NCERT Solutions For Class 11 Chemistry Chapter 7 - Equilibrium - .

Download as pdf or txt
Download as pdf or txt
You are on page 1of 64

NCERT Solutions for Class 11

Chemistry
Chapter 7 – Equilibrium

1. A liquid is in equilibrium with its vapour in a sealed container at a fixed


temperature. The volume of the container is suddenly increased.
(a). What is the initial effect of the change on vapour pressure?
Ans: The vapour pressure would first fall if the container's volume was rapidly
increased. This is due to the fact that the amount of vapour remains constant while
the volume increases rapidly. As a result, the same amount of vapour is spread
over a wider surface area.

(b). How do rates of evaporation and condensation change initially?


Ans: The rate of evaporation is also constant because the temperature is constant.
The density of the vapour phase reduces as the container volume increases. As a
result, the rate of vapour particle collisions drops as well. As a result, the rate of
condensation initially slows.

(c). What happens when equilibrium is restored finally and what will be the
final vapour pressure?
Ans: The rate of evaporation equals the rate of condensation when equilibrium is
eventually restored. Only the volume changes in this situation, but the temperature
remains fixed. Temperature, not volume, determines vapour pressure. As a result,
the final vapour pressure will be the same as the system's initial vapour pressure.

2. What is K c for the following equilibrium when the equilibrium


concentration of each substance is: [SO2 ]  0.60M , [O2 ]  0.82M and [SO3 ]  1.90M
? 2SO2 (g)  O2 (g) 2SO3 (g)

Ans: The equilibrium constant for the given reaction will be:

Class XI Chemistry www.vedantu.com 1


SO3 
2

Kc 
SO2  O2 
2

(1.90) 2 M 2

(0.60) 2 (0.821)M 3

K c  12.239M1 (approximately)

Therefore, the equilibrium constant for the given reaction is 12.239M1 .

3. At a certain temperature and total pressure of 105 Pa, iodine vapour


contains 40% by volume of iodine atoms. I2 (g) 2I (g) . Calculate K P for the
equilibrium.
Ans: Partial pressure for I atoms:
40
p1   p total
100
40
 105
100
 4  104 Pa

Partial pressure for I 2 molecules:

60
p l2   p total
100

60
 105
100

 6 104 Pa

Now for, the given reaction:

(pI) 2
Kp 
p12


 4 10  Pa
4 2

6 104 Pa

Class XI Chemistry www.vedantu.com 2


 2.67 104 Pa

4. Write the expression for the equilibrium constant, K c for each of the
following reactions:
(i). 2NOCl (g) 2NO (g)  Cl2 (g)

Ans: The expression for the equilibrium constant is:

[NO]2 [Cl2 ]
Kc 
[NOCl]2

(ii). 2Cu(NO3 )2 (s) 2CuO (s)  4NO2 (g)  O2 (g)

Ans: The expression is:

[CuO]2 [NO2 ]4 [O2 ]


Kc 
[Cu(NO3 )2 ]2

Kc  [NO2 ]4 [O2 ]

(iii). CH3COOC2 H5 (aq)  H2O (l) CH3COOH (aq)  C2H5OH (aq)

Ans: The expression will be:


[CH3COOH] [C2 H5OH]
Kc 
[CH3COOC2 H5 ] [H 2O]

[CH3COOH] [C2 H5OH]


Kc 
[CH3COOC2 H5 ]

(iv). Fe3+ (aq)  3OH (aq) Fe(OH)3 (s)

Ans: The expression will be:


[Fe(OH)3 ]
Kc 
[Fe3 ][OH  ]3

1
Kc 
[Fe ][OH  ]3
3

Class XI Chemistry www.vedantu.com 3


(v). I2 (s)  5F2 2IF5

Ans: The expression will be:

[IF5 ]2
Kc 
[I2 ][F2 ]2

[IF5 ]2
Kc 
[F2 ]2

5. Find out the value of K c for each of the following equilibria from the value
of K p :
(i). 2NOCl (g) 2NO (g)  Cl2 (g) ; K p  1.8 102 at 500K

Ans: The relationship between K p and K c is given as:

K p  K c (RT)Δn

n  3  2  1

R  0.0831 barLmol1K 1

T = 500K

K p  1.8 102

Now, K p  Kc (RT)Δn

1.8 102  Kc (0.0831 500)1

1.8 102
Kc 
0.0831 500

K c  4.33 104 (Approximately)

(ii). CaCO3 (s) CaO (s)  CO2 (g) ; K p  167 at 1073K

Ans: Here,

Class XI Chemistry www.vedantu.com 4


n  2 1  1

R  0.0831 barLmol1K 1

T = 1073K
K p  167

K p  K c (RT)Δn

167  Kc (0.08311073)1

167
Kc 
0.08311073

K c  1.87 (Approximately)

6. For the followingequilibrium, K c  6.3 1014 at 1000K


NO (g)  O3 (g) NO2 (g)  O2 (g) Both the forward and reverse reactions in the
equilibrium are elementary bimolecular reactions. What is K c for the reverse
reaction?
Ans: According to the question:

The K c for the forward reaction is 6.3 1014

Then, K c for the reverse reaction will be:

1
K 'c 
Kc

1
K 'c 
6.3 1014

K 'c  1.59 1015

The equilibrium constant for the reverse reaction will be: 1.59 1015 .

Class XI Chemistry www.vedantu.com 5


7. Explain why pure liquids and solids can be ignored while writing the
equilibrium constant expression?
Ans: For a pure substance which is both a solid and a liquid:
Number of moles
[Pure substance] 
Volume

Mass / Molecular weight


[Pure substance] 
Volume

Mass
[Pure substance] 
Volume  Molecular mass

Density
[Pure substance] 
Molecular mass

The molecular mass and density of a pure substance (at a given temperature) are
now always fixed and accounted for in the equilibrium constant. As a result, the
equilibrium constant statement does not include the values of pure substances.

8. Reaction between nitrogen and oxygen takes place as follows:


2N2 (g)  O2 (g) 2N2O (g) If a mixture of 0.482 mol of N 2 and 0.933 mol of O 2
is placed in a 10 L reaction vessel and allowed to form N 2O at a temperature
for which Kc  2.0 1037 , determine the composition of equilibrium mixture.

Ans: Let the concentration of N 2O at equilibrium be x.

The initial concentration of N 2 is 0.482mol.

The initial concentration of O 2 is 0.933mol.

At equilibrium the concentration of N 2 is (0.482-x)mol, the concentration of O 2 is


(0.933-x)mol and the concentration of N 2O is x mol.

The reaction occurs in a 10L reaction vessel:


0.482  x 0.933  x / 2 x
[N 2 ]  , [O2 ]  , [N 2O] 
10 10 10

Class XI Chemistry www.vedantu.com 6


The value of equilibrium constant i.e. Kc  2.0 1037 is very small. Therefore, the
amount of nitrogen and oxygen reacted is also very small. Thus, x can be neglected
from the expressions of molar concentrations of nitrogen and oxygen. Then,
0.482 0.933
[N 2 ]   0.0482 molL1 and [O2 ]   0.0933 molL-1
10 10

Now, according to the equation:

[N 2O]2
Kc 
[N 2 ]2 [O2 ]

x
( )2
2.0 1037  2
(0.0482)2 (0.0933)

x2
 2.0 1037  (0.0482) 2 (0.0933)
100

x2  43.35 1040

x  6.6 1020

x 6.6 1020
[N 2O]  
10 10

[N2O]  6.6 1021

9. Nitric oxide reacts with Br2 and gives nitrosyl bromide as per reaction
given below: 2NO (g)  Br2 (g) 2NOBr (g) When 0.087 mol of NO and 0.0437
mol of Br2 are mixed in a closed container at constant temperature, 0.0518
mol of NOBr is obtained at equilibrium. Calculate equilibrium amount of NO
and Br2 .

Ans: The given reaction is:


2NO (g)  Br2 (g) 2NOBr (g)

Class XI Chemistry www.vedantu.com 7


Now, 2 mol of NOBr are formed from 2 mol of NO . Therefore, 0.0518 mol of
NOBr are formed from 0.0518 mol of NO . Again, 2 mol of NOBr are formed
from 1 mol of Br .
0.0581
Therefore, 0.0518 mol of NOBr are formed from mol of Br , or 0.0259 mol
2
of NO .
The amount of NO and Br present initially is as follows:

[NO]  0.087mol and [Br2 ]  0.0437mol

Therefore, the amount of NO present at equilibrium is:


[NO]  0.087  0.0518  0.0352mol

And, the amount of Br present at equilibrium is:


[Br2 ]  0.0437  0.0259  0.0178mol

10. At 450K, K p  2.0 1010 bar -1 for the given reaction reaction at equilibrium.
2SO2 (g)  O2 (g) 2SO3 (g) , What is K c at this temperature?

