CHEMICAL EQUILIBRIUM

A chemical equilibrium can only occur in a closed system. A closed system is a system that
allows no loss or gain of matter/material to or from the surroundings but allows transfer of
energy across its boundary.

Very many chemical reactions are reversible and exist in a state of equilibrium between the
reactants and products.
A reversible chemical reaction is a reaction that proceeds in both the forward and reverse
directions depending on the reaction conditions. For example the equilibrium between dinitrogen
tetraoxide and nitrogen dioxide represented by the equation below:
N2O4(g) 2NO2(g)

Such a reversible reaction is said to be in dynamic equilibrium when the rates of the forward
and reverse reactions are equal. The position of equilibrium depends on three factors:
temperature, pressure and the concentration of reactants and products.

During a reversible reaction:

 The concentration of the reactants decreases while that of products increases with time.
 As the concentration of the reactants reduces the rate of the forward reaction reduces while
the rate of the reverse reaction increases as the concentration of products increases with time.

(a) Graph of concentration against time for a reversible reaction:

(b) Graph of rate against time for a reversible reaction

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Characteristics of a chemical system in equilibrium
1. The rates of the forward and reverse reactions are equal.
2. The concentration/amount of reactants and products remains unchanged.
3. No change in macroscopic properties such as colour, pH and density
4. The equilibrium can be achieved from either the forward or the reverse direction.
5. The equilibrium is dynamic in nature and not static. Both the forward and reverse reactions
continue to occur but no change in concentration occurs.
6. If temperature, pressure, or concentration of reactants or products is changed, the
equilibrium is affected, demonstrating its dynamic nature.

The Equilibrium Law

The exact position of at which equilibrium of a reversible reaction is achieved can be established
using the equilibrium law.
The equilibrium law states that “if a reversible reaction is allowed to reach equilibrium, the
product of the molar concentrations of the products (raised to the powers of their stoichiometric
co-efficients) divided by the product the molar concentrations of the reactants (raised to the
powers of their stoichiometric co-efficients) has a constant value at a constant temperature”
This constant value is called the equilibrium constant, Kc
Consider the following gaseous homogenous equilibrium:
aA(g) + bB(g) cC(g) + dD(g)
The expression for the equilibrium constant in terms of the equilibrium molar concentrations of
reactants and products is given by:
[𝐶]𝑐 [𝐷]𝑑
𝐾𝑐 =
[𝐴]𝑎 [𝐵]𝑏

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Where: KC = the equilibrium constant;
[A], [B], [C] and [D] are the equilibrium molar concentrations of A, B, C and D
respectively;
a,b,c and d are the stoichiometric coefficients of A, B, C and D respectively.

Units of Kc
The units of KC are (moldm-3)∆n;
Where ∆n = (sum of the stoichiometric coefficients of products) - (sum of the stoichiometric
coefficients of the reactants)

Consider the following equilibrium: 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)

[𝑵𝑯𝟑 ]𝟐
The Kc expression is given by: 𝑲𝒄 =
[𝑵𝟐 ][𝑯𝟐 ]𝟑

𝑎𝑛𝑑 𝑡ℎ𝑒 𝐾𝑐 𝑢𝑛𝑖𝑡𝑠 𝑎𝑟𝑒 (𝑚𝑜𝑙𝑑𝑚−3 )2−4 = (𝑚𝑜𝑙𝑑𝑚−3 )2−4 = (𝑚𝑜𝑙𝑑𝑚−3 )−2 = 𝒅𝒎𝟔 𝒎𝒐𝒍−𝟐

However if the sum of the stoichiometric co-efficients of the products and reactants is the same,
then the Kc value has no units. Stoichiometric co-efficient of
Consider the following equilibrium: 𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔) reactants and products are equal.
[𝑯𝑰]𝟐
The Kc expression is given by: 𝑲𝒄 =
[𝑯𝟐 ][𝑰𝟐 ]
−3 2−2
𝑎𝑛𝑑 𝑡ℎ𝑒 𝐾𝑐 𝑢𝑛𝑖𝑡𝑠 𝑎𝑟𝑒 (𝑚𝑜𝑙𝑑𝑚 ) = (𝑚𝑜𝑙𝑑𝑚−3 )0 = 1. 𝑺𝒐 𝒏𝒐 𝒖𝒏𝒊𝒕𝒔

Calculating KC for Homogeneous Systems

A homogeneous reaction is one in which all the reactants and products are in the same physical
state (state of matter).

For example:
 The esterification below is an example of a liquid homogeneous system
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯(𝒍) + 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯(𝒍) ⇌ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 (𝒍) + 𝑯𝟐 𝑶(𝒍)
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ][𝐻2 𝑂]
𝐾𝑐 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻]
 Decomposition of hydrogen iodide is a homogeneous gaseous system
[𝐻2 ][𝐼2 ]
2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔) 𝒂𝒏𝒅 𝐾𝑐 =
[𝐻𝐼]2
 Equilibrium between nitrogen monoxide, oxygen and nitrogen dioxide is a homogeneous systems
[𝑁𝑂2 ]2
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔) 𝒂𝒏𝒅 𝐾𝑐 =
[𝑁𝑂]2 [𝑂2 ]
 Equilibrium between phosphorous (V) chloride, phosphorous (III) chloride and chlorine is another
homogeneous gaseous system
[𝑃𝐶𝑙3 ][𝐶𝑙2 ]
𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔) 𝒂𝒏𝒅 𝐾𝑐 =
[𝑃𝐶𝑙5 ]

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Example 1
Nitrogen monoxide combines with oxygen according to the following equation:
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)
a) Write an expression for an equilibrium constant, KC
b) 3 moles of nitrogen monoxide and 1.5 moles of oxygen were kept in a 1 litre vessel which
was heated to 400oC. When equilibrium was established the vessel was found to contain 0.5
moles of oxygen. Calculate the value KC at this temperature
c) When the temperature was raised to 600oC the mixture in (b) was found to contain 25% of
the initial amount of nitrogen monoxide at equilibrium. Calculate the value of KC at this
temperature
d) From your results in (b) and (c) above deduce whether the reaction is endothermic or
exothermic

Solution
[𝑁𝑂 ]2
a) 𝐾𝑐 = [𝑁𝑂]22
[𝑂2 ]
b) Equation: 2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔) At equilibrium there are 0.5
𝐼𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦: 3𝑚𝑜𝑙 1.5𝑚𝑜𝑙 0 𝑚𝑜𝑙 moles of oxygen.
𝐶ℎ𝑎𝑛𝑔𝑒: − 2𝑥𝑚𝑜𝑙 − 𝑥𝑚𝑜𝑙 + 2𝑥 𝑚𝑜𝑙 (1.5 – 𝑥) = 0.5
𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚: (3 – 2𝑥) (1.5 − 𝑥) 2𝑥 𝑚𝑜𝑙 𝑥 = 1 𝑚𝑜𝑙𝑒.
= 1 𝑚𝑜𝑙 0.5 𝑚𝑜𝑙 2 𝑚𝑜𝑙
1
[𝑁𝑂] = 𝑚𝑜𝑙𝑑𝑚−3 = 1 𝑚𝑜𝑙𝑑𝑚−3
1
0.5
[𝑂2 ] = 𝑚𝑜𝑙𝑑𝑚−3 = 0.5 𝑚𝑜𝑙𝑑𝑚−3
1
2
[𝑁𝑂2 ] = 𝑚𝑜𝑙𝑑𝑚−3 = 2 𝑚𝑜𝑙𝑑𝑚−3
1
22
𝐾𝑐 = 2 = 𝟖 𝒅𝒎𝟑 𝒎𝒐𝒍−𝟏
1 × 0.5

c) Equilibrium: 2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)

𝐴𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑡ℎ𝑒𝑟𝑒 𝑎𝑟𝑒 25% 𝑜𝑓 3
𝐼𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦: 3𝑚𝑜𝑙 1.5𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑂 = 0.25 × 3
𝐶ℎ𝑎𝑛𝑔𝑒: − 2𝑥𝑚𝑜𝑙 − 𝑥𝑚𝑜𝑙 + 2𝑥 𝑚𝑜𝑙 = 0.75 𝑚𝑜𝑙
𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚: (3 – 2𝑥) (1.5 − 𝑥) 2𝑥 𝑚𝑜𝑙 (3 – 2 𝑥) = 0.75
= 0.75 mol 0.375 mol 2.25 mol 𝑥 = 1.125 𝑚𝑜𝑙
0.75
[𝑁𝑂] = 𝑚𝑜𝑙𝑑𝑚−3 = 0.75 𝑚𝑜𝑙𝑑𝑚−3
1
0.375
[𝑂2 ] = 𝑚𝑜𝑙𝑑𝑚−3 = 0.375 𝑚𝑜𝑙𝑑𝑚−3
1
2.25
[𝑁𝑂2 ] = 𝑚𝑜𝑙𝑑𝑚−3 = 2.25 𝑚𝑜𝑙𝑑𝑚−3
1

2.252
𝐾𝑐 = = 𝟐𝟒 𝒅𝒎𝟑 𝒎𝒐𝒍−𝟏
0.752 × 0.375

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 The reaction is endothermic since increase in temperature (from 400oc to 600oc) leads to an
increase in the value of KC (from 8 to 24)

Example 2
At 400oC hydrogen iodide has a degree of dissociation of 20%.

