MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 1

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 2







Maximum Marks: 180


Question paper format and Marking scheme:

1. This question paper has 55 questions.

2. Q No 1 to 10 carry 1.5 marks each ( 15 marks)

3. Q No 11 to 35 carry 3 marks each ( 75 marks)

4. Q No 36 to 55 carry 4.5 marks each ( 90 marks)

















MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 3

96. HBr reacts with CH
2
= CH OCH
3
under anhydrous conditions at room temperature to give
(1) CH
3
CHO and CH
3
Br (2) BrCH
2
CHO and CH
3
OH
(3) BrCH
2
CH
2
OCH
3
(4) H
3
C CHBr OCH
3


Sol. (4)
Electrophilic addition reaction is more favourable


-
HBr Br
H C = CH- OCH H C- CH- OCH H C- CH- OCH
2 3 2 3 3 3
Br
H


97. The IUPAC name of the compound shown below is

Cl
Br

(1) 2-bromo-6-chlorocyclohex-1-ene (2) 6-bromo-2-chlorocyclohexene
(3) 3-bromo-1-chlorocyclohexene (4) 1-bromo-3-chlorocyclohexene

Sol. (3)
Priority is given to double bond. Numbering must be along the double bond


98. The increasing order of the rate of HCN addition to compounds A D is
(A) HCHO (B) CH
3
COCH
3

(C) PhCOCH
3
(D) PhCOPh
(1) A < B < C < D (2) D < B < C < A
(3) D < C < B < A (4) C < D < B < A

Sol. (3)
Addition of HCN to carbonyl compounds is a nucleophilic addition reaction.
Reactivity order :

O
||
H C H > R C H > R C R
O
||
O
||

Ketones are less reactive than aldehydes due to +I effect of alkyl; group and steric hindrance.
As the size of alkyl group increases , reactivity of ketones further decreases.
Aromatic aldehydes and aromatic ketones are less reactive than their aliphatic analogues due to + R
effect of benzene ring

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 4

99. How many moles of magnesium phosphate, Mg
3
(PO
4
)
2
will contain 0.25 mole of oxygen atoms?
(1) 0.02 (2) 3.125 10
2

(3) 1.25 10
2
(4) 2.5 10
2


Sol. (2)
1 mole of
( )
Mg PO
3 4
2
has 8 moles of O atoms
? 0.25 moles of O atoms

0.25
8
=

2
25
8 100
3.125 10

=


100. According to Bohrs theory, the angular momentum of an electron in 5
th
orbit is
(1)
h
25

(2)
h
1.0

(3)
h
10

(4)
h
2.5

Sol. (4)
Angular momentum of e
-
in an orbit,
nh

mvr =

5h
2
h
2.5

=
=


101. Which of the following molecules/ions does not contain unpaired electrons?
(1)
2
2
O

(2) B
2

(3)
2
N
+
(4) O
2


Sol. (1)

2
2
O

:
2 * 2 2 * 2 2 2 2 * 2 * 2
1 1 , 2 2 , 2 , 2 2 , 2 2 s s s s p p p p p
z x y x y
= = ( All paired e
-
- Diamagnetic)
2
B :
2 * 2 2 * 2 1 1
1 1 , 2 2 2 2 s s s s p p
x y
= (2 unpaired e
-
- Paramagnetic)
2
N
+
:
2 * 2 2 * 2 2 2 1
1 1 , 2 2 2 2 2 s s s s p p p
x y z
= ( 1 unpaired e
-
- Paramagnetic)
2
O :
2 * 2 2 * 2 2 2 2 * 1 * 1
1 1 , 2 2 2 2 2 2 2 s s s s p p p p p
z x y x y
= = (2 unpaired e
-
- Paramagnetic)


MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 5

102. Total volume of atoms present in a face-centre cubic unit cell of a metal is (r is atomic radius)
(1)
3
20
3
r (2)
3
24
3
r
(3)
3
12
3
r (4)
3
16
3
r

Sol. (4)
FCC unit cell contains 6Face centred and 8corner particles

1 1
6 8
2 8
x x + = 4
So , FCC unit cell contains 4 particles
Total volume of atoms present in a face-centre cubic unit cell of a metal
=
3
4
4
3
r
| |

|
\

=
3
16
3
r

103. A reaction was found to be second order with respect to the concentration of carbon monoxide. If
the concentration of carbon monoxide is doubled, with everything else kept the same, the rate of
reaction will
(1) remain unchanged (2) triple
(3) increase by a factor of 4 (4) double

