CHM 101 LECTURE NOTE

COURSE TITLE: INTRODUCTORY PHYSICAL CHEMISTRY

CREDIT UNIT: 03

PART TITLE: CHEMICAL EQUILIBRIUM

COURSE LECTURER: DR. S.A. AHMED

 COURSE SYNOPSIS

- The concept of equilibrium

- Equilibrium Law ( Law of Mass action )
- Relationship between Kp and Kc
- Relationship between G and K
- Effect of temperature on the equilibrium
constant.
- Homogenous chemical equilibria
- Heterogeneous equilibria system
- Factors affecting equilibrium constants
- Chemical equilibrium in solution
 water dissociation constant
 hydrolysis and hydrolysis constant
- Solubility equilibria
- Common-ion effects
RECOMMENDED TEXTBOOKS/
REFERENCES
1. Principle of physical chemistry by J.M. Gross
2. Physical chemistry by Atkins
3. Essentials of physical chemistry by Bahl and Bahl
4. Chemistry: The central science by Brown, Lemay,
Bursten and Murphy.
5. Physical chemistry by K.K. Sharma and L.K.
Sharma
 Concept of Equilibrium
Consider this direct reaction,

aA + bB → cC + dD
The reaction stops when the reactants are used up.
However, for a reversible reaction like this
aA + bB cC + dD
the equilibrium is attained when the rate of forward
reaction is equal to the rate of backward reaction.
Chemical equilibrium is the state of a reversible
reaction when the two opposing reactions occur
simultaneously.
At equilibrium, the concentrations of reactants and
products do not change with time.

The Equilibrium Law (Law of Mass action)

The law states that “at constant temperature, the rate
at which a substance reacts is directly proportional to
the active masses of the reactant”
Active mass is a thermodynamic quantity and it is
expressed a=fc, where a -active mass, f- activity co-
efficient (fugacity), c- molar concentration.
For ideal gaseous and solution reaction, f = 1.
Therefore, the active mass is equal to molar
concentration.

According to the law, R f  Aa B b

 Rf = Kf Aa B b
Also, Rb  C c D d

 Rb = K b C c D d
At equilibrium, K f Aa B b = K b C c D d
Kf

C  D
c d
 Kc
Kb Aa Bb
K c is the equilibrium constant in term of
concentration,
In term of activities,

 a C c a D d 
K A   a b  ,

 Aa  a B  

The concept of activity addresses the deviation from

ideal behaviour. Therefore, it can be defined as an
idealized concentration. K A is exact and does not
depend on pressure.
In term of pressure,

PCc PDd
K  a b c d
p
P Aa P Bb where P A , PB , PC and P D are
the partial pressure of various gaseous species at
equilibrium.

Relationship between K p and K c

In a gaseous reaction, the concentration of the gases

at any given temp is expressed in term of their partial
pressures.
Consider this gaseous reaction
aA(g) + bB(g) cC(g) + dD(g),
the equilibrium constant in term of pressure is
expressed as

PCc PDd
K  a b c d
p
P Aa P Bb where P A , PB , PC and P D are
the partial pressure of various gaseous species at
equilibrium.
However, K p and K c are not numerically equal, the
relationship can be derived as follow

For an ideal gases,

PV  nRT
n
 P  RT
V
n
But V = C

 P  CRT
c d
C Cc RT  C Dd RT 
Kp  a a b
C A RT  C Bb RT 

(c  d )
C Cc C Dd RT 
 a b (a b)
C A C B RT 

Recall that
 c d
CC DD
Kc  a b
AA B B

 K p  K c RT  n

   
Where n  c  d  a b i.e change in the amount
of gaseous reagents

When  n is positive,  the number of molecules

of products are larger than those of the reactants i.e
Kp  Kc

When  n is zero,  the number of molecules of

products = the number of molecules of the reactants
i.e K p  K c

When  n is negative,  the number of molecules of

products are smaller than those of the reactants i.e
K p  Kc

If the equilibrium constant is expressed in term of

mole fractions, X it is related to K p by
 ( X C P)c X C P 
d
Kp 
( X A P )a X B P 
b

 ( X C ) X D  
K p     P c  d  a  b 
 ( X A ) X B  

 K p  K x P n

where ∆n = c d   ab 

Relationship between ∆G and the equilibrium constant

The change in free energy of a reaction and the
equilibrium constant K are related to each other by the
expressions

