It prevents mixing of two electrolytes
Therefore value of all the colligative properties
2. It completes the electrical circuit
decreases with the dilution. e.g. a pure liquid has
3. It maintains the electrical neutrality of the
zero-concentration and will show maximum vapour
solutions in both half cells.
pressure means relative lowering in V.P is zero, or
elevation in Boiling point in zero. 199. Where is electrolysis used?
195. What are cells ? Name the two types of cells. Ans : COMP 2014
Ans : DELHI 2010

Electrolysis is mainly used in :
A device used to convert chemical energy into (i) Electro-plating i.e. thin coating of desire metal
over some other metal.
electrical energy or electrical energy into chemical
energy is called cell. (ii) Electro-refining i.e. purification of metals.
Cells are of two types : 200. What do you mean by electrode potential?
1. Electrolytic Cell : It is used to convert electrical Ans : DELHI 2002
energy into chemical energy. The tendency of an electrode to lose or gain electrons is
2. Electrochemical Cell : It is used to convert called electrode potential OR The electrical potential
chemical energy into electrical energy. It is also difference set up between the metal and its ions in the
called Galvanic cell or Voltaic cell. solution is called electrode potential.
196. Give the representation of a galvanic cell. 201. Draw the diagram of Daniel Cell.
or Ans : FOREIGN 2001
How an electrochemical cell is represented by cell The diagram of Daniel Cell is given below.
notation?
205. Write down the half cell reaction and cell reaction for
the Daniel cell.
Zn (s) | Zn+2 (aq.) (1M) | | Cu+2 (aq.) (1M) | Cu (s)
Ans : DELHI 2010
Half cell- reactions :

At anode : Zn (s) $ Zn2+ (aq) + 2e-
At cathode : Cu2+ (aq) + 2e- $ Cu (s)
M
Cell reaction : Zn (s) + Cu2+ (aq) Zn2+ (aq) (M) + Cu (s)
206. What is electrochemistry ?

Ans : FOREIGN 2004
Electro-chemistry is the study of production of

Daniel cell haing electrode of zinc and copper electricity from energy released during spontaneous
dipping in the solutions of their respective salts. chemical reactions and the use of electrical energy to
bring about non-spontaneous chemical transformation.
202. Why is it not possible to measure the single electrode Electricity chemical reaction
potential?
Ans : OD 2004 207. Write difference between EMF and Potential
It is not possible to measure single electrode potential difference.
because the half cell containing single electrode Ans : OD 2003
cannot exist independently, as charge cannot flow on The difference between EMF and Potential difference
its own in a single electrode. Thus, another electrode are as follows :
is needed to complete the electric circuit which is
called reference electrode. E.M.F. Potential Difference
1. It is the potential It is the difference
203. Define standard reduction potential of electrode.
difference between the between electrode
Ans : SQP 2007
two electrodes when potentials of two
Standard reduction potential (Ec) is the reduction no current is flowing electrodes when
potential of an element when the concentration of its through the circuit i.e., current is flowing
ions in solution is 1 M and the temperature is 298 K in the open circuit. through the circuit.
(When the concentrations of all the species involved 2. It is the maximum It is always less than
in a half-cell in is unity then the electrode potential is voltage obtainable the emf of the hell.
called standard electrode potential). from the hell.
204. Derive equilibrium constant from Nernst equation. 3. The work calculated The work calculated
Ans : COMP 2008, DELHI 2005 from emf is the from potential
maximum work difference is less than
Consider the following cell reaction :
obtainable from a cell. the maximum work
aA + bB cC + dD obtainable from a cell.
Nernst equation for this cell reaction at 298 K is 4. it is responsible for the It is not responsible
c d
[C ] [D ] flow of steady current for the flow of steady
o
E cell = E cell - 2.303RT log a b through the circuit. current through the
nF [A] [B]
circuit.
o
= E cell - 0.0591 log QC
n +
208. Given the standard electrode potentials KK = - 2.93 V
Where QC is concentration quotient. Ag+
Hg 2+ 2+
= 0.79 V , Mg
2+
Ag = 0.80V, Hg Mg = - 2.37 V , CrCr

At equilibrium, E cell = 0 and QC = KC = - 0.74 V .
Arrange these metals in their increasing order of
or E ccell = 0.0591 log KC (at 298 K) reducing power.
n
Ans : SQP 2011

G* = l = Rk
Higher the oxidation potential, more easily it is A
oxidised and hence greater is the reducing power.
k = 1 #G* c
1 = G = Conductance m
Thus, increasing order of reducing power will be R R
Ag < Hg < Cr < Mg < K 211. Write four differences between metallic conductors
and electrolytic conductors.
209. How is standard Gibbs energy of a reaction is related Ans : FOREIGN 2012
to its equilibrium constant?
The differences between metallic conductors and
Ans : COMP 2013 electrolytic conductors are as follows :
o
If standard emf of a cell is E cell and n F is the amount
of charge passed, then standard gibbs energy of the Metallic conductors Electrolytic Conductors
reaction, 1. Flow of electricity Flow of electricity takes
TrGc = - nFE ccell takes place without place accompanied by
the decomposition of the decomposition of
Further, we know
the substance. the substance.
E ccell = RT ln KC 2. Flow of electricity Flow of electricity is
nF
is due to the flow of due to the movement
Hence, Tr Gc = - nF # RT ln KC electrons i.e. there is of ions and hence there
nF
no flow of matter. is flow of matter.
= - RT ln KC
= - 2.303 RT log KC 3. The electrical The electrical
conduction decreases conduction increases
210. Write a note on conductivity cell. with increases of with increases of
Ans : DELHI 2017 temperature. This temperature. This
is because kernels is generally due to
Conductivity cell is used to measure the resistance
start vibrating which increase in dissociation
of an solution. It consists of two platinum electrodes
produce hinderance in or decrease in the
coated with platinum black. These have area of cross
the flow of electrons. interionic attraction.
section equal to 'Al and are separated by distance 'l '.
Therefore, solution confined between these electrodes 4. The resistance offered The resistance show by
is a column of length l and area of cross section A. by metal is also due to an electrolyte solution is
The resistance of such a column of solution is given vibrating kernels. due to factors like inter-
by the equation. ionic attraction etc.
R =rl = l 212. Depict the galvanic cell in which the reaction

A kA
2Zn (s) + 2 Ag+ (aq) " Zn2+ (aq) + 2Ag (s)
takes place, Further show
1. Which of the electrodes is negatively charged?
2. The carriers of the current in the cell.
3. Individual reaction at each electrode.
Ans : OD 2002
The cell will be represented as :

Zn (s) + Zn2+ (aq) ;; Ag+ (aq) ; Ag (s)
1. Anode i.e., zinc electrode will be negatively
charged.
2. The current will flow from silver to Zinc in the
external circuit.
3. At anode :
Two different types of conductivity cells Zn (s) " Zn2+ (aq) + 2e-
The quantity l
is called cell constant denoted by the At cathode :
A
symbol. G * Ag+ (aq) + e- " Ag
213. Suggest a way to determine the Lmo value of water. 217. Give the structure and working of standard hydrogen
Ans : SQP 2004 electrode (SHE).
L mo (H O) = l Ho+ + l OH
o -
Ans : OD 2009
2
Standard hydrogen electrode (SHE) is a reference

We find out L mo (HCl) Lmo (NaOH) and Lmo (NaCl) Then electrode. It is also called normal hydrogen electrode
/mo (H O) = Lmo (HCl) + L mo (NaOH) - Lmo (NaCl)
2
(NHE). It consists of a platinum electrode coated with
platinum black. The electrode is dipped in an acidic
214. What do you mean by Faraday?
solution and pure hydrogen gas is bubbled through it.
Ans : COMP 2006
The concentration of both the reduced and oxidised
We know that charge on one electron is equal to forms of hydrogen is maintained at unity. The pressure
1.6021 # 10-19 C of hydrogen gas is one bar and the concentration of
Therefore, the charge on one mole of electrons is equal hydrogen ion in the solution is one molar. Standard
to : electrode potential is represented by
N A # 1.6021 # 10-19 Pt (s) ; H 2 (g) ; H+ (aq)
C = 6.02 # 1023 mol-1 # 1.6021 # 10-19
C = 96487 C mol-1
For approximate calculation we use IF - 96500 C mol-1 .
This quantity of electricity is called Faraday and is
represented by the symbol F.
For the electrode reaction :
Al3+ (l) + 3e- " Al (s)
One mole of Al3+ required 3 mol of electrons (3F).
215. Explain with one example each the terms weak and
strong electrolytes.
Ans : DELHI 2002
Those electrolytes which dissociate almost completely

in the aqueous solution or in the molten state are 218. Define Primary cells and Secondary cell.
called strong electrolytes e.g., HCl, HNO 3 , H 2 SO 4 Ans : SQP 2015
etc. Those electrolytes which have low degree of Cells in which the reaction occurs only once and then
dissociation and hence conduct electricity to a small it becomes dead after use over period of time and
extent are called weak electrolytes e.g., NH 4 OH, Ca cannot be reused again are called primary cells or
(OH) 2 etc. batteries. For example : dry cell, mercury cell, etc.
216. What is electrolysis? Give the reactions occurring at Cells which can be recharged by passing current
two electrodes during electrolysis of molten sodium through it in opposite direction so that it can be
chloride. used again are called Secondary cells or batteries. For
Ans : FOREIGN 2011, OD 2003 example : lead storage batter, NI-Cd Cell etc.
Electrolysis : The process of decomposition of an 219. Write short note on dry cell.
electrolyte when electric current is passed through Ans : COMP 2003
its aqueous solution or in the molten state is called Dry cell (known as Leclanche cell after its discoverer)
electrolysis. consists of a zinc container that act as anode and
Electrolysis of molten NaCl. the cathode is a carbon (graphite) rod surrounded
NaCl (l) Na+ (l) + Cl-1 (l) by powdered manganese dioxide and carbon. The
space between the electrodes is filled by a moist paste
At cathode : Na+ + e- " Na of ammonium chloride (NH 4 Cl) and zinc chloride
At anode : Cl- - e- " Cl (ZnCl 2).
Cl + Cl " Cl 2 (g) When the cell is working, zinc loses electrons to give
Zn2+ ions. The electrons pass around the external
Overall reaction
circuit and are taken up at the cathode. This causes
Electrolysis
2 Na Cl (l) 2Na (l) + Cl 2 (g) discharge of NH +4 ions.
At cathode At anode
Overall reaction
Zn (Hg) + HgO (s) " ZnO (s) + Hg (l)
The cell potential is approximately 1.35 V
222. What is galvanisation ?

Ans : OD 2004
Electrode reactions :
Galvanisation- Covering of iron surface with a layer of
At anode : Zn (s) " Zn2+ + 2e- zinc is called galvanisation. It is done by electroplating
At cathode : or by dipping the iron article in molten zinc or by
spraying molten zinc cover iron article.
[MnO 2 + NH +4 + e- " MnO (OH) + NH 3] # 2
By covering of iron with zinc, iron can be protected
Zn (s) + 2MnO 2 + 2NH +4 " Zn2+ + 2MnO (OH) + 2NH 3 from rusting.
IN the reaction at cathode, manganese is reduced 223. Write short note on lead storage battery.
from the +4 oxidation state to the +3 state. Ammonia Ans : SQP 2006, DELHI 2003
produced in the reaction forms a complex with Zn2+
Lead storage battery is a secondary cell used in
to give [Zn (NH 3) 4] 2+ .
automobiles and inverters.
The cell has a potential of nearly 1.5 V
It consists of : Cathode : Grid of lead packed with lead
220. Discuss the factors responsible for rusting of iron. dioxide (PbO 2).
Ans : DELHI 2000 Electrolyte : 38% solution of sulphuric acid.
1. Air and moisture : These are responsible for A 12 V lead storage battery is generally used which
rusting of iron. consists of 6 cells each producing 2 V. Cell reactions
2. Presence of Impurities : Impurities in general, (During discharging).
increase the rate of corrosion.
Anode : Pb (s) + SO 24- (aq) " PbSO 4 (s) + 2e-
3. Presence of electrolyte in water : Rate of corrosion
is more in saline water. Cathode : PbO 2 (s) + SO 24- (aq) + 4H+ (aq) + 2e-
4. Strain : Strain in metal increases the rate of " PbSO 4 (s) + 2H 2 O (l)
corrosion.
Pb (s) + PbO 2 (s) + 2H 2 SO 4 (aq)" PbSO 4 (s) + 2H 2 O (l)
221. Give the electrode reaction of mercury cell. Give its
uses.
Ans : FOREIGN 2001
Mercury cell suitable for low current devices like

hearing acids, watches etc.
It consist of :
Anode : Zinc-mercury amalgam
Cathode : Paste of HgO and Carbon
Electrolyte : A paste of KOH and ZnO
Electrode reactions :
Anode Zn (Hg) + 2OH- " ZnO (s) + H 2 O + 2e-
HgO (s) + H 2 O + 2e- " Hg (l) + 2OH-
Lead storage battery of 6 volts
On charging the battery the reaction is reversed and 229. Write the cell reaction taking place in the cell.
PbSO 4 (s) on anode and cathode is converted in Pb Cu (s) ; Cu (+aq2 ) < Ag (+aq) ; Ag (s)
and PbO 2 respectively. Ans : COMP 2007
224. Define corrosion. What is the chemical formula of Given cell is
rust. Cu (s) ; Cu (+aq2) < Ag (+aq) ; Ag (s)
Ans : COMP 2001
Cu " Cu+2 + 2e- (Oxidation)
Corrosion is a process of deterioration of a metal as a
+ -
result of its reaction with air and water (environment) 2Ag + 2e " 2 Ag (Reduction)
surrounding it. It is due to the formation of compounds
230. What is standard hydrogen electrode ?
such as sulphides, oxides, carbonates, hydroxides etc.
Ans : DELHI 2012
Example : Rusting of iron
The electrode whose potential is known as standard
Rust is hydrated ferric oxide Fe 2 O 3 .xH 2 O
electrode (or) standard hydrogen electrode.
225. What is a galvanic cell or a voltaic cell? Give one To determine the potential of a single electrode
example. experimentally it combine with standard hydrogen
Ans : DELHI 2007 electrode and the EMF of cell so constructed is
Galvanic cell : A device which converts chemical measured with potentiometer.
energy into electrical energy by the use of spontaneous 231. Give a neat sketch of standard hydrogen electrode.
redox reaction is called Galvanic cell (or) voltaic cell.
Eg. : Daniel cell.
226. Write the chemical reaction used in the construction
of the Daniel cell together with the half-cell reactions.
Ans : FOREIGN 2003
The chemical reactions used in the construction of the

Daniel cell.
Zn $ Zn+2 + 2e- (Oxidation)

Cu+2 + 2e- $ Cu (Reduction)
Overall reaction Zn + Cu+2 $ Zn+2 + Cu
227. Name the two half-cell reactions that are taking place
in the Daniel cell.
Ans : OD 2010
The two half cell reactions that are takes place in the
Daniel cell are oxidation and reduction. 232. What is Nernst equation ? Write the equation
Zn $ Zn+2 + 2e- (Oxidation) for an electrode with electrode reaction
Cu+2 $ Cu (Reduction) M n+ (aq) + ne- M (s).
Ans : OD 2009
228. How is a galvanic cell represented on paper as per
IUPAC convention? Give one example. The electrode potential at any concentration measure
with respect to standard hydrogen electrode is
Ans : SQP 2001
represented by Nernst equation.
Representation of a Galvanic cell :
Nernst equation is
As per IUPAC convention
" Oxidation half cell represented on the left side. E = E o + RT ln [M n+] [Metal Electrodes]
nF
" Reduction half cell represented on the right side.
Given electrode reaction is M (naq+) + ne- M (s)
" Oxidation half cell and reduction half cell are
For the above electrode reaction Nernst equation is
connected by a salt bridge indicated by two vertical
parallel lines. E(M /M) = E (oM /M) + RT ln [M n+]
n+ n+
nF
Eg. : Cu (s) ; Cu (+aq2 ) < Ag (+aq) ; Ag (s)
Here, E(M n+
/M) = Electrode potential
Eo(M n+
/M) = Standard Electrode potential
R = gas constant = 8.314 J/k . mole 237. Define molar conductivity /m and how is it related to
conductivity (k) ?
F = Faraday = 96487 c/mole
Ans : OD 2003
T = temperature
Molar conductivity : The conductivity of a volume
[M ] = concentration of species M n+
n+
of solution containing one gram molecular weight of
the electrolyte placed between two parallel electrodes
233. Write the cell reaction for which separated by a distance of unit length of 1 meter is
[Mg2+] called molar conductivity (Lm)
0
E cell = E cell - RT ln
2F [Ag+] 2 Relation between conductivity and molar conductivity:
Ans :
Lm = k
SQP 2014
2+
[Mg ] c
Given 0
E cell = E cell - RT ln Hence, c = constant
2F [Ag+] 2
+
The cell reaction is Mg (s) /Mg (2aq +
) < Ag (aq) ; Ag (s)
238. Give the mathematical equation which gives the
variation of molar conductivity with Lm the molarity
Mg $ Mg2+ + 2e- (Oxidation) (c) of the solution?
2Ag+ + 2e- $ Ag (Reduction) Ans : SQP 2011
+ +2
Mg + 2Ag $ Mg + Ag The mathematical equation which gives the variation
of molar conductivity
234. How is E0 cell related mathematically to the Lm with the molarity (c) of the solution is
equilibrium constant Kc of the cell reaction ?
Lm = k
Ans : COMP 2002
1000 (lit/cm3) # molarity (moles/lit)
Relation between E0 cell and equilibrium constant KC k # 1000 (cm3 /lit)
of the cell reaction =
molarity (mole/lit)
0
E cell = 2.303RT log KC 239. State Kohlrausch’s law of independent migration of
nF
ions.
n = Faraday = 96500 C mol-1
T = Temperature Kohlrausch’s law of independent migration of ions
R = gas constant . The limiting molar conductivity of an electrolytes
can be represented as the sum of the individual
235. How is Gibbs energy (G) related to the cell emf (E) contributions of the anion and the cation of the
mathematically? electrolytes.
Ans : DELHI 2006
l m0 (AB) = l A0 + l B0
+ -
Relation between Gibb’s energy (G) and emf (E) 0

mathematically l m = Limiting molar conductivity of cation.
0
0
TG = nFE(cell) l B = Limiting molar conductivity of anion.
TG = change in Gibb’s energy 240. State Faraday’s first law of electrolysis.
n = number of electrons involved Ans : DELHI 2001
The amount of chemical reaction which occurs at any

F = Faraday = 96500 C mol-1 electrode during electrolysis is proportional to the
236. What is cell constant of a conductivity cell ? quantity of current passing through the electrolyte.
Ans : FOREIGN 2001 or
Cell constant : The mass of the substance deposited at an electrode
during the electrolysis of electrolyte is directly
Resistance R = r. l = l proportional to quantity of electricity passed through
A k.A
1 = cell constant it.
A m \ Q m \ c#t
Cell constant G * = l = R # k m = Ect ; m = Ect
A 96, 500
The cell constant of a conductivity cell is the product
e = electrochemical equivalent
of resistance and specific conductance.
c = current in amperes 246. What is a fuel cell? How is it different from a

conventional galvanic cell?
t = times in seconds
E = Chemical equivalent
A fuel cell is a galvanic cell in which the chemical
241. What are the products obtained at the platinum energy of fuel oxidant system is converted directly
anode and the platinum cathode respectively in the into electrical energy.
electrolysis of fused or molten NaCl ? 1. Conventional Galvanic cell converts chemical
Ans : FOREIGN 2009 energy into electrical energy by spontaneous
In the electrolysis of fused (or) molten NaCl with redox reactions.
platinum anode and platinum cathode, sodium metal 2. Fuel cell convert energy of combustion of fuels
obtained at cathode and chlorine gas at anode. like hydrogen, methane etc., into electrical energy.
These cause less polution.
2 NaCl $ 2 Na+ + 2 Cl-
247. Give the chemical equation that represents the
2Cl- $ Cl 2 + 2e- (anode) reduction of liquid water H 2 O (l) at the platinum
2Na+ + 2e- $ 2 Na (cathode) cathode.
Ans : OD 2002
242. Give the products obtained at the platinum electrodes
(cathode and anode) when aqueous solution of K 2 SO 4 The chemical equation that represents the reduction
is electrolysed. of liquid water H 2 O (l) at the platinum cathode is
Ans : OD 2007 H 2 O (l) + e- $ 12 H 2 + OH-
(g)
During the electrolysis of aq. K 2 SO 4 using pt-anode

248. Give the electrode reactions occurring at the anode
and pt-cathode hydrogen gas liberated at cathode and
and at the cathode in H 2 , O 2 , fuel cell.
oxygen gas at anode.
Ans : SQP 2006
K 2 SO 4 $ 2K+ + SO -4 2
At cathode : O 2 (g) + 2H 2 O (l) + 4e- $ 4OH (-aq)
+4e- -
4H 2 O 2H 2 + 4 OH (cathode)
At anode : 2H 2 (g) + 4OH (-aq) $ 4H 2 O (l) + 4e-
-
-4e +
2H 2 O O 2 + 4H (anode) Overall reaction : 2H 2 (g) + O 2 (g) $ 2H 2 O (l)
243. Write the chemical equation corresponding to the 249. Write the Nernst equation for the EMF of the cell
oxidation of H 2 O (l) at the platinum anode. + 2+
Ni (s) ; Ni (2aq) < Ag (aq) ; Ag
Ans : SQP 2002
Ans : COMP 2000
The chemical equation corresponding to the oxidation + 2+
of H 2 O (l) at the platinum anode is Given cell is Ni (s) ; Ni (2aq) < Ag (aq) ; Ag
Nernst equation for the cell is

2H 2 O (l) $ O 2 + 4H+(aq) + 4e-
(g)
[Ag+]
244. Give one example for a secondary battery. Give the
0
E cell = E cell + RT ln
nF [Ni] +2
cell reaction.
250. What is metallic corrosion? Give one example.
Ans : COMP 2018
Ans : DELHI 2007
Lead storage batter is an example of secondary
battery. The natural tendency of conversion of a metal into
its mineral compound form on interaction with the
The cell reactions when the battery is in use are
environment is known as metallic corrosion. Eg. :
Pb (s) + SO -4 (2aq) $ PbSO 4 (s) + 2e- (Anode) 1. Iron converts itself into its oxide
PbO 2 (s) + SO -2
4 (aq) $ 4H +
(aq) + 2e $ PbSO 4 (s) + 2H 2 O (l) ^Cathodeh
-
[Rusting] (Fe 2 O 3)
Over all reaction is 2. Silver converts itself into it’s sulphate
[tarnishing] (Ag 2 S)
Pb (s) + PbO 2 (s) + 2H 2 SO 4 (aq) $ 2PbSO 4 (s) + 2H 2 O (l)
251. How is molar conductivity of an aqueous electrolyte
245. Give the cell reaction of nickel-cadmium secondary solution measured experimentally?
battery.
Ans : FOREIGN 2019
Ans : DELHI 2005
The conductivity of a volume of solution containing
The reaction of nickel cadmium secondary batter is one gram molecular weight of the electrolyte placed
Cd (s) + 2Ni (OH) 3 (s) " CdO (s) + 2Ni (OH) 2 (s) + H 2 O (l) between two parallel electrodes separated by a
distance of unit length of 1 meter is called molar 253. What is electrolysis? Give Faradays’s first law of
conductivity (Lm). electrolysis.
Relation between conductivity and molar conductivity: Ans : SQP 2000
Lm = k ; Hence c = constant
The decomposition of a chemical compound in the
c molten state or in the solution state into its constituent
1. The conductance of a solution measured in a elements under the influence of an applied EMF is
conductivity cell. called electrolysis.
2. By using the conductivity cells The amount of chemical reaction which occurs at any
electrode during electrolysis is proportional to the
Resistance (R) = l
k#A quantity of current passing through the electrolyte.
l = distance between electrodes ; or
A = Area of cross section The mass of the substance deposited at an electrode
during the electrolysis of electrolyte is directly
k = conductivity proportional to quantity of electricity passed through it.
G * = l = cell constant m \ Q; m \ c # t
A
3. Cell constant is measured by measuring the m = etc.; m = Ect
96, 500
resistance of the cell containing a solution whose
e = electrochemical equivalent
conductivity is known.
4. Cell constant determined is used for measuring c = Current in amperes
the resistance (or) conductivity. t = time in second
Hence, Molar conductivity
E = Chemical equivalent
k (Scm-1)
L(m) = -3 254. What are the products obtained at the cathode and
1000 (L.m ) molarity (moles/lit)
anode during the electrolysis of the following when
252. What is metallic corrosion ? Explain it with respect platinum electrodes are used in the electrolysis
to iron corrosion. (a) Molten KCl
Ans : OD 2019, SQP 2011
(b) Aq. CuSO 4 solution
Metallic corrosion : The natural tendency of (c) Aq. K 2 SO 4 solution
conversion of a metal into its mineral compound form
Ans : COMP 2003
on interaction with the environment is known as
(a) During the electrolysis of molten KCl using
metallic corrosion.
platinum electrodes. Potassium is obtained at
eg. : cathode and chlorine at anode.
(1) Iron converts itself into its oxide [Rusting] (Fe 2 O 3)
2 KCl $ 2K+ + 2Cl-
(2) Silver converts itself into it’s sulphate [tarnishing]
[Ag 2 S] 2 Cl- $ Cl 2 + 2e- (anode)
Rusting of iron : Iron converts it self into its oxide 2K+ + 2e- $ 2K (cathode)
Fe 2 O 3
(b) During the electrolysis of aq. CuSO 4 solution
The electrochemical reaction that represents the using platinum electrodes, O 2 gas liberated at
corrosion or rusting of iron is anode and Cu deposited at cathode.
Anode : 2Fe (s) $ 2Fe2+ + 4e- 2 CuSO 4 $ 2 Cu+2 + 2 SO -4 2
0
E (Fe2+ /Fe) = - 0.44 V 2 Cu+2 + 4e- $ 2 Cu (cathode)
Cathode : 2 H 2 O - 4e- $ O 2 + 4H+ (anode)
O 2 + 4H (+aq) + 4e- $ 2H 2 O (l)
(g) During the electrolysis of aq. K 2 SO 4 using pt-
anode and pt-cathode hydrogen gas liberated at
E HQ /O /H O = 1.23 V
-
2 2
cathode and oxygen gas at anode.
Overall reaction :
K 2 SO 4 $ 2K+ + SO -4 2
+ +2
2 Fe (s) + O 2 + 4H
(g) (aq) $ 2 Fe aq + 2H 2 O (l) +4e-
Q
4 H2O 2 H 2 + 4 OH- (cathode)
E (cell) = 1.67 V
-4e-
2H 2 O O 2 + 4H+ (anode)
255. What are the fuel cells? How are they different from 257. Explain the variation of molar conductivity with the
galvanic cells? Give the construction of H 2 , O 2 fuel change in the concentration of the electrolyte. Give
cell? reasons.
Ans : DELHI 2007 Ans : OD 2015, FOREIGN 2008
A fuel cell is a galvanic cell in which the chemical Molar conductivity of a solution at a given
energy of fuel-oxidant system is converted directly concentration is the conductance of the volume of
into electrical energy. solution containing one mole of electrolyte kept
1. Conventional Galvanic cell converts chemical between two electrodes with area of cross section A
energy into electrical energy by spontaneous and distance of unit length.
redox reactions.
2. Fuel cell convert energy of combustion of fuels Molar conductivity Lm = kA
l
like hydrogen, methane etc., into electrical energy. Lm = k # V (Since, l = 1, A = V )
These cause less pollution.
H 2 - O 2 fuel cell : In this cell, hydrogen and V = Volume containing 1 mole of electrolyte
oxygen are bubbled through porous carbon Molar conductivity increase with decrease in
electrodes into Conc. NaOH solution. Electrodes concentration of electrolyte (or) increase in dilution.
are embedded with suitable catalysts. The This is due to total volume V of solution containing
electrode reactions are : one mole of electrolyte also increases.
+4e-
O 2 + 2H 2 O (l)
(g)
4OH (-aq) (Cathode)
2H 2 + 4OH (-aq) $ 4H 2 O (l) + 4e- (Anode)
(g)
Overall reaction :
2H 2 + O 2 $ 2H 2 O (l)
(g) (g)
256. Write short note on nickel-cadmium cell.

Ans : FOREIGN 2005
Nickel-cadmium cell or Nicad cell is a rechargable cell

which is becoming more and more popular especially
in the calculators. It consists :
Anode : Cadmium
Cathode : A metal grid containing nickel (IV) oxide When concentration approaches to zero, the molar
conductivity is known as limiting molar conductivity
Electrolyte : KOH solution
and its is represented by Lom
The overall cell reaction (during discharging)
For strong electrolytes molar conductivity is given by
Cd (s) + 2Ni (OH) 3 (s) " CdO (s) + 2Ni (OH) 2 + H 2 O (l)
Lm = Lom - Ac1/2
The cell potential is approximately 1.4 V.
For weak electrolytes limiting molar conductivity is
given by
l AB = l A + l B (Kohlrausch law)
+ + -
258. What is the difference between ferromagnetism and

paramagnetism?
Ans : DELHI 2011
Paramagnetism refers to materials like aluminium,

which become magnetized in a magnetic field but
their magnetism disappears when the field is removed.
Example- O 2 , Cu2+ , Fe2+ , Cr3+ etc.
Ferromagnetism refers to materials (such as iron and
nickel) that can retain their magnetic properties when
the magnetic field is removed.
Example- Iron, Cobalt, Nickel etc.
259. For the cell shown below : 261. What is electrochemical series? Write its applications.
Zn (s) | ZnSO 4 (aq) | | CuSO 4 (aq) | Cu (s) Ans : COMP 2007
Calculate standard cell potential if standard state The standard electrode potential of various electrodes
reduction electrode potential for are given in the decreasing order of their reducing
strength in a series called electromotive force series or
Cu2+ | Cu and Zn2+ | Zn are + 0.34 V and - 0.76 V
electrochemical series.
respectively.
Applications of Electrochemical Series :
Ans : DELHI 2011
The Applications of Electrochemical series are as
Zn ; ZnSO 4 (aq) < CuSO 4 (aq) ; Cu (s)
The cell reaction- follows :
At anode : Oxidation 1. Calculation of standard EMF of the cell- Standard
EMF of cell can be calculated as follows :
Zn (s) $ Zn2+ (aq) + 2e-1
EMF = E Cathode
c
- E cAnode
Eo, Zn (s) | Zn2+ (aq) = + 0.34 V
Ec cathode and Ec Anode can be found out from
At cathode- Reduction
the electrochemical series.
Cu2+ (aq) + 2e- $ Cu (s) 2. Comparison of the reactivity of metals : A metal
o 2+
E Cu (aq) | Cu (s) = 0.34 V occupying lower position in the series can displace
According to formula, the metal lying above it from the solutions of their
salts. It is due to the fact that an element with
E oCell = EoCathode - E oanode
higher reduction potential is easier to reduce.
= 0.34 - (- 0.76) 3. Predicting the feasibility of a redox reaction : If
= 0.34 + 0.76 EMF of the hypothetical cell calculated comes
out to be positive the redox reaction is feasible.
o
E Cell = 1.10 V 4. To predict whether a metal reacts with dilute
acid to give H 2 gas or not : A metal which lies
below hydrogen in the electrochemical series can
LONG ANSWER QUESTIONS form positive ions more readily than hydrogen.
Therefore, such a metal can displace hydrogen
260. How would you determine the standard electrode from dilute acid.
potential of Mg2+ ; Mg ? For example :
Ans : SQP 2004 Zn + 2H+ $ Zn2+ + H 2
We will set up a cell consisting of Mg ; MgSO 4 (1M) Metals like Cu, Ag etc. which lies above hydrogen
as one electrode (by dipping a magnesium plate in 1 can not liberate H 2 from dilute acids.
M MgSO 4 solution) and standard hydrogen electrode 262. Explain Nernst equation.
Pt, H 2 (1 atm); H+ (1M) as the second electrode and
Ans : FOREIGN 2013, SQP 2003
measure the EMF of the cell. Note the direction of
deflections which shows that electrode flow from If the electrolyte concentration is different from 1 M
magnesium electrode to hydrogen electrode i.e., and temperature is different from 298 K the electrode
oxidation takes place on magnesium electrode and potential has a different value. This value is obtained
reduction on hydrogen electrode. using Nernst equation. Nernst established a relation
between the electrode potential and concentration of
Hence, the cell may be represented as follows :
ions in solution.
Mg ; Mg2+ (1M) ; H+ (1M) ; H 2 (1 atm) Pt
For the reaction :
o
E cell = E Ho , + 1
H2 - E cMg 2+
Mg
2
M n+ (aq) + ne- " M (s)
o
Put E H+, 12 H 2 =O [M]
E = Ec - 2.303 RT log n+
Hence, E o
Mg2+, Mg
o
= - E cell nF [M ]
The electrode potential of an electrode is given a Here, E is reduction potential Ec is standard reduction
negative sign if oxidation takes place at this electrode potential, R is gas constant (8.314 JK-1 Mol-1 ). T is
when connected to hydrogen electrode. The standard temperature on Kelvin scale, F is one Faraday (96500
electrode potential of an electrode is given a positive sign Coulombs) and [M n+] is molar concentration of ions in
if reduction takes place at this electrode when connected solution. Since molar concentration of solids, liquids
with standard hydrogen electrode to form the cell. or a gas at one atmosphere is taken as unity.
Thus, [M ] = 1 Equivalent conductivity

[1] = Specific conductivity # V
E = Ec - 2.303 RT log n+
nF [M ] Leq = k # V
Substituting value of R (8.314 JK-1 mol-1), T (298 K) If the solution has a concentration of c gram
and F (96500 C), we get equivalent per litre then the volume of the solution
containing one gram equivalent will be 1000
E = Ec - 0.0591 log 1n+ c
n [M ] 1000
i.e., V =
c
Thus reduction potential of an electrode is directly
proportional to the concentration of its ions in Leq = k # 1000
ceq
solution.
263. Define the following : = k # 1000
Normality
1. Resistance Units : ohm-1 cm2 (g) (eq) -1 or W-1 cm2 eq-1
2. Conductance
or S cm2 eq-1 or Sm2 eq-1 in SI units
3. Conductivity
5. Molar Conductivity : Molar conductivity is the
4. Equivalent conductivity conductivity of all the ions produced by dissolving
5. Molar conductivity one gram mole of an electrolyte in solution.
Ans : OD 2017 It is denoted by Lm .
1. Resistance (R)- Resistance (R) is the obstruction
Lm = k # V or Lm = k # 1000
to the ^R = EI h flow of electric current through C
the conductor. It is directly proportional to its 1000
= k#
length (l) and inversely proportional to its area of Molarity
cross section (A). Units : ohm-1 cm2 mol-1 or S cm2 mol-1 .
R a l or R = r l or W-1 cm2 mol-1 or S m2 mol-1 in SI units.
A A
The constant of proportionality r (rho) is called 264. State and explain Kohlrausch law.
specific resistance or resistivity. Resistance is Ans : SQP 2008
measured is measured in Ohm (W), which is terms Kohlrausch law of independent migration of ions :
of SI base units is equal to (kg m2 /S3 A2 ). SI units Limiting molar conductivity of an electrolyte is the
of resistivity is ohm metre (W m). sum of the individual contributions of the anion
2. Conductance : The inverse of resistance, R is and cation of the electrolyte. If an electrolyte on
called conductance, G dissociation gives v+ cations and v- anions then its
G = 1 = A = kA limiting molar conductivity is given by :
R rl l
The SI unit of conductance is siemens, represented /mo = v+ l +o + v_ l _o
by the symbol S and is equal to ohm- (or mho) Here,
or W- . l +o = Limiting molar conductivities of cations
3. Conductivity : The inverse of resistivity is called
conductivity (specific conductance) is represented l -o = Limiting molar conductivities of anions
by symbol k (Greek kappa). Unit = ohm-1 cm-1 For example : If l Nao
+ and l Cl
o -
are limiting molar
The SI units of conductivity are Sm-1 . conductivities of the sodium and chloride ions
respectively, then the limiting conductivity for sodium
G = k A when A = 1 m2 , 1 = 1 m
l chloride is given by the equation :
G =k o
/ mo (NaCl) = / Na
+
o
+ / Cl -
Conductivity of a material is its conductance Application of Kohlrausch law

when it is 1 m long and its area of cross section
1. Calculation of Limiting molar conductivity
is 1 m2 .
of weak electrolytes : It is not possible to find
4. Equivalent Conductivity : Equivalent conductivity /mo for a weak electrolyte like CH 3 COOH by
is the conductivity of all the ions produced by extrapolation, we can find it as following using
dissolving one gram-equivalent of an electrolyte in Kohlrausch’s law.
its aqueous solution. It is denoted by Leq (Greek /mo (CH COOH) = l mo (CH 3 COO-) + l mo (H+)
3
lambda)
This equation can be arrived at by knowing the 2. Electrolysis of aqueous solution of AgNO 3 with
molar conductivities at infinite dilution for the platinum electrodes :
strong electrolytes KCl, CH 3 COOK and HCl. At cathode : Ag+ + e - " Ag (s)
o o o
/ m (KCl) =l K+ +l Cl -
At anode : Out of OH- and NO -3 ions. OH- ions have
o - o
/ m (CH 3 COOH) = lcCH 3 COO + l , k+ lower discharge potential.
L om (HCl) = l oH + l oCl
+ - Hence OH- ions will be discharged in preference to
NO -3 ions, which then decompose to give out O 2
Hence, we have
OH- (aq) " OH + e-
l o
CH 3 COO- + l oH = ^l oCH COO + l ok h + ^l oH + l oCl h - ^l ok + l oCl h
+
3
- + + - + -
4OH " 2H 2 O (l) + O 2 (g)

i.e., L om (CH COOH) = Lom (CH COOK) + Lom (HCl) - Lom (KCl)
3. A dilute aqueous solution of H 2 SO 4 with platinum
3 3
2. Calculation of the Degree of Dissociation : electrodes:

Degree of dissociation
c
H 2 SO 4 (aq) " 2H+ (aq) + SO 24- (aq)
(a) = L om H 2 O ? H+ + OH-
Lm
Here, L cm = Molar conductivity of a solution at At Cathode : H + + e- " H
any concentration c H + H " H 2 (g)
L om = Limiting molar conductivity At Anode : OH- " OH + e-
or 4OH " 2H 2 O + O 2 (g)
Molar conductivity at infinite dilution Thus, H 2 is liberated at the cathode and O 2 at
3. Calculation of dissociation constant of a weak the anode.
electrolyte : 4. Electrolysis of aqueous solution of CuCl 2 with
2 platinum electrodes :
Dissociation constant (K C) = ca
1-a CuCl 2 (S) + aq " Cu2+ (aq) + 2Cl- (aq)
c = Concentration H 2 O ? H+ + OH-
a = Degree of dissociation At cathode : Cu2+ ions will be reduced in preference
265. Predict the products of electrolysis of the following : to H+ ions
1. An aqueous solution of AgNO 3 with silver Cu2+ + 2e- " Cu
electrodes
At anode : Cl- ions will be oxidised in preference to
2. An aqueous solution of AgNO 3 with platinum OH- ions
electrodes
Cl- " Cl + e-
3. An dilute aqueous solution of H 2 SO 4 with
platinum electrodes Cl + Cl " Cl 2 (g)
4. An aqueous solution of CuCl 2 with platinum Thus, Cu will be deposited on the cathode and Cl 2
electrodes. will be liberated at the anode.
o o
(Given E Ag /Ag ) = + 0.80 V , E Cu /Cu = + 0.34 V )
+ 2+
266. Give the reactions occurring at two electrodes during
Ans : COMP 2012, OD 2007
electrolysis of aqueous sodium chloride solution.
1. Electrolysis of aqueous solution of AgNO 3 with Ans : DELHI 2016
silver electrodes :
During the electrolysis of aqueous sodium chloride
AgNO 3 (s) + aq " Ag (+aq) + NO -3 (aq) solution, the products are NaOH, Cl 2 and H 2 . In this
H 2 O ? H+ + OH- case besides Na+ and Cl- ions we also have H+ and
At cathode : Ag+ ions have lower discharge potential OH- ions along with the solvent molecules H 2 O .
that H+ ions. Hence Ag+ ions will be deposited. At the cathode there is competition between the
Ag+ + e- " Ag (s) following reduction reactions :
At Anode : As Ag anode is attacked by NO -3 ions. Na+ (aq) + e- " Na (aq)
Ag of the anode will dissolve to form Ag+ ions in the E ccell = - 2.71 V
solution
H+ (aq) + e- " 1 H 2 (g)
Ag " Ag+ + e- 2
o
E cell = 0.00 V Construction and working : Hydrogen and oxygen
The reaction with higher value of Ec is preferred are bubbled through porous carbon electrodes into
and therefore, the reaction at the cathode during concentrated aqueous sodium hydroxide solution.
electrolysis is : Catalyst like finely divided platinum or palladium
metal are incorporated into the electrodes for
H+ (aq) + e- " 1 H 2 (g) ....(1) increasing the rate of electrode reactions. The
2
But H+ (aq) is produced by the dissociation of H 2 O electrode reactions are :
i.e., Anode : 2H 2 (g) + 4OH- (aq) " 4H 2 O (l) + 4e-
H 2 O (l) " H+ (aq) + OH- (aq) ....(2) Cathode : O 2 + 2H 2 O + 4e- " 4OH- (aq)
Therefore the net reaction at the cathode may be Overall reaction :
written as the sum of (1) and (2) and we have 2H 2 (g) + O 2 (g) " 2H 2 O (l)
H 2 O (l) + e- " 1 H 2 (g) + OH- ....(3) Advantage of fuel cells :
2
Advantage of fuel cells are as follows:
At the anode the following oxidation reaction are
possible : 1. The fuel runs continuously as long as the reactants
are supplied.
Cl- (aq) " 1 Cl 2 (g) + e- 2. Fuel cells produced electricity with an efficiency
2
o of about 70% compared to thermal plants whose
E cell = 1.36 V ....(4)
efficiency is about 40%.
+ -
2H 2 O (l) " O 2 (g) + 4H (aq) + 4e 3. Fuel cells are pollution free.
o
E cell = 1.23 V ....(5)
The reaction at anode with lower value of Ec is
preferred and therefore, water should get oxidised
in preference to Cl- (aq). However on account of
overpotential of oxygen reaction (iv) is preferred.
Thus, the net reaction may be summarised as :
H2O
NaCl (aq) Na+ (aq) + Cl- (aq)
Cathode : H 2 O (l) + e- " 1 H 2 (g) + OH- (aq)

2
Anode : Cl- (aq) " 1 Cl 2 (g) + e-
2
Net reaction :
NaCl (aq) + H 2 O (l) " Na+ (aq) + OH- (aq) + 1 H 2 (g) + 1 Cl 2 (g)
2 2 268. Explain how rusting of iron is envisaged as setting of
an electrochemical cell.
267. What are fuel cells? Discuss H 2 - O 2 fuel cell. List or
some advantages of fuel cells over other cells?
Discuss the electrochemical theory of corrosion.
or
Ans : OD 2000
Explain a fuel cell with two characteristics.
Corrosion (rusting of iron) is an electrochemical
phenomenon.
Fuel Cell : Galvanic cells that are designed to convert At a particular spot of an object made of iron oxidation
the energy of combustion of fuels like hydrogen, takes place and that spot behaves as anode
methane, methanol etc. directly into electrical energy
are called fuel cells. Anode : 2Fe (s)" 2Fe2+ + 4e- (E Fe
o
2+
/Fe = - 0.44 V)
H 2 - O 2 fuel Cell : It is one of the most successful fuel Electron released at anodic spot move through the
cells uses the reaction of hydrogen and oxygen to form metal and go to another spot on the metal and reduce
water. The cell was used for providing electrical power oxygen in presence of H+ (Which is believed to be
in the Apollo space programme. The water vapour available from H 2 CO 3 formed due to dissolution of
produced during the reaction were condensed and carbon dioxide from air into water.) This spot behaves
added to the drinking water supply for the astronauts. as cathode with the reaction.
Cathode : Magnesium is oftenly employed in the cathodic

O 2 (g) + 4H (aq) + 4e " 2H 2 O (l) Ê
+ - o
= 1.23 Vh
protection of iron pipes buried in the moist soil
H + /O 2 /H 2 O
etc.
The overall reaction :
2Fe (s) + O 2 (g) + 4H+ (aq) " 2Fe2+ (aq) + 2H 2 O (l)
o
E cell = 1.67 V
The Ferrous ions are further oxidised by atmospheric
oxygen to ferric ions which come out as rust in the
form of hydrated ferric oxide Fe 2 O 3 . xH 2 O and with
further production of hydrogen gas.
270. What is the function of salt bridge in an electrochemical

cell?
Ans : COMP 2006, OD 2001
Some important functions of a salt bridge are
described below.
Oxidation : Fe (s) " Fe2+ (aq) + 2e- 1. A salt bridge acts as an electrical contact between
Reduction : the two half-cells. When in a galvanic cell two
O 2 (g) + 4H+ (aq) + 4e- " 2H 2 O (l) solutions are kept in separate containers, an
electrical contact between the two is needed to
Atmospheric oxidation : complete the circuit. A salt bridge completes the
2Fe2+ (aq) + 2H 2 O (l) + 12 O 2 (g)" Fe 2 O 3 (s) + 4H+ (aq) circuit by allowing the migration of anions from
the cathodic half-cell into the salt bridge and
269. Give three methods to protect iron from rusting. from the salt bridge into the anodic half-cell.
Ans : SQP 2018
2. A salt bridge prevents the transference/diffusion of
1. Barrier Protection : The metal surface is not the electrolytes from one half-cell to the other. The
allowed to come in contact with moisture, oxygen agar-agar gel does not allow any physical transfer
and carbon dioxide. This can be achieved by the of electrolyte from one half-cell to another.
following methods : 3. A salt bridge helps in maintaining the charge
(i) By painting the surface of the metal. balance in the two half-cells. A salt bridge helps
(ii) By coating the metal surface with a thin film in maintaining the charge balance in the two half-
of oil or grease. cells by releasing counter ions into the solution as
(iii) By coating metal with some non-corroding shown in Figure.
metal such as nickel, chromium, aluminium,
zinc, tin, etc.
2. Sacrificial protection : In this iron surface is
covered with a layer of metal which is more active
(electropositive) than iron and thus prevents the
iron from losing electrons. The metal which is
most often used for covering iron is zinc and the
process is called galvanisation.
3. Electrical Protection : Cathodic Protection : The 4. A salt bridge minimises/eliminates the liquid
iron object is connected to a more active metal junction potential. A direct liquid-liquid junction
either directly or through a wire. The iron object is thermodynamically unstable state. The unequal
acts as cathode and the protecting metal acts as rates of migration of the cations and anions across
anode. The anode is gradually used up due to a liquid-liquid junction gives rise to a potential
oxidation of the metal to its ions due to loss of difference across the junction. This potential
electrons. These electrons are transferred through difference across the liquid-liquid junction is called
the wire to H+ ions present around the iron object liquid junction potential. A salt bridge eliminates
and thus protect if from rusting. As iron object a direct contact between the two solutions, and
acts as cathode, it is called cathodic protection. thus minimises the liquid junction potential.
271. Write and Explain Faraday’s second law of Electrolysis. Z1 It = E1

Ans : DELHI 2010
Z2 It E2
Faraday’s second law of electrolysis can be stated as Z1 = E1
Z2 E2
follows:
When the same quantity of electricity is passed through E \Z
the solutions of different electrolytes connected in E = F#Z ...(3)
series, the masses of the substances liberated (or Here, F is a constant known as Faraday’s constant.
deposited) at the electrodes are directly proportional One Faraday (1 F ) is the charge carried by one mole
to their equivalent masses. of electrons.
Suppose three voltameters connected in series
Thus, F = NA e- ...(4)
contain aqueous solutions of silver nitrate, copper
sulphate and dilute sulphuric acid respectively The value of Faraday’s constant is 96500 coulombs.
as shown in Figure. On passing electric current, From Eq. (3), we have
electrolysis takes place in all the three cells and the
Z =E ...(5)
substances produced at the cathodes of these cells F
are Ag (s), Cu (s) and H 2 (g) respectively. If the same i.e., Electrochemical equivalent
current is passed for the same time, it is found that, Equivalent mass
=
Mass of silver deposited Equivalent mass of silver Faraday's constant
=
Mass of copper deposited Equivalent mass of copper Equivalent mass
= g $ C-1
and 96500
Mass of hydrogen gas liberated Equivalent mass of hydrogen
=
Eq. (5) helps us to calculate the electrochemical
Mass of silver deposited Equivalent mass of silver equivalent of a substance. It is generally expressed in
the units of g $ C-1 .
272. Write the chemistry of recharging the lead storage
battery, highlighting all the material that are involved
during recharging.
Ans : FOREIGN 2004
Chemical Changes During Recharging : Consider

a discharged lead-acid cell having both the plates
converted to lead sulphate (PbSO 4). In order to
recharge the cell, direct current is passed through the
cell in the reverse direction to that in which the cell
Voltameters Containing Aqueous Solutions of
provided current. To do so, the anode is connected
AgNO 3 , CuSO 4 and Dilute H 2 SO 4 and Connected to the positive terminal of the dc source and cathode
in Series
to the negative terminal of the source as shown in
Figure. The electrolyte (H 2 SO 4) splits into hydrogen
These results are in accordance to the above statement
ions (2H+) and sulphate ions (SO -- 4 ) . Hydrogen ions
and thus verify the second law of electrolysis.
move towards cathode and sulphate ions move towards
If W1 and W2 are the masses of the substances anode causing the following chemical reactions:
liberated by passing the same quantity of electricity
At anode
and E1 and E2 are their equivalent masses respectively,
then according to the Faraday’s second law of SO --
4 - 2e
-
$ SO 4 (Radical)
electrolysis, SO 4 + H 2 O $ H 2 SO 4 + O
W1 = E1 ...(2) The oxygen in the atomic state (i.e., O) is very active
W2 E2
and reacts chemically with anode material (PbSO 4) to
If Z1 and Z2 respectively are the electrochemical produce the following chemical change:
equivalents of the two substances and I is the current
passed for t seconds, we have PbSO 4 + O + H 2 O $ PbO 2 + H 2 SO 4
W1 = Z1 It At cathode
2H+ + 2e- $ 2H
and W2 = Z2 It
Therefore, Eq. (1) can be written as PbSO 4 + 2H $ Pb + H 2 SO 4
The inner side of glass vessel near the open end

is coated with black paint. It acts as a reflector for
ammonium chloride crystals as they have a tendency
to creep along the glass wall. This helps to maintain
the concentration of ammonium chloride solution.
Action
The action of the cell can be described as follows:
Recharging of a Lead-acid Cell
As the charging process goes on, the anode is converted

into PbO 2 and cathode into Pb. The H 2 SO 4 produced
in the above chemical reactions increases the specific
gravity of the electrolyte. The chemical change that
occur during recharging can be summed up as under:
1. The positive plate (anode) is converted into PbO 2
and the negative plate (cathode) into Pb.
2. H 2 SO 4 is formed in the reactions. Therefore,
specific gravity of the electrolyte (H 2 SO 4) is
raised. When the cell is fully charged, the specific
gravity of H 2 SO 4 rises to about 1.28.
3. The emf of the cell rises. The emf of a fully Leclanche Cell
charged cell is about 2.1 V.
The ammonia gas escapes. The hydrogen ions diffuse
4. Electrical energy supplied is converted into
through the pores of the porous pot. Hydrogen
chemical energy which is stored in the cell.
ions react with manganese dioxide according to the
273. Explain the construction and working of Leclanche following reaction :
cell. 2H+ + 2MnO 2 $ Mn 2 O 3 + H 2 O + 2 units of positive
Ans : OD 2014, 2005 charge
Leclanche cell The positive charge is transferred to the carbon rod.
This cell is also primary cell. It was invented by So, the carbon rod becomes positive with respect to
George Leclanche in the year 1865. the electrolyte.
Construction The emf of the Leclanche cell is nearly 1.5 V . The
This cell consists of two electrodes an amalgamated cell has an internal resistance varying from 0.5 W to 5 W
zinc rod and a carbon rod. The carbon rod is put . The internal resistance depends upon the choice of
in a porous pot packed with manganese dioxide and carbon powder. The cell can supply a current of 0.25 A .
charcoal powder. Manganese dioxide acts as the MnO 2 is slow in action. The hydrogen is liberated
depolariser. The charcoal powder helps to make the quicker than MnO 2 can use it up. The chemical
manganese dioxide electrically conducting and this reaction inside the porous pot is rather slow due to the
reduces the internal resistance of the cell. The carbon use of solid depolariser. So, after a time, polarisation
electrode acts as the positive electrode. sets in. The current falls off after some time.
Both the zinc rod and the porous pot are dipped When the cell is allowed to rest for some time,
in strong solution of ammonium chloride contained in Mn 2 O 3 changes back to MnO 2 by taking oxygen from
a glass bottle. While the ammonium chloride solution the atmosphere.
acts as the electrolyte of the cell, the amalgamated 2Mn 2 O 3 + O 2 $ 4MnO 2
zinc rod acts as the negative electrode.
The cell is now again ready for operation
274. What do you mean by electrochemistry? What is the an electrolyte which ionises in solution is called the
difference between galvanic cell and electrolytic cell? degree of ionisation or degree of dissociation.
Ans : SQP 2018 Degree of ionisation or degree of dissociation of an
The branch of chemistry which deals with the study electrolyte is given by the formula:
of conversion of chemical energy info electrical energy Degree of ionisation
or vice-versa and their mutual relationship is referred Number of molecules ionised
=
to as electrochemistry. Total number of molecules dissolved in the solvent
Electrochemical Cell Electrolytic Cell Percentage ionisation or dissociation is calculated by

(Galvanic Cell) multiplying degree of ionisation with 100.
Factors affecting the degree of ionization
1. Converts chemical Uses electrical energy
Different electrolytes ionise to different extent when
energy into electrical to effect a non-
dissolved in a solvent such as water. Hence, the degree
energy. spontaneous chemical
of ionisation of different electrolytes is different.
change.
The degree of ionisation depends upon the following
2. Two half-cells linked Usually consists of factors:
by a semipermeable one container and one
Nature of the Electrolyte
membrane, such as a electrolyte.
salt bridge. Strong electrolytes ionise almost completely in the
solution, i.e., they have high degree of ionisation and
3. The anode is the The anode is the
hence, conduct electricity to a large extent.
negative electrode, the positive electrode, the
site where oxidation site where oxidation Weak electrolytes ionise to a small extent in the
occurs. occurs. solution, i.e., they have low degree of ionisation and
hence, conduct electricity to a smaller extent.
4. The cathode is the The cathode is the
Nature of the Solvent
positive electrode, the negative electrode, the
site where reduction site where reduction The nature of the solvent affects the extent of ionisation
occurs. occurs. of an electrolyte. The solvent cuts the forces of binding
between the two ions and thus separates them. This
5. Electrons flow from An external power effect of solvent is due to its dielectric constant. Any
anode ^-h to cathode source acts as an solvent which has high value of dielectric constant
^+h through an electron pump and
(i.e., polar solvent) has the capacity to separate the
external conductor. pulls electrons to it
ions in solution. As a result, electrolytes ionise to a
from the anode ^+h
greater extent in polar solvents (such as water and
and drives electrons
ammonia) than in non-polar solvents (such as benzene
onto the cathode ^-h .
and carbon disulphide). Thus, greater the polarity
6. Positive ions move Ions (or molecules or (or dielectric constant) of the solvent, greater is the
from the anode half- atoms) at the cathode ionisation and higher is the degree of ionisation.
cell to the cathode accept electrons
half-cell through the (reduction). Ions (or
salt bridge. Negative molecules or atoms)
ions migrate in the at the anode give up
opposite direction. electrons (oxidation).
Example: Dry cell, Example: Changing
Lead storage battery. lead storage battery.
Separation of ions by solvent like water
275. Define degree of ionization. What are factors affecting
Note: Dielectric constant is defined as the capacity of
the degree of ionization.
solvent to weaken the forces of attraction between the
Ans : COMP 2005
ions immersed in that solvent.
Degree of ionization or degree of dissociation
Concentration of the Solution
The extent of ionisation or electrolytic dissociation
The extent of ionisation of an electrolyte is inversely
of an electrolyte in solution is described in terms
proportional to the concentration of the solution.
of the degree of ionisation or degree of dissociation.
Thus, the degree of ionisation increases with decrease
The fraction of the total number of molecules of
in the concentration of the solution, i.e., it increases
as the solution is diluted. In very dilute solutions, NUMERICAL QUESTIONS

the greater number of solvent molecules separate the
ions of the electrolyte. Thus in very dilute solutions,
277. Conductivity of 2 # 10-3 M methanoic acid is
ionisation of the electrolyte is considered to be almost
8 # 10-5 S cm-1. Calculate its molar conductivity
complete and degree of ionisation approaches unity.
and degree of dissociation if / º m for methanoic
Temperature acid is 404 S cm2 mol-1.
At high temperature, the molecular velocities are Ans : FOREIGN 2007
increased. As a result, the ions overcome the forces
We know,
of attraction between them and consequently the
ionisation is more. Thus, degree of ionisation increases lm = k # 1000
Concentration (C)
with increase in temperature, i.e., it is directly -5
proportional to temperature. = 8 # 10 #-31000
2 # 10
276. Give five postulates of Arrhenius theory of ionisation.
= 40 S cm2 mol-1
Ans : DELHI 2001
Main Postulates or Assumptions of the Theory a diss = l mº = 40

/m 404
1. On dissolution of electrolytes (like acids, bases and
= 0.099 = 9.9 %
salts) in water, their molecules yield two kinds of
charged particles : one having positive charge (s) 278. Calculate the D, G º and log Kc for the given reaction
known as cation and other having negative charge at 298 K :
(s) known as anion.
Ni (s) + 2Ag+ (aq) Ni2+ (aq) + 2Ag (s)
water + -
AB A + B Given : Ec = - 0.25V, EcAg = 0.80 V
Cation Anion Ni2+ /Ni
+
/Ag
e.g., 1 F = 96500 C mol-1.2
water + -
(a) NaCl Na + Cl Ans : FOREIGN 2007
Cation Anion
water D r G º = nF E ºCell
(b) NH 4 OH NH +4 + OH-
Anion
Cation
E º Cell = E cathode - E Anode
2. Cations are metallic ions obtained by loss of
electrons from metallic atoms. Anions are non- = + 0.80 - (- 0.25) = 1.05V
metallic ions obtained by gain of electrons from n =2
non-metallic atoms or group of non-metallic
atoms. For example F = 96500 C mol-1
(a) Na $ Na+ + e- D Gº = - 2 # 96500 # 1.05

Metal Cation
D r Gº = - 202650 J mol-1
(b) Cl + e- $ Cl-
Non - metal Anion D n Gº = - 202.650 kJ mol-1
3. The total number of positive charges is equal to Again, we know
the total number of negative charges in solution. DG = - 2.303 RT # log Kc
Hence, the solution as a whole is electrically
neutral. 202650 = - 2.303 # 8.314 # 298 # log Kc
4. The number of positive charges on the cation log Kc = - 35.516
and the number of negative charges on the anion
represents the valency of the atom of an element 279. The resistance of a conductivity cell containing
from which the ion is obtained. 0.001 M KCl solution at 298 K is 1500 W . What is
5. Molecules of solute (or electrolyte) are constantly the cell constant if the conductivity of 0.001 M KCl
splitting up into its ions and the ions present solution at 298 K is 0.146 # 10-3 S cm-1 ?
in solution are constantly reuniting to form Ans : OD 2011
undissociated molecules (original molecules).
Given,
Therefore, a dynamic equilibrium exists between
the ions and the undissociated molecules of the Conductivity, k = 0.146 # 10-3 S cm-1
electrolyte in solution. Hence, the process of Resistance, R = 1500 ohm
ionisation or electrolytic dissociation is generally
As we know that,
reversible.
Conductivity, (k) Hence, Cell constant = 1.29 (S m-1) # 100 W

Cell constant =
Conductance (G)
= 129 m-1
= Conductivity (k) # Resistance (R)
or = 1.29 cm-1
Hence, Cell constant
Step II. Calculation of conductivity of 0.02 M KCl
= 0.146 # 10-3 ohm-1 cm-1 # 1500 ohm solution.
= 0.219 cm-1 Resistance of solution = 520 W
280. The conductivity of 0.20 M KCl solution at 298 K is Cell constant (G *) = 1.29 cm-1
0.025 S cm-1 . Calculate its molar conductivity.
Conductivity, k = Cell constant
Ans : SQP 2015 Resistance
-1
Given, = 1.29 cm
520 W
k = 0.25 S cm-1 , C = 0.20 M
= 0.248 # 10-2 S cm-1
Molar conductivity
Step III. Calculation of molar conductivity.
Lm = k # 1000
C
Lm = 1000 # k
C
Hence, Lm = 0.025 # 1000
0.20
C = 0.02 M ,
= 125.0 S cm2 mol-1
k = 0.248 # 10-2 S cm-1
281. Calculate the equivalent conductivity of 1 M H 2 SO 4 -2
Hence, Lm = 1000 # 0.248 # 10
solution whose conductivity is 26 # 10-2 ohm-1 cm-1 . 0.02
Ans : COMP 2019, OD 2017 = 124 S cm2 mol-1
Given,
283. A conductivity cell when filled with 0.01 M KCl has
Conductivity = 26 # 10-2 ohm-1 cm-1 a resistance of 747.5 W at 25cC . When the same cell
Concentration = 1MH 2 SO 4 = 98 g/litre was filled was an aqueous solution of 0.05 M CaCl 2
solution the resistance was 876 W . Calculate
Equivalent weight of H 2 SO 4 = 49
1. Conductivity of solution
Gram equivalent per litre = 98 = 2 2. Molar conductivity solution.
49
k [Conductivity of 0.01 M KCl = 0.14114 S m-1 ]
Equivalent conductivity = # 1000
C Ans : FOREIGN 2009
-2 Calculation of cell constant.
= 26 # 10 # 1000
2 Resistance of KCl solution,
= 130 ohm-1 cm2 equiv-1 (R) = 747.5 S-1
282. Resistance of a conductivity cell filled with 0.1 M Conductivity of KCl solution,
KCl solution is 100 W . If the resistance of the same
(k) = 0.14114 S m-1
cell when filled with 0.02 M KCl solution is 520 W ,
calculate the conductivity and molar conductivity of Conductivity, (k) = 1 # G *
0.02 M KCl solution. (The conductivity of 0.1 M KCl R
solution is 1.29 S m-1 ) or G* = R#k
Ans : DELHI 2005 = (747.5 S-1) # 0.14114 S m-1
Step I. Let us first calculate the cell constant.
= 105.5 m-1
Cell constant, G * = Conductivity (k)
Calculation of conductivity and molar conductivity
# Resistance (R) for CaCl 2 solution
Resistance of 0.1 M KCl solution 1. Conductivity
= 100 W Conductivity, k = Cell constant
R
Conductivity of 0.1 M KCl solution -1
= 1.29 S m-1 = 105.5 m = 0.1204 S m-1

876 S-1
2. Molar conductivity Lc (CH 3 COONa) = 91.0 S cm2 mol-1

Conc. of solution, C = 0.005 M = 0.005 mol dm-3 Lc (HCl) = 425.9 S cm2 mol-1
Lm = k # 1000 Lc (NaCl) = 126.4 S cm2 mol-1
C
Lc (CH 3 COOH) = 91.0 + 425.9 - 126.4
Hence, Lm = 0.1204 # 1000
0.005 = 390.5 S cm2 mol-1
2 -1
= 0.0241 S m mol
286. The molar conductivities at infinite dilution for NaI,
284. A potential difference of 20 V applied to the ends of
CH 3 COONa and (CH 3 COO) 2 Mg are 12.69, 9.10 and
a column of 0.1 M AgNO 3 solution, 4 cm in diameter
18.78 mSm2 mol-1 respectively at 25cC . What is the
and 12 cm in length gave a current of 0.20 amperes.
molar conductivity of MgI 2 at infinite dilution?
Calculate
Ans : COMP 2003
1. Conductivity and
Molar conductivity at infinite dilution for MgI 2 may
2. Molar conductance of the solution
be calculated as :
Ans : OD 2013, SQP 2006
Lc (MGI 2)= Lc [(CH 3 COO) 2 Mg] + 2Lc (NaI) - 2Lc (CH 3 COONa)
1. According to Ohm’s law,
Lc [(CH 3 COO) 2 Mg] = 18.78 m S m2 mol-1
Resistance of solution, R = V
I Lc (NaI) = 12.69 m S m2 mol-1
= 20 = 100 W Lc (CH 3 COOH) = 9.10 m S m2 mol-1
0.20
Radius of column = 4 cm = 2 cm Hence, Lc (MgI 2) = 18.78 + 2 (12.69) - 2 (9.10)
2
Area of cross-section of the column, = 25.96 m S m2 mol-1
a = pr2 = 22 # (2) 2 cm2 287. The molar conductances of ammonium hydroxide

7
at concentrations 0.1 M and 0.001 M are 3.6 and
= 12.57 cm2 34.0 S cm2 mol-1 respectively. Calculate the degree
Length of column (distance between electrodes) of dissociation of NH 4 OH at these concentrations.
l = 12 cm Molar conductance at infinite dilution for NH 4 OH is
271.1 ohm-1 cm2 mol-1 .
2. Conductivity, k = G # l
a Ans : DELHI 2008
= 1 # 12 Degree of dissociation is given as

100 12.57 c
= 9.55 # 10-3 S cm-1 a =L

Lc
3. Molar conductivity, Lm = k # 1000 where, Lc is the molar conductance at concentration
C C and Lc is the molar conductance at infinite dilution.
-3
= 9.55 # 10 # 1000 1. At C = 0.1 M , Lc = 3.6
0.1
= 95.5 S cm2 mol-1 Lc = 271.1
285. The molar conductivities at infinite dilution for Hence, a = 3.6 = 0.013
sodium acetate, hydrochloric acid and sodium chloride 271.1
are 91.0, 425.9 and 126.4 S cm2 mol-1 respectively at i.e., 1.3% dissociated.
298 K. Calculate the molar conductivity of acetic acid 2. At C = 0.001 M , Lc = 34.0 ,
at infinite dilution.
Lc = 271.1
Ans : SQP 2021
Molar conductivity at infinite dilution of acetate acid Hence, a = 34.0 = 0.125

271.1
can be calculated as :
i.e., 12.5% dissociated.
Lc (CH 3 COOH) = l Ho + l CH
+
o
COO -
3
288. Calculate the molar conductivity of a solution of
o o o o o o
= l CH COO + l Na + l H + l Cl - l Na - l Cl
3
- + + - + -
MgCl 2 at infinite dilution given that the molar ionic
Lc (CH 3 COOH) conductivities of lc (Mg2+) = 106.1 S cm2 mol-1 and
lc (Cl-) = 76.3 S cm2 mol-1 .
= Lc (CH 3 COONa) + Lc (HCl) - Lc (NaCl)
Ans : FOREIGN 2012

Radius = 0.5 cm
2+ -
Lc (MgCl 2) = lc (Mg ) + 2lc (Cl ) Area of cross-section,
lc (Mg2+) = 106.1 S cm2 mol-1 a = pr2
lc (Cl-) = 76.3 S cm2 mol-1 = 3.14 # (0.5) 2 = 0.785 cm2
Hence, Lc (MgCl 2) = 106.1 + 2 (76.3) Hence, G * = 50 = 63.694 cm-1
0.785
= 258.7 S cm2 mol-1
1. Resistivity, r = R
289. The molar conductivity at infinite dilution of G*
Al 2 (SO 4) 3 is 858 S cm2 mol-1 . Calculate the R = 5.55 # 103 W
molar ionic conductivity of Al3+ ionic given that 3
lc (SO 24-) = 160 S cm2 mol-1 . Hence, r = 5.55 # 10 -W1 = 87.135 W cm
63.694 cm
According to Kohlrausch’s law, 2. Conductivity, k = 1 = 1

r 87.135
Lc [Al 2 (SO 4) 3] = 2lc (Al3+) + 3lc (SO 24-) = 1.148 # 10-2 S cm-1
Lc [Al 2 (SO 4) 3] = 858 S cm2 mol-1 3. Molar conductivity,
lc (SO 24-) = 160 S cm2 mol-1 L = k # 1000
C
858 = 2lc (Al3+) + 3 # 160
M = 0.05 M
or 2lc (Al3+) = 858 - 480 = 378 -2
Hence, L = 1.148 # 10 # 1000
0.05
Hence, lc (Al3+) = 378 = 189 S cm2 mol-1
2
= 229.6 S cm2 mol-1
290. The molar conductivity at infinite dilution for HCl, 292. The conductivity of a 0.01 M solution of acetic acid
KCl and CH 2 ClCOOK are 4.26 # 10-2 , 1.50 # 10-2 at 298 K is 1.65 # 10-4 S cm-1 Calculate
and 1.13 # 10-2 S m2 mol-1 respectively. Calculate the 1. Molar conductivity of the solution
molar conductivity at infinite dilution for monochloro 2. Degree of dissociation of CH 3 COOH
acetic acid (CH 2 ClCOOH).
3. Dissociation constant for acetic acid.
Ans : SQP 2001
Given that,
Molar conductivity at infinite dilution for monochloro
lc (H+) = 349.1
acetic acid (CH 2 ClCOOH) may be calculated as :
Lc (CH 2 Cl COOH)= Lc (CH 2 Cl COOK) + Lc (HCl) - Lc (KCl) and lc (CH 3 COO-) = 40.9 S cm2 mol-1
Lc (CH 2 Cl COOK) = 1.13 # 10-2 S m2 mol-1 Ans : DELHI 2004
1. Calculation of molar conductivity of solution.
Lc (HCl) = 4.26 # 10-2 S m2 mol-1
L = k # 1000
Lc (KCl) = 1.50 # 10-2 S m2 mol-1 C
Hence, k = 1.65 # 10-4 S cm-1 ,
/c (CH 2 ClCOOH) = 1.13 # 10-2 + 4.26 # 10-2 - 1.50 # 10-2 C = 0.01 M
-2 2 -1
= 3.89 # 10 S m mol 4
Hence, L = 1.65 # 10 # 1000
0.01
291. The electrical resistance of a column of 0.05 M
NaOH solution of diameter 1 cm and length 50 cm is = 16.5 S cm2 mol-1
5.55 # 103 ohm. Calculate its 2. Calculation of degree of dissociation of acetic acid.
1. Resistivity c
a =L
2. Conductivity, and Lc
3. Molar conductivity Lc (CH 3 COOH) = lc (H+) + lc (CH 3 COO-)
Ans : COMP 2017
= 349.1 + 40.9
Cell constant, G * = 1 = 390 S cm2 mol-1
a
l = 50 cm , diameter = 1 cm Hence, a = 16.5 = 0.0423
390
3. Calculation of dissociation constant, K Dissociation constant,

Acetic acid dissociates as : [CH 3 COO-] [H+]
Ka =
CH 3 COOH CH 3 COO- + H+ [CH 3 COOH]
(ca) (ca) 2
= = ca
c (1 - a) 1 - a
Initial conc. c 0 0
Assuming 1 - a c 1, we get Ka = ca2
Equilibrium conc. c (1 - a) ca ca 1
or a = b Ka l2
[CH 3 COO-] [H+] c
Dissociation constant, K =
CH 3 COOH
Now, a = om = Lm
L
= ca # ca Lm 390.7
c (1 - a) Substituting the values, we get
2
K = ca Lm = 1.8 # 10-5
1
or b 0.01 l
2
1-a 390.7
0.01 # (0.0423) 2 = 4.243 # 10-2
Substituting the values, K =
1 - 0.0423
= 1.87 # 10-5 Hence, Lm = 4.243 # 10-2 # 390.7
= 16.58 S cm2 mol-1
293. The specific conductance of a saturated
295. Calculate the potential of hydrogen electrode in
solution of AgCl at 298 K is found to be
contact with a solution whose pH is 10.
1.386 # 10-6 S cm-1 . Calculate its solubility
o
( l Ag
+ = 62.0 S cm2 mol-1 and l Cl
o
= 76.3 S cm2 mol-1 )
-
Ans : SQP 2019
Ans : FOREIGN 2011 Given,

As we know that, pH = 10
+ -
o
L (AgCl) = lc (Ag ) + lc (Cl )
m pH = - log [H+]
= 62.0 + 76.3 [H+] = 10-10 mol L-1
= 138.3 S cm2 mol-1 Now, EH +
/H 2 = E Ho + /H - 0.0591 log 1+
2
1 [H ]
k = 1.386 # 10-6 S cm-1
= 0- 0 . 0591 1
log -10
1
Lmo = k # 1000 = k # 1000 10
M Solubility 0 . 0591
= 0- log 1010
1
Hence, Solubility = k # 1000
Lom EH + = 0.591 V
/H 2
-6
= 1.386 # 10 # 1000 Calculate the emf of the cell in which the following
138.3 296.
reaction takes place:
= 1.0 # 10-5 mol L-1
Ni (s) + 2Ag+ (0.002 M)" Ni2+ (0.160 M) + 2Ag (s)
or = 1.0 # 10-5 # 143.5 g L-1
Given that E ccell = 1.05 V
= 1.435 # 10-3 g L-1
Ans : COMP 2000
294. The molar conductance of acetic acid at infinite Ni (s) $ Ni (aq) + 2e 2+ -
dilution is 390.7 S cm2 mol-1 . Calculate the molar

2Ag (aq) + 2e- $ 2Ag (s)
+
conductance of 0.01 M acetic acid solution, given that
the dissociation constant of acetic acid is 1.8 # 10-5 . Ni (s) + 2Ag+ (aq) $ Ni2+ (aq) + 2Ag (s)
Ans : OD 2015, SQP 2012
[Ni2+]
Acetic acid dissociates as :
o
E cell = E cell - 0.0591 log
2 [Ag+] 2
CH 3 COOH CH 3 COO- + H+ = 1.05 V - 0.0591 log 0.16 2
2 (0.002)
Initial conc. c 0 0 = 1.05 V - 0 . 0591 log 0.16 -6
2 4 # 10
Equilibrium conc. c (1 - a) ca ca 0 . 0591
= 1.05 V - log 4 # 10 4
2
= 1.05 V - 0.0591 [log 4 + log 10 4] 299. If a current of 0.5 ampere flows through a metallic wire
2 for 2 hours, then how many electrons flow through the
= 1.05 V - 0.0591 [0.6021 + 4.0000] wire?
2 Ans : OD 2018
= 1.05 V - 0.0591 # 4.6021 Q = I#t

2
= 0.5 # 2 # 60 # 60
= 1.05 V - 0.2719
2
= 3600 C
= 1.05 V - 0.1359
= 0.9141 V Since, 1.602 # 10-19 C is the charge on 1 electron.
297. The cell in which the following reaction occurs Hence, 3600 C charge will be on
1 3600
2Fe3+ (aq) + 2I- (aq) " 2Fe2+ (aq) + I 2 (s) # 3600 = 1.602 # 1019
1.602 # 10-19
o
has E cell = 0.236 V at 298 K = 2.25 # 1022 electrons
Calculate the standard Gibbs energy and the
300. How much charge is required for the following reductions:
equilibrium constant of the cell reaction.
1. 1 mol of Al3+ to Al?
Ans : DELHI 2006
o 2. 1 mol of Cu2+ to Cu?
E cell = 0.236 V
3. 1 mol of MnO -4 to Mn2+ ?
2Fe3+ + 2e- " 2Fe2+
Ans : SQP 2006
2I - $ I2 + 2e- 3+ -
1. Al (aq) + 3e $ Al (s)
TGc = - nEcF = - 2 # 0.236 V # 96500
3 F = 3 # 96500 C
TGc = 0.472 # 96500 = - 45548 J mol-1
= 289500 C = 2.895 # 105 C
-1
= - 45.54 KJ mol
2. Cu2+ (aq) + 2e- $ Cu (s)
nEcF = 2.303 RT log KC
2 F = 2 # 96500 C
log Kc = nEcF = nEc = 193000 C = 1.93 # 105 C
2.303RT 0.0591
= 2 # 0.236 = 0.472 = 7.99 b 8.00 3. MnO -4 + 5e- + 8H+ = Mn2+ + 4H 2 O
0.0591 0.0591
8
Mn7+ + 5e- $ Mn2+
Kc = 10
5 F = 5 # 96500 C
298. The molar conductivity of 0.025 mol L-1 methanoic
acid is 46.1 S cm2 mol-1 . Calculate its degree = 482500 C = 482500 C
of dissociation and dissociation constant. Given = 4.825 # 105 C
lc (H+) = 349.6 S cm2 mol-1 and lc (HCOO-)
2
= 54.6 S cm mol -1 301. Consider the reaction :
Cr2 O 72- + 14H+ + 6e- " 2Cr3+ + 7H 2 O
What is the quantity of electricity in coulomb needed
lcHCOOH = lcH+ + lcHCOO-
to reduce 1 mol of Cr2 O 72- ?
= 349.6 + 54.6 Ans : COMP 2001
= 404.2 S cm2 mol-1 Cr2 O 72- + 14H+ + 6e- " 2Cr3+ + 7H 2 O

-1
6 # 96500 C = 579000 C
a = Lom = 46.1 S cm 2mol -1
2
Hence,
Lm 404.2 S cm mol of electricity is required to reduce 1 mol of Cr2 O 72-
= 0.114
302. Calculate the standard cell potentials of galvanic cell
2
20.025 # (0.114) in which the following reactions take place :
Ka = Ca =
1-a 1 - 0.114 1. 2Cr (s) + 3Cd2+ (aq) $ 2Cr3+ (aq) + 3Cd (s)
= 0.025 # 0.114 # 0.114 2. Fe2+ (aq) + Ag2 (aq) $ Fe3+ (aq) + Ag (s)
0.886
= 3.67 # 10-4 mol L-1 Calculate the TrGc and equilibrium constant of the
reaction.
Ans : DELHI 2005 Ans : FOREIGN 2009

3+ -
1. 2Cr (s) $ 2Cr (aq) + 6e 1. Mg (s) $ Mg (aq) + 2e- 2+
3Cd2+ (aq) + 6e- $ 3Cd (s) Cu2+ (aq) + 2e- $ Cu (s)

2Cr (s) + 3Cd2+ (aq) $ 2Cr3+ (aq) + 3Cd (s) Mg (s) + Cu2+ (aq) $ Mg2+ (aq) + Cu (s)
n =6 [Mg2+]
o
E cell = E Cu 2+
/Cu
o
- E Mg 2+
/Mg - 0.0591 log
o o o 2 [Cu2+]
E cell = E Cd 2+
/Cd - E Cr 3+
/Cr
= - 0.40 V - (- 0.74 V) = + 0.337V - (- 2.37V) - 0.0591 log 0.001

2 0.0001
= + 0.34 V = 2.707 V - 0.0591 log 10
2
TrGc = - n EcF
= 2.707 V - 0.0295 V
TrGc = - 6 # 0.34 V # 96500 C mol-1
= 2.6775 = 2.68 V
= - 196860 J mol-1
2. Fe (s) $ Fe2+ (aq) + 2e-
= - 196.86 KJ mol-1
2H+ + 2e- $ H 2 (g)
log Kc = nEc Fe (s) + 2H+ (aq) $ Fe2+ (aq) + H 2 (g)
0.0591
= 6 # 0.34 V = 2.04 V
2+
o
E cell = (E Ho + H - E Fe 0.0591 log [Fe ]
0.0591 0.0591 + Fe) - 2
2
2 +
[H ] 2
= 34.5177 (0.001)
= 0 - (- 0.44V) - 0.0591 log
Hence, KC = Antilog of 34.5177 2 (1) 2
= 3.294 # 1034 = + 0.44 V - 0.0591 log 10-3
2
2. Fe2+ (aq) $ Fe3+ (aq) + e- = + 0.44 V + 0.1773 = 0.44 V + 0.1773

2 2
Ag+ (aq) + e- $ Ag (s) = 0.44 + 0.0886 = 0.5286 V
Fe2+ (aq) + Ag+ (aq) $ Fe3+ (aq) + Ag (s)
3. Sn (s) $ Sn2+ (aq) + 2e-
o o o
E cell =E Ag+ /Ag -E Fe 3+ /Fe2+ 2H+ (aq) + 2e- $ H 2 (g)
= + 0.80 V - (+ 0.77 V) Sn (s) + 2H+ (aq) $ Sn2+ (aq) + H 2 (g)
= + 0.03 V [Sn2+] (p H )
E cell = (E Ho +
/H 2
o
- E Sn 2+
/Sn ) - 0.0591 log 2
TrGc = - n EcF 2 [H+] 2

= - 1 # 0.03 V # 96500 C mol-1 = [0 - (- 0.14V)] - 0.0591 log 0.05 #21
-1
2 (0.02)
TrGc = - 2895J mol
= + 0.14V - 0 . 0591 log 500
= - 2.895 kJ mol-1 2 4
log KC = nEc = + 0.14V - 0.0591 log 125

0.0591 2
= + 0.14 V - 0.0295 # 2.0969 V
= # 0.03V = 0.5076
1
0.0591
= + 0.14 V - 0.06 V = 0.08 V
KC = Antilog of 0.5076 = 3.218
4. At anode: 2Br- (aq) $ Br2 (l ) + 2e-
303. Write the Nernst equation and e.m.f. of the following
cells at 298 K. At cathode: 2H+ (aq) + 2e- $ H 2 (g)
1. Mg (s) ; Mg2+ (0.001 M) < Cu2+ (0.0001M) ; Cu (s) 2Br- (aq) + 2H+ (aq) $ Br2 (l ) + H 2 (g)
2. Fe (s) ; Fe2+ (0.001M) < H+ (1M) ; H 2 (g) (1 bar) ; Pt (s) o
E cell = E cell - 0.0591 log 1
n [Br-] 2 [H+] 2
3. Sn (s) ; Sn2+ (0.050 M) < H+ (0.020M) ; H 2 (g) (1 bar) ; Pt (s)
= (E Ho o
- E Br 0.0591 log 1
4. Pt (s) ; Br2 (l) ; Br- (0.010M) < H+ (0.030M) < H 2 (g) (1 bar) ; Pt (s) +
/H 2 2
/Br) -
2 (10-2) 2 (3 # 10-2) 2
8
A solution of Ni (NO 3) 2 is electrolysed between
= (0 - 1.09 V) - 0.0591 log 10
306.
2 9 platinum electrodes using a current of 5.0 amperes
for 20 minutes. What mass of Ni is deposited at the
= - 1.09V - 0.0591 (log 108 - log 9)
2 cathode? [At. wt. of Ni = 58.9 u ]
= 1 - 1.09V - .0591 (8.0000 - 0.9542)
0 Ans : COMP 2003
2
Ni2+ + 2e- $ Ni (s)
= 1.09V - 0 . 0591 7.0458
2 # Eq. Wt. = At.Wt. = 58.9
Valency 2
= - 1.09V - 0.4164 Eq.wt.
2 Z = = 58.9
96500 2 # 96500
= - 1.09V - 0.2082 = 1.2982 V
Hence, m = Z#I#t
304. In the button cells widely used in watches and other
devices the following reaction takes places : = 58.9 5 20 60 s
2 # 96500 # # #
Zn (s) + Ag 2 O (s) + H 2 O (l) " Zn2+ (aq) + 2Ag (s) + 2OH- (aq)
Determine Ec and TrGc for the reaction. = 58.9 # 30 = 1767 = 1.83 g
965 965
Ans : OD 2013
307. The resistance of a conductivity cell containing 0.001
2+ -
Zn (s) $ Zn (aq) + 2e M KCl solution at 298 K is 1500 W . What is the cell
2Ag+ (aq) + 2e- $ 2Ag (s) constant if the conductivity of 0.001 M KCl solution
at 298 K is 0.146 # 10-3 S cm-1 ?
Zn (s) + 2Ag+ (aq) $ Zn2+ (aq) + 2Ag (s)
Ans : DELHI 2017, OD 2010
o o o
E cell = (E SRP cathode - E SRP anode) Given, R = 1500 W ,
= + 0.80 V - (- 0.76 V) k = 0.146 # 10-3 S cm-1
= + 1.56 V
k = 1# l
R A
TrGc = - n EcF l =k R
A #
TrGc = - 2 # 1.56 V # 96500
= 0.146 # 10-3 S cm-1 # 1500 ohm
= - 301080 J mol-1
Hence, Cell constant,
= - 301.080 kJ mol-1
l
b A l = 219 # 10 cm = 0.219 cm
-3 -1 -1
305. Conductivity of 0.00241 M acetic acid is
7.896 # 10-5 S cm-1 . Calculate its molar conductivity. 308. How much electricity in terms of Faraday is required
If Lmo for acetic acid is 390.5 S cm2 mol-1 , what is its to produce
dissociation constant? 1. 20 g of Ca from molten CaCl 2 ?
Ans : SQP 2002
2. 40 g of Al from molten Al 2 O 3 ?
k = 7.896 # 10-5 S cm-1 Ans : FOREIGN 2014
-5 1. Ca2+ (aq) + 2e- $ Ca (s)
Lm = 1000 k = 1000 # 7.896 # 10
M 0.00241 2 F is required for 40 g of Ca
3 1 F is required for 20 g of Ca
= 7.896 # 10 = 7896 2. Al3+ (aq) + 3e- $ Al (s)
241 241
= 32.76 S cm2 mol-1 Atomic weight
Eq. wt. = = 27 = 9
Valency 3
a = Lm = 32.76 = 0.08389 Eq.wt.
Lm 390.5 Z = = 9
96500 96500
a = 8.389 % = 8.4 %
Now, m = Z#Q
2
Ka = Ca 9
1-a 40 = Q
2
96500 #
0.00241 # (0.084) -5
= = 1.7 # 10 Q = 40 # 96500 = 4.2889 # 105 C
(1 - 0.084) 0.916 9
= 1.86 # 10-5 mol L-1 5
= 4.2889 # 10 F = 4.44 F
96500
309. Three electrolytic cells A, B and C containing 2. 2Ag+ (aq) + Cu (s) $ Cu2+ (aq) + 2Ag (s)
solutions of zinc sulphate (ZnSO 4), silver nitrate o o o
E cell = E Ag +
/Ag - E Cu 2+
/Cu
(AgNO 3) and copper sulphate (CuSO 4), respectively
are connected in series. A steady current of 1.5 amperes = + 0.80 V - 0.34 V = 0.46 V
was passed through them until 1.45 g amperes was o
It is feasible because E cell is +ve.
passed through them until 1.45 g of silver deposited
at the cathode of cell B . How long did the current 3. 2Fe3+ (aq) + 2Br- (aq) $ 2Fe2+ (aq) + Br2
flow? What mass of copper and zinc was deposited in o
E cell o
= E Fe 3+
/Fe2+
o
- E Br /Br
2
the concerned cells? (Atomic masses of Ag = 108 , Zn

= 0.77 V - 1.09 V = - 0.32 V
= 65.4 , Cu = 63.5 )
o
Ans : OD 2007
Since, E cell is –ve, therefore, reaction is not feasible.
WCu W 4. Ag (s) + Fe3+ (aq) $ Fe2+ (aq) + Ag+ (aq)
= Ag = WZn
ECu E Ag EZn o
E cell o
= E Fe 3+
o
- E Ag +
/Fe2+ /Ag
W # Eq.Wt.of Cu
WCu = Ag = 0.77 V - 0.80 V = - 0.03 V
Eq.Wt. of Ag
o
1 . 45 # 31.75 Since E cell is –ve, therefore, reaction is not feasible.
=
108 5. Br2 + 2Fe2+ (aq) $ 2Br- (aq) + 2Fe3+ (aq)
[Eq. Wt. of Zn = 65 = 32.5 ] o o o
2 E cell = E Br /Br - E Fe /Fe
2
- 3 2+
= 0.436 g [Eq. Wt. of Zn = 108 = 108 ] = 1.09 V - 0.77 V = 0.32 V