Sol. (3)
[ ]
2
R CO - (1)
[ ]
' 2
2 R CO - (2)

'
4
R
R
=
' 4 R R =

104. Which of the following chemical reactions depicts the oxidizing behaviour of H
2
SO
4
?
(1) 2HI + H SO I + SO + 2H O
2 4 2 2 2
(2) ( ) Ca OH + H SO CaSO + 2H O
2
2 4 4 2

(3) NaCl + H SO NaHSO + HCl
2 4 4
(4)
5
2PCl + H SO 2POCl + 2HCl + SO Cl
2 4 3 2 2


Sol. (1)
2HI + H SO I + SO + 2H O
2 4 2 2 2

In this reaction , oxidation no of iodine is increased from 1 to 0 and that of S is decreased from +6 to
+4. Therefore H
2
SO
4
is an oxidizing agent and HI is a reducing agent



MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 6

105. The IUPAC name for the complex [Co(NO
2
)(NH
3
)
5
]Cl
2
is
(1) nitrito-N-pentaamminecobalt (III) chloride (2) nitrito-N-pentaamminecobalt (II) chloride
(3) pentaammine nitrito-N-cobalt (II) chloride (4) pentaammine nitrito-N-cobalt (III) chloride

Sol. (4)
[Co(NO
2
)(NH
3
)
5
]Cl
2

pentaammine nitrito-N-cobalt (III) chloride


106. The term anomers of glucose refers to
(1) isomers of glucose that differ in configurations at carbons one and four (C-1 and C-4)
(2) a mixture of (D)-glucose and (L)-glucose
(3) enantiomers of glucose
(4) isomers of glucose that differ in configuration at carbon one (C-1)

Sol. (4)
A pair of stereoisomers which differ in configuration at C -1 are called anomers and the carbon is called
anomeric carbon
- D (+) glucose and - D (+) glucose are anomers.


107. In the transformation of
238
92
Uto
234
92
U, if one emission is an -particle, what should be the other
emission(s)?
(1) Two

(2) Two

and one
+

(3) One

and one (4) One

+
and one

Sol. (1)

238 234 4 0
U U + He + 2 e
92 92 2 -1
i.e., two

108. Phenyl magnesium bromide reacts with methanol to give
(1) a mixture of anisole and Mg(OH)Br (2) a mixture of benzene and Mg(OMe)Br
(3) a mixture of toluene and Mg(OH)Br (4) a mixture of phenol and Mg(Me)Br

Sol. (2)

6 5 3 6 6 3
( ) C H MgBr CH OH C H Mg OCH Br + +

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 7

109.
3 3
CH Br Nu CH Nu Br

+ +
The decreasing order of the rate of the above reaction with nucleophiles (Nu

) A to D is
( ) ( ) ( ) ( )
3
, , , Nu A PhO B AcO C HO D CH O

( =


(1) D > C > A > B (2) D > C > B > A
(3) A > B > C > D (4) B > D > C > A

Sol. (1)

3
CH O HO PhO AcO

> > >
If the nucleophilic atom is same , nucleophilicity parallels basicity. i.e., greater the basicity, stronger is
the nucleophile.
Weaker acid has the strong conjugate base

110. The pyrimidine bases present in DNA are
(1) cytosine and adenine (2) cytosine and guanine
(3) cytosine and thymine (4) cytosine and uracil

Sol. (3)
DNA contains
purines, Adenine and Guanine
Pyrimidines Thymine and Cytosine

111. Among the following the one that gives positive iodoform test upon reaction with I
2
and NaOH is
(1) CH
3
CH
2
CH(OH)CH
2
CH
3
(2) C
6
H
5
CH
2
CH
2
OH
(3) (4) PhCHOHCH
3



Sol. (4)
Iodoform test is given by compounds having Methyl keto group ( CH
3
CO -) and Methyl carbinol(
CH
3
CHOH -) groups