a) Calculate the KC for dissociation of hydrogen iodide at this temperature

b) What would be the equilibrium composition of the reaction mixture if 1 mole of hydrogen
and 1 mole of iodine vapour were reacted to equilibrium at 400oC

Solution
(a)𝐄𝐪𝐮𝐚𝐭𝐢𝐨𝐧: 2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔)
𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 1 𝑚𝑜𝑙 0 𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑪𝒉𝒂𝒏𝒈𝒆: − 0.2 𝑚𝑜𝑙 + 0.1 𝑚𝑜𝑙 + 0.1 𝑚𝑜𝑙
𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎: (1 − 0.2) 0.1 𝑚𝑜𝑙 0.1 𝑚𝑜𝑙
= 0.8 𝑚𝑜𝑙 0.1 𝑚𝑜𝑙 0.1 𝑚𝑜𝑙
0.8 0.1 0.1
[𝑯𝑰] = 𝑚𝑜𝑙𝑑𝑚−3 ; [𝑯𝟐 ] = 𝑚𝑜𝑙𝑑𝑚−3 ; [𝑰𝟐 ] = 𝑚𝑜𝑙𝑑𝑚−3
𝑣 𝑣 𝑣
0.1 0.1
[𝐻2 ][𝐼2 ] ( 𝑣 ) ( 𝑣 ) (0.1)(0.1)
𝐾𝑐 = = = = 𝟎. 𝟎𝟏𝟓𝟔𝟐𝟓
[𝐻𝐼]2 0.8 2 (0.8)2
(𝑣 )

(𝑏) 𝐿𝑒𝑡 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 𝑦 𝑚𝑜𝑙𝑒𝑠

Equation: 𝐻2 (𝑔) + 𝐼2 ⇌ 2𝐻𝐼(𝑔) 1
𝐼𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦: 1 𝑚𝑜𝑙 1 𝑚𝑜𝑙 0 𝑚𝑜𝑙 𝐾𝑐 = = 𝟔𝟒
𝐶ℎ𝑎𝑛𝑔𝑒: − 𝑦 𝑚𝑜𝑙 − 𝑦 𝑚𝑜𝑙 + 2𝑦 𝑚𝑜𝑙 0.015625

𝐸𝑞𝑚: (1 − 𝑦)𝑚𝑜𝑙 (1 − 𝑦)𝑚𝑜𝑙 2𝑦 𝑚𝑜𝑙

(2𝑦)2
𝐾𝑐 = = 64
(1 − 𝑦)(1 − 𝑦)
(2𝑦)2 2𝑦 8
√ 2
= √64; 𝒘𝒉𝒊𝒄𝒉 𝒈𝒊𝒗𝒆𝒔 = 8; 𝒂𝒏𝒅 𝑦 = = 𝟎. 𝟖
(1 − 𝑦) 1−𝑦 10
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐼 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = (2 × 0.8) = 𝟏. 𝟔 𝒎𝒐𝒍𝒆𝒔

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻2 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = (1 − 0.8) = 𝟎. 𝟐 𝒎𝒐𝒍𝒆𝒔

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐼2 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = (1 − 0.8) = 𝟎. 𝟐 𝒎𝒐𝒍𝒆𝒔

Example 3
1.00 moles of ethanoic acid and 1.00 moles of ethanol were mixed at 100oC in a 2 litre closed
vessel. When equilibrium was attained 0.33 moles of ethanol was found to be present. Calculate
the value of the equilibrium constant, KC at 100oC for the following equilibrium:

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𝑪𝑯𝟑 𝑪𝑶𝑶𝑯(𝒍) + 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯(𝒍) ⇌ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 (𝒍) + 𝑯𝟐 𝑶(𝒍)
Solution
Equation: 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯(𝒍) + 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯(𝒍) ⇌ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 (𝒍) + 𝑯𝟐 𝑶(𝒍)
𝐼𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦: 1.00 𝑚𝑜𝑙 1.00 𝑚𝑜𝑙 0 𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝐶ℎ𝑎𝑛𝑔𝑒: − 𝑥 𝑚𝑜𝑙 − 𝑥 𝑚𝑜𝑙 + 𝑥 𝑚𝑜𝑙 + 𝑥 𝑚𝑜𝑙
𝐸𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚: (1 − 𝑥) 𝑚𝑜𝑙 (1 − 𝑥) 𝑚𝑜𝑙 𝑥 𝑚𝑜𝑙 𝑥 𝑚𝑜𝑙
= 0.33 𝑚𝑜𝑙 0.33 𝑚𝑜𝑙 0.67 𝑚𝑜𝑙 0.67 𝑚𝑜𝑙
0.33
[𝐶𝐻3 𝐶𝑂𝑂𝐻] = [𝐶𝐻3 𝐶𝐻2 𝑂𝐻] = = 0.165 𝑚𝑜𝑙𝑑𝑚−3 (1 – 𝑥) = 0.33
2
0.67 𝑥 = 0.67 𝑚𝑜𝑙𝑒𝑠
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ] = [𝐻2 𝑂] = = 0.335 𝑚𝑜𝑙𝑑𝑚−3
2
[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ][𝐻2 𝑂] (0.335 )(0.335 )
𝐾𝑐 = = = 4.12
[𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻] (0.165)(0.165)

Example 4
Ethanol and ethanoic acid react according to the following equation:
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯(𝒍) + 𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯(𝒍) ⇌ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝑯𝟐 𝑪𝑯𝟑 (𝒍) + 𝑯𝟐 𝑶(𝒍)
3.0g of ethanoic acid and 2.3g of ethanol were allowed to reach equilibrium at 100oC for an hour
and then quickly cooled in an ice bath. 50cm3 of 1.0moldm-3 aqueous sodium hydroxide were
added. When the mixture was titrated with 0.5moldm-3 of hydrochloric acid 66.7cm3 of acid was
required for complete neutralization.
a) Why was the mixture cooled rapidly in an ice bath?
b) Calculate the number of moles of excess sodium hydroxide
c) The number of moles of ethanoic acid at equilibrium
d) Calculate the value of the equilibrium constant

Solution
a) The mixture was cooled rapidly in an ice bath in order to quench the reaction (bringing the
reaction to an immediate halt).
b) Sodium hydroxide reacted with hydrochloric acid at equilibrium according to the following
equation:
𝐻𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝑂𝐻(𝑎𝑞) ⟶ 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙)
0.5 × 66.7
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = ( ) = 0.03335
1000
∴ 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒆𝒙𝒄𝒆𝒔𝒔 𝑵𝒂𝑶𝑯 = 𝟎. 𝟎𝟑𝟑𝟑𝟓
1×50
c) 𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 = ( 1000 ) = 0.05
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑙) + 𝐻2 𝑂(𝑙)
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓𝑁𝑎𝑂𝐻 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
= (0.5 − 0.03335) = 0.01665 𝑚𝑜𝑙𝑒𝑠
∴ 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 𝟎. 𝟎𝟏𝟔𝟔𝟓 𝒎𝒐𝒍𝒆𝒔
d) 𝑅𝐹𝑀 𝑜𝑓 𝐶𝐻3 𝐶𝑂𝑂𝐻 = (12 × 2) + (4 × 1) + 60

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 𝑅𝐹𝑀 𝑜𝑓 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 = (12 × 2) + (5 × 1) + 16 = 46
3
𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝐻3 𝐶𝑂𝑂𝐻 = = 0.05
60
2.3
𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 = = 0.05
46
𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑙) + 𝐻2 𝑂(𝑙)
𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 0.05𝑚𝑜𝑙 0.05𝑚𝑜𝑙 0𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑪𝒉𝒂𝒏𝒈𝒆: − 𝑥 𝑚𝑜𝑙 − 𝑥 𝑚𝑜𝑙 + 𝑥 𝑚𝑜𝑙 + 𝑥 𝑚𝑜𝑙
𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎: (0.05 − 𝑥)𝑚𝑜𝑙 (0.05 − 𝑥)𝑚𝑜𝑙 𝑥𝑚𝑜𝑙 𝑥 𝑚𝑜𝑙
= 0.01665𝑚𝑜𝑙 0.01665𝑚𝑜𝑙 0.03335𝑚𝑜𝑙 0.03335𝑚𝑜𝑙
(0.05 − 𝑥) = 0.01665
𝑥 = 0.05 − 0.01665 = 𝟎. 𝟎𝟑𝟑𝟑𝟓

[𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 ][𝐻2 𝑂] (0.03335)(0.03335)

𝐾𝑐 = = = 4.01
[ 𝐶𝐻3 𝐶𝑂𝑂𝐻][𝐶𝐻3 𝐶𝐻2 𝑂𝐻] (0.01665)(0.01665)

Example 5
Hydrogen iodide decomposes according to the following equation:
2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔) ∆𝐻 = +11.3 𝑘𝐽𝑚𝑜𝑙 −1
a) Write an expression for KC of the reaction
b) 1.54g of hydrogen iodide was heated in a 600cm3 bulb at 530oC. When equilibrium was
established the bulb was rapidly cooled to room temperature and broken under potassium
iodide solution. The iodine formed from the decomposition required 67cm3 of 0.1M sodium
thiosulphate solution for complete reaction.
Calculate:
i) the number of moles of hydrogen iodide in 1.54g (H=1, I = 127)
ii) the number of moles of iodine formed when hydrogen iodide decomposed.
iii) the value of KC at 530oC
c) State what would be the effect on the value KC if;
i) the temperature was raised from 530oC to 800oC
ii) the volume the bulb was raised to 1200cm3

