CHEMICAL EQUILIBRIUM

MODULE-1

Equilibrium
Equilibrium
Equilibrium Ionic
Law of Chemical Equilibria
in in
Relation between Kp and Kc Characteristics and application of K Lechaterlees Principle Relation between standard free energy charge and K Solubility product Buffer Hydrolysis of salt
Equilibrium
pH Dissociation constant of weak acid and base Acids and Base

Physical
Chemical
ProcessProcess

TOPIC OVERVIEW
• Equilibrium in physical process
• Equilibrium in chemical process
• Law of chemical equilibria
• Relation between Kp and Kc.
• Characteristics of K
• Application of K.

Introduction
• Equilibrium represents a state in which the properties like temperature, pressure,
concentration of the system does not show any change with the passage of time.
• Equilibrium may be established in physical as well as chemical processes.

EQUILIBRIUM IN PHYSICAL PROCESSES

https://www.youtube.com/watch?v=COrZ6OS-SqU
I) Equilibrium in phase transformations-
[A] SOLID-LIQUID equilibrium
For eg-H2O(s) H2O(l)

At equilibrium
Rate of freezing = Rate of melting,
(at 273K & 1atm, in an insulated closedflask)
The temperature at which solid and liquid forms of a substance are at
equilibrium, at the atmospheric pressure is called normal freezing point or
melting point of a substance.
At equilibrium melting point / freezing point remains constant at
atmospheric pressure.

[B] LIQUID-GAS equilibrium

EgH2 O(l) H2 O(g)

At equilibrium
Rate of evaporation = Rate of condensation
(at a given temperature, in a closed vessel)
In such an equilibrium state, the pressure exerted by the vapours of the liquid
known as vapour pressure.
At Equilibrium, vapor pressure is constant at a given temperature.

II) Equilibrium involving dissolution of solids or gases in liquids-

A) Solids in liquids

For eg-sugar sugar

(solid) (solution)
At equilibrium,
Rate of dissolution = Rate of precipitation
(for a saturated solution at a given temperature)
At equilibrium solubility (amount of solute in a given amount of a solvent)
remains constant at a given temperature.
 [B] Gases in liquids-
EgCO2 (g) CO2(aq)

The solubility of a gas in a liquid decreases with increase in temperature &

increases with increase in pressure.
According to HENRY’S LAW,
The mass of a gas dissolved in a given mass of a solvent at a particular
temperature, is proportional to the pressure of the gas above the solvent.
m a porm = k p( kis Henry’s constant)
[CO2 ]aq
At equilibrium
[CO2 ](g ) is constant at a given temperature.

CHARACTERISTICS OF PHYSICAL EQUILIBRIUM

• Equilibrium is possible in closed systems.
• The process(reaction) does not stop at equilibrium, instead opposing reaction(process)
occur at same rate & there is dynamic equilibrium.
• Equilibrium is characterized by a constant value of one of the parameter at a given
temperature.
• Magnitudes of such quantities indicate the extent to which the reaction has proceeded
before reaching equilibrium.

EQUILIBRIUM IN CHEMICAL PROCESSES

https://www.youtube.com/watch?v=MVjItVOuq-A
For a general reversible reaction -A+B C+D
At equilibrium,
Rate of forward reaction = rate of backward reaction.
Depending upon the extent to which reaction has proceeded,the state of equilibrium
can be classified into three groups:
(i) Reaction has almost gone to completion
(ii) Reaction has just started and more of the reactant and less of product will remain at
equilibrium
(iii) Reaction has proceeded midway and the concentration of reactant and product are
comparable at equilibrium.

CHARACTERISTICS OF A CHEMICAL EQUILIBRIUM

• Chemical equilibrium is possible in a closed container.
• Equilibrium is dynamic in nature as the rate of forward reaction is equal to the rate of
backward reaction.
• Equilibrium can be attained from the either direction.

Eg: H2+I2 2HI

• Catalyst does not alter the state of equilibrium because it affects both forward and
 backward reaction to the same extend.

EQUILIBRIUM CONSTANT AND LAW OF CHEMICAL EQUILIBRIUM

https://www.youtube.com/watch?v=1GiZzCzmO5Q
• Consider the reaction aA + bB cC + dD
The Law of mass action states that-
At a given temperature, the rate of a chemical reaction is directly proportional to the
product of the molar concentrations of the reactants, each term raised to the respective
stoichiometric coefficients.
a b
Rate of forward reaction ∝ [A] [B]
a b
=Kf [A] [B]
Similarly rate of backward reaction = Kb [C]c [D]d
Where Kf and Kb are the rate constant.