12. The increasing order of stability of the following free radicals is
(1)
( ) ( ) ( ) ( )

CH CH< CH C C H CH C H C
3 3 6 5 6 5
2 2 2 2
< <
(2)
( ) ( ) ( ) ( )

C H C< C H CH< CH C< CH CH
6 5 6 5 3 3
3 2 3 2

(3)
( ) ( ) ( ) ( )

C H CH< C H C< CH C< CH CH
6 5 6 5 3 3
2 3 3 2

(4)
( ) ( ) ( ) ( )

CH CH< CH C< C H C< C H CH
3 3 6 5 6 5
2 3 3 2



MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 8

Sol. (1)
The order of stability of free radicals is 3
0
> 2
0
> 1
0

Benzyl free radicals are stabilized by resonance. So they are more stable than alkyl free radicals.
As the no of phenyl groups attached to the carbon atom having odd e
-
increases, stability increases

113. Uncertainty in the position of an electron (mass = 9.1 10
31
kg) moving with a velocity 300 ms
1
,
accurate upto 0.001%, will be
(1)
2
19.2 10 m

(2)
2
5.76 10 m

(3)
2
1.92 10 m

(4)
2
3.84 10 m

( )
34
6.63 10 Js h

=

Sol. (3)

h
x.V
4m


34
31
h 6.63 10
x
0.001
4mV
4 3.14 9.1 10 300
100

=



34
31 3
6.63 10
4 3.14 9.1 10 10

=


= 0.01933
=
2
1.93 10

114. Phosphorus pentachloride dissociates as follows, in a closed reaction vessel,
( ) ( ) ( )
5 3 2
PCl g PCl g Cl g +
If total pressure at equilibrium of the reaction mixture is P and degree of dissociation of PCl
5
is x,
the partial pressure of PCl
3
will be

(1)
1
x
P
x
| |
|
+
\
(2)
2
1
x
P
x
| |
|

\

(3)
1
x
P
x
| |
|

\
(4)
1
x
P
x
| |
|

\


Sol. (1)
( ) ( ) ( )
5 3 2
PCl g PCl g Cl g +
1 0 0
(1-x) x x
Total no of moles = 1+ x
Partial pressure = Mole fraction x P
total


1
3
x
P P
PCl
x
| |
=
|
+
\


MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 9

115. The standard enthalpy of formation
( )
0
H
f
at 298 K for methane, CH
4
(g), is 74.8 kJ mol
1
. The
additional information required to determine the average energy for C H bond formation would
be
(1) the dissociation energy of H
2
and enthalpy of sublimation of carbon
(2) latent heat of vapourization of methane
(3) the first four ionization energies of carbon and electron gain enthalpy of hydrogen
(4) the dissociation energy of hydrogen molecule, H
2


Sol. (1)

( ) ( ) ( )
1
2
2 ; 74.8
4
C s H g CH g H kJmol

+ =
In order to calculate the average energy of C H bond formation , the following data is needed
( ) ( ); C s C g H ( enthalpy of sublimation of carbon)
( ) ( )
2
2 ; H g H g H ( enthalpy of bond dissociation of H
2
)

116. Among the following mixtures, dipole-dipole as the major interaction, is present in
(1) benzene and ethanol (2) acetonitrile and acetone
(3) KCl and water (4) benzene and carbon tetrachloride

Sol. (2)

Dipole dipole interactions are present between the polar molecules, I which the positive pole of one
molecule is attracted by the negative pole of another molecule.

117. Fluorobenzene (C
6
H
5
F) can be synthesized in the laboratory
(1) by heating phenol with HF and KF
(2) from aniline by diazotisation followed by heating the diazonium salt with HBF
4

(3) by direct fluorination of benzene with F
2
gas
(4) by reacting bromobenzene with NaF solution

Sol. (2)


Ar NH + NaNO + 2 HCl Ar N N + NaCl + 2H O
2 2 2
Cl

BALZ SCHIEMANN REACTION

+
+
N
2
Cl

HBF
4
-HCl
N
2
BF
4
F
+ N
2
+ BF
3




MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 10

118. A metal, M forms chlorides in its +2 and +4 oxidation states. Which of the following statements
about these chlorides is correct?
(1) MCl
2
is more volatile than MCl
4