Solution
[𝐻2 ][𝐼2 ]
(a) 𝐾𝑐 =
[𝐻𝐼]2
(b) (i) 𝑀𝑟 𝑜𝑓 𝐻𝐼 = 1 + 127 = 128
1.54
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐼 =  𝟎. 𝟎𝟏𝟐𝟎𝟑𝟏𝟐𝟓
128
(ii) 𝐼2 (𝑎𝑞) + 2𝑆2 𝑂3 2− (𝑎𝑞) → 𝑆4 𝑂6 2− (𝑎𝑞) + 2𝐼 − (𝑎𝑞)
0.1 × 67
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆2 𝑂3 2− 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = ( ) = 0.0067
1000

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 1 1
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐼2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = ( × 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆2 𝑂3 2− ) = ( × 0.0067) = 0.00335
2 2
(iii) 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: 2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔)
𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 0.01203125 𝑚𝑜𝑙 0 𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑪𝒉𝒂𝒏𝒈𝒆: − 2𝑥 + 𝑥 𝑚𝑜𝑙 + 𝑥 𝑚𝑜𝑙
𝑬𝒒𝒎: (0.01203125 – 2𝑥)𝑚𝑜𝑙 𝑥 𝑚𝑜𝑙 𝑥 𝑚𝑜𝑙
= 0.00533125 𝑚𝑜𝑙 0.00335 𝑚𝑜𝑙 0.00335 𝑚𝑜𝑙
𝒙 = 𝟎. 𝟎𝟎𝟑𝟑𝟓 𝒎𝒐𝒍𝒆𝒔

0.00533125
[𝐻𝐼] = ( ) = 8.885 × 10−3 𝑚𝑜𝑙𝑑𝑚−3
0.6
0.00335
[𝐻2 ] = [𝐼2 ] = ( ) = 5.5833 × 10−3 𝑚𝑜𝑙𝑑𝑚−3
0.6
(5.5833 × 10−3 )(5.5833 × 10−3 )
𝐾𝑐 = = 𝟎. 𝟑𝟗𝟔
(8.885 × 10−3 )
(c) i) The value of KC would increase. Since the forward reaction is endothermic, increase in
temperature would shift equilibrium from the left to the right forming more products and
less of reactants. Consequently the value of KC would increase.
ii) The value of KC remain constant; change in volume has no effect on the KC value at a
constant temperature

Calculating KC for heterogeneous Systems

A heterogeneous reaction is one in which the different substances involved in the reaction are
not in the same state of matter.

In such reactions the concentration of solid reactants are ignored while calculating the KC value.

Example
Iron reduces chromium(III), Cr3+ ions according to the following equation:
2𝐶𝑟 3+ (𝑎𝑞) + 𝐹𝑒(𝑠) ⇌ 2𝐶𝑟 2+ (𝑎𝑞) + 𝐹𝑒 2+ (𝑎𝑞)
To a solution containing 0.1moldm-3 of Cr3+ ions, 0.2moldm-3 of Cr2+ ions and 0.075moldm-3 of
Fe2+ excess iron powder was added and at equilibrium the concentration of Cr3+ ions was found
to be 0.03moldm-3.
a) Calculate the value of KC at the prevailing temperature
b) State any assumptions made in your calculation

Solution
a) 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: 2𝐶𝑟 3+ (𝑎𝑞) + 𝐹𝑒(𝑠) ⇌ 2𝐶𝑟 2+ (𝑎𝑞) + 𝐹𝑒 2+ (𝑎𝑞)
𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 0.1𝑚𝑜𝑙𝑑𝑚−3 0.2𝑚𝑜𝑙𝑑𝑚−3 0.075𝑚𝑜𝑙𝑑𝑚−3
𝑪𝒉𝒂𝒏𝒈𝒆: − 2𝑥 𝑚𝑜𝑙𝑑𝑚−3 + 2𝑥 𝑚𝑜𝑙𝑑𝑚−3 + 𝑥 𝑚𝑜𝑙𝑑𝑚−3
𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎: (0.1 − 2𝑥)𝑚𝑜𝑙𝑑𝑚−3 (0.2 + 2𝑥)𝑚𝑜𝑙𝑑𝑚−3 (0.075 + 𝑥) 𝑚𝑜𝑙𝑑𝑚−3
= 0.03𝑚𝑜𝑙𝑑𝑚−3 0.27𝑚𝑜𝑙𝑑𝑚−3 0.11𝑚𝑜𝑙𝑑𝑚−3
(0.1 – 2𝑥) = 0.03 𝑎𝑛𝑑 𝒙 = 𝟎. 𝟎𝟑𝟓𝒎𝒐𝒍𝒅𝒎−𝟑
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©Samuel Sembatya_0755614546
 [𝑪𝒓𝟑+ ] = 0.03 𝑚𝑜𝑙𝑑𝑚−3
[𝑪𝒓𝟐+ ] = (0.2 + 2𝑥0.035) = 0.27 𝑚𝑜𝑙𝑑𝑚−3
[𝑭𝒆𝟐+ ] = (0.075 + 0.035) = 0.11 𝑚𝑜𝑙𝑑𝑚−3
[𝑪𝒓𝟐+ ][𝑭𝒆𝟐+ ] (0.27)𝟐 (0.11)
𝑲𝒄 = = = 𝟖. 𝟗𝟏
[𝑪𝒓𝟑+ ] (0.03)2

b) The concentration of iron powder is constant since it is in solid form.

Equilibrium constant in terms of partial pressures, Kp

This only applies to reactions involving gases because solids and liquids are incompressible
making it impossible to measure their partial pressures. For example:
1) Equilibrium for the reaction between nitrogen monoxide and oxygen to form nitrogen
dioxide
(𝑃𝑁𝑂2 )2
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔) 𝒂𝒏𝒅 𝐾𝑝 =
(𝑃𝑁𝑂 )2 (𝑃𝑂2 )
2) Equilibrium between nitrogen and hydrogen to form ammonia
(𝑃𝑁𝐻3 )2
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔) 𝒂𝒏𝒅 𝐾𝑝 =
(𝑃𝑁2 )(𝑃𝐻2 )3
3) Equilibrium for the decomposition of phosphorous(V) chloride into phosphorous(III)
chloride and chlorine
𝑃𝑃𝐶𝑙3 × 𝑃𝐶𝑙2
𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔) 𝒂𝒏𝒅 𝐾𝑝 =
𝑃𝑃𝐶𝑙5
Calculation of Kp for homogeneous reactions
Example 1
Nitrogen reacts with hydrogen according to the following equation:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
a) Write an expression for KP
b) Stoichometric amounts of nitrogen and hydrogen reacted at 50 atmospheres at a certain
temperature T and at equilibrium 0.8 moles of ammonia were found to be present. Calculate
the amounts of nitrogen and hydrogen present at equilibrium. Hence determine the value of
KP at temperature T
Solution
2
(𝑃𝑁𝐻3 )
(a) 𝐾𝑝 = 3
(𝑃𝑁2 )(𝑃𝐻2 )
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓𝑁𝐻 𝑎𝑡 𝑒𝑞𝑚 = 𝟎. 𝟖
3
(b) 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
∴ 2𝑥 = 0.8 𝑎𝑛𝑑 𝑥 = 4
𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 1 𝑚𝑜𝑙 3 𝑚𝑜𝑙 0 𝑚𝑜𝑙 𝐴𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚:
𝑪𝒉𝒂𝒏𝒈𝒆: − 𝑥 𝑚𝑜𝑙 − 3𝑥 𝑚𝑜𝑙 + 2𝑥 𝑚𝑜𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2 = (1 − 0.4) = 𝟎. 𝟔
𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎: (1 − 𝑥)𝑚𝑜𝑙 (3 − 3𝑥)𝑚𝑜𝑙 2𝑥 𝑚𝑜𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻2 = (3 − 3 × 0.4)
= 𝟏. 𝟐 𝒎𝒐𝒍𝒆𝒔
= 𝟎. 𝟔 𝟏. 𝟖 𝟎. 𝟖 𝒎𝒐𝒍
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = (0.6 + 1.8 + 0.8) = 𝟑. 𝟐

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©Samuel Sembatya_0755614546
 𝑛𝑁2 0.6
𝑃𝑁2 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 50) = 9.375 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 3.2
𝑛𝐻2 1.8
𝑃𝐻2 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 50) = 28.125 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 3.2
𝑛𝑁𝐻3 0.8
𝑃𝑁𝐻3 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 50) = 12.5 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 3.2
2
(𝑃𝑁𝐻3 ) 12.52
𝐾𝑝 = 3 = = 7.49 × 10−4 𝑎𝑡𝑚−2
(𝑃𝑁2 )(𝑃𝐻2 ) 9.375 × 28.1253

Example 2
The Haber process involves the equilibrium:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
a) Write an expression for KP
b) Stoichiometric amounts of nitrogen and hydrogen were allowed to react at a pressure of 200
atmospheres and a temperature of 427oC. At equilibrium the mixture contained 15% by volume
of ammonia. Calculate the value of KP
Solution
2
(𝑃𝑁𝐻3 )
(a) 𝐾𝑝 = 3
(𝑃𝑁2 )(𝑃𝐻2 )

