CHAPTER 2:

CHEMICAL EQUILIBRIUM

1
 Learning Outcomes
(i) Deduce expressions for equilibrium constants in terms of
concentrations, Kc and partial pressures, Kp and their relationship.
(ii) Deduce the effect of changing concentration, direction, multiplying
the coefficients by a factor and adding chemical equations on K.
(iii) Calculate the quantities present at equilibrium from given
appropriate data.
(iv) Calculate the value of the equilibrium constants in terms of
concentrations or partial pressures from appropriate data.
(v) Calculate the reaction quotient, Q and predict the direction of
reaction.
(vi) State Le Chatelier’s principle and use it qualitatively from given
information.
(vii) Discuss the effect of changes in concentration, pressure,
temperature or catalysts on a system at equilibrium, using Le
Chatelier’s principle.

2
 Topics
1. Basic Concepts
2. The Equilibrium Constant
3. Variation of Kc with the Form of the Balanced
Equation
4. Equilibrium constant Kp, and Partial pressure
5. Relationship between Kp and Kc
6. Heterogeneous Equilibria
7. The Reaction Quotient
8. Disturbing a System at Equilibrium: Predictions
9. Disturbing a System at Equilibrium: Calculations

3
 Concept Maps
Chemical Reaction

Reversible Reaction Non-reversible Reaction

Dynamic Equilibrium

Equilibrium Constant, Kc

Expression/Formula
Calculation
Variation of Kc from balanced equation

Equilibrium Constant, Kp

Relationship Kc and Kp
Heterogeneous Equilibria

Reaction Quotient

Disturbing a System at Equilibrium

Haber Process –Commercial

Prediction Calculation
Application of Equilibrium

Changing Concentrations of Reactants and Products

Changing Pressure or Volume

Changing Temperature

Adding Catalyst

4
 Basic Concepts

Reversible reaction and dynamic equilibrium:

A chemical reactions may occur in a
- non-reversible or in
- reversible manner
Reaction of solution of:
NaCl(aq) + AgNO3(aq)  AgCl(s) + NaNO3(aq)
• non-reversible reaction
• single arrow () indicates the reaction occur in one
direction towards the products.
• when a stoichiometric amount of reactants were mixed,
all reactants will be converted to products.

5
 Basic Concepts
Reversible reaction and dynamic equilibrium:
Reaction between gas:
H2(g) + I2(g) ⇌ 2HI(g)
•reversible reaction:
•double arrow (⇌) indicates that the reaction occur in two directions,
forward (⇀) and reverse (↽).
•when the product HI(g) started to form, some of it will dissociated
back to H2(g) and I2(g) in the reverse reaction.
•as the reaction proceeds, the rate of forward reaction decreases
while the rate of reverse reaction increases.
•when the rate of forward reaction is equal to the rate of reverse
reaction, the reaction is said to be in equilibrium.
•at equilibrium the forward and reverse reactions still continue at the
same rate and the concentrations of the product and the reactant
remain constant. This is call dynamic equilibrium.
•at equilibrium the HI(g) produced is less than the stoichiometric
amount and the reactants H2 and I2 gaseous still exist in the reaction
mixture.
6
 Basic Concepts
• A reversible reactions do not go to completion.
– They can occur in either direction
– In general, this can be represented as:
cC +d D
a Ag  + b Bg   g  g 
• Chemical equilibrium exists when two opposing
reactions occur simultaneously at the same rate.
– A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.
• Chemical equilibria are dynamic equilibria.
– Molecules are continually reacting, even though
the overall composition of the reaction mixture
does not change.
7
 Basic Concepts

• Graphically, this is a representation of the rates for

the forward and reverse reactions for this general
reaction.
cC +dD
a Ag  + b Bg   g  g 