(2) MCl
2
is more soluble in anhydrous ethanol than MCl
4

(3) MCl
2
is more ionic than MCl
4

(4) MCl
2
is more easily hydrolysed than MCl
4


Sol. (3)
Acc to Fajan, Low charge on the ion favours formation of ionic bond and high charge on the ion
favours covalent bond formation

119. Which of the following statements is true?
(1) H
3
PO
3
is a stronger acid than H
2
SO
3

(2) In aqueous medium HF is a stronger acid than HCl
(3) HClO
4
is a weaker acid than HClO
3

(4) HNO
3
is a stronger acid than HNO
2


Sol. (4)
Higher the oxidation state of the central atom, greater is the acidic nature
So, HNO
3
is a stronger acid than HNO
2


HClO
4
is a stronger acid than HClO
3

Greater the electro

negativity and higher the oxidation state of central atom, greater is the acidic nature
So, H
2
SO
3
is a stronger acid than H
3
PO
3

Due to higher bond dissociation energy and molecular association in HF , it is weaker than HCl

120. The molar conductivities
0
NaOAc and
0
HCl at infinite dilution in water at 25
o
C are 91.0 and
426.2 S cm
2
/mol respectively. To calculate o
0
HOAc , the additional value required is
(1)
0
H O
2
(2)
0
KCl
(3)
0
NaOH (4)
0
NaCl

Sol. (4)


( ) - +
3
3
0 0 0
CH COONa
CH COO Na
= + ............... 1

( )
0 0 0
HCl
CH
= + .................. 2
Cl
+
( )
0 0 0
NaCl Na
= + .................. 3
Cl


3 3
0 0 0 0
CH CH COONa HCl NaCl
=
COOH
+





MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 11

121. Which one of the following sets of ions represents a collection of isoelectronic species?
(1)
+ - 2+ 3+
K ,Cl ,Ca ,Sc (2)
2+ 2 + 2
Ba ,Sr ,K ,S
+

(3)
3 2 2
N ,O ,F ,S

(4)
2 2
Li ,Na ,Mg ,Ca
+ + + +


Sol. (1)

+ - 2+ 3+
K ,Cl ,Ca ,Sc
All of them have 18 e
-


122. The correct order of increasing acid strength of the compounds is
(a) CH
3
CO
2
H (b) MeOCH
2
CO
2
H
(c) CF
3
CO
2
H (d)

(1) b < d < a < c (2) d < a < c < b
(3) d < a < b < c (4) a < d < c < b

Sol. (3)
+I groups decrease the acidic nature( Me-)
-I groups increase the acidic nature ( - F and OMe)

123. In which of the following molecules/ions are all the bonds not equal?
(1) SF
4
(2) SiF
4

(3) XeF
4
(4)
4
BF

Sol. (1)
In SF
4
, Hybridisation of central atom S is sp
3
d. Its shape is distorted tetrahedral or see saw.
Due to repulsion with equatorial bonds , axial bonds are elongated. So, the bond lengths of two axial
bonds are greater than the three equatorial bonds



124. What products are expected from the disproportionation reaction of hypochlorous acid?
(1) HClO
3
and Cl
2
O (2) HClO
2
and HClO
4

(3) HCl and Cl
2
O (4) HCl and HClO
3


Sol. (4)

3
3 ClO ClO 2 Cl H H H +
Oxidation state of Cl is increased from +1( HOCl) to +5(HClO
3
) and decreased to -1(HCl)

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 12

125. Nickel (Z = 28) combines with a uninegative monodentate ligand X

to form a paramagnetic
complex [NiX
4
]
2
. The number of unpaired electron(s) in the nickel and geometry of this complex
ion are, Respectively
(1) one, tetrahedral (2) two, tetrahedral
(3) one, square planar (4) two, square planar

Sol. (2)

2 2 6 2 6 2 8
28
Ni:1s 2s 2p 3s 3p 4s 3d

2 2 2 6 2 6 8
Ni :1s 2s 2p 3s 3p 3d
+


No of unpaired e
-
= 2

126. In Fe(CO)
5
, the Fe C bond possesses
(1) -character only (2) both and characters
(3) ionic character (4) -character only

