Chemical Equilibrium

CHEMISTRY : CHEMICAL EQUILIBRIUM
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Irreversible and Reversible Reactions

Those reactions which proceeds in forward direction and reaches
almost to completion are called irreversible reactions. For example
2KClO3(s) MnO
2KCl
(s) 3O 2(g) (Thermal decomposition)
NaOH (aq) HCl(aq)
NaCl
(aq) H 2 O (Strong acidstrong base
neutralisation reaction)
2AgNO3 BaCl
2AgCl
Ba(NO 3 ) 2
(Precipitation reaction)
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Whereas, those reactions which proceed in forward and backward
directions both and never reaches completion are called reversible
reactions. These reactions can be initiated in any direction. For
example,
2
PCl5(g) PCl3(g) Cl2(g) (Thermal dissociation)

CH3COOH NaOH
CH 3COONa H 2O (Neutralisation reactions)
Weak acid
strong base
N 2(g) 3H 2(g)
2NH3(g) (synthesis reaction)
But when Fe(s) is heated and water vapour is passed over it in open
vessel, it is converted to Fe 3O4(s) along with the evolution of hydrogen
gas.
3Fe(s) 4H 2 O(g)
Fe3O
4(s)
4H 2(g)
and when Fe3O4 is reduced with hydrogen gas, it gives Fe (s) and H2O
Fe3O 4(s) 4H 2(g)
3Fe
(s)
4H 2 O(g)
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But, if the reaction is carried out in a closed container, this reaction

becomes reversible.
3Fe(s) 4H 2 O(g)
Fe3O 4(s) 4H 2(g)
State of Equilibrium
It has generally been observed that many changes (physical and
chemical) do not proceed to completion when they are carried out in
a closed container. Consider for example vapourisation of water,
Water
Vapour
At any temperature, vapourisation of water takes place, initially the

concentration of water is much greater than the concentration of
vapour, but with the progress of time, concentration of vapour
increases whereas that of water remains constant and after a
certain interval of time, there is no change in concentration of
vapour, this state is known as state of physical equilibrium.
In a similar way, this has also been found for chemical reactions, for
example, when PCl5(g) is heated in a closed container, its dissociation
starts with the formation of PCl3(g) and Cl2(g). Initially, only PCl5(g) was
taken, but with the progress of reaction, PCl 3(g) and Cl2(g) are formed
due to dissociation of PCl5(g). After a certain interval of time, the
concentration of PCl5(g), PCl3(g) and Cl2(g) each becomes constant. It
does not mean that at this point of time, dissociation of PCl 5(g) and
its formation from PCl3(g) and Cl2(g) has been stopped. Actually the
rate of dissociation of PCl5 and the rate of formation of PCl5(g)
becomes equal. This state is called the state of chemical
equilibrium. So, the state of chemical equilibrium is dynamic.
PCl 5(g)
PCl 3(g) +Cl 2(g)
This can be shown graphically.

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So, state of chemical equilibrium can be defined as the state when

the rate of forward reaction becomes equal to rate of reverse
reaction and the concentration of all the species becomes constant.
Law of Mass Action
Guldberg and Waage in 1807 gave this law and according to this
law, At constant temperature, the rate at which a substance reacts
is directly proportional to its active mass and the rate at which a
chemical reaction proceeds is directly proportional to the product of
active masses of the reacting species.
The term active mass of a reacting species is the effective
concentration or its activity (a) which is related to the molar
concentration (C) as
a = f C
where f = activity coefficient. f 1 but f increases with dilution and
as V i.e. C 0, f 1 i.e., a C. Thus at very low
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concentration the active mass is essentially the same as the molar

concentration. It is generally expressed by enclosing the formula of
the reacting species in a square bracket.
To illustrate the law of mass action, consider the following general
reaction at constant temperature,
aA (g) bB(g) cC(g) dD(g)
Applying law of mass action,

Rate of forward reaction,
Rf [A]a [B]b
or Rf = kf[A]a[B]b
(i)
Where kf = rate constant of forward reaction
Similarly,
Rate of reverse reaction
Rr [C]c [D]d
or Rr = kr[C]c [D]d
(ii)
where kr = rate constant of reverse reaction.
At equilibrium,
Rate of forward reaction = Rate of reverse reaction
i.e., Rf = Rr
So, from equations (i) and (ii), we get
kf[A]a [B]b = kr[C]c[D]d
or,
k f [C]c [D]d
k r [A]a [B]b
or
kf
[C]c [D]d
Kc
kr
[A]a [B]b
Where, Kc is the equilibrium constant in terms of molar

concentration.
Equilibrium Constant (Kp) in terms of Partial Pressures:
Consider the same general reaction taking place at constant
temperature,
aA(g) + bB(g) cC(g) + dD(g)

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From law of mass action,

[C]c [D]d
[A]a [B]b
Kc
(1)
From ideal gas equation

PV = nRT
or,
n
RT
V
At constant temperature,
P
n
V
Thus, we can say in a mixture of gases, Partial pressure of any

component (say A)
PA [A]
Similarly, PB [B]
PC [C]
PD [D]
So, equation (1) can be rewritten as
Kp
PCc PDd
PAa PBb
(2)
Relationship Between Kp and Kc

From the above, for the same general reaction at constant
temperature.
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Kc
[C]c [D]d
[A]a [B]b
and,
Kp
(1)
PCc PDd
PAa PBb
(2)
From the ideal gas equation,

PV = nRT
P
n
RT
V
So, PB = [B]RT ; PD = [D]RT

Similarly, PA [A]RT; PC [C]RT
Substituting the values of PA, PB, PC and PD in equation (2), we get
Kp
or
[C]c (RT) c [D]d (RT) d

[A]a (RT)a [B]b (RT) b
Kp
[C]c [D]d (RT)(c d)
[A]a [B]b (RT)(a b)
or K p K c (RT)
Where, n = (c + d) (a + b)
i.e., n = sum of no. of moles of gaseous products sum of no. of
moles of gaseous reactants.
If n 0, Kp Kc
If n = 0, Kp = Kc
and if n 0, Kp Kc
Illustration 1:
Calculate the Kc and Kp for the following
reactions and also deduce the relationship
between Kc and Kp
i) 2SO2(g) + O2(g) 2SO3(g)
n
ii)
Solution:
i)
1
3
N 2(g) + H 2(g) NH 3(g)
2
2
2SO2(g) + O2(g) 2SO3(g)
Applying law of mass action,

Kc
Kp
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[SO3 ]2
[SO 2 ]2 [O 2 ]
2
PSO
3
2
PSO
PO2
2
(i)
(ii)
We know that

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K p K c (RT) n
n = 2 (2+1) = 1
ii)
1
3
N 2(g) H 2(g) NH3(g)
2
2
[NH 3 ]
Kc
[N 2 ]1/ 2 [H 2 ]3/ 2
PNH
K p 1/ 2 3 3/ 2
PN 2 PH2
Now,
Kp
Kc
RT
(i)
(ii)
K p K c (RT) n
3 1
1
2 2
n 1
Kp
Kc
RT
Illustration 3: At 400K for the gaseous reaction

2A + 3B 3C + 4D
the value of Kp is 0.05. Calculate the value of K c (R
= 0.082 dm3 atm K1 mol1)
Solution:
From the given data
For the reaction 2A + 3B 3C + 4D
n = (3 + 4) (2 +3) = 2
Since R is given in dm3 atm. K1 mol1, we shall take
P = 1 atm.
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Substituting these values in the equation

n
CRT
1 0.082 400
, we get 0.05 K c
1
P
0.05
Kc
0.082 0.082 400 400
K p Kc
Kc = 4.648 105Type of Chemical reactions
Irreversible reactions: The reactions which goes to completion and the products fail to recombine
to give back reactants, are called irreversible reactions.
Reversible reactions: The reactions which never go to completion and that can occur in either
direction i.e. both possibilities are there in reversible reaction (products can give reactants and
reactants can give products).
In chemical equilibrium, we will analyse reversible chemical reaction, consider the following
reactions.A chemical reaction is never complete. This is due to the reversible nature of it.
Reversible means reaction taking place both in the forward and backward directions. The
reaction between reactants yielding product(s) is the forward reaction while the reaction between
products giving back reactants is the backward reaction. As the reaction progresses, a state of
equilibrium is reached when the rate of forward reaction becomes equal to that of the backward
reaction. After this there is no progress in the reaction although reactions are taking place in both
the directions. This is called the state of chemical equilibrium. It is due to the attainment of a
chemical equilibrium that chemical reaction does not go to completion. However, in some
chemical reaction equilibrium is attained when the reaction is almost complete. Such reversible
reactions are called irreversible reactions. The reversibility of a reaction is denoted by the
symbol
as shown below:
i)
N 2 3H 2 2NH3
ii)
H 2 I 2 2HI
A reversible reaction may be made irreversible if one of the products is allowed to escape away
from the reaction mixture. For example the reaction
CaCO3(s)
CaO (s) CO 2(g)
will be reversible in a closed container but it would become irreversible in an open container
due to escaping of CO2(g). That is CaCO3 CaO(s) + CO2(g) (open container)
Each reversible reaction consists of two reactions: one is forward reaction i.e. reactants combine
to give products and other is backward reaction i.e. product reaction recombine to give back
reactants.

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At one stage during reversible reactions, two reactions i..e forward and backward reactions
proceed with the same speed, the reaction is said to be in equilibrium.
Law of Mass Action: In 1863 two Chemistry Guldberg and Waage stated that, at constant
temperature, the rate at which a substance reacts is directly proportional to its active mass and
rate of a chemical reaction is directly proportional to the product of active masses (raised to
power their stoichiometric coefficients) of reactants.
Suppose,
A Products
R [A]
or
A B Products
R [A][B]
Now if we consider the reversible reaction.

m1A m 2 B n1C n 2 D
Forward reaction:
m1A m 2 B
n1C n 2 D
Rate of forward reaction
(rf ) [A]m1 [B]m 2
[ ]: denotes activity or active mass

rf k f [A]m1 [B]m2
where k f is know as rate constant or velocity constant or specific reaction rate for forward
reaction.
Backward reaction:
n1C n 2 D
m
1A m 2 B
Rate of backward reaction (rb ) (k b ) [C]n1 [D]n 2

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or rb K b [C]n1 [D]n 2
where Kb is rate constant for backward reaction.
rf rb
At equilibrium
k f [A]m1 [B]m 2 K b [C]n1 [D]n 2

Kf
[C]n1 [D]n 2
K eq
Kb
[A]m1 [B]m2
Keq is known as equilibrium constant.

Initially A and B are mixed and they react. When they react, the rate of forward reaction
decreases since concentration of A and B decrease. As C and D are formed, they react to form A
and B. The rate of backward reaction increases with time because there is an increase in the
concentration of C and D. When the two rates are equal, we say that system is in equilibrium.
At equilibrium state
i)
Rate of forward reaction = Rrate of backward reaction.
ii)
Equilibrium is dynamic in nature i.e. reaction does not stops at equilibrium but two
reactions have equal rate.
iii)
Once equilibrium is achieved the relative concentrations of reactants and products will
remain constant.
iv)
External change in pressure, temperature and concentration at equilibrium causes

disturbance in equilibrium state. Again a new equilibrium will be reached after some
adjustment (in detail this is to be discussed in Le-Chatliers principle).
Note: i)
ii)
Activity or active mass is denoted by a or [ ].

Activity of dilute aqueous solutions is expressed in concentration isn mole/litre
i.e. molartiy. Actually for solutions.
a Cf
C = Concentration in mole/litre
f = activity coefficient
for dilute solutions f = 1 so a = C
iii)
Activity of gases is expressed in partial pressure
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iv)
Activity of pure solids and pure liquids is taken to be unity.
v)
When activities are expressed in concentration (mole/litre) then equilibrium

constant Keq is denoted as Kc.
vi)
For gaseous reactions, the activities are expressed in terms of partial pressure
(total pressure mole fraction) the equilibrium constant Keq is denoted as Kp.
Suppose a reaction
N 2(g) 3H 2(g) 2NH 3(g)
P P
2
Kp
NH3
N2
H2
vii)
Only a change in temperature can change the value of equilibrium constant Kp or

Kc. There is no effect of change in pressure or concentrations on the value of
equilibrium constant (exact variation of equilibrium constant with temperature
will be discussed latter).
viii)
A very large value of Kc or Kp signifies that reaction is going in forward direction

i.e. the equilibrium largely lies towards forward direction or we can say reaction
almost goes to completion.
ix)
The equilibrium constant of a reaction and its reverse reaction are reciprocal of
each other.
If A B C D (Equilibrium constant = K)
Then C D A B (Equilibrium constant K
1
)
K
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x)
If a chemical equation is multiplied by a certain factor, its equilibrium constant

must be raised to a power equal to that factor in order to obtain the equilibrium
constant for new reaction.
1
2
Then 2NO O 2 2NO 2 Equilibrium constant K K 2
If NO O 2 NO 2 Equilibrium constant = K
ix)
If a reaction is obtained by adding two reactions then its equilibrium constant

will be equal to the product of the equilibrium constants of two reactions. If K1
and K2 are step-wise equilibrium constant for
(i)
A B
(ii)
B C
K K1 K 2
Then for A C
x)
If a reaction is obtained by substracting two reactions then its equilibrium

constant will be equal to the ratio of equilibrium constants of two reactions.
If K1 be the equilibrium constant for A B
K2 be the equilibrium constant for B C
Then equilibrium constant for reaction
A C B D i.e. A+D B C is
K1
K2
Reaction Quotient (Q)

At any point in a reversible reaction, ratio of the concentration terms in the same form as in the
expression of equilibrium constant can be formulated. This ratio is referred to as reaction
quotient (Q). Consider a general reaction.
m1A m 2 B n1C n 2 D
Q
[C]n1 [D]n 2
(in terms of concentration)
[A]m1 [B]m2
n
n
PC PD
Q
(in terms of partial pressure)
PA m PB m
1
or
Comparing the value of Q with the standard value of K eq at a given temperature, one can
comment on the status of reversible system. If
Q K eq
It means equilibrium has not yet reached. The system is moving in forward
direction increasing product concentration i.e. at this instant forward reaction is
dominant over backward reaction.
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Q K eq
It means equilibrium is established and concentrations of reactants and

products will remain constant.
Q K eq
It means equilibrium has not yet established. The reaction must proceed in
backward direction for the attainment of equilibrium.
Illustration 1:
Kc for equilibrium A (g)

B(g) C(g) is 0.45 at 200C. One litre of a
container holds 0.2 mole of A, 0.3 mole of B and 0.3 mole of C at
equilibrium. Calculate the new equilibrium concentrations of A, B and C if
the volume of container at same temperature is: a)
Halved;
(b)
Doubled
Solution:
A(g)
t = teq 0.2 M
0.4 M
0.4 x
Q
B(g) + C(g)
0.3 M
0.3M
0.6 M
0.6 M Volume is reduced to half
0.6-x
0.6-x
t = tnew eq.
0.6 0.6
K C , So system is not at equilibrium and shifts in
0.4
backward direction.
KC = 0.45 =
(0.6 x )2
0.4 x
on solving, x = 0.12
[B] = [C] = 0.48 M
[A] = 0.52 M
A(g)
B(g)
+ C(g)
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t = teq 0.2 M
0.1 M
-x
(0.1 x)
KC = 0.45 =
0.3 M
0.3M
0.15 M
0.15M
Not at equal
+x
+x_______
(0.15 + x) (0.15 + x)
(0.15 x )2
0.1 x
On solving, x = 0.03M
[A] = 0.07 M
[B] = [C] = 0.18M
DRILL EXERCISE I
1.
Three moles of N2 react with 2 moles of O2 in a two litre container to form one mole of
NO. What will be the number of mole of N2 per litre at equilibrium.
(A)
0.75 (B)
1.50
(C)
1.25 (D)
None of these
0.75
For the reaction A + 2B
2C + D, initial concentration of A is a and that of B is
1.5 times that of A. concentration of A and D are same at equilibrium. What should be
the concentration of B at equilibrium.
a
a
(A)
(B)
4
2
3a
(C)
(D) All of the above
4
a
2
Under similar conditions
K P1
2NH 3
N 2 3H 2
1.
2.
2.
3.
K P2
1
3
NH 3
N 2 H 2
2
2
Which of the following is true for K P1 ?
(A) K P2
(C) (K P2 )
(B)
2
K P2
2
2
(D) (K P1 )
(K P2 ) 2
3.
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Illustration 1: Consider the reaction SO2 Cl2 (g)

SO 2 (g) Cl 2 (g) ; at 37C the value of
equilibrium constant for the reaction is 0.0032. It was observed that concentration of the three
species is 0.050 mol/lt each at a certain instant. Discuss what will happen in the reaction vessel?
Solution:
In this question, concentration of three species i.e. SO2 Cl2 , SO2 and Cl2 (g) each
is given, but is is not mentioned that whether the system is at equilibrium or not.
So first check it. Find reaction coefficient for given equation.
Q
[SO 2 ][Cl2 ] (0.05)(0.05)
0.05
[SO 2 Cl2 ]
(0.05)
Q K , so system is not at equilibrium state.

As Q > K, the concentrations must adjust till Q = K for equilibrium. This can
happen only if reaction shifts backwards, and products recombine to give back
reactants. Hence in the reaction vessel, the system will move backward so that it
can achieve equilibrium state.
Relationship between Kp and Kc

Consider a gaseous reaction
m1A m 2 B n1C n 2 D
P PD
Kp c m
PA PB n
n1
n2
2
(i)
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Kc
[C]n1 [D]n 2
[A]m1 [B]m2
(ii)
Applying ideal gas equation

PV = nRT
P
or
n
RT
V
P = CRT
Where C is molarity
PA CA RT ; PB C B RT
PC CC RT ; PD C D RT
Substittuing this in equation (i)

n
n
CC RT CD RT
CA RT m CB RT m
n n
RT
CCn C nD
= m
CA CmB RT m m
1
= K c (RT)(n1 n 2 ) (m1 m2 )
K p K c (RT) n
n = [number of moles of gaseous products in gaseous state number of moles of gaseous
reactants in gaseous state..
If Case I
n 0
K p Kc
e.g.
H 2(g) I2(g) 2HI(g)
N 2(g) O 2(g) 2NO(g)
Type I:
Gaseous equilibria are of two types

In which n 0
to K p K c
e.g.
H 2(g) I2(g) 2HI(g)

N 2(g) O 2(g) 2NO(g)
Type II
Case - II
16
In which n 0
n 0
So K p K c
e.g.
PCl5(g) PCl3(g) Cl 2(g) ; n=1+1-1=1

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Kp = Kc(RT)1
Kp Kc
Case III
n 0
N 2(g) 3H 2(g)
2NH3(g)
n 2 (3 1) 2
Kp = Kc(RT)2
Kp Kc
N 2(g) 3H 2(g) 2NH 3(g) ; n 0
Illustration 2:
fFor a homogenous gaseous reaction X 2Y

Z, at 473 K, the value
of K c 0.35 concentration units. When 2 moles of Y are mixed with 1
mole of X, at what pressure 60% of X is converted to Z?
Solution:
Since pressure is to be calculated, so first find K p using the relation between

K c and K p ,
K c 0.35, R 0.0821, T 473, n 1 3 2
K p K c (RT) n 0.35 (0.0821 473) 2 2.32 10 4
The expression for K p is : K p
Moles
X
Initially
1
At equilibrium
1x
total moles n T 3 2x
Let P = equilibrium pressure
pZ
p X (p Y ) 2
Y
1
2 2x
Z
0
X
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1 x
2 2x
x
P, PY
P, Pz
P
3 2x
3 2x
3 2x
X
P
x(3 2x) 2
3 2X
Kp
2
P 2 (1 x)(2 2x) 2
1 x 2 2x
P
P
3 2x 3 2x
x = 0.6 (given)
0.6(3 1.2) 2
Kp 2
2.32 10 4
P (1 0.6) 2 1.2) 2
P 2 (1.8 102 ) 2
P = 180 atm
PX
DRILL EXERCISE II
1.
A mixture of hydrogen and iodine (molecular ratio is 2 : 1) is reacted to form HI. The
total moles at equilibrium will be:
(A) 3 x
(B) 3
(C) 2 2x
(D) 3 4x
3
In the reaction, A + B
C + D in a one-litre container, concentration of B at fixed
temperature was n mole and initial concentration of A was 3n mole. If the concentration
of C at equilibrium is equivalent to that of B, the concentration of D will be
n
(A)
(B) n
4
n
n
(C)
(D)
3
2
n
4
Which of the following should be added in the equilibrium reaction 2SO2 + O2
2SO3 for generation of heat, if the forward reaction is exothermic and the backward
reaction is endothermic?
(A) SO3
(B) SO2 and O2
(C) SO2, O2 and SO3 in equal amount
(D) None of these
SO2 and O2
1.
2.
2.
3.
3.
BRAIN TEASER 1:
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i)
The vapour density of a mixture consisting of NO 2 and N2O4 is 38.3 at 26.7C. Calculate the
number of moles of NO2 in 100 gm mixture.
ii)
Establish a relationship between Kc and Kp for the following reactions.
a) N2(g) + O2(g) 2NO(g)
b) (NH 4 ) 2 CO3(s) 2NH 3(g) CO 2(g) H 2 O(g)
Application of Law of Mass Action

1.
Synthesis of Hydrogen Iodide: Suppose a moles of H2 and b moles of I2 are

heated at 444C in a closed container of volume V litre and at equilibrium, 2x moles of
HI are formed.
H2(g) +
I2(g)
2HI(g)
Initial concentration (mol L1)
a
V
Equilibrium concentration(mol L1)

Kc
[HI]2
[H 2 ][I 2 ]
ax
V
b
V
0
bx
V
2x
V
(i)
Substituting the equilibrium concentrations of H2, I2 and HI in equation (i), we get

2
Kc
Kp
2x
V
4x 2

a x b x
(a x)(b x)
V
V
2
PHI
PH 2 PI2
(ii)
(iii)
Suppose the total pressure of the equilibrium mixture at 444C is P, then

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PHI = mole fraction of HI Total pressure
2x
P
ab
PHI =
Similarly,
(a x)
bx
P and PI2
P
(a b)
(a b)
PH 2
Substituting these values in equation (iii) we get
Kp
Kp
2x
2
a b P
a x
b x
P
P
a b
a b
4x 2
(a x)(b x)
(iv)
So, one can see from equations (iii) and (iv), that
Kp = Kc
This is so, because n= 0 for the synthesis of HI from H2 and I2.
Thermal Dissociation of Phosphorus Pentachloride
PCl5(g) dissociates thermally according to the reaction,
PCl5(g) PCl3(g) + Cl2(g)
2.
Let us consider that 1 mole of PCl 5 has been taken in a container of volume V litre and at
equilibrium x moles of PCl5(g) dissociates. Thus
1
Initial concentration (mol L )1

Equilibrium concentration(mol L1)
PCl5(g) PCl3(g)
+
0
0
1 x
V
x
V
Cl2(g)
x
V
According to law of mass action, at constant temperature,

Kc =
and
Kp =
[PCl3 ][Cl 2 ]
[PCl5 ]
PPCl3 PCl2
PPCl5
(1)
(2)
Substituing the values of equilibrium concentration, in equation (1), we have
or
x x
V V
Kc = 1 x
V
x2
Kc
V(1 x)
Now, total number of moles at equilibrium = 1 x + x + x = 1 + x

20

20
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M
C
E
C
H
2
1
Mole fraction of PCl3 = Mole fraction of Cl2 =
and mole fraction of PCl5 =
x
1 x
1 x
1 x
Suppose total pressure at equilibrium is P, then we have from equation (2),

x
x 2
P
1
x
1
x
Kp
1 x
P
1 x
or
Kp
K
x 2P
1
x 1 K p x 2 P x p x
2
(1 x )
P
P
Similarly, we can apply law of mass action on any reaction at equilibrium.

BRAIN TEASER 2:
Derive an expression for Kc and Kp for the reaction
2NH3(g)
N2(g) + 3H2(g)
Assuming that in a container of volume V, initially 1 mole of N 2 and 3 moles of H 2 were taken and at
equilibrium 2x moles of NH3 is formed.
Illustration 3:
For the chemical equilibrium

2NO(g) + O2(g)
2NO2(g)
2
Kp = 1.3 10 at 1000K. What is the value of Kc at 1000K?
Solution:
1.3 10-2 = KC (0.821 1000)-1

KC = 1.3 10-2 82.1 = 1.067
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DRILL EXERCISE III

What concentration of CO2 be in equilibrium with 2.5 102 mol litre1 of CO at 100C
for the reaction
FeO(s) + CO(g)
KC = 5.0
Fe(s) + CO2(g);
2
1
12.5 10 mol litre
The equilibrium constant KC for A(g)
B(g) is 1.1. Which gas has a molar
concentration greater than 1?
If [B] = 1; [A] = 0.91
0.1 mole of N2O4(g) was sealed in a tube under atmospheric conditions at 25C.
Calculate the number of mole of NO 2(g) present, if the equilibrium N 2O4(g)
2NO2(g), (Kp = 0.14) is reached after some time.

