Equilibria by Xhex

7
7.1 Chemical Equilibria

7.2 Ionic Equilibria
7.3 Partition Coefficients
7.1 Chemical Equilibria

Reversible Reactions
 A reversible reaction is one which

can be made to go in either
direction depending on the
conditions.
 As the reaction proceeds, the rate

of the forward reaction decreases
and the rate of the reverse
reaction increases. Eventually, the
reaction will reach a stage where
both forward and backward
reactions are proceeding at the
same rate.
Fig.7.1 Relationship between rate of forward and backward
reactions at equilibrium
 Dynamic equilibrium is when the rate of the forward reaction is equal to the rate of the backward
reaction.
Characteristics of Dynamic Equilibrium

 It can only be achieved in a closed system. A closed system is one from which reactants and products
cannot escape.
 At equilibrium, the observable properties of the system, such as concentration and colour, remain
unchanged.
 The equilibrium can be reached from either direction, i.e. the equilibrium can be achieved by starting
with reactants only, or products only, or a mixture of both.
Le Chatelier’s Principle
 “If a constraint is imposed on a system at equilibrium, the system will respond in such a way as to
oppose the effect of that constraint.” Such constraints can be the addition or removal of one of the
reactants or products, a change in pressure, a change in temperature, the addition of a catalyst, etc.
Produced by: F Mbonderi, THE SCIENCE INSTITUTE, HARARE  0777 033 011 143 | P a g e
a) Change in Concentration
 If the concentration of 𝐴 or 𝐵 is increased, the rate of 𝑨 + 𝑩 𝑪 + 𝑫

the forward reaction, but not the reverse reaction, is
increased. Therefore the equilibrium position moves
Position of equilibrium moves to the right
to the right.
if:
 If the concentration of 𝐴 or 𝐵 is decreased, the rate 1. the concentration of A or B is
of the forward reaction, but not the reverse reaction, increased, or
is decreases. Therefore the equilibrium shifts to the 2. the concentration of C or D is
left. decreased.
 If the concentration of a product (𝐶 or 𝐷) is increased, 𝑨 + 𝑩 𝑪 + 𝑫

the position of equilibrium shifts to the left to
counteract that. Decreasing the concentration of 𝐶 or
𝐷 will move equilibrium position to the right. Position of equilibrium moves to the left if:
. 1. the concentration of A or B is
decreased, or
2. the concentration of C or D is
increased.
b) Change in Pressure
The pressure in a system is proportional to the number of moles of gas molecules present per unit
volume.
Le Chatelier's Principle predicts that:
 If the pressure of a system at equilibrium is

𝑨(g) + 𝟐𝑩(g) 𝑪(g) + 𝑫(g)
increased, the equilibrium position shifts to the side
which has fewer gas moles.
 If the pressure is increased,
equilibrium position shifts to the right.
 If the pressure of the system is decreased, the
 If the pressure is decreased, the
equilibrium will move towards the side which has
equilibrium position shifts to the left.
more gas moles.
 If the number of gas moles on both sides is the same, then pressure has no effect on the equilibrium
position.
 Example 1: 𝟐𝑺𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑺𝑶𝟑 (𝒈)

There are 3 moles of gas to the left side, and 2 moles of gas to the right side of the equation. If the
pressure is increased, the system will move to the right. If the pressure is decreased, the system will
move to the left.
 Example 2: 𝟐𝑯𝟐 𝑺(𝒈) + 𝑺𝑶𝟐 (𝒈) 𝟑𝑺(𝐬) + 𝟐𝑯𝟐 𝑶(𝒈)

There are 3 moles of gas to the left side, and 2 moles of gas to the right side of the equation. If the
pressure is increased, the system will move to the right. If the pressure is decreased, the system will
move to the left.
 Example 3: 𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)

There are 2 moles of gas to the left side, and 2 moles of gas to the right side of the equation. Changing
the pressure will have no effect on the position of this equilibrium.
NB: Since pressure is inversely proportional to volume, an increase in volume is taken as a decrease
in pressure, and vice versa.
c) Change in Temperature
In this case one needs to know whether the reaction is exothermic or endothermic.
 An increase in temperature will 𝑨 + 𝑩 𝑪 + 𝑫, ∆𝑯 = −250 kJmol−1

favour the endothermic side of If the forward reaction is exothermic, then an increase in
the reaction, and a decrease in temperature will cause the system to shift to the left, and a
temperature will favour the decrease in temperature will cause the system to shift to the right.
exothermic side of the reaction.
 If the forward reaction is endothermic, then an increase in temperature will cause the equilibrium to
shift to the right, and a decrease in temperature will cause the equilibrium to shift to the left.
 If ∆𝐻 = 0, then a change in temperature will have no effect on the position of equilibrium.
 Example 1: 𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) 𝟐𝑵𝑯𝟑 (𝒈), ∆𝐇 < 𝟎

The forward reaction is exothermic and so is favoured by decreasing the temperature. The reverse
reaction is endothermic and so is favoured by increasing the temperature.
 Example 2: 𝑪𝒂𝑪𝑶𝟑 (𝒔) 𝑪𝒂𝑶(𝒔) + 𝑪𝑶𝟐 (𝒈), ∆𝐇 > 𝟎

The forward reaction is endothermic and so is favoured by increasing the temperature. The reverse
reaction is exothermic and so is favoured by decreasing the temperature.
d) Adding a Catalyst
 The addition of a catalyst has no effect on the position of equilibrium. This is because a catalyst speeds
up the rate of the forward and the backward reaction by the same factor. The position of equilibrium
remains unchanged.
Chemical Equilibria in the Chemical Industry

 Many large-scale industrial processes involve reversible reactions, and Le Chatelier’s Principle can be
used to predict the conditions which will maximise the yield (amount of product formed).
 However, when choosing the best conditions for an industrial reaction, other factors which must be
considered are:
1. The yield of product;
2. The rate of reaction;
3. The cost of maintaining the reaction conditions.
a) The Contact Process

 An important step in the manufacture of sulphuric acid by the Contact Process is the conversion of
sulphur dioxide to sulphur trioxide:
𝟐𝑺𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑺𝑶𝟑 (𝒈), ∆𝐻 = −197 kJmol−1 .
 The reaction is exothermic, and has fewer moles of gas going forward. Thus Le Chatelier’s Principle
predicts that the best yield is obtained if the temperature is low and the pressure is high.
 But such conditions are not used because:

i) At low temperature, the rate of reaction would be too slow.
ii) At high pressure, the production cost becomes high in terms of the maintenance costs and the
strong vessels needed to withstand the high pressure.
The optimum conditions for this reaction are 400 – 450°C, 1-2 atm pressure and a vanadium (V) oxide
catalyst. Under these conditions, a 99.5% yield is achieved.
Fig.7.2 Flow diagram for the manufacture of sulphur trioxide
 The sulphur trioxide formed is not directly dissolved in water to produce sulphuric acid. This is because
such a reaction is so highly exothermic that it would turn the sulphuric acid into mist which would be
difficult to condense. Instead, the sulphur trioxide is absorbed in concentrated sulphuric acid to form
oleum which can then be safely diluted:
𝟐𝑺𝑶𝟑 (𝒈) + 𝑯𝟐 𝑺𝑶𝟒 (𝒍) 𝑯𝟐 𝑺𝟐 𝑶𝟕 (𝒍)
(oleum)
𝑯𝟐 𝑺𝟐 𝑶𝟕 (𝒍) + 𝑯𝟐 𝑶(𝒍) 𝟐𝑯𝟐 𝑺𝑶𝟒 (𝒂𝒒)
b) The Haber Process

 The Haber Process involves the manufacture of ammonia by the following reaction:
𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) 𝟐𝑵𝑯𝟑 (𝒈), ∆𝐻 = −92 kJmol−1 .
 The reaction is exothermic, and has fewer moles of gas going forward. Thus Le Chatelier’s Principle
predicts that a high yield is obtained if the temperature is low and the pressure is high.
 But such conditions are not used because:

i) At low temperature, the rate of reaction would be too slow.
ii) At high pressure, the production cost becomes high in terms of strong vessels needed to withstand
the high pressure, and the maintenance costs.
The optimum conditions for this reaction are 450°C, 200 atm pressure and iron powder catalyst. Under
these conditions, a 15% yield is achieved. The unreacted nitrogen and hydrogen are recycled.
Fig.7.3 Flow diagram for the manufacture of ammonia
 The forward reaction can also be favored by removing ammonia from the system from time to time
by liquefying it.
Equilibrium Constants
 An equilibrium constant is the ratio of the equilibrium concentrations of the products raised to
appropriate powers, to the equilibrium concentrations of the reactants raised to appropriate powers.
“Appropriate power” in this case refers to the stoichiometric coefficients. 𝐾𝑐 is the equilibrium constant
in terms of concentration; 𝐾𝑝 is in terms of partial pressure.
 For the reversible reaction

𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) 𝟐𝑵𝑯𝟑 (𝒈),
[𝑁𝐻3 ]2 𝑷𝟐 (𝑁𝐻3 )
𝑲𝒄 = 𝑲𝒑 =
[𝑁2 ] [𝐻2 ]3 𝑷(𝑁2 ) 𝑷𝟑 (𝐻2 )
Units: 𝒎𝒐𝒍−𝟐 𝒅𝒎𝟔 Units: 𝑷𝒂−𝟐
Factors Affecting Equilibrium Constants

 If the reaction is exothermic, then an increase in temperature will cause the value of 𝐾𝑐 or 𝐾𝑝 to
decrease. If the reaction is endothermic, then an increase in temperature will cause the value of 𝐾𝑐 or
𝐾𝑝 to increase.
 Pressure, concentration and use of catalyst have no effect on an equilibrium constant.
 Table 7.1 below shows the effects of various factors on equilibrium position and on equilibrium
constants.
Effect on equilibrium Effect on equilibrium

Change Type of change
position constant
Add reactant or remove
Moves to the right No effect
product
Concentration
Add product or remove
Moves to the left No effect
reactant
Moves to side with
Increase pressure No effect
fewer gas moles
Pressure
Moves to side with
Decrease pressure No effect
more gas moles
Catalyst Add/remove catalyst No effect No effect
𝐾𝑐 or 𝐾𝑝 decreases if
Moves to endothermic
Increase temperature ∆𝑯 < 𝟎.
side
Temperature
Moves to exothermic 𝐾𝑐 or 𝐾𝑝 increases if
Decrease temperature
side ∆𝑯 > 𝟎.
Table 7.1 Effects of various factors on equilibrium position and equilibrium constant
Question
1.00 mol nitrogen and 3.00 mol hydrogen are reacted at constant temperature in a 1.00 𝒅𝒎𝟑 vessel. At equilibrium,
0.40 mol of nitrogen has reacted. Calculate 𝐾𝑐 .
Solution
To obtain the concentrations of each substance at equilibrium, first obtain the amount (moles) of each substance at
equilibrium.
Every 1.00 mol of nitrogen reacts with 3.00 moles hydrogen, so the 0.40 mol of nitrogen that have reacted, have reacted
with 1.20 mol hydrogen.
Every 1.00 mol of nitrogen that reacts will from 2.00 mol ammonia, so 0.40 mol nitrogen form 0.8 mol ammonia:
𝑵𝟐 (g) + 𝟑𝑯𝟐 (g) 𝟐𝑵𝑯𝟑 (g),

Initial moles: 1.00 3.00 0
Moles at equilibrium: 0.60 1.80 0.80
(0.40 reacted) (3x0.40 reacted) (2x0.40 formed)
𝑛
Equilibrium concentration :( ) 0.60 1.80 0.80
𝑉
Calculation of 𝐾𝑐 :
[𝑁𝐻3 ]2 (0.80)2
𝐾𝑐 = 3
= = 𝟎. 𝟏𝟖𝟑 𝒎𝒐𝒍−𝟐 𝒅𝒎𝟔 .
[𝑁2 ] [𝐻2 ] (0.60)(1.80)3
Question
1.00 mol nitrogen and 3.00 mol hydrogen are reacted at 200 atm pressure. At equilibrium, 0.40 mol of nitrogen
has reacted. Calculate 𝐾𝑝 .
Solution
Obtain equilibrium amounts as before. Then obtain equilibrium mole fraction for each substance, as well as its
equilibrium partial pressure. Formulae for mole fraction and partial pressure are as below, using nitrogen as an
example:
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
Equilibrium mole fraction of 𝑁2 = 𝑡𝑜𝑡𝑎𝑙 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑚𝑜𝑙𝑒𝑠
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚

Equilibrium partial pressure of 𝑁2 = 𝑡𝑜𝑡𝑎𝑙 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑚𝑜𝑙𝑒𝑠
𝑥 𝑡𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
Calculation of 𝐾𝑝
𝑵𝟐 (g) + 𝟑𝑯𝟐 (g) 𝟐𝑵𝑯𝟑 (g),
Initial moles: 1.00 3.00 0
Moles at equilibrium: 0.60 1.80 0.80
Total moles at equilibrium = 0.60 + 1.80 + 0.80 = 3.20
0.60 1.80 0.80
Equilibrium mole fraction :
3.20 3.20 3.20
0.60 1.80 0.80

Equilibrium partial pressure: 𝑥200 𝑥200 𝑥200
3.20 3.20 3.20
37.5 112.5 50
𝑃2 (𝑁𝐻3 ) (50)2
𝐾𝑝 = = = 4.68 𝑥 10−5 𝑎𝑡𝑚−2 .
𝑃(𝑁2 ) 𝑃3 (𝐻2 ) (37.5)(112.5)3
Question
Carbon monoxide is widely used in the production of methanol. It may be formed by reacting carbon dioxide with
hydrogen:
𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝑪𝑶(𝒈) + 𝑯𝟐 𝑶(𝒈), 𝐾𝑐 = 1.21 𝑎𝑡 1 000𝐾
A mixture containing 0.85 mol 𝐶𝑂2 , 0.85 mol 𝐻2 , 0.24 mol 𝐶𝑂 and 0.24 mol 𝑯𝟐 𝑶 was placed in a 1.00 𝒅𝒎𝟑 and
allowed to reach equilibrium at 1000K.
Calculate the moles of each substance present in the flask at equilibrium at 1 000K.
Solution
Initial amounts have a little of each substance in the reaction, but too much of the reactants. A good guess is that as
equilibrium is achieved, the amount of reactants will decrease while that of the products will increase.
Let the amount of each reactant decrease by x. Then the amount of each product will increase by x, since the
stoichiometric coefficients are each equal to 1.
𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝑪𝑶(𝒈) + 𝑯𝟐 𝑶(𝒈)

Initial moles: 0.85 0.85 0.24 0.24
Equilibrium moles: 0.85 – x 0.85 – x 0.24 + x 0.24 + x
[𝐶𝑂][𝐻2 𝑂] (0.24 + 𝑥)2

𝐾𝑐 = = = 1.21
[𝐻2 ][𝐶𝑂2 ] (0.85 – 𝑥)2
Taking a square root of both sides:

(0.24 + 𝑥)
= √1.21
(0.85 – 𝑥)
0.24 + 𝑥 = 1.1(0.85 – 𝑥)
1.21𝑥 = 0.695
𝑥 = 0.574
Hence the equilibrium moles are:
𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝑪𝑶(𝒈) + 𝑯𝟐 𝑶(𝒈)
∴ Equilibrium moles: 0.276 0.276 0.814 0.814
_____________________________________________________________________________________________
Practice 7.1
1. In the last century the Haber process was sometimes run at pressures of 1 000 𝑎𝑡𝑚 and higher. Now it
is commonly run at pressures below 100 𝑎𝑡𝑚.
What is the reason for this change?
A. An iron catalyst is used.
B. Maintaining the higher pressures is more expensive.
C. The equilibrium yield of ammonia is increased at lower pressures.
D. The rate of the reaction is increased at lower pressures.
2. For the reaction

𝑾(𝒂𝒒) + 𝟐𝑿(𝒂𝒒) 𝟐𝒀(𝒂𝒒) + 𝟑𝒁(𝒂𝒒)
what are the correct units for the equilibrium constant K c ?
A. moldm−3
B. mol2 dm−6
C. mol−1 dm−3
D. mol−2 dm−6
3. At a total pressure of 1.0 𝑎𝑡𝑚, dinitrogen tetraoxide is 50% dissociated at a temperature of 60 oC,
according to the following equation.
𝑵𝟐 𝑶𝟒 𝟐𝑵𝑶𝟐
What is the value of the equilibrium constant,K 𝐩 , for this reaction at 60oC?
1 2 4
A. atm B. atm C. atm D. 2atm
3 3 3
4. Which of the following changes can affect the value of the equilibrium constant?
A. Introducing a catalyst
B. Changing the concentrations of species
C. Changing the temperature inside the reaction vessel
D. Changing the initial concentrations of species
5. Which of the following best describes the relationship between K c and temperature for an endothermic
reaction?
6. Methanol can be produced by the following:

𝑪𝑶(𝒈) + 𝟐𝑯𝟐 (𝒈) 𝑪𝑯𝟑 𝑶𝑯(𝒈) + 𝑯𝑬𝑨𝑻
The conditions that are necessary to maximize the equilibrium yield of 𝐶𝐻3 𝑂𝐻 are
A. low temperature and low pressure.
B. high temperature and low pressure.
C. low temperature and high pressure.
D. high temperature and high pressure.
7. Consider the following equilibrium:

𝟒𝑵𝑯𝟑 (𝒈) + 𝟓𝑶𝟐 (𝒈) 𝟒𝑵𝑶(𝒈) + 𝟔𝑯𝟐 𝑶(𝒈)
Which of the following will cause the equilibrium to shift to the left?
A. adding 𝐻2 𝑂(𝑔)
B. removing some 𝑁𝑂(𝑔)
C. increasing the volume
D. decreasing the temperature
8. Which of the factors below is not a condition necessary for equilibrium?

A. a closed system
B. a constant temperature
C. equal forward and reverse reaction rates
D. equal concentrations of reactants and products
9. Consider the following equilibrium system:

𝟐𝑺𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑺𝑶𝟑 (𝒈), 𝐾𝑐 = 12 000 𝑃𝑎
If additional 𝑆𝑂2 is added to the system, what happens to the equilibrium and the value of K c ?
Equilibrium 𝐾𝑐
A. Shifts left Decreases
B. Shifts right Increases
C. Shifts right No change
D. No change No change
10. Consider the following equilibrium:

𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈), ∆𝑯 = −71 kJmol−1
Colourless Purple Colourless
Which of the following would allow you to conclude that the system has reached equilibrium?
A. The pressure remains constant.
B. The reaction rates become zero.
C. The colour intensity remains constant.
D. The system shifts completely to the right
11. The Contact process for the manufacture of sulfuric acid was originally patented in the 19th century and
is still in use today.
The key step in the overall process is the reversible conversion of sulfur dioxide to sulfur trioxide in the
presence of a vanadium (V) oxide catalyst.
𝟐𝑺𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑺𝑶𝟑 (𝒈), ∆𝑯 = −𝟏𝟗𝟕 𝐤𝐉𝐦𝐨𝐥−𝟏
(a) One way in which the sulfur dioxide for this reaction is produced is by heating the sulfide ore iron
pyrites, 𝐹𝑒𝑆2 , in air. Iron (III) oxide is also produced. Write an equation for this reaction.
[2]
(b) The sulfur trioxide produced in the Contact process is reacted with 98% sulfuric acid. The resulting
compound is then reacted with water to produce sulfuric acid.
(i) Explain why the sulfur trioxide is not first mixed directly with water.
(ii) Write equations for the two steps involved in the conversion of sulfur trioxide into sulfuric acid.
[1 + 2]
(c) (i) Sulfur dioxide and sulfur trioxide both contain only 𝑆 = 𝑂 double bonds.
Draw labelled diagrams to show the shapes of these two molecules.
(ii) For your diagrams in (i), name the shapes and suggest the bond angles.
[2 + 2]
(d) The conversion of sulfur dioxide into sulfur trioxide is carried out at a temperature of 400 °𝐶.
(i) With reference to Le Chatelier’s Principle and reaction kinetics, state and explain one advantage
and one disadvantage of using a higher temperature.
(ii) State the expression for the equilibrium constant, 𝐾𝑝 , for the formation of sulfur trioxide from
sulfur dioxide.
(iii) 2.00 moles of sulfur dioxide and 2.00 moles of oxygen were put in a flask and left to reach
equilibrium.
At equilibrium, the pressure in the flask was 2.00 𝑥 105 𝑃𝑎 and the mixture contained 1.80 moles
of sulfur trioxide.
Calculate 𝐾𝑝 . Include the units.
[4 + 1 + 5]
[Total 19 marks]
[© UCLES 2014 9701/21/O/N/14]
12. Ammonium nitrate fertiliser is manufactured from ammonia. The first reaction in the manufacture of the
fertiliser is the catalytic oxidation of ammonia to form nitrogen monoxide, 𝑁𝑂. This is carried out at
about 1.00 𝑥 103 𝑘𝑃𝑎 (10 atmospheres) pressure and a temperature of 700 to 850 °𝐶.
𝟒𝑵𝑯𝟑 (𝒈) + 𝟓𝑶𝟐 (𝒈) 𝟒𝑵𝑶(𝒈) + 𝟔𝑯𝟐 𝑶(𝒈), ∆𝐻 = −906 kJmol−1
(a) Write the expression for the equilibrium constant, 𝐾𝑝 , stating the units.
[2]
(b) What will be the effect on the yield of 𝑁𝑂 of each of the following?
In each case, explain your answer.
(i) increasing the temperature
(ii) decreasing the applied pressure
[4]
[Total 6 marks]
[© UCLES 2013 9701/21/M/J/13]
13. Nitrogen dioxide, 𝑁𝑂2 , can enter the atmosphere in a variety of ways.
(a) (i) State one natural and one man-made source of atmospheric 𝑁𝑂2 .
(ii) Write an equation to show how 𝑁𝑂2 leads to the formation of nitric acid in acid rain.
(iii) Use equations to illustrate the catalytic role of 𝑁𝑂2 in the formation of sulfuric acid in acid rain.
[1 + 1 + 3]
(b) Nitrogen dioxide exists in equilibrium with dinitrogen tetroxide, 𝑁2 𝑂4 .
𝟐𝑵𝑶𝟐 (𝒈) 𝑵𝟐 𝑶𝟒 (𝒈)
2.00 𝑚𝑜𝑙 of dinitrogen tetroxide was sealed in a container at 350 𝐾. After equilibrium had been
established the total pressure was 140 𝑘𝑃𝑎 and the mixture of gases contained 1.84 𝑚𝑜𝑙 of
dinitrogen tetroxide.
(i) Give the expression for the equilibrium constant, 𝐾𝑝 , for this equilibrium.
(ii) Calculate the number of moles of 𝑁𝑂2 present at equilibrium.
(iii) Calculate the total number of moles of gas present at equilibrium and hence the mole fraction
of each gas present at equilibrium.
(iv) Calculate the partial pressure of each gas present at equilibrium.
(v) Calculate the value of the equilibrium constant, 𝐾𝑝 , at 350 𝐾.
Give your answer to three significant figures and include the units.
[1 + 1 + 2 + 2 + 2]
[Total 13 marks]
[© UCLES 2014 9701/23/M/J/14]
14. Each of the Group VII elements chlorine, bromine and iodine forms a hydride.
(a) (i) Outline how the relative thermal stabilities of these hydrides change from 𝐻𝐶𝑙 to 𝐻𝐼.
(ii) Explain the variation you have outlined in (i).
[3]
Hydrogen iodide can be made by heating together hydrogen gas and iodine vapour. The reaction is
incomplete.
𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)
(b) Write an expression for 𝐾𝑐 and state the units.
[2]
(c) For this equilibrium, the numerical value of the equilibrium constant 𝐾𝑐 is 140 at 500 𝐾 and
59 at 650 𝐾.
Use this information to state and explain the effect of the following changes on the equilibrium
position.
(i) increasing the pressure applied to the equilibrium
(ii) decreasing the temperature of the equilibrium
[4]
(d) A mixture of 0.02 𝑚𝑜𝑙 of hydrogen and 0.02 𝑚𝑜𝑙 of iodine was placed in a 1 𝑑𝑚3 flask and allowed
to come to equilibrium at 650 𝐾.
Calculate the amount, in moles, of each substance present in the equilibrium mixture at 650 𝐾.
𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)
Initial moles 0.02 0.02 0
[4]
[Total 13 marks]
[© UCLES 2012 9701/22/O/N/12]
15. (a) The following equation represents an equilibrium reaction:
𝑵𝟐 𝑶𝟒 (𝒈) 𝟐𝑵𝑶𝟐 (𝒈), ∆𝑯𝜽 = +𝟓𝟖 𝐤𝐉𝒎𝒐𝒍−𝟏
colourless brown
(i) State Le Chatelier’s principle.
(ii) Describe and explain the colour changes, if any, that might take place when:
1. A mixture of 𝑁2 𝑂4 (𝑔) and 𝑁𝑂2 (𝑔) is compressed at constant temperature;
2. A mixture of 𝑁2 𝑂4 (𝑔) and 𝑁𝑂2 (𝑔) is heated at constant pressure.
[5]
(b) In an experiment to determine the equilibrium constant for the reaction in (a) at 200 ℃, the initial
concentrations of 𝑁2 𝑂4 (𝑔) and 𝑁𝑂2 (𝑔) were 0.075 𝑚𝑜𝑙 𝑑𝑚−3 and 0.025 𝑚𝑜𝑙 𝑑𝑚−3 respectively. If
the equilibrium concentration of 𝑁2 𝑂4 (𝑔) was 0.00275 𝑚𝑜𝑙 𝑑𝑚−3 ,
1. calculate the equilibrium concentration of 𝑁𝑂2 (𝑔);
2. determine the 𝐾𝑐 value of the 𝑁2 𝑂4 (𝑔) / 𝑁𝑂2 (𝑔) system at 200 ℃.
[4]
(c) 𝑁𝑂2 can catalyse the conversion of atmospheric sulphur dioxide to sulphur trioxide.
(i) Write equations to illustrate this conversion.
(ii) Explain the type of catalysis exhibited by 𝑁𝑂2 in this conversion.
[3]
[Total 12 marks]
[© ZIMSEC 9189/1 J2014]
7.2 Ionic Equilibria
The Brønsted-Lowry Definitions of Acids and Bases
 An acid is a proton (𝐻 + ) donor. An example is ethanoic acid:
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯+ .
 A base is a proton (𝐻 + ) acceptor. An example is ammonia:

𝑵𝑯𝟑 + 𝑯+ 𝑵𝑯𝟒+ .
Conjugate Pairs
 When an acid (acid-I) loses a proton it becomes a conjugate base (base-I). When a base (base-II)
accepts a proton it becomes a conjugate acid (acid-II).
 The general equation for a Brønsted-Lowry acid-base reaction is:

𝑯𝑨 + 𝑩− 𝑨− + 𝑯𝑩
acid-I base-II base-I acid-II
Example 1: 𝑯𝟐 𝑶 + 𝑵𝑯𝟑 𝑵𝑯𝟒+ + 𝑶𝑯−

acid-I base-II acid-II base-I
Example 2: 𝑯𝑪𝒍 + 𝑯𝟐 𝑶 𝑯𝟑 𝑶+ + 𝑪𝒍−

acid-I base-II acid-II base-I
Amphoteric Substances
 A substance is amphoteric if it can act as either an acid or a base.
 The 𝐻2 𝑂 molecule in Example 1 above is acting as an acid, donating a proton to form 𝑂𝐻 − . The 𝐻2 𝑂
molecule in Example 2 above is acting as a base, accepting a proton to form 𝐻3 𝑂+ . Hence the water
molecule is amphoteric.
 The 𝐻𝑆𝑂4− ion is also amphoteric:

𝑯𝑺𝑶𝟒− 𝑺𝑶𝟐−
𝟒 + 𝑯+ : 𝐻𝑆𝑂4− is acting as an acid.
𝑯𝑺𝑶𝟒− + 𝑯+ 𝑯𝟐 𝑺𝑶𝟒 : 𝐻𝑆𝑂4− is acting as a base.
 Amphoteric substances can undergo acid-base reactions with themselves. Examples of this are:
𝑯𝟐 𝑶 + 𝑯𝟐 𝑶 𝑯𝟑 𝑶+ + 𝑶𝑯−
𝑯𝑪𝑶𝟑− + 𝑯𝑪𝑶𝟑− 𝑪𝑶𝟐−
𝟑 + 𝑪𝑶𝟐 + 𝑯𝟐 𝑶
𝑵𝑯𝟑 + 𝑵𝑯𝟑 𝑵𝑯𝟐− + 𝑵𝑯𝟒+
Strong and Weak Acids and Bases

 A strong acid is one which dissociates completely in aqueous solution. There are 7 main strong acids:
𝐻𝐶𝑙, 𝐻𝐵𝑟, 𝐻𝐼, 𝐻2 𝑆𝑂4 , 𝐻𝑁𝑂3 , 𝐻𝐶𝑙𝑂3 , and 𝐻𝐶𝑙𝑂4 .
 An acid is monoprotic if it gives one mole of hydrogen ions per mole of acid that dissociates. A diprotic
acid gives two moles of hydrogen ions per mole of acid that dissociates.
𝑯𝑵𝑶𝟑 𝑯+ + 𝑵𝑶𝟑− (monoprotic)
𝑯𝟐 𝑺𝑶𝟒 +
𝟐𝑯 + 𝑺𝑶𝟒 𝟐−
(diprotic)
 A weak acid is one which only dissociates partially in aqueous solution. The dissociation of a weak acid
reaches an equilibrium. This is shown by the reversible arrow:
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯+ (about 1% dissociated)
 A strong base is one which dissociates completely in aqueous solution. An example of a strong base
is sodium hydroxide:
𝑵𝒂𝑶𝑯 𝑵𝒂+ + 𝑶𝑯−
 A weak base is only slightly ionised in water. An example of a weak base is ammonia:
𝑵𝑯𝟑 + 𝑯𝟐 𝑶 𝑵𝑯𝟒+ + 𝑶𝑯−
pH and Hydrogen Ion Concentration

 The pH of a solution is the negative logarithm to base ten of the molar hydrogen ion concentration.
Mathematically,
𝑝𝐻 = − 𝑙𝑜𝑔10 [𝐻 + ]
Hence,
[𝐻 + ] = 10−𝑝𝐻 .
The Ionic Product of Water, 𝐾𝑤