8
 The Equilibrium Constant

For a simple one-step mechanism reversible

reaction such as:
c C  d D
a A(g)  b B(g)  (g) (g)
Where a, b, c, d are the stoichiometric
coefficients
The rates of the forward and reverse reactions
can be represented as:
Ratef  k f A  B which represents the forward rate.
a b

 c
 
Rater  k r C D which represents the reverse rate.
d

kf and kf are rate constants

9
 The Equilibrium Constant
When system is at equilibrium: Ratef = Rater
Substitute for the rate relationsh ip to give :
k f A  B  k r C D
a b c d

which rearranges to
k f C D
c d

k r A a Bb

Because the ratio of two constants is a constant

we can define a new constant as follows :
k
 K  equilibrium constant
f
c
k r

K 
C D
c d

c
A  B
a b

10
 The Equilibrium Constant, Kc

• The equilibrium constant Kc is defined as

the ratio of multiplied equilibrium concentrations
of products (in M) to the multiplied equilibrium
concentrations (in M) of reactants (each raised
to the power of the respective stoichiometric
coefficient in balanced equation) at constant
temperature

• The value of Kc is constant at a given temperature.

• Kc changes if the temperature changes
• does not depend on the initial concentrations of
reactants
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 Unit of Equilibrium Constant, Kc

• In thermodynamic, definition of equilibrium constant

involves activity rather than concentration. The
activity of a component in a mixture is ratio of its
concentration or partial pressure to a standard
concentration (1.0 M) or pressure (1 atm). So that
activity of each reactant and product is
dimensionless.
• The equilibrium constant is there for has no unit or
dimensionless.

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 Significant of Equilibrium Constant, Kc

Kc >> 1
Large equilibrium constants indicate that most of the
reactants are converted to products. The concentration
of the products are higher than the reactants. The
reaction is called product-favoured.
Kc << 1
Small equilibrium constants indicate that only small
amounts of products are formed. The reaction is called
reactant-favoured.
Kc  1
The forward reaction proceeds about halfway; neither
direction is favoured.
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 The Equilibrium Constant, Kc

Example 2.1: Write equilibrium expression for reactions:

a) H2(g) + I2(g) ⇌ 2HI(g)
b) 2SO2(g) + O2(g) ⇌ 2SO3 (g)
c) Fe3+(aq) + 6CN(aq} ⇌ Fe(CN)63-(aq)
d) Au3+(aq) + 4Cl-(aq) ⇌ AuCl4-(aq)

a) 2 [SO 3 ]2
Kc 
[HI] b) Kc 
[H 2 ][I 2 ] [SO 2 ]2 [O 2 ]

d)
c)

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 The Equilibrium Constant, Kc
Exercise 2.1:
Write the equilibrium constant, Kc for the following reactions:
N O
a) PCl5 (g) PCl3 (g) + Cl2 (g) b) 2 NO 2g   2 4 g 

 
   Kc =
Kc   2
 
c)  4 HCl + O
2 Cl 2g  + 2 H 2 O g  g  2 g 

Kc 
 4  
 2  2
d) Ni2+(aq) + 6NH3(aq) ⇌ Ni(NH3)62+(aq)

e) Sn2+(aq) + 2Fe3+(aq) ⇌ Sn4+(aq) + 2Fe2+(aq)

15
 The Equilibrium Constant, Kc

• Example 2.2: One liter of equilibrium mixture from the

following system at a high temperature T1 was found
to contain 0.336 mole of phosphorus trichloride, 0.088
mole of chlorine, and 0.056 mole of phosphorus
pentachloride. Calculate Kc for the reaction.
PCl5 (g) PCl3 (g) + Cl2 (g)

Kc = 0.53

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 The Equilibrium Constant, Kc

• Example 2.3: The decomposition of PCl5 was studied

at another temperature T2. Amount of 0.60 mole of
PCl5 was introduced into an evacuated 1.00 liter
container. The system was allowed to reach
equilibrium at the new temperature. At equilibrium
0.40 mole of PCl3 was present in the container.
Calculate the equilibrium constant, Kc, at this
temperature.

