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CHEMICAL EQUILIBRIUM
Total Sessions – 06
SESSION – 1
AIM - To introduce the concept of equilibrium
TYPES OF REACTIONS
1. Irreversible Reactions:
The chemical reactions in which the products formed do not combine to give
back the reactants are known as irreversible reaction.
Properties of irreversible reactions
a. Reactions in which reactant react to form product only.
b. Reactions proceed in one single direction.
c. Always proceed to completion.
d. In this type of reactions, if product is gaseous in state, then they can
escape from reacting site and if they are solid in state they will
precipitate.
Examples:
a. Thermal decomposition in open vessel. 2KClO3 ⟶ 2KCl + 3O2
b. All the neutralization reaction of strong acid and strong base.
NaOH + HCl ⟶ NaCl + H2 O
c. Ionic precipitation reaction. AgNO3 + NaCl ⟶ AgCl + NaNO3

d. Oxidation-reduction reaction SnCl2 + 2FeCl2 ⟶ SnCl4 + 2FeCl2

2. Reversible Reactions:
The reactions in which the products can react with one another to give back
the reactants again under suitable conditions called as reversible reaction.
Properties of reversible reactions
a. In these types of reactions, reactant react to form product and product
further react to form reactant.
b. Reactions proceed in both directions.
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c. These types of reactions never complete in nature.

d. Products neither escape nor precipitate.
Examples
a. Thermal dissociation in closed vessel.

PCl5 ⇌ PCl3 + Cl2

b. Salt hydrolysis except strong acid and strong base
NH4 Cl + H2 O ⇌ NH4 OH + HCl
c. All normal gaseous reactions in closed vessel.
N2 + O2 ⇌ 2NO
H2 + I2 ⇌ 2HI
N2 + 3H2 ⇌ 2NH3 2SO3 ⇌ 2SO2 + O2
d. All the reactions of organic hydrolysis.
CH3 C OC2H5 + H OH CH3 C OH + C2H5 OH
O O
Reversible reactions are also of two types:
I. Homogenous Reversible Reactions:
If in a reversible reactions physical state of reactant and product are same
it is called as homogenous reversible reaction.
N2 (g) + O2 (g) ⇌ 2NO(g)
N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
CH3 COOC2 H5 (l) + H2 O(l) ⇌ CH3 COOH(l) + C2 H5 OH(l)
Graphite (s) ⇌ Diamond (s)
SRh (s) ⇌ Smono (s)
II. Heterogeneous Reversible Reactions:
If in a reversible reaction physical state of reactant and product are
different it iscalled as heterogeneous reversible reaction.
CaCO3 (s) ⇌ CaO(s) + CO2 (g)
FeO(s) + CO(g) ⇌ Fe(s) + CO2 (g)
3Fe(s) + 4H2 O(g) ⇌ Fe3 O4 (s) + 4H2 (g)
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State Of Equilibrium
In general, reactions (physical and chemical) do not proceed to completion
when they are carried out in a closed container. Consider vaporization of
water, in closed vessel
Liquid water ⇌ Water vapour
• At any temperature, vaporization 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.
• Similarly, in chemical reactions, for exp, 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, PCl3(g) and Cl2(g) are
formed due to dissociation of PCl5(g) . After a certain interval of time, the
concentration ofPCl5(g), PCl3(g) and Cl2(g)each becomes constant.
It does not mean that at this point of time, dissociation of PCl5(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.
ex: PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
This can be shown graphically.

Reactant
Forward Rate
Mole/litre
Concentration

Rate

Backward Rate
Product
Equilibrium
Equilibrium
Time Time

So, state of chemical equilibrium in a reversible reaction at which both forward and
can be defined as the state backward reactions occur of the same speed.
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Classification of equilibrium:
A. Equilibrium in Physical Process:
1. Solid - Liquid equilibrium:- Certain amount of ice & water are taken in
a thermo flask. Exp- H2 O(s) ⇌ H2 O(L)
When temperature remains constant, the mass of ice & water remains
constant. Some liquid molecules adhere to ice and simultaneously some
molecules of ice enter into liquid. The no. of molecules of water forming ice &
no. of molecules of ice forming water are same i.e., eq. is attained ∴ no
change in mass of ice & water.
The temperature at which the solid & the liquid phase are at equilibrium at
atmospheric pressure is called freezing point.
2. Liquid – Vapour equilibrium:- Liquid water is taken in closed vessel at
room temp, it starts evaporating.
Exp- H2 O(l) ⇌ H2 O(g)
As process continuous, more water molecules escape & pressure increases
later, condensation takes place. Finally, rate of evaporation becomes equal
to rate of condensation.
The pressure exerted by the vapour over the liquid when it is in equilibrium
with it is called vapor pressure of the liquid.
The temperature at which the Vapour Pressure of liquid is equal to
atmospheric Pressure, is called Boiling Point.
Different liquids have different vapour pressure. At the same temperature,
the liquid which has a higher Vapour Pressure is more volatile or boils at a
lower temperature.
3. Solid – Vapour equilibrium:- This exists when solid sublimes to vapour.
I2(s) ⇌ I2(g)
When we heat some I2 in a closed vessel, it sublimes & vessel filled with
violet vapours. After sometime, intensity of violet colour remains constant. At
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this state equilibrium is attained i.e., Rate of sublimation of solid I2 to form

vapour is equal to rate of condensation of I2 vapour to give solid I2 .
4. Solid – Solution equilibrium:
Sugar (in solution) ⇌ Sugar(Solid)
When more and more amount of sugar is added into a fixed volume of water
at room temperature, after sometime no more sugar dissolves and settles at
the bottom. The solution is now said to be saturated and the concentration
of sugar in the solution remains constant.
This indicates that a state of equilibrium has been reached
between the undissolved sugar & dissolved sugar.
5. Gas – Solution equilibrium: In carbonated drinks,
CO2(g) ⇌ CO2 (in solution)
At a given temperature, a liquid can dissolve only a
certain definite mass of the gas. This suggests that a state of equilibrium
exists between the molecules in the gaseous state and the molecules dissolved
in the liquid.
The solubility of a gas in the liquid depends on the pressure.
It is explained by Henry’s law.
i.e., the mass of a gas dissolved in a given mass of solvent at a particular
temp is directly proportional to the pressure of the gas above the solvent.
m ∝ p ⟹ m = kp

B. Equilibrium in Chemical Process:

Ex 1. Decomposition of 𝐂𝐚𝐂𝐎𝟑:
When CaCO3 is heated in a closed vessel at 8000 C, it decomposes into
CaO & CO2 . Due to production of CO2 , pressure will increases in the vessel.
After sometime, it is observed that pressure becomes constant at constant
temperature, even though some CaCO3 is still present. This constancy confirms
that equilibrium has been reached.
CaCO3 (s) ⇌ CaO(s) + CO2 (g)
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Ex 2. Reaction between 𝐇𝟐 & 𝐈𝟐:

When H2 & I2 are heated in a closed vessel, HI is formed. At the beginning
the reaction mixture is deep violet in colour due to presence of I2 . As the
reaction proceeds the intensity of the colour decreases due to decrease in
concentration of I2 and increase in concentration of HI . After some time,
the intensity of colour remains constant. This confirms that equilibrium has
been attained.
H2 + I2 ⇌ 2HI
Characteristics of Chemical Equilibrium:
1. Equilibrium is attained for reversible reactions only in a closed vessel.
2. At equilibrium, the rate of forward reaction is equal to rate of backward
reaction.
3. For a reversible reaction, the equilibrium constant for the forward reaction is
inverse of the equilibrium constant for the backward reaction.
In general, K forward reaction = K′ 1
backward reaction

4. At Equilibrium, all observable or measurable properties such as pressure,

concentration, colour and density etc remains constant.
5. It is dynamic in nature i.e. reaction takes place in both the directions at
same speed although appears to be stopped.
6. At equilibrium, concentration of reactants and products remains constant.
7. Catalyst has no effect on the position of chemical equilibrium, but it helps to
attain the Equilibrium state rapidly.
A catalyst has the same effect on both forward and backward reactions.
8. Change in pressure, temperature or concentration favours either forward or
backward reaction and thus shifts the equilibrium point in one direction.
9. Change in free energy is equal to zero at equilibrium.
10. Equilibrium can be homogeneous or heterogeneous.
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11. Equilibrium can be attained in either direction. The value of an equilibrium

constant tells the extent to which a reaction proceeds in the forward or
reverse direction.