(b) 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)

𝑰𝒏𝒊𝒕𝒊𝒂𝒍𝒍𝒚: 1 𝑚𝑜𝑙 3 𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑪𝒉𝒂𝒏𝒈𝒆: − 𝑥 𝑚𝑜𝑙 − 3𝑥 𝑚𝑜𝑙 + 2𝑥 𝑚𝑜𝑙
𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎: (1 − 𝑥)𝑚𝑜𝑙 (3 − 3𝑥)𝑚𝑜𝑙 2𝑥 𝑚𝑜𝑙

𝒏𝒕𝒐𝒕𝒂𝒍 = (1 − 𝑥 + 3 − 3𝑥 + 2𝑥) = (𝟒 − 𝟐𝒙) 𝐴𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚:

𝑛𝑁𝐻3 2𝑥 𝑛𝑁2 = (1 − 𝑥) = 1 − 0.26 = 𝟎. 𝟕𝟒
( )= = 0.15
𝑛𝑡𝑜𝑡𝑎𝑙 4 − 2𝑥 𝑛𝐻2 = (3 − 3𝑥) = 3 − 3(0.26) = 𝟐. 𝟐𝟐
2𝑥 0.15 𝑛𝑁𝐻3 = 2𝑥 = 2(0.26) = 𝟎. 𝟓𝟐
=
4 − 2𝑥 1 𝒏𝒕𝒐𝒕𝒂𝒍 = 4 − 2(0.26) = 𝟑. 𝟒𝟖
0.6
2.3𝑥 = 0.6 𝑎𝑛𝑑 𝑥 = = 𝟎. 𝟐𝟔
2.3
𝑛𝑁2 0.74
𝑃𝑁2 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 200) = 𝟒𝟐. 𝟓 𝒂𝒕𝒎
𝑛𝑡𝑜𝑡𝑎𝑙 3.48
𝑛𝐻2 2.22
𝑃𝐻2 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 200) = 𝟏𝟐𝟕. 𝟔 𝒂𝒕𝒎
𝑛𝑡𝑜𝑡𝑎𝑙 3.48
𝑛𝑁𝐻3 0.52
𝑃𝑁𝐻3 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 200) = 𝟐𝟗. 𝟗 𝒂𝒕𝒎
𝑛𝑡𝑜𝑡𝑎𝑙 3.48
2
(𝑃𝑁𝐻3 ) 29.92 −𝟓
𝐾𝑝 = 3 = 42.5 × 127.63 = 𝟏. 𝟎𝟏 × 𝟏𝟎 𝒂𝒕𝒎−𝟐
(𝑃𝑁2 )(𝑃𝐻2 )

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 Example 3
1 mole of phosphorous(V) chloride placed in a container of volume 10 litres at 400oC was
found to be 10% dissociated at 6.0 atmospheres.
a) Calculate the equilibrium constant, KP.
b) If 2 moles of phosphorous(V) chloride were placed in the same container at 400oC, what
would be the effect on KP
c) Given that the enthalpies of formation of phosphorous(V) chloride and phosphorous(III)
chloride are -375KJmol-1 and -287KJmol-1 respectively, calculate the enthalpy of
dissociation of phosphorous(V) chloride.

Solution
(a) Equation 𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
Initially: 1 mol 0 mol 0 mol
Change: - 0.1 mol +0.1 mol +0.1mol
Equilibrium: 0.9 mol 0.1 mol 0.1mol

𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = (0.9 + 0.1 + 0.1) = 1.1

𝑛𝑃𝐶𝑙5 0.9
𝑃𝑃𝐶𝑙5 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 6.0) = 4.91 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 1.1
𝑛𝑃𝐶𝑙3 0.1
𝑃𝑃𝐶𝑙3 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 6.0) = 0.55 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 1.1
𝑛𝐶𝑙2 0.1
𝑃𝐶𝑙2 = ( × 𝑃𝑡𝑜𝑡𝑎𝑙 ) = ( × 6.0) = 0.55 𝑎𝑡𝑚
𝑛𝑡𝑜𝑡𝑎𝑙 1.1
0.55 × 0.55
𝐾𝑝 = = 0.0622 𝑎𝑡𝑚
4.91
(b) KP remains constant. Change in pressure has no effect on the KP value provided temperature
remains constant
(c) 𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
∆𝐻 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑃𝐶𝑙5 = ∑(∆𝐻𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑(∆𝐻𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
= (−287 + 0) − (−375) = +𝟖𝟖 𝒌𝑱𝒎𝒐𝒍−𝟏

Calculation of Kp for heterogeneous reactions

When calculating the Kp for heterogeneous reactions, the partial pressures of solid and liquid
reactants are ignored since solids and liquids are incompressible.
For example:
a) Thermal decomposition of calcium carbonate
𝐶𝑎𝐶𝑂3 (𝑠) ⇌ 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)
𝐾𝑝 = 𝑃𝐶𝑂2
The partial pressures of calcium carbonate and calcium oxide, being solids, are constant.

b) Dissociation of ammonium hydrogensulphide

𝑁𝐻4 𝐻𝑆(𝑠) ⇌ 𝑁𝐻3 (𝑔) + 𝐻2 𝑆(𝑔)

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 𝐾𝑐 = [𝑁𝐻3 ][𝐻2 𝑆]𝑎𝑛𝑑 𝐾𝑝 = 𝑃𝑁𝐻3 × 𝑃𝐻2 𝑆

c) Dissociation of silver carbonate

𝐴𝑔2 𝐶𝑂3 (𝑠) ⇌ 𝐴𝑔2 𝑂(𝑠) + 𝐶𝑂2 (𝑔)
𝐾𝑝 = 𝑃𝐶𝑂2

d) Reaction between steam and iron

3𝐹𝑒(𝑠) + 4𝐻2 𝑂(𝑔) ⇌ 𝐹𝑒3 𝑂4 (𝑠) + 4𝐻2 (𝑔)
4
(𝑃𝐻2 )
𝐾𝑝 = 4
(𝑃𝐻2 𝑂 )
Example
Silver carbonate decomposes on heating to silver oxide and carbon dioxide
a) Write equation for decomposition of silver carbonate
b) At 120oC and a pressure of 1 atmosphere air contains 1.0% of carbon dioxide
(i) Calculate the partial pressure of carbon dioxide in air at 120oC
(ii) State whether there would be change in the mass of silver carbonate at equilibrium when the
percentage of carbon dioxide in air was increased to 3.0%. Give reason for your answer
Solution
(a) 𝐴𝑔2 𝐶𝑂3 (𝑠) ⇌ 𝐴𝑔2 𝑂(𝑠) + 𝐶𝑂2 (𝑔)
1.0
(b) (i) 𝑃𝐶𝑂2 = 𝑋𝐶𝑂2 × 𝑃𝑡𝑜𝑡𝑎𝑙 = (100 × 1) = 0.01 𝑎𝑡𝑚
(ii) The mass of silver carbonate would increase. Increase in the partial pressure of carbon dioxide
would shift equilibrium from the right-hand side to left-hand side thereby increasing the mass of
silver carbonate.
Interpreting the magnitude of Kc or Kp
 If Kc >>>> 1, then the position of equilibrium lies more to the right hand side indicating that
the products are favored over the reactants at the equilibrium temperature. The reaction is
almost complete.
 If Kc = 1, this indicates equal amounts of reactant and products. Neither reactants nor
products are favoured
 If Kc <<<<< 1, then the position of equilibrium lies more to the left hand side indicating that
only a small proportion of reactants has been converted into products. Reactants are favored
over products.
 The same interpretation applies to Kp values.

Different values of the equilibrium constant for the same reaction

 Kc for the reverse reaction is equal to the reciprocal of Kc for the forward reaction
1
Kc ( Re verse reaction) 
K C ( foward reaction)
 Halving the co-efficients of the reaction
New K ' c  K c before halving the stoichiometric co-efficients
 Doubling the stoichiometric co-efficients of the reaction
 𝑁𝑒𝑤 𝐾𝐶, = (𝐾𝑐 𝑏𝑒𝑓𝑜𝑟𝑒 𝑑𝑜𝑢𝑏𝑙𝑖𝑛𝑔 𝑡ℎ𝑒 𝑠𝑡𝑜𝑖𝑐ℎ𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜 − 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡𝑠)2

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 For a sequence of n reversible reactions,
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐾𝑐 = 𝐾1 × 𝐾2 × 𝐾3 × … … . . 𝐾𝑛
 The same interpretation applies to KP values.

