Chemical Equilibrium

Chapter 6
6.0 Chemical Reaction

Chemical reaction may occur in two ways:-

a) a non-reversible reaction
- occurs in one direction

b) a reversible reaction
- occurs in both direction
i.e (forward & reverse reaction)
6.1.1 A non-reversible reaction

Example 1

NaCl + AgNO3 AgCl + NO3

One/both reactants will be completely

consumed and amount of products formed
depends on the limiting reactant.
A single arrow () is used to represent
reaction.
6.1.2 Reversible Reaction
Example 2
H2(g) + I2(g) 2HI(g)

Occurs in both direction.

shows that reactants react to form product,
and product reacts to form reactants.
Amount of products formed does not depend
on the amount of reactant used.
Reaction will reach equilibrium when the
concentration of products & reactants
remained constant.
6.2 Equilibrium System

A system is at equilibrium when there is no

observable change occurs.

Equilibrium system can be observed in:

a. Physical Equilibrium
b. Chemical Equilibrium
6.2.1 Physical Equilibrium
Example 3
vaporisation in a closed container.
H2O (l) H2O (g)
Involves physical change of substance.

Level of H2O in the container remains

constant at equilibrium because the rate of
evaporation equals the rate of
condensation.
6.2.2 Chemical Equilibrium
Example 4
2NO2(g) N2O4(g)

Initially NO2 molecules combine to form N2O4

(brown gas appears)

As soon as N2O4 is formed, it undergoes

reverse reaction to form NO2.

At equilibrium, the system contains a constant

amount of NO2 & N2O4.
6.3 Dynamic Equilibrium
A system reaches a dynamic equilibrium when

the rate of forward reaction equals the rate of

reverse reaction.

the concentrations of both reactants and

products remain constant.

no observable change occurs but the

conversions of reactants to products and
products to reactants continue.
concentration After time t1, both concentrations
remain constant.

[N2O4] at equilibrium

[NO2 ]at equilibrium

The reaction does not stop
but the rate of forward
reaction equals the rate of
reverse reaction.
t1 time
6.4 Equilibrium constant, K
Since concentrations at equilibrium remain
constant, the equilibrium can be expressed by
a constant.

Consider:
aA (g) + bB (g) cC (g) + dD (g)
[C]c[D]d
Kc =
[A]a[B]b
Kc is known as equilibrium constant
Concentrations of species are expressed in
molar.
Table 6.1

N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4] constant
 6.5 Equilibrium Law: Law of Mass
Action
When a system has reached equilibrium, the
ratio of multiplied concentrations of products to
the multiplied concentrations of reactants (each
raised to the power of the respective
stoichiometric coefficient) is a constant at
constant temperature.
OR
Value of equilibrium constant, Kc is a constant at
constant temperature.
6.6 Types of System in Chemical Equilibrium

a) Homogeneous equilibrium
Homogenous equilibrium applies to reactions in
which all reacting species are in the same
phase.

b) Heterogeneous equilibrium
A system in which the reactants and products
are not in the same phase.
6.7 Homogeneous Equilibrium System

6.7.1 Liquid phase

Important variable: concentration
Equilibrium constant: Kc

Example 5
CH3COOH (l) + CH3OH (l) CH3COOCH3 (l) + H2O (l)
Kc =
Example 6

CH3COOH (aq) CH3COO- (aq) + H+ (aq)

Kc=
6.7.2 Gas phase

The quantitative aspects to be considered are

the concentration and pressure.

We can use Kcand Kp to represent the

equilibrium constant.

(PC)c (PD)d the pressure of gases are

Kp = expressed in atm or other
(PA)a (PB)b units of pressure
Example 7
Write the equilibrium law in the form of Kp
and Kc for the following reactions:

a) N2(g) + 3H2(g) NH3(g)

b) 2NO(g) + O2(g) N2O4(g)

Answer:
Kp =
Kc =
Expression of Kc
Expression of Kc depends on the equilibrium
equation given

Example 8
2SO3 (g) 2SO2 (g) + O2 (g) Kc = [SO2]2 [O2]
[SO3]2
1. SO3 (g) SO2 (g) + O2 (g) Kc1 = [SO2] [O2]1/2
[SO3]
2. 2SO2 (g) + O2 (g) 2SO3 (g) Kc2 = [SO3]2
[SO2]2 [O2]
Example 9
Find the relationship between Kc1 and Kc2 for the
following equilibrium equations.