G    RT ln K

Temperature dependence on the equilibrium constant

The value of equilibrium constant varies with
temperature change. The relationship between the
equilibrium constants at two different temperatures
and the enthalpy change is given by

K p2 H o  T2  T1 
log   
K p1 2.303R  T 1 T2 

Where K p 2 and K p1 are the equilibrium constants at

temperature T 2 and T1 respectively.
In terms of change in internal energy ( E o ), the
equation becomes

K p2 E o  T2  T1 
log   
K p1 2.303R  T 1 T2 

HOMOGENOUS CHEMICAL EQUILIBRUM

Homogenous equilibrium is an equilibrium in which
the reactants and the products are in the same phase.
-Homogenous gaseous equilibria
Case I: The Hydrogen-Iodide system
Consider a reaction
A +B 2C

e.g H 2( g ) + I 2( g ) 2 HI ( g )

t=0 a b
t=t a-x b-x 2x
if V (in dm3 ) is the total volume of the reaction
mixture

ax bx 2x
then, V V V

Kc 
HI  2
2 xV 2

Hence, H 2 I 2  =  a  x  b  x 
  
 V  V 
 4 x2
Kc  K c is independent of the
a  x a  b 
volume

In term of partial pressure,

PC2
Kp 
PA  PB
nA nB n
But PA   P, PB   P and PC  C  P
N N N

Where N  n A  nB  nC  total number of moles,

P  total (external) pressures PA , PB & PC are partial

pressures of A, B and C respectively.
2
 nC 
  P
 N  nC2
Kp  
 n
 A   n  n A  nB
  P  B  P
N  N 
Examples:
1. A mixture of 1 mole of H2 and 1 mole of I2 in a
flask was heated until the equilibrium is reached.
 On analysis, the equilibrium mixture is found to
contain 0.7mole of HI. Calculate the Kc
2. Consider this reaction H 2( g ) + I 2( g )
2 HI ( g )
Given that the partial pressures of the following
substances at 45oC are PH = 0.065atm, P I =0.45
2 2

atm. and P HI =0.245 atm. Calculate (a) the

equilibrium constant Kp for the reaction at 45oC (b)
the equilibrium constant Kp for the backward
reaction

3. Kc for this reaction SO 2 ( g ) + 1 O2 ( g ) SO 3 ( g )

2

at 727oC is16.7, calculate Kp for this reaction at

727oC.
N.B- Solutions to these examples shall be treated
during the lecture hours

Exercises:
1. The Kp for this equilibrium reaction:
NH 4 Cl ( s ) NH 3( g ) + HCl ( g ) is 0.11 at 25oC,
calculate Kc at this temperature.
 2. The following results were obtained during
CO 2 ( g ) H 2( g )
analysis of a reaction +
CO ( g )  H 2 O( g )

PCl 5
3. At 25oC and 4 atm., is 10% dissociated,
PCl 5 ( g )
calculate the Kp for this reaction,
PCl 3( g ) + Cl 2 ( g )

Case II: A 2B
e.g. Decomposition of N 2O 4 , i.e N 2O 4 2 NO 2

Kc 
NO 2  2  V
2x 2

N 2 O 4  ax
 
 V 

4 x2
 Kc 
a  x V
In term of Kp,
2

Kp 
NO2 
2

PNO 2

N 2O4  PN O 2 4

Also, while considering the equation, if x represent

the degree of dissociation, then 2x of NO 2 will be
produced, then 1-x of N 2 O 4 will be left. then, the total
number of moles present at equilibrium = (1-x)
+2x=1+x.

1 x   2x 
 PN O   P PNO2  P
2 4
1 x  &
1 x 

2
 2 x  
2
PNO  1  x  P 
  
Kp  2

So, PN2O4 1 x 
 P
1 x 

4x2P
 Kp 
1  x2
Examples:
1. N2O4 at 1 atm and 25oC dissociated by 18.5%,
calculate its Kp at this temperature. If the
atmospheric temperature was reduced to half its
original value at the same temperature, calculate
the degree of dissociation of the gas.

