Chemical Equilibria Notes

Chemical equilibria: reversible reactions, dynamic equilibrium;
a) explain, in terms of rates of the forward and reverse reactions, what is meant by a reversible
reaction and dynamic equilibrium
b) state Le Chatelier’s principle and apply it to deduce qualitatively (from appropriate

information) the effects of changes in temperature, concentration or pressure on a system at
equilibrium
c) state whether changes in temperature, concentration or pressure or the presence of a

catalyst affect the value of the equilibrium constant for a reaction
d) deduce expressions for equilibrium constants in terms of concentrations, Kc , and partial

pressures, Kp (treatment of the relationship between Kc and Kp is not required)
e) calculate the values of equilibrium constants in terms of concentrations or partial pressures

from appropriate data
f) calculate the quantities present at equilibrium, given appropriate data (such calculations will
not require the solving of quadratic equations)
g) describe and explain the conditions used in the Haber process and the Contact process, as
examples of the importance of an understanding of chemical equilibrium in the chemical
industry
Ionic equilibria:
a) show understanding of, and use, the Brønsted-Lowry theory of acids and bases, including the
use of the conjugate acid, conjugate base (acid-I base-I, acid-II base-II) concept
b) explain qualitatively the differences in behaviour between strong and weak acids and bases
and the pH values of their aqueous solutions in terms of the extent of dissociation
Chemical equilibrium: A state in which the rates of the forward and reverse reactions are equal
and the concentrations of Equilibrium
Equilibrium is the state of a process in which the properties like temperature, pressure, and
concentration etc of the system do not show any change with passage of time.
In all processes which attain equilibrium, two opposing processes are involved.
Equilibrium is attained when the rates of the two opposing processes become equal.
If the opposing processes involve only physical changes, the equilibrium is called Physical
Equilibrium.
If the opposing processes are chemical reactions, the equilibrium is called Chemical Equilibrium.
Physical Equilibriumthe reactants and products remain constant.
Equilibrium in Chemical Process
 Reversible reaction: A reaction in which not only the reactants react to form the
products under certain conditions but also the products react to form reactants under
the same conditions
Examples: 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
 Irreversible reaction: A reaction cannot take place in the reverse direction, i.e. the
products formed do not react to give back the reactants under the same condition.
Example: AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(g)
 Generally, a chemical equilibrium is represented as

Where A, B are reactants and C, D are products.
The equilibrium state is dynamic and not static in nature. A reaction is said to have attained
equilibrium when the rate of forward reaction equals that of backward reaction
 Homogeneous equilibrium: ?All the reactants and products of any reaction under
equilibrium are in same physical state. Example: N2(g) + 3H2(g) 2NH3 (g)
 Heterogeneous equilibrium? :Physical state of one or more of the reacting species may
differ i.e. all the reactants and products are not in same physical state.Example
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)?
Characteristics of Equilibrium State
It can be attained only if the reversible reaction is carried out in closed vessel.
It can be attained from either side of the reaction.
A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium.
It is dynamic in nature i.e. reaction does not stop but both forward and backward reactions take
place at equal rate.
Change of pressure, concentration or temperature favours one of the reactions (forward or

backward) resulting in shift of equilibrium point in one direction
Fore reaction
Rate of reaction ∝ [A]a.[B]b
or rate of reaction = K[A]a[B]b
where K is rate constant or velocity constant of the reaction at that temperature.
Unit of rate constant (K)

aA + bB cC + dD
Rate of forward reaction [A]a[B]b
or Rf = Kf [A]b [B]b
Similarly for backward reaction
Rb = Kb[C]c [D]d
At equilibrium Kf[A]a[B]b = Kb[C]c[D]d
above equation is known as equilibrium equation and Kc is known as equilibrium constant.
Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant for the
reaction in the forward direction
Consider the equilibrium
aA +bB cC +dD
At equilibrium
The Le–Chatelier’s Principle:
Statement:
“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.”
Effect of Addition of Inert Gases:
 Addition of inert gas at constant volume: No effect on equilibrium.
 Addition of inert gas at constant pressure: Equilibrium shifts in a direction where there
is increase in number of moles of gases.
Effect of Change in Temperature:
 In a system at equilibrium, both exothermic and endothermic reactions take place