1. SO3 (g) SO2 (g) + O2 (g) Kc1 = [SO2] [O2]1/2

[SO3]

2. 2SO2 (g) + O2 (g) 2SO3 (g) Kc2 = [SO3]2

[SO2]2 [O2]
Example 10

Consider the following reaction:

A(g) + B(g) 2C(g)

If 5 moles of A are allowed to mix and react

with 3 moles of B in 1dm3 container, 2 moles
of C are produced at equilibrium. What is the
value of Kc for this reaction?
(Ans: 0.5 )
Example 11
Consider the reaction:

CO(g) + 2H2(g) CH3OH(g)

The following equilibrium concentrations are

achieved at 400K:
[CO] = 1.03M
[H2] = 0.332M
[CH3OH] = 1.56M

Determine the equilibrium constant at 400K

(Ans: 13.74 M-2)
Example 12

Nitrogen gas reacts with oxygen gas at high

temperature to form nitrogen monoxide gas,
NO. The equilibrium constant for the reaction is
4.1 x 10-4 at 200oC.

If the concentration for both N2(g) and O2(g) at

equilibrium are 0.40 moldm-3 and 1.3 moldm-3
respectively, calculate the concentration of NO
gas at equilibrium?
(Ans: 0.0146 M)
Example 13

The equilibrium constant Kp for the reaction;

2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure
of O2 if the P NO2 = 0.400 atm and PNO = 0.270
atm?
Answer;
2
PNO PO
2
Kp =
2
PNO
2

2
PNO
PO = Kp 2
2 2
PNO

PO2 = 158 x (0.400)2

(0.270)2

= 347 atm
6.7.3 Relationship between Kp and Kc

Consider
aA (g) + bB (g) cC (g) + dD (g)

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

Thus, Since P = nRT

V
{PC /(RT)}c {PD / (RT)}d
Kc =
{PA /(RT)}a {PB /(RT)}b
[ ]= P
RT
For the reaction
aA (g) + bB (g) cC (g) + dD (g)

PCc PDd (RT) (a + b) (c+d)

Kc =
PAa PBb

Kc = Kp (RT) (a + b) (c+d)

Kp = Kc (RT) (c + d) (a+b)

Kp = Kc (RT)n
1. The equilibrium concentrations for the reaction
between carbon monoxide and chlorine to form
COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054
M, and [COCl2] = 0.14 M. Calculate the
equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

Answer;

[COCl2] 0.14
Kc = =
[CO][Cl2] 0.012 x 0.054
= 220 M -1

Kp = Kc(RT)n n = 1 2 = -1

Kp = 220 x (0.08206 x 347)1

= 7.7 atm1
6.8 Heterogeneous Equilibrium system

Heterogenous equilibrium applies to

reactions in which reactants and products are
in different phases.

Kc and Kp can be used to represent the

equilibrium constant.

The concentration of solids and pure

liquids are not included in the expression
for the equilibrium constant.
1. CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]

H2O a pure liquid, has a constant concentration

and thus is not included in the expression.

Therefore, the equilibrium constant is written as,

[CH3COO-][H3O+]
Kc =
[CH3COOH]
Unit : M
2. CH3COOH (aq) + C2H5OH (aq) CH3COOC2H5 (aq) + H2O (l)
Carboxylic Alcohol Ester
acid

[CH3COOC2H5]
Kc =
[CH3COOH] [C2H5OH]
3. CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2]
Kc =
[CaCO3]

[CaCO3] = constant
[CaO] = constant

Kc = [CO2]
Kp = PCO2
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

5. Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)

The partial pressure of each gas is 0.265 atm.