Ans: For the given reaction:


Δn  2  3  1
T  450K
R  0.0831 bar L bar K 1mol1
K p  2.0 1010 bar 1

We know that,
K p  K c (RT)n

2.0 1010  K c (0.0831 450) 1


2.0 1010
Kc 
(0.0831 450)
K c  74.79 1014 Lmol

Class XI Chemistry www.vedantu.com 8


11. A sample of HI (g) is placed in flask at a pressure of 0.2 atm. At
equilibrium the partial pressure of HI (g) is 0.04 atm. What is K p for the
given equilibrium? 2HI (g) H2 (g)  I2 (g)

Ans: The initial concentration of HI is 0.2 atm. At equilibrium, it has a partial


pressure of 0.04 atm. Therefore, a decrease in the pressure of HI is 0.2 – 0.04 =
0.16. The given reaction is:
0.16
At equilibrium the pressure of HI is 0.04 atm, the pressure for H 2   0.08atm
2
0.16
and the pressure for O2   0.08atm .
2

Therefore, the value of K p at equilibrium is 4.0.

12. A mixture of 1.57 mol of N 2 , 1.92 mol of H 2 and 8.13 mol of NH3 is
introduced into a 20 L reaction vessel at 500 K. At this temperature, the
equilibrium constant, K c for the reaction is 1.7 102 . The reaction is:
N2 (g)  3H2 (g) 2NH3 (g) . Is the reaction mixture at equilibrium? If not, what
is the direction of the net reaction?
Ans: For the given reaction: N2 (g)  3H2 (g) 2NH3 (g)

The given concentration of various species is


1.57 1.92
 N2   molL1  H 2   molL1
20 20
8.13
 NH3   molL1
20

Now, reaction quotient Qc is:

Class XI Chemistry www.vedantu.com 9


 NH 3 
2

QC 
 N 2  H 2 
3

2
 (8.13) 
 
 
20 
QC 3
 1.57  1.92 
  
 20  20 
QC  2.4 103

Since, ≠ , the reaction mixture is not at equilibrium.

Again, > . Hence, the reaction will proceed in the reverse direction

13. The equilibrium constant expression for a gas reaction is:

[NH3 ]4 [O2 ]5
Kc 
[NO]4 [H 2O]6

Write the balanced chemical equation corresponding to this expression.


Ans: The balanced chemical equation corresponding to the given expression can
be written as:
4NO (g)  6H2O (g) 4NH3 (g)  5O2 (g)

14. One mole of H 2O and one mole of CO are taken in 10 L vessel and heated
to 725 K. At equilibrium 40% of water (by mass) reacts with CO according to
the equation: H2 (g)  CO(g) H2 (g)  CO2 (g) Calculate the equilibrium constant
for the reaction.
Ans: The given reaction is:

Class XI Chemistry www.vedantu.com 10


H 2 O(g) +CO(g) H 2(g) +CO 2(g)
1 1
M M 0 0
10 10
1-0.4 1-0.4 0.4 0.4
M M M M
10 10 10 10
=0.06M =0.06M =0.04M =0.04M

Therefore, the equilibrium constant for the reaction:


[H 2 ] [CO 2 ]
Kc 
[H 2 O] [CO]
0.04  0.04
Kc 
0.06  0.06
K c  0.444

15. At 700 K, equilibrium constant for the reaction H2 (g)  I2 (g) 2HI (g) is
54.8. If 0.5molL1 of HI (g) is present at equilibrium at 700 K, what are the
concentration of H2 (g) and I2 (g) assuming that we initially started with HI (g)
and allowed it to reach equilibrium at 700 K?
Ans: It is given that equilibrium constant K c for the reaction

H2 (g)  I2 (g) 2HI (g) is 54.8

Therefore, at equilibrium, the equilibrium constant K 'c for the reaction

2HI (g) H2 (g)  I2 (g)

1
[HI]  0.5molL1 will be:
54.8

Let the concentrations of hydrogen and iodine at equilibrium be x molL1

[H2 ]  [I2 ]  x molL1

[H 2 ] [I2 ]
Therefore,  K 'c
[HI]2

Class XI Chemistry www.vedantu.com 11


x x 1
2

(0.5) 54.8
0.25
 x2 
54.8
 x  0.06754

x  0.068 molL-1 (approximately)

Hence, at equilibrium, [H2 ]  [I2 ]  0.068 molL-1

16. What is the equilibrium concentration of each of the substances in the


equilibrium when the initial concentration of ICI was 0.78 M?

2ICI (g) I2 (g)  Cl2 (g) ; K c  0.14

Ans: For the given reaction:


2ICI (g) I2 (g)  Cl2 (g)

The initial concentration of ICI is 0.78M and for I 2 and Cl2 is zero (0).

At equilibrium, the concentration for ICI is (0.78  2 x)M and for I 2 and Cl2 is x M .

Now, we can write:


[I 2 ] [Cl2 ]
 Kc
[ICI]2
x x
 0.14
(0.78  2 x) 2
x
  0.374
0.78  2 x
 x  0.292  0.748 x
 1.748 x  0.292
 x  0.167

Therefore, at equilibrium

Class XI Chemistry www.vedantu.com 12


[H 2 ]  [I 2 ]  0.167M
[HI]  (0.78  2  0.167)M
[HI]  0.446M

17. K p  0.04atm at 899 K for the equilibrium shown below. What is the
equilibrium concentration of C2 H6 when it is placed in a flask at 4.0 atm
pressure and allowed to come to equilibrium? C2H6 (g) C2H4 (g)  H2 (g)

Ans: Let p be the pressure exerted by ethene and hydrogen gas (each) at
equilibrium. Now, according to the reaction
C2 H6 (g) C2 H4 (g)  H2 (g)

The initial concentration of C2 H6 is 4.0 atm and that of C2 H 4 and H 2 is zero (0).

At equilibrium, the concentration of C2 H6 is (4.0 – p) and that of C2 H 4 and H 2 is p.

Then we can write,


pC2 H 4  pH 2
 Kp
pC2 H 6
p p
 0.04
40  p
p 2  0.16  0.04 p
p 2  0.04 p  0.16  0
0.04  (0.04) 2  4 1 (0.16)
p
2 1
0.04  0.08
p
2

If we take positive value:


0.76
p
2
p  0.38

So, at equilibrium:

Class XI Chemistry www.vedantu.com 13


[C2 H 6 ]  4  p  4  0.38  3.62 atm

18. A sample of pure PCl5 was introduced into an evacuated vessel at 473 K.
After equilibrium was attained, concentration of PCl5 was found to be
0.5 101 molL-1 . If value of K c is 8.3 103 , what are the concentrations of PCl3
and Cl2 at equilibrium? PCl5 (g) PCl3 (g)  Cl2 (g)

Ans: Let the concentrations of both PCl3 and Cl2 at equilibrium be x molL-1 . The
given reaction is:
PCl5 (g) PCl3 (g)  Cl2 (g)

At equilibrium the concentration of PCl5 is 0.5 101 molL-1

It is given that the value of equilibrium constant K c is 8.3103

The expression for equilibrium will be:


[PCl3 ] [Cl 2 ]
 Kc
[PCl5 ]
x x
1
 8.3 103
0.5 10
 x 2  4.15 104
 x  2.04 10 2
 x  0.0204

Therefore at equilibrium:
[PCl3 ]  [Cl2 ]  0.02 molL1

19. One of the reactions that takes place in producing steel from iron ore is the
reduction of iron (II) oxide by carbon monoxide to give iron metal and CO2 .
FeO (s)  CO (g) Fe (s)  CO2 (g) ; K p  0.0265 at 1050 K.

What are the equilibrium partial pressures of CO and CO2 at 1050 K if the
initial partial pressures are: pCO  1.4 atm and pCO  0.80 atm ?
2

Class XI Chemistry www.vedantu.com 14


Ans: For the given reaction:
FeO (s)  CO (g) Fe (s)  CO2 (g)

The initial concentration of FeO is 1.4 atm and the initial concentration of CO2 is
0.80 atm.
p CO2
Qp 
p CO
0.80
Qp 
1.4
Q p  0.571

It is given in the that, K p  0.265 .