NO2 = 0.017 2 = 0.034 mole
1.
1.
2.
2.
3.
3.
The degree of dissociation at a certain or given temperature of PCl 5 at 2 atm is found to be

0.4. At what pressure, the degree of dissociation of PCl 5 will be 0.6 at the
same temperature? Also calculate the equilibrium constant for the reverse
reaction.
Solution:
The dissociation of PCl5 takes place according to the equation,
PCl5 PCl3(g) + Cl2(g)
Let 1 mole of PCl5 is taken in a closed container. Then
Mole(s) before dissociation
1
0
0
Mole(s) at equilibrium
1
As degree of dissociation() is given at 2 atm

1 = 1.0 0.4 = 0.6
Total moles at equilibrium
= 1 + + = 1 0.4 + 0.4 + 0.4 = 1.4
0.4
0.4
2
2
1.4
1.4
K
Now, p
=
0.6
PPCl5
2
1.4
0.4 0.4 4 1.4 0.32
Kp
0.6 2 1.4 1.4 0.84

PPCl3 PCl2
Now, as temperature remains the same, Kp will also remain the same. So for
= 0.6
Mole before dissociation 1
0
0
Moles at equilibrium
1 0.6
0.6
0.6
22

22
S
M
C
E
C
H
2
3
0.6 0.6
P2
1.6
1.6
Again, K p
0.4
P
1.6
0.6 0.6 1.6
P
0.4 1.6 1.6
32 9
32 4 128
P P =
= 0.677 atm
84 16
9 21 189
BRAIN TEASER 3:
i) Calculate the percentage dissociation of H2S(g), if 0.1 mole of H2S is kept in 0.4 litre
vessel at 1000K. For the reaction, 2H2S(g) 2H2(g) + S2(g), the value of Kc = 1.6 106
ii) A sample of HI was found to be 22% dissociated when equilibrium was reached. What
will be the degree of dissociation if hydrogen is added in the proportion of 1 mole for
every mole of HI originally present, the temperature and volume of the system being
kept constant?
Kp
Equilibrium Constant for Heterogeneous Equilibria
The equilibrium which involves reactants and products in different physical states. The law of
mass action can also be applied on heterogeneous equilibria as it was applied for homogeneous
equilbria (involving reactants and products in same physical states).
i)
Thermal Dissociation of Solid Ammonium Chloride: The thermal

dissociation of NH4Cl(s) takes place in a closed container according to the equation:
NH4Cl(s) NH3(g) + HCl(g)
Let us consider 1 mole of NH4Cl(s) is kept in a closed container of volume V litre at
temperature TK and if x mole of NH4Cl dissociates at equilibrium, then
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NH4Cl(s) NH3(g)
Initial moles
1
0
Moles at equilibrium 1 x
x
Applying law of mass action, K c
HCl(g)
0
x
[NH 3 ][HCl]
[NH 4 Cl]
As NH4Cl is a pure solid, so there is no appreciable change in its concentration. Thus,

Kc = [NH3] [HCl]
Kc
x x x2

V V V2
and K p PNH3 PHCl

Thermal Dissociation of Ag2CO3: Ag2CO3(s) dissociates thermally according to
the equation.
ii)
Ag2CO3(s) Ag2O(s) + CO2(g)

Applying law of mass action, at constant temperature, we get,
Kc
[Ag 2 O][CO 2 ]
[Ag 2 CO3 ]
Now, let us consider that 1 mol of Ag 2CO3(s) is heated in a closed container of volume V
and x mol of Ag2CO3(s) dissociates at equilibrium, then
Ag2CO3(s) Ag2O(s) + CO2(g)
Initial moles
1
0
0
Equilibrium moles
1x
x
x
Now, as Ag2CO3 and Ag2O are solids, so their concentration can be assumed to be
constants. tThus
K c [CO 2 ]
K P PCO2
x
V
The LeChateliers Principle

This principle, which is based on the fundamentals of a stable equilibrium, states that
When a chemical reaction at equilibrium is subjected to any stress, then the equilibrium
shifts in that direction in which the effect of the stress is reduced.
24

24
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M
C
E
C
H
2
5
Confused with stress. Well by stress here what we mean is any change of reaction conditions
e.g. in temperature, pressure, concentration etc.
This statement will be explained by the following example.
endo
N2 (g) + 3H2 (g)
Let us consider the reaction: 2NH3 (g) exo
Let the moles of N2, H2 and NH3 at equilibrium be a, b and c moles respectively. Since the
reaction is at equilibrium,
PN 2 PH 2
NH3
= Kp =
N 2 .PT
H 2 .PT
NH3 .PT
Where,
X terms denote respective mole fractions and PT is the total pressure of the system.
a
b

a b c PT a b c PT
2
c
a b c PT
Here,
Kp
a
= mole fraction of N2
abc
b
= mole fraction of H2
abc
c
= mole fraction of NH3
abc
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PT
ab3
2
= Kp
c
a b c 2
2
Since
PT =
a b c
RT
V
2
3
ab RT
2
= KP
c
V
( assuming all gases to be ideal)

(1)
Now, let us examine the effect of change in certain parameters such as number of moles,
pressure, temperature etc.
If we increase a or b, the left hand side expression becomes Q P ( as it is disturbed from
equilibrium) and we can see that QP > KP
The reaction therefore moves backward to make QP = KP.
If we increase c, QP < KP and the reaction has to move forward to revert
back to equilibrium.
If we increase the volume of the container (which amounts to decreasing the pressure), Q P < KP
and the reaction moves forward to attain equilibrium.
If we increase the pressure of the reaction, then equilibrium shifts towards backward direction
since in reactant side we have got 2 moles and on product side we have got 4 moles. So pressure
is reduced in backward direction.
If temperature is increased, the equilibrium will shift in forward direction since the forward
reaction is endothermic and temperature is reduced in this direction.
However from the expression if we increase the temperature of the reaction, the left hand side
increases (QP) and therefore does it mean that the reaction goes backward (since QP > KP)?.
Does this also mean that if the number of moles of reactant and product gases are equal, no
change in the reaction is observed on the changing temperature (as T would not exist on the left
hand side)?. The answer to these questions is No. This is because KP also changes with
temperature. Therefore, we need to know the effect of temperature on both Q P and KP to decide
the course of the reaction.
Effect of Addition of Inert Gases to A a Reaction Aat Equilibrium
Addition at constant pressure
1.
Let us take a general reaction

aA + bB
cC + dD
26

26
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M
C
E
C
H
2
7
c
We know, K p
n

C
PT
n

A
PT
nD
PT
n
nB
PT
n
Where,
nC nD, nA, nB denotes the no. of moles of respective components and P T is the total
pressure and n = total no. of moles of reactants and products.
Now, rearranging,
n c n dD PT
K P ac
n A n bB
n
Where n = (c + d) (a + b)
Now, n can be equal to = 0, 0 or 0
Let us take each case separately.
a) n = 0 : No effect
b) n = +ve :
Addition of inert gas increases the n i.e.
PT
is decreased and so is
PT
. So
products have to increase and reactants have to decrease to maintain constancy of Kp.
So the equilibrium moves forward.
c) n = ve :
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In this case
PT
decreases but
PT
increases. So products have to decrease
and reactants have to increase to maintain constancy of Kp. So the equilibrium moves
backward.
Addition at Constant Volume: Since at constant volume, the pressure increases
2.
with addition of inert gas and at the same time n also increases, they almost counter
balance each other. So
PT
can be safely approximated as constant. Thus addition of
inert gas has no effect at constant volume.

.
Dependence of Kp or Kc on Temperature
Now we will derive the dependence of KP on temperature.
Starting with Arrhenius equation of rate constant
k f Af e
E a f / RT
(i)
Where, kf = rate constant for forward reaction, Af = Arrhenius constant of forward reaction,
E a f = Energy of activation of forward reaction
k r Are
E a r / RT
(ii)
Dividing (i) by (ii) we get,

k f Af
e
k r Ar
We know that
Ea r Eaf
RT
kf
K (equilibrium constant )
kr
K = k f Af e
k r Ar
Ea r Eaf
RT
At temperature T1
28

28
A
K T1 f e
Ar
Ea r Eaf
RT1
S
M
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E
C
H
2
9
(iii)
At temperature T2
K T2
A
fe
Ar
Ear Eaf
RT2
(iv)
Dividing (iv) by (iii) we get
K T1
Ear Eaf
log
K T2
K T1
1
1

T1
T2
E a r E a f 1 1

2.303 R T2 T1
The enthalpy of a reaction is defined in terms of activation

energies as E a f E a r = H
log
log
K T2
K T1
K T2
K T1
H 1 1

2.303 R T2 T1
H 1 1
-
2.303 R T1 T2
Eaf
Ear
Energy
K T2
(v)
Reaction co-ordinate
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For an exothermic reaction, H would be negative. If we

increase
the
temperature
of
the
system
(T2>T1), the right hand side of the equation (V) becomes
negative.
K T2 < K T1 ,
that is, the equilibrium constant at the higher

temperature would be less than that at the lower
temperature.
Now let us analyse our question. Will the reaction go forward or

backward?
Before answering this, we must first
encounter another
problem. If temperature is increased, the new K P would
either increase or decrease or may remain same. Let us
assume it increases.
Now, QP can also increase, decrease or remain unchanged. If KP
increases and QP decreases, then QP K P , therefore the
reaction moves forward. If KP increase and QP remains
T2
same, then
Q PT Q PT K PT
2
T2
. Again, the reaction moves forward.
What, if KP increase and QP also increases?

Will
or QP K P or QP K P ? This can be answered by

simply looking at the dependence of Q P and KP on
temperature. You can see from the equation that K P
depends on temperature exponentially. While Qs
dependence on T would be either to the power g,l,t..
Therefore the variation in KP due to T would be more than
in QP due to T.
QPT K PT
2
T2
T2
T2
T2
KP would still be greater than QP and the reaction moves

forward again.
30

30
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M
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H
3
1
Therefore, to see the temperature effect, we need to look at K P

only. If it increases, the reaction moves forward, if it
decreases, reaction moves backward and if it remains
fixed, then, no change at all.Variation of Equilibrium
Constant with Temperature
As we have discussed that only a change in temperature can change the value of the equilibrium
constant.
According to Arrhenius equation
K A.e Ea / RT
K = rate constant
A = frequency factor
E a Energy of activation
so for forward reaction
K f A f .e Eaf / RT
similarly for backward reaction
K b A b .e Eab / RT
E ab E af
RT
Kf
A
K eq f e
Kb
Ab
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Let K1 be the equilibrium constant at temperature T1 and K 2 be the equilibrium constant at

temperature T2
K1
A f EabRT Eaf
e
Ab
A
K2 f e
Ab
E ab E af 1
1

R
T2 T2
K 2 E ab E af 1
1
K1
R
T2 T1
but H E af E ab
ln
K 2 H
K1
R
K
H
ln 2
K1
R
ln
log
Notes:
i)
If
1
1

T2 T1
1
1

T1 T2
K2
H T2 T1
K1 2.303 R T1T2
T2 T1 and reaction is endothermic (H 0) then right hand side is +ve so K 2 K1 i.e.
for endothermic reactions increase in temperature increases the value of equilibrium constant and
decrease in temperature will decrease the value of equilibrium constant.
ii) For exothermic reactions ( H 0) and increase in temperature decreases the value of
equilibrium constant and decrease in temperature increases the value of equilibrium constant.
Illustration 4:
Under what conditions will the following reactions go in the forward

direction ?
1. N2(g)+ 3H2(g)
2NH3(g) + 23 k cal.
2. N2(g) + O2(g)
2NO(g) - 43.2 k cal.
3. C(s) + H2O(g)
CO2(g) + H2(g) + X k cal.
4. N2O4(g)
2NO2(g) - 14 k cal.
Solution:
1.
2.
3.
4.
Low T, High P, excess of N2 and H2.

High T, any P, excess of N2 and O2
Low T, Low P, excess of C and H2O
High T, Low P, excess of N2O4.
DRILL EXERCISE IV
In the reaction, C(s) + CO2(g)

2CO(g), the equilibrium pressure is 12 atm. If
150% of CO2 reacts, calculate Kp.
16 atm.
1.
1.
32

32
2.
2.
3.
3.
4.
4.
5.
5.
S
M
C
E
C
H
3
3
At 298 K, the equilibrium between N2O4 and NO2 may be represented by the following
equation N2O4(g)
2NO2(g). If the total pressure of the equilibrium mixture is P
and the degree of dissociation of N2O4(g) at 298 K is x, which one of the following is
the pressure of N2O4(g) under this condition:
(1 x) P
2x P
(A)
(B)
(1 x)
(1 x)
2x P
2 P
(C)
(D)
(1 x)
3
(1 x) P
(1 x)
One mole of SO3 was placed in one litre vessel at a certain temperature. The following
equilibrium was established 2SO3
2SO2 + O2. At equilibrium 0.6 moles of SO2
were formed. The equilibrium constant of the reaction will be:
(A) 0.36
(B) 0.45
(C) 0.54
(D) 0.675
0.675
2 moles of PCl5 were heated in a closed vessel of 2 litre capacity. At equilibrium, 40%
of PCl5 dissociated into PCl3 and Cl2. The value of equilibrium constant is:
(A) 0.267
(B) 0.53
(C) 2.63
(D) 5.3
0.267
For reaction: PCl3(g) + Cl2(g)
PCl5(g)
the value of KC at 250C is 26. The value of Kp at this temperature will be:
(A) 0.61
(B) 0.57
(C) 0.83
(D) 0.3
0.61
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Illustration 4: Under what conditions will the following reactions go in the forward direction ?
1.
2.
3.
4.
N2(g)+ 3H2(g)
2NH3(g) + 23 k cal.
N2(g) + O2(g)
2NO(g) - 43.2 k cal.
C(s) + H2O(g)
CO2(g) + H2(g) + X k cal.
N2O4(g)
2NO2(g) - 14 k cal.
Solution:
1. Low T, High P, excess of N2 and H2.

2. High T, any P, excess of N2 and O2
3. Low T, Low P, excess of C and H2O
4. High T, Low P, excess of N2O4.
BRAIN TEASER 4:
Under what conditions will the following reactions go in the forward direction?
1. 2SO2(g) + O2(g)
2SO3(g) + 45 k cal.
2. 2NO(g) + O2(g)
2NO2(g) + 27.8 k cal.
3. PCl5(g)
PCl3(g) + Cl2(g)- X k cal.
Le-Chateliers Principle and Physical Equilibria: Le Chateliers principle, as
already stated, is applicable to all types of equilibria involving not only chemical but physical
changes as well. A few examples of its application to physical equilbria are discussed below.
Vapour pressure of a liquid: Consider the equilibrium
1.
Liquid Vapour
It is well known that the change of a liquid into its vapour is accompanied by absorption
of heat whereas the conversion of vapour into liquid state is accompanied by evolution of
heat. According to Le Chateliers principle, therefore, addition of heat to such a system
will shift the equilibrium towards the right. On raising the temperature of the system,
liquid will evaporate. This will raise the vapour pressure of the system. Thus, the vapour
pressure of a liquid increases with rise in temperature.
Effect of pressure on the boiling point of a liquid: The conversion of liquid into
2.
vapour, as represented by the above equilibrium, is accompanied by increase of pressure

(vapour pressure). Therefore, if pressure on the system is increased, some of the vapours
will change into liquid so as to lower the pressure. Thus, the application of pressure on
the system tends to condense the vapour into liquid state at a given temperature. In order
to counteract it, a higher temperature is needed. This explains the rise of boiling point of
a liquid on the application of pressure.
Effect of pressure on the freezing point of a liquid (or melting point of a
solid): At the melting point, solid and liquid are in equilibrium:
3.
Solid Liquid
34

34
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C
E
C
H
3
5
Now, when a solid melts, there is usually a change, either increase or decrease, of
volume. For example, when ice melts, there is decrease in volume, or at constant volume,
there is decrease in pressure. Thus, increase of pressure on ice water system at a
constant temperature will cause the equilibrium to shift towards the right, i.e., it will
cause the ice to melt. Hence, in order to retain ice in equilibrium with water at the higher
pressure it will be necessary to lower the temperature. Thus, the application of pressure
will lower the melting point of ice.
When sulphur melts, there is increase in volume or at constant volume, there is increase
in pressure. From similar considerations, it follows that if the pressure on the system,
sulphur (solid) sulphur (liquid) is increased, the melting point is raised.
4.
Effect of temperature on solubility: In most cases, when a solute passes into
solution, heat is absorbed, i.e., cooling results. Therefore according to Le Chateliers

principle, when heat is applied to a saturated solution in contact with solute, the change
will take place in that direction which absorbed heat (i.e., which tends to produce
cooling). Therefore, some more of the solute will dissolve. In other words, the solubility
of the substance increases with rise in temperature.
Dissociation of a few salts (e.g., calcium salts of organic acids) is accompanied by
evolution of heat. In such cases, evidently, the solubility decreases with rise in
temperature.
Free Energy and Chemical Equilibrium

The Gibbs free energy function is a true measure of chemical affinity under conditions of
constant temperature and pressure. The free energy change in a chemical reaction can be
defined as
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G = G(products) G(reactants)
When G = 0, there is no net work obtainable. The system is in a state of equilibrium. When G
is positive, net work must be put into the system to effect the reaction, otherwise it cannot take
place. When G is negative, the reaction can proceed spontaneously with accomplishment of the
net work. The larger the amount of this work that can be accomplished, the farther away is the
reaction from equilibrium. For this reason G has often been called the driving force of the
reaction. From the statement of the equilibrium law, it is evident that the driving force depends
on the concentration of the reactants and products. It also depends upon the temperature and
pressure which determine the molar free energies of the reactants and products.
The reaction conducted at constant temperature (i.e., in a thermostat)
G = H + TS
The driving force is made up of two parts, H term and TS term. The H term is the heat of
reaction at constant pressure and TS is heat involved when the process is carried out reversibly.
The difference is the amount of heat of reaction which can be converted into net work (G),
i.e., total heat minus unavailable heat.
If the reaction is carried out at constant volume, the decrease in Helmholtz function G = E
+ TS would be the proper measure of affinity of the reactant or the driving force of the reaction.
Now we can see why Berthollet and Thompson were wrong in assuming that driving force of the
reaction was the heat of reaction. They neglected the TS term. The reasons for the apparent
validity of their principle was that for many reactions, H term far outweighs the TS term. This
is especially true at low temperature, since at higher temperature, TS term increases.
The fact that driving force for a reaction is large (G is large negative quantity) does not mean
that the reaction will necessarily occur under any given conditions.
For example, the reaction
1
H 2 O
2
2
H 2 O;
H
228.6kJ
does not occur at the laboratory temperature. The reaction mixture may be kept for years without
any detectable formation of water. Here H factor favours, but S factor disfavours the reaction.
Similarly, the reaction
2Mg(s) + O2 (g)
2MgO (s);
G H = 570.6kJ
36

36
S
M
C
E
C
H
3
7
is not favoured. However, the thermite reaction

2Al(s) +
3
O2(g)
2
Al2O3(s)
with large value of G proceeds favourably.

Standard Free Energy and Equilibrium Constant: The change in free energy for a
reaction taking place between gaseous reactants and products represented by the general
equation.
aA bB cC dD
According to Vant Hoff reaction isotherm

G G 0 RT ln
pcC pdD
= G0 + RTlnQp
paA p Bb
the condition for a system to be at equilibrium is that

G = 0
Thus at equilibrium
pcC pdD
G 0 RT ln K 0p
a
b
p
p
A B
0 G 0 RT ln
Whence G0 = RTlnK0p
Hence ln K 0p
G 0
RT
Note: 1. In the reaction, where all gaseous reactants and products; K represents Kp
2. In the reaction, where all solution reactants and products; K represents Kc
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3. a mixture of solution and gaseous reactants; Kx represents the thermodynamic

equilibrium constant and we do not make the distinction between Kp and Kc.
we may conclude that for standard reactions, i.e., at 1 M or 1 atm.
When
G0 = ve or K 1: forward reaction is feasible
G0 = +ve or K 1: reverse reaction is feasible
G0 = 0 or K = 1: reaction is at equilibrium (very rare)
Illustration 45: Kc for the reaction N2O4 2NO2 in chloroform at 291 K is 1.14.
Calculate the free energy change of the reaction when the concentration
of the two gases are 0.5 mol dm3 each at the same temperature. (R = 0.082
lit atm K1 mol1.)
Solution:
From the given data
T = 291 K; R = 0.082 lit atm K1 mol1
Kc = 1.14; C NO2 C N2O4 = 0.5 mol dm3
The reaction quotient Qc for the reaction N 2 O 4 2NO 2 ,
Qc
[NO 2 ]2 0.5 0.5
0.5
[N 2 O 4 ]
0.5
Since Qp = Qc(RT)n and n = 2 1 = 1 in this case

Qc = 0.5 (0.082 291) = 11.93
Kp = Kc(RT)n = 1.14 (0.082 291) = 27.1
Substituting these values in the equation
G
= G0 + RTlnQp = RT ln Kp + RT ln Qp, we get
= 2.303 RT (log Kp log Qp)
G
= (0.082 291 2.303) [log 27.2 log 11.93]
= 54.95 (1.4346 1.0766) = 19.67 lit atm
Illustration 6:
Ammonium hydrogen sulphide dissociates according to the equation

NH4HS(s)
NH3(g) + H2S(g). If the observed pressure of the mixture
is 1.12 atmosphere at
106C, what is the equilibrium constant K p of the
reaction?
NH4HS(s)
Solution:
t=0
t = teq
PT = 2x = 1.12
x = 0.56
KP = x2 = 0.3136 amt2
0
x atm
NH3(g)
0
x atm
H2S(g)
Illustration 56:
Calculate the pressure of CO 2 gas at 700K in the heterogeneous
equilibrium reaction CaCO3(s) CaO(s) + CO2(g) if G0 for this reaction is
130.2 kJ mol1.
Solution:
Here Kp = PCO2
38

38
Also,
ln K p
S
M
C
E
C
H
3
9
G 0 RT ln K p
G 0
130.2 103 Jmol1
10
p CO2 K p 1.94 10 atm

1
1
RT (8.314JK mol )(700K)
Illustration 67: For the equilibrium NiO(s) + CO(g) Ni(s) + CO2(g), G0 (J mol1)
= 20,700 11.97 T. Calculate the temperature at which the product gases
at equilibrium at 1 atm will contain 400 ppm (parts per million) of carbon
monoxide.
Solution:
For the given reaction K p pCO2 / pCO

p CO p CO2 , hence
Since
Kp
1
1
2,500
pCO 400 106
G 0 RT ln K p
ln K p
G 0 20,700 11.97T
RT
RT
The equation when solved for T using R = 8.314 K1 mol1, gives T = 399K.
Illustration 8:
0C
13
Equilibrium constants are given (in atm) for the following reactions at
a) SrCl26H2O(s)
Kp = 6.89 1012
SrCl22H2O(s) + 4H2O(g),
b) Na2HPO412H2O(s)
Na2HPO47H2O(s) + 5H2O(g), Kp = 5.25 10
c) Na2SO410H2O(s)
Na2SO4(s) + 10H2O(g)
Kp = 4.08 1025
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The vapour pressure of water at 0C is 4.58 torr.

i) Calculate the pressure of water vapour in equilibrium at 0C with each
of (a), (b) and (c).
ii) Which is the most effective drying agent at 0C?
iii) At what relative humidities, Na2SO210H2O be efflorescent when
exposed to air at 0C?
iv) At what relative humidities will Na 2SO4 be deliquescent (i.e,. absorb
moisture) when exposed to air at 0C?
Solution :
4
(a) KP = PH2 O = 6.89 10-12
5
KP = PH2O = 5.25 10-13
PH2O = 1.62 10-3 atm
PH2O = 3.5 10-3 atm
10
KP = PH2O = 4.08 10-25 PH2 O = 3.6 10-3 atm
(b) SrCl2.2H2O, Since it has lowest vapour pressure water in equilibrium
(c) The hydrate will loss water (efforesce) below.