Relationship between KC and KP

Consider the following equilibrium:

𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
2
[𝑁𝐻3 ]2 (𝑃𝑁𝐻3 )
𝐾𝑐 = 3
𝑎𝑛𝑑 𝐾𝑃 = 3
[𝑁2 ][𝐻2 ] (𝑃𝑁2 )(𝑃𝐻2 )

𝑃𝑉 = 𝑛𝑅𝑇
𝑛𝐻 𝑅𝑇 𝑛𝑁 𝑅𝑇 𝑛𝑁𝐻3 𝑅𝑇
𝑃𝐻2 = ( 2 ) = [𝐻2 ]𝑅𝑇; 𝑃𝑁2 = ( 2 ) = [𝑁2 ]𝑅𝑇; 𝑃𝑁𝐻3 = ( ) = [𝑁𝐻3 ]𝑅𝑇
𝑉 𝑉 𝑉

𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑖𝑛 𝑡ℎ𝑒 𝐾𝑝 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑔𝑖𝑣𝑒𝑠:

([𝑁𝐻3 ]𝑅𝑇 )2 [𝑁𝐻3 ]2
𝐾𝑃 = = (𝑅𝑇)−2
([𝑁2 ]𝑅𝑇)([𝐻2 ]𝑅𝑇)3 [𝑁2 ][𝐻2 ]3

[𝑁𝐻3 ]2
𝐾𝑃 = (𝑅𝑇)−2
[𝑁2 ][𝐻2 ]3

𝐾𝑃 = 𝐾𝑐 (𝑅𝑇)−2

In general (for gaseous reactions):

𝑲𝑷 = 𝑲𝒄 (𝑹𝑻)𝒏
∆𝑛 = ∑ 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑒𝑖𝑒𝑛𝑡𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑒𝑖𝑒𝑛𝑡𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

For gaseous reactions that proceed without change in volume (number of molecules), ∆n = 0 and
Kc = Kp.

Reaction quotient, Q
This is the ratio of the concentrations of the products to reactants (raised to the appropriate
powers) at any point in time. By comparing the value of Q with the equilibrium constant, Kc, the
direction of reaction can be predicted
 If Q < Kc the reaction will move to the right, generating more product to reach equilibrium.
 If Q = Kc the reaction is at equilibrium.
 If Q > Kc the reaction will move to the left, generating more reactants to reach equilibrium.

Example
The following equilibrium was established at 1700°C.
𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ⇌ 𝐻2 𝑂(𝑔) + 𝐶𝑂(𝑔); 𝐾𝑐 = 4.0 𝑎𝑡 1700𝑜 𝐶
1.5 moles of carbon dioxide gas, 1.5 moles of hydrogen gas, 1.5 moles of steam and 1.5 mole of
carbon monoxide were mixed in a one litre vessel at 1700oC.
(a) Calculate the reaction quotient, Q
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(b) State, with a reason, the direction in which the reaction will proceed.
(c) Calculate the number of moles of each gas at equilibrium.
Solution
(a)
[𝐻2 𝑂][𝐶𝑂] 1.5 × 1.5
𝑄= = = 1.0
[𝐶𝑂2 ][𝐻2 ] 1.5 × 1.5

(b) Since𝑄 < 𝐾𝑐 , the reaction shifts from left to the right to generate enough products to
reach equilibrium.
(c) 𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ⇌ 𝐻2 𝑂(𝑔) + 𝐶𝑂(𝑔)
Initial: 1.5 mol 1.5 mol 1.5 mol 1.5 mol
Change: −𝑥 𝑚𝑜𝑙 −𝑥 𝑚𝑜𝑙 +𝑥 𝑚𝑜𝑙 +𝑥 𝑚𝑜𝑙
Equilibrium: (1.5 − 𝑥) (1.5 − 𝑥) (1.5 + 𝑥) (1.5 + 𝑥)

[𝐻2 𝑂][𝐶𝑂] (1.5 + 𝑥)(1.5 + 𝑥)

𝐾𝐶 = = = 4.0
[𝐶𝑂2 ][𝐻2 ] (1.5 − 𝑥)(1.5 − 𝑥)

(1.5 + 𝑥)2
√ = √4.0
(1.5 − 𝑥)2

1.5 + 𝑥
= 2.0 𝑎𝑛𝑑 𝑥 = 0.5
1.5 − 𝑥

The amounts, in moles, at equilibrium are as follows:

𝐶𝑂2 = (1.5 − 0.5) = 1.0 𝑚𝑜𝑙𝑒𝑠; 𝐻2 = (1.5 − 0.5) = 1.0 𝑚𝑜𝑙𝑒𝑠
𝐻2 𝑂 = (1.5 + 0.5) = 2.0 𝑚𝑜𝑙𝑒𝑠; 𝐶𝑂 = (1.5 + 0.5) = 2.0 𝑚𝑜𝑙𝑒𝑠

Le’ Chatelier’s principle

States that “if any constraint is applied to any chemical system at equilibrium, then the system will adjust itself
in such a way to counteract this constraint as far as possible”.
The constraint may be change in temperature, pressure or concentration

Factors affecting equilibrium of a reaction

These include:
a) Change in concentration
b) Change in Pressure
c) Change in temperature

Effect of temperature change on equilibrium

Change in temperature affects:
 the position of equilibrium
 the value of the equilibrium constant and
 the rate attainment of equilibrium

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 Increase in temperature:
 shift equilibrium in a direction in which
the reaction is endothermic
 increases the value of Kc or Kp if the
reaction is endothermic
 increases the rate of attainment of
equilibrium for both exothermic and
endothermic reactions.
Decrease in temperature:
 shift equilibrium in a direction in
which the reaction is exothermic
 decreases the value of Kc or Kp if the
reaction is exothermic
 decreases the rate of attainment of
equilibrium for both exothermic and
endothermic reactions.

𝑁2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂(𝑔); ∆𝐻 = +180 𝑘𝐽𝑚𝑜𝑙 −1

Increase in temperature;
 shifts equilibrium from the left to the right by allowing nitrogen and oxygen to combine forming
more nitrogen monoxide which will absorb the excess heat supplied in order to lower the temperature
again.
 increases value of the equilibrium constant due to increase in the concentrations of the products and
reduction in the concentrations of the reactants.
 increases the rate of attainment of equilibrium by increasing the fraction of particles with energy
greater or equal to the activation energy and by increasing the average kinetic energy of the particles
resulting into more frequent successful collisions.

Decrease in temperature;
 will shift equilibrium to the left by allowing nitrogen monoxide to dissociate into nitrogen and
oxygen gases in an exothermic reaction. This allows temperature to rise again.
 decreases the value of the equilibrium constant due to decrease in concentration of the products and
reduction in the concentration of reactants
 decreases the rate of attainment of equilibrium by decreasing the fraction of particles with energy
greater or equal to the activation energy and by decreasing the average kinetic energy of the particles
resulting into less frequent successful collisions.

Effect of pressure on equilibrium

Change in pressure affects only equilibrium of reactions involving gases since solids and liquids cannot
easily be compressed.

For gaseous reactions change in pressure:

 has no effect on the value of the equilibrium constant provided temperature is kept constant.
 affects the position of equilibrium for reactions that proceed with a change in volume (or in which
number of molecules of reactants and products are different) but has no effect on the position of
equilibrium for reactions that proceed without change in volume (number of molecules).
 affects the rate of attainment of equilibrium all gaseous reactions.

Increase in pressure: Decrease in pressure:

 shift equilibrium in a direction in  shift equilibrium in a direction in
which the molecules are fewer. which the molecules are more.
 has no effect on the value of Kc or Kp  has no effect on the value of Kc or Kp
at constant temperature. at constant temperature.

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  increases the rate of attainment of
equilibrium by increasing the number
of molecules per unit volume thereby
increasing the frequency of successful
collisions.
 decreases the rate of attainment of
equilibrium by decreasing the number
of molecules per unit volume thereby
decreasing the frequency of successful
collisions.

a) Reactions that proceed with change volume

𝑒. 𝑔. 𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔); ∆𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1
Increase in pressure shifts equilibrium in a direction that allows for a decrease in the total number
of molecules. In this case from left to right resulting into formation of more ammonia. As the
number of molecules decreases, the volume also reduces and the system is relieved of the excess
pressure.
The equilibrium will shift in such a way that the equilibrium constant remains unaltered as long as
temperature is kept constant.
Decrease in pressure will shift equilibrium in a direction that allows for an increase in the total
number of molecules; in this case from right to left leading to dissociation of ammonia. As the
number of molecules increases more pressure is exerted on the walls of the container thereby
increasing pressure again.
The equilibrium will shift in such a way that the equilibrium constant remains unaltered as long as
temperature is kept constant.

b) Reactions that proceed without change volume

𝑒. 𝑔. 𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔); ∆𝐻 = −11.3 𝑘𝐽𝑚𝑜𝑙 −1
Increase or decrease in pressure has no effect on the position of equilibrium and the value of the
equilibrium constant of such reactions.
Increase in pressure increases the rate of attainment of equilibrium and decrease in pressure
decreases the rate of attainment of equilibrium.

Effect of adding an inert gas on gaseous equilibrium

a) Reactions in which the number of molecules of reactants and products is the same
𝑒. 𝑔. 2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔); ∆𝐻 = +11.3 𝑘𝐽𝑚𝑜𝑙 −1
Addition of an inert gas will only increase the total pressure of the system without affecting the
number of moles and the partial pressures of the reactants and products. Consequently the value
of KC and the position of equilibrium are not affected.

b) Reactions in which the number of molecules of reactants and products is different

𝑒. 𝑔. 2𝐻𝐶𝑙(𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
i) Addition of an inert gas at constant volume
The value of Kc or Kp will not be affected since the equilibrium concentrations and
equilibrium partial pressures of both the reactants and products are not affected at constant
volume.
ii) Addition of an inert gas at constant pressure
This results into an increase in the volume of the reaction mixture and consequently
equilibrium shifts in a direction with more molecules. In this case the equilibrium shifts
from the left to the right causing phosphorus(V) chloride to dissociate into phosphorous(III)
chloride and chlorine.