Since Qp  K p , the reaction will proceed in the backward direction.

Therefore, we can say that the pressure of CO will increase while the pressure of
CO2 will decrease. Now, let the increase in pressure of CO be equal to the
decrease in pressure of CO2 be ‘p’. Then, we can write:

p CO2
Kp 
p CO
0.80  p
0.265 
1.4  p
0.371  0.265 p  0.80  p
1.265 p  0.429
 p  0.339

Therefore, equilibrium partial of CO2 will be, pCO  0.080  0.339  0.461 atm
2

And, equilibrium partial pressure of CO will be, pCO  1.4  0.339  1.739 atm

20. Equilibrium constant, K c for the reaction N2 (g)  3H2 (g) 2NH3 (g) at 500
K os 0.061. At a particular time, the analysis shows that composition of the
reaction mixture is 3.0 molL1 N 2 , 2.0 molL1 H 2 and 0.5 molL1 NH3 . Is the

Class XI Chemistry www.vedantu.com 15


reaction at equilibrium? If not in which direction does the reaction tend to
proceed to reach equilibrium?
Ans: The given reaction is:
N2 (g)  3H2 (g) 2NH3 (g)

At a particular time, the concentration of N 2 is 3.0 molL1 , for H 2 is 2.0 molL1 and
for NH3 is 0.5 molL1 .

Now, we know that:

[NH 3 ]2
Qc 
[N 2 ][H 2 ]3
(0.5) 2
Qc 
(3.0)(2.0)3
Qc  0.0104

It is given that Kc  0.061

Since Qc  K c , the reaction is not at equilibrium.

Since Qc  K c , the reaction will proceed in the forward direction to reach


equilibrium.

21. Bromine monochloride, BrCl decomposes into bromine and chlorine and
reaches the equilibrium: 2BrCl (g) Br2 (g)  Cl2 (g) for which K c  32 at 500 K. If
initially pure BrCl is present at a concentration of 3.3 103 molL1 , what is its
molar concentration in the mixture at equilibrium?
Ans: Let the amount of bromine and chlorine formed at equilibrium be ‘x’. The
given reaction is:
2BrCl (g) Br2 (g)  Cl2 (g)

At equilibrium the concentration of BrCl is (3.3103  2x )

Now, we can write.

Class XI Chemistry www.vedantu.com 16


[Br2 ][Cl2 ]
 Kc
[BrCl]
x x
 32
(3.3 103  2 x) 2
x
 5.66
3.3 103  2 x
 x  18.678  103  11.32 x
 12.32 x  18.678  103
 x  1.5  103

Therefore, at equilibrium

[BrCl]  3.3 103  (2 1.5 103 )


[BrCl]  3.3 103  3.0 103
[BrCl]  3.0 104 molL1

22. At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in


equilibrium with solid carbon has 90.55% CO by mass:
C (s)  CO2 (g) 2CO (g) . Calculate K c for this reaction at the above
temperature.
Ans: Let, the total mass of the gas mixture = 100 gm

Mass of CO = 90.55 gm

And, mass of CO2 = (100 – 90.55) = 9.45 gm

90.55
Now, the number of moles of CO , nCO   3.234 mol
28

9.45
Number of moles of CO2 , n CO   0.215 mol
2
44

nCO
Partial pressure of CO , pCO   ptotal
nCO  nCO2

Class XI Chemistry www.vedantu.com 17


3.234
pCO  1
3.234  0.215
pCO  0.938 atm

Partial pressure of CO2 ,

nCO2
pCO2   ptotal
nCO  nCO2
0.215
pCO2  1
3.234  0.215
pCO2  0.062 atm

Therefore,
[CO]2
Kp 
[CO 2 ]
(0.938) 2
Kp 
0.062
K p  14.19

For the given reaction:

n  2 1  1

We know that,

K p  K c (RT) n
14.19  K c (0.082 1127)1
14.19
Kc 
0.082 1127
K c  0.154

23. Calculate:
(a). G and
(b). the equilibrium constant for the formation of NO2 from NO and O 2 at 298 K
1
NO (g)  O2 (g) NO2 (g)
2

Class XI Chemistry www.vedantu.com 18


Where:

 f G (NO2 )  52 kJ/mol
 f G (NO)  87.0 kJ/mol
 f G (O 2 )  0 kJ/mol

Ans: For the given reaction:


1
NO (g)  O2 (g) NO2 (g)
2

(a). The G for the given reaction will be:

G  G (Products)  G (Reactants)
G  52.0  [87.0  0]
G  35.0 kJmol1

(b). We know that:

G  RT log K c
G  2.303RT log K c
35.0 103
log K c 
2.303  8.314  298
log K c  6.134
K c  antilog (6.134)
K c  1.36 106

Hence, the equilibrium constant for the given reaction K c is 1.36 106 .

24. Does the number of moles of reaction products increase, decrease or


remain same when each of the following equilibria is subjected to a decrease
in pressure by increasing the volume?
(a). PCl5 (g) PCl3 (g)  Cl2 (g)

Ans: The amount of moles produced by the reaction will rise. According to Le
Chatelier's principle, as pressure is reduced, the equilibrium swings in the direction
of a greater number of moles of gas. The number of moles of gaseous products in
the reaction is greater than the number of moles of gaseous reactants. As a result,

Class XI Chemistry www.vedantu.com 19


the reaction will be propelled ahead. As a result, there will be more moles of
reaction products.

(b). CaO (s)  CO2 (g) CaCO3 (s)

Ans: When the given equation is subjected to a decrease in pressure the number of
moles of reaction products will decrease.

(c). 3Fe (s)  4H2O (g) Fe3O4 (s)  4H2 (g)

Ans: When the given equation is subjected to a decrease in pressure the number of
moles of reaction products will remain same.

25. Which of the following reactions will get affected by increasing the
pressure? Also, mention whether change will cause the reaction to go into
forward or backward direction.
(a). COCl2 (g) CO (g)  Cl2 (g)
(b). CH4 (g)  2S2 (g) CS2 (g)  2H2S (g)
(c). CO2 (g) C (s)  2CO (g)
(d). 2H2 (g)  CO (g) CH3OH (g)
(e). CaCO3 (s) CaO (s)  CO2 (g)
(f). 4NH3 (g)  5O2 (g) 4NO (g)  6H2O (g)

Ans: By increasing the pressure, the reactions in (i), (iii), (iv), (v), and (vi) will be
changed. Because the number of moles of gaseous reactants is greater than the
number of moles of gaseous products, the reaction in (iv) will proceed in the
forward direction. Because the number of moles of gaseous reactants is smaller
than that of gaseous products, the reactions in (i), (iii), (v), and (vi) will shift
backward.

26. The equilibrium constant for the following reaction is 1.6 105 at 1024 K.
H2 (g)  Br2 (g) 2HBr (g) , Find the equilibrium pressure of all gases if 10.0 bar
of HBr is introduced into a sealed container at 1024 K.

Ans: The K p for the given reaction H2 (g)  Br2 (g) 2HBr (g) is 1.6 105 .

Class XI Chemistry www.vedantu.com 20


Therefore, for the reversed reaction: 2HBr (g) H2 (g)  Br2 (g) the equilibrium constant
will be:
1
K 'p 
Kp
1
K 'p 
1.6 105
K 'p  6.25 106

Now, let p be the pressure of both H 2 and Br2 at equilibrium.

So, at equilibrium the concentration of HBr will be (10  2p)

Now, we can write:


pBr2  pH 2
2
 K'p
p HBr

p p
 6.25  106
(10  2 p ) 2
p
 2.5  103
10  2 p
p  2.5  102  (5.0 103 ) p
p  (5.0 103 ) p  2.5 102
(1005  103 ) p  2.5  102
p  2.49  102 bar  2.5  102 bar

Therefore, at equilibrium:

[H 2 ]  [Br2 ]  2.49 102 bar


[HBr]  10  2  (2.49 102 )  9.95 bar

27. Dihydrogen gas is obtained from natural gas by partial oxidation with
steam as per following endothermic reaction:
CH4 (g)  H2O (g) CO (g)  3H2 (g)

(a). Write as expression for K p for the above reaction.