2.77 torr
100% 60.5% relative humidity
2.77 torr i.e.,
4.58torr
(d) The dehydrated salt will absorb H2O above 60.5% relative humidity.
BRAIN TEASER 5:
i)
Calculate the partial pressure of HCl gas above solid a sample of NH 4Cl(s) as a result of its
decomposition according to the reaction:
NH4Cl(s) NH3(g) + HCl(g) Kp =?
ii)
Calculate the equilibrium constant of a reaction at 300 K if G0 at this temperature for
the reaction is 29.29 kJ mol1.
Illustration 78: For the formation of ammonia the equilibrium constant data at 673K and
773K respectively are 1.64 104 and 1.44 105 respectively. Calculate heat of the reaction.
Given R = 8.314 JK1 mol1.
Solution:
Substituting the values in the equation
ln
K p2
K p1
H T2 T1
, we get
R T2 T1
1.44 105
H 773 673
4
8.314 773 673
1.64 10
H(100)
2.303log(0.0878)
8.314 773 673
2.303log
100H = 2.303 (1.0565) 673 773 8.314

whence, H
673 773 2.303 1.0565 8.314

= 105216J = 105.216kJ
100
BRAIN TEASER 6:
40

40
S
M
C
E
C
H
4
1
The equilibrium constant KP for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.6 10-4 atm at
400oC. What will be the equilibrium constant at 500 oC if heat of the reaction in this
temperature range is 25.14 k cal?
Relation between Vapour Density and Degree of Dissociation

In the following reversible chemical equation
A yB
Initial mol
1
0
At equilibrium
(1 x) yx
x = degree of dissociation
Number of moles of A and B at equilibrium = 1 x + yx = 1 + x(y 1)

If initial volume of 1 mole of A is V, then volume of equilibrium mixture of A and B is
= [1 + x(y 1)]V
Molar density before dissociation,
Molar density after dissociation
molecular weight m
volume
V
m
d
[1 x(y 1)]V
D
[1 x(y 1)]1
d
Dd
x
d(y 1)
D
Note: y is the number of moles of products from one mole of reactant.
D
is also called Vant
d
Hoff factor.
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Thus for the equilibria

PCl5(g) PCl3(g) Cl 2(g) , y = 2
I:
N 2 O 4(g) 2NO 2(g) , y = 2
II:
1
2NO 2 N 2 O 4 , y =
2
Dd
x
d
2(d D)
x
d
III:
Also
D 2 = Molecular weight (theoretical value)

d 2 = Molecular weight (abnormal value) of the mixture
Illustration 89:
Vapour density of the equilibrium mixture of NO 2 and N2O4 is found to be

40 for the equilibrium
N2O4 2NO2
Calculate (i) abnormal molecular weight
ii) degree of dissociation
iii) percentage of NO2 in the mixture
Solution:
i) N2O4 2NO2
Observed value of vapour density (d) = 40
Hence, abnormal molecular weight = 40 2 = 80
ii) D 2 = theoretical molecular weight = 2
92
46
2
D d 46 40
0.15
x
d
40
iii)
N2O4 2NO2
Initial mol
1
0
At equilibrium
(1 x)
2x
0.85
0.30
Total moles at equilibrium = (1 + x) = 1 + 0.15 = 1.15
26.08%
Percentage of NO2 =
2x
0.30
100
100 =
1 x
1.15
42

42
S
M
C
E
C
H
4
3
DRILL EXERCISE V
1.
1.
2.
2.
3.
3.
4.
An equilibrium mixture for the reaction: 2H2S(g)

2H2(g) + S2(g) has 0.5 mole
H2S, 0.1 mole of H2 and 0.4 mole S2 in a one litre vessel. The equilibrium constant of
this reaction is given by:
(A) 0.004 mole litre1
(B) 0.08 mole litre1
1
(C) 0.016 mole litre
(D) 0.160 mole litre1
0.016 mole litre1
Mole percentage of CO in vapour state is 50 at equilibrium at constant temperature and
pressure for the reaction, C(Graphite) + CO2(g)
2CO(g). What will be degree of
dissociation.
(A) 0.33
(B) 0.25
(C) 0.033
(D) 0.50
0.33
The volume occupied by 3.6 g of PCl5 is 1 litre on complete vaporization at 1
atmospheric pressure and 200C. Partial dissociation of PCl 5 gives PCl3 and Cl2. What
should be the percentage of dissociation of PCl5 at the same temperature
(A) 4.9%
(B) 0.49%
(C) 49%
(D) 0.049%
49%
If x, y and z are the initial moles of PCl5, PCl3 and Cl2 for PCl5
PCl3 + Cl2 and a
is amount of dissociation and P is total pressure, the mole fraction of PCl3 will be
y ax
x az
(A)
(B)
x y z ax
x y z ax
x y ax
z ax
(C)
(D)
x y z ax
x y z ax
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44
y ax
x y z ax
4.
Answer to Drill Exercises
Drill Exercise I
1. 0.75
a
2.
2
2
3. (K P2 )
Drill Exercise II
1. 3
n
2.
4
3. SO2 and O2
1. 12.5 102 mol litre1
2. If [B] = 1; [A] = 0.91
3. NO2 = 0.017 2 = 0.034 mole
1. 16 atm.
(1 x) P
2.
(1 x)
3. 0.675
4. 0.267
5. 0.61
1. 0.016 mole litre1
2. 0.33
3. 49%
y ax
4.
x y z ax
Drill Exercise III
Drill Exercise IV
Drill Exercise V
Solved Problems
Objective
BRAIN TEASER 7:
N2O4(g) 2NO2(g). In this reaction, NO2 is 20% of the total volume at equilibrium.
Calculate
a) Vapour density
b) abnormal molecular weight
c) percentage dissociation of N2O4
Answers to Brain Teaser

44

44
Brain Teaser 1:
i) 0.43
ii) a) Kp = Kc
b) Kp = Kc (RT)4
Brain Teaser 2:
Kc
Brain Teaser 3:
Brain Teaser 4:
i) 2%; (ii) 0.037

1. Low T, High P, excess of SO2 and O2.
2. Low T, High P, excess of NO and O2
3. High T, Low P, excess of PCl5
(i) 1.02 108 atm; (ii) K0p = 7.96 106
Brain Teaser 5:
Brain Teaser 6:
Brain Teaser 7:
S
M
C
E
C
H
4
5
4x 2 V 2
16x 2 (2 x) 2
K
and
p
27(1 x) 4
27(1 x)4 P 2
K P2 4.835
a) 41.1; b) 8.28; c) 11.1%
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46
Solved Problems
Objective

2C(g), the rate constants for the forward and
Problem 1: For the reaction, A(g) + 2B(g)
the reverse reactions are 1 104 and 2.5 102 respectively. The value of
equilibrium constant, K for the reaction would be
(a) 1 104
(b) 2.5 102
(c) 4 103
(d) 2.5 102.
Solution:
Apply the formula, K

(c)
kf
1104
= 4 103.
k b 2.5 102
Problem 2: The equilibrium constant for the reaction,
A 2 (g) B 2 (g)
2AB(g)
is 20 at 500 K. The equilibrium constant for the reaction,

2AB(g)
A2(g) + B2(g), would be
(a) 20
(b) 0.5
(c) 0.05
(d) 10.
Solution:
When the equation is reversed, the equilibrium constant for the reaction is
reciprocal of the K for the forward reaction
1
1
K2
= 5 102 or 0.05.
K1 20
(c)
Problem 32: At a certain temperature, the equilibrium constant K c is 16 for the reaction,
SO2(g) + NO2(g)
SO3(g) + NO(g). If 1.0 mol each of all the four gases is
taken in a one litre container the concentration of NO2 at equilibrium would be
(a) 1.6 mol L1
(b) 0.8 mol L1
1
(c) 0.4 mol L
(d) 0.6 mol L1.
Solution:
SO2(g)
+
NO2(g)
1
1
1x
1x
[SO3 ][NO] (1 x)(1 x)
K
[SO 2 ][NO 2 ] (1 x)(1 x)
16
46
(1 x) 2
(1 x) 2
SO3(g)
1
1+x
(1 x)
4 or
(1 x)
+ NO(g)
1
1+x
Initial conc.
At equilibrium
x = 0.6

46
S
M
C
E
C
H
4
7
[NO2] = 1 x = 1 0.6 = 0.4 mol L1.

(c)
Problem 43: HI was heated in sealed tube at 400C till the equilibrium was reached. HI was
found to be 22% decomposed. The equilibrium constant for dissociationis

(a) 1.99
(b) 0.0199
(c) 0.0796
(d) 0.282
Solution:
2HI
1
H2
+
I2
0
0
x
x
1x
2
2
1 0.22 = 0.78 0.11
0.11
22
1 0.22
x = 22% of 1 mole =
100
[H ][I ] 0.11 0.11
K 2 22
= 0.0199
[HI]
(0.78) 2
(b)
Problem 5: For the gas phase reaction

1
2NO
N2 + O2; H = 43.5 kcal mol , which one of the statement below is
true for N2(g) + O2(g)
2NO(g)
(a) K is independent of T
(b) K increases as T decreases
(c) K decreases as T decreases
(d) K varies with the addition of NO

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Solution:
For the reverse reaction,

N 2(g) O 2(g)
2NO(g) ;
H 53.5kcal / mol
i.e. the reaction is endothermic in nature. Thus, equilibrium constant K decreases

with decrease in temperature.
(c)
Problem 64: When ich sulphur in the form of S8 is heated at 900K, the initial pressure of one
atm falls by 29% at equilibrium. This is because of conversion of some S 8 to S12.

Find the value of equilibrium constant for this reaction
(a) 1.16 atm3
(b) 0.71 atm3
3
(c) 2.55 atm
(d) 5.1 atm3
Solution:
S8(g)
4S2(g)
At start
At eqbm
1
0
1 0.29
4 10.29
= 0.71 atm
= 1.16 atm
4
4
[pS2 ]
(1.16)
Kp
2.55atm3
[pS8 ]
(0.71)
(c)
Problem 75: The following reactions are known to occur in the body
+
1
CO2 + H2O
H2CO3
H + HCO3
If CO2 escapes from the system
(a) pH will decreases
(b) Hydrogen ion concentration will diminish
(c) H2CO3 concentration will remain unchanged
(d) The forward reaction will be favoured
Solution:
This is according to Le-Chateliers principle

(b)
Problem 86: For which of the following reactions, the degree of dissociation cannot be
calculated from the vapour density data

I. 2HI(g)
H2(g) + I2(g)
II. 2NH3(g)-
N2(g) + 3H2(g)
III.2NO(g)
N2(g) + O2(g)
IV. PCl5(g)
PCl3(g) + Cl2(g)
(a) I and III
(b) II and IV
(c) I and II
(d) III and IV
48

48
Solution:
S
M
C
E
C
H
4
9
The degree of dissociation cannot be calculated from the vapour density data.
Becaluse here it the number of moles remains unchanged before and after
reaching equilibrium
(a)

Problem 79: X2 + X
X3 (x = iodine)
This reaction is set up in aqueous medium. We start with 1 mol of X 2 and 0.5
mol of X in 1L flask. After equilibrium is reached, excess of AgNO 3 gave 0.25
mol of yellow ppt. equilibrium constant is
(a) 1.33
(b) 2.66
(c) 2.00
(d) 3.00
Solution:
X2 +
X

X 3
1
0.5
0
(1 x)
(0.5 x)
x
(0.5 x) = unreacted X
X Ag + 0.25
x = 0.25
[X3 ]
0.25
Kc
1.33
[X 2 ][X ] 0.75 0.25

(a)
Problem 10: For the reaction (1) and (2)
A
B + C
(i)
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50
2E (ii)
Given KP1 : KP2 :: 9 : 1
If the degree of dissociation of A and D be same then the total pressure at
equilibrium and (2) are in the ratio
(a) 3 : 1
(b) 36 : 1
(c) 1 : 1
(d) 0.5 : 1
Solution:
For these reaction
x 2 P1
(1 x) 2
4x 2 P2
K P2
(1 x) 2
K P1
P
36 P1
1 or
K P2 4P2
1 P2
K P1
Q
and
(b)
Problem 811:
A reaction mixture containing H2, N2 and NH3 has partial pressures 2 atm,
1 atm and 3 atm respectively at 725 K. If the value of K p for the reaction, N2(g) +
3H2(g)
2NH3(g) is 4.28 105 atm2 at 725 K, in which direction the net
reaction will go ?
(a) Forward
(b) Backward
(c) No net reaction
(d) Direction of reaction cannot be predicted.
P
=
P P
2
Solution:
Qp
NH3
N2
H2
(3) 2
9
atm 2 = 1.125 atm2.
3
(1)(2)
8
Since value of Qp is larger than Kp (4.28 105 atm2), it indicates net reaction will
proceed in backward direction.
(b)
Problem 12: An equilibrium system for the reaction between hydrogen and iodine to give hydrogen
iodide at 765 K in a 5 litre volume contains 0.4 mole of hydrogen, 0.4 mole of iodine
and 2.4 moles of hydrogen iodide. The equilibrium constant for the reaction is:

2HI(g), is
H2(g) + I2(g)
(a) 36.0
(c) 0.067
(b) 15.0
(d) 0.028.
50

50
Solution:
S
M
C
E
C
H
5
1
The concentration of various species at equilibrium are :
0.4
= 0.08 mol L1
5
0.4
[I2] =
= 0.08 mol L1
5
2.4
[HI] =
= 0.48 mol L1
5
[HI]2
K
[H 2 ][I 2 ]
[H2] =
Substituting the various values in the above expression of K, we get
(0.48) 2
K
36.0 .
(0.08)(0.08)
(a)
Problem 913:
2.0 mol of PCl5 were introduced in a vessel of 5.0 L capacity at a particular

temperature. At equilibrium, PCl5 was found to be 35% dissociated into PCl 3
and Cl2. The value of Kc for the reaction is
(a) 1.89
(b) 0.377
(c) 0.75
(d) 0.075.
Solution:
2 35
= 0.7
100
Moles of PCl5 left undissociated = 2 0.7 = 1.3 mol
1.3
0.7
0.7
[PCl5] =
M, [PCl3] =
M, [Cl2] =
M
5
5
5
Moles of PCl5 dissociated =
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0.7 0.7
[PCl3 ][Cl 2 ] 5
5
0.75
[PCl5 ]
1.3

5
(c)
Problem 14: K1 and K2 are equilibrium constant for reactions (1) and (2)

N2(g) + O2(g)
2NO(g)
(1)
1
1

NO(g)
N2(g) + O2(g)
(2)
Then,
1
(a) K1
K 2
1
(c) K1
K2
Solution:
2
2
(b) K1 K 2
0
(d) K1 (K 2 ) .

2NO
N2 + O2
K1

2NO
N2 + O2
1

N 2 O2
NO
1
K2
K1
1
K2
K1
1
K1
(K 2 ) 2
(a)
1/ 2
2
or K 2
1
K1
1/ 2
1
K1
Problem 105:
For the reaction

2HI(g)
H2(g) + I2(g)
The degree of dissociation ( ) of HI(g) is related to equilibrium constant, K p by
the expression
1 2K p
1 2 Kp
(a)
(b)
2
2
52

52
(c)
(d)
Solution:
S
M
C
E
C
H
5
3
2K p
1 2K p
2 2K p
1 2 K p
2HI(g)
H2(g) + I2(g)
1
2
2
2

PT
2
Kp
2 2
(1 ) PT
2 Kp
1
2 Kp
1 2 K p
(d)
Problem 16: In a reversible reaction, study of its mechanism says that both the forward and reverse
reaction follows first order kinetics. If the half life of forward reaction (t 1/2)f is 400 sec
and that of reverse reaction (t1/2)r is 250 sec. The equilibrium constant of the reaction is
(a) 1.6
(b) 0.433
(c) 0.625
(d) 1.109
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54
Solution:
0.693
0.693
sec 1 ; K r
sec 1
400
250
k
250
K f
0.625
k r 400
Kf
(c)
Problem 117:
At temperature T, a compound AB2(g) dissociates according to the reaction

2AB2(g)
2AB(g) + B2(g) with degree of dissociation , which is small
compared with unity. The expression for Kp, in terms of and the total
pressure, PT is
PT 3
2
P 3
(c) T
3
(a)
Solution:
PT 2
3
P 2
(d) T .
2
(b)
For the given equilibrium, the equilibrium concentration are

2AB2(g)
2AB(g) + B2(g)
c
Equilib. conc. c(1 )
c
2
c
3 PT
(c) 2 PT
(PB2 )(PAB ) 2
K
2
KP
; P
2(1 ) 2 1
(PAB2 )
[c(1 )]2 [c(1 )]
2
Since, is small compared to unity, so 1 ; 1 and 1 + ; 1 .

2
3
PT
KP
2
(a)

Problem 18: For the reaction: NH2COONH4(s)
2NH3(g) + CO2(g)
The equilibrium constant Kp = 2.9 105 atm3. The total pressure of gases at
equilibrium when 1.0 mole of reactant was heated will be
(a) 0.0194 atm
(b) 0.0388 atm
(c) 0.058 atm
(d) 0.0667 atm
Solution:
54

NH2COONH4(s)
2NH3(g) + CO2(g)
Moles initially
1
0
0
Moles at equib.
(1 x)
2x
x
Total moles of gaseous substances at equilibrium = 3x
Equilibrium pressure = PT
PNH3
2
P
PT , PCO2 T
3
3

54
S
M
C
E
C
H
5
5
K P (PNH3 ) 2 PCO2
2.9 105
4(PT )3
27
PT = 0.058 atm
(c)
Problem 129:
In equilibrium reaction, x moles of the reactant A decompose to give 1 mole

each of C and D. If the fraction of A decomposed at equilibrium is independent
of initial concentration, then the value of x would be
(a) 1
(b) 2
(c) 3
(d) 4
Solution:
The fraction of A decomposed at equilibrium is independent of initial

concentration means the equilibrium constant expression is free from
concentration term. The equilibrium reaction is
xA
C
+
D
Initial conc.
c
0
0
c
c
Conc. at. equil.
c(1 )
x
x
c c

[C][D] x
(c) 2
x
KC
[A]x
[c(1 )]x
x 2 [c(1 )]x
The expression of KC would be free from concentration term only when value of
x is 2. Putting x = 2, gives
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KC
c2 2
2
4[c(1 )]2 4(1 ) 2
(b)
Problem 20: At a certain temperature the following equilibrium is established,
CO(g) + NO2(g)
CO2(g) + NO(g).
One mole of each of the four gases is mixed in one litre container and the
reaction is allowed to reach equilibrium state. When excess of baryta water is
added to the equilibrium mixture, the weight of white precipitate obtained is
236.4 g. The equilibrium constant, KC of the reaction is
(a) 1.2
(b) 2.25
(c) 2.1
(d) 3.6.
Solution:
CO(g) + NO2(g)
CO2(g) + NO(g).
Moles initially
1
1
1
1
Moles at equib.
1x
1x
1+x
1+x
CO2 + Ba(OH)
BaCO3 + H2O
2
236.4
1.2
Moles of BaCO3 =
197
Moles of CO2 at equilibrium = 1.2 or, 1 + x = 1.2; x = 0.2
2
2
1 x 1.2
KC

2.25
1 x 0.8
(b)
Problem 13: In the reversible reaction A + B
C + D, the concentration of each C and
D at equilibrium was 0.8 mole/litre, then the equilibrium costant Kc will be
(a) 6.4
(b) 0.64
(c) 1.6
(d) 16.0
Solution:
(d) Suppose 1 mole of A and B each taken then 0.8 mole/litre of C and D each
formed remaining concentration of A and B will be (1 0.8) = 0.2 mole/litre each.
Kc
C D 0.8 0.8 16.0

A B 0.2 0.2
Problem 14: 4 moles of A are mixed with 4 moles of B. At equilibrium for the reaction A + B
56

C + D, 2 moles of C and D are formed. The equiibrium constant for the
reaction will be
(a) 1/4
(b) 1/2
(c) 1
(d) 4

56
Solution:
S
M
C
E
C
H
5
7
(c)
A + B
Initial conc.
4,
4
After T time conc. (4-2)
(4-2)
C D 2 2
Equilibrium constant =
A B 2 2
C + D
0
0
2
2
1
Problem 15: On a given condition, the equilibrium concentration of HI, H2 are 0.80, 0.10
and 0.10 moe/litre. The equilibrium constant for the reaction
H2 + I2
2HI will be
(c) 8
Solution:
(a) 64 (b) 12
(d) 0.8
(a) H2 + I2
2HI; [HI] = 0.80, [H2] = 0.10, [I2] = 0.10
2
HI 0.80 0.80 64
Kc
H 2 I 2 0.10 0.10
Problem 16: In which of the following, the reaction proceeds towards completion
(a) K = 103
(c) K = 10
Solution:
(b) K = 10-2
(d) K = 1
(a) Those reaction which have more value of K proceeds towards completion.
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Problem 17: A reversible chemical reaction having two reactants in equilibrium. If the
concentration of the reactants are doubled, then the equilibrium constant will
(a) Also be doubled
(b) Be halved
(c) Become one-fourth
(d) Remain the same
Solution:
(d) Kc is a characteristic constant for the given reaction.
Problem 18: The equilibrium constant in reversible reaction at a given temperature
(a) Depends on the initial concentration of the reactants

(b) Depends on the concentration of the products at equilibrium
(c) Does not depend on the initial concentrations
(d) It is not characteristic of the reaction
Solution:
Equilibrium constant is independent of original concentration of reactant.
Problem 19: Pure ammonia is placed in a vessel at temperature where its dissociation
constant ( ) is appreciable. At equilibrium
(a) Kp does not change significantly with

pressure
(b) does not change with pressure
(c) Concentration of NH3 does not change with pressure
(d) Concentration of H2 is less than that of N2
Solution :
Kp is constant and does not change with pressure.
Problem 20: Partial pressure of A, B, C and D on the basis of gaseous system
A + 2B
C + 3D are A = 0.20; B = 0.10; C = 0.30 and D = 0.50 atm.
The numerical value of equilibrium constant is
(a) 11.25
(b) 18.75
(c) 5
(d) 3.75
Solution:
(b) A + 2B
C + 3D
3
pC pD 0.30 0.50 0.50 0.50 18.75
K
0.20 0.10 0.10
pA pB
58

58
S
M
C
E
C
H
5
9
Problem 21: 2 moles of PCl5 were heated in a closed vessel of 2 litre capacity.
At
equilibrium, 40% of PCl5 is dissociated into PCl3 and Cl2. The value of
equilibrium constant is
(a) 0.266
(d) 5.3
(c) 2.66
Solution :
(b) 0.53
(a) PCl5
PCl3 + Cl2
2
0
0
2 60
2 40
2 40
100
100
100
Volume of container = 2 litre.
2 40 2 40
K c 100 2 100 2 0.266

2 60
100 2
Problem 22: Which of the following factors will not disturb the equilibrium state of the
reaction,
N2(g) + O2
(a) Change in pressure

(c) Addition of catalyst
2NO (g)
(b) Change in temperature
(d) Addition of N2.
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Solution:
(a, c)
Pressure does not disturb equilibrium state in this reaction because np = nR or
n = 0.
Problem 23: For the reaction
2A (g) + B (g)
the reactants ?
(a) Low pressure
(c) Low temperature
Solution:
C(g), H = +x kJ, which of the following favour

(b) High pressure
(d) Catalyst
(a, c)
Backward reaction is exothermic and is accompanied by increase in number of
moles of gaseous species. Hence it is favoured by low temperature and low
pressure.
Problem 24: For which of the following reactions at equilibrium at constant temperature
doubling the volume will cause a shift to the right ?

(a) N2O4 (g)
(b) CaCO3 (s)
2NO2 (g)
CaO(s) + CO2(g)
(c) 2CO(g) + O2(g)
2CO2(g) (d) N2(g) + O2(g)
2NO (g)
Solution:
(a, b)
Doubling the volume would reduce the pressure and shift the equilibrium in the
direction where there is more number of moles of gases. In choices (a) and (b),
the equilibrium will shift to the right.

Problem 25: The reaction, SO2 (g) + Cl2(g)
SO2Cl2 (l) is exothermic and reversible.

To the above reaction, at equilibrium, a certain quantity of extra SO 2 is
introduced keeping the volume constant. Which of the following are true?
(a) The pressure inside the container increases
(b) The temperature will increase
(c) The temperature will decreases
(d) The temperature will remain same.
60

60
Solution:
S
M
C
E
C
H
6
1
(a, b)
The equilibrium shifts in the forward direction according to Le-Chateliers
principle. The forward reaction being exothermic, temperature increases.
Pressure increases due to extra SO2.

Problem 26: For the reaction PCl5 (g)
PCl3(g)
constant temperature is favoured by
Cl2(g), the forward reaction at
(a) introducing an inert gas at constant volume

(b) introducing chlorine gas at constant volume
(c) introducing an inert gas at constant pressure
(d) increasing the volume of the container
(e) introducing PCl5 at constant volume
Solution:
(c, d, e) Apply Le-Chatelier principle.
Problem 27: Match the List I, List II and select the answers from the given codes:
(a)
(b)
(c)
(d)
Column I (Mixture)
Keq < 1
Degree of dissociation
Equilibrium constant
Melting of ice
Column II (pH)
(p) may be affected by temperature
(q) affected by pressure
(r) Kf < Kb
(s) Kf > Kb
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Solution:
(A - R), (B P, Q), (C - P), (D P, Q)
Solved Problems
Subjective
Write-up I
If the composition of the system does not change with time, the system is said to be in
chemical equilibrium. It is the state in which net reaction of a system is zero. in another
words we can say that in reversible reactions, a stage is reached when the rate of
transformation of reactants into products equals the rate of transformation of products
into reactants. At this stage, the composition of reactants and products does not change
with time. This does not mean that the reaction has ceased, as both reverse and forward
reactions are still taking place but with equal place. Such equilibria are called dynamic
equilirbria.
Let us consider a reaction of the type
A(g) + B(g)
C(g) + D(g)
KC
C D
A B
where KC is equilibrium constant when the ratio of the concentrations of the product to
reactants
P P
KP C D
PA PB
where KP is the equilibrium constant for the ratio of partial pressure & of products to
reactants. The relation between KP and KC is as follows
KP = KC(RT)n
1.
The mass ratio of steam and hydrogen is found to be 1 : 2 at equilibrium.

