CLASS-11 CHEMISTRY EQUILIBRIUM PROBLEMS-I

Equilibrium State – It is a state of balance or a stable

situation where opposing actions cancel each other, because
of no net change occurs.
Static and Dynamic Equilibrium
Static Equilibrium – No changes occur, opposing changes are
at a halt.
Dynamic Equilibrium – Changes occur. But the system
appears to be stationary as the rate of the two opposing rates
are equal.
Graphical Representation – Equilibrium State
When in a system involving reversible reaction, reactants
and products are in the same phase, then the system is
called as homogeneous system.
Reaction Quotient
It is the ratio of the product of the concentrations of the
reaction products to the product of the concentrations of the
reactants of a reversible chemical reaction, when each
concentration term is raised the respective stoichiometric
coefficient.
Once the system reaches the equilibrium, Q = constant
Then we called it equilibrium constant, K
Reaction quotient at equilibrium is known as equilibrium
constant K.

When we define equilibrium constant, we should mention

after the attainment of equilibrium.
• Law of Chemical Equilibrium
At a given temperature, the product of concentrations of the
reaction products raised to the respective stoichometric
coefficient in the balanced chemical equation divided by the
product of concentrations of the reactants raised to their
individual stoichometric coefficients has a constant value.
This is known as the Equilibrium Law or Law of Chemical
Equilibrium.
Equilibrium constant is the ratio of the products of the
concentration of the products to the product of concentrations
of the reactants, each concentration term raised the respective
stoichiometric coefficient, after the attainment of equilibrium.
Expression for K
It is derived from the law of Mass Action.
aA + bB ⇌ cC + Dd
Law of Mass Action states that the rate of the reaction is
directly proportional to the concentration of the reactants.
Rate of forward reaction, rf ∝ [A]a [B]b
rf =kf [A]a [B]b
rate of reverse reaction, rr = kr[C]c [D]d
At equilibrium, rf = rr
We can write, kf [A]a [B]b = kr[C]c [D]d
kf/ kr = [C]c [D]d /[A]a [B]b = KC, equilibrium constant
Symbol of equilibrium constant is K and subscript C
represents the ratio of concentrations.
If the reaction is a homogeneous gas phase reaction, then the
molar concentration of a substance is directly proportional to
partial pressure p at constant temperature.
In that case, the equilibrium constant is expressed in terms of
partial pressures of the reactants and products.
Such equilibrium constant is denoted by Kp

Relationship between KC and Kp

1.Ammonia reacts with oxygen at 800℃ to produce nitric

oxide and water. This is a reversible reaction.
Find KC for the equilibrium established between these four
components, if 1mole of each of NH3 and O2 were taken
initially in a 1L reaction flask and 60% of oxygen was found
to be reacted at equilibrium.
Ans: Balanced equation, 4NH3 + 5O2 ⇋ 4NO + 6 H2O
Stoichiometric ratio = 4:5:4:6
NH3 O2 NO H 2O
Initial 1 1 0 0
number of
moles
No. of moles [4/5]0.6 [60/100]1
reacted =0.48 = 0.6
No. of moles 0.48 [6/4]0.4
produced 8 =0.72
No. of moles 1-0.48= 0.52 1-0.6=0.4 0.48 0.72
at
equilibrium
Equilibrium 0.52/1=0.52 0.4/1=0.4 0.48 0.72M
concentratio M M M
n
Molarity =
n/V

KC = [NO]4 [H2O]6/ [NH3]4[O2]5

= 9.87
2. 2moles of nitrogen and 1mole of hydrogen were taken in a
1L reaction flask at 700K to produce ammonia. At
equilibrium, 60% of hydrogen was found to be reacted.
Calculate the equilibrium constant.
Ans: Balanced equation, N2 + 3H2⇋ 2NH3
Stoichiometric ratio = 1:3:2
N2 H2 NH3
Stoichiometric 1 3 2
ratio
Initial no. of 2 1 0
moles
No. of moles 0.6/3=0.2 [60/100]1 0.4
reacted/produce =0.6
d
No. of moles 2-0.2 =1.8 1-0.6 = 0.4 0.4
present at
equilibrium
Equilibrium 1.8/1 = 0.4/1=0.4M 0.4/1 =
concentration 1.8M 0.4M
M =n/V
KC = [NH3]2/ [N2] [H2]3= [0.4]2/ [1.8] [0.4]3 = 1.39
3. 2moles of nitrogen and 4 moles of hydrogen were taken in
a 4L reaction flask at 700K to produce ammonia. At
equilibrium, 60% of nitrogen was found to be reacted.
Calculate the equilibrium constant.
Ans: Equation: N2(g)+ 3H2⇋ 2NH3(g)
N2 H2 NH3
Stoichiometric 1 3 2
ratio
Initial no. of 2 4 0
moles
No. of moles [60/100]2=1. 1.2×3= 3.6 1.2×2 =2.4
reacted/produce 2
d
No. of moles 2-1.2 =0.8 4-3.6 = 0.4 2.4
present at
equilibrium
Equilibrium 0.8/4 =0.2M 0.4/4=0.1 2.4/4=0.6
concentration M M
(n/V)
KC = [NH3]2/ [N2] [H2]3 = [0.6]2/[0.2][0.1]3 = 1800