Ans: For the given equation:

Class XI Chemistry www.vedantu.com 21


pCO  p3 H 2
Kp 
pCH 4  pH 2O

(b). How will the values of K p and composition of equilibrium mixture be


affected by
(i). Increasing the pressure
Ans: The equilibrium will shift in the backward direction, according to Le
Chatelier's principle.

As the reaction shifts in the backward direction as the pressure is increased, the
value of K p decreases.

(ii). Increasing the temperature


Ans. Because the reaction is endothermic, the equilibrium will shift forward,
according to Le Chatelier's principle.

The value of K p will grow as the temperature rises because the rection will shift
forward.

(iii). Using a catalyst?


Ans: The existence of a catalyst has no effect on the reaction's equilibrium. A
catalyst does nothing but speed up a reaction. As a result, equilibrium will be soon
achieved.

Because the catalyst only changes the rate of reaction, the value of K p is
unaffected.

28. Describe the effect of the following on the equilibrium of the reaction:
2H2 (g)  CO (g) CH3OH (g)
(a). Addition of H 2

Ans: According to Le Chatelier's principle, when H 2 is added to a reaction, the


equilibrium shifts in the forward direction.

(b). Addition of CH3OH

Class XI Chemistry www.vedantu.com 22


Ans: The equilibrium will shift backwards with the addition of CH3OH .

(c). Removal of CO
Ans: When CO is removed from the equation, the equilibrium shifts backward.

(d). Removal of CH3OH

Ans: When CH3OH is removed from the equation, the equilibrium shifts forward.

29. At 473 K, equilibrium constant K r for decomposition of phosphorus


pentachloride, PCl5 is 8.3103 . If decomposition is depicted as:

PCl5 (g) PCl3 (g)  Cl2 (g) , r H  124.0 kJmol 1

(a). Write an expression for K c for the reaction.

Ans: The expression for K c will be:

[PCl3 ] [Cl2 ]
Kc 
[PCl5 ]

(b). What is the value of K c for the reverse reaction at the same temperature?

Ans:. Value of K c for the reverse reaction at the same temperature is:

1
K 'c 
Kc
1
K 'c  3
 1.2048 102
8.3 10

(c). What would be the effect on K c if


(i). More PCl5 is added?

Ans: Because the temperature is constant in this scenario, K c will remain constant.

(ii). Pressure is increased?

Class XI Chemistry www.vedantu.com 23


Ans: At constant temperature, K c remains constant. As a result, K c would not alter
in this scenario.

(iii). The temperature is increased?

Ans: In an endothermic process, the value of K c rises as the temperature rises.


Because the reaction in is an endothermic reaction, the value of K c will rise as the
temperature rises.

30. Dihydrogen gas used in Haber’s process is produced by reacting methane


from natural gas with high temperature steam. The first stage of two stage
reaction involves the formation of CO and H 2 . In second stage, CO formed
in first stage is reacted with more steam in water gas shift reaction:
CO (g)  H2O (g) CO2 (g)  H2 (g) If a reaction vessel at 400°C is charged with an
equimolar mixture of CO and steam such that pCO  pH O  4.0 bar , what will be
2

the partial pressure of H 2 at equilibrium? K p  10.1 at 400°C.

Ans: Let the partial pressure of both carbon dioxide and hydrogen gas be p. The
given reaction is:
CO (g)  H2O (g) CO2 (g)  H2 (g)

At equilibrium the concentration of CO and H 2O will be (4.0  p) .

It is given that, K p  10.1

Now,
p CO2  p H 2
 Kp
p CO  p H 2O
pp
 10.1
(4.0  p)  (4.0  p)
p
  3.178
40  p
 p  12.712  3.178p
 4.178p  12.712
 p  3.04

Class XI Chemistry www.vedantu.com 24


Hence, at equilibrium, the partial pressure of H 2 will be 3.04 bar.

31. Predict which of the following reaction will have appreciable


concentration of reactants and products:
(a). Cl2 (g) 2Cl (g) ; Kc  5 1039
(b). Cl2 (g)  2NO (g) 2NOCl (g) ; Kc  3.7 108
(c). Cl2 (g)  2NO2 (g) 2NO2Cl (g) ; Kc  1.8

Ans: If the value of K c lies between 103 and 103 , a reaction has appreciable
concentration of reactants and products. Thus, the reaction given in (c) will have
appreciable concentration of reactants and products.

32. The value of Kc for the reaction 3O2 (g) 2O3 (g) is 2.0 1050 at 25°C. If the
equilibrium concentration of O 2 in air at 25°C is 1.6 102 , what is the
concentration of O3 ?

Ans: The given reaction is:


3O2 (g) 2O3 (g)

2
O3( g ) 
KC   3
O2( g ) 

KC  2.0 1050 and O2( g )   1.6 102

2
50
O3( g ) 
2.0 10  3
1.6 102 

 
2 3
 O3( g )   2.0 1050  1.6 102
2
 O3( g )   8.192 1050
 O3( g )   2.86 1028 M

Hence, the concentration of O3 is 2.86 1028 M .

Class XI Chemistry www.vedantu.com 25


33. The reaction CO (g)  3H2 (g) CH4 (g)  H2O(g) is at equilibrium at 1300 K in
a 1L flask. It also contain 0.30 mol of CO , 0.10 mol of H 2 and 0.02 mol of
H 2O and an unknown amount of CH 4 in the flask. Determine the
concentration of CH 4 in the mixture. The equilibrium constant, K c for the
reaction at the given temperature is 3.90.
Ans: Let the concentration of methane at equilibrium be x.
CO (g)  3H2 (g) CH4 (g)  H2O(g)

At equilibrium, the concentration of CO is 0.3 M , H 2 is 0.1 M and H 2O is 0.02


M
Therefore,

CH 4( g )   H 2O( g ) 
3
 Kc
CO( g )   H 2( g ) 
x  0.02
  3.90
0.3  (0.1)3
3.90  0.3  (0.1)3
x
0.02
0.00117

0.02
 0.0585M
 5.85 102 M

Hence, the concentration of CH 4 at equilibrium is 5.85 102 M .

34. What is meant by the conjugate acid-base pair? Find the conjugate
acid/base for the following species:
HNO2 ,CN , HClO4 , F ,OH ,CO32 ,S

Ans: A conjugate acid-base pair varies from one other by only one proton. In the
table below, the conjugate acid-base for each species is listed.

Species Conjugate acid-base

Class XI Chemistry www.vedantu.com 26


HNO2 NO3 (base)

CN  HCN (acid)

HClO4 ClO4  (base)

F HF (acid)

OH  H 2O (acid) / O2 (base)

CO32 HCO3 (acid)

S HS (acid)

35. Which of the followings are Lewis acids? H2O, BF3 , H+ , NH4 .

Ans: Lewis acids are those acids which can accept a pair of electrons. For
example: BF3 , H+ , NH4+ are Lewis acids.

36. What will be the conjugate bases for the Brönsted acids: HF, H2SO4 , HCO3

Ans: The table below lists the conjugate bases for the given Bronsted acids:

Bronsted Acid Conjugate Base


HF F

H 2SO4 HSO4 

HCO3 CO32

37. Write the conjugate acids for the following Brönsted bases:
NH2 , NH3 , HCOO

Ans: The table below lists the conjugate acids for the given Bronsted bases:

Class XI Chemistry www.vedantu.com 27


Bronsted Base Conjugate Acid
NH 2  NH3

NH3 NH 4 

HCOO HCOOH

38. The species: H2O, HCO3 , HSO4 , NH3 can act both as Brönsted acids and bases.
For each case give the corresponding conjugate acid and base.
Ans: The table below lists the conjugate acids and conjugate bases for the given
species.

Species Conjugate Acid Conjugate Base


H 2O H 3O + OH

HCO3 H 2CO3 CO32

HSO4 H 2SO4 SO24

NH3 NH +4 NH 2

39. Classify the following species into Lewis acids and Lewis bases and show
how these act as Lewis acid/base:
(a). OH 
Ans: OH  is a Lewis base since it can donate its lone pair of electrons

(b). F
Ans: F is a Lewis base since it can donate a pair of electrons.

(c). H +
Ans: H + is a Lewis acid since it can accept a pair of electrons.

(d). BCl3

Class XI Chemistry www.vedantu.com 28


Ans: BCl3 is a Lewis acid since it can accept a pair of electrons.