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 The number of moles of phosphorus(V) chloride will decrease while those of phosphorus
(III) chloride and chlorine will increase but the changes are in such a way that the value of
Kc or Kp is kept constant at constant temperature.

Effect of concentration on equilibrium

Change in concentration:
 affects the position of equilibrium
 the rate of attainment of equilibrium but
 has no effect on the value of the equilibrium constant.
𝑒. 𝑔. 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (𝑙) + 𝐻2 𝑂(𝑙)
 Increase in the concentration of ethanoic acid shifts equilibrium from left to right. This allows ethanol
to combine with ethanoic acid so as to reduce the acid concentration again.
 Decrease in the concentration of ethanoic acid shifts equilibrium from right to left by allowing the ester
and water to react thereby increasing the concentration of the acid again.
 Increase or decrease in concentration does not affect the value of the equilibrium constant because
equilibrium will shift in such a way that the value of KC remains constant as long as temperature is
constant.
 Increase in concentration increases the rate of attainment of equilibrium due to increase in the number
of particles per unit volume which increases the number of successful collisions per unit time.
 Decrease in concentration reduces the rate of attainment of equilibrium due to decrease in the number
of particles per unit volume which in turn decreases the number of successful collisions per unit time.

Effect of a catalyst on equilibrium

A catalyst has no effect on both the position of equilibrium and the value of the equilibrium constant but only
increases the rate of attainment of equilibrium by providing an alternative path with reduced activation
energy.
SUMMARY OF FACTORS AFFECTING EQUILIBRIUM
Factor Constraint Effect on KC or Kp Effect on position of equilibrium Effect on rate
value of attainment
of equilibrium
Concentration Increase in No change Shifts in the opposite direction Increases
concentration
Decrease in No change Shifts in a direction where the Decreases
concentration concentration has decreased
Pressure Increase in No change Shifts in a direction with fewer Increases
pressure molecules and no change if a
reaction proceeds without change
in the number of
molecules/volume.
Decrease in No change Shifts in a direction with more Decreases
pressure molecules and no change if the
reaction proceeds without change
in the number of
molecules/volume.
Catalyst Addition of a No change No change Increases
catalyst

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Temperature Increase in Increases if the Shifts in the endothermic direction. Increases
temperature reaction is
endothermic and
decreases if reaction
is exothermic
Decrease in Decreases if the Shifts in the exothermic direction Decreases
temperature reaction is
endothermic and
increases if the
reaction is
exothermic.

Application of the equilibrium law to industrial processes

a) The contact process/manufacture of sulphuric acid
Highly purified sulphur dioxide and air, in slight excess are passed over vanadium(V) oxide catalyst at a
temperature of about 450oC and a pressure slightly above 1 atmosphere. Under these conditions sulphur
dioxide reacts with oxygen forming sulphur trioxide.
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔); ∆𝐻 𝜃 = −94.6 𝑘𝐽𝑚𝑜𝑙 −1
The reaction is exothermic and the temperature rises to about 600oC; the gases are cooled by passing them
through a heat exchanger.
The sulphur trioxide formed is absorbed in concentrated sulphuric acid in the absorption tower forming
oleum.
𝑆𝑂3 (𝑔) + 𝐻2 𝑆𝑂4 (𝑙) → 𝐻2 𝑆2 𝑂7 (𝑙)
The oleum is diluted with a calculated amount of water forming 98% concentrated sulphuric acid.
𝐻2 𝑆2 𝑂7 (𝑙) + 𝐻2 𝑂(𝑙) ⟶ 2𝐻2 𝑆𝑂4 (𝑎𝑞)
The unreacted sulphur dioxide (being poisonous) is removed by absorbing it in calcium hydroxide
solution. The heat extracted from the heat exchanger is used to heat up more sulphur dioxide - oxygen
mixture.

Sources of sulphur dioxide used in the process

1. Zinc blend (zinc sulphide, ZnS) – by roasting it in air
2𝑍𝑛𝑆(𝑠) + 3𝑂2 (𝑔) → 2𝑍𝑛𝑂(𝑠) + 2𝑆𝑂2 (𝑔)
2. Iron pyrite (FeS2) – by roasting it in air
4𝐹𝑒𝑆2 (𝑠) + 5𝑂2 (𝑔) → 2𝐹𝑒2 𝑂3 (𝑠) + 4𝑆𝑂2 (𝑔)
3. Hydrogen sulphide from oil refining – by burning it in air
𝐻2 𝑆(𝑔) + 𝑂2 (𝑔) → 𝐻2 𝑂(𝑙) + 𝑆𝑂2 (𝑔)
4. Sulphur from sulphur deposits - by burning it in air
𝑆(𝑠) + 𝑂2 (𝑔) → 𝑆𝑂2 (𝑔)

b) The Haber process/manufacture of ammonia

Nitrogen (from air) and hydrogen (from steam or petroleum) are reacted together at a pressure of 200
atmospheres in presence of finely divided iron catalyst at a 450oC. Under these conditions about 15%
of the gases are converted to ammonia. The gases are cooled while still under pressure, and the condensed
ammonia removed as a liquid. The unreacted nitrogen and hydrogen are recycled for further conversion to
ammonia.

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𝐻2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔); ∆𝐻 𝜃 = −92.0 𝑘𝐽𝑚𝑜𝑙 −1

Note: In accordance with Le Chatelier’s principle, the percentage yield of ammonia can be increased by:
 increasing the concentration of one of the reactants (shifts equilibrium to the right to counteract
the increase in the concentration of the reactant).
 removing ammonia from the reaction mixture as it forms (shifts equilibrium to the right to
compensate for the loss in the concentration of ammonia).
 increasing the gas pressure (As the forward reaction proceeds with a decrease in the number of
molecules, increasing pressure shifts equilibrium to the right).
 decreasing the temperature (As the forward reaction is exothermic, temperature decrease shifts
equilibrium to the right).

c) Manufacture of nitric acid

Nitric acid is manufactured by catalytic oxidation of ammonia. A mixture of ammonia and air is passed
over platinum-rhodium catalyst at about 850oC to form nitrogen monoxide and steam.
4NH3 (g) + 5O2 (g) 
platinum-rhodium
850o C
 4NO(g) + 6H 2O(l)
After cooling, the nitrogen dioxide and excess air react in the oxidizing chamber forming nitrogen
dioxide.
2𝑁𝑂(𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂2 (𝑔)
The nitrogen dioxide, in presence of excess air, is then absorbed in water at 350oC to form nitric acid.
4𝑁𝑂2 (𝑔) + 𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) → 4𝐻𝑁𝑂3 (𝑎𝑞)

EXERCISE
1. When air (assume 20% oxygen, 80% nitrogen) is heated to 2000K at a pressure of 100kPa, 3.0% of
the oxygen is convert to nitrogen monoxide in the equilibrium:
𝑁2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑁𝑂(𝑔)
Calculate the partial pressure of O2, N2 and NO at equilibrium.
2. When ammonium hydrogen sulphide is heated it dissociates according to the equilibrium below:
𝑁𝐻4 𝐻𝑆(𝑠) ⇌ 𝑁𝐻3 (𝑔) + 𝐻2 𝑆(𝑔)
The value of Kc for this equilibrium at a particular temperature is 0.00001mol2dm-6.
a) Write the expression for Kc and state its units. State any assumptions made in your answer
b) Calculate the concentration of ammonia at equilibrium
c) If some ammonia gas was injected at a constant pressure and temperature, how would this affect
i) The mass of solid present?
ii) The concentration of hydrogen sulphide
iii) The value of Kc

3. A gaseous mixture of hydrogen, iodine and hydrogen iodide are in equilibrium according to the
equation:
𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔); ∆𝐻 = +56 𝑘𝐽𝑚𝑜𝑙 −1

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 State how the position of equilibrium will be affected by the following changes and explain your
reasoning:
a) Decreasing the temperature
b) Adding more hydrogen at constant pressure
c) Increasing the total pressure

4. The equations of some reactions are given below:

𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞); 𝐾1 = 1.7 × 10−10
+
𝐴𝑔+ (𝑎𝑞) + 2𝑁𝐻3 (𝑎𝑞) ⇌ 𝐴𝑔(𝑁𝐻3 )2 (𝑎𝑞); 𝐾2 = 1.7 × 10−7
a) Derive an expression in terms of K1 and K2, for the equilibrium constant for the following
reaction:
+
𝐴𝑔𝐶𝑙(𝑠) + 2𝑁𝐻3 (𝑎𝑞) ⇌ 𝐴𝑔(𝑁𝐻3 )2 (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞)
b) Calculate the value of the equilibrium constant in (i)
5. Iodine vapour dissociates into its atoms according to the following equation:
𝐼2 (𝑔) ⇌ 2𝐼(𝑔)
At a certain temperature and a total pressure of 1 atmosphere, iodine vapour contains 40% by
volume of iodine atoms.
a) Calculate Kp for the equilibrium
b) At what total pressure (without change in temperature) will the percentage of iodine atoms be
20%?
6. Consider the following equilibrium:
𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔)
a) Write an expression for the equilibrium constant in terms of partial pressures
b) At a certain temperature analysis of an equilibrium mixture of the gases yielded the following
results:
𝑃𝐻2 = 0.25 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
𝑃𝐼2 = 0.16 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
𝑃𝐻𝐼 = 0.40 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑒𝑠
Calculate the equilibrium constant for the reaction and state its units

c) In the second experiment at the same temperature iodine and hydrogen iodide were mixed
together with each gas at a partial pressure of 0.3 atmospheres. What are the equilibrium partial
pressures of hydrogen, iodine and hydrogen iodide