At equilibrium, Rate of forward reaction = Rate of backward reaction

Kf [A]a[B]b= Kb [C]c [D]d

Kf
= Kc =
[C ]c [D]d
Or K b [A]a [B ]b

• The law of chemical equilibrium states that-

At a given temperature, the ratio of the product of the concentrations of the products to
that of the product of the concentrations of the reactants, each term raised to its
stoichiometric coefficient; is a constant.

• For gas phase reaction, the equilibrium constant can be expressed in terms of partial
pressures also. Therefore, for a reaction

aA (g ) + bB (g ) cC (g ) + dD (g )
p cC .p dD
a b
Kp = p A . p B

RELATION BETWEEN Kp&Kc

p cC .p dD
a b
We knowKp = p A . p B ….(i)

According to the ideal gas equation-

PV = nRT
&P =
orP = cRT
Therefore ,pA = [A] RT andso on…
Substituting for pA, pB, pC & pDin (i)

Kp =
[C ]c [D]d
[A]a [B]b [ RT] (c+d-(a+b)

Kp =Kc(RT)Δ n
Where n =difference between gaseous moles of products & reactants.

CHARACTERISTICS OF EQUILIBRIUM CONSTANT

• The value of K c is independent of the initial concentrations of the reactants.

• Kc has a definite value for a given reaction at a given temperature.

• If the reaction is reversed, the value of equilibrium constant is inversed.

• On multiplying a factor ‘n’’ , Kc changes as -

na A+nb B nc C+nd D
n
Kc ‘=( Kc )

• If an equilibrium reaction is written in 2 steps, then the equilibrium constant for the overall
reaction will be product of the equilibrium constant of individual reactions.
• The unit of K depends upon the no. of moles of the reactants &the products.
For eg.H 2+I 2 2HI

K=
[HI ]2
[H 2 ] [I 2 ] ; K has no units
c

& N 2+3 H2 2NH3;K =(mol/L)-2

TYPES OF CHEMICAL EQUILIBRIA

(I) Homogeneous equilibrium-
Here all the reactant & product of a reaction are in the same phase.
Eg2 SO2(g)+O2 (g) 2 SO3 (g)

C2 H5 OH(l)+CH3 COOH(l) CH 3 COOC2 H 5 (l)+H2 O(l)

(II) Heterogeneous Equilibrium-

Here the reactants and the products are not in the same phase-
For eg-CaCO3(s) CaO(s)+CO2(g)

Note:The concentration of pure solids and liquids are taken as constant and is given a
value equal to 1.
• [solids] and [pure liquids] = 1

APPLICATIONS OF EQUILIBRIUM CONSTANT

https://www.youtube.com/watch?v=MJZhF2CHCCc
1) Predicting the Extent of reaction-

(a) When Kc > 103, the reaction proceeds nearly to completion and the the conc.
of products is far greater than reactants
(b) When Kc<10-3 ; the reaction has taken place to a small extent and the conc.
of products is far less than reactants.
(c) If Kc is in between 103 to 10-3, the reaction has proceeded to an appreciable
extent (midway).

2. Predicting the direction of Reaction

For a general reaction-aA+ b B cC+d D, the reaction quotient Qc is given as-

Qc =
[C ]c [D]d
[A]a [B]b ,
where [A], [B], [C], [D] represent the concentration at any stage of the reaction and
not the equilibrium concentration.

• When Qc<Kc, the reaction will proceed in the forward direction.

• When Qc >Kc ,the reaction proceeds in the backward direction.

• When Qc=Kc , the reaction is at equilibrium.

3. Calculating equilibrium concentration

Following steps are followed –
(a) Write the balanced chemical equation.
(b) Write the initial conc. ofthe reactants and the products.
(c) Write the equilibrium conc. of the reactants & products assuming x moles to
have reacted-
E.g.- 2A+B C+3D
Initial conc.1100
Eqm.conc.1-2x1-xx3x

Kc =
(3x )(x )
(1 − 2 x )(1 − x )

(d) Solve for x.

SOLVED QUESTIONS

Q1. A sample of pure PCl5 was introduced into an evacuated vessel at 473 K. After
-1
equilibrium was attained, concentration of PCl5 was found to be 0.5 × 10 mol/L.
 If the value of Kc = 8.3 × 10-3, what are the conc. of PCl3 and Cl2 at equilibrium?
Ans:PCl5 PCl3 + Cl2

At eqm. 0.5 ×10-1 x mol/L x mol/L

Kc = = 8.3 × 10-3 (Given)
2 -3 -1 -4
Or x = (8.3 × 10 ) (0.5 × 10 ) = 4.15 × 10
Or x = (4.15 × 10-4 )1/2 = 2.04 × 10-2 = 0.02 M
Hence, [PCl3]eq = [Cl2]eq = 0.02 M

Q2. At 773 K, the equilibrium constant Kc for the reaction,

−2 2 -2
N2 (g) + 3 H2 (g) 2 NH3 (g) is 6.02 × 10 L mol .