40. The concentration of hydrogen ion in a sample of soft drink is 3.8 103 M .
what is its pH?
Ans: Given,

[H+ ]  3.8 103 M

Therefore, the pH value of the soft drink:

pH   log[ H  ]
pH   log(3.8 103 )
pH   log 3.8  log103
pH   log 3.8  3
pH  0.58  3
pH  2.42

41. The pH of a sample of vinegar is 3.76. Calculate the concentration of


hydrogen ion in it.
Ans: Given the, pH  3.76

It is known as:

pH   log[H  ]
log[H  ]  pH
[H  ]  antilog( pH)
[H  ]  antilog( 3.76)
[H  ]  1.74 104 M

Hence, the concentration of hydrogen ion in the given sample of vinegar is


1.74 104 M .

Class XI Chemistry www.vedantu.com 29


42. The ionization constant of HF, HCOOH, HCN at 298 K are 6.8 104 , 1.8 104
and 4.8 109 respectively. Calculate the ionization constants of the
corresponding conjugate base.
Ans: It is known as:
Kw
Kb 
Ka

Given, K a of HF is 6.8 104

Hence, K b of its conjugate base F :

Kw
Kb 
Ka
1014
Kb 
6.8  104
K b  1.5 1011

Given K a of HCOOH is 1.8 104

Hence, K b of its conjugate base HCOO :

Kw
Kb 
Ka
1014
Kb 
1.8  104
K b  5.6 1011

Given K a of HCN is 4.8 109

Hence, K b of its conjugate base CN  :

Kw
Kb 
Ka
1014
Kb 
4.8  109
K b  2.08 106

Class XI Chemistry www.vedantu.com 30


43. The ionization constant of phenol is 1.0 1010 . What is the concentration of
phenolate ion in 0.05 M Ans:of phenol? What will be its degree of ionization if
the Ans:is also 0.01M in sodium phenolate?
Ans: According to the reaction of ionization of phenol:

C6 H5OH  H2O C6 H5O  H3O

The initial concentration of C6 H5OH is 0.05 M.

At equilibrium, the concentration of C6 H5O and H3O+ will be x, then the


concentration of C6 H5OH will be (0.05  x) .

C6 H 5O    H 3O  
Ka 
C6 H 5OH 
x x
Ka 
0.05  x

As the value of the ionization constant is very less, x will be very small. Thus, we
can ignore x in the denominator.

 x  11010  0.05
 5 1012
 2.2 106 M   H 3O  
Since  H 3O    C6 H 5O  
C6 H 5O    2.2 106 M

Now, let α be the degree of ionization of phenol in the presence of 0.01 M


C6 H5ONa

C6 H5OH  H2O C6 H5O  H3O

The concentrations are as follows:


[C6 H5OH]  0.05  0.05 ; 0.05 M
[C6 H5O  ]  0.01  0.05 ; 0.01 M
[H3O ]  0.05

Class XI Chemistry www.vedantu.com 31


[C6 H 5O  ][H 3O  ]
Ka 
[C6 H 5OH]
(0.01)(0.05 )
Ka 
0.05
1.0 10  0.01
10

  1108

44. The first ionization constant of H 2S is 9.1108 . Calculate the


concentration of HS ion in its 0.1 M solution. How will this concentration be
affected if the Ans:is 0.1 M in HCl also? If the second dissociation constant of
H 2S is 1.2 1013 , calculate the concentration of S2 under both conditions.

Ans: To calculate the concentration of HS ion:

Case I (in the absence of HCl ):


Let the concentration of HS be x M:
H2S H+  HS

The final concentration of H 2S will be (0.1  x)

Then,

 H    HS  
K ai 
 H2S 
( x)( x)
9.1108 
0.1  x
 9.110  (0.1  x)  x
8 2

Taking, 0.1  xM ;0.1M we have  9.1108  (0.1)  x2

9.1109  x 2
x  9.1109
 9.54 105 M
  HS    9.54  105 M

Class XI Chemistry www.vedantu.com 32


Case II (in the presence of HCl ):

In the presence of 0.1 M of HCl , let [HS ] be y M.

H2S H+  HS

The final concentration of H 2S will be (0.1  y)

Now,

[HS ][H  ]
K a1 
[H 2S]
y (0.1  y )
K a1 
(0.1  y )
y  0.1
9.1 108 
0.1
8
y  9.110

The concentration of [HS ]  9.1108

To calculate the concentration of [S2 ]

Case I (in the absence of 0.1 M of HCl ):

HS H  S2

[HS ]  9.54 105 M

Let [S2 ] be X .

Also, [H ]  9.54 105 M

 H    S 2 
K a2 
 HS  

K a2 
 9.54 10  ( X )
5

9.54 105
1.2 1013  X   S 2 

Case II (in the presence of 0.1 M of HCl ):

Class XI Chemistry www.vedantu.com 33


The concentration of S2 be X' M

[HS ]  9.1108 M

[H ]  0.1 M

Then,

 H    S 2 
K a2 
 HS  

(0.1)  X  
1.2 1013 
9.1108
10.92 1021  0.1X 

10.92 1021
 X
0.1
1.092 1020

X 
0.1
 1.092 1010 M
 K a1  1.74 105

45. The ionization constant of acetic acid is 1.74 105 . Calculate the degree of
dissociation of acetic acid in its 0.05 M solution. Calculate the concentration of
acetate ion in the Ans:and its pH.
Ans: For the reaction:
CH3COOH  H2O CH3COO  H3O

The final concentration of CH3COO and H3O+ is 0.05 . Then the final
concentration of CH3COOH will be (0.05  0.05 ) .

Class XI Chemistry www.vedantu.com 34


(.05 )(.05 )
Ka 
(.05  0.05 )
(.05 )(0.05 )

.05(1   )
.05 2

1

.05 2
1.74 105 
1
1.74 10  1.74 105   0.05 2
5

0.05 2  1.74 105   1.74 105


D  b 2  4ac

   
2
 1.74 105  4(.05) 1.74 105
 3.02 1025  .348 105

Ka

c
1.74 105

.05
34.8 105 10

10
 3.48 106

CH3COO    0.05 1.86 103


0.93 103

1000
 .000093

pH   log  H  


  log .093 102 
 pH  3.03

Hence, the concentration of acetate ion in the Ans:is 0.00093 M and its pH is 3.03.

Class XI Chemistry www.vedantu.com 35


46. It has been found that the pH of a 0.01M Ans:of an organic acid is 4.15.
Calculate the concentration of the anion, the ionization constant of the acid
and its pK a .

Ans: Let the organic compound be HA .

HA H  A

Concentration of HA is 0.01 M and its pH is 4.15.

 log  H    4.15
 H    7.08 105
 H    A 
Now,K a 
[ HA]
 H     A   7.08  105
[ HA]  0.01

Now,

[H  ][A  ]
Ka 
[HA]
[H  ]  [A  ]  7.08 105
[HA]  0.01

Then,

Ka 
 7.08 10  7.08 10 
5 5

0.01
K a  5.01 107
pK a   log K a
  log K a

 5.01 107 
pK a  6.3001

47. Assuming complete dissociation, calculate the pH of the following


solutions:

Class XI Chemistry www.vedantu.com 36


(i). 0.003 M HCl

Ans: H2O  HCl H3O  Cl

Since HCl is completely ionized.

[H 3O  ]  [HCl]
 [H 3O  ]  0.003
pH   log[H 3O  ]
pH   log(0.003)
pH  2.52

Hence, the pH of the Ans:is 2.52.

(ii). 0.005 M NaOH

Ans: NaOH (aq) Na + (aq)  OH (aq)

[OH  ]  [NaOH]
 [OH  ]  0.005
pOH   log[OH  ]
pOH   log(0.005)
pOH  2.30
pH  14  pOH
pH  14  2.30
pH  11.70

Hence, the pH of the Ans:is 11.70.

(iii). 0.002 M HBr

Ans: HBr  H2O H3O  Br 

[H 3O  ]  [HBr]
 [H 3O  ]  0.002
pH   log[H 3O  ]
pH   log(0.002)
pH  2.69

Class XI Chemistry www.vedantu.com 37


Hence, the pH of the Ans:is 2.69.

(iv). 0.002 M KOH

Ans: KOH (aq) K  (aq)  OH (aq)

[OH  ]  [KOH]
 [OH  ]  0.002
pOH   log[OH  ]
pOH   log(0.002)
pOH  2.69
pH  14  pOH
pH  14  2.69
pH  11.31

Hence, the pH of the Ans:is 11.31.