2. N2O4 is 25% dissociated at 30oC and 1 atm.,

calculate
(a) The equilibrium constant for the decomposition
(b) The amount of NO2 that would be attained if
there had been 4 moles of N2O4 at the same
temperature and pressure.
N.B- Solutions to these examples shall be treated
during the lecture hours

Exercises:
1. N2O4 is 25% dissociated at 370C and 1 atm.,
calculate
(i) The Kp and (ii) the % dissociation at 0.1 atm
and 37oC
 2. An equilibrium mixture at 27oC contains N2O4 and
NO2 having 0.28 atm. and 1.1 atm. pressures
respectively. If the volume of the container is
doubled, calculate the new equilibrium pressure
of the gases.

Case III: A + 3B 2C
e.g. synthesis of Ammonia

N 2  g   3H 2  g  2 NH 3 g 

ax bx 2x
V V V

Kc 
 NH 3 

2  V
2x 
2

N 2 H 2   a  x 
3
 b  x 
3

  
 V   V 

4 x 2V 2
Kc 
 a  x b  x 3

Also,
 2
PNH
Kp  3

PN 2  PH32
Examples:
1. In an experiment, H2 and N2 in the mole ratio 3:1
produced 0.0735mole fraction of NH3 at 350oC and
total pressure of 1013KNm-2. Calculate Kp for the
forward and reverse reactions
2. The Kp for this equilibrium reaction
N2 (g) + 3H2 (g) 2NH3 (g) is 1.45 x 10-5
at 500oC. Calculate the partial pressure of NH3
when the partial pressure of H2 is 0.928atm and
that of N2 is 0.432atm.
Exercise:
1. The dissociation pressure of CaCO3 is 342mmHg at
840oC and at 860oC, the dissociation pressure is
420mmHg. Calculate the heat of dissociation of the
carbonate. Given that R=8.314KJmol-1.

2. consider this reaction

N2 (g) + 3H2 (g) 2NH3 (g),
The Kp is 1.64x10-4 at 400oC. calculate (i) the ∆G
of the reaction (ii) ∆G when the partial pressure
 of N2, H2 and NH3 are 10atm, 30 atm and 3 atm
respectively.

HOMOGENOUS (LIQUID) EQUILIBRIA

A (l) + B (l) C (l) + D (l)
e.g. CH3COOH (l) +C2H5OH (l) CH3COOC2H5 (l) +H2O
(l)

t=0 a b 0 0
t=t a-x b-x x x

x x
  
V V
Kc     
ax bx
  
 V   V 

x2
 Kc 
a  x b  x 
The equation above is the general expression for the
liquid equilibria. However, in the example above where
water molecule is involved, the expression can be
written as

Kc 
CH3COOC2 H 5 H 2O
CH3COOHC2 H5OH 

Kc '
 Kc 
CH3COOC2 H 5 
H2O CH3COOHC2H5OH
'
The above expression is written in term of K c
because the concentration of water is taken to be
'
constant, K c has the unit of Concn  but K c has no
1

unit.
Example:
1. In an esterification process between 1 mole of
ethanoic acid and 1 mole of ethanol at 25oC,
66.7% of the acid is esterified calculate the
equilibrium constant and ∆Go.
2. When 1 mole of ethanoic acid and 1 mole of
ethanol were heated together at a temperature of
 25oC until the equilibrium is reached. Titration of
the reaction mixture shows that 2/3 of the acid
have been used up. Calculate the equilibrium
constant.

HETEROGENEOUS EQUILIBRIA SYSTEM

Heterogeneous equilibrium is an equilibrium in which
the reactants and the products are not in the same
phase.
e.g. 3Fe(s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

Kc 
Fe3O 4 H 2 
4

1  H 2 
4

H2 
4

Fe3 H 2O4 1  H 2O

4
H 2O4
N.B: the concentration of substances in solid
phase is taken to be unity.

In term of Kp ,

PH4 2
K p 
PH4 2 O
Exercises: Express the equilibrium constants Kp, for
the following reactions.
 1. CaCO3(s) CaO(s) +CO2(g)
2. 2H2O(l) 2H2(g) + O2(g)
3. NH4Cl(s) NH3(g) + HCl(g)

Le-Chatelier’s Principle
It states that “if a chemical system is in equilibrium
and one of the factors involved in the equilibrium is
altered, the equilibrium will shift, so as to neutralize
the effect of the change”.