3 Fe (s) + 4 H2O(g)
Fe3O4(s) + 4 H2(g)
The value of equilibrium constant (KC) for the above reaction is
(a) 3.05 103
(b) 1.05 105
(c) 0.75 102
(d) None of the above
2.
KC for the reaction
1
1
1
N 2 (g) O 2 (g) Br2 (g )
2
2
2
NOBr(g) from the following
information at 298 K
2 NO( g )
N2(g) + O2(g) K1 = 2.4 1030
1
NO( g ) Br2( g )
NOBr(g) K2 = 1.4
2
(a) 3.15 109
(b) 6.35 5 1018
(c) 9.03 1016
(d) 17 1017
62

62
S
M
C
E
C
H
6
3
3.
The equilibrium constant for the reaction 2 SO 2 + O2

2 SO3 at 1000 K is 3.5. What
would the partial pressure of oxygen gas have to be to give equal moles of SO2 and SO3 ?
(a) 0.29 atm
(b) 3.5 atm
(c) 0.53 atm
(d) 1.87 atm
4.
For the reaction

NH2COONH4(s)
2 NH3(g) + CO2(g)
The equilibrium constant KP = 2.9 105 atm3. The total pressure of gases at equilibrium
when 1 mole of reactant was heated will be
(a) 0.0194 atm
(b) 0.0388 atm
(c) 0.0580 atm
(d) 0.0667 atm
Solution :
1.
(b) Since n = 0, so Kc = Kp = Kx
X 4H 2
(2 / 2) 4
184 1.05 105

Kx = 4
4
X H 2O (1/18)
2.
(c)
1/ 2
1
1
1
N 2 ( g ) O 2 ( g )
Kc =
NO( g )
30
2
2
2.4 10
1
NO (g) + Br2 ( g )
K2 = 1.4
NOBr (g)
2
1
1
1
N 2 ( g ) O2 ( g ) Br2 (g)
NOBr( g ) K = KC K2 = 9.03 10-16
2
2
2
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3.
(a) Kp =
2
PSO
3
PSO2 .PO2
2
1
1
atm 0.29 atm

PO2
K P 3.5
(c) Kp = PNH 3
4.
K
P = P
4
.PCO2 (2 p ) 2 P 4p3
1/ 3
0.0667 atm
Write-up II
A chemical reaction in the laboratory is carried out under the condition of constant
temperature and pressure. The condition of spontaneity in terms of enthalpy and entropy
are, respectively, H 0 and S 0 whereas condition of equilibrium are, respectively,
H = 0 and S = 0. An endothermic reaction is driven by increase in entropy i.e. increase
in disorderness. The two criteria combined together, the condition of reversibility and
irreversibility are as follows:
GP, T = H TS 0, where equal to sign refers to reversibility and less than sign refers
to irreversibility. Reversibility is the condition of equilibrium whereas irreversibility is
the condition of spontaneity. A reversible reaction is characterised by equilibrium
constant (K), the magnitude of which measures the position of equilibrium i.e. how far a
chemical reaction will go to completion before attainment of equilibrium. The position of
equilibrium constant of a reaction with temperature is given by Vant Hoff equation of
thermodynamics which is as follows:
d ln K H
dT
RT 2
This equation can be integrated assuming H to be independent of temperature. Within
the short interval of temperature.
For a gaseous equilibria k can be expressed Kc and Kp related as
K p K c (RT)
n g
Where the symbols have their usual meanings. ng of a reaction can be found out from
the unit of equilibrium, though it is not customary to write unit of equilibrium constant.
Another way of finding ng of a reaction is to use the equation
H = E + ng RT
Where the terms have their usual meanings.
Knowing K and reaction quotient it is possible to calculate free energy change of a
reaction using the equation:
G = G0 + RTlnQ
At equilibrium Q = K and GP, T = 0
64

64
S
M
C
E
C
H
6
5
So, G0 = RTlnK where G0 is the free energy change of the reaction in the standard
state.
The standard state of a substance is defined as the state of unit activity at 25C. In the
case of solution of a substance the activity is taken to be molar concentration while for a
gas it is pressure in atm.
The standard free energy of an element is taken to be zero.
1.
At 27C the heat of reaction at constant pressure is 600 cals more than that at constant
volume. The ratio of Kp to Kc of the reaction is:
(a) 24.63
(b) (24.63)2
(c) 0.6
(d) 0.36
2.
For the reaction:

NH 4 HS(s)
NH 3(g) H 2S(g)
Kp and Kc are interrelated as
(a) Kp = KcRT
(c) Kp = Kc(RT)2
Kc
(RT) 2
(d) Kp = Kc/RT
(b) Kp =
3.
The Kp of a reaction is 10 atm2 at a temperature T on Kelvin scale. Hence

(a) Kp = Kc
(b) Kp Kc
(c) Kp Kc
(d) Cant be predicted
4.
The Kc of a reaction is 4.0 mol2L2 at 27C. Hence Kp of the reaction is:

(a) 4 (0.0821 300)2 atm2
(b) 4 (2 300)2 atm2
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(c)
4
(0.0821 300) 2 atm 2
(d)
4
(2 300) 2 atm 2
Solution :
1.
From question,
H - E = 600 cals. = n 2 300 cals.
n = 1
Q KP = KC (RT)n
KP/KC = (RT)n = (0.821 300)1 = 24.63
2.
KP = KC(RT)n, where n = total no. of gaseous product molecules total no. of

gaseous reactant molecules
Q n = ( 1 + 1 0) = 2
KP = KC(RT)2
3.
KP = 10 atm-2. from unit of KP, we can calculate

n = -2
KP = KC(RT)n = KC(RT)-2 =
KC
(RT)2
KP < K C
The unit of KC is mol2 L-2, hence n = 2
4.
Subjective
1
3
NH3(g)
N2(g) +
H2(g)
2
2
Show that degree of dissociation of NH3 is given as :
3 3 P
1
4 K p
1 / 2
where P is equilibrium pressure. If Kp of the above reaction is 78.1 atm at

400C, calculate KC.
Solution:
66
NH3(g)
moles
Initial moles t = 0
1
N2(g) +
2
3
H2(g). Total
2

66
S
M
C
E
C
H
6
7
Moles equilibrium
Partial pressure
p
1
Kp
/2
p
2
(
1
3 /2
1+
3
p
2
(
1
)
[ N 2 ]1 / 2 [ H 2 ]3 / 2
[ NH 3 ]
1/ 2
3
p
p
2
(
1
)
2
(
1
1 p
3/ 2
p 2
27
4(1 2 )
Solving for ` we get :
3 3 p
1
4 K p
1/ 2
We know,
K p K C ( RT ) n
78.1 = K C (0.0821 673)1

KC = 1.413 moles litre1
Problem 21: At 700 K, CO2 and H2 react to form CO and H2O. For this process K is 0.11. If a
mixture of 0.45 mole of CO2 and 0.45 mole of H2 is heated to 700 K, then
i) Find out the amount of each gas at equilibrium.
ii) After equilibrium is reached, another 0.34 mole of CO 2 and 0.34 mole of H2
are added to the reaction mixture. Find the composition of the mixture at
the new equilibrium state.
Solution:
i) The given equilibrium is

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At t = 0
At equilibrium
KC
0.l1 =
CO2(g)
0.45
(0.45 x)
+ H2(g)
0.45
(0.45 x)
CO(g)
0
x
+ H2O(g)
0
x
x2
(0.45 x ) 2
x2
(0.45 x ) 2
x = 0.112
[CO2] = [H2] = (0.45 x) = (0.45 0.112) = 0.3379
0.34 mole
each
[CO] = [H2O] = x = 0.112 mole each
ii) When 0.34 mole of CO2 and H2 are added in above equilibrium then following
case exists.
At t = 0
At eqbm
KC
0.11 =
CO2(g)
(0.34 + 0.34)
(0.68 )
H2(g)
(0.34 + 0.34)
(0.68 )
CO(g)
0.11
(0.11 +
)
+ H2O(v)
0.11
(0.11 + )
[CO][H 2 O]
[CO 2 ][H 2 ]
(0.11 ) 2
(0.68 ) 2
= 0.086
[CO2] = [H2] = 0.68 - = (0.68 0.086)

= 0.594 mole each
[CO] = [H2O] = 0.11 +

= 0.11 + 0.086 = 0.196 mole each
Problem 3: Kp for the reaction N2O4 (g)
2NO2 (g) is 0.66 at 46 C. Calculate the
percent dissociation of N2O4 at 46 C and a total pressure of 0.5 atm. Also
calculate the partial pressure of N2O4 and NO2 at equilibrium.
Solution:
This problem can be solved by two methods.
Method (1) Let the number of moles of N2O4 initially be 1 and is the degree
of dissociation of N2O4.
N2O4
2NO2
Initial moles
1
0
Moles at equilibrium
1
2
Total moles at equilibrium = 1 + 2 = 1+
1
p N 2 O4
PT
1
2
p NO2
PT
1
68

68
S
M
C
E
C
H
6
9
Kp =
2
NO2
p N 2O 4
4 2 PT
4 2 0.5
1 1 1 2
= 0.5 i.e., 50% dissociation
Hence, partial pressure of N2O4 = 0.167 atm.
and partial pressure of NO2 = 0.333 atm.
Method (2) Let the partial pressure of NO2 at equilibrium be p atm, than the
partial pressure of N2O4 at equilibrium will be (0.5p)atm.
p2
0.66
Kp =
0.5 p
p2 + 0.66 p0.33 = 0
On solving p = 0.333 atm.
p NO 2 = 0.333 atm and p N2O4 = 0.167 atm.
Problem 4: The value of Kc for the reaction: H2(g) + I2(g)
2HI(g) is 45.9 at 773 K. If
one mole of H2, two mole of I2 and three moles of HI are taken ina 10 L flask,
find the concentrations of I2 and HI at equilibrium at 773 K.
[HI]2
32
9
Solution:
Calculate Q. Q =
[H 2 ][I 2 ] 1 2 2
Note: When = 0, not only Kp = KC, but volume terms always cancels in the
expression of K.
Q K (= 45.9). Hence the reaction proceeds to forward direction to achieve
equilibrium. Let x mole of H2 and I2 combine to produce 2x mole of HI.
Moles
H2
I2
2HI
Initially
1
2
3
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at equilibrium
1-x
2-x
3 + 2x
2
[HI]
KC =
= 45.9
[H 2 ][I 2 ]
Concentration of species at equilibrium are:
[H2] = (1-x)/1, [I2] = (2-x)/1, [AB] = (3 + 2x)/1
2
3 2x
(3 2x) 2
1
Kc=
= 45.9
(1 x)(2 x)
1 x 2 x
1
1
x = 0.68
[I2] = 2 x = 2 0.68 = 1.32 M
(Note that volume = 1.0L)
[HI] = 3 + 2x = 3 + 1.36 = 4.36 M
Problem 5: At 1000 K, the pressure of iodine gas is found to be 0.112 atm due to partial
dissociation of I2(g) into I. Had there been no dissociation, the pressure would
have been 0.074 atm. Calculate the value of K p for the reaction:
I2(g)
2I(g).
Solution:
Analysing in terms of pressure directly
Partial pressure
I2
2I
Initial
0.074
0
At equilibrium
0.074- p
2p
total pressure at equilibrium
= (0.074 p) + 2p = 0.112 (given) p = 0.038 atm
Kp =
PI
PI2
2p
0.074 p
Substituting value of p Kp = 0.16 atm

Problem 26: For the reaction: CO2(g) + H2(g)
CO(g) + H2O(g), K is 0.63 at 700 C and
1.66 at 1000 C
a) What is the average H for the temperature range considered?
b) What is the value of K at 800 C
Solution:
a) T1 = 700 + 273 = 973 K,

T2 = 1000 + 273 = 1273 K
K1 = 0.63, K2 = 1.66
Using the Vant Hoff equation
70

70
S
M
C
E
C
H
7
1
K2
H 0 T2 T1
log
K1 2.303R T1T2
K
H0 T2 T1
1.66
H o 1273 973
log
log 2
K1 2.303R T1T2
2.303(1.99)
0.63
1273 973
H = 8.0 103 cal = 8.0 kcal

Note: The units of R and H must be same
b) Let K2 be the equilibrium constant at T2 = 1073 K, T1 = 973 K and then
K1 = 0.63
8.0 103 1073 973

K2
log

2.303(1.99) 1073 973

0.63
8.0 103 1073 973

K2
K2 = 0.93
2.303(1.99) 1073 973
0.63
log
Problem 137:
The equilibrium constant for the reaction H2 + I2

2HI; is found to be
64 at 450C. If 6 mole of hydrogen are mixed with 3 mole of iodine in a litre
vessel at this temperature; what will be the concentration of each of the three
components, when equilibrium is attained ?
If the volume of reaction vessel is reduced to half; then what will be the effect
on equilibrium?
Solution:
The given equilibrium reaction is :

H2
+
At t = 0
6
At equilibrium
6x
6x
concentration at
equilibrium
1
I2
3
3x
3 x
1
2HI
0
2x
2x
1
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KC
(2x) 2
(6 x)(3 x)
4x 2
x 2 18 9x
16(x 2 9x 18) x 2
64
On solving x = 2.84
2x 2 2.84
5.68
1
1
6 x 6 2.84
3.16
[H2] =
1
1
3 x 3 2.84
0.16
[I2] =
1
1
[HI] =
In the present reaction n = 0 hence, volume change will not affect the
equilibrium.
Problem 428:
5 gm of PCl5 were completely vaporized at 250C in a vessel of 1.9 litre

capacity. The mixture at equilibrium exerted a pressure of one atmosphere.
Calculate the degree of dissociation KC and Kp for this reaction.
Solution:
No. of mole of PCl5

Weight
5
0.024
=
=
Molecular weight
208.5
The equilibrium for dissociation of PCl5 maybe represented as
PCl5
3
At t = 0
0.024
At equilibrium (0.024 - )
Total moles of gas components
= 0.024 + +
= (0.024 + )
We know,
PV = nRT
1 1.9 = (0.024 + ) 0.0821 523
(0.024 + ) =
= 0.0202
1 .9
0.0821 523
0.0202
= 0.843
0.024
0.024 0.024 0.0202 0.0038
[PCl5] =
1.9
1. 9
1. 9
0.0202
[PCl3] = [Cl2] =
V
1.9
Degree of dissociation =
72

72
0.0202
[ PCl 3 ][Cl 2 ] 1.9
Kc =
0.0038
[PCl 5 ]
1 .9
S
M
C
E
C
H
7
3
2
4.08 10 4
= 0.0565 mole/litre
1.9 0.0038
Kp = Kc (RT) n
Where Kc = 0.0565
n=21=1
Problem 539:
If a mixture of N2 and H2 in the ratio 1 : 3 at 50 atmosphere and 650C

is allowed to react till equilibrium is reached. Ammonia present at equilibrium
was at 25 atm pressure. Calculate the equilibrium constant for the reaction.
N2(g) + 3H2(g)
2NH3(g)
Solution:
Equilibrium of formation of NH3 may be given as,

N2
3H2
3
At t = 0
1
3
At equilibrium (1 - x)
3(1 x)
Total moles at equilibrium = 1 x+ 3 (1 x) + 2x = 4 2x
2x
(4 2x)
2x
2x
p =
50
Partial pressure of NH3 =
(4 2x)
(4 2x)
2x 50
25 =
or = 0.666
(4 2x)
Mole fraction of NH3 =
Kp =
16x 2 (2 x) 2
16 (0.666) 2 ( 2 0.666) 2
=
= 1.677
27p 2 (1 x) 4
27 (50) 2 (0.334) 2
103
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Problem 6410:
16 moles of H2 and 4 moles of N2 are sealed in a one litre vessel. The

vessel is heated at a constant temperature until the equilibrium is established, it
is found that the pressure in the vessel has fallen to 9/10 of its original value.
Calculate
KC for the reaction
N2(g) + 3H2(g)
2NH3(g)
Solution:
The given equilibrium is

At t = 0
At equilibrium
Total gaseous moles at equilibrium
= 4 x + 16 3x + 2x = (20 2x)
Since, pressure has fallen to 9/10 of its original value, hence no. of mole will also
fall up to the same extent.
(20 2x) =
9
20 18
10
x=1
4 x 4 1
3 mole/litre
1
1
16 3x
[H2] =
= 13 mole/litre
1
2x
[NH3] =
= 2 mole/litre
1
[NH3 ]2
22
KC =
= 6.07 104
[N 2 ][H 2 ]3 (3)(13)3
[N2] =
Problem 511:
The value of K for the reaction

O3(g) + OH(g) H(g) + 2O2(g)
Changed from 0.096 at 298K to 1.4 at 373K. Above what temperature will the
reaction become thermodynamically spontaneous in the forward direction
assuming that H0 and S0 values for the reaction do not change with change
in temperature? Given that, S2980 =10.296JK1.
Solution:
We have,
log
K2
H 0 (T2 T1 )
K1 2.303R T1T 2
log
1.4
H 0
373 298
0.096 2.303 8.314 373 298
H0= 33025J
74

74
S
M
C
E
C
H
7
5
Now the temperature above which the forward reaction will be spontaneous is
actually the temperature at which the reaction attains equilibrium, that is, when
K = 1 or log K = 0
G0 = 2.303 RT log K = 2.303 RT log 1.0 = 0
From thermodynamics, we get
G0 = H0 TS0
0 = 33025 T 10.296
or T = 320.75 K
Problem 6712: A mixture of SO3, SO2 and O2 gases is maintained in a 10.0 litre flask at a
temperature at which equilibrium constant Kc for the reaction

2SO2(g) + O2(g)
2SO3(g) is 100.
i) If the number of mole of SO2 and SO3 in the flask are equal how many mole
of O2 are present ?
ii) If the number of mole of SO3 in the flask is twice the number of mole of
SO2,how many mole of O2 are present ?
Solution:
The given equilibrium is

2SO2(g) + O2(g)
2SO3(g)
2
[SO 3 ]
KC
[SO 2 ] 2 [O 2 ]
(i)
i) If [SO3] = [SO2]
Then
[O 2 ]
KC
1
[O 2 ]
1
1
0.01 mole/litre
K C 100
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Total moles of O2 present = 0.01
Q Volume of vessel is 10 litre
10 = 0.1 mole
ii) When [SO3] = [SO2]

Then K C
100
[SO 2 ]2
[SO 2 ]2 [O 2 ]
from Eq. (i)
4
[O 2 ]
[O2] = 4/100 = 0.04 mole/litre

Total moles of O2 in vessel at equilibrium = 0.04
10 = 0.4 mole

Problem 8: The equilibrium constant Kp of the reaction 2SO2(g) + O2(g)
2SO3 (g)
is 900 atm-1 at 800 K. A mixture containing SO 3 and O2 having initial partial
pressures of 1 atm and 2 atm, respectively, is heated at constant volume to
equilibrate. Calculate the partial pressure of each gas at 800K.
Solution:
If 2x is the partial pressure of SO3 that is decreased at equilibrium, we would have

+ O2(g)
2SO3(g)
t=0
2 atm
1 atm
teq
2 atm + x
1 atm 2x
2
( pSO3 )
(1 atm 2 x) 2
900 atm 1
Hence, K p
( pSO2 ) 2 ( pO2 ) (2 x) 2 (2 atm x)
2SO2(g)
0
2x
Assuming x << 2 atm, we get

(1 atm 2 x) 2
(1atm 2 x) 2
1 atm
1
900
atm
1800 or
1 42.43
or
2
2
(2 x) (2 atm)
(2 x)
2x
1
or x =
atm = 0.0115
2 43.43
Hence, p(SO2) = 2x = 0.023 atm; p(O2) = 2 atm + x = 2.0115 atm
and p(SO3) = 1 atm 2x = 0.977 atm

Problem 9: H2S dissociates according to the equation 2H2S (g)
2H2(g) + S2(g). If
is the degree of dissociation of H2S, show that Kp of the reaction is given as

3 p
Kp
2(1 ) 2 (1 / 2)
At 11250C, the value of the is found to be 0.31 when the equilibrium pressure
is 1 atm. Determine the values of Kp and Kc.
76

76
Solution :
S
M
C
E
C
H
7
7
We have
2H2S (g)
2H2 (g) + S2(g)
n(1 - )
n
+ n(/2)
Total amount of gases = n(1 + /2)
1
/2
p; p H 2
p; p S 2
p
Hence, pH 2 S
1 / 2
1 / 2
1 / 2
2
/2

p
p
2
( pH 2 ) ( ps2 ) 1 / 2 1 / 2
3 p
Thus, K p
2
( pH 2 S ) 2
2(1 ) 2 (1 / 2)
1
p
1 / 2
Substituting the given value of , we get
(0.31)3 (1atm)
Kp
2.71102 atm
2(1 0.31) 2 (1 0.31/ 2)
(0.31)3 (1atm)
Kp
2.71102 atm
2(1 0.31) 2 (1 0.31/ 2)
For the given reaction, vg = +1
Hence, Kc = Kp(RT)-vg
= (2.71 10-2 atm) {(0.0821 L atm K-1 mol-1) (1380 K)}-1
= 2.39 10-4 mol L-1

Problem 10: COCl2 gas dissociates according to the equation COCl2
CO + Cl2. When
COCl2 is heated to 724 K at 1atm, the density of gas mixture at equilibrium was
found to be 1.162 g L-1. Calculate (a) the degree of dissociation and (b) Kp of the
reaction.
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Solution :
(a) Let n be the initial amount of COCl2 and be its degree of dissociation. We
will have
COCl2
CO + Cl2
t=0
n
teq
n(1-)
n
n
Total amount of gases = n(1 - ) + n + n = n(1 + )
Now, the volume of the flask would be
n(1 ) RT
V
p
The density of the mixture would be
nM COCl2
nM COCl2 p
pM COCl2
V
n(1 ) RT (1 ) RT
pM COCl2
1
or
=
RT
Substituting the given values, we get
(1atm)(99 g mol 1 )
1 1.433 1 0.433
(1.162 g L1 )(0.0821 L atm K 1mol 1 )(724 K )
(b) The partial pressures of the species involved in the reactions are
1
pCOCl2
p; pCO
p; pCl2
p;
1
1
1
pCO pCl2
2
K
p
Hence, p
pCOCl2
1 2
(0.433) 2
(1atm) 0.231
Which gives K p
1 (0.433) 2
Problem 11: The density of an equilibrium mixture of N2O and NO2 at 1 atm and 348 K is
1.84 g dm-3. Calculate the equilibrium constant of the reaction

N2O4 (g)
2NO2 (g)
Solution:
78
Let n be the amount of N2O4 at t = 0 and let be the degree of dissociation of

N2O4 at equilibrium. Then
N2O4 (g)
2NO2 (g)
t=0
n
0
teq
n(1 - )
n(2)
Total amount at equilibrium = n(1 + )
Using the ideal gas equation, we get

78
S
M
C
E
C
H
7
9
m
(1 ) RT
M
or
pM = (1 + )RT
pM
1
or
=
RT
Substituting the given data, we get
(1 atm)(92 g mol 1 )
1 1.752 1 0.752
=
(1.84 g dm 3 )(0.082 dm3 atm K 1mol 1 )(348K )
pV = n(1 + )RT =
Hence, K p
p 2 NO2
pN 2O4
[2 p /(1 )]2
4 2
4(0.752) 2
(1atm) 5.206atm
(1 ) p /(1 ) 1 2
1 0.752 2
Problem 12: For the reaction, N2O5(g) = 2NO2 (g) + 0.5O2 (g), calculate the mole fraction
of N2O5(g) decomposed at constant volume and temperature, if the initial

pressure is 600 mmHg and the pressure at any time is 960 mm Hg. Assuming
ideal gas behaviour.
Solution:
If p is the partial pressure of N2O5 that has decomposed,

1
N2O5 (g)

2NO2(g) + O2 ( g )
2
600 mmHg p
2p
p/2
Pressure at any time = (600mmHg p) + 2p + p/2 = 600 mmHg + (3/2)p
Equating this to 960 mmHg, we get
p = (2/3) (960 600) mmHg = 244 mmHg
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The mole fraction of N2O5 decomposed would be

244mmHg
x
0.407
600 mmHg
Problem 13: When 3.06 g of solid NH4HS is introduced into a two-litre evacuated flask at
2700C, 30% of the solid decomposes into gaseous ammonia and hydrogen
sulphide. (i) Calculate Kc and Kp for the reaction at 270C. (ii) What would
happen to equilibrium when more solid NH4HS is introduced into the flask?
Solution:
The reaction along with the given data is

NH4HS(s)
NH3(g)
+ H2S(g)
t = 0 3.06g (=0.06 mol)

0
0
teq
0.7 0.06 mol
0.3 0.06 mol
0.3 0.06 mol = 0.018 mol
= 0.018 mol
(i) The equilibrium constant Kc is
0.018 mol 0.018mol
K c [ NH 3 ][ H 2 S ]
8.1105 (mol / L) 2
2
L
2
L
The equilibrium constant Kp is

Kp = Kc (RT)vg = (8.1 10-5 mol2/L2)[(0.082 atm L mol-1K-1)(300 K)]2
= 4.90 10-2 atm2
(ii) There will not be any effect on the equilibrium by introducing more of solid
NH4HS as the equilibrium constant is independent of the quantity of solid.
SECTION - I
LEVEL - I
Objective Single Choice
Problem 713:
A saturated solution of iodine in water contains 0.33g of I 2 per litre of

solution. More than this can dissolve in KI solution because of the following
equilibrium.
I2(aq) + I I3
A 0.1 M KI solution actually dissolves 12.5g of I 2/litre, most of which is
converted to I3. Assuming that the concentration of I2 in all saturated solutions
is the same, calculate the equilibrium constant for the above reaction.
Solution:
I2
Initially
At equb.
12.5
M
254
0.33
M
254
I3
0.1M
0.1M
12.5 0.33
254 254 M
12.17
0.1 254 M
Thus,
80

80
S
M
C
E
C
H
8
1
12.17
[I3 ]
254
K
708
[I 2 ][I ] 0.33 13.23
254 254
For the reaction Ag(CN)2 Ag+ + 2CN, the KC at 25C is 4 1019.