CLASS EXERCISE
1. An example of reversible reaction is:
a) Pb(NO3 )2 + 2 NaI = PbI2 + 2NaNo3
b) AgNO3 + HCl = AgCl + HNO3
c) 2Na + 2H2 O = 2 NaOH + H2
d)KNO3 + NaCl = KCl + NaNO3
2. Which of the following is not a reversible reaction?
a) 2HI(g) = H2 (g) + I2 (g) b)PCl5(g) = PCl3 (g) + Cl2 (g)
c) 2KClO3 (s) = 2KCl(s) + 3O2 (g) d)CaCO3 (s) = CaO(s) + CO2 (g)
3. Which one is not correct for a reversible reaction?
a) The reaction is never completed
b) The reactants are present in the initial stage but after that the
reactants and products are always present in the mixture.
c) At equilibrium only products are present
d)When the reaction is carried out in a closed vessel, it attains equilibrium
state after suitabletime.
4. The state of equilibrium refers to
a) State of rest b) Dynamic state
c) Stationary state d) State of inertness
5. In time kiln, the reversible reaction;CaCO3(g) ⇌ CaO(s) + CO2(g) proceeds to
completion because:
a) Of high temperature b) CO2 escapes out
c) CaO is removed d) Of low temperature
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HOME EXERCISE
1. A reversible reaction is one which
a) proceeds in both directions b) proceeds in one direction
c) proceeds spontaneously d) All the above statements are wrong
2. Which of the following is a characteristic of a reversible reaction?
a) It can never proceed to completion
b) It can be influenced by a catalyst
c) Number of moles of reactants and products are equal
d) None of the above
3. All reactions which have chemical disintegration are
a) exothermic b) reversible
c) reversible and exothermic
d) reversible or irreversible and endothermic or exothermic
4. In any chemical reaction, equilibrium is supposed to be establish when
a) mutual opposite reactions undergo
b) velocity of mutual reactions become equal
c) concentration of reactants and resulting products are equal
d) the temperature of mutual opposite reactions become equal
5. In chemical reaction,A ⇌ B,the system will be known in equilibrium when
a) 50% of A changes to B
b) A completely changes to B
c) only10% of A changes to B
d) the rate of change of A to B and B to A on both the sides are same
NCERT Text Book Questions :7. 1, 7. 32.
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SESSION – 2AND 3
AIM - To introduce rate or velocity, active mass, equilibrium constant through Law
of Mass Action.
Rate or Velocity of a reaction – is the change in molar concentration of the
reactants or products in unit time.
𝐝𝐱
It is denoted by , where dx is the change in concentration of the reactants or
𝐝𝐭
products in a given time dt.
For a reaction R ⟶ P
−𝐝𝐑
Rate = ,where -dR indicates the decrease in the concentration id reactants.
𝐝𝐭
𝐝𝐏
For product, Rate = , +dp indicates the increase in concentration of products.
𝐝𝐭
Unit of the rate of reaction is mol L-1 s-1
Active Mass- is also known as molar concentration.It is shown by square brackets [ ].
The number of g molecules present in unit volume (say 1 litre) is called active
mass.
Weight of subs tance in g
g molecule = Molecular weight

gram molecule
Active mass = Volume (in liter)

Weight of subs tance in g

or Active mass = Molecular weight  Volume

The unit of active mass is g molecule/Litre

The active mass or partial pressure of solids is regarded as unity because molecules
are closely packed in solids
Example: What should be the respective active masses in g mole/litre when 4g of
H2 and 128g of HI are present in a two-litre container
4g
Solution : (a) Active mass of H2 = = 1 gm mol/lit
2 2

(Molecular weight of H2 = 2)
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128
(b) Active mass of HI = = 0.5g mole/litre
128  2

(Molecular weight of HI = 1 + 127 = 128)

Remember -
1 g molecule H2 = 2g
1 g molecule O2 = 32g
1 g molecule N2 = 28g
1 g molecule NH3 = 17g
1 g molecule I2 = 254g

Example: If 4g molecule of H2 is present in a two-litre container, the active mass

will be
g molecule 4
Solution: Active mass = Volume = 2 = 2 g mole/litre

LAW OF MASS ACTION

Guldberg and Waage in 1807 gave this law and according to this law, “At
constant temperature, the rate of a reaction is directly proportional to the
product of active masses(molar concentrations) of the reactants”.
For a reactation, A ⟶ Product
𝐝𝐱
Rate,
𝐝𝐭
= K[A] where K is Rate constant.
For a reaction, A + B ⟶ Product
Rate = K [A] [ B]
For a reaction, 2A + 3B ⟶ Product
Rate = K [A] [A] [ B] [B] [B]
Rate = K [A]2 [ B]3
aA + bB ⟶ Product
Rate = K [ A]a [ B]b
EX.1: 8.5grams of ammonia are dissolved to form 4L aqueous solution. Calculate
the active mass.
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weight 8.5
n= = = 0.5;
Sol. Grammolecular weight 17
n 0.5
=
Active mass = V = 0.125 mol L-1
4

EX.2: What is the active mass of one litre of Nitrogen gas at NTP?
Sol. At STP, active mass of Nitrogen = 1 atm
At STP,22.4 litres of Nitrogen= 1 mole
n 1
= = = 0.0446
Active mass V 22.4 mol L-1

EX.3: Determine the active mass of NaOH in a solution containing 4gm of NaOH in
500ml.
no.of moles 4 1
Solution Active mass = = × = 0.2mL−1
Vol.of solution inL 40 0.5

EX.4: Calculate the active masses of ethanol and carbon tetrachloride taking
their densities to be 0.8 and 1.58g per ml respectively.
Solution - Active mass = Molar conc. = No. of Moles Litres–1.
(i) Active mass of ethanol
1litre of ethanol = 1000ml of ethanol
= 1000 × 0.8m of ethanol.
[Q density of C2H5OH = 0.8gl–1] = 800gm of ethanol.
No. of moles/ litre of ethanol = 800 = 17.39 [Q Mol wt. of C2H5OH=46]
46

Hence active mass of ethanol = 17.39moles/litre.

(ii) Calculation of active mass of CCl4
1 litre of CCl4 = 1000ml of CCl4
= 1000 × 1.58g [Q density of CCl4 =1.58 gl–1]
= 1580g of CCl4
No. of moles/litre = 1580
154
= 10.26 [Q Mol wt. of CCl4 = 154]

Hence active mass of CCl4 = 10.26moles/litre

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Equilibrium Constant Kc in terms of concentration:

Consider the following reversible reaction
aA + bB ⇌ cC + dD
Rate of forward reaction, R f ∝ [A]a [B]b
R f = k f [A]a [B]b --------(i)
Where k f =rate constant of forward reaction
Rate of reverse reaction, R b ∝ [C]c [D]d
R b = k b [C]c [D]d --------(ii)
Where k b =rate constant of reverse reaction
At equilibrium,
Rate of forward reaction = Rate of reverse reaction
i.e .R f = R b
So, from equations (i) and (ii) we get
k f [A]a [B]b = k b [C]c [D]d
kf [C]c [D]d
or, = [A]a [B]b
kb
kf [C]c [D]d
= Kc =
kb [A]a [B]b

Where, 𝐊 𝐜 is the equilibrium constant in terms of molar concentration.