FACTORS AFFECTING EQUILIBRIUM

The factors are: temperature, concentration and
pressure of the reactants and products, catalyst.
N.B: catalyst does not change the position of
equilibrium, but affects the reaction equally in
both directions.
1. Effect of temperature changes on equilibrium
mixture: If a chemical system is in equilibrium and the
temperature is lowered, the equilibrium position
according to Le-Chatelier’s Principle will shift so as to
neutralize the cooling effect by releasing more heat.
 Conversely, if the temperature is raised, the
equilibrium position will shift so as to neutralize the
heating effect by absorbing more heat.
e.g. H2O (l) H2O (g) ∆H=+ve
Since the forward reaction is an endothermic, if the
temperature is raised, more steam will be produced
and the equilibrium position will shift to the right. On
the other hand, if the temperature is lowered, the
equilibrium position shifts to the left and more water
will be formed as the steam condenses.

The table below summarises the effect of temperature

change on the equilibrium position.
Reversible reactions When the temp. of equilibrium system
where forward rxn is
endothermic increases decreases

N2O4(g) 2NO2(g) Equilibrium Equilibrium

position shifts to position shifts to
N2(g) +O2(g) 2NO(g)
right, favouring left, favouring
PCl5(g) PCl3 (g+Cl2(g) forward rxn. K backward rxn. K
increases decreases
Forward rxn is
exothermic
Equilibrium Equilibrium
2SO2(g)+O2(g) 2SO3(g) position shifts to position shifts to
left, favouring right, favouring
2H2(g)+O2(g) 2H2O(g)
backward rxn. K forward rxn. K
N2(g)+3H2(g) 2NH3(g) decreases increases

2. Effect of pressure changes on equilibrium mixture:

This effect occurs in gaseous state reactions in which
the total numbers of moles of gaseous molecules on
the left hand side of the equation differ from that on
the right hand side of the equation.
When the pressure of a system at equilibrium is
increased, then the reaction that involves a reduction
in pressure will be favoured. This is in line with the Le-
Chatelier’s principle. Conversely, if the pressure is
lowered for a system at equilibrium, the reaction that
will increase the pressure will be favoured.
e.g N2 (g) +3H2 (g) 2NH3 (g)
4 moles 2 moles
The forward reaction involves a decrease in the
number of moles and hence, a decrease in the
pressure of the system. Also, the backward reaction
gives an increase in the number of moles, and hence
an increase in the pressure of the system.
In the formation of ammonia, a high pressure will
favour the forward reaction (where a reduction in
volume occurs). This causes the equilibrium position
to shift to the right. on the other hand, a low pressure
will cause the equilibrium position to shift to the left,
favouring the backward reaction.
The table below summarises the effect of a change in
pressure on the equilibrium position.

Reversible reactions Shift in equilibrium

position when the
pressure
1.Forward rxns (decrease in Increases decreases
vol)

2SO2(g)+O2(g) 2SO3(g) right Left

3H2(g) +N2(g) 2NH3(g) right Left
2CO(g)+O2(g) 2CO2(g) right Left

2.Forward rxns (increase in

vol)
Left right
N2O4(g) 2NO2(g)
 3.No change in volume

H2(g) +I2(g) 2HI2 (g) _______ _________

3Fe(s)+4H2O(g) Fe3O4(s) ________ _________
2H2(g)

NB: the value of K remain constant irrespective of the

shift in the equilibrium position.
3. Effect of concentration changes on equilibrium
mixture: if the concentration of any of the substances
present is changed without a change in any of the
other conditions. According to Le-chatelier’s
principle, the equilibrium position will move to
increase the concentration of the added substance.
e.g. N2 (g) +O2 (g) 2NO (g)
The addition of more reactants (either N2 or O2 or
both)will upset the equilibrium. For the system to
adjust, the equilibrium position will shift to the right
thereby favourig the forward reaction. This results in a
proportional increase in the concentration of the
product.
 Similarly, if the product formed is continually removed
fom the system, the equilibrium position will shift to
the right to produce more of the product.

The effect of concentration change on equilibrium can

be summarise in the table below

Reversible reactions Addition of removal of

reactants or reactants or
removal of addition of
products products
CaCO3(g)
CaO2(g)+CO2(g) Equilibrium Equilibrium
N2 (g) +O2 (g) 2NO (g) position shifts to position shifts to
3Fe(s)+4H2O(g) Fe3O4(s) the right the left
+4H2(g)

NB: the value of K remain constant irrespective of the

shift in the equilibrium position.