7. At a certain temperature to 400oC, hydrogen iodide has a degree of dissociation of 20%. Calculate
the equilibrium constant, Kp for the following equilibrium:
2𝐻𝐼(𝑔) ⇌ 𝐻2 (𝑔) + 𝐼2 (𝑔)

8. A mixture of nitrogen and hydrogen was allowed to come to equilibrium at 400oC. The original
amount of each gas was 2 moles. At equilibrium 0.2 moles of nitrogen had reacted. The value of Kp
at 400oC is 40.7 atm-2. Calculate the total pressure of the mixture

9. a) Write:
i) an equation for the reaction between hydrogen and nitrogen
ii) expression for the equilibrium constant of the reaction in a(i) above

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 b) When hydrogen was reacted with nitrogen at 895K, the total pressure for the system at
equilibrium was 30 atmospheres and the partial pressure of nitrogen and hydrogen were 2 and 6
atmospheres respectively.
i) Determine the partial pressure of ammonia in the equilibrium
ii) Calculate the equilibrium constant for the following reaction:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
10. The exothermic reaction between nitrogen and hydrogen takes place according to the following
equation:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
a) Write an expression for the equilibrium constant Kc for the forward reaction
b) At 500oC the equilibrium concentration of hydrogen is 0.250 mol dm-3 and nitrogen is
2.7moldm-3. Calculate the equilibrium concentration of ammonia at the same temperature given
Kc = 6.0x10-2 dm3mol-2
c) What would happen to the concentration of ammonia if:
i) Helium was added to the equilibrium mixture at 500oC?
ii) The temperature was increased?

11. A piece of lead metal was suspended in a one litre solution which contained 0.43 moles of tin(IV)
ions. The reaction was allowed to continue until equilibrium was reached. At equilibrium was
reached. At equilibrium the resultant solution contained 0.21 moles of tin (IV) ions.
a) Write equation for the reaction that took place
b) Calculate the equilibrium constant for the reaction:
𝑆𝑛4+ (𝑎𝑞) + 𝑃𝑏(𝑠) ⇌ 𝑆𝑛2+ (𝑎𝑞) + 𝑃𝑏 2+ (𝑎𝑞)
12. Phosphorus (V) chloride when heated decomposes according to the following equation:
𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
A sample of 1 mole pure phosphorus (V) chloride was heated in a closed vessel to 250oC. When
equilibrium was attained the vessel was found to contain 40.7% of chlorine.
Calculate:
a) The molar concentration of phosphorus (V) chloride at equilibrium
b) The equilibrium constant Kc for the reaction at 250oC

13. Nitrogen reacts with hydrogen according to the following equation:

𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)
a) Write an expression for the equilibrium constant and indicate its units
b) Stoichometric amounts of nitrogen and hydrogen reacted at 50 atmospheres and at equilibrium
0.8 moles of ammonia were found to be present. Calculate:
i) The amount of hydrogen and nitrogen present at equilibrium
ii) The value of the equilibrium constant for the reaction

14. Ethanal decomposes according to the following equilibrium:

15. 𝐶𝐻3 𝐶𝐻𝑂(𝑔) ⇌ 𝐶𝐻4 (𝑔) + 𝐶𝑂2 (𝑔); ∆𝐻 = −𝑣𝑒
a) Write an expression for the equilibrium constant, Kp for the reaction
b) Explain how the Kp would be affected by:
i) Increasing temperature
ii) Increasing pressure

16. Hydrogen reacts with nitrogen to produce ammonia according to the following equation:
𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)

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 a) Write an expression for the equilibrium constant, Kc
b) State, giving reasons, what would be happen to the equilibrium constant when:
i) Pressure was increased at constant temperature
ii) Argon was added to the reaction mixture at constant pressure
iii) Argon was added to the reaction mixture at constant volume

17. For the industrially important reaction:

2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔); ∆𝐻(298𝐾) = −94.5 𝑘𝐽
Describe, giving reasons, the effect on the position of equilibrium of:
i) Increasing temperature
ii) Decrease in pressure
iii) Adding a platinum catalyst
iv) Adding excess oxygen

18. At 1300K and a total pressure of 1 atmosphere, the partial pressure at equilibrium are 0.27
atmospheres for sulphurdioxide and 0.41 atmospheres for oxygen.Calculate the equilibrium constant
Kp and give its units

19. a) Discuss the effect of each of the following on the position of equilibrium of a reversible reaction,
the rate of attainment of equilibrium and the value of the equilibrium constant
i) catalyst
ii) pressure
iii) temperature
b) Write an expression for the equilibrium constant Kc or Kp as appropriate for the following
reaction at equilibrium and indicate the units in each case.
𝐴 + 𝐵 ⇌ 𝐶 + 2𝐷
When under the following conditions:
(i) A, B, C and D are all gases
(ii) A, B, C and D are all liquids
(iii) A,B,C are all solids and D a gas

20. (a) State Le Chatelier’s principle

(b) For the reaction
𝐻2 (𝑔 + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔); ∆𝐻 = +52 𝑘𝐽 𝑚𝑜𝑙 −1
Give the expression for the equilibrium constant in terms of partial pressures
(c) What would be the effect, if any, on the equilibrium above of:
(i) increasing the total pressure
(ii) increasing the temperature

(d) The following table gives concentrations of the components in the above equilibrium at 600K.
[H2] [I2] [HI]
1.71x10-3 moldm-3 2.91x10-3 moldm-3 1.65x10-2 moldm-3
Calculate the value of Kc at this temperature

21. a) Explain what is meant by dynamic equilibrium

b) The hydrogenation of coal can be used to manufacture substitute natural gas. The major reaction
involved is
𝐶(𝑠) + 2𝐻2 (𝑔) ⇌ 𝐶𝐻4 (𝑔)
Write expressions for Kp and Kc for the reaction above

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 For the reaction in (b) above describe and explain the effect of the following changes on both the
position of equilibrium and the value of Kp
i) Increase in temperature at constant pressure
ii) Increase in partial pressure of methane at constant volume
iii) Increase in total pressure at constant temperature
iv) Addition of a catalyst
22. (a) What is meant by the terms homogeneous equilibrium and equilibrium constant?
(b) Consider the following reaction:
𝑃𝐶𝑙5 (𝑔) ⇌ 𝑃𝐶𝑙3 (𝑔) + 𝐶𝑙2 (𝑔)
For such a system, of total volume of 1dm3 and total pressure of 206.6kPa, at equilibrium the
percentage dissociation of phosphorus (V) chloride at temperatures of 200oC and 300oC are 48.5
and 97.0 respectively.
i) Write the expression that represents the equilibrium constant, Kp
ii) Calculate the value of Kp at 200oC
iii) What percentage dissociation of phosphorus (V) chloride would result if the pressure of the
system was reduced to 135.1kPa? (Assume temperature is kept constant)
iv) Explain your answer in b(iii) above in terms of Le Chatelier’s principle
v) What conclusion can be drawn from the information in (b) above about the enthalpy change
for the reaction
(c) How would the position of equilibrium be affected by:
(i) a decrease in total pressure
(ii) the presence of a catalyst
(iii) an increase in concentration of chlorine
(iv) a decrease in temperature
23. (a) For the reaction
𝐴 + 𝐵 ⇌ 2𝐶 + 2𝐷
Give an expression for and state the units of the appropriate equilibrium constant (K c or Kp) for
each of the following situations when:
(i) reactants and products are liquids
(ii) reactants and products are all gases
(iii) A and D are gases but B and C are liquids
(b) For the reaction:
𝑁2 (𝑔) + 3𝐻(𝑔) ⇌ 2𝑁𝐻3 (𝑔); ∆𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1
Discuss the effect on equilibrium of:
(i) increasing temperature at constant pressure
(ii) decreasing pressure at constant temperature
(iii) adding a catalyst
(c) 1 mole of nitrogen and 3 moles of hydrogen were mixed at 593K and 2x107 Pa. At equilibrium
the mixture contained 1.5 moles of ammonia
(i) Write an expression for Kp
(ii) Find the mole fraction of each component and thus their partial pressures
(iii) Use these values, from (ii), to calculate the the value of Kp
(iv) Explain why these physical conditions are not used in practice

24. Sulphurdioxide reacts with oxygen according to the following reaction:

2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔); ∆𝐻(298𝐾) = −98 𝑘𝐽
a) State and explain what will happen to the position of equilibrium when:
i) pressure is increased at constant temperature
ii) temperature is increased at pressure

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 b) Explain why on industrial scale temperature of 800oC, pressure of 1 atmosphere and a catalyst
are used
25. Nitrogen reacts with hydrogen according to the following equation:
𝑁2 (𝑔) + 3𝐻(𝑔) ⇌ 2𝑁𝐻3 (𝑔); ∆𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1
a) Calculate the mole percentage of ammonia in the equilibrium mixture formed at 400oC and
3x107 Pa pressure, when gaseous hydrogen and nitrogen are mixed in a ratio 3:1, and there is
61% conversion of nitrogen to ammonia
b) Write an expression for Kp in terms of thee partial pressures of the three gases
c) Given that the value of Kp at 400oC is 2.0x10-14 Pa-2, calculate the pressure at which ammonia
is 95% dissociated into its elements at 400oC.