The equilibrium constant, at a given temperature, is the ratio of rate constant of
forward and backward reactions. Or
𝐊 𝐜 is defined as the ratio of the product of molar concentration of
the products and to the product of the molar concentration of the reactants in
which concentration terms raised to the power of respective stoichiometric
coefficient in a balanced chemical equation at constant T.
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Problem.1: When alcohol and acetic acid are mixed together in equimolecular
proportions, 66.5% are converted into ester. Calculate the equilibrium
constant of the reaction.
Solution The concerned reaction is
CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O
Let initial conc. of alcohol = 100moles
initial conc. of acid = 100moles
conc. of ester at equb. = 66.5moles
conc. of water at equb. = 66.5moles
conc. of alcohol at equb. = 100 – 66.5moles = 33.5moles
[CH3 COOC2 H5 ][H2 O] 66.5×66.5
K= = ≈4
[CH3 COOH][C2 H5 OH] 33.5×33.5

Problem.2: 1.1mol of A is mixed with 2.2mol of B and the mixture is kept in a one
litre flask till the equilibrium, A + 2B ⇌ 2C + D is reached. At equilibrium
0.2mol of C is formed. Calculate the equilibrium constant for the above
reaction.
Solution
At start 1.1 mol 2.2 mol 0 0
A + 2B ‡ˆ ˆˆ †ˆ 2C + D
At equb (1.1 − 0.1) mol (2.2 − 0.2) mol 0.2 mol 0.1 mol
= 1 mol = 2mol
0.2 0.1 1 2
Thus, [C] = mL−1 ; [D] = mL−1 [A] = mL−1 ; [B] = mL−1
1 1 1 1
[C2 ] [D] (0.2)2  0.1 0.2  0.2  0.1
KC = = = = 1  10 −3
[A] [B] 2
1 2 2
1 2  2

Equilibrium Constant (𝐊 𝐩 )in terms of Partial Pressures:

Consider the same general reaction taking place at constant temperature,
aA(g) + bB(g) ⇌ cC(g) + dD(g)
From law of mass action,
[C]c [D]d
K c = [A]a [B]b ------- (1)
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n
From ideal gas equation PV = nRT or, P = V RT
𝐧
At constant temperature, 𝐏 ∝ 𝐕
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
Pcc × PDd
Kp =
PAa × PBb

Relationship between KP & KC

aA(g) + bB(g) ⇌ cC(g) + dD(g)
[C]c [D]d PcC ×Pd
D
K c = [A]a [B]b and, K p =
PaA ×Pb
B

From the ideal gas equation,

PV = nRT
n
P = RT
V
So, PA = [A]RT ; PB = [B]RT; PC = [C]RT ; PD = [D]RT
Substituting the values of PA, PB, PC and PD, we get
[C]c (RT)c × [D]d (RT)d
Kp =
[A]a (RT)a × [B]b (RT)b
[C]c [D]d (RT)(c+d)
Or K p = [A]a [B]b × (RT)(a+b)
Or K p = K c (RT)Δn
Where, Δn = (c + d) − (a + b)
i.e., Δn =no of moles of gaseous products - no. of moles of gaseous reactants.
Case (i): If Δn = O; K c = K p
Ex: H2(g) + I2 (g) ⇌ 2HI(g)
Case (ii): If Δn is positive; K p > K c
Ex: PCl5(g) ⇌ PCl3(g) + Cl2 (g)
Δn = 2 − 1 = 1
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∴ K p = K c (RT)
Case (iii): If Δn is negative; K p < K c
Ex: N2(g) + 3H2(g) ⇌ 2NH3(g)
Δn = 2 − 4 = −2
Kp = Kc (RT)−2

Example 1. The value of KP for the reaction 2H2O(g) + 2Cl2(g) ⇌ 4HCl(g) + O2(g) is
0.035atm at 400oC, when the partial pressures are expressed in
atmosphere. Calculate KC for the reaction 12 O2(g) + 2HCl(g) ⇌ Cl2(g) + H2O(g)
Solution: K P = K C (RT)Δn

Δn = Moles of product – moles of reactance =5−4=1

R = 0.082Latm/molK, T = 400 + 273 = 673K
∴ 0.035 = K C (0.082 × 673)
K C = 6.342 × 10−4 moll−1
1
∴ K′C for the reverse reaction would be KC
.
1
∴ K′C = = 1576.8(moll−1 )−1 .
6.342 × 10−4
When a reaction is multiplied by any number n (integer or a fraction)
the K′C or K′P becomes(KC )n or (KP )n of the original reaction.
1
∴ K C for 2 O2 (g) + 2HCl(g) ⇌ Cl2 (g) + H2 O(g) is √1576.8 = 39.7(mol. l−1 )−½

Problem 2. K P for the equilibrium, FeO(s) + CO(g) ⇌ Fe(s) + CO2(g) at 1000°C is 0.4. If
CO(g) at a pressure of 1atm and excess FeO(s)are placed in container
at 1000oC, what are pressures of CO(g) and CO2 (g) when equilibrium is
attained?
Solution: Acc, to ideal gas equn, partial pressures are proportional to the no. of
moles present. Since moles of CO2 formed equals moles of CO consumed,
the drop in partial of CO will equal the partial pressure of CO2
produced. Let the partial pressure of CO2 at equilibrium be ′x′ atm.
Then, partial pressure of CO will be (1 − x)atm.
P x
Since K p = PCO2 = 1−x = 0.4 ⇒ x = 0.286
CO

Hence PCO = 1 − x = 𝟎. 𝟕𝟏𝟒𝐚𝐭𝐦

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Problem 3. 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 Pand the total pressure P.
Solution 2AB2 (g) ⇌ 2AB(g) + B2 (g)
Mole before dissociation 1 0 0
𝑥
Mole after dissociation (1 − x) x
2
x x
Total mole at equilibrium (∑n) = 1 − x + x + 2 = 1 + 2
nB2 ×(nAB )2 P Δn
Now, Kp =
(nAB2 )
×[ ]
∑n
x 1
,(x)2 P 𝑥3
KP = 2
(1−x)2
×[
1+2
x] =
2
[Q x is small, 1 − x  1 and1 + x  1 ]
2
3 2KP
or x= √
P

Problem 4. In which case does the reaction go farthest to completion:

K = 1; K = 1010 ; K = 10−1 and why?
[Product]
Solution The ratio [Reactant] is maximum when K = 1010 and thus reaction goes
farthest to completion when K = 1010 .

Problem 5. The K C for A2 (g) + B2 (g) ⇌ 2AB(g) at 100°C is 50. If one litre flask
containing one mole of A2 is connected with a two litre flask containing
2mole of B2 . how many mole of AB will be formed at 100°C?
Solution A2 (g) + B2 (g) ⇌ AB2
Initial mole 1 2 0
Final mole at equilibrium (1 − x) (2 − x) 2x

Total volume of both containers on joining becomes 3 litre.

At equilibrium, [A2 ] = 1−x
3
; [B2 ] =
2−x
3
; [AB] =
2x
3
[AB]2 4x2 4x2
 KC = = 1−x 2−x = (2−3x+x2 ) = 50
[A2 ][B2 ] 9( 3 )( 3 )

 4𝑥 2 = 100 − 150𝑥 + 50𝑥 2

or 46x 2 − 150x + 100 = 0
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x = 0.93 mol and 2.326 which is not valid since x | 2

Mole of AB = 2x = 2(0.93) = 𝟏. 𝟖𝟔

Problem 6. NH3 is heated at 15atm from 27°C to 247°C assuming volume constant.
The new pressure becomes 50atm at equilibrium of the reaction
2NH3 ⇌ N2 + 3NH2 . Calculate % of mole of NH3 actually decomposed.
Solution 2NH3 ⇌ N2 + 3H2

Initial mole a 0 0
Mole at equilibrium (a − 2x) x 3x
Initial pressure of a mole of NH3 of NH3 = P atm at 347°C
15 P
 =
300 620
 P = 31atm
At constant volume and at 347°C mole  pressure

a ∝ 31 (Before equilibrium)
a + 2x ∝ 50 (After equilibrium)
𝑎+2𝑥 50
 = 31
𝑎
19
 x= a
62
2x 2×19a
 % of NH 3 decomposed = × 100 = × 100
a 62×a
= 𝟔𝟏. 𝟑%

Characteristics of Equilibrium Constant:

The value of equilibrium constant is independent of the following factors:
1. Initial concentrations of the reactants involved
2. The presence of a catalyst
3. The direction from which the equilibrium has been attained
4. The presence of inert materials
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Factors determining the value of equilibrium constant:

The value of equilibrium constant depends in the following factors:
1. The mode of representation of the reaction:
A+B⇌ C+D
The equilibrium constant for the reaction,
[C][D]
K c = [A][B] …(i)
Now, for backward reaction,
C+D⇌A+B
The equilibrium constant for the reaction is
[A][B]
K ′c = … … … … . (ii)
[C][D]
1
The equilibrium constant, K ′c is the reciprocal of K c i.e., K ′c = K
c

2. Stoichiometry of the chemical equation:

Example 1 :
2NO2 ⇌ N2 + 2O2 … (i)
1
Or NO2 ⇌ N2 + O2 ….(ii)
2
[N2 ][O2 ]2
For equation (i), the value of Kc = [NO2 ]2
1
[N2 ]2 [O2 ]
For equation (ii), the value of K ′c = [NO2 ]

Thus, the two constants are related as

𝐊 ′𝐜 = √𝐊 𝐜
In general, when a given reversible system is divided by n , the numerical
value of equilibrium constant is obtained by taking n√k of the original system.
Example 2:
1 1
H2 + I2 ⇌ HI … (i)
2 2
H2 + I2 ⇌ 2HI …(ii)
1 1
[H2 ]2 [I2 ]2
For equation (i), the value of Kc = [HI]
ACTIVE SITE EDUTECH - 9844532971

[H2 ][I2 ]
For equation (ii), the value of K ′c = [HI]2
Thus, the two constants are related to each other
𝐊 ′𝐜 = 𝐊 𝟐𝐜
In general, when a balanced equation having equilibrium constant K c , is
multiplied by a certain value n, the equilibrium constant for the new equation
will be equal to (K c )n .