APPLICATIONS OF EQUILIBRIUM CONSTANT

 To predict the extent of a reaction
 To predict the direction of the reaction
 To calculate equilibrium concentrations
(i)Predicting the extent of reaction based on the magnitude
of equilibrium constant

KC ¿ 10-3 If KC is in the KC ¿ 103

range 10-3 to 103
The reaction Appreciable The reaction
proceeds rarely concentrations of proceeds nearly to
reactants and completion
product are
present
(ii) To predict the direction of the reaction, calculate QC
and compare with KC

QC¿KC -Reaction in the forward direction

QC¿KC – Reaction in the reverse direction
Calculation of equilibrium Composition
Given: Initial Number of moles of the reactants and
products Equilibrium constant KC
Q. 1 mole of Hydrogen and 2moles of Iodine were taken in
a 1L flask. Find the equilibrium composition if KC for the
reaction H2 + I2 ⇋ 2HI is 4 at the experimental temperature.
Ans: H2 +I2⇌ 2HI
Equation H2 I2 HI
Stoichiometric 1 1 2
ratio
Initial no. of 1 2 0
moles
No. of moles x x 2x
reacted/produced
No. of moles at (1-x) (2-x) 2x
equilibrium
Equilibrium (1-x)/1 = (2-x)/1 = 2xM
concentration (1-x) M (2-x) M
M=n/V
KC = [HI]2/ [H2] [I2] = (2x)2/(1-x) (2-x)
X=0.67
[H2] = 1-x = 1-0.67 = 0.33 M
[I2] = 2-x = 2-0.67 = 1.33M
[HI] = 2x = 1.34M
Q. 1mole each of hydrogen and iodine were taken in a 1L
flask. Find the equilibrium composition if KC for the
reaction H2 + I2 ⇋ 2HI is 4 at the experimental temperature.
Stochiometric 1 1 2
ratio
Initial no. of 1 2 0
moles
No. of moles x x
reacted
No. of moles 2x
produced
(1-x) (2-x) 2x
No. of moles
at equilibrium
Equilibrium (1-x)/1= (2 -x)/1 = 2x/1=2xM
concentration (1-x) M (2-x) M
M= n/V
KC = [HI]2 / [H2] [I2] = [2x]2/ (1-x) (2-x)
x= 0.67
[H2] = 1- 0.67 = 0.33M
[I2] = 2-x = 2-0.67 = 1.33M
[HI] = 2x = 2× 0.67 = 1.34M
Q. 1 mole each of hydrogen and iodine were taken in a
1L flask. Find the equilibrium composition if Kc for the
reaction H2 + I2 ⇌ 2HI is 4 at the experimental
temperature.
Ans:
Hydrogen Iodine Hydrogen
iodide
Stochiometric 1 1 2
ratio
Initial no. of 1 1 0
moles
No. of moles x x
reacted
No. of moles 2x
produced
No. of moles 1-x 1-x 2x
at equilibrium
Equilibrium (1-x)/1L = (1-x)/1L = 2xM
concentration (1-x) M (1-x) M
M= n/V
KC = [HI]2 / [H2] [I2] = [2x]2/ (1-x) (2-x)
4 = 4x2/ (1-2x+x2), x = 0.5
[H2] = 1-x = 1- 0.5 = 0.5M
[I2] = 1-x = 1- 0.5 = 0.5M
[HI] = 2x= 2× 0.5 = 1 M
Q. The value of KC = 4. 24 at 8ooK for the reaction
CO(g) + H2O(g) ⇋ CO2(g) + H2(g)
Calculate equilibrium concentrations of CO 2, H2, CO2 at
800K, if only CO and H2O are present initially at
concentrations of 0.1M each.
Ans: CO(g) + H2O(g) ⇋ CO2(g) + H2(g)
CO H2O CO2 H2
Stoichiometric 1 1 1 1
ratio
Initial number of 0.1 0.1 0 0
moles
No. of moles x x x x
reacted/produced
No. of moles at (0.1-x) (0.1-x) x x
equilibrium
Equilibrium (0.1-x) (0.1-x) xM xM
concentration M M
M = n/V
KC = [CO2] [H2]/ [ CO] [H2O] =x2/ (0.1-x) (0.1-x)
4.24 = x2/ 0.01 – 0.1x + x2
3.24x2 – 0.848x + 0.0424 = 0
ax2 + bx + c = 0
a = 3.24, b= -0.848. c = 0.0424