 In aqueous solution water is slightly ionised:
𝑯𝟐 𝑶(𝒍) 𝑯+ (𝒂𝒒) + 𝑶𝑯− (𝒂𝒒)
 The equilibrium expression for this reaction can be written:

[H + ][𝑂𝐻 − ]
𝐾𝑐 =
[𝐻2 𝑂]
Hence
𝐾𝑐 [𝐻2 𝑂] = [H + ][𝑂𝐻 − ]
 Since water is only slightly ionised, the concentration of water is virtually constant. Hence:
𝐾𝑤 = [H + ][𝑂𝐻 − ]
where 𝐾𝑤 = 𝑖𝑜𝑛𝑖𝑐 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟.
 The ionic product of water, 𝐾𝑤 , has a value of 1.0 x 10−14 𝑚𝑜𝑙 2 𝑑𝑚−6 at 25°C. In pure water, the [H + ]
and [𝑂𝐻 − ] concentrations are equal. So [H + ] = [𝑂𝐻 − ] = √𝐾𝑤 = 1.0 x 10−7 𝑚𝑜𝑙𝑑𝑚−3 . Any solution
in which the concentrations of H + and 𝑂𝐻 − are equal is said to be neutral.
 The value of 𝐾𝑤 varies with temperature,

Variation of the pH of Pure Water with Temperature
The dissociation of water is an endothermic process.
just like any equilibrium constant.
𝑯𝟐 𝑶(𝒍) 𝑯+ (𝒂𝒒) + 𝑶𝑯− (𝒂𝒒)
 𝐾𝑤 increases with increasing temperature, T(˚C) 𝑲𝒘 (𝒎𝒐𝒍𝟐 𝒅𝒎−𝟔 ) x 𝟏𝟎−𝟏𝟒 pH
suggesting that the dissociation of water 0 0.11 7.47
is endothermic. 10 0.29 7.27
 The relationship between 𝐾𝑤 and 𝑝𝐾𝑤 is
20
25
0.68
1.01
7.08
7.00
𝑝𝐾𝑤 = − 𝑙𝑜𝑔10 (𝐾𝑤 ).
30 1.47 6.92
 At room temperature 𝑝𝐾𝑤 has a value of 40 2.92 6.77
− 𝑙𝑜𝑔10 (1.0 x 10−14 ) = 14. 50 5.48 6.63
100 51.3 6.14
Table 7.2 Variation of pH of pure water with temp.
Thus the pH of pure water falls as the temperature increases. This is because the dissociation of water is an
endothermic process, meaning that [𝐻 + ] increases as temperature increases.
A word of warning! If the pH decreases as temperature increases, does this mean that water becomes more acidic
at higher temperatures? NO!
A solution is acidic if there is an excess of hydrogen ions over hydroxide ions. In the case of pure water, there are
always the same number of hydrogen ions and hydroxide ions. That means the water remains neutral - even if its pH
changes.
At 100°C, the pH of pure water is 6.14. That is the neutral point on the pH scale at this higher temperature.
A neutral solution is one in which [H + ] = [𝑂𝐻 − ]. Therefore a neutral solution is pH 7 only at a temperature of
25°C (298K).
Example Question
3 –3
(a) At 298 K, 25.0 cm of a solution of a strong acid contained 1.50 × 10 mol of hydrogen ions.
(i) Calculate the hydrogen ion concentration in this solution and hence its pH.
3
(ii) Calculate the pH of the solution formed after the addition of 50.0 cm of 0.150 M NaOH to the original
3
25.0 cm of acid.
(b) A solution of a strong acid was found to have a pH of 0.5.

(i) Calculate the hydrogen ion concentration in this solution.
3
(ii) Calculate the volume of water which must be added to 25.0 cm of this solution to increase its pH from 0.5
to 0.7
Solution
𝑚𝑜𝑙𝑒𝑠 0.0015
a) (i) conc. = 𝑣𝑜𝑙𝑢𝑚𝑒 = = 0.06 𝑚𝑜𝑙𝑑𝑚−3
(25÷1000)
– 0.15
(ii) mol of OH added = 50 x = 0.0075
1000
+
mol of H used = 0.0015
–
mol of OH excess = 0.0060
–
[OH ] = (0.0060/75)÷1000 = 0.080
+ –14 –2 –13
[H ] = (1 x 10 /80×10 ) = 125 × 10
pH = 12.9
(b) (i) [𝐻 + ] = 10−𝑝𝐻 = 10−0.5 = 0.316 𝑚𝑜𝑙𝑑𝑚−3
(ii) [𝐻 + ] at pH = 0.7 is 10−0.7 = 0.199 𝑚𝑜𝑙𝑑𝑚 −3

𝑐1 𝑣1 = 𝑐2 𝑣2
∴ 0.316 x 25 = 0.199 x 𝑣
𝑣 = 37.5
3
∴ Water added = 37.5 – 25.0 = 12.5 cm
pH Values of some Common Substances
Fig. 7.4 pH of some common substances
The Acid Dissociation Constant, 𝐾𝑎

 Any weak acid is slightly dissociated in aqueous solution. For ethanoic acid, 𝐶𝐻3 𝐶𝑂𝑂𝐻:
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯+
The equilibrium constant is called the acid dissociation constant, 𝑲𝒂 :
[𝐶𝐻3 𝐶𝑂𝑂− ][𝐻 + ]
𝑲𝒂 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻]
𝒑𝑲𝒂 = −𝑙𝑜𝑔10 (𝑲𝒂 )
 The larger the 𝑲𝒂 , the greater the extent of dissociation of the acid and the stronger the acid. The
lower the value for 𝒑𝑲𝒂 , the stronger the acid.
(a) Calculating pH of Strong Acids
Question 1
Calculate the pH of 𝟎. 𝟏𝟐𝟓 𝑚𝑜𝑙𝑑𝑚−3 𝐻𝑁𝑂3 at 25°C.
Solution
The acid is strong, hence dissociates fully:
𝑯𝑵𝑶𝟑 𝑯+ + 𝑵𝑶𝟑−
Ratio of moles 𝐻𝑁𝑂3 : 𝐻 + = 1: 1.
∴ [𝐻 + ] = 0.125 𝑚𝑜𝑙𝑑𝑚−3
𝑝𝐻 = − 𝑙𝑜𝑔10 [𝐻 + ]
𝑝𝐻 = − 𝑙𝑜𝑔10 (0.125)
𝒑𝑯 = 𝟎. 𝟗𝟎
Question 2
p Calculate the pH of 𝟎. 𝟏𝟐𝟓 𝑚𝑜𝑙𝑑𝑚−3 𝐻𝑠 𝑆𝑂4 at 25°C.
Solution
The acid is strong, hence dissociates fully:
𝑯𝟐 𝑺𝑶𝟒 𝟐𝑯+ + 𝑺𝑶𝟐− 𝟒
Ratio of moles 𝐻2 𝑆𝑂4 : 𝐻 + = 1: 2.
∴ [𝐻 + ] = 0.125x2 = 0.250 𝑚𝑜𝑙𝑑𝑚−3
𝑝𝐻 = − 𝑙𝑜𝑔10 [𝐻 + ]
𝑝𝐻 = − 𝑙𝑜𝑔10 (0.250)
𝒑𝑯 = 𝟎. 𝟔𝟎
(b) Calculating the pH of Strong Bases
Question 1
Determine the pH of 𝟎. 𝟎𝟏𝟎 𝑚𝑜𝑙𝑑𝑚−3 𝑁𝑎𝑂𝐻 at 25˚C.
Solution
The alkali is strong, hence dissociates fully:
𝑵𝒂𝑶𝑯 𝑵𝒂+ + 𝑶𝑯−
Ratio of moles 𝑁𝑎𝑂𝐻:𝑂𝐻 − = 1: 1.
[H + ][𝑂𝐻 − ] = 1.0 x 10−14 𝑚𝑜𝑙 2 𝑑𝑚−6
1.0 x 10−14
[H + ] = = 10−12
0.01
𝑝𝐻 = − 𝑙𝑜𝑔10 [𝐻 + ]
𝒑𝑯 = 𝟏𝟐. 𝟎
Question 2
p Determine the pH of 𝟎. 𝟎𝟏𝟎 𝑚𝑜𝑙𝑑𝑚−3 𝐵𝑎(𝑂𝐻) at 25℃.
2
Solution
The alkali is strong, hence dissociates fully:
𝑩𝒂(𝑶𝑯)𝟐 𝑩𝒂𝟐+ + 𝟐𝑶𝑯−
−
Ratio of moles 𝐵𝑎(𝑂𝐻)2:𝑂𝐻 = 1: 2.
[H + ][𝑂𝐻 − ] = 1.0 x 10−14 𝑚𝑜𝑙 2 𝑑𝑚−6
1.0 x 10−14
[H + ] = = 5.0 𝑥 10−13
0.02
𝑝𝐻 = − 𝑙𝑜𝑔10 [𝐻 + ]
𝑝𝐻 = − 𝑙𝑜𝑔10 (5.0 𝑥 10−13 )
𝒑𝑯 = 𝟏𝟐. 𝟑
p c) Calculating the pH of Weak Acids and Weak Bases
Question 1
Determine the pH of 𝟎. 𝟑𝟎 𝒎𝒐𝒍𝒅𝒎−𝟑 ethanoic acid, 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯, with 𝑲𝒂 = 𝟏. 𝟖 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 at 25℃.
Solution
The acid is weak, hence dissociates partially:
Very few 𝐶𝐻3 𝐶𝑂𝑂𝐻 molecules will actually dissociate, so that the concentration of 𝐻 + cannot be determined by ratio
of [𝐶𝐻3 𝐶𝑂𝑂𝐻]. Instead, the acid dissociation constant is used.
[𝐶𝐻3 𝐶𝑂𝑂 − ][𝐻 + ]

𝐾𝑎 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻]
But [𝐶𝐻3 𝐶𝑂𝑂− ] = [ 𝐻 + ]
𝑲𝒂 [𝐶𝐻3 𝐶𝑂𝑂𝐻] = [𝐶𝐻3 𝐶𝑂𝑂 − ][ 𝐻 + ] = [𝐻 + ]2
[H + ] = √𝑲𝒂 [𝐶𝐻3 𝐶𝑂𝑂𝐻]

[H + ] = √(1.8 x 10−5 )(0.3)
[H + ] = 2.32 x 10−3
𝒑𝑯 = − 𝒍𝒐𝒈𝟏𝟎 [𝑯+ ] = 𝟐. 𝟔𝟑
Question 2
Determine the pH of 0.20 𝒎𝒐𝒍𝒅𝒎−𝟑 ammonia, with 𝑲𝒃 = 𝟏. 𝟖 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 at 25˚C.
Solution
The base is weak, hence dissociates partially:
𝑵𝑯𝟑 + 𝑯𝟐 𝑶 𝑵𝑯𝟒+ + 𝑶𝑯−
Very few 𝑁𝐻3 molecules will actually dissociate, so that the concentration of 𝑂𝐻 − cannot be determined by ratio of
[𝑁𝐻3 ]. Instead, the base dissociation constant, 𝐾𝑏 , is used.
[𝑂𝐻 − ][𝑁𝐻4+ ] Alternative Method
𝑲𝒃 =
[𝑁𝐻3 ] Since [H + ][𝑂𝐻 − ] = 1.0 x 10−14
But [𝑂𝐻 − ] = [ 𝑁𝐻4+ ]
𝑲𝒃 [𝑁𝐻3 ] = [𝑂𝐻 − ][ 𝑁𝐻4+ ] = [𝑂𝐻 − ]2
1.0 x 10−14
(1.8 x 10−5 )(0.20) = [𝑂𝐻 − ]2 [H + ] =
[𝑂𝐻 − ]
[𝑂𝐻 − ] = √𝑲𝒃 [𝑁𝐻3 ]
[𝑂𝐻 − ] = √(1.8 x 10−5 )(0.20) 1.0 x 10−14
[H + ] =
[𝑂𝐻 − ] = 1.90 x 10−3 1.90 x 10−3
[H + ] = 5.26 x 10−12
−
𝑝𝑂𝐻 = − 𝑙𝑜𝑔10 [𝑂𝐻 ] = 2.72
𝒑𝑯 = − 𝒍𝒐𝒈𝟏𝟎 [𝑯+ ] = 𝟏𝟏. 𝟑
𝒑𝑯 = 𝟏𝟒 − 𝒑𝑶𝑯 = 𝟏𝟏. 𝟑
Theory of Indicators
 An acid-base indicator is a weak acid which dissociates to give an anion of a different colour. Consider
a weak acid 𝐻𝐼𝑛:
𝑯𝑰𝒏(𝒂𝒒) 𝑯+ (𝒂𝒒) + 𝑰𝒏− (𝒂𝒒)
Red Blue
 𝐻𝐼𝑛 and its conjugate base 𝐼𝑛− are of different colours in aqueous solution. If the indicator 𝐻𝐼𝑛 is
placed in a strongly acidic solution, the above equilibrium will be shifted to the left and solution
becomes red. In alkaline medium, 𝐼𝑛− dominates giving a blue solution.
 The actual colour observed will depend on the proportion of each the two colours present.
 A good indicator must:

1. have an easily observed colour change;
2. change quickly in the required pH range over the addition of ‘half’ a drop of reagent.
The following are some indicators and their colours and pH ranges:
Indicator Colour in acid Colour in alkali pH range

Thymol blue red yellow 1.2 – 2.8
Methyl orange red yellow 3.2 – 4.4
Methyl red red yellow 4.2 – 6.3
Litmus pink blue 5.0 – 8.0
Bromothymol blue yellow blue 6.2 – 7.6
Phenolphthalein colourless pink 8.2 – 10.0
Table 7.3 pH ranges and colour changes of some indicators
Acid-Base Titrations
 An acid-base titration is an analytical technique for determining the concentration of a dissolved acid
or base and for determining the 𝐾𝑎 for a weak acid. During a titration, a neutralisation reaction is
performed by slowly adding a solution of a base to a solution of an acid (or vice versa) until the
equivalence point is reached. An equivalence point is when the stoichiometric amount of moles of
acid equals that of base and only a salt remains.
 Consider a titration of an acid solution whose

concentration is unknown with a base whose
concentration is known. The base is the titrant and it
is added slowly to the acid.
 When the titration begins, the base is the limiting

reactant and is completely consumed (because
neutralization reactions go to completion). Excess
acid and the salt produced by the reaction are now in
the flask. Fig. 7.5 Acid-base titration setup
 As the titration continues, more and more of the acid is consumed. Eventually all of the acid (and
p added base) is consumed, and only a salt remains. This point is called the equivalence point.
Fig. 7.6 Acid-base titration curves
 An indicator is used to determine when the equivalence point has been reached. If the titration is
continued beyond the equivalence point, the base becomes the excess reagent and it simply
accumulates but no more salt is produced. (This is assuming the base is in the burette).
 If the acid is weak, 𝐾𝑎 can be determined by monitoring the pH during the titration. As demonstrated
below (see half-neutralisation), the 𝐾𝑎 is equal to the pH half-way to the equivalence point.
 Weak acid - weak alkali titrations behave as buffer solutions throughout the titration. There is no sharp
pH change at the end-point. The pH of the end-point is usually around 7, but it depends on the relative
strengths of the acid and the alkali. No suitable indicator can be used for weak acid-weak alkali
titrations.
 When carrying out titrations, only one or two drops of indicators should be used since they are
themselves acidic and might influence the end-point if too much is added. Suitable indicators for
specific titrations:
Titration End-point pH pH range Suitable indicator