4.Effect of Catalyst: Addition of catalyst has no effect

on either the equilibrium constant or shift. It only
speed up the rate at which the equilibrium is reached.

CHEMICAL EQUILIBRIUM IN SOLUTION

 a. Dissociation of water:
H2O(L) H+ + OH –

K 
H OH 
 

H 2 O 
  


 7
But H  OH  10 mol/dm3 at 25oC and
H2O= constant

 K  H OH   1  10
w
   14

Kw is the water dissociation constant.

Examples
1. Calculate the [OH -] of the 0.01M HCL
2. Calculate the [H +] of the 0.0001M NaCL

(b). Hydrolysis and hydrolysis constant

when a salt of a strong acid and a strong base

dissolved in water, the water remains neutral.
However, when a salt formed from a strong acid and
a weak base or vice versa is dissolved in water, it
either make the water acidic or basic.

e.g. (a) salt of strong base-weak acid like sodium

ethanoate
(CH3COONa) react with water to give an alkaline
solution.
CH3COO - +H2O CH3COO - + H+ +OH –
CH3COOH + OH –

As the CH3COO – consume the H+from water to form

ethanoic acid, more of the water molecules dissociate
to produce more of their ions.

At equilibrium,
HEt OH  
Ka 
Et  H 2O

But
HEtOH    H OK  Kh
Et  2 a

K h is the hydrolysis constant, but K w  H  OH  

Kw Kw
    

OH   
H Ka
The hydrolysis constant Kh is related to the aci
dissociation constant by the expression
 Kw
Kh 
Ka

The degree of hydrolysis, α, is the fraction of the salt

which has undergone hydrolysis when equilibrium is
reached and it is given by

Kw
α= Kh  C

(b). salt of weak base-strong acid, e.g NH4Cl.

NH4(aq)+ + H2O(aq) NH4OH(aq) + H+(aq)

NH4OHH  
Kh 
 NH  4


K
but H   OH



w


Kw
K 
 h Kb

c. Salt of weak acid-weak base, e.g CH3COONH4

NH4+(aq) + Et - (aq) NH3(aq) + HEt (aq)
 The hydrolysis constant is given by

Kw
Kh 
Ka  Kb

and the degree of hydrolysis is given by

Kw
α= K a K b

Solubility Product

When a sparingly soluble salt e.g AgCl dissolves in

water at a given temperature, a stage will be reached
when it will not dissolve further and both the solid
and and solution will co-exist in equilibrium.
AgCl(aq) Ag+(aq) + Cl-(aq)
 K
Ag Cl 
 

AgCl
   
K AgCl  Ag  Cl   K sp
Examples
1. Calculate the hydrolysis of a base whose
dissociation constant is 1.75 x 10-5.
2. The solubility of CuBr is found to be 2.0 x 10-4
mol/L at 25oC. calculate Ksp value for CuBr.
3. The solubility of Mg(OH)2 at 25oC is 0.00764g/L.
what is the value of Ksp for Mg(OH)2?

Exercises
1. Calculate the Ksp of AgCl whose solubility at 25oC
is 1.05x 10-5 mol/L.
2. The solubility of BaSO4 at 18oC is 0.00233g/L.
what is the value of Ksp for BaSO4?

Common-ion Effect
When a soluble salt (say, A+C-) is added to a solution
of another salt (A+B-) containing a common ion (A+),
the dissociation of AB will be suppressed.

AB A+ + B-
By the addition of the salt (AC), the concentration of
A+ increases. In line with the Le-chatelier’s principle,
the equilibrium will shift to the left, thereby decreasing
the concentration of A+ ( i.e the degree of dissociation
of AB will be reduced).
Thus, the reduction of the degree of dissociation of a
salt by the addition of a common-ion is called the
common-ion effect.

Examples
1. Calculate the [H+] when 0.1 mol acetic acid was
treated with 0.2 mol acetate ion. The equilibrium
constant is 1.8x 10-5.
2. Calculate the [H+] when 1 mol of sodium formate
was added to 0.5 mol formic acid. Given that K=
1.8x 10-5.