1 o
m = Z#I#t Since E cell is +ve, therefore, reaction will be feasible.
311. Calculate the potential for half-cell containing
1.45 g = 108 # 1.5 # t 0.10 M K 2 Cr2 O 7 (aq), 0.20 M Cr3+ (aq) and
96500
1.0 # 10-4 M H+ (aq)
t = .45 # 96500
1
108 # 10.5 The half-cell reaction is
= 863.7 seconds Cr2 O 72- (aq) + 14H+ (aq) + 6e- $ 2Cr3+ (aq) + 7H 2 O (l)
and the standard electrode potential is given as Ec
= 863.7 minutes = 1.33 V
60
= 14.395 Ans : COMP 2013, SQP 2004
[Cr3+] 2
minutes or 14 minutes 24 seconds o
E cell = E cell - 0.0591V log
6 [Cr2 O 72] [H+] 14
310. Using the standard electrode potentials, predict if the (0.2) 2
reaction between the following is feasible : = 1.33V - 0.0591V log
6 (0.1) (1.0 # 10-4) 14
1. Fe3+ (aq) and I- (aq) -2
= 1.33V - 0.0591V log 4 # 10 -57
2. Ag+ (aq) and Cu (s) 6 1.0 # 10
3. Fe3+ (aq) and Br- (aq) = 1.33V - 0.0591V log 4 # 1055
6
4. Ag (s) and Fe3+ (aq)
= 1.33 V - 0.0591 V # 55.6021
6
5. Br2 (aq) and Fe2+ (aq)
Ans : SQP 2015 = 1.33 V - 3.286 V
6
o
A reaction will be feasible only when its E cell value is
= 1.33 V - 0.5476 V = 0.7824 V
positive.
1. 2Fe3+ + 2I - $ 2Fe2+ + I2 312. How many moles of mercury will be produced by
electrolysing 1.0 M Hg (NO 3) 2 solution with a current
o
o
E cell = E Fe 3+
/Fe2+ - E Io /I
2
-
of 2.00 A for 3 hours?
= 0.77 V - 0.54 V [Hg (NO 3) 2 = 200.6 g mol-1]
= + 0.23 V Ans : DELHI 2002
o
It is feasible, because E cell is +ve. m = Z#I#t
Hence, TGc = - ve = 200.6 # 2 # 3 # 60 # 60
2 # 96500
m = 43329.6 = 22.45 g 315. The conductivity of 0.20 M KCl at 298 K is 0.025 S

1930 cm-1 . Calculate its molar conductivity.
Number of moles = 22.45 = 0.112 mol Ans : OD 2001
200.6
As we know that
313. A voltanic cell is set up 25c C with the following Lm = 1000k
M
half-cells Al3+ (0.001 M) and Ni2+ (0.50 M). Write
-2
an equation for the reaction that occurs when the cell = 1000 # 0.025 # 10
generates and electric current and determine the cell 0.20
potential. = 125 S cm2 mol-1
o o
(Given; E Ni /Ni = - 0.25 V , E Al /Al = - 1.66 V )
2+ 3+
316. Zinc rod is dipped in 0.01 M solution of ZnSO 4 . the

Ans : DELHI 2002
salt is 95% dissociated at this dilution at 298 K.
Calculate the electrode potential.
[Al (s) $ Al3+ (aq) + 3e-] # 2
o
Given E Zn 2+ = - 0.76 V
[Ni2+ (aq) + 2e- $ Ni (s)] # 3 /zn
Ans : SQP 2009

2Al (s) + 3Ni2+ (aq) $ 2Al3+ (aq) + 3Ni (s)
[Zn2+] = 0.1 # 95 = 0.095 M
3+ 2
[Al ] 100
o
E cell = (E Ni 2+
o
- E Al 3+ ) - 0.0591 log 2+ 3
/Ni /Al
6 [Ni ] Zn2+ + 2e- $ Zn (s)
= [- 0.25V - (- 1.66V)] - 0.0591V log

(10-3) 2 EZn 2+
/Zn
o
= E Zn - 0.0591 log 12+
2+
/Zn
6 2 [Zn ]
(0.50) 3
-6
= - 0.76V - 0 . 0591 log 1
= 1.41 V - 0.0591V log 8 # 10 2 0.095
6 1
0 . 0591 V = - 0.76V - 0.0591 [log 1000 - log 95]
= 1.41 V - [log 8 + log 10-6] 2
6
= - 0.76V - 0 . 0591 V [3.000 - 1.9777]
= 1.41 V - 0.0591V [0.9031 - 6.0000] 2
6
= - 0.76V - 0.0591V # 1.0223
= 1.41V - 0.0591V # [- 5.0969] 2
6
= - 0.76V - 0.0604 V
= 1.41V + 0.3012V 2
6
= - 0.76V - 0.0302 = - 0.7902 V
= 1.41V + 0.0502 V
= 1.4602 V 317. The resistance of 0.01 M KCl solution is 200 ohms.
= 1.46 V Calculate the specific conductivity and molar
conductivity if cell constant is equal to unity.
314. The standard electrode potential (Ec) for Daniel cell
is +1.1 V. Calculate the TGc for the reaction :
As we know that,
Zn (s) + Cu2+ (aq) $ Zn2+ (aq) + Cu (s)
Cell constant, l = 1 cm-1
A
(1 F = 96500 C)
k = l # l = 1 #1
Ans : FOREIGN 2006 R A 200
Zn (s) $ Zn (aq) + 2e 2+ -
= 5.0 # 10-3 S cm-1
Cu2+ (aq) + 2e- $ Cu (s) -3
Lm = 1000k = 1000 # 5.0 # 10
2+
Zn (s) + Cu (aq) $ Zn (aq) + Cu (s) 2+ M 0.01
o = 500 S cm2 mol-1
E cell = 1.10 V
318. Determine the values of equilibrium constant (Kc) and
TGc = - n EcF
TGc for the following reaction :
= - 2 # 1.10 V # 96500 C Ni (s) + 2Ag+ (aq) $ Ni2+ (aq) + 2Ag (s),
1000
= - 212.3 kJ mol-1 Ec = 1.05 V (1F = 96500 C Mol-1)
Ans : DELHI 2001

321. Calculate emf of the following cell at 25cC :
n =2
Fe ; Fe2+ (0.001M) < H+ (0.01M) ; H 2 (g) (1 bar) ; Pt (s)
TGc = - n EcF = - 2 # 1.05V # 96500 C
Ec (Fe2+ ; Fe) = - 0.44 V Ec (H+ ; H 2) = 0.00 V
-1
= - 202.65 kJ mol Ans : SQP 2003
We know that, Given, n =2
TGc = - 2.303 RT log Kc [Fe2+]
o
E cell = E cell - 0.0591 log + 2
- n EcF = - 2.303 RT log Kc 2 [H ]
log Kc = nEc = 2 # 1.05 = 2.10 = Ê Ho + /H - E Fe 0.0591 log 10-3

h-
o
2+
0.0591 0.0591 0.0591 2
2 /Fe
[10-2] 2
Kc = 35.5329 (antilog) = [0 - (- 0.44V)] - 0.0591 log 10
2
Kc = 3.411 # 1035
= + 0.44V - 0.0295
319. The conductivity of 0.001 M acetic acid is
= 0.4105 V
4 # 10-5 S cm-1 . Calculate the dissociation constant
of an acid, if molar conductivity at infinite dilution for
322. Conductivity of 2.5 # 10-4 M methonoic acid is
acetic acid is 390 S cm2 mol-1 .
5.25 # 10-5 S cm-1 . Calculate its molar conductivity
Ans : FOREIGN 2011
and degree of dissociation.
As we know that,
Given l0 (H+) = 349.5 S cm2 mol-1
Lm = 1000 k
M and l0 (HCOO-) = 50.5 S cm2 mol-1
-5
= 1000 # 4 # 10 = 40 S cm2 mol-1 Ans : COMP 2012, DELHI 2009
0.001
Given,
^Lm h
a = = 40 = 0.1026 k = 5.25 # 10-5 S cm-1 ,
^Lm h c 390
2 0.001 # (0.1026) 2 M = 2.5 # 10-4 M
Ka = Ca =
1-a 1 - 0.1026 l 0HCOOH = l (0HCOO ) + l 0H
- +
-3 -2
= 10 # 1.053 # 10 = 349.5 + 50.5
0.8974
-5 = 400 S cm2 mol-1
= 1.053 # 10 = 1.17 # 10-5 mol L-1
0.8974
Hence, Lm = 1000k
M
320. Calculate the time to deposit 1.27 g of copper at
-5
cathode when a current of 2 A was passed through = 1000 # 5.25 # 10
the solution of CuSO 4 . 2.5 # 10-4
(Molar mass of Cu = 63.5 g mol-1 , 1 F = 96500 C mol-1) = 1000 # 525
10 # 2.5 # 100
Ans : OD 2007
Lm = 525 = 5250
t = ? , m = 1.27 g , I = 2 A 2.5 25
m = Z#I#t = 210 S cm2 mol-1
Eq.Wt
1.27 = 2 t a = Lmo = 210
96500 # # Lm 400
1.27 # 96500 = Atomic Wt # 2 # t = 21 = 0.525

Valency 40
a = 0.525 # 100%
1.27 # 96500 = .5 # 2 # t
63
2
= 52.5%
t = 1.27 # 96500
63.5 323. The electrical resistance of a column of 0.05 mol
L-1 NaOH solution of diameter 1 cm and length
= 127 # 10 # 96500
100 # 635 50 cm is 5.55 # 103 ohm . Calculate its resistivity,
t = 2 # 965 = 1930 seconds conductivity and molar conductivity.
Ans : DELHI 2011

Also, log K = nEc
As we know that, 0.0591
A = pr2 = 3.14 # (0.5) 2 cm2 = 4 # - 2.487 = - 9.948
0.0591 0.0591
= 0.785 cm2
= - 168.2348 + 1 - 1
r (resistivity) = R # A K = 169.6752 (Antilog)
l
-169
3 2
K = 4.739 # 10
= 5.55 # 10 W # 0.785 cm
50 cm
326. Equilibrium constant (Kc) for the given cell reaction
= 87.135 W cm o
is 10. Calculate E cell
k =1 = 1
A (s) + B2+ (aq) A2+ (aq) + B (s)
r 87.135 W cm
= 0.01148 S cm-1 Ans : SQP 2011
2+ 2+
A (s) + B (aq) $ A (aq) + B (s)
Lm = k # 1000
M A (s) $ A2+ (aq) + 2e-
= 0.01148 # 1000 B2+ (aq) + 2e- $ B (s)
0.05 M
A (s) + B2+ (aq) $ A2+ (aq) + B (s)
= 229.6 S cm2 mol-1
324. Calculate the emf of the following cell at 25cC n =2
o
Zn ; Zn2+ (0.001M) < H+ (0.01M) ; H 2 (g) (1 bar) ; Pt (s) nE cell F = 2.303 RT log Kc
o
E (0Zn /Zn) = - 0.76 V ; E (0H
2+ +
/H 2) = 0.00 V log Kc = nE cell # 96500
2.303 # 8.314 # 298
Ans : FOREIGN 2008
o
Zn (s) $ Zn (aq) + 2e 2+ -
= n # E cell
0.0591
2H+ (aq) + 2e- $ H 2 (g) o
+ 2+ log 10 = 2 # E cell
Zn (s) + 2H (aq) $ Zn (aq) + H 2 (g) 0.0591
n =2 Hence, o
E cell = 0.0591
2
[Zn2+] = 0.0295 V [Since, log 10 = 1]
Now, E cell = E ccell - 0.0591 log + 2
n [H ]
327. How much electricity is required in coulomb for the
= (E cH - E Zn 0.0591 log 10-3
/Zn) - oxidation of
+
c 2+
/H 2
2 [10-2] 2
1. 1 mol of H 2 O to O 2 ?
= [0 - (- 0.76 V)] - 0.0591 log 10 2. 1 mol of FeO to Fe 2 O 3 ?
2
= 0.7305 V
1. H 2 O $ 2H+ + 1 O 2 + 2e- , i.e.,
325. Estimate potential difference needed to reduce Al 2 O 3 2
at 500cC and equilibrium constant 'Kl. 2 Faradays = 2 # 96500 C
2 Al O $ 4 Al (s) + O (g), T G = 960 kJ , = 193000 C = 1.93 # 105 C
r
3 2 3 3 2
2. Fe2+ $ Fe3+ + e- , i.e.,

F = 96500 C
Ans : OD 2001 1 Faraday = 96500 C
2 2 Al3+ + 4e- $ 4 Al = 9.65 # 10 4 C
3# 3
n =4 328. Calculate E ccell and TrGc for the following reaction at
TrGc = 960 # 1000 J = - n EcF 25cC .
960 # 1000 = - 4 # Ec # 96500 A2+ (aq) + B+ (aq) $ A3+ (aq) + B (s)

[Given Kc = 1010 , 1F = 96500 C , R = 8.314 JK-1
Hence, Ec = - 960 # 1000 = - 2.487 V mol-1 ]
4 # 96500
Ans : DELHI 2011

CASE BASED QUESTIONS
2+ 3+ -
A $ A +e
+ -
B (aq) + e $ B (s) 331. During the construction of some public building the
contractor intends to fix iron frames for windows
A2+ (aq) + B+ (aq) $ A3+ (aq) + B (s) and railings to reduce the cost of construction. After
due considerations, it is finally recommended to use
log Kc = 0.0591 aluminium for window and steel railings instead of iron.
nEc
Ec # 10 = 0.0591 (i) As a chemistry student, do you agree with the
new recommendation.
Ec = 0.00591 V
(ii) Name the phenomenon in which iron undergoes.
TGc = - nEcF (iii) Give one reason in which aluminium and steel
= 1 # 0.00591 # 96500 railing is good as compared to iron railing.
(iv) Why steel railing does not undergoes corrosion.
= - 510.315 J
Ans :
329. Limiting molar conductivities of NH 4 Cl , NaOH and (i) Yes, the new recommendation are more
NaCl are respectively 129.8, 217.4 and 108.9 S cm2 appropriate in the light of long-term benefit.
and the molar conductivity of 10-2 M solution of (ii) Rusting of iron.
NH 4 OH is 9.33 S cm2 mol-1 . Calculate the degree of (iii) Iron railings are more prone appropriate in the
dissociation of NH 4 OH . light of long-term benefit.
Ans : FOREIGN 2000 (iv) Steel is an alloy. Therefore, it does not undergoes
LcNH 4 OH = LcNH 4 Cl + LcNaOH - LcNaCl corrosion.
= 129.8 + 217.4 - 108.9 332. Rahul and his father were going in a boat in the river.
Rahul’s father threw away the cell used in watches
= 238.3 S cm2 mol-1 and hearing aids into the water. Rahul prevented him
Hence, Degree of dissociation from doing so.
a = Lom = 9.33 = 0.03915
(i) What type of cell used in watches and hearing
Lm 238.3 aids.
= 0.03915 # 100% (ii) Why Rahul advise his father not to through the
cell in the water body.
a = 3.915%
(iii) State one limitation of primary cell.
330. How long a current of 3 amperes has to be passed (iv) Give an example of cell which does not cause
through a solution of silver nitrate to coat a metal environmental pollution.
surface of 80 cm2 with a 0.005 mm thick layer? Ans :
Density of Ag is 10.5 g cm-3 . At Wt. of Ag = 108.0 u (i) Primary cells.
Ans : OD 2005
(ii) The cell used in watches are mercury cells. The
Volume = Area # thickness mercury can pollute water. This contaminated
water leads to accumulation of mercury in the
= 80 cm2 # 0.005 # 1 cm = 0.04 cm3 body of the fishes and other aquatic life.
10
Mass of Ag = Volume # Density (iii) Primary cell cannot be charged again.
(iv) Hydrogen-oxygen fuel cell.
= 0.04 cm3 # 10.5 g cm-3 = 0.42 g
333. Molar conductivity of a solution is the conductance
m = Z#I#t of solution containing one mole of electrolyte, kept
between two electrodes having unit length between
0.42 = 108 # 3 # t ,
96500 them and large cross-sectional area, so as to contain
Atomic weight 108 the electrolyte. In other words, molar conductivity
;Eq.Wt.of Ag = Valency
=
1
= 108E is the conductance of the electrolytic solution kept
between the electrodes of a conductivity cell at unit
t = 0.42 # 96500 distance but having area of cross-section large enough
3 # 108
40530 to accommodate sufficient volume of solution that
= = 125.09 seconds. contains one mole of the electrolyte.
324
It is denoted by L m .
The molar conductivity is related to conductivity as: or

(iv)
L m = k # V = 1000 # k = k # 1000
C Molarity Given, k = 7.896 # 10-5 S cm-1
Unity of L m (molar conductivity) shall be ohm–1 cm–1
mol–1 or S cm2 mol–1. M = 0.00241 M
Thus, knowing molar concentration (C ) and We have, molar conductivity,
conductivity (k ), L m can be calculated. Lc m is called L m = k # 1000
molar conductivity at infinite dilution. The molar M
-5
conductivity of strong electrolytes is found to vary = 7.896 # 10 # 1000
with concentration according to the equation, 0.00241
LCm = Lc m - A C = 32.76 S cm2 mol-1
This equation is called Debye-Huckel Onsager Hence, the molar conductivity of the solution is
equation. 32.76 S cm2 mol-1 .
Here, A is constant depending upon the type 334. Electrolytes dissociate into ions. In case of electrolytes
of electrolyte taken and nature of solvent and if we determine their molar mass using colligative
temperature. property, the value of molar mass is found to be
In the context of given passage, answer the following abnormal because colligative property depends on
questions: number of ions. Greater the number of ions, more will
(i) The molar conductivity of HCl increases with be colligative property. van’t Hoff factor(i ) is ratio of
dilution. Can you suggest what may be the reason normal molar mass to the abnormal molar mass. It is
for this? also equal to ratio of observed colligative property to
the calculated colligative property.
(ii) Here are given the different molarities of NaCl.
Which of them will exhibit the highest molar A student determined value of i at various
conductivity? concentration of NaCl, KCl, MgSO4 and K2SO4. The
values are given in the following table.
0.005 M NaCl, 0.1 M NaCl, 0.5 M NaCl,
0.01 M NaCl . Table: Values of van’t Hoff factor, i , at Various
Concentrations for NaCl, KCl, MgSO4 and K2SO4.
(iii) Molar conductivity of a solution is
1.26 # 102 W-1 cm2 mol-1 . Its molarity is 0.01. Salt Values of i van’t Hoff Factor i for
What will be its specific conductivity? complete dissociation
0.1 m 0.01 m 0.001 m of solute
or
(iv) The conductivity of 0.00241 M acetic acid is NaCl 1.87 1.94 1.97 2.00
7.896 # 10-5 S cm-1 . What shall be the molar KCl 1.85 1.94 1.98 2.00
conductivity of the solution in S cm–1 mol–1 ? MgSO4 1.21 1.82 1.82 2.00
Ans : K2SO4 2.32 2.84 2.84 3.00
(i) The molar conductivity of HCl increases with
dilution due to decrease in interionic forces. * represent i values for incomplete dissociation.
Answer the following questions based on above table.
(ii) 0.005MNaCl will exhibit the highest molar
conductivity as it has the lowest concentration of (a) How is van’t Hoff factor related to molality and why?
solute. Molar conductivity increases with increase (b) What is value of i in case of (i) electrolyte (ii)
in dilution. non-electrolyte?
(iii) We know that molar conductivity and the specific (c) Determine the amount of CaCl2 (i = 2.47 ) dissolved
conductance are related as in 2.5 L of water such that its osmotic pressure
is 0.75 atm at 27°C. [R = 0.082 L atm K-1 mol-1]
L m = k # 1000 [Ca = 40u, Cl = 35.5u]
M
Given, L m = 1.26 # 102 W-1 cm2 mol-1 or
and M = 0.01 M (d) Determine the osmotic pressure of a solution
prepared by dissolving 25 mg of K2SO4 in 2 L
Hence, 1.26 # 102 = k # 1000 solution at 25°C
0.01
Assuming it is completely ionised.
or, k = 1.26 # 10-3
[R = 0.082 L atm K-1, K = 39u, s = 32u, O = 16u]
Hence, the specific conductivity = 1.26 # 10-3
Ans : Answer the following questions :

(a) As molality decreases, van’t factor increases (a) Give reason why conductivity of CH 3 COOH
because degree of ionisation is inversely decreases on dilution.
proportional to concentration.
(b) The value of T %m of Al 2 (SO 4) 3 is 858 S cm2 mol-1 ,
(b) (i) i 2 1, (ii) i = 1 while l% SO 24- is 160 S cm2 mol-1 calculate the
(c) pV = i n RT = i WB # R # T limiting ionic conductivity of Al3+ .
MB
(c) Calculate T %m for acetic acid.
0.75 atm # 2.5 L = 2.47 # WB # 0.082 # 300 K Given that :
111
WB = 0 . 75 # 2.5 # 111 = 3.425 g T %m (HCl) = 426 S cm2 mol-1
2.47 # 24.6
T %m (NaCl) = 126 S cm2 mol-1
No. of moles = 3.425 = 0.03 mol T %m (CH 3 COONa) = 91 S cm2 mol-1
111
or or
(d) (d) Calculate the degree of dissociation of acetic acid
at 298 K , given that :
K2SO4 $ 2K+ + SO 24-
T m (CH 3 COOH) = 11.7 S cm2 mol-1
i =n =3
T m (CH 3 COO-) = 49.9 S cm2 mol-1
pV = i nB RT [Hence, a = 100% ]
T %m (H+) = 349.1 S cm2 mol-1
335. The study of the conductivity of electrolyte solutions Ans :
is important for the development of electrochemical (a) Conductivity of CH 3 COOH (weak electrolyte)
devices, for the characterisation of the dissociation Decreases with dilution because the number of
equilibrium of weak electrolytes and for the current carrying particles i.e., ions present per cm3
fundamental understanding of charge transport by of the solution becomes less and less on dilution.
ions. The conductivity of electrolyte is measured for
(b) T %m Al 2 (SO 4) 3 = 2l %m Al3+ + 3l %m SO 24-
electrolyte solution with concentrations in the range
of 10-3 to 10-1 mol L-1 as solution in this range of 858 = 2l %m Al3+ + 3 # 160
concentrations can be easily prepared. The molar l %m Al3+ = 858 - 480
conductivity (Am) of strong electrolyte solutions can 2
be nicely fit by Kohlrausch equation. = 189 S cm2 mol-1
Am = T %m - K C ...(1) (c) T %m (HCl) = l %H + l %Na + +
Where, T3 %m is the molar conductivity at infinite T %m (NaCl) = l %Na + l %Cl + -
dilution and C is the concentration of the solution. K T %m (CH 3 COONa) = l %CH COO + l %Na 3
- +
is an empirical proportionality constant to be obtained T %m (CH 3 COOH) = l %CH COO + l %H - +

3
from the experiment. The molar conductivity of weak

=l %+
H +l % -
Cl +l %
(CH 3 COO- +l % +
Na -l % -
Cl -l % +
Na
electrolytes, on the other hand, is dependent on the
degree of dissociation of the electrolyte. At the limit = T (HCl) + T (CH 3 COONa)
%
m
%
m
of very dilute solution, the Ostwald dilution law is
= - T %m NaCl
expected to be followed,
= 426 + 91 - 126 = 391 S cm2 mol-1
1 = 1 + T %m CA ...(2)
T %m T %m (T %m) 2 Kd or
Where, CA is the analytical concentration of the (d) According to Kohlraucht law,
electrolyte and Kd is dissociation constant. The molar
TCH 3 COOH = l%CH 3 COO- + l% H+
conductivity at infinite dilution can be decomposed
Degree of dissociation,
into the contributions of each ion.
T %m = V+ l %+ + V- l %- ...(3) a = T %m
Tm
Where, l + and l - are the ionic conductivities of 11.7 S cm2 mol-1
positive and negative ions, respectively and V+ and =
(49.9 + 349.1) S cm2 mol-1
l - are their stoichiometric coefficients in the salt
molecular formula. = 11.7 = 3 # 10-2
390
CLASS 12

CLASS 10

336. The standard electrode potentials are very important

and we can extract a lot of useful information from
them. If the standard electrode potential of an
electrode is greater than zero then its reduced form
is more stable compared to hydrogen gas. Similarly,
if the standard electrode potential is negative then
hydrogen gas is more stable than the reduced form of
the species. It can be seen that the standard electrode
potential for fluorine is the highest indicating that
fluorine gas (F2) has the maximum tendency to get
reduced to fluoride ions (F-) and therefore fluorine gas
is the strongest oxidising agent and fluoride ion is the
weakest reducing agent.
(i) Which is the weakest agent and why ?
(ii) What does a + ive E° value represents ?
(iii) Complete the following reaction :
Zn ^s h + Cu2+ âq h $
Ans :
(i) Lithium has the lowest electrode potential
indicating that lithium ion is the weakest oxidising
agent.
(ii) A positive E means that the redox couple is a
weaker reducing agent than the H+ /H 2 Couple.
(iii) Zn ^s h + Cu2+ âq h $ Zn2+ (aq) + Cu ^s h
337. We can construct innumerable number of galvanic cells

on the pattern of Daniell cell by taking combinations
of different half - cell. Each half - cell consists of a
metallic electrode dipped into an electrolyte. The two
half-cells are connected by a metal - lic wire through
a voltmeter and a switch externally. The electrolytes
of the two half cells are connected internally through
a salt bridge.
(i) What is the function of salt bridge ?
(ii) What is used as cathode in Daniel cell.
Ans :
(i) Salt bridge or ion bridge, in electrochemistry, is
a laboratory device used to connect the oxidation
and reduction half-cells of a galvanic cell.
(ii) What is used as cathode in Daniel cell. Zinc.
***********
Page 148 Chemical Kinetics Chap 3
CHAPTER 3
Chemical Kinetics
SUMMARY 3. FACTORS AFFECTING THE RATE OF REACTION

Following factors are affecting that rate of reaction :
(a) Conc. of reactants :
1. CHEMICAL KINETICS
Rate of reaction ? Conc. of reactants.
It is that branch of chemistry which deals with the
(b) Temperature of the system :
study of rates of chemical reactions, the factors
affecting them and the mechanisms of the reactions. Rate of reaction ? Temperature
(c) Nature of reactants and products
2. RATE OF REACTION Rate of reaction
It is change in concentration of a reactant or product 1
per unit time. ?
Bond dissociation energies of reactants
(a) Average rate of reaction
(d) Presence of catalyst
It is defined as the rate of reaction measured over
The rate of a reaction increases in the presence
a long period of time.
of a catalyst.
Let a reaction aA + bB $ cC + dD (e) Surface area
T [A ]
Average rate of reaction = - 1 Rate of reaction ? Surface area of reactants.
a Tt
(f) Exposure to radiation
T [B]
= -1 The rate of a reaction is increased by the use of
b Tt certain radiations.
T [C ] T [D ]
=1 =1
c Tt d Tt 4. RATE LAW
(b) Instantaneous rate of reaction The mathematical expression which denotes the
It is defined as the average rate of reaction when experimentally observed rate of a reaction in terms
it is measured over a very small interval of time. of the concentration of the reactants which actually
or influence the rate of reaction is called rate law.
It is the rate of change of concentration of any
Let a reaction aA + bB $ Products
one of the reactants or products at a particular
instant of time. So, Rate of reaction = k [A] a [B] b
Let a reaction aA + bB $ cC + dD a and b are the powers of concentration of reactants
Instantaneous rate of reaction which actually influence the rate of the reaction.
d [A ] d [B]
r =- 1 =-1 Where k = rate constant and a # a , b # b .
a dt b dt
d [C ] d [D ]
=1 =1 5. ORDER OF THE REACTION
c dt d dt
It is defined as the sum of powers to which the
It may be noted that negative sign before the concentration terms are raised in the rate law for the
expression of a reactant indicates that its conc.
reaction.
decreases with the passage of time. Units of rate
of reaction are mol L-1 time-1 or atm time-1 Order of reaction = a + b
Chap 3 Chemical Kinetics Page 149
6. RATE CONSTANT AND ITS UNIT 9. EXPERIMENTAL DETERMINATION OF ORDER OF REACTION

It is defined as the rate of reaction, when the concentration (a) Graphical method
of each of the reactants is unity. In general, the units of This method is used when there is only one reactant.
rate constant for the reaction of nth order are. In this method, a graph is plotted between rate of
Units of k = mol1 - n Ln - 1 time-1 reaction and concentration.
For the gaseous reaction.
Units of k = atm1 - n time-1
7. MOLECULARITY
Molecularity of a simple reaction is defined as the
total number of molecules of reactants which collide
simultaneously to bring a chemical reaction.
Let a reaction aA + bB $ Products
So, Molecularity = a + b
8. INTEGRATED RATE EXPRESSION

The integrated rate expression for different reaction
are as follows:
(a) For a zero order reaction
[A ] 0 - [A ]
k = =x
t t
Where [A] 0 = initial conc. of reactant (b) Integrated rate expression method
[A] = conc. of reactant after t time In this method, the kinetic data (obtained from
experiment) is fitted to different integrated rate
and [A ] 0 = a , equations, whenever the data fits with the equation
and [A ] = a - x for the correct order of the reaction, it will give
[A0] constant value of rate constant.
Note : If [A] = , then (c) Initial rate method
2
[A] 0
[A ] 0 - This method is used to calculate the order of those
k = 2
reactions, which contain more than one reactants and
t 1
2
[A ] 0 order may be zero, whole number or a fraction.

So, t 1 =
2
2k (d) Ostwald’s isolation method
Where t 1
2
= half-life time This method is used to find the order of a reaction
(b) For a first order reaction with respect to one reactant at a time. The total order
[A ] 0 of the reaction is then equal to the sum of the orders
k = 2.303 log of reaction for individual reactants.
t [A ] t
(e) Half-life period method
k = 2.303 log a
t a-x In this method, the graphs are plotted between t 1
2
Where a = initial conc. of [A] 0 (a - x) and [A] 0 .

[A] t conc. after time t . These graphs are given below:
When half reaction is completed, then
[A ]
k = 2.303 log [A]
t 1
2
0
k = 0.693
t 1
2
t = 69301
.
k2
In general, t ? 1n - 1
1
[A ] 0
2
Talking logarithm, we have

log k = log A - Ea
2.303 RT
13. CALCULATION OF ACTIVATION ENERGY, Ea

Activation energy can be determined by measuring the
; values of rate constant at two different temperatures.
Let k1 and k2 are the rate constants for the reaction at
temperatures T1 and T2 respectively, then
10. PSEUDO CHEMICAL REACTIONS
Those reactions which appear to be of higher order log k2 = Ea : 1 - 1 D
k1 2.303 R T1 T2
but actually follow lower order kinetics are called
Pseudo chemical reactions. 14. AMOUNT OF SUBSTANCE
Example : Amount of substance left after n half lines
Following reactions follows first order kinetics. [A ]
H+ = n0
C 12 H 12 O 11 + H 2 O T
C 6 H 12 O 6 + C 6 H 12 O 6 2
Sugar (Excess) Glu cos e Fructose
For this reaction, Rate ? [C 12 H 22 O 11] 15. RATE CONSTANT (K)

It is because water is present in such a large excess
(a) For reaction N 2 O 5 $ 2NO 2 + 1 O 2
that its conc. remains almost constant during the 2
reaction.
k = 2.303 log V3
t V3 - Vt
11. COLLISION THEORY OF REACTION RATES
Where Vt = Volume of O 2 after time t
According to collision theory, the rate of a reaction
V3 = Volume of O 2 after infinite time
depends upon the collision frequency (z) and the
fraction of effective collisions (f ). So, (b) For reaction NH 4 NO 2 (aq) $ 2H 2 O + N 2
Same expression as above is used and volume of
Rate of reaction ? z # f
N 2 is taken into account.
(a) With the increase in temperature, the kinetic
energy of molecules increases and this leads to (c) For reaction H 2 O 2 $ H 2 O + 1 O 2
2
an increase in collision frequency (z), as the
V
average kinetic energy of the molecules is directly k = 2.303 log 0
t Vt
proportional to absolute temperature.
Where V0 = Volume of KMnO 4 used for titration
(b) For effective collision, the colliding molecules
must have more than or equal to certain minimum at t = 0 ,
amount of energy called threshold energy (Ec) Vt = Volume of KMnO 4 used for titration
and proper orientation.
On increasing the temperature, the fraction of after time t .
effective collisions (f ) increases due to which rate (d) For reaction
of reaction increases. CH 3 COOC 2 H 5 + H 2 O
H+
CH 3 COOH + C 2 H 5 OH
12. ARRHENIUS EQUATION
k = 2.303 log 3 - 0
V V
t V3 - Vt
This equation gives us the variation of rate constant
Where V0 , Vt , V3 are volumes of NaOH used for
of a reaction with temperature. This equation
titration of same volume of reaction mixture after
gives a relationship between rate constant (k) and
0, t and 3 time.
temperature (T) as
(e) For reaction
k = Ae-E /RT a
H+
C 12 H 22 O 11 + H 2 O C 6 H 12 O 6 + C 6 H 12 O 6
Where, A = frequency factor Glu cos e Fructose
k = 2.303 log 0 - 3
Ea = activation energy r r
t r0 - rt
T = absolute temperature Where r0 , rt and r3 are polarimetric readings
R = Gas constant after time 0, t and 3 respectively.
(f) In the Arrhenius equation, when T " 3, 3. If the rate of a reaction is expressed by, Rate
then k = A . ec = n and rate becomes independent = k A 2 B . Then the order of reaction will be
of temperature. Further in a reaction, (a) 2 (b) 3
when Ea = 0 , then k = A (c) 1 (d) 0
i.e., Every collision of reactant molecules is Ans : SQP 2015, DELHI 2006
effective, Thus, activation energy of a reaction For the given rate - expression
cannot be zero.
(Rate) r = k 6A@ 2 6B@
Since, the sum of powers of the concentration terms as
given in the rate-law is known as the order of reaction.
***********
Hence, order of reaction = 2 + 1 = 3
OBJECTIVE QUESTIONS dt = k 6H @ and rates becomes 100 times when pH

+ n
4. If dx
changes from 2 to 1, the order of reaction is –
d [B]
(a) 1 (b) 2
1. For the reaction 3A $ 2B , rate of reaction + dt is
(c) 3 (d) 0
equal to
d [A ] d [A ] Ans : COMP 2001
(a) - 3 (b) - 2
2 dt 3 dt Rate = k 6H @+ n
(c) - 1
d [A ]
(d) +
2d [A] Where pH = 2, 6H+@ = 10-2 M
3 dt dt
pH = 2 , the rate is k 610-2@
n
At
Ans : COMP 2023
At pH = 1, the rate is k 610-1@n
- 1 d [A] = + 1 d [B] + d [B] = - 2 d [A]
3 dt 2 dt dt 3 dt Since the rate is increased by 100 times
Thus (b) is correct option. k 610-1@ = 100k 610-2@n
n
2. Which of the following graph represents a zero order 10-n = 102 # 10-2n = 102 - 2n
reaction?
^2n - n h = 2 or n = 2
5. For a zero order reaction:
1
(a) t1 2 \ a (b) t1 2 \ a
(c) t1 2 \ a2 (d) t1 2 \ 1
a2
Ans : DELHI 2003
The half life of a zero order reaction depends on initial

concentration of reacting species and the rate constant,
K. It is directly proportional to initial concentration
of the reactant whereas it is inversely proportional to
the rate constant, K.
Ans : OD 2023 6. t1/2 for first order reaction is :
Rate equation for zero order reaction is
(a) 0.6 (b) 0.693
rate = k 6A@0 = k k k
0 . 683 0 . 10
6A0@ - 6A@ = kt
(c) (d)
k k
A graph of rate vs time for a zero order reaction is a Ans : FOREIGN 2007
straight line with down ward slope. Half life for first order reaction is constant and
A graph of 6A@ versus t is a straight line with slope depends on the value of rate constant.
equal to - k . It is equal to 0.693
k .
The order of reaction H 2 (g) + Cl 2 (g)

sunlight
d [Br2] d [Br-]
7. 2HCl =- 3
in water is : dt 5 dt
(a) 3 (b) 2 Thus (d) is correct option.
(c) 1 (d) 0 11. According to the collision theory of reaction rates, the
Ans : OD 2005 rate of reaction increases with temperature due to
Reaction between hydrogen and chlorine under the (a) greater number of collision
influence of sunlight is the photochemical combination
(b) higher velocity of reacting molecules
of hydrogen and chlorine. The reaction does not take
place in the dark. This is a zero-order reaction as the (c) greater number of molecules having the activation
rate is independent of concentration of both hydrogen energy
and chlorine goes in a closed glass vessel containing (d) decrease in the activation energy
calculated amount of water which can dissolve the Ans : FOREIGN 2004
product H 2 + Cl " 2HCl .
12. Consider the reaction N 2 (g) + 3H 2 (g) $ 2NH 3 (g)
8. The unit of rate constant of first order reaction is :
d [NH 3] d [H 2]
(a) time-1 (b) mole litre-1 sec-1 The equality relationship between dt and dt is
(c) litre mole-1 sec (d) litre mole-1 sec-1 d [NH 3] d [H 2] d [NH 3] d [H 2]
(a) + =- 2 (b) + =- 3
Ans : SQP 2011
dt 3 dt dt 2 dt
d [NH 3] d [H 2] d [NH 3] d [H 2]
The rate of first order reaction may be expressed as (c) =- (d) =- 1
dt dt dt 3 dt
Rate = K [A]
Ans : OD 2006
mol L-1 = K (mol L-1) If we write rate of reaction in terms of concentration
S
of NH 3 and H 2 , then
K = S-1 = time-1
d [NH 3] d [H 2]
Thus (a) is correct option. Rate of reaction = 1 =- 1
2 dt 3 dt
The rate of reaction depends upon the d [NH 3] d [H 2]
9.
So, =- 2
(a) volume (b) force dt 3 dt
(c) pressure (d) conc. of reactants
Ans : COMP 2014, SQP 2012 13. In a first-order reaction A " B , if k is the rate constant
The rate of reaction is the speed at which the reactants and initial concentration of the reactant A is 0.5 M,
are converted into products. It depends upon the then the half-life is
concentration of reactants. e.g. for the reaction log 2 log 2
(a) (b)
k k 0.5
A + B $ Product ; r ? [A] [B]
(c) ln 2 (d) 0.693
Thus (d) is correct option. k 0.5k
10. In the following reaction, how is the rate of Ans : SQP 2010
appearance of the underlined product related to the For a first order reaction
rate of disappearance of the underlined reactant? k = 2.303 log 10 a
BrO -3 (aq) + 5Br- (aq) + 6H+ (aq) $ 3Br2 (1) + 2H 2 O (1) t a-x
when t = t1/2
d [Br2] d [Br-] d [Br2] d [Br-]
(a) =- 5 (b) =-
dt 3 dt dt dt k = 2.303 log 10 a a
t1/2 a- 2
d [Br2] 3 d [Br-] d [Br2] d [Br-]
(c) = (d) =- 3
dt 5 dt dt 5 dt t1/2 = 2.303 log 10 2
k
Ans : DELHI 2009
Rate of reaction = ln 2
k
d [Br-] d [Br2] Thus (c) is correct option.
-1 =+ 1
5 dt 3 dt
14. The temperature dependence of rate constant (k) of (c) It is not affected with the stoichiometric coefficient
a chemical reaction is written in terms of Arrhenius of the reactants
equation, k = Ae -RTE . Activation energy (E a*) of the
*
a
(d) Order cannot be fractional
reaction can be calculated by plotting
Ans : FOREIGN 2013
(a) log k vs 1 (b) k vs T Order of a reaction can be fractional. Rest of all
log T
are true. Order of a reaction can be determined
(c) k vs 1 (d) log k vs 1
log T T experimentally.
Ans : COMP 2011 Thus (d) is correct option.
k = Ae-E /RT
a
17. The plot of concentration of the reactant vs. time for
Ea a reaction is a straight line with a negative slope. The
log k = log A - reaction follows a
2.303RT
Comparing the above equation with (a) zero order rate equation
y = mx + c (b) first order rate equation
y = log k , x = 1
T
(c) second order rate equation
Thus A plot of log 10 k vs T1 should be a straight line, (d) third order rate equation
-E
with slope equal to 2.303a
RT and intercept equal to log A
Ans : SQP 2009
For a first reaction

Since, Slope = - Ea dx = k (a - x)
2.303R
dt
Ea = - 2.303R # Slope
on integration
dx
# (a - x)
= kdt#
i.e. - ln (a - x) = kt + c
kt = ln a - ln (a - x)
kt 2.303 [log a - log (a - x)]
Thus if we plot a graph between log a and t ,we get

15. The rate constant of a reaction depends on
(a) temperature
(b) initial concentration of the reactants
(c) time of reaction
(d) extent of reaction
18.
It is a constant of a particular reaction at a given

temperature. It does not depend upon initial
concentration of the reactants, time of reaction and
extent of reaction. Half-life of this reaction is independent of concentration
Thus (a) is correct option. of reactant. After 10 minutes volume of N 2 gas is 10
16. Which of the following statement for order of reaction litre and after complete reaction 100 litre. The rate
is not correct? constant of the reaction in min-1 unit is –
(a) Order can be determined experimentally (a) 2.303 (b) 2.303 log 5.0
10 10
(b) Order of reaction is equal to sum of the powers of 2 . 303 log 2.0
concentration terms in differential rate law (c) (d) 303 log 4.0
2 .
10 10
Ans : OD 2001 d [B]

21. 3A $ 2B , rate of reaction dt is equal to
Given, Half life of the reaction is independent of
d [A ] d [A ]
concentration of reactant. (a) - 3 (b) - 2
2 dt 3 dt
So, it is a 1st order reaction.
d [A ] d [A ]
Given, Time t = 10 minutes (c) - 1 (d) + 2
3 dt dt
Initial reactant ni = 100 litre
Ans : FOREIGN 2012
Final reactant n f = 10 litre
3A $ 2B
Thus, k = 2.303 # log e ni o Rate of appearance of B is equal to rate of
t nf
disappearance of A
So, putting the values in the formula
1 d [B] = - 1 d [A]
k = 2.303 # log c 100 m 2 dt 3 dt
10 10
d [B] d [A ]
= 2.303 # 1 = 2.303 =- 2
10 10 dt 3 dt
19. Activation energy of a chemical reaction can be 22. If the rate of the reaction is equal to the rate constant,
determined by the order of the reaction is
(a) evaluating rate constant at standard temperature (a) 3 (b) 0
(b) evaluating velocities of reaction at two different (c) 1 (d) 2
temperatures Ans : OD 2009
(c) evaluating rate constants at two different Since, r = k [A ] n
temperatures
if n =0
(d) changing concentration of reactants
r = k [A ] 0
Ans : COMP 2004
We know that the activation energy of chemical or r =k

reaction is given by formula Thus for zero order reactions rate is equal to the rate
constant.
= log k2 = Ea :T2 - T1 D ,
k1 2.303 T1 T2 Thus (b) is correct option.
Where, k1 is the rate constant at temperature T1 d [NH 3]
and k2 is the rate constant at temperature T2 and Ea 23. For the reaction, N 2 + 3H 2 $ 2NH 3 dt = 2 # 10-4
is the activation energy. Therefore activation energy mol L-1 s-1 , the value of -
d [H 2]
would be
dt
of chemical reaction determined by evaluating rate
constant at two different temperatures. (a) 4 # 10-4 mol L-1 s-1 (b) 6 # 10-4 mol L-1 s-1
Thus (c) is correct option. (c) 1 # 10-4 mol L-1 s-1 (d) 3 # 10-4 mol L-1 s-1
20. Which of the following statements is incorrect?
Ans : SQP 2013, OD 2009
(a) Activation energy for the forward reaction equals
Rate of disappearance of
activation energy for the reverse reaction
H 2 =Rate of formation of NH 3
(b) For a reversible reaction, an increase in
d [H 2] d [NH 3]
temperature increase the reaction rate for both -1 =1
the forward and the backward reaction 3 dt 2 dt
d [H 2] d [NH 3]
(c) The larger the initial reactant concentration for a - =3
dt 2 dt
second order reaction, the shorter its half-life
(d) When Dt is infinitesimally small, the average rate = 3 # 2 # 10-4
2
equals the instantaneous rate = 3 # 10-4 mol L-1 s-1
Ans : DELHI 2008
Ea (F.R.) ! Ea (B.R.)
24. A catalyst is used (c) the concentration of the product

(a) only for increasing the velocity of the reaction (d) the material of the vessel in which reaction is
(b) for altering the velocity of the reaction carried out
(c) Only for decreasing the velocity of the reaction Ans : OD 2000
(d) All a, b and c are correct

For zero order reaction, dx
dt = k [reactant]°.
Thus the rate of zero order reaction is independent of
Ans : COMP 2016
concentration of reactants.
A catalyst is used for increasing or decreasing the
velocity of a reaction.
Thus (b) is correct option. 28. Order of reaction can be
(a) zero (b) fraction
25. The enzyme which can catalyse the conversion of
glucose to ethanol is (c) whole number (d) integer, fraction, zero
(a) zymase (b) invertase Ans : SQP 2005
(c) maltase (d) diastase Order of reaction is equal to the number of molecules
whose concentration is changing with times. It can be
Ans : DELHI 2004
zero or in fractions or an integer.
Zymase catalyses the conversion of glucose to ethanol.
29. The unit of rate constant for a zero order reaction is
26. The rate of a chemical reaction
(a) mol L-1 s-1 (b) L mol-1 s-1
(a) increases as the reaction proceeds
(c) L2 mol-2 s-1 (d) s-1
(b) decreases as the reaction proceeds
Ans : COMP 2010, OD 2007
(c) may increase or decrease during the reaction 0
Rate = K (A)
(d) remains constant as the reaction proceeds
Unit of K = mol L-1 s-1
Ans : FOREIGN 2002
The rate of a chemical reaction is directly proportional
to the concentration of the reactants i.e. rate of 30. In the Haber process for the manufacture of ammonia
reaction decreases with decrease of concentration the following catalyst is used
and increases with increase in concentration. As the (a) platinized asbestos
reaction progresses the reactant is converted into (b) iron with molybdenum as promoter
the product and thus the concentration of reactants
(c) copper oxide
decreases while that of the products increases.
(d) alumina
Ans : DELHI 2014
In Haber’s process, ammonia is manufactured from

N 2 and H 2 using iron as catalyst with molybdenum as
promoter at high temperature and pressure
Fe 2 O 3 (catalyst)
N 2 + 3H 2 MO (catalytic promoter)
2NH 3
31. The rate of a reaction does not depend upon
(a) temperature (b) concentration
(c) catalyst (d) none of these
Ans : FOREIGN 2017
Thus (b) is correct option. Rate of reaction depends upon all the three factors
27. A zero order reaction is one whose rate is independent i.e., temperature, concentration and catalyst.
of (i) As the concentration of reactants increases, the
(a) the concentration of the reactants reaction rate increases.
(ii) Catalyst is a substance that increases the rate of
(b) the temperature of reaction reaction.
(iii) Rate of reaction increases with increase in Ans : DELHI 2001
temperature. The reaction involving two different reactant can

Thus (d) is correct option. never be unimolecular.
32. Regarding criteria of catalysis which one of the
following statements is not true? 36. Half life period of a first-order reaction is 1386 seconds.
(a) The catalyst is unchanged chemically at the end The specific rate constant of the reaction is
of the reaction (a) 0.5 # 10-2 s-1 (b) 0.5 # 10-3 s-1
(b) A small quantity of catalyst is often sufficient to (c) 5.0 # 10-2 s-1 (d) 5.0 # 10-3 s-1
bring about a considerable amount of reaction Ans : FOREIGN 2013
(c) In a reversible reaction the catalyst alters the As we know that

equilibrium position
t1/2 = 0.693
k
(d) The catalyst accelerates the reaction
k = 0 . 693
Ans : OD 2000 1386
Catalyst does not alter the position of equilibrium in = 0.5 # 10-3 s-1
a reversible reaction.
dil H 2 SO 4 37. Rate of reaction can be expressed by Arrhenius
33. C 12 H 22 O 11 + H 2 O C 6 H 12 O 6 (aq) + C 6 H 12 O 6 (aq) equation as : k = Ae-E /RT . In this equation E
a
In this reaction, dil H 2 SO 4 is called represents

(a) homogeneous catalysis (a) the total energy of the reacting molecules at a
(b) heterogeneous catalysis temperature, T
(b) the fraction of molecules with energy greater than
(c) homogeneous catalyst
the activation energy of the reaction
(d) heterogeneous catalyst
(c) the energy below which all the colliding molecules
Ans : SQP 2005 will react
The catalyst is in the same phase as the reactants and (d) the energy below which colliding molecules will
products. not react
Therefore, in this reaction, H 2 SO 4 is called as Ans : SQP 2007
homogeneous catalyst. -E/RT
dil H 2 SO 4
In Arrhenius equation K = Ae , E is the energy of
C 12 H 22 O 11 + H 2 O C 6 H 12 O 6 (aq) + C 6 H 12 O 6 (aq) activation, which is required by the colliding molecules
(solid)
to react resulting in the formation of products.
34. A catalyst can affect reversible reaction by
38. In respect of the equation k = Ae-E /RT in chemical
a
(a) changing equilibrium constant kinetics, which of the following statements is correct?
(b) slowing forward reaction (a) A is adsorption factor
(c) attaining equilibrium in both directions (b) Ea is energy of activation
(d) none of the above (c) R is Rydberg’s constant
Ans : COMP 2009, SQP 2005 (d) k is equilibrium constant
A catalyst can affect reversible reaction by attaining Ans : OD 2011
equilibria in both directions. In equation
K = Ae-E /RT ;
a
35. A reaction involving two different reactants can never

be A = frequency factor,
(a) bimolecular reaction K = velocity constant,
(b) second order reaction R = gas constant
(c) first order reaction and Ea = energy of activation
(d) unimolecular reaction Thus (b) is correct option.
39. Select the rate law that corresponds to data shown for 41. The rate of reaction between A and B increases by a
the following reaction factor of 100, when the concentration of A is increased
A + B $ products 10 folds, the order of reaction with respect to A is
(a) 10 (b) 1
Exp. [A ] [B] Initial rate (c) 4 (d) 2
1 0.012 0.035 0.1 Ans : FOREIGN 2002
2 0.024 0.070 0.8 l
(Rate 1) = K [A] [B] ; m
3 0.024 0.035 0.1 (Rate) 2 = K (10 [A]) l [B] m

4 0.012 0.070 0.8 (Rate) 2
Hence, = 100 = 10l
(a) rate = k [B] 3
(b) rate = k [B] 4 (Rate) 1
102 = 10l
(c) rate = k [A] [B] 3 (d) rate = k [A] 2 [B] 2
Ans : COMP 2016
l =2
From data 1 and 3, it is clear that keeping [B] constant, Thus (d) is correct option.
[A] is doubled, rate remains unaffected. Hence rate is
42. For an exothermic reaction, the energy of activation
independent of [A]. From 1 and 4, keeping [A] constant,
of the reactants is
[B] is doubled, rate become 8 times. Hence rate ? [B] 3 .
(a) equal to the energy of activation of products.
(b) less than the energy of activation of products.
40. The plot that represents the zero order reaction is
(c) greater than the energy of activation of products.
(d) sometimes greater and sometimes less than that
of the products.
Ans : OD 2003
Ea (Forward) + DH = Ea (Backward)
For Exothermic reaction, DH = - ve and
Hence, Activation energy of reactant is less than the
energy of activation of products.
Ans : DELHI 2005
For zero order reaction, Thus (b) is correct option.

rate, r = k [R] °
43. 3A $ B + C , it would be a zero order reaction
dR = k when
dt
(a) the rate of reaction is proportional to square of
R = kt + R0 concentration of A.
Where, R0 is the concentration of reactant at time (b) the rate of reaction remains same at any
t = 0. concentration of A.
(c) the rate remains unchanged at any concentration (a) 2 (b) - 2

of B and C . (c) 1 (d) - 1
(d) the rate of reaction doubles if concentration of B Ans : FOREIGN 2002
is increased to double. x y
Rate 1 = k [A] [B] ...(1)
Ans : SQP 2000
Rate 1 = k [A] x [2B] y ...(2)
For reaction 3A $ B + C 4
If it is zero order reaction r = k [A] 0 , i.e. the rate
or Rate 1 = 4k [A] x [2B] y
remains same at any concentration of 'A' . i.e.
independent upon concentration of A. From (1) and (2) we get
Thus (b) is correct option. k [A] x [B] y
= k [A] x [2B] y
4
44. For the reaction 2A + B $ 3C + D
[B] y
which of the following does not express the reaction = [2B] y
4
rate?
1 = 2B y
(a) -
d [B]
(b)
d [D ] or
4 bB l
dt dt
1 = 2y or 2-2 = 2y
d [A ] d [C ]
(c) - 1 (d) - 1 4
2 dt 3 dt
Ans : COMP 2009
d [C]
47. The reaction of first order with respect to H 2 (g) and
In the given options - 13 dt will not represent the ICl (g), following mechanisms were proposed
reaction rate. It should not have - ve sign as it is
product. H 2 (g) + 2ICl (g) $ 2HCl (g) + I 2 (g)
Since 1 d [C]
shows the rate of formation of product C Mechanism A:
3 dt
which will be positive. H 2 (g) + 2ICl (g) $ 2HCl (g) + I 2 (g)
Thus (d) is correct option. Mechanism B:
45. The reaction A " B follows first order kinetics. The H 2 (g) + ICl (g) $ HI (g); slow
time taken for 0.8 mole of A to produce 0.6 mole of B
is 1 hour. What is the time taken for conversion of 0.9 HI (g) + ICl (g) $ HCl (g) + I 2 (g); fast
mole of A to produce 0.675 mole of B ? Which of the above mechanism(s) can be consistent
(a) 2 hours (b) 1 hour with the given information about the reaction?
(c) 0.5 hour (d) 0.25 hour (a) A and B both (b) neither A nor B
Ans : DELHI 2014, OD 2007 (c) A only (d) B only
A " B for a first order reaction. Ans : OD 2016
given a = 0.8 mol, (a - x) = 0.8 - 0.6 = 0.2 As the slowest step is the rate determining step thus
the mechanism B will be more consistent with the
k = 2.303 log 0.8 given information also because it involve one molecule
1 0.2
or k = 2.303 log 4 of H 2 and one molecule of ICl it can expressed as
r = k [H 2] [ICl]
Again, a = 0.9 Which shows that the reaction is first order w.r.t.
(a - x) = 0.9 - 0.675 = 0.225 both H 2 and ICl.
k 2.303 log 0.9
t 0.225
48. For the reaction H 2 (g) + Br2 (g) 2HBr (g), the
2.303 log 4 = 2 . 303 log 4
t rate law is rate = k [H 2] [Br2] , which of the following
1
2
Thus (b) is correct option. statement is true about this reaction

46. The rate of reaction between two reactants A and (a) The reaction is a second order one
3
B decreases by a factor of 4 if the concentration of (b) Molecularity of the reaction is 2
reactant B is doubled. The order of this reaction with (c) The unit of k is s-1
respect to reactant B is (d) Molecularity of the reaction is 2
Ans : SQP 2006

51. A substance 'A' decomposes by a first order reaction
H 2 (g) + Br2 (g) 2HBr (g) starting initially with [A] = 2.00 m and after 200 min,
1
[A] becomes 0.15 m. For this reaction t1/2 is
Rate law R = k [H 2] [Br2] 2 (a) 53.72 min (b) 50.49 min
Order of reaction = 1 + 1 = 3 (c) 48.45 min (d) 46.45 min
2 2
Molecularity of reaction = 2 Ans : FOREIGN 2009
R Given, initial concentration (a) = 2.00 m; Time taken

The unit of k = 1 (t) = 200 min. and final concentration (a - x) = 0.15
[H 2] [Br2] 2
m. For a first order reaction rate constant,
= mole L-1 s-1
1
[mole L-1] [mole L-1] 2 k = 2.303 log a
r a-x
= mole-1/2 L1/2 s-1 2 . 303
= log 2.00
Thus (d) is correct option. 200 0.15
= 2.303 # (0.31 + 0.824)
49. Units of rate constant of first and zero order reactions 200
in terms of molarity M unit are respectively = 1.29 # 10-2 min-1
(a) sec-1, M sec-1 (b) sec-1, M
Further (t1/2) = 0.693
(c) M sec-1, sec-1 (d) M, sec-1 k
Ans : COMP 2017, DELHI 2015 = 0.693 = 53.49 min.
1.29 # 10-2
For a zero order reaction.
rate = k [A] °
52. For the reaction A " B , the rate law expression is rate
i.e. rate = k = k [A] . Which of the following statements is incorrect?
Hence, Unit of k = M. sec-1 (a) The reaction follows first order kinetics.
For a first order reaction. (b) The t1/2 of reaction depends on initial concentration
of reactants.
rate = k [A]
-1 (c) k is constant for the reaction at a constant
k = M. sec = sec-1 temperature.
M
(d) The rate law provides a simple way of predicting
the concentration of reactants and products at
50. In a reversible reaction the energy of activation of the any time after the start of the products at any
forward reaction is 50 kcal. The energy of activation time after the start of the reaction.
for the reverse reaction will be Ans : OD 2015
(a) <50 kcal. For first order reaction t1/2 independent of initial
(b) 50 kcal. concentration.
(c) >50 kcal. Thus (b) is correct option.
(d) either greater than or less than 50 kcal. 53. Half life a first order reaction is 4 s and the initial
Ans : DELHI 2002 concentration of the reactants is 0.12 M. The
concentration of the reactant left after 16 s is
DH = Ea (forward) - Ea (backward)
(a) 0.0075 M (b) 0.06 M
Thus energy of activation for reverse reaction depend
upon whether reaction is exothermic or endothermic. (c) 0.03 M (d) 0.015 M
If reaction is exothermic, Ans : COMP 2006
DH = - ve Ea (backward) > Ea (forward) Given,

If reaction is endothermic t1/2 = 4 s
DH = + ve Ea (backward) < Ea (forward) T = 16
Thus (d) is correct option. As we know that, n = T
t12
= 16 = 4 (` T = n # t1/2) As DH = Ea (forward reaction) - Ea (backward reaction)

4
For exothermic reaction
A = A° b 1 l
n
2 DH = - ve
= 0.12 # b 1 l - DH = Ea (forward reaction) - Ea (backward reaction)

4
2
or Ea (forward reaction) = Ea (backward reaction) - DH
= 0 . 12 = 0.0075 M
16 Ea (forward reaction) < Ea (backward reaction)
Thus (a) is correct option. For endothermic reaction
54. When a biochemical reaction is carried out in DH = + ve
laboratory in the absence of enzyme then rate of
reaction obtained 10-6 times, then activation energy DH = Ea (forward reaction) + Ea (backward reaction)
of reaction in the presence of enzyme is Ea (forward reaction) = DH + Ea (backward reaction)
6
(a) RT Thus (d) is correct option.
(b) different from Ea obtained in laboratory. 56. The rate of a first order reaction is 1.5 # 10-2
(c) P is required. mol L-1 min-1 at 0.5 M concentration of the reactant.
The half life of the reaction is
(d) can’t say anything.
(a) 0.383 min (b) 23.1 min
Ans : SQP 2017
(c) 8.73 min (d) 7.53 min
The presence of enzyme (catalyst) increases the speed
of reaction by lowering the energy barrier, i.e. a new Ans : COMP 2003
path is followed with lower activation energy. For a first order reaction,
A $ products
r = k [A ]
-2
or k = r = 1.5 # 10
[A ] 0.5
= 3 # 10-2
Further, t1/2 = 0.693 = 0.693-2 = 23.1 min

k 3 # 10
57. For the reaction 2N 2 O 5 $ 4NO 2 + O 2 , rate

and rate constant are 1.02 # 10-4 mol L-1 s-1 and
3.4 # 10 -5 sec -1 respectively then concentration of
Here, Er is the threshold energy. N 2 O 5 at that time will be
Ea and Ea1 is energy of activation of reaction in (a) 1.732 M (b) 3 M
absence and presence of catalyst respectively.
(c) 3.4 # 105 M (d) 1.02 # 10-4 M
Ans : DELHI 2006, 2005
55. The activation energy for a simple chemical reaction
A $ B is Ea in forward direction. The activation 2N 2 O 5 $ 4NO 2 + O 2
energy for reverse reaction from the unit of rate constant it is clear that the reaction
(a) is always double of Ea . follow first order kinetics. Hence by rate law equation
(b) is negative of Ea . r = k [N 2 O 5]
(c) is always less than Ea . where r = 1.02 # 10-4 ,
(d) can be less than or more than Ea . k = 3.4 # 10-5
Ans : SQP 2002 1.02 # 10-4 = 3.4 # 10-5 N 2 O 5
The activation energy of reverse reaction will depend
[N 2 O 5] = 3 M
upon whether the forward reaction is exothermic or
endothermic. Thus (b) is correct option.
58. If 60% of a first order reaction was completed in 60 60. The chemical reaction 2O 3 $ 3O 2 proceeds as
minutes, 50% of the same reaction would be completed follows:
in approximately O3
Fast
O 2 + O; O + O 3
Slow
2O 2
(a) 45 minutes (b) 60 minutes
the rate law expression should be
(c) 40 minutes (d) 50 minutes
(a) r = k [O 3] 2 (b) r = k [O 3] 2 [O 2] -1
(log 4 = 0.60, log 5 = 0.69)
(c) r = k3 [O 3] [O 2] 2 (d) r = [O 3] [O 2] 2
Ans : FOREIGN 2009
For a first order reaction Ans : SQP 2017

Fast Slow
O3 O 2 + O; O + O 3 2O 2
k = 2.303 log a
t a-x
[O 2] [O]
when t = 60 and x = 60% k = (I)
[O 3]
k = 2.303 log 100 Rate = k ' [O 3] [O]
60 100 - 60
k ' [O 3] K [O 3]
2 . 303 100 put [O] from (I) r =
= log [O 2]
60 40
r = k [O 3] 2 [O 2] -1
Now, t1/2 = 2.303 log 100
0.0153 100 - 50 Thus (b) is correct option.
= 2.303 # log 2 61. Consider a reaction aG + bH $ Products . When
0.0153
concentration of both the reactants G and H is
= 2.303 # 0.3010 = 45.31 min. doubled, the rate increases by eight times. However,
0.0153
Thus (a) is correct option. when concentration of H fixed, the rate is doubled.
The overall order of the reaction is
59. The rate constants k1 and k2 for two different reactions
(a) 0 (b) 1
are 1016:e-2000/T and 1015:e-1000/T , respectively. The
temperature at which k1 = k2 is (c) 2 (d) 3
Ans : COMP 2000
(a) 1000 K (b) 2000 K
2.303 Overall order = sum of orders w.r.t. each reactant.
(c) 2000 K (d) 1000 K Let the order be x and y for G and H respectively
2.303
Ans : OD 2015, SQP 2012 Exp.No. [G] mole [H] mole rate(mole
Given, litre-1 litre-1 litre-1 time-1 )
2000
k1 = 1016 e- T 1. a b r
1000
2. 2a 2b 8r
and k2 = 1015 e- T 3. 2a b 2r
when k1 and k2 are equal at any temperature T , we have
Applying r = k [G] x [H] y we get, x = 1, y = 2
16 - 2000 15 - 1000
10 e T = 10 e T Hence, For (1) and (3), the rate is doubled when
15 - 2000 1000 concentration of G is doubled keeping that of H
10 # 10 e T = 1015 e- T
constant.
2000 1000
10e- T = e- T i.e., rate ? [G]
ln 10 - 2000 = 1000 Hence, x =1
T T
From (2) and (3), y =2
ln 10 = 2000 - 1000 Hence, Overall order is 3.
T T
2.303 log 10 =
T
62. During the kinetic study of the reaction
2.303 # 1 # T = 1000 [` log 10 = 1]
2A + B $ C + D , following results were obtained
T = 1000 K
2.303
Run [A] /mol L-1 [B] /mol L-1 Initial rate of (c) increasing the concentration of the Cl 2
formation of (d) doing all of the above
D/mol L-1 min -1 Ans : FOREIGN 2001
-1
I 0.1 0.1 6.0 # 10 2NO (g) + Cl 2 (g) $ 2NOCl (g)
-1
II 0.3 0.2 7.2 # 10 Rate = k [NO] 2 [Cl]
III 0.3 0.4 2.88 # 10-1 The value of rate constant can be increased by
increasing the temperature.
IV 0.4 1 2.40 # 10-1
Based on the above data which one of the following
65. For a first order reaction A " B the reaction rate
correct?
at reactant concentration of 0.01 M is found to be
(a) rate = k [A] 2 [B] (b) rate = k [A] [B] 2.0 # 10-5 mol L-1 s-1 . The half life period of the
(c) rate = k [A] 2 [B] 2 (d) rate = k [A] [B] 2 reaction is
Ans : SQP 2005
(a) 30 s (b) 220 s
In case of (II) and (III) keeping concentration of [A] (c) 300 s (d) 347 s
constant, when the concentration of [B] is doubled, the Ans : OD 2009
rate quadruples. Hence it is second order with respect Given,
to [B]. In case of I and IV keeping the concentration
[A] = 0.01 M
of [B] constant, when the concentration of [A] is
increased four times, rate also increases four times. Rate = 2.0 # 10-5 mol L-1 s-1
Hence, the order with respect to A is one, For a first order reaction
Hence, Rate = k [A] [B] 2 Rate = k [A]
Thus (d) is correct option. -5
k = 2.0 # 10 = 2 # 10-3
63. For the reaction [0.01]
[N 2 O 5 (g) $ 2NO 2 (g) + 12 O 2 (g)] the value of rate t1/2 = 0 .693 = 347 s
of disappearance of N 2 O 5 is given as 6.25 # 10-3 2 # 10-3
mol L-1 s-1 . The rate of formation of NO 2 and O 2 is Thus (d) is correct option.
given respectively as
66. For the reaction A + B $ products , it is observed
(a) 6.25 # 10-3 mol L-1 s-1 and 6.25 # 10-3 mol L-1 s-1 that
(b) 1.25 # 10-2 mol L-1 s-1 and 3.125 # 10-3 mol L-1 s-1 1. On doubling the initial concentration of A only,
(c) 6.25 # 10-3 mol L-1 s-1 and 3.125 # 10-3 mol L-1 s-1 the rate of reaction is also doubled and
2. On doubling the initial concentrations of both A
(d) 1.25 # 10-2 mol L-1 s-1 and 6.25 # 10-3 mol L-1 s-1
and B , there is a change by a factor of 8 in the
Ans : DELHI 2015, OD 2011 rate of the reaction.
[N 2 O 5 (g) $ 2NO 2 (g) + O 2 (g)]
1
2 The rate of this reaction is given by
(a) rate = k [A] [B] 2 (b) rate = k [A] 2 [B] 2
- d [N 2 O 5] = + 1 d [NO 2] = 2 d [O 2]
dt 2 dt dt (c) rate = k [A] [B] (d) rate = k [A] 2 [B]
d [NO ] = 1.25 10-2 mol L-1 s-1
dt 2 # Ans : SQP 2016
d [O ] = 3.125 10-3 mol L-1 s-1 When concentration A is doubled,rate is doubled.

dt 2 #
Hence order with respect to A is one.
When concentration of both A and B are doubled,
64. The rate of the reaction rate increases by 8 times hence order with respect to
2NO + Cl 2 $ 2NOCl is given by the rate equation B is 2.
rate = k [NO] 2 [Cl2] Hence, rate = k [A] 1 [B] 2
The value of the rate constant can be increased by Total order = 1 + 2 = 3
(a) increasing the concentration of NO Thus (a) is correct option.
(b) increasing the temperature
67. For the reaction N 2 (g) + O 2 (g) 2NO (g), the Ea > DH
equilibrium constant is K1 . The equilibrium constant Thus (c) is correct option.
is K2 for the reaction 69. If concentration of reactants is increased by 'x' , then
2NO (g) + O 2 (g) 2NO 2 (g) k becomes
What is K for the reaction (a) ln k (b) k
x x
NO 2 (g) 1
2 N 2 (g) + O 2 (g) ? (c) k + x (d) k
1 1 Ans : FOREIGN 2007
(a) (b)
(2K1 K2) (4K1 K2) Rate of constant does not change with concentration.
1
(c) ; 1 E2 (d) 1
(K1 K2) (K1 K2) 70. The Arrhenius equation expressing the effect of
Ans : COMP 2011 temperature on the rate constant of the reaction is
For the reaction (a) k = e-E/Rt (b) k = Ea
RT
N 2 (g) + O 2 (g) 2NO (g) E
(c) k = log e a (d) k = Ae-E /RT a
[NO 2] 2 RT
K1 =
[N 2] [O 2] Ans : OD 2017, DELHI 2010
For the reaction Thus (d) is correct option.
2NO (g) + O 2 (g) 2NO 2 (g) 71. The rate of the reaction 2N 2 O 5 $ 4NO 2 + O 2 can
[NO 2] 2
be written in three ways:
K2 =
[NO] 2 [O 2] d [N 2 O 5] d [NO2]
For the reaction - = k [N 2 O 5], = k l [N2 O5],
dt dt
NO 2 (g) 1
N 2 (g) + O 2 (g) d [O 2]
2 = k m [N 2 O 5]
1
dt
[N 2] 2 [O 2] The relationship between k and kl and between k
K =
[NO 2] and km are
Hence, K = 1 1 (a) kl = 2k; kl = k (b) kl = 2k; k m = k2
K1 # K2
1 1 1 (c) kl = 2k; k m = 2k (d) kl = k; k m = k
[N ] 2 [O 2] 2 [NO] [O 2] 2
K = 2 # Ans : SQP 2001
[NO] [NO 2]
1 Rate of disappearance of reactants = Rate of
[N ] 2 [O 2] appearance of products
= 2
[NO 2]
d [N 2 O 5] d [NO 2] d [O 2]
Thus (c) is correct option. -1 =1 =
2 dt 4 dt dt
68. For an endothermic reaction, energy of activation is 1 k [N O ] = 1 kl [N O ] = k m [N O ]
Ea and enthalpy of reaction of DH (both of these in 2 2 5
4 2 5 2 5
kJ/mol). Minimum value of Ea will be k = kl = k m

(a) less than DH (b) equal to DH 2 4
(c) more than DH (d) equal to zero kl = 2k
Ans : DELHI 2002
km = k
2
72. In a 1st order reaction, reactant concentration C varies
with time t as
(a) C1 increases linearly with t
(b) log C decreases linearly with t
1
(c) C decreases with t
1
(d) log C decreases with t
Ans : COMP 2006

76. The hypothetical reaction
A2 + B2 $ 2AB ; follows the following mechanism
Fast Slow
A2 A + A, A + B 2 AB + B ,
Fast
A+B AB .
The order of the overall reaction is
(a) 0 (b) 1
3
(c) 2 (d) 2

Thus (b) is correct option. A2 + B2 $ 2AB ;
73. In the reaction 2A + B $ A2 B , if the concentration Fast
of A is doubled and that of B is halved, then the rate A2 A + A;
of the reaction will Slow
A + B2 AB + B
(a) increase 2 times (b) increase 4 times
(c) decrease 2 times (d) remain the same Rate law = k [A] [B2]
Ans : DELHI 2000 put value of [A] from first reaction since A is
2A + B $ A2 B intermediate
r1 = k [A] 2 [B] ...(1) k [A2] = A

Rate law equation = K k [A2][B2]
When, [A] = [2A], [B] = :B D
2
Hence, Order = 1 + 1 = 3
2 2
r2 = k [2A] 2 :B D
= k4A2 B = k2A2 B 77. A graph plotted between log K vs 1
for calculating
2 T
activation energy is shown by
r1 = kA2 B = 2r1
Hence, Rate of reaction is increased two times.
74. For the following homogeneous reaction,
k
A+B C the unit of rate constant is
(a) sec-1 (b) sec-1 mol L-1
(c) sec-1 mol-1 L (d) sec-1 mol-2 L2
Ans : OD 2008
-1 1 - n -1
k = (mol L ) time
For given reaction n = 2
Hence, k = mol-1 L sec-1
Thus (c) is correct option. Ans : OD 2002
75. Order of reaction is decided by

(a) temperature
(b) mechanism of reaction as well as relative
concentration of reactants
(c) molecularity
(d) pressure
Ans : SQP 2015
The order of a chemical reaction is given by
concentration of reactants appearing in the lowest step. In accordance with Arrhenius equation.
78. The following data are for the decomposition of Ans : SQP 2011
ammonium nitrite in aqueous solution: For a first order reaction

t1/2 = 0.693 i.e.
Vol. of N 2 in cc Time (min) K
6.25 10 for a first reaction t1/2 does not depend up on the
concentration. From the given data, we can say that
9.00 15 order of reaction with respect to B = 1 because
11.40 20 change in concentration of B does not change half
life. Order of reaction with respect to A = 1 because
13.65 25
rate of reaction doubles when concentration of B is
32.65 Infinity doubled keeping concentration of A constant.
The order of reaction is Hence, Order of reaction = 1 + 1 = 2 and units of
(a) zero (b) one second order reaction are L mol-1 sec-1 .
(c) two (d) three
81. The rate law for a reaction between the substances A
Ans : SQP 2014
and B is given by
NH 4 NO 2 $ N 2 + 2H 2 O
Volume of N 2 formed in successive five minutes are Rate = k [A] n [B] m
2.75 cc, 2.40 cc and 2.25 cc which is in decreasing order. On doubling the concentration of A and halving the
So rate of reaction is dependent on concentration of concentration of B , the ratio of the new rate to the
NH 4 NO 2 . As decrease is not very fast so it will be earlier rate of the reaction will be as
first order reaction. (a) (m + n) (b) (n - m)
Thus (b) is correct option. 1
(c) 2(n - m) (d)
79. For the reaction A + B $ C + D . The variation of 2(m + n)
the concentration of the products is given by the curve Ans : DELHI 2013, OD 2005
n m
Rate 1 = k [A] [B] ;
Rate 2 = k [2A] n [ 12 B] m
n 1 m
Hence, Rate 2 = k [2A] [ 2 B]
Rate 1 k [A] [B] n m
= [2] n [ 12 ] m
= 2n 2-m
82. The following mechanism has been proposed for the
reaction of NO with Br2 to form NOBr:
NO (g) + Br2 (g) NOBr2 (g)
(a) Z (b) Y NOBr2 (g) + NO (g) $ 2NOBr (g)

If the second step is the rate determining step, the
(c) W (d) X
order of the reaction with respect to NO(g) is
Ans : COMP 2006
(a) 3 (b) 2
The curve Y shows the increase in concentration of
products with time. (c) 1 (d) 0
Thus (b) is correct option. Ans : FOREIGN 2005
(i) NO (g) + Br2 (g) NOBr2 (g)
80. Consider the reaction, 2A + B $ products . When
concentration of B alone was doubled, the half-life did (ii) NOBr2 (g) + NO (g) $ 2NOBr (g)
not change. When the concentration of A alone was Rate law equation = k [NOBr2] [NO]
doubled, the rate increased by two times. The unit of
But NOBr2 is intermediate and must not appear in
rate constant for this reaction is
the rate law equation
(a) s-1 (b) L mol-1 s-1
[NOBr2]
(c) no unit (d) mol-1 s-1 from Ist step KC =
[NO] Br2
[NOBr2] = KC [NO] [Br2] Ans : OD 2015
The order of a reaction can have fractional value.

Rate law equation = k : KC [NO] 2 [Br2]
Assertion is true.
Hence order by reaction is 2 w.r.t. NO. The order of a reaction can not be written from
Thus (b) is correct option. balanced equation of a reaction because its value
83. The given reaction changes with pressure, temperature and concentration.
2FeCl 3 + SnCl 2 $ 2FeCl 2 + SnCl 4 is an example of It can only be determined experimentally. Thus the
reason is also correct, but the reason is not the correct
(a) first order reaction (b) second order reaction
explanation of assertion.
(c) third order reaction (d) none of the above Thus (b) is correct option.
Ans : OD 2009
Thus (c) is correct option. 86. Assertion : In rate law, unlike in the expression for
equilibrium constants, the exponents for concentrations
do not necessarily match the stoichiometric coefficients.
ASSERTION AND REASON Reason : It is the mechanism and not the balanced
chemical equation for the overall change that governs
the reaction rate.
from the options given below:
84. Assertion : According to transition state theory for is not the a correct explanation of the Assertion.
the formation of an activated complex one of the (c) Assertion is correct but Reason is incorrect.
vibrational degree of freedom. (d) Both the Assertion and Reason are incorrect.
Reason : Energy of the activated complex is higher
Ans : DELHI 2010
than the energy of reactant molecules.
Rate law is always written according to the slowest
step and thus the exponents for concentrations do not
necessarily match the stiochiometric coefficients.
(c) Assertion is correct but Reason is incorrect. 87. Assertion : The rate of the reaction is the rate of
(d) Both the Assertion and Reason are incorrect. change of concentration of a reactant or a product.
Reason : Rate of reaction remains constant during the
Ans : COMP 2020
course of reaction.
The formation of an activated complex takes place
when vibrational degree of freedom covert into a
translational degree of freedom. This statement
is given by transition statement theory. Also the (b) Both Assertion and Reason are correct but Reason
energy of activated complex is higher than the energy is not the a correct explanation of the Assertion.
of reactant molecule is true but is not the correct (c) Assertion is correct but Reason is incorrect.
explanation of the assertion.
Ans : SQP 2008
85. Assertion : The order of a reaction can have fractional
Rate of reaction does not remain constant during
value.
the complete reaction because rate depends upon the
Reason : The order of a reaction cannot be written
concentration of reactants which decreases with time.
from balanced equation of a reaction.
Reason is a correct explanation of the Assertion. 88. Assertion : If the activation energy of a reaction is
(b) Both Assertion and Reason are correct but Reason zero, temperature will have no effect on the rate
is not the a correct explanation of the Assertion. constant.
(c) Assertion is correct but Reason is incorrect. Reason : Lower the activation energy, faster is the
reaction.
(a) Both Assertion and Reason are correct and The rate constant of a first order reaction is directly
Reason is a correct explanation of the Assertion. proportional to the concentration of the reactant.
(b) Both Assertion and Reason are correct but Reason Ans : FOREIGN 2008, DELHI 2004
is not the a correct explanation of the Assertion. The rate of a first order reaction is directly
(c) Assertion is correct but Reason is incorrect. proportional to the concentration of the reactants.
Rate of a reaction \ 6Concentration of reactant@n
where, n = order of reaction.
Ans : FOREIGN 2008
For first order,
Rate of reaction \ 6Concentration of reactant@1
-
According to Arrhenius equation, k=Ae Ea /RT
When, Ea = 0
92. Define molecularity of a reaction. Give one difference
k =A between the order of a reaction and its molecularity.
Thus (b) is correct option. Ans : OD 2011
89. Assertion : The kinetics of the reaction- Molecularity is the number of reacting species taking
mA + nB + pC $ mlX + nlY + plZ part in a chemical reaction to bring about the chemical
change in a single step.
Obey the rate expression as dx = k [A] m [B] n . Difference between molecularity and order of a
dt
reaction Molecularity of a reaction is always a whole
Reason : The rate of the reaction does not depend
number, while order of a reaction may be zero or a
upon the concentration of C.
fractional number.
Reason is a correct explanation of the Assertion. 93. What is the order of reaction whose rate constant has
the same unit as the rate of reaction?
Ans : SQP 2016
Zero order of reaction whose unit of rate constant and
(c) Assertion is correct but Reason is incorrect. rate of reaction has the same unit, i.e. mol L-1 s-1 .
(d) Both the Assertion and Reason are incorrect. 94. If the half-life period of a first order reaction is 69.3 s.
Ans : OD 2020 What is the value of its rate constant?
Rate expression dX = k [A] m [B] n shows that the total Ans : COMP 2002
dt
order of reaction is m + n + 0 = m + n Given, half-life period, t1/2 = 69.3 s
As the rate of reaction is independent of concentration Rate constant, k =?
of C , i.e., the order with respect to C is zero. This k = 0.693 = 0.01 s1
is the reason that C does not figure in the rate 69.3
expression. 95. Name the order of reaction which proceeds with a
Thus (a) is correct option. uniform rate throughout.
Zero order reaction.

VERY SHORT ANSWER QUESTIONS
96. Write a general expression for half life period of a
reaction of nth order.
90. Identify the order of reaction from each of the following
Ans : SQP 2012
units of rate constant (k).
(i) mol L-1 s-1 t1/2 = 1n - 1
[R] 0
(ii) mol-1 L s-1
97. Write Arrhenius equation.
Ans : COMP 2017
Ans : OD 2005
(i) molL-1 s-1 " Zero order reaction.
Arrhenius equation can be expressed as
(ii) mol-1 Ls-1 " Second order reaction
k = Ae-Ea /RT
91. Correct the following statement by changing the where, k = rate constant,
underlined part of the sentence.
A = collision or frequency factor
(Do not change the whole sentence.)
Ea = activation energy 102. Prove that the half-life of a first order reaction is
independent of the initial concentration.
R = universal gas constant
Ans : FOREIGN 2012
T = temperature (in K) Rate constant for the first order reaction is
6R@o
98. Correct the following statement. k = 2.303 log
t 6R@
The rate constant of a reaction increases linearly with
6R@
increase in temperature. At t1 2 6R@ = 2 o
Ans : SQP 2019
6R@o
According to Arrhenius equation, Thus, k = 2t.303 log 6R@o
1 2
k = Ae-Ea /Rt 2
The rate constant of a reaction increases exponentially t1= 2.303 log 2

2
k
with increase in temperature.
t1 2 = 0 . 693
k
Therefore, the half time of a first order reaction is
SHORT ANSWER QUESTIONS independent of the concentration of the reactant.
103. If in a chemical reaction A + B $ product, rate law
is given by R = K 6A@2 6B@2 , find the order of reaction.
1 3
99. The conversion of molecule A to B followed second
order kinetics. If concentration of A is increased to Ans : FOREIGN 2015
three times, how will it affect the rate of formation Given,

of B ? Rate law for a chemical reaction A + B $ product as:
(Rate) R = K 6A@2 6B@2
1 3
Ans : COMP 2023
For second order kinetics, We know that, Order of any reaction is equal to the
rate = k 6A@2 sum of powers of each concentration term given in the
If concentration of ‘A’ increased by three times. rate-Law.
New rate = k 63A@2 = 9.k 6A@2 Hence Order of reaction = 1 + 3 = 2
2 2
The rate of formation of B increased by 9 times. 104. Show that half-life of first order reaction is independent
100. Define Pseudo first order reaction with an example. of initial concentration.
Ans : COMP 2014
Ans : COMP 2023
The time in which the concentration of a reactant is
Pseudo first order reactions are not truly first order
reduced to one half of its initial concentration is called
but show first order kinetics under certain conditions.
the half life of that reaction. It is represented as t1/2 .
These reactions are bimolecular but have order one.
For the first order reaction,
Example : acidic hydrolysis of an ester :
[R]
CH 3 COOC H 5 + H 2 O êxcessh k = 1 ln 0
+
H
Ester 2 t [R]
CH 3 COOH + C 2 H 5 OH where, [R] 0 = initial concentration
[R] = concentration at time t1/2
101. Describe thermodynamical changes when a gas is
[R]
absorbed on a solid. or k = 2.303 log 0
Ans : OD 2018
t [R]
Physisorption is an exothermic process R0
At t1/2 , [R] =
2
Solid + Gas m Gas/Solid + Heat [R]
k = 2.303 log [R] 0 = 2.303 log 2
(Adsorbent) (Adsorbate) (Gas adsorbed on solid) Therefore,
t1/2 t1/2
0
According to Le Chatelier’s principle, if we increase 2
the temperature, equilibrium will shift in the backward k = 2.303 # 0.301

direction i.e., gas is released from the absorbed surface. t1/2
Thus physisorption decrease with increase in t1/2 = .693
0
k
temperature.
Hence for first order reaction, t1/2 is independent of [R] 0 .
105. Define the following terms : 108. Differentiate between average and instantaneous rate
1. Order of reaction of reaction.
2. Threshold energy Ans : COMP 2020
Ans : DELHI 2016, OD 2011 Average rate of reaction : Change in concentration of

1. Order of reaction : In the rate equation of a reactant or product in unit time (Time interval).
reaction, in which the sum of the power of For a reaction : R $ P
concentration of reactant terms is called order of Average rate of reaction
reaction. - T [R] + T [P]
Let us suppose that rate of reaction is given by: (rav) = =
Tt Tt
Rate of section = K $ C1n # C2n # C3n
1 2 3
Instantaneous rate of reaction : Change in
where, n1 , n2 , n3 power of concentration terms. concentration of reactant or product at the particular
Then, Order of reaction = (n1 + n2 + n3) instant of time
2. Threshold energy : The minimum value of the Instantaneous rate of reaction (rinst)
energy of photon which is required from outsides - d [R] + d [P]
by the electron on a surface of a metal to comes =
dt dt
out from the surface is called threshold energy.
The threshold energy is always greater than or 109. Express the rate of the following reaction
equal to the rest energy of the desired particle. 2HI (g) $ H 2 (g) + I 2 (g)
106. What is chemical kinetics? Ans : COMP 2008
Ans : OD 2002 For expressing the rate of such a reaction, rate of
The branch of chemistry which deals with the study disappearance of any of the reactants or the rate of
of the rates of chemical reactions, the factors affecting appearance of products is divided by their respective
the rates of the reactions and the mechanism by which stoichiometric coefficients. Since rate of consumption
the reactions proceed is known as Chemical kinetics of HI is twice the rate of formation of H2 or I2 to
(Greek; Kinesis = movement). make them equal the term T [HI] is divided by 2. The
rate of this reaction is given by
107. Define rate of reaction.
T [HI]
Ans : FOREIGN 2002 Rate of reaction = - 1
2 Tt
Rate of reaction or speed of reaction is the change in
T [H2] T [I2]
concentration of a reactant or product in unit time. = =
Tt Tt
For a reaction: R " P
Rate of reaction = Rate of disappearance of R 110. Mention the factors that effect the rate of a chemical
reaction.
= Decrease in Conc. of R Ans : COMP 2015, OD 2008
Time taken
- T [R] Factors affecting the Reaction Rate:
= 1. Nature of the reactants : Rate of reaction depends
Tt
upon the bond enthalpies of reactants and
Rate of reaction = Rate of appearance of P
products.
= Increase in Conc. of P 2. Concentration of reactants : The Rate of reaction
Time taken increases with increase in the concentration of
+ T [P] reactants due to increase in number of collisions.
=
Tt 3. Temperature : The rate of reaction increases with
Rate of reaction is always positive. The minus sign along increase in temperature. In most of the cases, the
with the concentration of reactants is used to show rate of reaction becomes nearly double for 10c rise
that the concentration of the reactant is decreasing of temperature.
i.e. TR is a negative so that (-) # (-) = + . 4. Presence of catalyst : A catalyst generally
The plus sign with the conc. of Product show that the increases the speed of a reaction without itself
conc. of the product is increasing. being consumed in the reaction.
Units of rate of reaction : Concentration time-1 5. Surface area of reactants : For solid reactants,
or mol L-1 s-1 the smaller is the particle size i.e. greater is the
surface area, the faster is the reaction.
For gaseous reactions : atm s-1
6. Presence of light : Some reactions do not take (ii) In, case of an endothermic reaction (TH = + ve)
place in the presence of light. , the equilibrium constant increases with rise in
For example : H 2 + Cl 2 $ 2HCl temperature and hence, the reaction moves in
Such reactions are called photochemical reactions. forward direction.
111. Define Rate constant and write its characteristics. 114. Explain the Rate law or Rate Equation.
Ans : OD 2012 Ans : OD 2001
Rate constant is the rate of the reaction when the For a general reaction : aA + bB $ Products
molar concentration of each reactant is taken as unity. According to law of Mass Action
That is why it is also called specific reaction rate.
Rate a [A] a [B] b
Characteristics of rate constant-
1. Rate constant is a measure of the rate of reaction. Rate = K [A] a [B] b
Greater is the value of the rate constant, faster is Suppose, experimentally the rate of the reaction is
the reaction. found to depend upon x concentration terms of A
2. Each reaction has a definite value of the rate and y concentration terms of B . Then
constant at a particular temperature.
Rate a [A] x [B] y
3. The value of the rate constant for the same
reaction changes with temperature. or Rate = K [A] x [B] y
4. The value of the rate constant of a reaction Where [A] and [B] are the molar concentrations of A
does not depend upon the concentrations of the and B respectively and K is rate constant. The above
reactants. expression is called Rate law.
5. The units of the rate constant depend upon the The representation or reaction in terms of concentration
order of reaction. of the reactants is known as rate law. It is also called
112. State law of mass action. as rate equation or rate expression.
Ans : OD 2022 115. What is activation energy? Establish the relation
Law of mass action : According to this law, the rate at between rate constant of a reaction and activation
which a substance reacts is directly proportional to its energy.
active mass and the rate at which a chemical reaction or
proceeds is proportional to the product of active What is activation energy? How is the rate constant
masses of reacting substances with each concentration of a reaction related to its activation energy?
term raised to the power of stoichiometric coefficient
Ans : SQP 2015, OD 2013
of that species in the chemical equation. The term
The energy needed to form the intermediate called
active mass means the molar concentration, i.e.,
activate complex (C) is known as activation energy
number of moles per litre. It is expressed by enclosing
Ea . It is the extra energy needed by the reactant
the formula of substance in square brackets as [ ],
molecules that results into effective collision between
Thus, active mass of H 2 can be represented as [H 2].
them to form the products. The fraction of molecules
Active mass = Number of moles colliding with energies more than Ea $ Activation
Volume in liter Energy is
113. What is the effect of temperature on reaction?
Equation k = Ae-E /RT , a
Ans : OD 2002
The factor e-E /RT represents the fraction of molecules
a
Effect of Temperature on reaction : Temperature that have kinetic energy more than the activation
directly affects the value of equilibrium constant, Ke energy. It is clear from the equation that increasing
and rates of reactions. Increased temperature shifts the the temperature or decreasing the activation energy
equilibrium in such a direction where heat is absorbed will result in an increase in the rate of the reaction
and decreased temperature shift the equilibrium in and an exponential increase in the rate constant.
such direction where heat is released. Taking natural logarithm on both sides, the equation
Thus, in general. becomes,
(i) In case of an exothermic reaction (TH = - ve),
the equilibrium constant decreases with rise in ln k = - Ea + ln A
RT
temperature and hence, to make it constant the Above is the established relation between rate constant
reaction proceeds in backward direction. (k ) of a reaction and Activation energy Êa h .
116. Define the following- 4. It is applicable to It is applicable only for

1. Half life time elementary as well as elementary reactions.
2. Order of reaction complex reactions. For complex reaction it
3. Molecularity of reaction has no meaning.
Ans : COMP 2012 5. For complex For complex reaction
1. Half life time : The half life period of a reaction is reaction, order is molecularity of the
the time in which the concentration of a reactant given by the slowest slowest step is same as
is reduced to one half of its initial concentration. step. the order of the overall
1
It is represented as t . 2
reaction.
t = 0.693
1
2
K 119. From the rate expressions for the following reactions,

2. Order or reaction : The sum of powers of the determine their order of reaction and the dimensions
concentration of the reactants in the rate law of the rate constants:
expression is called the order of that chemical 1. 3NO (g) $ N 2 O (g) + NO 2 (g);
reaction. Rate = K [NO] 2
For the reaction aA + bB $ Products
Rate law expression is : 2. H 2 O 2 (aq) + 3I- (aq) + 2H+ $ 2H 2 O (I) + I -3 ;
Rate = K [H 2 O 2] [I-]
Rate = K [A] x [B] y
The order of reaction w.r.t. reactants A and B 3. CH 3 CHO (g) $ CH 4 (g) + CO (g);
are x and y respectively and overall order of Rate = K [CH 3 CHO] 32
reaction = x + y .
4. C 2 H 5 Cl (g) $ C 2 H 4 (g) + HCl (g);
3. Molecularity of reaction : The number of reacting
species (atoms, ions or molecules) which must Rate = K [C 2 H 5 Cl]
collide simultaneously in order to bring about Ans : COMP 2001
a chemical reaction is called molecularity of 1. Order = 2 ,
a reaction. Molecularity is applicable only for
elementary reactions. Dimension of K = Rate2
[NO]
117. Give one example of zero order reaction. -1 -1
Ans : COMP 2000

= mol L -s1 2 = L mol - 1 s-1
(mol L )
Thermal decomposition of ammonia over the surface 2. Order = 2 ,
of platinum catalyst:
Pt
Dimension of K = L mol-1 s-1
2NH 3 (g) N 2 (g) + 3H 2 (g)
Order = 3 ,
1130 K
3.
2
118. What is the difference between order of reaction and
molecularity of reaction? Dimension of K = Rate
[CH 3 CHO] 3/2
-1 -1
The difference between order of reaction and = mol L-1s 3/2 = L mol s-1
1 1
2 2
molecularity of reaction are as follows : (mol L )

4. Order = 1,
Order of Reaction Molecularity of
Dimension of K = Rate
Reaction [C 2 H 5 CI]
1. It is the sum of It is the number -1 -1
the power of the of reacting species = mol L -s1 = s-1

(mol L )
concentration terms undergoing
120. The decomposition of dimethyl ether leads to
in the rate law simultaneous collision in
formation of CH 4 , H 2 and CO and the reaction rate
expression. the reaction.
is given by Rate = K [PCH OCH ] 3/2 . If the pressure is
3 3
2. It is experimental It is a theoretical measured in bar and time in minutes then what are
determined quantity. concept. the units of the rate and rate constants?
3. It can be zero and It is always a whole Ans : SQP 2008
even a fraction. number. In terms of pressure,
units of rate = bar min–1
Units of K = Rate all collisions do not lead to the formation of products.