Calculate [Ag+] in solution which was originally 0.1 M in KCN and 0.03 M in
AgNO3.
Problem 814:
Solution:
2KCN + AgNO3
Ag(CN ) 2 + KNO3 + K+
0.1
0.03
0
0
0
(0.1 0.06)
0
0.03
0.03 0.03
[Ag(CN ) 2 ] = 0.03 M
Now use
Ag(CN ) 2
Ag+ + 2CN
0.03
0
0.04
(0.03 a)
a
0.04 + a = 0.04
Since K C is too small and dissociation of Ag(CN ) 2 is very less and thus,
0.04 + a 0.04 and 0.03 a 0.03
[Ag(CN ) 2 ] = 0.03; [Ag+] = a; [CN] = 0.04
[ Ag ][CN ] 2
Now
KC
a = 7.5
[Ag(CN) 2 ]
a (0.04) 2
0.03
1018
Problem 915:
When baking soda is heated in a sealed tube, following equilibrium

exits:
2NaHCO3(s)
Na2CO3(s) + CO2(g) + H2O(g)
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If the equilibrium pressure is 1.04 atm at 398 K, calculate the equilibrium

constant for the reaction at 398 K.
Solution:
Since, there are only two gaseous species in the above equilibrium
p CO 2 p H 2O
1
total total pressure
2
1
1.04 0.52atm
2
K p p CO 2 p H 2O [0.52] 2 =0.2704 atm
82

82
S
M
C
E
C
H
8
3

1
3
NH3(g)
N2(g) +
H2(g)
2
2
Show that degree of dissociation of NH3 is given as :
3 3 P
1
4 K p
1 / 2
where P is equilibrium pressure. If K p of the above reaction is 78.1 atm at

400C, calculate KC.
Solution:
1
N2(g) +
2
NH3(g)
moles
Initial moles t = 0
Moles equilibrium
Partial pressure
1
1
/2
p
1
p
2(1 )
3
H2(g). Total
2
0
3 /2
1
1+
3
p
2(1 )
[ N 2 ]1 / 2 [ H 2 ]3 / 2
Kp
[ NH 3 ]
1/ 2
3
p
p
2(1 )
2(1 )
1
1 p
3/ 2
p 2
27
4(1 2 )
Solving for ` we get :
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84
3 3 p
1
4 K p
1/ 2
We know,
K p K C (RT ) n
78.1 = K C (0.0821 673)1

KC = 1.413 moles litre1
OBJECTIVE
Problem 1: A reaction mixture containing H2, N2 and NH3 has partial pressures 2 atm, 1
atm and 3 atm respectively at 725 K. If the value of K p for the reaction, N2(g) +
3H2(g)
2NH3(g) is 4.28 105 atm2 at 725 K, in which direction the net
reaction will go ?
(a) Forward
(b) Backward
(c) No net reaction
(d) Direction of reaction cannot be predicted.
P
=
P P
2
Solution:
Qp
NH3
N2
H2
(3) 2
9
atm 2 = 1.125 atm2.
3
(1)(2)
8
Since value of Qp is larger than Kp (4.28 105 atm2), it indicates net reaction will
proceed in backward direction.
(b)
Problem 2: An equilibrium system for the reaction between hydrogen and iodine to give
hydrogen iodide at 765 K in a 5 litre volume contains 0.4 mole of hydrogen, 0.4
mole of iodine and 2.4 moles of hydrogen iodide. The equilibrium constant for
the reaction is:
2HI(g), is
H2(g) + I2(g)
(a) 36.0
(b) 15.0
(c) 0.067
(d) 0.028.
Solution:
The concentration of various species at equilibrium are :

0.4
[H2] =
= 0.08 mol L1
5
0.4
[I2] =
= 0.08 mol L1
5
2.4
[HI] =
= 0.48 mol L1
5
[HI]2
K
[H 2 ][I 2 ]
84

84
S
M
C
E
C
H
8
5
Substituting the various values in the above expression of K, we get

(0.48) 2
K
36.0 .
(0.08)(0.08)
(a)
Problem 3: 2.0 mol of PCl5 were introduced in a vessel of 5.0 L capacity at a particular
temperature. At equilibrium, PCl5 was found to be 35% dissociated into PCl 3

and Cl2. The value of Kc for the reaction is
(a) 1.89
(b) 0.377
(c) 0.75
(d) 0.075.
Solution:
2 35
= 0.7
100
Moles of PCl5 left undissociated = 2 0.7 = 1.3 mol
1.3
0.7
0.7
[PCl5] =
M, [PCl3] =
M, [Cl2] =
M
5
5
5
0.7 0.7
[PCl3 ][Cl 2 ] 5
5 0.75
K
(c)
[PCl5 ]
1.3

5
Moles of PCl5 dissociated =
Problem 4: K1 and K2 are equilibrium constant for reactions (1) and (2)
N2(g) + O2(g)
2NO(g)
1
1
NO(g)
N2(g) + O2(g)
2
2
Then,
(1)
(2)
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1
(a) K1
K 2
1
(c) K1
K2
Solution:
N2 + O2
2NO
2NO
N2 + O2
1
N2 O2
NO
2
(b) K1 K 2
0
(d) K1 (K 2 ) .
K1
1
K1
1
K2
K1
1/ 2
1/ 2
1
1
2
K2
or K 2
K1
K1
1
K1
(a)
(K 2 ) 2
2HI(g)
H2(g) + I2(g)
The degree of dissociation ( ) of HI(g) is related to equilibrium constant, K p by
the expression
1 2K p
1 2 Kp
(a)
(b)
2
2
2 2K p
2K p
(c)
(d)
1 2K p
1 2 K p
Solution:
2HI(g)
H2(g) + I2(g)
1
2
2
2

PT
2
Kp
(1 ) 2 PT2
2 Kp
1
2 Kp
1 2 K p
(d)
86

86
S
M
C
E
C
H
8
7
Problem 6: In a reversible reaction, study of its mechanism says that both the forward and
reverse reaction follows first order kinetics. If the half life of forward reaction
(t1/2)f is 400 sec and that of reverse reaction (t1/2)r is 250 sec. The equilibrium
constant of the reaction is
(a) 1.6
(b) 0.433
(c) 0.625
(d) 1.109
Solution:
0.693
0.693
sec 1 ; K r
sec 1
400
250
k f 250
K
0.625
k r 400
(c)
Kf
Problem 7: At temperature T, a compound AB 2(g) dissociates according to the reaction
2AB2(g)
2AB(g) + B2(g) with degree of dissociation , which is small
compared with unity. The expression for K p, in terms of and the total
pressure, PT is
PT 3
(a)
2
P 3
(c) T
3
Solution:
PT 2
(b)
3
P 2
(d) T .
2
For the given equilibrium, the equilibrium concentration are

2AB2(g)
2AB(g) + B2(g)
c
Equilib. conc. c(1 )
c
2
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c
3 PT
(c) 2 PT
K
2
KP
; P
2(1 ) 2 1
(PAB2 )
[c(1 )]2 [c(1 )]
2
Since, is small compared to unity, so 1 ; 1 and 1 + ; 1 .

2
3
PT
KP
2
(a)
(PB2 )(PAB ) 2

Problem 8: For the reaction: NH2COONH4(s)
2NH3(g) + CO2(g)
The equilibrium constant Kp = 2.9 105 atm3. The total pressure of gases at
equilibrium when 1.0 mole of reactant was heated will be
(a) 0.0194 atm
(b) 0.0388 atm
(c) 0.058 atm
(d) 0.0667 atm
Solution:
NH2COONH4(s)
2NH3(g) CO2(g)
Moles initially
1
0
0
Moles at equib.
(1 x)
2x
x
Total moles of gaseous substances at equilibrium = 3x
Equilibrium pressure = PT
2
P
PNH3 PT , PCO2 T
3
3
2
K P (PNH3 ) PCO2
4(PT )3
2.9 10
27
PT = 0.058 atm
5
(c)
Problem 9: In equilibrium reaction, x moles of the reaction A decompose to give 1 mole
each of C and D. If the fraction of A decomposed at equilibrium is independent

of initial concentration, then the value of x would be
(a) 1
(b) 2
(c) 3
(d) 4
Solution:
The fraction of A decomposed at equilibrium is independent of initial

concentration means the equilibrium constant expression is free from
concentration term. The equilibrium reaction is
xA
C
+
D
Initial conc.
c
0
0
88

88
Conc. at. equil.
c(1 )
S
M
C
E
C
H
8
9
c
x
c
x
c c

[C][D] x
(c) 2
x
KC
[A]x
[c(1 )]x
x 2 [c(1 )]x
The expression of KC would be free from concentration term only when value of
x is 2. Putting x = 2, gives
c2 2
2
KC
4[c(1 )]2 4(1 ) 2

(b)
Problem 10: At a certain temperature the following equilibrium is established,
CO(g) + NO2(g)
CO2(g) + NO(g).
One mole of each of the four gases is mixed in one litre container and the
reaction is allowed to reach equilibrium state. When excess of baryta water is
added to the equilibrium mixture, the weight of white precipitate obtained is
236.4 g. The equilibrium constant, KC of the reaction is
(a) 1.2
(b) 2.25
(c) 2.1
(d) 3.6.
Solution:
CO(g) + NO2(g)
CO2(g) + NO(g).
Moles initially
1
1
1
1
Moles at equib.
1x
1x
1+x
1+x
CO2 + Ba(OH)
BaCO3 + H2O
2
236.4
1.2
Moles of BaCO3 =
197
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Moles of CO2 at equilibrium = 1.2 or,
2
2
1 x 1.2
KC

2.25
1 x 0.8
1 + x = 1.2; x = 0.2
(b)
Assignments (New Pattern)

Single Choice Questions
SECTION I
Level - I
1.
In a vessel containing SO3, SO2 and O2 at equilibrium, some helium gas is introduced so
that the total pressure increases while temperature and volume remains constant.
According to Le Chateliers principle, the dissociation of SO3
(c) remains unaltered
(a) increases (b) decreases

(d) changes unpredictably.
2.
In the reaction, N2(g) + 3H2(g)

2NH3 (g)
the value of the equilibrium constant depends on
(a) volume of the reaction vessel
(b) total pressure of the system
(c) the initial concentration of nitrogen and hydrogen
(d) the temperature
3.
The reaction in which the yield of the products cannot be increased by the application of
high pressure is
(c) N2 (g) + 3H2 (g)

2NH3 (g)
4.
(a) PCl3 (g) + Cl2(g)

PCl5(g)
(b) N2 (g) + O2(g)
2NO(g)
(d) 2SO2 (g) + O2(g)
2SO3(g)
In the equilibrium reaction involving the dissociation of CaCO3

CaCO3 (s)
CaO (s) + CO2 (g)
the equilibrium constant is given by
90

90
(a)
(c)
5.
PCaO PCO2
PCaCO3
PCaO
PCaCO3
S
M
C
E
C
H
9
1
(b) CCaO
PCO2
CCaCO3
(d) PCO2
Consider the reaction, PCl5 (g)

PCl3 (g) + Cl2(g) in a closed container at
equilibrium at a fixed temperature. What will be the effect of adding more PCl5 on the
equilibrium concentration of Cl2 (g) ?
(a) it decreases
(b) it increases
(c) it remains unaffected
(d) it cannot be predicted without the value of Kp.
6.
7.
G (HI, g) ; +1.7 kJ, what is the equilibrium constant at 250C for

2HI (g)
H2(g) + I2(g) ?
(a) 24.0
(b) 3.9
(c) 2.0
(d) 0.5
In a reversible reaction, two substances are in equilibrium. If the concentration of each
one is doubled, the equilibrium constant will be
(a) reduced to half of its original value
(b) reduced to one fourth of its original value
(c) Doubled
(d) Constant.
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8.
For which of the following systems at equilibrium at constant temperature, doubling the
volume will cause a shift to the right
(a) H2(g) + Cl2 (g)
(b) 2CO(g) + O2 (g)
2HCl(g)
2CO2(g)
(c) N2 (g) + 3H2 (g)
(d) PCl5 (g)
2NH3 (g)
PCl3(g) + Cl2 (g)
9.
In a reaction, A + 2B 2C, 2.0 mole of A, 3.0 mole of B and 1.0 mole of C are
placed in a 2.0L flask and the equilibrium concentration of C is 1.0 mole/L. The
equilibrium constant (K) for the reaction is:
(a) 0.33
(b) 1.33
(c) 0.44
(d) 0.6
10.
In a system A (s)
2B (g) + 3C (g). If the concentration of C at equilibrium is
increased by a factor 2, it will cause the equilibrium concentration of B to change to:
(a) two times of its original value
(b) one half of its original value
(c) 2
times of its original value
(d)
1
2 2
times of its original value
1
.
In a chemical reaction Kp is greater than Kc when

(a) the number of molecules entering into the chemical reaction is more than the number
of molecules produced.
(b) the number of molecules entering into the chemical reaction is the same as the
number of molecules produced.
(c) the number of molecules entering into the chemical reaction is less than the number
of molecules produced.
(d) the total number of moles of reactants is less than the number of moles of products.
11
2.
Which of the following statements is not correct about the equilibrium constant ?
(a) Its value does not depend upon the initial conc. of the reactants
(b) Its value does not depend upon the initial conc. of the products
(c) Its value does not depend upon nature of the reactants.
(d) Its value does not depend upon presence of catalyst.
3.
An acid reacts with glycerine to form complex and equilibrium is established. If the heat
of reaction at constant volume for above reaction is 1200 cal more than at constant
pressure and the temperature is 300 K, then which of the following expression is true ?
(a) K p K c
(b) K c K p
(c) K p K c
(d) none of these.
92

92
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4.
The equilibrium constant for the reaction,

N2(g) + O2(g)
2NO(g) is 4 104
at 2000 K. In presence of a catalyst, equilibrium is attained ten times faster. Therefore,
the equilibrium constant, in presence of the catalyst, at 2000 K is
(a) 40 104
(b) 4 104
3
(c) 4 10
(d) difficult to compute without more data.
125.
At a given temperature, the equilibrium constant for the reaction,

PCl5 (g)
PCl3(g) + Cl2 (g)
is 2.0 103. At the same temperature, the equilibrium constant for the reaction,
PCl3(g) + Cl2(g)
PCl5 (g) will be
3
(a) 2.0 10
(b) 2.0 103
2
(c) 5.0 10
(d) 5.0 103.
136.
In which of the following does the reaction go almost to completion ?

(a) K = 106
(b) K = 103
6
(c) K = 10
(d) K = 1012.
147.
When pressure is applied to the equilibrium system

Ice
Water
which of the following phenomenon will happen ?
(a) More ice will be formed
(b) Water will evaporate
(c) More water will be formed
(d) Equilibrium will not be disturbed.
8.
Which of the following is not favourable condition for the formation of SO3?
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2SO2(g) + O2(g)
2SO3(g); H = 188 kJ
(a) High pressure
(c) Decreasing [SO3]
(b) High temperature

(d) Increasing [SO2].
XY2 dissociates as XY2(g)

XY(g) Y(g) . When the initial pressure of XY2 is 600
mm of Hg, the total pressure developed is 800 mm of Hg. K p for the reaction is
159.
(a) 200
(c) 100
(b) 50
(d) 150.
1610. The reactions

PCl5(g)
PCl3(g) Cl2(g) and COCl2(g)
CO(g) Cl2(g)
are simultaneously in equilibrium in an equilibrium box at constant volume. A few moles
of CO(g ) are later introduced into the vessel. After some time, the new equilibrium
concentration of
(a) PCl5 will remain unchanged
(b) Cl2 will be greater
(c) PCl5 will become less
(d) PCl5 will become greater.
A
vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO 2 is converted
into CO on the addition of graphite. The value of K p if the total pressure at equilibrium is
0.8 atm is
(a) 1.8 atm
(b) 3 atm
(c) 0.3 atm
(d) 0.18 atm
.
1711. PCl5 is 50% dissociated into PCl3 and Cl2 at one atmosphere. It will be 40% dissociated
at :
(a) 1.75 atm
(b) 1.84 atm
(c) 2.00 atm
(d) 1.25 atm.
1812. One mole of N 2 O 4(g) at 300 K is kept in a closed container under one atmosphere. It is
heated to 600 K when 20% of N 2 O 4(g ) decomposes to NO 2(g) . The resultant pressure is
(a) 1.2 atm
(c) 2.0 atm
(b) 2.4 atm

(d) 1.0 atm.
1913. For the reversible reaction, N 2(g) 3H 2(g)

2NH 3(g) at 500C, the value of K p is
5
1.44 10 when partial pressure is measured in atmospheres. The corresponding value
of K c with concentration in mole litre 1 , is
(a) 1.44 10 5 /(0.082 500) 2
(c) 1.44 10 5 /(0.082 773) 2
(b) 1.44 10 5 /(8.314 773) 2

(d) 1.44 10 5 /(0.082 773) 2 .
94

94
214.
For the reaction : 2HI(g)

H 2(g) I 2(g) ; the degree of dissociation ( ) of HI(g) is
related to equilibrium constant K p by the expression
(a)
(c)
105.
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M
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E
C
H
9
5
1 2 Kp
2
2K p
1 2K p
(b)
(d)
1 2K p
2
2 Kp
1 2 Kp
Sulphide ions is alkaline solution react with solid sulphur to form polyvalent sulphide
ions. The equilibrium constant for the formation of S22- and S32- from S and S2- ions are
1.7 and 5.3 respectively. Equilibrium constant for the formation of S32- from S22- and S is:
(a) 1.33
(b) 3.11
(c) 4.21
(d) 1.63
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For which of the following reactions, the degree of dissociation cannot be calculated from the
vapour density data
I 2HI(g)
II 2NH 3(g)
H 2(g) I 2(g)
N 2(g) 3H 2(g)
III 2NO(g)
N 2(g) O 2(g)
IV PCl5(g)
PCl3(g) Cl2(g)
(a) I and III

(c) I and II
(b) II and IV
(d) III and IV.
Level - II
116.
At 30C, Kp for the dissociation reaction

SO2Cl2(g)
SO2(g) + Cl2(g)
2
is 2.9 10 atm. If the total pressure is 1 atm, the degree of dissociation of SO2Cl2 is
(a) 87%
(b) 13%
(c) 17%
(d) 29%
2.
The oxidation of SO2 by O2 to SO3 is an exothermic reaction. The yield of SO3 will be
maximum if
(a) temperature is increased and pressure is kept constant
(b) temperature is reduced and pressure is increased
(c) both temperature and pressure are increased
(d) both temperature and pressure are reduced.
17.
A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted
into CO on the addition of graphite. The value of K if the total pressure at equilibrium is
0.8 atm is
(a) 1.8 atm
(b) 3 atm
(c) 0.3 atm
(d) 0.18 atm
138.
In the reaction PCl5 PCl3 + Cl2, the amounts of PCl5, PCl3 and Cl2 at equilibrium are
2 mole each and the total pressure is 3 atm. The equilibrium constant Kp is
(a) 1.0 atm
(b) 2.0 atm
(c) 3.0 atm
(d) 6.0 atm
149.
When 20g of CaCO3 were put into 10 litre flask and heated to 800C, 35% CaCO3
remained unreacted at equilibrium, Kp for decomposition of CaCO3 is
(a) 1.145 atm
(b) 0.145 atm
(c) 2.145 atm
(d) 3.145 atm
520.
The decomposition of N2O4 to NO2 is carried out at 280C in chloroform. When

equilibrium is reached, 0.2 mol of N2O4 and 2 103 mol of NO2 are present in 2 litre
solution. The equilibrium constant for the reaction, N 2 O 4 2NO 2 is
96

96
6.
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9
7
(a) 1 103
(c) 1 105
(b) 2 103
(d) 2 105
For the reaction :

H2(g) + I2 (g) 2HI (g)
the equilibrium constant Kp changes with
(a) total pressure
(c) the amounts of H2 and I2 present
(b) catalyst
(d) temperature
21.
(a) 0.33
(b) 1.33
(c) 1.66
(d) 0.6
722.
Two moles of an equimolar mixture of two alcohols, R 1 OH and R 2 OH are

esterified with one mole of acetic acid. If 80% of the acid is consumed and the quantities
of ester formed under equilibrium are in the ratio of 3 : 2, the value of the equilibrium
constant for the esterification of R1 OH with acetic acid is
(a) : 3.3
(b) : 3.7
(c) : 3.5
(d) : 3.9 .
23.
In a reversible reaction, study of its mechanism says that both the forward and backward
reactions follow first order kinetics. If the half life of forward reaction (t1/ 2 )f is 400 sec.
and that of backward reaction (t1/ 2 ) b is 250 sec. The equilibrium constant of the
reaction is CO(g) NO 2(g)
CO 2(g) NO(g)
(a) 1.6
(b) 0.433
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(c) 0.625
(d) 1.109.
The CaCO3 is heated in a closed vessel of volume 1 litre at 600 K to form CaO and CO 2
. The minimum weight of CaCO3 required to establish the equilibrium
CaCO3(s)
CaO(s) CO 2(g) is (K p 2.25 atm)
24.
(a) 2g
(c) 10g
(b) 4.57 g
(d) 100 g.
For the reaction: 2AB(g)

A 2(g) B2(g) ; the degree of dissociation ( ) of HI(g) is
8.
(a)
(c)
1 2 Kp
2
2K p
1 2K p
(b)
(d)
1 2K p
2
2 Kp
1 2 Kp
9.
Two moles of an equimolar mixture of two alcohols, R1 OH and R 2 OH are

constant for the esterification of R 1 OH with acetic acid is
(a) : 3.3
(b) : 3.7
(c) : 3.5
(d) : 3.9 .
10.
reactions follow first order kinetics. If the half life of forward reaction (t1/ 2 ) f is 400 sec.
and that of backward reaction (t1/ 2 )b is 250 sec. The equilibrium constant of the
CO 2(g) NO(g)
(a) 1.6
(c) 0.625
(b) 0.433
(d) 1.109.
11.
Steam at pressure of 1 atm is passed through a furnace at 2000 K wherein the reaction
H 2 O(g)
K p 6.4 10 5 occurs. The percentage of oxygen in the
H 2(g) 1 2 O 2(g) ;
exit stream would be
(a) 0.32
(b) 0.08
(c) 0.04
(d) 0.16
LEVEL - II
More than one choice
98

98
25.
H 2 O(g)
H 2(g) 1 2 O 2(g) ;
(a) 0.32
(c) 0.04
SECTION III
1.
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9
9
(b) 0.08
(d) 0.16
May be mMore than one choice
The dissociation of ammonium carbamate onate may be represented by the reaction

NH 4 CONH 2(g)
2NH 3(g) CO 2(g)
H for the forward reaction is negative. The equilibrium will shift from right to left if
there is
(a) a decrease in pressure
(b) an increase in temperature
(c) an increase in the concentration of ammonia
(d) an increase in the concentration of carbondioxide
22.
Catalyst
2NH 3 heat
N 2(g) 3H 2(g) 500
C
In the above reaction, the direction of equilibrium will be shifted to the right by
(a) increasing the concentration of nitrogen
(b) compressing the reaction mixture
(c) removing the catalyst
(d) decreasing the concentration of ammonia
3.
The equilibrium of which of the following reactions will not be disturbed by the addition
of an inert gas at constant volume
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3.
5.
6.
7.
8.
(a) H 2(g) I 2(g)

2HI(g)
(b) N 2O 4(g)
2NO 2(g)
(c) CO(g) 2H 2(g)

CH3OH (g)
(d) C(s) H 2 O (g)

CO (g) H 2(g)
For the chemical reaction 3X (g) + Y(g) X3Y(g), the 4.

following factors will increase solubility of NH3(g) in H2O
NH 3(g) H 2 O (aq)
NH 4OH (aq)
Which of the
(a) increase in pressure

(b) addition of water
(c) liquefaction of NH3
(d) decrease in pressureamount of X3Y at
equilibrium is affected by
(a) temperature and pressure
(b) temperature only
(c) By adding X(g) and Y(g)
(d) by adding catalyst.
The condition for spontaneity in a chemical reaction is
(a) (G)T, P 0
(b) (U)S, V 0
(c) (H)S, P 0
(d) (S)U, V 0
For the gas phase reaction C2H4(g) + H2(g)
C2H6(g); H = 32.7 kcal carried out in
a vessel, the equilibrium concentration of C2H4 can be increased by
(a) increasing temperature
(b) decreasing pressure
(c) removing some H2
(d) adding some C2H6
When NaNO3 is heated in a closed vessel, O 2 is liberated and NaNO2 is left behind. At
equilibrium.
(a) addition of NaNO2 favours reverse reaction
(b) addition of NaNO3 favours forward reaction
(c) increasing temperature favours forward reaction
(d) increasing pressure favours forward reaction
For which of the following reactions is the equilibrium constant called an acidity
constant?
(a) 2H 2 O
(b) H 2S H 2O
H 3O OH
H 3O HS
(c) HONO H 2O
ONO H 3O
(d) H 3O CH 3 NH 2
CH3 NH 3 H 2 O
49.
For which of the following statements about the reaction quotient, Q, are correct?
(a) the reaction quotient, Q, and the equilibrium constant always have the same
numerical value
(b) Q may be >< = Keq
(c) Q (numerical value) varies as reaction proceeds
(d Q = 1 at equilibrium
5.
Which of the following statements about the reaction quotient Q, are correct ?
(a) The reaction quotient Q, and the equilibrium constant always have the same numerical
value
(b) Q may be > < = Keq.
(c) Q (numerical value) varies as reaction proceeds
(d) Q = 1 at equilibrium
100

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1
10.
Which represents variation of Keq with temperature

H
H
(a) log e K eq =constant(b) log10 K eq =constantRT
RT
d log10 K eq H
d log e K eq H
(c)
(d)
dt
R T2
dt
R T2
611.
Which of the following factors will affect solubility of CaO in H2O?

