TUTORIAL 5 – Chemical Equilibrium

1. Write expressions for the equilibrium constant Kc and state

its units for each of the following reactions:
(a) 2CO(g) + O2(g) 2CO2(g)

[CO2 ] 2
Kc 
[CO ] 2 [O2 ]
(mol dm 3 ) 2
Unit of K c 
(mol dm 3 ) 2 (mol dm 3 )
= mol-1 dm3
(b) CaCO3(s) CaO(s) + CO2(g)

K c  [CO2 ]

Unit of Kc = mol dm-3

(c) 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

[ H 2 ]4
Kc 
[H 2O]4
(mol dm 3 ) 4
Unit of K c 
(mol dm 3 ) 4
= No units
(d) Co(H2O)62+(aq) + 4Cl-(aq) CoCl42-(aq) + 6H2O(l)
2
[CoCl 4 ]
Kc  2
[Cl  ] 4 [Co( H 2 O) 6 ]

(mol dm 3 )
Unit of K c 
(mol dm 3 ) 4 (mol dm 3 )
= mol-4 dm12
(e) NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

[ NH 4 ][OH  ]
Kc 
[ NH 3 ]

(mol dm 3 )(mol dm 3 )
Unit of K c 
(mol dm 3 )
= mol dm-3
2. Dynamic equilibrium exists between phosphorus trichloride
(PCl3), chlorine gas (Cl2) and phosphorus pentachloride (PCl5)
as follows:
PCl3(g) + Cl2(g) PCl5(g)
(a) What is meant by the term dynamic equilibrium?

A dynamic equilibrium is one where

 Rate of forward reaction = Rate of backward reaction
 The substances are still reacting together even though the
concentration of the reactants and products remains constant.
2(b) The equilibrium mixture in a 9.00 dm3 vessel contained
0.360 mol of PCl3, 0.360 mol of Cl2 and 0.250 mol of PCl5.
Calculate Kc for this reaction at 225C.

[PCl5 ]
Kc 
[PCl3 ][Cl2 ]
0.250
[ PCl 5 ]  mol dm 3
9
0.360
[ PCl 3 ]  mol dm 3
9
0.360
[Cl 2 ]  mol dm 3
9
0.250
( )
Kc  9  17.4 mol 1 dm 3
0.360 0.360
( )( )
9 9
 3. Consider the following reaction:
CO(g) + Cl2(g) COCl2(g)
When 2.00 mol of CO and 3.50 mol of Cl2 are added to a 5.00
dm3 vessel at 395C, 1.25 mol of COCl2 is formed at
equilibrium. Calculate Kc for this reaction at 395C.

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

Initial no. of mol 2.00 3.50 0

Change in no. of mol – 1.25 – 1.25 + 1.25
No. of mol at Eqm 0.75 2.25 1.25

[COCl 2 ]
Kc 
[CO ][Cl 2 ]
1 .25
5
=  0 .75  2 .25 
 5  5 
= 3.70 mol-1 dm3
 4. Consider the following reaction:
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
(a) When 8.28g of C2H5OH were heated with 60g of CH3COOH,
50.04g of CH3COOH remained at equilibrium at 500C.
Calculate the value of Kc at 500C.
8.28
Initial no. of mol of C2H5OH = 2(12)  6(1)  16 = 0.180 mol
60
Initial no. of mol of CH3COOH = 2(12)  4(1)  2(16) = 1.00 mol
50.04
No. of mol of CH3COOH at equilibrium = 2(12)  4(1)  2(16) = 0.834 mol

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

Initial no. of mol 1.00 0.180 0 0
Change in no. of
-0.166 -0.166 +0.166 +0.166
mol
No. of mol at Eqm 0.834 0.014 0.166 0.166

Let the volume of the vessel be V dm3.

[CH 3COOC2 H 5 ][ H 2O]
Kc 
[CH 3COOH ][C2 H 5OH ]

 0.166  0.166 
  
 V  V 
=  0.834  0.014  = 2.36
  
 V  V 
 (b) What mass of CH3COOC2H5 should be present in the
equilibrium mixture formed at 500C when 13.8g of
C2H5OH and 12g of CH3COOH were heated?
13.8
Initial no. of mol of C2H5OH = 2(12)  6(1)  16 = 0.300 mol

12
Initial no. of mol of CH3COOH = 2(12)  4(1)  2(16) = 0.200 mol

Let the no. of mol of CH3COOC2H5 formed at equilibrium be x.

CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
Initial no. of mol 0.200 0.300 0 0
Change in no. of
-x -x +x +x
mol
No. of mol at Eqm 0.200 - x 0.300 - x x x

Let the volume of the vessel be V dm3.

[CH 3COOC2 H 5 ][ H 2O]

Kc 
[CH 3COOH ][C2 H 5OH ]
 x  x 
  
 V  V 
2.36 =  0.200  x  0.300  x 
  
 V  V 

1.36x2 – 1.18x + 0.1416 = 0

x = 0.724 (rejected) or 0.144
 Therefore, no. of mol of CH3COOC2H5 formed at
equilibrium
= 0.144 mol

Mass of CH3COOC2H5 present at equilibrium

= 0.144 [4(12)+8(1)+2(16)]
= 12.7g

5. When a mixture containing 2:1 ratio of NO and O2 at a total

initial pressure of 3 atm is allowed to react at 400C, the
partial pressure of NO2 formed at equilibrium was found to
be 1.76 atm.
(a) Calculate the equilibrium partial pressures of NO and O2.

Let the initial no. of mol of O2 be x.

Therefore, initial no. of mol of NO = 2x
2x
Initial partial pressure of NO = 3 x  3

= 2 atm
x
Initial partial pressure of O2 = 3 x  3

= 1 atm
2NO(g) + O2(g) 2NO2(g)

Initial partial pressure / atm 2 1 0

Change in partial pressure / atm – 1.76 – 0.88 + 1.76
Partial pressure at Eqm / atm 0.24 0.12 1.76
 Equilibrium partial pressure of NO = 0.240 atm
Equilibrium partial pressure of O2 = 0.120 atm

(b) Hence, determine the percentage conversion of NO

and the equilibrium constant Kp.
1.76
% conversion of NO = 2  100 %

= 88.0 %

P  2

Kp 
NO2

PNO 2 PO 2

(1.76) 2
= (0.24) 2 (0.12)

= 448 atm-1
6. Nitrogen and hydrogen gases are related in a 1:3 mole ratio at
700K. Calculate the total pressure required to achieve 30%
yield of ammonia at equilibrium given that the Kp for this
reaction at 700 K is 2.18 x 10-6 atm-2.
N2(g) + 3H2(g) 2NH3(g)

Let the initial no. of mol of N2 be x

Theoretical yield of NH3= 2x mol
Actual yield
% yield = Theoretica l yield  100 %

Actual yield
30% =  100 %
2x
Actual yield of NH3 = 0.6x mol
Therefore, no. of mol of NH3 formed at equilibrium = 0.6x mol
N2(g) + 3H2(g) 2NH3(g)

Initial no. of mol x 3x 0

Change in no. of
– 0.3x – 0.9x +0.6x
mol
No. of mol at Eqm 0.7x 2.1x 0.6x

Total no. of mol at equilibrium = 0.7x + 2.1x + 0.6x

= 3.40x mol

Let P be the total pressure at equilibrium.

At equilibrium,
 0 .7 x 2.1x
PN 2  P PH 2  P
3.40 x 3.40 x
0.6 x
PNH 3  P
3.40 x

P  2


NH 3

P P 
Kp 3
N2 H2

2
 0 .6 
 P
 3 .4 
2.18 x 10-6 = 0 .7  2 .1 
3

P P
3 .4  3 .4 

P = 543 atm

7. (a) State Le Chatelier's Principle.

If a system in equilibrium is subjected to a change which
disturbs the equilibrium, the system responds in such a
way so as to counteract the effect of the change.

(b) In relation to the following equilibrium,

Equilibrium I
H2O(g) + C(s) H2(g) + CO(g) H = +131 kJmol-1
Equilibrium II
2CrO4-(aq) + 2H+(aq) Cr2O72-(aq) + H2O(l)

Use Le Chatelier's Principle to predict and explain the effect of

 (i) increasing the pressure on Equilibrium I

(ii) increasing the temperature on Equilibrium I

(iii) increasing [H+(aq)] on Equilibrium II

(b) (i) increasing the pressure on Equilibrium I

 No. of mol of gaseous products > No. of mol of gaseous
reactants
 By Le Chatelier’s Principle, equilibrium shift to the left
towards the reduction in total no. of mol of gas.

(ii) increasing the temperature on Equilibrium I

 System reacts in such a way so as to absorb the heat.
 By Le Chatelier’s Principle, equilibrium shifts to the right
towards the endothermic reaction to absorb the heat.