3. Use of partial pressures instead of concentrations: When the reactants and

products are in gaseous state, the partial pressures can be used instead of
concentrations at a definite temperature, as the partial pressure of a
substance is proportional to its concentration in the gas phase.
K p = K c (RT)Δn
K p can be equal or less than or greater than Kc, depending upon the
chemical reaction.
4. Temperature: According to Arrhenius equation,
E
−
K = A. e …(i) RT

Where, k = rate constant,

E = activation energy,
R= gas constant.
T = absolute temperature and e = exponential constant.
k2 −E 1 1
log = [ − ] …. (ii)
k1 2303R T2 T1

When, T2 > T1
For forward reaction,
kf Ef 1 1
log ( 2 ) = − [ − ] … . (iii)
k f1 2.303R T2 T1
For backward reaction,
ACTIVE SITE EDUTECH - 9844532971

kb Eb 1 1
log ( 2 ) = − [ − ] … … … . . (iv)
k b1 2.303R T2 T1
Subtracting eq. (iii) from eq. (iv), we get
Kf2
Kb (Ef − Eb ) 1 1
log ( k 2 ) = − [ − ]
f1 2.303R T2 T1
k b1
k2 ΔH 1 1
log ( )=− [ − ] … … . (v)
k1 2.303R T2 T1
Where, ΔH is the heat of reaction at constant volume and K1 and K2 are the
equilibrium constants of a reaction at temperatures T1 and T2 (T2 > T1 )
The effect of temperatures can be studied in the following three cases
First Case:- ΔH = 0, i.e. neither heat is evolved, not absorbed.
k2 ΔH 1 1
log ( )=− [ − ]
k1 2.303R T2 T1
So, log K 2 − log K1 = 0
Or log k 2 = log k1
Or K 2 = K1
Thus, equilibrium constant remains the same at all temperatures.
Second case:- When, ΔH = +ve , i.e., heat is absorbed endothermic reaction. The
temperature T2 is higher than T1 .
k ΔH 1 1
log ( 2) = − [ − ]
k 2.303R T
1 T 2 1
1 1
Thus,(𝑇 − 𝑇 ) is negative,
2 1
So, logK2 − logK1 = +ve
Or logK2 > logK1
Or K 2 > K1
The value of equilibrium constant increases with increase in temperature in the
case of endothermic reactions.
Third case:- When ΔH = −ve , i.e, heat is evolved in exothermic reaction. The
temperature T2 is higher than T1 (T2 > T1)
k ΔH 1 1
log ( 2) = − [ − ]
k 1 2.303R T T 2 1
1 1
Thus (𝑇 − 𝑇 ) is positive,
2 1
So, log K 2 − logK1 = −ve
ACTIVE SITE EDUTECH - 9844532971

Or log K1 > log K 2

Or K1 > K 2
The value of equilibrium constant decreases with increase in temperature in the
case of exothermic reactions.

Problem 1. At 10650C, Kp = 0.0118atm for the reaction

2H2S(g) 2H2(g)+ S2(g)
The enthalpy of the reaction is 177.3kJ/mol. Calculate the equilibrium
constant at 12000C. (Given R = 8.314J)
Solution: The effect of temperature over the equilibrium constant is given by,
Van’t Hoff equation:
K 11 ΔH T2 −T1
log p
= 2.303R
[
T1 T2
]
K 1p

K 1p and K 11
are the equilibrium constants at temperatures T1 and T2
p

T1 = 1065 + 273 = 1338K and K = 0.0118 1

p

T2 = 1200 + 272 = 1473K and K = ? 11

p

K11
p 177 .3 1473 − 1338 
log =  1473  1338 
−3  
K1p 2.303  8.314  10
177 .3  135
=
2.303  8.314  1473  1338  10 − 3
177 .3  135  10 3
= 2.303  8.314  1473  1338
= 0.6342

K11
p
= 4.307
K1p
p =4.307 K p = 4.307  0.0118atm = 0.0508atm
K 11 1

Problem 2. For the reaction N2(g)+3H2(g) 2NH3(g) at 773K, the equilibrium

constant Kp=1.40410-5Pa-2. Calculate the value of Kc for this equilibrium
with concentration units of mol/L and mol/m3. [R = 8.134J/k/mol]
Solution: N2(g) + 3H2(g) 2NH3(g)
n= - 2.0
Kp = 1.404  10-5Pa-2 = 1.404  10-5(N/m2)2
Kp = Kc.(RT)-2
−2 2
Kc = Kp. (RT)2 = 1.404  10-5  N 
 2 
 8.314 
  (773 K )
2
m   K.mol 
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= 1.404  10 − 5 m 4

(8.314 )2  N 2 m 2 (773 K )2
N2 K 2 .mol 2
5.798  10 −10 m 6 5.798  10 −8
= =
mol 2 mol 2 / m 6
= 5.79810-8C-2
where C = conc. in mol/m3

Units of Equilibrium Constant- The units of equilibrium constant vary in case of

different reactions.
- ‘K’ has no units for a reaction in which total number of moles of
reactants and products are the same.
For exp , for dissociation of nitric oxide, Kc has no units.
2NO ⇌ N2 + O2
[N2 ][O2 ]
Kc =
[NO]2
- 𝐊𝐜will have units for a reaction in which the total number of moles of
reactants and products are different.
For exp, for decomposition of PCl5, the Kc has mol/litre units.
PCl5 ⇌ PCl3 + Cl2
[PCl3 ][Cl2 ]
Kc =
[PCl5 ]
In the formation of ammonia,
N2 + 3H2 ⟶ 2NH3
[NH3 ]2
K c = [N 3
Kc has 𝐥𝐢𝐭𝐫𝐞𝟐 𝐦𝐨𝐥−𝟐 units
2 ][H2 ]

In general; unit of K c = [M]Δn

Where, M = mol litr −1
Δn =no, of gaseous moles of products – no, of gaseous moles of reactants.

Note: (i) The above relation can be used in homogeneous liquid system.
(ii) Similarly, the unit of K p = [atm]Δn
ACTIVE SITE EDUTECH - 9844532971

NOTE
• If Kc > 103 , products predominate over reactants. If Kc is very large, the
reaction proceeds almost all the way to completion.
• If Kc < 10−3 , reactants predominate over products. If Kc is very small, the
reaction proceeds hardly at all.
• If Kc is in the range 10−3 to 103 , appreaciable concentration of both
reactants and products are present.
Kc
Reaction proceeds Reaction proceeds to
hardly at all 10–3 103 completion
Both reactants and products
are present at equilibrium

Reaction Quotient OR Mass Action Ratio

Let us consider a reaction:
A + B ⇌C + D
[C][D]
Q = [A][B]
Q is denoted as Qc or Qp depending upon whether the concentration is taken
in terms of moles per litre or partial pressures respectively.
With the help of mass action ratio we can determine whether the reaction is
at equilibrium or not.
I. When, 𝐐𝐜 = 𝐊 𝐜 𝐨𝐫 𝐐𝐩 = 𝐊 𝐩 , then the reversible reaction is at equilibrium,
i.e, the rate of forward and backward reaction becomes equal.
II. When, 𝐐𝐜 < 𝐊 𝐜 𝐨𝐫 𝐐𝐩 < 𝐊 𝐩 . The reaction will be fast in forward direction,
i.e, reaction has tendency to form product/products.
Rate of forward reaction > Rate of backward reaction.
III. When, 𝐐𝐜 > 𝐊 𝐜 𝐨𝐫 𝐐𝐩 > 𝐊 𝐩 . The reaction will be fast in backward direction,
i.e, have a tendency to form reactants.
Rate of forward reaction < Rate of backward reaction.