PCl5 (g) PCl3 (g) + Cl2 (g)

We have to find equilibrium concentrations of reactant and other product using ICE
table

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 The Equilibrium Constant, Kc
Example 2.3 continue:
We have to find equilibrium concentrations of the product using ICE table
Only 1 M initial conc PCl5 and 0.40 M equilibrium conc PCl3 is known

Kc 
PCl3 Cl 2  K  (0.40)(0.4 0)  0.80 at T
PCl5  c
(0.20)
2

KcT2 > KcT1

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 The Equilibrium Constant, Kc

Example 5.4: Kc is 49 for the following reaction at

450 oC. If 2.0 mole of H2 and 2.0 mole of I2 are allowed to
reach equilibrium in a 6.0-liter vessel,
• Calculate the equilibrium concentrations of all
reactants and product.
• How many moles of I2 remain unreacted at
equilibrium?

H  I 2 g   2 H I
2 g  g 

Given Kc to calculate equilibrium concentrations

19
 The Equilibrium Constant, Kc
Example 2.4
cont…

[HI] 2 (2x) 2 2x
Kc   49   7.0 
[H2 ][I2 ] (0.33  x) 2
0.33  x

9x = 2.3; x = 0.259 M

[H2] = [I2] = (0.33-x) M= 0.071 M

[HI] = 2x = 0.52 M
Number of moles I2 = 0.071 mol/L  6 L = 0.426 mol

20
 The Equilibrium Constant, Kc

• Example 2.5: The equilibrium constant, Kc, is 3.00 for

the following reaction at a given temperature. If 2.00
mole of SO2 and 2.00 mole of NO2 are put into an
evacuated 4.00 L container and allowed to reach
equilibrium, what will be the concentration of each
compound at equilibrium?

SO2 (g)+ NO2 (g) ⇌ SO3 (g) + NO (g)

21
 The Equilibrium Constant, Kc
SO 2(g)  
NO 2(g)  SO 3(g)  NO (g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500  x M 0.500  x M xM xM

Kc 
SO 3 NO
 3.00 
 x  x 
SO 2 NO 2  0.500  x 0.500  x 
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500  x
0.865 - 1.73 x  x; 0.865  2.73 x; x  0.865
2.73
x  0.316 M  SO 3   NO
0.500  x M  0.184 M  SO 2   NO 2 
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 The Equilibrium Constant, Kc

• One of the fundamental ideas of chemical

equilibrium is that equilibrium can be established
from either the forward or reverse direction.
• Consider the reversible reaction of sulphur dioxide
with oxygen to form sulphur trioxide at 1000 K

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

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The equilibrium for the reaction can be established
either by the reaction of
(a)sulphur dioxide and oxygen to form sulphur
trioxide, the forward reaction (Figure 2.2a) or
(b)dissociation of sulphur trioxide to form sulphur
dioxide and oxygen, the reverse reaction (Figure
2.2b).
Table 2.1 summarized the example experimental
results of initial and equilibrium concentrations of the
two reactions.

24
The Equilibrium Constant, Kc

25
The Equilibrium Constant, Kc

26
 The Equilibrium Constant, Kc

Table 2.1 An experimental results of initial and equilibrium

concentrations for reaction of (a) SO2 with O2 and
(b) the dissociation of SO3

Experiment (a) Experiment (b)

[SO2] [O2] [SO3] [SO2] [O2] [SO3]
Initial
0.800 0.400 0 0 0 0.800
concentrations
Equilibrium
concentration 0.688 0.316 0.122 0.590 0.441 0.113
(M)

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 The Equilibrium Constant, Kc

Exercise 2.2: Use data in Table 2.1, calculate

the equilibrium constant for reactions
(a) 2SO2(g) + O2(g) ⇌ 2SO3 (g) and
(b) 2SO3 (g) ⇌ 2SO2(g) + O2(g)

Experiment (a) Experiment (b)

[SO2] [O2] [SO3] [SO2] [O2] [SO3]
Initial
0.800 0.400 0 0 0 0.800
concentrations
Equilibrium
concentration 0.688 0.316 0.112 0.590 0.441 0.113
(M)

Answer a) Kc = 0.084
b) Kc = 12.022
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 The Equilibrium Constant, Kc

Exercise 2.3:
At a given temperature 0.400 mole of N2 and
0.450 mole of H2 were placed in an evacuated
1.00 L container. At equilibrium 0.065 mole of
NH3 was present. Calculate Kc for the reaction.
Determine whether the reaction is product
favored or reactant favored.