Calculate Kp and Kc for the reaction?
Answer;
Kp = PNH PH S = 0.265 atm x 0.265 atm
3 2
= 0.0702 atm2

Kp = Kc(RT)n n = 2 0 = 2
T = 295 K

Kc = 0.0702 atm2
(0.08206 atm L mol1 K1 x 295 K )2

= 1.2 x 104 mol2 L2

= 1.2 x 104 M2
6. The value of Kc for the following equation is 1.0 x 10 3 M
at 200C.
2NOBr (g) 2NO (g) + Br2 (g)

Calculate Kc for the following equation at 200C.

NO (g) + Br2 (g) NOBr (g)

Answer;
Kc = [NO]2 [Br2] Kc = [NOBr]
[NOBr]2 [Br2]1/2 [NO]

1
1 = = [NOBr]2
Kc [NO]2 [Br2] [NO]2 [Br2]
[NOBr]2

1 [NOBr]
= = Kc
Kc [NO] [Br2]
Kc = 1
Kc

Kc = 1
1.0 x 103 M

= 31.6 M-

= 31.6 dm3/2 mol

7. At 440C, the equilibrium constant Kc for reaction,
H2(g) + I2(g) 2HI(g)
has a value of 49.5. If 0.200 mole of H2 and 0.200
mole of I2 are placed into a 10.0 L vessel and
permitted to react at this temperature, what will be
the concentration of each substance at
equilibrium?
Answer;

[H2]0 = 0.200 /10.0 = 0.0200 M

[I2]0 = 0.200 /10.0 = 0.0200 M

H2 (g) + I2 (g) 2HI (g)

[ ]0 / M 0.0200 0.0200 0
[ ] / M -x -x +2x
[ ] / M 0.0200 - x 0.0200 - x +2x
 Kc = [HI]2
[H2] [I2]

49.5 = (2x)2
(0.0200 x) (0.0200 x)

7.036 = 2x
0.0200 - x

x = 0.0156
 H2 (g) + I2 (g) 2HI (g)
[ ]0 / M 0.0200 0.0200 0
[ ] / M -x -x +2x

[ ] / M 0.0200 - x 0.0200 - x +2x

= 0.0044 = 0.0044 = 0.0312

Therefore concentration of each substance at equilibrium:

[H2] = 0.0044 M
[I2] = 0.0044 M
[HI] = 0.0312 M
8. A 1.000-L flask is filled with 1.000 mol of H2 and
2.000 mol of I2 at 448C. The value of the
equilibrium constant, Kp for the reaction,

H2 (g) + I2 (g) 2HI (g)

at 448C is 50.5. What are the partial pressures

of H2 , I2 and HI in the flask at equilibrium.
Answer;

Initial pressures of H2 and I2.

PH = nH2 RT = (1.000)(0.08206)(721)
2
V 1.000
= 59.19 atm

PI = nI2 RT = (2.000)(0.08206)(721)
2
V 1.000
= 118.4 atm
 H2 (g) + I2 (g) 2HI (g)
P0 59.19 118.4 0
P -x -x +2x
P 59.19 - x 118.4 - x +2x

50.5 =
Kp = PHI
2
(2x)2
PH P I (59.19 x) (118.4 x)
2 2

46.5x2 8969x + 353904 = 0

Partial pressure of gases at equilibrium:

PH = 3.89 atm ; P = 63.1 atm ; PHI = 110.6 atm
2 I2
6.2.6 Degree of Dissociation,

The fraction of a molecule dissociated.