simultaneously.
 Increase in temperature would shift the equilibrium in the direction of endothermic

reaction.
 Decrease in temperature would shift the equilibrium in the direction of exothermic

reaction.
Effect of Change in Concentration:
 When the concentration of reactants increased, equilibrium shifts in forward direction.
 When the concentration of the products is increases, equilibrium shifts in backward

direction.\
Effect of Change in Pressure:
 Increase in pressure shifts the equilibrium in the direction of lesser number of gaseous
molecules.
 Decrease in pressure shifts the equilibrium in the direction of larger number of gaseous
molecules.
Effect of Catalyst:
Catalyst does not change the equilibrium.
Thermodynamics of chemical equilibrium:
ΔG = ΔG0 + 2.303 RT log Q
At equilibrium:
ΔG = ΔG0 + 2.303 RT log K = 0
or
ΔG0 = - 2.303 RT log K
Also
Acids and Bases:
1. Arrhenius Definition:
a. Acids give H+ ions aqueous solutions.
b. Bases give OH- ions in aqueous solution.
2. Bronsted – Lowry Definition:
a. Acid is a proton donor .
b. Base is a proton acceptor.
3. Strong and Weak Acids:
a. Strong acid dissociate completely in aqueous solution.
Example: HCl
b. Weak acid dissociates partially in aqueous solution.
Examples: CH3COOH
Degree of dissociation (a) =(Ka/C)1/2
Where,
Ka = [CH3COO-][H+]/[CH3COOH]
And
C = Initial concentration of acid.
Also
[H+] = Ca = (Ka×C)1/2
c. Ionic Product of Water:
H2O H+ + OH–
K[H2O] = [H+] [OH–] = 10-14

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Chemical equilibria: reversible reactions, dynamic equilibrium;

b) state Le Chatelier’s principle and apply it to deduce qualitatively (from appropriate

c) state whether changes in temperature, concentration or pressure or the presence of a

d) deduce expressions for equilibrium constants in terms of concentrations, Kc , and partial

e) calculate the values of equilibrium constants in terms of concentrations or partial pressures

Physical Equilibriumthe reactants and products remain constant.

Equilibrium in Chemical Process

Examples: 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

 Generally, a chemical equilibrium is represented as

2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)?

Characteristics of Equilibrium State

It can be attained from either side of the reaction.

Change of pressure, concentration or temperature favours one of the reactions (forward or

Rate of reaction ∝ [A]a.[B]b

or rate of reaction = K[A]a[B]b

where K is rate constant or velocity constant of the reaction at that temperature.

Unit of rate constant (K)

Rate of forward reaction [A]a[B]b

Similarly for backward reaction

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

above equation is known as equilibrium equation and Kc is known as equilibrium constant.

Consider the equilibrium

The Le–Chatelier’s Principle:

 Addition of inert gas at constant volume: No effect on equilibrium.

Effect of Change in Temperature:

 In a system at equilibrium, both exothermic and endothermic reactions take place

 Increase in temperature would shift the equilibrium in the direction of endothermic

 Decrease in temperature would shift the equilibrium in the direction of exothermic

Effect of Change in Concentration:

 When the concentration of reactants increased, equilibrium shifts in forward direction.

 When the concentration of the products is increases, equilibrium shifts in backward

Effect of Change in Pressure:

Catalyst does not change the equilibrium.

Thermodynamics of chemical equilibrium:

ΔG = ΔG0 + 2.303 RT log Q

ΔG0 = - 2.303 RT log K

Acids and Bases:

a. Acids give H+ ions aqueous solutions.

b. Bases give OH- ions in aqueous solution.

2. Bronsted – Lowry Definition:

a. Acid is a proton donor .

b. Base is a proton acceptor.

3. Strong and Weak Acids:

a. Strong acid dissociate completely in aqueous solution.

b. Weak acid dissociates partially in aqueous solution.

Degree of dissociation (a) =(Ka/C)1/2

C = Initial concentration of acid.

c. Ionic Product of Water:

K[H2O] = [H+] [OH–] = 10-14

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