[PCH OCH ] 3/2
3 3 For a collision to be effective, the colliding molecules
-1 must have energy more than a particular value called
= bar min
1
= bar min-1 2
bar 3/2 threshold energy and also have proper orientation.

121. Write general expression for the amount of the For example, formation of methanol from bromoethane
substance left after n half lives. depends upon the orientation of reactant molecules.
Ans : OD 2017 The proper orientation of reactant molecules lead to
Amount of the substance left after n half lives bond formation whereas improper orientation makes
them simply bounce back and no products are formed.
[R]
= n0 125. Define Collision frequency.
2
Here [R] 0 = Initial concentration. Ans : OD 2013
The number of collisions per second per unit volume

122. What are pseudo first order reactions. Give example.
of the reaction mixture is known as collision frequency
Ans : OD 2000
(Z).
Reactions which are not truly of the first order but
126. Draw the graphs that relate the concentrations (C)
under certain condition become reactions of the first
of the reactants and the reaction times (t) and the
order are called pseudo first order reactions.
concentrations of the products (C) and the reaction
Example : times (t) in chemical reactions.
1. Acid catalysed hydrolysis of ethyl acetate Ans : FOREIGN 2018
H+
CH 3 COOC 2 H 5 + H 2 O CH 3 COOH + C 2 H 5 OH
Ethylacetate Acetic Acid Ethyl alcohol
Rate = K [CH 3 COOC 2 H 5]

2. Acid-catalysed inversion of cane-sugar
H+
C 12 H 22 O 11 + H 2 O C 6 H 12 O 6 + C 6 H 12 O 6
Sucrose Glu cos e Fructose
Rate = K [C 12 H 22 O 11]
Both the above reactions are bimolecular but are
found to be of the first order because water is present
in such a large excess that its concentration remains
almost constant during the reaction
123. What is the effect of temperature on the rate constant
of reaction? How can this temperature effect on the
rate constant be represented quantitatively?
or Figure: (a)
What is the effect of temperature on rate constant?
The rate constant of a reaction increase with increase

of temperature and becomes nearly double for every
10c rise of temperature. The effect can be represented
quantitatively by Arrhenius equation.
K = Ae-Ea/RT
Where, Ea represents the activation energy of the
reaction and A represents the frequency factor.
124. Write short note on collision theory of chemical
reaction.
Ans : SQP 2001
According to this theory, the reactant molecules are
assumed to be hard spheres and reaction between
them occur when they collide with each other, But Figure: (b)
127. What is rate law? Illustrate with an example. 131. What are complex reactions? Name one complex reaction.
Ans : OD 2014 Ans : FOREIGN 2001
The equation that describes mathematically A sequence of elementary reactions, reactants give the
the dependence of the rate of a reaction on the products, the reactions are called complex reactions.
concentration terms of the reactions is known as the Eg.- Oxidation of Ethane to CO 2 and H 2 O passes
rate equation (or) rate law. through a series of intermediate steps in which alcohol,
Example : 2A + 3B $ 3C aldehyde and acid are formed.
Rate of the given reaction ? [A] 2 [B] 3 132. Define molecularity of a reaction. Illustrate with an
128. Assuming that the volume of the system is constant, example.
derive the expression for the average rate of the Ans : SQP 2002
system R $ P in terms of R and P . [time = t sec] The number of reaction species (atoms, ions or
[R = reactant, P = product]. molecules) talking parts in an elementary reaction,
Ans : DELHI 2015 which must colloid simultaneously to bring about a
chemical reaction is called molecularity of a reaction.
R$P
NH 4 NO 2 $ N 2 + 2H 2 O (Unimolecular)
O = concentration
2HI $ H 2 + I 2 (Bimolecular)
At time t1 C is [R1] [P1] 2NO + O 2 $ 2NO 2 (Trimolecular)
At time t2 C is [R2] [P2]
133. Define Order of a reaction. Illustrate your answer
Change in C is [R2 - R1] [P2 - P1] with an example.
Hence, Ans : DELHI 2012, SQP 2004
(R2 - R1) The sum of the powers of the concentration terms of

Average rate of reaction = the reactants present in the rate equation is called
(t2 - t1)
order of a reaction.
+ (P2 - P1)
= Order of a reaction can be 0,1,2,3, and even a fraction.
t2 - t1
129. Write the equation for the rate of the reaction Example :
5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l) 1. N2O5 $ N2O4 + 1 O2
2
Ans : COMP 2002
Rate ? [N 2 O 5]
Given reaction is
Hence, It is a first order reaction.
5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l)
2. 2N 2 O $ 2N 2 + O 2
T [Br-] - T [BrO -3 ]
Rate of reaction = - 1 = Rate ? [N 2 O] 2
5 Tt Tt
T [H+] T [Br2] Hence, It is Second order reaction.
= -1 = -1
6 Tt 3 Tt
134. Give the units of rate constants for Zero, first order
T [H 2 O]
=1 and second order reactions.
3 Tt
Ans : DELHI 2008
130. Mention a reaction for which the exponents of
concentration terms are not the same as their Reaction Order Units of rate constant
stoichiometric coefficients in the rate equation. Zero order 0 mol L-1 1
# = mol L-1 s -1
Ans : COMP 2002 reaction s (mol L-1) 0
The following are the reactions for which the First order 1 mol L-1 1
exponents of concentration terms are not the same as # = s -1
reaction s (mol L-1) 1
their stoichiometric coefficients in the rate equation.
Second order 2 mol L-1 1 = mol -1 L s -1
CHCl 3 + Cl 2 $ CCl 4 + HCl reaction s #
(mol L-1) 2
Rate = K [CHCl 3] [Cl 2] 1/2
135. Give the mechanism for the decomposition reaction of
CH 3 COOC 2 H 5 + H 2 O $ CH 3 COOH + C 2 H 5 OH
H 2 O 2 in alkaline medium catalysed by I - ions.
Rate = K [CHCOOC 2 H 5] [H 2 O]
Ans : OD 2018
139. What are pseudo first order reactions? Give one
Chemical equation of decomposition of H 2 O 2 in example.
alkaline medium is Ans : SQP 2000
I-
2H 2 O 2 Alkaline medium
2H 2 O + O 2 C 12 H 22 O 11 + H 2 O
H+
C 6 H 12 O 6 + C 6 H 12 O 6
Mechanism :
Order = 1
It is a first order reaction w.r.t. both H 2 O 2 ,I- . This
reaction takes place is two steps. molecularity = 2
- -
(i) H 2 O 2 + I $ H 2 O + IO 140. Give two examples for gaseous first order reactions.
- -
(ii) H 2 O 2 + IO $ H 2 O + I + O 2 Ans : COMP 2018
The following are the examples for gaseous first order

136. Write the equation relating [R],[R] 0 and reaction time t reactions
for a zero order reaction. [R]= concentration of reactant
at time t and [R] 0 = initial concentration of reactant. N 2 O 5(g) $ N 2 O 4(g) + 1 O 2(g)
2
Ans : OD 2008
SO 2 Cl 2(g) $ SO 2(g)
[R] 0 - [R]
Zero order reaction Rate constant k = For the reaction A (g) $ B (g) + C (g) , write the
t 141.
Example : Decomposition of NH 3 integrated rate equation in terms of total pressure P
Pt and the partial pressures pA, pB, pC .
2NH 3(g) 1130 K
N 2 (g) + 3H 2 (g)
Rate = k [NH 3] 0 = k
Given
Hence, Tx = k A (g) $ B (g) + C (g)
Tt
Tx = Tt # k p = pA + pB + pC
p
137. Draw the graph that relates the concentration R , of k = b 2.303 l log e 0 o
t pA
the reactant and t the reaction time for a zero order
p0
k = 2.303 log b
2pi - pt l
reaction.
t
Ans : OD 2009
p0 = initial pressure
pi = Total pressure
pA , pB , pC are partial pressures.
142. Explain the term activation energy of a reaction with
a suitable diagram.
Ans : COMP 2006
Activation Energy : The energy required to for an

intermediate called activated complex (C) during a
chemical reaction is called activation energy.
Variation in the Concentration vs Time Plot for a

Zero Order Reaction
138. Write the integrated equation for a first order reaction

in terms of [R], [R] 0 and t .
Ans : SQP 2014
[R] = Concentration of reaction after time t

[R] 0 = Initial concentrations of reactant
[R]
Hence, k = 2.303 log 0
t [R]
This is the integrated Equation for a first order reaction.
143. Write the equation useful to calculate half-life (t1/2) - T [BrO -3 ]

=
values for zero and first order reactions. Tt
Ans : COMP 2001 T [H+]
= -1
[R] 0 6 Tt
Half life (t1/2) [R] =
2 T [Br2]
= -1
[R] 0 3 Tt
t1/2 = 2
T [H 2 O]
k
=1
[R ] 3 Tt
Hence, t1/2 = 0
2k 146. What is rate equation? How is it obtained? Write the
Half life of a first order reaction rate equations for
1. 2NO (g) + O 2(g) $ 2NO 2(g)
t1/2 = 0.693
k 2. CHCl 3 + Cl 2 $ CCl 4 + HCl
k = rate constant 3. CH 3 COOC 2 H 5 (l) + H 2 O (l) $ CH 3 COOH (aq) + C 2 H 5 OH (aq)
144. Write the Arrhenius equation for the rate constant (k) Ans : COMP 2006
of a reaction. The equation that describes mathematically
Ans : SQP 2003 the dependence of the rate of a reaction on the
Arrehenius equation is concentration terms of the reactions is known as the
rate equation (or) rate law.
k = A # e-Ea/RT
Example : 2A + 3B $ 3C
k = Rate constant Rate of the given reaction ? [A] 2 [B] 3
Ea = activation energy How to obtain : Each concentration term is raised to
some power which may or may not be same as the
R = gas constant
stoichiometric coefficient of the reacting species.
T = Temperature (K) 1. 2NO (g) + O 2(g) $ 2NO 2(g)
145. Define average rate of a reaction. How is the rate T [R]
= k [NO] 2 [O 2]
of reaction expressed in terms of change in the Tt
concentration of reactants and products for the 2. CHCl 3 + Cl 2 $ CCl 4 + HCl
following reactions.
T [R]
1. 2HI (g) $ H 2 (g) + I 2 (g) = k [CHCl 3] [Cl 2] 1/2
Tt
2. Hg (l) + Cl 2 (g) $ HgCl 2 (g) 3. CH 3 COOC 2 H 5 (l) + H 2 O (l) $ CH 3 COOH (aq) + C 2 H 5 OH (aq)
3. 5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l) T [R]
= k [CH 3 COOC 2 H 5]
Ans : OD 2013 Tt
Average rate of a reaction : The change in the 147. How will rate of a reaction change when [A] 0 is
concentration of any one of the reactants or products doubled and tripled for
per unit time is called average rate of a reaction. 1. zero order reaction
1. 2HI (g) $ H 2 (g) + I 2 (g) 2. second order reaction?
T [HI] T [H 2] T [I 2] Ans :
Rate of reaction = - 1
FOREIGN 2017, DELHI 2011
= =
2 Tt Tt Tt When [A] 0 is doubled
2. Hg (l) + Cl 2 (g) $ HgCl 2 (g) 1. the rate of zero order reaction remains unchanged.
T [Hg] T [Cl 2] 2. the rate of second order reaction becomes four
Rate of reaction = =-
Tt Tt times.
T [HgCl 2] When [A] 0 is tripled
=
Tt 1. the rate of zero order reaction remains unchanged
3. 5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l) 2. the rate of second order reaction becomes 9 times.
Given reaction is Pt
148. For a reaction : 2NH 3 (g) N 2 (g) + 3H 2 (g)
5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l)
Rate = k
T [Br-]
Rate of reaction = - 1 1. Write the order and molecularity of this reaction.
5 Tt
2. Write the unit of k .
Ans : OD 2015 Ans : COMP 2010
2NH 3 (g)
Pt
N 2 (g) + 3H 2 (g) For a second order reaction,
Rate = k [A] 2
Rate = k
If the concentration of A is reduced to half, rate will
1. Order of reaction : Zero order become 1/4 of the original value.
Molecularity = 2 (bimolecular) Units of k
2. Unit of k = mol L-1 s-1 or atm s-1 mol L-1 = k (mol L-1) 2
s
149. State the order with respect to each reactant and 1
k =
overall order for the following reaction mol L-1 s
2NOBr (g) $ 2NO (g) + Br2 (g) = mol-1 L s-1
Rate = k [NOBr] 2 153. For reaction, rate law is give as rate = k [A] [B] 1/2 .
What are the units of rate constant? What is the order of reaction?
Ans : FOREIGN 2013 Ans : COMP 2014
Order w.r.t. NOBr = 2 For an elementary reaction, order of a reaction

should be equal to molecularity of the reaction and
Overall order = 2
molecularity should be integral. For the given reaction,
Units of rate constant = mol-1 L s-1 order of reaction is 32 (1 + 12 ). Since molecularity cannot
150. Identify the order of a reaction from each of the be fractional, therefore, for the given reaction, order
following rate constant- is not equal to molecularity. Hence, given reaction,
1. k = 2.3 # 10-5 L mol-1 s-1 cannot be elementary reaction.
2. k = 3.1 # 10-4 s-1 154. A reaction is first order in reactant A and second
3. k = 9.3 # 10-4 mol L-1 s-1 order in reactant B .
Ans : SQP 2002 1. Write differential rate equation.
Order can be predicted by the inspection of units of 2. How is the rate affected when concentration of B
rate constant alone is increased to three times?
3. How is the rate affected when concentration of
1. Second order reaction
both A and B are doubled?
2. First order reaction
3. Zero order reaction
-1
1. Rate = k [A] [B] 2
151. If the concentration be expressed in mol L units and
time in seconds, what would be units for rate constant, k 2. Rate becomes (3) 2 = 9 times
1. for a zero order reaction 3. Rate becomes (2)(2) 2 = 8 times
2. for a first order reaction 155. For the reaction
Ans : SQP 2005 B+
C 12 H 22 O 12 + H 2 O C 6 H 12 O 6 + C 6 H 12 O 6
1. For a zero order reaction
Rate = k [A] 0 Write :
1. Rate of reaction expression,
mol L-1 = k 1 2. Rate law equation.
s #
3. Molecularity,
or k = mol L-1 s-1 4. Order of reaction
2. For a first order reaction Ans : COMP 2005
Rate = k [A] d [C 12 H 22 O 11] - d [H 2 O ]

1. Rate = - =
dt dt
mol L-1 = k mol L-1
s d [C 6 H 12 O 11] d [C 6 H 12 O 6]
= =
dt dt
or k = s-1
2. Rate law equation:
152. A reaction is of second order with respect to a Rate = k [C 12 H 22 O 11]
reactant. How is the rate of reaction affected if the
concentration of the reactant is reduced to half? 3. Molecularity = 2
What is the unit of rate constant for such a reaction? 4. Order = 1
156. Consider the decomposition of hydrogen peroxide in if Ea is zero then k = A

alkaline medium which is catalysed by iodide ions. i.e., every collision between molecules leads to the
OH- /I-
2H 2 O 2 2H 2 O + O 2 chemical reaction. This is not true. Thus, Ea cannot
be zero.
This reaction takes place in two steps as given below :
160. Why molecularity is applicable only for elementary
Step-I : H 2 O 2 + I- $ H O + IO- (Slow)
2
reactions and order is applicable for elementary as

Step-II : H 2 O 2 + IO- $ H 2 O + I- + O 2 (fast) well as complex reactions?
1. Write the rate laq expression and determine the Ans : SQP 2004
order of reaction w.r.t. H 2 O 2 . A complex reaction occurs through several elementary
2. What is the molecularity of each individual step? reactions, Numbers of molecules involved in each
Ans : SQP 2018, OD 2012 elementary reaction may be different i.e., the
1. Rate = k [H 2 O 2] [I-] molecularity of each step may be different. Therefore,
the molecularity of overall complex reaction is
order w.r.t. H 2 O 2 = 1 meaningless. On the other hand, order of a complex
2. Molecularity : Step I = 2 , Step II = 2 reaction is experimentally determined by the slowest
157. For a chemical reaction variation in rate with cone is step in its mechanism and it therefore, applicable even
shown: in the case of complex reactions.
1. What is the order of the reaction? 161. With the help of diagram explain the role of activated
2. What are the units of rate constant k for the complex in a reaction.
reaction? Ans : SQP 2009
Activated complex is intermediate compound between

reactants and products as shown. It is highly instable
as it has highest energy. It readily changes into
product. Those molecules which can form activated
complex can lead to the formation of products, e.g.
Ans : SQP 2001

1. Order of reaction is zero.
2. Units of rate constant is mol L-1 s-1 .
158. Thermodynamic feasibility of the reaction alone
cannot decide the rate of the reaction. Explain with
the help of one example.
Ans : COMP 2018
Thermodynamic feasible (negative TG) cannot alone

decide the rate of reaction because the reaction may
be feasible but its rate may be very slow because of
very high activation energy. For example, conversion of
diamond to graphite is highly feasible but this reaction
is very slow because it has high activation energy. For
example, conversion of diamond to graphite is highly
feasible but this reaction is very slow because it has
high activation energy.
159. Can activation energy for reactions be zero?
Ans : COMP 2009
162. Why can we not determine the order of a reaction
In the Arrhenius equation,
by taking into consideration the balanced chemical
k = Ae-Ea /RT equation?
Ans : OD 2016
Suppose that the initial concentration is 6A0@ g -mole
Balanced chemical equation often leads to incorrect per unit-volume and the conc. after a time t is 6A@ g
order or rate law. For example, the following reaction -mole, then
appears to be a tenth order reaction. d 6A@
- = k.dt
KCIO 3 + 6FeSO 4 + 3H 2 SO 4 $ KCI + 3H 2 O + 3Fe 2 (SO 4) 3
6A@
However, this is actually a second order reaction.
on integrating the above equation, we get
Actually the reaction is complex and occurs is several
# - d66AA@@
t=1
steps. The order of such reaction is determined by = # k.dt
the slowest step in the reaction mechanism. Order t=0
is determined experimentally and gives the actual or - ln 6A@ = kt + I

dependence of observed rate of reaction on the At t = 0,
concentration of reactants.
I = - ln 6A0@
163. What is physical significance of energy of activation?
Explain with diagram. Hence the above equation becomes
Ans : OD 2009, SQP 2005 6A0@
kt = ln
Energy of activation is the extra energy which must 6A@
6A0@
be supplied to the reactants so that these can change or k = 2.303 log
into products. It is the difference between energy of t 6A@
reactants and energy of activated complex as shown This is called the kinetic equation of a first order
in diagram. reaction.
The reactants molecules which possess activation Here, 6A@0 is the initial concentration of A. From
energy and collide in proper orientation lead to the the last equation, it is correct that mathematically,
formation of product molecules. 6A@ > 0 for all t < 3. Thus, A can never be zero
as long as infinity is not defined. Hence first order
reaction can never completed.
165. What do you mean by first order reaction ? Find the
expression for first order reaction
Ans : COMP 2013
The first order reaction is defined as, the reaction in

which the reaction rate is determined by the change
of one concentration term of the reactant only, e.g. In
the reaction,
t = 2.303 log a
k (a - x)
2 . 303 [R] 0
or t = log
k [R]
where, t = time
a or [R] 0 = initial concentration
LONG ANSWER QUESTIONS k = rate constant
(a - x) or [R] = concentration of a after time t
164. Describe the kinetics of a first order reaction. Why is
According to rate-law, first order reaction can be
a first order reaction never completed?
represented as:
Ans : DELHI 2018
Rate, (r) = k $ [a - x]
First order reaction is that in which the reaction-rate
is determined by one concentration variable. Consider Expression for First Order Reaction :
the reaction, Let for a reaction,
A " Products Reactant ( R ) $ (P ) Product.
d 6A@ d [R]
Rate of reaction = - = k 6A@ Rate = -
dt
= k [R]
dt
d [R] C is the constant of integration

or = - kdt
[R] At t = 0 , x = 0 then equation (1) we have
After integration of the reaction, we get C = ln a
ln [R] = - kt + I ...(1) Putting the value of C in equation (1)
where, I = constant of integration ln a - ln â - x h
= Kt
In the beginning, when
1
K = ln
a
t =0 t a-x
and R = [R] 0 Hence, K = 2.303 log a ...(2)
t a-x
[R] 0 being the initial concentration of the reactant. Above is the general expression for specific rate
Hence, Equation (1) can be rewritten as constant of first order reaction.
ln [R] 0 = - k # 0 + I 167. Define rate constant of a reaction. Derive an expression
ln [R] 0 = I for the rate constant of 1st order reaction
Substituting ln [R] 0 = I in the Eq. (1), Ans : DELHI 2009, SQP 2006
ln [R] 0 = - kt + ln [R] 0 According to this law at a given temperature the rate

of a chemical reaction is directly proportional to the
[R] product of the molar concentration of the reactants.
ln = - kt
[R] 0
The molar concentration of the reactant is also called
1 ln [R] = - kt active mass. Let us consider a simple reaction of the
t [R] 0
type.
[R]
k = 1 ln 0 A + B $ 2AB
t [R]
[R] According to law of mass action, rate of the reaction
= 2.303 log 0 may be written as :
t [R]
Rate = k [A] [B]
166. Define order of reaction and molecularity of reaction.
Derive a general expression for specific rate constant where, [A] and [B] are the molar concentrations of
of first order reaction. reactants, k is constant of proportionality and is
Ans : SQP 2006
called rate constant. The rate constant is also called
velocity constant and is a measure of rate of the
Order of reaction is the sum of exponents of the molar
reaction.
concentrations of the reactants in the rate equation:
Now, if concentration of each of the reactants involved
For a general reaction aX - bY " Product
in the reaction is unity i.e., [A] = [B] = 1, then
Rate = k 6X@m . 6Y@n substituting these values in above expression, we get
Order of reaction = m + n Rate of reaction = k # 1 # 1 = k
Molecularity of reaction: It is the number of atoms, Thus, the rate constant of a reaction at a given
ions or molecules that collides with one another temperature may be defined as rate of the reaction
simultaneously so as to result into a chemical reaction. when the molar concentration of each of the reactants
General Expression is unity.
A $ Product That is why the rate constant is also called specific
reaction rate.
A is â - Xh mol l-1
e.g. Consider the general first order reaction
For First order reaction
dX = k a - X R $ Products
dt ^ h Let [R] is the concentration of the reaction R and k is
where k is the rate constant. the rate constant for the first order reaction. For the
dX = kdt (integrating) first order reaction, the rate of the reaction is directly
Hence,
a-X proportional to the concentration of the reactant R.
dx = k dt Thus,
# a-X # d [R]
Rate = - = k [R] ...(1)
- ln â - X h = Kt + C ...(1) dt
This form of rate law is known as differential rate Here [R]O = Initial concentration
equation. Integrated form of rate low can be written [R] [R]O
as follow: t1/2 = 1 ;[R]O - O E =
K 2 2K
[R] Thus half life t1/2 of a zero order reaction is directly
K = 2.303 log 0 ,
t [R] proportional to be initial concentration of the reactants
where [R]0 = initial concentration. and inversely proportional to the rate constant.
[R] = concentration at time 't' 169. Derive the integrated rate equation for a first order
168. Define zero order reaction. Derive integrated rate reaction.
equation for zero order reaction and derive an Ans : SQP 2005
expression for half life period of a zero order reaction. In first order reaction, the rate of the reaction is
Ans : OD 2019 proportional to the first power of the concentration of
1. Zero order reaction : The reaction for which the reactant R for example. R $ P
the rate of reaction does not depend upon - d [R]
Rate = = K [R]
concentration of reactant is called a zero order dt
reaction. For such a reaction : - d [R]
or = - Kdt
Rate = K [R]c = K R
2. Integrated rate equation for a zero order reaction Integrating this equation, we get.
: Consider the reaction R $ P [R] = - Kt + I ...(i)
- d [R] Here, I is the constant of integration
Rate = = K [R]c
dt When t = 0 , R = [R] 0 Where [R] 0 is initial
As any quantity raised to power zero is unity. concentration of the reactant.
d [R] Therefore equation (i) can be written as
Rate = - = K#I
dt
ln [R]O = - K # O # I
d [R] = - Kdt
ln [R]O = I
Integrating both sides
Substituting the value of I in the equation (i)
[R] = - Kt + I ...(1)
ln [R] = - Kt + ln [R]O
Where, I is the constant of integration At t = 0 , the
concentration of the reactant R = [R] 0 . Where [R] 0 is Rearranging the equation
initial concentration of the reactant. [R]
ln = - Kt
Substituting in equation (1) [R]O
[R]
[R] 0 = - K # O + I K = 1 ln O
t [R]
[R] 0 = I [R]
K = 2.303 log O
Substituting the value of I in the equation (1) t [R]
[R] = - Kt + [R]O ...(2)
Kt = [R]O - [R]
[R]O - [R]
K = ...(3)
t
Comparing (2) with equation of a straight line, y
= mx + c , if we plot [R] against t , we get a straight
line with slope = - K and intercept equal to [R]O
3. Half life period of a zero order reaction : The
half life period of a reaction is that in which the
concentration of a reactant is reduced to one half
of its initial concentration.
It is represented as t1/2 .
[R]O A Plot between [R ] and t for a First Order Reaction
t = t1/2 ; R =
2
The energy required to form the activated complex is

known as activation energy (Ea).
171. Give two examples for each of zero order and first
order reactions. Write the equations for the rate of
reaction in terms of concentration changes of reactants
and products for the following reactions.
1. A (g) + B (g) $ C (g) + D (g)
2. A (g) $ B (g) + C (g)
3. A (g) + B (g) $ C (g)
[R ] 0
Plot of log [R ] vs Time for a First Order Reaction Pt
1. 2NH 3(g) 1130 K
N 2(g) + 3H 2(g)
170. Define threshold energy and activation energy. How gold
2. 2HI (g) H 2(g) + I 2(g)
are they related? T
Ans : OD 2010 Examples of first order reaction:

Threshold energy is the minimum amount of energy N 2 O 5(g) $ N 2 O 4(G) + 1 O 2(g)
2
which the reactant molecules must possess for the
effective collisions. SO 2 Cl 2(g) $ So 2 + Cl 2(g)
( g)
Activation energy : The minimum extra amount of 1. A (g) + B (g) $ C (g) + D (g)
energy required by the reactant molecules so that
their energy becomes equal to threshold value is T [A] T [B ]
Rate = - =-
called activation energy OR the difference between Tt Tt
the threshold energy and the average kinetic energy T [C] T [D]
=+ =
of the reactant molecules is called activation energy. Tt Tt
Activation energy = Threshold energy - Average 2. A (g) $ B (g) + C (g)
(E a) (E t)
kinetic energy of the reactants. T [A] T [B ] T [C]

=+ =+
Tt Tt Tt
Example : H 2 (g) + I 2 (g) $ 2HI (g)
3. A (g) + B (g) $ C (g)
T [A] T [B ] T [C]
Rate = - =- =+
Tt Tt Tt
172. Explain the effect of temperature on rate of a reaction.
or
What is temperature coefficient of a reaction? Why
According to Arrhenius, this reaction can take place only
temperature coefficient for most of the reactions at
when a molecule of hydrogen and a molecule of iodine
room temperature is nearly two?
collide to form an unstable intermediate called activated
complex (C). It exists for a very short time and then Ans : DELHI 2002
breaks up to form two molecules of hydrogen iodide. Temperature coefficient is the ratio of two rates of
reactions or rate constants that differ by 10 K
Temperature coefficient = Rate of reaction at 310K
Rate of reaction at 300K
For most of the reaction its value is approximately 2.
This can be explained as follows:
Explanation : All the reacting molecules do not have
the same kinetic energy. However, fractions of molecule
having a particular kinetic at a particular temperature
remains constant. At a particular temperature, if
fractions of molecules are plotted versus corresponding
kinetic energies, a graph of the type shown in is obtained
(called Maxwell’s distribution of energies). The peak
of the curve represents the kinetic energy possessed
by the maximum fraction of molecules and is called ln K2 = ln A - Ea ...(iv)

most probable kinetic energy. If the point a represent RT2
threshold energy, the shaded area a bed represents Subtracting equation (iv) from equation (iii), we get
the fraction of molecules having energy greater than ln K2- ln K1 = - Ea - b- Ea l
threshold value. RT2 RT1
E
ln K2- ln K1 = a - a E
RT1 RT2
ln K2 = Ea : 1 - 1 D
K1 R T1 T2
Converting to common logarithm
log K2 = Ea :T2 - T1 D
K1 3.303 R T1 T2
When the temperature is increased to T + 10c, the

curve shift as shown in Now the fraction of molecule
having kinetic energy greater than threshold value is
represented by the shaded area abef which is almost
double than the area abed. Thus the increase in the
rate of reaction with increase in temperature is mainly
due to increase in the number of effective collisions.
173. Derive Arrhenius equation. 174. Briefly explain the effect of adding catalyst on the
or rate of reaction.
How does Arrhenius equation explain the effect of Ans : SQP 2013, OD 2011
temperature on the rate constant. A catalyst is a substance which increase the rate of
a reaction without itself undergoing any permanent
Ans : OD 2020
chemical change. For example MnO 2 catalyses the
Quantitatively the effect of temperature on the rate
following reaction to increase its rate considerably
of a reaction and hence on the rate constant K was MnO 2
proposed by Arrhenius (1889). The equation, called 2KClO 3 2KCl + 3O 2
Arrhenius equation. The action of the catalyst is explained by intermediate
K = Ae-Ea/RT ...(i) complex theory. According to this theory, a catalyst
participates in a chemical reaction by forming
Where A is constant known as frequency fact1or (It temporary bonds with the reactants resulting in an
gives the frequency of binary collisions of the reacting intermediate complex. This has a transitory existence
molecules per second per litre) Ea is the energy of and decomposes to yield products and the catalyst.
activation, R is gas constant and R is the absolute
temperature. The two quantities A and Ea are
collectively called Arrhenius parameters.
Taking logarithm equation (i)
ln K = ln A + In e-Ea/RT
ln K = ln A - Ea ln e
RT
ln K = ln A - Ea
RT
[Hence, ln e = 1] ...(ii)
If K1 and K2 are the values of rate constant at
temperature T1 and T2 then,
ln K1 = ln A - Ea ...(iii)
RT1 Effect of Catalyst on Activation Energy
2HI $ H 2 + I 2
2NO + O 2 $ 2NO 2
Molecularity has only integer values (1,2,3..........)
It has non zero, non fraction values while order has
The catalyst provides an alternate pathway of zero, 1,2,3..... and fractional values.
reaction mechanism by reducing the activation energy It is determined by reaction mechanism, order is
between reactants and products and hence lowering determined experimentally.
the potential energy.
(d) Molecularity of a reaction : Zero order reaction
175. Explain the following terms with suitable examples. is the reaction is the reaction in which rate of
(a) Average rate of a reaction reaction does not depends on the concentration of
(b) Slow and fast reactions reactants.
(c) Order of a reaction R$P
(d) Molecularity of a reaction - d [R]
Rate = = k [R]c
(e) Activation energy of reaction dt
Ans : - d [R]
SQP 2006 Rate =
dt
(a) Average rate of a reaction : The change in the
concentration of any one of the reactants or d [R] = - k.dt
products per unit time is called average rate of a Integrating on both sides
reaction.
[R] = - kt + I ...(i)
1. 2HI (g) $ H 2 (g) + I 2 (g)
T [HI] T [H 2] T [I2] I = Integration constant
Rate of reaction = - 1 = =
2 Tt Tt Tt At t = 0 " R
2. Hg (l) + Cl 2 (g) $ HgCl 2 (g)
= [R] 0 initial concentration
T [Hg] T [Cl 2]
Rate of reaction = =- I = [R] 0
Tt Tt
Substituting I = [R] 0 in the above equation (i)
T [HgCl 2]
= [R] = - kt + [R] 0
Tt
3. -
5Br + BrO - +
+ 6H $ 3Br2 (aq) + 3H 2 O (l) [R0] - [R]
(aq) 3 (aq) (aq)
k =
Given reaction is t
5Br (-aq) + BrO -3 (aq) + 6H (+aq) $ 3Br2 (aq) + 3H 2 O (l) This is the integrated rate equation for a zero order
reaction.
T [Br-] - T [BrO -3 ]
Rate of reaction = - 1 = (e) Activation energy of reaction : The energy
5 Tt Tt
required to for an intermediate called activated
T [H+] T [Br2]
= -1 = -1 complex (C), during a chemical reaction is called
6 Tt 3 Tt activation energy.
T [H 2 O]
=1
3 Tt
(b) 1. Fast Reactions : In case of ionic compounds
reactions takes place fastly i.e. rate is high.
NaCl + AgNO 3 $ NaNO 3 + AgCl
2. Slow reactions : In case of covalent compounds
reactions takes place slowly i.e., rate is low.
H+
CH 3 COOC 3 H 5 + H 2 O CH 3 COOH + C 2 H 5 OH
(c) Order of reaction : The number of reacting
species (atoms, ions or molecules) taking parts
in an elementary reaction, which must colloid
simultaneously to bring about a chemical reaction
is called molecularity of a reaction.
Diagram Showing Plot of Potential Energy vs
NH 4 NO 2 $ N 2 + 2H 2 O Reaction Co-ordinated
NUMERICAL QUESTIONS (Where n = number of half life’s)

25 = 100
176. A first order reaction is 50% complete in 30 minutes at 2n
300 K and in 10 minutes at 320 K. Calculate activation 2n = 100 = 4 = (2) 2
energy Êa h for the reaction. [R = 8.314 JK-1 mol-1] 25
[Given : log 2 = 0.3010, log 3 = 0.4771, log 4 = 0.602] n = 2 (number of half-life’s)
Ans : COMP 2023
Also, Total time ^ t h = n # t1 2
k 0.693 For 1st order, t1 = 0.693

T1/2 2
K
At 300 K, Given, K = 60 sec-1
k1 = 0.693 = 0.0231 min-1
30 t1 2 = 0.693 = 0.0115 sec
60
At 320 K,
^ t h = 2 # 0.0115
k2 = 0.693 = 0.0693 min-1 Time taken to reduce (75%) = 0.023 sec
10
According to Arrhenius equation 179. For a chemical reaction the energy of activation is
80 kJ mol-1 . If frequency factor is 4.0 # 1010 L mol-1 .
log k2 = Ea b 1 - 1 l What is rate constant at 400 K ?
k1 2.303 R T1 T2
Ans :
Ea = b log k2 l # 2.303 # R # T1 # T2
SQP 2009, OD 2007
k1 20 Given,
Ea = b log k2 l # 2.303 # R # T1 # T2 Ea = 80 kJ mol-1
k1 20
= 80 # 103 J mol-1
Ea = 43.484 kj/mol
A = 4 # 1010 litre mol-1
177. Half-life period of first order reaction is 10 minutes.
Calculate the rate constant of the reaction. T = 400 K
Ans : SQP 2022 R = 8.314 Jk-1 mol-1
We know that We know that,
t1/2 = 0.693 Ea = log 10 A
k 2.303RT k
k = 0.693 k = Ae- RT
Ea
t1/2
Here, t1/2 = 10 min = 600 sec log k = log A - Ea
2.303RT
k = 0.693 = 0.001155 s-1
600 s = log ^4 # 1010h - 80 # 103
Hence rate constant is 0.001155 s-1 . 2.303 # 8.314 # 400
= ^log 22 + log 1010h - 10.44
178. The rate constant of a first order reaction is 60 sec-1 .
How much time will it take to reduce 75% of its initial = ^0.6020 + 10h - 10.44
concentration?
= 10.6020 - 10.44
Ans : OD 2020
log k = 0.162
Given,
Order of reaction = 1st k = anti log 0.162
Use antilog table for calculate the value of k , we get
Rate constant k = 60 sec-1
k = 1.4521
Let, Initial concentration
â h = 100% 180. A first order reaction is 75% completed in 60 min.
Find the half-life period of the reaction.
Concentration at time ^ t h
Ans : FOREIGN 2010
i.e., at â - x h = 100 - 75 = 25%
Let initial quantity,
a
â - x h = 2n , a = 100
If x = quantity consumed, Ans : OD 2006
The energy rate of reaction can be calculated as:

Quantity after 60 min,
[R] - [R] 1
(a - x) = 100 - 75 = 25 rav = - 2
Tt
Since, (a - x) = an [R1] [R2] t1 s t2 s rav (mol L-1 s -1)
2
# 10 -3 # 10 -3
where, n = number of half life’s
160 80 0 5 (80 # 160) # 10 -3
25 = 100
- = 16 # 10 -3
5-0
2n
80 40 5 10 (40 - 80) # 10 -3
2n = 100 = 4 -
10 - 5
= 8 # 10 -3
25
n =2 40 10 10 20 (10 - 40) # 10 -3
- = 3 # 10 -3
10
Also, (Total time)
T = n # t1/2 (half life) 10 2.5 20 30
-
(2.5 - 10) # 10 -3
= 0.75 # 10 -3
30 - 20
60 = 2 # t1/2
It can be seen that the average rate decreases from
Since, t1/2 Half life = 60 = 30 min
2 16 # 10-3 to 0.75 # 10-3 mol L-1 s-1 during the time
181. Express the rate of the following reactions: interval 0 to 30 s .
1. 4PH 3 $ P4 + 6H 2 183. From the concentration of C 4 H 9 Cl (butyl chloride) at
2. 2NO 2 $ 2NO + O 2 different times given below, calculate the average rate
In terms of the concentration of reactants and products. of reaction:
Ans : DELHI 2014, SQP 2010 C 4 H 9 Cl + H 2 O $ C 4 H 9 OH + HCl during different
1. For the reaction, intervals of time.
4PH 3 $ P4 + 6H 2 t (s) C 4 H 9 Cl (mol L-1) t (s) C 4 H 9 Cl (mol L-1)

d [PH 3] 0 0.100 300 0.0549
4 dt 50 0.0905 400 0.0439
d [P4] d [H 2]
= =1 100 0.0820 500 0.0335
dt 6 dt
2. For the reaction, 150 0.0741 700 0.0210
2NO 2 $ 2NO + O 2 200 0.0671 800 0.017
d [NO 2] Ans :
DELHI 2001
2 dt Average rate of reaction in the interval t1 to t2 can be
d [NO] d [O 2]
=1 = calculated as:
2 dt dt {[C 4 H 9 Cl] t2 - [C 4 H 9 Cl] t1}
rav = -
182. The concentrations of a reactant R at different times t2 - t1
are given below: At t =0 [C 4 H 9 Cl] = 0.100 mol L-1
t (s) [R](mol L-1) At t = 50 s [C 4 H 9 Cl] = 0.0905 mol L-1
0 160 # 10-3 rav (in time interval 0 - 50 s )
5 80 # 10-3 = - 0.0905 - 0.100

(50 - 0)
10 40 # 10-3 = 1.90 # 10-4 mol L-1 s-1
At t = 50 s [C 4 H 9 Cl] = 0.0905 mol L-1
20 10 # 10-3
At t = 100 s [C 4 H 9 Cl] = 0.0820 mol L-1
30 2.5 # 10-3
rav (in time interval 50 - 100 s )
Calculate the average rate of reaction, R $ P (0.0820 - 0.09205)
during different intervals of time. =-
100 - 50
= 1.70 # 10-4 mol L-1 s-1 d [NO] d [H 2 O]

=1 =1
-1 4 dt 6 dt
At t = 100 s [C 4 H 9 Cl] = 0.820 mol L
1. Rate of disappearance of ammonia
At t = 150 s [C 4 H 9 Cl] = 0.0741 mol L-1 Rate of disappearance of NH 3
rav (in time interval 100 - 150 s ) = Rate of appearance of NO
(0.0741 - 0.0820) = 3.6 # 10-3 mol L-1 s-1
=-
150 - 100
2. Rate of formation of water
= 1.58 mol L-1 s-1 Rate of formation of H 2 O
At t = 150 s [C 4 H 9 Cl] = 0.0741 mol L-1 d [H 2 O]
= From rate equation,
At t = 200 s [C 4 H 9 Cl] = 0.0671 mol L-1 dt
1 d [H 2 O] = 1 d [NO]
rav (in time interval 150 - 200 s ) 6 dt 4 dt
(0.0671 - 0.0741) d [H 2 O]
=-
200 - 150 Hence, = 6 # 3.6 # 10-3
dt 4
= 1.40 mol L-1 s-1 = 5.4 # 10-3 mol L-1 s-1
Similarly, we can calculate in other time intervals.
rav (200 - 300 s) = 1.22 # 10-4 mol L-1 s-1 186. The decomposition of N 2 O 5 in CCl 4 solution at 318K
has been studied by monitoring the concentration of
rav (300 - 400 s) = 1.10 # 10-4 mol L-1 s-1 N 2 O 5 in the solution. Initially, the concentration of
rav (400 - 500 s) = 1.04 # 10-4 mol L-1 s-1 N 2 O 5 id 2.33M and after 184 minutes, it is reduced
to 2.08M . The reaction takes place according to the
rav (500 - 700 s) = 0.625 # 10-4 mol L-1 s-1 equation:
rav (700 - 800 s) = 0.4 # 10-4 mol L-1 s-1 2N 2 O 5 $ 4NO 2 + O 2
It is clear that the average rate of reaction decreases Calculate the average rate of this reaction in terms
from of hours, minutes and seconds. What is the rate of
1.90 # 10-4 mol L-1 s-1 to 0.4 # 10-4 mol L-1 s-1 production of NO 2 during this period?
184. Identify the reaction order from each of the following Ans : OD 2003
rate constants. [ N O ]
T 2 5
(i) k = 2.3 # 10-5 L mol-1 s-1 2 Tt

(ii) n = 3 , the units are: mol-2 L2 s-1 (2.08 - 2.33) mol L-1
=- 1
Ans : DELHI 2006 2 184 min
Order of a reaction can be predicted from the units of = 6.76 # 10-4 mol L-1 min-1
rate constant.
If time = 184 min = 3.067 hr
(i) The unit of second order rate constant is L mol-1 s-1
and therefore, k = 2.3 # 10-5 L mol-1 s-1 (2.08 - 2.33) mol L-1
Rate = - 1 #
represents a second order reaction. 2 3.067 hr
(ii) The unit of a first order rate constant is s-1 and = 4.07 # 10-2 mol L-1 hr-1
therefore, k = 3.2 # 10-4 s-1 represents a first If time = 184 # 60 = 11040 s
order reaction.
(2.08 - 2.33) mol L-1
185. Ammonia and oxygen react at high temperature as: Rate = - 1
2 11040s
4NH 2 (g) + 5O 2 (g) $ 4NO (g) + 6H 2 O (g)
= 1.13 # 10-5 mol L-1 s-1
In an experiment, rate of formation of NO is 3.6 # 10-3
T [NO 2]
mol L-1 s-1 . Calculate Rate = 1
4 Tt
1. rate of disappearance of ammonia, T (NO 2)
2. rate of formation of water. Hence, = 4 # Rate
Tt
Ans : SQP 2020
= 4 # 6.79 # 10-4 mol L-1 min-1
4NH 2 (g) + 5O 2 (g) $ 4NO (g) + 6H 2 O (g)
= 2.72 # 10-3 mol L-1 min-1
d [NH 3] d [O 2]
Rate = - 1 =- 1
4 dt 5 dt
187. Dinitrogen pentoxide decomposes at 475K as: 2. The reaction A + B $ C has zero order.
Write rate of equation.
N 2 O 5 (g) $ N 2 O 4 (g) + 1 O 2 (g)
2 Ans : DELHI 2017
If the initial pressure is 125 mm and after 30 minutes 1. (i) Rate = k [A] 1/2 [B] 3/2
of the reaction, total pressure of the gaseous mixture
is 148 mm, calculate the average rate of reaction in Order of reaction = 1 + 3 = 2
2 2
1. atm min-1 i.e., second order.
2. mol L-1 s-1 (ii) Rate = k [A] 3/2 [B] -1
Ans : COMP 2022
Order of reaction = 3 + (- 1) = 1
1. Let p is the decrease in pressure of N 2 O in 30 2 2
minutes then. i.e., half order.
2. For zero order reaction,
N 2 O 5 (g) $ N 2 O 4 (g) + 1 O 2 (g)
2 A+B $ C
Initial pressure 125mm 0 0 Rate equation is:

Rate = k [A]c [B]c
After 30 min 125 - p p 1p
2 189. Write the units of the rate constant for a nth order
reaction. Deduce from this the units of rate constant
Total pressure = 15 - p + p + 1 p = 148 for a (i) half order reaction, (ii) 32 th order reaction,
2
(iii) third order reaction.
125 + 1 p = 148
2 Ans : DELHI 2013, COMP 2010
1 p = 148 - 125 = 23 mm The units of the rate constant for nth order reaction
2 are:
p = 2 # 23 mm = 46 mm Rate = k [A] n
Hence, Decrease in pressure in 30 min mol L-1 = k [mol L-1] n
s
= 46mm = 46 atm
760
or k = (mol L-1) 1 - n s-1
Average rate of reaction
46 (i) n = 1 , units are: mol1/2 L-1/2 s-1
atm 2
= 760
30 min
(ii) n = 3 , units are: mol - 1/2 L1/2 s-1
= 2.02 # 10-3 atm min-1 2
(iii) n = 3 , the units are: mol-2 L2 s-1
2. Applying pV = nRT
190. The activation energy for the reaction
n = p -1
V RT 2HI (g) $ H 2 + I 2 (g) is 209.5 kJ mol at 581 K .
Calculate the fraction of molecules of reactants having
Decrease in molar concentration
energy equal to or greater than activation energy?
46
atm
= 760 Ans : FOREIGN 2011
0.0821 L atm K-1 mol-1 # 475K -Ea /RT
The factor e corresponds to the fraction of
Average rate of reaction molecule possessing kinetic energy greater than Ea .
= 0.001552 mol L-1 Fraction of molecule = e-Ea /RT
Hence, Average rate of reaction
log[Fraction of molecules] =- Ea log e
RT
= 0.001552
30 # 60 3
-7 -1 -1 = - 209.5 # 10
= 8.62 # 10 mol L s 8.314 # 581 K
188. 1. Calculate the overall order of a reaction, which = - 43.3708
has the rate expression: In (Fraction of molecules) = - 43.3708
(i) Rate = k [A] 1/2 [B] 3/2 log (Fraction of molecules) = - 43.3708
2.303
(ii) Rate = k [A] 3/2 [B] -1 [Hence, log e = 2.303 log 10 and In is log e ]
= - 18.8323 + 1 - 1 [A ] = [A ] 0 - 3 [A ] 0 = 1 [ A ] 0
4 4
= 19.1677
[A ]
Hence, Fraction of molecules possessing Ea or greater Thus, t3/4 = 2.303 log 1 0
k
than Ea . 4 [A] 0
= Antilog of 19.1677 = 1.471# 10-19 = 2.303 log 4 ...(i)

k
191. Calculate the half life period of a first order reaction Now, for half of a reaction to take place,
where the specific rate constant is: t = t1/2 ;
(i) 200s-1
(ii) 2 min-1 [A ] = [A ] 0 - 1 [A ] 0 = 1 [A ] 0
2 2
(iii) 4 year-1 [A ]
Ans : Thus, t1/2 = 2.303 log [A] 0
OD 2011 k 0
2
For the first order reaction.
= 2.303 log 2 ...(ii)
t1/2 = 0.693 k
k Dividing equation (i) by equation (ii)
(i) k = 200s-1 t3/4 log 4
=
t1/2 log 2
Hence, t1/2 = 0.693 = 3.465 # 10-3 s
200
= .6020 = 2
0
(ii) k = 2 min-1 0.3010
Thus, the time required for 3/4 th of the reaction to
Hence, t1/2 = 0.693 = 0.3465 min. occur is two times that required for half of the reaction.
2
(iii) k = 4 year-1 195. For the reaction R $ P , the concentration of a
reactant changes from 0.03 M to 0.02 M in 25 minutes.
Hence, t1/2 = 0.693 = 0.1732 year. Calculate the average rate of reaction using units of
4
time both in minutes and seconds.
192. A first order reaction is found to have a rate constant, Ans : OD 2007
k = 5.5 # 10-14 s-1 . Find the half life period of the T [R]
reaction. Rate = -
Tt
Ans : FOREIGN 2003
[0.02 M - 0.03 M]
For the first order reaction, =-
25
t1/2 = 0.693 = 0.693
= 0 . 01 mol L-1 min-1
k 5.5 # 10-14 s-1 25
= 1.26 # 1013 s = 4 # 10-4 mol L-1 min-1
-4 -1
193. For a reaction, A + B $ Products ; the rate law is = 4 # 10 mol L
60 s
given by, r = k [A] 1/2 [B] 2 . What is the order of the
reaction? = 0.067 # 10-4
Ans : DELHI 2016, OD 2014 = 6.7 # 10-4 mol L-1 s-1
Order of reaction = 1 + 2 = 2 1 or 2.5. 196. A first order reaction has a rate constant 1.15 # 10-3 s-1 .
2 2
How long will 5 g of this reactant take to reduce to
194. For a first order reaction, calculate the ratio between 3 g?
the time taken to complete three-fourth of the reaction Ans : OD 2019
and the time taken to complete half of the reaction. Given; k = 1.15 # 10-3 s-1 , [R] 0 = 5g , [R] = 3 g
Ans : SQP 2010
[R]
For first order reaction, k = 2.303 log 0
t [R]
[A ] 0
t = 2.303 log t = 2.303 log 5
k [A ] 1.15 # 10-3 3
For 3/4 of a reaction to take place, 3
t = 2.303 # 10 [log 5 - log 3]
t = t3/4 1.15
= 2.303 # 103 [0.6990 - 0.4771] Hence, [B] = 0.20 - 0.02 = 0.18 mol L-1
1.15
Rate = k [A] [B] 2 = 2.0 # 10-6 # (0.06) (0.18) 2
= 2.303 # 103 # 0.2219
1.15 = 2 # 10-6 # 6 # 10-2 # 3.24 # 10-2
= 0.511 # 103 = 38.88 # 10-10
1.15
= 4.443 # 102 s = 444.3 s = 3.888 # 10-9 mol L-1 s-1
= 3.89 # 10-9 mol L-1 s-1
197. In a reaction, 2A $ Products , the concentration
of A decreases from 0.5 mol L-1 to 0.4 mol L-1 in 10 200. The decomposition of NH 3 on platinum surface is a
minutes. Calculate the rate during the interval. zero order reaction. What are the rates of production
of N 2 and H 2 if k = 2.5 # 10-4 mol-1 L s-1 ?
Ans : DELHI 2005
Ans : SQP 2010
2A $ Products Pt
2NH 3 (g) heat
N 2 (g) + 3H 2 (g)
T [A] (0.4 # 0.5)
Rate = 1 =- 1 #
2 Tt 2 10 d [NH 3] d [N 2]
Rate = - 1 =+
(- 0 . 1 ) 2 dt dt
=- 1 #
2 10 d [ H ]
=+ 1 2
= k [NH 3]c
= 0.005 mol L-1 min-1 3 dt
Rate of production of
= 5 # 10-3 mol L-1 min-1
+ d [N 2]
N2 = = 1 # Rate
198. Time required to decompose SO 2 Cl 2 to half of its dt
initial amount is 60 minutes. If the decomposition is = 2.5 # 10-4 mol L-1 s-1
a first order reaction, calculate the rate constant of
Rate of production of
the reaction.
+ d [H 2]
Ans : COMP 2003 H2 = = 3 # Rate
dt
Given,
= 3 # 2.5 # 10-4 mol L-1 s-1
t1/2 = 60 min
= 7.5 # 10-4 mol L-1 s-1
As we know that,
-2 201. The rate of the chemical reaction doubles for an
k = 0.693 = 0.693 = 69.3 # 10 increase of 10 K in absolute temperature from 298 K.
t1/2 60 60
= 1.155 # 10-2 min-1 Calculate Ea .
= 1.155 # 10-2 = 1.925 # 10-4 s-1 t1/2 = 60 min
60
199. For the reaction: 2A + B $ A 2 B the rate log k2 = Ea b 1 - 1 l
= k [A] [B] 2 with k = 2.0 # 10-6 mol-2 L2 s-1 . Calculate k1 2.303 R T1 T2
the initial rate of the reaction when [A] = 0.1 mol L-1 , Ea 1 - 1
2.303 # 8.314 b 298 308 l
log 2 =
[B] = 0.2 mol L-1 . Calculate the rate of reaction after
[A] is reduced to 0.06 mol L-1 . Ea = 2.303 # 8.314 # 298 # 308 # 0.3010 Jmol-1
10
Ans : COMP 2021
-1
Rate of reaction Ea = 19.147 # 298 # 308 # 0.3010 kJmol
10 # 1000
= - [A] 1 [B] 2 -1
= 5705.8 # 308 # 0.3010 kJmol
= 2.0 # 10-6 mol-2 L2 s-1 # 0.1 # (0.2) 2 10000
= 8 # 10-9 mol L-1 s-1 = 52.897 KJ mol-1
= 8 # 109 M s-1 202. In a pseudo first order hydrolysis of ester in water, the
following results were obtained:
After [A] is reduced to 0.06 mol L . –1
When 2 moles of A react, then 1 mole of B reacts. t/s 12 30 60 90

When 0.01 – 0.06 = 0.04 moles of A react, then 0.2
[Ester] /mol L-1 0.55 0.31 0.17 0.085
moles of B will react.
1. Calculate the average rate of reaction between the 203. A reaction is of first order in A and second order in B .
time interval 30 to 60 seconds. 1. Write the differential rate equation.
2. Calculate the pseudo first order rate constant for 2. How is the rate affected on increasing the
the hydrolysis of ester. concentrations of B three times?
Ans : OD 2006 3. How is the rate affected when the concentrations
1. Average rate of both A and B are doubled?
Ans : SQP 2003
= - bC2 - C1 l
t2 - t1 dx = k [A] 1 [B] 2
1.
dt
= - b 0.17 - 0.31 l
60 - 30 2. If concentration of B is tripled, the rate will
0 . 14 become 9 times.
=+ = 14 # 1
30 100 30 dx = k [A] 1 [3B] 2 = 9k [A] 1 [B] 2
14 -3 -1 -1 dt
= 10 mol L s
3 #
3. When the concentrations of both A and B are
= 4.67 # 10-3 mol L-1 s-1 doubled, the rate will become 8 times.
[A ] 0 dx = k [2A] 1 [2B] 2 = 8k [A] 1 [B] 2
2. k1 = 2.303 log dt
t [A ]
2 . 303 204. The rate constant for a first order reaction is 60 s-1 .
= log .55
0
30 0.31 How much time will it take to reduce the initial
1 th
concentration of the reactant to its 16 value?
= 2.303 (log 55 - log 31)
30 Ans : COMP 2011, DELHI 2009
= 2.303 (1.7404 - 1.4914) Given,

30
R = 60 s-1 ,
= 2.303 (0.249) = 0.573 [A]0
30 30
t = 2.303 log = 2.303 log 16
-2 -1 k [A]0/16 60
= 1.91 # 10 s
= 2.303 # 1.2042 = 4.62 # 10-2 s
k2 = 2.303 log 0.55 60
60 0.17
The following results have been obtained during the
= 2.303 (log 55 - log 17)
205.
60 kinetic studies of the reaction: 2A + B $ C + D
= 2.303 (1.7404 - 1.2304) Experiment [A] mol/L-1 [B] /mol L-1 Initial rate of
60
formation of
= 1.17453 = 1.957 # 10-2 s-1 D/mol L-1 minute -1
60
2 . 303 I 0.1 0.1 6.0 # 10-3
k3 = log 0.55
90 0.085 II 0.3 0.2 7.2 # 10-2
= 2 . 303 (log 55 - log 8.5)
90 III 0.3 0.4 2.88 # 10-1
= 2.303 (1.7404 - 0.9294) IV 0.4 0.1 2.40 # 10-2
90
Determine the rate law and the rate constant for the
= 2.303 # 0.8110
90 reaction.
= 2.075 # 10-2 s-1 Ans : OD 2020
As we know that,
Rate constant,
dx = k [A] x [B] y
k1 + k2 + k3
k = dt
3
7.2 # 10-2 = k [0.3] x [0.2] y ...(i)
(1.91 + 1.957 + 2.075) # 10-2
= -1 x y
3 2.88 # 10 = k [0.3] [0.4] ...(ii)
= 5.942 # 10-2 Dividing (i) by (ii), we get
3
1 = 1
= 1.98 # 10-2 s-1 4 2y
2y = 2 2 Ans : DELHI 2010
y =2 (i) t1/2 = 0.693 = 0.693-1

k 200 s
Also, 6.0 # 10-3 = k [0.1] x [0.1] 2 ...(iii) = 3.465 # 10-3 s = 3.47 # 10-3 s
x 2
2.40 # 10 = k [0.1] [0.1]
-2
...(iv) (ii) t1/2 = 0.693 = 0.3465 minute
Dividing (iii) by (iv), we get 2 minute-1
1 = 1 = 3.465 # 10-1 minute
4 4x
(iii) t1/2 = 0.693-1 = 0.17325 years
x =1 4 year
dx = k [A] x [B] y = k [A] 1 [B] 2 = 1.7325 # 10-1 years
Therefore,
dt The half-life for radioactive decay of 14
208. 6 C is 5730 years.
-3 1 2
6.0 # 10 = k [0.1] [0.1] An archaeological artefact containing wood had only
Hence, k = 6.0 L2 mol-2 min-1 80% of the 14 6 C found in a living tree. Estimate the
age of the sample.
206. The reaction between A and B is of first order with Ans : OD 2004
respect to A and zero order with respect to B . Fill in
Given, t1/2 = 5730 years
the blanks in the following table:
Experiment [A] /mol L-1 [B] /mol L-1 Initial rate in k = 0.693 = 0.693
t1/2 5730
mol L-1 min ute -1 N
Also, t = 2.303 log 0
I 0.1 0.1 2.0 # 10 -2 k N
= 2 . 303 log 100
II 0.2 4.0 # 10 -2 0.693 # 80
III 0.4 0.4
t = 2 . 303 5730 [log 5 - log 4]
0.693 #
IV 0.2 2.0 # 10 -2
t = 2.303 # 5730 # 0.0969
Ans : COMP 2017, SQP 2012 0.693
dx = k [A] 1 [B] 0 = 5730 # 0.0969 = 555.237
dt 0.3010 0.3010
From Experiment I, = 1844.64 - 1845 years.
-2
2.0 # 10 = k # 0.1 209. During a nuclear explosion, one of the products is
-1 -1 90 Sr with half-life of 28.1 years. If 1 mg of 90 Sr was
k = 2 # 10 minute
absorbed in the bones of a new born baby instead of
From Experiment II,
calcium, how much of it will remain after 10 years and
4.0 # 10-2 = 2 # 10-1 # [A] 1 60 years if it is not lost metabolically?
[A] = 0.2 mol L-1 Ans : COMP 2007
From Experiment III, As we know that,

Rate = k [A] 1 k = 0.693 = 0.693
t1/2 28.1 years
= 2 # 10-1 # 0.4 = 0.8 # 10-1 [N ]
Also, t = 2.303 log 0
= 8 # 10-2 mol L-1 min-1 k [N ]
From Experiment IV, When t = 10 years ,
1 mg
2.0 # 10-2 = 2 # 10-1 # [A] 1 10 = 2.303 # 28.1 # log
0.693 N
[A] = 0.1 mol L-1
[Here, N 0 = 1 mg]
207. Calculate the half-life of a first order reaction from its
rate constants given below: log 1 = 10 # 0.3010 = 3.01 = 0.1071
N 28.1 28.1
(i) 200 s-1 1 = Antilog of 0.1071
N
(ii) 2 minutes-1
1 = 1.279
(iii) 4 year-1 N
N = 1 Initial pressure pi 0 0
1.279
= 0.7818 mg (microgram) Final pressure pi - x x x
When t = 60 years pt = pi - x + x + x = pi + x
60 = 2.303 # 28.1 # log 1 pi - pi = x

0.693 N
pi - x = pi - pt + pi = 2pi - pt
log 1 = 60 # 0.3010 p
N 28.1
k360 = 2.303 log
t p0
= 18.06 = 0.6427
28.1 pi
= 2.303 log
1 = Antilog of 0.6427 = 4.392 t (2pi - pt)
N
= 2.303 log 35
360 (2 # 35 - 54)
N = 1 = 0.227 mg
4.392
= 2.303 log 35
360 16
210. A first order reaction takes 40 minutes for 30 %
decomposition. Calculate t1/2 . = 2.175 # 10-3 s-1
Ans : FOREIGN 2006
k720 = 2.303 log 35
[ R] 720 (2 # 35 - 63)
k = 2.303 log 0
t [R] = 2.303 log 35
720 7
2 . 303 [R]0
= log = 2.235 # 10-3 s-1
t [R]0 - 100
30
[R]0
= 2.303 log 10 (2.175 + 2.235) # 10-3
t 7 Average rate constant =
2
= 2.303 # (log 10 - log 7) = 2.205 # 10-3 s-1
40
The following data were obtained the first order
= 2.303 # (1.000 - 0.8451)
212.
40 thermal decomposition of SO 2 Cl 2 at a constant
volume.
k = 2.303 # 0.1549
40 SO 2 Cl 2 (g) $ SO 2 (g) + Cl 2 (g)
Now, t1/2 = 693
0 .
k Experiment Time/s-1 Total pressure/atm
t1/2 = 0.693 # 40 1 0 0.5
2.303 # 0.1549
2 100 0.6
= 0.3010 # 40
0.1549
Calculate the rate of the reaction when total pressure
= 77.73 minutes. is 0.65 atm.
211. For the decomposition of azoisopropane to hexane and Ans : SQP 2000
nitrogen at 543 K, the following data are obtained: SO 2 Cl 2 (g) $ SO 2 (g) + Cl 2 (g)
t (sec) PP(mm of Hg)
pi 0 0
0 35.0
pi - x x x
360 54.0
pi - x + x + x = pi
720 63.0
pi
Calculate the rate constant. k = 2.303 log
t 2pi - pi
Ans :
k = 2.303 log 0.5
COMP 2000
100 2p i - p i
= 2.303 log 0.5
100 0.4
= 2.303 [log 5 - log 4]
100
= 2.303 [0.6990 - 0.602]

100
= 2.303 [0.0969]
100
= 2.23 # 10-3 s-1
pi - x + x + x = 0.65
0.50 + x = 0.65
x = 0.15
Slope of the line = - Ea ,
Rate = k (pSO Cl )2 2
2.303 R
= 2.23 # 10-3 (0.5 - 0.15) slope = tan q , if we plot log k vs 1 .
T
= 2.23 # 10-3 # 0.35 Thus, measuring the slope of the line, the value of
Ea can be calculated. Look up the values of 2.303
Rate = 7.805 # 10-4 atm s-1
log k, In k = 2.303 log k corresponding to 3031
K-1 and
1 -1
213. For a first order reaction, show that time required 323 K .
for 99% completion is twice the time required for the 215. The rate constant for the decomposition of
completion of 90% of reaction. In other words, prove hydrocarbons is 2.418 # 10-5 s-1 at 546 K. If the
that t99% = 2t90% for a first order reaction. energy of activation is 179.9 kJ/mol , what will be the
Ans : OD 2016, SQP 2014 value of pre-exponential factor?
[A ]
t99% = 2.303 log 1 0 Ans : SQP 2007
k 100 [A]0 k = Ae-E /RT
a
= 2 . 303 log 100

k In k = In A - Ea
Rt
= 2.303 # 2 = 4.606 Ea
k k log k = log A -
2.303 RT
[A ]
t 90% = 2.303k
log 10 0 179.9 # 1000
100 [A]0 log(2.418 # 10-5) = log A -
2.303 # 8.314 # 546
= 2.303 log 10 = 2.303 log 2.418 + log 10-5 = log A - 179900
k k 10454.262
Hence, t99% = 2t90%
0.3834 - 5.000 = log A - 179900
10454.262
214. The rate constant for the decomposition of N 2 O 5 at
- 4.6166 = log A - 17.2083
various temperatures is given below:
log A = 12.5917
T/cC 0 20 40 60 80
A = Antilog of 12.5917
105 # k/s-1 0.0787 1.70 25.7 178 2140
Pre-exponential factor (A) = 3.907 # 1012 s-1
Draw a graph between ln k and T1 and calculate the 216. Consider a certain reaction A $ Products with
values of A and Ea . Predict the rate constant at 30 cC k = 2.0 # 10-2 s-1 . Calculate the concentration of A
and 50 cC . remaining after 100 s if the initial concentration of A
Ans : SQP 2011 is 1.0 mol L-1 .
E Ans : OD 2014
Since ln k = - a + ln A
RT [A ] 0
k = 2.303 log
Ea t [A ]
or log k = - + log A
2.303 RT 2 . 303
2 # 10 =-2
log 1
This equation is of the form y = mx + c , i.e. the 100 [A ]
equation of a straight line. Thus, log k vs T1 is a log 1 = 2 = 0.86
straight line. [A ] 2.303
1 = Antilog of 0.86 = 7.244
[A ]
[A ] = 1 220. The rate constant for the first order of decomposition

7.244 of H 2 O 2 is given by the following equation.
= 0.135 mol L-1 log k = 14.34 - 1.25 # 10 4 K/T
217. Sucrose decomposes in acid solution into glucose and Calculate Ea for this reaction and at what temperature
fructose according to the first order rate law, with will its half-period be 256 minutes?
t1/2 = 3.00 hours. What fraction of sample of sucrose Ans : OD 2022
remains after 8 hours ? 4

log k = 14.34 - 1.25 # 10 K ...(i)
Ans : SQP 2011, DELHI 2008 T
0 . 693 0 . 693 Also, log k = log A - Ea ...(ii)
k = = h-1 2.303 RT
t1/2 3
[R] On comparing (i) and (ii), we have
Now, t = 2.303 log 0
k [R] Ea 4
- = - 1.25 # 10 K
2 . 303 [R]0 2.303 RT T
8 = log
k [R] Hence, Ea = 1.25 # 10 4 # 8.314 # 2.303
[R]
8 = 2.303 # 3 log 0 Ea = 103.92 kJ mol-1 # 2.303
0.693 R
[R] Ea = 239.3375 kJ mol-1
log 0 = 8 # 0.693 = 5.544
[R] 6.909 6.909
Now, k = 0.693 # 1 = 4.51 # 10-5 s-1
[R]0 256 60
= Antilog of 0.8024 = 6.345 4
[R]
From (i), log k = 14.34 - 1.25 # 10 K
1 = 6.345 T
[R] 4
log 4.51 # 10-5 = 14.34 - 1.25 # 10 K
T
[R] = 1 = 0.1576 M = 0.158 M
6.345 4
0.65 - 5.00 = 14.34 - 1.25 # 10 K
218. The decomposition of hydrocarbon follows the T
equation k = (4.5 # 1011 s-1) e-28000K/T . Calculate Ea . - 4.35 = 14.34 - 1.25 # 10 K
4
Ans : DELHI 2003

T
4
k = (4.5 # 1011 s-1) e-
28000 K
T ...(i) T = 1.25 # 10
18.69
Also, k = Ae-Ea /RT ...(ii) = 12500 = 668.80 K
18.69
Comparing equation (i) and (ii)
4.5 # 10-11 s-1 # e T
-28000 K
= A # e-Ea /RT 221. The time required for 10% completion of a first order
reaction at 298 K is equal to that required for its 25 %
Hence, - Ea = - 28000 K completion at 308 K. If the value of A is 4 # 1010 s-1 ,
RT T
calculate k at 318 K and E .
[Here A = 4.5 # 1011 s-1]
Ans : OD 2015
Ea = 28000 K # 8.314 JK-1 mol-1 [R]
t = 2.303 log 90 0 [R]0
Ea = 232.792 kJ mol-1 k 100
[R]
219. The rate constant for a first order reaction is 60 s-1 . Also, t = 2.303 log 75 0
How much time will it take to reduce the concentration k2 100 [R]
1 th
of the reactant to 10 of its initial value? Hence,
Ans : COMP 2010
2.303 log 10 = 2.303 log 4
k1 9 k1 3
k = 60s-1 ,
4
k2 = log 3 = log 4 - log 3
[R]
t = 2.303 log 0 k1 10
log 9 log 10 - log 9
k [R]
[R]
t = 2.303 # log 1 0 = 0.6021 - 0.4771
60 1.0000 - 0.9542
10 [R]0
t = 2 . 303 = 3.83 # 10-2 s = 0.1250 = 2.729

60 0.0458
CLASS 12

CLASS 10

Also, log k2 = Ea b 1 - 1 l Ea = 19.147 # 313 # 293 # 0.6021

k1 2.303R 293 308 20 # 1000
log 2.729 = E # 10 = 52.86 kJ mol-1
19.147 298 # 298
224. Calculate the rate constant of a reaction at 293 K,
Ea = 19.147 # 298 # 308 # 0.4360 given that; E a = 103 kJ mol-1 , k = 7.87 # 10-7 s-1 at
10
273 K, R = 8.314 JK-1 mol-1 .
= 76.623 kJ mol-1
Ans : OD 2017
Now, log k = log A - E
2.303 RT log k2 = Ea ` T1 - T1 j
k1 2.303 1 2
10
log k = log (4 # 10 ) - 76.623 # 1000
2.303 # 8.314 # 318 log k 2
= 103 # 1000 J b 1 - 1 l
7.87 # 10h - 7 2.303 # 8.314 J 273 293
= 10.6021 - 76623 J k2 = 103.00 b 20
13.147 293 # 273 l
6088.79 J log
7.87 # 10-7
log k = 10.6021 - 12.5843
log k2 = 1.345
log k = - 1.9822 + 1 - 1 = 2.0178 7.87 # 10-7
k2 = 345 (Antilog) = 22.13
log k = 2.0178
7.87 # 10-7
k = Antilog of 2.0178 k = 22.13 # 7.87 # 10-7
k = 1.044 # 10-2 s-1 = 1.74 # 10-5 s-1
222. The decomposition of A into product has value of 225. The thermal decomposition of HCO 2 H is a first order
k as 4.5 # 103 s-1 at 10 cC and energy of activation reaction with a rate constant of 2.4 # 10-3 s-1 at a
60 kJ mol-1 . At what temperature would k be certain temperature. Calculate how long will it take
1.5 # 10 4 s-1 ? for three-fourths of initial quantity of HCO 2 H to
Ans : DELHI 2011, OD 2007 decompose. (log 0.25 = - 0.6021)
log k2 = Ea bT2 - T1 l
Ans : FOREIGN 2000
k1 2.303 R T1 T2 [ R ]
4 -1 k = 2.303 log 0
log 1.5 # 10 3 s-1 = 60 # 1000 bT2 - 283 l

t [R]
4.5 # 10 s 2.303 # 8.314 283 T2 [R ]
2.4 # 10-3 s-1 = 2.303 log 1 0
log 10 = 60000 bT2 - 283 l t3/4 4 [R 0]
3 19.147 282T2
t3/4 = 2.303 log 4
(1.000 - 0.4771) = 60000 bT2 - 283 l 2.4 # 10-3
19.147 283 T2
283 # 19.147 # 0.5229 T2 = 60000 T2 - 60000 # 283 = 2.303 # 0.6021
2.4 # 10-3
2833.39 T2 = 60000 T2 - 60000 # 283 3
t3/4 = 1.386 # 10
2.4
57166.61T2 = 60000 # 283 2
= 13.86 # 10
T2 = 16980000 = 297 K 2.4
57166.61
t3/4 = 5.77 # 102 s
T2 = 297 - 273 = 24 cC
223. The rate of a reaction quadruples when the 226. For the reaction 2NO (g) + Cl 2 (g) $ 2NOCl (g)
temperature changes from 293 K to 313 K. Calculate the following data were collected. All the measurements
the energy of activation of the reaction assuming that were taken at 263 K.
it does not change with temperature. Exp. No, Initial [NO] Initial [Cl2] Initial rate of
Ans : OD 2004 (M) (M) disappearance of
Cl2 (M/ min)
log k2 = Ea bT2 - T1 l
k1 2.303 R T1 T2 1. 0.15 0.15 0.60
Ea = 2.303 R # T1 T2 log k2 2. 0.15 0.30 1.20
T1 - T1 k1
2 . 303 # 8 . 314 # 313 # 293 # log 4 3. 0.30 0.15 2.40
=
20 4. 0.25 0.25 ?
1. Write the expression for rate law. Initial conc. 0.80 0.20 0
2. Calculate the value of rate constant and specify
its units. Final conc. 0.80 - x 0.20 - x 2x
3. What is the initial rate of disappearance of Cl 2 in [NO] 2
experiment no. 4 ? K =
[N 2] [O 2]
Ans : SQP 2021 (2x) 2
1.0 # 10-5 =
dx = k [A] x [B] y (0.8 - x) (0.2 - x)
dt Since x is very small, so, 0.8 - x . 0.8 and
dx = k [NO] x [Cl ] y 0.2 - x . 0.2 , hence,
2
dt
(2x) 2
0.60 = k (0.15) x (0.15) y ...(i) 1.0 # 10-5 =
0.8 # 0.2
Also, 1.20 = k (0.15) x (0.30) y ...(ii) x = 6.3245 # 10-4 mol L-1
Dividing (i) by (ii), we get [NO] = 2x = 6.3245 # 10-4 # 2
1 = 1
2 2y = 1.2649 # 10-3 mol L-1
2y 21 = 1.26 # 10-3 mol L-1
y =1 [NO] = 0.8 - x
Again, 2.40 = k (0.30) x (0.15) y ...(iii) = 0.80 - 6.3245 # 10-4
Dividing (i) by (ii), we get = 0.79936 mol L-1
1 = 1
4 2x = 0.7994 mol L-1
2x = 2 2 [O 2] = 0.2 - x
x =2 = 0.2 - 6.3245 # 10-4
dx = k [NO] 2 [Cl ] 1 = 0.19936 mol L-1
1. 2
dt
= 0.1994 mol L-1
2. From (ii), putting the values of x and y , we have
0.60 = k (0.15) 2 (0.15) 228. Consider the reaction: 2A + B $ C + D
0.60 Following results were obtained in experiments
k = designed to study the rate of reaction:
(0.15) 2 (0.15)
= 177.77 L2 mol-2 min-1 Exp. Initial concentration (mol L-1) Initial rate
No. formation
k = 1.78 # 102 L2 mol-2 min-1
dx = 1.78 102 (0.25) 2 (0.25) [A] [B ] [D](M/ min)
3. # #
dt 1. 0.10 0.10 1.5 # 10-3
-1 -1
= 2.781 mol L min 2. 0.20 0.20 3.0 # 10-3
The reaction, N 2 (g) + O 2 (g) 2NO (g) 3. 0.20 0.40 6.0 # 10-3
227. Contributes to air pollution whenever a fuel is burnt 1. Write the rate law for the reaction.
in air at a high temperature. At 1500 K, equilibrium 2. Calculate the value of rate constant for the
constant K for it is 1.0 # 10-5 . Suppose in a case reaction.
[N 2] = 0.80 mol L-1 and [O 2] = 0.20 mol L-1 before 3. Which of the following possible reaction
any reaction occurs. Calculate the equilibrium mechanisms is constant with the rate law found
concentrations of the reactants and the product after in (a)?
the mixture has been heated to 1500 K. (I) A + B $ C + E (slow)
Ans : DELHI 2007
A + E $ D (fast)
N 2 (g) + O 2 (g) 2NO (g) ; (II) B $ C + E (slow)
K = 1.0 # 10-5 A + E $ F (fast)
A + F $ D (fast)
N 2 (g) + O 2 (g) 2NO (g)
Ans : FOREIGN 2004

[R]
dx = k [A] x [By] t90% = 2.303 log 10 0
k 100 [R] 0
dt
[90% is complete, 10 % is left]
1.5 # 10-3 = k (0.1) x (0.1) y ...(i)
= 2.303 # 100 log 10 = 100
3.0 # 10-3 = k (0.20) x (0.20) y ...(ii) 2.303 # 0.3980 0.3980
6.0 # 10-3 = k (0.20) x (0.40) y ...(iii) = 251.26 min . [Hence log 10 = 1]
Dividing (ii) by (iii), we get 230. Rate constant k of a reaction varies with T according
1 = 1 to the equation
2 2y
log k = log A - Ea b 1 l
2y = 21 2.303 R T
Where Ea is the activation energy. When a graph
y =1
is plotted for log k vs T1 , a straight line with a slope
Dividing (i) by (ii), we get - 4250 K is obtained. Calculated Ea for the reaction.
1 = 1 1 y (R = 8.314 J K-1 mol-1)
x #b l
2 2 2 Ans : COMP 2016, OD 2013
1
= #b l 1 1
2 2
[Hence, y = 1] Slope = - Ea
2.303 R
1 =1 - Ea
2x - 4250 K =
2.303 # 8.314
2x = 1 Hence, Ea = 4250 # 19.147 J
x 0
2 =2 = 81374.75 J mol-1
x =0 = 81.375 kJ mol-1
1. dx = k [A] 0 [B] 1
dt 231. The activation energy of a reaction is 75.24 kJ mol -1
in the absence of a catalyst and 50.14 kJ mol-1 with
2. 1.5 # 10-3 = k (0.1) 1 a catalyst. How many times will the rate of reaction
-3
= 1.5 # 10 = 1.5 # 10-2 min-1 grow in the presence of the catalyst if the reaction
0.1 proceeds at 25 cC ?
3. (II) B $ C + E (slow) is the possible reaction Ans : OD 2001
mechanism which is in agreement with the rate E
law, rate = k [A] 0 [B]. In k1 = ln A - a 1
RT
A first order reaction takes 100 minutes for completion E
229. ln k2 = ln A - a 1
of 60% of the reaction. Fine the time when 90% of the RT

reaction will be completed. ln k2 - ln k1 = 1 (Ea - Ea )
RT 1 2
Ans : DELHI 2000
As we know that log k2 = 2.3031 RT (75.24 kJ mol-1 - 50.14 kJ mol-1)

k1
[R]
k = 2.303 log 0 k
log 2 = 25100 = 4.40
t [R] k1 5705.8
[R]
= 2.303 log 40 0 k2 = Antilog of 4.40 = 2.5 10 4
#
100 100 [R]0 k1
[60 % is complete, 40 % is left] The rate of reaction will grow by 25000 times in
presence of catalyst. The decrease in activation energy
k = 2.303 (log 5 - log 2) takes place by 75.24 - 50.14 = 25.1 kJ mol-1 .
100
k = 2.303 (0.6990 - 0.3010) 232. The half-life for the reaction:
100
N 2 O 5 $ 2NO 2 + 1 O 2 is 2.4 hours at 30 cC .
2
= .303 # 0.3980 min-1
2
100 1. Starting with 100 grams of N 2 O 5 how many gram
[R] will remain after 9.6 hours?
t90% = 2.303 log 0
k [R] 2. What time would be required to reduce 5 # 1010
molecules of N 2 O 5 to 108 molecules?
Ans : OD 2012 Ans : OD 2005
0.693 Ea 1 - 1
2.303 R bT1 T2 l
1. t1/2 = log k2 =
k k1
0.693 -7
Ea
log 2.39 # 10-8 = 1 - 1
2.303 # 8.314 b 650 700 l
k =
2.4 2.15 # 10
Also, k = 2.303 log 100 19.147 # 650 # 700 # (log 23.9 - log 2.15)
9.6 x Ea =
50
0.693 = 2.303 log 100 19.147 # 650 # 700 # (1.3783 - 0.3324)
2.4 9.6 x =
50
log 100 = 1.2040 = 19 . 147 # 650 # 700 # 1.0459
x 50 # 1000
100 = Antilog of 1.2040
x Ea = 19.147 # 13 # 7 # 1.0459 = 182.23 kJ/mol
10
100 = 16
x 235. For the hydrolysis of methyl acetate in aqueous
solution, the following results were obtained:
x = 100 = 6.25 g
16
t/s 0 30 60
[A ]
2. k = 2.303 log 0 , [CH 3 COOCH 3] /mol L-1 0.60 0.30 0.15
t [A ]
10
t = 2.303 # 2.4 log 5 # 10 1. Show that it follows pseudo first order reaction,
0.693 108 as the concentration of water remains constant.
= 2.303 # 2.4 log 500 2. Calculate the average rate of reaction between the
0.693 time interval 30 to 60 seconds.
t = 2.303 # 2.4 # 2.6990 (Given: log 2 = 0.3010, log 4 = 0.6021)
0.693
Ans : FOREIGN 2014
= 21.526 min .
[R]
1. k = 2.303 log 0
233. In general it is observed that the rate of chemical t [R]
reaction doubles with every 10c rise in temperature. If 2 . 303
= log .60
0
the generalization holds good for the reaction in the 30 0.30
temperature range 295 K to 305 K , what would be
= 2.303 # 0.3010 = 0.693
the value of activation energy for the this reaction? 30 30
(R = 8.314 J mol-1 K-1) = 2.31 # 10-2 s-1
Ans : OD 2002
Also, k = 2.303 log 0.60
T1 = 295 K , T2 = 305 K , k2 = 2k1 (given) 60 0.15
2 . 303 log 4 = 2.303 # 0.6021
Hence, log k2 = Ea bT2 - T1 l =
60 60
k1 2.303 R T1 T2
Ea 305 - 295 = 1.386 = 2.31 # 10-2 s-1
2.303 # 8.314 b 305 # 295 l
log 2 = 60
Since k is constant, therefore, it follows pseudo first
Ea = 19.147 # 305 # 295 # 0.3010 order reaction.
10
change in conc.
[Here, log 2 = 0.3010 ] 2. Average rate =
time interval
Ea = 51854.8 J mol-1 = 51.85 kJ mol-1
= .30 - 0.15 = 0.15
0
30 30
234. For a decomposition reaction the values of rate
= 5 # 10-3 mol L-1 s-1
constant, k at two different temperatures are given
below: 236. For a reaction A + B $ P , the rate is given by
-8
k1 = 2.15 # 10 L mol s -1 -1
at 650 K Rate = k [A] [B] 2
-7 -1 -1 (i) How is the rate of reaction affected if the
k2 = 2.39 # 10 L mol s at 700 K
concentration of B is doubled?
Calculate the value of activation energy for this (ii) What is the overall order of reaction if A is
reaction. (R = 8.314 J K-1 mol-1) present in large excess?
Ans : OD 2007
239. For a chemical reaction R $ P , the variation in
(i) If the concentration of B is doubled, the rate of the concentration, In [R] vs, time (s) plot is given as
reaction becomes four times. shown in figure.
(ii) It A is present in large excess, overall order of (i) Predict the order of the reaction.
reaction will be equal to 2. (ii) What is the slope of the curve?
237. A first order reaction takes 30 minutes for 50% (iii) Write the unit of rate constant for this reaction.
completion. Calculate the time required for 90% Ans : OD 2010
completion of this reaction. (log 2 = 0.3010) (i) The reaction is of first order.
Ans : OD 2007 (ii) slope = - k
[R] (iii) Unit of rate constant is s-1 .
k = 2.303 log [R] 0
t1/2 0
2 240. Show that the time required for 99% completion is

2.303 log 2 = 2.303 0.3010 double of the time required for the completion of 90%
30 min 30 # reaction.
= 0.693
30
-2
= 6.93 # 10
3
k = 2.31 # 10-2 min-1
[R]
Also, t90% = 2.303 log 10 0
k 100 [R]0
t90% = 2.303 log 10

k
Ans : OD 2010
= 2.303 = 99.70 min [R]
2.31 # 10-2 t = 2.303 log 0
k [R]
[R] 0
238. A first order reaction takes 10 minutes for 25% t99% = 2.303 log
decomposition. Calculate t1/2 for the reaction. k 1
[R] 0 # 100
(Given: log 2 = 0.3010 , log 3 = 0.4771, log 4 = 0.6021) [Here, [R] = [R] 0 - 100
99
[R] 0
t99% = 2.303 log 100 = 2.303 # 2 ...(i)
t25% = 10 min. k k
[ R]
[R]
k = 2.303 log 0 Also, t90% = 2.303 log 0
t [R] k 10
[R] 0 # 100
[R] [Here, [R] = [R0] - 100
90
[R] 0]
t25% = 2.303 log 3 0
k 4 [R]0
t90% = 2.303 log 10 = 2.303 ...(ii)
Here, 25% of reactants has been changed into products k k
> H From equations (i) and (ii)
[R] = [R]0 - 100
25
[R] 0 = 100
75
[R]0 = 34 [R]0
t99% = 2 # t90%
k = 2.303 [log 4 - log 3]
10 min
241. The rate constant of a first order reaction increases
k = 2.303 # (0.6021 - 0.4771) from 4 # 10-2 to 8 # 10-2 when temperature changes
10
from 27 cC to 37cC . Calculate the energy of activation
= 2.303 # 0.1250 (Ea). log 2 = 0.3010 , log 3 = 0.4771, log 4 = 0.6021.
10
[R] Ans : COMP 2004
Now, t1/2 = 2.303 log [R] 0 = 2.303 log 2
k k log k2 = Ea b 1 - 1 l
0
2
k1 2.303 R T1 T2
t1/2 = 2.303 # 10 3010
2.303 # 0.1250 # Here T1 = 27 cC + 273 = 300 K
= 3.010 = 24.08 min . T2 = 37 cC + 273 310 K ,

0.1250
k1 = 4 # 10-2 k2 = 8 # 10-2
= 2.303 [1.6021 - 1.1790]

-2
Hence, log 8 # 10-2 = Ea 1 - 1
4 # 10 2.303 # 8.314 b 300 310 l 60
log 2 = Ea b 10 l = 2.303 # 0.4231