Q Kc Q Kc Q Kc

Reactants → Products Equilibrium Reactants  Products

ACTIVE SITE EDUTECH - 9844532971

Problem 1. For the reaction,

A(g) + B(g) 2C(g) at 25°C, in a 2litre vessel contains 1, 2, 3 moles
of respectively. Predict the direction of the reaction if
(a) Kc for the reaction is 3
(b) Kc for the reaction is 6
(c) Kc for the reaction is 4.5
Solution: A(g) + B(g) 2C(g)
3 2
[C]2 (2) 9
Reaction quotient Q = [A][B]
= 1 2 = = 4.5
2
×
2 2
(a) ∴ Q > Kc , therefore, backward reaction will be followed
(b) ∵ Q < K c ∵The forward reaction is followed
(c) Q = Kc  The reaction is at equilibrium

Problem 2. For the reaction: A(aq)+ B(aq) ⇌ C(aq) +D(aq) , the net rate of
consumption of B at 25C and at any time 't' is as given below
d [B ]
- dt = {410-4[A] [B] – 1.3310-5 [C] [D]} mol L-1 min-1.
Predict whether the reaction will be spontaneous in the direction as
written in reaction mixture in which each A, B, C and D is having a
concentration of 1mol L-1?
K1
Solution: K= K2
4×10−4
= = 30
1.33×10−5
[C][D]
Q= [A][B]
1×1
= 1×1= 1 < K
Since Q < K, so the above reaction is spontaneous in the forward direction.

CLASS EXERCISE
1. The concentration of reactants is increased by x, then equilibrium constant
K becomes
K 𝐾
a) ln x b) c) K + x d) K
𝑥
ACTIVE SITE EDUTECH - 9844532971

2. In which of the following reactions ;K p > K c ?

a)N2 (g) + 3H2 (g) ⇌ 2NH3 (g) b) H2 (g) + I2 (g) ⇌ 2HI(g)
c)PCl3 (g) ⇌ Cl2 (g) ⇌ Cl5 (g) d)2SO3 (g) ⇌ 2SO2 (g) + O2 (g)
3. The equilibrium constant for a reaction A + 2B ⇌ 2C is 100. The equilibrium
constant for reaction C ⇌ B + 12 A is
1 1 1/2 1 2
a) b)( ) c)( ) d) 100
100 100 100
4. The equilibrium constant for the reaction N2 (g) + 3H2 (g) ⇌ 2NH3 (g) is K and
for the reaction 12 N2 (g) + 32 H2 (g) ⇌ NH3 (g) is K’2 K and ‘K’ will be related
to each other as
a) K = K1 b) K1 = √K c)K = √K ′ d)K × K1 = 1
5. If equilibrium constant for the reaction 2HI(g) ⇌ H2 (g) + I2 (g) is 0.25. Then
the equilibrium constant for the reverse reactionwill be
a) 1 b) 2 c) 3 d) 4
6. In the gas phase reaction C2 H4 + H2 ⇌ C2 H6 , the equilibrium constant can be
expressed in the units of
a) liter −1 mol−1 b)mol2 litre−2 c)litre mol−1 d) mol litre
7. The reaction quotient (Q) for the reaction N2 (g) + 3H2 (g) ⇌ 2NH3 (g)is given
[𝑁𝐻3 ]2
by 𝑄𝑐 = [𝑁 The reaction will proceed from right to left if
2 ][𝐻2 ]

a) Q = 0 b) Q = K c c)Q < K c d)Q > K c

8. The ratio of K p toK c for the following equilibrium
N2 (g) + 3H2 (g) ⇌ 2NH3 (g) at 400 K is(R=2 Cal/K mole)
a)8.21 × 10-2 b)1.56 × 10-6 c)1.56 × 10-4 d)8.21× 10-6
9. If for the equilibrium; 2SO2(g) + O2(g) ⇌ 2SO3, Kp = 2.0 × 1010 bar at 450K, the
value of K c at this temperature is
a)7.48 × 109 L mol−1 b) 2.0 × 1010 L mol−1
c) 7.48 × 1011 L mol−1 d)7.389 × 1011 L mol−1
ACTIVE SITE EDUTECH - 9844532971

10. At 3000K, the equilibrium pressure of CO2 , CO and O2 are 0.6 0.4 and 0.2
atm respectively. K pfor the reaction,2CO2 ⇌ 2CO + O2 , is
a) 0.089 b) 0.098 c) 0.189 d) 0.198

HOME EXERCISE
1. The ratio of K p /Kcfor the reaction 1
CO(g) + O2 (g) ⇌ CO2 (g)is
2

c) 1 b) RT c)(RT)1/2 d)(RT)−1/2
2. For the chemical reaction 2A + B ⇌ C, the units of K pis
a) atm−2 b) atm−3 c)atm−1 d) dimensionless
3. What will be the effect of increasing temperature on the equilibrium
constant, if the reaction either absorbs heat nor releases heat?
a) Equilibrium constant will remain constant
b) Equilibrium constant will decrease
c) Equilibrium constant will increase
d) Cannot be predicted
4. At a given temperature, the equilibrium constant for the reactions
1
NO(g) + O2 (g) ⇌ NO2 (g) and 2NO2 (g) ⇌ 2NO(g)O2 (g) are
2

K1 and K 2 respectively. If K1 is 4 × 10−3 , then

will be K2
a) 8 × 10−3 b)16 × 10−3 c)6.25 × 104 d)6.25 × 106
5. When two reactants A and B are mixed to give products C and D, the
reaction quotient, Q, at the initial stages of the reaction
a) is zero b) decreases with time
c) is independent of time d) increases with time
6. The active mass of 45g of KCl in a 3L flask would be
a) 0.20 b) 2.0 c) 3 d) 4
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7. The rate constant for forward reaction and backward reaction of hydrolysis
of ester are 1.1 × 10−2 and 1.5 × 10−3 per minute respectively. Equilibrium
constant for the reaction is
𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 + 𝐻2 𝑂 ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶2 𝐻5 𝑂𝐻
a) 33.7 b) 7.33 c) 5.33 d) 33.3
8. For the reaction, PCl3 (g) + Cl2 (g) ⇌ PCl5 (g) , the value of Kp at 250°C is
0.67 atm−1 . The value of K c at this temperature will be
mol −1 −1 −1 mol −1
a) 15 ( L
) b)26 (mol
L
) c)35 (mol
L
) d) 52 (
L
)

NCERT Text Book Questions: 7. 2,7. 4,7. 5,7. 6,7. 7,7. 13

ACTIVE SITE EDUTECH - 9844532971

SESSION – 4 AND 5
AIM - To apply law of Mass Action to different reversible systems
APPLICATIONS OF LAW OF MASS ACTION
1. Synthesis of Hydrogen Iodide:
Suppose ‘a’ moles of H2 and ‘b’ moles of I2 are heated at 444°𝐶 in a closed
container of volume ‘V’ liter and at equilibrium, 2x moles of HI are formed.
H2(g) + I2(g) ⇄ 2HI(g)
Initial moles a b o
Initial concentration a b 0
(mol L−1 ) V V
Equilibrium moles a− x b− x 2x
Equilibrium a−x b−x 2X
concentration (mol L−1 ) V V v

[HI]2
Kc =
[H2 ][I2 ]
Substituting the equilibrium concentrations of H2 , I2 and HI in above equation,
we get
2x 2
( ) 4x 2
V
Kc = a−x b−x
=
( )( ) (a − x)(b − x)
V V
2
P HI
Kp =
PH2 , PI2
Total no. of moles at equilibrium = (a – x) + ( b – x) + 2x = ( a + b)
a−x
PH2 = P × xH2 = P × a+b
P×(b−x)
Similarly, PI2 = (a+b)
P×2x
PHI = (a+b)
2x 2
(P× )
a+b
Kp = a−x b−x
P× ×P×
a+b a+b
4x2
∴ K p = (a−x)(b−x) ----------(iv)

From equations (iii) and (iv), that

Kp = Kc
This is so, because n = 0 for the synthesis of HI from H2 and I2
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2. Thermal dissociation of PhosphorusPentachloride