Answer: Kc = 0.262

29
 Variation of Kc with the
Form of the Balanced Equation
Equilibrium constant for a new reaction can be derived from previous
reaction of a known equilibrium constant
Consider a general reaction:
aA(g) + bB(g) ⇌ cC(g) + dD(g)………K1
c d
[C] [D]
K 
1 a b
[A] [B]
(1) When the reaction equation is multiplied by a factor:
for example by a factor of 2 and become

2aA(g) + 2bB(g) ⇌ 2cC(g) + 2dD(g)………K2

the new equilibrium constant, K2 for this reaction:

30
 2
2c
 [C] [D] 
2d c d
K2 
[C] [D]
2a 2b
  a b  K1 2

[A] [B]  [A] [B] 

K2 increased by factor power of two of the
previous reactions; K2 = (K1)2

Similarly when the reaction multiplied by a factor of less than 1, for

example by a half and become:
 ½ (aA(g) + bB(g) ⇌ cC(g) + dD(g) )

c d 1
[C]2 [D]2  [C] [D]
c d
2
1
K3  a b
  a b   (K1) 2
[A] 2 [B] 2 
[A] [B] 

the new equilibrium constant for the reaction, K3 = (K1) ½.

31
(2) When the reaction is reversed,
the reaction become

cC(g) + dD(g) ⇌ aA(g) + bB(g) ………K4

[A] a [B]b 1 1
K4  c d
  (K 1 )
[C] [D] K 1

32
(3) When an overall reaction can be expressed as the sum of two or
more individual reactions:

the equilibrium constant for the overall reaction is given by the

multiplication of the equilibrium constants of the individual reactions.

For example, reaction (6) below is obtained by addition of reaction (1)

and reaction (5). The equilibrium constant for reaction (6), K6 = K1K5

Reaction 1: aA + bB ⇌ cC + dD………K1
Reaction 5: cC + dD ⇌ eE + fF……….K5
Reaction 6: aA + bB ⇌ eE + fF… …..K6

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 [C]c [D]d [E]e [F]f [E]e [F]f
K1  K5  K6 
[A] a [B]b [C]c [D]d [A] a [B]b

[C]c [D]d [E]e [F]f [E]e [F]f

K1  K 5     K6
[A] a [B]b [C]c [D]d [A] a [B]b

K6 = K1K5

34
 Variation of Kc with the
Form of the Balanced Equation
Example 2.6: Determine the equilibrium constant for
reaction

N2 (g) + 1/2O2 (g) N2O (g)

N2 (g) + O2 (g) 2NO (g) K1= 8.2 x 10-31
2NO (g) N2O (g) + 1/2O2 (g) K2 = 1.2 x 1013

N2 (g) + 1/2O2 (g) N2O (g) K3 = ?

K3 = K1 x K2
= (8.2 x 10-31) (1.2 x 1013)
= 9.7 x 10-18

35
 Variation of Kc with the
Form of the Balanced Equation
Exercise 2.4: Use the equilibrium constants for the following
reactions
2NO(g) N2(g) + O2(g) K1 = 4.8 x 1030
2NO(g) + O2(g) 2NO2(g) K2 = 4.8 x 1012
to determine the equilibrium constant for the reaction below:
N2 (g) + 2O2(g) 2NO2(g) K3

First determine the relationship between the equation with the two
equations with given Kc values

Answer K3 = 1x10-18

36
 Equilibrium Constant, Kp and Partial Pressure
For gas phase reactions the equilibrium constants can be expressed
in partial pressures, Kp rather than concentrations, Kc. For general
reaction:
aA(g) + bB(g) ⇌ cC(g) + dD(g)
c d
(P ) (P )
K 
P
C
whereP is partialpressure
a
D
b
(P ) (P )
A B