(a) pressure
(b) temperature
(c) addition of water
(d) volume
12.
For the following equilibrium

NH 4 HS(s)
NH 3 (g) H 2S(g)
partial pressure of NH3 will increase:
(a) if NH3 is added after equilibrium is established
(b) if H2S is added after equilibrium is established
(c) temperature is increased
(d) volume of the flask is indecrcreased
The dissociation of ammonium carbonate may be represented by the reaction
A 2 B(s)
2A(g) CO 2 (g)
713.
14.
H for the forward reaction is negative. The equilibrium will shift from right to left if
there is
(a) a decrease in pressure
(b) an increase in temperature
(c) an increase in the concentration of ammonia
(d) an increase in the concentration of carbondioxide
Which are true statements for the following equilibrium?
H 2 O(l)
H 2O (g)
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(a)
(b)
(c)
(d)
increase in pressure will result in the formation of more liquid water

increase in pressure will increase boiling point
decrease in pressure will vaporize H2O(l) to a greater extent
increase in pressure will liquefy steam.
15.
Which is/are correct relation(s) for thermodynamic equilibrium constant?

(a) G = 2.303 RT logK
(b) G = G + 2.303 RT logK
0.0591
0.0591
0
0
log K
log K
(c) E cell
(d) E E
n
n
816.
Which is/are correct relation(s) for equilibrium constant K?In presence of a catalyst, what
happens to the chemical equilibrium ?
(a) Energy of activation of the forward and backwards reactions are lowered by same
amount
(b) Equilibrium amount is not disturbed
(c) Rates of forward and reverse reaction increase by the same factor
(d) More product is formed.
(a) G = 2.303 RT logK
(c) K
917.
[product]
[reactant]
2.303RT log K
nF
(d) log K log A
H
2.303RT
Volume of the flask in which species are transferred is double of the earlier flask. In
which of the following cases, equilibrium constant is affected?
(a) N 2(g) 3H 2(g)
(b) N 2(g) O 2
2NH3(g)
2NO(g)
(c) PCl5(g)
PCl3(g) Cl2(g)
10.
0
(b) E cell
(d) 2NO
N 2(g) O 2(g)
Constant the following equilibrium in a closed container

N2O4 (g) 2NO2 (g)
At a fixed temperature, the volume of the reaction container is halved. For this change,
which of the following statements holds true regarding the equilibrium constant (Kp) and
degree of dissociation () ?
(a) neither Kp and nor changes
(b) both Kp and change
(c) changes
(d) Kp does not change
LEVEL III
Other Engg. Exams
SECTION III
Other Engg. Exams Questions
102

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3
1.
AB2 dissociates as
AB2 (g)
AB(g) + B(g)
When the initial pressure of AB2 is 600 mm Hg, the total equilibrium pressure is 800 mm
Hg. Calculate K for the reaction assuming that the volume of the system remains
unchanged.
(a) 50
(b) 100
(c) 166.6
(d) 400.0
2.
The state of equilibrium refers to

(a) State of rest
(c) Stationary state
3.
(b) Dynamic state

(d) State of inertness
Consider the two gaseous equilibria involving SO 2 and the corresponding equilibrium
constants at 298 K
SO2 (g) +
1
O 2 (g)
SO3 (g)
2
. . . . .K1
2SO3 (g)
. . . . K2
2SO2 (g) + O2(g)
The values of the equilibrium constants are related by
(a) K2 = K1
(b) K2 = K12
1
1
(c) K2 = 2
(d) K 2
K1
K1
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4.
The factor which changes equilibrium constant of the reaction

A2 (g) + B2 (g)
2AB (g) is
(a) Total pressure
(b) Amounts of A2 and B2
(c) temperature
(d) Catalyst
5.
The reaction, SO2 + Cl2

SO2 Cl2 is exothermic and reversible. A mixture of SO2
(g), Cl2(g) and SO2Cl2 (l) is at equilibrium in a closed container. Now a certain quantity
of extra SO2 is introduced into the container, the volume remaining the same. Which of
the following is true ?
(a) The pressure inside the container will not change
(b) The temperature will not change
(c) The temperature will increase
(d) The temperature will decrease.
6.
At a certain temperature 2HI

H2 + I2, only 50% HI is dissociated at equilibrium.
The equilibrium constant is
(a) 0.25
(b) 1.0
(c) 3.0
(d) 0.5
7.
If is the fraction of HI dissociated at equilibrium in the reaction,

2HI (g)
H2 (g) + I2 (g), starting with 2 moles of HI, the total number of moles of
reactants and products at equilibrium are
(a) 1 +
(b) 2 + 2
(c) 2
(d) 2 -
8.
In a reaction N2 + 3H2
2NH3, the yield of NH3 increases on
(a) increasing the temperature
(b) increasing pressure
(c) increasing temperature as well as pressure
(d) decreasing temperature as well as pressure
9.
In a reaction A + 2B
2C, If 2.0 moles of A, 3.0 moles of B and 2.0 moles of C
are placed in a flask of 2L capacity and equilibrium concentration of C is 0.5 mol L-1.
The value of equilibrium constant Kc of the reaction is
(a) 0.073
(b) 0.147
(c) 0.05
(d) 0.026
10.
In a reaction A + B
C + D, the initial concentration of A and B were 0.9 mol.
-3
dm each. At equilibrium the concentration of D was found to be 0.6 mol dm-3. What is
the value of equilibrium constant for the reaction ?
(a) 8
(b) 4
(c) 9
(d) 3
104

104
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11.
For the reaction C(s) + CO2(g)

2CO(g) the partial pressure of CO2 and CO are
2.0 and 4.0 atm respectively at equilibrium. What is the value of Kp for this reaction ?
(a) 0.5 atm
(b) 4.0 atm
(c) 8.0 atm
(d) 32.0 atm
12.
Kp/Kc for the reaction,

1
CO (g) + O 2 ( g )
CO2 (g), is
2
(a) 1
1
(c)
RT
(b) RT
(d) (RT)1/2
13.
The reaction 2SO2 + 2O2

2SO3, H = -ve, will be favoured by
(a) high temperature and low pressure
(b) low temperature and high pressure
(c) low temperature and low pressure
(d) high temperature and high pressure
14.
A reaction is A + B
C + D. Initially we start with equal concentrations of A and
B. At equilibrium we find that the moles of C is two times of A. What is the equilibrium
constant of the reaction ?
(c) 4
15.
(a) 1/4
(d) 2
(b) 1/2
5 moles of SO2 and 5 moles of O2 are allowed to react to form SO3 in a closed vessel. At
the equilibrium stage 60% of SO2 is used up. The total number of moles of SO2, O2 and
SO3 in the vessel now is
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(a) 3.9
(c) 10.5
(b) 8.5
(d) 10.0
SECTION - II
LEVEL - I
Subjective
1.
At a certain temperature, equilibrium constant (K c) is 16 for the reaction

SO2 (g) + NO2(g)
SO3(g) + NO(g)
If we take one mole of all the four gases in a one litre container, what would be the
equilibrium concentrations of NO and NO2?
2.
Show that for the reaction AB(g)

A (g) B(g) , the total pressure at which AB is 50%
dissociated is numerically equal to three times of Kp.
3.
PCl5(g) at 500K at an initial pressure of 600 mm Hg dissociates as :

PCl5
PCl3 + Cl2 and the equilibrium pressure is 800 mm Hg at 500 K. Calculate K P
for the reaction assuming that no change in volume takes place.
4.
Gaseous NO2 forms N2O4 according to the reaction

2NO2(g)
N2O4(g)
when 0.10 mole of NO2 is added to 1.0 L flask at 25C, the concentration changes so that
at equilibrium, [NO2] = 0.016 M and [N2O4] = 0.042M.
a) What is the value of the reaction quotient before any reaction occurs?
b) What is the value of the equilibrium constant?
5.
For the following reaction,

PCl5(g)
PCl3(g) + Cl2(g)
0.4 mole of PCl5, 0.2 mole of PCl3 and 0.6 mole of Cl2 are taken in 1L flask. If Kc = 0.2
predict the direction in which reaction proceeds,
6.
The equilibrium constant Kc for the reaction

2NOg) + O2(g)
2NO2(g)
5
is 6.9 10 at 500K. A 5.0 L reaction vessel at this temperature was filled with 0.060
mole NO, 1.0 mole of O2 and 0.80 mole of NO2.
a) Is the reaction mixture at equilibrium? If not, in which direction does the reaction
proceed?
b) What is the direction of the reaction if the initial amounts are 5.0 10 3 mole NO,
0.20 mole of O2 and 4.0 moles of NO2?
c) Can reaction quotient be zero for the case in (b)?
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7.
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What is relation between Kp and Kc in the following equilibria?

a) CaCO3(s)
CaO(s) + CO2(g)
b) H2O(l)
H2O(g)
c) 3Fe(s) + 4H2O(g)
Fe3O4(s) + 4H2(g)
8.
The value of Kc for the following reaction at 900C is 0.28:

CS2(g) + 4H2(g)
CH4(g) + 2H2S(g)
What is Kp at this temperature?
9.
One mole of nitrogen is mixed with three moles of hydrogen in a 4-litre container. If
0.25% of nitrogen is converted to ammonia by the following reaction:
N2 (g) + 3H2 (g)
2NH3 (g)
calculate the equilibrium constant Kc. What will be the value of Kc for the following
equilibrium ?
1
3
N2(g) +
H2(g)
NH3(g)
2
2
10.
Consider the following heterogeneous equilibrium at 300 K :

NH4HS (s)
NH3(g) + H2S (g)
The total pressure of equilibrium mixture is 0.5 atm calculate Kp and Kc for the reaction.
LEVEL - II
1*.
Subjective
To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 1.09 M Fe 2+ solution and
the reaction is allowed to reach on equilibrium at 25C.
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3
Ag (aq) Fe2(aq)
Fe (aq) Ag (s)
For 25 mL of the solution, 30mL of 0.0832 M KMnO4 were required for oxidation.
Calculate equilibrium constant for the reaction at 25C.
2.
One mole of N2 and 3 mol of PCl5 placed in a 100 litre vessel are heated to 2270C. The
equilibrium pressure is 2.05 atm. Assuming ideal behaviour, calculate the degree of
dissociation of PCl5 and Kp for the reaction
PCl5(g)
PCl3 (g) + Cl2(g)
3.
What is the vapour density of mixture of PCl 5 at 250C when it has dissociated to the
extent of 80%.
4.
For the equilibrium

2
LiCl 3NH 3(s)
LiCl NH 3(s) 2NH 3 (g), K p 9 atm
at 40C. A 5 litre vessel contains 0.1 mole of LiClNH3. How many mole of NH3 should
be added to the flask at this temperature to derive the backward reaction for completion?
5*.
Consider the reaction SO 2 Cl 2 (g)

equilibrium constant for the reaction is 0.0032. It was observed that concentration of the
three species is 0.050 mol/lit. each at a certain instant. Discuss what will happen in the
reaction vessel?
6.
In an experiment starting with 1 mole C 2H5OH, 1 mole CH3COOH and 1 mole of water,
the equilibrium mixture on analysis shows that 54.3% of the acid is esterified.
Calculate Kc.
7.
0.15 mol of CO taken in a 2.5 L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place; CO(g) + 2 H 2 (g)
CH3OH(g) . Hydrogen is
introduced unitl the total pressure of the system is 8.5 atm. At equilibrium 0.08 mol of
methanol is formed. Calculate:
i) K p and K c
ii) The final pressure if the same amount of CO and H 2 as before are used but no
catalyst so that the reaction does not take place.
8*.
At some temperature and under a pressure of 4 atm. PCl 5 is 10% dissociated. Calculate
the pressure at which PCl5 will be 20% dissociated, temperature remaining same.
9.
When NO and NO2 are mixed, the following equilibria are readily obtained;
-1
2NO2
N2O4 Kp = 6.8 atm
and
NO + NO2
N2O3
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9
In an experiment when NO and NO2 are mixed in the ratio of 1: 2, the final total pressure
was 5.05 atm and the partial pressure of N2O4 was 1.7 atm. Calculate:
(a) The equilibrium partial pressure of NO
(b) Kp for NO + NO2
N2O3
10*.
NO and Br2 at initial pressures of 98.4 and 41.3 torr respectively were allowed to react at
300K. At equilibrium the total pressure was 110.5 torr. Calculate the value of equilibrium
constant , Kp and the standard free energy change at 300K for the reaction
2NO(g) Br2(g)
2NOBr(g)
SECTION IV
Mathc the Column
SECTION - III
A
Matrix-Match Type
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This section contains 2 questions. Each question contains statements given in two
column which have to be matched. Statements (A, B, C, D) in Column I have to be
matched with statements (p, q, r, s) in Column II. The answers to these questions
have to be appropriately bubbles as illustrated in the following example.
If the correct matches are Ap, As, Bq, Br, Cp, Cq and Ds, then the
correctly bubbled 4 4 matrix should be as follows :
1.
2.
Match the chemical reaction in equilibrium (in List I) with the pressure dependent of
degree of dissociation of the reaction (in List II):
List Column - I
List IIColumn - II
(aA) N2(g) + 3H2 (g)

2NH3 (g)
(Bb) 2SO2(g) + O2 (g)
2SO3 (g)
(p) x P
(Cc) PCl5(g)
PCl3 (g) + Cl2 (g)
(Dd) N2 + O2
2NO
(r) x P
(s) x P0
(q) x
1
P
Match List I (G), List II (S) and List III (direction ) :

List I
(a) G > 0
List II
(1) S > 0
List III
(p)
(b) G = 0
(2) S < 0
(q)
(c) G < 0
(3) S = 0
(r)
2.
Column I
(A) H = ve and S = +ve
temperature
`
(B) H = ve and S = ve
`
(C) H = +ve and S = ve
(D) H = +ve and S = +ve
B
Column II
(p) Reaction feasible only low
(q) Reaction feasible at any temperature
(r) Reaction will not occur at any
temperature
(s) Reaction feasible only at high
temperature
Linked Comprehension Type
Comprehension - I
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SECTION V
S
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C
E
C
H
1
1
1
Comprehension Type Questions
Write-up I
For the reaction CaCO3(s)
CaO(s) + CO2(g), KP(1000 K) = 0.059 and KP (1100 K)
= 0.08. Exactly 10 g of CaCO3 is placed in a 10 litre container at 1000 K. The equilibrium
is reached. Assume that air contains 10% by volume of CO2.
1.
The mass of CaCO3 remain unreacted at 1000 K is

(a) 1.485 g
(b) 0.325 g
(c) 9.282 g
(d) 4.56 g
2.
The ratio of degree of dissociation of CaCO3 at 1110 K and 1000 K is

(a) 4.256
(b) 1.356
(c) 5.286
(d) 3.456
3.
The temperature at which CaCO3 dissociates freely in air is

(a) 415C
(b) 913.2C
(c) 8.05. 4C
(d) 43C
4.
The value of H is
(a) 6699 cal
(b) 2399 cal

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(c) 4599 cal
(d) 2499 cal
Write-up IIComprehension - II
Life at high attitudes and hemoglobin production: In the human body, countless
chemical equilibria must be maintained to ensure physiological well being. Transport of
oxygen by blood depends on the reversible combination of oxygen with haemoglobin. In
blood, haemoglobin, oxygen and oxyhaemoglobin are in equilibrium.
haemoglobin (Hb) + O 2 Oxyhaemoglobin [Hb(O 2 )]
The equilibrium constant is, K c
[Hb(O 2 )]
[Hb][O 2 ]
The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3

concentrations.
[salt]
According to Hendersons equation pH log K a log
[acid]
An important component of blood is the buffer combination of H 2 PO 4 ion and the
HPO 4 ion. Consider blood with a pH of 7.44. Given K a1 6.9 103 , K a 2 6.2 108
13
and K a3 4.8 10 .
5.
6.
What volume of 5M NaHCO3 solution should be mixed with a 10 mL sample of blood

which is 2M in H2CO3, in order to maintain a pH of 7.47? K a for H2CO3 in blood is
7.8 107.
(a) 78.32 mL
(b) 92.08 mL
(c) 68.32 mL
(d) None
[H 2 PO 4 ]
What is the ratio of
?
[HPO 24 ]
(a) 0.59
(b) 0.69
(c) 0.79
(d) None
7.
2
2
What will be the pH, when 25% of the HPO 4 ions are converted to H 2 PO 4 ion?
(a) 7.16
(b) 8.16
(c) 9.16
(d) None
8.
What will be the pH, when 15% of the H 2 PO 4 ions are converted to HPO 4 ions?
(a) 7.55
(b) 8.55
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(d) None
Write-up IIIComprehension - III

Let G be the difference in free energy of the reaction when all the reactants and
products are in the standard state (1 atmospheric pressure and 298K) and KC and KP be
the thermodynamic equilibrium constant of the reaction. Both are related to each other at
temperature T by the following relation:
G = 2.303 RT log KC
and G = 2.303 RT log KP (incase of ideal gas)
This equation represents one of the most important results of thermodynamics and relates
to the equilibrium constant of a reaction to a thermodynamic property.
It is sometimes easier to calculate the free energy in a reaction rather than to measure the
equilibrium constant.
Standard free energy change can be thermodynamically calculated as
G = H TS
Here H = standard enthalpy change
S = standard entropy change.
9.
Which of the following statement is correct for a reversible process in state of

equilibrium
(a) G = 2.303 RT log K
(b) G = 2.303 RT log K
(c) G = 2.303 RT log K
(d) G = 2.303 RT log K
10.
At 490C, the value of equilibrium constant; KP is 45.9 the reaction

H2(g) + I2(g)
2HI(g)
Calculate the value of G for the reaction at that temperature
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(a) 3.5 kcal
(c) 5.79 kcal
(b) 3.5 kcal

(d) 5.79 kcal
11.
Calculate the equilibrium concentration ratio of C to A if 2.0 mol each of A and B were
allowed to come to equilibrium at 300 K
A + B
G = 460 Cal
C + D
(a) 1.0
(b) 0.5
(c) 0.8
(d) 0.679
Assertion and Reasoning
This section contains 4 questions numbered 1 to 4. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
Code
(A) Statement 1 is True, Statement 2 is True; Statement 2 is a correct explanation for
Statement 1.
(B) Statement 1 is True, Statement 2 is True; Statement 2 is NOT a correct explanation for
Statement 1.
(C) Statement 1 is True, Statement 2 is False.
(D) Statement 1 is False, Statement 2 is True.
1.
STATEMENT - 1
If Kp value for CaCO3(s)
CaO3 CO 2(g) be 8 atm at 500K, the final pressure
developed in 10 litre vessel on heating 50g of CaCO3(s) by enclosing in vessel at 500K
will be 8 atm.
STATEMENT - 2
This amount of calcium carbonate is insufficient to establish equilibrium under given set
of condition.
2.
STATEMENT - 1
The positive catalyst enhances the rate of equilibrium reaction, but does not change the
value of equilibrium constant at constant temperature.
STATEMENT - 2
Because the catalyst increases the value Kf and Kb in the same proportion at constant
temperature.
3.
STATEMENT - 1
Increasing the pressure formation of NH3 increases in the following equilibrium reaction
N 2 3H 2
2NH 3 H ve
STATEMENT - 2
The reaction is exothermic
4.
STATEMENT - 1
Reaction (s)
2B(s) C(g)
K c 0.28atm
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5
Will attain equilibrium soon if the reaction is carried out in an open vessel.
STATEMENT - 2
For the atoms reaction: Kp Kc
SECTION - IV
Previous IIT- JEE Problems
SECTION VI
1.
Objective
Subjective Questions
For the reaction:

H 2(g) I 2(g)
2HI(g)
The equilibrium constant kp changes with
(a)
(c)
2.
total pressure
catalyst
the amounts of H2 and I2 present
temperature
(b)
(d)
[1981]
Pure ammonia is placed in a vessel at a temperature where its dissociation constant (a) is
appreciable. At equilibrium
(a)
kp does not change significantly with
pressure
(b)
does not change with pressure
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(c)
pressure
(d)
of nitrogen
3.
concentration of NH3 does not change with

concentration of hydrogen is less than that
[1984]
At constant temperature, the equilibrium constant (kp) for the decomposition reaction
N 2O 4
2NO 2 is expressed by kp = (4x2P)/(1-x2), where P = pressure, x = extent of
decomposition. Which one of the following statements is true?
(a)
kp increases with increase of P
(b)
kp increases with increase of x
(b)
kp increases with decreases of x
(d)
kp remains constant with change in P and x
4.
The
Habers
process
for
the
formation
of
NH 3
at
298K
N 2 3H 2
2NH 3 ; H 46.0kJ; Which of the following is the correct statement
(a)
The
condition
for
equilibrium
is
G N2 3G H2 2G NH3 where G is Gibbs free energy per mole of the gaseous species
measured at that partial pressure.
(b)
On adding N2, the equilibrium will shift to
forward direction because according to IInd law of thermodynamics the entropy must
increase in the direction of spontaneous reaction
(c)
The catalyst will increase the rate of forward
reaction by 2 times and that of backward reaction by 1.5 times
(d)
None of these
[2006]
For the gas phase reaction:
C 2 H 4 H 2
C 2 H 6 (H 32.7kcal)
5.
6.
7.
is
Carried out in a vessel, the equilibrium concentration of C2H4 can be increased by

(a)
increasing the temperature
(b)
decreasing the pressure
(b)
removing some H2
(d)
adding some C2H6
[1984]
When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO 2 is left behind.
At equilibrium
(a)
addition of NaNO2 favours reverse reaction
(b)
addition of NaNO3 favours forward reaction
(c)
increasing temperature favours forward
reaction
(d)
increasing pressure favours reverse reaction
[1989]
The equilibrium
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7
SO 2 Cl 2(g)
SO 2(g) Cl 2(g)
Is attained at 25C in a closed container and an inert gas, helium is introduced. Which of
the following statements are correct?
(a)
Concentration of SO2, Cl2 and SO2Cl2 do not
change
(b)
More chlorine is formed
(c)
Concentration of SO2 is reduced
(d)
More SO2Cl2 is formed
[1991]
8.
9.
For the reaction

PCl5(g)
PCl
3(g) Cl2(g)
The forward reaction at constant temperature is favoured by
(a)
introducing an inert gas at constant volume
(b)
introducing chlorine gas at constant volume
(c)
introducing an inert gas at constant pressure
(d)
increasing the volume of the container
(e)
introducing PCl5 at constant volume
[1991]
For the reaction CO(g) H 2O (g)
CO 2(g) H 2(g) at a given temperature the
equilibrium amount of CO2(g) can be increased by
(a)
adding a suitable catalyst
adding an inert gas
(c)
decreasing the volume of the constant
increasing the amount of CO(g)
(b)
(d)
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Previous IIT- JEE Problems
Subjective
LEVEL I
1.
At a certain temperature, equilibrium constant (Kc) is 16 for the reaction

SO2 (g) + NO2(g)
SO3(g) + NO(g)
If we take one mole of all the four gases in a one litre container, what would be the
equilibrium concentrations of NO and NO2?
2.

3.

PCl5
4.

2NO2(g)
N2O4(g)
5.

PCl5(g)
PCl3(g) + Cl2(g)
6.

2NOg) + O2(g)
2NO2(g)
proceed?
7.

a) CaCO3(s)
CaO(s) + CO2(g)
b) H2O(l)
H2O(g)
c) 3Fe(s) + 4H2O(g)
Fe3O4(s) + 4H2(g)
118

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9
8.

CS2(g) + 4H2(g)
CH4(g) + 2H2S(g)
9.
One mole of nitrogen is mixed with three moles of hydrogen in a 4-litre container. If
0.25% of nitrogen is converted to ammonia by the following reaction:
N2 (g) + 3H2 (g)
2NH3 (g)
calculate the equilibrium constant Kc. What will be the value of Kc for the following
equilibrium ?
1
3
N2(g) +
H2(g)
NH3(g)
2
2
10.
Consider the following heterogeneous equilibrium at 300 K :

NH4HS (s)
NH3(g) + H2S (g)
The total pressure of equilibrium mixture is 0.5 atm calculate Kp and Kc for the reaction.
LEVEL II
1*.
To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 1.09 M Fe2+ solution and
3
Ag (aq) Fe 2 (aq)
Fe (aq) Ag (s)
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2.
One mole of N2 and 3 mol of PCl5 placed in a 100 litre vessel are heated to 2270C. The
equilibrium pressure is 2.05 atm. Assuming ideal behaviour, calculate the degree of
dissociation of PCl5 and Kp for the reaction
PCl5(g)
PCl3 (g) + Cl2(g)
3.
extent of 80%.
4.
For the equilibrium

2
LiCl 3NH 3(s)
LiCl NH 3(s) 2NH 3 (g), K p 9 atm
5*.
Consider the reaction SO 2 Cl2 (g)

SO 2 (g) Cl 2 (g) ; at 37C
the value of
reaction vessel?
6.
Calculate Kc.
7.
the following reaction can take place; CO(g) + 2 H 2 (g)
i) K p and K c
8*.
At some temperature and under a pressure of 4 atm. PCl 5 is 10% dissociated. Calculate
the pressure at which PCl5 will be 20% dissociated, temperature remaining same.
9.
When NO and NO2 are mixed, the following equilibria are readily obtained;
-1
2NO2
N2O4 Kp = 6.8 atm
and
NO + NO2
N2O3
In an experiment when NO and NO2 are mixed in the ratio of 1: 2, the final total pressure
was 5.05 atm and the partial pressure of N2O4 was 1.7 atm. Calculate:
(a) The equilibrium partial pressure of NO
(b) Kp for NO + NO2
N2O3
120

120
10*.
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C
H
1
2
1
2NO(g) Br2(g)
2NOBr(g)
LEVEL III (Judge yourself at JEE level)

1*.
+
0
-19
For the reaction Ag(CN)2
Ag + 2CN , the KC at 25 C is 4 10 . Calculate
[Ag+] in solution which was originally 0.1 M in KCN and 0.03 M in AgNO3.
2.
A sample of air consisting of N2 and O2 was heated to 2500K until the equilibrium
N 2(g) O 2(g)
2NO(g)
was established with an equilibrium constant KC = 2.1 103. At equilibrium, the moles
% of NO were 1.8. Estimate the initial composition of air in mole fraction of N2 and O2.
3*.
The degree of dissociation is 0.4 at 400K and 1.0 atm for the gaseous reaction
PCl5
PCl3 + Cl2. Assuming ideal behaviour of all the gases, calculate the density of
equilibrium mixture at 400K and 1.0 atmosphere. (Atomic mass of P = 31.0 and
Cl = 35.5)
4.
Calculate the value of log Kp for the reaction

N 2 (g) 3H 2 (g)
2NH 3 (g)
at 25C. The standard enthalpy of formation of NH 3(g) is 46kJ and standard entropies of
N2(g), H2(g) and NH3(g) are 191, 130, 192 JK1 mol1 respectively (R = 8.3 JK1 and mol1).
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5*.
Solid ammonium carbamate dissociates into NH3 and CO2 as

NH4COONH2(s)
2NH3(g) + CO2(g). The total pressure at equilibrium is
0.225atm. Calculate Kp.
6.
into CO on addition of graphite. Calculate the value of K, if total pressure at equilibrium
is 0.8 atm.
7.
At 817C, Kp for the reaction between CO2(g) and excess hot graphite(s) is 10 atm.
a) What are the equilibrium concentration of the gases at 817C and a total pressure
of 5 atm?
b) At what total pressure, the gas contains 5% CO2 by volume?
8.
For the reaction, CO(g) + 2H2(g)

CH3OH(g); H2 is introduced into a five litre flask at
327C, containing 0.2 mole of CO(g) and a catalyst till the pressure is 4.92 atmosphere. At
this point 0.1 mole of CH3OH(g) is formed. Calculate the KC and Kp.
9*.
The value of Kp is 1 103 atm1 at 25C for the reaction:

2NO + Cl2
2NOCl. A flask contains NO at 0.02 atm and at 25C. Calculate the
mole of Cl2 that must be added if 1% of the NO is to be converted to NOCl at
equilibrium. The volume of the flask is such that 0.2 mole of gas produce 1 atm pressure
at 25C. (Ignore probable association of NO to N2O2).
10.
When 1-pentyne (A) is treated with 4N alcoholic KOH at 175C, it is converted slowly
into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5%, of 12pentadiene (C). The equilibrium was maintained at 175C. Calculate G0 for the
following equilibria.:
B
G10 ?
A :
B
C :
G 02 ?
0
0
From the calculated value G1 and G 2 indicate the order of stability of (A), (B)
and (C).
18.
Which of the following statements is (are) correct?

