CHEMICAL EQUILIBRIA

H2 Chemistry Remedial Practice

1 Applying Le Chatelier’s Principle

1.1 If a dynamic equilibrium is disturbed by changing the conditions, the position of

equilibrium moves to counteract the change.

1.2 Worked Example

In relation to the following equilibria,

Equilibrium I
H2O(g) + C(s) Ý H2(g) + CO(g); H = +131 kJ mol−1

Equilibrium II
2CrO42−(aq) + 2H+(aq) Ý Cr2O72−(aq) + H2O(l)

use Le Chatelier’s principle to predict and explain the effect of

(a) increasing the pressure on Equilibrium I,
(b) Increasing the temperature on Equilibrium I,
(c) Increasing [H+(aq)] on Equilibrium II.

(a) In Equilibrium I, there is 1 mol gaseous reactant and 2 mol gaseous products.
According to Le Chatelier’s Principle, an increase in pressure shifts
equilibrium position left to favour the side of the reaction with fewer moles
of gas molecules, so as to reduce the increase in pressure.

(b) When temperature is increased, according to Le Chatelier’s Principle,

equilibrium position shifts right to favour the forward endothermic reaction
which absorbs the excess heat.

(c) When [H+(aq)] increases, according to Le Chatelier’s Principle, equilibrium

position shifts right as CrO42− reacts with some of the excess H+ ions so that
the increase in [H+(aq)] is reduced.

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2 Equilibrium Constant, Kc

2.1 Consider H2(g) + I2(g) Ý 2HI(g),

When equilibrium is established at 764 K, the mixture was found to contain 2.484
10−3 mol dm−3 hydrogen, 2.514 10−3 mol dm−3 iodine and 1.695 10−3 mol dm−3
hydrogen iodide. Calculate a value for Kc at this temperature.

Note:
 Although 1 mol H2 reacts with exactly 1 mol I2, it does not
necessary mean that [H2] is equal to [I2] at equilibrium.
 [H2] would only be equal to [I2] at equilibrium if
they are mixed initially in exactly the right proportions, i.e.
1 H2 : 1 I2.
only HI is present initially.

[HI] 2
KC
[H2 ][I2 ]
(1.695 10- 3 )2
(2.484 10- 3 )(2.514 10 3 )
46.0

2.2 Consider CH3COOC2H5(l) + H2O(l) Ý CH3COOH(l) + C2H5OH(l),

Exactly 1 mol CH3COOC2H5 was mixed with exactly 1 mol H2O in the presence of an
acid catalyst and allowed to reach equilibrium. The equilibrium mixture was analysed
and found to contain 0.300 mol ethanoic acid. Calculate a value for Kc at the
temperature of the reaction.

CH3COOC2H5(l) + H2O(l) Ý CH3COOH(l) + C2H5OH(l)

Initial / mol 1 1 0 0
Change / mol –0.300 –0.300 +0.300 +0.300
1 – 0.300 1 – 0.300
Eqm / mol 0.300 0.300
0.700 = 0.700
0.700 0.700 0.300 0.300
Eqm / mol dm−3
V V V V

[CH3COOH][C 2H5OH]
KC
[CH3COOC2H5 ][H 2O]
0.300 0.300
V V
0.700 0.700
V V
0.184

Note:
−3
 Concentrations (in mol dm ) must be used in the equilibrium
constant expression, not numbers of moles.
 Since volume of the mixture is not given, let V be the
volume. Conveniently, all “V” terms cancel out in this
example.

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3 Practice Questions Involving Equilibrium Constant, Kc

3.1

[43.9 mol−1 dm3]

3.2

[(a) 2.00 10−3 mol dm−3]

3.3

[0.643]

3.4

[0.0218]

3.5

[4.01]

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3.6

[0.249]

3.7

[0.050 mol]

3.8

[96 %]

3.9

[(b) (w = 1, f = 0.80), (w = 10, f = 0.75)]

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4 Equilibrium Constant, Kp

4.1 For reactions involving gases, it is much easier to measure gas pressures than gas
concentrations.

4.2 For a gas, concentration and pressure are proportional to each other at constant
temperature:
n
P RT
V
n
At constant temperature, P = concentration
V

4.3 For gaseous equilibria, it makes more sense to quote an equilibrium constant in
terms of pressures rather than concentrations.

4.4 Some Important Terms

4.4.1 Mole Fraction

If you have a mixture of gases (A, B, C etc.), the mole fraction of gas A is given as
follows:
number of moles of gas A
xA
total number of moles of gas

For example, if a mixture of nitrogen and hydrogen contains 25 % by volume of

nitrogen, the mole fraction of nitrogen is 0.25, and the mole fraction of hydrogen is
0.75.

4.4.2 Partial Pressure

The partial pressure of one of the gases in a mixture is the pressure which it would
exert if it alone occupied the whole container. The total pressure is made up of the
sum of the individual partial pressures.

Total pressure PT = PA + PB + PC + …

PA = xA PT

4.4.3 Consider A(g) Ý 2B(g) + C(g)

PB2 PC
Kp
PA
where PA, PB and PC are partial pressures of A, B and C respectively

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4.4.4 Consider N2O4(g) Ý 2NO2(g),

A vessel containing only dinitrogen tetroxide was held at a temperature of 350 K until
equilibrium was established. The equilibrium pressure was 123 kPa and the mole
fraction of nitrogen dioxide was found to be 0.800. Calculate the value of Kp at this
temperature.

N2O4(g) Ý 2NO2(g)
Mole fractions at eqm 1 – 0.800 = 0.200 0.800
Partial pressures / kPa 0.200 123 = 24.6 0.800 123 = 98.4

2
PNO
Kp 2

PN2O4
(98.4)2
24.6
394 kPa

5 Practice Questions Involving Equilibrium Constant, Kp

5.1

[160 kPa]

5.2

[11.7 kPa]

5.3

[0.0185]

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5.4

[8.10]

5.5

[29 900 atm−1]

5.6

[1.68 atm]

5.7

[(a) Moles of PSO2 = 1.00 mol, Moles of PO2 = 0.50 mol, Moles of PSO3 = 1.00 mol;
(b) PSO2 = 0.400 P, PO2 = 0.200 P, PSO3 = 0.400 P; (c) P = 38.5]

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5.8

[(a) Moles of N2O4 = 80.0, Moles of NO2 = 40.0;

(b) PN2O 4 = 0.667 P, PNO2 = 0.333 P;
(c) P = 0.690 atm;
(d) PN2O 4 = 0.460 atm, PNO2 = 0.230 atm]

5.9

[(a) PCl 2 = p, PPCl3 = p, PPCl5 = 400 – 2p;

(b) p = 139 kPa;
(c) PCl 2 = 139 kPa, PPCl3 = 139 kPa, PPCl5 = 122 kPa]

6 Equilibrium Constants for Heterogeneous Equilibria

6.1 In a heterogeneous equilibrium, more than one phase is present:

 gases in contact with solids
 gases in contact with liquids
 solids in contact with liquids

6.2 When writing an expression for the equilibrium constant for a heterogeneous
equilibrium, terms for pure solids or pure liquids are left out of the expression.

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7 Practice Questions Involving Heterogeneous Equilibria

7.1

[14.1 atm]

7.2

[f = 0.69]

7.3

[30 atm]

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