Strong acid - strong alkali 7.0 4 to 10 Bromothymol blue
Weak acid - strong alkali Approx. 9.0 7 to 10 phenolphthalein
Strong acid - weak alkali Approx. 5.5 4 to 7 Methyl red
Weak acid - weak alkali Approx. 7 No sudden No suitable indicator
change
Table 7.4 Suitable indicators for some common titrations
Half – Neutralisation
 A weak acid is half-neutralised when exactly half the volume of alkali required for neutralisation has
been added. For example:
𝑯𝑨 + 𝑶𝑯− 𝑨− + 𝑯𝟐 𝑶
If 0.50 moles of 𝑂𝐻 ions is added to 1.00 mole of 𝐻𝐴, half of the acid will be converted into its salt.
−
𝑯𝑨 + 𝑶𝑯− 𝑨− + 𝑯𝟐 𝑶
Initially : 1.00 0.50 − −
After reaction: 0.50 − 0.50 −
 At half-neutralisation the number of moles, and hence concentration, of the salt 𝐴− and acid 𝐻𝐴 will
be the same: [𝐻𝐴] = [𝐴− ].
 The acid-dissociation constant of the acid HA is:

[𝐴− ][𝐻 + ]
𝑲𝒂 =
[𝐻𝐴]
But if
[𝐻𝐴] = [𝐴− ] then 𝑲𝒂 = [𝐻 + ] and hence 𝑝𝐻 = 𝑝𝐾𝑎 .
 Therefore at half-neutralisation: 𝑝𝐻 = 𝑝𝐾𝑎 . The 𝐾𝑎 of an acid can be deduced from a graph of pH

against volume of alkali added.
The pH of the mixture after exactly half the required amount of alkali has been added corresponds to
the 𝑝𝐾𝑎 of the acid.
Other Titration Curves
 A diprotic acid is one that yields two 𝐻 + ions per acid molecule. Examples of diprotic acids are
sulphuric acid, 𝐻2 𝑆𝑂4 , and carbonic acid, 𝐻2 𝐶𝑂3 . A diprotic acid dissociates in water in two stages, e.g.
for 𝐻2 𝑆𝑂4 :
𝑯𝟐 𝑺𝑶𝟒 𝑯𝑺𝑶𝟒− + 𝑯+
𝑯𝑺𝑶𝟒− 𝑺𝑶𝟐−𝟒 + 𝑯
+
The titration curves of diprotic acids have two equivalence points due to these successive dissociations.
b) Adding Sodium Hydroxide to Sulphuric Acid
 The equation of the reaction occurring from

the beginning to the first equivalence point
is:
𝑵𝒂𝑶𝑯 + 𝑯𝟐 𝑺𝑶𝟒 𝑵𝒂𝑯𝑺𝑶𝟒 + 𝑯𝟐 𝑶
 The equation of the reaction occurring from

the first to the second equivalence point is:
𝑵𝒂𝑶𝑯 + 𝑵𝒂𝑯𝑺𝑶𝟒 𝑵𝒂𝟐 𝑺𝑶𝟒 + 𝑯𝟐 𝑶
 The equation of the overall reaction

occurring is:
𝟐𝑵𝒂𝑶𝑯 + 𝑯𝟐 𝑺𝑶𝟒 𝑵𝒂𝟐 𝑺𝑶𝟒 + 𝟐𝑯𝟐 𝑶
Fig. 7.7 Titration curve for sodium hydroxide and sulphuric acid
c) Adding Sodium Carbonate to Hydrochloric Acid

 The equation of the reaction occurring
from the beginning to the first end-
point is:
𝑵𝒂𝟐 𝑪𝑶𝟑 + 𝑯𝑪𝒍 𝑵𝒂𝑪𝒍 + 𝑵𝒂𝑯𝑪𝑶𝟑
 The equation of the reaction occurring

from the first to the second equivalence
point is:
𝑵𝒂𝑯𝑪𝑶𝟑 + 𝑯𝑪𝒍 𝑵𝒂𝑪𝒍 + 𝑪𝑶𝟐 + 𝑯𝟐 𝑶
 The equation of the overall reaction

occurring is:
𝑵𝒂𝟐 𝑪𝑶𝟑 + 𝟐𝑯𝑪𝒍 𝟐𝑵𝒂𝑪𝒍 + 𝑪𝑶𝟐 + 𝑯𝟐 𝑶
Fig. 7.8 Titration curve for sodium
carbonate and hydrochloric acid
 Note that for the sodium hydroxide-sulphuric acid titration, at the first equivalence point, all 𝐻 + ions
from the first dissociation have reacted with 𝑁𝑎𝑂𝐻. At the second equivalence point, all 𝐻 + ions from
both reactions have reacted (twice as many as at the first equivalence point). Therefore, the volume of
𝑁𝑎𝑂𝐻 added at the second equivalence point is exactly twice that of the first equivalence point.
Buffer Solutions
 A buffer solution is one which resists changes in pH when small amounts of acid or alkali are added
to it. A buffer is just a mixture of a weak acid and its conjugate base, or a weak base and its conjugate
acid.
 Many biological systems need a fairly constant pH, and rely on the use of buffer solutions to maintain
this pH. Examples are:
a) The pH of blood must be maintained at around 7.4. Hydrogencarbonate ions are used for this
purpose. If the pH varies by 0.5 it can lead to unconsciousness and coma. Carbon dioxide
produced by respiration can increase the acidity of blood by forming 𝐻 + ions in aqueous solution:
𝑪𝑶𝟐 (𝒂𝒒) + 𝑯𝟐 𝑶(𝒂𝒒) 𝑯+ (𝒂𝒒) + 𝑯𝟐 𝑪𝑶− 𝟑 (𝒂𝒒)
The presence of hydrogencarbonate ions in blood removes excess 𝐻 + :
𝑯+ (𝒂𝒒) + 𝑯𝑪𝑶𝟑− (𝒂𝒒) 𝑯𝟐 𝑪𝑶𝟑 (𝒂𝒒)
b) Many household and cosmetic products such as shampoo, baby lotion and fizzy lemonade need
pH control systems to remain in good state for long.
 Types of buffers:
1. Acidic buffer, which is a mixture of a strong acid and its sodium/potassium salt, e.g., the ethanoic
acid, 𝐶𝐻3 𝐶𝑂𝑂𝐻 and sodium ethanoate, 𝐶𝐻3 𝐶𝑂𝑂 − 𝑁𝑎+ mixture.
2. Alkaline buffer, which is a mixture of a weak base and its chloride salt, e.g., the ammonium
chloride, 𝑁𝐻4 𝐶𝑙 and ammonia, 𝑁𝐻3 mixture.
Action of a Buffer
 A buffer works by replacing a strong acid or base with a weak one, thus controlling the pH change.
 Consider the acidic buffer prepared by mixing ethanoic acid, 𝐶𝐻3 𝐶𝑂𝑂𝐻 and sodium ethanoate,
𝐶𝐻3 𝐶𝑂𝑂− 𝑁𝑎 + .
 𝐶𝐻3 𝐶𝑂𝑂𝐻 is a weak acid and partially dissociates. The equilibrium lies far to the left, meaning there is
a high concentration of 𝐶𝐻3 𝐶𝑂𝑂𝐻 in the mixture:
HIGH
 The sodium ethanoate fully dissolves, giving a high concentration of 𝐶𝐻3 𝐶𝑂𝑂− in the mixture:
𝑪𝑯𝟑 𝑪𝑶𝑶− 𝑵𝒂+ 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑵𝒂+
HIGH
 When a little amount of alkali 𝑂𝐻 − is added, it reacts with the acid, forming a weak alkali 𝐶𝐻3 𝐶𝑂𝑂−
(and so the pH changes only slightly):
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑶𝑯− 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯𝟐 𝑶
 When a little amount of acid 𝐻 + is added, it reacts with the alkali, forming a weak acid 𝐶𝐻3 𝐶𝑂𝑂𝐻
(and so the pH changes only slightly):
𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯+ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯
 Consider the alkaline buffer prepared by mixing ammonium chloride, 𝑁𝐻4 𝐶𝑙 and ammonia, 𝑁𝐻3 .
𝑁𝐻3 is a weak base and partially dissociates. The equilibrium lies far to the left, meaning there is a
high concentration of 𝑁𝐻3 in the mixture:
𝑵𝑯𝟑 + 𝑯𝟐 𝑶 𝑵𝑯𝟒+ + 𝑶𝑯−
HIGH
 The ammonium chloride fully dissolves, giving a high concentration of 𝑁𝐻4+ in the mixture:
𝑵𝑯𝟒 𝑪𝒍 𝑵𝑯𝟒+ + 𝑪𝒍−
HIGH
 When a little amount of alkali 𝑂𝐻 − is added, it reacts with the acid, forming a weak alkali 𝑁𝐻3 (and
so the pH changes only slightly):
𝑵𝑯𝟒+ + 𝑶𝑯− 𝑵𝑯𝟑 + 𝑯𝟐 𝑶
 When a little amount of acid 𝐻 + is added, it reacts with the alkali, forming a weak acid 𝑁𝐻4+ (and so
the pH changes only slightly):
𝑵𝑯𝟑 + 𝑯+ 𝑵𝑯𝟒+
Deriving the Formulae for Calculating the pH of Buffer Solutions
Acidic Buffer Alkaline Buffer

The buffer constituents dissolve thus: The buffer constituents dissolve thus:
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑯+ 𝑵𝑯𝟑 + 𝑯𝟐 𝑶 𝑵𝑯𝟒+ + 𝑶𝑯−
𝑪𝑯𝟑 𝑪𝑶𝑶 𝑵𝒂− +
𝑪𝑯𝟑 𝑪𝑶𝑶− + 𝑵𝒂+ 𝑵𝑯𝟒 𝑪𝒍 𝑵𝑯𝟒+ + 𝑪𝒍−
The acid dissociation constant of the weak acid is The base dissociation constant of the weak alkali is:
[ 𝑁𝐻4+ ][𝑂𝐻 − ]
[𝐶𝐻3 𝐶𝑂𝑂− ][𝐻 + ] 𝑲𝒃 =
[𝑁𝐻3 ]
𝑲𝒂 =
[𝐶𝐻3 𝐶𝑂𝑂𝐻] where [𝑁𝐻4 ] ≫ [ 𝑂𝐻 ] since a lot of 𝑁𝐻4+ is
+ −
coming from a fully-ionising salt.

where [𝐶𝐻3 𝐶𝑂𝑂 − ] ≫ [ 𝐻 + ] since a lot of 𝐶𝐻3 𝐶𝑂𝑂− is
coming from a fully-ionising salt. 𝑲𝒃 [𝑁𝐻3 ] = [ 𝑁𝐻4+ ][ 𝑂𝐻 − ]
𝑲𝒂 [𝐶𝐻3 𝐶𝑂𝑂𝐻] = [𝐶𝐻3 𝐶𝑂𝑂− ][ 𝐻 + ] Or
Or 𝑲𝒃 [𝑏𝑎𝑠𝑒] = [𝑠𝑎𝑙𝑡][ 𝑂𝐻 − ]
𝑲𝒂 [𝑎𝑐𝑖𝑑] = [𝑠𝑎𝑙𝑡][ 𝐻 + ] Hence,
Hence, 𝑲𝒃 [𝑏𝑎𝑠𝑒]
[𝑂𝐻 − ] =
𝑲𝒂 [𝑎𝑐𝑖𝑑] [𝑠𝑎𝑙𝑡]
[H + ] =
[𝑠𝑎𝑙𝑡]
Introducing (− 𝑙𝑜𝑔10 ) on either side:
Introducing (− 𝑙𝑜𝑔10 ) on either side:
𝐾𝑎 [𝑎𝑐𝑖𝑑] 𝐾𝑏 [𝑏𝑎𝑠𝑒]
− 𝑙𝑜𝑔10 [H + ] = − 𝑙𝑜𝑔10 − 𝑙𝑜𝑔10 [𝑂𝐻 − ] = − 𝑙𝑜𝑔10
[𝑠𝑎𝑙𝑡] [𝑠𝑎𝑙𝑡]
[𝑎𝑐𝑖𝑑] [𝑏𝑎𝑠𝑒]
− 𝑙𝑜𝑔10 [H + ] = − 𝑙𝑜𝑔10 (𝐾𝑎 ) − 𝑙𝑜𝑔10 ( [𝑠𝑎𝑙𝑡] ) − 𝑙𝑜𝑔10 [𝑂𝐻 − ] = − 𝑙𝑜𝑔10 (𝐾𝑎 ) − 𝑙𝑜𝑔10 ( [𝑠𝑎𝑙𝑡] )
[𝑠𝑎𝑙𝑡]
𝑝𝑂𝐻 = 𝑝𝐾𝑏 + 𝑙𝑜𝑔10
[𝒔𝒂𝒍𝒕] [𝑏𝑎𝑠𝑒]
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈𝟏𝟎 𝒑𝑯 = 𝟏𝟒 − 𝒑𝑶𝑯
[𝑎𝑐𝑖𝑑]
Question 1
Calculate the pH of a buffer solution containing benzoic acid, 𝑪𝟔 𝑯𝟓 𝑪𝑶𝑶𝑯 and sodium benzoate,
𝑪𝟔 𝑯𝟓 𝑪𝑶𝑶− 𝑵𝒂+ given that [𝑪𝟔 𝑯𝟓 𝑪𝑶𝑶𝑯] = 𝟎. 𝟏𝟎 𝒎𝒐𝒍𝒅𝒎−𝟑 and [𝑪𝟔 𝑯𝟓 𝑪𝑶𝑶− 𝑵𝒂+ ] = 𝟎. 𝟏𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 .
Assume 𝑲𝒂 of benzoic acid is 𝟔. 𝟑 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 .
Solution
[𝐶6 𝐻5 𝐶𝑂𝑂 − ][𝐻 + ]
𝐾𝑎 = [𝐶6 𝐻5 𝐶𝑂𝑂𝐻]
Re-arranging
𝐾𝑎 [𝐶6 𝐻5 𝐶𝑂𝑂𝐻]
[H + ] =
[𝐶6 𝐻5 𝐶𝑂𝑂− ]
(6.3 x 10−5 )(0.10)