PCl5(g) dissociates thermally according to the reaction,
PCl5(g) ⇄ PCl3(g) + Cl2 (g)
Let us consider that ‘a’ mole of PCl5 has been taken in a container of volume
V litre and at equilibrium x moles of PCl5(g) dissociates.
Thus PCl3(g) + Cl2(g)
PCl5(g) ⇄ PCl3(g) + Cl2(g)
Initial moles a 0 0
Initial concentration a 0 0
(mol L−1 ) v
Equilibrium moles (a – x) x x
Equilibrium a−x x x
concentration (mol L−1 ) V V V

According to law of mass action, at constant temperature,

[PCl3 ][Cl2 ]
Kc = ..............(i)
[PCl5 ]
PpCl3 ×PCl2
And K p = .............(ii)
PPCl5

Substituting the values of equilibrium concentration, in equation (1), we have

x x
× x2
V V
Kc = α−x or K c = V(a−x)
V

Now, total number of moles at equilibrium = a − x + x + x = a + x

a
Mole fraction of PCl3 = Mole fraction of Cl2 = a+x . P
a−x
and mole fraction of PCl5 = a+x . P
Suppose total pressure at equilibrium is P, then we have from equation (2),
x x 2
× P x2 P
a+x a+x
Kp = a−x or K p = (a−x)2
P
a+x

3. Thermal dissociation of solid ammonium chloride:

The thermal dissociation of NH4 Cl(s) takes place in a closed container
according to the equation: NH4 Cl(s) ⇌ NH3(g) + HCl(g)
ACTIVE SITE EDUTECH - 9844532971

Let us consider a mole of NH4 Cl(s) is kept in a closed container of volume ‘V’
litre at temperature TK and if x mole of NH4 Cl dissociates at equilibrium,
then
𝑁𝐻4 𝐶𝑙(𝑠) ⇄ 𝑁𝐻3(𝑔) + 𝐻𝐶𝑙(𝑔)
Initial moles a 0 0
Initial concentration 𝑎 0 0
(𝑚𝑜𝑙 𝐿−1 ) 𝑣
Equilibrium moles (𝑎 – 𝑥) x x
Equilibrium 𝑎−𝑥 𝑥 𝑥
concentration (𝑚𝑜𝑙 𝐿−1 ) 𝑉 𝑉 𝑉
[𝑁𝐻3 ][𝐻𝐶𝑙 ]
Applying law of mass action, 𝐾𝑐 = [𝑁𝐻4 𝐶𝑙 ]
As NH4 Cl is a pure solid, so there is no appreciable change in its
concentration. Thus,
K c = [NH3 ][HCl] and K p = PNH3 × PHCl

4. Decomposition of 𝐂𝐚𝐂𝐎𝟑:
CaCO3(s) ⟶ Cao(s) + CO2(g)
K c = [CO2 ] or K p = PCO2
When CaCO3 is heated in a closed vessel at a definite temperature, the
pressure or concentration of CO2 produced becomes constant irrespective of the
amount of CaCO3 taken.

5. Reaction of steam on heated iron:

3Fe(s) + 4H2 O(g) ⇌ Fe3 O4 (s) + 4H2 (g)
[H2 ]4 ′
PH42
Kc = or K p = 4 = 4√K p
[H2 O]4 PH2O

6. Reaction of steam on heated carbon:

C(s) + H2 O(g) ⇌ CO(g) + H2 (g)
[𝐶𝑂][𝐻2 ] 𝑃𝐶𝑂 ×𝑃𝐻2
𝐾𝑐 = [𝐻2 𝑂]
or 𝐾𝑝 = 𝑃𝐻2
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7. Dissociation of ammonium carbonate:

NH2 COCNH4 (s) ⇌ 2NH3 (g) + CO2 (g)
2
K c = [NH3 ]2 [CO2 ] ; K p = [PNH3 ] × [PCO2 ]
NOTE:- Relation between degree of dissociation (α) density of a gaseous system.
D−d
α=
d(n − 1)
D = initial vapour density
d = vapour density at equilibrium
n = no. of molecules formed on dissociation
Homogeneous equilibria,equations K (Equilibrium pressure in atm in a V L flask)
n = 0 ; K p = Kc n  0 ; K p  Kc n  0; K p  Kc

H 2 + I2 ⇌ 2 HI N 2 + 3 H 2 ⇌ 2 NH 3 2 SO 2 + O 2 ⇌ 2 SO 3 PCl 5 ⇌ PCl 3 + Cl 2
(g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (g)
(g)

Initial mole 1 1 0 1 30 2 1 0 1 0 0
Mole at (1–x) (1– x) 2x (1–x) (3–3x) 2x (2–2x) (1–x) 2x (1–x) x x
Equilibrium
Total mole at 2 (4 – 2x) (3 – x) (1 + x)
equilibrium

1 − x  1 − x   1 − x   1 − x   2x   2 − 2x   1 − x  1 − x 
Active masses 2x  2x  x x
      3               
 V   V  V  V   V   V   V   V   V   V  V V
Mole fraction 1 − x  1 − x  2x 1− x 31− x  x  2 − 2x   1 − x   2x  1− x   x   x 
                 
 2   2  2 2 (2 − x ) 2  2 − x  (2 − x )  3−x  3− x 3− x 1 + x  1 + x  1 + x 
Partial  1 − x   1 − x   2x   1 − x   3(1 − x )  Px  2 − 2x   2x  1− x   x   x 
p  p  p  P   P 
  P  P  1 − x  P   P  P  P 
pressure  2   2   2   2(2 − x ) _   2(2 − x )  (2 − x )  3−x  3 − x 3− x 1 + x  1 + x  1 + x 

Kc 4x2 4 x 2V 2 x 2V x2
(1 − x ) 2 27 (1 − x ) 4 (1 − x ) 3 (1 − x ) V
Kp 4x2 16 x 2 (2 − x ) 2 x 2 (3 − x ) Px 2
(1 − x ) 2
27 (1 − x ) P 4 2
P (1 − x ) 3
(1− x2 )
Heterogeneous equilibria and equation for equilibrium constant (Equilibrium pressure is P atm)
NH 4 HS (s) ⇌ NH 3 (g) + H2S (g) C(s) + CO2 (g) ⇌ 2CO (g) NH2CO2 NH4 (s) ⇌ 2 NH3 (g) + CO2 (g)

Initial mole 1 0 0 1 1 0 1 0 0
Mole at equilibrium (1–x) x x (1–x) (1–x) 2x (1–x) 2x x
Total moles at equilibrium 2x (1+x) 3x
(solid not included)
Mole fraction x
=
1 1 1 − x   2x 
   
2x 2 2 1 + x  1 + x  2 1
3 3
Partial pressure P P  1 − x   2x  2P P
P  P 
2 2 1 + x  1 + x  3 3

Kp P2 4P x2 4 P3
4 (1 − x 2 ) 27
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CLASS EXERCISE
1. An equilibrium mixture for the reaction 2H2S(g) ⇌ 2H2(g) + S2(g) has 1mole of H2 S ,
0.2mole of H2 and 0.8mole of S2 in a 2litre flask. The value of K c in molL−1is
a) 0.004 b) 0.08 c) 0.016 d) 0.160
2. The degree of dissociation ofPCl5 (α)obeying the equilibrium:
PCl5 ⇌ PCl3 + Cl2 is related to the pressure at equilibrium by
1 1
a)α ∝ P b) α ∝ √P c)α ∝ P2 d)α ∝ 1/P4
3. When 3moles of a reactant A and 1mole of the reactant B are mixed invessel of
1litre, the following reaction takes place A(g) + B(g) ⇌ 2C(g) . If 1.5mole of C is
formed at the equilibrium, then equilibrium constant (K c )for the reaction is
a) 0. 12 b) 0.50 c) 0.25 d) 4.0
4. For a reaction A + B ⇌ C + D, initially we start with equal concentration of A and B.
At equilibrium, we find that moles of C are two times of A. The value of equilibrium
constant for the reaction is
1 1
a) b) c) 4 d) 2
4 2
5. 4moles each of SO2 and O2 gases are allowed to react to form SO3in a closed vessel. At
equilibrium 25%of O2 is used up. The total number of moles of all the gases present
at equilibrium is
a) 6.3 b) 7.0 c) 8.0 d) 2.0
6. For the reaction 2A(g) + B(g) ⇌ 3C(g) + 4D(g) two moles each of A and B were taken
into a 1L flask. The following must always be true when the system attained
equilibrium
a) [A] = [B] b)[A] < [B] c)[B] = [C] d[A] + [B] < [C] + [D]