Calculate the value of Kp at the same temperature.

Ans: ∆ng = 2 – 4 = −2

KP = KC (RT)∆n
−2 2 -2 -2
= 6.02 × 10 L mol × (0.0821 L atm/K/mol × 773 K)
= 1.5 × 10-5 atm-2

Q3. KP for the reaction,N2 (g) + 3 H2 (g) 2 NH3 (g) is 49 at a certain

temperature. Calculate the value of Kp at the same temperature for the reaction

NH3 (g) ½ N2 (g) + 3/2 H2 (g)

Ans: Given - N2 (g) + 3 H2 (g) 2 NH3 (g), KP = 49

For the reverse reaction-2 NH3 (g) N2 (g) + 3H2 (g), Kp =
On dividing by 2, we have NH3 (g) ½ N2 (g) + 3/2 H2 (g) Kp = =

Q4. In a reaction between H2 and I2 at a certain temperature, the amount of H2, I2

and HI at equilibrium were found to be 0.45 mole, 0.39 mole and 3 moles
respectively. Calculate the equilibrium constant for the reaction at a given
temperature.
Ans: H2 + I2 2HI
Amounts of H2, I2 and HI at equilibrium are given to be H2 = 0.45 mole, I2 = 0.39
mole and HI = 3 moles.
Suppose the volume of the vessel (i.e. reaction mixture) = V litre
Then the molar concentrations at equilibrium will be
[H2] = 0.45/V mol/L, [I2] = 0.39/V mol/L, [HI] = 3/V mol/L
Applying the law of chemical equilibrium

= 51.28

Q5. For the reaction, N2 (g) + 3 H2 (g) 2 NH3 (g), the partial pressure of N2 and
 H2 are 0.80 and 0.40 atm respectively at equilibrium. The total pressure of the
system is 2.80 atm. What is the Kp for the above reaction?
Ans: N2 (g) + 3 H2 (g) 2 NH3 (g)
pN2 = 0.80 atm pH2 = 0.40 atm

pN2 + pH2 + pNH3 = 2.80 atm pNH3 = 2.80 − (0.80 + 0.40) = 1.60 atm

P 2 NH 3
PN 2 × P 3 H 2
Kp = = (1.60)2(0.80) × (0.40)3 = 50.0

Q6. Equilibrium constant Kc for the reaction, N2(g) + 3H2(g) 2NH3(g) at 500 K is
0.061. At particular time, the analysis shows that the composition of the reaction
-1 -1 -1
mixture is: 3.0 mol L of N2, 2.0 mol L of H2,0.50 mol L of NH3. Is the reaction
at equilibrium? If not, in which direction does the reaction tend to proceed to
reach the equilibrium?

Qc =
[NH 3 ]2 = (0.5)2 = 0.0104
Ans: [N 2 ][H 2 ]3 (3.0)(2.0)3
Given Kc = 0.061.
As QC ≠ KC, the reaction is not in equilibrium.
As QC< KC, the reaction will proceed in theforward direction.

Q7. AB2 dissociates as: AB2 (g) AB (g) + B (g) .

If the initial pressure is 500 mm of Hg and the total pressure at equilibrium is 700
mm of Hg, calculate Kp for the reaction.
Ans: After dissociation, suppose the decrease in pressure of AB2 at equilibrium is p
mm of Hg. Then
AB2 (g) AB (g) + B (g)

Initial pressure 500 mm 0 0

Pressure at equilibrium (500 − p) p p
Total pressure at equilibrium = 500 – p+ p +p mm = 500 + p mm
500 + p = 700 (given) or p = 200 mm
Hence, at equilibrium pAB2 = 500 – 200 = 300 mm, pAB= 200 mm, pB= 200 mm

Kp = pAB× pB / pAB2 = 200 × 200 / 300 = 133.3 mm

Q8. The value of Kc = 4.24 at 800 K for the reaction,

CO (g) + H2O (g) CO2 (g) + H2 (g)
Calculate equilibrium concentrations of CO2, H2, CO and H2O at 800K, if only
CO and H2O are present initially at concentrations of 0.10 M each.

Ans: For the reaction,

CO (g) + H2O (g) CO2 (g) + H2 (g)
 Initial concentration:
0.1 M 0.1M 0 0
Let x mole per litre of each of the product be formed.
At equilibrium:
(0.1-x) M (0.1-x) M xM xM
Where x is the amount of CO2 and H2 at equilibrium.