[H + ] =
0.15
= 4.2 x 10−5 𝑚𝑜𝑙𝑑𝑚−3
𝒑𝑯 = − 𝒍𝒐𝒈𝟏𝟎 [𝑯+ ] = 𝟒. 𝟑𝟖
Question 2
Calculate the pH of the solution formed whne 500 𝒄𝒎𝟑 of 0.10 𝒎𝒐𝒍𝒅𝒎−𝟑 of propanoic acid, 𝑪𝟐 𝑯𝟓 𝑪𝑶𝑶𝑯 is mixed
with 500 𝒄𝒎𝟑 of 0.20 𝒎𝒐𝒍𝒅𝒎−𝟑 solution of its salt, 𝑪𝟐 𝑯𝟓 𝑪𝑶𝑶− 𝑵𝒂+ . Assume 𝑲𝒂 of ethanoic acid is
𝟒. 𝟎 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 .
Solution
[𝐶2 𝐻5 𝐶𝑂𝑂− ][𝐻 + ]
𝐾𝑎 =
[𝐶2 𝐻5 𝐶𝑂𝑂𝐻]
Re-arranging
𝐾𝑎 [𝐶2 𝐻5 𝐶𝑂𝑂𝐻]
[H + ] =
[𝐶2 𝐻5 𝐶𝑂𝑂− ]
When the solutions are mixed, volume is now 1.00 𝑚𝑜𝑙𝑑𝑚−3 . Hence [𝐶2 𝐻5 𝐶𝑂𝑂𝐻] = 0.05 𝑚𝑜𝑙𝑑𝑚−3 and
[𝐶2 𝐻5 𝐶𝑂𝑂 − 𝑁𝑎+ ] = 0.10 𝑚𝑜𝑙𝑑𝑚−3 .
(4.0 x 10−5 )(0.05)
[H + ] =
0.10
= 2.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3
𝒑𝑯 = − 𝒍𝒐𝒈𝟏𝟎 [𝑯+ ] = 𝟒. 𝟕𝟎
Solubility Product Constant, 𝐾𝑠𝑝

 Many common ionic compounds have a very limited solubility in water, and are called slightly soluble
salts. A saturated solution of a slightly soluble ionic compound produces a dynamic equilibrium
between the compound and the dissociated ions. However, because the compound is only slightly
soluble, the solution has a low concentration of ions. For example, silver chloride, 𝐴𝑔𝐶𝑙:
𝑨𝒈𝑪𝒍(𝒔) 𝑨𝒈+ (𝒂𝒒) + 𝑪𝒍− (𝒂𝒒)
 The equilibrium constant is written

[𝐴𝑔+ ][𝐶𝑙− ]
𝐾𝑐 = [𝐴𝑔𝐶𝑙]
But [𝐴𝑔𝐶𝑙] is a constant at constant temperature, since the silver chloride is in solid state. Therefore,
𝐾𝑐 [𝐴𝑔𝐶𝑙] = [𝐴𝑔+ ][𝐶𝑙 − ]
𝑲𝒔𝒑 = [𝑨𝒈+ ][𝑪𝒍− ] Units: 𝒎𝒐𝒍𝟐 𝒅𝒎−𝟔
The equilibrium constant is called the solubility product constant, or just the solubility product. The
value of 𝐾𝑠𝑝 has units and it depends on the temperature.
𝑩𝒂𝑺𝑶𝟒 (𝒔) 𝑩𝒂𝟐+ (𝒂𝒒) + 𝑺𝑶𝟐− 2+ 2−
𝟒 (𝒂𝒒), 𝐾𝑠𝑝 = [𝐵𝑎 ][𝑆𝑂4 ] units: 𝑚𝑜𝑙 2 𝑑𝑚 −6
𝑷𝒃𝑪𝒍𝟐 (𝒔) 𝑷𝒃𝟐+ (𝒂𝒒) + 𝟐𝑪𝒍− (𝒂𝒒), 𝐾𝑠𝑝 = [𝑃𝑏 2+ ][𝐶𝑙 − ]2 units: 𝑚𝑜𝑙 3 𝑑𝑚 −9
𝑭𝒆(𝑶𝑯)𝟑 (𝒔) 𝑭𝒆𝟑+ (𝒂𝒒) + 𝟑𝑶𝑯− (𝒂𝒒), 𝐾𝑠𝑝 = [𝐹𝑒 3+ ][𝑂𝐻 − ]3 units: 𝑚𝑜𝑙 4 𝑑𝑚 −12
𝟒 (𝒂𝒒), 𝐾𝑠𝑝 = [𝑀𝑔 ] [𝑃𝑂3 ] units: 𝑚𝑜𝑙 𝑑𝑚

𝟑𝑴𝒈𝟐+ (𝒂𝒒) + 𝟐𝑷𝑶𝟑− 2+ 3 2− 2 5 −15
𝑴𝒈𝟑 (𝑷𝑶𝟒 )𝟑 (𝒔)
 Solubility varies with temperature and a solution becomes saturated when no more solute can dissolve
at the given temperature.
 Consider barium sulphate, 𝐵𝑎𝑆𝑂4 :
Calculating Solubility
Solubility products can be used to calculate solubility,
𝑩𝒂𝑺𝑶𝟒 (𝒔) 𝑩𝒂𝟐+ (𝒂𝒒) + 𝑺𝑶𝟐− 𝟒 (𝒂𝒒), and vice-versa.
𝐾𝑠𝑝 = 1.5 x 10−9 𝑚𝑜𝑙 2 𝑑𝑚−6 at 25˚C.
Every mole of 𝐵𝑎𝑆𝑂4 that dissolves forms one Example 1
mole of 𝐵𝑎2+ and one mole of 𝑆𝑂42− ions. The At 25˚C, the solubility product of lead (II) sulphide,
concentrations of the 𝐵𝑎 2+ and 𝑆𝑂42− can be 𝑷𝒃𝑺, is 𝟒. 𝟎 𝐱 𝟏𝟎−𝟐𝟖 𝒎𝒐𝒍𝟐 𝒅𝒎−𝟔 . Calculate the
found. solubility of lead (III) sulphide at 25˚C.
𝟐+ 𝟐−
𝑩𝒂𝑺𝑶𝟒 𝑩𝒂 + 𝑺𝑶𝟒
Initial: excess 0 0 Solution
At eqm.: excess 𝑥 𝑥 𝑷𝒃𝑺(𝒔) 𝑷𝒃𝟐+ (𝒂𝒒) + 𝑺𝟐− (𝒂𝒒)
𝐾𝑠𝑝 = [𝑃𝑏 2+ ][𝑆 2− ]
2+ 2− 𝟐
𝐾𝑠𝑝 = [𝐵𝑎 ][𝑆𝑂4 ] = 𝒙 Since 1 mol 𝑃𝑏𝑆 gives 1 mol 𝑃𝑏 2+ , the solubility of
𝑃𝑏𝑆 is equal to the concentration of 𝑃𝑏 2+ at saturation.
2+
𝑥 = √𝐾𝑠𝑝 = [𝐵𝑎 ] = [𝑆𝑂4 ] 2− The ratio of 𝑃𝑏 2+ : 𝑆 2− = 1: 1, so that
[𝑃𝑏 2+ ] = [𝑆 2− ]
𝒙 = √𝟏. 𝟓 𝐱 𝟏𝟎−𝟗 = 𝟑. 𝟗 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑
Thus,
𝐾𝑠𝑝 = [𝑃𝑏 2+ ]2
Therefore, the solubility of 𝐵𝑎𝑆𝑂4 in pure
water at 25˚C is 𝟑. 𝟗 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 . [𝑃𝑏 2+ ] = √𝐾𝑠𝑝 = √4.0 x 10−28
[𝑃𝑏 2+ ] = 2.0 x 10−14 𝑚𝑜𝑙𝑑𝑚−3
 How does the solubility of 𝐵𝑎𝑆𝑂4 change
Solubility of 𝑷𝒃𝑺 = 𝟐. 𝟎 𝐱 𝟏𝟎−𝟏𝟒 𝒎𝒐𝒍𝒅𝒎−𝟑
when placed in a solution containing 0.001
NB: Solubility may also be given in 𝑔𝑑𝑚−3 .
𝑚𝑜𝑙𝑑𝑚−3 𝑆𝑂42− ions?
[mass = moles x 𝑀𝑟 ]
Note that 0.001 is much bigger than
𝑀𝑟 (𝑃𝑏𝑆) = 239
3.9 x 10−5 .
∴ Solubility of 𝑃𝑏𝑆 = (239 𝑥 2.0 x 10−14 )
𝑩𝒂𝑺𝑶𝟒 (𝒔) 𝑩𝒂𝟐+ (𝒂𝒒) + 𝑺𝑶𝟐− 𝟒 (𝒂𝒒) Solubility of 𝑷𝒃𝑺 = 𝟒. 𝟕𝟖 𝐱 𝟏𝟎−𝟏𝟐 𝒈𝒅𝒎−𝟑
Initial: excess 0 0
At eqm: excess 𝑥 (0.001 + 𝑥)
 Since 𝑥 is a much smaller value than 0.001, the equilibrium concentration of 𝑆𝑂42− is taken as 0.001
𝑚𝑜𝑙𝑑𝑚−3 .
𝐾𝑠𝑝 = [𝐵𝑎2+ ][𝑆𝑂42− ]
 The solubility of 𝐵𝑎𝑆𝑂4 in a solution containing 0.001 𝑚𝑜𝑙𝑑𝑚−3 𝑆𝑂42− ions can be calculated:
𝐾𝑠𝑝
[𝐵𝑎2+ ] =
[𝑆𝑂42− ]
1.5 x 10−9
[𝐵𝑎 2+ ] = = 𝟏. 𝟓 𝐱 𝟏𝟎−𝟔 𝑚𝑜𝑙𝑑𝑚−3
[0.001]
Hence, the solubility of 𝐵𝑎𝑆𝑂4 is 𝟏. 𝟓 𝐱 𝟏𝟎−𝟔 𝑚𝑜𝑙𝑑𝑚 −3 in a solution containing 0.001 𝑚𝑜𝑙𝑑𝑚−3 𝑆𝑂42− ions.
Example 2
At 25˚C, the solubility of silver carbonate, 𝑨𝒈𝟐 𝑪𝑶𝟑 , is 𝟏. 𝟐 𝐱 𝟏𝟎−𝟒 𝒎𝒐𝒍𝒅𝒎−𝟑 . Calculate the solubility product of
𝑨𝒈𝟐 𝑪𝑶𝟑 at 25˚C.
Solution
𝑨𝒈𝟐 𝑪𝑶𝟑 (𝒔) 𝟐𝑨𝒈𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐− 𝟑 (𝒂𝒒)
+ 2 2−
𝐾𝑠𝑝 = [𝐴𝑔 ] [𝐶𝑂3 ]
Since 1 mol 𝐴𝑔2 𝐶𝑂3 gives 1 mol 𝐶𝑂32− , the solubility of 𝐴𝑔2 𝐶𝑂3 is equal to the concentration of 𝐶𝑂32− at saturation:
[𝐶𝑂32− ] = 1.2 x 10−4 𝑚𝑜𝑙𝑑𝑚−3
Thus [𝐴𝑔+ ] = 2 x [𝐶𝑂32− ] = 2.4 x 10−4
𝐾𝑠𝑝 = [𝐴𝑔+ ]2 [𝐶𝑂32− ]
𝐾𝑠𝑝 = (2.4 x 10−4 )2 (1.2 x 10−4 )
𝑲𝒔𝒑 = 𝟔. 𝟗𝟏 𝐱 𝟏𝟎−𝟏𝟐 𝒎𝒐𝒍𝟑 𝒅𝒎−𝟗
The Common Ion Effect

 The solubility of 𝐵𝑎𝑆𝑂4 in pure water at 25˚C is 3.9 x 10−5 𝑚𝑜𝑙𝑑𝑚−3, but reduces to 1.5 x 10−6 𝑚𝑜𝑙𝑑𝑚−3
if the solution contains some 𝑆𝑂42− ions. This example illustrates the Common Ion Effect:
The presence of common ion decreases the solubility of a slightly soluble ionic compound.
𝑩𝒂𝑺𝑶𝟒 (𝒔) 𝑩𝒂𝟐+ (𝒂𝒒) + 𝑺𝑶𝟐−
𝟒 (𝒂𝒒),
 According to Le Chatelier's Principle, the position of the equilibrium shifts to the left if is placed in a
solution which already has either 𝑆𝑂42− (𝑎𝑞) or 𝐵𝑎2+ (𝑎𝑞) ions. This reduces the solubility as confirmed
by calculation.
Similarly, 𝑃𝑏𝐶𝑙2 (𝑠) is more soluble in pure water than in, say, 𝑁𝑎𝐶𝑙(𝑎𝑞) or 𝑃𝑏(𝑁𝑂3 )2 (𝑎𝑞).
Precipitation and Selective Precipitation
 Consider the partially soluble 𝐵𝑎𝑆𝑂4 . It follows that, if:

[𝐵𝑎2+ ][𝑆𝑂42− ] = 𝐾𝑠𝑝 ⇒ Solution is saturated, but no precipitate forms;
2+ 2−
[𝐵𝑎 ][𝑆𝑂4 ] < 𝐾𝑠𝑝 ⇒ Solution is not saturated;
[𝐵𝑎2+ ][𝑆𝑂42− ] > 𝐾𝑠𝑝 ⇒ Solution is saturated, and a precipitate forms.
Example 1
If equal volumes of 𝟐. 𝟎 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 𝑨𝒈𝑵𝑶𝟑 (𝒂𝒒) and 𝟐. 𝟎 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 𝑵𝒂𝑪𝒍(𝒂𝒒) are mixed, will
a precipitate of 𝑨𝒈𝑪𝒍 form? [𝑲𝒔𝒑 (𝑨𝒈𝑪𝒍) = 𝟏. 𝟐𝟎 𝐱 𝟏𝟎−𝟏𝟎 𝒎𝒐𝒍𝟐 𝒅𝒎−𝟔 ].
Solution
𝑨𝒈𝑵𝑶𝟑 (𝒂𝒒) 𝑨𝒈+ (𝒂𝒒) + 𝑪𝒍− (𝒂𝒒)
Therefore, in the 2.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3 𝐴𝑔𝑁𝑂3 (𝑎𝑞), [𝐴𝑔+ (𝑎𝑞)] = 2.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3 , by ratio.
𝑵𝒂𝑪𝒍(𝒂𝒒) 𝑵𝒂+ (𝒂𝒒) + 𝑪𝒍− (𝒂𝒒)
Therefore, in the 2.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3 𝐴𝑔𝑁𝑂3 (𝑎𝑞), [𝐶𝑙 − (𝑎𝑞)] = 2.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3 , by ratio.
When equal volumes are mixed, the concentrations are halved. Thus in the mixture,
[𝐴𝑔+ (𝑎𝑞)] = 1.0 x 10−5 𝑚𝑜𝑙𝑑𝑚−3 = [𝐶𝑙 − (𝑎𝑞)]
[𝐴𝑔 ][𝐶𝑙 − ] = (1.0 x 10−5 )(1.0 x 10−5 ) = 1.0 x 10−10 𝑚𝑜𝑙 2 𝑑𝑚−6
+
Since [𝑨𝒈+ ][𝑪𝒍− ] < 𝑲𝒔𝒑 , no precipitation occurs.
Example 2
If 20.0 𝒄𝒎𝟑 of 𝟎. 𝟎𝟓 𝒎𝒐𝒍𝒅𝒎−𝟑 𝑷𝒃(𝑵𝑶𝟑 )𝟐 (𝒂𝒒) is mixed with 30.0 𝒄𝒎𝟑 of 𝒎𝒐𝒍𝒅𝒎−𝟑 𝑵𝒂𝑪𝒍(𝒂𝒒), will 𝑷𝒃𝑪𝒍𝟐
precipitate?
[𝑲𝒔𝒑 (𝑷𝒃𝑪𝒍𝟐 ) = 𝟏. 𝟔𝟎 𝐱 𝟏𝟎−𝟓 𝒎𝒐𝒍𝟑 𝒅𝒎−𝟗 ]
Solution
20
Moles of 𝑃𝑏 2+ in the mixture = concentration x volume = 𝑥 0.05 x 10−5 = 0.0010 𝑚𝑜𝑙.
1000
30
Moles of 𝐶𝑙 − in the mixture = concentration x volume = 𝑥 0.05 x 10−5 = 0.0030 𝑚𝑜𝑙.
1000
0.0010
Therefore, in the 50 𝑐𝑚3 mixture, [𝑃𝑏 2+ (𝑎𝑞)] = = 0.020𝑚𝑜𝑙𝑑𝑚−3 .
0.050
0.0030
[𝐶𝑙 − (𝑎𝑞)] = = 0.060𝑚𝑜𝑙𝑑𝑚−3 .
0.050
Thus,
[𝑃𝑏 2+ ][𝐶𝑙 − ]2 = (0.02)(0.06)2 = 7.2 𝑥 10−5 > 𝐾𝑠𝑝
Since [𝑷𝒃𝟐+ ][𝑪𝒍− ]𝟐 > 𝑲𝒔𝒑 , 𝑷𝒃𝑪𝒍𝟐 precipitate forms.
 The presence of certain ions, such as 𝐶𝑙 − , 𝐼 − , 𝑆𝑂42− , 𝐴𝑔+ , etc. in water can be determined qualitatively
and quantitatively by precipitation method. 𝐶𝑙 − , and 𝐼 − can be precipitated as 𝐴𝑔𝐶𝑙 and 𝐴𝑔𝐼,
respectively, by adding 𝐴𝑔𝑁𝑂3 solution.
 Because of the different solubility of compounds, the separation of ions from a mixture of solution
can be accomplished by selective precipitation. This is carried out by adding the precipitating ion
until the ion product of the more soluble compound is almost equal to its 𝐾𝑠𝑝 , but the 𝐾𝑠𝑝 of the less
soluble compound is exceeded as much as possible.
For example, because of the different solubility of 𝐶𝑎𝑆𝑂4 (𝐾𝑠𝑝 = 6.1 x 10−5 ), and 𝐵𝑎𝑆𝑂4 (𝐾𝑠𝑝
1.5 x 10−9 ), 𝐶𝑎2+ and 𝐵𝑎 2+ can be separated from a solution by selectively precipitating 𝐵𝑎𝑆𝑂4 using
𝑁𝑎2 𝑆𝑂4 or 𝐻2 𝑆𝑂4 solution.
Qualitative Analysis: Identifying Ions in Mixtures of Cations

