Equilibrium synopsis

Chapter - 7
Equilibrium

 A chemical equilibrium is a state at which the composition of a chemical system becomes constant
under given set of conditions. It is dynamic in nature. Both forward and backward reactions are in
progress with the same speed. Presence of a catalyst does not affect the final state of the
equilibrium.
 According to law of mass action the rate of forward reaction is directly proportional to the product
of molar concentrations (active masses) of the reactants with each concentrations term raised to
the power equal to the number of times that reactant appear in the balanced equation.
A + bB    cC + dD

According to law of mass action.

Rate of forward reaction, rf  [A]a [B]b

Rate of backward reaction, rb  [C]c [D]d

Active mass of a gas or liquid is equal to its molar concentration and the active mass of solids is
constant and taken as unity.

 Law of chemical equilibrium.

A  bB    cC  dD

 C  D 
c d

Kc 
 A   B
a b

where [A], [B], [C] and [D] are molar concentrations of A, B, C and D it equilibrium and K C is the
equilibrium constant.

Equilibrium constant in terms of partial pressure

p  p 
c d

KP  C a D b
 p A   pB  where, pA, pB, pC and pD are the partial pressures of A, B, C and D at
equilibrium respectively. KC and Kp have no units for a reaction when n = 0
 Relationship between Kp and Kc
Kp = Kc (RT)n (where, n = nproducts – nreactants)

 Equilibrium constant in terms of mole fractions

A + bB    cC + dD

 xC   xD 
C d

Kx 
 xA   xB 
 b

Kx depends upon temperature, pressure and volume.

Kp = Kx (p)n (where, p is the external pressure)

 Reaction quotient (Q) is tophe ratio of concentration terms having the same form as equilibrium
constant expression at each point in a reaction.
 Q = Kc reaction is in equilibrium
 Q < Kc reaction proceeds in forward direction
 Q > Kc reaction proceeds in backward direction
 Relation between vapour density and degree of dissociation.
Dd M  Mv
  c
d  y  1 M v  y  1
Degree of dissociation,

where, D are d are theoretical vapour density before and after dissociation and M c and Mv are
theoretical and observed molecular mass respectively and y are the number of moles of
products formed by one mole of reactant.

 Le-Chatelier’s principle
If a stress is applied to a reaction mixture at equilibrium, reaction occurs in that direction that
relieves the stress.

 On increasing concentration of reactants, reaction goes in a direction that tends to decrease

concentration and vice-versa.
 On increasing pressure (or decreasing volume), reaction goes in a direction that tends to
decreases pressure and vice-versa.
 On increasing temperature, reaction moves in a direction that tends to decrease the
temperature.
 1
x 
 For an approximation, quantity of product (x) is dependent on pressure by equation p

n = +ve, increased pressure shifts equilibrium in backward direction.

n = ve, increased pressure shifts equilibrium in forward direction.

n = 0, change in pressure have no effect.

 Presence of catalyst increases the rates of forward and backward reaction with the same rate.
 Ostwald dilution law
For a weak electrolyte of the type AB.

C 2
K  C 2
Dissociation constant 1 

K
  KV
C , where, C is the concentration in mol 1 L and V is the volume of solution in L having
1 mol of electrolyte for weak monobasic acids.

Ka
  KaV
C

Kb
  KbV
For weak monoacidic bases, C

 Relative strengths of two weak monobasic acids

strength of acid HA1 K a1
 
strength of acid HA2 K a2

 Conjugate acid-base pairs

Conjugate base of an acid is formed by the loss of a portion from acid. While conjugate acid is
formed from a base by the gain of H + (proton). Such a pair of substances which can be formed from
one another by the loss or gain of a proton are known as conjugate acid base pairs.

 pH = log [H3O+], pOH =  log [OH]

pKw = pH + pOH = 14 at 298 K

pKa = log Ka, pKb =  log Kb

 pKa + pKb = pKw
y x
Solubility product of a sparingly soluble salt AxBy is AxBy    xA  yB
 

Ksp = [Ay+]x, [Bx]y

In an ionic reaction precipitation takes place only if ionic product is greater than solubility product.

 Henderson equation
 Salt 
 pH of an acidic buffer  pH = pKa + log  Acid 
 Salt 
 pH of a basic buffer  pOH = pKb + log  Base
pH = 14 – pOH

 Salt hydrolysis
 For salts of weak acid and strong base
K
Kh  w
Hydrolysis constant Ka

Kh Kw
h 
C KaC
Degree of hydrolysis,

1
  pK a  pK w  log C
pH 2

1
7  pK a  log C 
2

 For salts of strong acid and weak base

K
Kh  w
Hydrolysis constant, Kb

Kh Kw
h 
C K b .C
Degree of hydrolysis,

1
pH   pK w  pK b  log C
2

1
7  pK b  log C 
2
 For salts of weak acid and weak base
Kw h2
Kh  
Hydrolysis constant K a .K b 1  h 2

Kw
h  Kh 
K a .K b
Degree of hydrolysis

1
pH   pK w  pK a  pK b 
2

1
7  pK a  pK b 
2

 Generally in salt hydrolysis

Ka = Kb , pH = 7

Ka > Kb , pH < 7

Ka < Kb , pH > 7

Ka > Kb , pH < 7

Ka < Kb , pH > 7