C C = changes in concentration
=
C0 C0 = initial concentration

A complete dissociation occurs if = 1

 AB A+ + B

C0 / M a 0 0

C / M -x +x +x

C / M a-x +x +x

x
=
a
9. The concentration of H+ ion measured for HCOOH
0.5 M is 0.0089 M. What is the degree of dissociation
of the compound?
a = 0.5 x = 0.0089

HCOOH H+ + HCOO
C0 / M 0.5 0 0
C / M -0.0089 +0.0089 +0.0089
C / M 0.5-0.0089 0.0089 0.0089
= 0.4911

x 0.0089
= = = 0.0178 = 1.78%
a 0.5
6.2.7 Predicting the direction of reaction

For any reversible reaction, we can determine

the direction of a reaction (whether is moving
forward or reverse) by comparing the value of
Q with Kp or Kc.

Q is the reaction quotient

Q has the same expression of Kc and Kp but

the numerical value gained is NOT at
equilibrium.
 Predicting the direction of reaction:
aA (g) + bB (g) cC (g) + dD (g)
[C]c[D]d
Qc =
[A]a[B]b

If Q = K The system is at equilibrium

If Q < K Reaction is moving forward

- more reactants are present in the
mixture at t

If Q > K Reaction is reversed

- more products are present in the
mixture at t
10. At 12800C the equilibrium constant (Kc) for the
reaction
Br2 (g) 2Br (g)
is 1.1 x 10-3. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
Br2 (g) 2Br (g)
C0/M 0.063 0.012

[Br]2
Qc = = (0.012)2 = 2.29 x 103
[Br2]
0.063
Q c > Kc Equilibrium position shifts
from right to the left.
 Br2 (g) 2Br (g)
C0/M 0.063 0.012
C/M +x - 2x
C/M 0.063 + x 0.012 - 2x

[Br]2
Kc =
[Br2]

(0.012 2x)2
1.1x10-3 =
0.063 + x
4x2 0.048x + 1.44x10-4 = 6.93x10-5 + 1.1x10-3x

4x2 0.0491x + 7.47x10-5 = 0

x = 0.0105 x = 1.78x10-3

C [Br] = 0.012 2x [Br2] = 0.063 + x

If x = 0.0105 = -0.009 M = 0.0735 M

If x = 1.78x10-3 = 0.00844 M = 0.0648 M

11. The equilibrium constant Kc for the reaction
I2 (g) + H2(g) 2HI (g)
is 54.0 at certain temperature. At equilibrium, the conc. of
I2, H2 and HI are 0.200 M, 0.200 M and 1.47 M
respectively. If 0.500M of HI is added, what are the conc.
when equilibrium is re-established?

[HI]2 Since Qc > Kc, the system

Qc =
[H2] [I2] is not at equilibrium
(1.47 + 0.5)2 The net reaction will
= proceed from RIGHT to
(0.200) (0.200)
LEFT until equilibrium is re-
= 97.0 established.
 H2 (g) + I2 (g) 2HI (g)
C0/M 0.200 0.200 1.47 + 0.500 Kc = 54
C/M +x +x -2x Qc = 97
C/M 0.200 + x 0.200 + x 1.97 2x
= 0.2535 = 0.2535 = 1.863

Kc = [HI]2
[H2] [I2]
54.0 = (1.97 2x)2 7.35 = 1.97 2x
(0.200 + x) (0.200 + x) 0.200 + x
x = 0.0535M
6.3 Factors affecting the equilibrium
position
The position of equilibrium in a system is affected
by:
a) concentration
b) pressure
c) temperature

The effects can be predicted & explained by

the :
Le Chateliers Principal
6.3.1 Le Chteliers Principle

If an external stress is applied to a

system at equilibrium, the system
adjusts in such a way that the stress
is partially offset as the system
reaches a new equilibrium position.
A) Effect of Concentration:
Changing the concentration of the reactants or
products causes the equilibrium to shift to the
direction that will reduce the effect .