 The separation and identification of ions in a mixture is called qualitative analysis. The technique
employs the different solubility of ionic compounds in aqueous solution as well as the ability of
certain cations to form complex ion with ligands. For many transition metals, their complex ions are
often colored, which can be used in their identification.
7.3 Partition Coefficients
Partition Coefficient
 Partition Coefficient is the ratio of concentrations of a solute in two immiscible solvents at equilibrium.
 The partition or distribution coefficient of a solute 𝑋 between two phases Phase-1 and Phase-2 is
written as
[𝑋𝑝ℎ𝑎𝑠𝑒 1 ]
𝐾𝑝𝑐 =
[𝑋𝑝ℎ𝑎𝑠𝑒 2 ]
 If it involves two immiscible liquids, 𝐾𝑝𝑐 has no units. If a gas

and a solution are involved, then appropriate units must be
used for the partition, e.g.,
𝑪𝑶𝟐 (𝒈) 𝑪𝑶𝟐 (𝒂𝒒)
𝐾𝑝𝑐 might have units 𝑃𝑎 𝑚𝑜𝑙 −1 𝑑𝑚3 . 𝐾𝑝𝑐 is temperature-

dependent, just like other equilibrium constants.
Fig. 7.8 Solute X in equilibrium between two immiscible solvents

 If a solute 𝑋 is added to a system of two immiscible solvents, it will distribute itself between the
immiscible liquids so that the ratio of the solute concentrations remains the same at constant
temperature independently of the total quantity of 𝑋 in the same molecular state. That is called
the partition equilibrium or distribution law.
 The partition coefficient is a measure of the differential solubility of the solute between these two
solvents.
The partition of iodine between the water and the The partition of ammonia between the water and
tetrachloromethane solvents: trichloromethane phases:
𝑰𝟐 (𝒂𝒒) 𝑰𝟐(𝑪𝑪𝒍𝟒 ) 𝑵𝑯𝟑 (𝒂𝒒) 𝑵𝑯𝟑(𝑪𝑯𝑪𝒍𝟑 )
[𝐼2(𝑎𝑞) ] [𝑁𝐻3 (𝑎𝑞)]

𝐾𝑝𝑐 = = 0.012 𝐾𝑝𝑐 = = 26
[𝐼2(𝐶𝐶𝑙4 ) ] [𝑁𝐻3(𝐶𝐻𝐶𝑙3 ) ]
The non–polar iodine is much more soluble in the non– Ammonia is highly polar and can form hydrogen-
polar organic solvent 𝐶𝐶𝑙4 than in the highly polar bonds with the more polar water molecules, hence
water solvent. The iodine cannot disrupt the strong ammonia's much greater solubility in water than the
intermolecular hydrogen bonds between water less polar trichloromethane.
molecules.
Example
𝟐𝟎 𝒈 of butanedioic acid (BDA) was shaken with a mixture of 𝟏𝟎𝟎 𝒄𝒎𝟑 ether and 𝟏𝟎𝟎 𝒄𝒎𝟑 water at 𝟐𝟓 ˚𝑪. After
titration with standard sodium hydroxide the concentration of the acid was found to be 𝟎. 𝟎𝟐𝟒 𝒎𝒐𝒍𝒅𝒎𝟑 in ether
and 𝟎. 𝟏𝟔 𝒎𝒐𝒍𝒅𝒎𝟑 in water.
i) Calculate the distribution coefficient 𝑲𝒑𝒄 for butanedioic acid between ether and water.
ii) If 𝟏𝟎 𝒈 of BDA had been shaken with 𝟓𝟎 𝒄𝒎𝟑 of each solvent at 𝟐𝟓 ˚𝑪, what value would expect for 𝑲𝒑𝒄 if
the layers were again analysed?
iii) If 𝟏𝟎 𝒈 of butanedioic acid was dissolved in 𝟒𝟎 𝒄𝒎𝟑 of ether at 𝟐𝟓 ˚𝑪, calculate how much of the acid can
be extracted with 𝟓𝟎 𝒄𝒎𝟑 of water.
Solution
i)
[𝐵𝐷𝑒𝑡ℎ𝑒𝑟 ] 0.024
𝐾𝑝𝑐 = = = 0.15
[𝐵𝐷(𝑤𝑎𝑡𝑒𝑟) ] 0.16
ii) 0.15, since the partition law states the ratio of concentrations remains constant at constant
temperature.
iii) Let 𝑥 be the mass in g of acid extracted into the water. Then (10 – 𝑥)g reains in the ether.
Substituting into the equation:
10 − 𝑥
( )
40 = 0.15
𝑥
( )
50
50(10 − 𝑥)
= 0.15
40𝑥
500 − 50𝑥 = 6𝑥
500 = 56𝑥
𝒙 = 𝟖. 𝟗𝟑 𝒈 𝑩𝑫
Solvent Extraction
 Partition coefficients are useful in calculating how much solute can be extracted from a solvent.
 It can be shown by calculation that more solute can be extracted if smaller portions of extracting
solvent is used, rather than one whole amount. In the example above, 50 𝑐𝑚3 water extracted 8.93 𝑔
BD once-off. If two successive extractions are carried out using 25 cm3 of water each time, the amount
of BD extracted is more.
First extraction:
Let 𝑥 be the mass in g of acid extracted into the first 25 cm3 water. Then (10 – 𝑥)g reains in the ether.
Substituting into the equation:
10 − 𝑥
( )
40 = 0.15
𝑥
( )
25
25(10 − 𝑥)
= 0.15
40𝑥
250 − 25𝑥 = 6𝑥
250 = 31𝑥
𝒙 = 𝟖. 𝟎𝟔 𝒈 𝑩𝑫
This leaves 1.94𝑔 of the BD in the ether.
Second Extraction:
Let be the mass in g of acid extracted into the second portion of 25 cm3 water. Then (1.94 – 𝑦)g reains in
the ether. Substituting into the equation:
1.94 − 𝑦
( )
40 = 0.15
𝑦
( )
25
25(1.94 − 𝑦)
= 0.15
40𝑦
48.5 − 25𝑦 = 6𝑦
48.5 = 31𝑦
𝒚 = 𝟏. 𝟓𝟔 𝒈 𝑩𝑫
 Thus total amount of BD extracted using two portions is 9.62 g, which is more than the 8.93 g extracted
using a single portion.
 Using smaller portions of solvents has several other advantages. Solvents are often flammable, hence
small amounts are safer. Also, most solvents are expensive and environmentally unfriendly.
Examination Practice 7
Section A: MULTIPLE CHOICE
1. Hydrogen for use in ammonia production is produced by the endothermic reaction:
𝑪𝑯𝟒 (𝒈) + 𝑯𝟐 𝑶(𝒈) 𝑪𝑶(𝒈) + 𝟑𝑯𝟐 (𝒈)
Which of the following will increase the equilibrium yield of hydrogen?
A Decrease the methane concentration
B Decrease the temperature
C Decrease the pressure
D Add a catalyst
2. The partition coefficient for the above system can be altered by

A adding more iodine
B adding more cyclohexane
C changing the temperature
D shaking the mixture thoroughly.
3. Under certain conditions liquid ammonia ionises as shown below:

𝟐𝑵𝑯𝟑 𝑵𝑯𝟒+ + 𝑵𝑯𝟐−
Which line in the table shows the correct conjugate acid and conjugate base for this ionisation?
conjugate acid conjugate base

A 𝑁𝐻3 𝑁𝐻4+
B 𝑁𝐻4+ 𝑁𝐻3
C 𝑁𝐻2− 𝑁𝐻4+
D 𝑁𝐻4+ 𝑁𝐻2−
4. Consider the equilibrium:

𝑷𝑪𝒍𝟓 𝑷𝑪𝒍𝟑 + 𝑪𝒍𝟐
Adding 𝑃𝐶𝑙3 to the above system will
A increase the value of the equilibrium constant
B decrease the value of the equilibrium constant
C increase the concentration of 𝑃𝐶𝑙5 and decrease the concentration of 𝐶𝑙2
D decrease the concentration of 𝑃𝐶𝑙5 and increase the concentration of 𝐶𝑙2
5. At a particular temperature, 8.0 mole of 𝑁𝑂2 was placed in a 1 𝑑𝑚3 container and the 𝑁𝑂2 dissociated
by the following reaction:
𝟐𝑵𝑶𝟐 (𝒈) 𝟐𝑵𝑶(𝒈) + 𝑶𝟐 (𝒈)
At equilibrium the concentration of 𝑁𝑂(𝑔) is 2.00 𝑚𝑜𝑙𝑑𝑚−3 .
What is the value of the equilibrium constant?
A 0.11 B 0.22 C 0.33 D 9.00.
6. A buffer solution can not be made from

A 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻 and 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝑁𝑎
C 𝐻𝑁𝑂3 and 𝑁𝑎𝑁𝑂3
D 𝑁𝐻3 and 𝑁𝐻4 𝐶𝑙
7. 5.00 𝑐𝑚3 of a solution of hydrochloric acid was diluted to exactly 250 𝑐𝑚3 with water. The pH of this
diluted solution was 2.00.
The concentration of the original undiluted solution, in 𝑚𝑜𝑙𝑑𝑚−3 , was
A 2.00 𝑥 10−2 B 4.00 𝑥 10−2 C 4.00 𝑥 10−1 D 5.00 𝑥 10−1
8. The graph below shows the pH changes when 0.1 𝑚𝑜𝑙𝑑𝑚−3 ammonia solution is added to 50 𝑐𝑚3 of
0·1 𝑚𝑜𝑙𝑑𝑚−3 hydrochloric acid solution.
Which line in the table shows an indicator which is not suitable for use in determining the equivalence
point for the above reaction?
indicator pH range of indicator

A methyl orange 3.1 − 3.4
B bromophenol red 5.2 − 6.8
C bromothymol blue 6.0 − 7.6
D phenolphthalein 8.3 − 10.0
9. Phosphoric acid is a weak acid and undergoes partial dissociation according to the equation
𝐻3 𝑃𝑂4 𝐻2 𝑃𝑂4− + 𝐻 +
The position of equilibrium would be shifted to the right by the addition of
A a catalyst
B sulphuric acid
C sodium hydroxide
D sodium dihydrogenphosphate.
10. Substance 𝑿 is distributed between equal volumes of two immiscible liquids as shown in the diagram.
The number of dots represents the relative distribution of 𝑿 in the two liquids at equilibrium.
𝑿(𝒂𝒒) 𝑿(𝒉𝒆𝒙𝒂𝒏𝒆)
The partition coefficient for this system is
A 0.46 B 0.50 C 2.00 D 2.17.
11. Which of the following decreases when an aqueous solution of ethanoic acid is diluted?
A pH B [𝐻 + ] C 𝑝𝐾𝑎 D The degree of dissociation
12. Iodide ions are oxidised by acidified nitrite ions according to the equation
𝟐𝑵𝑶− −
𝟐 + 𝟐𝑰 + 𝟒𝑯
+
𝟐𝑵𝑶 + 𝑰𝟐 + 𝟐𝑯𝟐 𝑶
Addition of sodium ethanoate to the reaction mixture slows down the formation of iodine. The most
likely explanation for this effect is that ethanoate ions
A remove iodine
B reduce the concentration of iodide ions
C react with nitrite ions
D react with hydrogen ions.
13. Which of the following indicators should be used in the titration of potassium hydroxide solution with
ethanoic acid solution?
A Phenolphthalein, pH range 8.0 – 9.8
B Bromothymol blue, pH range 6.0 – 7.6
C Methyl red, pH range 4.2 – 6.2
D Methyl orange, pH range 3.1 – 4.4
14. A reaction in dynamic equilibrium is one in which

A the concentration of the product is always independent of reaction conditions
B the enthalpy changes for the forward and the reverse reactions are equal
C the activation energies for the forward and the reverse reactions are equal
D the rates of the forward and the reverse reactions are equal.
15. The diagram below represents an equilibrium mixture for the reaction
𝑵𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑵𝑶(𝒈)
What is the value of equilibrium constant?