7. At 550K, the Kc for the following reaction is 104 L mol−1

1 1
X(g) + Y(g) ⇌ Z(g)At equilibrium, it was observed that [X] = 2 (Y) + 2 (Z). What is the

value of [Z] in mol L−1 at equilibrium?

a) 2 × 10−4 b) 10−4 c)2 × 104 d)104
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8. A sample of HI(g) is placed in a flask at a pressure of 0.2atm. If the partial

pressure of HI(g) at equilibrium is 0.04atm, the value of K p is
a) 2 b) 4 c) 6 d) 8
9. A nitrogen-hydrogen mixture initially in the molar ratio of 1:3 reached equilibrium to
form ammonia when 25% of the material had reacted. If the total pressure of the
system was 21atm, the partial pressure of ammonia at the equilibrium was
a) 4. 5atm b) 3.0atm c) 2.0atm d) 1.5atm
10. The vapour density of PCl5 is 104.25 but when heated to 230°C, its vapour density
is reduced to 62. The degree of dissociation of PCl5 at this temperature will be
a) 6.8% b) 68% c)46% d) 64%

HOME EXERCISE
1. If, in the reaction N2O4 ⇌ 2NO2 , x is that part of N2 O4 which dissociates, then the
number of molecules at equilibrium, will be
a) 1 b) 3 c) (1 + x) d) (1 + 𝑥 )2
2. What is K c for the following equilibrium when the equilibrium concentration of
eachsubstance is [SO2] = 0.60M, [O2 ] = 0.82Mand [SO3] = 1.90M?
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
a) 11.229 b) 12.229 c) 3.861 d) 7.33
3. When 3moles of ethyl alcohol are mixed with 3moles of acetic acid, 2moles of esters are formed
at the equilibrium point. The value of equilibrium constant is
a) 4 b) 2/9 c) 2 d) 4/9
4. 1.1mole of A are mixed with 2.2moles B and the mixture is kept in a 1L vessel till the
equilibrium is established in the reaction. If the molar conc. of C at the equilibrium
point is 0.2mole, the value of equilibrium constant for the reaction A + 2B ⇌ 2C + D is
a) 0.001 b) 0.002 c) 0.003 d) 0.004
5. 5moles of SO2 and 5moles of O2 are allowed to react to form SO3 in the closed vessel.
At equilibrium state, 60% of SO2 is used. The total number of moles of SO2, O2 and SO3
in thevessel now is
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a) 10.0 b) 8.5 c) 10.5 d) 3.9

6. 1mole of hydrogen and 2moles of iodine are taken initially in a 2litre vessel. The
number of moles of hydrogen at equilibrium is 0.20 Then the number of moles of iodine
and hydrogen iodide at equilibrium are
a) 1.2, 1.6 b) 1.8, 1.0 c) 0.4, 2.4 d) 0.8, 2.0
7. A sample of pure PCl5 was introduced into an evacuated vessel at 473K. After
equilibrium was attained, concentration of PCl5 was found to be 0.5 × 10−1 mol L−1 . If
value of K c is 8.0 × 103 , what are concentrations of PCl3 and Cl2 at
equilibrium?
a) 0.01M b) 0.02M c) 0.05M d) 2.82M
8. XY2 dissociates as XY2 (g) ⇌ XY(g) + Y(g) when the initial pressure of XY2 is 600mm Hg,
the total equilibrium pressure is 800mm Hg. Calculate K for the reaction assuming
that the volume of the system remains unchanged.
a) 50 b) 100 c) 166.6 d) 400
9. For the reaction N2O4(g) ⇌ 2NO2(g) , the reaction connecting the degree of
dissociation(α) of N2O4(g) with the equilibrium constant K pis
𝐾𝑝
𝑃 𝐾𝑝
a)𝛼 = 𝐾𝑝 b)𝛼 =
4+ 𝑃 4+𝐾𝑝

𝐾𝑝 1/2
1/2
𝑃 𝐾𝑝
c)𝛼 = [ ] d)𝛼 = [ ]
4+𝐾𝑝 \𝑃 4+𝐾𝑝

NCERT Text Book Questions: 7.3, 7.8 , 7. 9 , 7. 10 , 7. 11, 7. 12, 7. 14, 7. 15, 7. 16, 7. 17,
7. 18, 7. 19, 7. 20, 7.21, 7.22, 7.23, 7.24, 7.27, 7.33, 7. 34.
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SESSION – 6
AIM - To introduce LeChateleir’s Principle, to explain factors which can change
the state of equilibrium in a reversible system.
LE CHATELIER’S PRINCIPLE
Three main factors which can change the state of equilibrium in a reversible
system i.e., concentration, pressure and temperature.
Le Chatelier explained the effect of change in concentration, pressure and
temperature on any reversible system whether physical or chemical.
According to him, if a system at equilibrium is subjected to a change of
concentration, pressure or temperature, the equilibrium shifts in the direction
that tends to undo the effect of the change,
(OR)
If a system at equilibrium is subjected to a change in concentration,
pressure or temperature, the system adjusts itself in such a way as to
nullifies the effect of that change.

1. Change in concentration: If an additional amount of reactant or product is

added to the system, the stress is relieved as the reaction that consumes
the added substance occurs more rapidly than its reverse reaction,
i.e., in general, increasing the concentrations of the
reactants results in shifting the equilibrium towards products while increasing
concentrations of the products results in shifting the equilibrium towards
reactants.
2. Change of pressure: At equilibrium, when medium consists of gases, then the
concentrations of all the components can be altered by changing the
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pressure. When the pressure on the system is increased, the volume decreases
proportionately.
i.e., If pressure is increased, then process will move in that
direction where number of moles of gaseous species are fewer and vice versa.
3. Change in temperature: In a reversible chemical reaction, if one reaction is
endothermic, other will be exothermic in nature.
When heat energy is added by raising temperature, the system can
relieve itself from the stress if the reaction which absorbs heat moves faster,
i.e, endothermic reaction is always favoured with increase of temperature.
So for exothermic process - increase in temperature favours backward
reaction and vice versa.
For endothermic process - increase in temperature favours forward reaction
and vice versa.
4. Addition of an inert gas: When inert gas added to a system at
equilibrium, inert gas neither reacts with reactants nor with products.
Case I: Addition of inert gas at constant pressure process will move in
that direction where number of moles of gaseous species are greater.
Addition of inert gas will increase the total volume at equilibrium. Now
• When Δn = 0 e.g., 2HI ⇌ H2 + I2
x2
For this equilibrium Kc = Kp =
4(1−x)2
; where x is the degree of
dissociation
The equation is independent of P and V terms and thus there is no effect
of addition of inert gas to this type of equilibrium.
• When Δn > 0; eg., PCl5 ⇌ PCl3 + Cl2
Moles at t = 0 1 0 0
Moles at equilibrium (1–x) x x
x2
Kc =
V(1 − x)
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Where x is the degree of dissociation

Since V increases and thus to keep 𝐾𝑐 constant, ‘x’ must increase i.e.,
degree of dissociation of PCl5 increases or [PCl3 ] and [Cl2] increases at equilibrium and
the [PCl5 ]decreases at equilibrium
Case II: Addition of inert gases at constant volume to an equilibrium will increase
the pressure at equilibrium. Now
• Δn = 0, 2HI ⇌ H2 + I2
x2
For the equilibrium Kc = Kp =
4(1−x2 )

Where x is the degree of dissociation.

Since the equation is independent of P and V terms and thus no effect of
addition of inert gas to this type of equilibrium.
• Δn = 0 PCl5 ⇌ PCl3 + Cl2
x2
For this equilibrium Kc =
V(1−x)

Where ‘x’ is the degree of dissociation.