Example:
Increasing the concentration of reactant/s causes
the equilibrium position to shift forward in order to
reduce the disturbance (to eliminate the additional
concentration of reactant/s)

more products will be formed until the equilibrium is

reached again (i.e: composition of equilibrium
reaches Kc value which remains the same at a
fixed temperature).
Example ;

N2 (g) + 3H2 (g) 2NH3 (g)

Change Equilibrium Shift

Increase concentration of product(s) To the left

Decrease concentration of product(s) To the right
Increase concentration of reactant(s) To the right
Decrease concentration of reactant(s) To the left
 Example :

Consider the reaction below:

Fe 3+(aq) + SCN-(aq) Fe(SCN)2+(aq)
(Yellowish) (Blood red)

Discuss the effect of adding the following

substances to the equilibrium mixture.
a) Iron (III) or Fe+3
b) Sodium hydroxide, NaOH
Answer;
Consider the reaction below:
Fe 3+(aq) + SCN-(aq) Fe(SCN)2+(aq)
(Yellowish) (Blood red)

a) When Fe3+ is added to the equilibrium,

the concentration of Fe3+ in the system
increases.
the position of equilibrium shifts to right in
order to eliminate the effect of the increasing
Fe3+ ions.
more products will be formed and the
solution turns blood red.
 b) When NaOH is added to the system:

Consider the reaction below:

Fe 3+(aq) + SCN-(aq) Fe(SCN)2+(aq)
(Yellowish) (Blood red)

It reacts with Fe3+ to form Fe(OH)3; thus the

concentration of Fe3+ decreases.
In order to achieve equilibrium, the position of
equilibrium moves to the left to replace the Fe 3+
that has reacted.
More Fe3+ ions will be formed and the solution
becomes yellowish brown.
 B) Effect of Temperature:

The effect of temperature on an equilibrium

depends on the type of reactions, whether it
is:
i) an endothermic reaction
or
ii) an exothermic reaction

Temperature is the only factor that affects the

value of Kc
i) Endothermic reaction
An endothermic reaction is a reaction that
absorbs heat to form products.

Example:
Consider the following system:
N2O4(g) 2NO2(g) H = +57 kJ

+ sign indicates that for the forward reaction

absorbs heat
If forward reaction absorbs heat, then the
reverse reaction releases heat.
 N2O4(g) 2NO2(g) H = +57 kJ

Increasing the temperature:

Means that heat is added to the system
Reaction will move forward (forward reaction
absorbs heat) so as to reduce the added heat.
More NO2 gas will be released.
Since the amount of product increases, value
of Kc increases
N2O4(g) 2NO2(g) H = +57 kJ

Lowering the temperature:

Heat is removed from the system
The position of equilibrium will move from
right to left to replace the heat lost. (since
reverse reaction is exothermic)
More N2O4 will be formed.
Since more product is formed, value of Kc
decreases 2
[ NO2 ] Concentration of
Kc
[ N 2O4 ] N2O4 increases, thus
Kc value decreases
 Example:
Consider the reaction:
Co(H2O)62+(aq)+ 4HCl(aq) CoCl42+(aq) + H2O H = +ve
pink blue
To overcome the
low temperature
reaction should
System at
release heat equilibrium

Disturbance:
High
Low temperature temperature
C) Effect of Pressure

The pressure of a system may be changed by:

i) changing the moles of reactant or product
ii) changing the volume
iii) adding inert gas to the system

Affects only the reversible reaction involving

gaseous reactants/products
i) Changing moles of reactant or product
Adding or removing the gaseous reactant or
product at constant volume has the same effect as
changing the concentration

Example:
Consider the following system at equlibrium
2SO2(g) + O2(g) 2SO3(g)
When SO2 gas is added to the system, the partial
pressure of SO2 increases (which means [SO2]
increases)
Equilibrium shifts to the right to reduce the effect
of high concentration of SO2.
ii. Changing the volume of the container:

Decreasing the volume:

Causes the pressure of the system to
increase
The position of equilibrium will shift in a
direction that will lower down the pressure
The pressure can be brought down by having
reaction that produces less number of
molecules
Example
N2(g) + 3H2(g) 2NH3(g)

Consider the above system at equilibrium:

When the Vol. of the container decreases, the P
of the system increases.
position of equilibrium will shift in the direction
that brings the pressure down by reducing the
number of moles present in the system
The equilibrium shifts to the right to produce less
number of moles of gases in the system
More ammonia is formed
Value of Kc remains the same
ii. Changing the volume of the container