48. Calculate the pH of the following solutions:


(a). 2 g of TlOH dissolved in water to give 2 litre of solution.
Ans: For 2g of TlOH dissolved in water to give 2 L of solution:
2
TIOH ( aq )   g / L
2
2 1
  M
2 221
1
 M
221

TlOH (aq)  Tl (aq)  OH (aq)

Class XI Chemistry www.vedantu.com 38


TIOH ( aq )  Tl(aq )  OH (aq )
1
OH (aq )   TIOH ( aq )   M
221
K w   H   OH  
 1 
1014   H    
 221 
221 1014   H  


 pH   log  H     log 2211014 

  log 2.211012 
 11.65

(b). 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution.

Ans: Molecular weight of Ca(OH)2 is 74g.

0.3
So, 0.3g Ca(OH)2 = mole
74

Moles in Solution
Molar Concentration =
Volume in Solution

0.3
mole
Molar concentration of Ca(OH)2 = 74  8.11103 M
0.5 L

Ca(OH)2  Ca 2  2OH

[OH  ]  2[Ca(OH) 2 ]
[OH  ]  2  (8.1110 1 ) M
[OH  ]  16.22 101 M
pOH   log(16.22  101 )
pOH  3  1.2101
pOH  1.79
pH  14  1.79
pH  12.21

(c). 0.3 g of NaOH dissolved in water to give 200 mL of solution.

Class XI Chemistry www.vedantu.com 39


Ans: 1 mole of NaOH = 40g
Since, 40 gm of NaOH = 1 mole of NaOH
0.3
So, 0.3 gm of NaOH = moles
40

Moles in Solution
Molar Concentration =
Volume in Solution

0.3
Moles
Molar concentration = 40  3.75 101 M
0.2 L

[OH  ]  3.75 102 M


pOH   log(3.75 102 )
pOH  1.43
pH  14  1.43
pH  12.57

(d). 1mL of 13.6 M HCl is diluted with water to give 1 litre of solution.
Ans: For this question:
M1V1  M 2 V2
13.6 1 mL  M 2  1000 mL
13.6 103  M 2 1 L
M 2  1.36 102
[H  ]  1.36 102
pH   log(1.36  102 )
pH  0.1335  2
pH  1.87

49. The degree of ionization of a 0.1M bromoacetic acid Ans:is 0.132.


Calculate the pH of the Ans:and the pK a of bromoacetic acid.

Ans: Degree of ionization,   0.132


Concentration, c = 0.1 M

Class XI Chemistry www.vedantu.com 40


Thus, the concentration of H3O  c.

[H 3O  ]  0.1 0.132
[H 3O  ]  0.0132
pH   log[H  ]
pH   log(0.0132)
pH  1.88

Now,

K a  C 2
K a  0.1 (0.132) 2
K a  0.0017
pK a  2.75

50. What is the pH of 0.001 M aniline solution? The ionization constant of


aniline can be taken from Table 7.7. Calculate the degree of ionization of
aniline in the solution. Also calculate the ionization constant of the conjugate
acid of aniline.

Ans:

K b  4.27 1010
c  0.001M
pH  ?
 ?
ka  C 2
4.27 1010  0.001  2
4270 1010   2
65.34 105    6.53  104

Then, concentration of anion:

[anion]  c.  0.01 65.34 105


[anion]  0.65 105

Class XI Chemistry www.vedantu.com 41



pOH   log .065 105 
 6.187
pH  7.813

K a  Kb  K w
 4.27 1010  K a  K w
1014
Ka 
4.27 1010
 2.34 105

Thus, the ionization constant of the conjugate acid of aniline is 2.34 105 .

51. The degree of ionization of a 0.1M bromoacetic acid Ans:is 0.132.


Calculate the pH of the Ans:and the pK a of bromoacetic acid.

Ans:
Degree of ionization,   0.132

Concentration, c  0.1M

Thus, the concentration of H3O  c. 

 0.1 0.132
 0.0132

pH   log  H  
  log(0.0132)
 1.879 :1.88

Now

K a  C 2
 0.1 (0.132) 2
K a  .0017
pK a  2.75

Class XI Chemistry www.vedantu.com 42


52. What is the pH of 0.001M aniline solution? The ionization constant of
aniline can be taken from Table 7.7. Calculate the degree of ionization of
aniline in the solution. Also calculate the ionization constant of the conjugate
acid of aniline.

Ans:

K b  4.27 1010
c  0.001M
pH  ?
 ?
ka  C 2
4.27 1010  0.001  2
4270 1010   2
65.34 105    6.53 104
Then, [anion]= c  0.01 65.34 10 5
 0.65 105
pOH 
  log .065 105 
 6.187

pH  7.813

Now,
K a  Kb  K w
 4.27 1010  K a  K w
1014
Ka 
4.27 1010
 2.34 105

Thus, the ionization constant of the conjugate acid of aniline is 2.34 105 .

53. Calculate the degree of ionization of 0.05M acetic acid if its pK a value is
4.74. How is the degree of dissociation affected when its Ans:also contains
(a) 0.01M

(b) 0.1M in HCl ?

Class XI Chemistry www.vedantu.com 43


Ans:
c  0.05M
pK a  4.74
pK a   log  K a 
K a  1.82 105

Ka
K a  c 2  
c
1.82 105
 2
 1.908 102
5 10

When HCl is added to the solution, the concentration of H  ions will increase.
Therefore, the equilibrium will shift in the backward direction i.e., dissociation of
acetic acid will decrease. Case I: When 0.01MHCl is taken.
Let x be the amount of acetic acid dissociated after the addition of HCl.

CH3COOH H  CH3COO
Initial conc. 0.05M 0 0
Afterdissociation 0.05  x 0.01  x x

As the dissociation of a very small amount of acetic acid will take place, the values
i.e., 0.05  x and 0.01  x can be taken as $0.05$ and $0.01$ respectively.

CH 3COO    H  
Ka 
CH 3COOH 
(0.01) x
 Ka 
0.05
1.82 105  0.05
x
0.01
x  1.82 103  0.05M

Now,
Amount of acid dissociated

Amount of acid taken
1.82 105  0.05

0.05
 1.82 103

Class XI Chemistry www.vedantu.com 44


Case II: When 0.1MHCl is taken.

Let the amount of acetic acid dissociated in this case be X . As we have done in the
first case, the concentrations of various species involved in the reaction are:

CH3COOH   0.05  X ;0.05M


CH 3COO    X
 H    0.1  X ;0.1M
CH 3COO    H  
Ka 
CH3COOH 
(0.1) x
 Ka 
0.05

1.82 105  0.05


x x  1.82 104  0.05M Now,
0.1

Amount of acid dissociated



Amount of acid taken
1.82 104  0.05

0.05
 1.82 104

54. The ionization constant of dimethylamine is 5.4104. Calculate its degree of


ionization in its 0.02M solution. What percentage of dimethylamine is ionized
if the Ans:is also 0.1M in NaOH?
Ans:
Kb  5.4 104
c  0.02M

Kb 5.4 104
c  0.02M Then,     0.1643
c 0.02

Now, if 0.1M of NaOH is added to the solution, then NaOH (being a strong base)
undergoes complete ionization.

Class XI Chemistry www.vedantu.com 45


NaOH( aq )  Na (aq )  OH(aq )
0.1M 0.1M

And,

 CH3 2 NH  H 2O   CH3 2 NH 2  OH
(0.02  x) x
;0.02M
Then,  CH 3 2 NH 2   x
OH    x  0.1;0.1

 CH 3 2 NH 2  OH  
 Kb 
 CH3 2 NH 
x  0.1
5.4 104 
0.02
x  0.0054

It means that in the presence of 0.1MNaOH,0.54% of dimethylamine will get


dissociated.

55. Calculate the hydrogen ion concentration in the following biological fluids
whose pH are given below:

Ans:
(a) Human muscle fluid 6.83
pH  6.83pH   log  H  
 6.83   log  H  
 H    1.48 107 M

(b) Human stomach fluid, 1.2:


pH  1.2 
1.2   log  H  
  H    0.063

Class XI Chemistry www.vedantu.com 46


(c) Human blood, 7.38:
pH  7.38   log H 
 H   4.17 108 M

(d) Human saliva, 6.4:


pH  6.4 
6.4   log  H  
 H    3.98 107

56. The pH of milk, black coffee, tomato juice, lemon juice and egg white are
6.8,5.0,4.2,2.2$ and 7.8 respectively. Calculate corresponding hydrogen ion
concentration in each.