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

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

37
 Equilibrium Constant, Kp and Partial Pressure

Example 2.7: At equilibrium in the following reaction at

room temperature, the partial pressures of the gases
are found to be nitrogen = 0.188 atm, hydrogen = 0.078
atm, and ammonia = 0.012 atm. What is the Kp for the
reaction?
N2(g) + 3H2(g) 2NH3 (g)
2
PNH3 (g)
Kp =
PN2 (g) × PH32 (g)
(0.012)2
Kp = 3 = 1.61
(0.188)(0.078)

38
 Equilibrium Constant, Kp and Partial Pressures

• Example 2.8: Nitrosyl bromide, NOBr, is 48%

dissociated by the following reaction at 25 oC, in a
vessel in which the total pressure is 0.06 atmosphere.
What is the value of Kp?

2NOBr ⇌2NO + Br2

Construct ICE table

39
Equilibrium Constant, Kp and Partial Pressures
Let initial pressure for NOBr is x atm
2NOBr (g) ⇌ 2NO (g) + Br2 (g)
Initial (atm) x 0 0
Change (atm) ˗0.48x 0.48x 0.24x
Equilibrium (atm) x-0.48 0.48x 0.24x
PTot = PNOBr +PNO + PBr2
0.06 =(x - 0.48x) + 0.48x + 0.24x
x = 0.048 atm.
PNOBr = (x-0.48x) = 0.52x = 0.520.048 = 0.025 atm
PNO = 0.48x =0.023atm
PBr2 = 0.24x = 0.012 atm

(PNO )2 (PBr2 ) (0.023) 2 (0.012) -3

Kp = = = 9.9 × 10
(PNOBr )2 (0.025) 2
40
 Equilibrium Constant, Kp and Partial Pressures

Exercise 2.5
Bromine gas reacts with chlorine gas at 400oC to form
bromine monochloride.

Br2(g) + Cl2(g) ⇌ 2BrCl(g)

The initial pressure of Br2 and Cl2 is 0.17 atm and 0.255
atm, respectively. Calculate Kp for the reaction if the partial
pressure of BrCl is 0.230 atm at equilibrium.

Answer Kp = 6.87
41
 Relationship Between Kp and Kc
Consider this system at equilibrium at T K.
aA(g) + bB(g) ⇌ cC(g) + dD(g)

[C]c [D]d (PC )c (PD )d

Kc  Kp 
[A] a [B]b (PA )a (PB )b

For gases partial pressure is proportional to the concentration. Assume as

ideal gas: PV = nRT

where P is pressure, V is volume, n number of mole, T is temperature in

Kelvin and R is the gas constant = 0.0821 L atm.mol-1 K-1.
n
P RT or
V
n
P  MRT where M   concentrat ion of the gas in molar
V
P
and M 
RT
42
 [C]c [D]d
Kc 
[A]a [B] b

c d
PC PD c d 1 (c+d) (c+d)-(a+b)
RT RT (PC ) (PD ) ( ) 1
Kc = = × RT =K =Kp RT -((c+d)-(a+b))
a b p
PA PB (PA ) a (PB ) b 1 (a+b) RT
( )
RT RT RT

Let the difference between the total number of mole products and total
number of mole of reactants, (c+d)-(a+b)=n

Kc = Kp (RT)-n or Kp = Kc (RT)n

43
 Heterogeneous Equilibria
• Heterogeneous equilibria have more than one phase
present.
• For example, reaction of iron with steam at 500 C to produce
hydrogen gas and iron oxide Fe3O4(s) involve two phases, gas
and solid.
3Fe (s) + 4H2O (g) ⇌ Fe3O4 (s) + 4H2 (g) (at 500 C)
– Pure solids and liquids have activities of unity.
– Solvents in very dilute solutions have activities that are essentially unity.
– The Kc and Kp for the reaction shown above are:

Since [Fe3O4(s)]=1 and [Fe(s)]=1

44
Similarly

Since

45
 Heterogeneous Equilibria
Example 2.9
What are Kc and Kp for this reaction?
(a) CaCO3(s) ⇌ CaO(s) + CO2(g) (at 500 C)

Since [CaCO3(s)], (PCaCO3 (s) ) [CaO(s)] (PCaO(s) ) are unity

Kc = [CO2] and K p  PCO2

(b) SO2(aq) + H2O(l) ⇌ H2SO3(aq)

Since the H2O is liquid solvent the activity is unity
[H2SO3 ]
Kc 
[SO2 ]
and since there is no gas phase involve in the reaction, the Kp
value is undefined.

46
 Heterogeneous Equilibria

• What are Kc and Kp for this reaction?

( c ) C a F 2 s   C a 2   2 F 1 - o
(at 2 5 C )
aq  aq 
Kc = Ca  2
F 
 2
K p is undefined

47
 Heterogeneous Equilibria
Exercise 2.6
Consider the following reactions and for each determine
whether Kc equals Kp. Explain.
a. Sn(s) + 2H2O (g) ⇌ SnO2(s) +2H2(g)
b. 2C2H6(g) + 7O2(g) ⇌ 4CO2(g) + 6H2O(g)
c. NH4Cl(s) ⇌ NH3(g) + HCl (g)
d. CaCO3(s) ⇌ CaO(s) + CO2(g)

48
 The Reaction Quotient

• The mass action expression or reaction quotient has

the symbol Q. Q has the same form as KC

• The major difference between Q and KC is that the

concentrations used in Q are not necessarily
equilibrium values.

For this general reaction :

aA + bB  cC + dD

Q
C D
c d

Aa Bb
49
 The Reaction Quotient
• Why do we need the reaction quotient that does not use
equilibrium concentrations?
• Q will help us predict how the equilibrium will respond
to the reaction,
- when certain concentrations of reactants and
products are mixed at initial stage,
- and when stress (changes in concentration) is applied.
• To make this prediction we compare Q with Kc.
When :
Q = Kc The system is at equilibriu m.
Q  K c The reaction occurs to the left to a greater extent.
Q  K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.
50
 The Reaction Quotient
Example 2.10:
The equilibrium constant for the following reaction is 49 at 450 oC. If
0.22 mole of I2, 0.22 mole of H2, and 0.66 mole of HI were put into an
evacuated 1.00-liter container, would the system be at equilibrium? If
not, what must occur to establish equilibrium?
First, calculate Q to see whether the conditions already at equilibrium or not.

Q = 9.00 < Kc = 49

Since Q < Kc the reaction will shift to the right to

establish the equilibrium.

51
 Disturbing a System at Equilibrium: Predictions

• Le Chatelier’s Principle - If a change of conditions

(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to reduce
the stress in reaching a new state of equilibrium.

• Some possible stresses to a system at equilibrium

are:
a. Changes in concentration of reactants or products.
b. Changes in pressure or volume (for gaseous
reactions)
c. Changes in temperature.
d. Introduction of catalyst
52
 Disturbing a System at Equilibrium: Predictions

a. Changes in Concentration of Reactants and/or Products

• Also true for changes in pressure for reactions involving gases.
– Look at the following system at equilibrium at 450 oC.
 2 HI
H 2  I2  g 

Kc 
HI 
2
 49
H 2 I 2 
If we remove some H 2 , Q > K c
This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side.

53
 Disturbing a System at Equilibrium: Predictions

b. Changes in Volume
• (and pressure for reactions involving gases)
– Predict what will happen if the volume of this system at
equilibrium is changed by changing the pressure at constant
temperature:
2 NO  N O
2 g  2 4 g 

Kc =
N 2O 4 
NO2 2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.
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Disturbing a System at Equilibrium: Predictions

N O
2 NO2g   2 4 g 

Kc =
N 2O 4 
NO2 2
If the volume is increased, which decreases the pressure, Q > K c .
This favors the reactants or the reverse reaction.
More moles of gas are produced.