Increasing the volume:

Causes the pressure in the system to
decrease
The equilibrium position will shift in the
direction that will raise the pressure up.
It moves to the direction that produces more
number of molecules (higher number of
moles)
Example

Consider the reaction:

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

when the volume of the container increases,

the pressure of the system decreases
Equilibrium position will shift to the direction
that produces more moles
The equilibrium shifts to the left.
iii) Changing pressure by adding inert gas

a) Adding inert gas at constant volume:

Adding inert gas causes the total pressure in

the container to increase.
However the partial pressure of each gas
reacting in the reversible reaction remains
the same.
Since the partial pressure of the gases
remain the same & Kp is constant at constant
temperature, the equilibrium position does not
change.
b) Adding inert gas at constant pressure:

Adding inert gas to the system increases the

total pressure.
In order to keep pressure constant, the
volume of the container has to expand.
This causes the partial pressures of the
gases to drop.
System will move in the direction that
produces higher number of moles
 Example:

For the following chemical equation,

N2 (g) + O2 (g) 2NO (g)
The value of Kc for the reaction is 1x103 at high
temperature and 4.8x1031 at 25C. Is the forward
reaction exothermic or endothermic?

Kc = [NO]2 T Kc [NO]

[N2] [O2] Equilibrium position

shifts from LEFT to the RIGHT

Forward reaction is ENDOTHERMIC.

 D) The effect of Catalyst

Catalysts are substances that increase the rate

of a chemical reaction but are not used up in
the reaction.

The rate of forward reaction and reverse

reaction increase.

A catalysts allows a system to reach equilibrium

faster but does not shift the position of an
equilibrium system.
 Le Chteliers Principle
Change Equilibrium
Change Equilibrium shift Constant, K
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
Example :

Consider the chemical reaction at equilibrium given below

CaCO3 (s) CaO (s) + CO2 (g) H =+ve

(a) Calculate the values of Kp and Kc for the system

at 525oC, with the equilibrium pressure of CO2 is
0.220 atm.
(b) Predict the equilibrium position when the following
changes are made to the system
(i) some of the CaO is removed from the system
(ii) the pressure of the system is increased
(iii) the temperature of the system is raised
(iv) Helium gas is added at constant volume
(v) Helium gas is added at constant pressure
Kp = PCO2 = 0.220 atm

Kp = Kc(RT)n n = 1 0 = 1

Kp= Kc(RT)

Kc = Kp
(RT)

= 0.220 atm
0.08206 atm L mol 1 K 1 x 798 K

= 3.36 x 103 M
(b)(i) Does not change
(the partial pressure of CO2 is not affected by
the removal of SOLID CaO from the system).
(ii) Shifts to the LEFT.
(P, ; to the side with less number of moles of gas).
(iii) Shifts to the RIGHT.
(Endothermic, T, shifts to the right to reduce heat).
(iv) Does not change
(Addition of inert gas at constant V does not change
the partial pressure of gas).
(v) Shifts to the RIGHT.
(Addition of inert gas at constant P, V increase,
therefore equilibrium position shifts to the side with
greater number of moles of gas).
 HABER PROCESS

A process that produces ammonia from

H2 and N2

The process is introduced by German

scientists Fritz Haber and Karl Bosch.
(sometimes called Haber-Bosch) in 1912.

Main objectives of the industry are to obtain a

high yield of the product while keeping the cost
down
Consider
N2(g) + 3H(g) 2NH3(g) H = -92.6 kJ
A higher yield of NH3 can be obtained by carrying out
reaction under high pressures and at the lowest
temperature possible.
However the rate of production is low at a lower
temperature. Commercially, faster production is
preferable.
So combination of high-pressure, high temperature and
proper catalyst is the most efficient way to produce
ammonia on a large scale.

Temperature used = 500oC

Pressure = 500 1000 atm
Catalyst = Osmium and Ruthenium