Ans:
The hydrogen ion concentration in the given substances can be calculated by using
the given relation: pH   log H 

(i) pH of milk  6.8

Since, pH   log H 

6.8   log H  log

 H    6.8

H   anitlog(6.8)

 1.5 197 M

(ii) pH of black coffee  5.0

Since, pH   log H 

5.0   log H  log

 H    5.0

Class XI Chemistry www.vedantu.com 47


H   anitlog(5.0)

 105 M

(iii) pH of tomato juice  4.2

Since, pH   log H 

4.2   log H  log

 H    4.2

H   anitlog(4.2)

 6.31 105 M

(iv) pH of lemon juice  2.2

Since, pH   log  H  

2.2   log H   log

 H    2.2

H   anitlog(2.2)

 6.31 103 M

(v) pH of egg white  7.8

Since, pH   log H 

7.8   log H  log

 H    7.8

H   anitlog(7.8)

 1.58 108 M

Class XI Chemistry www.vedantu.com 48


57. If 0.561g of KOH is dissolved in water to give 200 mL of Ans:at 298 K .
Calculate the concentrations of potassium, hydrogen and hydroxyl ions. What
is its pH ?

Ans:
0.561
 KOH aq   g/L
1
5
 2.805g/L

1
 2.805  M
56.11
 .05M
KOH aq  K (aq )  OH (aq )
OH    .05M   K  
 H    H    K w
Kw
 H   
OH  
1014

0.05
 2  1011 M
 pH  12.70

58. The solubility of Sr(OH)2 at 298 K is 19.23 g / L of solution. Calculate the


concentrations of strontium and hydroxyl ions and the pH of the solution.

Ans:

Solubility of Sr(OH)2  19.23 g / L

Then, concentration of Sr(OH)2

Class XI Chemistry www.vedantu.com 49


19.23
 M
121.63
 0.1581M

Sr(OH ) 2( aq )  Sr(2aq )  2 OH   ( aq )

  Sr 2   0.1581M
OH    2  0.1581M  0.3126M

Now,

K w  OH    H  
1014
 H  
0.3126  
  H    3.2 1014
 pH  13.495;13.50

59. The ionization constant of propanoic acid is 1.32 105. Calculate the degree
of ionization of the acid in its 0.05M Ans:and also its pH . What will be its
degree of ionization if the Ans:is 0.01M in HCl also?

Ans:
Let the degree of ionization of propanoic acid be  . Then, representing propionic
acid as HA, we have:

HA  H 2 O  H3O  + A
(.05  0.0 )  0.5 .05 .05

 H 3O    A 
Ka 
[ HA]
(.05 )(.05 )

0.05
 .05 2
Ka

.05
 1.63 102

Class XI Chemistry www.vedantu.com 50


Then, H3O   .05  .05 1.63 102  Kb .15 104 M

 pH  3.09

In the presence of 0.1M of HCl , let  ' be the degree of ionization.

Then, H3O   0.01

 A   005 
[ HA]  .05
0.01 .05 
Ka 
.05
1.32  105  .01  
   1.32 105

60. The pH of 0.1M Ans:of cyanic acid (HCNO) is 2.34. Calculate the ionization
constant of the acid and its degree of ionization in the solution.
Ans:
c  0.1M
pH  2.34
 log  H    pH
 log  H    2.34
 H    4.5 103

Also,

4.5 103
 H    c 4.5 10  0.1 
3
   4.5 103  .045 Then,
0.1
K a  c 2

 
2
 0.1 45 103
 202.5 106
 2.02 104

Class XI Chemistry www.vedantu.com 51


61. The ionization constant of nitrous acid is 4.5104 . Calculate the pH of
0.04M sodium nitrite Ans:and also its degree of hydrolysis.

Ans: NaNO2 is the salt of a strong base (NaOH) and a weak acid  HNO2  .

NO 2  H 2O  HNO 2  OH 
 HNO2  OH  
Kb 
 NO 2 
K 1014
 w   .22 1010
K a 4.5 1014

Now, If x moles of the salt undergo hydrolysis, then the concentration of various
species present in the solution, it will be:

 NO2   .04  x;0.04


 HNO2   x
OH    x
x2
Kb   0.22  1010
0.04
x  .0088 1010
2

x  .093 105

 OH    0.093 105 M


1014
 H 3O    5
 10.75 109 M
.093 10

 pH   log 10.75 109 
 7.96

Therefore, degree of hydrolysis

x .093 105
 
0.04 .04
5
 2.325 10

62. A 0.02M solution of pyridinium hydrochloride has pH  3.44 . Calculate the


ionization constant of pyridine

Class XI Chemistry www.vedantu.com 52


Ans:
pH  3.44

We know that,

pH   log H     H    3.63 104

3.63 10 
2
4

Then, Kb  ( concentration  0.02M)


0.02

 Kb  6.6 106

Kw
Now, Kb 
Ka

Kw 1014
 Ka   6
 1.51109
K a 6.6 10

63. Predict if the solutions of the following salts are neutral, acidic or basic:
NaCl, KBr, NaCN, NH4 NO3 , NaNO2 and KF

Ans:
(i) NaCl :
NaCl  H2O  NaOH  HCl

Strong base Strong base

Therefore, it is a neutral solution.

(ii) KBr:
KBr  H2O  KOH  HBr

Strong base Strong base

Therefore, it is a neutral solution.

Class XI Chemistry www.vedantu.com 53


iii) NaCN :
NaCN  H2O  HCN  NaOH

Weak acid Strong base

Therefore, it is a basic solution.

(iv) NH4 NO3

NH4 NO3  H2O  NH4OH  HNO3

Weak acid Strong base


Therefore, it is an acidic solution.

(v) NaNO2

NaNO2  H2O  NaOH  HNO2

Strong base Weak acid


Therefore, it is a basic solution.
(vi) KF
KF  H2O  KOH  HF

Strong base Weak acid

Therefore, it is a basic solution.

64. The ionization constant of chloro acetic acid is 1.35103. What will be the
pH of 0.1M acid and its 0.1M sodium salt solution?

Ans:

It is given that K a for ClCH2COOH is 1.35 103

Ka 1.35 103
 Kb  c 2    ( concentration of acid  0.1M)
c 0.1

Class XI Chemistry www.vedantu.com 54


  1.35 103  0.116
  H    c
 0.1 0.116
 .0116
 pH   log  H    1.94

ClCH2COONa is the salt of a weak acid i.e., ClCH2COOH and a strong base i.e.,
NaOH .

ClCH 2COO   H 2O  ClCH 2COOH  OH 


ClCH 2COOH  OH  
Kb 
ClCH 2COO  
Kw
Kb 
Ka
1014
Kb 
1.35 103
 0.740 1011

x2
Also, Kb  (where x is the concentration of OH  and ClCH2COOH 
0.1

x2
0.740 10 11 
0.1
0.074 10 11  x 2
 x 2  0.74 10 12
x  0.86 10 6
OH    0.86 10 6
Kw
  H   
0.86 10 6
1014

0.86 10 6
 H    1.162 10 8

pH   log  H  

 7.94

Class XI Chemistry www.vedantu.com 55


65. Ionic product of water at 310 K is 2.7 1014 . What is the pH of neutral
water at this temperature?

Ans:
Ionic product,

K w   H   OH  
Let  H    x

Since  H    OH   , K w  x 2 .
 K w at 310 K is 2.7 1014
 2.7  1014  x 2
 x  1.64  107
  H    1.64  107
 pH   log  H  
  log 1.64  107 
 6.78

Hence, the pH of neutral water is 6.78.

66. Calculate the pH of the resultant mixtures:

a) 10 mL of 0.2MCa(OH)2  25 mL of 0.1MHCl

25  0.1
Ans: Moles of H3O   .0025 mol
1000

10  0.2  2
Moles of OH    .0040 mol
1000

Thus, excess of OH   .0015 mol

b) 10 mL of 0.01MH2SO4  10 mL of 0.01MCa(OH)2

2 10  0.1
Ans: Moles of H3O   .0002 mol
1000

Class XI Chemistry www.vedantu.com 56


2 10  0.1
Moles of OH    .0002 mol
1000

Since there is neither an excess of H3O or OH 

The solution is neutral. Hence, pH  7 .

c) 10 mL of 0.1MH2SO4  10 mL of 0.1MKOH

2 10  0.1
Ans: Moles of H3O   .002 mol
1000

10  0.1
Moles of OH    0.001mol
1000

Excess of H3O  .001mol

.001 103
Thus,  H 3O   3
 3
 .05  pH   log(0.05)  1.30
20 10 20 10

67. Determine the solubility of silver chromate, barium chromate, ferric


hydroxide, lead chloride and mercuries iodide at 298 K from their solubility
product constants given in Table 7.9 (page 221). Determine also the molarities
of individual ions.
Ans:

(1) Silver chromate: Ag2CrO4  2Ag  CrO42

Then,
2
K sp   Ag   CrO42 

Let the solubility of Ag 2CrO4 be s .