Since volume remains constant during the change and the addition of inert
gas at constant volume will also have no influence on the equilibrium
concentration for this type of equilibrium.
Conclusions:
1. Increase in concentration of any substance favours the reaction in which it is used up.
2. High pressure is favourable for the reaction in which there is decrease in volume.
3. A rise in temperature favours the endothermic reaction.
4. Effect of inert gas addition:
Condition Effect
ΔV = 0, V = ConstantΔn ≠ 0, Δn = 0, +ve or − ve No effect
= Constant Δn = 0 No effect
ΔV ≠ 0, V ≠ ConstantΔV ≠ 0, V Δn > 0 Forward shift
≠ Constant Δn < 0 Backward shift
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5. Effect of temperature and pressure:

Nature of reaction Effect of increased 𝛥𝑛 ; side with fewer Effect of increase in P
temperature mole of gas
1. Exothermic backward shift 0; No shift
2. Exothermic backward shift -ve; right forward shift
3. Endothermic forward shift -ve; right forward shift
4. Endothermic forward shift +ve; left backward shift
5. Exothermic backward shift +ve; left backward shift
6. Exothermic backward shift -ve tight forward shift
7. Endothermic forward shift +ve left backward shift
8. Endothermic forward shift +ve left backward shift

Applications of LeChatelier’s Principle:

a. Formation of HI:
H2 (g) + I2 (g) ⇌ 2HI(g) + 3000cal
• Effect of concentration: When concentration of H2 and I2 is increased at
equilibrium, the system moves in a direction which decreases the
concentration, i.e., the rate of forward reaction increases.
• Effect of pressure: As there is no change in the number of moles in the
reaction, the equilibrium state remains unaffected by change of pressure.
• Effect of temperature: By increasing temperature, the equilibrium state
shifts towards the reaction which moves with absorption of heat. The
formation of HI is an exothermic reaction. Thus, the backward reaction
moves faster when temperature is increased.
In short, we can say that the favorable conditions for greater yield of HI are:
(i) High concentrations of H2 and I2 and
(ii) Low temperature
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b. Formation of Nitric Oxide:

N2 (g) + O2 (g) ⇌ 2NO(g) − 43200cal
• Effect of concentration: When concentration of N2 or O2 is increased,
the system moves in a forward reaction thereby increasing the
concentration of NO.
• Effect of pressure:In the formation of nitric oxide, the number of
moles remains the same, i.e, no change in volume occurs. Consequently,
the equilibrium state is not affected by any change in pressure.
• Effect of temperature: The formation of NO is endothermic in nature.
If the temperature is raised, the equilibrium shifts in the direction in
which heat is absorbed. The concentration of NO will, therefore, be
higher at higher temperature.
Thus, favourable conditions for greater yield of nitric oxide are
(i) High concentrations of N2 or O2 or both.
(ii) High temperature

c. Dissociation of PCl5 :
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) − 15000cal
• Effect of concentration: When concentration of PCl5 is increased, the
rate of forward reaction increases as to decrease the added
concentration. Thus, more of PCl5 & Cl2are formed.
• Effect of pressure: The volume increases in the dissociation of PCl5.
When pressure is increased, the system moves in the direction in which
there is decrease in volume. Thus, high pressure does not favors
dissociation of PCl5.
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• Effect of temperature: The dissociation of PCl5 is an endothermic

reaction. Thus, increase of temperature favours the dissociation.
Thus, favorable conditions for dissociation of PCl5 are
(i) High concentration of PCl5.
(ii) Low pressure and
(iii) High temperature

d. Formation of Ammonia:
Fe
N2 (g) + 3H2 (g) → 2NH3 (g); ΔH = −22.4 kcal/mol
• At high pressure reaction will shift in forward direction to form more product
• When concentration of N2 and H2 is raised or concentration of NH3 is
lowered, then equilibrium shifts in forward direction to from more amonmia.
• The reaction shifts in forward direction at low temperature.
But at very low temperature the rate of reaction becomes very low;
thus moderate temperature is favourable for this reaction.
Example 1. At what conditions will the following reaction go in the forward direction?
1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g) + 23kcal.
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) + 45kcal
3. N2 (g) + O2 (g) ⇌ 2NO(g) − 43.2kcal
4. 2NO(g) + O2 (g) ⇌ 2NO2 (g) + 27.8kcal
5. C(s) + H2 O(g) ⇌ CO2 (g) + H2 (g) + Xkcal
6. PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) − Xkcal
7. N2 O4 (g) ⇌ 2NO2 (g) − 14kcal
Solution: 1. Low T, High P, excess of N 2 and H 2
2. Low T, High P, excess of SO2 and O2
3. High T, any P, excess of N 2 and O2
4. Low T, High P, excess of NO and O2
5. Low T, Low P, excess of C and H 2O
6. High T, Low P, excess of PCl5
7. High T, Low P, excess of N 2O4
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Applications of Le-Chateleirs Principle to Physical Equilibria:

1. Vapour pressure of a liquid: Consider the equilibrium
Liquid ⇌ Vapour
Change of a liquid into its vapour is done by absorption of heat whereas the
conversion of vapour into liquid state is done by evolution of heat.
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.
2. Effect of pressure on the boiling point of a liquid: 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.
3. Effect of temperature on solubility:In most cases, when a solute passes into
solution, heat is absorbed, i.e., cooling results. 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.
i.e., the solubility of the substance increases with rise in temperature.

CLASS EXERCISE
1. In what manner will increase of pressure affect the following equation?
C(S) + H2 O(g) ⇌ CO(g) + H2 (g)
a) Shift in the forward direction b) Shift in the reverse direction
c) Increase in the yield of hydrogen d) No effect
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2. For the reactionCO(g) + H2 O(g) ⇌ CO2 (g) + H2 (g) at a given temperature,

the equilibrium amount of CO2 (g)can be increased by
a) adding a suitable catalyst b) adding an inert gas
b) decreasing the volume of the container d) increasing the amount of CO(g)
3. The reaction N2 + O2 ⇌ 2NO is endothermic. The forward reaction is
a) favoured by decrease in T b) favoured by increase in pressure
c) unchanged on increasing P d) equilibrium shifts by adding catalyst
4. In the chemical reaction 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) increasing the total
pressure leads to
a) increase in amount of SO3 b) increase in partial pressure of O2
c) increase in partial pressure of SO2 d) change in equilibrium constant
5. On the basis of Lechatelier’s principle, predict which of the following
conditions would be unfavourable for the formation of SO3 in the reaction
2SO2 (g) + O2 (g) ⇌ 2SO3 (g); ΔH = −176.0 kJ
a) Low temperature b) High pressure
c) High temperature d) High conc. of 𝑆𝑂2
6. If chemical system is in equilibrium, the addition of catalyst would result in
a) increase in rate of forward reaction
b) increase in rate of reverse reaction
c) a new reaction path
d) increase in amount of heat evolved in the reaction

HOME EXERCISE
7. Which of the following is not affected by change in pressure?
a) 2NO2 (g) ⇌ N2 O4 (g) b) CO2 (g) ⇌ +H2 O(l) CO2 (solution)
c) 2HI(g) ⇌ H2 (g) + I2 (g) d) 2O3 (g) ⇌ 3O2 (g)
8. In which case, the forward reaction is favoured by high pressure?
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N2 (g) + O2 (g) ⇌ 2NO(g)

a) H2 (g) + I2 (g) ⇌ 2HI(g) b)N2 (g) + O2 (g) ⇌ 2NO(g)
c) 2NH3 (g) ⇌ N2 (g) + 3H2 (g) d) 2SO2 (g) + O2 (g) ⇌ 2SO3
9. For the reaction PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)the forward reaction at constant
temperature is favoured by
a) introducing an inert gas at constant volume
b) introducing PCl3 (g) at constant volume
c) introducing PCl5 (g) at constant volume
d) introducing Cl2 (g) at constant volume
10. Which of the following reactions will be favoured at low pressure?
a)H2 (g) + I2 (g) ⇌ 2HI(g) b)PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
c) N2 (g) + 3H2 (g) ⇌ 2NH3 (g) d)N2 (g) + O2 (g) ⇌ 2NO(g)
11. Of the following which change will shift the reaction towards the
product? I2 (g) ⇌ 2I(g), Δr H0 (298K) = +150kJ
a) increase in concentration of I b) decrease in concentration of I2
c) increase in temperature d) increase in total pressure
12. Which of the following is not affected by increase in pressure?
a) 2NH3 (g) ⇌ N2 (g) + 3H2 (g) b)N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
c) N2 (g) + O2 (g) ⇌ 2NO(g) d)2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

NCERT Text Book Questions:7. 25, 7.26, 7.28, 7.29, 7.30, 7. 31.
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IONIC EQUILIBRIUM CONTINUED IN NEXT

PART- 2