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Disturbing a System at Equilibrium: Predictions

c. Changing the Reaction Temperature

Consider the following reaction at equilibrium:
2SO2 (g) + O2 (g) ⇌ 2SO3 (g) Hrxn = - 198 kJ

This reaction produces heat:

By decreasing the reaction temperature, the reaction will response in
producing more heat, this favours the forward reaction or product
favoured

By Increasing temperature, reactions will response in producing less heat,

this favours the reverse reaction or reactant favoured.

56
 Disturbing a System at Equilibrium: Predictions
d. Introduction of a Catalyst
– Catalysts decrease the activation energy of both the
forward and reverse reaction equally.

This is only helps the

reaction reaches equilibrium
faster but does not change
the equilibrium position or
equilibrium concentration.

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 Disturbing a System at Equilibrium: Predictions

Example 2.11: The reaction below is at equilibrium in a closed

container at 500 C and 200 atm. The following changes could shift the
reaction to a new equilibrium. Predict and explain the effect of each of
the changes on the amount of NH3 produced: (a) increasing the
temperature (b) lowering the temperature (c) increasing pressure by
decreasing volume (d) increasing concentration of H2 (e) decreasing
concentration of NH3–removing some product from reaction vessel (f)
introducing platinum catalyst.

N 2(g)  3 H 2(g) 
2 NH3(g) H orxn  92 kJ/mol

58
Disturbing a System at Equilibrium: Predictions

N 2(g)  3 H 2(g) 
2 NH3(g) H orxn  92 kJ/mol

59
 Disturbing a System at Equilibrium: Predictions
Haber – Bosch process
At 200oC and pressures above
1000 atm there is an almost
100% conversion of reactants
to the ammonia product.
•However in actual industrial
process it chooses a higher
temperature (500 C) and a
lower pressure (200 atm)
where only about 30 %
conversion is achieved. Why?
How the conditions are chosen
to increase the product?

60
Disturbing a System at Equilibrium: Predictions

Production of Ammonia: Haber Process

61
 Disturbing a System at Equilibrium: Predictions
(1) Temperature: The data in Figure 2.6 shows that the reaction is
exothermic; at lower temperature the reaction shifts to the right and
more NH3 will be produced. However at low temperature, the kinetic
of the reaction is too slow where the reaction takes too long time to
occur, so a higher temperature is used to increase the kinetic so that
the product is form in a reasonable time.
(2) Pressure: There are 4 moles of reactants on the left of the
reaction equation and only 2 moles of product on the right. So
increased the pressure favours the reaction that produces smaller
moles of products; more ammonia will be produced. However due to
safety of equipment a lower pressure was chosen instead.
(3) Catalyst: A cheap catalyst iron oxide was added to the process; a
catalyst lowers the activation energy and this speeds up both forward
and reverse reaction. This allows the NH3 to be produced faster and
in a lower temperature; this extends the life of equipment.
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Disturbing a System at Equilibrium: Predictions

(4) Removing the Product: The reaction mixture is cooled

down to form liquid ammonia and removed. This prevents the
reaction reaching equilibrium and favours forward reaction.
(5) Addition of more reactant (stress): Excess N2 is added to
favor reaction to the right to increase the product.
Choice of conditions in Haber process:
By using a pressure of around 200 atm a temperature of about
500oC and addition of iron oxide catalyst the yield of ammonia
can be increased by separation of product and increased
amount of the reactant (NH3), while costs and safety
concerns in the building and during operation of the plant are
minimized.

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 Disturbing a System at Equilibrium: Predictions

Example 2.12: How will an increase in pressure

(caused by decreasing the volume) affect the
equilibrium in each of the following reactions?