We get two values, x = 0.1944 and x = 0.0673

0.1944 is more than the initial concentration of the reactant,
that is 0.1M, which is not possible
So, we can select x = 0.0673
[CO] = 0.1 × 0.0673 = 0.0327M
[H2O] = 0.1x = 0.1 × 0.0673 = 0.0327M
[H2] = x = 0.0673M
[CO2] = x = 0.0673M
Calculation using the relation between KP and KC
Q. Given KC =4 at 300K, for the reaction
CH4 (g) + 2S2(g) ⇋ CS2(g) + 2H2S (g) Calculate KP
Ans:

∆n = np – nr = 3-3 =0
KP = KC (RT)0
KP = K C = 4
Q. Given KC = 3 at 727℃, for the reaction
CO(g) + C(s) ⇋ 2CO(g) Calculate KP
Ans: ∆ n = np – nr = 2-1 = 1

KP = KC (RT)1
= 3× 0.0821 × 1000 = 249.3
Q. Given KP = 0.04 at 627℃ for the reaction,
C6H6(g) ⇋ C2 H4 (g) + H2 (g) Find KC.
 Ans:

KP = KC (RT)1
0.04 = KC ×0.0821×900
KC = 0.04/ 0.0821×900 = 5.35×10-4
Q. The partial pressure of an equilibrium mixture of
nitrogen, hydrogen and Ammonia were measured to be
PN2 = 0.3bar PH2 =0.2bar PNH3 = 0.6bar at 700K
Calculate KP for the reaction.
Ans: N2 (g) + 3H2 (g) ⇋ 2NH3 (g)

KP = [PNH3]2/ [PN2][PH2]3= [0.6]2/ [0.3][0.2]3= 150

Problem 7:6
The value of Kp for the reaction
CO2(g) + C(s) → 2CO (g) is 3 at 1000K. If initially PCO2 = 0.48 bar
and PCO = 0 bar and pure graphite is present, Calculate the
equilibrium partial pressure of CO and CO2.
CO2 Carbon (Solid) CO
Stoichiometric 1 1 1
Ratio
Initial 0.48 0
pressure
Decrease in x
pressure
Increase in 2x
pressure
Equilibrium 0.48-x 2x
pressure
CO2(g) + C(s) → 2CO
KP = [PCO]2/PCO2
3 = (2x)2/ (0.48 -x)
4x2 +3x -1.44 =0
x = 0.3325 [ neglect negative value]
PCO = 2x =2× 0.3325 = 0.665 bar
PCO2 = 0.48 -x = 0.48 – 0.3325 = 0.1475bar

RELATION BETWEEN EQUILIBRIUM CONSTANT

FOR A REACTION AND ITS MULTIPLES
Chemical equation Equilibrium constant
aA + bB ⇋ cC + dD KC
cC + dD ⇋ aA + bB KC’ = [1/KC]
naA + nbB ⇋ ncC + ndD KC” = [KCn]
Q. Find KC of the following reaction if the KC for the
reaction, A + B ⇋ C +D is 16
Reaction KC
A + B ⇋ C+ D KC = [C][D]/[A][B] = 16
2A + 2B ⇋ 2C + 2D KC = [C]2[D]2/[A]2[B]2
= [16]2 = 256
½A+½B⇋½C+½D
KC = [C]1/2[D]1/2/[A]1/2[B]1/2
= [16]1/2 = 4

PROBLEM 7: 8
13.8g of N2O4 was placed in a 1L reaction vessel at 400K
and allowed to attain equilibrium, N2O4(g) ⇌ 2NO2(g)
The total pressure at equilibrium was found to be 9.15
bar. Calculate KC, KP and equilibrium partial pressure at
equilibrium.
Ans: pV = nRT
p× 1 = [13.8/92] ×0.0821×400 = 4.986bar
initial pressure of dinitrogen tetroxide, N2O4 = 4.986bar