A 0.083 B 0.50 C 2.00 D 12
16. The solubility of ammonia in water is represented by the equilibrium

𝑵𝑯𝟑 (𝒈) + 𝑯𝟐 𝑶(𝒍) 𝑵𝑯𝟒+ (𝒂𝒒) + 𝑶𝑯− (𝒂𝒒) ∆𝑯 = −𝟑𝟔 𝐤𝐉𝐦𝐨𝐥−𝟏
The solubility of ammonia in water will be increased by

A increasing pressure and cooling
B decreasing pressure and cooling
C decreasing pressure and warming
D increasing pressure and warming.
17. According to the Brønsted-Lowry theory, a base is a(n)

A. Proton donor.
B. Proton acceptor.
C. Electron donor.
D. Electron acceptor.
18. In the reaction

𝑵−𝟑 + 𝑯𝟐 𝑶 𝑯𝑵𝟑 + 𝑶𝑯− ,
the Brønsted-Lowry base is
A. N3− B. H2O C. HN3 D. OH −
19. Which of the following is produced in the first step of the dissociation of the acid H3 PO4 ?
A. H3 PO3 B. H2 PO4− C. HPO4− D. PO3−4
20. Acid dissociation constants give information about

A. the strengths of acids.
B. the number of nonacidic hydrogens present in acids.
C. whether acids are polyprotic.
D. whether acids can neutralize bases.
21.The pH of a solution for which [OH − ] = 1.0 x10−6 is

A. 1.00. B. 8.00. C. 6.00. D. –6.00.
22. Which of the following does not describe an acidic solution?

A. The pH is less than 7.0
B. The [OH − ] is greater than 1.0 x.10−7
C. The [H3 O+ ] is greater than the [OH − ]
D. The [OH − ] is 6.0 x 10−10
23. If the pH of a solution increases from 4.0 to 6.0, the hydronium ion concentration
A. increases by a factor of 1.5.
B. increases by a factor of 100.
C. decreases by a factor of 1.5.
D. decreases by a factor of 100.
The graph below shows the titration curve that results when 100. cm3 of 0.0250 moldm−3 acetic acid is
titrated with 0.100 moldm−3 NaOH. Study the graph and answer questions 8 – 9.
24. Which of the following indicators is the best choice for this titration?
indicator pH range of colour
A. Methyl Orange 3.2 − 4.4
B. Methyl Red 4.8 − 6.0
C. Bromothymol blue 6.1 − 7.6
D. Phenolphthalein 8.2 − 10.0
25. Which part of the curve corresponds to the optimum buffer action for the acetic acid / acetate ion pair?
A. Point V B. Point X C. Point Z D. Along all of section WY
26. In a saturated solution of Zn(OH)2 at 25 oC, the value of [OH − ] is 2.0 x 10−6 moldm−3 . What is the value
of the solubility-product constant, K sp, for Zn(OH)2 at 25 oC?
A. 4.0 x 10−18 B. 8.0 x 10−18 C. 1.6 x 10−16 D. 4.0 x 10−12
27. The pH of a solution of sodium citrate will be:

A. the same as pure water.
B. greater than 7
C. less than 7
D. cannot determine without additional information.
28. The K b of ammonia is 1.8 x 10−5 . Its conjugate acid

A. has a pK a greater than 5
B. is NH3+
C. is a moderately strong acid
D. all of the above.
29. Nitrate ion has no effect on solution pH because:

A. it is small
B. it is a weak acid
C. it is the conjugate base of a strong acid
D. it has only a −1 charge
30. NH3 and CH3COOH solutions are mixed. Which of the following are a conjugate acid base pair?
A. NH3 and CH3COOH
B. NH4+ and NH3
C. CH3COOH and NH4+
D. NH3 and CH3COO-
31. Consider the following reaction:

𝑯𝑺𝑶𝟒− + 𝑯𝟐 𝑶 𝑯𝟑 𝑶+ + 𝑺𝑶𝟐−
𝟒
Which substance behaves as a Brønsted-Lowry base?
A. HSO4− B. H2O C. H3O+ D. SO2−
4
Section B: FREE RESPONSE
32. (a) The diagram below shows the effect of temperature and pressure on the equilibrium yield of the
product in a gaseous equilibrium.
10 MPa
30 MPa
50 MPa
Yield/%
Temperature
(i) Use the diagram to deduce whether the forward reaction involves an increase or a decrease in
the number of moles of gas. Explain your answer.
(ii) Use the diagram to deduce whether the forward reaction is exothermic or endothermic.
Explain your answer.
(6)
3
(b) When a 0.218 mol sample of hydrogen iodide was heated in a flask of volume V dm , the following
equilibrium was established at 700 K.
𝟐𝑯𝑰(𝒈) 𝑯𝟐(𝒈) + 𝑰𝟐(𝒈)
The equilibrium mixture was found to contain 0.023 mol of hydrogen.
(i) Calculate the number of moles of iodine and the number of moles of hydrogen iodide
in the equilibrium mixture.
(ii) Write an expression for Kc for the equilibrium.
(iii) State why the volume of the flask need not be known when calculating a value for Kc.
(iv) Calculate the value of Kc at 700 K.
(v) Calculate the value of Kc at 700 K for the equilibrium
𝟐𝑯𝑰(𝒈) 𝑯𝟐(𝒈) + 𝑰𝟐(𝒈)
(7)
(Total 13 marks)
33. As a first step in the manufacture of nitric acid it has been suggested that nitrogen monoxide, NO, can
be formed from nitrogen and oxygen in a reversible reaction.
(a) Write an equation for this reaction and deduce an expression for the equilibrium constant, Kc
(2)
(b) The sketch graph below shows how the value of Kc for this reaction changes with temperature.
Kc
Temperature
Use this graph to deduce whether the reaction is exothermic or endothermic. Explain your answer.
(2)
–5
(c) The value of Kc for this reaction is 1 × 10 at 1500 K.
Explain the significance of this value for an industrial chemist interested in manufacturing nitrogen
monoxide by the direct combination of the elements.
(2)
(d) When cooled, nitrogen monoxide reacts with oxygen to form gaseous nitrogen dioxide, NO2, in a
reversible reaction.
(i) Write an equation for this reaction.
(ii) State how an increase in pressure would change the position of the equilibrium and the value of
the equilibrium constant for this reaction.
(3)
(Total 9 marks)
34. The manufacture of methanol can be achieved in two stages. In the first stage, methane and steam
react according to the following equation.
ο –1
𝑪𝑯𝟒(𝒈) + 𝑯𝟐𝑶(𝒈) 𝑪𝑶(𝒈) + 𝟑𝑯𝟐(𝒈) ∆H = +210 kJ mol
Discuss, with reasons, the effects of increasing separately the temperature and the pressure on the
yield of the products and on the rate of this reaction.
(6)
(Total 6 marks)
35. The reaction between hydrogen and iodine can be represented by the following equation:
–1
𝑯𝟐(𝒈) + 𝑰𝟐(𝒈) 𝟐𝑯𝑰(𝒈) ∆H = +52 kJ mol
(a)Write a Kc expression for the decomposition of hydrogen iodide. At a given temperature, the
value of Kc for this reaction is 20. What will be the value of Kc for the reaction between hydrogen
and iodine at this temperature?
(2)
(b) The pressure of an equilibrium mixture of hydrogen iodide, hydrogen and iodine was increased.
State what, if anything, would happen to:
(i) the rates of both forward and reverse reactions;
(ii) the position of equilibrium;
(iii) the value of the equilibrium constant.
(4)
(Total 6 marks)
36. (a) A flask containing a mixture of 0.200 mol of ethanoic acid and 0.110 mol of ethanol was
maintained at 25 °C until the following equilibrium had been established.
𝑪𝑯𝟑𝑪𝑶𝑶𝑯(𝒍) + 𝑪𝟐𝑯𝟓𝑶𝑯(𝒍) 𝑪𝑯𝟑𝑪𝑶𝑶𝑪𝟐𝑯𝟓(𝒍) + 𝑯𝟐𝑶(𝒍)
3 –3
The ethanoic acid present at equilibrium required 72.5 cm of a 1.50 mol dm solution of
sodium hydroxide for complete reaction.
(i) Calculate the value of the equilibrium constant, Kc, for this reaction at 25 °C.
(ii) The enthalpy change for this reaction is quite small. By reference to the number and type of
bonds broken and made, explain how this might have been predicted.
(5+3)
(Total 8 marks)
37. When ammonia gas is heated, a homogeneous, dynamic equilibrium is established
between ammonia and its constituent elements. This decomposition is endothermic.
(a) Explain the terms homogeneous, dynamic and equilibrium. Write an equation for this
decomposition and derive an expression for the equilibrium constant, Kc
(5)
(b) State and explain the conditions under which a high equilibrium concentration of hydrogen
would be obtained.
(4)
(c) The decomposition of ammonia might in the future be used as an industrial method for the
manufacture of hydrogen.
Explain why an industrial chemist might decide to use conditions different from those you have
given in part (b) if large quantities of hydrogen were to be produced by this decomposition.
Discuss the effect that using a catalyst would have on the equilibrium yield and on the amount
of hydrogen which could be produced in a given time.
(6)
(Total 15 marks)
38. At a temperature of 107°C, the reaction

𝑪𝑶(𝒈) + 𝟐𝑯𝟐(𝒈) 𝑪𝑯𝟑𝑶𝑯(𝒈)
reaches equilibrium under a pressure of 1.59 𝑀𝑃𝑎 with 0.122 𝑚𝑜𝑙 of carbon monoxide
3
and 0.298 mol of hydrogen present at equilibrium in a vessel of volume 1.04 dm .
Use these data to answer the questions that follow.
(a) Assuming ideal gas behaviour, determine the total number of moles of gas present.
Hence calculate the number of moles of methanol in the equilibrium mixture.
(3)
(b) Calculate the value of the equilibrium constant, Kc, for this reaction and state its units.
(3)
(Total 6 marks)
39. (a) The expression for an equilibrium constant, Kc, for a homogeneous equilibrium reaction is
given below.
Kc 
A2 B
C  D3
(i) Write an equation for the forward reaction.
(ii) Deduce the units of Kc
(iii) State what can be deduced from the fact that the value of Kc is larger when the equilibrium
is established at a lower temperature.
(3)
3
(b) A 36.8 g sample of N2O4 was heated in a closed flask of volume 16.0 dm . An equilibrium was
established at a constant temperature according to the following equation.
𝑵𝟐𝑶𝟒(𝒈) 𝟐𝑵𝑶𝟐(𝒈)
The equilibrium mixture was found to contain 0.180 mol of N 2O4.
(i) Calculate the number of moles of N2O4 in the 36.8 g sample.
(ii) Calculate the number of moles of NO2 in the equilibrium mixture.
(iii) Write an expression for Kc and calculate its value under these conditions.
(iv) Another 36.8 g sample of N2O4 was heated to the same temperature as in the original
experiment, but in a larger flask. State the effect, if any, of this change on the position of
equilibrium and on the value of Kc compared with the original experiment.
(9)
(Total 12 marks)
40. Tetrafluoroethene, 𝐶2𝐹4, is obtained from chlorodifluoromethane, 𝐶𝐻𝐶𝑙𝐹2, according
to the equation:
𝟐𝑪𝑯𝑪𝒍𝑭𝟐(𝒈) 𝑪𝟐𝑭𝟒(𝒈) + 𝟐𝑯𝑪𝒍(𝒈) H = +128 kJ mol –1
3
(a) A 1.0 mol sample of 𝐶𝐻𝐶𝑙𝐹2 is placed in a container of volume 18.5 dm and heat. When
equilibrium is reached, the mixture contains 0.20 mol of 𝐶𝐻𝐶𝑙𝐹2
(i) Calculate the number of moles of 𝐶2𝐹4 and the number of moles of
𝐻𝐶𝑙 present at equilibrium.
(ii) Write an expression for Kc for the equilibrium.
(iii) Calculate a value for Kc and give its units.
(6)
(b) (i) State how the temperature should be changed at constant pressure to increase
the equilibrium yield of 𝐶2𝐹4.
(ii) State how the total pressure should be changed at constant temperature to increase
the equilibrium yield of 𝐶2𝐹4.
(2)
(Total 8 marks)
41. Nitrogen dioxide dissociates according to the following equation.
𝟐𝑵𝑶𝟐(𝒈) 𝟐𝑵𝑶(𝒈) + 𝑶𝟐(𝒈)
When 21.3 g of nitrogen dioxide were heated to a constant temperature, T, in a flask of volume 11.5
3
dm , an equilibrium mixture was formed which contained 7.04 g of oxygen.
(a) Calculate the number of moles of oxygen present in this equilibrium mixture and deduce the
number of moles of nitrogen monoxide also present in this equilibrium mixture.
Calculate also the number of moles in the original 21.3 g of nitrogen dioxide and hence calculate
the number of moles of nitrogen dioxide present in this equilibrium mixture.
(4)
(b) Write an expression for the equilibrium constant, Kc, for this reaction. Calculate the value of this
constant at temperature T and give its units.
(4)
(c) The total number of moles of gas in the flask is 0.683. Use the ideal gas equation to determine
5
the temperature T at which the total pressure in the flask is 3.30 × 10 Pa.
(3)
(d) State the effect on the equilibrium yield of oxygen and on the value of Kc when the same mass
of nitrogen dioxide is heated to the same temperature T, but in a different flask of greater
volume.
(2)
(Total 13 marks)
42. The manufacture of sulphuric acid is carried out on a large scale in most industrialised countries because
it is needed by many other industries. In most countries the raw material is sulphur. The process consists
of three main stages - the burning of sulphur in air, the conversion of sulphur dioxide to sulphur trioxide
and the formation of sulphuric acid. The equation for the conversion to sulphur trioxide is
𝟐𝑺𝑶𝟐(𝒈) + 𝑶𝟐(𝒈) 𝟐𝑺𝑶𝟑(𝒈)
(a) For the conversion to sulphur trioxide, the effect of temperature on the percentage yield at
equilibrium is shown in Figure 1.
% yield of
sulphur 100
trioxide 90
80
300 400 500 600 700 800

temperature / ºC
Figure 1
(i) State whether this reaction is exothermic or endothermic and justify your answer by reference
to Figure 1.
(ii) Give the name of the catalyst used in this reaction. State the effect of the catalyst on the
percentage yield at equilibrium of sulphur trioxide and on the rates of both forward and reverse
reactions.
(iii) A typical operating temperature is 450 °C. State one advantage and one disadvantage of
operating the process at a temperature 50 °C lower.
(b) The operating pressure for the conversion of sulphur dioxide to sulphur trioxide is slightly higher
than atmospheric pressure.
(i) State the effect on the rate of the reaction of using a much higher pressure.
(ii) State the effect of using this much higher pressure on the percentage yield at equilibrium of
sulphur trioxide and give a reason for your answer.
43. (a) (i) Define the term Brønsted-Lowry acid.
(ii) What is meant by the term strong when describing an acid?
(iii) Give the value of the ionic product of water, Kw, measured at 298K, and state its units.
(4)
3 –3
(b) At 298 K, 25.0 cm of a solution of a strong acid contained 1.50 × 10 mol of hydrogen ions.
(i) Calculate the hydrogen ion concentration in this solution and hence its pH.
3 –3
(ii) Calculate the pH of the solution formed after the addition of 50.0 cm of 0.150 moldm 𝑁𝑎𝑂𝐻
3
to the original 25.0 cm of acid.
(8)
(c) A solution of a strong acid was found to have a pH of 0.5.
(i) Calculate the hydrogen ion concentration in this solution.
3
(ii) Calculate the volume of water which must be added to 25.0 cm of this solution to increase its
pH from 0.5 to 0.7
(5)
(Total 17 marks)
–3
44. (a) The pH of a 0.15 moldm solution of a weak acid, HA, is 2.82 at 300 K.
(i) Write an expression for the acid dissociation constant, Ka, of HA, and determine the value of Ka
for this acid at 300 K, stating its units.
(ii) The dissociation of HA into its ions in aqueous solution is an endothermic process. How would
its pH change if the temperature were increased? Explain your answer.
(8)
(b) Solution A contains n moles of a different weak acid, HX. The addition of some sodium hydroxide
to A neutralises one third of the HX present to produce Solution B.
(i) In terms of the amount, n, how many moles of HX are present in Solution B?
[HX]
(ii) Determine the ratio in Solution B.
[X – ]
–4 –3
(iii) Solution B has a hydrogen ion concentration of 4.2 × 10 moldm . Use this information and
your answer to part (b)(ii) to determine the value of the acid dissociation constant of HX.
(5)
(c) Why is methyl orange not suitable as an indicator for the titration of HX with sodium hydroxide?
(2)
(d) Solution B can act as a buffer. Explain what this means and write an equation that shows how
Solution B acts as a buffer if a little hydrochloric acid is added.
(3)
(Total 18 marks)
45. (a) Explain the terms acid and conjugate base according to the Brønsted-Lowry theory.
(2)
(b) For each of the following reactions, give the formula of the acid and of its conjugate base.
–