19.147 93000 60
Ea = 19.147 # 9300 # 0.3010 J = 0.9739
60
= 53589.19 J mol-1
= 0.01623 min-1
= 53.589 mol-1
k = 0.01625 + 0.01623 + 0.01623
3
242. Nitrogen pentoxide decomposes according to the
= 0.016236 min-1
equation
2N 2 O 5 (g) $ 4NO 2 (g) + O 2 (g) (ii) Initial rate
This first order reaction was allowed to proceed = k [N 2 O 5] = 0.016236 # 0.4
at 40 cC and the data given below were collected:
= 0.00649 mol L-1 s-1
[N 2 O 5] (M) Time (min) [R]
(iii) k = 2.303 log 0
0.400 0.00 t [R]
k = 2 . 303 log 0.4
0.289 20.00 t 0.35
0.209 40.00 2.303
t = (log 40 - log 35)
0.151 60.00 1.6236 # 10-2
0.109 80.00 t = 2.303 (1.6021 - 1.5441)

1.625 # 10-2
(i) Calculate the rate constant for the reaction.
2
Include units with your answer. Hence, t = 2.30310 # 0.0580
1.6236
(ii) Calculate the initial rate of reaction.
(iii) After how many minutes will [N 2 O 5] be equal = 13.3574 = 8.227 min .
1.6236
to 0.350 M ?
Ans : COMP 2014, SQP 2007 243. A first order reaction takes 23.1 minutes for 50%
(i) completion. Calculate the time required for 75%
completion of this reaction.
[R]
k = 2.303 log 0 log 2 = 0.301 log 3 = 0.4771, log 4 = 1.6021
t [R]
Ans : OD 2008
= 2.303 log 0.400
20 0.289 t1/2 = 23.1 min .
= 2.303 [log 0.400 - log 0.289] [R]
k = 2.303 log [R] 0
20 t1/2 0
2
= 2.303 [1.6021 - 1.4609]
20 t1/2 = 2.303 log 2
k
= 2.303 # 0.1412
20 k = 2.303 # 0.3010 min-1
23.1
= 3251 = 0.01625 min-1
0 .
[R]
20 Also, t75% = 2.303 log [R] 0
k 0
k = 2 . 303 log 0.400 4

40 0.209
= 2.303 # 23.1 log 4
2.303 # 0.3010
= 2.303 [log 0.400 - log 0.209]
40
t75% = 23.1 # 0.6021
0.3010
= 2.303 # 0.2820
40 = 46.2 min
= 0.6494 = 0.01623 min-1 244. The experimental data for decomposition of N 2 O 5 ;
40
[2N 2 O 5 $ 4NO 2 + O 2] in gas phase at 318 K are
k = 2.303 [log 0.400 - log 0.151] given as follows:
60
t/s 102 # [N 2 O 5] /mol L-1 2400 - 2.2757

0 1.63 2800 - 2.3752
400 1.36 3200 - 2.4559
800 1.14
1200 0.93
1600 0.78
2000 0.64
2400 0.53
2800 0.43
3200 0.35
(i) Plot [N 2 O 5] against t .
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log [N 2 O 5] and t .
(iv) What is the rate law?
(v) Calculate the rate constant.
(iii) The graph of log [N 2 O 5] vs t will be a straight line
(vi) Calculate the half-life period from k and compare with - ve slope.
it with (ii).
(iv) Rate = k [N 2 O 5] as it is the first order reaction.
Ans : SQP 2004
(i) Shape of the graph of [N 2 O 5] vs t will be as (v) Slope = - k
2.303
follows:
= - 0.295
1420 s
k = 2.303 # 0.295 s-1 = 4.78 # 10-4 s-1

1420
From the graph, t1/2 = 1420 .
(ii) Half life is the time in which initial concentration (vi) t1/2 = 0.693
k
of N 2 O changes from 1.63 # 10-2 molar to half of 0.693
its value i.e. 0.815 # 10-2 molar and in the graph, = s = 1450 s
4.78 # 10-4
it is equal to 1420 s.
245. The decomposition of phosphine (PH 3) proceeds
t log [N 2 O 5] according to the following equation:
4PH 3 (g) $ P4 (g) + 6H 2 (g)
0 - 1.7918
It is found that the reaction follows the following rate
400 - 1.8665 equation:
800 - 1.9431 Rate = k [PH 3]
The half-life of [PH 3] is 37.9 s at 120 cC .
1200 - 2.0315
(i) How much time is required for 34 th of PH 3 to
1600 - 2.1079
decompose?
2000 - 2.1933 (ii) What fraction of the original sample of PH 3
remains behind after - 1 minute?
Ans : COMP 2019 Ans :

(i) (i) Independent
t1/2 = 37.9 s (ii) k = 0.693
t1/2
k = 0.693 (iii) Zero order.
t1/2
(iv) Unit of k indicate, it is a second order reaction.
= 0.693 = 0.0183 s-1
37.9 s 247. Read the passage given below and answer the following
[R] questions :
t3/4 = 2.303 log [R] 0
k 0
When the overall order of reaction is 1, the reaction
4
2.303 # log 4 is said to be a first order reaction. When the overall

= order is 2, the reaction is said to be second order
k
2.303 # 0.6021 reaction. In case the overall order is 3, the reaction is
t3/4 = referred as a third order reaction. The order is usually
0.0183
1.386 = 75.7675 sec. a whole number. However, it can be zero or fractional
= also. It can be even negative (for inhibitors).
0.0183
2.303 log [R]0 (i) Give two examples zero order reaction.
(ii) k = (ii) Why molecularity of reaction cannot exceeds
t [R]
2.303 log 1 three ?
k = (iii) Why is the unit of rate constant for first order
60 [R]
reactions ?
1 min = 60 seconds.
(iv) Name the order of reaction which proceeds with
log 1 = 0.0183 # 60 = 0.4768 uniform rate throughout.
[R] 2.303
Ans :
1 = Antilog 0.4768 = 2.997 1130 K
[R] (i) (a) 2NH 3 Pt catalyst
N 2 + 3H 2
[R] = 1 = 0.3337 (b) 2HI

D
H2 + I2
2.997
Hence, Fraction of PH 3 remains = 0.3337 or 33.37% (ii) Molecularity of reaction cannot exceeds three
because more than three molecules cannot collide
with each other effectively.
CASE BASED QUESTIONS (iii) time-1 i.e., s-1 or min-1
(iv) Zero order reaction.
246. Read the passage given below and answer the following 248. The rate law for a chemical reaction relates the
questions : reaction rate with the concentrations or partial
The time taken by the reaction to go to completion is pressures of the reactants. For a general reaction
difficult to be measured because most of the reaction aA + bB $ C with no intermediate steps in its
become very slow at the verge of their completion. reaction mechanism, meaning that it is an elementary
Therefore, usually time taken for 98% completion is reaction, the rate law is given by r = k [A] x [B] y , where
measured. This time is referred to as reaction life time. [A] and [B] express the concentrations of A and B
The time, taken for 50% completion of the reaction is in moles per litre. Exponents x and y vary for each
called half life of reaction. Dining the half-life of a reaction and are determined experimentally. The value
reaction; the concentrations of reactants are reduced of k varies with conditions that affect reaction rate,
to half of 118 their original value. such as temperature, pressure, surface area, etc. The
(i) The half-life of a first order reaction is ...... of the sum of these exponents is known as overall reaction
initial concentration of the reactant. order. A zero order reaction has a constant rate that
(ii) Write down formula of rate constant ^k h for the is independent of the concentration of the reactants.
first order reaction. A first order reaction depends on the concentration
(iii) If the half-life of reaction depends on the initial of only one reactant. A reaction is said to be second
concentration of reactants [A] 0 . What will be the order when the overall order is two. Once we have
order of reaction ? determined the order of the reaction, we can go back
(iv) If, for any reaction k = 2.3 # 105 L mol-1 s-1 then and plug in one set of our initial values and solve for
identify the order of reaction. k.
In the context of the given passage, answer the behaves normally in solution. In case, it undergoes
following questions : association or dissociation, the observed molar mass
(i) Calculate the overall order of a reaction which has gives different results. The nature of the solute in
the following rate expression : solution is expressed in terms of van’t Hoff factor (i)
Rate = k [A] 1/2 [B] 3/2 which may be 1 (if the solute behaves normally), less
than 1 (if the solute associates) and more than 1 (if
(ii) What is the effect of temperature on rate of
the solute dissociates). The extent of association or
reaction?
dissociation is represented by cc which is:
(iii) A first order reaction takes 77.78 minutes for 50%
completion. Calculate the time required for 30% i-1
a= i-1
(1/n - 1) or (for dissociation)
completion of this reaction log 10 = 1, log 7 = n-1
0.8450. (for association)
(iv) A first order reaction has a rate constant 1 # 10-3 Based on the above passage, answer the following
per sec. How long will 5g of this reactant take to questions :
reduce to 3 g? (i) What is common in all the four colligative
(log 3 = 0.4771; log 5 = 0.6990) properties?
Ans : (ii) What is the expected value of van’t Hoff factor
for K 4 8Fe ^CNh6B when it completely dissociates in
(i) Overall order of reaction = 1 + 3 + 4 = 2 water?
2 2 2
(ii) The rate of reaction increases on increasing the (iii) What is the value of van’t Hoff factor fora dilute
temperature. solution of K 2 SO 4 in water?
(iii) For first order reaction, or
t50% = t1/2 = 0.693 (iv) In the determination of molar mass of A+ B using
k
colligative property, what will be the van’t Hoff
77.78 = 0.693 factor if the solute is 40% dissociated?
k
0 . 693 Ans :
k = = 0.009
77.78 (i) All of them depend upon the number of the
particles of the solute in the solution as well as its
and t30% = 2.303 log a
k (a - x) molar concentration.
2 . 303 100
=
0.009
log (ii) K 4 ^Fe (CN) 6h dissocoates as: 4K+ + ^Fe (CN) 6h3-
(100 - 30)
= 255.89 (log 10 - log 7) a = i - 1 or 1 = i - 1 or i = 4 + 1 = 5
(n - 1) 5-1
= 255.89 (1 - 0.8450) (iii) K 2 SO 4 dissociates completely in water as:
= 39.66 minutes K 2 SO 4
(aq)
2K+ (aq) + SO 42- (aq)
(iv) Given,
a = i - 1 or 1 = i - 1
[A ] 0 = 5 g , [A ] = 3 g (n - 1) 3-1
and k = 1 # 10-3 Per sec or i = 2 + 1 = 3

[A ] 0
t = 2.303 log
or
Using,
k A + -
(iv) Dissociation of A B may be expressed as:
= 2.303-3 log 5 (aq)
1 # 10 3 A + B- A+ (aq) + B- (aq) (n = 2)
a = i - 1 ; 0.4 = i - 1
3
= 2.303 # 10 (log 5 - log 3)
(n - 1) 2-1
= 2.303 (0.6990 - 0.4771)
i = 1 + 0.4 = 1.4
. 511 sec
250. For the first order decomposition reaction are as
249. The four colligative properties of the dilute solutions follows :
help in calculating the molecular mass of the solute (CH 3) 3 COOC (CH 3) 3 " 2CH 3 COCH 3 + C 2 H 6
which is often called observed molecular mass. It In the gaseous phase, the pressures of the system at
may be same as the theoretical molecular mass t = 0 and t = 15 min were found to be 169.3 Torr and
(calculated from the molecular formula) if the solute 256 Torr, respectively.
Answer the following questions according to the above

given paragraph:
(a) What is the pressure of C 2 H 6 at time t ?
(b) Write integrated rate law expression for this
reaction.
(c) Find out the value of rate constant k .?
or
(d) What is the total pressure of the system after 9
minutes?
Ans :
(a) (CH 3) 3 COOC (CH 3) 3 " 2CH 3 COCH 3 + C 2 H 6
t=0 p0 0 0
t p0 - p 2p p For first order of reaction,
t 0.693
Total pressure at time t , 1
2
k
pt = p0 + 2p
This means t1/2 is independent of initial concentration.
p - p0 Figure shows that typical variation of concentration
p = 1
2 of reactant exhibiting first order kinetics. It may be
Thus, from the given data at t = 0 and t = 15 min. noted that though the major portion of the first order
256 = 169.3 + 2p kinetics may be over in a finite time, but the reaction
will never cease as the concentration of reactant will
p = 256 - 169.3 be zero only at infinite time.
2
= 43.55 Torr Read the above passage and answer the following
questions:
(b) The integrated expression, (a) A first order reaction has a rate constant
kt = 2.303 log
2p0 k = 3.01 # 10-3 s-1 . How long will it take to
3p0 - pt decompose half of the reactant ?
(c) p0 - p = 169.3 - 43.35 = 125.95 Torr (b) Draw the plot of t1/2 vs initial concentration [A] 0
for a first order reaction.
k = 2.303 log 169.3
15 125.95 (c) The rate constant for a first order reaction is
= 0.0197 min-1 7.0 # 10-4 s-1 . If initial concentration of reactant
is 0.080 M, what is the half life of reaction?
or or
p0 (d) The rate of a first order reaction is 0.04 mol L-1 s-1
(d) k # t = 2.303 log
p0 - p
after 10 minutes and 0.03 mol L-1 s-1 after 20 minutes
0.0197 # 9 = 2.303 log 169.3 of initiation. What is the half-life of reaction?
(p0 - p)
Ans :
p0 - p = 141.9
(a) For a first order reaction :
p = 27.38
t1/2 = 0.693
pt = (p0 - p) + 3p = p0 + 2p k
k = 3.01 # 10-3 s-1
= 169.3 + 2 # 27.38
= 224.06 t1/2 = 0.693 = 230.3 s
3.01 # 10-3
251. The half-life of a reaction is the time required for the (b) For a first order reactions,
concentration of reactant to decrease by half, i.e., t1/2 = k [A] 00 = k
[A ] t = 1 [A ] Thus t1/2 is independent of initial concentration.
2
Hence plot of t1/2 vs [A] 0 will be a horizontal line.
a molecule about a double bond is not easy, because

it involves a distortion of the electron clouds forming
the double bond. A considerable increase in energy is
required to twist one end of cis-2-butene around the
other. This is shown in figure.
(c) Half life (t1/2) of a first order reaction is given is :

t = 0.693 = 0.693 -4
1
2
k 7.0 # 10
= 990 s
or
(d) Let the concentrations of the reactant after l0 min
The minimum quantity of energy required to surmount
and 20 min be C1 , and C2 , respectively.
an energy barrier during a chemical reaction is called
Rate after 10 min = k.C1 the activation energy, Ea and the molecular species at
= 0.04 # 60 mol L-1 min-1 the top of the barrier is called the activated complex
and or transition state.
In the sample of gaseous cls-2-butene at room
rate after 20 min = k.C2
temperature, only a tiny fraction of molecules have
= 0.03 # 60 mol L-1 min-1 enough energy to surmount the activation energy
C1 = 4 barrier. Not only do few molecules have enough
C2 3 energy to overcome the activation energy barrier,
but fewer still have that energy concentrated so that
Let the reaction starts after 10 minutes.
it can cause the atomic movements needed for the
k = 2.303 log C1 reaction to occur. For a uni-molecular process, the
10 C2
reaction rate must always be directly proportional
= 2 . 303 log 4 = 0.02878 to the concentration of the reacting species. For a
10 3
general uni-molecular process, A " products, the rate
t1/2 = 0 . 6932 = 0.6932
k 0.02878 equation is, Rate = k [A], where [A] =concentration
of A.
= 24.086 min
252. A reaction is said to be unimolecular if, on the questions:
microscopic level, rearrangement of the structure of (a) With the help of diagram, explain the physical
a single molecule produces the appropriate product significance of energy of activation (Ea) in
molecules. An example of a unimolecular process is chemical reactions.
conversion of cis-2-butene to trans-2-butene (in the (b) Can molecularity of a reaction be zero ?
absence of any catalyst).
(c) Over a given period of time only a very small
fraction of cis-2-butene molecule will be converted
to trans-2-bttene. Give reason.
or
(d) How is the rate of reaction affected if the
concentration of cis-2-butene is doubled ?
All that is required for this reaction to occur is a twist Ans :
or rotation around the double bond interchanging the (a) The energy required to form activated complex
methyl group with the hydrogen atom on the right- is called activation energy. It is the difference
hand side. Only one cis-2-butene molecule need to be between the threshold energy and the average
involved as a reactant in this process. Rotating part of energy possessed by the reacting molecules.
(b) No, the molecularity can never be zero or a t V3 - Vt 1 log V3 =k

fractional number as it shows the number of t V3 - Vt
reactants taking part in a reaction which can
never be zero. 10 28.45 1 log 34.75 = 0.00868
10 28.45
(c) In case of cis-2-butene, a very small fraction of
molecules have enough energy to overcome the 15 25.80 1 log 34.75 = 0.00862
15 25.80
activation energy barrier and very few of the high
energy molecules have their energy distributed 20 23.85 1 34.75 = 0.00863
so that most of it is causing a twist around the 20 log 23.35
double bond to form trans-2-butene. For this This shows that reaction is of first order.
reason, over a given period of time, only a very (iii) The hydrolysis of ethyl acetate or methyl acetate
small fraction of the cis-2-butene molecules will in the presence of a mineral acid as catalyst, is a
be converted to trans-2-butene. first order reaction.
+
H
or CH 3 COOC 2 H 5 + H 2 CH 3 COOH + C 2 H 5 OH
ethyl acetate acetic acid
(d) Rate1 = k [cis - 2 - butane] In this reaction, water is taken in excess. The
If [cis - 2 - bu tan e] is doubled concentration of water does not get altered much
during the course of the reaction. So, in the rate
Rate2 = k # 2 [cis - 2 - butane] = 2 equation water can be taken as constant.
Rate1 254. Zero order reactions are relatively uncommon but
i.e., rate will also be doubled. they occur under special conditions. Some enzyme
catalysed reactions and reactions which occur on metal
253. The half-life of a reaction is the time in which the surfaces are a few examples of zero order reactions. The
concentration of a reactant is reduced to one half decomposition of gaseous ammonia on a hot platinum
of its initial concentration. It is represented as t1/2 . surface is a zero order reaction at high pressure.
For a zero order reaction, t1/2 is directly proportional
to the initial concentration of the reactants and
inversely proportional to the rate constant. For a
first order reaction, half-life period is constant,
i.e., it is independent of initial concentration of the
reacting species. The half-life of a first order equation
Is readily calculated from the rate constant and vice
versa.
For zero order reaction t1/2 \ [R] 0 For first order
reaction I Is independent of [R] 0 .
(i) What is the unit of first order reaction?
(ii) From the following data for the decomposition of
N 2 O 5 . in CCl 4 solution at 48ºC, show that the
reaction is of the first order
Rate constant can be given as :
t(mts) 10 15 20 3 [R] 0 - [R]
k =
Vol of O 2 evolved 6.30 8.95 11.40 34.75 t
(i) Give an example of zero order reaction.
(iii) Why hydrolysis of ester follows first order kinetics?
(ii) On what factors does the half life of zero order
Ans :
reaction depends ?
(i) S-1
Ans :
(ii) For a first order reaction the integrated equation
(i) The thermal decomposition of HI on gold surface.
is
(ii) The half life of zero order reaction depends on initial
1 log V3 =t
t V3 - Vt concentration of reactant and the rate constant.
***********
Page 208 The d and f-block Elements Chap 4
CHAPTER 4
The d and f-block Elements
SUMMARY 7. Formation of coloured ions : Most of the

compounds of these metals are coloured in the
solid or solution form due to the presence of
1. d -BLOCK ELEMENTS unpaired electrons in (n - 1) d sub shell.
In these metal ions, the electrons can be easily
The elements of the group 3rd to 12th of the periodic
promoted form one energy level to another in the
table are called d -block elements. Their general
same d -orbital. It is called d - d transition.
outer electronic configuration is (n - 1) d1 - 10 ns1 - 2 (n
represent valence shell). 8. Magnetic properties : The compounds of d
-block elements may be both paramagnetic and
2. TRANSITION ELEMENTS diamagnetic. But most of the compounds are
paramagnetic.
The elements which have partially filled d -orbitals in
their elementary forms or in their commonly occurring Paramagnetic character is directly proportional
oxidation states are called transition elements. to the number of unpaired electrons.
Magnetic moment (m) = n (n + 2) B .M
3. GENERAL TRENDS IN TRANSITION ELEMENTS (Spin only) (Bohr Magneton)
1. Atomic radius : The atomic radius first decreases, where n = no. of unpaired electrons.
then remains almost constant and then increases
in a particular transition series. 9. Tendency to form complexes : These metal ions
have great tendency to form complexes due to
2. Metallic character and Enthalpy of atomisation : small size, high nuclear charge and presence of
All the transition elements are metals due to their vacant d -orbitals to accept a lone pair of electrons
low I.E. and presence of vacant d -orbitals. The donated by ligands.
hardness of these metals suggests the presence
of strong bonding due to overlap of half-filled 10. Formation of interstitial compounds : These
orbitals containing unpaired electrons. So these metals form interstitial compounds (compounds
elements have high enthalpy of atomisation. in which small atoms like H, C, N, etc. are trapped
inside the crystal lattice) due to the presence of
3. Density : All these metals have high density. In a vacant d -orbitals.
particular period,
11. Catalytic properties : These metals and their
Density ? 1 compounds act as good catalysts due to the
Atomic radius following reasons:
4. Melting Point and Boiling Point : Due to strong (i) Tendency to form reaction intermediates with
metallic bonds, these metals have high Melting suitable reactants, which give a reaction path
Point and Boiling Point. of lower Ea , so rate of reaction increase.
5. Ionisation energy : I.E. of these metals is generally (ii) Provide larger surface area on which the
very high. These metals show irregular variation reactants may be adsorbed.
in their ionisation energies due to irregular 12. Alloy formation : These metals form alloys due
variation in size. to their similar size in a particular transition
6. Oxidation states : These metals show a variety series and , therefore, the atoms of one metal can
of oxidation states from +2 to +7 due to the substitute the atoms of other metal in its crystal
tendency of (n - 1) d as well as ns -electrons to lattice.
take part in bond formation.
6.2 General Properties of Actinoids

They include 14 elements having atomic number 90
Structure :
to 103.
1. All of them are radioactive in nature.
2. The most common O.S. is +3 but they also show
+2, +4, +5 and +6 O.S.
6. f -BLOCK ELEMENTS 3. They are paramagnetic in nature.
The elements in which the last electron enters in the 4. They form coloured ions.
(n - 2) f -orbital of antipenultimate shell are called f 5. They form oxo-cations in higher O.S.
-block elements. 6. They are basic in nature.
The general outer electronic configuration of these 7. They also show actinoid contraction due to
elements is (n - 2) f 1 - 14 (n - 1) d0 - 1 ns2 . They consist ineffective shielding by intervening 5f -electrons.
of two series of elements placed at the bottom of the
main body of the periodic table, named Lanthanoid
***********
series and Actinoid series.
6.1 General Properties of Lanthanoids

OBJECTIVE QUESTIONS
They include 14 elements having atomic numbers 58
to 71. These are also called rare earth.
1. Which of the following characteristics of transition
1. They exhibit a common stable O.S. of +3. In
metals is associated with their catalytic activity ?
addition some lanthanoids show +2 and +4
O.S. also to attain the stable f 0 , f 7 and f 14 (a) Paramagnetic nature
configuration. (b) Colour of hydrated ions
2. Most of the lanthanoids are coloured due to the (c) High enthalpy of atomisation
presence of unpaired (n - 2) f -electrons. They (d) Variable oxidation states
undergo f - f transition
Ans : COMP 2023
3. They are paramagnetic in nature due to the
Due to large surface area and variable oxidation state,
presence of unpaired electrons in (n - 2) f
d-block elements show catalytic activities.
-orbitals.
4. They are highly electropositive and reactive Thus (d) is correct option.
metals. 2. Copper sulphate solution on treatment excess of KI
5. Their nitrates, chlorides, acetates are soluble in gives white precipitate. The precipitate is –
water while carbonates, oxalates, hydroxides, (a) CuI 2 (b) Cu 2 I 2
fluorides, sulphates are insoluble in water.
(c) Cu 2 SO 4 (d) I 2
6. There is a steady decreases in their atomic size
with increase in atomic number called lanthanoid Ans : OD 2018
contraction. It is due to the increases in effective The whitish precipitate is copper iodide.
nuclear charge and poor screening effect of 4f The reaction is as follows:
-electrons. Due to landthanoid contraction : CuSO 4 + 2KI $ CuI 2 + K 2 SO 4
(i) The elements of second and third transition
Here all the products and reactants are in aqueous
series resemble each other much more than
state except CuI 2 which is the insoluble solid and is
the elements resemble each other much
therefore the precipitate.
more than the elements of first and second
transition series. Thus (a) is correct option.
(ii) It is very difficult to separate the elements in 3. Oxidation number of gold metal is :
pure state because, their chemical properties (a) +1 (b) 0
are quite similar. (c) –1 (d) all of these
(iii) The basic strength of the hydroxides of
Ans : OD 2016
lanthanoids decreases with increase in atomic
number. Any metal, which is less reactive is available in free
state in nature. The metal (elements) as which are
Chap 4 The d and f-block Elements Page 211
available in free-state are considered having Zero (0) Ans : SQP 2017
oxidation state. As gold is very less reactive. Hence The ‘d’ block elements are called as transition
oxidation-state of gold is Zero. elements. In the transition elements the ultimate
Thus (b) is correct option. (n shell) and penultimate ^n - 1h shell of atoms are
incompletely filled with electrons. The differentiating
4. Which of the following elements is liquid at normal electron enters in ‘d’ orbitals of the penultimate shell.
temperature?
Hence, the general electronic configuration of
(a) Zinc (b) Mercury transition element is s (n - 1), d (1 - 10), ns (1 - 2).
(c) Aluminum (d) Water Thus (b) is correct option.
Ans : SQP 2015 8. Which of the following is not an element of first row
25cC temperature is considerer as normal-temperature. of transition series?
Mercury is a metal, but exist as liquid at normal (a) Fe (b) Cr
Temperature. (c) Mg (d) Ni
Zinc is solid at normal temperature. Ans : COMP 2004
Bromine is liquid at normal temperature. A Transition metal should exhibit following
Water (H 2 O) is liquid at normal temperature, but is characteristics.
not an element. It is compound. 1. It should have partially filled d orbitals.
Thus (b) is correct option. 2. The valance configuration should have at least an
5. The highest magnetic moment shown by the transition unpaired electron.
metal ion with the outermost electronic configuration Mg metal has the following configuration:
is: Mg = 1s2 , 2s2 , 2p6 , 2s2
(a) 3d 5 (b) 3d 2 Hence it is not a transition element.
7 9
(c) 3d (d) 3d Thus (c) is correct option.
Ans : OD 2017, DELHI 2013 9. Statement I : Zn++ is diamagnetic.
The highest magnetic moment shown by the transition Statement II : The electrons are lost from 4s -orbital
metal ion with the outermost electronic configuration to form Zn++ .
is 3d 5 because it has 5 unpaired electrons which shows (a) Both the statements are true and Statement II is
highest magnetic moment. the correct explanation of Statement I.
Thus (a) is correct option. (b) Both the statements are true, but Statement II is
6. Which one of the following is diamagnetic ion? not the correct explanation of Statement I.
(a) Co2+ (b) Ni2+ (c) Statement I is true, but Statement II is false.
2+ 2+
(c) Cu (d) Zn (d) Statement I is false, but Statement II is true.
Ans : COMP 2013, OD 2009 Ans : COMP 2013
In transition metals, the species contain unpaired In +2 state of Zn, Zn (30) becomes Zn (28). Electronic
electrons in d-subshell are paramagnetic while those configuration is 6Ar@3d10 4sc, so here 2 electron is
have no unpaired electrons are diamagnetic in nature. out from 4s -orbital, which results in no unparing of
The metals (ions/atoms) with d1 to d9 electrons are electron in +2 state also As Zn2+ has all electrons
paramagnetic while metals with d0 or d10 - outermost paired, So it is diamagnetic.
electronic configuration are diamagnetic. Thus (a) is correct option.
(a) Co2+ " has d7 electrons, thus is paramagnetic.
(b) Ni2+ " has d8 electrons, thus is paramagnetic. DIRECTION : For the following Question Nos. 10 to 12 a
passage is given. Read carefully the passage and select the
(c) Cu2+ " has d9 electrons, thus is paramagnetic.
correct answer out of given four options :
(d) Zn2+ " has d10 electrons, thus is diamagnetic.
Thus (d) is correct option. Transition elements show variable oxidation states.
This is due to their valence electrons which are found
7. The general electronic configuration of transition in two different orbitals i.e., ns and (n - 1) d . Up to
elements is: (+II) oxidation state ns electrons are involved, but
(a) (n - 1) d 5 (b) (n - 1) d (1 - 10) ns0.1 or 2 in higher oxidation states, electrons of (n - 1) d sub-
(c) (n - 1) d (1 - 10) ns 1 (d) none of these shells are involved.
(c) (n - 1) d1 - 10 , ns1 - 2 Ans : SQP 2006
Transition elements form coloured salts due to

(d) nd1 - 10 , ns-2
presence of incompletely filled d-orbitals.
Ans : OD 2015
General electronic configuration of transition elements
is (n - 1) d1 - 10 ns1 - 2 . 21. Which of the following characteristics of the transition
Thus (c) is correct option. metals is associated with their catalytic activity?
(a) Variable oxidation states
17. Of the following transition metals, the maximum
(b) High enthalpy of atomization
numbers of oxidation states are exhibited by:
(c) Paramagnetic behaviour
(a) Chromium (Z = 24) (b) Manganese (Z = 25)
(d) Colour of hydrated ions
(c) iron (Z = 26) (d) Titanium (Z = 22)
Ans : FOREIGN 2010
Ans : SQP 2011
Transition metals have the ability to utilize (n - 1)
Manganese shows max. no. of oxidation states + 2 , d-orbitals. Thus variable oxidation states enables the
+ 3, + 4 , + 5, + 6, + 7 . transition element to associate with the reactants in
Cr = + 2 , + 3 , + 4 , + 5 , + 6 different forms.
Fe = + 2 , + 3 Thus (a) is correct option.
Ti = + 2 , + 3 , + 4 22. The oxidation state of Cr in K 2 Cr2 O 7 is:

Thus (b) is correct option. (a) + 5 (b) + 3
(c) + 6 (d) + 7
18. The electronic configurations of our elements are
given below. Which element does not belong to the Ans : OD 2017, SQP 2015
+1 x
same family as others?: K Cr = + 2 + 2x - 14 = 0
2 2
(a) [Xe] 4f 14 5d10 6s2 (b) [Kr] 4d10 5s2 or x =+ 6

(c) [Ne] 3s2 3p5 (d) [Ar] 3d 4s2 Thus (c) is correct option.
Ans : COMP 2000
2 5 23. Statement I : Metals are reducing agent.
[Ne] 3s 3p is the electronic configuration of a p -block
element whereas other configuration are those of d Statement II : Metals have tendency to lose electrons.
-block elements. (a) Both the statements are true and Statement II is
Thus (c) is correct option. the correct explanation of Statement I.
(b) Both the statements are true, but Statement II is
19. Statement I : KMnO 4 is a coloured compound.
not the correct explanation of Statement I.
Statement II : Colour of KMnO 4 is due to charge
transfer. (c) Statement I is true, but Statement II is false.
(a) Both the statements are true and Statement II is (d) Statement I is false, but Statement II is true.
the correct explanation of Statement I. Ans : COMP 2002
(b) Both the statements are true, but Statement II is Metals act as a reducing agent because they have
not the correct explanation of Statement I. tendency to donate electrons and get oxidized.
(c) Statement I is true, but Statement II is false. Whereas non-metals act as an oxidizing agent because
non-metal have a tendency to gain electrons and get
(d) Statement I is false, but Statement II is true.
reduced.
Ans : DELHI 2003 Thus (a) is correct option.
Charge transfer occurs in KMnO 4 because, photons
24. When MnO 2 is fused with KOH, a coloured compound
promote an electron from the highest energy level MO,
is formed, the product and its colour is:
in one of the Mn - O to an empty d -orbital of Mn.
(a) K 2 MnO 4 , purple green
(b) KMnO 4 , purple
20. Which forms coloured salts?
(c) Mn 2 O 3 , brown
(a) Metals (b) Non-metals
(d) Mn 3 O 4 , black
(c) p -Block elements (d) Transition elements
For third ionization enthalpy Mn has stable Scandium ions doesn’t contain any unpaired electron
configuration due to half filled d-orbital. in d-orbitals hence it form colourless compound.
31. Which of the following metals corrodes readily in 36. General electronic configuration of lathanides is:
moist air?
(a) (n - 2) f 1 - 14 (n - 1) s2 p6 d 10 ns2
(a) Gold (b) Silver
(b) (n - 2) f 10 - 14 (n - 1) d 0 - 1 ns2
(c) Nickel (d) Iron
(c) (n - 2) f 0 - 14 (n - 1) d10 ns2
Ans : SQP 2002
In moist air, corrosion of iron takes place in the form (d) (n - 2) d 0 - 1 (n - 1) f 1 - 14 ns2
of rust (Fe 2 O 3 + Fe (OH) 3). As iron is most reactive Ans : COMP 2013
among all. The Lanthanides are transition metals from atomic 58
Thus (d) is correct option. (Ce) to 71 (Lu).
32. The common oxidation states of Ti are: Hence the electron configuration becomes:
(a) + 2 , + 3 (b) + 3 , + 4 (n - 2) f 1 - 14 (n - 1) s2 p6 d 0 - 1 ns2 .
(c) - 3 , - 4 (d) + 2 , + 3 , + 4
Ans : DELHI 2015 37. Which of the following oxidation states are the most
The minimum oxidation state in transition metal is characteristic for lead and tin respectively?
equal to the number of electrons in 4s shell and the (a) + 2 , + 4 (b) + 4 , + 4
maximum oxidation state is equal to the sum of the (c) + 2 , + 2 (d) + 4 , + 2
4s and 3d electrons. Ti 3d2 4s2 .
Ans : DELHI 2003
Hence minimum oxidation state is + 2 and maximum
All the group IV elements show tetra-valency which
oxidation state is + 4 . Thus the common oxidation
can be explained on the basis of shifting of one e- of
states of Ti are + 2 , + 3 and + 4 .
ns to the vacant np orbital. These four orbitals give
Thus (d) is correct option. rise to four sp3 hybrid orbitals.
33. Actinides When ns2 electrons of the outermost shell do not
(a) are all synthetic elements. participate in bonding it is called inert pair and the
(b) include element 104. effect is called inert pair effect. The last three elements
(c) have any short lived isotopes. of group 4 i.e. Ge, Sn and Pb, have a tendency to
(d) have variable valency. form divalent as well as tetravalent ions. Since the
inert pair effect increases from Ge to Pb, the stability
of tetravalent ions decreases and that of divalent ion
Actinides have variable valence due to very small increases that is why Pb++ is more stable than Pb 4+
difference in energies of 5f , 6d and 7s orbitals. Actinides and Sn 4+ ions is more stable than Sn2+ .
are the elements from atomic number 89 to 103.
38. Which of the following shows maximum number of
34. The electronic configuration of gadolinium (Atomic oxidation states?
number 64) is:
(a) Cr (b) Ve
(a) [Xe] 4f 8 5d0 6s2 (b) [Xe] 4f 3 5d 5 6s2
(c) Mn (d) V
(c) [Xe] 4f 6 5d2 6s2 (d) [Xe] 4f 7 5d1 6s2
Ans : FOREIGN 2007
Ans : OD 2003 5 2
Mn: [Ar] 3d 4s
Shows + 2 , + 3 , + 4 , + 5 , + 6 and + 7 oxidation states.
35. Which of the following forms colourless compound? Thus (c) is correct option.
(a) Sc3+ (b) V3+
39. Lanthanoids are
(c) Ti3+ (d) Cr3+ (a) 14 elements in the sixth period (atomic no. = 90
Ans : SQP 2009 to 103) that are filling 4f sublevel.
Sc +3 18 0
" [Ar] 3d ; V +3 18
" [Ar] 3d 2 (b) 14 elements in the seventh period (atomic no.
= 90 to 103)that are filling 5f sublevel.
Ti+3 " [Ar] 18 3d1; Cr+3 " [Ar] 18 3d3
51. Cuprous ion is colourless while cupric ion is coloured Oxides of transitional metals in low oxidation state
because: i.e., + 2 and + 3 are generally basic except Cr2 O 3 .
(a) Both have half filled p -and d -orbitals. Thus (a) is correct option.
(b) Cuprous ion has incomplete d -orbital and cupric 55. Ammonium dichromate is used in some fireworks.
ion has a complete d -orbital. The green coloured powder blown in the air is:
(c) Both have unpaired electrons in the d-orbitals. (a) CrO 3 (b) Cr2 O 3
(d) Cuprous ion has complete d -orbital and cupric (c) Cr (d) CrO (O 2)
ion has an incomplete d -orbital. Ans : DELHI 2000
Ans : OD 2015 D
+ 10
(NH 4) 2 Cr2 O 7 + Cr2 O 3 + N 2 + 4H 2 O
In Cu [Ar] 3d there is no unpaired electron, (green)
Cu2+ [Ar] 3d9 contains one unpaired electron hence Thus (b) is correct option.
coloured. 56. The lanthanide contraction is responsible for the fact
Thus (d) is correct option. that:
52. The correct order of ionic radii Y3+ , La3+ , Eu3+ and (a) Zr and Y have about the same radius
Lu3+ is: (b) Zr and Nb have similar oxidation state
(a) La3+ < Eu3+ < Lu3+ < Y3+
(c) Zr and Hf have about the same radius
(b) Y3+ < La3+ < Eu3+ < Lu3+
(d) Zr and Zn have the same oxidation states
(c) Y3+ < Lu3+ < Eu3+ < La3+
(Atomic numbers: Zr = 40 , Y = 39 , Nb = 41,
(d) Lu3+ < Eu3+ < La3+ < Y3+ Hf = 72, Zn = 30 )
Ans : SQP 2017, FOREIGN 2005 Ans : FOREIGN 2011
(Atomic nos.Y = 39 , La = 57 , Eu = 63 , Lu = 71) We know that regular decrease in the size of the atoms
In lanthanide series there is a regular decrease in the and ions is called lanthanide contraction. In vertical
atomic as well as ionic radii of trivalent ions (M3+) column of transition elements there is a very small
as the atomic number increases. Although the atomic change in size and some times size is found same from
radii do show some irregularities but ionic radii second member to third member. The similarity in
decreases from La(103 pm) to Lu(86 pm). size of the atoms of Zr and Hf is evident due to the
Thus (c) is correct option. object of lanthanide contraction. Therefore Zr and Hf
both have same radium 160 pm.
53. A blue colouration is not obtained when:
(a) Ammonium hydroxide dissolves in copper sulphate
57. Which of the following combines with Fe (II) ions to
(b) Copper sulphate solution reacts with K 4 [Fe (CN)6]
form a brown complex?
(c) Ferric chloride reacts with sod. ferro-cyanide
(a) NO (b) N 2 O
(d) Anhydrous CuSO 4 is dissolved in water
(c) N 2 O 3 (d) N 2 O 5
Ans : OD 2006
Ans : OD 2014
2CuSO 4 + K 4 [Fe (CN) 6 $ Cu 2 [Fe (CN) 6] + 2K 2 SO 4
We know that when nitrogen oxide (NO) combines
Chocolate ppt. with Fe (II) ions, a brown complex is formed this
Thus (b) is correct option. reaction is called brown ring test.
54. The basic character of the transition metal monoxides Thus (a) is correct option.
follows the order: 58. Which of the following statement is incorrect?
(a) TiO>VO>CrO>FeO (a) Silver glance mainly contains silver sulphide.
(b) VO>CrO>Ti>FeO (b) Gold is found in native state.
(c) CrO>VO>FeO>TiO
(c) Zinc is blende mainly contains zinc chloride.
(d) TiO>FeO>VO>CrO
(d) Copper pyrites also contain Fe 2 S 3 .
Ans : COMP 2005
Ans : SQP 2003
The basic character of the transition metal monoxide
is TiO>VO>CrO>FeO because basic character Zinc blende mainly contains ZnS and not ZnCl 2 .
of oxides decrease with increase in atomic number. Thus (c) is correct option.
Ans : OD 2001 Ans : SQP 2008

When steel is heated in presence of NH 3 , iron nitride [Cu (NH 3) 4] 2+ on addition of excess of aqueous HNO 3
on the surface of steel is formed which imparts a hard give [Cu (H 2 O)4] 2+ .
coating. This process is called nitriding. Thus (b) is correct option.
74. An extremely hot copper wire reacts with steam to
68. Which one of the following elements shows maximum give:
number different oxidation states in its compounds? (a) CuO (b) Cu 2 O
(a) Eu (b) La
(c) Cu 2 O 2 (d) CuO 2
(c) Ge (d) Am
Ans : SQP 2005
2Cu + H 2 O $ Cu 2 O + H 2 -
We know that lanthanides Eu, La, Gd shows + 2 , Hot Steam
+ 3 , + 3 and + 3 oxidation states respectively only. Thus (b) is correct option.

While actinides, Am shows + 2 , + 3 , + 4 , + 5 and + 6 75. An acidic solution of X does not give precipitate on
oxidation state. passing H 2 S through it. X gives white precipitate
Therefore American (Am) has maximum number of when NH 4 OH is added to it. The white precipitate
oxidation state. dissolves in excess of NaOH solution. Pure X fumes in
Thus (d) is correct option. air and dense white fumes are obtained when a glass
69. Among the lanthanides the one obtained by synthetic rod dipped in NH 4 OH is put in the fumes. Compound
method is: X can be:
(a) Lu (b) Pm (a) ZnCl 2 (b) FeCl 3
(c) Pr (d) Gd (c) AlCl 3 (d) SNCl 2
Ans : COMP 2017

Ans : SQP 2017
Pm is obtained by synthetic method. X

NH 4 OH
White ppt
excess
70. Stainless steel contains iron and: NaOH Acidic solution (soluble)
(No ppt with H2 S)
(a) Cr + Ni (b) Cr + Zn Given reaction (white precipitate with H 2 S in presence

(c) Zn + Pb (d) Fe + Cr + Ni of NH 4 OH ) indicate that X should be ZnCl 2 which
Ans : DELHI 2000 explains all given reactions.
Stainless steel contains 73% Fe, 18% Cr and 8% Ni. ZnCl 2 + 2H 2 O $ Zn (OH) 2 + HCl -
white fumes
Thus (d) is correct option. +
NH 4 OH + HCl - -H 2 O
NH Cl -
4
71. K 2 Cr2 O 7 on heating with aqueous NaOH gives: white fumes Dense whtie funes
(a) CrO 2- 4 (b) Cr (OH) 3 ZnCl 2 + 2NaOH $ Zn (OH) 2 + NaCl

2-
(c) Cr2 O 7 (d) Cr (OH) 2 Zn (OH) 2
2NaOH
Na 2 ZnO 2 + 2H 2 O
Excess
Ans : FOREIGN 2010
K 2 Cr2 O 7 + 2NaOH $ K 2 CrO 4 + Na 2 CrO 4 + H 2 O
Thus (a) is correct option. 76. Cuprous compounds such as CuCl, CuCN and CuSCN
are the only salts stable in water due to:
72. CrO 3 dissolves in aqueous NaOH to give:
(a) highly hydration energy of Cu+ ions.
(a) Cr2 O 72- (b) Cr2 O 2-
4
(b) their inherent tendency not do disproportionate.
(c) Cr2 (OH) 3 (d) Cr2 (OH) 2
(c) diamagnetic nature.
Ans : OD 2016
(d) insolubility in water.
CrO 3 + 2NaOH $ Na 2 CrO 4 + H 2 O
Ans : DELHI 2012
The smaller is this size of cation, the more is heat of
73. The addition of excess of aqueous HNO 3 to a solution hydration. Since hydration is exothermic process, thus
containing [Cu (NH 3)4] 2+ produces: heat evolves and hence system having lower energy
(a) Cu+ (b) [Cu (H 2 O)4] 2+ are stable.
(c) Cu (OH) 2 (d) Cu (NO 3) 2 Thus (a) is correct option.
84. Acidified K 2 Cr2 O 7 solution turns green when Na 2 SO 3 89. When the same amount of zinc is treated separately
is added to it. This is due to the formation of: with excess of H 2 SO4 and excess of NaOh, the ration
(a) Cr2 (SO 4) 3 (b) CrO 2-
4
of volumes of H 2 evolved is:
(c) Cr2 (SO3) 3 (d) Cr2 SO 4 (a) 1 : 1 (b) 1 : 2
Ans : SQP 2009

(c) 2 : 1 (d) 9 : 4
The green colour appears due to the formation of Ans : OD 2015
Cr+++ ion Zn + H 2 SO 4 $ ZnSO 4 + H 2
Cr2 O 23- + 3SO 23- + 8H+ $ 3SO 24- + 4H 2 O
Zn + 2NaOH $ ZnO 2 + H 2
1 mole atom of zinc produces the same amount of
85. Which of the following metals is not present in H 2 (2g) in each case.
German silver?
(a) Cu (b) Ni
(c) Zn (d) Sn
Ans : COMP 2015 ASSERTION AND REASON
German silver contains 50% Cu, 25% Zn and 25%
Ni. The corrosion resistance increases with increase in
percentage of Ni. It has a lusture like silver, hence the DIRECTION : Given below are two statements labelled as
name German silver. Assertion and Reason. Select the most appropriate answer
90. Assertion : Copper is a non-transition element.
86. For the four successive transition elements (Cr, Mn,
Fe, and Co), the stability of +2 oxidation state will be Reason : Copper has completely filled d-orbitals in its
there in which of the following order? ground state.
(a) Mn>Fe>Cr>Co (b) Fe>Mn>Co>Cr (a) Both Assertion and Reason are true and Reason
is the correct explanation of Assertion
(c) Co>Mn>Fe>Cr (d) Cr>Mn>Co>Fe
Ans : COMP 2010
(b) Both Assertion and Reason are true, but Reason
Thus (a) is correct option. is not the correct explanation of Assertion.
(c) Assertion is true, but Reason is false.
87. Which is not amphoteric?
(a) Al3+ (b) Cr 3+ (d) Assertion is false, but Reason is true.
(c) Fe3+ (d) Zn2+ Ans : COMP 2020
Copper exhibit +2 oxidation state where it has

completely filled d -orbitals ^3d10 4s°h Hence, it is a
Oxides of metal in their low oxidation states are generally
transition element.
basic whereas oxides of metals in their intermediate
oxidation state are generally amphoteric in nature. Fe3+
is not amphoteric as it is in its highest oxidation state. 91. Assertion : Pure iron is not used for making tools and
Thus (c) is correct option. machines.
Reason : Pure iron is hard.
88. What is the effect of shaking dil. H 2 SO4 with a small (a) Both Assertion and Reason are correct and
quantity of anhydrous CuSO4 ? Reason is a correct explanation of the Assertion.
(a) The white solid dissolves to from a colourless solution
(b) The white solid dissolves to form a blue solution is not the a correct explanation of the Assertion.
(c) The white solid dissolves to form a green solution (c) Assertion is correct but Reason is incorrect.
(d) The white solid turns blue but does not dissolve. (d) Both the Assertion and Reason are incorrect.
Ans : FOREIGN 2002 Ans : DELHI 2007
Anhydrous CuSO 4 (white)is reduced into blue Pure iron is not used for making tools and machines
CuSO 4 .5H 2 O which dissolves in dil. H 2 SO 4 to give as it is soft. However, an alloy of iron with carbon is
blue solution. hard and less reactive than pure iron.
(a) Both Assertion and Reason are correct and VERY SHORT ANSWER QUESTIONS
(b) Both Assertion and Reason are correct but Reason 101. Give reason Zn2+ salts are white but Cu2+ salts are
is not the a correct explanation of the Assertion. blue in colour.
(c) Assertion is correct but Reason is incorrect. Ans : FOREIGN 2019, 2014, SQP 2013, 2010
(d) Both the Assertion and Reason are incorrect. The transition metal ions having completely filled
d-orbitals or completely empty d-orbitals are colourless
Ans : FOREIGN 2006
or white.
Due to larger surface area and variable valencies to Since, Zn2+ possesses completely filled d-orbitals as
form intermediate absorbed complex easily, transition electronic configuration of Zn2+ is
metals are used as catalysts.
1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 3d 10 .
Thus, its salts are white or colourless. On the other
99. Assertion : Magnetic moment values of actinides are hand, Cu2+ possesses an electronic configuration of
lesser than the theoretically predicted values. 1s2 2s2 2p6 3s2 3p6 3d 9 .
Reason : Actinide elements are strongly paramagnetic. This suggest that it has partly filled d-orbitals (an
(a) Both Assertion and Reason are correct and unpaired e- ) which undergoes d-d transition. Hence,
Reason is a correct explanation of the Assertion. Cu2+ salts are coloured.
(b) Both Assertion and Reason are correct but Reason 102. What is the electronic configuration of chromium
is not the a correct explanation of the Assertion. atom (Z = 24)? Give a reason for your answer.
Ans : OD 2012
The electronic configuration of chromium atom
(d) Both the Assertion and Reason are incorrect. ^Z = 24h is 1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 4s1 , 3d 5
Ans : DELHI 2007 To maximise stability, electron from 4s -orbital jumps
The magnetic moment values are lesser than the to 3d -orbital. So, that maximum number of half-filled
theoretically predicted values due to the fact that orbitals can be obtained which is a stable arrangement
5f electrons of actinides are less effectively shielded of electrons.
which results in quenching of orbital contribution. 103. Explain, why Cu+ is diamagnetic but Cu2+
Thus (b) is correct option. paramagnetic ^Z = 29h ?
100. Assertion : C - O bond in metal carbonyls is long.
The electronic configuration of
Reason : There is delocalisation of electrons from filled
d orbitals into the empty orbitals on the CO ligands. Cu+ = 1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 4s0 , 3d 10 and
(a) Both Assertion and Reason are correct and Cu2+ = 1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 4s0 , 3d 9
Reason is a correct explanation of the Assertion. In Cu+ ion, all electrons are paired. Hence, Cu+ is
(b) Both Assertion and Reason are correct but Reason diamagnetic in nature. Whereas, Cu2+ has one
is not the a correct explanation of the Assertion. unpaired electron thus, shows paramagnetic character.
(c) Assertion is correct but Reason is incorrect. 104. Why is zinc not regarded as a transition element?
(d) Both the Assertion and Reason are incorrect. (Atomic number Zn = 30)
Ans : COMP 2018
Ans :
Zinc with electronic configuration 6Ar@3d 10 4s2 has
SQP 2012
In metal carbonyls a pair of p -bond arises from

completely filled shells of d-orbitals and therefore,
overlap of filled d -orbital on the metal with a pair of
it is not regarded as transition element. However,
p -anti-bonding orbitals projecting from the carbon of
it is often studied with transition elements because
the CO.
of similarities in some of its properties to those of
The p bonding has the effect of weakening the transition elements.
C - O bond as compared with free CO. Hence C - O
bond in metal carbonyls is long. Hence assertion 105. K 2 Cr2 O 7 acts as a powerful oxidising agent in acidic
and reason both are true and reason is a correct medium. Explain.
explanation of assertion. Ans : COMP 2020
In K2Cr2O7 the oxidation number of Cr is +6 which
is the highest oxidation number of Cr. Thus, K2Cr2O7
116. Name a transition element which does not exhibit

variable oxidation state.
Ans : FOREIGN 2006
Scandium (Z=21), shows an oxidation state of +3

only. Hence, electron configuration of
117.
2+
Why are Mn compounds more stable than Fe 2+ Cu+ = 3d10, 45c
towards oxidation to their +3 state?
Ans : SQP 2012
2+ 5
It is because in Mn had 3d configuration which is
half filled and hence stable therefore 3rd ionization
enthalpy is very high compared to 3rd. I.E. of Fe2+
which has 3d 6 configuration. 120. Transition elements form coloured compound. Explain.
or
Why do transition elements form coloured compounds?
SHORT ANSWER QUESTIONS Explain.
Transition elements form coloured compounds due to

118. What is a transition element? Give two examples.
the following reason:
or
Most of the compounds of transition metals are
What are the characteristics of the transition elements
coloured due to d -d transition, structure defects
and why are they called transition elements? Which
and charge transfer. Transition metal ions having d 0
of the d -block elements may not be regarded as the
configuration are colourless.
transition elements?
The explanation is that in d -d transition, free metal
Ans : SQP 2002
ions has degenerate d -orbital which splits into
Transition element : An element which has two levels according to the geometry of complex.
incompletely filled d -orbital in its ground state or in Compounds absorb light of visible range for the
any or its oxidation state is called transition element. excitation of electrons from lower to higher level and
e.g. Cr, Fe, Ni etc. thus show complementary colour of light is seen.
Characteristics of transition elements :
121. Any transition series contains only ten elements.
1. All transition elements have metallic structure Why?
except Mercury (Hg) which is liquid.
Ans : FOREIGN 2014
2. They have high melting and boiling point, high
enthalpies of vaporisation and atomisation. Transition series elements belongs to d-block. Outer
most electron in each series of transition metal
3. Their first ionisation enthalpies are higher than
belongs to d -sub-shell. Also any d -sub-shell can only
s -block elements and less than p -block elements.
accommodate maximum number of ten (10) electrons.
4. They are electro-positive in nature.
As one electron is added in each next element, as we
5. They show variable oxidation state, form coloured proceed in a period, in any transition series.
compounds, complexes interstitial compounds.
Therefore, only 10 elements are possible in each series
119. Write the electronic configuration of Cu+ . of transition elements.
Ans : OD 2014, SQP 2013
Atomic number of copper, 122. Why are Cd2+ salts white?

Ans : DELHI 2011
(Cu) = 29
Transition element exhibit colour to d -d transition.
i.e. (Z = 29) d -d transition will be possible only when d -subshell
When Cu changes to Cu+ ion, one of its electron is is not fully filled. The electronic configuration of Cd2+
removed from 4s , Thus number of electrons in is Cd10 . It means it has fully filled d -subshell. Thus
Cu+ = 28 there will no d -d transition takes place, so Cd2+ is
Since, outermost electron configuration of white.
Cu = 3d10, 4s1 123. Why does H 3 PO 3 acts as reducing agent but H 3 PO 4

does not?
Ans : DELHI 2011

128. On what ground can you say that scandium (Z=21) is
The reducing nature depends on the number of a transition element but zinc (Z=30) is not?
hydrogen atoms bonded to the central atom. In Ans : SQP 2017
H 3 PO 3 , It has 1P-H bond whereas in H 3 PO4 there no
Sc(Z=21) has incompletely filled 3d orbital (3d 1) but
such bonds. Therefore, H 3 PO 3 can release hydrogen
zinc (Z=30) has completely filled d -orbitals (3d 10),
and is a better reducing agent. H 3 PO3 is a better
therefore as per definition Scandium is a transition
reducing agent than H 3 PO4 .
element but zinc is not.
124. Write the name of elements of 3d series with their 129. Silver atom has completely filled d -orbitals (4d 10)
atomic number. in its ground state. How can you say that it is a
Ans : COMP 2005 transition element.
Ans : FOREIGN 2001
ATOMIC NAME ELECTRONIC
In ground state configuration of Ag (Z=47) is 4d 10 5s1
NO. CONFIGURATION
but in oxidation state of +2, the configuration is d 9
21 Scandium (Sc) = [Ar] 18 3d 1 4s2 i.e. the d -subshell is not completely filled. Hence it is
a transition element.
22 Titanium (Ti) = [As] 18 3d 2 4s2
130. Why do transition metals show variable oxidation
23 Vanadium (V) 18
= [Ar] 3d 4s 3 2 state?
Ans : OD 2009
24 Chromium (Cr) = [Ar] 18 3d 5 4s1
Transition metals show variable oxidation-states due
25 Manganese (Mn) = [Ar] 18 3d 5 4s2 to involvement of ns and (n - 1) d electrons, which
have very small energy difference.
26 Iron (Fe) = [Ar] 18 3d 6 4s2
131. In what way is the electronic configuration of transition
27 Cobalt (Co) 18
= [Ar] 3d 4s 7 2 metals different from non-transition metals?
Ans : COMP 2011, OD 2010
28 Nickel (Ni) = [Ar] 18 3d 8 4s2 Transition elements contain partially filled d -subhell
whereas non-transition elements have ns1 - 2 or np1 - 6
29 Copper (Cu) = [Ar] 18 3d 10 4s1
in their valence shells, they have no d -subshell or
30 Zinc (Zn) = [Ar] 18 3d 10 4s2 their d -subshell is completely filled.
132. What is the trend in melting point of transition metals
125. Write the electronic configuration of Cr and Cu. when we move left to right in a series?
Ans : OD 2001 Ans : COMP 2012
Cr (Z = 24) : [Ar] 18 3d 5 4s1 On moving left to right in a series the melting points
of these metals rise to a maximum at d 5 then fall as
Cu (Z = 29) : [Ar] 18 3d 10 4s1
the atomic number increases.
126. Why Zinc, Cadmium and Mercury are not regarded as 133. Write the electronic configuration of
transition elements? 1. Co2+ (27)
Ans : SQP 2007
2. Ce 4+ (58)
Zinc (Zn), Cadmium (Cd) and Mercury (Hg) have
3. Lu2+ (71)
filled d 10 configuration in their ground state as well as
in the common oxidation states. Hence they are not Ans : DELHI 2004
regarded as transition elements. 1. Co2+ (t = 27) [Ar] 3d 7 4sc

2. Ce 4+ (t = 58) [Xe] 4f c5dc6sc
127. Write main series of transition metals.
Ans : FOREIGN 2009 3. Lu2+ (t = 71) [Xe] 4f 14 5d 1 6sc
There are four main series of transition metals 134. Write down the electronic configuration of
1. 3d series or first transition series : 21Sc to 30Zn 1. Cr3+ 2. Cu+
2. 4d series or second transition series : 39Y to 48Cd 3. Co2+ 4. Mn2+
3. 5d series or third transition series : 57 La to 80Hg
5. Pm3+ 6. Ce 4+
4. 6d series or fourth transition series : 89Ac to 112Cn
7. Lu2+ 8. Th 4+
There is decrease in second ionization enthalpy from Ans : SQP 2009
Cr to Mn form Cu to Zn because after removal of

Ions No. of unpaired electrons
1 st electron, Cr and Cu gain a stable configuration
i.e. d 5 and d 10 . Hence irregular variation of I.E. is Mn3+ , 3d 4 4
mainly due to varying degree of stability of different
Cr3+ , 3d 3 3
3d -configurations.
145. To what extent do the electronic configurations decide to V3+ , 3d 2 2
stability of oxidation states in the first series of transition
Ti3+ , 3d 1 1
elements? Illustrate your answer with example?
Ans : FOREIGN 2011 Cr3+ is most stable in aqueous solution because it has
In the first series of transition elements the oxidation half filled t2g level (see next unit).
state which lead to stable configuration i.e. d 0 , d 5 ,
d 10 are more stable. Sc shows only +3 oxidation state 150. Which of the 3d series of the transition metals exhibits
with 3d 0 , most stable oxidation state of Mn is +7 the largest number of oxidation states and why?
with 3d 5 , Zn shows only +2 oxidation state with 3d 10 . Ans : COMP 2010
146. What may be the stable oxidation state of the Manganese (Z=25)+2 to +7 because its atom has the
transition element with the following d electrons maximum number electrons for bond formation.
configurations in the ground state of their atoms : 151. How is the variability in oxidation states of transition
3d 3 , 3d 5 , 3d 8 and 3d 4 ? metals different from that of the non transition
Ans : OD 2018, DELHI 2009 metals? Illustrate with examples.
Stable oxidation states are : Ans : SQP 2016
3d 3 (Vanadium) : +3, +4 and +5 The oxidation state in transition elements vary from
3d 5 (Chromium) : +3, +4, +6 +1 to any highest oxidation state by one. For example
3d 5 (Manganese) : +2, +4, +6, +7 the oxidation states of Manganese are +2, +3, +4, +5,
+6, +7. In the non transition elements the variation
3d 8 (Cobalt) : +2, +3 (in complexes)
is selective and always differing by like +2, +4 or +3,
3d 4 No element has d 4 configuration in the ground +5, +4 or +6 etc.
state.
152. Unlike Cr3+ , Mn2+ , Fe3+ and the subsequent M3+ ions
147. Name the oxometal anions of the first series of the of 3d series of elements, the 4d and 5d series metals
transition metals in which the metal exhibits the generally do not form stable cationic species. Give
oxidation state equal to its group number. reason.
Ans : DELHI 2000
Ans : FOREIGN 2003
Oxometal anions Oxidation Group In the 4d and 5d series metals higher oxidation states
state no. are more stable and in higher oxidation states mostly
covalent bonds are formed therefore they do not form
1. Vanadate VO -3 +5 5
cationic species.
2. Chromate CrO 2-
4 +6 6 153. Why is Cr2+ reducing and Mn3+ oxidising when both
Dichromate Cr2 O 2-
7 have d 4 configuration?
Ans : OD 2008
3. Permanganate MnO -4 +7 7 2+
Cr is reducing because after the loss of one electron
its configuration changes from d 4 to d 3 , the latter
148. Which metal in the first series of transition metals
having a half filled t2g level (see next unit). Mn3+
exhibits +1 oxidation state most frequently and why?
is oxidizing because after taking one electron its
Ans : OD 2005
configuration changes form d 4 to d 5 (Mn3+ to Mn2+)
10 1
Copper, because its configuration is 3d , 4s . After configuration which has extra stability.
loss of one electron it gets stable configuration 3d10 .
154. Which metal of 3d series having positive standard
149. Calculate the number of unpaired electrons in the electrode potential (M2+ " Mc)?
following gaseous ions : Mn3+ , Cr3+ , V3+ and Ti3+ . Ans : DELHI 2012
Which one of these is the most stable in aqueous
Copper having positive Ec but others negative Ec.
solution?
absorb blue-green colour from visible region, and the Ans : SQP 2021
complex appears violet in colour. 1. In the oxide of lowest oxidation state like MnO
(Mn = + 2 ) ionic bonds are formed and metal
oxides are ionic, which are soluble in water, give
OH- ions. Hence they are basic.
In the oxides of highest oxidation state like Mn 2 O 7
(Mn = + 7 ) covalent bonds are formed (transition
metals show non metallic character), oxides get
hydrolysed by water forming acids.
2. Because of small size and high electronegativity
163. Calculate the magnetic moment of a divalent ion in oxygen and fluorine can oxidise the metal to the
aqueous solution. If its atomic number is 25. highest oxidation state.
Ans : SQP 2014 3. In oxoanions for example MnO -4 (Mn = + 7 ),
With atomic number 25 (Mn), the divalent ion Mn2+ CrO -4 (Cr = + 6 ), the highest oxidation state is
in aqueous solution will have d 5 configuration (five exhibited because oxygen is a strong oxidising
unpaired electron, n = 5 ).The magnetic moment m is agent.
m = 5 (5 + 2) = 5.92 B.M. 167. How would you account for the increasing oxidising
power in the series VO +2 < Cr2 O 72- < MnO -4 ?
164. Why is the highest oxidation state of a metal exhibited
in its oxides or fluorides only? Ans : COMP 2017
Ans : OD 2004
This is due to the increasing stability of the lower
species to which they are reduced,
Because of small size and high electronegativity O
and F can oxidise the metal to the highest oxidation VO +2 " VO2+ MnO -4 " Mn2+ Cr2 O 72- " Cr3+
state.
168. Calculate the ‘spin only’ magnetic moment of
165. What is meant by disproportionation ? Give two examples M2+(aq) ion (Z = 27)
of disproportionation reaction in aqueous solution.
Ans : COMP 2010, 2007
or
27 Co = [Ar] 3d7 4s2
What is meant by disproportionation of oxidation
state? Example. Co2+ = [Ar] 3d7
or 3 unpaired electrons are present.
Explain why Cu+ ion is not stable in aqueous solution? p = n (n + 2) B.M.
Ans : DELHI 2006
= 3 (3 + 2) = 15 B.M.
Disproportionation means a substance undergoes
oxidation as well reduction in a reaction i.e. oxidation = 3.87 B.M.
state of an element of the reactant increases is one 169. How would you account for the fact that the transition
product and decreases in another product example, metals and their compounds are found to be good
1. Many copper (I) compounds are unstable in catalyst in many process?
aqueous solution and undergo disproportionation. or
2Cu+ " Cu2+ + Cu Explain giving reason : Transition metals and their
(Cu =+ 1) (Cu =+ 2) (Cu = 0)
2. Chromium (V) undergoes disproportionation in many compounds act as good catalyst.

acidic medium. Ans : FOREIGN 2003
CrO 34- + 8H+ " 2CrO 24- + Cr3+ + 4H 2 O Transition metals and their many compounds act as
(Cr =+ 3)
(Cr =+ 5) (Cr =+ 6) good catalyst due to the following reasons.
166. Give example and suggest reasons for the following 1. Presence of unpaired electrons in transition
features of the transition metal chemistry elements incomplete d -orbitals and hence possess
1. The lowest oxide of transition metal is basic, the the capacity to absorb and re-emit energy.
highest is acidic. 2. Transition elements show variable oxidation states.
2. A transition metal exhibits higher oxidation Hence they can form intermediate compounds.
states in oxides and fluorides. 3. Transition elements provide a large surface area
3. The highest oxidation state is exhibited in with free valancies on which the reactants are
oxoanions of a metal. absorbed which increase the rate of reaction.
176. Write chromyl chloride test. 179. What do you mean by f -block elements or inner
Ans : DELHI 2014 transition elements?
On heating potassium dichromate with a chloride and Ans : SQP 2003
conc. sulphuric acid, reddish brown vapour of chromyl The elements in which the last electron enters the
chloride are obtained. ante-penultimate shell i.e., (n - 2) f orbitals are called
K 2 Cr2 O 7 + 4KCl + 6H 2 SO 4 " 2CrO 2 Cl 2 + 6KHSO 4 + 3H 2 O f -block elements, they are also called inner transition
(Chromyl chloride)
(Red vapour) elements because the last electron in them enters into
(n - 2) f -orbitals which is inner to the penultimate
177. (a) What happens when acidified KMnO 4 is treated shell and they form a transition series within the
with transition series.
1. KI, 2. H 2 S , 3. KNO 2 , 4. H 2 O 2 180. Write the electronic configuration of the element with
(b) What happens when KMnO 4 is heated? Give reaction. the atomic number 61, 91, 101 and 109.
Ans : FOREIGN 2005 Ans : OD 2018
(a) KMnO 4 is a powerful oxidising agent because it
Promethium (Pm) = 61 = [Xe] 4f 5 6s2
liberates nascent oxygen in acidic solution.
1. It oxidises potassium iodide to iodine Protactinium (Pa) = 91 = [Rn] 5f 2 6d 1 7s2
2KMnO 4 + 8H 2 SO 4 + 10KI Mendelevium (Md) = 101 = [Rn] 5f 13 7s2
" 6K 2 SO 4 + 2MnSO 4 + 8H 2 O + 5I 2 Meitnerium (Mt) = 109 = [Rn] 5f 14 6d 7 7s2
- + - 2+
or 2MnO + 16H + 10I " 2Mn + 8H 2 O + 5I 2
4
181. Write down the electronic configuration of
2. It oxidises H 2 S to S
1. Pm3+ (At No. 61) 2. Ce 4+
2KMnO 4 + 3H 2 SO 4 + 5H 2 S
" K 2 SO 4 + 2MnSO 4 + 3H 2 O + 5S 3. Lu2+ (At No. 71) 4. Th 4+ (At No.90)
or Ans : COMP 2008
2MnO -4 + 16H+ + 5S2- " 2Mn2+ + 8H 2 O + 5S 1. Pm3+ = [Xe] 4f 4 2. Ce 4+

= [Xe]
3. It oxidise nitrite (NO -2 ) to nitrate (NO -3 ) 3. Lu2+ = [Xe] 4f 14 5d 1 4. Th 4+ = [Rn] 6d 0 7s0
5KMnO 4 + 3H 2 SO 4 + 5KNO 2
182. How would you account for the irregular variation
" K 2 SO 4 + 2MnSO 4 + 3H 2 O + 5KNO 3 of ionisation enthalpies (first and second) in the first
or series of the transition elements?
2MnO + 6H + 5NO -2 " 2Mn2+ + 3H 2 O + 5NO -3
-
4
+ Ans : DELHI 2019, OD 2014
4. It oxidise H 2 O 2 to H 2 O and O 2 Irregular variation of ionization enthalpies is primarily

2KMnO 4 + 3H 2 SO 4 + 5H 2 O 2 due to varying degree of stability of different 3d
-configuration for example, d0 , d5 and d10 are exceptionally
$ K 2 SO 4 + 2MnSO 4 + 8H 2 O + 5O 2
stable. As loss of one electron gives stable 3d5 electronic
or configuration so Cr has low first ionization energy and
2MnO + 6H + 5H 2 O 2 $ 2Mn2+ + 8H 2 O + 5O 2
-
4
+
much higher second ionization energy.
(b) On heating at 513K KMnO 4 decomposes to give 183. The third ionisation enthalpies for Mn and Zn are
green colour K 2 MnO 4 unusually high, why?
2KMnO 4
513K
K 2 MnO 4 + MnO 2 + O 2 Ans : DELHI 2017
Purple Green (Ti H c) III = 3260 kJ/mol
Mn+2 (3d 5) Mn+3 (3d 4) + e-
178. Draw the structure of permanganate ion (MnO -4 ) and
magnate ion (MnO 2-
4 ). Zn+2 (3d10)
(T i H c) III = 3829 kJ/mol
Zn+3 (3d9) + e-
Ans : DELHI 2001
This is due to greater difficulty of removing an electron
from Mn+2 and Zn+2 ions, as they have exceptionally
stable d5 and d10 configuration.
184. Write the uses of lanthanoids and actinoids.
Ans : OD 2000
Lanthanoids : They are used as alloy example misch

metal (Ln = 95% , Fe = 5% , S, C, Cs, Al = traces) in
190. Calculate the ‘spin only’ magnetic moment of M2+ (aq) Ans : COMP 2019
ion (Z = 27). 1. The transition metals have voids in their crystal

Ans : DELHI 2016
lattice into which small atoms like H, C, N, are
trapped inside, resulting in the formation of
Metal M interstitial compounds.
Atomic No. 27 2. Cr2+ ion is reducing as its configuration changes
from d 4 to d 3 , the later having half-filled
Ion M 2+
configuration. While the change from Mn2+ to
Electronic configuration M [Ar] 3d 7 4s 2 Mn3+ results in half-filled (d 5) configuration
M 2+ which has extra stability.
3. Because of large number of unpaired electrons
Unpaired electrons (n) 3 in their atoms they have stronger interatomic
The ‘spin only’ magnetic m = 3 (3 + 2) interactions and hence stronger bonding between
moment atoms resulting in higher enthalpies of atomisation.
= 15 = 3.87 BM
m = n (n + 2) BM
195. “Describe the general trends in the following properties
191. Account for the following : of the first series of the transition elements.
(i) Transition metals form alloys. 1. Stability of +2 oxidation state.
(ii) Ce4+ is a strong oxidising agent. 2. Formation of oxometal ions.
Ans : COMP 2023
Ans : COMP 2022
(i) Alloy is a homogeneous mixture of two or more 1. Most of the transition metals show +2 oxidation
metals. Transition metal forms alloy because of state. Mn2+ is more stable due to half filled d
similar atomic radii. -orbitals.
(ii) Electronic configuration of Ce is 4f 1 5d1 6s2 Ce is 2. They form oxometal ions because they show
most stable in +3 state. In +4 state it is the strong variable oxidation states and form stable
oxidising agent because, in +4 state it can give an oxoanions like MnO -4 , CrO 2- 2-
4 and Cr 2 O 7 .
electron to become more stable at +3 state. 196. Assign reason for each of the following.
192. Write one similarity and one difference between 1. Transition elements exhibits variable oxidation
chemistry of Lanthanoids and Actinoids. states.
Ans : COMP 2023 2. Transition metal ions are usually coloured.
Similarity : Both lanthanoid and actinoids involve Ans : SQP 2020
filling of ^n - 2h f - orbitals. 1. Transition metals show variable oxidation states

Difference : Lanthanoids show maximum +4 oxidation because electrons form both 's' and 'd' orbitals
state of while actinoids show oxidation state of +3, take part in bond formation.
+4, +5, +6 and +7. 2. Transition metal ions have unpaired electrons
193. Complete the following chemical reaction equations: due to which they can undergo d - d transition
by absorbing light from the visible region and
1. Fe2+ (aq) + MnO -4 (aq) + H+ (aq) $
radiating complementary colour.
2. Cr2 O 72- (aq) + I- (aq) + H+ (aq) $
197. Write the steps involved in the preparation of
Ans : COMP 2019, OD 2015
2+ - + 1. K 2 Cr2 O 7 from Na 2 CrO 4
1. 5Fe (aq) + MnO 4 (aq) + 8H (aq)
2. KMnO 4 from K 2 MnO 4
$ Mn2+ (aq) + 4H 2 O (l) + 5Fe3+ (aq)
Ans : OD 2010
2. Cr2 O 72- (aq) + 6I- (aq) + 14H+ (aq)
1. 2Na 2 CrO 4 + H 2 SO 4
$ 2Cr3+ (aq) + 7H 2 O (l) + 3I 2 (g)
$ Na 2 Cr2 O 7 + Na 2 SO 4 + H 2 O
194. Explain the following observations :
1. Transition elements are known to form many Na 2 Cr2 O 7 + 2KCl $ K 2 Cr2 O 7 + 2NaCl
Electrolysis
interstitial compounds. 2. MnO 2-
4 MnO -4 + e-
2. With the same d 4 configuration Cr2+ ions is
reducing while Mn3+ ion is oxidising. 198. What is meant by lanthanoid contraction ? What
3. The enthalpies of atomisation of transition effect does it have on the chemistry of elements which
elements are quite high. follow lanthanoids?
Ans : OD 2011
LONG ANSWER QUESTIONS
In acidic medium, K 2 MnO 4 changes to give purple
coloured solution along with a black precipitate.
4H+
209. Account for the following :
3MnO 24- + 2MnO -4 + MnO 2 + 2H 2 O (i) E° value for Mn3+/Mn2+ couple is much more
Green Purple Black
compound
positive than that for Cr3+/Cr2+.
It is called disproportionation reaction. (ii) Sc3+ is colourless whereas Ti3+ is coloured in an
aqueous solution.
206. Explain why do transition elements show variable
(iii) Actinoids show wide range of oxidation states.
oxidation elements show variable oxidation states.
Write all the possible oxidation states of an element Ans : COMP 2023
3+ 2+
having atomic number 25. (i) The Ec value for the Mn /Mn couple is much
Ans : COMP 2015 more positive than that of the Cr3+ /Cr2+ couple.
2+
This is because the Mn ion is particularly stable
Transition metals show variable oxidation states
due to the extra stability of its half filled valence
because electrons form both’s as well as 'd' -orbitals
electronic configuration ^3d5h .
take part in bond formation.
(ii) Sc3+ has electronic configuration of 3dº4sº with
Mn (25) shows +2, +3, +4, +6, +7 oxidation states.
zero unpaired electrons. Hence it is colourless
207. Compare the chemistry of actinoids with that of the whereas Ti3+ has electronic configuration of
lanthanoids in reference to 3d1 4sº with one unpaired electron. This unpaired
1. Atomic and ionic size electron in d-subshell undergo d-d transition.
2. Oxidation states. Hence, it is coloured.
Ans : FOREIGN 2002 (iii) Actinoids shows wide range of oxidation state
1. Actinoids show actinoid contraction like ranging from +2 to +7 due to comparable
lanthanoids but the contraction is greater from energies of 5f , 6d and 7s orbitals. Therefore, all
element to element in their series resulting from their electrons take part in bond formation.
poor shielding by 5f electrons. 210. Describe the general characteristics of transition
2. Lanthanoids show +3 as most common oxidation elements with special reference to the following:
state along with +2 and +4 shown by some of (i) Formation of colour salt
elements. Actinoids show +2, +3, +4, +5, +6 (ii) Variable oxidation state
and +7 oxidation states due to lesser ionisation
energy.
Characteristics of transition element with respect to :
208. What happens when– (i) Formation of colour salt : Most of the compounds
Ethyne is allowed to react with cold basic KMnO 4 of transition metals are coloured due to d -d
solution. transition structure defects and charge transfer
Ans : COMP 2016 Transition metal ions having dc configuration are
KMnO 4 (cold) in basic medium oxidies ethyne to 1-2 colourless.
ethane diol. The explanation is that in d -d transition, free
metal ion has degenerate d -orbital which splits
into two levels, according to the geometry of
complex. Compounds absorb light of visible range
for the excitation of electrons from lower to higher
level and complementary colour of light is seen.
The wavelength of the light absorbed depends
On further oxidation it gives oxalic acid. upon the nature of the ligand.
When ligand has free electrons, the transfer of
electron from anion to cation takes place. In this
case energy is absorbed during this process which
is responsible for colour.
(ii) Variable oxidation states : Transition metals show
different oxidation states variable valency except
the first and the last element this is because of the
fact that the difference in the energy of (n - 1) d
(iii) It oxidises sulphur dioxide to sulphuric acid. 214. What is lanthanoid contraction? Give its cause. What
2KMnO 4 + 5SO 2 + 2H 2 O are the consequences of lanthanoid contraction?
" K 2 SO 4 + 2MnSo 4 + 2H 2 SO 4 Ans : COMP 2006
Lanthanoid contraction is the regular decrease

or 2MnO -4 + 5SO 2 + 2H 2 O " 5SO 24- + 2Mn2+ + 4H+
(contraction)in the atomic and ionic radii of
Uses of KMnO 4 : Lanthanoids from lanthanum of leutecium.
1. It is used in volumetric analysis. Cause of lanthanoid contraction : As we move from
2. Used as disinfectant, germicide and deodrant. left to right in the series nuclear charge increases by
3. Used for purification of water. one unit with that an additional electron enters into
4. Used for the bleaching of wool, cotton, silk etc. 4f orbital. But electrons do not effectively screen the
nucleus (because of the shape of f orbital), due to this
213. Explain giving reasons: poor shielding by 4f electrons, the effective nuclear
1. Transition metals and many of their compounds charge increases and size decreases.
show paramagnetic behaviour.
Consequences of lanthanoid contraction :
2. The enthalpies of atomisation of the transition
1. Difficulty in separation of lanthanoids : Due to
metals are high.
very small difference in ionic radii of lanthanoids
3. The transition metals generally form coloured their chemical properties are similar, therefore the
compounds. separation of the lanthanoids in the pure state is
4. Transition metals and their many compounds act difficult.
as good catalysts. 2. Similarity in the size of elements of second and
Ans : SQP 2008 third transition series : The size of the atom of
1. Transition elements have unpaired electrons. any element of the third transition series is almost
Each unpaired electron has a magnetic moment same as that of the atom of the element lying in
associated with its spin angular momentum and the same group of the second transition series, the
orbital angular momentum. This is the reason of similarity in size is due to the effect of landthanoid
paramagnetism in transition metals. contraction.
2. The reason for the high enthalpy of atomisation 3. Effect of the basic strength of hydroxides : With
is the presence of large number of unpaired decrease in size of lanthanoid ions from La3+ to
electrons in their atoms. These atoms have strong Lu3+ , the covalent character of the hydroxide
interatomic interaction and hence, stronger increase and hence the basic strength decreases.
bonding between them. La (OH) 3 is most basic and Lu (OH) 3 is least
3. Formation of coloured compounds by transition basic.
metals is due to partial adsorption of visible light. 215. Compare the chemistry of actinoids with that of
The electron absorbs the radiation of a particular lanthanoids with special reference to
frequency (of visible region) and jumps into next 1. Electronic configuration
orbital.
2. Oxidation state
4. Catalysts, at the solid surface, involve the
3. Atomic and ionic size
formation of bonds between reactants molecules
and atoms of the surface of the catalyst (I row 4. Chemical reactivity
transition metal utilise 3d and 4s -electrons for Ans : OD 2020, COMP 2018
bonding). This has the effect of increasing the 1. Electronic configuration : The general electronic
concentration of the reactant at the catalyst configuration of lanthanoids is [Xe] 4f 1 - 14 5d 0 - 1 6s2
surface and also lowering of the activation energy.
and actinoids is [Rn] 5f 1 - 14 6d 0 - 1 7s2 .
Transition metal ions show variable oxidation states,
2. Oxidation state : Lanthanoids show limited
so they are effective catalysts.
oxidation states +2, +3 and +4 out of which
e.g. Reaction +3 is most common, because of large energy gap
Fe 3+
2I- + S 2 O 28- I 2 + 2SO 24- between 4f and 5d subshell whereas actinoids
show a large number of oxidation states because
Mechanism of catalysing action of Fe3+ in the above
of small energy gap between 5f, 6d and 7s subshell.
reaction
3. Atomic and ionic size : Both show decreases
(a) 2Fe3+ + 2I- $ 2Fe2+ + I 2 in size,in lanthanoids it is called lanthanoid
(b) 2Fe2+ + S 2 O 28- $ 2Fe3+ + 2SO 24- contraction, and in actinoids it is called actinoid
contraction.
3. Ions of transition metals with d 1 configuration tend 3. Atomic and ionic size Atomic and ionic size
to lose one electron to acquire d 0 configuration Size of atom/ion Size of atom/ion
that is quite stable. Therefore, such ions (with d 1 ) decreases across the decreases along the
undergo either oxidation or disproportionation period. period.
hence unstable. In the group, size of Actinoid has largest
lanthanoid element size in its own group.
220. Give examples and suggest reasons for the following
is smaller than the
features of the transition metals.
actinoid of its own
1. The lowest oxide of transition metal is basic, the group.
highest is amphoteric/acidic.
2. A transition metal exhibits highest oxidation 4. Chemical reactivity Chemical reactivity
state in oxides and fluorides. i Less tendency i Stronger tendency
3. The highest oxidation state is exhibited in towards complex towards complex
oxoanions of a metal. formation. formation.
Ans : OD 2022 ii Except ii All the actinoids
1. Acidic strength of oxides increases with the promethium, are radioactive.
increase in oxidation state of the element they are non-
Eg. : MnO (Mn2+) is basic whereas Mn 2 O 7 (Mn7+) radioactive.
is acidic in nature. iii They do not form iii They form
2. Both oxygen and fluorine being highly oxocations. oxocations like
electronegative can increase the oxidation state UO 22+, PuO 22+, UO +,
of a particular transition metal. In certain etc.
oxides, the element oxygen is involved in multiple
bonding with the metal and this is responsible for iv Oxides and iv Oxides and
the higher oxidation state of the metal. hydroxides are less hydroxides are
basic. more basic.
3. This is also due to high electro-negativity of
oxygen 222. Give reasons for the following :
Eg. : Chromium exhibits oxidation states of 1. Transition metals have high enthalpies of atomisation.
+6 in oxoanion [CrO 4] 2- and manganese shows
2. Among the lanthanoids, Ce (III) is easily oxidised
oxidation state of +7 in oxoanion [MnO 4] -
to Ce (IV).
221. Compare the chemistry of actinoids with that of the 3. Fe3+ /Fe2+ redox couple has less positive electrode
lanthanoids with special reference to : potential than Mn3+ /Mn2+ couple.
4. Copper (I) has d 10 configuration while copper (II)
1. electronic configuration
has d 9 configuration. Still copper (II) is more
2. oxidation state
stable in aqueous solution than copper (I).
3. atomic and ionic sizes and 5. The second and third transition series elements
4. chemical reactivity have almost similar atomic radii.
Ans : OD 2010 Ans : DELHI 2008
1. Due to strong interatomic interactions between
Lanthanoids Actinoids
the unpaired valence electrons.
1. Electronic Electronic 2. Ce (IV) has extra stability due to empty f 0 orbital.
configuration configuration 3. In Mn2+ (d 5) configuration leads to extra stability
[Xe] 54 4f 1 - 14 5d 0 - 1 6s 2 [Rn] 86 5f 1 - 14 6d 0 - 1 7s 2 as it represents half-filled configuration, so Mn3+
Eg. : 57 La = [Xe] 5d 1 6s 2 Eg. : 89Ac = [Rn] 6d 1 7s 2 ions (d 4) tends to get converted to stable (d 5)
configuration of Mn2+ by accepting an electron
58 Ce = [Xe] 4f 1 5d 1 6s 2 90Th = [Rn] 6d 2 7s 2
so Mn3+ /Mn2+ redox couple has more positive
2. Oxidation state (s) Oxidation state (s) potential thanFe3+ Fe2+ couple.
(d5) (d 4)
Most common Most common 4. Due to more negative enthalpy of hydration of
oxidation state = + 3 oxidation state = + 3 Cu2+ (aq) than Cu+ (aq), which compensates for
Other oxidation state Other oxidation states second ionisation enthalpy of copper, Cu(II) is
= + 2, + 4 = + 4, + 5, + 6 more stable than Cu(I).
5. In the third transition series after lanthanum, 2Cr2 O 3 + 8NaOH + 3O 2 $ 4Na 2 CrO 4 + 4H 2 O
'A' Yellow
there is lanthanoid contraction, due to ineffective ' B'
shielding by intervening 4f -orbital electrons and
2Na 2 CrO 4 + H 2 SO 4 $ Na 2 Cr2 O 7 + Na 2 SO 4 + H 2 O
hence second and third transition series elements ' B' Orange
have similar atomic radii. 'C '
223. Give reason : 2NH 4 Cl + Na 2 Cr2 O 7 $ (NH 4) 2 Cr2 O 7 + 2NaCl

(Orange)
1. Among transition metals, the highest oxidation 'D'
states is exhibited on oxoanions of a metal. heat

(NH 4) 2 Cr2 O 7 N 2 + Cr2 O 3 + 4H 2 O
2. Ce+ is used as an oxidising agent in volumetric Ammonium Green
analysis. dichromate
3. Transition metals form a number of interstitial 225. Account for the following:
compounds. 1. Mn shows the highest oxidation state of +7 with
4. Zn2+ salts are white while Cu2+ salts are blue. oxygen but with fluorine, it shows the oxidation
Ans : FOREIGN 2015, OD 2012 sate of +4.
1. In these oxoanions the oxygen atoms are directly 2. Cr2+ is a strong reducing agent.
bonded to the transition metal atom/ion. Since 3. Cu2+ salts are coloured, while Zn+2 salts are
oxygen is highly electronegative, therefore, the white.
oxoanions bring out the highest oxidation state of Ans : DELHI 2015
the metal. 1. In case of oxygen, Mn shows the highest oxidation
2. Ce 4+ has the tendency to attain +3 oxidation state of +7. This is because Mn forms pp - dp
state in volumetric analysis. multiple bonds using 2p orbitals of oxygen and 3d
3. This is due to the presence of voids of appropriate orbitals of Mn. With F, Mn displays an oxidation
size in their crystal lattices. state of +4 because of the single bond formation
4. Zn2+ ions has all its orbitals completely filled caused by the unavailability of 2p orbitals of F
whereas in Cu2+ ions there is one half filled 3d for multiple bonding.
-orbital. It therefore has a tendency to form 2. Cr2+ is strongly reducing in nature. It has a
coloured salts whereas Zn2+ has no such tendency. d 4 configuration. While acting as a reducing
224. Explain the following : agent, it gets oxidised to Cr3+ (with electronic
configuration d 3 ). This d 3 configuration, which
1. Transition elements tend to be unreactive with
increasing atomic number in the series. represents a more stable configuration.
2. d -block elements exhibit more oxidation state
than f -block elements.
3. A green chromium compound (A), On fusion
with alkali gives yellow compound (B) which on
acidification gives an orange coloured compound
(C). ‘C’ on treatment with NH 4 Cl gives an
3. Zn2+ salts have a completely filled set of d
orange coloured product (D) which on heating
decomposes to give back compound (A). Identify -orbitals (3d 10), while Cu2+ has an incompletely
A, B, C and D. Write equation for the reactions. filled set of d -orbitals (3d 9), and therefore, d - d
transition is possible in Cu2+ , leading to its blue
Ans : SQP 2022
colour.
1. Transition metals can form layer of oxides on their
surface due to which they become unreactive.
Secondly, reactivity decreases with increase in CASE BASED QUESTIONS
the atomic number due to decrease in size and
increases in ionisation energy.
226. Read the passage below and answer the following
2. In d -block elements, electrons of s -orbital and questions :
d -orbitals both take part in bond formation. In
f -block elements due to poor shielding effect of The elements belonging to d-block of the periodic
f -electrons, effective nuclear charge increases. table are called transition elements. In these elements
Therefore, lesser number of oxidation states are electrons enter into (n -1) d-subshell. In the periodic
shown. table these elements are placed in between the
highly electropositive s -block elements and highly
hc (c) Which of following cations are coloured in aqueous

So l is higher bSince E = l l absorbed blue
solutions and why ?
colour, is radiated as compared to l = 498 nm Sc3+ , V3+ , Ti 4+ , Mn2+
is absorbed by [Ti(H2O)6]3+ and violet colour is (At. nos..Sc = 21, V = 23 , Ti = 22 , Mn = 25)
radiated.
or
(c)
(d) How would you account for the following :
(i) Tt = 4 T 0 Transition metals form coloured compounds ?
9
4 Ans :
= # 27000 cm-1
9 (a) Cu(I) compounds have completely filled d -orbitals
= 12000 cm-1 and there are no vacant d -orbitals for promotion
of electrons whereas in Cu(II) compounds have
(ii) It is because Ti4+ does not have unpaired one unpaired electron which is responsible for
electron, can’t undergo d-d transition by colour formation.
absorbing light from visible region and does (b) Zn2+ ion has completely filled d -subshell and
not radiate colour. no d - d transition is possible. So zinc salts are
(d) [Co(CN)6]3- < [Co(NH3)6]3+ < [Cu(H2O)4]2+ white. Configuration of Cu2+ is [Ar] 3d 9 . It has
Since, CFSE follows [Co(CN)6]3- < [Co(NH3)6]3+ < partly filled d -subshell and hence it is coloured
[Cu(H2O)4]2+ due to d - d transition.
(c) Only those ions will be coloured which have
[Since, CFSE is inversely proportional to l
partially filled d -orbitals facilitating d - d
absorbed.]
transition. Ions with d 0 and d 10 will be colourless.
229. Colour may arise from a entirely different cause in From electronic configuration of the ions, V3+ (3d 2)
ions with incomplete d or f shells. This source of and Mn2+ (3d 5), are all coloured. Ti 4 (3d 0) and
colours very important in most of the transition metal Sc3+ (3d 0) are colourless.
ions. In free isolated gaseous ion the five d orbitals or
are degenerate, i.e. they are identical in energy. In real (d) Due to presence of vacant d -orbitals and d - d
life situations, the ion will be surrounded by solvent transitions, compounds of the transition metals
molecules if it is in solution; by other ligands if it are generally coloured. When an electron from a
is in a complex; or by other ions if it is in crystal lower energy d -orbital is excited to a higher energy
lattice. The surrounding groups affect the energy of d -orbital, the energy of excitation corresponds to
some orbitals more than others. Thus the d orbitals the frequency which generally lies in the visible
are no longer degenerate, and they form two groups region. The colour observed corresponds to the
of orbitals of different energies. Thus in transition complementary colour of the light absorbed. The
element ions with a partly filled d shell, it is possible frequency of the light absorbed is determined by
to promote electrons from d level to another d level the nature of the ligand.
of higher energy. The corresponds to a fairly small
energy difference and so light is absorbed in the visible 230. The unique behaviour of Cu, having a positive Ec
region. The colour of a transition meltal complex is , accounts for its inability to liberate H 2 from acids.
dependent on how big the energy difference is between Only oxidising acids (nitric and hot concentrated
the two d levels. This in turn depends on the nature sulphuric) react with Cu, the acids being reduced.
of the ligand, and on the type of complex formed. The high energy to transform Cu (s) to Cu (2+ aq) is not
Thus the octahedral complex [Ni (NH 3) 6] 2+ is blue, balanced by its hydration enthalpy. The general trend
[Ni (H 2 O) 6] 2+ is green and [Ni (NO 2) 6] 4- is brown-red. towards less negative Ec values across the series is
The colour changes with the ligand,used the colour related to the general increase in the sum of the first
also depends on the Number of ligands and the shape and second ionisation enthalpies. It is interesting to
of the complex formed. note that the value of Ec for Mn, Ni, and Zn are more
Answer the following questions : negative than expected from the trend.
(a) Account for the following : Copper(I) compounds The stability of the half-filled d sub-shell in Mn2+
are white whereas copper(II) compounds are and the completely filled d10 configuration in Zn are
coloured. related to their E- values, whereas E° for Ni is related
(b) Cu2+ salts are coloured, while Zn2+ salts ire white. to the highest negative T hyd H° .
compounds such as benzene. The photographic

industry relies on the special light-sensitive properties
of AgBr.
(i) What are coinage metals ?
(ii) Which compound is used in photography ?
(iii) Whose complexes are used in polymerisation of
alkynes ?
Ans :
(i) The elements of Group 11 are called the coinage
metals.
(ii) Silver bromide.
(iii) Nickel complexes are useful in the polymerisation
of alkynes.
232. Given below is diagrammatic representation of
chemical properties of lanthanoids. Answer the
following questions based on this.
(i) What happens when lanthanoids burns in carbon?