Sol. (2)
In metal carbonyls, metal Carbon bond possesses both and characters

127. The increasing order of the first ionization enthalpies of the elements B, P, S and F (lowest first) is
(1) F < S < P < B (2) P < S < B < F
(3) B < P < S < F (4) B < S < P < F

Sol. (4)
IE increase from left to right in a period and decreases down the group.
IE of P is greater than that of S, due to half filled configuration of P

128. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If T
i
is the
initial temperature and T
f
is the final temperature, which of the following statements is correct?
(1)
( ) ( )
T > T
f f
irrev rev

(2) T
f
> T
i
for reversible process but T
f
= T
i
for irreversible process
(3)
( ) ( )
T T
f f
rev irrev
=
(4) T
f
= T
i
for both reversible and irreversible processes

Sol. (1)
>W
irrev rev
W

( ) ( )
T > T
f f
irrev rev

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 13

129. In Langmuirs model of adsorption of a gas on a solid surface
(1) the rate of dissociation of adsorbed molecules from the surface does not depend on the surface
covered
(2) the adsorption at a single site on the surface may involve multiple molecules at the same time
(3) the mass of gas striking a given area of surface is proportional to the pressure of the gas
(4) the mass of gas striking a given area of surface is independent of the pressure of the gas

Sol. (3)
Langmuir Adsorption Isotherm gives information about the mass of gasn adsorbed per gram of
adsorbent is related to the equilibrium pressure by the expression

aP
x / m
1 bp
=
+


130. Rate of a reaction can be expressed by Arrhenius equation as:

/ E RT
k Ae

=
In this equation, E represents
(1) the energy above which all the colliding molecules will react
(2) the energy below which colliding molecules will not react
(3) the total energy of the reacting molecules at a temperature, T
(4) the fraction of molecules with energy greater than the activation energy of the reaction

Sol. (2)

/ E RT
k Ae

=
Where E is activation energy i.e., min amount of energy required to be possessed by the reactant
molecule for their collision lkead to the formation of products

131. The structure of the major product formed in the following reaction is


Cl
I
NaCN
DMF

(1) (2)

CN
CN

Cl
I

(3) (4)
Cl
CN

I
CN

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 14


Sol. (4)
Alkyl halides are more reactive than aryl halides. So, side chain is attacked

Cl
I
NaCN
DMF
I
CN


132. Reaction of trans-2-phenyl-1-bromocyclopentane on reaction with alcoholic KOH produces
(1) 4-phenylcyclopentene (2) 2-phenylcyclopentene
(3) 1-phenylcyclopentene (4) 3-phenylcyclopentene

Sol. (4)
According to E
2
mechanism.


133. Increasing order of stability among the three main conformations (i.e. Eclipse, Anti, Gauche) of
2-fluoroethanol is
(1) Eclipse, Gauche, Anti (2) Gauche, Eclipse, Anti
(3) Eclipse, Anti, Gauche (4) Anti, Gauche, Eclipse

Sol. (3)
2-Fluoroethanol



Anti (or) staggered Eclipsed Skew or Gauche Fully eclipsed

In gauche form , there is possibility of intra molecular hydrogen bonding


MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 15

134. The structure of the compound that gives a tribromo derivative on treatment with bromine water
is
(1) (2)

CH
3
OH

CH OH
2

(3) (4)

CH
3
OH

CH
3
OH


Sol. (1)
Since the compound on treatment with Br
2
H
2
O gives a tri bromo derivative , it must be m Cresol
Because it has one o- and two p - positions free with respect to OH group


135. The decreasing values of bond angles from NH
3
(106
o
) to SbH
3
(101
o
) down group-15 of the
periodic table is due to
(1) increasing bp-bp repulsion (2) increasing p-orbital character in sp
3

(3) decreasing lp-bp repulsion (4) decreasing electronegativity

Sol. (4)
In a group, from top to bottom , as the size of the atom increases , pure p orbitals are involved in
bonding

136.