(iii) increasing [H+(aq)] on Equilibrium II

 By Le Chatelier’s Principle, equilibrium shift right to
decrease the concentration of H+
8. The graphs show the effects of temperature and pressure
on the decomposition substance A into products B and C.
All three substances are gases.

Graph I Graph II

(a) From the graphs, predict the effect of

(i) pressure on the percentage of B and C in the
equilibrium mixture

Decomposition of A:

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

Increasing the pressure (from 1000 to 1500 kPa)

causes an increase in the % of A remaining in the
equilibrium mixture.
Therefore, the % of B and C decreases.

(ii) temperature on the percentage of B and C in the

equilibrium mixture
 Decomposition of A:

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

Increasing the temperature (from 300oC to 500oC)

causes a decrease in the % A remaining in the
equilibrium mixture.
Hence, the % of B and C increases.

(b) Is the decomposition of A exothermic or

endothermic? Explain your answer.

From the Graph I, an increase in temperature causes

an increase in the % of B and C.

Decomposition of A:

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

The position of equilibrium shifted to the right.

When temperature is increased, system reacts in such a

way so as to absorb the heat.

By Le Chatelier’s Principle, the equilibrium shifts in the

direction favouring the endothermic reaction so as to
absorb the heat.

Therefore, forward reaction is endothermic.

 (c) Explain why the graphs show that the reaction
cannot be:
2HI(g) H2(g) + I2(g)

2 mol 2 mol

Total no. of mol gaseous reactants = Total no. mol of gaseous products
 Any change in pressure would NOT affect the equilibrium of
the above reaction.
However, from Graph II, an increase in pressure causes a
decrease in the % of B and C.

Decomposition of A:

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

The position of equilibrium shifted to the left.

9. Equal no of moles of A and B reacted together to reach

equilibrium in the reaction below.

Graph I shows the results of this reaction

 A (g) + B (g) C (g) + D (g) H = + 100 kJ

The experiment was repeated several times under different

conditions given below.

Choose from Graphs II to VI the most likely graph that would be

obtained in each case. Give a reason for your choice.

(a) The experiment was repeated using a catalyst.

Graph II

Reason:
 Catalyst increases the rate of the forward and backward
reactions to the same extent hence the equilibrium is
reached faster (steeper gradient indicate faster rate)
 Catalyst has NO EFFECT on the concentration of the
products and reactants hence no. of moles of A
remaining remains unchanged.
(b) The experiment was repeated using a higher temperature
A (g) + B (g) C (g) + D (g) H = + 100 kJ

Graph III

Reason:
 By Le Chatelier’s Principle, increasing the temperature
causes the equilibrium to shift right towards the
endothermic reaction to absorb heat.
 Hence the no. of moles of A remaining would decrease.
 Since rate of reaction is proportional to temperature,
rate of reaction would increase and the equilibrium would
be reached faster.

(c) The experiment was repeated using a lower temperature.

A (g) + B (g) C (g) + D (g) H = + 100 kJ

Graph VI

Reason:
 By Le Chatelier’s Principle, decreasing the temperature
causes the equilibrium to shift left towards the
exothermic reaction to generate heat.
 The no. of moles of A remaining would increase.
  Since rate of reaction is proportional to temperature,
rate of reaction would decrease and the equilibrium
would be reached slower.

(d) The experiment was repeated using a higher pressure.

A (g) + B (g) C (g) + D (g) H = + 100 kJ

Graph II
 There is no change in the total number of moles of gas in
the gaseous reaction.
 Total number of mole of reactants (g) = Total number of
mole of products (g)
 Any pressure changes will have no effect on the
temperature of the equilibrium mixture and will not change
the position of the equilibrium.
 The reactants for both the forward and backward reactions
are gases, hence an increase in pressure increases the rate
of both the forward and backward reactions to the same
extent. The equilibrium is reached faster.
Multiple Choice Questions
1. The dissociation of dinitrogen tetraoxide into nitrogen dioxide is represented by the
equation below.

N2O4 (g) 2NO2 (g); ∆HӨ = +57.2 kJ mol-1

If the temperature of an equilibrium mixture of the gases is increased at constant

pressure, the volume of the mixture will

A increase, but only because of a shift of equilibrium towards the right.

B increase, both because of a shift of equilibrium towards the right and also
because of thermal expansion
C stay the same, because any thermal expansion could be exactly counteracted by
a shift of equilibrium towards the left.
D decrease, because a shift of equilibrium towards the left would more than
counteract any thermal expansion.