26. The Haber process for the synthesis of ammonia may operate at a temperature of 450 °C and
pressure of 1.50 x 107 Pa using an iron catalyst.
𝑁2 (𝑔) + 3𝐻(𝑔) ⇌ 2𝑁𝐻3 (𝑔); ∆𝐻 = −92 𝑘𝐽𝑚𝑜𝑙 −1
a) Suggest why the temperature of more than 450°C is not used even though the rate of reaction
would be faster.
b) Suggest why the reaction is carried out at a high pressure rather than at normal atmospheric
pressure. Explain your answer.
c) Explain why the removal of ammonia as soon as it is formed is an important part of this
industrial process.

27. Formation from ethyl ethanoate involves the following equilibrium.

CH3CO2H(l) + C2H5OH(l) CH3CO2C2H5(l) + H2O(l)
This reaction is an example of a dynamic equilibrium.
(a) Explain what is meant by the term dynamic equilibrium.
(b) Write the expression for the equilibrium constant for this reaction, Kc.
(c) For this equilibrium, the value of Kc is 4.0 at 298K.
A mixture containing 0.5 moles of ethanoic acid, 0.5 moles ethanol, 0.1 moles ethyl ethanoate
and 0.1 moles water was set up and allowed to reach equilibrium at 298K. Calculate the amount,
in moles, of each substance present at equilibrium.

28. Nitrogen monoxide can be formed when nitrosyl chloride, NOCl, dissociates according to the
following equation.
2NOCl (g) 2NO(g) + Cl2(g)
Different amounts of the three gases were placed in a closed container and allowed to come to
equilibrium at 230°C. The experiment was repeated at 465°C.
The equilibrium concentrations of the three gases at each temperature are given in the table below.
Concentration in moldm-3
O
Temperature ( C) NOCl NO Cl2
−3 −3
230 2.33 × 10 1.46 × 10 1.15 × 10−2
−4 −3
465 3.68 × 10 7.63 × 10 2.14 × 10−4

(a) Write the expression for the equilibrium constant, Kc, for this reaction. Give the units.
(b) Calculate the value of Kc at:
(i) 230 °C = 4.52 x 10-3 moldm-3
(ii) 465 °C = 9.00x10-2 moldm-3
(c) Is the forward reaction endothermic or exothermic? Explain your answer.

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 (d) State and explain the effect on the equilibrium concentration of NOCl when:
(i) the pressure of the system is halved at constant temperature.
(ii) a mixture of NOCl(g) and NO(g) containing equal numbers of moles of each gas is
introduced into the container at constant temperature.

29. 2.00 moles of methane, 2.00 moles of carbon disulphide, 4.00 moles of hydrogen sulphide,
and 4.00 moles of hydrogen were mixed in a 500 cm3 vessel at 687oC. At this temperature
the following equilibrium is established.
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)
o
The Kc at 687 C for this equilibrium is 0.046.
a) Calculate the reaction quotient, Q
b) What direction will the reaction proceed to reach equilibrium? Explain your answer.
c) If the concentration of methane at equilibrium was 4.96 moldm-3, what are the
equilibrium concentrations of the other substances?

30. The equilibrium constant, Kc for the reaction N2 (g) + 3H2 (g) ⇌ 2NH3 (g) at 500 K is 0.061.
At a particular time, the analysis shows that composition of the reaction mixture is 3.0M of
N2, 2.0M of H2 and 0.5M of NH3. Is the reaction at equilibrium? If not in which direction
does the reaction tend to proceed to reach equilibrium?

31. At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride, PCl 5 is

8.3 ×10-3. The decomposition occurs according to the following equation
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) ∆H = +124.0 kJmol–1
a) Write an expression for Kc for the reaction.
b) What is the value of Kc for the reverse reaction at the same temperature?\
c) What would be the effect on Kc if:
(i) more PCl5 is added
(ii) pressure is increased
(iii) the temperature is increased ?
32. Hydrogen chloride undergoes a reversible reaction with oxygen.
4𝐻𝐶𝑙 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝐶𝑙2 (𝑔) + 2𝐻2 𝑂(𝑔)
When 1.6 moles of hydrogen chloride are mixed in a sealed container with 0.5 moles of oxygen at
400°C, 0.6 moles of chlorine and 0.6 moles of water are formed at equilibrium.
The total pressure inside the container is 1.50 ×105 Pa.
(a) Calculate the moles of hydrogen chloride and oxygen in the equilibrium mixture.
(b) (i) Write an expression for KP
(ii) Calculate the partial pressure of each gas in the equilibrium mixture
(iii) Calculate the value of Kp and state its units

33. Methanol, CH3OH, can be produced industrially by reacting carbon monoxide, CO, with hydrogen,
H2 according to the following equation:

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 𝐶𝑂(𝑔) + 2𝐻2(𝑔) ⇌ 𝐶𝐻3𝑂𝐻(𝑔); 𝛥𝐻 = – 91 𝑘𝐽 𝑚𝑜𝑙 −1
The reaction was carried out at a pressure of 40 atmospheres and a temperature of 1150K.
(a) State Le Chatelier's Principle.
(b) Explain the effect on the yield of methanol if
(i) The temperature was decreased below 1150K
(ii) The pressure was increased above 40 atomspheres
(c) The carbon monoxide for use in the production of methanol may be formed by reacting carbon
dioxide with hydrogen.
𝐶𝑂2 (𝑔) + 𝐻2 (𝑔) ⇌ 𝐶𝑂(𝑔) + 𝐻2 𝑂(𝑔); 𝐾𝑐 = 1.44 𝑎𝑡 1200 𝐾
A mixture containing 0.7moles of CO2, 0.7moles of H2, 0.3 moles of CO and 0.3 moles of H2O
was placed in a 1 dm3 flask and allowed to come to equilibrium at 1200K.
Calculate the amount, in moles, of each substance present in the equilibrium mixture at 1200 K.

34. In the contact process sulphur trioxide is obtained according to the following equation:
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 2𝑆𝑂3 (𝑔)
(a) State the conditions under which sulphur trioxide is manufactured in the contact process
(b) At a pressure of 1.50 × 105 Pa, 1.0 moles of sulfur dioxide gas was mixed with 1.0moles of
oxygen gas. The final equilibrium mixture formed was found to contain 0.5 moles of oxygen.
(i) Write an expression for Kp
(ii) Calculate the amount, in moles, of sulphur dioxide and sulphur trioxide in the equilibrium
mixture.
(iii) Determine the value of KP and state its units

35. For the gaseous equilibrium:

𝐶𝑂(𝑔) + 𝐶𝑙2 (𝑔) ⇌ 𝐶𝑂𝐶𝑙2 (𝑔)
(a) Write the expression for the equilibrium constant Kc
(b) The concentrations of the various species at a particular temperature are given below.
[CO] = 0.800 moldm-3
[Cl2] = 0.600 moldm-3
[COCl2] = 0.200 moldm-3
Calculate the value of the equilibrium constant Kc, giving appropriate units.
(c) If the pressure of the system is suddenly increased so that the volume halves, calculate
i) the new concentrations
ii) the value of Kc
(d) What would be the effect on equilibrium of halving the volume of the container? Explain your
answer.
36. Consider the reaction: 𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔). When 46 g of I2 and 1.00 g of H2 are heated to
470oC, the equilibrium mixture contains 1.90 g of I2.
(a) How many moles of each gas are present at equilibrium?
(b) Calculate the equilibrium constant, Kc at 470oC.

37. The following equilibrium was established between dinitrogen tetra oxide and nitrogen dioxide.
𝑁2 𝑂4 (𝑔) ⇌ 2𝑁𝑂2 (𝑔; 𝐾𝐶 = 41 𝑎𝑡 500𝐾
1.0 moles of N2O4 and 1.0 moles of NO2 were mixed in a one litre container at 500K.

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 (a) Determine the direction of the reaction. Explain your answer.
(b) Determine the concentration of each gas at equilibrium.

References
1. Freemantle H.F (1987). Chemistry in Action, 1st Edition, Palgrave Macmillan.
2. Heys, H.L, (1986). Physical chemistry, 6th Edition. Oxford, Heinman Education Books
Limited.
3. Ramsden E.N (1994). A level Chemistry, 3rd Edition, London: Stanley Thornes Ltd.
4. Talbot C, (2015). Chemistry for the IB Diploma, 2nd Edition, Hodder Education.
5. Steven O, (2014). Chemistry for the IB Diploma, 2nd Edition, Cambridge, Latmer Trend.
6. Sergey B, (2014). Chemistry Course Companion IB Diploma Program, 1st Edition 2014,
Oxford University Press.
7. Lawrie R, (2014). Cambridge International AS and A Level Chemistry Course book, 2nd
Edition, Cambridge University Press
8. Graham H, (2000).Chemistry in context, 5th Edition, Nelson Thornes.
9. Liptrot G.Fl, (1982). Modern Physical Chemistry, 1st Edition, Collins Educational.
10. Green J, (2009). Higher Level Chemistry for IB Diploma, Pearson.
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Melbourne: Pearson Education Australia.
12. Rosenberg J.L (2007). Theory and Problems of College Chemistry, 9th Edition, Schaum’s
Outline Series, McGraw-Hill.

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