Step: I Stoichiometric Calculation

N2O4(g) ⇌ 2NO2(g)
Stoichiometric 1 2
ratio
Initial pressure 4.986 0
Decrease/increase x 2x
in pressure
Pressure at 4.986-x 2x
equilibrium

Step: II Apply Dalton’s Law of Partial Pressure

Ptotal = PN2O4 + PNO2
9.15 = [4.986 -x] +2x, x = 4.164
PN2O4 = 4.986 -4.164 = 0.822
PNO2 = 2x = 2× 4.164 = 8.328
Step: III Calculation of KC and KP
KP = [PNO2]2/ PN2O4 = [8.328]2/ 0.822 = 84.375
KP = KC (RT) Δn, Δn = np -nr = 1
KC = 84.375/ 0.0832 × 400 = 2.5384
Q. 22.8g of ammonia taken in a 10L reaction flask at 800K
was found to be decomposed reversibly into nitrogen and
hydrogen. After the attainment of equilibrium, the total
pressure in the flask was found to be 10.324 bar. Calculate
KP and KC
Ans: pV = nRT
p× 10 = [22.8/17]× 0.0831× 800
initial pressure of ammonia = 8.916 bar
2NH3(g) ⇌ N2(g) + 3H2(g)
Stoichiometric 2 1 3
Ratio
Initial pressure 8.916 0 0
Decrease/increase 2x x 3x
in pressure
Equilibrium [8.916-2x] x 3x
pressure
By Dalton’s Law of partial pressure.
PTOTAL = PNH3 + PN2+ PH2
10.324 = [8.916-2x]+ x+3x, x =0.704
PNH3 = [8.916-2x]= 8.916 - 2×0.704 = 8.212
PN2 = x = 0.704
PH2 = 3x = 3×0.704 = 2.112
2NH3(g) ⇌ N2(g) + 3H2(g)
KP =(PN2)(PH2)3/ (PNH3)2 = 0.704×9.407/(8.212)2=9.8×10-2
KP = KC (RT) Δn, Δn = np -nr = 4-2=2
9.8×10-2 = KC× [0.0821×800]2
KC = 2.22×10-5
Relation Between Equilibrium Constant and Gibbs Energy
∆G = negative Spontaneous
∆ G = positive Non-spontaneous
∆ G =0 Equilibrium

Gibb’s energy change of a reaction is related to the reaction

quotient by the expression, ∆ G = ∆ G0 + RTlnQ
At equilibrium, ∆ G =0, Q =K
0 = ∆ G0 + RTlnK
∆ G0 = -RTlnK
∆ G0 = -2.303 RTlog K
lnK = -∆ G0/RT
Calculation of Standard Gibb’s Energy Change
Given: Equilibrium Constant
Problem 7: 11
Hydrolysis of sucrose gives,
Sucrose + Water ⇋ Glucose + Fructose
Equilibrium constant KC for the reaction is 2×1013 at 300K
Calculate ΔGO at 300K

= - 2.303×8.314×300×log2×1013
=- 2.303×8.314×300×13.3010 = 76402.84Jmol-1
Problem 7: 12
Calculate Δ G0 for the conversion of Oxygen to Ozone
3/2 O2(g) → O3(g) at 298K. If KP for this conversion is
2.47×10-29
 = -2.303 ×8.314×298×log(2.47×10-29)
= -2.303 ×8.314×298×[-28.6073] = 163228.9Jmol-1
Problem7:14
At 60℃, dinitrogen tetroxide is 50% dissociated. Calculate the
standard free energy change at this temperature at one
atmosphere.
N2O4(g) ⇋ 2NO2(g)
N2O4 NO2
Stoichiometric 1 2
ratio
Initial number of 100 0
moles
Number of moles 50 2×50=100
reacted/produced
No. of moles at 100-50=50 100
equilibrium
Mole fraction, 50/150=1/3 100/150=2/3
x = no. of moles of
one
component/total
no. of moles
P = PTOTAL× mole PN2O4 = PNO2=
fraction 1×[1/3]=1/3 atm 1[2/3]=2/3atm