2. For the reaction

Ag2CO3 (s) Ag2O (s) + CO2 (g)

the value of the equilibrium constant Kp is 3.16 x 10-3 atm at 298 K, and is 1.48 atm at
500 K.

Which one of the following statements is correct?

A The value of ∆H for the forward reaction is negligible.

B The yield of carbon dioxide will increase at higher pressure.
C The yield of carbon dioxide is independent of temperature.
D The forward reaction is endothermic.

3. The equilibrium constant for the reaction H2 (g) + I2 (g) 2HI (g) is 60 at 450 °C.
The number of moles of hydrogen iodide in equilibrium with 2 mol of hydrogen and
0.3 mol of iodine at 450 °C is

A 1 / 100
B 1 / 10
C 6
D 36

4. A gas X dissociates on heating to set up the equilibrium below.

X (g) Y (g) + Z (g)

A quantity of X was heated at constant pressure p at a certain temperature. The

equilibrium partial pressure of X was found to be 1/7 p. What is the equilibrium
constant Kp at this temperature?

A 6/7p
 B 9/7p
C 36 / 7 p
D 6p

5. Which one of the following systems will have an increased proportion of products at
equilibrium, in separate experiments, both when the pressure is reduced at constant
temperature and when the temperature is increased at constant pressure?

A N2 (g) + 3H2 (g) 2NH3 (g); ∆H = –92kJ mol-1

B N2O4 (g) 2NO2 (g); ∆H = +57kJ mol-1

C 2SO2 (g) + O2 (g) 2SO3 (g); ∆H = –197kJ mol-1

D H2 (g) + I2 (g) 2HI (g); ∆H = +53kJ mol-1

6. Two equilibria are shown below.

reaction I: 2X2 (g) + Y2 (g) 2X2Y (g)

reaction II: X2Y (g) X2 (g) + ½ Y2 (g)

The numerical value of Ke for reaction I is 2. Under the same conditions, what is the
numerical value of Ke for reaction II?

A 1 / √2
B ½
C ¼
D -1

7. A sample of 1 mol of N2O4 was placed in an empty 1 dm3 container and allowed to
reach equilibrium according to the following equation.

N2O4 (g) 2NO2 (g)

At equilibrium, x mol of the N2O4 had dissociated. What is the value of the equilibrium
constant, Kc, at the temperature of the experiment?

A 2x / (1 – x)2
B 2x2 / (1 – x)
C 4x / (1 – x)
D 4x2 / (1 – x)

8. An equilibrium is represented by the following equation.

N2 (g) + 3H2 (g) 2NH3 (g); ∆HӨ = –x kJ mol-1

Which of the following changes would affect both the value of the equilibrium
constant, Kp and the proportion of ammonia present at equilibrium?

A adding a catalyst of finely divided iron

B reducing the temperature
C increasing the mass of nitrogen
D increasing the pressure
9. A nitrogen-hydrogen mixture, initially in the mole ratio of 1:3, reached equilibrium
with ammonia when 50% of the nitrogen had reacted. The total final pressure was p.

N2 + 3H2 2NH3

What was the partial pressure of ammonia in the equilibrium mixture?

A p/8
B p/6
C p/4
D p/3

10. Nitrogen dioxide decomposes on heating according to the following equation,

2NO2 (g) 2NO (g) + O2 (g)

When 4 mol of nitrogen dioxide were put into a 1 dm3 container and heated, the
equilibrium mixture contained 0.8 mol of oxygen.

What is the numerical value of the equilibrium constant, Kc, at the temperature of the
experiment?

A 0.8 x 0.8 / 2.4

B 0.82 x 0.8 / 42
C 1.6 x 0.8 / 2.42
D 1.62 x 0.8 / 2.42

11. The equilibrium

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

is established with the gases having the following partial pressures, p

(arbitrary units)

gas p
N2 1
H2 9
NH3 1

What is the numerical value of the equilibrium constant, Kp?

A 1 / 729
B 1 / 27
C 1/9
D 9

12. In the mixture of NO and CO2 (initially containing 4 mol of NO and 0.9 mol of CO2)
reaction occurs according to the equation below.

NO (g) + CO2 (g) NO2 (g) + CO (g)

At equilibrium, 0.1 mol of CO2 was present. What is the equilibrium constant, Kc, at
the temperature of this experiment?

A 0.2
B 0.5
C 1.6
D 2.0