Me
Me
N
Et
n-Bu
OH

The alkene formed as a major product in the above elimination reaction is
MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 16

(1) (2) CH
2
= CH
2


Me

(3) (4)

Me

Me


Sol. (4)

Me
Me
N
Et
n-Bu
OH

Me


In Hofmann elimination, less sterically hinderd hydrogen is eliminated and hence less substituted
alkene is the major product

137. The spin-only magnetic moment [in units of Bohr magneton,(
B
)] of Ni
2+
in aqueous solution
would be (Atomic number of Ni = 28)
(1) 2.84 (2) 4.90
(3) 0 (4) 1.73

Sol. (1)
2 2 2 6 2 6 8 0
1 2 2 3 3 3 4 Ni s s p s p d s
+


As H
2
O is a weak field ligand, no forcible pairing occurs
Hence the complex formed will be sp
3
hybridized and tetrahedral in geometry.
No of unp[aired e
-
s = 2
Therefore, spin only magnetic moment ( 2) n n = +
2(2 2) = + = 8 2.84 = = B.M

138. The equilibrium constant for the reaction
( ) ( ) ( )
3 2 2
1
SO g SO g + O g
2

is
2
4.9 10
c
K

= . The value of K
c
for the reaction
( ) ( ) ( )
2 2 3
2SO g +O g 2SO g will be
(1) 416 (2) 2.40 10
3

(3) 9.8 10
2
(4) 4.9 10
2

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 17

Sol. (1)
Equation is reversed and multiplied by 2;
2
1
K =
2
K
1


2 2 2
1
(4.9 10 )
K

| |
=
|

\


4
10 100 100
4.9 4.9 24.01

= =

= 416.49

139. Following statements regarding the periodic trends of chemical reactivity of the alkali metals and
the halogens are given. Which of these statements gives the correct picture?
(1) The reactivity decreases in the alkali metals but increases in the halogens with increase in
atomic number down the group
(2) In both the alkali metals and the halogens the chemical reactivity decreases with increase in
atomic number down the group
(3) Chemical reactivity increases with increase in atomic number down the group in both the
alkali metals and halogens
(4) In alkali metals the reactivity increases but in the halogens it decreases with increase in atomic
number down the group

Sol. (4)

140. Given the data at 25
0
C,

0
Ag + I AgI + e ; E 0.152V

=

0
Ag Ag ; E 0.800V e
+
+ =
What is the value of
sp
log K for AgI?

RT
2.303 =0.059V
F
| |
|
\

(1) -8.12 (2) +8.612
(3) -37.83 (4) -16.13

Sol. (4)
( ) ( )
0
AgI s +e Ag s +I ; E 0.152

=

0
Ag Ag ; E 0.800V e
+
+ =
( )
+ 0
AgI s Ag + I ; E 0.952

=

0
cell
0.059
E logK
n
=

sp
0.059
0.952 logK
1
=

sp
0.952
logK 16.135
0.059
= =
MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 18

141. The following mechanism has been proposed for the reaction of NO with Br
2
to form NOBr:
( ) ( ) ( )
2 2
NO g Br g NOBr g +
( ) ( ) ( )
2
NOBr g NO g 2NOBr g +
If the second step is the rate determining step, the order of the reaction with respect to NO(g) is
(1) 1 (2) 0
(3) 3 (4) 2

Sol. (4)
( ) ( ) ( )
2 2
NO g Br g NOBr g +
( ) ( ) ( )
2
NOBr g g 2NOBr g NO + ( Rate determining step)
Therefore, [ ][ ]
2
R = K NOBr NO

[ ] [ ][ ]
[ ][ ][ ]
2 c 2
c 2
NOBr =K NO Br
K.K NO Br NO R =


[ ]
2 '
=K NO Br
2
(


Therefore order of the reaction w r t NO is 2

142. Lanthanoid contraction is caused due to
(1) the appreciable shielding on outer electrons by 4f electrons from the nuclear charge
(2) the appreciable shielding on outer electrons by 5d electrons from the nuclear charge
(3) the same effective nuclear charge from Ce to Lu
(4) the imperfect shielding on outer electrons by 4f electrons from the nuclear charge

Sol. (4)
Lanthanoid contration is due to ineffective shielding offered by f orbitals which inturn is due to their
dispersed shape

143. Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is
100 . The conductivity of this solution is 1.29 S m
1
. Resistance of the same cell when filled with
0.2 M of the same solution is 520 . The molar conductivity of 0.2 M solution of the electrolyte
will be
(1)
4 2 1
124 10 S m mol