N2O4(g) ⇋ 2NO2(g)
KP = (PNO2)2/(PN2O4) =(2/3)2/(1/3)=1.33
= -2.303 ×8.314×333×log1.33
=- 2.303 ×8.314×333×0.1239 = -790Jmol-1
Problem 7:13
Find out the value of equilibrium constant for the following
reaction at 298K.
2NH3(g) + CO2(g) ⇋ NH2CONH2(aq) + H2O(l)
Standard Gibb’s Energy change, △G0 at the given temperature
is -13.6 kJmol-1
Ans:

logK = - △G0/2.303RT
= -[-13.6×103/ 2.303×8.314×298] = 2.3835
K = Antilog 2.3835 = 241.82
Problem 7: 10
The value of △G0 for the phosphorylation of glucose in
glycolysis is 138kJ/mol. Find the value of KC at 298K.
Ans:

logK = - △G0/2.303RT
 = -13.8×103/2.303×8.314×298= -2.4186
K = Antilog -2.4186=0.00381=3.81×10-3
Factors Affecting Equilibrium
Equilibrium is a state of balance, the balance can be disturbed by
external stresses. When the equilibrium state is disturbed, it returns to
equilibrium by counteracting the disturbance.
If a chemical The system loses the And the net reaction
equilibrium is equilibrium state takes place in some
subjected to a change direction until the
in concentration, system returns to
pressure, or equilibrium once
temperature. again.
Le- Chatelier’s Principle
A change in any of the factors that determine the equilibrium
conditions will cause the system to change in such a manner
to reduce or to counteract the effect of the change.
1.Effect of change in Concentration
Increase in concentration of Reaction in the forward
reactant/ Decrease in the direction
concentration of the products
Increase in concentration of Equilibrium will be shifted in
products/decrease in the reverse direction
concentration of reactant
Example: N2(g) + 3H2(g) ⇋ 2NH3(g)
Increase in concentration of Froward direction
N2or H2
Decrease in concentration of Forward direction
NH3
Decrease in concentration of Reverse reaction
N2 or H2
 Increase in the concentration Reverse direction
of NH3
2.Effect of change in Temperature
Increase in temperature shifts the equilibrium to the
endothermic direction. Decrease in temperature shifts the
equilibrium to the exothermic direction.
N2(g) + 3H2(g) ⇋ 2NH3(g), ΔH = -92kJ
Low temperature favours the formation of Ammonia.
High temperature favours the decomposition of Ammonia.
3. Effect of Change in Pressure
Decrease in pressure shifts Increase in pressure shifts the
the equilibrium to the equilibrium to the direction
direction where there are a where there are lesser
greater number of gaseous number of moles of gaseous
components. components.
N2(g) + 3H2(g) ⇋ 2NH3(g)
Formation of Ammonia: Number of moles decreases;
therefore, high pressure favours the formation of NH3
Decomposition of NH3: Number of moles increases;
therefore, low pressure favours the decomposition of NH3
Conditions for Good Yield of Ammonia
N2(g) + 3H2(g) ⇋ 2NH3(g) [Haber Process]
(i) High pressure, 200atm
(ii) 400℃ - 450℃
(iii) Catalyst -FeO [reaction is speeded in the presence
of catalyst]
(iv) Promoter – Al2O3 + K2O [ which increases the
efficiency of catalyst]
Various Concepts of Acids and Bases
 1. How can BF3 act as an acid, in spite of the absence of
hydrogen ion?
Ans: BF3 does not have a proton but still acts as an acid
and reacts with NH3 by accepting its lone pair of
electrons. The reaction can be represented by
BF3 + NH3 →BF3← NH3
2. What type of substances can act as Lewis acids/Lewis
bases?
Ans: Electron deficient species like AlCl3, Co3+3, Mg+2
etc can act as Lewis acids while species like H2O, NH3,
OH-1etc donate a pair of electrons, can act as Lewis
bases.
Problem 7:15
Classify the following species into Lewis acids and Lewis
bases and show these act as such:
(a) OH-1 (b) F-1 (c) H+1 (d) BCl3
Solution
(a) Hydroxyl ion is a Lewis base as it can donate an
electron lone pair [:OH-1]
(b) Fluoride ion acts as a Lewis base as it can donate any
one of its four electron lone pair
(c) A proton is a Lewis acid as it can accept a lone pair of
electrons from bases like hydroxyl ion and fluoride ion
(d) BCl3 acts as a Lewis acid as it can accept a lone pair of
electrons from species like ammonia or amine
molecule
Species Conjugate acid Conjugate base
HF F-1
H2SO4 HSO4-1
NH2-1 NH3
HCOO-1 HCOOH
H2O H3O+1 OH-1
HCO3-1 H2CO3 CO3-2
HSO4-1 H2SO4 SO4-2
NH3 NH4+1 NH2-1
Amphoteric Nature → Some species are able to produce
both conjugate acid and conjugate base