(a) An irreversible reaction goes to almost completion
(b) A reversible reaction always goes to completion if carried out in a closed vessel
(c) At equilibrium, the rate of forward reaction becomes equal to that of backward
reaction
(d) In the beginning, the rate of backward reaction is much greater than that of forward
reaction.
19.
The value of equilibrium constant of a reversible reaction at a given temperature

(a) depends on the initial concentration of reactants
(b) depends on the concentration of products at equilibrium
(c) gets reversed when the mode of representation of the reaction is reversed
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(d) changes when the unit of active mass is changed

20.
Which of the following statements is (are) correct?

(a) The value of equilibrium constant for a particular reaction is constant under all
conditions of temperature and pressure
(b) The units of Kc for the reaction H 2 O
H 2 O(g) are mol L1
(c) In the reaction
CaCO3(s)
CaO(s) CO 2(g) , [CaCO3 ] [CaO] 1
(d) Kp is always greater than Kc for a particular reaction
21.
In the dissociation of 2HI

H 2 I 2 , the degree of dissociation will be affected by the
(a) addition of inert gas
(b) addition of H2 and I2
(c) increase of temperature
(d) increase of pressure
22.
In which of the following gaseous equilibria, Kp is less than Kc?

(a) N 2O 4
(b) 2HI
2NO 2
H 2 I 2
(c) 2SO 2 O 2
(d) N 2 3H 2
2SO3
2NH 3
23.
Which of the following equilibria is (are) not affected by pressure?

(a) 2SO 2(g) O2(g)
(b) H 2(g) I 2(g)
2SO3(g)
2HI(g)
(c) 2NO(g) O 2(g)
2NO 2(g)
24.
(d) N 2(g) O 2(g)

2NO (g)
Which of the following will favour the formation of products in the following reaction?
A (g) 2B(g)
3C
(g) D(g) heat
(a) An increase in temperature
(b) An increase in pressure

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(c) Addition of B
25.
(d) Removal of C
The equilibrium concentration of C2H4 in the gas phase reaction

C 2 H 4 H 2
C 2 H 6 H 32.7kcal , can be increased by
(a) removal of C2H6
(b) removal of H2
(c) decreasing temperature
(d) increasing pressure
Comprehension Type Questions
SECTION III
Write-up I
A chemical reaction in the laboratory is carried out under the condition of constant
temperature and pressure. The condition of spontaneity in terms of enthalpy and entropy
are, respectively, H 0 and S 0 whereas condition of equilibrium are, respectively,
H = 0 and S = 0. An endothermic reaction is driven by increase in entropy i.e. increase
in disorderness. The two criteria combined together, the condition of reversibility and
irreversibility are as follows:
GP, T = H TS 0, where equal to sign refers to reversibility and less than sign refers
to irreversibility. Reversibility is the condition of equilibrium whereas irreversibility is
the condition of spontaneity. A reversible reaction is characterised by equilibrium
constant (K), the magnitude of which measures the position of equilibrium i.e. how far a
chemical reaction will go to completion before attainment of equilibrium. The position of
equilibrium constant of a reaction with temperature is given by Vant Hoff equation of
thermodynamics which is as follows:
d ln K H
dT
RT 2
This equation can be integrated assuming H to be independent of temperature. Within
the short interval of temperature.
For a gaseous equilibria k can be expressed Kc and Kp related as
K p K c (RT)
n g
Where the symbols have their usual meanings. ng of a reaction can be found out from
the unit of equilibrium, though it is not customary to write unit of equilibrium constant.
Another way of finding ng of a reaction is to use the equation
H = E + ng RT
Where the terms have their usual meanings.
Knowing K and reaction quotient it is possible to calculate free energy change of a
reaction using the equation:
G = G0 + RTlnQ
At equilibrium Q = K and GP, T = 0
124

124
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5
So, G0 = RTlnK where G0 is the free energy change of the reaction in the standard
state.
The standard state of a substance is defined as the state of unit activity at 25C. In the
case of solution of a substance the activity is taken to be molar concentration while for a
gas it is pressure in atm.
The standard free energy of an element is taken to be zero.
1.
At 27C the heat of reaction at constant pressure is 600 cals more than that at constant
volume. The ratio of Kp to Kc of the reaction is:
(a) 24.63
(b) (24.63)2
(c) 0.6
(d) 0.36
2.
For the reaction:

NH 4 HS(s)
NH 3(g) H 2S(g)
Kp and Kc are interrelated as
(a) Kp = KcRT
(c) Kp = Kc(RT)2
Kc
(RT) 2
(d) Kp = Kc/RT
(b) Kp =
3.
The Kp of a reaction is 10 atm2 at a temperature T on Kelvin scale. Hence

(a) Kp = Kc
(b) Kp Kc
(c) Kp Kc
(d) Cant be predicted
4.
The Kc of a reaction is 4.0 mol2L2 at 27C. Hence Kp of the reaction is:

(a) 4 (0.0821 300)2 atm2
(b) 4 (2 300)2 atm2
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(c)
4
(0.0821 300) 2 atm 2
(d)
4
(2 300) 2 atm 2
Write-up II
Life at high attitudes and hemoglobin production: In the human body, countless
chemical equilibria must be maintained to ensure physiological well being. Transport of
oxygen by blood depends on the reversible combination of oxygen with haemoglobin. In
blood, haemoglobin, oxygen and oxyhaemoglobin are in equilibrium.
haemoglobin (Hb) + O 2 Oxyhaemoglobin [Hb(O 2 )]
The equilibrium constant is, K c
[Hb(O 2 )]
[Hb][O 2 ]
The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3

concentrations.
[salt]
According to Hendersons equation pH log K a log
[acid]
An important component of blood is the buffer combination of H 2 PO 4 ion and the
HPO 4 ion. Consider blood with a pH of 7.44. Given K a1 6.9 103 , K a 2 6.2 108
13
and K a3 4.8 10 .
5.
6.
What volume of 5M NaHCO3 solution should be mixed with a 10 mL sample of blood

which is 2M in H2CO3, in order to maintain a pH of 7.47? K a for H2CO3 in blood is 7.8
107.
(a) 78.32 mL
(b) 88.32 mL
(c) 68.32 mL
(d) None
[H 2 PO 4 ]
What is the ratio of
?
[HPO 24 ]
(a) 0.59
(b) 0.69
(c) 0.79
(d) None
7.
2
2
What will be the pH, when 25% of the HPO 4 ions are converted to H 2 PO 4 ion?
(a) 7.16
(b) 8.16
(c) 9.16
(d) None
8.
What will be the pH, when 15% of the H 2 PO 4 ions are converted to HPO 4 ions?
(a) 7.55
(b) 8.55
(c) 9.55
(d) None
Write-up III
Let G be the difference in free energy of the reaction when all the reactants and
products are in the standard state (1 atmospheric pressure and 298K) and KC and KP be
126

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C
H
1
2
7
the thermodynamic equilibrium constant of the reaction. Both are related to each other at
temperature T by the following relation:
G = 2.303 RT log KC
and G = 2.303 RT log KP (incase of ideal gas)
This equation represents one of the most important results of thermodynamics and relates
to the equilibrium constant of a reaction to a thermodynamic property.
It is sometimes easier to calculate the free energy in a reaction rather than to measure the
equilibrium constant.
Standard free energy change can be thermodynamically calculated as
G = H TS
Here H = standard enthalpy change
S = standard entropy change.
9.
Which of the following statement is correct for a reversible process in state of

equilibrium
(a) G = 2.303 RT log K
(b) G = 2.303 RT log K
(c) G = 2.303 RT log K
(d) G = 2.303 RT log K
10.
At 490C, the value of equilibrium constant; KP is 45.9 the reaction

H2(g) + I2(g)
2HI(g)
Calculate the value of G for the reaction at that temperature
(a) 3.5 kcal
(b) 3.5 kcal
(c) 5.79 kcal
(d) 5.79 kcal
11.
Calculate the equilibrium concentration ratio of C to A if 2.0 mol each of A and B were
allowed to come to equilibrium at 300 K
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A + B
C + D
(a) 1.0
(c) 0.8
G = 460 Cal
(b) 0.5
(d) 0.679
Write-up IV
The equilibrium constants (Kp and Kc) of a gaseous equilibria say

aA (g) bB(g)
cC(g) dD(g)
are interrelated as :
n
K p K c (RT) g
where ng = (c + d) (a + b
The heat of reactions : H and E are interrelated according to the equation:
H = E + ngRT.
12.
H of a reaction is 600 cals more than E at 27C. What is the ratio of K p and Kc of a
reaction at 27C? (R = 1.987 2 cals K1 mol1) = 0.0821 L atm K1 mol1.
(a) 1.2
(b) 24.63
(c) 49.26
(d) 2.4
13.
Solid A was heated in a sealed vessel when pressure developed 65.68 atm at 127C due to
the attainment of following equilibrium
A (s)
B(g) C(g)
Hence Kc of the reaction at 127C is:
1
(a)
32.84
2
(c)
32.84
(b) 1.0
(d) cant be calculated
Write-up V
Ammonia is manufactured by the Haber process represented by the equilibrium:

N 2(g) 3H 2(g)
H0 = 184.4 kJ
2NH3(g)
The optimum conditions for the production of ammonia are a pressure of about 200 atm
and a temperature of around 700K. Iron oxide containing small amounts of K 2O and
Al2O3 is used as catalyst so as to increase the rate of attainment of equilibrium. Annual
world production of ammonia now exceeds 10 million tonnes.
14.
According to Le-Chateliers principle the favourable condition for good yield of NH3
(a) Low pressure and low temperature
(b) High pressure and low temperature
(c) Low pressure and high temperature
(d) High pressure and high temperature
128

128
15.
S
M
C
E
C
H
1
2
9
In absence of catalyst during Habers process of ammonia synthesis

(a) yield of NH3 will decrease
(b) yield of NH3 will remain the same
(c) equilibrium position will get shifted in the backward direction
(d) equilibrium will never set up
SECTION IV
Subjective Questions
LEVEL I
1.
Kc for equilibrium A (g)

B(g) C(g) is 0.45 at 200C. One litre of a container holds
0.2 mole of A, 0.3 mole of B and 0.3 mole of C at equilibrium. Calculate the new
equilibrium concentrations of A, B and C if the volume of container at same temperature
is: a) Halved; (b) Doubled
2.

3.

PCl5
4.

2NO2(g)
N2O4(g)
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5.

PCl5(g)
PCl3(g) + Cl2(g)
6.

2NOg) + O2(g)
2NO2(g)
5
proceed?
7.

a) CaCO3(s)
CaO(s) + CO2(g)
b) H2O(l)
H2O(g)
c) 3Fe(s) + 4H2O(g)
Fe3O4(s) + 4H2(g)
8.

CS2(g) + 4H2(g)
CH4(g) + 2H2S(g)
9.

2NO(g) + O2(g)
2NO2(g)
2
Kp = 1.3 10 at 1000K. What is the value of Kc at 1000K?
10.
Following reaction occurs in a blast furnace

Fe2O3(s) + 3CO(g)
2Fe(l) + 3CO2(g)
Use Le Chateliers principle to predict the direction of reaction when an equilibrium
mixture is disturbed by
a) adding Fe2O3
b) removing CO2
c) removing CO
LEVEL II
130

130
1.
S
M
C
E
C
H
1
3
1
To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 12.09 M Fe 2+ solution and
3
Ag (aq) Fe 2 (aq)
Fe (aq) Ag (s)
2.
Ammonium hydrogen sulphide dissociates according to the equation

NH4HS(s)
NH3(g) + H2S(g). If the observed pressure of the mixture is 1.12
atmosphere at 106C, what is the equilibrium constant Kp of the reaction?
3.
extent of 80%.
4.
For the equilibrium

LiCl 3NH 3(s)
LiCl NH 3(s) 2NH 3 ,
K p 9 atm 2
5.
Consider the reaction SO 2 Cl 2 (g)

SO 2 (g) Cl 2 (g) ; at 37C
the value of
reaction vessel?
6.
Calculate Kc.
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7.
the following reaction can take place; CO(g) + H 2 (g)
i) K p and K c
8.
Equilibrium constants are given (in atm) for the following reactions at 0C
a) SrCl26H2O(s)
Kp = 6.89 1012
13
b) Na2HPO412H2O(s)
Na2HPO47H2O(s) + 5H2O(g), Kp = 5.25 10
c) Na2SO410H2O(s)
Kp = 4.08 1025
Na2SO4(s) + 10H2O(g)
i) Calculate the pressure of water vapour in equilibrium at 0C with each of (a), (b) and
(c).
ii) Which is the most effective drying agent at 0C?
iii) At what relative humidities, Na2SO210H2O be efflorescent when exposed to
air at 0C?
iv) At what relative humidities will Na2SO4 be deliquescent (i.e,. absorb moisture) when
exposed to air at 0C?
9.
For the reaction: CO 2 (g) H 2 (g)

CO(g) H 2O(g), K is 0.63 at 700C and 1.66 at
1000C.
a)
What is the average H for the temperature range considered?
b)
What is the value of K at 800C ?
10.
2NO(g) Br2(g)
2NOBr(g)
LEVEL III (Judge yourself at JEE level)
1.
At temperature T, a compound AB2(g) dissociates according to the reaction:

2AB2(g)
2AB(g) + B2(g) with a degree of dissociation x which is small compared to
unity. Deduce the expression for x in terms of the equilibrium constant K p and the total
pressure P.
2.
N 2(g) O 2(g)
2NO(g)
132

132
S
M
C
E
C
H
1
3
3
3.
PCl5
Cl = 35.5)
4.

N 2(g) 3H 2(g)
2NH3(g)
at 25C. The standard enthalpy of formation of NH 3(g) is 46kJ and standard entropies of
5.
When S in the form of S8 is heated at 900K, the initial pressure of 1 atmosphere falls by
29% at equilibrium. This is because of conversion of some S8 to S2. Find the Kp for
reaction.
6.
A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO 2 is converted
is 0.8 atm.
7.
a) What are the equilibrium concentration of the gases at 817C and a total pressure
of 5 atm?
b) At what total pressure, the gas contains 5% CO2 by volume?
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8.

9.

2NO + Cl2
10.
into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5%, of 12pentadiene (C). The equilibrium was maintained at 175C. Calculate G0 for the
B
G10 ?
A :
B
C :
G 02 ?
0
0
and (C).
SECTION V
1.
Match the following

List I (Entities)
(A) Kc when n = 1
(B) Kp when n = 1
(C) R (gas constant)
(D) F (Faraday constant)
Codes
(A)
(B)
(C)
(D)
(a) Y
X
Z
W
(c) X
Y
W
Z
Miscellaneous Questions
List II (Units)
W JV1 mol1
X. (mol/L)2
Y bar2
Z KPa dm3 mol1 K1
(A)
(b) X
(d) Y
(B)
Y
X
(C)
Z
W
(D)
W
Z
The following questions (2to 10) consists of two statements, one labelled as ASSERTION (A)
and REASON (R). Use the following key to chose the correct appropriate answer.
(a) (A) and (R) both are correct and (R) is the correct explanation of (A)
(b) (A) and (R) both are correct but (R) is not the correct explanation of (A)
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct
ASSERTION (A)
REASONING (R)
2.
The endothermic reactions are favoured at When a system in equilibrium is

lower temperature and the exothermic disturbed by changing the temperature,
reactions are favoured at higher temperature.
it will tend to adjust itself so as to
134

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overcome the effect of change.

3.
The equilibrium constant of the exothermic

K
H 1 1

Since ln 2
and for
reaction at high temperature decreases.
K1
R T1 T2
exothermic reaction, H = ve and
K2
ve
thereby ln
K1
4.
Even at constant temperature, on changing the Because the equilibrium depends upon
stoichiometric coefficients of the reaction, the the ratio of concentration of product
equilibrium constant changes.
and reaction in which the stoichiometric
coefficients becomes, thereby the
equilibrium constant depends upon the
stoichiometric coefficients.
5.
For the reaction A (g) B(g)

C(g) D(g) at
the given temperature, there will be no effect
by addition of inert gas either at constant
pressure or at constant volume.
For the reaction where n = 0, there is

effect of inert gas either at constant
volume or at constant pressure because
Kp becomes purely a number.
6.
for the physical equilibrium ice

water
on increasing temperature and increasing
pressure more water will form.
The equilibrium remains undisturbed by the
addition of inert gas at constant volume.
Since forward reaction is endothermic

in nature and volume of water is lesser
than that of the volume of ice.
7.
8.
Since Kp remains constant at constant

volume and at constant temperature by
the addition of inert gas at equilibrium.
The catalyst does not alter the equilibrium Because for the catalysed reaction and
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constant at constant temperature
uncatalysed reaction H remains same

and equilibrium constant depends on
H and temperature.
9.
The addition of inert gas for the reaction N2(g) Because the addition of inert gas at
+ 3H2
2NH3(g) at constant pressure constant pressure favours the backward
reaction.
decreases the rate of formation of NH3.
10.
At equilibrium, G at unit activity

= RTlnKc
Since G = G + RT ln Q and at
equilibrium, G = 0, and Q becomes Kc
at unit activity.
136

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Answers to Assignments
SECTION - I
LEVEL - I
1.
5.
9.
13.
17.
(c)
(b)
(c)
(a)
(a)
2.
6.
10.
14.
18.
(d)
(d)
(d)
(b)
(b)
3.
7.
11.
15.
19.
(b)
(d)
(b)
(c)
(d)
4.
8.
12.
16.
20.
(d)
(d)
(c)
(a)
(b)
LEVEL - II
SECTION - I
1.
2.
(C)
(BC)
3.
(AA)
4.
(AB)
5.
6.
7.
8.
9.
9
10.
101.
(CC)
(DA)
(C)
(DB)
(BC)
20.
7
8
(CC)
(BA)
12.
13.
14.
15.
(B)
(D)
(D)
(A)
16.
17.
18.
19.
(C)
(A)
(A)
(A)
21.
22.
(B)
(B)
(C)
138

138
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9
23.
24.
25.
(C)
(B)
(B)
SECTION - IILEVEL - II
1.
(a), (b), (c), (d)
2.
(a), (b), (c), (d)
3.
(aa), (b), (c), (d), (c)
4.
5.
6.
(ba), (cb)
(ba), (b), (c), (d)), (c)
(a), (b), (c), (d)
7.
8.
9.
(a), (b), (c), (d)

(ab), (c), (c)
(ab), (c), (b), (c)
10.
11.
12.
(aa), (c)
(b), (c)
(a), (c), (d)
13.
14.
15.
(A), (B), (C)

(A), (B),(C), (D)
(A), (C)
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16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
(A),
(A),
(A),
(C),
(B),
(B),
(C),
(B),
(A),
(B),
(B), (D)
(C)
(C)
(D)
(C)
(C)
(D)
(D)
(C), (D)
(C)
SECTION - IILEVEL - IIIIII
1.
(a)
2.
(c)
3.
(b)
4.
(a)
5.
6.
7.
8.
(b)
(a)
(b, c)
(d)
9.
10.
11.
12
(c)
(d)
(d)
(b)
13.
(b)
14. (b)
(b)
15.
SECTION - II
LEVEL I
1.
[NO2] = 0.4 M and [NO] = 1.6 M
3. 100 mm/Hg
a) 0; b) 164.06M1
5.
right to left
a) forward; b) backward; c) no
7.
a) Kp = KcRT; b) Kp = KcRT; c) Kp = Kc
3.02 105
9.
1.49 10-5 (mol L-1)-2
3.86 10-3 (mol L-1)-1
4.
6.
8.
140

140
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E
C
H
1
4
1
Kp = 0.0626; Kc = 2.82 10-5
10.
LEVEL II
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Kc = 3.1420
= 0.33; Kp = 0.205 atm
57.92
0.7833 mole
In this question, concentration of three species i.e. SO2 Cl2 , SO 2 and Cl2 (g) each is
given, but is not mentioned that whether the system is at equilibrium or not. So first
check it. Find reaction coefficient for given equation.
[SO 2 ][Cl 2 ] (0.05)(0.05)
Q
0.05
[SO 2Cl 2 ]
(0.05)
As Q > K, the concentrations must adjust till Q = K for equilibrium. This can happen
only if reaction shifts backwards, and products recombine to give back reactants. Hence
in the reaction vessel, the system will move backward so that it can achieve equilibrium
state.
Kc = 4.012
(i) Kc = 187.84, Kp = 0.0495
(ii) P = 12.438 atm
3
3
3
(i) PH2O 1.62 10 atm , PH2O 3.53 10 atm , PH2O 3.64 10 atm , (ii) SrCl2.2H2O
(iii)
60.5%; (iv) 60.5%
(a) PNO = 1.05 atm
(b) KP = 3.43 atm-1
12.22 kJ mol-1.
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SECTION - IV
SECTION - IIIV
Match the following
Write-up
Assertion and Reasoning
(A) (r)
1.
(B) (p)
3.
(C) (q)
5.
(D) (s)
7.
(A) (q)
9.
(B) (p)
11.
(C) (r)
(D) (s)
(a - r), (b - p), (c - q), (d - s)
(a 2-q), (b 3 - r), (c 1 - p),
(c)
(b)
(a)
(d)
(a)
(d)
2.
4.
6.
8.
10.
(b)
(a)
(a)
(a)
(a)
1.
2.
3.
4.
(A)
(D)
(B)
(D)
SECTION IV
Previous IIT- JEE Problems Objective
1
3.
5.
7.
9.
(d)
(d)
(a), (b), (c), (d)
(a)
(b), (c)
2.
4.
6.
8.
(a)
(a)
(c), (d)
(c), (d), (e)
Previous IIT- JEE Problems Subjective

SECTION - V
1.
(c)
2.
(b)
3.
(b)
4.
(a)
5.
(a)
6.
(a)
7.
(d)
8.
(a)
9.
(a)
10.
(a)
142

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LEVEL I
SECTION - VI
LEVEL I
1.
a) [A = 0.52M, B = C = 0.48M];
[NO] = 1.6 M
b) [A = 0.07M, B = C = 0.18M][NO2] = 0.4 M and
3.
100 mm/Hg
4.
a) 0; b) 1.64.06M1
5.
right to left
6.
7.
8.
3.02 105
9.
1.0671.49 10-5 (mol L-1)-2

3.86 10-3 (mol L-1)-1
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10.
Kp = 0.0626; Kc = 2.82 10-5a) no effect; b) forward; c) backward

LEVEL II
1.
Kc = 3.1420
2.
= 0.33; Kp = 0.205 atm0.3136
3.
57.92
4.
0.78337 mole
5.
In this question, concentration of three species i.e. SO 2 Cl2 , SO 2 and Cl 2 (g) each is
given, but is not mentioned that whether the system is at equilibrium or not. So first
Q
[SO 2 ][Cl 2 ] (0.05)(0.05)
0.05
[SO 2 Cl 2 ]
(0.05)
state.
6.
Kc = 4.012
7.
(i) Kc = 187.84, Kp = 0.0495

(ii) P = 12.438 atm
8.
3
3
3
(i) PH2O 1.62 10 atm , PH2O 3.53 10 atm , PH2O 3.64 10 atm , (ii) SrCl2.2H2O
(iii)
9.
60.5%; (iv) 60.5%
(a) PNO = 1.05 atm8.0 cal