(ii) What In file nature of oxides formed by reaction
of lanthanoids ?
Ans :
(i) The carbides, Ln 3 C, Ln 2 C 3 and LnC 2 are formed
when the metals are heated with carbon.
(ii) Hydroxides are basic in nature.
***********
Page 246 Coordination Compounds Chap 5
CHAPTER 5
Coordination Compounds
SUMMARY Hexadentate ligand has six donar atoms example

EDTA 4- .
Ambidentate Ligand
Unidentate ligands which have more than one
1. DEFINITION OF SOME IMPORTANT TERMS
coordination atoms are called ambidentate ligands
Coordination Compounds or Complex Compounds example NO -2 .
Those compounds in which the central metal atom
is linked to ions or neutral molecules by coordinate
bond are called coordinate compounds or complex e.g.
K 4 [Fe (CN) 6].
Complex Ion
Chelate
Ion formed by coordinate bond between central metal
atom and donor is called complex ion. When a bidentate or a polydentate ligand is attached
There are three types of complexes: by two or more donar atoms to the central atom
forming a ring, the ligand is called chelate ligand
1. Cationic complex e.g., [Co (NH 3) 6] 3+
and the complex is called chelate the effect is called
2. Anionic complex e.g., [Ag (CN) 2] -
chelate effect.
3. Neutral complex e.g., [Ni (CO) 4].
Coordination Number
Double Salts
Total number of coordinate bonds formed with the
These salt are formed by the combination of two simple central metal atom or ion by the ligands.
salts in equimolar ratio. They lose then identity in the
solution e.g., FeSO 4 (NH 4) 2 SO 4 $ 6H 2 O . Coordination Ion
The ionizable group which are written outside the
FeSO 4 (NH 4) 2 SO 4 $ 6H 2 O $ Fe2+ + 2NH +4 + 2SO 24- + 6H 2 O
bracket are called counter ion.
(Mohr's salt)
Complex compound do not lose their identity in the
solution.
K 4 [Fe (CN) 6] $ 4K+ + [Fe (CN) 6] 4-
Ligand
The donor species which donate a pair of electrons to
the metal atom is called ligand.
Denticity Oxidation Number
The number of coordinating groups present in a ligand Oxidation number or oxidation state of the central
is called the denticity of the ligand. metal atom is calculated from the charge on the
Monodentate ligand have one donar atoms example complex ion. [Fe (CN) 6] 4-
NH 3, H 2 O . x + 6 (- 1) = - 4
Bidentate ligand can donate two lone pair of electrons x =+ 2
example : en, ox.
Oxidation state of Fe = + 2
It is a diamagnetic complex due to absence of

unpaired electron.
8. Formation of [CoF6] 3-
Primary valencies are represented by dotted lines

and secondary valencies by solid lines.
2. Limitations of Werner’s theory:
(i) Why only certain elements form coordination
compounds?
(ii) Why the coordination sphere has a definite
geometry?
It is strongly paramagnetic due to presence of five
(iii) Why do coordination compounds possess
unpaired electrons.
definite magnetic and optical properties?
9. Drawbacks of valence bond theory:
3. Valence Bond Theory:
(i) It cannot explain why some complexes of a
(i) Metal ligand bond is formed by the donation
metal ion in a particular oxidation state are
of pairs of electron by ligand to the metal
inner orbital complexes while some other
atom.
complexes of the same metal ion in the some
(ii) Metal atom must possess vacant orbitals to oxidation state are outer spin orbital complex.
accommodate these electrons. These orbitals
(ii) It could not give any explanation for the
are obtained by hybridisation.
colour of the complex.
(iii) Sometimes the unpaired (n-1) d electrons pair
(iii) It does not distinguish between weak and
up prior to hybridization for making some (n-
strong ligands.
1) d orbitals vacant.
(iv) It does not give a clear explanation of
(iv) Metal-ligand bonds are formed by the overlap
thermodynamic stabilities of coordination
of these orbitals with ligand orbitals, these
compounds.
bonds are of equal strength and directional in
nature. 5. CRYSTAL FIELD THEORY
4. Octahedral complexes are formed by d2 sp3 or
sp3 d2 hybridisation. Square planar complexes The main postulates of crystal field theory are as
are formed by dsp2 hybridisation, tetrahedral follows:
complexes are formed by sp3 hybridisation. (i) Metal ligand bonds are ionic having electrostatic
5. d2 sp3 hybridized complex involve the inner (n-1) interaction, similar to ions in a crystal, therefore
d orbitals these complexes are called inner orbital named as crystal field theory (CFT).
or low spin complexes. (ii) Ligand is treated as a point of negative charge.
Examples : [Co (NH 3) 6] 3+ , [Fe (CN) 6] 3- The arrangement of the ligands around the central
6. sp3 d2 hybridized complex involve the outer (nd) ion is such that the repulsion between them are
orbitals, these complexes are called outer orbital minimum.
or high spin complexes. (iii) In free transition metal ion all the five d-orbitals
Example : [Fe (H 2 O) 6] 3+ , [(CoF6)] 3- have equal energies i.e. they are degenerate. Due
7. Formation of [Co (NH 3) 6] 3+ to ligand the degeneracy is split because those
orbitals which have lobes along the axes towards
ligands fell greater repulsion. The splitting of the
degenerate level due to presence of ligand is called
crystal field splitting.
5. IUPAC name of H 2 6PtCl 6@ is – The no. of unpaired electrons in 6Ni ^COh4@ = 0 . So,
(a) Hydrogen hexachloro platinate (IV) the magnetic moment = 0 .
The number of unpaired electrons in 7Fe ^CNh6A = 0
-4
(b) Hydrogen hexachloro platinate (II)
(c) Hydrogen hexa chlorido Pt (IV) So, the magnetic moment = 0 .
Therefore, the highest magnetic moment is present for
(d) Hydrogen hexa chlorido Pt (II)
the ion 6Fe ^H 2 Oh6@Cl 2 .
Ans : DELHI 2018
IUPAC name of H 2 6PtCl 6@ is hydrogen hexachloro
platinate (IV). 9. Which of the following compounds has tetrahedral
Thus (a) is correct option. geometry?
(a) 6Ni ^CNh4@2- (b) 6Pd ^CNh4@2-
6. Mercuric chloride reacts with ammonia gas and forms
white precipitate. The molecular formula of white (c) 6PdCl 4@2- (d) 6NiCl 4@2-
precipitate is – Ans : DELHI 2016, SQP 2012
(a) HCl 2 $ 2NH 3 (b) Hg ^NH 3h2 Cl 2 3
Coordinate compounds with Sp hybridization for
(c) Hg ^NH 2h Cl 2 (d) Hg ^NH 2h Cl central metal can show tetrahedral geometry mostly
with weak-ligand like Cl-ligand can form such
Ans : COMP 2018
complexes.
Mercury(II) chloride when reacted with ammonia
Since, They do not go for go for pairing.
gas or ammonium chloride produces a fusible white
In [Nicl 4] 2- , Ni is in Ni2+
precipitate of diammine mercury(II) chloride.
Outer most electronic configuration for Ni2+ is-
HgCl 2 + 2NH 3 ^g h $ Hg ^NH 3h2 Cl 2
fusible white precipitate
7. The EAN of cobalt in the complex ion 6Co ênh2 Cl 2@5
is :
(a) 27 (b) 36 Chlorine is a weak-ligand, d-electron of Ni2+ do not go
for pairing and [NiCl 4] 2- show sp3 hybridization and
(c) 33 (d) 35 tetrahedral geometry.
Ans : SQP 2017 Thus (d) is correct option.
EAN of cobalt in complex [CO (en) 2 Cl 2] + .
10. What is the coordination number of sodium in sodium
Atomic number = 27 oxide ^Na 2 Oh ?
Ground electronic configuration = 3d 7 4s 2 (a) 6 (b) 4
Co+3 electronic configuration = 3d 6 4s0 (c) 8 (d) 2
EAN = 27 - (+ 3) + (4 # 2) + (2 # 2) = 36 Ans : DELHI 2012, OD 2010
Thus (b) is correct option. The coordination number of Na in Na 2 O is 4. Na+
8. Which complex has maximum paramagnetic moment ion is surrounded by four oxide ions and O 2- ion is
value amongst the following – surrounded by eight Na+ ions, hence the coordination
number of Na in Na 2 O is 4.
(a) 6Cr ^H 2 Oh6@3+ (b) 6Fe ^H 2 Oh6@Cl 2
(c) 6Fe ^CNh6@4- (d) 6Ni ^COh4@
11. The oxidation state of nickel in 6Ni ^COh4@ is :
Ans : SQP 2018 (a) 1 (b) 0
Magnetic moment ^m h = n ^n + 2h (c) 2 (d) 3
where n = no. of unpaired electrons Ans : OD 2009
The no. of unpaired electrons in 6Cr ^H 2 Oh6@ = 3 . So,
3+
Oxidation number is the charge left on the central
the magnetic moment atom when all the bonding pair of electrons are
= 3 (3 + 2) = 15 removed. Oxidation state of metal atom in metal
carbonyl is always zero. Here also oxidation state of
The no. of unpaired electrons in 6Fe ^H 2 Oh6@Cl 2 = 4 . Ni is zero.
So, the magnetic moment
= 2 ^4 + 2h = 12
20. The complexes 6Co ^NH 3h6@6Cr ^CNh6@ and 24. The coordination number of a central metal atom in a
6Cr ^NH 3h6@6Co ^CNh6@ are the examples of which type complex is determined by
of isomerism? (a) the number of ligands around a metal ionbonded
(a) Linkage isomerism by sigma and pi-bonds both.
(b) Ionisation isomerism (b) the number of ligands around a metal ion bonded
by pi-bonds.
(c) Coordination isomerism
(c) the number of ligands around a metal ion bonded
(d) Geometrical isomerism
by sigma bonds.
Ans : DELHI 2004
(d) the number of only anionic ligands bonded to the
Coordination isomerism occurs when cationic and
metal ion.
anionic complexes of different metal ions are present
in a salt. Interchange of ligand between the complexes Ans : COMP 2017
give isomers e.g. The coordination number of central metal atom in a

6Co ^NH 3h6@6Cr ^CNh6@ is an isomer of 6Co ^CNh6@6Cr ^NH 3h6@ complex is equal to number of monovalent ligands,
Thus (c) is correct option. twice the number of bidentate ligands and so on,
around the metal ion bonded by coordinate bonds.
21. Which of the following pairs represent linkage isomers? Hence coordination number = no. of s bonds formed
(a) 7Pd ^P Ph 3h2 ^NCSh2A and 7Pd ^P Ph 3h2 ^SCNh2A by metals with ligands.
(b) 7Co ^NH 3h5 NO 3A SO 4 and 7Co ^NH 3h5 SO 4A NO 3
Coordination compounds have great importance
(c) 6PtCl 2 ^NH 3h4@ Br2 and 6PtBr2 ^NH 3h4@Cl 2
25.
in biological systems. In this context which of the
(d) 6Cu ^NH 3h4@6PtCl 4@ and 6Pt ^NH 3h4@6CuCl 4@ following statements is incorrect?
Ans : FOREIGN 2007 (a) Cynacobalamin is B 12 and contains cobalt
-
The SCN ion can coordinate through S or N atom (b) Haemoglobin is the red pigment of blood and
giving rise to linkage isomerism contains irons
M ! SCN thiocyanato (c) Chrolophylls are green pigments in plants and
contain calcium
M ! NCS isothiocyanato
(d) Carboxyperptidase - A is an enzyme and contains
zinc.
22. Which of the following is common donor atom in ligands?
Ans : SQP 2000
(a) Arsenic (b) Nitrogen
The chlorophyll molecule plays an important role in
(c) Oxygen (d) Both (b) and (c) photosynthesis, contain porphyrin ring and the metal
Ans : OD 2012, SQP 2007 Mg not Ca.
In the formation of a coordinate bond, the ligands donate Thus (c) is correct option.
a pair of electrons to the metal atom. Further nitrogen and
oxygen has great tendency to donate the pair of electrons 26. Among the following, the compound that is both
in most of the compounds. Therefore both nitrogen and paramagnetic and coloured is
oxygen are common donor atoms in ligands. (a) K 2 Cr2 O 7 (b) ^NH 4h2 ^TiCl 6h
Thus (d) is correct option. (c) CoSO 4 (d) K 3 6Cu ^CNh4@
23. Which of the following may be considered to be an Ans : DELHI 2003
organometallic compound? In ^NH 4h2 ^TiCl 6h , Ti 4+ ^3d0 4s0h has no unpaired
(a) Nickel tetracarbonyl (b) Chlorophyll electrons.
(c) K 3 6Fe ^C 2 O 4h3@ (d) 6Co ênh3@Cl 3 In K 2 Cr2 O 7 , Cr6+ ^3p6 4d0h has no unpaired electrons.
Ans : SQP 2015
In CoSO 4 , Co2+ ^d7h has three unpaired electrons in d
Organometallic compounds are those compounds -orbitals so it is both paramagnetic and coloured.
in which there is a bond which involve metal. In In K 3 6Cu ^CNh4@ , Cu+ ^3d10h , no unpaired electron.
chlorophyll there is bond involving metal Mg. Thus (c) is correct option.
33. Hybridisation of Ag in the linear complex 6Ag ^NH 3h2@+ 36. The number of unpaired electrons in the complex ion
is 6CoF6@3- is (Atomic no.: Co = 27)
(a) dsp2 (b) sp (a) zero (b) 2
(c) sp2 (d) sp3 (c) 3 (d) 4
Ans : OD 2017 Ans : DELHI 2015
In 6Ag ^NH 3h2@+ ground state configuration of Co here is in + 3 oxidation state

Ag = 4d10 5s1 excited state configuration of Ag Unpaired electrons = 4 and sp3 d2 hybridisation and
octahedral shape.
= 4d10 5s0 .
sp hybridisation in Ag+ ion.
37. Ammonia forms the complex ion [Cu (NH 3) 4] 2+ with
copper ions in alkaline solutions but not in acidic
solutions. What is the reason for it?
(a) In acidic solutions protons coordinate with
ammonia molecules forming NH +4 ions and NH 3
molecules are not available
(b) In alkaline solutions insoluble Cu (OH) 2 is
The two sp hybrid orbitals in Ag+ overlap with the precipitated which is soluble in excess of any
filled atomic orbitals of N in NH 3 molecules. alkali
(c) Copper hydroxide is an amphoteric substance
(d) In acidic solutions hydration protects copper ions
Ans : FOREIGN 2000
(acid medium) +
p 3 + H+
NH NH 4

38. 6EDTA@4- is a
(a) monodentate ligand
34. Correct name of K 4 6Fe ^CNh6@ is
(b) bidentate ligand
(a) Potassium ferricyanide
(c) quadridentate ligand
(b) Potassium ferrocyanide
(d) hexadentate ligand
(c) Potassium hexacyanoferrate (II)
Ans : OD 2005
(d) Potassium hexacyanoferrate (III)
6EDTA@ is a hexadentate ligand, because it has six
4-
Ans : SQP 2013

donor atoms and donate 6 pair of electrons to central
Oxidation state of iron is + 2 in K 4 6Fe ^CNh6@ metal atom in the complex.
So, its correct name is potassium hexacyanoferrate Thus (d) is correct option.
(II).
39. K 4 6Fe ^CNh6@ is a
(a) double salt
35. CH 3 - Mg - Br is an organometallic compound due (b) complex compound acid
to
(c) acid
(a) Mg - Br bond (b) C - Mg bond
(d) base
(c) C - Br bond (d) C - H bond Ans : SQP 2016
Ans : COMP 2009, OD 2005 Complex compounds do not dissociate into constituent
Compounds that contain at least one carbon metal ions.
bond are known as organometallic compounds. K 4 6Fe ^CNh6@ $ 4K+ 6Fe ^CNh6@4-
In CH 3 - Mg - Br (Grignard’s reagent) a bond is
Hence, It is a complex because no CN- is formed on
present between carbon and Mg (Metal) hence it is an
dissociation.
organometallic compound.
46. Among the following complexes, optical activity is 50. Which of the following will show paramagnetism
possible in corresponding to 2 unpaired electrons? (Atomic
(a) 6Co ^NH 3h6@3+ numbers: Ni = 28, Fe = 26)
(a) 6FeF6@3- (b) 6NiCl 4@2-
(b) 6Co ^H 2 Oh2 ^NH 3h2 Cl 2@+
(c) 6Fe ^CNh6@3- (d) 6Ni ^CNh4@2-
(c) 6Cr ^H 2 Oh2 Cl 2@
+
Ans : SQP 2000
(d) 6Co ^CNh5 NC@ As in 6NiCl 4@2- Chloride ion being a weak ligand is
Ans : DELHI 2014
not able to paired the electron in d orbital.
It is optically active when two Cl atoms are in cis Thus (b) is correct option.
position. 51. Which of the following complexes will have four
Thus (b) is correct option. different isomers?
47. The total number of possible isomers for the complex (a) 6Co ênh2 Cl 2@Cl (b) 6Co ênh^NH 3h Cl 2@Cl
compound 6Cu II ^NH 3h4@6Pt II Cl 4@ (c) 6Co ^PPH 3h2 Cl 2@Cl (d) 6Co ênh3 Cl 3@
(a) 3 (b) 6
Ans : COMP 2005
(c) 5 (d) 4 Complex 6Co ênh^NH 3h Cl 2@Cl will have four different
Ans : FOREIGN 2003 isomers.
The total number of isomers for the complex compound (i) Geometrical isomers
6Cu11 ^NH 3h4@6Pt11 Cl 4@ is four.
These four isomers are
6Cu ^NH 3h3 Cl@6Pt ^NH 3h Cl 3@ ,
6Cu ^NH 3h Cl 3@6Pt ^NH 3h3 Cl@ ,
6CuCl 4@6Pt ^NH 3h4@ and 6Cu ^NH 3h4@6PtCl 4@
The isomer 6Cu ^NH 3h2 Cl 2@6Pt ^NH 3h2 Cl 2@ does not
exist due to both parts being neutral.
(ii) Optical isomers
48. IUPAC name of 6Pt ^NH 3h3 ^Brh^NO 2h Cl@Cl is
(a) Triamminechlorobromonitroplatinum (IV) chloride
(b) Triamminebromonitrochloroplatinum (IV) chloride
(c) Triamminebromochloronitroplatinum (IV) chloride
(d) Triamminnenitrochlorobromoplatinum (IV) chloride
Ans : SQP 2016
We know that IUPAC name of 6Pt ^NH 3h3 ^Brh^NO 2h Cl@Cl

is triamminebromochloronitroplatinum (IV) chloride
52. The complex ion 6Co ^NH 3h6@3+ is formed by sp3 d2
49. The hypothetical complex chlorodiaquatriammine
hybridisation. Hence the ion should possess
cobalt (III) chloride can be represented as
(a) Octahedral geometry
(a) 6CoCl ^NH 3h3 ^H 2 Oh2@Cl 2
(b) Tetrahedral geometry
(b) 6Co ^NH 3h3 ^H 2 Oh@Cl 3
(c) Square planar geometry
(c) 6Co ^NH 2h3 ^H 2 Oh2 Cl@
(d) Tetragonal geometry
(d) 6Co ^NH 3h3 ^H 2 Oh3@Cl 3
Ans : DELHI 2006
Ans : OD 2011, FOREIGN 2007
According to VSEPR theory, a molecule with six
Chlorodiaquatriammine cobalt (III) chloride is
bond pairs must be octahedral.
6CoCl ^NH 3h3 ^H 2 Oh2@Cl 2 Thus (a) is correct option.
60. The number of unpaired electrons in the complex

6Cr ^NH 3h6 Br3@ is (Atomic no. Cr = 24)
= 4 unpaired e- (a) 4 (b) 1
(c) 2 (d) 3
Ans : FOREIGN 2017
= 2 unpaired e - In 6Cr ^NH 3h6 Br3@ , Cr is in + 3 oxidation state etc.
As Ni has minimum no. of unpaired e- thus this is

++
least paramagnetic.
57. A co-ordination complex compound of cobalt has the
molecular formula containing five ammonia molecules,
one nitro-group and two chlorine atoms for one cobalt
atom. One mole of this compound produces three
mole ions in an aqueous solution. On reacting this
solution with excess of AgNO 3 solution, we get two Its ion is octahedral in nature. Due to the presence of
moles of AgCl precipitate. The ionic formula for this three unpaired electrons it is paramagnetic.
complex would be Thus (d) is correct option.
(a) 6Co ^NH 3h4 ^NH 2h Cl@6^NH 3h Cl@ 61. Which statement is incorrect?
(b) 6Co ^NH 3h5 Cl@6Cl ^NO 2h@ (a) Ni ^COh4 - Tetrahedral, paramagnetic
(c) 6Co ^NH 3h5 ^NO 2h@Cl 2 (b) 6Ni ^CNh4@2- - Square planar, diamagnetic
(d) 6Co ^NH 3h5@6^NO 2h2 Cl 2@ (c) Ni ^COh4 - Tetrahedral, diamagnetic
Ans : COMP 2001 (d) 6NiCl 4@2- Tetrahedral, paramagnetic
6Co ^NH 3h5 ^NO 2h@Cl 2 $ 6Co ^NH 3h5 ^NO 2h@ + 2Cl-
++
Ans : OD 2015
-
2Cl + 2AgNO 3 $ 2AgCl + 2NO -
3
(CO) carbonyl group being a strong ligand paired all
electrons present in d -orbital of Ni. Hence from dsp2
hybrid orbitals and hence the shape of molecule is
58. Oxidation number of Ni in 7Ni ^C 2 O 4h3A4- is square planar.
(a) 3 (b) 4 In Ni ^COh4 complex, Ni will have 3d10
configuration. It has tetrahedral geometry but
(c) 2 (d) 6
diamagnetic as there are no unpaired electrons.
Oxidation number of Ni in 7Ni ^C 2 O 4h3A4-
62. CuSO 4 when reacts with KCN forms CuCN, which is
= x + 3 (- 2) = - 4 insoluble in water. It is soluble in excess of KCN due
x =- 4 + 6 = 2 to formation of the following complex
Thus (c) is correct option. (a) K 2 6Cu ^CNh4@ (b) K 3 6Cu ^CNh4@
59. Which of the following will give maximum number is (c) CuCN 2 (d) Cu 6K Cu ^CNh4@
isomers? Ans : COMP 2000
(a) 6Ni ^C 2 O 4hênh2@2+ Copper sulphate react with KCN to give white ppt
(b) 6Ni ênh^NH 3h4@2+ of Cu ^CNh2 and cyanogen gas. The insoluble copper
cynaide dissolve in excess of KCN and give soluble
(c) 6Cr ^SCNh2 ^NH 3h4@+ potassium cuprocyanide
(d) 6Co ^NH 3h4 Cl 2@ CuSo 4 + 2KCN $ K 2 SO 4 + Cu ^CNh2
Ans : SQP 2015
2Cu ^CNh2 $ 2CuCN + CN - CN
6Cr ^SCNh2 ^NH 3h4@ shows likange, gemoetrical and
+
insoluble cyanogen
optical isomerism. Hence produces maximum no. of
CuCN + 3KCN $ K 3 6Cu ^CNh4@
isomers. Soluble
Chap 5 Coordination Compounds Page 259
63. According to IUPAC nomenclature sodium Ans : OD 2017
nitroprusside is named as
(a) Sodium pentacyanonitrosyl ferrate (III)
(b) Sodium nitroferrocyanide
(c) Sodium nitroferrocyanide
(d) Aodium pentacyanonitrosyl ferrate (II)
Ans : DELHI 2005
IUPAC nomenclature sodium nitroprusside

Na 2 6Fe ^CNh5 NO@ is sodium pentacyanonitrosyl
ferrate (III) because in it NO is neutral ligand. Hence
2 # O.N. of Na + O.N. of Fe + 5 # O.N. of CN Transform of 6M ÂAh2 a 2@n ! does not shows optical
1 # O.N. of NO = 0 isomerism.
2 # (+ 1) + O.N. of Fe + 5 # (- 1) + 1 # 0 = 0
66. Atomic number of Cr and Fe are respectively 25 and
26, which of the following is paramagnetic?
64. Which of the following coordination compounds would (a) 6Cr ^COh6@ (b) 6Fe ^COh5@
exhibit optical isomerism?
(a) pentamminenitrocobalt (III) iodide (c) 6Fe ^CNh6@-4 (d) 6Cr ^NH 3h6@3+
(b) diamminedichloroplatinum (II) Ans : SQP 2015

3+ 0 3
(c) trans-dicyanobis (ethylenediamine) chromium Cr and 4s 3d electronic configuration with 3
(III) chloride unpaired electrons, hence paramagnetic. In other
cases pairing of d -electrons take place in presence of
(d) tris-(ethylendiamine) cobalt (III) bromide
strong field ligands such as CO or CN- .
In Cr ^COh6 molecule 12 electrons are contributed
The optical isomers are pair of molecules which are by CO group and it contains no odd electron.
non super imposable mirror images of each other
The two optically active isomers are collectively called

enantiomers.
65. Which one of the following is expected to exhibit
optical isomerism? (en=ethylenediamine)
(a) cis - 6Pt ^NH 3h2 Cl 2@ 67. Which one of the following is an inner orbital complex
(b) trans - 6Pt ^NH 3h2 Cl 2@ as well as diamagnetic in behaviour? (Atomic no.:
Zn = 30, Cr = 24, Co = 27, Ni = 28)
(c) cis - 6Co ênh2 Cl 2@
(a) 6Zn ^NH 3h6@2+ (b) 6Cr ^NH 3h6@3+
(d) trans - 6Co ênh2 Cl 2@ (c) 6Co ^NH 3h6@3+ (d) 6Ni ^NH 3h6@2+
72. 6Cr ^H 2 Oh6 Cl 3@ (atomic no. of Cr=24) has a magnetic Ans : COMP 2011
moment of 3.83 B.M. The correct distribution of 3d The octahedral coordination compounds of the type
-electrons in the Chromium of the complex is MA 3 B 3 exhibit fac-mer isomerism.
(a) 3dxy , (3dx - y ) 1, 3dyz
1 2 2 (b) 3dxy , 3dyz , 3dxz
1 1 1 1
(c) 3dxy , 3dyz , 3dz

1 1 2 (d) (3dx - y ) 1, 3dz , 3dxz
2 2 2 1
Ans : SQP 2016
m = n (n + 2)
3.83 = n (n + 2)
on solving n = 3
as per magnetic moment, it has three unpaired
electron.
Cr3+ will have configuration as
Cr 1s2 2s2 2p6 3s2 3p6 3d 4 4s2
Cr3+ 1s2 2s2 2p6 3s2 3p6 3d3
So, 3dxy , 3dyz , 3dxz

1 1 1

75. Which of the following complex ion is not expected to
73. Which of the following will give a pair of enantiomorphs? absorb visible light?
(a) 6Cr ^NH 3h6@6Co ^CNh6@ (b) 6Co ênh2 Cl 2@Cl (a) 6Ni ^CNh4@2- (b) 6Cr ^NH 3h6@3+
(c) 6Pt ^NH 3h4@6PtCl 6@ (d) 6Co ^NH 3h4 Cl 2@NO 2
(c) 6Fe ^H 2 Oh6@2+ (d) 6Ni ^H 2 Oh6@2+
(en = NH 2 CH 2 CH 2 NH 2)
Ans : SQP 2013
Ans : SQP 2015
6Ni ^CNh4@ : Number of unpaired electrons = 0
2-
Non super-imposable mirror images are called optical

isomers and may be described as ‘chiral’. They are 6Cr ^NH 3h6@3+ : Number of unpaired electrons = 3
also called enantiomers and rotate plane polarised
6Fe ^H 2 Oh6@2+ : Number of unpaired electrons = 4
light in opposite directions.
6Ni ^H 2 Oh6@2+ : Number of unpaired electrons = 2
76. Crystal field stablisation energy for high spin d 4
octahedral complex is
(a) - 1.8D 0 (b) - 1.6D 0 + P
(c) - 1.2D 0 (d) - 0.6D 0
d 4 in high spin octahedral complex

74. Which of the following does not show optical
isomerism?
(a) 6Co ^NH 3h3 Cl 3@0 (b) 6Co ênh Cl 2 ^NH 3h2@+
(c) 6Co ênh3@3+ (d) 6Co ênh2 Cl 2@+

CFSE = [0.6 # 1] + [- 0.4 # 3] = - 0.6D 0
(en = ethylenediamine)
83. The complex, 6Pt ^Pyh^NH 3h BrCl@ will have how many 87. Which of the following complex compounds will
geometrical isomers? exhibit highest paramagnetic behaviour?
(a) 3 (b) 4 (Atom No.: Ti = 22, Cr = 24, Co = 27, Zn = 30)
(c) 0 (d) 2 (a) 6Ti ^NH 3h6@3+ (b) 6Cr ^NH 3h6@3+
Ans :
(c) 6Co ^NH 3h6@3+ (d) 6Zn ^NH 3h6@2+
OD 2017
Complexes of the type M ABCD may exist in three

Ans : FOREIGN 2015
isomeric forms.
(a) 6Ti ^NH 3h6@ : 3d configuration and thus has one
3+ 1
unpaired electron.
(b) 6Cr ^NH 3h6@3+ : In this complex Cr is in + 3
oxidation state.
Similarly, 6Pt ^Pyh^NH 3h BrCl@ may exist in three

isomeric form in which M = PtA = Py, B = NH 3,
C = Br, D = Cl .
84. On mixing concentration NH 4 OH to Cu2+ salt, the
following blue complex is formed Thus, the complex is paramagnetic.
(a) 6Cu ^NH 4h4@ 2+
(b) 6Cu ^NH 3h2@ 2+
(c) 6Co ^NH 3h6@3+ : In this complex are cobalt ion is in
+ 3 oxidation state with 3d6 configuration.
(c) 6Cu ^NH 3h4@ 2+
(d) 6Cu ^NH 4h2@2+
Ans : SQP 2015
On mixing concentration NH 4 OH to a Cu2+ salt, the

NH 4 OH + Cu2+ $ Cu ÔHh2
blue ppt.
6Cu ^NH 3h4@+

NH 4 OH
dark blue solution

85. 6Cr ^H 2 Oh6@Cl 3 (atomic no. of Cr = 24) has a magnetic

moment of 3.83 B.M. The correct distribution of 3d (inner orbital or d2 sp3 hybrid orbital low spin
electrons in the Chromium of the complex is complex) diamagnetic
(a) 3dxy , (3dx - y ) 1, 3dyz
1 2 2 1 (d) In this complex Zn exists as
Zn++ ion
(b) 3dxy , 3dyz 3dxz
1 1 1
Zn++ ion : 3d10 4s0

(c) 3dxy , 3dyz 3dz
1 1 2
(d) (3dx - y ) 1, 3dz , 3dxz

2 2 2 1
Ans :
Zn++ ion in 7Zn ^NH 3h4A2+
COMP 2012, OD 2007

86. A square planar complex is formed by hybridisation of
which atomic orbitals?
(a) s, px , py, dyz (b) s, px , py, dx - y 2 2
(c) s, px , py, dz 2 (d) s, py, pz , dxy

Ans : DELHI 2002 Due to presence of paired electrons complex is
A square planar complex is formed by hybridisation of diamagnetic in nature.
s, px , py and dx - y atomic orbitals.
2 2 Thus (b) is correct option.
93. Assertion : The [Ni (en)3] Cl2 (en = ethylene-diamine) all the 3d 5 electrons are not paired up. One electron
has lower stability than [Ni (NH3)6]Cl2. remains unpaired. So, it is paramagnetic.
Reason : In [Ni (en)3]Cl2, the geometry of Ni is trigonal Fe2+ in presence of CN- in K 4 (Fe(CN)6)
bipyramidal.
Fe3+ in presence of CN- in K 3 [Fe (CN)6]
Ans : SQP 2020
[Ni (en)3] Cl2 is more stable than [Ni (NH 3) 6] Cl 2

because ethylene-diamine is a bidentate ligand, hence
it forms chelating ring with Ni2+ ion.
Thus (d) is correct option. However, the reason is false because crystal field
splitting in ferrocyanide is less than in ferricyanide
94. Assertion : [Co(NO2)3 (NH3)3] does not show optical
ion (higher the oxidation state of the metal, greater
isomerism.
the crystal field splitting).
Reason : It has a plane of symmetry.
Reason is a correct explanation of the Assertion. 96. Assertion : Ethylenediaminetetraacetate ion forms an
octahedral complex with the metal ion.
Reason : It has six donor atoms which coordinate
simulatneously to the metal ion.
(c) Assertion is correct but Reason is incorrect. (a) Both Assertion and Reason are correct and
(d) Both the Assertion and Reason are incorrect. Reason is a correct explanation of the Assertion.
Ans : DELHI 2020 (b) Both Assertion and Reason are correct but Reason
Optical isomerism is found in octahedral complexes is not the a correct explanation of the Assertion.
with 1, 2 or 3 sysmmetrical bidentate ligands only. (c) Assertion is correct but Reason is incorrect.
Since given compound is not having any bidentate
ligand, it will not show optical isomerism. It is
because it has plane of symmetry, a plane which is Ans : COMP 2006
perpendicular to equatorial plane. Thus (a) is correct option.
Thus (a) is correct option. 97. Assertion : A chelating ligand must possess two or
95. Assertion : Potassium ferro-cyanide is diamagnetic, more lone pairs at such a distance that it may form
whereas potassium ferricyanide is paramagnetic. suitable strain free rings at the metal ion.
Reason : Crystal field splitting in ferrocyanide ion is Reason : H2N - NH2 is a chelating ligand.
greater than that of ferricyanide ion. (a) Both Assertion and Reason are correct and
(a) Both Assertion and Reason are correct and Reason is a correct explanation of the Assertion.
Reason is a correct explanation of the Assertion. (b) Both Assertion and Reason are correct but Reason
(b) Both Assertion and Reason are correct but Reason is not the a correct explanation of the Assertion.
is not the a correct explanation of the Assertion. (c) Assertion is correct but Reason is incorrect.
(c) Assertion is correct but Reason is incorrect. (d) Both the Assertion and Reason are incorrect.
(d) Both the Assertion and Reason are incorrect. Ans : OD 2018
Ans : FOREIGN 2015 H 2 N - NH 2 does not act as chelating ligand. The
In potassium ferrocyanide, Fe is in the form Fe2+ and coordination by hydrazine leads to a three membered
in potassium ferricyanide, Fe is in the form Fe3+ CN- highly unstable strained ring and thus, it does not act
is a strong leg-and. So, it will pair up all the 3d 6 as chelating agent.
electrons of Fe3+ and make it diamagnetic. In Fe2+, Thus (c) is correct option.
NH3 is a strong field ligand, it causes pairing of 3d 6

electrons.
Thus,
(i) Coordination number of the complex is 6. Hence,

hybridisation is d 2 sp3 , so geometry is octahedral.
(ii) Since, there is one unpaired electron, so it is
paramagnetic.
104. Draw the structural isomer of 6Co ^NH 3h5 NO 2@Cl 2 and (i) Coordination number of the complex is 6. Hence,
name the type of isomerism. hybridisation is d 2sp3 .
Ans : COMP 2012 (ii) All electrons are paired. So, it is diamagnetic.
The isomerism is linkage isomerism, i.e. more than
106. What do you mean by ligand?
one atom in a monodentate ligand may functions as
Ans : COMP 2008
donor. For this, in NO -2 ion, either nitrogen or an
oxygen atom may functions as donor. The donor species (atom, molecule or ion) which
donate a pair of electrons to the metal atom is called
ligand.
SHORT ANSWER QUESTIONS
107. (a) Write the IUPAC names of the following :

Pentaamminemtrito-O-cobalt (III) ion
(i) [Co (NH 3) 5 (ONO)] 2+
(ii) K 2 [NiCl 4]
or
(b) (i) What is a chelate complex ? Give one example.
(ii) What are heteroleptic complexes ? Give one
example.
Ans : COMP 2023
(a) (i) Pentaamminenitrito-o-cobalt(III) ion

Pentaamminenitro-N-cobalt (III) ion
(ii) Potassium tetrachloridonickelate(11)
105. For the complex ion of 6Co ^NH 3h6@3+ or
(i) state the hybridisation of the complex. (b) (i) A chelate complex is a type of coordination
(ii) state the magnetic nature of the complex. compound where a ligand forms a ring
Ans : OD 2014, SQP 2011 structure with central metal ion, holding it
Oxidation number of Co in the complex 6Co ^NH 3h6@3+ in place. Example : ethylene diamine ligand
is co-ordinate to the copper ion throiigh both
its nitrogen atom, forming a chelate ring
x + 6 # ^0 h = + 3 , x = + 3
structure.
Electronic configuration of Co is 6Ar@3d 7 4s2 . (ii) Heteroleptic complexes are co-ordination
compounds containing different types of
ligands. Example : 8Fe ^CNh5 NOB2- .
108. Discuss the following terms :

(a) Coordination Number
(b) Effective Atomic Number
115. Define a complex ion and write the types of complexes.

Ans : COMP 2004
Ion formed by coordinate bond between central metal

atom and donars is called complex ion.
Types of complexes:
(i) Cationic complex, e.g. [Co (NH 3) 6] 3+
(ii) Anionic complex, e.g. [Ag (CN) 2] -
(iii) Neutral complex, e.g. [Ni (CO) 4] 120. Define the following:
(i) Coordination number
116. Write and IUPAC name of the following coordination (ii) Coordination sphere
compounds : (iii) Counter ions.
(a) K 4 6Fe ^CNh6@ (b) Ni ^COh4 Ans : DELHI 2012
(c) K 2 6Pt ^Clh6@ (d) Fe 4 6Fe ^CNh6@3 (i) Coordination Number : Total number of
coordinate bonds formed with the central metal
Ans : DELHI 2017
atom or ion by the ligands.
(a) K 4 6Fe ^CNh6@ Potassium hexacyanoferrate (II) Example : The coordination number of cobalt in
(b) Ni ^COh4 tetracarbonylnickel (0) [CoCl (NH 3) 5] Cl 2 is six.
(ii) Coordination Sphere : The central atom and the
(c) K 2 6Pt ^Clh6@ Potassium hexachlorido palatinate ligands are enclosed in square brackets and are
(IV) called coordination sphere.
(d) Fe 4 6Fe ^CNh6@3 iron (III) hexa cyano ferrate (II) (iii) Counter Ions : The ionizable group which are
written outside the bracket are called counter
117. What do you mean by coordination compound? ions.
Those compounds in which the central metal atom

is linked to ions or neutral molecules by coordinate
bond (donation of lone pairs of electrons) are called
coordinate compounds or complex compounds.
118. What do you mean by chelate? 121. Give oxidation state and co-ordination number of
Ans : OD 2000 central metal ion in (NH 4) 2 [CoF4].
When a bidentate or a polydentate ligand is attached Ans : DELHI 2008
by two or more donor atoms to the central atom Assume that the oxidation state of metal atom is x .
forming a ring, the ligand is called chelating ligand (NH 4) 2 [CoF4]
and the complex is called chelate, the effect is called
chelate effect. 2 (+ 1) + x + 4 (- 1) = 0
x =+ 2
Hence, Oxidation state of Co = + 2
Coordination number of Co = 4
122. What do you mean by denticity?
Ans : FOREIGN 2014
The number of coordinating groups (donor atoms)

present in a ligand is called the denticity of the ligand.
119. What are ambidentate ligands?
(i) Monodentate or Unidentate Ligand : Ligand has
Ans : OD 2006
one donar atom.
Those unidentate ligands which have more than one Example: NH 3 , H 2 O , Cl- .
coordinating atoms are called ambidentate ligands. (ii) Bidentate Ligand : Ligand which can donate two
Example: lone pair of electrons to central metal atom.
Example:
129. How does the magnitude of T0 decide the actual

configuration of d-orbitals in a coordination entity?
Ans : FOREIGN 2018
th
If T0 < P (pairing energy), the 4 electron enters
one of the eg orbitals giving the configuration t 23g e 1g
thus forming high spin complexes. The ligands for
which T0 < P are called weak field ligands. If T0 > P,
the 4 th electron pairs up in one of the t 2g orbitals
giving the configuration t 24g e 0g thus forming low spin 132. Out of the following two coordination entities, which
complexes. The ligand for which T0 > P are called is chiral (optically active)?
strong field ligands.
(i) cis-[CrCl 2 (ox) 2] 3-
130. [Fe (H 2 O) 6] 3+ is strongly paramagnetic whereas
(ii) trans-[CrCl 2 (ox) 2] 3- .
[Fe (CN) 6] 3- is weakly paramagnetic. Explain.
Ans : FOREIGN 2005
Ans : OD 2001
[Fe (CN 6)] 3- : Iron is in + 3 oxidation state (

3d5 ) hybridisation is d2 sp3 . There is only one
unpaired electron which makes the complex weakly
paramagnetic.
[Fe (H 2 O) 6] 3+ : Iron is in + 3 oxidation state (3d5)
hybridisation is sp3 d2 .
133. Draw figures to show splitting of degenerated orbitals

in square planar crystal field and tetrahedral crystal
field.
[Fe (H 2 O) 6] 3+ is strongly paramagnetic due to presence Ans : FOREIGN 2001
of five unpaired electrons. (i) Splitting of d-orbitals in a square planar crystal
131. Name the following coordination entities and draw field.
the structures of their stereoisomers:
(i) [Cr (C 2 O 4) 3] 3-
(ii) [Co (NH 3) 3 Cl 3].
Ans : FOREIGN 2002
(i) [Cr (C 2 O 4) 3] 3- trioxalatochromate (III) ion.
(ii) Splitting of d-orbitals in a tetrahedral crystal

field.
(ii) [Co (NH 3) 3 Cl 3] triamminetrichloridocobalt (III).

140. Write the IUPAC names of the following: (i) K [Cr (H 2 O) 2 (C 2 O 4) 2]

(i) [Co (NH 3) 6] Cl 3 (ii) [CO (en) 3] Cl 3
(ii) [Co (NH 3) 5 Cl] Cl 2 (iii) [CO (NH 3) 5 (NO 2)] (NO 3) 2
(iii) K 3 [Fe (CN) 6] (iv) [Pt (NH 3) (H 2 O) Cl 2]
(iv) K 3 [Fe (C 2 O 4) 3] Ans : COMP 2002
(v) K 2 [PdCl 4] (i) Both geometrical (cis, trans) and optical isomer
for cis-form.
(vi) [Pt (NH 3) 2 Cl (NH 2 CH 3)] Cl
Ans : OD 2002
(i) Hexaamine cobalt (III) chloride.
(ii) Pentaamine chloridocobalt (III) chloride.
(iii) Potassium hexacyanoferrate (III).
(iv) Potassium trioxalatoferrate (III).
(v) Potassium tetrachlorido palladate (II).
(vi) Diamminechlorido (methylamine) platinum (II)
chloride.
141. Discuss briefly giving an example in each case the role
of coordination compounds in
(i) Biological system
(ii) Analytical chemistry
(iii) Medicinal chemistry
(iv) Extraction/metallurgy of metals.
(i) Biological System : Biologically important
coordination compounds are: (ii) Two optical isomers can exist.
(a) Chlorophyll is a coordination compound of
Magnesium.
(b) Haemoglobin of blood is a coordination
compound of Iron.
(c) Vitamin B 12 is a coordination compound of
Cobalt.
(ii) Analytical Chemistry :
(a) Presence of Co2+ ion is tested by K 3 [Fe (CN) 6] .
(b) Presence of Fe3+ ion is tested by K 4 [Fe (CN) 6] .
(c) In volumetric analysis the solutions of metal (iii) Linkage isomers [Co (NH 3) 5 ONO] (NO 3) 2 and
ion can be titrated against the solution of the [Co (NH 3) 5 NO 2] (NO 3) 2 .
polydendate ligands like EDTA. (iv) Geometrical isomerism.
(iii) Medicinal Chemistry :
(a) EDTA is used for treatment of lead poisoning.
(b) The platinum complex cis-platin
[Pt (NH 3) 2 Cl 2] is used in cancer therapy.
(iv) Extraction/metallurgy of Metals : The noble
metals like silver and gold are extracted from their
ores through the formation of cyanide complexes
[Ag (CN) 2] - and [Au (CN) 2] - respectively. 143. Explain on the basis of valence bond theory that
142. Indicate the types of isomerism exhibited by the [Ni (CN) 4] 2- ion with square planar structure is
following complexes and draw the structures for these diamagnetic and the [NiCl 4] 2- ion with tetrahedral
isomers: geometry is paramagnetic.
CLASS 12

CLASS 10

Ans : COMP 2011

In the presence of CO ligand the 4s electrons shift
Nickel in [Ni (CN) 4] 2- is the + 2 oxidation state, i.e. to 3d orbital to pair up the 3d electrons. Thus,
nickel is present as Ni2+ ion. there is no unpaired electron present. Hence it is
diamagnetic.
146. Give evidence that [Co (NH 3) 5 Cl] SO 4 and

[CO (NH 3) 5 SO 4] Cl are ionisation isomers.
Ans : COMP 2018
When they are dissolved in water, they will give

different ions in the solution which can be tested by
adding AgNO 3 solution and BaCl 2 solution. When
Cl- ions are the counter ions, a white precipitate will
be obtained with AgNO 3 solution. If SO 2- 4 ions are
the counter ions, a white precipitate will be obtained
with BaCl 2 solution.
[Co (NH 3) 5 Cl] SO 4 (aq) + BaCl 2 (aq) " BaSO 4 (s) .
ppt
[Co (NH 3) 5 Cl] SO 4 (aq) + AgNO 3 " No reaction

dsp2 - hybrid orbitals
[Co (NH 3) 5 SO 4] Cl (aq) + BaCl 2 (aq) " No reaction
- Diamagnetic
CN- is a strong ligand as it approaches the metal ion, [Co (NH 3) 5 SO 4] Cl (aq) + AgNO 3 (aq) " AgCl (s) .
ppt
so the electrons should get paired up.
In [NiCl 4] 2- , Cl- provides a weak ligand field. It is 147. [Fe (H 2 O) 6] 3+ is strongly paramagnetic whereas
therefore unable to pair up the unpaired electrons of [Fe (CN) 6] 3- is weakly paramagnetic. Explain.
the 3d orbital. Ans : SQP 2008
Hence, the hybridisation is sp3 and it is paramagnetic. In both the complexes, Fe is in + 3 oxidation state
144. A solution of [Ni (H 2 O) 6] 2+ is green but a solution of with the configuration 3d 5 , CN- is a strong field
[Ni (CN) 4] 2- is colourless. Explain. ligand. In its presence, 3d electrons pair up leaving
only one unpaired electron. The hybridisation is
Ans : DELHI 2002
2+ 8 d 2 sp3 forming inner orbital complex. H 2 O is a weak
In [Ni (H 2 O) 6] : Ni is in + 2 state (3d ). It has
ligand. In its presence 3d electrons do not pair up.
two unpaired electrons which do not pair up in the
The hybridisation is sp3 d 2 forming an outer orbital
presence of the weak H 2 O ligand. The d-d transition
complex containing five unpaired electrons, hence it is
absorb red light and the complementary light emitted
strongly paramagnetic.
is green.
In [Ni (CN) 4] 2- : Ni is in + 2 state (3d8) but in presence 148. Explain [Co (NH 3) 6] 3+ is an inner orbital complex
of strong CN- ligand, the two unpaired electron in the whereas [Ni (NH 3) 6] 2+ is an outer orbital complex.
3d orbitals pair up. Thus there is no unpaired electron Ans : DELHI 2004
present therefore it is colourless. In [Co (NH 3) 6] 3+ ,
145. [NiCl 4] 2- is paramagnetic while [Ni (CO) 4] is Oxidation state of Co = + 3
diamagnetic though both are tetrahedral. Why?
Electronic configuration = 3d 6
Ans : COMP 2003
2-
In presence of NH 3 , 3d electrons pair up leaving two
In [NiCl 4] , Ni is in + 2 oxidation state with electronic
d -orbitals empty. Hence, the hybridisation is d 2 sp3
configuration = 3d 8 4s0 .
forming an inner orbital complex.
In [Ni (NH 3) 6] 2+ ,
Oxidation state = + 2
Electronic configuration = 3d 8
-
Cl is a weak ligand. It cannot pair up the electrons in In the presence of NH 3 , 3d electrons do not pair up.
3d orbitals. Hence, it is paramagnetic. In [Ni (CO) 4] The hybridisation involved is sp3 d 2 and it forms an
, Ni is in zero oxidation state and its configuration is outer orbital complex.
- 3d 8 4s2 .
156. Specify the oxidation numbers of the metals in the 159. Aqueous copper sulphate solution (blue in colour) gives:
following coordination entities: (i) A green precipitate with aqueous potassium fluoride.
(i) [Co (H 2 O) (CN) (en) 2] 2+ (ii) A bright green solution with aqueous potassium
(ii) [CoBr2 (en) 2] + chloride. Explain these experimental results.
Ans : OD 2007
(iii) [PtCl 4] 2-
Aqueous CuSO 4 solution exists as [Cu (H 2 O) 4] SO 4
(iv) [Cr (NH 3) 3 Cl 3] which has blue colour due to [Cu (H 2 O) 4] 2+ ions.
(v) K 3 [Fe (CN) 6] (i) When KF is added, the weak H 2 O ligands are
Ans : COMP 2016
replaced by F- ligands forming [CuF4] 2- ions
which is a green precipitate.
(i) x + (0) + (- 1) + (0) = + 2
[Cu (H 2 O) 4] 2+ + 4F- " [CuF4] - + 4H 2 O
x =+ 3 (Green ppt)
-
(ii) x - 4 =- 2 (ii) When KCl is added, Cl ligands replace the weak
x =+ 2 H 2 O ligands forming [CuCl 4] 2- ion which has
bright green colour.
(iii) x + 0 + 3 (- 1) = 0
[Cu (H 2 O) 4] 2+ + 4Cl- " [CuCl ] 4
2-
+ 4H 2 O
x-3 = 0 Tetrachlorocuprate II
(Green solution)
x =+ 3
160. What is spectrochemical series? Explain the difference
(iv) x + 2 (- 1) + 0 = + 1
between a weak field ligand and a strong field ligand.
x =+ 3 Ans : DELHI 2018
(v) x + 6 (- 1) = - 3 The arrangement of ligands in the order of their
x =+ 3 increasing field strength the increasing crystal
field splitting energy (CFSE) values is called
157. Using IUPAC norms write the systematic names of spectrochemical series.
the following:
The ligands with small value of CFSE (T0 ) are
(i) [Co (NH 3) 6] Cl 3
called weak field ligands.
(ii) [Pt (NH 3) 2 Cl (NH 2 CH 3)] Cl 161. What is crystal field splitting energy? How does the
(iii) [Ti (H 2 O) 6] 3+ magnitude of T0 decide the actual configuration of d
-orbitals in a coordination entity?
(iv) [Co (NH 3) 4 Cl (NO 2)] Cl
Ans : SQP 2016
Ans : OD 2004
When ligands approaches a transition metal ion, the d
(i) Hexaammine cobalt (III) chloride -orbitals splits up into two sets one with lower energy
(ii) Diammine dichlorido (methylamine) platinum and other with higher energy. The difference of energy
(II) chloride between the two set of orbitals is called crystal field
(iii) Hexaaqua titatium (III) ion splitting energy (T0 for octahedral field).
(iv) Tetraammine chloridonitrito-N-Cobalt (III) If T0 < P (pairing energy) then the 4th electron
chloride enters one of the e g orbitals giving the configuration
158. A solution of [Ni (H 2 O) 6] 2+ is green but a solution of t 23g e g1 , thus forming high spin complexes.
[Ni (CN) 4] 2- is colourless. Explain. If T0 > P , the 4th electron gets paired up in
Ans : DELHI 2005 one of the t2g orbitals giving the configuration t 24g e g0
2+
In [Ni (H 2 O) 6] , Ni is again in + 2 oxidation state thereby forming low spin complexes.
with the configuration 3d 8 , i.e. it has two unpaired Such ligands for which T0 > P are called strong
electrons which do not pair up in the presence of weak field ligands.
H 2 O ligand. Hence, it is coloured. The d -d transition 162. Amongst the following the most stable complex is:
absorbs red light and the complementary light (i) [Fe (H 2 O) 6] 3+
emitted is green. In case of [Ni (CN) 4] 2-, Ni is again in
+ 2 oxidation state with the configuration 3d 8 but in (ii) [Fe (NH 3) 6] 3+
the presence of strong CN- ligand, the two unpaired (iii) [Fe (C 2 O 4) 3] 3-
electrons in the 3d orbitals pair up. Thus, there is no
(iv) [FeCl 6] 3-
unpaired electron present. Hence it is colourless.
Ans : SQP 2002 Ans : OD 2008
The oxidation states of Cr is + 3 , Fe is + 2 and that Coordination Entity

of Zn is also + 2. This entity usually constitutes a central metal atom
Electronic configuration of Cr3+ = , or ion, to which are attached a fixed number of other
no. of unpaired electrons = 3 (inner orbital complex). atoms or ions or groups by coordinate bond. Examples
are [Ni (CO) 4], [COCl 3 (NH 3) 3] etc.
Electronic configuration of Fe2+ = 3d 6 , no. of complex
unpaired electrons = 4 (outer orbital complex). Ligands
Electronic configuration of Zn2+ = 3d 10 , no. of It is ion having at least one lone pair of electrons and
unpaired electrons = 0 (inner orbital complex). are capable of forming a coordinate bond with the
central metal atom/ion in the coordination entity.
m = n (n + 2)
Examples are : Cl- , (OH) - , (CN) -, etc.
Hence, (ii) has the highest magnetic moment. Coordination Number
169. What will be the correct order for the wavelengths of The total number of coordinate bonds with which
absorption in the visible region for the following : central metal atom/ion is linked to ligands in the
coordination entity is called the coordination number
[Ni (NO 2) 6] 4- , [Ni (NH 3) 6] 2+ , [Ni (H 2 O) 6] 2+ ?
of the central metal atom/ion.
Ans : COMP 2015
Coordination Polyhedron
As metal ion is fixed, the increasing field strengths
The spatial arrangement of the ligands which are
(CFSE) values of the ligands form the spectrochemical
directly attached to the central metal atom/ion
series are in order:
defines a coordination polyhedron about the central
H 2 O < NH 3 < NO -2 metal atom/ion.
Thus, the energies absorbed for excitation will be in Examples :
the order: [Co (NH 3) 6] 3+ is octahedral, [Ni (CO) 4] is tetrahedral.
[Ni (H 2 O) 6] 2+ < [Ni (NH 3) 6] 2+ < [Ni (NO 2) 6] 4- Homoleptic and Heteroleptic Complexes
The order of wavelength absorbed will be opposite Complexes in which a metal is bound to only one kind
of it. of donor group are known as homoleptic complexes.
Example : [Co (NH 3) 6] 3+ .
Since, E = hc
l Complexes in which a metal is bound to more than one
kind of donor groups are called hetroleptic complexes.
170. What is meant by stability of a coordination compound
Example : [Co (NH 3) 4 Cl 2] + .
in solution? State the factors which govern stability of
complexes. 172. Give the oxidation state, d -orbital occupation and
Ans : SQP 2011 coordination number of the central metal ion in the
The stability of a complex in solution refers to the following complexes:
degree of association between the two species involved (i) K 3 [Co (C 2 O 4) 3]
in the state of equilibrium. The magnitude of the (ii) cis -[Cr (en) 2 Cl 2] Cl
equilibrium constant for the association, quantitatively (iii) (NH 4) 2 [CoF4]
expresses the stability. (iv) [Mn (H 2 O) 6] SO 4
Factors which govern the stability of a complex are: Ans : FOREIGN 2019, OD 2011
(i) Smaller the size of cation, greater will be the (i) Oxidation state of K 3 [Co (C 2 O 4) 3] 3-
stability of complex, e.g. Fe3+ ion forms more x - 6 =- 3
stable complex than Fe2+ .
(ii) Greater the charge on the central metal ion, more (Coordination no. = - 6 )
stable will be the complex. x =+ 3
(iii) Stronger the ligand, more stable will be the d -orbital occupation of Co 3+
= 3d 6 = t 26g e g0
complex formed, e.g. CN- forms more stable
No. of unpaired electrons = 0
complex than NH 3 .
(ii) cis -[Cr (en) 2 Cl 2] + Cl-
171. Explain with two examples each of the following: Oxidation State, x = + 3 (Coordination no. = - 6 )
Coordination entity, ligands, coordination number,
Cr3+ = 3d 3 = t 23g
coordination polyhedron, homoleptic and heteroleptic
complexes. (No. of unpaired electrons = 3 )
Ans : OD 2017
(b) Haemoglobin is a coordination compound of
(a) Based on his extensive research on coordination iron.
compound. Alfred warner in 1893 put forward (c) Vitamin B 12 , cyanocobalamin, the
a theory to explain the nature of bonding in
antipernicious anaemia factor is a coordination
coordination or complex compounds. In brief the
compound of cobalt.
warner’s theory may be stated as follows:
1. Central ion in any complex ion/compound 177. How would you account for the fact that [Fe (CN 6)] 3-
exhibits two types of valencies : Primary is weakly paramagnetic while [Fe (CN) 6] 4- is
valency and Secondary valency. diamagnetic?
2. The primary valency is ionisable and Ans : SQP 2004
corresponds to the oxidation state of the [Fe (CN) 6] 3-

metal forming the central ion. The secondary Iron is in + 3 oxidation state = 3d 5
valency is non-ionisable.
3. Every central ion has a fixed number of
secondary valencies. This number is called
the coordination number of the central ion.
4. The primary valency of the metal ion is
always satisfied by negative ion.
5. The secondary valencies are satisfied by
negative ions or neutral molecules.
6. Every element must satisfy all its primary
and secondary valencies. In order to meet this
requirement the negative ion may have a dual
role, i.e., in satisfying both the primary and The presence of one unpaired electron makes the
secondary valencies. complex weakly paramagnetic.
(b) Monodentate ligands have only one atom capable [Fe (CN) 6] 4-
of binding to a central atom or ion. H 2 O is a Iron is in + 2 oxidation state = 3d 6
ligand, oxygen is the donor atom binding to the
metal.
176. Briefly describe the importance of coordination
compounds in:
(i) Qualitative analysis
(ii) Extraction of metals
(iii) Biological systems
Ans : FOREIGN 2003
(i) Qualitative Analysis
(a) EDTA is used for the estimation of Ca2+ and
Mg2+ ions in hard water.
There is no unpaired electron therefore it is
(b) Ni2+ ion is tested and estimated by DMG diamagnetic.
(dimethyl glyoxime).
(ii) Extraction of Metals 178. Explain bonding in coordination compounds with the
help of crystal field theory.
(a) Silver and gold are extracted by treating zinc
with their cyanide complexes. Ans : COMP 2014, OD 2006
(b) Bauxite is purified by forming complexes with The main points of crystal field theory are:
NaOH. 1. Metal ligand bonds are ionic having electrostatic
interaction similar to ions in a crystal, therefore
(c) Impure nickel is converted to [Ni (CO) 4],
named as crystal field theory (CFT).
which is decomposed to yield pure nickel.
2. Ligand is treated as a point of negative charge.
(iii) Biological Systems
The arrangement of the ligands around the central
(a) The pigment responsible for photosynthesis, ion is such that the repulsion between them are
i.e. chlorophyll is a coordination compound of minimum.
Mg.
6. Ending the Name of Metal Ion or Atom : When 20. K2 [Pd Cl 4] potassium
the complex ion is anionic, the name of central tetrachloridopalladate (II)
metal atom ends in - ate and in cationic or
21. [Ti (H2 O) 6] 3+ hexaaquatitanium (III) ion
neutral complexes, the name of metal is written
as such. 22. [Co (en) 3] 3+ tris (ethane-1, 2-diamine)
7. Oxidation State of Central Metal Ion : Oxidation cobalt (III) ion
state is indicated by a Roman numeral and 23. [Co (NH3) 4 Cl (NO2)] Cl tetraamminechloridonitrito-
written after metal in brackets. N-cobalt (III) chloride
Example: 24. [NiCl 4] 2- tetrachloridonickelate (II) ion
Complex Name 25. [Ni (NH3) 6] Cl2 hexaamminenickel (II) chloride
Compound
26. [Mn (H2 O) 6] 2+
hexaaqua manganese (II) ion
1. K 4 [Fe (CN) 6] potassium hexacyanoferrate
(II)
181. Discuss the nature of bonding in the following
2. K3 [Fe (CN) 6] potassium hexacyanoferrate coordination entities on the basis of valence bond theory.
(III)
(i) [Fe (CN) 6] 4-
3. [Co (NH3) 6] Cl3 hexaammine cobalt (III) (ii) [FeF6] 3-
chloride
(iii) [Co (C 2 O 4) 3] 3-
4. K3 [Co (CN) 5 (NO)] potassium pentacyanonitrosyl (iv) [CoF6] 3-
cobaltate (II)
Ans : FOREIGN 2008
5. K [Pt (NH3) Cl3] potassium 4-
(i) [Fe (CN) 6] : Iron is in + 2 oxidation state
amminetrichloridoplatinate (II)
(3d 6), Hybridisation is d 2 sp3 , octahedral and
6. [Pt (NH3) 2 Cl (NO2)] diamminechloridonitrito-N- diamagnetic.
platinum (II)
(ii) [FeF6] 3- : Iron is in + 3 oxidation state (3d 5),
7. [Ni (CO) 4] tetracarbonyl nickel (O) hybridisation sp3 d 2 , octahedral.
8. K3 [Cr (C2 O 4) 3] potassium
trioxalatochromate (III)
9. [Co (NH3) 4 (H2 O) (Cl)] Cl2 tetraamineaquachlorido cobalt
(III) chloride
10. K2 [Zn (OH) 4] potassium tetrahydroxozincate
(II)
11. [Ag (NH3) 2] [Ag (CN) 2] diamminesilver (I)
dicyanoargentate (I)
12. K3 [Al (C2 O 4) 3] potassium trioxalato
aluminate (III)
[FeF6] 3- is strongly paramagnetic due to presence
13. Hg [Co (SCN) 4] mercury of five unpaired electrons.
tetrathiocyanatocobaltate (III)
(iii) [Co (C 2 O 4) 3] 3- : Cobalt is in + 3 oxidation state,
14. [Co (NH3) 5 (CO3)] Cl pentaammine carbonatocobalt (3d 6) hybridisation is d 2 sp3 , octahedral.
(III) chloride
15. K3 [Fe (C2 O 4) 3] potassium trioxalatoferrate
(III)
16. [Pt (NH3) 2 Cl (NH2 CH3)] Cl diamminechloridomethanamine
platinum (II) chloride
17. [Cr (NH3) 3 (H2 O) 3] Cl3 triammine triaquachromium
(III) chloride
18. [Co (en) 3] 2 (SO 4) 3 tris (ethylenediammine) cobalt
(III) sulphate
19. [CoCl2 (en) 2] Cl dichloridobis (ethane-1,
2-diamine) cobalt (III) chloride
[Co (C 2 O 4) 3] 3- is diamagnetic due to absence of
unpaired electron.
(d) Octahedral Complex (Co. No. = 6 ) :

[CoCl 2 (en) 2] + . trans [CoCl 2 (en) 2] +
(e) Octahedral Complex (Co. No. = 6 ) :

[Pt (NH 3) (Br) (Cl) (I) (NO 2) (py)] forms 15 Square planar complexes do not show optical
different geometrical isomers. because they contain a plane of symmetry.
(ii) Optical Isomerism : Optical isomers rotate the 183. (i) Draw all the possible isomers having the formula
plane polarised light in opposite direction i.e.,
Cr [(NH 3) 4 Cl 2] + .
right and left are called dextro (d) and laevo (l)
(ii) Illustrate the following with an example:
isomers.
The d and l isomers of a compound are called (a) Linkage isomerism
enantiomers. (b) Coordination isomerism.
The two isomers are non-superimposable mirror (iii) Why is [NiCl 4] 2- is paramagnetic (Ni = 28 )?
image of each other are called Chiral and this Ans : DELHI 2001
property is called Chirality. (i)
Examples:
(a) [Co (en) 3] 3+
(ii) (a) Linkage Isomerism : The isomerism in which

a ligand can form linkage with metal through
different atoms, e.g., nitro group (- NO 2) can
link to metal either through nitrogen atom or
(b) [CoCl 2 (en) 2] + : Its isomers is optically active through oxygen atom, e.g.
but trans isomer is optically inactive. [Co (NH 3) 5 ONO] Cl 2
dichlorobis (ehtane-1, 2-diamine) IUPAC Name : Pentaamminenitrito-o-cobalt
cobalt (III) ion. (III) chloride.
cis [CoCl 2 (en) 2] + [Co (NH 3) 5 NO 2] Cl 2
IUPAC Name : Pentaamminenitrito-N-cobalt
(III) chloride.
Overall dissociation constant is the reciprocal of

overall stability constant.
Hence, overall dissociation constant.
K = 1
b4
= 1
2.1 # 1013
= 4.7 # 10-14
(ii) [Ni (CN) 4] 2-

CASE BASED QUESTIONS
Nickel is in + 2 oxidation state = 3d 8 .
188. Hard water does not form leathers with soap.

Neelam uses a washing powder containing sodium
metapolyphosphate and ethylene diamine tetracetate
(EDTA) while Manju is using ordinary washing
powder.
(i) Which washing powder is more effective for
washing clothes in hard water ?
(ii) Which type of ligand is EDTA ?
(iii) Give an example of monodentate ligand.
(iv) Draw the structure of ethylene diamine (en).
[Ni (CN) 4] 2- ion is diamagnetic since it contains Ans :
no unpaired electron. (i) Washing powder containing EDTA.
(iii) [Ni (CO) 4] (ii) It is a hexadentate ligand.
Nickel is in 0 oxidation state = 3d 8 4s2 . (iii) NH 3, H 2 O (any one).
(iv)
Ethylene diamine (en)

189. Anjali went to an exhibition, where she found now-a-
days younger generation girls are interested in wearing
ornaments made up of white metal platinum.
(i) Are you interested in wearing ornaments made of
[Ni (CO) 4] is diamagnetic since it contains no platinum or will you save platinum by not wearing
unpaired electron.
it ? Give reason.
(ii) Name the life saving drug prepared from platinum.
NUMERICAL QUESTIONS (iii) Which disease can be cured by that complex ?

(iv) Write down the structure of cis platin.
187. Calculate the overall complex dissociation equilibrium Ans :
constant for Cu (NH 3) 2+
4 ion, give that b 4 for this (i) No, I will not wear ornaments made up of platinum
complex is 2.1 # 1013 . but I will save it for medicinal use.
Ans : OD 2012 (ii) Cis platin.
Overall stability constant, (iii) It is used to cure cancer.
b 4 = 2.1 # 1013 (iv) cis 6Pt ^NH 3h2 C1 2@.
192. There is growing interest in the use of chelate therapy

in medicinal chemistry. An example is the treatment
of problems caused by the presence of metals in toxic
proportions in plan/animal systems. Thus, excess
of copper and iron are removed by the chelating
ligands D -penicillamine and desferrioxime B via the
formation of coordination compounds. EDTA is used
in the treatment of lead poisoning. Some coordination
compounds of platinum effectively inhibit the growth
of tumours. Examples are : cis - platin and related
compounds.
(i) What are chelates ?
(ii) Write the chemical name of EDTA.
Ans :
(i) When a di-or polydentate ligand uses its two or
more donoratoms to bind a single metal ion, it is
said to be a chelate ligand.
(ii) Ethylenediaminetetraacetic acid.
***********
Chap 6 Haloalkanes and Haloarenes Page 289
CHAPTER 6
Haloalkanes and Haloarenes
SUMMARY 2. Halogen derivatives of arenes are called haloarenes.

E.g. X - C 6 H 5 .
1. ALKYL HALIDES OR HALOALKANES

Organic compounds in which one or more hydrogen atom
of an alkane have been substituted by a halogen atom.
For example, chloromethane, CH 3 Cl , dibromoethane,
CH 2 BrCH 2 Br , etc. Haloalkanes can be formed by direct
reaction between alkanes and halogens using ultraviolet
radiation. They are usually prepared by the reaction of (i) Vicinal Dihalides : Halogen derivatives where
an alcohol with a halogen carrier. the two halogen atoms are attached on the
adjacent carbon atom.
2. REACTIONS OF HALOALKANES INVOLVE CH 2 Cl
1. Nucleophilic substitution E.g., y
2. Elimination reaction CH 2 Cl
3. Reaction with metals (ii) Geminal Dihalide : Where the two halogen
Nucleophilic substitution reactions are categorised as atoms are attached to the same carbon atom.
S N1 and S N2 on the basis of kinetic properties. For e.g., CH 3 CHBr2 .
A S N2 reaction proceeds with stereo-chemical
Nomenclature
inversion while a S N1 reaction proceeds with
racemisation. Structure Common Name IUPAC Name
Optically Active Molecule CH3 CH2 CH (Cl) CH3 Sec-Butyl 2-Chlorobutane

chloride
It is a molecule that cannot be superimposed on its
mirror image. It is also called chiral molecule. (CH3) 3 CCH2 Br Neo-Pentyl 1-Bromo-2,
bromide 2-dimethyl
Asymmetric Carbon propane
It is the carbon atom that is bonded to four different
(CH3) 3 CBr Tert-Butyl 2-Bromo
groups. It is also called chiral carbon. bromide -2-methyl propane
Enantiomers
CH2 - CHCl Vinyl chloride Chloroethane
These are optical isomers that are mirror images of
each other. CH2 - CHCH2 Br Allyl bromide 3-Bromo propene
Diastereoisomers
o-Chlorotoluene 1-chloro-2-
These are optical isomers that are not mirror images methylbenzene
of each other.
3. FORMATION OF HALOALKANES
Benzyl chloride a -Chlorotoluene/
RH + X 2 $ R - X + HX Chloromethyl
1. Halogen derivatives of alkanes are called benzene
haloalkanes. For e.g., X - CH 3 .
6.5 Mechanism of Nucleophilic Substitution Reactions 3. Higher level of methylene chloride in air causes
dizziness, nausea, tingling and numbness in
S N1 S N2 fingers and toes.
4. In humans, direct skin contact with methylene
1. Nucleophilic substitution Nucleophilic substitution chloride causes intense burning and mild redness
is uni-molecular. is bimolecular. of the skin, direct contact with eyes can also burn
2. It takes place in two It takes place in one the cornea.
steps. step.
7.2 Trichloromethane (Chloroform)
3. They are first order They are mostly
reactions. second order reactions. Applications
1. Chloroform is employed as a solvent for fats,
4. It leads to It leads to inversion of
alkaloids and other substances.
racemisation. configuration.
2. In the production of refrigerant, freon R-22.
Step:1
Harmful Effects of Chloroform
(CH 3) 3 CBr (Reactant)
1. Breathing of even about 900 parts of chloroform
per million parts of air for a short period of time
can cause dizziness, fatigue and headache.
2. Chronic chloroform exposure may cause damage
to the liver and kidneys.
3. Chloroform is slowly oxidised by air in the presence
Step:2 of light to an extremely poisonous gas named
carbonyl chloride, also known as phosgene. It is
therefore stored in closed dark coloured bottles
completely filled so that air can be kept out.
7.3 Tri-iodomethane (Iodoform)

6.6 Wurtz-Fitting Reaction
A yellow volatile solid sweet smelling haloform, made
by the haloform reaction.
Application
It was earlier used as an antiseptic. Due to its
objectionable smell, it has been replaced by other
formulations containing iodine.
7. POLYHALOGEN COMPOUNDS 7.4 Tetrachloromethane (Carbon tetrachloride), CCl 4
Carbon compounds containing more than one A colourless volatile liquid with a characteristic colour,
halogen atom are usually referred to as polyhalogen virtually soluble in water but it is miscible with many
compounds. organic liquids, such as ethanol and benzene.
7.1 Dichloromethane Applications
1. Used in the manufacture of refrigerants and
Applications
propellants, for example aerosol.
1. Widely used as a solvent as a paint remover and 2. In the synthesis of chlorofluorocarbons and other
as a processing solvent in the manufacture of chemicals.
drugs.
3. It is widely used as a cleaning fluid.
2. It is also used in metal cleaning and as a finishing
4. It is also used as a fire extinguisher.
solvent.
Harmful Effects of CCl 4
Harmful Effects of Dichloromethane
1. Most common effects are dizziness, slight
1. Methylene chloride can severely harm the human
headache, nausea and vomiting, which an even
central nervous system.
cause permanent damage to the nerve cells.
2. Exposure to lower level of methylene chloride
2. Exposure to CCl 4 can make the heart beat
in air can lead to slightly impaired hearing and
irregular or even stops it.
vision.
of carbocation. Here 1c alkyl group has only

one alkyl group. Hence it is hardly form 1c
carbocation by SN1 reaction. Instead it will prefer
SN2 reaction and avoid the formation of unstable
carbocation.
6. Alkyl halide is converted into an alcohol by :
(a) Addition reaction
(b) Substitution reaction
(c) Elimination reaction
(d) Dehydrohalogenation reaction
Alkyl halides are converted into alcohols by
substitution reaction. When alkyle halides are treated 9. Ethyl acetate reacts with CH 3 MgBr to form :
with aqueous KOH, alcohols are formed. This is a (a) Secondary Alcohol (b) Tertiary Alcohol
nucleophilic substitution reaction. Equation for the (c) Primary Alcohol (d) Carboxylic Acid
reaction is as follows : Ans : COMP 2017
aq. KOH
R-X R - OH
7. Which of the following reactions is an example of
nucleophilic substitution reaction ?
(a) 2RX + 2NA " R - R + 2NaX
(b) RX + H 2 " RH + HX
(c) RX + Mg " RH + HX
(d) RX + KOH " ROH + KX
Ans : FOREIGN 2000
In nucleophilic substitution, a nucleophile provides an

electron pair to the substrate and the leaving group
departs with an electron pair.
These are usually written as S N (S stands for

substitution and N for nucleophilic) and are common
in aliphatic compounds especially in alkyl halides and
acyl halides. Thus (b) is correct option.
Thus (d) is correct option. 10. Which of the following possesses highest melting
8. Chlorobenzene give DDT when it reacts with : point?
(a) charcoal (b) chloral (a) Chlorobenzene (b) m -dichlorobenzene
(c) naphthalene (d) benzenoid (c) o -dichlorobenzene (d) p -dichlorobenzene
Ans : DELHI 2009

Ans : FOREIGN 2005
DDT is synthesised by heating a mixture of chloral Para-di-chlorobenzene has most symmetrical structure
(1 mol) with chlorobenzene (2 mol) in the presence of than others. It is found as crystalline lattice form,
concentrated H 2 SO 4 therefore, it has highest melting point (52cC) due to
symmetrical structure.
Page 294 Haloalkanes and Haloarenes Chap 6
13. obtained by chlorination of
n- butane, will be
(a) l -form (b) d-form
(c) Meso form (d) Racemic mixture
Ans : SQP 2017
Thus (d) is correct option. Chlorination of n- butane taken place via free radical
formation i.e.,
11. Which one is most reactive towards S N 1 reaction?
(a) C 6 H 5 CH (C 6 H 5) Br
(b) C 6 H 5 CH (CH 3) Br
(c) C 6 H 5 C (CH 3) (C 6 H 5) Br
(d) C 6 H 5 CH 2 Br
Ans : OD 2008
S N 1 reactions involve the formation of carbocations,

hence higher the stability of carbocation, more will
Cl $ may attack on either side and give a racemic
be reactivity of the parent alkyl halide. Thus tertiary
mixture of 2 chloro butane which contain 50% d-form
carbocation formed from (c) is stabilized by two phenyl
and 50% l -form.
groups and one methyl group, hence most stable.
14. A Grignard reagent may be made by reacting
12. In a S N 2 substitution reaction of the type
magnesium with
R - Br + Cl- $ R - Cl + Br- (a) Methyl amine (b) Diethyl ether
which one of the following has the highest relative (c) Ethyl iodide (d) Ethyl alcohal
rate?
Ans : COMP 2011
(a) CH 3 - CH 2 - CH 2 Br
Dry
CH 3 CH 2 l + Mg Ether
CH 3 CH 2 Mgl
(b) Ethyl magnesium
iodide
15. Benzene reacts with n- propyl chloride in the presence

(c) of anhydrous AlCl 3 to give
(a) 3-Propyl - 1 - chlorobenzene
(d) CH 3 CH 2 Br (b) n-Propylbenzene
Ans : SQP 2015, OD 2011 (c) No reaction
2
The rate of S N substitution reaction is maximum in (d) Isopropylbenzene
case of CH 3 CH 2 Br because S 2N mechanism is followed
Ans : DELHI 2007
in case of primary and secondary halides i.e., S 2N
reaction is favoured by small groups on the carbon Anhyd.
atom attached to halogens so C 6 H 6 + CH 3 CH 2 CH 2 Cl AlCl 3
16. Which chloro derivative of benzene among the

following would undergo hydrolysis most readily
with aqueous sodium hydroxide to furnish the
Thus (d) is correct option. corresponding hydroxy derivative?
23. Oxidation of primary alcohols with chlorine yields 26. Chloropicrin is obtained by the reaction of
(a) Acyl chloride (b) Alkyl chloride (a) steam on carbon tetrachloride
(c) Aldehyde (d) Ketone (b) nitric acid on chlorobenzene
Ans : COMP 2009 (c) chlorine on picric acid
Primary alcohol on oxidation produce an aldehyde. (d) nitric acid on chloroform
X2 {O}
ROH RX -2HX
RCHO Ans : SQP 2017
Pri.Chloride Aldehyde
Chloropicrin is nitrochloroform. It is obtained by the
Thus (c) is correct option. nitration of chloroform with HNO 3 .
24. The replacement of chlorine of chlorobenzene to give HNO 3
phenol requires drastic conditions, but the chlorine of HCCl 3 O 2 NCCl 3
Chloroform Chloropicrin
2,4-dinitrochlorobenzene is readily replaced since,
Chloropicrin is a liquids, poisonous and used as an
(a) nitro groups make the aromatic ring electron rich insecticide and a war gas.
at ortho/para positions.
(b) nitro groups withdraw electrons from the meta
27. Bromine gives substitution reaction products with
positions of the aromatic ring.
benzene readily in presence of
(c) nitro groups donate electrons at meta position. (a) Sunlight
(d) nitro groups withdraw electrons from ortho/para (b) Platinum
positions of the aromatic ring.
(c) FeBr3 at 35c C
Ans : SQP 2014
(d) FeBr3 at high temperature
- NO 2 group is electron attractive group, so it is able
to deactivate the benzene ring. Ans : COMP 2001

28. Haloforms are trihalogen derivatives of
Hence withdraw of electrons from ortho & para (a) Ethane (b) Methane
position cause easy removal of - Cl atom due to (c) Propane (d) Benzene
development of + ve charge on o - and p positions. Ans : DELHI 2003
Thus (d) is correct option. Haloform compounds with the formula CHX 3 , where
25. Which of the following is responsible for depletion of X is a halogen atom.
the ozone layer in the upper strata of the atmosphere? Haloforms are trihalogen derivatives of methane.
(a) Polyhalogens (b) Ferrocene Example : Chloroform CHCl 3 .
(c) Fullerens (d) Freons Thus (b) is correct option.
Ans : OD 2017, DELHI 2011 29. Which of the following compounds is used as a
Chloroflurocarbons, e.g. CF2 Cl 2 , CHF2 Cl 2, refrigerant?
HCF2 CHCl 2 . These are non-inflammable colour (a) Acetone (b) CCl 4
less and stable upto 550cC . These are emitted as (c) CF4 (d) CCl 4 F2
propellants in aerosol spray, cans refrigerators, fire
fighting reagents etc. They are chemically inert and Ans : FOREIGN 2008
hence do not react with any substance with which Under ordinary conditions freon is a gas. Its boiling
they come in contract and therefore float through the point is - 29.8cC . It can easily be liquefied. It is
atmosphere. There they absorb UV-rays and due to chemically inert. It is used in air-conditioning and
this they produce free atomic chlorine which cause in domestic refrigerators for cooling purposes (as
depletion of ozone layer. refrigerant)
Thus (d) is correct option. Thus (d) is correct option.
Hence B - I being a weakest bond break most easily.

Hence R - I is most reactive.
41. When CH 3 CH 2 CHCl 2 is treated with NaNH 2 , the
product formed is
(a) CH 3 - CH = CH 2
(b) CH 3 - C / CH
(c) CH 3 - C / CH 2
(d) CH 3 - CH / CH
Ans : OD 2016
NaNH 2
CH 3 - CH 2 - CHCl 2 O
NaNH 2
CH 3 - CH = CHCl CH 3 - C / CH
Thus (c) is correct option. O
Final Product
39. An organic compound A(C 4 H 9 Cl) on reaction with
Na/diethyl ether gives a hydrocarbon which on 42. Identify X , Y , Z in the following series
monochlorination gives only one chloro derivative, alc $ KOH Br2 KCN
C2H5I X Y Z
then A is
(a) tert-butyl chloride (b) sec-butyl chloride (a) BrCH 2 CH 2 Br
(c) isobutyl chloride (d) n-butyl chloride (b) BrCH 2 CH 2 CN
Ans : FOREIGN 2000

(c) CN - CH 2 - CH 2 - CN
(d) Br - CH - CH - CN
Ans : SQP 2000

43. Industrial preparation of chloroform employs acetone
and
(a) Phosgene
(b) Calcium hypochlorite
40. Reactivity order of halides for dehydrohalogenation is
(a) R - F > R - Cl > R - Br > R - I (c) Chlorine gas
(b) R - I > R - Br > R - Cl > R - F (d) Sodium chloride
(c) R - I > R - Cl > R - Br > R - F Ans : COMP 2006, OD 2014
By distilling ethanol or acetone with a paste of

(d) R - F > R - I > R - Br > R - Cl
bleaching powder (laboratory and commercial
Ans : SQP 2006 method).
The order of atomic size of halogens decrease in the CaOCl 2 + H 2 O $ Ca (OH) 2 + Cl 2
order I > Br > Cl > F
Cl 2 , so obtained acts as a mild oxidising as well as
i.e. on moving down a group atomic size increases.
chlorinating agent
Further the bond length of C - X
(a) CH 3 COCH 3 + 3Cl 2 $
bond decreases in the order
C - I > C - Br > C - Cl > C - F CCl 3 $ CO $ CH 3 + 3HCl (Chlorination)
and hence the bond dissociation energy decreases in (b) 2CCl 3 $ CO $ CH 3 + Ca (OH) 2 $
the order 2CHCl 3 + (CH 3 COO) 2 Ca (Hydrolysis)
R - F > R - Cl > R - Br > R - I Thus (b) is correct option.
50. Which of the following will have the maximum dipole 54. The number of structural and configurational isomers
moment? of a bromo compound C 5 H 9 Br , formed by the addition
(a) CH 3 F (b) CH 3 Cl of HBr to 2-pentyne respectively
(c) CH 3 Br (d) CH 3 I (a) 1 and 2 (b) 2 and 4
(c) 4 and 2 (d) 2 and 1
Ans : OD 2015
CH 3 Cl has higher dipole moment than CH 3 F due Ans : FOREIGN 2002
to much longer C - Cl bond length than the C - F Addition of HBr of 2-pentyne gives two structural
bond. The much longer bond length of the C-C isomers (I) and (II)
bond outweighs the effect produced by lower electro- CH 3 - C = C - CH 2 CH 3
HBr
CH 3 C (Br) = CHCH 2 CH 3
negativity of Cl than that of F. (I)
+ CH 3 CH = C (Br) CH 2 CH 3
Thus (b) is correct option. (II)
51. The reaction conditions leading to the best yields of Each one of these will exist as a pair of geometrical
C 2 H 5 Cl are isomers. Thus, there are two structural and four
uv light configurational isomers.
(a) C 2 H 6 (excess) + Cl 2
dark
(b) C 2 H 6 + Cl 2 room temperature 55. Zerevitinov’s determination of active hydrogen in a
(c) C 2 H 6 + Cl 2 (excess)
uv light compound is based
(a) Na (b) CH 3 Mgl
uv light
(d) C 2 H 6 + Cl 2 (c) Zn (d) Al
Ans : SQP 2002
Chlorination beyond monochlorination during the Number of active hydrogen in a compound corresponds
preparation of alkyl halides in presence of UV light to the number of moles of CH 4 evolved per mole of
can be suppressed by taking alkane in excess. the compound.
Thus (a) is correct option. - OH , - NH 2 , - SH , - OH or
52. The reaction of toluene with chlorine in presence of CH 3 MgI
- C = CH CH 4 - (2CH 4 from - NH 2)
ferric chloride gives predominantly
(a) benzoyl chloride
56. 2-Bromopentane is heated with potassium ethoxide in
(b) m -chlorotoluene
ethanol. The major product obtained is
(c) benzyl chloride
(a) 2-ethoxypentane (b) pentene-1
(d) o - and p - chlorotoluene (c) trans-2-pentene (d) cis-pentene-2
The given reaction is an example of electrophilic Potassium ethoxide is a strong base and
substitution. Further, CH 3 group in toluene is o , p 2-bromopentance is a 2c bromide, so elimination
-directing reaction predominates
Thus (d) is correct option. CH 3 CH (Br) CH 2 CH 2 CH 3
53. A salt solution is treated with chloroform drops. Then OC 2 H -5
CH 3 CH = CHCH 2 CH 3 + CH 2 = CHCH 2 CH 2 CH 3
it is shaken with chlorine water. Chloroform layer Pentene - 2 (major) trans Pentene - 1 (min or) cis
becomes violet. Solution contains. Since trans - alkene is more stable than cis. Thus
(a) NO -2 ion (b) NO -3 ion trans - pentene-2 is the main product.
(c) Br- ion (d) I- ion
Ans : DELHI 2015
57. C - X bond is strongest in
Cl 2 water being aqueous and CHCl 3 being organic (a) CH 3 Cl (b) CH 3 Br
form two layers. Cl 2 water oxidizes I- " I 2 which (c) CH 3 F (d) CH 3 I
shows its colour (violet) in organic layer (CHCl 3). Ans : COMP 2001
This is layer test which is used for detection of I- and
Because of the small size of F, the C-F bond is
Br- in a solution. Br+ gives brown layer.
strongest in CH 3 F .
Ans : OD 2008

In this reaction both hydrogen and halogen atom has
72. The above structural formula refers to
been removed so it is known as dehydro halogenation
reaction.
68. Which of the following alkyl halides is used as a
methylating agent
(a) C 2 H 5 Br (b) C 6 H 5 Cl
(c) CH 3 I (d) C 2 H 5 Cl (a) BHC (b) DNA
Ans : SQP 2017

(c) DDT (d) RNA
C 2 H 5 Br and C 6 H 5 Cl are ethyl letting agents, while Ans : OD 2016
C 6 H 5 Cl is inert. Thus (c) is correct option.