(2)
4 2 1
1240 10 S m mol


(3)
4 2 1
1.24 10 S m mol

(4)
4 2 1
12.4 10 S m mol



Sol. (4)
1
K =
R
l
a
| |
|
\

1
1.29 =
100
l
a
| |
|
\

1
129 m
l
a

| |
=
|
\

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 19

R = 520 , C = 0.2 M
( )
1 1
1 1
129 m
520
l
K
R a

| |
= =
|
\

1000
K
i
m
Molar ty
=
6 3
1 1000
129 10
520 0.2
m

=
6
129 1000
10
520 0.2

=
3
1.24 10

=
=
4 2 1
12.4 10 S m mol



144. The ionic mobility of alkali metal ions in aqueous solution is maximum for
(1) K
+
(2) Rb
+

(3) Li
+
(4) Na
+


Sol. (2)
Smaller the size, heavier is the hydration and lesser is the ionic mobility and vice versa.
Rb
+
is the largest ion among given. So it is least hydrated. Hence it will have maximum ionic
mobility

145. Density of a 2.05 M solution of acetic acid in water is 1.02 g/mL. The molality of the solution is
(1)
1
1.14 mol kg

(2)
1
3.28 mol kg

(3)
1
2.28 mol kg

(4)
1
0.44 mol kg

Sol. (3)

'
1000 M
m
1000 d MM

=



'
1000 2.05
m
1000 1.02 2.05 x 60

=


= 2.28

146. The enthalpy changes for the following processes are listed below:
( ) ( )
2
Cl g 2Cl g , =
1
242.3 kJ mol

( ) ( )
2
l g 2l g , =
1
151.0 kJ mol

( ) ( ) ( ) ICl g l g Cl g , = +
1
211.3 kJ mol

( ) ( )
2 2
I s l g , =
1
62.76 kJ mol

Given that the standard states for iodine and chlorine are I
2
(s) and Cl
2
(g), the standard enthalpy
of formation for ICl(g) is
(1) -14.6
1
kJ mol

(2) -16.8
1
kJ mol

(3) +16.8
1
kJ mol

(4) +244.8
1
kJ mol

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 20


Sol. (3)
( ) ( )
2 2
1 1
I Cl ICl g
2 2
s +

( ) ( )
1 1 1
2 2 2
2 2
H H H H H
I l Cl Cl I Cl I s l g
(
(
= + + (

(


( )
1 1 1
62.76 151.0 242.3 211.3
2 2 2
| |
= + +
|
\

= 228.03 211.3
H =16.73

147. How many EDTA (ethylenediaminetetraacetic acid) molecules are required to make an octahedral
complex with a Ca
2+
ion?
(1) Six (2) Three
(3) One (4) Two

Sol. (3)
EDTA is a hexa dentate ligand

148.

OH
+ CHCl +NaOH
3
ONa
+
CHO

The electrophile involved in the above reaction is
(1) dichloromethyl cation
( )
CHCl
2
(2) dichlorocarbene( :CCl
2
)
(3) trichloromethyl anion
( )
CCl
3
(4) formyl cation
( ) CHO


Sol. (2)
This is Reimer Tiemann reaction, in which the electrophile involved is dichloro carbene

149. 18 g of glucose (C
6
H
12
O
6
) is added to 178.2 g of water. The vapour pressure of water for this
aqueous solution at 100
o
C is
(1) 759.00 Torr (2) 7.60 Torr
(3) 76.00 Torr (4) 752.40 Torr

MAHESH JANMANCHI AIEEE 2006

visit us at www.chemistrycrest.com Page 21

Sol. (4)
0
S
S
P P n
P N

=
S
S
18 1
760 P 0.1
180 10
178.2
P 9.9 9.9
18

= = =
S S
1
760 P P
99
=
S S
760 99 P 99=P
S
760 99 100P =
S
760 99
P 752.4
100

= =

150. (H U) for the formation of carbon monoxide (CO) from its elements at 298 K is

( )
1 1
R=8.314 J K mol


(1) -1238.78
1
J mol

(2) 1238.78
1
J mol

(3) -2477.57
1
J mol

(4) 2477.57
1
J mol

Sol. (1)

2
1
C + O CO
2

g
H U n RT =
g
1
n = 1- 1
2


1
8.314 298
2
=
1238.78 =