Hence, equilibrium constant can be written as,

Kc = x2 / (0.1-x)2 = 4.24
x2 = 4.24 (0.01 + x2 – 0.2x)
x2 = 0.0424 + 4.24 x2 -0.0848x
3.24x -0.848x + 0.0424 = 0

2
x=
(− b ± b 2 4ac )
(for quadratic equation ax + bx + c = 0, 2a
On solving , we get two values of x ,0.067 and 0.197

The value of 0.194 should be neglected because it will give concentration of the
reactant which is more than initial concentration.
Hence the equilibrium concentrations are,
[CO2] = [H2] = x = 0.067 M
[CO] = [H2O] = 0.1 – 0.067 = 0.033 M

ASSIGNMENT
MCQ

1. A state of equilibrium is reached when

a) The rate of forward reaction is greater than the rate of reverse reaction
b) The concentration of products and reactants are equal
c) More product is present than reactant
d) The concentration of products and reactants have reached constant value.
2. The numerical value of equilibrium constant depends on
a) Temperature
b) Pressure
c) Concentration of reactants
d) All of these
3. The value of Kp for the reaction, 2 SO2 (g) + O22 SO3 (g) is 5. What will be the partial
pressure of O2 at eqm. when equal moles of SO2 and SO3 are present at equilibrium?
a) 0.5
b) 0.3
c) 0.2
d) 0.1
4. Following 3 gaseous equilibrium are occurring at 27°C
 A- 2CO + O2 2CO2
B- PCl5 PCl3 +Cl2
C- 2HI H2 + I2
The correct order of Kp/Kc for the following reaction is
a) A < C < B
b) A < B < C
c) C < B < A
d) B < C < A
5. The temperature at which Kc and Kp will have the same value for the equilibrium,
N2O4 (g) 2 NO2 (g) is
a) 0 K
b) 273 K
c) 1 K
d) 12.18 K
6. For the reaction CO (g) + Cl2 (g) COCl2 (g), Kp/Kc is equal to
a)
b) RT
c) 1/RT
d) 1.0
0 -5
7. The dissociation constant of acetic acid and HCN at 25 C are 1.5 × 10 and4.5 × 10-5
respectively. The equilibrium constant for the reaction
CN- + CH3COOH HCN + CH3COO- would be
-5
a) 3.0 × 10
-4
b) 3.0 × 10
4
c) 3.0 × 10
5
d) 3.0 × 10
8. When 2 reactant A and B are mixed to give product C and D, the reaction quotient, Q at
the initial stages of the reaction is
a) Zero
b) Decreases with time
c) Independent of time
d) Increases with time
-
9. If the conc. of OH ions in the reaction

Fe(OH)3 (s) Fe+3 (aq) + 3 OH- (aq)

is decreased by ¼ times, then equilibrium concentration of Fe+3 will increase by
a) 8 times
b) 16 times
c) 64 times
d) 4 times
10. A + B C + D, Kc = 10. If 1, 2, 3, 4 mol/l of A, B, C, and D respectively are present in
a container at 250 C, the direction of reaction will be
a) From left to right
b) From right to left
 c) Reaction is at equilibrium
d) Unpredictable

CONCEPTUAL QUESTIONS
1. What are the characteristics for physical equilibria?
2. What do you mean by dynamic nature of equilibrium?
3. For the reaction N2(g) + 3H2(g) 2NH3(g), at 400 K, Kp = 41. Find the value of Kp for each
of the following reaction at the same temperature:
(i) 2 NH3 (g) N2 (g) + 3H2 (g)
(ii) ½ N2 (g) + 3/2 H2 (g) NH3 (g)

(iii) 2 N2 (g) + 6 H2 (g) 4 NH3 (g)

4. What are the factors on which value of equilibrium constant depends?
5. What is the effect on equilibrium and on equilibrium constant on adding catalyst?

NUMERICAL QUESTIONS

1. A vessel at 1000 K contains carbon dioxide with a pressure of 0.5 atm. Some of the CO2 is
converted into CO (carbon monoxide) on addition of graphite. Calculate the value of
Kp if the total pressure at equilibrium is 0.8 atm.
2. The degree of dissociation of PCl5 at a certain temperature and atmospheric pressure is 0.2.
Calculate the pressure at which it will be half (50%) dissociated at the same
temperature.
3. For an equilibrium reaction, the rate of constant for forward and backward reaction are
2.38 × 10-4 and 8.15 × 10-5respectively. Calculate the equilibrium constant for the
reaction.
4. For the reaction A (g) + B (s) C (g) + D (g), Kc = 49 mol dm-3 at 127° C. Calculate Kp.
5. For the reaction 2 NO (g) + Cl2 (g) 2 NOCl (g) if partial pressure pNOCl = 0.32 atm, pNO2
= 0.22 atm, pCl2 = 0.11 atm, then find Kc.

NCERT EXERCISE QUESTIONS

Solve question no. 7.1 to 7.23 and 7.30 to 7.34

LINKS-

• https://www.youtube.com/watch?v=BPOde7AgZJs
• https://www.youtube.com/watch?v=wlD_ImYQAgQ
• https://www.youtube.com/watch?v=aJ0KNQ5-KaI