Thus (c) is correct option. 73. The reaction of toluene with Cl 2 in presence of FeCl 3
69. Which of the following is not used in Friedel-Crafts gives X and reaction in presence of light gives Y .
reaction? Thus, X and Y are
(a) N-Phenyl acetanilide (b) Bromobenzene (a) X = Benzal chloride,
(c) Benzene (d) Chlorobenzene Y = o -chlorotoluene
Ans : COMP 2009 (b) X = m - Chlorotoluene
N-Phenyl acetanilide, C 6 H 5 N (C 6 H 5) COCH 3 , Y = p -Chorotoluene
precipitates out to a complex with anhydrous AlCl 3 .
(c) X = o -and p -Chlorotoluene
Y = Trichloromethyl-benzene
70. A set of compounds in which the reactivity of halogen
(d) X = Benzyl chloride
atom in the ascending order is
(a) chlorobenzene,vinyl chloride, chloroethane Y = m -Chlorotoluene
(b) chloroethane, chlorobenzene, vinyl chloride Ans : SQP 2010
(c) vinyl chloride, chlorobenzene, chloroethane

(d) vinyl chloride, chloroethane, chlorobenzene
On the same basis as above

CH 3 CH 2 Cl > CH 2 = CHCl > C 6 H 5 Cl
71. Mg reacts with RBr best in
(a) C 2 H 5 OC 2 H 5
(b) C 6 H 5 OCH 3
(c) C 6 H 5 N (CH 3) 2
74. Which one of the following is most reactive towards
(d) Equally in all the three nucleophilic substitution reaction?
Ans : FOREIGN 2000 (a) CH 2 = CH - Cl (b) C 6 H 5 Cl
Although all the three compounds can be used (c) CH 3 CH = CH - Cl (d) ClCH 2 - CH = CH 2
for preparing Grignard reagents, diethyl ether is
considered as the best because it provides electron Ans : COMP 2013
pairs to Mg of the reagent fully for coordination, in More the stability of the carbecation, higher will be
case of C 6 H 5 OCH 3 and C 6 H 5 N (CH 3) 2 electron pair the reactivity of the parent chloride. Allylchloride>
on O and N are partialy delocalised over the benzene Vinyl chloride > Chlorobenze
and hence are less available for coordination with Mg. Thus (d) is correct option.
81. Assertion : CHCl3 is stored in dark bottles. 84. Assertion : Reimer-Tiemann reaction of phenol with
Reason : CHCl3 is oxidised in dark. CCl4 in NaOH at 340 K gives salicylic acid as the
(a) Both Assertion and Reason are correct and major product.
Reason is a correct explanation of the Assertion. Reason : The reaction occurs through intermediate
formation of dichlorocarbene.
is not the a correct explanation of the Assertion. (a) Both Assertion and Reason are correct and
(d) Both the Assertion and Reason are incorrect. is not the a correct explanation of the Assertion.
Ans : SQP 2015
CHCl3 is stored in dark bottles to prevent oxidation of
CHCl3 in-presence of sunlight.
Thus (c) is correct option. Ans : OD 2006
Dichlorocarbene (CCl2) attacks on the orthodox-

82. Assertion : SN2 reaction of an optically active aryl
position of the phenol-ate ion to form an intermediate
halide with an aqueous solution of KOH always gives
which on hydrolysis gives salicylic acid.
an alcohol with opposite sign of rotation.
Reason : SN2 reactions always proceed with retention
of configuration. 85. Assertion : Alkyl iodide can be prepared by treating
(a) Both Assertion and Reason are correct and alkyl chloride/bromide with NaI in acetone.
Reason is a correct explanation of the Assertion. Reason : NaCl/NaBr are soluble in acetone while NaI
is not.
is not the a correct explanation of the Assertion. (a) Both Assertion and Reason are correct and
Ans : OD 2020
Assertion if false, because aryl halides do not undergo
nucleophilic substitution under ordinary conditions.
This is due to resonance, because of which the carbon Ans : DELHI 2009
chlorine bond acquires partial double bond character, Alkyl halides on treatment with NaI in presence of
hence it becomes shorter and stronger and thus acetone forms alkyl iodide. This is called Finkelstein
cannot be replaced by nucleophiles. Also, Reason is reaction.
false because SN2 reactions proceeds with inversion R - X + NaI
acetone
R - I + NaX
of configuration.
Here NaI is soluble in acetone but NaBr/NaCl are not
soluble. Hence due to precipitation of slat, equilibrium
83. Assertion : Alkyl-benzene is not prepared by Friedel- is shifted to forward direction. Hence assertion is true
Crafts alkylation of benzene. but reason is false.
Reason : Alkyl halides are less reactive than acyl Thus (c) is correct option.
halides.
86. Assertion : SN2 reactions always proceed with
(a) Both Assertion and Reason are correct and inversion of configuration.
Reason : SN2 reaction of an optically active aryl
(b) Both Assertion and Reason are correct but Reason halide with an aqueous solution of KOH always gives
is not the a correct explanation of the Assertion. an alcohol with opposite sign of rotation.
(d) Both the Assertion and Reason are incorrect. Reason is a correct explanation of the Assertion.
Ans : DELHI 2013 (b) Both Assertion and Reason are correct but Reason
Alkyl halides give polyalkylation products. is not the a correct explanation of the Assertion.
Thus (c) is correct option. (c) Assertion is correct but Reason is incorrect.
93. Draw the structure of 2-bromopentane. 98. Write the IUPAC name of the following compound.
Ans : SQP 2015
Ans : OD 2010
94. Write the IUPAC name of ^CH 3h2 CH .CH ^Clh CH 3 .
Ans : DELHI 2019
99. Write the IUPAC name of the following compound.
95. Write the IUPAC name of the following compound

CH 2 = CHCH 2 Br .
Ans : DELHI 2018
96. Write the IUPAC name of

CH 3 - CH - CH 2 - CH = CH 2
y Numbering will be done in alphabetically manner.
Cl
100. A hydrocarbon C 5 H 12 gives only one monochlorination
Ans : DELHI 2002
product. Identify the hydrocarbon.
Ans : COMP 2003
Hydrocarbon which gives only one monochlorination

product is
(As double bond is given preference over halogen)

97. Write the IUPAC name of
101. Draw the structure of the following compound:

3-(4-chloropheny1)-2-methylpropane
Ans : FOREIGN 2014
Ans : FOREIGN 2006

Ans : COMP 2003

114. Complete the following chemical equation, Peroxide
Ans : SQP 2001

Peroxide
CH 3 CH 2 CH = CH 2 + HBr
CH 3 - CH 2 - CH 2 - CH 2 Br
1 - bromobu tane (Major)
111. Give the IUPAC name of the following compound.
+ CH 3 - CH 2 - CH ^Brh CH 3
^Minorh
115. Write the IUPAC name of ClCH 2 C / CCH 2 Br .

Ans : OD 2004
Ans : DELHI 2005
116. Draw the structure of the following compound

4-bromo-3 -methylpent-2-ene.
Ans : COMP 2014
112. Write the IUPAC name of the following compound:
117. Draw the structure of the compound, 1-chloro-4-

ethylcyclohexane.
Ans : OD 2012
118. Write the balanced chemical equation for ethyl

113. Write a chemical reaction in which the iodide ion chloride treated with alcoholic potassium hydroxide.
replaces the diazonium group in a diazonium salt. Ans : OD 2019
Ans : COMP 2008 When ethyl chloride is treated with alcoholic KOH, it
undergoes elimination reaction to form ethene.
C 2 H 5 Cl + alc. KOH $ C 2 H 4 + KCl + H 2 O
119. What will be the product formed when chlorobenzene

is heated with sodium metal in the presence of dry
ether?
Ans : COMP 2018
Chlorobenzene is heated with sodium metal in the

presence of dry ether gives diphenyl compound.
Ans : OD 2010
When iodo-form is heated with silver powder,

acetylene (ethyne) is formed.
CH 3 I + 6Ag + CH 3 I $ CH / CH + 5AgI
Acetylene
126. Out of ethyl bromide and ethyl chloride which has

higher boiling point and why?
120. Give the balanced equation for the following name Ans : OD 2000
reaction.
The boiling point of ethyl bromide is higher due to
Wurtz-Fittig reaction
greater magnitude of the van der Waals’ forces which
Ans : DELHI 2016
depends upon molecular size of the halogen atom.
127. What are polyhalogen compounds? Give examples.
Ans : COMP 2012
Carbon compounds containing more than one halogen

121. How can the following conversions be brought about ? atom are called polyhalogen compounds, example is
Chlorobenzene to phenol chloroform, Iodoform.
Ans : COMP 2015 128. Which isomer of C 5 H 10 gives a single monochloro
compound C 3 H 9 Cl in bright sunlight ?
Ans : COMP 2023
The isomer of C 5 H 10 gives a single monochloro

compound C 5 H 9 Cl in bright sunlight is cyclopentane.
This reaction is an example of photo chlorination
where chlorine react with cyclopentane in presence of
sunlight to form a single monochloro compound.
122. Write the chemical equation for the following reaction
129. Arrange the following compounds in increasing order
Acetone with sodium hypoiodite.
of reactivity towards SN 2 reaction :
Ans : OD 2005
2-Bromopentane, 1-Bromopentahe, 2-Bromo-2-
In the preparation of iodoform, sodium hypoiodite can
methylbutane.
also be used in place of sodium hydroxide with acetone.
CH 3 COCH 3 + 3NaOI $ CH 3 COCl 3 + 3NaOH
The order of reactivity towards S N 2 reaction is as
CH 3 COCI 3 + NaOH $ CH 3 COONa + CHI 3 follows :
1-Bromopentane < 2-Bromopentanc < 2-Bromo-2-
123. Draw the structure of the following organic compound: methylbutane
2-chloro-3-methylpentane.
This is because the reactivity order of S N 2 reaction is
Ans : FOREIGN 2012
1° 2 2° 2 3°
130. Why p -dichlorobenzene has higher melting point than
those of ortho- and meta-isomers ?
Ans : COMP 2023
This is because p -isomer is more symmetrical i.e.

more closely packed arrangement of molecules in the
crystal lattice.
124. Out of ethyl bromide and ethyl chloride, which has
higher boiling point and why? 131. Identify A and B in the following :
Ans : COMP 2001
For the same alkyl group, boiling point increases with

the size of the halogen atom. Thus, boiling point of
ethyl bromide is higher than ethyl chloride.
125. What happens when iodo-form is heated with silver
powder? Write the chemical equation.
137. Explain as to why haloarenes are much less reactive (ii) Diastereoisomers : Those pairs of stereoisomers
than haloalkanes towards nucleophilic substitution which are not mirror images of each other and
reactions. differ in optical rotation.
Ans : FOREIGN 2005 Enantiomers : They are non-superimposable
Haloarenes are much less reactive than haloalkanes mirror images of molecules with each other. They
towards the nucleophilic substitution reactions due to have optical rotation equal in magnitude but
the following reasons: opposite in sign.
(i) Resonance Effect : In haloarenes the electron pair 140. Does the presence of two chiral carbon atoms always
on the halogen atom is in conjugation with the p make the molecule optically active? Explain giving an
-electrons of the ring and the following resonating example.
structures are possible. Ans : DELHI 2010
No the presence of two chiral carbon atoms not always

make the molecule optically active. For example, meso-
tartaric acid is optically inactive because if upper half of
molecule rotates the plane polarised light towards the
left, then lower half rotate it towards the right, such that
net optical rotation is zero due to internal compensation.
C - Cl bond acquires a partial double bond
character due to resonance. As a result, the bond
cleavage in haloarene is difficult than in case of
haloalkanes and therefore, they are less reactive
towards nucleophilic substitution reaction.
(ii) The C - Cl bond length in haloalkane is 177 pm
while in haloarene is 169 pm. Since it is difficult to
break shorter bond than a longer bond. Therefore,
haloarenes are less reactive than haloalkanes
(iii) Phenyl cation is less stable than the alkyl 141. Account for the following:
carbocation. The treatment of an alkyl chloride with aqueous KOH
leads to the formation of alcoholic whereas in the
138. Complete the following reaction equations : presence of alcoholic KOH, alkene is the major product.
(i) C 6 H 5 N 2 Cl + KI $ Ans : DELHI 2001
Aqueous KOH gives OH- ions which can replace

(ii) .................. Cl- ions and carry out the nucleophilic substitution
Ans : SQP 2012
reaction, whereas alc. KOH gives C 2 H 5 O- which is
a stronger nucleophile and abstracts H+ from the b
(i) C 6 H 5 N 2 Cl- + KI $ C 6 H 5 I + KCl + N 2
carbon atom and carry out the elimination reaction,
thus leading to the formation of an alkene.
(ii)
142. Write the structure of the main product:
(i) Chlorination of benzene in the presence of UV
139. Point out the difference between: light.
(i) Chirality and chiral centre. (ii) Propene is treated with HBr is presence of benzoyl
(ii) Diastereoisomers and Enantiomers. peroxide.
Ans : FOREIGN 2018, OD 2011 (iii) Chlorobenzene is treated with NaOH at 623 K
(i) Chirality : The phenomena of a molecule containing and high pressure.
a carbon atom attached to four different atoms Ans : SQP 2006
or groups of atom and thus making the mirror
image of the molecule non-superimposable on the
molecule is called chirality. (i)
Chiral Centre : The carbon atom which is
attached to four different atoms or groups of
atoms is called the chiral centre.
Ans : OD 2011
(ii)
(i)
(iii)
(ii)
(iv)
155. Which one of the following has the highest dipole

moment?
(i) CH 2 Cl 2
152. Give the reason of dipole in C - X bond.
(ii) CHCl 3
Ans : SQP 2019
Since halogen atoms are more electronegative than (iii) CCl 4

carbon, the carbon halogen bond is polarized; the Ans : COMP 2008
carbon atom bears a positive charge whereas the

halogen atom bears a partial negative charge.
153. Which would undergo S N 1 reaction faster in the

following pair and why?
156. How Alkyl halides are prepared from alcohols?
Ans : DELHI 2015, COMP 2005
The hydroxyl group of an alcohol is replaced by

halogen on reaction with concentrated halogen acids,
phosphorous halides or thionyl chloride.
Ans : FOREIGN 2011 ZnCl 2
R - OH + HCl R - Cl + H 2 O
3° carbocation > 2° carbocation > 1° carbocation
ZnCl 2
> CH +3 . Therefore, the reactivity of alkyl halides C 2 H 5 OH + HCl C 2 H 5 Cl + H 2 O
towards S N 1 reactions decreases in the same order.
3CH 3 OH + PCl 3 $ 3CH 3 Cl + H 3 PO 3
Among the given compounds bromoethane is primary
alkyl halide which forms a 1° carbocation intermediate C 2 H 5 OH + PCl 5 $ C 2 H 5 Cl + POCl 3 + HCl
in the S N 1 reaction. The other compound is 2-chloro red P/X
2-methylpropane which is a tertiary alkyl halide which C 2 H 5 OH X 2 = Br2, I 2
R-X
forms a tertiary carbocation intermediate in the S N 1 C 2 H 5 OH + SOCl $ C 2 H 5 Cl + SO 2 - + HCl -
2
reaction. Ethanol Thionyl chloride Chloroethane
Hence, 2-bromo-2-methylpropane undergoes an S N 1 Preparation with thionyl chloride is preferred because

reaction faster than bromoethane. the other two products SO 2 and HCl are escapable
154. Write the isomers of the compound having formula gases.
C 4 H 9 Br . 157. Complete the following reactions:
Ans : FOREIGN 2002 Cl 2 /UV light
(i) CH 3 CH 2 CH 2 CH 3
C 4 H 9 Br follows the formula C n H 2n + 1 Br (Saturated
Compound). The compound has four isomers,
(i) (ii)
163. Of the two bromo derivatives C 6 H 5 CH (CH 3) Br and

C 6 H 5 CH (C 6 H 5) Br , which one is more reactive in S N 1
substitution reaction and why?
Ans : SQP 2002
In S N 1 reactions, reactivity depends upon the stability

167. Write the structural formula of the organic compounds
of the intermediate carbocation.
A, B, C and D in the following sequence of reaction:
Ans : DELHI 2014
The carbocation (b) is stabilised by + R effect of the

two C 6 H 5 -group but the carbocation (a) is stabilized
by + R effect of one C 6 H 5 group and + I effect of the
- CH 3 group. Since + R effect is much stronger than
+ 1 effect, therefore carbocation (b) is more stable
than carbocation (a). Thus C 6 H 5 CH (C 6 H 5) Br is more
reactive than C 6 H 5 CH (CH 3) Br in S N 1 substitution
reaction.
164. What is a racemic mixture? Give one example.
Ans : SQP 2007, OD 2005
A 50 : 50 mixture of two enantiomers of any optically

active compound is called a racemic mixture. It is
optically inactive. Since rotation caused by the molecules
of one enantiomer is exactly cancelled by equal and 168. A hydrocarbon C 5 H 10 does not react with chlorine
opposite rotation caused by the same molecules of the but gives a single monochloro compound C 5 H 9 Cl in
other enantiomers. For example an equimolar mixture bright sunlight. Identify the hydrocarbon.
of (+)-2-bromobutane and (-)-2- bromobutane. Ans : SQP 2004
165. Which compound in each of the following pairs will Hydrocarbon C 5 H 10 follow C n H 2n , it may be an alkene
react faster in S N 2 reaction with OH- ? or cycloalkane.
(i) CH 3 Br or CH 3 I Since the hydrocarbon does not react with Cl 2 in the
absence of bright sunlight, it cannot be an alkene but
(ii) (CH 3) 3 CCl or CH 3 Cl must be a cycloalkane.
Ans : DELHI 2013 Because C 5 H 9 Cl is a single monochloro compound,
(i) Since I ion is a better leaving group than Br-
-
therefore, all the ten hydrogen atoms of the
ion, therefore CH 3 I reacts faster than CH 3 Br in cycloalkane must be equivalent, hence the cycloalkane
S N 2 reaction with OH- ion. is cyclopentane.
(ii) 1° alkyl halides are more reactive than tert-
alkyl halides in S N 2 reaction on steric ground.
Therefore CH 3 Cl will react at a faster rate than
(CH 3) 3 CCl in a S N 2 reaction with OH- ion.
166. A small amount of ethanol is usually added to
chloroform bottles. Why?
Ans : DELHI 2009 169. The treatment of alkyl chloride with aqueous KOH
0.6-1% ethanol is added to chloroform bottle because leads to the formation of alcohols but in presence
ethanol combines with the poisonous phosgene gas of alcoholic KOH, alkenes are the major products.
and convert it into non-toxic diethyl carbonate. Explain why?
176. How will you convert CH 3 - CH 2 - Br into following? LONG ANSWER QUESTIONS
(i) CH 3 - CH 3
(ii) C 2 H 5 - O - C 2 H 5 179. What are haloalkanes and haloarenes? Give their
(iii) CH 3 - CH 2 - CN classification.
Ans : OD 2017 Ans : FOREIGN 2015
(i) Reduction : When one or more hydrogen atoms of aliphatic or
Ni
CH 3 CH 2 Br + H 2 T
CH 3 CH 3 + HBr . aromatic hydrocarbon are replaced by halogen
(ii) By Williamson’s Synthesis Method : atom (s), alkyl halide (haloalkane) and aryl halide
(haloarene) are formed respectively.
+
T
CH 3 CH 2 Br + C 2 H 5 O- Na C 2 H 5 OC 2 H 5 + NaBr Classification
(iii) By the use of KCN : Haloalkanes and haloarenes may be classified as
CH 3 CH 2 Br + KCN $ CH 3 CH 2 CN + KBr follows:
(i) On the Basis of Number of Halogen Atoms :
177. Chloroform is stored in dark coloured bottles Depending upon number of halogen atoms (F,
completely filled so that air is kept out. Explain. Cl, Br, I) they are classified as mono, di or poly
Ans : SQP 2001 halogen compounds. For example,
Chloroform is stored in dark coloured bottles because
it is oxidised by air in presence of flight to form
an extremely posionous gas carbonyl chloride or
phosgene.
178. The presence of electron withdrawing group at

ortho and para positions increases the reactivity of
haloarenes toward nucleophilic substitution reaction.
Explain.
Ans : COMP 2019
The presence of electron with drawing group such

as, - NO 2 , - CN at O- and p -position withdraws
electrons from the benzene ring thus facilitates d, e, f are types of arylhalide or haloarene in
the attract of the nucleophile on haloarene. The which-X is attach to an aromatic ring.
carbocations thus formed is stabilized by resonance (ii) Compounds Containing sp3 C - X Bond
as shown below : (X = F, Cl, Br, I) :
(a) Alkyl Halides or Haloalkanes (R - X ) :
They are classified as primary, secondary and
tertiary according to the nature of carbon to
which halogen is attached.
(b) Allylic Halides : In these compounds halogen

atom is bonded to an sp3 hybridised carbon
atom next to carbon-carbon double bond
(C = C) i.e. to an allylic carbon.
(iii) Kharasch effect

(iv) Swarts reaction
(v) Finkelstein reaction
(vi) Hundsdiecker reaction
(vii) Sandmeyer reaction
(viii) Preparation of Iodobenzene
(c) Benzylic Halides : In these compounds the
(ix) Balz-Schiemann reaction
halogen atom is bonded to an sp3 -hybridised
carbon atom next to an aromatic ring. (x) Gattermann reaction.
Ans : COMP 2007
(i) Allylic Halogenation : Reactions in which
halogenation occurs at the allylic position of an
alkene are called allylic halogenation reaction. It
occurs in alkene other then ethene.
Example :
CH - CH = CH 2 + Cl 2 $
3
Propene
(iii) Compounds Containing sp2 C - X Bond :
Cl - CH 2 - CH = CH 2 + HCl
Vinylic Halides : In these compounds halogen 3 - Chloroprop - 1 - ene
atom is bonded to an sp2 hybridised carbon atom (ii) Markovnikov’s Rule : The addition of
of a carbon-carbon double bond (C = C). unsymmetrical reagents like HX, H 2 O etc. to
unsymmetrical alkenes occurs in such a way that
the negative part of adding molecule goes to that
carbon atom of the double bond which carries
lesser number of hydrogen atoms.
Example :
d+d-
180. Write IUPAC names of the following : CH 3 CH = CH 2 + HI $
CH 3 CH 2 CH 2 I + CH 2 CHICH 3
(Minor) (Major)
(i) (ii)
(iii) Kharasch Effect : In presence of peroxide like
benzoyl peroxide (C 6 H 6 CO - O - O - COC 6 H 5),
the addition of HBr to unsymmetrical alkenes
takes place opposite to Markovnikov’s rule. This
is known as Peroxide effect or Kharasch effect.
(iii) (iv)
Example :
(C 6 H 5 COO) 2
CH 3 CH = CH 2 + HBr CH 3 CH 2 - CH 2 Br
(Propene) 1 - Bromopropane
(iv) Swarts Reaction : Synthesis of alkyl fluoride

(v) (vi) (fluoroalkane) by heating an alkyl chloride/
bromide in the presence of metallic fluoride like
AgF, Hg 2 F2 or SbF3 is called Swarts reaction.
Ans : FOREIGN 2010, DELHI 2008 H 3 C - Br + AgF $ H 3 C - F + AgBr
(i) 4-Bromopent-2-ene (v) Finkelstein Reaction : Preparation of alkyl iodide
(ii) 3-Bromo-2-methylbut-1-ene by the reaction of alkyl chlorides/bromides with
(iii) 4-Bromo-3-methylpent-2-ene NaI in dry acetone is known as finkelstein reaction.
(iv) 1-Bromo-2-methylbut-2-ene 182. Write the following:
(v) 1-Bromobut-2-ene (i) Hundsdiecker reaction
(vi) 3-Bromo-2-methylpropene (ii) Sandmeyer reaction
181. Write the following: (iii) Preparation of Iodobenzene
(i) Allylic halogenation (iv) Balz-Schiemann reaction
(ii) Markovnikov’s rule (v) Gattermann reaction.
Ans : COMP 2007
(i) Hundsdiecker Reaction : (ii)

CCl 4, Reflux
CH 3 CH 2 COOAg + Br2
Silver propanoate
CH 3 CH 2 - Br + CO 2 + AgBr
Bromoethane
(ii) Sandmeyer Reaction : (iii)
(iv)
Ans : SQP 2016, OD 2014
(i)
(iii) Preparation of Iodobenzene :
(ii)
(iv) Balz-schiemann Reaction :

(iii)
(iv)
(v) Gattermann Reaction :
184. What do you mean by nucleophilic substitution

reactions? Give examples.
Ans : COMP 2018
When a nucleophile reacts with haloalkane (the

substrate) having a partial positive charge on the
carbon atom bonded to halogen. A substitution
reaction takes place and halogen atom called leaving
group departs as halide ion. Since the substitution
reaction is initiated by a nucleophile, it is called
183. Draw the structures of major monohalo products in nucleophilic substitution reaction.
each of the following:
(i)
Example : (a) CH 3 C / N + H 2 O
(i) conc. HCl
CH 3 CONH 2
(ii) H 2 O
Ethanenitrile Ethanamide
Reagent Nucleophile Substitution Class Dil. acid
(b) CH 3 - C / N + 2H 2 O CH 3 COOH + NH 3
(Nu - ) Product of Main Ethanenitrile Ethanoic acid
R-Nu Product Na/C 2 H 5 OH

(c) CH 3 - C / N + 4 [H] CH 3 CH 2 - NH 2
Ethanenitrile Ethanamine
NaOH or OH -
ROH Alcohol
KOH 186. Explain the mechanism of nucleophilic substitution
H2 O H2 O ROH Alcohol reactions.
Ans : DELHI 2008
NaOR' RO - ROR' Ether
There are two types of nucleophilic substitution reactions:
NaI I- R-I Alkyl iodide
(i) S N 2 (Substitution Nucleophilic Bimolecular)
NH3 NH3 R - NH3 Primary : The recation between methyl chloride and
amine hydroxide ion to form methanol and Cl- ion
R'NH2 R'NH2 RNHR’ Secondary follows second order kinetic.
amine Rate = K [CH 3 Cl] [OH-]
R'R''NH R'R''NH RNR'R'' Tert. amine When incoming nucleophile (OH- ) approaches the
KCN - C / N: RCN Nitrile alkyl halide C - Cl bond starts breaking and new
(Cyanide) C - OH bond starts forming. These two process
take place simultaneously in a single step and no
AgCN AgCN : RNC Isonitrile
(isocyanide) intermediate is formed, therefore S N 2 reactions
are concerted reactions i.e., take place in one step.
KNO2 O = N-O R-O-N = O Alkyl nitrite
AgNO2 Ag - O - N = O R - NO2 Nitroalkane
R'COOAg R'COO - R'COOR Ester
LiAlH 4 H- RH Hydrocarbon
R - M+ R'- RR’ Alkane The attack of nucleophile (OH- ) occurs from
the back side and the leaving group (Cl- ) leaves
185. Write the following: from the front side. As a result S N 2 reactions are
(i) Willamson synthesis always accompanied by inversion of configuration.
(ii) Reaction of alkyl halide with dry silver oxide This inversion is called Walden inversion. The
(iii) Uses of alkyl cyanides. reactivity in S N 2 depends upon steric hindrance;
more the steric hindrance slower the reaction.
Ans : FOREIGN 2003
(ii) S N 1 (Substitution Nucleophilic Unimolecular) :
(i) Willamson Synthesis :
S N 1 reactions are generally carried out in polar
protic solvents (like water, alcohol acetic acid
etc.). The reaction between tert-butyl bromide
and hydroxide ion (OH-) to form tert-butyl
alcohol and Br- ion follows I st order kinetics.
(ii) Reaction of Alkyl Halide with Dry Silver Oxide :
(iii) Use of Alkyl Cyanides : Alkyl cyanides R - CN It occurs in two Steps.

are very useful compounds since they can be Step I
converted into (i) amines on partial hydrolysis Tert-butyl bromide undergoes ionization to produce
with conc. HCl or conc. H 2 SO 4 followed by tert-butyl carbocation and bromide ion.
treatment with H 2 O (ii) Carboxylic acid on
complete hydrolysis with dilute mineral acids or
alkalies and (iii) primary amines by reduction
with sodium and alcohol or catalytically with H 2
/Ni or with LiAlH 4 .
This step is slow and reversible and hence it is the Ans : FOREIGN 2009
rate determining step. (i) on ionization gives 3° carbocation

Step II
Carbocation formed in step I is very reactive, it is
immediately attacked by the nucleophile i.e., OH- ion
to give tert-butyl alcohol.
on ionization gives 2° carbocation
Since 3° carbocations are more stable than 2°

This step is fast and hence does not affect the rate of carbocation, therefore will react fast in
reaction. S N 1 reaction.
We can sum up the order of reactivity of alkyl halides
towards S N 1 and S N 2 reactions as follows: (ii)
Since 2° carbocation are more stable than 1°

carbocation therefore will react faster in
S N 1 reaction.
188. Arrange the compounds of each set in order of
reactivity towards S N 2 displacement:
3° alkyl halide undergo S N 1 reaction very fast (i) (a) 2-Bromo-2-methylbutane
because of the high stability of 3° carbocation for (b) 1-Bromopentane
the same reasons, allylic and benzylic halides show (c) 2-Bromopentane
high reactivity towards the S N 1 reaction, because (ii) (a) 1-Bromobutane-3-methylbutane
the carbocation thus formed gets stabilised through (b) 2-Bromo-2-methylbutane
resonance as shown below:
(c) 2-Bromo-3-methylbutane
(iii) (a) Bromobutane
(b) 1-Bromo-2, 2-dimethylpropane
(c) 1-Bromo-2-methylbutane
(d) 1-Bromo-3-methylbutane.
(i) (a)
For a given alkyl group, the reactivity of the halide,
R - X follows the same order in both the mechanism
R - I > R - Br > R - Cl > R - F .
(b)
187. In the following pairs of halogen compounds which
compound undergo faster S N 1 reaction?
(c)
(i) and
The reactivity in S N 2 depends upon steric hindrance
hence the order of reactivity in S N 2 reaction is
(ii) and
1° > 2° > 3° therefore order of reactivity is:
1-Bromopentane>2-Bromopentane>2-Bromo-2- (vii) CH 3 CH 2 CH = CH 2 + HBr

Peroxide
methylbutane.
(viii) CH 3 CH = C (CH 3) 2 + HBr $
Ans : COMP 2004
(ii) (a)
(i) CH 3 CH 2 CH 2 I
(ii)
(b)
(iii)
(iv) CH 3 CH 2 - CN
(v) C 6 H 5 - O - C 6 H 5
(c)
(vi) CH 3 CH 2 CH 2 Cl
(vii) CH 3 CH 2 CH 2 CH 2 Br
The order of reactivity towards S N 2 displacement
is: (viii)
1-Bromo-2-methyl butane (1°)
>2-Bromo-3-methylbutane (2°)
190. Predict the alkenes that would be formed by
>2-Bromo-2-methylbutane (3°) dehydrohalogenation of the following halides. With
sodium ethoxide in ethanol and identity the major
(iii) (a)
alkene.
(i) 1-Bromo-1-methyl cyclohexane
(ii) 2-Chloro-2-methylbutane
(b) (iii) 3-Bromo-2, 2, 3-trimethylpentane
Ans : COMP 2001
(i) In 1-bromo-1-methylcyclohexane, the b
-hydrogens on either side of the Br atom are
(c) equivalent therefore only 1-alkene is formed.
(d)
The order of steric hindrance is b > c > d > a a

hence the order of reactivity is: (ii) 2-chloro-2-methyl butane has two different sets of
1-Bromobutane>1-Bromo-3-methylbutane>1- equivalent b -hydrogen.
Bromo-2-methylbutane>1-Bromo-2,
2-dimethylpropane.
189. Write the structure of the major organic product in
each of the following reaction:
acetone, heat
(i) CH 3 CH 2 CH 2 Cl + Nal
ethanol heat
(ii) (CH 3) 3 CBr + KOH
Water
(iii) CH 3 CH (Br) CH 2 CH 3 + NaOH
aq ethanol
(iv) CH 3 CH 2 Br + KCN
According to Saytzeff’s rule, more highly
(v) C 6 H 5 ONa + C 2 H 5 Cl $
substituted alkene (b) being more stable, is the
(vi) CH 3 CH 2 CH 2 OH + SOCl 2 $ major product.
(iii) 192. Give the preparation of chlorobenzene from benzene

diazonium chloride and give its reaction with:
(i) Na
(ii) CH 3 Cl is the presence of anhydrous AlCl 3
(iii) H 2 SO 4
(iv) HNO 3 in the presence of cone. H 2 SO 4 .
Ans : DELHI 2006
Preparation
191. Write one use of each of the following:

(i) Chloroform (i) Fitting Reaction :
(ii) Iodoform
(iii) Freons
(iv) DDT
(v) Carbon-tetrachloride
(i) Chloroform or Trichloromethane, CHCl 3 :
(a) It is used as a solvent for rubbers, resins, oil
and fats, alkaloids and other substances.
(b) It is used in the production of the freon
refrigerant. (ii) Friedel-Crafts Alkylation :
(ii) Idoform or Triodomethane, CHI 3 : It was earlier
used as an antiseptic for dressing wounds, now a
days it has been replaced by other formulations
containing iodine because of its unpleasant smell.
(iii) Freons :
(a) It is used as a refrigerant (cooling agent) in
refrigerators and air conditioners.
(b) It is used as a propellant in aerosols and foams
(iii) Sulphonation :
(i.e., hair sprays, deodrants, shaving cream etc.).
(iv) DDT
(a) It is used as insecticide for sugarcane and
fodder crops.
(b) It is used to kill mosquitoes and other insects,
particularly against Anopheles mosquitoes
which spread malaria.
(v) Carbon-tetrachloride or Tetrachloromethane,
CCl 4 : (iv) Nitration :
(a) It is used in the manufacture of refrigerants
and propellants for aerosols cans.
(b) It is used in the synthesis of freons.
(c) It is used as a solvent in the manufacture of
pharmaceuticals.
(d) It is used as a fire extinguisher under the
name pyrene.
193. Write the following reaction: 194. How will you bring about the following conversions?
(i) Friedel-Crafts acylation (i) Ethanol to but-1-yne
(ii) Wurtz-Fitting reaction (ii) Ethane to bromoethene
(iii) Dow’s process (iii) Propene to 1-nitropropane
(iv) Ullmann biaryl synthesis (iv) Ethanol to ethyl fluoride
Ans : SQP 2003 (v) Toluene be benzyl alcohol
(i) Freidel-Crafts Acylation : (vi) Propene to propyne
(vii) Bromomethane to propanone
(viii) But-1-ene to but-2-ene
Ans : DELHI 2000
(i) Ethanol to but-1-yne :
SOCl 2
CH 3 CH 2 OH -SO 2, - HCl
CH 3 CH 2 - Cl
HC / C- Na+
Sod. acetylide
-NaCl
CH 3 CH 2 - C / CH
:HC HC / C-1 Na+ + NH 3D

Liq. NH 3
/ CH + NaNH 2
Acetylene Sodium acetylide
(ii) Ethane to Bromoethene :

hv
CH 3 - CH 3 + Br2 -HBr
CH 3 CH 2 - Br
Ethane Bromoethane
(ii) Wurtz-Fitting Reaction : KOH (alc) Br2 /CCl 4

-HBr
CH 2 / CH 2 BrCH 2 - CH 2 - Br
Ethene 1, 2 - Dibromoethane
KOH (alc)
-HBr
CH 2 = CHBr
Bromoethene
(iii) Propene to 1-nitropropane :

HBr, ROOR
CH 3 - CH = CH 2 Peroxide effect
CH 3 - CH 2 - Br
Propene Bromoethane
AgNO 2 (alc)
-AgBr
CH 3 - CH 2 - CH 2 - NO 2
1 - Nitropropane
(iv) Ethanol to Ethyl Fluoride :

(iii) Dow’s Process : SOCl 2
CH 3 CH 2 - OH -SO 2, - HCl
CH 3 CH 2 - Cl
Ethanol Chloroethane
AgF
CH 3 - CH 2 - F
Ethyl fluoride
(v) Toluene be Benzyl Alcohol :
(iv) Ullmann Biaryl Synthesis : (Reaction with Cu

powder of Iodobenzene) When an iodobenzene is
heated with Cu powder in a sealed tube, diaryl is
formed.
(vi) Propene to Propyne :
Br2 /CCl 4
CH 3 - CH = CH 2 CH 3 - CHBr - CH 2 Br
Propene 1, 2 - Dibromopropane
2KOH (alc)
-2KBr, - 2H 2 O
CH 3 - C / CH
Propyne
(vii) Bromomethane to Propanone :

KCN (alc.)
CH 3 - Br -KBr
CH 3 - C / N
Bromomethane Acetonitrile
197. How will you bring about the following conversions? 198. What are haloarenes? How are they classified? Give
(i) 1-Chlorobutane to n-Octane one method each for the preparation of nuclear and
(ii) Benzene to biphenyl side chain substituted haloarenes.
(iii) Ethene to dibromoethane Ans : COMP 2004
(iv) Aniline to iodobenzene Haloarenes

(v) Propene to propan-1-ol The replacement of hydrogen atom (s ) in an aromatic
(vi) 1-Bromopropane to 2-bromopropane hydrocarbon chain by the halogen atom (s ) which
Ans : OD 2010, COMP 2005
results in the formation of aryl halide (haloarene).
Haloarenes contain halogen atom (s ) attached to the
(i) 1-Chlorobutane to n-Octane :
sp2 hybridised carbon atom (s ) of aryl group.
2CH 3 - CH 2 - CH 2 - CH 2 - Cl + 2Na
(i) Nuclear Halogen Derivatives : Halogen derivatives
Dry ether
CH 3 - CH 2 - CH 2 - CH 2 - CH 2 of aromatic hydrocarbons in which the halogen
atom (F, Cl, Br, or I) is directly attached to
- CH 2 - CH 2 - CH 3
an aromatic ring are called aryl halides. Some
(ii) Benzene to Biphenyl : examples of aryl halids are:
(iii) Ethene to Dibromoethane :

Preparation : They are prepared by direct
halogenation of aromatic hydrocarbons.
(iv) Aniline to Iodobenzene :
(ii) Side Chain Halogen Derivatives : Halogen

derivatives of aromatic hydrocarbons in which the
halogen atom is linked to one of the carbon atoms
of the side chain carrying the aryl group are called
aryl halides. For example:
(v) Propene to Propan-1-ol :
CH 3 - CH = CH 2
Propene
HBr/Peroxide
(Anti Mark. Addition)
CH 3 - CH 2 - CH 2 Br
KOH (aq)
-KBr
CH 3 CH 2 CH 2 OH
Propan 1 - ol
(vi) 1-Bromopropane to 2-bromopropane :

CH 3 - CH 2 - CH 2 - Br Preparation : By the direct halogenation of a
1 - Bromopropane
suitable arene.
(iii) When methl chloride is treated with AgCN, occur, the polarity of the carbon halogen bond is
methyl cyanide is formed: responsible for these substitution reactions. The rate
CH 3 - Cl + AgCN $ CH 3 - C / N + AgCl of S N 1 reactions are governed by the stability of
Methyl chloride Methyl cyanide
carbocation whereas for S N 2 reactions steric factor
is the deciding factor. If the starting material is a
chiral compound, we may end up with an inverted
CASE BASED QUESTIONS product or racemic mixture depending upon the
type of mechanism followed by alkyl halide. Cleavage
of ethers with HI is also governed by steric factor
203. Read the passage given below and answer the following
and stability of carbocation, which indicates that in
questions :
organic chemistry, these two major factors help us in
A farmer cultivating his land near the village pond
deciding the kind of product formed.
was also drawing water from it for irrigation. He used
Answer The following questions :
insecticide excessively to protect his crops and improve
the harvest, over a period of time his agricultural growth (a) Out of chlorobenzene and benzyl chloride, which
improved vastly. But the pond lost his aquatic life. one gets easily hydrolysed by aqueous NaOH and
why?
(i) Give the IUPAC name of compound used as an
insecticides. (b) Predict the stereochemistry of the product formed
if an optically active alkyl halide undergoes
(ii) Contrast the activity in plants and aquatic life
substitution reaction by S N 1 mechanism.
with insecticides.
(c) Following compounds are given to you :
(iii) Is the above used insecticides is bio-degradable ?
2-Bromopentane, 2-Bromo-2-methylbutane,
(iv) Give any alternative which helps farmers.
1-Bromopentane
Ans :
(i) Write the compound which is most reactive
(i) 2, 2-Bis (4-chloropheny1)-1, 1, 1-trichloro-ethane. towards S N 2 reaction.
(ii) Plant growth improved because it is a very (ii) Write the compound which is optically active.
effective insecticides but aquatic life got destroyed
(d) What are the points of similarities between S N 1
as it is highly toxic to fish.
and S N 2 reactions?
(iii) No, above used insecticide i.e., DDT is non-
Ans :
biodegradable.
(a) Benzyl chloride gets easily hydrolysed by aq. NaOH
(iv) Instead of DDT, farmers can use neem powder
due to formation of stable benzyl carbocation.
which will not harm the soil as well as aquatic life.
But due to partial double bond character of C–Cl
204. Raj is a student of class VI, he fell down during bond in chlorobenzene, it does not hydrolyse.
playing. His friends immediately took him to the (b) Stereochemical aspects of nucleophilic substitution
doctor and the doctor dressed the would with the reaction in S N 1 proceeds with racemisation.
halogen compound. (c) (i) 1-Bromopentane
(i) What is the name and formula of the compound ? (ii) 2-Bromopentane
(ii) Write any one method of preparation. (d) Both S N 1 and S N 2 reactions undergo substitution
(iii) The above used halogen compound shows which of a nucleophile by other nucleophile. In both
property ? the reactions configuration of product changes,
(iv) Give an example of halogen compound, used as partially in S N 1 and completely in S N 2 .
an anaesthetic.
206. When haloalkanes with (b -hydrogen atom are
Ans : boiled with alcoholic solution of KOH, they undergo
(i) Iodoform, CHI 3 . elimination of hydrogen halide resulting in the
(ii) CH 3 CH 2 OH + NaOI " CHI 3 + HCOOH formation of alkenes. These reactions are called b
(iii) The above halogen compound has antiseptic -elimination reactions or dehydrohalogenation
property. reactions. These reactions follow Saytzeff’s rule.
(iv) Chloroform. Substitution and elimination reactions often compete
with each other. Mostly bases behave as nucleophiles
205. The substitution reaction of alkyl halide mainly occurs and therefore can engage in substitution or elimination
by S N 1 or S N 2 mechanism. Whatever mechanism reactions depending upon the alkyl halide and the
alkyl halides follow for the substitution reaction to reaction conditions.
haloalkane and therefore, are less reactive

(ii) In halorenes, halogen is attached to sp2
-hybridised carbon while in haloalkanes,
halogen is attached to sp3 -hvbridised carbon.
(b)
Read the above passage carefully and answer the (c) The presence of nitro group at ortho and para
following questions : positions withdraws the electron density from the
benzene ring and thus facilitates the attack of the
(a) Chlorobenzene is extremely less reactive towards
nucleophile on aryl halide. The carbanion thus
a nucleophilic substitution reaction. Give two
formed is stabilised by resonance. The negative
reasons for the same.
charge appeared at ortho- and parc-positions with
(b) Write the product formed when p
respect to the halogen substituent is stabilised by
-nitrochlorobenzene is heated with aqueous
- NO 2 , group while in case of meta-nitrobenzene
NaOH at 443 K followed by acidification.
none of the resonating structures bear the
(c) Why NO 2 , group shows its effect only at ortho negative on carbon atom bearing the - NO 2 ,
and para-positions and not at meta-position? group. Therefore, the presence of - NO 2 , group
(d) Aryl halides are extremely less reactive towards at meta position does not stabilise the negative
nucleophilic substitution. Predict and explain the charge and hence no effect on reactivity of - NO 2
order of reactivity of the following compounds , group at meta position.
towards nucleophilic substitution : (d) III > II > I. Presence of an electron withdrawing
group (like - NO 2 ) at ortho and para positions
increases the reactivity of haloarenes towards
nucleophilic substitution.
Ans :
(a) Haloarenes are much less reactive than haloalkanes
towards nucleophilic substitution reactions due to
the following reasons.
(i) Resonance effect : In haloarenes the electron
pairs on halogen atom are in conjugation
with p -electrons of the ring and the following 208. Chemically, chloroform is employed as a solvent for
resonating structures are possible. fats, alkaloids, iodine and other substances. The major
use of chloroform today is in the production of the
freon refrigerant R-22. It was once used as a general
anaesthetic in surgery but has been replaced by less
toxic, safer anaesthetics, such as ether. As might be
expected from its use as an anaesthetic, inhaling
chloroform vapours depresses the central nervous
C-Cl bond acquires a partial double bond system. Breathing about 900 parts of chloroform
character due to resonance. As a result, the per million parts of air (900 parts per million) for a
bond cleavage in haloarene is difficult than short time can cause dizziness, fatigue, and headache.
Chronic chloroform exposure may cause damage to the

liver (where chloroform is metabolised to phosgene)
and to the kidneys, and some people develop sores
when the skin is immersed in chloroform. Chloroform
is slowly oxidised by air in the presence of light to
an extremely poisonous gas, carbonyl chloride, also
known as phosgene. It is therefore stored in closed
dark coloured bottles completely filled so that air is
kept out.
(i) Which gas is formed when chloroform is oxidised
in air ?
(ii) Name the freon refrigerant used now a days ?
(iii) What might happen if chloroform is inhaled for
longer time ?
Ans :
(i) Phosgene,
(ii) R-22
(iii) Chronic chloroform exposure may cause damage
to the liver (where chloroform is metabolised to
phosgene) and to the kidneys, and some people
develop sores when the skin is immersed in
chloroform.
209. Alkyl halides are best prepared from alcohols, which
are easily accessible. The hydroyl group of an alcohol
Is replaced by halogen reaction on with concentrated
halogen acids, phosphorus halides or thionyl chloride.
Thionyl chloride is preferred because the other two
products are escapable gases. Hence the reaction
gives pure alkyl halides. Phosphorus tribromide and
triiodide are usually generated in situ (produced in the
reaction mixture) by the reaction of red phosphorus
with bromine and iodine respectively. The preparation
of alkyl chloride is carried out either by passing dry
hydrogen chloride gas through a solution of alcohol
or by heating a solution of alcohol in concentrated
aqueous acid.
(i) What is the condition to obtain good yield of
R-I ?
(ii) Is the above method suitable for preparation of
aryl halides. Why and why not ?
Ans :
(i) Good yields of R—I may be obtained by heating
alcohols with sodium or potassium iodide in 95%
phosphoric acid.
(ii) Because the carbon-oxygen bond in phenols has
a partial double bond character and is difficult to
break being stronger than a single bond.
***********
Page 332 Alcohols, Phenols and Ethers Chap 7
CHAPTER 7
Alcohols, Phenols and Ethers
SUMMARY 4. From Grignard Reagent :
1. STRUCTURE OF ALCOHOLS
In alcohols, the oxygen of -OH group is bonded to the
sp3 hybridised carbon by a sigma bond. This bond is
formed by the overlapping of sp3 hybrid of carbon.
With One sp3 hybrid orbital of oxygen. The remaining

three sp3 hybrid orbitals of carbon overlap with 1s
orbitals of hydrogen. In the case of oxygen, one sp3
hybrid orbital overlaps with 1s orbital of hydrogen
and the remaining two sp3 hybrid orbitals contain
lone pairs of electrons.
2. GENERAL METHODS OF PREPARATION OF ALCOHOLS

1. From Haloalkanes :
T
C 2 H 5 Br + KOH (aq) C 2 H 5 OH + KBr
2. By Reduction of Aldehydes and Ketones :

Pd
RCHO + H 2 RCH 2 OH
NaBH 4
RCORl + H 2 R - CH - Rl
| 5. From Alkenes :
OH (i) Hydration of Alkenes :
3. By Reduction of Carboxylic Acids and Esters :

LiAlH 4
RCOOH H2O
RCH 2 OH
Na/C 2 H 5 OH
RCOORl 4 [H]
RCH 2 OH + RlOH
2. From Diazonium Salts : (ii) With Zn Dust :
3. From Sodium Salicylate :
(iii) With NH 3 :
4. From Grignard Reagent :
(iv) Schotten-Baumann Reaction (Name

Reaction) :
5. Dow’s Process (Name Reaction) :
2. Reaction of Benzene Ring :

(i) Bromination : It is a test reaction of phenol.
6. From Cumene :
(ii) Sulphonation :
7. PHYSICAL PROPERTIES OF PHENOLS
Physical properties of phenols are as follows :
1. Phenols are weakly acidic in nature but more
acidic than alcohols.
2. Phenols have high boiling point due to H-bonding.
3. Phenols are slightly soluble in water.
8. CHEMICAL PROPERTIES OF PHENOLS

1. Reactions of -OH Group :
(i) With Active Metals like Na, K :
10. CHEMICAL PROPERTIES OF ETHERS (iii) Alkylation :

Chemical properties of Ethers are as follows :
1. Reaction of Ethereal Oxygen Atom :
(i) With cold, conc. H 2 SO 4 :
5. Nitration :
2. Reactions Due to the Cleavage of C-O Bond :

(i) With HX : (HBr, HI)
R - O - R + 2HX $ 2RX + H 2 O
(ii) With Dilute H 2 SO 4 :
Dil.H 2 SO 4
R - O - R + H2O 2ROH
T
6. Sulphonation :
(iii) With PCl 5 :
T
R - O - R + PCl 5 2RCl + POCl 3
3. Reaction of Alkyl Group :

(i) Halogenation :
11. STRUCTURE OF ETHERS

In these compounds the functional group (- O -) is
bonded to two alkyl group by s -bonds making a bond
angle of 110c as:
4. Ring Substitution in Aromatic Ethers :

(i) Halogenation :
Distinction Between 1c, 2c, 3c Alcohols :

The following tests are used :
1. Victor Meyer’s test
(ii) Acylation : 2. Lucas test
3. Action with hot reduced copper at 573 K
4. Oxidation
Distinction Between Alcohols and Phenols :
The following tests are used :
1. Blue litmus solution used
2. Br2 water test
3. Action with FeCl 3
4. Dye test.
***********
8. Propene, CH 3 CH = CH 2 can be converted into Ans : SQP 2005
1-propanol by oxidation. Indicate which set of The acidic nature of phenol is due to the formation of
reagents amongst the following is ideal to effect the stable phenoxide ion in solution
above conversion ? C 6 H 5 OH + H 2 O C H O + H 3 O+
6 5
-
Phenoxide ion
(a) KMnO 4 (alkaline)
(b) Osmium tetraoxide (OsO 4 /CH 2 Cl 2) The phenoxide ion is stable due to resonance.
(c) B 6 H 6 and alk. H 2 O 2

(d) O 3 /Zn
Ans : FOREIGN 2017
KMnO 4 (alkaline) and OsO 4 /CH 2 Cl 2 are used for

hydeoxylation of double bond while O 3 /Zn is used
for ozonolysis. Therefore, the right option is (c), i.e.,
BH 3 in THF
3CH 3 CH = CH 2 (CH 3 CH 2 CH 2) 3 B
3H 2 O 2
NaOH
3CH 3 CH 2 CH 2 OH + H 3 BP3
1-propanol.
The negative charge is delocalized in the benzene ring
9. Which of the following alcohols gives 2-butene on which is a stabilizing factor in the phenoxide ion and
dehydration by concentration H 2 SO 4 ? increase acidity of phenol. Whereas no resonance is
(a) 2-Methyl propene-2-ol possible in alkoxide ions (RO-) derived from alcohol.
The negative charge is localized on oxygen atom.
(b) 2-Methyll 1-propanol Thus, alcohols are not acidic.
(c) Butane-2-ol Thus (c) is correct option.
(d) Butane-1-ol 12. When phenol is treated with excess bromine water,
Ans : DELHI 2011 it gives:
When Butane -2-ol is heated with concentrated (a) m-Bromophenol
sulphuric acid at 443 K, dehydration takes place and (b) o-and p-Bromophenol
2-butene is formed. In this reaction concentrated
(c) 2, 4-Dibromophenol
sulphuric acid acts as a dehydrating agent.
Thus (c) is correct option. (d) 2, 4, 6-Tribromophenol
Ans : OD 2011, SQP 2005
10. Which of the following will not form Phenol or
phenoxide :
(a) C 6 H 5 N 2 Cl (b) C 6 H 5 SO 3 Na
(c) C 6 H 5 Cl (d) C 6 H 5 CO 2 H
Ans : COMP 2000
Benzoic acid (C 6 H 5 COOH) will not form phenol or

phenoxide.
Thus (d) is correct option. Thus (d) is correct option.
11. The ionization constant of phenol is higher than that 13. When phenol is heated with CHCl 3 and alcoholic
of ethanol because: KOH when salicyladehyde is produced. This reaction
(a) phenoxide ion is bulkier than ethoxide is known as
(a) Rosenmund’s reaction
(b) phenoxide ion is stronger base than ethoxide
(b) Reimer-Tiemann reaction
(c) phenoxide ion is stabilized through delocalization
(c) Friedel-Crafts reaction
(d) phenoxide ion is less stable than ethoxide
(d) Sommelet reaction
Chap 7 Alcohols, Phenols and Ethers Page 341
28. Consider the following reaction : 31. Primary and secondary alcohols on action of reduced
Zn dust CH 3 Cl Alkaline KMnO 4 copper gives
Phenol X Anhydrous AlCl 3
Y Z
(a) Aldehydes and ketones respectively.
The product Z is :
(b) Ketones and aldehydes respectively.
(a) benzaldehyde (b) benzoic acid
(c) Only aldehydes.
(c) benzene (d) toluene
(d) Only ketone.
Ans : SQP 2012
Ans : FOREIGN SQP 2006
Alcohols are oxidized by removal of H 2 in presence of

a heated metal catalyst (Cu).
Cu
CH 3 CH 2 OH 300c
CH 3 CHO + H 2
1c alcohol Aldehyde

29. Among the following four compounds
1. phenol
2. methylphenol
3. meta-nitrophenol
4. para-nitrophenol Thus (a) is correct option.
the acidity order is : 32. Phenol can be converted into salicylic acid by :
(a) ii > i > iii > iv (b) iv > iii > i > ii (a) Etard reaction
(c) iii > iv > i > ii (d) i > iv > iii > ii (b) Kolbe reaction
Ans : COMP 2010 (c) Reimer-Tiemann reaction
(d) Cannizzaro’s reaction
Ans : OD 2013, SQP 2011
Conversion of phenol into salicyclic acid can be carried

out by Riemer-Tiemann reaction.

30. In the reduction Thus (c) is correct option.
R - CHO + H 2 " RCH 2 OH 33. The reaction given below is known as
the catalyst used is : C 2 H 5 ONa + IC 2 H 5 " C 2 H 5 OC 2 H 5 + Nal
(a) Ni (b) Pd (a) Kolbe’s synthesis (b) Wurtz’ synthesis
(c) Pt (d) Any of these (c) Williamson’s synthesis (d) Grignard’s synthesis
Ans : DELHI 2016

Ans : SQP 2000
Any one of Ni, Pt or Pd can be used in the reduction Preparation of ethers by reacting sodium ethoxide
of aldehydes. with alkyl halide is called Williamson synthesis.
Thus (d) is correct option. Thus (c) is correct option.
42. An industrial method of preparation of methanol is : 46. Diethyl ether on heating with conc. HI gives two
(a) catalytic reduction of carbon monoxide in presence moles of
of ZnO - Cr2 O 3 (a) ethanol (b) iodoform
(b) by reacting methane with steam at 900c C with a (c) ethyl iodide (d) methyl iodide
nickel catalyst Ans : FOREIGN 2005
(c) by reducing formaldehyde with lithium aluminium C 2 H 5 OC 2 H 5 + 2HI
T
2C 2 H 5 I + H 2 O
hydride
(d) by reacting formaldehyde with aqueous sodium
hydroxide solution 47. Which statement is not correct about alcohol ?
(a) Molecular weight of alcohol is higher than water
Ans : OD 2009
Cr2 O 3 - ZnO (b) Alcohol of less number of carbon atoms is less
CO + H 2 + H 2 CH 3 OH
14
4 24 43 300c C
Methanol soluble in water than alcohol of more number of
water gas
carbon atoms
(c) Alcohol evaporates quickly
43. Which of the following compounds is oxidised to
(d) All of these
prepare methyl ethyl ketone ?
(a) 2-Propanol (b) 1-Butanol Ans : OD 2002
The solubility of alcohols depend on number of

(c) 2-Butanol (d) t-Butyl alcohol
C-atoms of alcohols. The solubility of alcohols in
Ans : COMP 2016, SQP 2014 water is decreased by increasing number of C-atoms
Secondary alcohols oxidise to produce kenone. of alcohol. As resulting molecular weight increases,
CH 3 CHOHCH 2 CH 3
(O)
CH 3 COCH 2 CH 3 the polar nature of O - H bond decreases and hence
2 - Butanol Ethyl methyl ketone strength of hydrogen bond decreases.
44. If there be a compound of the formula CH 3 C (OH) 3 48. Most acidic is :
which one of the following compounds would be
obtained from it without reaction with any reagent ?
(a) CH 3 OH (b) C 2 H 5 OH
(c) CH 3 COOH (d) HCHO
Ans : SQP 2011
-2H 2 O
CH 3 C (OH) 3 CH 3 COOH
45. An alkene, obtained by the dehydration of an alcohol
(A), on ozonolysis gives two molecules of acetaldehyde Ans : SQP 2008
for every molecule of alkene. The alcohol (A) is
Phenol is acidic in nature and the acidic nature of
(a) CH 3 CH 2 CH 2 OH (b) CH 3 CH 2 OH phenol is increased by the presence of - I (electron
(c) CH 3 CH = CHCH 2 OH attracting) groups at o - and p -position of the
- OH groups. However, benzoic acid is more acidic
Ans : DELHI 2000, than nitro-phenol.
49. How many isomers of C 5 H 11 OH will be primary
alcohols ?
(a) 5 (b) 4
(c) 2 (d) 3
Ans : COMP 2013
Four primary alcohols of C 5 H 11 OH are possible.

Thus (d) is correct option. These are :
57. When phenol is reacted with CHCl 3 and NaOH 59. n -Propyl alcohol and isopropyl alcohol can be
followed by acidification, salicyladehyde is obtained. chemically distinguished by which reagent ?
Which of the following species are involved in the (a) PCl 5
above mentioned reaction as intermediate ?
(b) Reduction
(c) Oxidation with potassium dichromate.
(d) Ozonolysis
Ans : SQP 2005
Primary alcohol on oxidation give aldehyde which

on further oxidation give carboxylic acid whereas
secondary alcohols give ketone.
Riemer-Tiemann reaction involves electrophilic

substitution on the highly reactive phenoxide ring.
CH 3 Cl 3 + OH- H 2 O + C - Cl 3 $ : CCl 2 + Cl- Thus (c) is correct option.

60. Which one of the following compounds has the most
acidic nature?

58. Increasing order of acid strength among p
-methoxyphenol, p -methylphenol and p -nitrophenol
is
Ans : COMP 2003
(a) p -Nitrophenol, p -Methoxyphenol, p -Methylphenol
Phenol is most acidic because its conjugate base
(b) p -Methylphenol, p -Methoxyphenol, p -Nitrophenol is stabilised due to resonance, while the rest three
(c) p -Nitrophenol, p -Methylphenol, p -Methoxyphenol compounds are alcohols, hence their corresponding
(d) p -Methoxyphenol, p -Methylphenol, p -Nitrophenol conjugate bases do not exhibit resonance.
Ans : OD 2000
Electron-donating groups (- OCH 3, - CH 3 etc.) 61. Ethylene glycol, on oxidation with periodic acid, gives
tend to decrease and electron withdrawing groups (a) Oxalic acid (b) Glycol
(- NO 2, - OCH 3 etc.) tend to increase the acidic (c) Formaldehyde (d) Glycolic acid
character of phenols. Since - OCH 3 is a more
Ans : DELHI 2010
powerful electron-donating group than - CH 3 group,
therefore, p -methylphenol is slightly more acidic than When three - OH groups are attached with a single C
p -methoxyphenol while p -nitrophenol is the strongest atom the compound is unstable. Hence get dissociated
acid. Thus, option (d), i.e. p -methoxyphenol, p and form carboxylic acid on leaving 2 - OH molecules
-methylphenol, p -nitrophenol is correct. of H 2 O . Oxidation with periodic acid (HIO 4 or H 5 IO 6 )
gives formaldehyde HCHO.
69. Glycerol is very highly viscous compared to propanol 72. Final product formed on reduction of glycerol by
though both are organic alcohols. It is because of hydroiodic acid is
(a) relatively more extensive H-bonding in glycerol (a) Propane (b) Propanoic acid
than in propanol (c) Propene (d) Propyne
(b) the absence of H-bonding in propanol Ans : DELHI 2009
(c) the formation of an addition compound in propanol
(d) a large value of surface tension of glycerol
Ans : SQP 2015
Glycerol has more extensive H-bonding than propanol.

70. In the reaction:
Which of the following compounds will be formed ?

73. Diethyl ether can be decomposed by heating with
(a) HI (b) NaOH
(c) Water (d) KMnO 4
Ans : FOREIGN 2011
Ethers are readily cleaved by HI as follows:
Ans : COMP 2000 Thus (a) is correct option.

In the cleavage of mixed ethers with two different 74. Rectified spirit is a mixture of
alkyl groups, the alcohol and alkyl iodide that form (a) 95% ethyl alcohol + 5% water
depend on the nature of alkyl group. When primary
(b) 94% ethyl alcohol + 4.53% water
or secondary alkyl groups are present, it is the lower
alkyl group that forms alkyl iodide therefore (c) 94% ethyl alcohol + 4.43% water
(d) 95.87% ethyl alcohol + 4.13% water
Ans : OD 2013, SQP 2012
Rectified spirit or rectified alcohol is high concentration

alcohol purified by the process of rectification
(repeated or fractional distillation). It is a mixture of
95.87% ethyl alcohol + 4.13% water.
75. Glycerol is very highly viscous compared to propanol
71. Ether in air forms :
though both are organic alcohols. It is because of
(a) Oxide (b) Peroxide
(a) relatively more extensive H-bonding in glycerol
(c) alkenes (d) Alkanes than in propanol
Ans : SQP 2004 (b) the absence of H-bonding in propanol
Ether exists as peroxide in air. (c) the formation of an addition compound in propanol
(d) a large value of surface tension of glycerol
ASSERTION AND REASON When a group having + M effect is at p -position (like

halide group) it decreases the acidity of phenols.
86. Assertion : ter-Butyl methyl ether is not prepared by the
reaction of ter-butyl bromide with sodium methoxide.
Reason : Sodium methoxide is a strong nucleophile.
83. Assertion : Phenyl is used as a household germicide. (a) Both Assertion and Reason are correct and
Reason : Phenyl is phenol derivative and phenol is an Reason is a correct explanation of the Assertion.
effective germicide. (b) Both Assertion and Reason are correct but Reason
Ans : DELHI 2020
The given order of dehydration is correct due to
(d) Both the Assertion and Reason are incorrect. following reasons.
Ans : COMP 2023 1. Alcohols leading to conjugated alkenes are
As benzyl cation (C 6 H 5 CH 2+) is more stable than dehydrated more readily.
methyl cation (CH 3+), so the product is C 6 H 5 CH 2 I 2. 2-Cyclohexenol is dehydrated more easily than
and CH 3 OH . 3-cyclohexenol because the carbocation from the
Thus (a) is correct option. former is more stable than the latter.
84. Assertion : Benzyl bromide when kept in acetone
water, it produces benzyl alcohol.
Reason : The reaction follows SN2 mechanism.
Ans : OD 2019
3. Phenol is not dehydrated due to its highly stable
Phenols turn FeCl3 solution purple Resorcinol has
character due to resonance.
phenolic group.
87. Assertion : Phenol undergo Kolbe reaction, ethanol
85. Assertion : The major products formed by heating
does not.
C 6 H 5 CH 2 OCH 3 with HI are C 6 H 5 CH 2 I and CH 3 OH .
Reason : Phenoxide ion is more basic than ethoxide
Reason : Benzyl cation is more stable than methyl
ion.
cation.
Ans : FOREIGN 2019
Ans : SQP 2011
On using ter-butyl bromide and sodium ethoxide as
Phenol is strong acid than ethanol because phenoxide
reactants, the major product would be 2-methylpropene
ion is resonance stabilised.
and ethanol (elimination reaction).
94. Give the chemical equation for the following.

Williamson’s synthesis
Ans : SQP 2015
In this method, alkyl halide is treated with a suitable

sodium (or potassium) alkoxide.
R - O- Na+ + RlX $ R - O - Rl + NaX
Sodium alkoxide Alkyl Ether
halide These two isomers have the same molecular formula,
95. How can the following conversions be brought about? i.e. C 4 H 10 O but they differ in the position of — OH
Glycerol to formic acid group. Thus, the two compounds are showing position
Ans : COMP 2015
isomerism.
99. Write chemical equation for the given reaction and
name the main product. Oxalic acid with glycerol at
260°C.
Ans : SQP 2005
When glycerol is heated with oxalic acid at 260°C,

glyceryl dioxalate is formed. It decomposes at once
into CO2 and allyl alcohol.
96. Name the type of isomerism exhibited by the following
pairs of compounds.
1-butanol and 2-methyl-l-propanol
Ans : DELHI 2013
The given two compounds will show chain isomerism.

The structural formula of the two compounds are
100. Identify the compounds A and B in the given reaction.
The two compounds have the same molecular formula

but different number of carbon atoms present in their Ans : OD 2010
parent chain.
97. Give balanced equation for the following reaction.
1-butanol and hydrogen chloride
Alcohol (butan-l-ol) reacts with hydrogen chloride to

form chloroalkane (chlorobutane).
101. Glycerol (propane-1, 2, 3-triol) is more viscous than

ethylene glycol (ethane-1, 2-diol). Explain.
Ans : SQP 2016
Glycerol (propane-1, 2, 3-triol) has three – OH groups

per molecules, while ethylene glycol (ethane-1, 2-diol)
98. Draw a pair of isomers for C4H10O and name the type has two – OH groups. The viscosity depends on the
of isomerism. amount of hydrogen bonding between molecules and
the more number of – OH bonds. There is greater
Ans : OD 2011
hydrogen bonding in glycerol than ethylene glycol. So,
The two isomers of C 4 H 10 O are
glycerol is more viscous than ethylene glycol.
Ans : FOREIGN 2013

attraction. More be the intermolecular force of
1. Structural formula of 4, 4 dimethyl-2-pentanol is, attraction, more is the boiling point.
Alcohols have strong hydrogen bonding along
with dipole-dipole interaction while ethers due to
steric-hinderence do not form hydrogen bonding
thus boiling point of alcohols are much higher
than of ethers.
2. Phenol is more acidic than alcohol : Acidity of
2. Structural formula of 2-butanol is,
any acid depends on the stability of its conjugate.
More stable is the conjugate, more acidic be the
given acid.
As conjugate of phenol (i.e. phenoxide ion) is
more stable due to resonance, while conjugate of
alcohol does not, the phenol is more acidic than
alcohols.
110. What happens when :
1. ethanol is oxidised with acidified KMnO 3 113. Give one test from which methyl alcohol and ethyl
solution? alcohol are distinguished.
2. ethanol is treated with PCl 5 ? Ans : OD 2009
Ans : FOREIGN 2011
KMnO4 Test Methyl alcohol Ethyl alcohol
1. CH 3 CH 2 OH CH 3 COOH
Iodo form test No yellow Yellow
When ethanol is added to alkaline KMnO4 On heating I2 compound is compound with
solution, the ethanol get oxidise to ethanoic acid and NaOH formed characteristic
due to formation of nascent oxygen. KMnO4 odour is formed.
act as an oxidising agent. The pink colour of
the KMnO4 vanishes, as it is being used up in
114. What are alcohols?
oxidation process.
Ans : COMP 2002
2. Chloroethene will be formed.
Alcohols are the hydroxy derivatives of aliphatic
C 2 H 5 OH + PCl 5 " C 2 H 5 Cl + POCl 3 + HCl
hydrocarbons.
Solid phosphorus chloride reacts violently with An alcohol is formed when one or more hydrogen
alcohols at room temperature producing clouds of atom (s) in an aliphatic hydrocarbon is replaced by
hydrogen chloride gas.
hydroxyl (OH) group (s). An alcohol is represented as
111. How are alcohols classified? R - OH .
Ans : COMP 2008
115. What are ethers?
Alcohols are classified as primary, secondary, or Ans : OD 2012
tertiary according to the 1c, 2c, or 3c carbon that
Ether can be visualised as a compound formed by
bears the hydroxy (-OH) group.
substituting the hydrogen atom of hydroxyl group of
an alcohol or phenol by an alkyl or aryl group.
Ether is formed when one or more hydrogen atoms
(s) in a hydrocarbon is replaced by an alkoxy (RO -)
or aryloxy (ArO -) group. Ether is represented as
R - OR or R - OAr .
112. Account for the following : 116. What are phenols?

1. The boiling point of ether is much lower than that Ans : OD 2006
of alcohol. Phenols are the hydroxy derivatives of aromatic

2. Phenol is more acidic than alcohol. hydrocarbons in which the hydroxyl group is directly
Ans : OD 2010, COMP 2008
attached to the carbon atom of the aromatic ring.
1. The boiling point of ether is much lower than that Phenol is formed when one or more hydrogen atom (s)
of alcohol : Boiling point of any liquid depends in an aromatic hydrocarbon is replaced by hydroxyl
on the strength of the inter molecular force of (OH) group (s). Phenol is represented as Ar - OH .
129. Write the IUPAC name of the following compounds : Ans : DELHI 2000
1. CH 3 CH 2 CH 2 OH
Bu tan - 1 - o l
132. Alcohols are comparatively more soluble in water

than hydrocarbons of comparable molecular masses.
Explain this fact.
Ans : OD 2008
Alcohols can form H-bonds with water, therefore they

are soluble in water.
But hydrocarbons cannot form H-bond with water

hence are insoluble in water.
Ans : DELHI 2009 133. Write the IUPAC name of the following compounds :
(i) 2- Methylphenol
(ii) 4-Methylphenol
(iii) 2, 5- Dimethylphenol
(iv) 2, 6-Dimethylphenol
130. You are given benzene, conc. H 2 SO 4 and NaOH.
Write the equations for the preparation of phenol
using these reagents.
Ans : SQP 2001
4. HOCH 2 - CHOH - CH 2 OH
Ans : SQP 2018, OD 2017
1. 2, 2, 4- Trimethylpentan-3-ol
2. 5-Ethylheptane-2, 4-diol
3. Butane-1, 3-diol
4. Propane-1, 2, 3- triol
134. Explain why propanol has higher boiling point than
that of the hydrocarbon, butane?
Ans : FOREIGN 2016
The molecules of butane are held together by weak

131. Give the structures and IUPAC names of products Vander Waals forces of attraction while those of
expected from the following reactions : propanol are held together by stronger intermolecular
1. Catalytic reduction of butanal hydrogen bonding.
2. Hydration of propene in presence of concentrated
sulphuric acid.
3. Reaction of propanone with methyl magnesium
bromide followed by hydrolysis.
141. Arrange the following compounds in increasing order Ans : DELHI 2006
of their acid strength :

1. Propan-1-ol
2. 2, 4, 6-trinitrophenol
3. 3-nitrophenol
4. 3, 5-dinitrophenol
5. phenol
6. 4-methyl phenol
Ans : SQP 2018
Propan -1- ol < 4-methylphenol < phenol <

3-nitrophenol < 3, 5-dinitrophenol < 2, 4,
6-trinitrophenol.
142. Draw the structure and name the product formed if

the following alcohols are oxidised. Assume that an
excess of oxidising agent is used.
1. CH 3 CH 2 CH 2 CH 2 OH
2. 2- butenol
3. 2-methyl-1-propanol. 144. p -Nitrophenol is more acidic than phenol explain
Ans : SQP 2016, COMP 2013 why?
K 2 Cr2 O 7 /H 2 SO 4
1. CH 3 CH 2 CH 2 CH 2 OH [O]
CH 3 CH 2 CH 2 CHO Ans : OD 2008
K 2 Cr2 O 7 /H 2 SO 4
p -Nitrophenol is more acidic than phenol because
[O]
CH 3 CH 2 COOH nitro group is e -withdrawing group. It helps in
releasing H+ ion easily as comppared to phenol. After
2. Oxidation of unsaturated alcohols such as
2-butenol is carried out with PCC because strong releasing H+ ion phenol forms phenoxide ion, the
oxidising agent like K 2 Cr2 O 7 /H 2 SO 4 will bring negative charge in oxygen atom of phenoxide ion is
about cleavage at the double bond. stabilises by the electron withdrawing - NO 2 group.
PCC
It helps in delocalization of negative charge of xoygen
CH 3 - CH = CH - CH 2 OH CH 3 - CH = CH - CHO atom and makes it stable.
2 - Butenol 2 - Butenal
143. When 3- methyl butan-2-ol treated with HBr, the 145. Define fermentation. How ethanol is formed by
following reaction takes place : fermentation.
Ans : OD 2000
Breaking down of large organic molecules into simple

ones in presence of enzymes is called fermentation.
Sucrose in converted to glucose and fructose in the
presence of enzyme interface. Glucose and fructose
Give a mechanism for the reaction. undergo fermentation in the presence of another
enzyme, zymase, which is found in yeast.
or
Invertase
What happen when 3-methybutan-2-ol is treated with C 12 H 22 O 11 + H 2 O C 6 H 12 O 6 + C 6 H 12 O 6
HBr? Write the chemical reaction and mechanism of
Zymase
this reaction. C 6 H 12 O 6 2C 2 H 5 OH + 2CO 2
Ethanol
CLASS 12

CLASS 10

153. Write the mechanism of the reaction of HI with 157. Explain why is -OH group in phenols more strongly
methoxymethane. held as compared too OH group in alcohols.
Ans : COMP 2005 Ans : DELHI 2017
2
CH 3 - O - CH 3 + HI " CH 3 I + CH 3 OH In Phenols, the -OH group is attached to sp hybrid
Mechanism : carbon of an aromatic ring. The carbon-oxygen bond
length (136 pm) in phenol is slightly less than that in
alcohol. This is due to partial double bond character of
C-O bond on account of the conjugation of unshared
electron pair of oxygen with the aromatic ring.
154. Explain the fact that in aryl alkyl ethers

1. The alkoxy group activates the benzene ring
towards electrophilic substitution.
2. It directs the incoming substituents to ortho and
para-position in benzene ring.
Ans : OD 2012
1. In aryl alkyl ethers the + R effect of the alkoxy
group (OR) increases the electron density in the
benzene ring (resonating structure I to V) there by
activating the benzene ring towards electrophilic
substitution reactions. 158. Suggest some chemical reagents for the chemical
reduction of carbonyl compounds (/ aldehydes and
ketones).
Ans : FOREIGN 2004
The chemical reagents for chemical reduction of

carbonyl compounds are as follows:
1. Sodium borohydride or sodium tetrahydridoborate
2. Since the electron density increases more at the (III) NaBH 4
two ortho and para position as compared to
2. Lithium aluminium hydride or lithium
m-position, therefore electrophilic substitution
tetrahydrido aluminate (III), LiAIH 4 .
reactions mainly occur at O- and p-positions.
159. What is an addition reaction?
155. Complete the following reactions :
373 K
1. CH 3 - O - C 2 H 5 + HI An addition reaction is one in which two substances
2. C 6 H 5 ONa + CH 3 Br
T are combined to form a single compound. Generally,
373 K
Unsaturated Organic molecules undergo addition
3. CH 3 - O - CH 2 CH 3 + HBr reactions.
Ans : COMP 2016
373 K
1. CH 3 - O - C 2 H 5 + HI CH 3 I + CH 3 CH 2 - OH
T
2. C 6 H 5 ONa + CH 3 Br C 6 H 5 OCH 3 + NaBr
373 K
3. CH 3 - O - CH 2 CH 3 + HBr CH 3 Br + CH 3 CH 2 - OH
156. How are ethers named in IUPAC system? 160. Discuss preparation of alcohols from alkenes by acid
Ans : FOREIGN 2018 catalysed hydration.
According to IUPAC system, ethers are regarded as Ans : OD 2016
hydrocarbon derivatives in which a hydrogen atom
is replaced by an “alkoxy group” (- OR), the larger
group (R) being chosen as the parent hydrocarbon.
Thus, in IUPAC system, ethers are named as
“alkoxyalkane”.
For example, Ans : COMP 2009
KOH (aq) Heating chlorobenzene with super heated steam at

CH 3 CH 2 Br CH 3 CH 2 OH + KBr 700 K in presence of a catalyst lead to the commercial
Bromoethane Ethanol
AgOH
production of phenol.
CH I3 Moist silver oxide
CH 3 OH + AgI
Iodomethane Methanol
168. How can one reduce carboxylic acid to alcohol?

Ans : FOREIGN 2002
The acids can be reduced to alcohols by using a strong

reducing agent, Lithium aluminium hydride (LiAlH 4) .
173. Write the name of product A and B :
The initial product is an alkoxide from which the
alcohol is liberated by hydrolysis :
4RCOOH + 3LiAlH 4 $ 4H 2 + 2LiAlO 2 + (RCH 2 O) 4 AlLi
H2O
4R - CH 2 OH
1cAlcohol
i.e., R - COOH
*(i) LiAlH 4
R - CH 2 OH Ans : OD 2011
(ii) H 2 O

Ans : SQP 2002
174. How will you convert benzene into phenol?

Ans : COMP 2008
Benzene on heating with fuming sulfuric acid (oleum)

undergoes sulphonation to produce benzene sulphonic
acid which on heating with molten sodium hydroxide
170. How will you convert benzene to chlorobenzene? at 570-620 K followed by acidification give phenol.
Ans : OD 2008, SQP 2005
Benzene and its homologues react with halogens

(Cl 2, Br2, etc) in the presence of a Lewis acid (e.g.,
FeCl 3 /FeBr3 ) as catalyst to yield haloarenes (or aryl
halides).
171. How will you convert chlorobenzene to phenol?

Ans : SQP 2003
Chlorobenzene is hydrolysed by treating it with sodium

hydroxide at 623 K and 320 atm pressure. Phenol is 175. Are alcohol stronger acid than alkanes?
obtained by acidification of sodium phenoxide. Ans : OD 2011
Alcohols are stronger aicds than alkanes and they

readily displace extremely weak acids (alkanes, R’H)
from Grignard reagents (R’ MgX).
172. How is phenol commercially prepared from

chlorobenzene?
183. What is Lucas reagent? 188. Why ethers cannot be made by dehydration of 2c and
or 3c alcohol?
Name one reagent which is used for the distinction of Ans : OD 2019
1c, 2c and 3c alcohols. Ethers are formed as a result of acid dehydration by

Ans : DELHI 2014 S N2 mechanism (from primary alcohols). It secondary
Lucas reagent is mixture of conc. hydrochloric acid or tertiary alcohols are used, due to steric rindrance,
(HCl) and Zinc chloride ((ZnCl 2)). Lucas test is alkenes are formed and not ethers.
based upon the difference in reactivity of 1c, 2c and 189. Write two properties of phenol.
3c alcohols toward hydrogen halides and is used for Ans : OD 2005
distinguishing the three classes or alcohols. Two properties of phenol are as follows:
184. How does Lucas reagent help in the distinction of 1c 1. Phenol is solid at room temperature. It’s melting
and 2c and 3c alcohols? point is 314 K.
Ans : COMP 2007 2. It is moderately soluble in water (8% at 298 K).
Alcohols of less than six carbons are than six carbons 190. How will you prepare thioalcohol from Grignard
are soluble in the Lucas reagent. The corresponding reagent?
alkyl chlorides are insoluble. When the chloride Ans : SQP 2004
separates from the solution, cloudiness appears
Like O 2 gas, Grignard reagent react with sulphur and
which indicates the formation of a chloride from an
the addition product on hydrolysis give thioalcohols.
alcohol. The time required for cloudiness to appear is
a measure of the reactivity of the alcohol.
185. How is phenol converted to benzene?
Ans : DELHI 2010
Reaction of phenol with zinc dust. On heating with

191. How is sodium alkoxide made?
zinc dust, phenol is converted to benzene
Ans : OD 2009
Sodium alkoxide is made by direct action of sodium

metal on dry alcohol
RO- Na+ + 1 H 2
Na
ROH
Alkoxide 2
192. Explain mechanism of Williamson Synthesis.
186. How is ethanol converted into diethyl ether? Ans : OD 2013
or The Williamson synthesis involves nucleophilic
How will you convert CH 3 CH 2 OH $ (CH 3 CH 2) 2 O ? substitution (S N 2) of alkoxide ion for halide ion.
Ans : DELHI 2012
The primary alcohols having unhindered alkyl group

are dehydrated to ethers in presence of sulphuric acid
at low temperature 410 K. 193. Alcohols are comparatively more soluble in water
H 2 SO 4
RCH 2 OH + HOCH 2 R 410 K
RCH 2 OCH 2 R than hydrocarbons of comparable molecular masses.
Primary alcohols Ether Explain this fact.
where R = H -, CH 3 -, CH 3 CH 2 - etc . Ans : OD 2017
187. How are 1c alcohols converted into alkenes? Alcohols can form H-bond with water molecules and
Ans : COMP 2016, OD 2011
break the H-bonds already existing between the water
molecules. Therefore, they are soluble in water.
If 1c alcohols are heated at 443 K in the presence of
H 2 SO 4 or H 3 PO 4 , they get dehydrated to alkenes.
On the other hand hydrocarbons do not have the

ability to form H-bond with water molecules. Hence
they are insoluble in water.
201. Explain, why propanol has higher boiling point than

that of the hydrocarbon butane?
Ans : OD 2012
The molecules of butane are held together by weak

van der Waals’ forces of attraction while those of
propanol are held together by stronger intermolecular 2. Reaction with NaOH : Phenol dissolves in NaOH
forces of hydrogen bonding. to form sodium phenoxide and water.
202. Write the reaction of Williamson synthesis of
2-ethoxy-3-methylpentane starting from ethanol and
3-methylpentan-2-ol.
Ans : OD 2009
205. Explain why is ortho nitrophenol more acidic than

ortho methoxyphenol ?
Ans : OD 2001
Ortho nitrophenol is more acidic than ortho

methoxyphenol because nitro group is an electron
withdrawing and it will increase + positive charge
on the oxygen atom to make it more acidic whereas
- OCH 3 group is an relectron eleasing group and it
will decrease + positive charge on the oxygen atom,
thus making it less acidic and hence the O-H bond
Then will not break easily.
206. Explain how does the - OH group attached to a
carbon of benzene ring activate it towards electrophilic
substitution?
Ans : FOREIGN 2012

Since there is negative charge at o and p-positions,
therefore, - OH group activates the benzene ring
Conc.H 2 SO 4, T
C6H6 (Sulphonation)
C H SO H
6 5 3 towards electrophilic substitution reactions.
Benzene Benzene sulphonic acid
NaOH, fuse, 573 K

207. Write the mechanism of hydration of ethene to yield
-Na 2 SO 3
C 6 H 5 ONa ethanol?
Sod. phenoxide
Dil.HCl
Ans : OD 2013
-Nacl
C 6 H 5 OH
Phenol
204. Give two reactions that show the acidic nature of

phenol. Compare acidity of phenol with that of
ethanol.
Ans : SQP 2006
The reactions showing acidic nature of phenol are :

1. Reaction with Sodium : Phenol reacts with active
metals like sodium to liberate H 2 gas.
3. 2-Methoxy-2-methylpropane LONG ANSWER QUESTIONS

4. 1-Methoxyethane
Ans : FOREIGN 2008
218. (i) Write the mechanism of the following reaction :
1. CH 3 - CH 2 - CH 2 - ONa + CH 3 CH 2 CH 2 I H+
Iodopropane 2CH 3 CH 2 OH 413 K
$ CH 3 CH 2 OCH 2 CH 2 CH 3 + NaI CH 3 - CH 2 - O - CH 2 - CH 3 + H 2 O
1 - Propoxypropane
(ii) Why ortho-nitrophenol is steam volatile while
para nitrophenol is not ?
Ans : COMP 2023
(i) This reaction proceeds through nucleophilic

bimolecular substitution reaction, i.e., S N 2
mechanism. This reaction completed in four steps:
Step I : Protonation of alcohol
Step II : Formation of carbocation :

4. CH 3 CH 2 ONa + CH 3 I $ CH 3 CH 2 OCH 3 + NaI
Sodium ethoxide Iodomethane
216. Write the mechanism of the reaction of HI with

methoxymethane.
Ans : OD 2016
With equimolar amounts of HI and methoxymethane, Step III : Attack of carbocation on alcohol :
a mixture of methyl alcohol and methyl iodide is
formed by the following mechanism:
Step 1.
Step IV : Attack of carbocation on alcohol :

Step 2.
217. How is 1-propoxypropane synthesised from propan-1-

(ii) ortho-nitrophenol is steam volatile because I
ol? Write the mechanism of this reaction?
tramolecular hydrogen bonding is present in
Ans : COMP 2011, FOREIGN 2003
ortho -nitrophenol whereas in Para-nitrophenol
CH 3 - CH 2 - CH 2 OH + Na intermolecular hydrogen bonding present due to
which it boils at relatively is higher temperature
$ CH 3 CH 2 CH 2 ONa + CH 3 CH 2 CH 2 I
due to the association of molecules.
$ CH 3 CH 2 CH 2 OCH 2 CH 2 CH 3 + Nal
219. What happens when
Mechanism : (i) Anisole is treated with CH3Cl/ anhydrous AlCl3 ?
CH 3 CH 2 CH 2 OH + Na $ CH 3 CH 2 ONa + 1 H 2 (g) (ii) Phenol is oxidised with Na2Cr2O7/H+ ?
2
(iii) (CH3)3—C—OH is heated . with Cu/573 K?
CH 3 CH 2 CH 2 ONa $ CH 3 CH 2 CH 2 O5 + Na+
Write chemical equation in support of your answer.
2. Compounds containing sp2 hybridised carbon 4. From Grignard Reagents : The first step of the
(i) Vinyl alcohol : CH 2 = CH - OH reaction is the nucleophilic addition of Grignard
reagent to the carbonyl group to form adduct.
(ii) Phenols :
Hydrolysis of the adduct yields an alcohol.
224. Write various methods of preparation of alcohol.

Ans : OD 2010, COMP 2005
Various methods of preparation of alcohol are as follows:

1. From Haloalkanes (alkyl halides)
CH 3 CH 2 - Br + KOH (aq) $ CH 3 CH 2 - OH + KBr
Bromoethane Ethanol
2. From Alkenes
(i) Hydration of Alkenes-(addition of a molecule
of water)
(ii) Hydroboration-oxidation
(i)(BH 3) 2
CH 3 - CH = CH 2 (ii) H 2 O 2 /OH-
CH 3 - CH 2 - CH 2 - OH
Propan - 1 - ol
(Anti Mark addition)

5. From aliphatic primary amines
3. From Carbonyl Compounds
(i) By reduction of aldehydes and ketones
H 2 /Ni or Na/C 2 H 5 OH
R - CHO or LiAlH 4 or NaBH 4
RCH 2 OH
Aldehyde 1c Alcohol
225. Write various methods of preparation of phenol.