144

144
S
M
C
E
C
H
1
4
5
(b) K2P = 3.43 atm-10.93
10.
12.22 kJ mol-1.
LEVEL III
2K p
1/ 3
1.
7.5 10
2.
3.
N2 = 79%, O2 = 21
4.53 g/litre
4. 5.845
4.53 g/L2.55 (atm)3
6. 1.8 atm
a) CO = 0.041 mole litre1, CO2 = 0.015 mol litre1,
5.
-18
7.
(b) 0.145 atm
8.
Kc = 279.64 litre2 mol2, Kp = 0.115 atm2
9.
0.02042
0
0
10.
G1 = 16.178kJ, G2 = 12.282 kJ, B > A, B > C, B > C > A
SECTION - V
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Assignments
LEVEL I (CBSE LEVEL)
1.
2.
3.
4.
5.
6.
7.
Review Your Concept

The equilibrium constant of an equilibrium represented by A (g)
B(g) is 1.1 which of
the two gases A and B has a molar concentration greater than 1 atm at equilibrium?
Kc for the equilibrium N 2O 4(g)
2NO 2(g) at 298C is 5.7 109. Which species has a
higher concentration at equilibrium?
State whether the following statement is false or true. If the equilibrium constant for
1
1
A 2 B2
A 2 B2 is 1/K.
2AB is K, the equilibrium constant for AB
2
2
Would you expect the equilibrium constant for the reaction I 2(g)
2I(g) to increase or
decrease as temperature increases? Why?
The equilibrium constant expression for a gas reaction is
[NH3 ]4 [O 2 ]5
Kc
[NO]4 [H 2O]6
Write the balanced chemical equation corresponding to this expression.
In the following equilibrium A + B
nC equilibrium constant is expressed in the
1
unit of L mol . Predict value of n.
Write the equilibrium constants for each of the following reactions:
a)
CO2(g) + C(s)
2CO(g)
b)
c)
2+
Hg(l) + Hg2+(aq)
Hg2 (aq)
2Fe(s) + 3H2O(g)
Fe2O3(s) + 3H2(g)
2H2O(l)
2H2(g) + O2(g)
Consider the reaction SO2 Cl2 (g)
reaction vessel?
2NO2(g)
N2O4(g)
d)
8.
9.
146

146
10.
11.
12.
a)
any reaction occurs?
b)
S
M
C
E
C
H
1
4
7
What is the value of the reaction quotient before

What is the value of the equilibrium constant?
PCl5(g)
PCl3(g) + Cl2(g)
2NOg) + O2(g)
2NO2(g)
5
a)
Is the reaction mixture at equilibrium? If not, in
which direction does the reaction proceed?
b)
What is the direction of the reaction if the initial
3
amounts are 5.0 10 mole NO, 0.20 mole of O2 and 4.0 moles of NO2?
c)
Can reaction quotient be zero for the case in (b)?
a)
CaCO3(s)
CaO(s) + CO2(g)
H2O(l)
H2O(g)
c)
3Fe(s) + 4H2O(g)
Fe3O4(s) + 4H2(g)
13.
CS2(g) + 4H2(g)
CH4(g) + 2H2S(g)
14.
2NO(g) + O2(g)
2NO2(g)
b)
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148
Kp = 1.3 102 at 1000K. What is the value of Kc at

1000K?
15.
Following reaction occurs in a blast furnace
Fe2O3(s) + 3CO(g)
2Fe(l) + 3CO2(g)
Use Le Chateliers principle to predict the direction of reaction when an equilibrium
mixture is disturbed by
a)
adding Fe2O3 b)
removing CO2
c)
removing CO
LEVEL II
Brush up Your Concepts
1.
Two solid compounds A and C dissociates into gaseous product at temperature T as
follows:
i)
A(s)
B(g) + D(g)
ii)
C(s)
E(g) + D(g)
At 20C pressure over excess solid A is 50 atm and that over excess solid C is 68 atm.
Find the total pressure of the gases over the solid mixture.
2.
0.15 mole of CO taken in a 2.5L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place:
CO(g)+2H2(g)
CH3OH(g)
Hydrogen is introduced until the total pressure of the system is 8.5 atmosphere at
equilibrium and 0.08 mole of methanol is formed. Calculate (a) KP and KC and (b) the
final pressure if the same amount of CO and H2 as before are used, but with no catalyst so
that reaction does not take place.
3.
When 3.06g of solid NH4HS is introduced into a two litre evacuated flask at 27C, 30%
of the solid decomposes into gaseous ammonia and hydrogen sulphide. (i) Calculate Kc
and Kp for the reaction at 27. (ii) What would happen to the equilibrium when more
solid NH4HS is introduced into the flask?
4.
4.5 gm of PCl5 (molecular weight 208.5) were completely vapourized at 250C and the
vapour occupied 1.7 litre at one atmospheric pressure. Calculate the degree of
dissociation and equilibrium constant Kp of PCl5 at this temperature.
5.
Phosphine decomposes at 300 K and 2.5 atmosphere as follows:
4PH3(g)
P4(g) + 6H2(g)
Calculate the vapour density of phosphine, if it dissociates to the extent of 40%.
6.
In a mixture of N2 and H2 in the ratio of 1 : 3 at 30 atmospheric pressure and 300C, the
percentage ammonia under equilibrium condition is 17.8 by volume. Calculate
equilibrium constant Kp for the reaction
N2 + 3H2
2NH3
7.
a)
At 27C and 1 atmospheric pressure, N2O4 is 20%
dissociated into NO2. What is the value of Kp under these conditions?
b)
Determine the percentage dissociation at 27C and a
total pressure of 0.10 atmosphere.
c)
What is extent of dissociation in 69 gm sample of
N2O4 confined in a 20 litre vessel
at 27C?
8.
For the reaction, N2 + 3H2
2NH3, Kp at 700 K is 1.7 104 atmosphere, what will be
the equilibrium constant at 800K, if heat of the reaction is 106 kJ/mole.
148

148
S
M
C
E
C
H
1
4
9
9.
The activation energy of H2 + I2

2HI in equilibrium for the forward reaction is 167
kJ mol1 whereas for the reverse reaction is 180 kJ mol1. The presence of catalyst lowers
the activation energy by 80 kJ mol1. Assuming that the reactions are made at 27C and
the frequency factor for forward and backward reactions are 4 104 and 2 103
respectively, calculate KC.
10.
In an evacuated vessel of capacity 110 litres, 4 moles of Argon and 5 moles of PCl5 were
introduced and brought to equilibrium at a temperature of 250oC. At equilibrium, the total
pressure of the mixture was found to be 4.678 atm. Calculate the degree of dissociation,
of PCl5 and KP for the reaction
PCl5
PCl3 + Cl2, at this temperature.
LEVEL III
Check Your Skills
1.
The value of K c for the reaction : H 2 (g) I 2 (g)
2HI(g) is 45.9 at 773 K. If one
mole of H 2 , two mole of I 2 and three moles of HI are taken in a 10 L flask, find the
concentrations of I 2 and HI at equilibrium at 773 K.
2.
3.
K p for the reaction PCl5

PCl3 Cl 2 at 250C is 0.82. Calculate the degree of
dissociation at given temperature under at total pressure of 5 atm. What will be the degree
of dissociation if the equilibrium pressure is 10 atm. at same temperature.
the following reaction can take place; CO(g) + H 2 (g)
K p and K c
i)
ii)
The final pressure if the same amount of CO and
H 2 as before are used but no catalyst so that the reaction does not take place.
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150
4.
If dt be the initial density and d0 be the density at equilibrium then derive expression for
degree of dissociation for following equilibria.
SO3(g) SO2(g) + 1/2O2(g)
5.
Ammonia under a pressure of 15 atm. At 27C is heated to 347C is a closed vessel in the
presence of catalyst. Under these conditions, NH3 partially decomposes to H2 and N2. The
vessel is such that the volume remains effectively constant, whereas the pressure
increases to 50 atm. Calculate the % age of NH3 actually decomposed.
6.
Solid NH4HS(s) (Ammonium hydrogen sulphide) dissociates to give NH3(g) and H2S(g) and
is allowed to attain equilibrium at 100C. If the value of Kp for its dissociation is found to
be 0.34. find the total pressure at equilibrium and partial pressure of each component.
7.
500 ml of 1.09 M Fe2+ solution were added to 500 ml of 0.150 M AgNO3 Solution and
the reaction is allowed to reach an equilibrium at 25C
Ag+ (aq) + Fe+2(aq)
Fe+3 (aq) + Ag(s)
For 25 ml of the solution, 30 ml of 0.0832 M KMnO4 were required for oxidation.
8.
Equilibrium constants are given (in atm) for the following reactions at 0C
a)
SrCl26H2O(s)
12
Kp = 6.89 10
b)
Na2HPO412H2O(s)
Na2HPO47H2O(s) +
13
5H2O(g),
Kp = 5.25 10
c)
Na2SO410H2O(s)
Na2SO4(s) + 10H2O(g) Kp =
25
4.08 10
i)
Calculate the pressure of water vapour in
equilibrium at 0C with each of (a), (b) and (c).
ii)
Which is the most effect drying agent at 0C?
iii)
At what relative humidities with Na2SO210H2O be
efflorescent when exposed to air at 0C?
iv)
At what relative humidities will Na2SO4 be
deliquescent (i.e,. absorb moisture) when exposed to air at 0C?
9.
For the reaction: CO 2 (g) H 2 (g)
CO(g) H 2O(g), K is 0.63 at 700C and 1.66 at
1000C.
What is the average H for the temperature range considered?
What is the value of K at 800C ?
10.
2NO(g) Br2(g)
2NOBr(g)
LEVEL IV
Judge yourself at JEE level
1.
At temperature T, a compound AB2(g) dissociates according to the reaction:
2AB2(g)
2AB(g) + B2(g) with a degree of dissociation x which is small compared to
150

150
2.
S
M
C
E
C
H
1
5
1
unity. Deduce the expression for x in terms of the equilibrium constant Kp and the total
pressure P.
N 2(g) O 2(g)
2NO(g)
3.
PCl5
Cl = 35.5)
4.
N 2(g) 3H 2(g)
2NH3(g)
5.
6.
7.
at 25C. The standard enthalpy of formation of NH3(g) is 46kJ and standard entropies of
When S in the form of S8 is heated at 900K, the initial pressure of 1 atmosphere falls by
29% at equilibrium. This is because of conversion of some S8 to S2. Find the Kp for
reaction.
is 0.8 atm.
a)
What are the equilibrium concentration of the gases
at 817C and a total pressure
of 5 atm?
b)
At what total pressure, the gas contains 5% CO2 by
volume?
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152
8.
9.
10.

2NO + Cl2
into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B)_ and 3.5%, of
1-2pentadiene (C). The equilibrium was maintained at 175C. Calculate G0 for the
B
G10 ?
A :
B
C :
G 02 ?
0
0
and (C).
Objective
LEVEL I
1.
In a chemical reaction Kp is greater than Kc when
152

152
S
M
C
E
C
H
1
5
3
(a)
the number of molecules entering into the chemical
reaction is more than the number of molecules produced.
(b)
reaction is the same as the number of molecules produced.
(c)
reaction is less than the number of molecules produced.
(d)
the total number of moles of reactants is less than
the number of moles of products.
2.
3.
4.
Which of the following statements is not correct about the equilibrium constant ?
(a)
Its value does not depend upon the initial conc. of
the reactants
(b)
Its value does not depend upon the initial conc. of
the products
(c)
Its value does not depend upon nature of the
reactants.
(d)
Its value does not depend upon presence of catalyst.
An acid reacts with glycerine to form complex and equilibrium is established. If the heat
of reaction at constant volume for above reaction is 1200 cal more than at constant
pressure and the temperature is 300 K, then which of the following expression is true ?
Kp Kc
Kc Kp
(a)
(b)
Kp Kc
(c)
(d)
none of these.
The equilibrium constant for the reaction,
N2(g) + O2(g)
2NO(g) is 4 104
at 2000 K. In presence of a catalyst, equilibrium is attained ten times faster. Therefore,
the equilibrium constant, in presence of the catalyst, at 2000 K is
(a)
40 104
(b)
4 104
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154
5.
6.
7.
8.
9.
10.
11.
12.
(c)
4 103
(d)
difficult to compute without
more data.
At a given temperature, the equilibrium constant for the reaction,
PCl5 (g)
PCl3(g) + Cl2 (g)
is 2.0 103. At the same temperature, the equilibrium constant for the reaction,
PCl3(g) + Cl2(g)
PCl5 (g) will be
(a)
2.0 103
(b)
2.0 103
2
(c)
5.0 10
(d)
5.0 103.
In which of the following does the reaction go almost to completion ?
(a)
K = 106
(b)
K = 103
6
(c)
K = 10
(d)
K = 1012.
When pressure is applied to the equilibrium system
Ice
Water
which of the following phenomenon will happen ?
(a)
More ice will be formed
(b)
Water will
evaporate
(c)
More water will be formed (d)
Equilibrium
will not be disturbed.
Which of the following is not favourable condition for the formation SO3 ?
2SO2(g) + O2(g)
2SO3(g); H = 188 kJ
(a)
High pressure (b)
High temperature
(c)
Decreasing [SO3]
(d)
Increasing [SO2].
XY2 dissociates as XY2(g) XY(g) Y(g) . When the initial pressure of XY2 is 600
mm of Hg, the total pressure developed is 800 mm of Hg. K p for the reaction is
(a)
200
(b)
50
(c)
100
(d)
150.
The reactions
PCl5(g)
PCl3(g) Cl2(g) and COCl2(g)
CO(g) Cl2(g)
are simultaneously in equilibrium in an equilibrium box at constant volume. A few moles
of CO(g) are later introduced into the vessel. After some time, the new equilibrium
concentration of
PCl5 will remain unchanged (b)
Cl2 will be
(a)
greater
PCl5 will become less
PCl5 will
(c)
(d)
become greater.
PCl5 is 50% dissociated into PCl3 and Cl2 at atmosphere. It will be 40% dissociated at :
(a)
1.75 atm
(b)
1.84 atm
(c)
2.00 atm
(d)
1.25 atm.
One mole of N 2 O4(g) at 300 K is kept in a closed container under one atmosphere. It is
heated to 600 K when 20% of N 2 O 4(g) decomposes to NO 2(g) . The resultant pressure is
(a)
154
1.2 atm
(b)
2.4 atm

154
13.
(c)
2.0 atm
(d)
1.0 atm.
For the reversible reaction, N 2(g) 3H 2(g)
2NH 3(g) at 500C, the value of K p is
1.44 10 5 when partial pressure is measured in atmospheres. The corresponding value
of K c with concentration in mole litre 1 , is
(a)
1.44 10 5 /(8.314 773) 2
14.
S
M
C
E
C
H
1
5
5
1.44 10 5 /(0.082 500) 2
(b)
(c)
1.44 10 5 /(0.082 773) 2
(d)
5
2
1.44 10 /(0.082 773) .
For the reaction : 2HI(g)
H 2(g) I2(g) ; the degree of dissociation ( ) of HI(g) is
(a)
(c)
15.
1 2 Kp
2
2K p
1 2K p
(b)
(d)
1 2K p
2
2 Kp
1 2 Kp
For which of the following reactions, the degree of dissociation cannot be calculated from
the vapour density data
2HI(g)
I
II
H 2(g) I2(g)
2NH 3(g)
N 2(g) 3H 2(g)
III
2NO(g)
N 2(g) O 2(g)
IV
PCl5(g)
PCl3(g) Cl 2(g)
(a)
I and III
(b)
II and IV
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(c)
I and II(d)
III and IV.
LEVEL II
N 2O 4
2NO 2 , K c 4 . This reversible reaction is studied
graphically as shown in figure. Select the correct
statements out of I, II and III.
I. Reaction quotient has maximum value at point A
1.
2.
3.
4.
5.
(b)
(d)
(a)
(a)
(a)
6.
7.
8.
9.
10.
A
Concentration
156
D
C
G
Time
(a)
(d)
(a)
(a)
(a)
2.
3.
4.
II.
Reaction proceeds left to right at a point when [N 2 O 4 ] [NO 2 ] 0.1M
K C Q when point D or F is reached :
III.
(a)
I, II
(b)
II, III
(c)
I, III (d)
I, II, III.
At 30C, Kp for the dissociation reaction
SO2Cl2(g)
SO2(g) + Cl2(g)
2
is 2.9 10 atm. If the total pressure is 1 atm, the degree of dissociation of SO2Cl2 is
(a)
87% (b)
13%
(c)
17% (d)
29%
into CO on the addition of graphite. The value of K if the total pressure at equilibrium is
0.8 atm is
(a)
1.8 atm
(b)
3 atm
(c)
0.3 atm
(d)
0.18 atm
In the reaction PCl5 PCl3 + Cl2, the amounts of PCl5, PCl3 and Cl2 at equilibrium are
2 mole each and the total pressure is 3 atm. The equilibrium constant Kp is
(a)
1.0 atm
(b)
2.0 atm
(c)
3.0 atm
(d)
6.0 atm
156

156
5.
6.
7.
8.
9.
10.
S
M
C
E
C
H
1
5
7
When 20g of CaCO3 were put into 10 litre flask and heated to 800C, 35% CaCO3
remained unreacted at equilibrium, Kp for decomposition of CaCO3 is
(a)
1.145 atm
(b)
0.145 atm
(c)
2.145 atm
(d)
3.145 atm
The decomposition of N2O4 to NO2 is carried out at 280C in chloroform. When
equilibrium is reached, 0.2 mol of N2O4 and 2 103 mol of NO2 are present in 2 litre
solution. The equilibrium constant for the reaction, N 2 O 4 2NO 2 is
(a)
1 103
(b)
2 103
(c)
1 105
(d)
2 105
(a)
0.33 (b)
1.33
(c)
1.66 (d)
0.6
For the equilibrium, NH 4 HS(s) NH 3(g) H 2S (g)
the value of Kp is 0.109 atm2 at 300K. The vapour pressure of NH4HS at 300K would be
(a)
0.33 atm
(b)
0.109 atm
(c)
0.66 atm
(d)
1.0 atm
Two moles of an equimolar mixture of two alcohols, R1 OH and R 2 OH are
constant for the esterification of R1 OH with acetic acid is
: 3.3 (b)
: 3.7
(a)
: 3.5 (d)
: 3.9 .
(c)
A 1 M solution of glucose reaches dissociation equilibrium according to the equation
given below: 6HCHO C6 H12 O6
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11.
12.
What is the concentration of HCHO at equilibrium, if equilibrium constant is 6 1022?

(a)
1.6 108M (b)
3.2 106M
(c)
3.2 104M (d)
1.6 104M
reactions follow first order kinetics. If the half life of forward reaction (t1/ 2 )f is 400 sec.
and that of backward reaction (t1/ 2 )b is 250 sec. The equilibrium constant of the
CO 2(g) NO(g)
(a)
1.6
(b)
0.433
(c)
0.625 (d)
1.109.
At 27C NO and Cl2 gases are introduced in a 10 litre flask such that their initial partial
pressures are 20 and 16 atm respectively. The flask already contains 24 g of magnesium.
After some time, the amount of magnesium left was 0.2 moles due to the establishment of
following two equilibria
2NO(g) Cl2(g)
2NOCl(g)
1
Cl 2(g) Mg (s)
MgCl 2(s) ; K p 0.2 atm
13.
14.
15.
The final pressure of NOCl would be

(a)
7.84 atm
(b)
18.06 atm
(c)
129.6 atm
(d)
64.8 atm.
The CaCO3 is heated in a closed vessel of volume 1 litre at 600 K to form CaO and CO 2
. The minimum weight of CaCO3 required to establish the equilibrium
CaCO3(s)
CaO(s) CO 2(g) is (K p 2.25 atm)
(a)
2g
(b)
4.57 g
(c)
10g
(d)
100 g.
H 2 O(g)
H 2(g) 1 2 O 2(g) ;
(a)
0.32 (b)
0.08
(c)
0.04 (d)
0.16
One mole of N2O(g) is kept in a closed container along with gold catalyst at 450 K under
one atmosphere. It is heated to 900 K when it dissociates to N2(g) and O2(g) giving an
equilibrium pressure of 2.4 atm. The degree of dissociation of N2O(g) is
(a)
20% (b)
40%
(c)
50% (d)
60%.
158

158
S
M
C
E
C
H
1
5
9
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Answers to Assignments (Subjective)

LEVEL I
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
B
N2O4
False
Increase, because for given reaction H 0
4NO(g) + 6H2O(g) 4NH3(g) + 5O2(g)
n=3
While writing chemical equilibrium equation, molar concentration or partial pressure of
the reactants and products are taken as unity thus,
[CO]2
p2
Kc
; K p CO
a)
[CO 2 ]
p CO2
b)
Kc
[Hg 22 ]
[Hg 2 ]
c)
Kc
p3H2
[H 2 ]3
,
K
p
[H 2O]3
p3H 2O
d)
K c [H 2 ]2[O 2 ], K p p 2H2PO
In this question, concentration of three species i.e. SO 2 Cl 2 , SO 2 and Cl2 (g) each is
given, but is is not mentioned that whether the system is at equilibrium or not. So first
[SO 2 ][Cl2 ] (0.05)(0.05)
Q
0.05
[SO 2 Cl2 ]
(0.05)

state.
a) 0; b) 1.64.06M1
right to left
3.02 105
1.067
a) no effect; b) forward; c) backward
LEVEL II
1.
H2 = 0.111 atm, I2 = 0.111 atm, HI = 0.778 atm
2.
[H2] = 0.316 mole litre1, [I2] = 1.316 mol litre1, [HI] = 4.368 mol litre1
3.
Kp = 50, 0.11 mole
160

160
S
M
C
E
C
H
1
6
1
4.
5.
i) 0.681; ii) CO2 = 0.34 atm, CO = 1.16 atm; iii) H2O = 0.16 atm
a)
CO2 = H2 = 0.338 mole, CO = H2O = 0.112 mole
b)
CO2 = H2 = 0.593 mole, CO = H2O = 0.197 mole
6.
a)
0.1 mole, (b) 0.4 mole
7.
480 mm
8.
N2O4 = 0.095 atm, NO2 = 0.64 atm
9.
Kp = 1.77 atm, KC = 4 102 mole litre1
10.
0.969 atm
LEVEL III
1.
2.
3.
[I2] = 1.32 M, [HI] = 4.36 M

37.5%, 27.5%
(i)
Kc = 187.84, Kp = 0.0495
(ii)
P = 12.438 atm
4.
x=
2(dt do)
do
5.
6.
7.
8.
61.2%
PT= 1.17, PH2S 0.585 , PNH3 0.585
3.1420
PH 2O 1.62 103 atm , PH 2O 3.53 103 atm , PH 2O 3.64 103 atm ,
(i)
(ii)
SrCl2.2H2O
(iii)
60.5%
(iv)
60.5%
9.
(a)
8.0 cal
(b)
K2 = 0.93
10.
12.22 kJ mol-1.
LEVEL IV
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30946351,
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2K p
P
N2 = 79%, O2 = 21
4.53 g/litre
5.845
2.55 (atm)3
1.8 atm
a) CO = 0.041 mole litre1, CO2 = 0.015 mol litre1, (b) 0.145 atm
Kc = 279.64 litre2 mol2, Kp = 0.115 atm2
0.02042
G10 = 16.178kJ, G20 = 12.282 kJ, B > A, B > C, B > C >
Objective
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162

162

Chemical Equilibrium

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Chemical Equilibrium

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CHEMISTRY : CHEMICAL EQUILIBRIUM

Irreversible and Reversible Reactions

PCl5(g) PCl3(g) Cl2(g) (Thermal dissociation)

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But, if the reaction is carried out in a closed container, this reaction

At any temperature, vapourisation of water takes place, initially the

This can be shown graphically.

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So, state of chemical equilibrium can be defined as the state when

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concentration the active mass is essentially the same as the molar

Applying law of mass action,

Where, Kc is the equilibrium constant in terms of molar

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From law of mass action,

From ideal gas equation

Thus, we can say in a mixture of gases, Partial pressure of any

Relationship Between Kp and Kc

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From the ideal gas equation,

So, PB = [B]RT ; PD = [D]RT

[C]c (RT) c [D]d (RT) d

[C]c [D]d (RT)(c d)

[A]a [B]b (RT)(a b)

Applying law of mass action,

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Illustration 3: At 400K for the gaseous reaction

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Substituting these values in the equation

Kc = 4.648 105Type of Chemical reactions

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Now if we consider the reversible reaction.

Rate of forward reaction

(rf ) [A]m1 [B]m 2

[ ]: denotes activity or active mass

Rate of backward reaction (rb ) (k b ) [C]n1 [D]n 2

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k f [A]m1 [B]m 2 K b [C]n1 [D]n 2

Keq is known as equilibrium constant.

Rate of forward reaction = Rrate of backward reaction.

External change in pressure, temperature and concentration at equilibrium causes

Activity or active mass is denoted by a or [ ].

Activity of gases is expressed in partial pressure

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Activity of pure solids and pure liquids is taken to be unity.

When activities are expressed in concentration (mole/litre) then equilibrium

Only a change in temperature can change the value of equilibrium constant Kp or

A very large value of Kc or Kp signifies that reaction is going in forward direction

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If a chemical equation is multiplied by a certain factor, its equilibrium constant

If a reaction is obtained by adding two reactions then its equilibrium constant

If a reaction is obtained by substracting two reactions then its equilibrium

Reaction Quotient (Q)