 Ag    2 s and CrO24   s

Then,

Class XI Chemistry www.vedantu.com 57


K sp  (2s ) 2  s  4s 3
 1.11012  4 s 3
.275 1012  s 3
s  0.65 104 M

Molarity of Ag   2s  2 0.65 104  1.30 104 M

Molarity of CrO42  s  0.65 104 M

(2) Barium chromate:

BaCrO4  Ba 2  CrO24

Then, Ksp   Ba 2  CrO42 

Let the solubility of BaCrO4 be s .

So,  Ba 2   s and CrO24   s  K sp  s 2

 1.2 1010  s 2

 s  1.09 105 M

Molarity of Ba 2  Molarity of CrO42  s  1.09 105 M

(3) Ferric hydroxide:

Fe(OH)3  Fe 2  3OH 
3
K sp   Fe2  OH  

Let s be the solubility of Fe(OH)3

Molarity of OH   3s  4.17 1010 M

(4) Lead chloride:

PbCl2  Pb 2  2Cl
2
K SP   Pb 2  Cl 

Let KSP be the solubility of PbCl2 .

Class XI Chemistry www.vedantu.com 58


 PB 2   s and Cl    2s
Thus, K sp  s.(2s ) 2
 4s3
 1.6 105  4s 3
 0.4 105  s 3
4 106  s 3  1.58 102 M  S .1

Molarity of PB2  s  1.58 102 M

Molarity of chloride  2s  3.16 102 M

(5) Mercurous iodide:

Hg 2 I 2  Hg 2  2 I 
2
K sp   Hg 22   I  

Let s be the solubility of Hg 2 I2 .

 Hg 22   s and  I    2s

Thus, Ksp  s(2s)2  K sp  4s3

$ 4.5 1029  4s3 $

1.125 1029  s 3
 s  2.24 1010 M

Molarity of Hg22  s  2.24 1010 M

Molarity of I   2s  4.48 1010 M

68. The solubility product constant of Ag 2CrO4 and AgBr are 1.11012 and
5.0 1013 respectively. Calculate the ratio of the molarities of their saturated
solutions.

Ans:

Let s be the solubility of Ag 2CrO4

Class XI Chemistry www.vedantu.com 59


Then, Ag2CrO4  Ag2  2CrO24

K sp  (2s) 2  s  4s 3
1.11012  4s 3
s  6.5 105 M

Let s be the solubility of AgBr .

AgBr( s )  Ag   Br 
K sp  s2  5.0 1013
 s  7.07 107 M

Therefore, the ratio of the molarities of their saturated solution is

s 6.5 105 M
  91.9
s 7.07 107 M

69. Equal volumes of 0.002M solutions of sodium iodate and cupric chlorate
are mixed together. Will it lead to precipitation of copper iodate?

(For cupric iodate Ksp  7.4 108 

Ans: When equal volumes of sodium iodate and cupric chlorate solutions are
mixed together, then the molar concentrations of both solutions are reduced to half
i.e., 0.001M . Then,

NalO3  Na   lO3
0.001M 0.001M
Cu  ClO3 2  Cu 2 2ClO3
0.001M 0.001M

Now, the solubility equilibrium for copper iodate can be written as:

Cu  lO3 2  Cu (2aq
 
)  2lO3( aq )

Ionic product of copper iodate:

Class XI Chemistry www.vedantu.com 60


2
 Cu 2   lO3 
 (0.001)(0.001) 2
 1109

Since the ionic product (1109  is less than Ksp  7.4 108  , precipitation will not
occur.

70. The ionization constant of benzoic acid is 6.46 105 and K sp for silver
benzoate is 2.5 1013 . How many times is silver benzoate more soluble in a
buffer of pH  3.19 compared to its solubility in pure water?

Ans:
Since pH  3.19,
 H 3O    6.46 104 M
C6 H 5COOH  H 2O  C6 H 5COO   H 3O
C6 H 5COO    H 3O  
Ka 
C6 H5COOH 
C6 H5COOH    H3O   6.46 104  10
C6 H 5COO   Ka 6.46 105

Let the solubility of C6 H5COOAg be xmol / L .

Then,

 Ag    x

C6 H 5COOH   C6 H 5COO    x


10 C6 H 5COO    C6 H 5COO    x
x
C6 H 5COO   
11
K sp  Ag   C6 H 5COO  
 x
2.5 1013  x  
 11 
6
x  1.66 10 mol / L

Class XI Chemistry www.vedantu.com 61


Thus, the solubility of silver benzoate in a pH 3.19 solution is 1.66 106 mol / L .
Now, let the solubility of C6 H5COOAg be x mol / L .

Then,  Ag    x M and C6 H5COO   x M

K sp   Ag   C6 H 5COO  

K sp   x 
2

x  K sp  2.5 1013  5 107 mol / L


x 1.66 106
   3.32
x 5 107

Hence, C6 H5COOAg is approximately 3.317 times more soluble in a low pH


solution.

71. What is the maximum concentration of equimolar solutions of ferrous


sulphate and sodium sulphide so that when mixed in equal volumes, there is
no precipitation of iron sulphide?

(For iron sulphide, Ksp  6.3 1018 

Ans: Let the maximum concentration of each solution be xmol / L . After mixing,
the volume of the concentrations of each solution will be reduced to half i.e., x / 2 .
x
  FeSO 4    Na2 S   M
2

x
Then,  Fe2    FeSO 4   M
2

x
Also,  S 2    Na2 S   M
2

FeS( x )  Fe(2aq )  S(2aq )

Class XI Chemistry www.vedantu.com 62


K sp   Fe 2   S 2 
 x  x 
6.3 1018    
 2  2 
2
x
 6.3 1018
4
 x  5.02 109

If the concentrations of both solutions are equal to or less than 5.02 109 M , then
there will be no precipitation of iron sulphide.

72. What is the minimum volume of water required to dissolve 1g of calcium


sulphate at 298 K? (For calcium sulphate, Ksp is 9.1 106 

Ans:

CaSO4( s )  Ca 2 ( aq )  SO4(2aq )
K sp  Ca 2  SO24 

Let the solubility of CaSO4 be s .

Then, K sp  s 2

9.1106  s 2
s  3.02 103 mol / L

Molecular mass of CaSO4  136 g / mol

Solubility of CaSO4 in gram/L

 3.02 103 136


 0.41g / L

This means that we need 1L of water to dissolve 0.41g of CaSO4

1
Therefore, to dissolve 1g of CaSO4 we require  L  2.44 L of water.
0.41

Class XI Chemistry www.vedantu.com 63


73. The concentration of sulphide ion in 0.1MHCl solution saturated with
hydrogen sulphide is 1.0 1019 M . If 10mL of this is added to 5 mL of 0.04M
solution of the following:

FeSO4 , MnCl2 , ZnCl2 and CdCl2 . in which of these solutions precipitation will take
place?

Givěn K sp for Fes  6.3 1018 , MnS  2.5 1013 , ZnS  1.6 1024

CdS  8.0 1027

Ans: For precipitation to take place, it is required that the calculated ionic product
exceeds the K sp value.

Before mixing:

 S 2   1.0 1019 M  M 2   0.04M


volume  10 mL volume  5 mL

After mixing:

 S 2   ?  M 2   ?

volume  (10  5)  15 mL volume  15 mL


1.0 1019 10
 S 2    6.67 1020 M
15
0.04  5
 M 2    1.33  102 M
15
Ionic product   M 2   S 2 

 
 1.33 102 6.67 1020 
 8.87 1022

This ionic product exceeds the Kspof Zns and CdS . Therefore, precipitation will
occur in CdCl2 and ZnCl2 solutions.

Class XI Chemistry www.vedantu.com 64

You might also like