Ans : OD 2005
Various methods of preparation of phenol are as

(ii) By reduction of carboxylic acid and esters follows:
(i) LIAlH 4 1. From benzenesulphonic acid
RCOOH (ii) H 2 O
RCH 2 OH
Carboxylic acid Alcohol
RlOH
RCOOH H+
RCOOR'
Carboxylic acid Ester
H2
Catalyst
RCH 2 OH + R'OH
(Commercial preparation)
Ans : SQP 2019 Ans : DELHI 2004

1. Friedel-Crafts alkylation :
2. Nitration of anisole :
The reaction proceeds by S N 1 mechanism. Since

the benzyl carbocation is more stable than the
ethyl carbocation therefore cleavage of C-O
bond gives ethyl alcohol and benzyl carbocation.
The benzyl carbocation
then reacts with I- ion to form benzyl 3. Bromination of anisole in ethanoic acid medium.
iodide.
4. Friedel-Craft acetylation of anisole

Aryl oxygen bond O-C 6 H 5 is more stable than
alkyl oxygen bond O-CH 3 . Therefore I- ion
breaks the weaker O-CH 3 bond forming methyl
iodide and phenol.
4. I- attacks at the smaller alkyl group of the
protonated ether to form 2-Methylbutan-1-ol and
iodo ethane.
229. How are the following conversions carried out?

1. Propene $ propan-2-ol
2. Benzyl chloride $ Benzyl alcohol
3. Ethylmagnesium chloride $ Propan-1-ol
4. Methyl magnesium bromide $ 2-Methyl
propan-2-ol
Ans : OD 2009, SQP 2008
228. Write equation of the following reactions:

1. Friedel-Crafts reaction-alkylation in anisole
2. Nitration of anisole
3. Bromination of anisole in ethanoic acid medium.
4. Friedel-Crafts acetylation of anisole.
233. Write structures of the products of the following

reactions:
H 2 O/H+
1. CH 3 - CH = CH 2
232. Show how are the following alcohols prepared by the

reaction of a suitable Grignard reagent on methanal?
1. CH 3 - CH - CH 2 OH
|
CH 3 Ans : DELHI 2007, OD 2004
Ans : OD 2016
CH 3 - CH - CH 2 OH
1. | : 2. NaBH 4 is weak reducing agent, it reduces the
CH 3 aldehydes and ketones but not the esters. Thus,
3. The - CHO group is reduced to CH 2 OH . Thus,
234. Write IUPAC names of the compounds :
4. C6H5 - O - C2H5
237. Write IUPAC names of the compounds :
239. Write structures of the compounds whose IUPAC

names are as follows :
1. 2-Ethoxy-3-methylpentane
2. Cyclohexymethanol
3. 3-Cyclohexypentan-3-ol
4. Cyclopent-3-en-1-ol
5. 3-Chloromethylpentan-1-ol
Ans : OD 2003

1. 2, 2, 4-Trimethylpentan-3-ol
2. 5-Ethylheptane -2, 4-diol
3. Butane-2, 3-diol
4. Propane-1, 2, 3
5. 2-Methylphenol
6. 4-Methylphenol
238. Write structures of the compounds whose IUPAC
names are as follows :
1. 2-Methyphenol-2-ol
2. 1-Phenyopropan-2-ol
3. 3, 5-Dimethylhexane-1, 3, 5-triol
4. 2, 3-Diethylphenol
5. 1-Ethoxypropane
Ans : COMP 2019
240. Name the reagents used in the following reactions:
1. Oxidation of a primary alcohol to a carboxylic
acid
2. Oxidation of a primary alcohol to aldehyde
3. Bromination of phenol to 2, 4, 6-tribromophenol
4. Benzyl alcohol to benzoic acid
5. Dehydration of propan-2-ol to propene
6. Butan-2-one to butan-2-ol
Ans : FOREIGN 2000
244. Write equations of the following reactions:

1. Friedel-Craft’s reaction-alkylation of anisole.
2. Nitration of anisole.
3. Bromiantion of anisole in ethanolic acid medium.
4. Friedel-Crafts acetylation of anisole.
Ans : OD 2007
245. Give reasons for the following:

1. o -nitrophenol is more acidic than o
-methoxyphenol.
2. Butan-1-ol has a higher boiling point than diethyl
either.
3. (CH 3) 3 C - O - CH 3 on reaction with HI gives
(CH 3) 3 C - I and CH 3 - OH as the main products
and not (CH 3) 3 C - OH and CH 3 - I .
1. The nitro group (- NO 2) is an electron-
withdrawing group. It decreases the electron
density on the O-H bond. Thus, the proton
can be easily lost. In the presence of an electron-
withdrawing group, the phenoxide ion gets more
stabilised. Due to the high stability of phenoxide
ion, the acidic nature increases. On the other
hand, the methoxy group is an electron-releasing
group. It increases the density in the O-H Bond.
Thus, the proton cannot be given out easily.
Thus, the phenoxide ion is less stabilised. Due
to this reason, o-nitrophenol is more acidic than
o-methoxyphenol.
Ans : COMP 2010

own lives but they are also a threat to the lives of
others. Anger and rule behaviour are some of its ill
effects.
(i) Given two uses of alcohol.
(ii) Comment on statement should production of alcohol
be banned. Give two valid reasons to justify.
(iii) Name an alcohol which causes blindness.
(iv) How ethanol can be obtained ?
Ans :
(i) (a) It is used in so many ways for medicines.
(b) It is used as solvent of resins, fats, oil etc.
(ii) (a) It causes death of many people.
(b) Many adolescents get affected out of it and
become addict to alcohol.
(iii) Methanol ^CH 3 OHh .
(iv) Ethanol can be obtained by fermentation of cane
sugar.
250. Phenols are acidic in nature. In substituted phenols,
CASE BASED QUESTIONS electron withdrawing groups such as —NO2, enhances
acidic strength of phenol, if —NO2 group is present at
248. Miss Kalpana was asked to synthesise alcohol by o- and p-position. It is due to effective delocalisation of
acidic hydration of 1-buctane. She was unware of the negative charge on phenoxide ion. Electron releasing
fact that the vessel she used has some coating of metal groups, such as alkyl groups, do not favour formation
and in addition to alcohol (b.p. 373 K) compound of phenoxide ions resulting in decrease in acid strength
Z (b.p. 353 K) was also isolated. Z forms bisulphite e.g. cresols are less acidic than phenols.
compound as well as 2, 4-dinitrophenyl hydrazone. The following table gives values of some Phenols and
Separation of alcohol could be made by physical as Ethanol.
well as chemical method.
Compound Formula pKa
(i) How is alcohol acid ‘Z’ formed ?
(ii) Can alcohol acid Z give iodoform test ? o-Nitrophenol o-O2N—C6H4—OH 7.2
(iii) Give any method of separation. m-Nitrophenol m-O2N—C6H4—OH 8.3
(iv) Draw the functional isomer of C 2 H 5 OH . p-Nitrophenol p-O2N—C6H4—OH 7.1
Ans :
Phenol C6H5OH 10.0
(i) Since ‘Z’ forms bisulphite and 2, 4- dinitro-phenol
hydrazone. It means Z has carbonyl group formed o-Cresol o-CH3—C6H4—OH 10.2
due to oxidation of alcohol. This oxidation is due m-Cresol m-CH3—C6H4—OH 10.1
to coating of metal (Cu). p-Cresol p-CH3—C6H4—OH 10.2
(ii) Alcohol and ‘Z’ both give iodoform test.
Ethanol C2H5OH 15.9
(iii) Distillation.
(iv) CH 3 —O—CH 3 Êtherh Answer the following questions :
Methoxy methane. (a) From the above data, how many times phenol is
more acidic than ethanol?
249. Ehanol, commonly called as alcohol is an excellent
(b) Out of phenols given in the table, which phenol is
solvent and is used in medicines and synthesis of many
most acidic and why?
chemical compounds. However in spite of its benefit
to man its impact on social behaviour has always (c) (i) Arrange the following in increasing order
been questioned. Media have often shown abnormal of acidic strength : phenol, o-nitro phenol,
behaviour of people while drunk. It is considered as m-nitro phenol, p-nitro phenol, p-cresol
a curse in the lives of those who addicted to alcohol (ii) Why are phenols less acidic than carboxylic
called alcoholic people because it not only affect their acids?
Chap 8 Aldehydes, Ketones and Carboxylic Acids Page 383
CHAPTER 8
Aldehydes, Ketones and Carboxylic Acids
SUMMARY 3. GENERAL METHODS OF PREPARATION OF ALDEHYDES

AND KETONES
(i) From alcohol :
1. CARBONYL GROUP (a) By oxidation :
The functional group > C = O is called carbonyl group.
Organic compounds containing carbonyl group are
aldehydes, ketones, carboxylic acids and their derivatives.
The general formulae of these compounds are
(b) By dehydrogenation :
(ii) From carboxylic acids :
2. STRUCTURE OF ALDEHYDES AND KETONES

These are carbonyl compounds and contain carbonyl
(> C = O) functional group. The C -atom of the
carbonyl group is sp2 hybridised and bonded to alkyl
group and one hydrogen atom by s -bonds in case of
aldehydes and two alkyl groups by s -bond in case of
ketones.
(iii) From acid chloride (Rosenmund’s reduction)
(Name Reaction) :
For ketones :
There is double bond between C and O made-up of a

strong s and weak p bond.
(b) With Grignard reagent : (e) With ammonia :

6HCHO + 4NH 3 $ (CH 2) 6 N 4 + 6H 2 O
(f) With primary amines :

RCHO + RNH 2 $ RCH = NR + H 2 O
Schiff's base
2. Oxidation reaction :
[O]
(c) With alcohols : RCHO KMnO 4 /H 2 SO 4
RCOOH
[O]
RCOR KMnO 4 /H 2 SO 4
RCOOH + CO 2 + H 2 O
3. Reduction :
(i)
Ketones do not react with monohydric alcohols but

they react with dihydric alcohols. (ii) Clemmensen’s reduction (Name Reaction) :
Zn/Hg
CH 3 CHO + 4 [H] HCl
CH 3 - CH 3 + H 2 O
Zn/Hg
CH 3 COCH 3 + 4 [H] HCl
CH 3 CH 2 CH 3 + H 2 O
(iii) Wolff-Kishner reduction (Name Reaction) :
(d) With ammonia derivatives : NH 2 NH 2
CH 3 CHO CH 3 - CH 3
(i) With hydroxylamine : KOH
H+ NH 2 NH 2
CH 3 CHO + H 2 NOH CH 3 CH = NOH + H 2 O CH 3 COCH 3 KOH
CH 3 CH 2 CH 3
Acetaldoxime
+
H
CH 3 COCH 3 + H 2 NOH (CH 3) 2 C = NOH + H 2 O 7. ALDOL CONDENSATION
Acetoxime
(ii) With hydrazine : It takes place between two molecules of aldehydes or

H +
ketones having a - H atoms.
CH 3 CHO + H 2 NNH 2 CH 3 CH = NNH 2 + H 2 O
Acetaldehyde hydrazone
H+
CH 3 COCH 3 + H 2 NNH 2 (CH ) C = NNH 2 + H 2 O
3 2
Acetone hydrazone
(iii) With phenylhydrazine :

H+
CH 3 CHO + H 2 NNHC 6 H 5 CH 3 CH = NNHC 6 H 5 + H 2 O
Acetone phenylhydrazone
H+
CH 3 COCH 3 + H 2 NNHC 6 H 5 (CH 3) 2 C = NNHC 6 H 5 + H 2 O
Acetaldehyde semicarbazone
(iv) With semicarbazide :

CH 3 CHO + H 2 NNHCONH 3
H+
CH 3 CHNNHCONH 2 + H 2 O
Acetaldehyde semicarbazone
CH 3 COCH 3 + H 2 NNHCONH 2
H+
(CH 3) 2 C = NNHCONH 2 + H 2 O
Acetone semicarbazone
Physical properties of carboxylic acids : (x) Kilbe’s electrolysis (Name Reaction) :

1. They are polar in nature from H -bonds and exist 2CH 3 COONa + 2H 2 O
as dimers. Electrolysis
C 2 H 2 + 2CO 2 + 2NaOH + H 2
2. Lower members are soluble in water because they
from H -bonds with water whereas the higher Acidic Nature of Monocarboxylic acids
members are insoluble in water. Presence of electron withdrawing substituents (e.g.,
3. Monocarboxylic acids have higher boiling points -Cl, NH 2 ,- NO 2 , - C 6 H 5 etc.) increase their acidity.
than alcohols although both involve H -bonds. Increase of number of electrons withdrawing
This is because in monocarboxylic acids : substituents increases their acidity. Thus,
1. There are more number of H -bonds CH 3 COOH < ClCH 2 COOH < Cl 2 COOH < Cl 3 CCOOH
Acetic acid Monochloro acetic acid Dichloro acetic acid Trichloro acetic acid
2. The hydrogen bonds are stronger than in
alcohols due to greater polarity of -O-H bonds As the electron withdrawing substituent is move away
from - COOH group, the acidity rapidly diminishes.
Acid strength of the halogen substituted carboxylic

acid decreases as follows:
4. Their acidic strength decreases with increases in
molecular mass.
Chemical properties of carboxylic acids :
(i) With active metals :
2RCOOH + 2Na $ 2RCOONa + H 2
(ii) With carbonates :
2RCOOH + Na 2 CO 3 $ 2RCOONa + CO 2 + H 2 O
(iii) With PCl 3 :
3RCOOH + PCl 3 $ RCOCl + H 3 PO 3 Ortho substituted aromatic carboxylic acids are
(iv) With PCl 5 stronger than para and meta substituted acids. Thus,
RCOOH + PCl 5 $ RCOCl + POCl 3 + HCl
(v) With alcohols :
Conc.H 2 SO 4
RCOOH + RlOH RCOORl + H 2 O
(vi) With NH 3 :
RCOOH + NH 3
T
RCOONH 4 $ RCONH 2 + H 2 O
(vii) Decarboxylation :
CaO
RCOOH + NaOH RH + Na 2 CO 3
(viii) Reduction :
LiAlH 4
RCOOH RCH 2 OH + H 2 O
HI/P
RCOOH R - R + 2H 2 O + 3I 2
(ix) Hell-Volhard Zelinsky reaction (Name Reaction):
Cl 2 /P
CH 3 COOH -HCl
ClCH 2 COOH
Monochloroacetic acid
Cl 2 /P
-HCl
Cl 2 CHCOOH
Dichloroacetic acid
Cl 2 /P
- -HCl
Cl 3 CCOOH
Trichloriacetic acid
8. The reaction is called : hydrogen present. So HCHO is expected to undergo

Pd/BaSO 4 Cannizzaro reaction.
RCOCl + H 2 RCHO + HCL
(a) Cannizzaro Reaction
12. Which of the following undergo aldol condensation?
(b) Rosenmund’s Reaction (a) HCHO (b) CH 3 CHO
(c) Haloform Reaction (c) C 6 H 5 CHO (d) None of these
(d) Clemensen’s Reaction Ans : OD 2000
Ans : SQP 2017 The criteria for an aldehyde or a ketone to undergo
The Rosenmund’s reduction is a hydrogenation aldol reaction is the presence of alpha hydrogen.
process in which an acyl chloride is selectively reduced The mentioned compound as CH 3 CHO have alpha
to analdehyde. hydrogen, it will undergo for aldol condensation
RCOCl + H 2
Pd/BaSO 4
RCHO + HCl reaction.
9. Which of the following compound is most reactive 13. In the following reaction, product ‘P’ is
towards nucleophilic addition?
O
||
O
||
(a) CH 3 - C - CH 3 (b) CH 3 - C - H
O
||
O
||
(c) C 6 H 5 - C - CH 3 (d) C 6 H 5 - C - C 6 H 5 (a) RCH 2 OH (b) RCOOH
Ans : COMP 2018

(c) RCHO (d) RCH 3
Presence of alkyl group in carbonyl compounds Ans : SQP 2013, DELHI 2010
decreases their reactivity towards nucleophilic

addition. Further greater the number of such groups
lesser will be the reactivity towards nucleophilic
addition.
O
||
Hence, CH 3 - C - H is most reactive towards Thus (c) is correct option.
nucleophilic addition.
14. In the Friedel Crafts acylation reaction, the effective
Thus (b) is correct option. electrophile is
10. Dry distillation of calcium formate gives : (a) RCOCl + (b) AlCl 3
(a) HCHO (b) HCOOH (c) RCOCl (d) RCO +
(c) CH 3 COOH (d) CH 3 CHO Ans : COMP 2001
Ans : SQP 2015
Calcium formate 8^COOHh2 CaB gives form aldehyde

on dry distillation.

15. Among the following the strongest acid is
(a) CH 3 COOH (b) CH 2 ClCH 2 COOH
(c) CH 2 ClCOOH (d) CH 3 CH 2 COOH
11. Which of the following undergoes Cannizzaro’s
reaction? Ans : DELHI 2005
(a) CH 3 CHO (b) CH 3 CH 2 CHO Chlorine is electron withdrawing group. Further

Inductive effect is stronger at a position than b
(c) ^CH 3h2 CHCHO (d) HCHO
-position i.e.,
Ans : COMP 2017 a b a
Carbonyl compound having no a hydrogen undergo CH 2 ClCOOH > CH 2 ClCH 2 COOH
cannizzaro reaction. In HCHO, there is no alpha Thus (c) is correct option.
20. In a set of reactions, ethylbenzene yielded a product Ans : FOREIGN 2016
D. This reaction is an example of Hell-Volhard Zelinsky

reaction. In this reaction acids containing a -H on
treatment with X 2 /P give di-halo substituted acid.
Br2 /P
CH 3 - CH 2 COOH CH 3 - CBr2 - COOH
22. Formalin is an aqueous solution of
(a) Fluorescein (b) Formic acid
(c) Formaldehyde (d) None of these
Ans : OD 2003
Formaline contains 40%HCHO,8%CH3OH and 52%
water. It is used as biological preservation.
23. Benzoic acid gives benzene on being heated with X
and phenol gives benzene on being heated with Y.
Therefore X and Y are respectively
(a) Soda-lime and copper
(b) Zn dust and NaOH
(c) Zn dust and soda-lime
(d) Soda-lime and zinc dust
Ans : SQP 2000
Soda - lim e (X)
C 6 H 5 COOH C 6 H 6 + Na 2 CO 3 + H 2 O
Zn dust (Y)
Ans : DELHI 2016 C 6 H 5 OH C 6 H 6 + ZnO
24. Among acetic acid, phenol and n-hexanol, when of
the following compounds well react with NaHCO 3
solution to give sodium salt and carbon dioxide?
(a) Acetic acid
(b) n-Hexanol
(c) Acetic acid and phenol
(d) Phenol
Ans : SQP 2008, FOREIGN 2005
Among acetic acid, phenol and n-hexanol only
Thus (d) is correct option. CH 3 COOH reacts with NaHCO 3 to evolve CO 2 gas.
21. Propionic acid with Br2 P yields a dibromo product. CH 3 COOH + NaHCO 3 $ CH 3 COONa + CO 2 + H 2 O
Its structure would be Thus (a) is correct option.
25. (CH 3) 3 C-CHO does not undergo Aldol condensation
due to
(a) three electron donating methyl groups
(b) CH 2 Br-CH 2-COBr (b) cleavage taking place between-C-CHO bond
(c) absence of alpha hydrogen atom in the molecule
(d) bulky (CH 3) 3C- group
Ans : COMP 2013
Aldol condensation is given by the compounds which
(d) CH 2 BR-CHBr-COOH contain a hydrogen atom. As the given compound
Thus acetone reacts with iodine to form iodoform in 33. Schotten-Baumann reaction is a reaction of phenols
the presence of NaOH. with
Thus (b) is correct option. (a) Benzoyl chloride and sodium hydroxide
30. Which one of the following on treatment with 50% (b) Acetyle chloride and sodium hydroxide
aqueous sodium hydroxide yields and corresponding (c) Salicylic acid and conc. H 2 SO 4
alcohol and acid?
(d) Acetyl chloride and conc. H 2 SO 4
(a) C 6 H 5 CHO
Ans : OD 2016
(b) CH 3 CH 2 CH 2 CHO
(d) C 6 H 5 CH 2 CHO
Ans : COMP 2009
Aldehydes containing no a -hydrogen atom on warming The function of NaOH is

with 50% NaOH of KOH undergo disproportionation 1. To convert phenol to more stronger nucleophile
i.e. self oxidation-reduction known as cannizzaro’s phO-
reaction. 2. To neutralize the acid formed.
50% NaOH
2C 6 H 5 CHO + NaOH C 6 H 5 COONa + C 6 H 5 CH 2 OH Thus (a) is correct option.
Thus (a) is correct option. 34. Aspirin is an acetylation product of
31. Which of the following is the correct decreasing order (a) o-hydroxybenzoic acid
of acidic strength of? (b) o-hydroxybenzene
(i) Methanoic acid
(c) m-hydroxybenzoic acid
(ii) Ethanoic acid
(d) p-dihydroxybenzene
(iii) Propanoic acid
(iv) Butanoic acid Ans : SQP 2007
(a) (i)>(ii)>(iii)>(iv) (b) (ii)>(iii)>(ii)>(i)

(c) (i)>(iv)>(iii)>(ii) (d) (iv)>(i)>(iii)>(ii)
Ans : DELHI 2013
An electron releasing substituent (+I effect) intensity

the negative charge on the anion resulting in the
decrease of stability and thus decreases the acidity Thus (a) is correct option.
of the acid. Hence acidic character decreases as the
35. Phenylmethyl ketone can be converted into
+I-effect of the alkyl group increases as
ethylbenzene in one step by which of the following
< CH 3 CH 2 CH 2 CH 3 CH 3 < CH 3 CH 2 < CH 3 CH 2 CH 2 reagents?
Hence the order of acidic strength becomes: (a) LiAlH 4 (b) Zn-Hg/HCl
(i)>(ii)>(iii)>(iv) (c) NaBH 4 (d) CH 3 Mgl
Ans : COMP 2010, OD 2005
32. Iodoform test is not given by
(a) 2-Pentanone (b) Ethanol
(c) Ethanal (d) 3-Pentanone
Ans : FOREIGN 2017
Iodoform test is exhibited by ethyl alcohol acetaldehyde,

acetone methyl ketones and those alchols which
possess CH 3 CH (OH)-group . As 3-pentanone does
not contain CH 3 CO -group as therefore it does not
give iodoform test. This reaction is known as Clemmensen’s reduction.
Thus (d) is correct option. Thus (b) is correct option.
42. 45. An ester is boiled with KOH. The product is cooled

and acidified with concentrated HCl. A white
crystalline acid separates. The ester is
(a) Methyl acetate (b) Ethyl acetate
(c) Ethyl formate (d) Ethyl benzoate
Ans : SQP 2015
Methyl acetate and ethyl acetate on hydrolysis give

The above compound describes a condensation
CH 3 COOH which is a liquid. Similarly ethyl formate
polymer which can be obtained in two ways: either
on hydrolysis will give formic acid which is also a
treating 3 molecules of acetone (CH 3 COCH 3) with
liquid. Only ethyl benzoate on hydrolysis acid which
conc. H 2 SO 4 or passing propyne (CH 3 C / CH)
is a solid.
through a red hot tube. The polymer is
(a) Phorone (b) Mesityl oxide
(c) Deacetonyl (d) Mesitylene 46. An ester (A) with molecular formula, C 9 H 10 O 2 was
treated with excess of CH 3 MgBr and the complex
Ans : FOREIGN 2000
so formed was treated with H 2 SO 4 to give an olefin
Acetone forms mesitylene (1,3,5-trimethyl benzene) (B). Ozonolysis of (B) gave a ketone with molecular
on distillation with conc. H 2 SO 4 . formula C 8 H 8 O which show positive iodoform test.
Thus (d) is correct option. The structure of (A) is
43. The reagent (s) which can be used to distinguish (a) C 6 H 5 COOC 2 H 5
acetophenone from benzophenone is (are) (b) C 2 H 5 COOC 6 H 5
(a) 2,4- Dinitrophenylhydrazine (c) H 3 COCH 2 COC 6 H 5
(b) Aqueous solution of NaHSO 3 (d) p-H 3 CO-C 6 H 4-COCH 3
(c) Benedict reagent Ans : COMP 2010
(d) I 2 and Na 2 CO 3
Ans : OD 2005
I2 and Na 2 CO 3 react with acetophenone

(C 6 H 5 COCH 3) to give yellow ppt. of CHI 3 but
benzophenone C 6 H 5 COC 6 H 5 does not and hence can
be used to distinguish between them.
44. Which of the following compound will undergo self
aldol condensation in the presence of cold dilute
alkali?
(a) CH 2 = CH-CHO (b) CH = C-CHO
(c) C 6 H 5 CHO (d) CH 3 CH 2 CHO
Ans : OD 2017, SQP 2007
Aldehydes which contain a a -hydrogen on a saturated

carbon, i.e., CH 3 CH 2 CHO undergo aldol condensation
47. Ketones
[ ,where R = Rl = alkyl groups ]
can be obtained in one step by

(a) oxidation of primary alcohols
(b) hydrolysis of esters
(c) oxidation of tertiary alcohols
(d) reaction of acid halides with alcohols
53. If formaldehyde and KOH are heated, then we get 56. In which of the following, the number of carbon
(a) Methane (b) Methyl alcohol atoms does not remain same when carboxylic acid is
obtained by oxidation?
(c) Ethyl formate (d) Acetylene
(a) CH 3 COCH 3 (b) CCl 3 CH 2 CHO
Ans : FOREIGN 2001
(c) CH 3 CH 2 CH 2 CH 2 OH (d) CH 3 CH 2 CHO
Aldehydes containing no a -hydrogen atom on warming
with 50% NaOH or KOH undergo disproportionation Ans : SQP 2017
i.e. self oxidation- reduction known as Cannizzaro’s Ketones on oxidation gives carboxylic acids with
reaction lesser number of carbon atoms, i.e.,
50% NaOH [O]
2HCHO + NaOH HCOONa + CH 3 OH CH 3 COCH 3 CH 3 COOH + CO 2 + H 2 O
Thus (b) is correct option. Thus (a) is correct option.
54.
57. Sodium formate on heating yields
(a) Oxalic acid and H 2
(b) Sodium oxalate and H 2
(c) CO 2 and NaOH
The above shown polymer is obtained when a carbonyl (d) Sodium oxalate
compound is allowed to stand. It is a white solid. The Ans : COMP 2013, SQP 2009
polymer is
(a) Trioxane (b) Formose
(c) Paraformaldehyde (d) Metaldehyde
Ans : OD 2005
58. (CH 3) 2 C = CHCOCH 3 can be oxidized to
(CH 3) 2 C = CHCOOH by
(a) Chromic acid (b) NaOl
(c) Cu at 300°C (d) KMnO 4
Ans : DELHI 2010
Chromic acid and KMnO 4 will cleave the molecule

at the site of double bond while Cu at 300°C cannot
Thus (a) is correct option. oxidise COCH 3 $ COOH . The only reagent
55. Reduction of aldehydes and ketones into hydrocarbons suitable for this conversation is NaOl or NaOH + l 2
using zinc amalgam and cone. HCl is called (iodoform test)
NaOl
(a) Cope reduction (CH 3) 2 C = CHCOCH 3 (CH 3) 2 C = CHCOCH + CHl 3
(b) Dow reduction Thus (b) is correct option.

(c) Wolf-Kishner reduction 59. Pinacolone is
(d) Clemmensen reduction (a) 2, 3-dimethyl-2 3-butanediol
(b) 3, 3-Dimethyl-2 butanone
Ans : SQP 2000
(c) I-Phenyl-2Propanone
(d) I, I-Diphenyl-2-ethandiol
Ans : FOREIGN 2014
Pinacolone is 3,3 -dimethyl-2 butanone.

e.g.,

66. Acetaldehyde reacts with semicarbazide and forms 69. In the reaction
semicarbazone. Its structure is CH 3 CHO + HNC " CH 3 CH (OH) CN
H.OH
CH 3 CH (OH) COOH
(a) CH 3 CH = NNHCON = CHCH 3
an asymmetric centre is generated. The acid obtained
(b) CH 3 CH = NNHCONH 2 would be
(a) 20%D+80%L-isomer
(b) D-isomer
(d) CH 3 CH = N-CONHNH 2 (c) L-isomer
Ans : SQP 2005 (d) 50% D+50% L-isomer
Ans : FOREIGN 2016

67. Reaction of phenylacetylene with dil. H 2 SO 4 and
HgSO 4 gives
(a) acetophenone (b) 2-phenylethanol
(c) phenylacetaldehyde (d) phenylacetic acid Thus (d) is correct option.
Ans : COMP 2000 70. A carbonyl compound reacts with hydrogen cyanide
to form cyanohydrin which on hydrolysis forms a
racemic mixture of a -hydroxy acid. The carbonyl
compound is
(a) acetone (b) diethyl ketone
(c) formaldehyde (d) acetaldehyde
Ans : OD 2010, SQP 2009
Out of given compound only acetaldehyde can

form optical active hydroxy acid as it contain one
68. Polarization of electrons in acrolein may be written as: asymmetric carbon atom as marked below:
d- d+
(a) CH 2 = CH-CH = O
d+ d-
(b) CH 2 = CH-CH = O
d+ d-
(c) CH 2 = CH-CH = O
d- d+
(d) CH 2 = CH-CH = O
Ans : DELHI 2011
71. Nucleophilic addition reaction will be most favoured
in
In CH 2 = CH - CHO due to - M effect of - CHO
group polarization of electron takes place as follows : (a) (CH 3) 2 C = O
(b) CH 3 CH 2 CHO
(c) CH 3 CHO
Hence partial polarization is represented as

d+ d- Ans : SQP 2002
CH 2 = CH-CH = O
Aldehydes are more reactive than ketones due to +I
Thus (c) is correct option. effect of - CH 3 group. There are two - CH 3 group
more acidic which can be removed as water. Moreover,

the positive charge on the intermediate carbocation is
relatively away from the C=O group.
77. The order of reactivity of phenyl magnesium bromide
(PhMgBr) with the following compounds
(a) III>II>I (b) II>I>III

(c) I>III>II (d) I>II>III
Ans : COMP 2015, OD 2010
The reactivity of the carbonyl group toward the

nucleophilic addition reactions depend upon the
magnitude of the positive charge on the carbonyl
carbon atom (electronic factor) and also on the
crowding around the carboxyl carbon atom in the
transition state (steric factor). Both these factors
predict the following order
(due to steric crowding).

78. Match the compounds given in List-I with List-II and
select the suitable option using the code given below:
List I List II
(A) Benzaldehyde (i) Phenolpthalein
(B) Phthalic anhydride (ii) Benzoin
condensation 79. Following compounds are given
(C) Phenyl benzoate (iii) Oil of wintergreen (i) CH 3 CH 2 OH
(D) Methyl salicylate (iv) Fries (ii) CH 3 COCH 3

rearrangement
(A) (B) (C) (D)

(a) (iv) (i) (iii) (ii) (iv) CH 3 OH
(b) (iv) (ii) (iii) (i) Which of the above compound (s), on being warmed
(c) (ii) (iii) (iv) (i) with iodine solution and NaOH, will give iodoform?
(d) (ii) (i) (iv) (iii) (a) (i) and (ii) (b) (i), (iii) and (iv)
(c) only (ii) (d) (i), (ii) and (iii)
Ans : DELHI 2010
Ans : FOREIGN 2000
Among the given compounds only CH 3 OH does not

give iodoform reaction.
(c) Assertion is correct but Reason is incorrect. (b) Both Assertion and Reason are correct but Reason
Ans : FOREIGN 2009

Isobutanal does not give iodoform test because it does (d) Both the Assertion and Reason are incorrect.
not have - COCH 3 group. Ans : DELHI 2009
Thus (c) is correct option. Carboxyl group only marginally decreases the electron
87. Assertion : Acetamide has more polar group density at m -position relative to o -and p -positions.
than ethyl acetoacetate. Thus (c) is correct option.
p 2 is more electron donating than OC
Reason : NH p 2H5
90. Assertion : Benzaldehyde is more reactive than
(a) Both Assertion and Reason are correct and ethanol towards nucleophilic attack.
Reason is a correct explanation of the Assertion. Reason : The overall effect of - I and +R effect of
(b) Both Assertion and Reason are correct but Reason phenyl group decreases the electron density on the
is not the a correct explanation of the Assertion. carbon atom of > C = O group in benzaldehyde.
Ans : OD 2014
Ans : SQP 2011
Benzaldehyde is less reactive than ethanol towards

As-NH2 is more basic than RO- hence acetamide has
nucleophilic attack. The combined effect of - I and
more polar group than OC2H5 group in ethyl +R effect of phenyl group is electron donating which
acetoacetate. Hence assertion and reason both are increases the electron density on the carbon atom of
true and reason is correct explanation of assertion. the >O = O in benzaldehyde.
88. Assertion : ROCOl, (RCO)2O and RCOOR’ all react 91. Assertion : The acetate ion is resonance stabilized.
with Grignard reagents to form 3c alcohols. Reason : Acetate ion is more basic than the methoxide
Reason : RCOCl reacts with R2 C d to form ketones ion.
but (RCO)2O and RCOOR’ do not react at all. (a) Both Assertion and Reason are correct and
(a) Both Assertion and Reason are correct and Reason is a correct explanation of the Assertion.
Reason is a correct explanation of the Assertion. (b) Both Assertion and Reason are correct but Reason
(b) Both Assertion and Reason are correct but Reason is not the a correct explanation of the Assertion.
is not the a correct explanation of the Assertion. (c) Assertion is correct but Reason is incorrect.
(c) Assertion is correct but Reason is incorrect. (d) Both the Assertion and Reason are incorrect.
(d) Both the Assertion and Reason are incorrect. Ans : OD 2012
Ans : COMP 2020 Assertion is correct as conjugate base of a strong
RCOCl, (RCO)2O and RCOOR’ all add two molecules acid is weak. Since CH3COOH is a stronger acid than
of Grignard reagents to give 3c alcohols. CH 3 OH , CH3COO- is a weaker base than OCH 3- .
89. Assertion : Nitration of benzoic acid gives m -intro- 92. Assertion : Aldol condensation can be catalysed both
benzoic acid. by acids and bases.
Reason : Carboxyl group increases the electron density Reason : b -Hydroxy-aldehydes or ketones readily
at meta-position. undergo acid-catalysed dehydration.
(a) Both Assertion and Reason are correct and (a) Both Assertion and Reason are correct and
Reason is a correct explanation of the Assertion. Reason is a correct explanation of the Assertion.
Ans : FOREIGN 2005, COMP 2003
^CH 2h6 N 4 + 6H 2 O
T
6HCHO + 4NH 3
Formaldehyde Urotropine
Urotropine is formed
106. Give one good chemical test to distinguish between
the following pair of organic compounds :
101. Write the balanced equation of the following reaction.
Benzaldehyde and acetone
Acetone and phosphorus pentachloride
Ans : COMP 2011
Ans : FOREIGN 2008
Due to the presence of CH 3 CO - group acetone gives
iodoform test, i.e. it gives a yellow ppt. of iodoform
when heated with iodine in the presence of an alkali
while benzaldehyde does not give this test.
107. How can the following conversion be brought about
acetaldehyde to propan-2-ol ?
102. Name the following reaction and write balanced
Ans : OD 2017
equation :
Acetaldehyde with dilute sodium hydroxide
Ans : OD 2002
108. How will you carry out the following conversion?

This reaction is called aldol condensation. Acetaldehyde to iso-propyl alcohol
103. Give balanced equation for the reaction of acetaldehyde Ans : FOREIGN 2002, SQP 2000
with hydroxylamine.
Ans : DELHI 2017
CH 3 CHO + NH 2 OH $ CH 3 - CH=NOH + H 2 O
Acetaldehyde Hydroxylamin e
104. Give the balanced equation for the following reaction.

Benzaldehyde treated with hydrogen cyanide.
Ans : DELHI 2010
109. How can the following conversions be brought about?

Acetaldehyde to formaldehyde
105. Write chemical equation for the following reaction and
Ans : FOREIGN 2014
name the main product :
6O@
Formaldehyde with ammonia CH 3 CHO K 2 Cr2 O 7 + H 2 SO 4
CH 3 COOH
Acetaldehyde
or
NH 3 T Br2 + KOH
How will you carry out the following conversion? CH 3 COONH 4 CH 3 CONH 2
Write the relevant equation. CH 3 NH 2
HNO 2
CH 3 OH
Cu
HCHO
T, (573 K) Formaldehyde
Formaldehyde to urotropine
120. The aqueous solution of sodium acetate is basic. Ans : DELHI 2014
Explain. Kolbe’s electrolytic reaction can be proceed as follows

Ans : DELHI 2015
Let us take an example
- +
Because, when it reacts with water, it produces strong 2CH 3 COONa $ 2CH 3 COO- + 2Na+
Sodium acetate Acetate ion
base, i.e. NaOH which makes the solution basic.
At anode,
121. How will you bring about the following conversion?
2CH 3 COO- $ CH 3 - CH 3 + 2CO 2 + 2e-
Acetaldehyde to acetamide Acetate ion Ethane
Ans : SQP 2009 At cathode,

Acetaldehyde to acetamide 2H 2 O 2H+ + 2OH-
6O@ +NH 3
CH 3 CHO K 2 Cr2 O 7 + H 2 SO 4
CH 3 COOH 2H+ + 2e- $ H 2
Acetaldehyde Acetic acid
CH 3 COONH 4
T
CH 3 CONH 2 2Na+ + 2OH- $ 2NaOH
-H 2 O
Ammonium acetate Acetamide
126. Carry out the following conversion:
122. Give the balanced equations for the following reactions. Benzene to benzoic acid.
Benzaldehyde and hydroxylamine Ans : FOREIGN 2011, COMP 2007
Ans : OD 2012 The conversion of benzene to benzoic acid have the
following steps.
123. Give chemical test to distinguish acetaldehyde and

acetic acid.
Ans : DELHI 2013
Tollen’s test Acetaldehyde reduces Tollen’s reagent to 127. Give the balanced equation for the following reaction.
give shining silver mirror but acetic acid does not. Benzoic acid and phosphorus pentachloride.
CH 3 CHO + 2 6Ag ^NH 3h2@+ + 3OH- $ Ans : OD 2012
Acetaldehyde Tollen's reagent
The balanced chemical equation is
CH 3 COO- + 2Ag . + 2H 2 O + 4NH 3
Acetate ion Silver mirror
CH 3 COOH $ No reaction
Tollen's reagent
124. Give the balanced equations for the following.

Acetone reacts with hydrogen in the presence of
heated copper.
Ans : OD 2011
128. How can the following conversion be brought about?
2-propanol to acetoxime
Ans : FOREIGN 2010
2-propanol to acetoxime
Cu +NH 2 OH
CH 3 CHOHCH 3 O 2, 573 K
CH 3 COCH 3
2 - Propanol Acetone
125. Give the balanced equations for the following reaction:
Kolbe’s electrolytic reaction ^CH 3h2 C = NOH + H 2 O
Acetoxime
1. Strong disinfectant longer alkyl group can hinder the oxygen atom
2. Tissue hardener of aldehydes, thus they can not able to form the
3. Preservative for biological and anatomical intermolecular hydrogen bonds with water and
specimens. therefore are not soluble in water.
4. An antiseptic for sterilising the surgical 139. How will you convert?
instruments. 1. CH 3 COOH $ CH 3 - CH 3
136. Why aldehyde’s are generally more reactive than 2. CH 3 COOH $ CH 3 - CH 2 - OH
ketones in nucleophilic addition reactions?
3. C 6 H 5 COOH $ C 6 H 4 - Br - COOH
Ans : SQP 2008
Ans : DELHI 2004
Aldehydes are generally more reactive than ketones
1. CH 3 COOH + 6HI Red P CH 3 - CH 3 + 2H 2 O + 3I 2
in nucleophilic addition reactions due to steric and
electronic reasons. Sterically the presence of two 2. CH 3 COOH
LiAlH 4
CH 3 CH 2 OH + H 2 O
relatively large substituents in ketones hinders the
approach of nucleophile to carbonyl carbone than in
aldehydes having only one substituent. Electronically,
aldehydes are more reactive than ketones because
two alkyl groups reduces the electrophilicity of the
carbonyl in ketones.
137. Why carboxylic acids do not give characteristics
reactions of Carbonyl group?
Ans : COMP 2022
140. Write the IUPAC names of :
Carboxylic acids do not give characteristic reactions 1. CH 3 - CH 2 Br - COOH
of carbonyl group because of resonance as shown. 2. COOH - CH 2 - CH 2 - COOH
1. 2-Bromo propanoic acid
2. Butane-1, 4-dioic acid
141. Write natural sources of formic acid, acetic acid and
As a result of resonance carboxyl group show single butyric acid.
and double bond characteristic i.e., delocalisation of Ans : FOREIGN 2000
charges, therefore, do not show reaction of carboxyl Formic acid (HCOOH) was first obtained from
group. red ants (Latin formica means ant), acetic acid
138. Give reasons for the following : (CH 3 COOH) from Vinegar (Latin; acetum), butyric
1. Ethyne is more acidic than ethane. acid (CH 3 CH 2 CH 2 COOH) from rancid butter (Latin :
2. Lower members of aldehyde are more soluble in butyrum, means butter)
water. 142. What happens when-
Ans : OD 2014 Acetaldehyde is heated with bleaching powder?
1. Ethyne is more acidic than ethane : More be the Ans : COMP 2014
s -character of the hybrid orbitals of the carbon, Acetaldehyde is heated with bleaching powder:
more it will be acidic in nature. (a) CH 3 CHO + 3Cl 2 $ CCl 3 CHO + 3HCl
As in CH / CH 3 , both the carbon atoms are
sp -hybrid, so has 50% S -character, while in (b) 2CCl 3 CHO + Ca ÔHh2 $ CHCl 3 + Ca (HCOO) 2
CH 3 - CH 3 , Both the carbon atoms are sp3 or
-hybrid, So has 25% S -character. Therefore CH 3 CHO + Ca ÔCl 2h $ CHCl 3 + Ca (HCOO)
CH / CH is more acidic in nature. (acetaldehyde) (bleaching powder) (chloroform)
2. Lower members of aldehyde are more soluble in 143. How pKa value govern the acidity of an acid.
water : In lower aldehydes, a single small alkyl
group (R) can not hinder the oxygen atom of Ans : COMP 2019
-CHO group, thus it can form the intermolecular Dissociation of an acid.

hydrogen bond with H 2 O (water) molecule and RCOOH + H 2 O H 3 O+ + RCOO-
is therefore soluble in water. On the other hand,
Methanoic acid Ethanoic acid

1. Methanoic acid gives Ethanoic acid does not
silver mirror test with give that test.
tollen’s reagent.
2. Methanoic acid gives Ethanoic acid does not
white precipitate with give that test.
mercuric chloride
solution.
HCOOH + HgCl 2 "
Hg 2 Cl 2 + CO 2 + 2HCl
3. It is diffused fehling’s It is no effect on 152. Arrange the following compounds in increasing order
solution. Fehling’s solution. of their reactivity toward HCN.
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl
150. Give the dissimilarities between bond and tert-butyl ketone.
Bond Ans : OD 2000
Ans : COMP 2021 The order of +I effect and steric hindrance is-
The p electron cloud of the is unsymmetrical
i.e., shifts towards oxygen due to greater electro-
negativity to O than C, therefore C atom acquires
a partial +ve charge and hence is readily
attached by nucleophiles. Thus the typical reactions
of bond are nucleophilic addition reactions.
The p electron cloud of is symmetrical
due to similar electro-negativities of the two carbon
atoms therefore it readily allow electrophile to react.
Thus the typical reactions of > C = C < bond are
electrophilic addition reaction.
Reactivity towards HCN addition decreases with
151. Predict the products of the following reactions. increases in +I effect and steric hindrance. Thus the
increasing order of reactivity is
Di-tert-cutyl ketone<Methyl-tert-butyl
ketone>Acetone <Acetaldehyde.
153. Write a note on Haloform reaction.

Ans : OD 2018
Aldehydes and Ketones containing CH 3 CO - group

on treatment with halogen in presence of alkali or
sodium hypohalite (NaOX) produces a haloform
(chloroform, bromoform, or iodoform). In this reaction
methyl group linked to the caboxy carbon atom is
converted to haloform.
CH 3 COCH 3 + 3NaOI " CH 2 COONa + CHI 3 + . 2NaOH

Acetone Sodium Sodium Iodoform
hypoiodite acetate (Yellow ppt)
Due to the formation of yellow ppt in this reaction,

Ans : DELHI 2004 it is known as iodoform test and is used for detection
of compounds containing CH 3 CO - group or
CH 3 CH (OH) - group which produces CH 3 CO group
on oxidation.
160. How substituents effect the acidity of carboxylic 163. How will you convert ethanol into the following
acids? compounds?
Ans : OD 2012 1. Butane-1, 3-diol
Electron withdrawing groups (EWG) increase the 2. But-2-enal
acidity of carboxylic acid by stabilising the condjugate 3. But-2-enoic acid
base through delocalisation of the negative charge. Ans : OD 2009
Electron donating groups (EDG) decrease the acidity Dil. NaOH
by destablishing the conjugate base. 1. 2CH 3 CHO (Aldol condenstion)
CH 3 - CHOH - CH 2 - CHO
Ethanal 3 - Hydroxy bu tan al
NaBH 4
reduction
CH 3 - CHOH - CH 2 - CH 2 - OH
Bu tan e - 1, 3 - diol
The effect of the following groups in increasing acidity 2.

order is
ph < I < Br < Cl < F < CN < NO 2 < CF3 . CH 3 - CH = CH - CHO
But - 2 - enal
(i) Dil.NaOH
161. Give two important used of carboxylic acids. 3. CH 3 CHO (ii) H 2 O+
CH 3 - CH = CHCHO
But - 2 - enal
Ans : COMP 2004
[Ag (NH 3) 2]+ OH-
The important uses of carboxylic acids are as follows: CH 3 CH = CHCOOH
Tollen reagent But - 2 - enoic acid
1. In the manufacturing of soaps.
2. Production of soft drinks and food products. 164. An organic compound with molecular formula C 9 H 10 O
Sodium salts of organic acids find application in forms, 2, 4-DNP derivatives, reduces Tollen’s reagent
preservatives. and undergoes cannizzaro reaction. On vigorous
3. In the manufacturing of drugs such as aspirin, oxidation, it gives 1,2- benzenedicarboxylic acid.
phenacetic etc. Identify the compound.
4. Acetic acids are often used as a coagulant in the Ans : SQP 2006
manufacturing of rubber. The given compound forms a 2, 4-DNP derivative and
5. In making dye stuff, perfumes and rayon. reduces Tollen’s reagent, it must be an aldehyde since
162. Write difference between carboxylic acid and phenol. it undergoes cannizaro reaction, therefore CHO group
is directly attached to the benzene ring.
The difference between carboxylic acid and phenol are On vigorous oxidation, it gives 1, 2-benzenedicarboxylic
as follows: acid, therefore it must be an ortho substituted
benzaldehyde and the only o-substituted aromatic
Carboxylic acid Phenols aldehyde having molecular formula C 9 H 10 O is 2- ethyl
benzaldehyde.
1. Carboxylic acid gives Phenol does not react
Reactions are as follows :
brisk effervescence due with NaHCO 3 .
to the evolution of CO 2
gas when treated with
NaHCO 3 solution.
CH 3 COOH + NaHCO 3
" CH 3
COONa + H 2 O + O 2 -
2. Carboxylic acid give Phenol gives a violet

ppt. when treated with colour with neutral
neutral FeCl 3 solution. FeCl 3 solution.
3CH 3 COOH + FeCl 3
" (CH 3 COO) 3 Fe + HCl
Ferric acetate (Buff
coloured ppt.)
is the lowest. The correct order of increasing order of 3. But-2-enal

boiling points is 4. Pentane-2, 4-dione
CH 3 CH 2 CH 3 < CH 3 OCH 3 < CH 3 OH < CH 3 CH 2 OH 5. 3,3,5-Trimethylhexa-2-one
6. 3,3-Dimethylbutanoic acid
168. Give the IUPAC names of the following compounds :
7. Benzene-1,4-dicarbaldehyde
1. PhCH 2 CH 2 COOH
171. An organic compound with the molecular formula
2. ^CH 3h2 C = CHCOOH C 9 H 10 O forms 2,4-DNP derivative, reduces Tollens’
reagent and undergoes Cannizzaro reaction. On
vigorous oxidation, it gives 1,2-benzenedicarboxylic
acid. Identify the compound.
Ans : DELHI 2006
The given compound forms 2-4, DNP derivative.
Therefore, it is an aldehyde or ketone. Since it
reduces Tollen’s reagent, it must be an aldehyde. The
compound undergoes Cannizzaro’s reaction. So it
does not contain a -hydrogen. On vigorous oxidation,
Ans : OD 2019, SQP 2012 it gives 1, 2, benzendicarboxylic acid, it means that
1. 3-Phenylpropanoic acid it must be contain an alkyl group at 2-position with
respect to - CHO group on the benzene ring.
2. 3-Methylcut-2-enoic acid
3. 3-Methylcyclopentanecarboxylic acid The molecular formula suggests it should be
4. 2, 4, 6-Trinitrobenzoid acid
169. Which acid of each pair shown here would you expect
to be stronger?
1. CH 3 CO 2 H or CH 2 FCO 2 H
2. CH 2 FCO 2 H or CH 2 ClCO 2 H
3. CH 2 FCH 2 CH 2 CO 2 H or CH 3 CHFCH 2 CO 2 H
Ans : OD 2010
1. CH 2 FCOOH
2. CH 2 FCOOH 172. An organic compound (A) (molecular formula
3. CH 3 CHFCH 2 COOH C 8 H 16 O 2 ) was hydrolysed with dilute sulphuric acid
to give a carboxylic acid (B) and an alcohol (C).
Oxidation of (C) with chromic acid produced (B). (C)
on dehydration gives but-1-ene. Write equation for
the reactions involved.
170. Name the following compounds according to IUPAC
Ans : COMP 2015
system of nomenclature :
1. Since the given compound on hydrolysis with dil.
1. CH 3 CH (CH 3) CH 2 CH 2 CHO
H 2 SO 4 gives carboxylic acid (B) and an alcohol
2. CH 3 CH 2 COCH (C 2 H 5) CH 2 CH 2 Cl
(C), it must be an ester.
3. CH 3 CH = CHCHO
2. Since the oxidation of alcohol (C) gives the acid
4. CH 3 COCH 2 COCH 3 B, therefore, both the carboxylic acid B and
5. CH 3 CH (CH 3) CH 2 C (CH 3) 2 COCH 3 alcohol C must contain same number of C atoms.
6. (CH 3) 3 CCH 2 COOH 3. Since ester (A) has eight carbon atoms, therefore,
7. OHCC 6 H 4 CHO - p both carboxylic acid (B) and the alcohol (C) must
Ans : DELHI 2005 contain four C atoms each.
1. 4-Mthylpentanal 4. Alcohol (C) on dehydration gives but-1-ene and
2. 6-Chloro-4-ethylhexan-3-one therefore, C must be a straight chain alcohol i.e.,
butan-1-ol.
Ans : COMP 2016
Structure Common Name IUPAC Name

Aldehydes
CH 3 CH 2 CH 2 CH 2 CHO Valeraldehyde Pentanal
e.g.,
CH 2 = CHCHO Acrolein Prop-2-enal
(CH 2) 2 - C - CH 2 CO $ CH 3
2 $ CH 3 $ CO $ CH 3 + NH 3 $ |
Phthaldehyde Benzene-1,2
NH 2
(diacetone) -dicarbaldehde
Ph - CH = CH - CHO b -phenyl 3-Phenylprop

175. Write common name and IUPAC name of the following acrolein -2-enal
compounds.
Cyclopentane Cyclopentane
Aldehydes
carbaldehyde carbaldehyde
(i) HCHO
(ii) CH 3 CHO 177. Write common name and IUPAC name of the following
(iii) (CH 3) 2 CHCHO compounds.
Ketones
(i) CH 3 COCH 2 CH 3
(ii) (CH 3) 2 CHCOCH (CH 3) 2
(v) CH 3 CH (OCH 3) CHO

Ans : SQP 2021

(iv) (CH 3) 2 C = CHCOCH 3
Aldehydes
(v) phCOph
HCHO Formaldehyde Methanal
Ans : OD 2004
CH 3 CHO Acetaldehyde Ethanal
(CH 3) 2 CHCHO Isobutyraldehyde 2-Methyl
proponal Ketones
l -Methyl 3-Methylcy CH 3 COCH 2 CH 3 Methyl n -propyl Pentan-2-one
cyclohexane clohexane ketone
carbaldehyde carbaldehyde (CH 3) 2 CHCOCH (CH 3) 2 Diisopropyl 2,3-Dimethyl
CH 3 CH (OCH 3) CHO a -Methoxy 2-Methoxy ketone pentan-3-one
propionaldehyde propanal a -Methylcy 2-Methylcyclo
clohexanone hexanone
176. Write common name and IUPAC name of the following
compounds.
Aldehydes (CH 3) 2 C = CHCOCH 3 Mesityl oxide 4-Methylpent
(i) CH 3 CH 2 CH 2 CH 2 CHO -3-en-2-one
(ii) CH 2 = CHCHO phCOph Benzophenone Diphenyl

methanone
178. Write the following reaction :

(i) Rosenmund reduction
(iv) Ph - CH = CH - CHO (ii) Stephen reaction
181. How ketones are prepared from (i) acyl chlorides (ii)
nitriles (iii) benzene
Ans : COMP 2005
(i) From acyl chloride : Treatment of acyl chloride
with dialkyl cadminum gives ketones
(ii) From nitriles : Treating a nitrile with Grignard

reagent followed by hydrolysis gives a ketone.
180. Write the following reactions for aldehydes and ketones. (iii) From benzene : When benzene is treated with
(i) Clemmensen reduction acid chloride in the presence of anhyd. AlCl 3 it
(ii) Wolf-Kishner reduction gives ketone. This reaction is known as Friedel-
(iii) Form action of P in a cols Crafts acylation reaction.
(iv) Reduction with HI+ Red P
(i) Clem mensen reduction- The carbonyl group of
aldehydes and ketones is reduced to CH 2 group on
treatement with zinc amalgam and concentrated
hydrochloric acid.
Zn - Hg, HCl
CH 3 CHO + 4 [H] CH 3 - CH 3 + H 2 O
Ethanal Ethane
Zn - Hg, HCl
CH 3 COCH 3 + 4 [H] CH 3 CH 2 CH 3 + H 2 O
Propanone Propane
(ii) Wolf-Kishner redcution- The carbonyl group of

aldehydes and ketones is reduced to CH 2 group 182. Write the structures of products of the following
on treatement with hydrazine (NH 2 NH 2) followed reactions.
by heating with sodium or potassium hydroxide
in high boiling solvent like ethylene glycol.
NH 2 NH 2 + KOH, glycol
CH 3 CHO -H 2 O
CH 3 CH 3 + N 2
CH 3 COCH 3
NH 2 NH 2 + KOH, glycol
CH 3 CH 2 CH 3 + N 2 (ii) (C 0 H 5 CH 2) 2 Cd + 2CH 3 COCl "
-H 2 O
Hg2+, H 2 SO 4
(iii) Formation of pinacoals- Ketones one reduction with (iii) H 3 C - C / C - HC
magnesium amalgam and water form pinacols.
MnO
(v) 2CH 3 COOH
(iv) Reduction with HI and Red P

Red P
CH 3 CHO + 4 HI CH 3 - CH 3 + H 2 O + 2I 2
Red P
CH 3 COCH 3 + 4HI CH 3 CH 2 CH 3 + H 2 O + 2I 2
present in the products. The aldol and ketol readily 185. Write the preparation of carboxylic acid by the
lose water to give a ,b -unsaturated carbonyl following :
compounds which are aldol condensation products (i) From primary alcohol
and the reaction is called Aldol condensation. (ii) From alkyl benzene
(ii) Cross aldol condensation : When aldol (iii) From nitriles and amides
condensation is carried out between two different
(iv) From grignard reagents
aldehydes or ketones. It is called Cross aldol
condensation. If both of them contain a -hydrogen (v) From acylhalides and anhydrides
atoms, it gives a mixture of four products. (vi) From esters
(vii) From ketones
Ans : SQP 2002
(i) From primary alcohol : Primary alcohol are
oxidised to carboxylic acids with KMnO 4 in
neutral, acidic or alkaline media or by K 2 Cr2 O 7
and chromium trioxide (CrO 3) in acidic media
[Jone’s reagent CrO 3 - H 2 SO 4 ]
1.alkaline KMnO 4
RCH 2 OH 2. H 2 O
R COOH
Cross aldol condensation between an aromatic CH 3 CH 2 OH

CrO 3, H 2 SO 4
CH 3 COOH
aldehyde and an aliphatic aldehyde or a ketone is
Ethanol Ethanoic acid
called claisen-schmidt condensation.
(ii) From alkyl benzenes : Aromatic carboxylic acids
prepared by oxidation of alkyl benzenes with
chromic acid or KMnO 4 . The entire side chain
is oxidised to the carboxyl group irrespective of
length of the side chain.
(iii) Cannizaro reaction : Aldehydes which do not have
an a -hydrogen atom, undergoes self oxidation
and reduction (disproportionation) reaction on
heating with concentrated alkali. In this reaction,
one molecule of the aldehyde is reduced to alcohol
while another is oxidised to carboxylic acid salt.
(iii) From nitriles and amides :
(iv) Mechanism of Cannizaro’s reaction :

188. Show how each of the following compounds could be (iii) Phenol and benzoic acid
converted to benzoic acid. (iv) Pentan-2-one and pentan-3-one
(i) Ethyl benzene (v) Benzaldehyde and acetophenone
(ii) Bromobenzene (vi) Ethanal and propanal
(iii) Acetophenone Ans : FOREIGN 2001
(iv) Phenyl ethene (Styrene) (i) Propanal (CH 3 CH 2 CHO) and propanone
(v) Benzene (CH 3 COCH 3) can be distinguished by the
following tests :
Ans : COMP 2020
(a) Iodoform Test : Propanone give iodoform test
with I 2 /NaOH or NaOI to give yellow ppt.
but propanal does not.
CH 3 COCH 3 + 3NaOI " CHI 3 . + CH 3 COONa + 2NaOH
Propanone Sod. hypo- Iodoform
iodite (Yellow ppt.)
NaOI
CH 3 CH 2 CHO No yellow ppt.
(b) Tollen’s reagent test : Propanal an aldehyde

reduces tollen reagent to give shining silver
mirror but propanone being a ketone does
not.
CH 3 CH 2 CHO + 2 [Ag (NH 3) 2] + + 3OH-
Propanal Tollen's reagent
CH 3 CH 2 COO- + 2Ag . + 4NH 3 + 2H 2 O

Silver
mirror
Tollen's reagent
CH 3 COCH 3 No silver mirror
Propanal
(c) Fehling solution test : Propanal reduces

Fehling’s solution to red ppt of Cu 2 O but
propanone does not.
Fehling solution
CH 3 COCH 3 No red ppt
Propanone
(ii) Acetophenone (C 6 H 5 COCH 3) and benzophenone

(C 6 H 5 COC 6 H 5) can be distinguished by the
iodoform test.
(a) Iodoform test : Acetophenone (a methyl
ketone) gives yellow ppt of iodoform with
NaOI but benzophenone does not.
189. Give simple chemical tests to distinguish between the C 6 H 5 COCH 3 + 3NaOI " C 6 H 5 COONa + CHI 3 + 2NaOH
following pairs of compounds : Acetophenone Sod. benzoate Iodoform
(yellow ppt.)
(i) Propanal and propanone C 6 H 5 COC 6 H 5 " No yellow ppt

Benzophenone
(ii) Acetophenone and benzophenoe
192. Complete the synthesis by giving missing starting

material or products.
dil. NaOH
(i) C 6 H 5 CHO + CH 3 CH 2 CHO
(i) NaBH 4
(ii) CH 3 COCH 2 COOC 2 H 5
(ii) H+
Ammonical - AgNO 3
(vi) CH 3 CH 2 CH 2 CHO (Tollen's reagent)
CH 3 CH 2 CH 2 COOH
Butanal Bu tan oic acid
191. How will you bring about the following conversations

in not more than two steps?
(i) Propanone to propene
(ii) Benzoic acid to Benzaldehyde Ans : FOREIGN 2019, DELHI 2015
(iii) Ethanol to 3-Hydroxybutanal
(i)
(iv) Benzene to m -Nitroacetophenone
(v) Benzaldehyde to Benzophenone
Ans : SQP 2003
(ii) Only keto group is reduced by NaBH 4 .

(iii) CH 3 COOH + NH 3
Ans : COMP 2006
196. How will you prepare the following compounds from

benzene? You may use any inorganic reagent and any
organic reagent having not more than one carbon atom.
(i) Methyl benzoate
(ii) m -Nitro benzoic acid
(iii) p -Nitrobenzoic acid
(iv) Phenyl acetic acid
(v) p -Nitrobenzaldehyde
Ans : FOREIGN 2015
197. Complete the synthesis by giving missing starting

material or products.
H 2 NCONHNH 2
(iii) C 6 H 5 CHO
199. Write the structures of the following compounds:

(i) a -Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentanecarbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone Ans : SQP 2012, COMP 2009
(vi) 4-Fluoroacetophenone.
Ans : OD 2006
201. What is meant by the following terms ? Give an

example in each case.
200. Predict the products of the following reactions : (i) Cyanohydrin
(ii) Semicarbazone
(iii) Hemiacetal
(iv) Ketal
(v) 2, 4- DNP-derivative
Ans : SQP 2019
(i) The compounds containing hydroxyl and
cyano groups on the same carbon atom are
called cyanohydrins. These are also called gem-
hydroxynitriles. These are obtained by the
addition of HCN to a carbonyl group in weakly
basic medium.
(iii) Oximes are formed when aldehydes or ketones or

react with hydroxyl amines in weakly acidic
medium.
(iv) Imines : These are the compounds containing

- CH = N - group and are produced when
aldehydes and ketones react with ammonia
derivatives.
C = O + H2N - Z " C = N - Z + H2O
I min es
Z = - NH 2 , - OH , - NHC 6 H 5 , etc.
(v) Schiff’s base Aldehydes and ketones react with
primary aliphatic or aromatic amines to form
azomethnies which are called Schiff’s bases.
204. Draw the structure of the following compounds :

(i) 3-Methylbutanal
(ii) p -Nitropropiophenone
203. Show how each of the following compounds could be (iii) p -methylbutanal
converted to benzoic acid : (iv) 4-Methylpent-3-en-2-one
(i) Ethylbenzene (v) 4-Chloropentan-2-one
(ii) Acetophenone Ans : DELHI 2000
(iii) Bromobenzene
(iv) Phenylethene (Styrene)
Ans : OD 2014, SQP 2011
The given reactions are:
207. Predict the product when cyclohexanec-arbaldehyde

reacts with following reagents :
(i) PhMgBr and then H 3 O+
(ii) Tollen’s reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid CASE BASED QUESTIONS
Ans : OD 2008
208. The carbon-oxygen double bond is polarised in

aldehydes and ketones due to higher electronegativity
of oxygen relative to carbon. Therefore, they undergo
nucleophilic addition reactions with a number of
nucleophiles such as HCN, NaHSO3,(alcohols, ammonia
derivatives and Grignard reagents. Aldehydes are
easily oxidised by mild oxidising agents as compared
to ketones. Carboxylic acids are considerably more
acidic than alcohols and most of simple phenols.
Now, Answer the following :
(a) Write the name of the product when an aldehyde
reacts with excess alcohol in presence of dry HCl.
(b) Why carboxylic acid is a stronger arid than
phenol?
(ii) Arrange the following in decreasing order of acidic (c) A compound A C5H10O does not give silver mirror
character : with Tollen’s reagent, it gives iodoform test with
CH 3 COOH, CHCl 2 COOH, CH 3 COOH I2 /NaOH. Write possible structures of compounds
and write the chemical reactions involved.
(iii) Out of acetic acid and benzoic acid which one
(d) What happens when :
stronger acid and why ?
(i) Pentan-2-one is oxidised with K2Cr2O7/
(iv) Complete the following reaction :
H2SO4(conc.) on heating.
R - COOH + H 2 O (ii) Acetophenone is oxidised on heating with
K2Cr2O7/H2SO4(conc).
Ans :
Ans :
(i) This is due to their association as they can form
intermolecular hydrogen bond. (a) It is because C—C bond is difficult to break and
needs more bond dissociation enthalpy than C—H
(ii) CHCl 2 COOH > CH 2 ClOOH > CH 3 COOH
bond.
(iii) Benzoic acid is stronger acid due to its – I effect. (b) Sodium salt of 2-methyl but-2-enoate and
- + chloroform are formed.
(iv) R - COOH + H 2 O RCOO + H O 3
Carboxylate ion Hydronium ion
211. Oxidation of Aldehydes and Ketones (Popoff’s Rule)

Aldehydes differ from ketones in their oxidation
reactions.
Aldehydes are easily oxidised to carboxylic acids on (c)
treatment with common oxidising agents like HNO3,
KMnO4, K2Cr2O7, etc. Even mild oxidising agents
mainly Tollen’s reagent, Fehling’s solution, Benedict
reagents, also oxidise aldehydes.
Ketones are difficult to oxidise. They are oxidised
by strong oxidising agents at elevated temperature.
Their oxidation involves C—C cleavage to form
mixture of carboxylic acids. The oxidation
of ketones is governed by Popoff’s rule. ‘In
unsymmetrical ketones, on oxidation of ketones to
carboxylic acids, group is retained by smaller

alkyl group’ is Popoff’s rule.
1 2 3
R - CH 2 - C - CH 2 - Rl
[O] (d) (i)
z K 2 Cr2 O 7 /H 2 SO 4 conc.
O T
R - COOH + RCH 2 COOH + RCH 2 COOH + Rl - COOH

[By cleavage of C 1 - C 2 bond] [By cleavage of C 2 - C 3 bond]
Ketones do not react with Tollen’s reagent and

Fehling’s solutions. Methyl ketones give yellow
precipitate of iodoform with I2 and NaOH. Ketones
can be oxidised by haloform reaction if they have one (ii)
methyl group.
Answer the following questions:
(a) Why is it difficult to oxidise ketone as compared
to aldehyde?
(b) What happens when 3-methyl-pentan-2-one
reacts with sodium hypochlorite? Write chemical
reaction involved?
Chap 9 Amines Page 437
CHAPTER 9
Amines
SUMMARY General methods for the preparation of amines :

(i) From alkyl halides (Hofmann’s ammonolysis)
(Name Reaction) :
Amines : Alcohol, 373 K
These are alkyl or aryl derivatives of ammonia and CH 3 Cl + NH 3 CH 3 NH 2 + HCl
are obtained by replacing one, two or three hydrogen
atoms by alkyl/aryl groups.
Nomenclature :
In common system, an aliphatic amine is named by
prefixing alkyl group to amine, i.e., alkylamine. In
IUPAC system, amines are names as alkanamines.
In secondary and tertiary amines, when two or more
groups are the same, the prefix di or tri is appended
before the name of alkyl group.
Classification :
(ii) From nitro compounds (By reduction) :

Sn + conc. HCl
RNO 2 + 6 [H] RNH 2 + 2H 2 O
(iii) From cyanides/isocyanides (By reduction) :
Structure :
Nitrogen orbitals in amines are sp3 - hybridised and the
geometry of amines is pyramidal. Due to the presence
of unshared pair of electrons, the angle C - N - E ,
(Where, E is C or H) is less than 109.5c.
Amines have trigonal pyramidal shapes in which N
atom undergoes sp3 hybridisation as : (iv) From amides (By reduction) :
LiAlH 4
CH 3 CONH 2 + 4 [H] EEt
CH 3 CH 2 NH 2 + H 2 O
(xii) With phosgene :

S
<
2RNH 2 + COCl 2 $ RNH - C - NH - R + 2HCl
(xiii) Bromination :
(xiv) Nitration :
***********
OBJECTIVE QUESTIONS
Structure of diazonium salts : 1. Among the following, which is the strongest base ?
The diazonium slats have the general formula ArN 2+ X-
and the group N +2 is called diazonium ion group.
Preparation of diazonium salts :
Physical properties of diazonium slats :

The Physical properties of diazonium slats are as Ans : COMP 2023
follows:
(i) They are readily soluble in water but less soluble
in alcohol.
(ii) They are sued in solution state otherwise they
explode in dry state.
Chemical properties of diazonium salts :
The Chemical properties of diazonium salts are as
follows: Thus (c) is correct option.
8. Reaction CH 3 CONH 2
NaOBr
gives: 11. An isocyanide is prepared:
(a) Friedel-Crafts reaction
(a) CH 3 Br (b) CH 4
(b) Perkin reaction
(c) CH 3 COBr (d) CH 3 NH 2
(c) Carbylamine reaction
Ans : DELHI 2009
o
(d) Wurtz reaction
This is Hofmann bromaide reaction in which 1 amine
Ans : SQP 2013
is obtained having one C atom less than the starting
amide. Carbylamine reaction:
Thus (d) is correct option. R - Nh 2 + 3KOH + CHCl 3 $ R - N / C + 3KCl + 3H 2 O
9. The correct order of the increasing basicity of methyl Thus (c) is correct option.
amine, ammonia and aniline is: 12. Which of the following reaction takes place when
(a) methyl amine<aniline<ammonia a mixture of conc. HNO 3 and H 2 SO 4 reacts with
(b) aniline<ammonia<methyl amine benzene at 300 K ?
(a) Sulphonation (b) Nitration
(c) aniline<methyl amine ammonia
(c) Hydrogenation (d) Dehydration
(d) ammonia<aniline<methyl amine
Ans : COMP 2006
Ans : FOREIGN 2001
A mixture of conc. HNO 3 and conc. H 2 SO 4 introduces
In aniline the lone pair on N is involved in
one-NO 2 group at 55 o C and two nitro groups at
delocalization with benzene ring and is not available
100 o C .
for protonation. Methyl amine is a stronger base than
ammonia because +I effect of methyl group increases
electron density on N making it more basic than NH 3 .
Cannot be protonated. least basic CH 3 " NH 2 13. The reaction of nitrous acid on ethyl amine gives:
+I Effect increases (a) Ethane (b) Ethyl nitrite
basicity.
Thus (b) is correct option. (c) Ethyl alcohol (d) Nitroethane
10. Which of the following is the most basic compound? Ans : DELHI 2009
(a) Aniline (b) p -nitroaniline +
C 2 H 5 NH 2 + HONO $ C 2 H 5 + N 2
(c) Acetanilide (d) Benzylamine +
Ans : OD 2016, COMP 2011

The carbonium ion C 2 H 5 may react with H 2 O to
form ethylacohol or lose a proton to form alkene.
14. Which of the following reagents will convert p-menthyl
benzene diazonium chloride into p-cresol?
(a) Cu powder (b) H 2 O
(c) H 3 PO 2 (d) C 6 H 5 OH
Ans : FOREIGN 2017
In (a), (b) and (c) nitrogen is directly attached
with benzene ring whereas in (d) nitrogen is not
directly linked with benzene ring. So lone pair of this
compound is relatively more free to be donated. So
(d) is most basic. In other rings substituent behaves
as electron withdrawing group which decreases the
basicity of aniline.
20. The correct order of increasing basic nature for the 23. The compound obtained by heating a mixture of
bases NH 3 , CH 3 NH 2 and (CH 3) 2 NH is: a primary amine and chloroform with ethanolic
potassium hydroxide (KOH) is:
(a) (CH 3) 2 NH < NH 3 < CH 3 NH 2
(a) an alkyl cyanide (b) a nitro compound
(b) NH 3 < CH 3 NH 2 < (CH 3) NH
(c) an alkyl isocyanide (d) an amide
(c) CH 3 NH 2 < (CH) 3 NH < NH 3 Ans : SQP 2016
(d) CH 3 NH 2 < NH 3 < (CH 3) 2 NH CH 3 CH 2 NH 2 + CHCl 3 + 3KOH $
Ans : FOREIGN 2000 CH 3 - CH 2 NC + 3KCl + 3H 2 O

The alkyl groups are electron releasing group (+I), In this reaction, bad smelling compound ethyl
thus increases then electron density around the isocyanide (CH 3 CH 2 NC) is produced. This equation
nitrogen thereby increasing the availability of the lone is known as carbyl amine reaction.
pair of electrons to proton or lewis acid and making Thus (c) is correct option.
the more basic. Hence more the number of alkyl group
24. Aniline on treatment with HCl and NaNO 2 gives:
more basic is the amine. Therefore the correct order is
(a) Nitroaniline (b) Chloroaniline
NH 3 < CH 3 NH 2 < (CH 3) 2 N .
Thus (b) is correct option. (c) Diazo salt (d) Aminophenol
21. Which one of the following is the strongest base in Ans : COMP 2012
aqueous solution? When aromatic primary amines are treated with

(a) Methylamine (b) Trimethylamine HNO 2 (an ice cold solution of NANO 2 and HCl
dilute), diazo salts are obtained.
(c) Aniline (d) Dimethylamine
Ans : SQP 2011, FOREIGN 2005
Aromatic amines are less basic than aliphatic amines.

Among aliphatic amines the order of basicity is
2 o > 10 > 3 o . The electron density is decreased in 3 o
amine due to crowding of alkyl group over N atom
which makes the approach and bonding by a proton
relatively difficult. Therefore the basicity decreases.
Further Phenyl group show-I effect, thus decreases
the electron density on nitrogen atom and hence the 25. The final product C, obtained in this reaction:
basicity.
Dimethylamine (2 o aliphatic amine) is strongest base
among given choices.
Therefore, the correct order of basic strength is
Dimethylamine>Methylamine>Trimethyl amine>Aniline.
22. Consider the following sequence of reactions: would be :
Reduction HNO 2
Compound [A] [B ] CH 3 CH 2 OH
The compound [A] is:
(a) CH 3 CH 2 CN (b) CH 3 NO 2
(c) CH 3 NC (d) CH 3 CN
Ans : OD 2007

CHCl 3 + KOH
33. Carbylamine test is performed in alcoholic KOH by 36. [A]
reduction
[B ]
heating a mixture of:
reduction
(a) Chloroform and silver powder [C] N - Methylaniline , A is:
(b) an alkyl cyanide and a primary amine (a) Formaldehyde (b) Trichloromethane
(c) an alkyl halide and a primary amine (c) Nitrobenzene (d) Toluene
(d) trihalogenated methane and a primary amine Ans : OD 2017
Ans : COMP 2016
Carbylamine test is for primary amine for example.

CH 3 NH 2 + CHCl 3 + 3KOH $ CH 3 NC + 3KCl + 3H 2
34. Which of the following in most basic?

(a) Benzamide (b) Butamine
(c) Nitrobenzene (d) Benzene
Ans : DELHI 2012

37. Which of the following is not correct?
(a) Ethylamine and aniline both have - NH 2 group
(b) Ethyl amine and aniline dissolve in HCl
Electron donar are bases. - NH 2 is electrondon (c) Ethyl amine and aniline both react with CHCl 3
dontaing group. So, but anamine is most basic among and KOH to form unpleasant smelling compound
the given choices. (d) Ethyl amine and aniline both react with HNO 2 in
Thus (b) is correct option. cold to give hydroxy compounds
Ans : SQP 2007, OD 2004
Nitrous acid reacts differently with aliphatic and

35. on reduction with lithium aluminium
aromatic amines in cold.
hydride gives:
(a) 4 o ammonium salt (b) 1 o amine C H NH 2 + HONO $ C 2 H 5 OH + N 2
2 5
1 o A min e Alcohol
o o
(c) 2 amine (d) 3 amine
Ans : FOREIGN 2013
LiAIH 4
R - CONH 2 R - NH 2

38. Aniline in a set of reactions yielded a product D.
The structure of the product D would be:

(a) C 6 H 5 NHOH (b) C 6 H 5 NHCH 2 CH 3
(c) C 6 H 5 CH 2 NH 2 (d) C 6 H 5 CH 2 OH
(c) methylamine salt and ethanoic acid. Ans : FOREIGN 2015
Benzaldehyde reacts with primary aromatic amine to

(d) ethylamine salt and methanoic acid.
form schiff’s base.
Ans : SQP 2000
C 6 H 5 CH = O + C 6 H 5 NH 2 $ C 6 H 5 CH = NC 6 H 5 + H 2 O
Ethyl isocyanide on hydrolysis form primary amines. Benzaldehyde Aniline Benzaldehyde aniline
H +
This is know as Schiff’s base reaction.
CH 3 CH 2 N = C + H2O CH 3 CH 2 NH 2 + HCOOH
"
Therefore it gives only one mono chloroalkane.
Thus (d) is correct option. 48. The constituent of the powerful explosive RDX is
formed during the nitration of:
45. What is the decreasing order of basicity of primary,
secondary and tertiary ethylamines and NH 3 ? (a) toluene (b) phenol
(a) NH 3 > C 2 H 5 NH 2 > (C 2 H 5) 2 NH > (C 2 H 5) 3 N (c) glycerol (d) urotropine
(b) (C 2 H 5) 3 N > (C 2 H 5) 2 NH > C 2 H 5 NH 2 > NH 3 Ans : OD 2002
(c) (C 2 H 5) 2 NH > C 2 H 5 NH 2 > (C 2 H 5) 3 N > NH 3 RDX is prepared by treating urotropine with furning
nitric acid. When the inner bridge system is destroyed
(d) (C 2 H 5) 2 NH > (C 2 H 5) 3 N > C 2 H 5 NH 2 > NH 3 by oxidation and the peripheral nitrogen atom are
Ans : COMP 2005 nitrated, it forms cyclonitrite (or RDX).
All aliphatic amines are stronger bases than NH 3 Thus (d) is correct option.
and among different ethylamines order of basicity is
2 o > 3 o > 1 o . Thus, the correct order is (d) i.e., 49. Intermediates formed during reaction of RCNH 2 with
||
(C 2 H 5) 2 NH > (C 2 H 5) 3 N > C 2 H 5 NH 2 > NH 3 Br2 and KOH are: O

This anomolous behaviour of tertiary ethyl amine (a) RNHBr and RCONHBr
is due to steric factors i.e., crowding of alkyl groups (b) RNCHOBr and RNCO
cover nitrogen atom from all sides and thus makes (c) RCONHBr and RNCO
the approach and bonding by a lewis acid relatively
(d) RCONBr2
difficult which results the maximum steric strain in
tertiary amines. The electrones are there but the path Ans : SQP 2006
is blocked resulting the reduction in its basicity. The mechanism of Hoffmann bromide reaction is:
Thus (d) is correct option. (i) RCONH 2 + Br2 " RCONHBr + HBr
46. Which is formed, when acetonitrile is hydrolysed
partially with cold concentrated HCl?
(a) Acetic acid
(b) Acetamide
(c) Methyl cyanide
(d) Acetic anhydrides
Ans : DELHI 2017, COMP 2014
Methyl cyanide on treatment with conc. HCl give

acetamide.
Conc.HCl
CH 3 C / N CH 3 CONH 2
Acetonitrile Aniline
47. When aniline reacts with oil of bitter almods 50.
(CH 6 H 5 CHO) condensation takes place and benzal
deriative is formed. This is known as:
(a) Million’s base
(b) Schiff’s reagent
(c) Schiff’s base
(d) Benedict’s reagent Product P in the above reaction is :
53. The major organic product formed form the following Ans : FOREIGN 2001
reaction:

55. Match the compounds given in List-I with their
characteristic reactions given in list-II. Select the
correct option.
List-I (Compounds) List-II (Reactions)

1. CH 3 CH 2 CH 2 CH 2 NH 2 (i) alkaline hydrolysis.
2. CH 3 C = CH (ii) with KOH produces
Thus (b) is correct option. (alcohol) and CHCl 3 bad smell.
3. CH 3 CH 2 COOCH 3 (iii) gives white ppt.
with ammonical
AGNO 3 .
4. CH 3 CH (OH) CH 3 (iv) with Lucas reagent
cloudiness appears
after 5 minutes.
54. Aniline is reacted with bromine water and the (a) 1-iv, 2-ii, 3-iii, 4-i
results product is treated with an aqueous solution (b) 1-ii, 2-i, 3-iv, 4-iii
of sodium nitrite in presence of dilute hydrochloric
(c) 1-iii, 2-ii, 3-i, 4-iv
acid. The compound so formced is converted into a
tetrafluoroborate which is subsequently heated dry. (d) 1-ii, 2-iii, 3-i, 4-iv
The final product is: Ans : OD 2017
(a) 1, 3, 5- tribromobenzene 1. CH 3 CH 2 - CH 2 - CH 2 - NH 2
(b) b -bromofluorobenzene (ii) with KOH (alcohol) and CHCl 3 produces bad
smell.
(c) p -bromoaniline
2. CH 3 / CH
(d) 2, 4, 6-tribromofluorobenzene
(iii) gives white ppt with ammonical AgNO 3
65. C 7 H 9 N has now many isomeric forms that contain a

benzene ring?
(a) 4 (b) 5
(c) 6 (d) 7
Ans : OD 2017
C 7 H 9 N having one benzene ring may be represented

Thus (a) is correct option. as C 6 H 5 CH 4 N , CH 4 N may be in the form of 1 o and
61. Acetanilide can be prepared from aniline with: 2 o amines in the following five isomeric forms.
(a) Ethanol (b) Acetaldehyde
(c) Acetic anhydride (d) None of the above
Ans : SQP 2015

66. Hinsberg reagent is:
(a) C 6 H 5 SO 3 H (b) C 6 H 5 NO
(c) CH 3 H 5 SO 2 Cl (d) C 6 H 5 N 2 Cl
Ans : SQP 2015

67. Which of the following gives primary amine on
reduction?
(a) CH 3 CH 2 NO 2
(b) CH 3 CH 3 - O - N = O
(c) C 6 H 5 N = NC 6 H 5
(d) CH 3 CH 2 NC
62. C 6 H 5 C = N and C 6 H 5 N"
= C exhibit which type of
isomerism? Ans : COMP 2002
(a) Position (b) Functional Thus (a) is correct option.

(c) Dextroisomerism (d) Position isomerism 68. Which of the following reactions will not give a
primary amine?
Ans : COMP 2001
Br2 /KOH
Thus (b) is correct option. (a) CH 3 CONH 2
63. Nitrobenzene on further excessive nitration gives: (b) CH 3 CN
LiAlH 4
(a) sym -Trinitrobenzene (b) m -Dinitrobenzene

LiAlH 4
(c) p -Dinitrobenzene (c) CH 3 NC
(d) All of these
LiAlH 4
Ans : DELHI 2006 (d) CH 3 CONH 2
Thus (b) is correct option. Ans : DELHI 2008
64. Which of the following compounds does not react CH 3 NC (methyl isocyanide) on reduction with
with NaNO 2 and HCl? LiAlH 4 gives secondary amine.
(a) C 6 H 5 OH (b) C 6 H 5 NH 2 Thus (c) is correct option.
(c) (CH 3) 3 CNO 2 (d) (CH 3) 3 CNO 2 69. Consider the following reaction:
C 6 H 5 NO 2
Sn/HCl
X
C 6 H 5 COCl
Y + CHl
With nitrous acid : (i) phenol gives p -nitrosophenol,
What is Y?
(ii) aniline gives diazonium salt, and (iii) 2 o nitro
compounds give pseudonitrole, while 3 o nitro (a) Acetanilide (b) Benzanilide
compounds do not react because they have no a (c) Azobenzene (d) Hydrazobenzene
-hydrogen atom.
Ans : SQP 2005
ASSERTION AND REASON 81. Assertion : p - O 2 N $ C 6 H 4 $ COCH 3 is prepared by

Freidel Craft’s acylation of nitrobenzene.
Reason : Nitrobenzene easily undergoes electrophilic
DIRECTION : Given below are two statements labelled as substitution reaction.
Assertion and Reason. Select the most appropriate answer (a) Both Assertion and Reason are correct and
from the options given below: Reason is a correct explanation of the Assertion.
78. Assertion : Amines are basic in nature
Reason : Presence of lone pair of electrons on nitrogen
atom.
Reason is a correct explanation of the Assertion. Ans : OD 2013
Nitrobenzene undergoes electrophilic substitution

reaction with difficulty because NO2 group is electron
withdrawing and therefore, it deactivates the benzene
(c) Assertion is correct but Reason is incorrect. ring.
(d) Both the Assertion and Reason are incorrect. Thus (d) is correct option.
Ans : COMP 2006 82. Assertion : Anilinium chloride is more acidic than
Amines are basic in nature due to presence of a lone ammonium chloride.
pair of electrons on nitrogen. Reason : Anilinium ion is resonance stabilized.
Thus (a) is correct option. (a) Both Assertion and Reason are correct and
79. Assertion : Benzene diazonium chloride does not give Reason is a correct explanation of the Assertion.
test for nitrogen. (b) Both Assertion and Reason are correct but Reason
Reason : Loss of N2 gas takes place during heating. is not the a correct explanation of the Assertion.
(a) Both Assertion and Reason are correct and (c) Assertion is correct but Reason is incorrect.
Reason is a correct explanation of the Assertion. (d) Both the Assertion and Reason are incorrect.
(b) Both Assertion and Reason are correct but Reason Ans : DELHI 2015
is not the a correct explanation of the Assertion. Anilinium chloride is more acidic than ammonium
(c) Assertion is correct but Reason is incorrect. chloride because it liberates aniline (resonance
stabilized) when heated with strong base.
Anilinium ions does not show resonance because
Ans : SQP 2006
charge dispersion at ring may involve pentavalent
Benzene diazonium chloride does not give test of nitrogen structure.
nitrogen as nitrogen gas is evolved on heating. Thus (c) is correct option.
83. Assertion : Aniline is better nucleophile than anilium
80. Assertion : Nitration of aniline can be conveniently ion.
done by protecting the amino group by acetylation. Reason : Anilium ion have positive charge.
Reason : Acetylation increases the electron-density in (a) Both Assertion and Reason are correct and
the benzene ring. Reason is a correct explanation of the Assertion.
Ans : OD 2011
It is fact that aniline is better nucleophile than
Ans : DELHI 2009
anilium ion. Anilium ion contain positive charge,
Acetylation decreases the electron density in the which reduces the tendency to donate lone pair of
benzene ring thereby preventing oxidation. electron C 6 H 5 NH 3+ (anilium ion).
90. Write the balanced chemical equation for the following

reaction and name the reaction. Acetamide is heated
with bromine and sodium hydroxide solution.
Ans : OD 2013
CH 3 CONH 2 + Br2 + 4NaOH $

Acetamide
CH 3 NH 2 + 2NaBr + Na 2 CO 3 + 2H 2 O
Methyla mine 95. Give a chemical test to distinguish between ethylamine
This reaction is known as Hofmann- bromamide and diethylamine.
reaction. Ans : FOREIGN 2014
91. Arrange the following in the increasing order of their Hinsberg’s test can distinguish between ^1ch
basic strength. ethylamine and ^2ch diethylamine.
C 2 H 5 NH 2 , C 6 H 5 NH 2 , ^C 2 H 5h2 NH 96. Write the equation for the preparation of acetanilide

from aniline.
Ans : OD 2018
Ans : SQP 2014
Basic character of amines depends upon the availability
of lone pair of electrons on nitrogen for donation.
Presence of electron releasing group increases the
electron density over nitrogen, thus lone pair of
nitrogen are available for donation. Hence, basic
character increases. Due to resonance in aniline, lone
pair of electron gets delocalised inside the benzene
ring, thus it is less available for protonation. This reaction is known as acetylation.
Thus, the correct increasing order of basic strength is 97. Complete the following reaction and name the
C 6 H 5 NH 2 < C 2 H 5 NH 2 < ^C 2 H 5h2 NH reaction.
C 3 H 7 NH 2 + CHCl 3 + 3KOH âlc.h
T
92. Convert benzoic acid to aniline.
Ans : DELHI 2016, OD 2013 ...... + 3KCl + 3H 2 O
Ans : DELHI 2012
C 3 H 7 NH 2 + CHCl 3 + 3KOH âlc.h

T
C 3 H 7 NC + 3KCl + 3H 2 O
This reaction is called carbylamine reaction.
98. Give the balanced equation for the following.
Acetamide is heated with sodium hydroxide.
Ans : OD 2011
- +
Boil
CH 3 CONH 2 + NaOH CH 3 COONa + NH 3
Acetamide Sodium acetate
This reaction is called hydrolysis of amide in alkaline

conditions.
99. Give the balanced equation for the following reaction.
93. Give the balanced equation for carbylamine reaction. Aniline is treated with benzoyl chloride.
Ans : SQP 2016 Ans : FOREIGN 2009
Carbylamine reaction
RNH 2 + CHCl 3 + 3KOH $ RNC + 3KCl + 3H 2 O
94. Give the balanced equation for Hofmann’s degradation
reaction.
Ans : OD 2015
Hofmann’s degradation reaction

CLASS 12

CLASS 10

110. Give balanced equation for the following reaction But, if the temperature is raised to 373 K ^100cCh , m
given below. -dinitrobenzene is formed.
Aniline is treated with a mixture of NaNO2 and excess
of HCl at low temperature.
Ans : FOREIGN 2007
NaNO 2
C 6 H 5 NH 2 + HNO 2 + HCl HCl at low temperature
+ -
C 6 H 5 N / NCl + 2H 2 O
111. How can the following conversion be brought about?
Acetic acid to methyl cyanide
114. Complete the reaction :
Ans : COMP 2014
112. Complete the following reaction and name the

intermediate products A, B and C. Ans : DELHI 2017, OD 2012
Ans : DELHI 2006 115. Write the names and structures of four isomeric
amines having the molecular formula C 3 H 9 N .
Ans : OD 2017
A is m-chloronitrobenzene Propylomine
B is m-chloroaniline
C is m-chlorobenzene diazonium chloride
SHORT ANSWER QUESTIONS
113. Describe method of nitration of benzene. IsoPropylamine

Ans : FOREIGN 2018 CH 3 - N - CH 3
Benzene when nitrated with a mixture of conc. HNO 3 |
and conc. H 2 SO 4 at a temperature below 333 K CH 3
^60cCh gives nitrobenzene.
N-methyl thanamine
CH 3 - CH - CH 3
|
NH 2
Propane-2-amine
Like ammonia, nitrogen atom of amines is trivalent 127. Arrange the following in
and carries an unshared pair of electrons. Nitrogen (i) increasing order of boiling point C 2 H 5 OH ,
orbitals in amines ae sp3 hybridised and the geometry (CH 3) 2 NH , C 2 H 5 NH 2
of amines is pyramidal. (ii) Increasing order of solubility in water C 6 H 5 NH 2 ,
(C 2 H 5) 2 NH , C 2 H 5 NH 2
Ans : FOREIGN 2019
(i) Alcohols form stronger H-bonds than amine
due to higher electro negativity of O than N.
Therefore boiling point of alcohols are higher
than amines of comparable molecular mass. In
amines the extent of H-bonding depends upon the
123. Give the classification of Amines. number of H-atom on the N-atom. Therefore 1c
Ans : OD 2003 amine C 2 H 5 NH 2 have higher boiling point than
Amines are classified as primary (1c), secondary 2c amine (CH 3) 2 NH. Thus the order of boiling
(2c) and tertiary (3c) depending upon the number point is
of hydrogen atoms replaced by alkyl or aryl groups in (CH 3) 2 NH < C 2 H 5 NH 2 < C 2 H 5 OH
ammonia molecule. (ii) Solubility increases with increases in the number
of H-atoms on the N-atom which form H-bonding
and decreases with increase in molecular mass
C 6 H 5 NH 2 (93), (C 2 H 5) 2 NH (73), C 2 H 5 NH 2 (45).
Thus the increasing order of solubility in water is
C 6 H 5 NH 2 < (C 2 H 5) 2 NH < C 2 H 5 NH 2
124. What are quaternary ammonium compounds?
128. Why do primary amines have higher boiling points
than tertiary amines?
Quaternary ammonium compounds are derivatives of Ans : SQP 2007
ammonium salts in which all the four H-atoms of the
Boiling point in amines increases with increase in
ammonium ion have been replaced by alkyl or aryl
H-bonding. Since primary amines have two H-atoms
groups.
on N-atoms but tertiary amines do not have H-atom,
Example : therefore primary amines have higher boiling points
[(CH 3) 4 N] + I- C 6 H 5 N+ (CH 3) 3 Br- than tertiary amines.
Tetamethylammonium iodide Trimethylphenyl ammonium bromide
125. Why Gabriel phthalimide syntehsis is preferred for

synthesis primary amines?
Ans : FOREIGN 2015
Gabriel phthalimide reaction gives pure 1c amines

without any contamination of 2c and 3c amines.
Therefore it is preferred for synthesis of 1c amines.
129. On which factors the basicity of an amine depends in
126. Complete the following reactions. aqueous solution?
LiAlH 4
(i) NaN 3 + CH 3 Cl Ans : FOREIGN 2013
LiAlH 4 The basicity of an amine in aqueous solution mainly

(ii) CH 3 CH = NOH or Na/C 2 H 5 OH depends upon the stability of the ammonium cation
(i) NH 3 formed by accepting a proton from water. The stability
(iii) CH 3 CHO (ii) H 2 /Ni
of the ammonium cation depends upon the following
Ans : OD 2001 three factors :
LiAlH 4 (i) +I-Effect of the alkyl groups
(i) NaN + CH 3 Cl
3 CH 3 NH 2 + N 2
Sodium azide Chloromethane
-NaCl
Methana min e (ii) Extent of H-bonding with water molecule.
LiAlH 4 (salvation effect)
(ii) CH 3 CH = NOH CH 3 CH 2 - NH 2
Acetaldoxime
or Na/C 2 H 5 OH
Ethana min e (iii) Steric effects of the alkyl group (when alkyl group
(i) NH 3 is bigger than-CH 3 group).
(iii) CH 3 CHO (ii) H 2 /Ni
CH 3 CH 2 - NH 2
Ethanal Ethana min e
be an amine. The only aromatic amine having

molecular formula C 6 H 7 N is C 6 H 5 NH 2 (aniline).
(ii) Since 'Cl is aniline, the amide from which it is
formed by must be benzamide (C 6 H 5 CONH 2).
Br2, KOH
C 6 H 5 NH 2 C 6 H 5 CONH 2
Aniline (C) Benzamide (B)
Thus, B is benzamide.
(iii) Since B is formed from A with aqueous ammonia
and heating, therefore, compound 'Al must be
benzoic acid.
aq. NH 3
C 6 H 5 COOH Heat
C 6 H 5 CONH 2
Benzoic acid Benzamide (B)
(A)
Thus, A = C 6 H 5 COOH ,
B = C 6 H 5 CONH 2
C = C 6 H 5 NH 2
139. Describe the method for the identification of primary,
secondary and tertiary amines. Also write chemicals
of involved.
137. Write IUPAC names of the following compounds and Ans : COMP 2017
classify them into primary, secondary and tertiary Primary, secondary and tertiary amines can be
amines. identified by using Husberg’s reagent. (Husberg’s
(i) (CH 3) 2 CHNH 2 reagent test)
(a) The reaction of benzenesulphonyl chloride with
(ii) CH 3 (CH 2) 2 NH 2
primary amine yield N-ethylbenzen sulphonamide
(iii) CH 3 NHCH (CH 3) 2 (I).
(iv) (CH 3) 3 CNH 2
(v) C 6 H 5 NHCH 3
(vi) (CH 3 CH 2) 2 NCH 3
(vii) m - BrC 6 H 4 NH 2
Ans : DELHI 2003
(i) Propan-2-amine (1c)
(ii) Propan-1-amine (1c)
(iii) N-methylpropan-2-amine (2c)
(iv) 2-Methylpropan-2-amine
(b) In the reaction with secondary amine, N,
(v) N-Methylbenzanamine N-diethylbenzenesulphonamide (II) is formed.
(vi) N-Ethyl-N-methylethanamine (2c)
(vii) 3-Bromobenzenamine or 3-Bromonaniline (1c)
138. An aromatic compound 'A' on treatement with aqueous
ammonia and heating forms compound 'Bl which on
heating with Br2 and KOH forms a compound 'Cl of
molecular formula C 6 H 7 N . Write the structure and
IUPAC names of compound A,B and C .
Ans : SQP 2006
(i) Since the compound C of molecular formula
C 6 H 7 N is formed B on treatment with Br2 and
KOH (Hoffmann bromamide reaction), therefore, (c) Tertiary amines do not react with benzenesulphonyl
the compound 'Bl must be an amide and 'Cl must chloride.