Reaction Effect on Equilibriu m

a. H 2g  + I 2g  
 2 HI g  no effect
b. 4 NH + 5 O  4 NO
3 g  2(g) g  + 6 H 2 O g  reverse - more reactants are formed
c. PCl 3g  + Cl 2g  
 PCl 5g  forward - more product is formed
d. 2 H  O 2 H O foorward - more product is formed
2 g  2 g  2 g 

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 Disturbing a System at Equlibrium: Predictions

Example 2.13: How will an increase in temperature

affect each of the following reactions?

Reaction Effect on Equilibrium

(a) 2NO2(g) ⇌ N2O4 Hrxn < 0 Reverse- produce more reactant
(b) H2(g) + Cl2(g) ⇌ 2HCl(g) + 92 kJ Reverse- produce more reactant
(c) H2(g) + I2(g) ⇌ 2HI(g) Hrxn = +25 kJ Forward- produce more product

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Disturbing a System at Equilibrium: Calculations
Example 2.14: An equilibrium mixture from the following
reaction was found to contain 0.80 mol/L of A, 0.60 mol/L of B,
and 0.60 mol/L of C. (a) What is the value of Kc for this reaction?

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Disturbing a System at Equilibrium: Calculations

(b) If the volume of the reaction vessel were

suddenly doubled while the temperature remained
constant, what would be the new equilibrium
concentrations?
1 Calculate Q, after the volume has been doubled

A(g) ⇌ B(g) + C(g)

Equilibrium [ ]’s 0.04 M 0.30 M 0.30 M

Since Q < Kc the reaction will shift to the right to re-establish the equilibrium

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 Disturbing a System at Equilibrium: Calculations
• Use algebra and ICE table to represent the new equilibrium
concentrations
A(g) ⇌ B(g) + C(g)
New initial [ ]’s 0.40 M 0.30 M 0.30M
Change -x M +x M +x M
_____________________________________________________________

New Equilibrium [ ]’s (0.40-x) M (0.30+x) M (0.30+x) M

x2 + 1.05x -0.09 = 0

X = 0.08 and -1.13

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Disturbing a System at Equilibrium: Calculations

The only possible value of x = 0.08 M.

[A] = (0.40 – x) M = 0.32 M

[B] = [C] = (0.30 + x) M = 0.38 M

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Disturbing a System at Equilibrium: Calculations

• (c) If the initial volume of the reaction vessel were

halved, while the temperature remains constant,
what will the new equilibrium concentrations be? Recall
that the original concentrations were: [A]=0.80 M,
[B]=0.60 M, and [C]=0.60 M.

When the volume was reduced by half the new concentration will
double:
A(g) ⇌ B(g) + C(g)
Instantaneous [ ]’s 1.60 M 1.20 M 1.20 M
Calculate Q to establish direction of reaction
[B][C] (1.2)(1.2) Q = 0.9 > Kc = 0.45 thus the equilibrium shifts
Q= = = 0.9
[A] (1.6) to the left or reactant side.

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Disturbing a System at Equilibrium: Calculations
Set up the algebraic expressions to determine the equilibrium concentration
using ICE table.
A(g) ⇌ B(g) + C(g)
New initial [M ] 1.60 1.20 1.20
Change [M] +x -x -x
New Equilibrium [M ] (1.60+x) (1.20-x) (1.20-x)

x2 – 2.85x + 0.72 = 0

of the limits are 0 < x < 1.60, so x= 0.28

[A] = (1.60 + x) M = 1.88 M

[B] = [C] = (1.20 – x) M = 0.92 M
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 Chemical Equilibrium

Good Luck &TQ

TUTORIAL ANSWER
1. K=1.83
2. (a) K=0.039 (b) K=25.45 ( c) K=0.339
3. [N2O4]=0.962 M, [NO2]=0.076 M
4. Kc=216 Kp=7.58
5. Kp=0.0308 Kc= 9.3610-6
6. Shift to the right; [I2] = 4.0010-2 [I] = 4.7310-7
7. -
8. -
9. -
10. (a) Kc= 20, (b) [CO]=0.223M; [Cl2]=0.623M; [COCl2] =2.777M

72