(i) CH 3 CH 2 CH 2 NH 2 + HCl " CH 3 CH 2 CH 2 NH 3 Cl- Four structural isomers are possible
n - propyla min e n - propylammonium chloride
+ CH 3 - CH - CH 3 CH 3 - N - CH 3
(ii) (C 2 H 5) 3 N + HCl " (C 2 H 5) 3 NHCl- CH 3 CH 2 CH 2 NH 2 ; CH 3 - NH - C 2 H 5
N - methyl ethana min e
;
Trithylammonium chloride Propan - 1 - a min e NH 2 (2c) CH 3
(1c) Propan - 2 - a min e N, N - Dimethylmethana min e
146. Write reaction of the final alkylation product of (1c) (3c)
aniline with excess of methyl iodide in the presence of

Only 1c amines react with HNO 2 to liberate N 2 gas.
sodium carbonate solution.
Ans : DELHI 2005 CH 3 CH 2 NH 2 + HNO 2 " CH 3 CH 2 CH 2 OH + H 2 O + N 2
Propan - 1 - a min e Propan - 1 - ol
C 6 H 5 NH 2 + CH 3 I $ 9C 6 H 5 NH 2 CH 3C I-
+
Aniline N - Methylanilinium iodide
2 [C 6 H 5 NH 2 CH 3] I- + Na 2 CO 3 " 2C 6 H 5 NHCH 3
N - Methylaniline
+ CO 2 + 2NaI
CH 3 I
p HCH 3
C6H5N C 6 H 5 N (CH 3) + CO 2 + 2NaI 150. Convert
Na 2 CO 3
N, N - Dimethyl aniline
1. 3-Methylaniline into 3-nitrotuluene
+
C 6 H 5 N (CH 3) 2 + CH 3 I " C 6 H 5 N (CH 3) 3 I- 2. Aniline into 1, 3, 5-tribromobenzene
N, N, N - Trimethylanilinium iodide Ans : DELHI 2000
+ +
2C 6 H 5 N (CH 3) 3 I- + Na 2 CO 3 " 2C 6 H 5 N (CH 3) 3 I- + Na 2 CO 3
147. Write chemical reaction of aniline with benzoyl

chloride and write name of the product obtained.
Ans : FOREIGN 2011
148. Ethylamine is soluble in water whereas aniline is not?

Ans : COMP 2001
Ethylamine is soluble in water due to the formation of

inter molecular H-bonding between Ethylamine and
water molecules.
151. Write the reaction involved in the following :

But in aniline due to the large hydrophobic part
(hydrocarbon part), the extent of H-bonding decreases (i) Carbylamine test
and hence aniline is insoluble in water. (ii) Gabriel phthalimide synthesis
149. Write structure of different isomers corresponding to
the molecular formula, C 3 H 9 N . Write IUPAC names (i) Carbylamine test :
of the isomers which will liberate nitrogen gas on CH 3 CH 2 NH 2 + CHCl 3 + 3KOH $ CH 3 CH 2 NC
treatment with nitrous acid. + 3KC1 + 3H 2
them to form H-bond. As a result the ammonium

ion formed during protonation is less stablilised
making it more difficult to accept a proton from
water and decreasing their basicity.
(iii) Ammonolysis of alkyl halide is not a good
method to prepare pure primary amines because
the process of ammonolysis yield a mixture of
primary, secondary, tertiary and quaternary
salts. The separation of mixture of amine, very
complicated process and difficult. Therefore, it is
difficult to prepare pure amines by ammonolysis
of alkyl halide.
156. Write common name and IUPAC name of following
amines.
(i) CH 3 CH 2 - NH
(ii) CH 3 CH 2 CH 2 - NH 2
(iv) CH 3 - NH - CH 2 CH 3
Amine Common name IUPAC name

(i) NH2 - CH2 - CH = CH2 Allylamine Prop-2-en-1-amine
(ii) NH2 - (CH2) 6 - NH2 Dexamethylene Hexane-1,6-diamine

diamine
(iii) Aniline Aniline or
Ans : FOREIGN 2003
Benzenamine
Amine Common name IUPAC name
(i) CH3 CH2 - NH Ethylamine Ethanamine
(ii) CH3 CH2 CH2 - NH2 n-Propylamine Propan-1-amine

(iv) o -Toluidine 2-Methylaniline
(iii) Isopropylamine Propan-2-amine
(iv) Ethyl N-Methyl (v) N, N-Dimethyl N, N-Dimethyl

methylamine ethanamine aniline benzenamine
(v) Trimethyla- N,N-Dimethyl-

mine methanamine
(vi) p-Bromo 4-Bromoaniline
(vi) N,N- N-N- aniline
Diethylbutyl- Dimethylbutan-
amine 1-amine
157. Write common name and IUPAC name of following

amines.
(vii) Benzylamine Phenylmethanamine
(i) NH 2 - CH 2 - CH = CH 2
(ii) NH 2 - (CH 2) 6 - NH 2
158. Write following methods of preparation of amines:

(i) Reduction of nitro compounds.
(ii) Ammonolysis
Ans : FOREIGN 2001

order of basicity of amines is 3c 2 2c 2 1c.
(i) All three classes of aliphatic amines are stronger The overall order of basicity is
bases than ammonia because alkyl groups are
(CH 3) 3 N > (CH 3) 2 NH > CH 2 NH 2 > NH 3
electron donating groups they increase the
electron density on the nitrogen atom and thus (ii) In aqueous solution basicity of methyl amines
amines can donate the lone pair of electrons more depends upon two factors-
easily than ammonia. (a) + I effect- According to this the basicity is
(CH 3) 3 N > (CH 3) 2 NH > CH 3 NH 2
(b) Solvation effect- On the basis of solvation effect
greater the number of H-atoms on N-atom,
more stable is the ammonium ion and hence
more basic is amine. The ammonium cation
derived form a 1c amines is the most stable
(ii) Aromatic amines are less basic than ammonia and
sincce it has three H-atoms which can form
aliphatic amines. The weaker basic character of
aniline is due to the following reasons: H-bonds with H 2 O , the ammonium cation
derived from 2c amine is less stable since it
(a) Resonance in aniline-
has two H-atoms which can form H-bands
and 3c amine is least stable since it has only
one H-atom which can form H-bond with
H 2 O . Hence the basicity should decrease in
the order: CH 3 Nh 2 > (CH 3) 2 NH > (CH 3) 3 N .
Due to resonance, the lone pair of electrons

on the nitrogen atom gets delocalised over
the benzene ring and thus is less available for
protonation. Therefore aromatic amines are
weaker bases than ammonia.
(b) Lower stability of anilinium ion- Aniline
is more stable than anilinium ion because
anilinium ion has only two resonating
structure. Hence aniline has very little
tendency to form anilinium ion by accepting
a proton.
The combined effect of these two opposite

factors (a) and (b) is that (CH 3) 2 NH is the
strongest base.
In case of CH 3 NH and (CH 3) 3 N the stability
due to H-bonding predominates over +I effect
160. Predict giving reasons, the order of basicity of the of the CH 3 groups. Thereby CH 3 NH 2 is more
following compounds is stronger than (CH 3) 3 N. Thus the overall
(i) gaseous phase and relative basicity of methylamines is in the
(ii) in aqueous solution (CH 3) 3 N , (CH 3) 2 N , CH 3 NH 2, order.
NH 3 (CH 3) 2 NH > CH 3 NH 2 > (CH 3) 3 N > NH 3
Ans : COMP 2007 161. Write the following Electrophilic substitution reaction
All amines are more basic than NH 3 due to + I effect for aniline.
of alkyl groups in amines. (i) Bromination
(i) In gaseous phase the basicity of amines depends (ii) Nitration
only on + I effect of the alkyl groups the + I (iii) Sulphonation
effect increases from 1c to 3c amine therefore the
Ans : FOREIGN 2005

Amines also react with benzyl chloride
(C 6 H 5 COCI)
This reaction is known as benzoylation.
CH 3 NH 2 + C 6 H 5 COCl $ CH 3 - NHCOC 6 H 5 + HCl
Methana min e Benzoyl chloride N - Methylbenzamide
Aq. NaOH
C 6 H 5 NH 2 + C 6 H 5 COCl C 6 H 5 NHCOC 6 H 5 + HCl
Aniline chloride N - phenylbenzamide
(Benzanilide)
(ii) Carbylamine reaction : Aliphatic and aromatic

primary amines on heating with chloroform and
ethanolic potassium hydroxide form isocyanides or
carbylamines which are foul smelling substances.
Secondary and tertiary amines do not show this
reaction. This reaction is known as carbylamine
reaction or isocyanide test and is used as a test
for primary amines.
(iii) C 6 H 5 NH 2 + CHCl 3 + 3KOH (alc) " C 6 H 5 N =
v C
Aniline Chloroform Heat
+ 3 KCl + 3H 2 O R - NH 2 + CHCl 3 + 3KOH (alc.) RN =
v C
1cA min e Chloroform alkyl
isocyanide
+ 3KCl + 3H 2 O
(v) C 6 H 5 NH 2 + CH 3 CO - O - COCH 3 " C 6 H 5 -

Aniline Acetic anhydride Ace tan ilide
NHCOCH 3 + CH 3 COOH (iii) Reaction with nitrous acid :

NaNO 2 + HCl
R - NH 2 + HNO 2 R - OH + N 2 + H 2 O
163. Write the following reactions of amines. 1ca min e Alcohol
(i) Acylation or Acetylation NaNO 2 + 2HCl

+
C 6 H 5 NH 2 C 6 H 5 - N 2 Cl- + NaCl + H 2 O
(ii) Carbylamine reaction Aniline 273 - 278K
Benzendiazonium
chloride
(iii) Reaction with nitrous acid
(iv) Reaction with aryl sulphonyl chloride (iv) Reaction with arysulphonyl chloride :
Ans : COMP 2012, SQP 2008 Benzenesulphonyl chloride (C 6 H 5 SO 2 Cl) known
as Hinsberg’s reagent reacts with primary and
(i) Acylation : Aliphatic and aromatic primary
secondary amines to form sulphonamides.
and secondary amines react with acid chlorides,
anhydrous and esters by nucleophilic substitution
reaction. This reaction is called acylation
(replacement of hydrogen atom of - NH 2 or
> N - H group by the acyl group - COR ).
The hydrogen attached to nitrogen in

sulphonamide is strongly acidic,hence it is
soluble in alkali.
isocyanide, dimethylamine is a secondary

amine and hence does not give this test.
or
(b) Nitrous acid test : Methyl amine being a
primary amine react with NaNO 2 and HCl
under cold condition and release N 2 gas.
Dimethyl amine does not give this test.
R - NH 2 + HNO 2 " R - OH + N 2 - + H 2 O
(ii) Hinsberg test : Secondary amine react with
Benzenesulphonyl chloride (C 6 H 5 SO 2 Cl) and
form sulphonamide which is insoluble in NaOH.
(iii) Azodye test : Aniline being an aromatic primary
amine when reacts with HNO 2 (NaNO 2 + HCl) at
273 - 278 K followed by treatment with alkaline
solution of phenol gives orange colour dye.
Ethylamine (an aliphatic primary amine) under
these condition give a brisk evolution of N 2
gas with formation of Ethanol and the solution
remains clear.
(iv) Azo dye test : Aniline reacts with HNO 2 at
273 - 278 K followed by treatment with alkaline
solution of Phenol gives orange dye. Benzylamine
does not give this test.
(v) Carbylamine test : Aniline being a primary amine
gives carbylamine test. When it is heated with
alcoholic KOH and CHCl 3 gives offensive smell
of phenyl isocyanide but N-methylaniline being a
secondary amine does not give this test.
167. Write short notes on the following :
(i) Carbylamine reaction
(ii) Diazotisation
(iii) Coupling reaction
(iv) Acetylation
Ans : SQP 2018
(i) Carbylamine reaction : Primary amines (both
aliphatic and aromatic) when heated with chloroform
and ethanolic potassium hydroxide from isocyanides
(also known as carbylamines) which have a foul
smell. This reaction is called carbylamine reaction
166. Give one chemical test to distinguish between the and is used as a test for primary amines. 2c and 3c
following pairs of compounds. amines do not show this reaction.
Heat
(i) Methylamine and dimethylamine R - NH 2 + CHCl 3 + 3KOH (alc) R - NC + 3KCl + 3H 2 O
(ii) Secondary and tertiary amine (ii) Diazotisation : Aromatic amines react with nitrous
(iii) Ethylamine and aniline acid (HNO 2) at low temperature (273 - 278 K) to
(iv) Aniline and benzylamine form diazonium salts. The process is known as
(v) Aniline and N-methylaniline diazotisation e.g.
(i) (a) Carbylamine test : Methylamine is a primary

amine, therefore it gives carbylamine test,
when it is heated with an alcoholic KOH
and CHCl 3 it gives offensive smell of methyl
KCN
CH 3 CH 2 I -KI
CH 3 CH 2 CN CH 3 CH 2 CN
H+ H 2 O
Hydrolysis
CH 3 CH 2 COOH
Propanoic acid
HONO P, I 2 KCN
(vi) CH 3 NH 2 CH 3 OH CH 3 I CH 3 CN
Na, C 2 H 5 OH
CH 3 CN Reduction
CH 3 CH 2 NH 2
Ethana min e
Sn, HCl
(vii) CH 3 NO 2 Reduction
CH 3 NH 2
Nitromethane
CHCl 3 .KOH Na, C 2 H 5 OH

T
CH 3 NC Reduction
CH 3 NHCH 3
Dimethyla min e
NH 3
(viii) CH 3 CH 2 COOH CH 3 CH 2 COONH 4
Propanoic acid
169. How will you convert T
(i) Ethanoic acid into methanamine CH 3 CH 2 CONH 2
(ii) Hexanenitrile into 1-aminopentane Br2 .KOH
CH 3 CH 2 NH 2
HONO
CH 3 CH 2 OH
(iii) Methanol to ethanoic acid Hoffmann
bromamide
reaction
(iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid K 2 Cr2 O 7 H+
CH 3 CHO
K 2 Cr2 O 7 H+
CH 3 COOH
Oxidation Oxidation
(vi) Methanamine into Methanamine Ethanal Ethanoic acid
(vii) Nitromethane into dimethylamine 170. Give plausible explanation for each of the following :
(viii) Propanoic acid into ethanoic acid ? (i) Why are amines less acidic than alcohols of
Ans : FOREIGN 2012 comparable molecular masses?
SOCl 2 (ii) Why are primary amines higher boiling than
(i) CH 3 COOH -SO 2, - HCl
CH 3 COCl tertiary amines?
Ethanoic acid
NH 3 (excess) Br2, KOH (iii) Why are aliphatic amines stronger bases than
CH 3 CONH 2 CH 3 NH 2 aromatic amines?
Hofmann Methana min e
bromamide
reaction Ans : COMP 2000
H 3 O+ (i) Loss of proton from amines give amide ion whereas

(ii) CH 3 (CH 2) 4 CN Hydrolysis
CH 3 (CH 2) 4 COOH loss of a proton from alcohol gives an alkoxide ion.
Hexanenitrile
SOCl 2
CH 3 (CH 2) 4 COCl RNH 2 " RNH- + H+
A min e Amide ion
NH 3 (excess)
CH 3 (CH 2) 4 CONH 2 Br2, KOH ROH " RO- + H+
T CH 3 (CH 2) 4 NH 2 Alcohol Alkoxide ion
Hoffmann 1 - A min open tan e
bromamide
reaction
Since O is more electronegative than N , therefore,
RO- can accommodate the - ve charge more
PCl 5 KCN alc
(iii) CH 3 OH CH 3 Cl CH 3 CN easily than RNH- . Consequently, RO- is more
Methanol
stable than RNH- . thus alcohols are more acidic
H 3 O+
CH 3 COOH acid amines.
Hydrolysis
Ethanoic acid
(ii) Primary amines (RNH 2) have two hydrogen atoms
HONO K 2 Cr2 O 7 H+
(iv) CH 3 CH 2 NH 2 CH 3 CH 2 OH Oxidation
on the N atoms and therefore, form intermolecular
hydrogen bonding.
K 2 Cr2 O 7, H+
CH 3 CHO Oxidation
CH 3 COOH
NH 3 (excess) T
CH 3 COOH CH 3 CONH 4
Br2, KOH
CH 3 CONH 2 CH 3 NH 2
Hoffmann Methana min e
Bromamide
reaction
Tertiary amines (R 3 N) do not have hydrogen
(v) CH 3 COOH
LiAlH 4
CH 3 CH 2 OH
P, I 2 atoms on the N atom and therefore, these do not
Reduction or PI 3
Ethanoic acid form hydrogen bonding in primary amines, they
have higher boiling points than tertiary amines
(i) Why methyl amine is more basic than ammonia ? 174. Amines constitute an important class of organic
(ii) Arrange the following amines in increasing order compounds derived by replacing one or more
of boiling point : hydrogen atoms of ammonia molecule by alkyl/
CH 3 CH 2 CH 2 NH 2, CH 3 —N—CH 3 CH 3 —CH 2 —NH aryl groups. Amines are usually formed from nitro
; ; compounds, halides, amides, etc. They exhibit
CH 3 CH 3 hydrogen bonding which influences their physical
properties. Alkyl amines are found to be stronger
(iii) Give a chemical test to distinguish between
bases than ammonia. In aromatic amines, electron
CH 3 NH 2 and (CH 3) 2 NH .
releasing and withdrawing groups, respectively
(iv) Write the IUPAC name of CH 3 - N - H. increase and decrease their basic character. Reactions
; of amines are governed by availability of the unshared
CH 3
Ans : pair or electrons on nitrogen. Influence of the number
(i) Due to + I effect. of hydrogen atoms at nitrogen atom on the type
of reactions and nature of products is responsible
(ii) CH 3 - N - CH 3 < CH 2 - CH 2 —NH
for identification and distinction between primary,
; ;
CH 3 CH 3 secondary and tertiary amines. Reactivity of aromatic
amines can be controlled by acylation process.
3º 2º
In the context of given passage, answer the following
< CH 3 CH 2 CH 2 NH 2 questions :
(iii) CH 3 NH 2 i.e., 1º amine show carbylamine reaction (i) Why does aniline not give Friedel-Crafts reaction?
whereas (CH 3) 2 NH i.e., 2º amine donot show this (ii) Arrange the following in the increasing order of
reaction. their pKb values :
(iv) N -Methyl methanamine. C6H5NH2, NH3, C2H5NH2, (CH3)3N
173. An organic compound Âh having molecular formula (iii) How can you distinguish between CH3CH2NH2
C 2 H 7 N on treatment with nitrous ‘add gives a and (CH3CH2)2 NH by Hinsberg test?
compound ^B h having molecular formula C 2 H 6 O . ^B h (iv) Write the structures of A and B in the following
on treatment with an .organic compound ^C h gives a reactions:
carboxylic acid ^D h and a sweet smelling compound
Ê h . Oxidation of ^B h with acidified potassium
dichromate also gives ^D h .
(i) Identify ‘A’ and draw its structure also. (a)
(ii) Identify ‘D’ . Br2 /alc. KOH
(iii) Write down the reaction of D with chlorine in, CH 3 CH 2 CONH 2 A
(b) CH 3 COCl
presence of red phosphorus. Pyridine
B
(iv) Out of A, C, E which substance used in making Ans :
perfumes. (i) Aniline forms salt with the lewis acid catalyst
Ans : i.e., AlCl3, which is used in Friedel-craft reaction.
(i) A is ethyl amine ^Structure - C 2 H 5 NH 2h . Further, nitrogen of aniline acquires positive
charge and hence acts as a strong deactivating
(ii) D is CH 3 COOH (Acetic acid).
Red P
group for further reaction. So, aniline doesn’t give
(iii) CH 3 COOH + 3Cl 2 CCl 3 COOH Friedal-Crafts reaction.
+ 3HCl (HVZ reaction)
(ii) C 6 H 5 NH 2 < NH 3 < C 2 H 5 NH 2 < (CH 3) 3 N
(iv) 'E ' is ethyl acetate (an ester) used in making
(iii) When ethylamine is shaken with benzene
perfumes.
sulphonyl chloride (Hinsberg’s reagent) and
aqueous KOH solution, it gives a clear solution.
C 6 H 5 SO 2 Cl + CH 3 CH 2 NH 2 " C 6 H 5 SO 2 NHCH 2 CH 3
KOH
[C 6 H 5 SO 2 - N - CH 2 CH 3] K + H 2 O
Potassium salt (Clear solution)
White diethylamine is 2c amine, on similar
treatment it forms an insoluble substance.
(a) What does oxidation of aniline in presence of which it can donate to electron deficient compounds.
MnO 2 , and, H 2 SO 4 produce ? Aliphatic amines are stronger bases than NH 3
(b) How will you distinguish cyclohexylamine and because of the + I effect of the alkyl groups. Greater
aniline ? the number of alkyl groups attached to N-atom,
(c) What is the major product obtained by acetylation higher is the electron density on it and more will be
of aniline followed by nitration (conc. HNO 3 + the basicity. Aniline is a weaker base compared to
conc. H 2 SO 4) and then alkaline hydrolysis ? ammonia. This is because the lone pair of electrons on
N-atom of aniline is less available for protonation due
(d) What does aniline produce in carbylamine
to its involvement in conjugation with the p -electrons
reaction? Write chemical equation of the reaction
of the benzene ring. Further the presence of electron
involved.
withdrawing groups decreases the basicity while, the
Ans :
presence of electron donating groups activates the
(a) benzene ring and also increases the basicity.
questions:
(a) (CH 3) 2 NH is more basic than (CH 3) 3 N in an
aqueous solution. Give reason
(b) Arrange the following in increasing order of basic
strength : C 6 H 5 NH 2 ,C 6 H 5 NHCH 3 , C 6 H 5 N (CH 3) 2
(c) (i) Arrange the following compounds in an
increasing order of basic strength :
C 6 H 5 NH 2 , C 6 H 5 N (CH 3) 2 , (C 2 H 5) 2 NH and
(b) Azo dye test is used to distinguish between CH 3 NH 2
cyclohexylamine and aniline.
(ii) Arrange the following compounds in a
(c) decreasing order of pKb values.
C 2 H 5 NH 2, C 6 H 5 NHCH 3, (C 2 H 5) 2 NH, and C 6 H 5 NH 2
(d) Arrange the following in increasing order of basic
strength : Aniline, p -nitroaniline and p -toluidine.
Ans :
(a) In aqueous solution, 2° amine is more basic than
3° amine due to the combination of inductive
effect, solvation effect and steric hindrance.
(b) Increasing order of basic strength in gaseous state
is as follows:
C 6 H 5 NH 2 1 C 6 H 5 NHCH 3 1 C 6 H 5 N (CH 3) 2
As the number of - CH 3 groups (+ I effect)
Attached to nitrogen increases, its basicity will
increase.
(d) Aniline gives phenyl isocyanide in carbylamine (c) (i) Increasing order of basic strength is
reaction.
C 6 H 5 NH 2 1 C 6 H 5 N (CH 3) 2
1 CH 3 NH 2 1 (C 2 H 5) 2 NH
(ii) Stronger the base, lower will be its pKb value.
Hence, the decreasing order of pKb values :
(d) Electron withdrawing group - (NO 2) on benzene
ring decreases the basicity and electron donating
group - (CH 3) on benzene ring increases the
basicity of the compound. Increasing order of
177. The amines are basic in nature due to the presence of basic strength :
a lone pair of electron on N-atom of the NH 2 group, p -nitroaniline 1 aniline 1 p -toluidine.
Chap 10 Biomolecules Page 479
CHAPTER 10
Biomolecules
SUMMARY 4. PROPERTIES OF GLUCOSE
1. BIOMOLECULES
Complex organic molecules which build up living
organisms and also are required for their normal
growth and development are called Biomolecules.
Example : Carbohydrates, amino acids, proteins,
enzymes, nucleic acid, lipids, etc.
2. CARBOHYDRATES
The polyhydroxy aldehydes or ketones are called
carbohydrates. They are of three types:
1. Monosaccharides : They are the simplest
carbohydrates which cannot be hydrolysed into
still simpler carbohydrates.
Examples : Glucose (C 6 H 12 O 6 ), Fructose (
C 6 H 12 O 6)
2. Oligosaccharides : They are the complex
carbohydrates which can be hydrolysed into small
number of monosaccharides.
Example : Disaccharides : Sucrose, lactose,
maltose (C 12 H 22 O 11)
Trisaccharides : Raffinose (C 18 H 32 O 16 )
Tetrasaccharides : Stachyose (C 24 H 42 O 21 ) etc.
3. Polysaccharides : They are also the complex
carbohydrates which can be hydrolysed into large
number of monosaccharides.
Example : Cellulose, starch, glycogen, etc.
3. PREPARATION OF GLUCOSE
Preparation of glucose are as follows :
From Sucrose
H+
C 12 H 22 O 11 + H 2 O T
C 6 H 12 O 6 + C 6 H 12 O 6
Sucrose Glu cose Fructose
From Starch
H+
(C 6 H 10 O 5) n + nH 2 O T
nC 6 H 12 O 6
14. AMINO ACIDS 18. PROTEINS

a -Amino acids are the building blocks of proteins. Proteins are large biological polymers of a -amino
They are organic compounds having both an amino acids linked by peptide bond. They are of two types:
group (- NH 2) and carboxylic group (- COOH) and 1. Fibrous Proteins : These types of proteins consist
represented as: of linear thread like molecules which tend to lie
side by side to form fibres. The molecules are held
together by H-bonds. They are insoluble in water.
Example : Keratin, Collagen.
2. Globular Proteins : In this type of proteins, the
molecules are folded together into compact form.
The amino acids are classified as acidic, basic or The peptide chains are held together by H-bonds.
They are soluble in water.
neutral depending upon the relative number of - NH 2
and - COOCH groups in the molecules. Example : Enzymes, hormones.
They are of two types: 19. STRUCTURE OF PROTEINS
1. Non-essential Amino Acids : These are the
amino acids which can be made by our bodies 1. Primary Structure : It tells the sequence in which
and therefore, we do not require them in our diet. the various a -amino acids are present in the
They are 10 in number. polypeptide chain.
Examples : Glycine, alanine. Each protein has a specific sequence of a -amino
2. Essential Amino Acids : These are the amino acids. If we change the sequence of any one a
acids which cannot be made by our bodies and -amino acid, then the biological function of
must be supplied to our diet. They are also 10 in protein gets changed.
number. 2. Secondary Structure : It gives the manner in which
Example : Tyrosine, valine. the polypeptide chains are folded or arranged.
There are two types of secondary structures:
15. PROPERTIES OF AMINO ACIDS (i) a -Helix Structure : If alkyl group of a -amino
The properties of amino acids are as follows: acid is large, then this structure is formed.
1. Colourless, crystalline solids. In this structure, the peptide chains are coiled
2. Soluble in water but insoluble in non-polar up to form a helix. The H-bonds are formed
solvent. between - CO group of one amino acid and
- NH group of other amino acid.
3. In aqueous solution, an amino acid behaves like a
dipolar ion called Zwitter ioin. Example : Keratin.
(ii) b -Pleated Sheet Structure : If alkyl group of
a -amino acid is small, then this structure is
formed.
It this structure, the peptide chains lie side
by side in a zig-zag manner with alternate
alkyl groups on the same side. These peptide
16. ISOELECTRIC POINT
chains are held together by H-bonds.
The pH at which a particular amino acid does not
migrate to any electrode under the influence of an 20. DENATURATION OF PROTEINS
electric field is called isoelectric point. A process that changes the physical and biological
At this point, amino acids have least solubility in properties of proteins without changing the chemical
water and this property is used for the separation of composition of protein is called denaturation. It is caused
amino acid. by changes in pH, temperature, presence of salts etc.
The important features of denaturation of proteins are:
17. PEPTIDES
1. It does not change the primary structure but
They are the compounds formed by the condensation changes the secondary structure of protein.
of two or more same or different a -amino acids. The 2. It may or may not be reversible depending upon
the nature of protein.
resulting linkage is called peptide bond. Example : Coagulation of milk, boiling of egg.
1. Water Soluble : B 1 , B 2 , B 6 , B 12 and C are water OBJECTIVE QUESTIONS

soluble vitamins.
2. Fat Soluble : A, D, E, K are fat soluble vitamins.
Important Vitamins are : 1. An a -helix is a structural feature of
Some important vitamins are as follows : (a) Sucrose (b) Polypeptides
(c) Nucleotides (d) Starch
Vitamin Chemical Deficiency Sources of
Name Disease Vitamin Ans : COMP 2023
A Retinal Xerophthalmia Cod liver In an a -helix, the peptide back bone of protein forms
(bright eye i.e., hardening oil, shark a spiral structure, with the amino acid side chains
vitamin) of cornea of liver oil, extending outward from the spiral.
eye, night carrot, rice Thus (c) is correct option.
blindness polishing,
liver, kidney. 2. Sweetest of all sugars is:
B1 Thiamine Beri-Beri; Milk, rice, (a) Glucose (b) Lactose
disease of yeast, nuts, (c) Sucrose (d) Fructose
nervous system eggs, green
vegetables. Ans : FOREIGN 2017
B2 Riboflavin Glossitis (dar Turnip, milk, Fructose is the sweetest of all natural sugar types.
red tongue), eggs, yeast, Fructose is somewhat sweeter, being rated at 1.7 times
dermatitis vegetables, the sweetness of sucrose. It is particularly effective at
and cheilosis liver, kidney. enhancing the flavour of fruit and berries.
(fissuring at
corners of
mouth and 3. Enzyme is :
lips) (a) Carbohydrate (b) Lipid
B6 Pyridoxine Dermatitis and Meat, fish, (c) Proteins (d) None of these
convulsions egg yolk,
whole cereal, Ans : SQP 2017
grams. Enzymes are soluble protein molecules that can
B12 Cyanoco- Pernicious Meat, eggs, speed up chemical reactions in cells. These reactions
balamin Anaemia, liver of ox, include respiration, photosynthesis and making new
inflammation sheep, pig, proteins. For this reason enzymes are sometimes
of tongue and fish etc. called biological catalysts.
mouth
C Ascorbic acid Scurvy Citrus fruits
(bleeding like orange, 4. Which is able to form Zwitterion?
of gums), lemon, (a) CH 3 NO 2 (b) CH 3 COOH
pyorrhea tomato,
green (c) CH 3 CH 2 NH 2 (d) H 2 NCH 2 COOH
vegetables. Ans : DELHI 2011
D Ergocalciferol Rickets and Milk, eggs, At low or acidic pH values, the hydrogen ions add to
osteomalacia cod liver oil the carboxyl group, making it neutral. This gives the
E Tocopherol Sterility Oils like amino acid a net charge + 1. At high, or basic, pH
cotton seed values, a hydrogen ion on N is removed by the excess
oil, soyabean base, neutralizing the amino group.
oil, wheat
gram oil.
5. Which of the following is carbohydrate ?
K Phylloquinone Haemophilia Cereals, leafy
(haemorrhagic vegetables. (a) Thiamine (b) Lactose
condition) (c) Glycerol (d) Insulin
H Biotin Dermatitis, Yeast, liver, Ans : OD 2017
loss of hair and kidney and
paralysis milk. Lactose in a carbohydrate having formula C 12 H 22 O 11,
its IUPAC name is b -D galactopyranose (1-4) D .
***********
are (1) Valine, (2) Leucine, (3) Isoleucine, (4) Phenyl Sucrose
Invertase
Glucose + Fructose
(Polymer) (Monomer)
alanine, (5) Threonine, (6) Methionine, (7) Lysine, (8)
Tryptho phone, (9) Arginine, (10) Histidine. Starch
amylase
Glucose
(Polymer) (Monomer)
14. For (peptide bond) 17. Which of the following statements about vitamin B 12
Which statement is incorrect about peptide bond? is incorrect?
(a) C - N bond length in proteins is longer than (a) It has a cobalt atom
usual bond length of the C - N bond (b) It also occurs in plants
(b) Spectroscopic analysis shows planar structure of (c) It is also present in rain water
the (d) It is needed for human body in very small amounts
Ans : SQP 2003
(c) C - N bond length in proteins is smaller than It is found in liver, egg, milk, meat and fish. Minute
usual bond length of the C - N bond amounts are probably present in all animal cells.
(d) None of the above Peculiarly, unlike other vitamins, B12 is not found in
Ans : OD 2015
significant amounts in green plants.
Due to resonance C - N bond in protein acquires Thus (c) is correct option.
double bond character and is smaller than usual 18. The pyrimidine bases present in DNA are
C - N bond. (a) cytosine and thymine
(b) cytosine and uracil
(c) cytosine and adenine
(d) cytosine and guanine
The pyrimidine bases present in DNA are cytosine
15. The helical structure of protein is stabilized by and thymine.
(a) dipeptide bonds (b) hydrogen bonds Thus (a) is correct option.
(c) ether bonds (d) peptide bonds 19. RNA is different from DNA because RNA contains
Ans : SQP 2002 (a) ribose sugar and thymine
The a -helix structure is formed when the chain of (b) ribose sugar and uracil
a -amino acids coils as a right handed screw (called
a -helix) because of the formation of hydrogen bonds (c) deoxyribose sugar and thymine
between amide groups of the same peptide chain, i.e., (d) deoxyribose sugar and uracil.
NH group in one unit is linked to carbonyl oxygen of Ans : FOREIGN 2004
the third unit by hydrogen bonding. This hydrogen
In RNA, the sugar is D-ribose and base is uracil where
bonding between different units is responsible for
as in DNA, the sugar is D-2 deoxyribose and the
holding helix in a position.
nitrogenous base is thymine.
16. The function of enzymes in the living system is to
20. The reason for double helical structure of DNA is
(a) transport oxygen operation of
(b) provide energy (a) dipole-dipole interaction
(c) provide immunity (b) hydrogen bonding
(d) catalyse biochemical reactions (c) electrostatic attractions
Ans : COMP 2012 (d) van der Waals’ forces
The function of enzymes in the living system is to Ans : OD 2016
catalyse biochemical reactions which occur in living
DNA consists of two polynucleotide chains, each chain
systems. e.g. invertase, pepsin, amylase.
forms a right handed spiral with ten bases in one turn
Ans : COMP 2003

30. The cell membranes are mainly composed of
Hb + CO $ HbCO ^stable compoundh (a) fats
carboxy haemoglobin
(b) proteins
Hb + O 2 HbO 2
oxyhaemoglobinûnstableh. (c) phospholipids
Thus (d) is correct option. (d) carbohydrates
28. Enzymes are made up of Ans : FOREIGN 2011
(a) Edible proteins Cell membranes (Plasma membranes) constitutes

(b) Proteins with specific structure bilayer of phospholipid with embedded proteins. In
humans, lipids accounts for upto 79% of cell membrane.
(c) Nitrogen containing carbohydrates
(d) Carbohydrates
31. The human body does not produce
Ans : DELHI 2009
(a) Vitamins (b) Hormones
Enzymes are made up of protein with specific
(c) Enzymes (d) DNA
structure.
Thus (b) is correct option. Ans : SQP 2001
Vitamins are organic substances which does not

29. Which one of the following structures represents the
provide energy but are essential for healthy growth
peptide chain?
and proper functioning of body. Vitamins are not
synthesized inside human body but they are essential
part of our diet.
32. Glucose contains
(a) one - CHO group
(b) one primary alcoholic group
(c) four secondary alcoholic groups
(d) all are correct
Ans : SQP 2001
The bond formed between two amino acids by the

elimination of a water molecule is called a peptide
linkage or bond. The peptide bond is simply another
name for amide bond. Thus (d) is correct option.
33. Cellulose is a polymer of
(a) Glucose (b) Fructose
(c) Ribose (d) Sucrose
Ans : SQP 2013
We know that cellulose ^C 6 H 12 O 6hn is the chief

The product formed by linking amino acid molecules constituent of cell walls of plants. It is the most
through peptide linkages - CO - NH -, is called a abundant organic substance found in nature. It is
peptide. polymer of glucose with 3500 repeat units in a chain.
46. The number of molecules of ATP produced in the

lipid metabolism of a molecule of palmitic acid is
(a) 130 (b) 36
(c) 56 (d) 86
Ans : FOREIGN 2012
We know that in the lipid metabolism, when palmitic

acid is oxidised, then two carbon fragments are
removed sequentially to form acetyl coenzyme. It
enters the citric acid cycle for production of 130 ATP.
47. Glucose molecule reacts with 'X' number of molecules
43. The secondary structure of a protein refers to of phenylhydrazine to yield osazone. The value of 'X' is
(a) fixed configuration of the polypeptide backbone (a) four (b) one
(b) a - helical backbone (c) two (d) three
(c) hydrophobic interactions Ans : OD 2017
(d) sequence of a - amino acids. We know that glucose reacts with one molecule of
phenyl hydrazine to give phenyl hydrazone. When
Ans : SQP 2002
warmed with excess of phenylhydrazine, the secondary
The secondary structure of a protein refers to the shape alcoholic group adjacent to the aldehyde group is
in which a long peptide chain can exist. There are two oxidized by another molecule of phenylhydrazine
different conformations of the peptide linkage present to a ketonic group. With this ketonic group, the
in protein, these are a - helix and b - conformation. third molecule of phenyl-hydrazine condenses to
The a - helix always has a right handed arrangement. glucosazone. Therefore, the value of X is 3.
In b - conformation all peptide chains are stretched
out to nearly maximum extension and then laid side
by side and held together by intermolecular hydrogen
bonds. The structure resembles the pleated folds of
drapery and therefore is known as b - pleated sheet.
44. Which of the following protein destroy the antigen
when it enters in body cell?
(a) Antibodies
(b) Insulin
(c) Chromoprotein
(d) Phosphoprotein
When antigens enter in to the body cells and destroy

them, then antibodies being proteins are synthesized
in the body and combine with antigens and destroy
these antigens by forming inactive complexes. 48. In both DNA and RNA, heterocylic base and
Therefore antibodies protein destroy antigens. phosphate ester linkages are at-
Thus (a) is correct option. (a) C '5 and C 1' respectively of the sugar molecule
45. Chemically considering digestion is basically (b) C 1' and C '5 respectively of the sugar molecule
(a) Anabolism (b) Hydrogenation (c) C '2 and C '5 respectively of the sugar molecule
(c) Hydrolysis (d) Dehydrogenation (d) C '5 and C '2 respectively of the sugar molecule
Ans : DELHI 2015 Ans : SQP 2002
Basically digestion means hydrolysis. In DNA and RNA heterocyclic base and phosphate ester
Thus (c) is correct option. are at C 1' and C '5 respectively of the sugar molecule.
56. A sequence of how many nucleotides in messenger 61. During the process of digestion, the proteins present
RNA makes a codon for an amino acid? in food materials are hydrolysed to amino acids. The
(a) Three (b) Four two enzymes involved in the process
EnzymeÂh Enzyme^Bh
(c) One (d) Two Proteins Polypeptides Amino acids
Ans : FOREIGN 2015

are respectively
The sequence of bases in mRNA are read in a serial (a) Diastase and Lipase
order in groups of three at a time. Each triplet of (b) Pepsin and Trypsin
nucleotides (having a specific sequence of bases) in (c) Invertase and Zymase
known as codon. Each codon specifies one amino acid.
Further since, there are four bases. Therefore, 43 = 64 (d) Amylase and Maltase
triplets or codons are possible. Ans : DELHI 2012
Thus (a) is correct option. Pepsin and Trypsin are two enzymes involved in the
57. The hormone that helps in the conversion of glucose process (hydrolysis of proteins)
to glycogen is Proteins
Pep sin /HCL
Proteases and Peptones
Stomach
(a) Cortisone (b) Bile acids
Tryp sin Peptidases
(c) Adrenaline (d) Insulin Chemotryp sin
Peptides Întistineh
A mino acids
^Pancreatic juice int estineh
Ans : OD 2000
Insulin helps in converting glucose to glycogen. Thus (b) is correct option.
Thus (d) is correct option. 62. Which one of the following is an amine hormone?
58. The enzyme which hydrolyes triglycerides to fatty (a) Thyroxine (b) Oxypurin
acids and glycerol is called (c) Insulin (d) Progesterone
(a) Maltase (b) Lipase Ans : OD 2010, DELHI 2007
(c) Zymase (d) Pepsin Thyroxine is an amino hormone.

Ans : SQP 2004 Thus (a) is correct option.
Triglycerides are lipids, hence these are hydrolysed by 63. The segment of DNA which acts as the instrumental
‘lipases’ to glycerol and fatty acids. manual for the synthesis of the protein is:
Thus (b) is correct option. (a) ribose (b) gene
59. The correct statement in respect of protein (c) nucleoside (d) nucleotide
haemoglobin is that it Ans : FOREIGN 2002
(a) functions as a catalyst for biological reactions The DNA sequence that codes for a specific protein
(b) maintains blood sugar level is called a Gene and thus every protein in a cell has a
(c) acts as an oxygen carrier in the blood corrosponding gene.
(d) forms antibodies and offers resistance to dieases
Ans : COMP 2015
64. Which one of the following does not exhibit the
Haemoglobin acts as an oxygen carrier in the phenomenon of mutarotation?
blood since it reacts with oxygen to form unstable (a) ^+h - Sucrose (b) ^+h - Lactose
oxyhaemoglobin which easily breaks to give back (c) ^+h - Maltose (d) ^-h - Fructose
haemoglobin and oxygen.
Ans : OD 2015
Sucrose does not have free - CHO or CO group, hence
60. Which one of the following is a peptide hormone? it does not undergo mutarotation.
(a) Testosterone (b) Thyroxin Thus (a) is correct option.
(c) Adrenaline (d) Glucagon 65. Which of the statements about “Denaturation” given
Ans : SQP 2013 below is/are correct?
Testorterone and Adrenaline are steroid harmone, (i) Denaturation of proteins causes loss of secondary
Thyroxin is non-steroided harmone glucagon is and tertiary structures of the protein.
peptide harmone. (ii) Denturation leads to the conversion of double
Thus (d) is correct option. strand of DNA into single strand.
Ans : FOREIGN 2011
Scurvey (bleeding of gums) is caused due to deficiency

ASSERTION AND REASON
of vitamin ‘C’ (ascorbic acid).Therefore option (b) is
correct. DIRECTION : Given below are two statements labelled as
Thus (b) is correct option. Assertion and Reason. Select the most appropriate answer
75. Which functional group participates in disulphide from the options given below:
bond formation in proteins? 78. Assertion : Hydrolysis of sucrose is known as inversion
(a) Thioester of cane sugar.
(b) Thioether Reason : Sucrose is a disaccharide.
(c) Thiol (a) Both Assertion and Reason are correct and
(d) Thiolactone
Ans : OD 2003
Example : Ans : COMP 2007
Sucrose is a disaccharide with specific rotation of

+ 66.5c. On hydrolysis, it gives 1 mole of D - (+)
glucose and 1 mole of D - (-) - fructose. The
hydrolysate is laevorotatory hence hydrolvsis is known
as inversion of sucrose.
76. Identify an element amongst the following which is 79. Assertion : Proteins on hydrolysis produce amino
responsible for oxidation of water to O 2 in biological acids.
processes Reason : Amino acids contain-NH2 and - COOH
(a) Fe (b) Mn group.
(c) Mo (d) Cu (a) Both Assertion and Reason are correct and
Ans : SQP 2006
Fe is responsible for oxidation of water to O 2 . (b) Both Assertion and Reason are correct but Reason
Thus (a) is correct option. is not the a correct explanation of the Assertion.
77. Which carbohydrate is used in silvering of mirrors? (c) Assertion is correct but Reason is incorrect.
(a) Sucrose (d) Both the Assertion and Reason are incorrect.
(b) Fructose Ans : DELHI 2008
(c) Glucose Proteins are polymides so, on hydrolysis, give amino

acids. Further it is a fact that amino acids contain
(d) Starch both- NH 2 as well as - COOH group. So assertion
Ans : COMP 2012 and reason, although both are correct but reason is
Aldehydes give this test. Aldehydes such as glucose not correct explanation of assertion.
are reducing agents and will reduce Ag+ (aq) ions Thus (a) is correct option.
to metallic silver. They themselves are oxidized to 80. Assertion : Sucrose undergoes mutarotation.
carboxlyate ions. The reaction that occurs is: Reason : Sucrose is a disaccharide.
CH 2 OH. ^CHOHh4 CHO (aq) + 2Ag ^NH 3h2+ âqh + 3OH- âqh (a) Both Assertion and Reason are correct and
$ 2Ag (s) + CH 2 OH (CHOH) 4 CO2- (aq) Reason is a correct explanation of the Assertion.
+ NH 3 (aq) + 2H+ (aq) + 2H 2 O (l) (b) Both Assertion and Reason are correct but Reason
There are reports of silvered flasks being kept for
several years as ornaments. (c) Assertion is correct but Reason is incorrect.
Thus (c) is correct option. (d) Both the Assertion and Reason are incorrect.
Reason : H+ ion given by carboxylic group (- COOH) (a) Both Assertion and Reason are correct and
is captured by amino group (- NH 2) having lone pair Reason is a correct explanation of the Assertion.
of electrons. (b) Both Assertion and Reason are correct but Reason
Ans : SQP 2020
During formation of proteins, - NH 2 group of one
(d) Both the Assertion and Reason are incorrect. amino acid condenses with - CO 2 H of the other with
Ans : COMP 2022 elimination of a water molecule to form a peptide bond.
All a -amino acids have - NH 2 group is basic and Thus (c) is correct option.
- COOH group is acidic, in neutral solution it exists 90. Assertion : Vitamin D cannot be stored in our body
as internal salt which is also called as zwitter ion. This
Reason : Vitamin D is fat soluble vitamin and is
zwitter ion is formed due to reason that proton of
excreted from the body in urine.
- COOH group is transferred to - NH 2 group.
Ans : FOREIGN 2020
Vitamin D is a fat soluble vitamin and can be stored

in the body since it is not excreted out of the body.
88. Assertion : Disruption of the natural structure of a
protein is called denaturation. VERY SHORT ANSWER QUESTIONS
Reason : The change in colour and appearance of egg
during cooking is due to denaturation. 91. What do you observe when glucose solution is heated
(a) Both Assertion and Reason are correct and with Tollen’s reagent?
Reason is a correct explanation of the Assertion. Ans : DELHI 2016
(b) Both Assertion and Reason are correct but Reason When glucose solution is heated with Tollen’s reagent,
is not the a correct explanation of the Assertion. silver mirror on the inner surface of the reaction vessel
is observed.
92. Give a test to distinguish between starch and cellulose.
Ans : COMP 2006
Ans : OD 2011
To distinguish between starch and cellulose, iodine
During denaturation, the protein molecule uncoils, test is done starch converts yellow coloured iodine to
form a more random conformation and ultimately blue black whereas cellulose does not.
precipitates from the solution. Further during
93. How will you convert glucose to gluconic acid?
denaturation, a protein molecule loses its biological
activity. Thus reason is correct but it is not the correct Ans : DELHI 2003
explanation of assertion. Glucose with bromine water form gluconic acid.

89. Assertion : Proteins are made up of a -amino acids.

Reason : During denaturation, secondary and tertiary
structures of proteins are destroyed.
110. What products would be formed when a nucleotide 116. Write two differences between DNA and RNA.
from DNA containing thymine is hydrolysed? Ans : COMP 2023
Ans : FOREIGN 2013
Besides thymine, the two other products are - 2 DNA RNA

deoxy-D-ribose sugar and phosphoric acid. 1. DNA contain the RNA contain the
sugar, i.e., deoxyribose sugar, i.e., ribose
111. What are monosaccharides?
2. It is double helical. It is single helical.
Ans : FOREIGN 2016
Monosaccharides are simple carbohydrates that 117. Name two vitamins and their deficiency diseases.
cannot be hydrolysed, e.g., glucose, fructose, galactose, Ans : DELHI 2017
ribose, deoxyribose, etc. Vitamin A : Vitamin A deficiency can cause
keratomalacia.
112. What are reducing sugars?
Vitamin B : Vitamin B deficiency causes beriberi and
Ans : COMP 2001
korsakoff syndrome.
Those sugars which can reduce Tollens’ reagent,
Fehling’s solution and Benedict’s reagent are called 118. What are Carbohydrates? Give the classification of
reducing sugars. For example, glucose and fructose. carbohydrates.
113. What are enzy mes? Carbohydrates are optically active polyhydroxy
Ans : OD 2015 aldehydes or polyhydroxy ketones or substances
Enzymes are biological catalysts which speeds up which give these on hydrolysis. Carbohydrates are
the chemical reactions in a biosystem. They are very also known as Saccharides.
specific and selective in their action chemically. All Classification
enzymes are essentially proteins. Carbohydrates are classified on the basis of their
114. What is the effect of denaturation on the structure of behavior on hydrolysis. They have been broadly
proteins? divided into following three groups.
Ans : FOREIGN 2001 (i) Monosaccharides : The simplest carbohydrates
During the denaturation process, 2° and 3° structure that can not be hydrolysed further to give simple
of proteins are destroyed but 1° structure remains unit of polyhydroxy aldehyde or ketone are called
Monosaccharides. About 20 monosaccharides are
intact. For example, curdling of milk.
known to occur in nature.
Examples : glucose, fructose, ribose etc.
SHORT ANSWER QUESTIONS (ii) Oligosaccharides : Carbohydrates which on

hydrolysis give 2 to 10 monosaccharides units are
called oligosaccharides. They are further classified as
115. (i) What type of isomers glucose and fructose are? disaccharides, trisaccharides, tetrasaccharides etc.
(ii) Name the functional group common to both depending upon the number of monosaccharides.
glucose and fructose. Examples : sucrose, maltose etc.
Ans : DELHI 2012
(iii) Polysaccharides : Carbohydrates which give
(i) Glucose and fructose are functional isomers. a large number of monosaccharides are called
(ii) Alcoholic (—OH) group is common in both, polysaccharides. Their general formula is
glucose and fructose. (C 6 H 10 O 5) n where n = 100 - 3000 .
Examples : starch, cellulose, glycogen, gums etc.
Polysaccharides are not sweet in taste, hence they
are called non-sugars. All the monosaccharides
and oligosaccharides are soluble in water and
sweet in taste, they are called sugars.
119. Define the terms:
(i) Biomolecules
(ii) Reducing Sugars
125. Write the meaning of D and L-notation. 127. Write any two reactions of glucose which cannot
Ans : DELHI 2014 be explained by the open chain structure of glucose
The letter D or L before the name of any compound molecule.
indicate the relative configuration of a particular Ans : DELHI 2005
stereoisomer. Glyceraldehyde contains one asymmetric The open chain structure of D-glucose with free
carbon atom and exists in two enantiomers forms as aldehyde (- CHO) group can explain most of its
shown below: properties but the following reactions could not be
explained by this structure.
(i) Despite having the aldehyde group, glucose does
not give 2, 4-DNP test, Schiff’s test and it does
not form the hydrogen sulphite addition product
with NaHSO 3 .
(ii) The pentaacetate of glucose does not react with
hydroxylamine indicating the absence of free
- CHO group.
For assigning the configuration of monosaccharides, The pentacetate is formed by acetylation of
the lowest asymmetric carbon atom is compared with glucose with acetic anhydride.
isomers of glyceraldehyde.
In (+) glucose - OH on the lowest asymmetric
carbon is on the right which is comparable to (+)
glyceraldehyde, so it is assign D-configuration (+)
represents dextrorotatory nature.
128. Draw the structure of fructose.

Ans : FOREIGN 2000
Fructose exist in two cyclic forms.

a -D-(-)-Fructofuranose and b -D-(-)-Fructofuranose
126. Write a reaction which shows the presence of a

primary alcoholic (- OH ) group in glucose.
or
What happens when D-glucose is treated with HNO 3 129. Draw the structure of Maltose.
? Ans : SQP 2019
Ans : COMP 2009, DELHI 2004 Maltose (Malt sugar) C 12 H 22 O 11 is composed of two a
On oxidation with nitric acid glucose gives a -D-glucose units.
dicarboxylic acid, saccharic acid. This indicates the
presence of primary alcoholic (- OH) group in glucose.
138. How do you explain the amphoteric behaviours of 141. What type of bonding helps in stabilising the a -helix
amino acids? structure of proteins?
Ans : DELHI 2007 Ans : COMP 2005
In aqueous solution, the carboxyl group of amino The a -helix structure of protein is stabilised by
acid can lose a proton and amino group can accept a intermolecular H-bonding between - NH group of
proton, giving rise to a dipolar ion known as zwitter amino acid residue and the > C = O of an adjacent
ion. This is neutral but contains both positive and amino acid.
negative charges. 142. Difference between globular and fibrous proteins.
Ans : DELHI 2002
The difference between globular and fibrous proteins

are as follows :
Globular Proteins Fibrous Proteins

1. Globular proteins have Fibrous proteins have
spherical shape due to fibre (thread) like
In Zwitter ionic form amino acids show amphoteric
folding of polypetide structure.
behavior as they react both with acids and bases. chains.
139. What are the common types of secondary (2°) 2. They are soluble in They are insoluble
structure of proteins? water e.g. insulin, in water e.g. Keratin
Ans : OD 2001 albumin, haemoglobin (present in hair, wool,
The secondary ( 2° ) structure of protein refers to the etc. silk), myosin (present
shape in which a long polypeptide chain can exist. in muscles) etc.
They are found to exist in two different types of
structure: 143. What are enzymes?
(i) a -helix Structure : a -helix is one of the most Ans : OD 2010
common ways in which a polypeptide chain Enzymes are biocatalyst. Almost all the enzymes are
forms all possible hydrogen bonds by twisting globular proteins. They are generally named after the
into a right handed screw (helix) with the - NH compound or class of compound upon which they work.
group of each amino acid hydrogen bonded to the For example, the enzyme that catalyses hydrolysis of
> C = O of an adjacent turn of the helix. maltose into glucose is named as maltase.
(ii) b -pleated Sheet Structure : In b -structure C 12 H 22 O 11
Maltase
2C 6 H 12 O 6
all peptide chains are streched out to nearly Maltose Glucose
maximum extension and then laid side by side The ending of the name of an enzyme is - ase , enzymes
which are held together by intermolecular are highly specific in their action due to presence of
hydrogen bonds. The structure resembles the active sites of definite size and shape on their surfaces
pleated folds of drapery and therefore is known as
so that only specific substances can fit into them.
b -pleated sheet structure.
144. How are vitamins classified? Name the vitamin
140. Write a note on tertiary (3°) and Quaternary (4°) responsible for coagulation of blood?
structure of proteins. Ans : FOREIGN 2006
Ans : FOREIGN 2011, COMP 2009 Vitamins are classified into two groups depending
Tertiary (3°) Structure of Proteins upon their solubility in water or fat.
The tertiary structure of proteins represents overall (a) Fat Soluble Vitamins : Vitamins, A, D, E, K are
folding of the polypeptide chains i.e., further folding soluble in fat and oils but insoluble in water.
of the secondary structure. It gives rise to two major They are stored in liver and adipose (fat storing)
molecular shapes viz. fibrous and globular. tissues.
Quaternary (4°) Structure of Proteins (b) Water Soluble Vitamins : B group vitamins and
Some of the proteins are composed of two or more vitamin C are soluble in water. Water soluble
polypeptide chain referred to as sub units. The spatial vitamins must be supplied regularly in diet
arrangement of these subunits with respect to each because they are readily excreted in urine and
other is known as quaternary structure. can not be stored (except vit B12) in our body.
150. Glucose or sucrose are soluble in water but cyclohexane 155. Classify the following into monosaccharides and
or benzene (simple six membered ring compounds) disaccharides.
are insoluble in water. Explain. Ribose, 2-deoxyribose, maltose, galactose, fructose
Ans : DELHI 2008 and lactose.
Glucose and sucrose molecules contain many - OH Ans : DELHI 2013
groups and hence are capable of forming H-bond with Monosaccharides : Ribose, 2-deoxyribose, galactose,
water molecules. On the other hand, cyclohexane and fructose.
benzene are hydrocarbon and hence they cannot form Disaccharides : Maltose, lactose.
H-bond with water. Therefore, glucose and sucrose 156. What do you understand by the term glycosidic
are soluble in water whereas cyclohexane and benzene linkage?
are insoluble in water.
Ans : FOREIGN 2009
151. What are the expected products of hydrolysis of In disaccharides or polysaccharides, monosaccharides
lactose? are joined together by an oxide linkage formed by
Ans : COMP 2016 loss of a water molecule. Such a linkage between two
Since lactose is a disaccharide, therefore on hydrolysis monosaccharide units through oxygen atom is called
it give two molecules of monosaccharides, i.e. one glycosidic linkage.
molecule each of D-(+)-glucose and D-(+)- galactose. 157. What is glycogen? How is it different from starch?
H 3 O+
C 12 H 22 O 11 + H 2 O C H O + C 6 H 12 O 6
6 12 6 Ans : OD 2005
or Lactase
Lactose D-(+) - glucose D-(+) - galactose
Glycogen is a polysaccharide stored in animal body.
152. The melting point and solubility in water of amino acids Its structure is similar to amylopectin and is rather
are generally higher than that of the corresponding highly branched. Whereas starch consists of both
halo acids. Explain. amylose and amylopectin.
Ans : SQP 2007
158. What are the hydrolysis product of
The amino acids exists as a Zwitter ions as: (i) Sucrose and
H 3 N+ - CHR - COO- (ii) Lactose ?
Due to this dipolar salt like structure they have strong Ans : OD 2011, DELHI 2010
dipole-dipole attraction or electrostatic forces of (i) Sucrose on hydrolysis gives glucose and fructose
attraction. Therefore, their melting points are higher in the presence of invertase enzyme.
than that of corresponding halo acids. (ii) Lactose on hydrolysis gives glucose and galactose
Due to slat like structure of amino acids their solubility in the presence of lactase enzyme.
is also higher than the corresponding halo acids. 159. What is the basic structural difference between starch
153. When RNA is hydrolysed, there is no relationship and cellulose?
among the quantities of different bases obtained. Ans : COMP 2014
What does this fact suggest about the structure of There is one major difference between Starch and
RNA? Cellulose. For starch, glucose repeat units are located
Ans : OD 2009 in the same direction, and each successive glucose unit
Since in RNA after complete hydrolysis there is no is rotated 180 degrees in cellulose.
relationship between the quantities of four bases (C, 160. What happens when D-glucose is treated with the
G, A and U) obtained. Therefore, as per the base - following reagents?
pairing principle, i.e. A pairs with U and C pairs with
(i) HI
G is not followed. Therefore, unlike DNA, RNA has a
(ii) Bromine water
single strand.
(iii) HNO 3
154. Write two main functions of carbohydrates in plants.
Ans : FOREIGN 2003
Ans : SQP 2004
Two main functions of carbohydrates in plants are as

follows:
(i) Cell wall of plants is made up of cellulose.
(ii) Carbohydrates are used as storage molecules as
starch in plants.
Non-essential Amino Acids Ans : FOREIGN 2007
The important structural and functional differences

The amino acids which can be synthesised in the body
between DNA and RNA are as follows :
by itself are known as non-essential amino acids. For
example, glycine, alanine. DNA RNA
167. Why are vitamin A and vitamin C essential to us? 1. The sugar present in The sugar present in
Give their important sources. DNA is 2-deoxy-D-(-) RNA is D-(-)-ribose.
Ans : FOREIGN 2005
-ribose.
(i) Vitamin A : Deficiency leads to Xerophthalmia 2. DNA has a double RNA has single
and night-blindness. stranded a -helix stranded a -helix
Sources of Vitamin A : Carrot, fish liver oil, milk, structure. structure.
butter, etc.
3. DNA contains cytosine RNA contains
(ii) Vitamin C : Deficiency leads to scurvy and and thymine as cytosine and uracil as
bleeding gums. pyrimidine bases. pyrimidine bases.
Sources of Vitamin C : Citrus fruits, amla, green
leafy vegetables. 4. DNA has a unique RNA usually does not
property to replicate. replicate.
168. What are nucleic acids? Mention their two important
functions. 5. DNA is responsible for RNA controls protein
Ans : OD 2019 heredity characters. synthesis.
Nucleic acids are polymers of nucleotides containing
a pentose sugar, heterocyclic base and a phosphate
group.
LONG ANSWER QUESTIONS
The two important function of nucleic acid are as
follows :
172. What are carbohydrates? How are they classified ?
(i) They help in synthesis of proteins.
(ii) They are also responsible for the transfer of According to modern definition optically active
genetic characters from one generation to the
polyhydroxy aldehydes or polyhydroxy ketones or
next generation.
compounds which can be hydrolysed to give monomers
169. What is the difference between a nucleoside and a (i.e. as final monosaccharides) product are called
nucleotide? carbohydrates.
Ans : SQP 2015, DELHI 2013 Classification of Carbohydrates
Nucleoside is formed by the condensation of a purine Carbohydrates are also known as saccharides and
or pyrimidine base with pentose sugar at position 1. classified according to their behavior towards hydrolysis.
When nucleoside is linked to phosphoric acid at 5
position of sugar moiety, we get a nucleotide. Hence, a
nucleotide has three units - phosphate group, pentose
sugar and a base, whereas nucleoside has two units -
pentose sugar and a base.
170. The two strand in DNA are not identical but are
complementary. Explain.
Ans : COMP 2018
The two strands in DNA are complementary to each

other because the hydrogen bonds are formed between
specific pair of bases. Adenine always form hydrogen
bond with thymine whereas cytosine always form
hydrogen bond with guanine.
171. Write the important structural and functional
differences between DNA and RNA.
(iii) 176. What are vitamins? Give the list of some important
vitamins, their sources and their deficiency diseases.
Ans : DELHI 2013
The organic compound which are in addition to normal

nutrients for regulating some of the body processes to
maintain health and growth are called vitamins. They
are essential dietary factors required by an organism
in minute quantities and their absence causes specific
deficiency diseases.
Name of Sources Deficiency

Vitamin Diseases
1. Vitamin A Fish liver oil, Xerophthalimia
(Retinol or carrots, butter, (hardening
bright eye milk of cornea of
175. Define the following as related to proteins. vitamin) eye) and night
(i) Peptide linkage blindness.
(ii) Primary structure 2. Vitamin B1 Yeast, Beri-beri (loss
(iii) Denaturation (Thiamine) milk, green of appetite,
vegetables and retarded
Ans : COMP 2019, OD 2018
cereals growth)
(i) Peptide Linkage : Proteins are condensation
3. Vitamin B2 Milk, egg-white, Cheilosis
polymers of a -amino acids, these amino acids are
(Riboflavin) liver, kidney (Cracking
connected by peptide bond or peptide linkage. at corners of
Chemically peptide linkage is an amide formed mouth and lips)
between - COOH group of one amino acids and
- NH 2 group of the other amino acid by loss of a 4. Vitamin B6 Milk, egg yolk, Convulsions
(Pyridoxine) cereals and (muscular
molecule of water.
grams contraction)
5. Vitamin B12 Meat, fish, egg Pernicious
(Cyanoco- and curd anaemia (RBC
balamin) deficient in
haemoglobin)
6. Vitamin C Citrus fruits, Scurvy
(Ascorbic acid) amla and green (bleeding gums)
leafy vegetables
7. Vitamin D Exposure to Rickets (bone
(Sunshine sun light, fish deformities in
Vitamin) and egg yolk children) and
Osteomalacia
(Soft bones and
joint pain in
(ii) Primary Structure (1°) : Proteins may have one adults)
or more polypeptide chains. Each polypeptide in
8. Vitamin E Vegetables Sterility (loss of
a protein has amino acids linked with each other.
(Tocopherol) oils like wheat sexual power of
The specific sequence in which the various a green oil, reproduction).
-amino acids forming a protein are linked to one sunflower oil Increasing
another is called its primary structure. etc. fragility of
(iii) Denaturation : When a protein is subjected to RBC.
physical changes such as change in temperature, 9. Vitamin K Green leafy Increased blood
pH etc. hydrogen bonds are broken. Due to (Phylloquinone) vegetables. clotting time.
cleavage of hydrogen bonds, unfolding of protein
molecule occurs and the protein loses in biological 177. What happens when D-glucose is treated with the
activity. This loss of biological activity is called following reagents?
denaturation. The coagulation of egg white on (i) HI
boiling is common example of denaturation. (ii) NH 2 OH
179. Propose a scheme for the conversion of open chain proves that glucose pentaacetate does not contain the
structure of glucose into cyclic hemiacetal structure. aldehyde group.
Ans : DELHI 2006 181. Amino acids may be acidic, alkaline or neutral. How
does this happen?
or
How are amino acids classified on the basis of relative
number of amino and carboxyl groups in their molecule?
or
What is the difference between acidic amino acid and
basic amino acid?
Ans : SQP 2012
Amino acids are classified as acidic, basic or neutral

Glucose forms a six-membered ring in which - OH
depending upon the relative number of amino and
at C-5 add to the - CHO group and form a ring or a
carboxyl groups in their molecule.
cyclic hemiacetal structure.
(i) Neutral Amino Acids : Neutral amino acids own
180. How do you explain the absence of aldehyde group in equal number of amino and carboxyl groups.
the pentaacelate of D-glucose? Examples :
Ans : OD 2017
Glycine (R /- H ),
Alanine (R /- CH 3)
Valine (R / (H 3 C) 2 CH -)
(ii) Basic Amino Acids : Basic amino acids own more

number of amino than carboxyl groups.
Examples :
(iii) Acidic Amino Acids : Acidic amino acids own

more number of carboxyl groups as compared to
amino groups.
Examples :
Glutamic acid (R /- CH 2 CH 2 COOH)
When glucose is reacted with acetic anhydride, the Aspartic acid (R /- CH 2 COOH)
five - OH groups at C1, C2, C3, C4 and C6 form
a pentaacetate. Due to the absence of free OH
group at C1, the pentaacetate o glucose cannot get
hydrolysed in aqueous solution to produce the open
chain aldehydic form. Thus, glucose pentaacetate does
not react with NH 2 OH to form glucose oxime. This
Although, figure (a) is a common way of writing 186. Polysaccharides may be very large molecules. Starch,
structural formulas for amino acids, it is not accurate glycogen, cellulose, and chitin are examples of
because it shows an acid (—COOH) and a base (— polysaccharides.
NH2) within the same molecule. These acidic and Starch is the stored form of sugars in plants and is
basic groups react with each other to form a dipolar made up of amylose and amylopectin (both polymers
ion or internal salt (figure (b). The internal salt of an of glucose). Amylose is soluble in water and can be
amino acid is given the special name Zwitter ion. Note hydrolyzed into glucose units breaking glycosidic
that a Zwitter ion has no net charge, it contains one bonds, by the enzymes a -amylase and b - amylase. It
positive charge and one negative charge. is straight chain polymer. b - mylopectin is a branched
Because they exist as Zwitter ions, amino acids have chain polymer of several D-glucose molecules. 80% of
many of the properties associated with salts. They are amylopectin is present in starch. Plants are able to
crystalline solids with high melting points and are fairly synthesize glucose, and the excess glucose is stored
soluble in water but insoluble in non-polar organic as starch in different plant parts, including roots and
solvents such as ether and hydrocarbon solvents. seeds. The starch that is consumed by animals is
According to the above passage, answer the following broken down into smaller molecules, such as glucose.
questions : The cells can then absorb the glucose. Glycogen is
(i) Amino acids are usually colourless, crystalline the storage form of glucose in humans and other
solids. They behave like salts rather than simple vertebrates, and is made up of monomers of glucose. It
amines or carboxylic acids. Why amino acids is structurally quite similar to amylopectin. Glycogen
show such a behaviour? is the animal equivalent of starch. It is stored in liver
(ii) Amino acids are essential and non-essential and skeletal muscles.
depending upon their need. One of the essential Cellulose is one of the most abundant natural
amino acid is lysine. Can you say why lysine is biopolymers. The cell walls of plants are mostly made
considered an essential amino acid? of cellulose, which provides structural support to the
(iii) Here are given some amino acids—lysine, cell. Wood and paper are mostly cellulosic in nature.
Tyrosine, Glycine, Alamine. One of these amino Like amylose, cellulose is a linear polymer of glucose.
acids is not optically active. Which one is that Cellulose is made up of glucose monomers that are
amino acid? Also, provide the reason. linked by bonds between particular carbon atoms in
(iv) The pka , and pka , of an amino acid are 2.3 and
1 2
the glucose molecule. Every other glucose monomer
9.7 respectively. What would be the isoelectric in cellulose is flipped over and packed tightly as
point of the amino acid? Calculate by defining it. extended long chains. This gives cellulose its rigidity
Ans : and high tensile strength—which is so important to
(i) Amino acids behave like salts rather than simple plant cells. Cellulose passing through our digestive
amines due to the presence of both acidic (— system is called dietary fiber.
COON) and basic (—NH2) groups. Based on the above passage, answer the following
(ii) Lysine is considered an essential amino acid as questions:
it cannot be formed in the body and has to be (i) Glycogen is a kind of polysaccharide and is the
supplemented to the body through the diet. storage form of glucose present in humans and
(iii) Among the given amino acids, glycine is not other vertebrates. It is the animal equivalent
optically active. It is the only amino acid which of starch but can you say where is it stored in
do not have asymmetrical carbon atom and is the animals?
simplest amino acid. (ii) What can you infer about the characteristic of
(iv) The isoelectric point is the pH at which the amino amylose from the passage?
acid does not migrate in an electric field. This (iii) Whenever glucose levels drop in our body, a
means that it is the pH at which the amino acid bipolymer breaks down to release glucose. Name
is neutral i.e., the Zwitter ion form is dominant. this bipolymer and it is structurally similar to
pk + pka which polymer?
Isoelectric point = a 1 2
2 (iv) Which polymer is important to plant cells? How?

= 2 . 3 + 9.7 = 12.0 = 6.0 Ans :
2 2 (i) Glycogen is stored in animals in liver and skeletal
So, the isoelectric point of the amino acid = 6.0 muscles.
Christiaan Eijkman reported in 1895, that chickens Answer the following questions :
that ate polished rice developed beri-beri. He was (a) What information is given by primary structure
awarded Noble Prize in 1929 for his contribution in of DNA?
discovery of vitamins. ‘Vita’ (Latin—for important (b) Name the types of nitrogeneous bases present in
to life), amine (a specific group which Funk believed nucleic acids.
is present in all vitamins). In the beginning vitamin
(c) Write the structural and functional difference
C was called Scurvy Vitamin, Vitamin-B was called
between DNA and RNA.
Beri-Beri vitamin when rats were fed a diet heavy in
(d) Name the bases present in RNA. Which one of
lard and olive oil, they died but with the addition of
these is not present in DNA?
tiny amount of butter fat they survived. McCollum
called vitamin in butter fat. Fat soluble Vitamin A, Ans :
Vitamin B12 and Vitamin D were discovered later. (a) Primary structure gives information regarding
Now we also know vitamin E, K and H also. the sequence of nucleotides in the chain of nucleic
Answer the following questions: acids.
(a) Name four vitamins that are stored in liver and (b)
adipose (fat storing) tissues. (i) Purines,
(b) Out of B, C and B12 which vitamin cannot be (ii) Pyrimidines
stored in our body and why? (c) Structural differences between DNA and RNA :
(c) Name a vitamin which helps in blood clotting and (i) The sugar in DNA is deoxyribose while that
name source of this vitamin. in RNA is ribose.
(d) Name a vitamin which is fat soluble and anti- (ii) DNA has a double-stranded helical structure,
oxidant. What are sources of this vitamin and its while
deficiency disease? RNA has a single-stranded helical structure.
Ans : Functional differences between DNA and RNA.
(a) A, D, E, K are stored in liver and adipose tissues. Functional differences between DNA and RNA.
(b) B and C are water soluble vitamins, therefore, (i) DNA is the chemical basis of heredity and
cannot be stored in our body. is responsible for maintaining the identity of
(c) Vitamin K helps in clotting of blood. It is present different species.
in green leafy vegetables. (ii) RNA molecules are responsible for protein
(d) Vitamin ‘E’ is fat soluble and anti-oxidant. synthesis but the message for the synthesis of
Its deficiency leads to loss of reproductive power. a particular protein is present in DNA.
Its sources are vegetable oils, wheat germ oil, sun (d) The bases present in RNA are adenine (A),
flower oil, etc. guanine (G) cytosine (C) and Uracil (U). Uracil
189. The sequence of bases along the DNA and RNA is not present in DNA.
chain establishes its primary structure which controls
the specific properties of the nucleic acid. An RNA 190. Pentose and hexose undergo intramolecular hemiacetal
molecule is usually a single chain of ribose-containing or hemiketal formation due to combination of the –OH
nucleotide. On the basis of X-ray analysis of DNA, J.D., group with the carbonyl group. The actual structure
Watson and F.H.C. Crick (shared noble prize in 1962) is either of five or six membered ring containing
proposed a three dimensional secondary structure for an oxygen atom. In the free state all pentoses and
DNA. DNA molecule is a long and highly complex, hexoses exist in pyranose form (resembling pyran).
spirally twisted, double helix, ladder like structure. However, in the combined state some of them exist
The two polynucleotide chains or strands are linked as five membered cyclic structures, called furanose
up by hydrogen bonding between the nitrogeneous (resembling furan).
base molecules of their nucleotide monomers. Adenine
(purine) always links with thymine (pyrimidine)
with the help of two hydrogen bonds and guanine
(purine) with cytosine (pyrimidine) with the help
of three hydrogen bonds. Hence, the two strands
extend in opposite directions, i.e., are antiparallel and
complimentary.
Answer the following questions : conception of the DNA molecule as a long thin fiber
(a) What is the name the first member of ketose sugar? is obtained from physico-chemical analysis involving
(b) How many optical isomers are present in sedimentation, diffusion, light scattering, and viscosity
CH 2 OH (CHOH) 4 CHO ? measurements. These techniques indicate that DNA
is a very asymmetrical structure approximately 20
(c) Write the reaction of glucose with hydroxylamine.
A° wide and many thousands of angstroms long.
(d) How many moles of acetic anhydride are needed
Estimates of its molecular weight currently centre
for acetylation of glucose? What does it confirm?
between 5 # 106 and 107 (approximately 3 # 10 4
Ans : nucleotides). Surprisingly each of these measurements
(a) The first member of ketose sugar is ketotriose. tend to suggest that the DNA is relatively rigid, a
(b) No. of chiral atoms = 4 puzzling finding in view of the large number of single
No. of optical isomers = 2 4 = 16 bonds (5 per nucleotide) in the phosphate-sugar back
(c) bone. Recently these indirect inferences have been
confirmed by electron microscopy.
(d) Acetylation of glucose with acetic anhydride gives

glucose pentacetate which confirms the presence
of five - OH groups attached to different carbon
atoms
Chemical formula (diagrammatic) of a single chain of

deoxyribonucleic acid.
192. The basic chemical formula of DNA is now well Answer the following questions :
established. As shown in figure it consists of a very long (a) Name the purines present in DNA.
chain, the backbone of which is made up of alternate (b) What is the name of the linkage between
sugar and phosphate groups, joined together in regular nucleotides in DNA?
3’ 5’ phosphate di-ester linkages. To each sugar is (c) (i) What is backbone of DNA?
attached a nitrogenous base, only four different kinds (ii) Out of four different kinds of nitrogenous
of which are commonly found in DNA. Two of these— bases which are commonly formed in DNA has
adenine and guanine— are purines, and the other two been replaced in some organisms.
thymine and cytosine-are pyrimidines. A fifth base, (d) (i) Which component makes DNA chiral?
5-methyl cytosine, occurs in smaller amounts in certain
(ii) Between which carbon atoms of deoxyribose
organisms, and a sixth, 5-hydroxy-methyl-cytosine,
sugars of nucleotide are phosphodiester linkage
is found instead of cytosine in the T even phages.
present?
It should be noted that the chain is unbranched, a
Ans :
consequence of the regular internucleotide linkage.
On the other hand the sequence of the different (a) Adenine and Guanine
nucleotides is, as far as can be ascertained, completely (b) regular phosphodiester, irregular
irregular. Thus, DNA has some features which are (c) (i) Phosphate-sugar forms backbone of DNA.
regular, and some which are irregular. A similar (ii) Cytosine
Page 516 Biomolecules Chap 10
(d) (i) D-sugar component 194. Hormones have several functions in the body. They
(ii) 5’ and 3’ carbon atoms help to maintain the balance of biological activities
in the body. The role of insulin in keeping the blood
193. Proteins are high molecular mass complex biomolecules
glucose level within the narrow limit is an example of
of amino acids. The important proteins required for
this function. Insulin is released in response to the rapid
our body are enzymes, hormones, antibodies, transport
rise in blood glucose level. On the other hand hormone
proteins, structural proteins, contractile proteins etc.
glucagon tends to increase the glucose level in the blood.
Except for glycine, all a -amino acids have chiral
The two hormones together regulate the glucose level
carbon atom and most of them have L -configuration.
in the blood. Epinephrine and nor-epinephrine mediate
The amino acids exists as dipolar ion called zwitter
responses to external stimuli. Growth hormones and
ion, in which a proton goes from the carboxyl group
sex hormones play role in growth and development.
to the amino group. A large number of a -amino acids
Thyroxine produced in the thyroid gland is an iodinated
are joined by peptide bonds forming polypeptides. The
derivative of amino acid tyrosine.
peptides having very large molecular mass (more than
10,000) are called proteins. The structure of proteins (i) What is the disease caused due to deficiency of
is described as primary structure giving sequence of iodine in our body. What are the symptoms ?
linking of amino acids; secondary structure giving (ii) Why hormones are needed in adequate quantities
manner in which polypeptide chains are arranged in our body ?
and folded; tertiary structure giving folding, coiling (iii) Which hormone is necessary for development of
or bonding polypeptide chains producing three secondary sexual characters in males ?
dimensional structures and quaternary structure Ans :
giving arrangement of sub-units in an aggregate (i) Goitre is caused due to deficiency of iodine. In
protein molecule. this disease there is enlargement of the thyroid
Answer the following questions : gland.
(a) What do you mean by proteins ? (ii) They help to maintain the balance of biological
(b) What is Zwitter ion ? activities in the body. Their excess or deficiency
(c) Which type of bond is present in polypeptide? causes diseases in body. Example, Insulin is
Give example ? released in response to the rapid rise in blood
(d) Which type of bonding is present in a -helix and ( glucose level. Its deficiency causes diabetes.
b -pleated structure of proteins. (iii) Testosterone.
Ans : 195. Complete hydrolysis of DNA (or RNA) yields a
(a) Proteins are high molecular mass complex pentose sugar, phosphoric acid and nitrogen containing
biomolecules of amino acids these are the polymer heterocyclic compounds (called bases). In DNA
of amino acid joined together through amide molecules, the sugar moiety is b - D - 2 - deoxyri.
linkages. bose whereas in RNA molecule, it is b - D -ribose.
(b) In aqueous solution, carboryl ion loses a proton
and amino group can accept a proton, dipolar ion
is formed called zwitter ion.
(c) Peptide linkage is present in polypeptides.
(i) Which structure is found in DNA molecule (a) or

(b) ?
(ii) Name the bases found in RNA.
Ans :
(i) (b), it is b–D–2–deoxyribose.
(ii) Adedine (A), guanine (G), cytosine (C) and uracil
(d) Intramolecular H-bonding is present in helix and (U).
intermolecular H-bonding is present in b -pleated
structure of proteins. ***********

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CBSE 2025

Chapter-wise Question Bank

NODIA AND COMPANY

CHAP 1. Solution 15-81

CHAP 2. Electrochemistry 82-147

CHAP 3. Chemical Kinetics 148-206

CHAP 4. The d and f-block Elements 207-244

CHAP 5. Coordination Compounds 245-287

CHAP 6. Haloalkanes and Haloarenes 288-330

CHAP 7. Alcohols, Phenols and Ethers 331-381

CHAP 8. Aldehydes, Ketones and Carboxylic Acids 382-435

CHAP 9. Amines 436-477

CHAP 10. Biomolecules 478-515

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Exam 2024 Solved Paper

3. Isotonic solutions have the same

In the presence of few drops of conc. H2SO4, alkenes

Ans : (b) 2 Ans : (b) II, III, IV

(c) Assertion (A) is true, but Reason (R) is false.

14. Assertion (A) : Inversion of configuration is observed

At t99% , if 6R0@ = 100 , 6R@ = 1 Dimethyl amine is secondary amine and do

22. Give the structure of the major product expected

23. A compound ‘X’ with molecular formula C3H9N Ans :

24. The rate constant of a reaction quadruples when

25. Write IUPAC names of the following coordination

29. Certain organic compounds are required in small

31. (a) An organic compound (A) with the molecular

or Zn has lowest enthalpy of atomisation due to

o pressure is 99.68ºC. How much sucrose

x = DTb # 342 # 500

x = 0.32 # 342 # 500 = 105.2 g

SUMMARY 5. Normality (N) : Number of gram equivalents of

7. Equivalent mass of : 1. Nature of the solute and solvent : Like dissolves

= Molecular mass or at mass The pressure exerted by the vapour of a liquid in

3. TVmixing = 0 (a) PA < PAcxA and PB < PBcxB

2. Elevation in boiling point : For a dilute solution,

TTf ? m 14. DEGREE OF ASSOCIATION

12. ABNORMAL MOLECULAR MASSES OBJECTIVE QUESTIONS

If i = 1 (Neither association nor dissociation)

^0.1 - ah + a + 2a 4. Which of the following aqueous solution should have

We know that Depression in freezing point is a collegative property.

Ans : DELHI 2010

Ans : FOREIGN 2003

Ans : COMP 2008

33. A solution contains non-volatile solute of molecular Ans : FOREIGN 2013

34. Camphor is often used in molecular mass determination Ans : OD 2008

because: Positive deviations are shown by such solutions in

Ans : COMP 2001 Ans : SQP 2015

Benzoic acid exists as dimer in benzene. According to Boyle-van’t Hoff Law,

Thus (b) is correct option. TTb = Kb # i # molality

(c) 0.1 M urea and 0.1 M MgCl 2 For an ideal solution

(d) 0.2 M urea and 0.1 M NaCl TH mixing = 0

Ans : OD 2016 TH = TH1 + TH2 + TH3

Na 2 SO 4 are isotonic. (b) Elevation of boiling point.

osmotic pressure measurements can be made at room Freezing point of solution,

Weight of solute or non-electrolyte,

Weight of solvent or water, Vw = 1 litre

wc = 68.4 gm Ans : DELHI 2006

As both the solutions are isotonic hence there is no net