(i) 𝑵𝑯𝟑 + 𝑯𝑩𝒓 𝑵𝑯 4 + 𝑩𝒓

(ii) 𝑯𝟐𝑺𝑶𝟒 + 𝑯𝑵𝑶𝟑 𝑯𝑺𝑶 4– + 𝑯𝟐𝑵𝑶 3
(2)
(c) (i) Write an equation to represent the dissociation of water.
(ii) Give the expression for the equilibrium constant, Kc, for the reaction in (c)(i) and use this to
derive the expression for the ionic product of water, Kw.
–14 2 –6
(iii) The ionic product of water is 2.92 × 10 mol dm at 313K. Calculate the pH of water at
this temperature.
(iv) Given that the pH of water is 7.00 at 298 K, state whether the dissociation of water is
endothermic or exothermic. Give a reason for your answer.
(10)
(Total 14 marks)
46. (a) Give the Brønsted–Lowry definition of a base. State the essential feature of an acid-base reaction
in aqueous solution, writing an ionic equation to illustrate your answer.
(3)
(b) Explain what is meant by the term weak when applied to acids and bases.
(1)
(c) In aqueous solution, the weak acid propanoic acid, 𝐶𝐻3𝐶𝐻2𝐶𝑂𝑂𝐻(𝑎𝑞), produces propanoate ions
𝐶𝐻3𝐶𝐻2𝐶𝑂𝑂 − (𝑎𝑞). Write an expression for the acid dissociation constant, Ka, of propanoic acid
and state its units.
(2)
(d) (i) Explain what is meant by the term buffer solution.
(ii) Identify two components that could be used to make a buffer solution.
(iii) Give an example of the use of a buffer solution.
(4)
(Total 10 marks)
–3 3
47. (a) The graph below shows how the pH changes when 0.12 moldm 𝑁𝑎𝑂𝐻 is added to 25.0 cm of a
solution of a weak monoprotic acid, HA.
14
13
12
11
10
8
pH
7
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Volume of 0.12 M NaOH/cm3
(i) Use the graph to calculate the initial concentration of the acid HA.
(ii) Write an expression for the dissociation constant. Ka, of the weak acid 𝐻𝐴.
(iii) Determine the volume of sodium hydroxide added when [𝐻𝐴] = [ 𝐴− ] and use the graph to
determine the pH at this point.
(iv) Use your answers to part (a)(ii) and part (a)(iii) to determine the value of Ka for the acid 𝐻𝐴.
(9)
(b) A buffer solution is formed, when approximately half of the original amount of the acid 𝐻𝐴(𝑎𝑞) has
been neutralised by the base 𝑁𝑎𝑂𝐻(𝑎𝑞). Explain how this buffer solution is able to resist change in
pH when
(i) a small amount of 𝑁𝑎𝑂𝐻(𝑎𝑞) is added,
(ii) a small amount of 𝐻𝐶𝑙(𝑎𝑞) is added.
(4)
(Total 13 marks)
–3 3
48. The graph below shows how the pH changes as 0.12 moldm 𝐻𝐶𝑙(𝑎𝑞) is added to 25.0 cm of a
3
solution of sodium carbonate. There are two end-points. The second end-point is at 30.0 cm .
12
A
10
B
8
pH D
C
6
E
2
F
0
0 10 20 30 40
Volume of 0.12 M HCl/cm3
(a) Write equations for the reactions which occur in the solution between point A and point B on the
graph and between point C and point D on the graph.
(2)
(b) Estimate the minimum volume of hydrochloric acid needed in this experiment for carbon dioxide
to be produced from a well-stirred solution of sodium carbonate.
(1)
(c) Name an indicator which can be used to determine the end-point occurring between points D and
E. Explain why this indicator does not change colour between points B and C.
(2)
(d) Use the end-point occurring between points D and E to calculate the concentration of sodium
carbonate in the given solution.
(3)
(e) If the original solution had contained, in addition to sodium carbonate, an equal molar
concentration of sodium hydrogen carbonate, at what volumes of hydrochloric acid would the two
end-points have been detected?
(2)
(Total 10 marks)
49. (a) Define the term Brønsted-Lowry acid.
(1)
(b) Write an equation for the reaction between gaseous hydrogen chloride and water.
State the role of water in this reaction, using the Brønsted-Lowry definition.
(2)
(c) Write an equation for the reaction between gaseous ammonia and water. State the role of water in
this reaction, using the Brønsted-Lowry definition.
(2)

(d) The ion 𝐻2𝑁𝑂 3 is formed in the first stage of a reaction between concentrated nitric acid and an
excess of concentrated sulphuric acid. In this first stage the two acids react in a 1:1 molar ratio. In
 
the second stage, the 𝐻2𝑁𝑂 3 ion decomposes to form the nitronium ion, 𝑁𝑂 2 . Write equations
for these two reactions and state the role of nitric acid in the first reaction.
(3)
(e) (i) Explain the term weak acid.
(ii) Write an expression for the acid dissociation constant, Ka, of HA, a weak monoprotic acid.
(iii) The value of the acid dissociation constant for the monoprotic acid HX is
–3
144 mol dm . What does this suggest about the concentration of undissociated HX in dilute
aqueous solution?
(iv) State whether HX should be classified as a strong acid or a weak acid. Justify your answer.
(5)
(Total 13 marks)
50. (a) Phenol is a weak acid. The dissociation of phenol in aqueous solution is represented by the
following equation:
+ –
𝑪𝟔𝑯𝟓𝑶𝑯(𝑎𝑞) + 𝑯𝟐𝑶(𝒍) 𝑯𝟑𝑶 (𝑎𝑞) + 𝑪𝟔𝑯𝟓𝑶 (𝑎𝑞)
What is meant by the term weak acid?
(1)
(b) (i) Write an expression for the acid dissociation constant, Ka, for phenol.
(ii) Write an expression linking Ka with pKa.
–10 –3
(iii) The value of the acid dissociation constant, Ka, for phenol is 1 × 10 moldm .
Calculate the pKa value of phenol.
(iv) Ethanoic acid is a stronger acid than phenol. State whether the p Ka value for ethanoic acid
will be greater or smaller than that of phenol.
(4)
(c) The indicator phenolphthalein is a weak acid which can be represented by the formula 𝐻𝐼𝑛. It
dissociates in solution and has a pKa value of 9.3.
𝑯𝑰𝒏(𝒂𝒒) 𝑯+ (𝒂𝒒) + 𝑰𝒏− (𝒂𝒒)
colourless red
(i) Suggest and explain, with reference to the pKa value, the pH range of phenolphthalein.
(2)
(ii) State the colour change that would be observed at the end point in an acid-base titration
using phenolphthalein if sodium hydroxide solution were being added from the burette.
Explain, in terms of the species present, why this colour is formed.
(2)
(iii) State why phenolphthalein is unsuitable for a titration between a strong acid and a weak base.
(1)
(Total 10 marks)
51. (a) (i) Define the term pH.
(ii) Write an expression for the dissociation constant Ka for the weak acid HX.
–5 –3. –3
(iii) For HX, Ka = 4.25 × 10 mol dm Calculate the pH of a 0.45 moldm solution of this acid.
(6)
(b) In a 0.25 M solution, a different acid HY is 95% dissociated.
(i) Calculate the pH of this solution.
(ii) Calculate the value of Ka for the acid HY.
(6)
(Total 12 marks)
52. (a) Define pKa
(1)
–3
(b) Calculate the pH of a 0.52 moldm aqueous solution of the weak monoprotic (monobasic) acid
HX (pKa = 3.72).
(4)
(c) Write an expression for the acid dissociation constant Ka for HX. Use this to show that the pH of
any sample of HX is 3.72 when half of the acid has been neutralised by a solution of sodium
hydroxide.
(3)
(d) Explain why indicators cannot be used to determine the end-point of a titration between a weak
acid and a weak base.
(2)
(Total 10 marks)
–5 –3
53. The value of the acid dissociation constant, Ka, for ethanoic acid is 1.74 × 10 mol dm at
298 K.
(a) (i) Write an expression for Ka for ethanoic acid.
–3
(ii) Calculate the pH at 298 K of a 0.220 mol dm solution of ethanoic acid.
(5)
–3
(b) A sample of the 0.220 mol dm solution of ethanoic acid was titrated against sodium hydroxide
solution.
–3
(i) Calculate the volume of a 0.150 mol dm solution of sodium hydroxide required to
3
neutralise 25.0 cm of the ethanoic acid solution.
(ii) From the list below, select the best indicator for this titration and explain your choice.
Name of indicator pH range
bromophenol blue 3.0 – 4.6
methyl red 4.2 – 6.3
bromothymol blue 6.0 – 7.6
thymol blue 8.0 – 9.6
(5)
3
(c) A buffer solution is formed when 2.00 g of sodium hydroxide are added to 1.00 dm of a 0.220
–3
mol dm solution of ethanoic acid. Calculate the pH at 298 K of this buffer solution.
(6)
(Total 16 marks)
54. (a) Titration curves labelled A, B, C and D for combinations of different acids and bases are
–3
shown below. All solutions have a concentration of 0.1 mol dm .
14 14
12 12
10 10
8 8
pH pH
6 6
4 4
2 2
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Volume/cm 3 Volume/cm 3
A B
14 14
12 12
10 10
8 8
pH pH
6 6
4 4
2 2
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Volume/cm 3 Volume/cm 3
C D
(i) Select from A, B, C and D the curve produced by the addition of
3
 ammonia to 25 cm of hydrochloric acid;
3
 ethanoic acid to 25 cm of sodium hydroxide;
3
 sodium hydroxide to 25 cm of hydrochloric acid.
(ii) A table of acid–base indicators and the pH ranges over which they change colour is shown
below.
Indicator pH range
Thymol blue 1.2 – 2.8
Bromophenol blue 3.0 – 4.6
Methyl red 4.2 – 6.3
Cresolphthalein 8.2 – 9.8
Thymolphthalein 9.3 – 10.5
Select from the table an indicator which could be used in the titration which produces curve
A but not in the titration which produces curve B.
(4)
(b) (i) Write an expression for the term pH.
(ii) A solution of potassium hydroxide has a pH of 11.90 at 25°C. Calculate the concentration
of potassium hydroxide in the solution.
(4)
–5 –3
(c) The acid dissociation constant, Ka, for propanoic acid has the value of 1.35 × 10 mol dm at
25°C.
[H  ][CH 3 CH 2 COO  ]
Ka 
CH 3 CH 2 COOH
In each of the calculations below, give your answer to 2 decimal places.
–3
(i) Calculate the pH of a 0.117 mol dm aqueous solution of propanoic acid.
3 –3
(ii) Calculate the pH of a mixture formed by adding 25 cm of a 0.117 mol dm aqueous solution
3 –3
of sodium propanoate to 25 cm of a 0.117 mol dm aqueous solution of propanoic acid.
(5)
(Total 13 marks)
55. In this question, give all pH values to 2 decimal places.
(a) (i) Write expressions for the ionic product of water, Kw, and for pH.
–14 2 –6
(ii) At 318 K, the value of Kw is 4.02 × 10 mol dm and hence the pH of pure water is 6.70
State why pure water is not acidic at 318 K.
3 –3
(iii) Calculate the number of moles of sodium hydroxide in 2.00 cm of 0.500 mol dm aqueous
sodium hydroxide.
(iv) Use the value of Kw given above and your answer to part (a)(iii) to calculate the pH of the
3 –3
solution formed when 2.00 cm of 0.500 mol dm aqueous sodium hydroxide are added
3
to 998 cm of pure water at 318 K.
(6)
(b) At 298 K, the acid dissociation constant, Ka, for propanoic acid, CH3CH2COOH, has the value
–5 –3
1.35 × 10 mol dm .
(i) Write an expression for Ka for propanoic acid.
–3
(ii) Calculate the pH of 0.125 mol dm aqueous propanoic acid at 298 K.
(4)
(c) Sodium hydroxide reacts with propanoic acid as shown in the following equation.
𝑵𝒂𝑶𝑯 + 𝑪𝑯𝟑𝑪𝑯𝟐𝑪𝑶𝑶𝑯 𝑪𝑯𝟑𝑪𝑯𝟐𝑪𝑶𝑶𝑵𝒂 + 𝑯𝟐𝑶
A buffer solution is formed when sodium hydroxide is added to an excess of aqueous propanoic
acid.
3 –3
(i) Calculate the number of moles of propanoic acid in 50.0 cm of 0.125 mol dm aqueous
propanoic acid.
(ii) Use your answers to part (a)(iii) and part (c)(i) to calculate the number of moles of propanoic
3 –3
acid in the buffer solution formed when 2.00 cm of 0.500 mol dm aqueous sodium
3 –3
hydroxide are added to 50.0 cm of 0.125 mol dm aqueous propanoic acid.
(iii) Hence calculate the pH of this buffer solution at 298 K.
(6)
(Total 16 marks)
–3
56. The pH curve shown below was obtained when a 0.150 mol dm solution of sodium hydroxide was
3
added to 25.0 cm of an aqueous solution of a weak monoprotic acid, HA.
pH 14
12
10
8
6
4
2
0
18.2
Volume of 0.150 mol dm –3 NaOH added/cm 3
(a) Use the information given to calculate the concentration of the acid.
(2)
(b) (i) Write an expression for the acid dissociation constant, Ka, for HA.
(ii) Write an expression for pKa
(iii) Using your answers to parts (b)(i) and (b)(ii), show that when sufficient sodium hydroxide has
been added to neutralise half of the acid,
𝑝𝐻 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑝𝐾𝑎 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝐻𝐴
(4)
(c) Explain why dilution with a small volume of water does not affect the pH of a buffer solution.
(2)
–3
(d) (i) Calculate the change in pH when 0.250 mol dm hydrochloric acid is diluted with water to
–3
produce 0.150 mol dm hydrochloric acid.
3 –3
(ii) Calculate the volume of water which must be added to 30.0 cm of 0.250 moldm
–3
hydrochloric acid in order to reduce its concentration to 0.150 moldm .
(4)
(Total 12 marks)
57. (a) Define an acid-base indicator.
(1)
(b) If an indicator can be conveniently represented as 𝑯𝑰𝒏 and its dissociation constant as 𝑲𝑰𝒏 , write
(i) the equation for the dissociation of 𝑯𝑰𝒏 in aqueous solution;
(ii) an expression for 𝑲𝑰𝒏 .
(2)
(c) Congo red, an acid-base indicator, is blue in acidic conditions and red in alkaline conditions. It has a
𝑲𝑰𝒏 value of 𝟏. 𝟐 𝒙 𝟏𝟎−𝟒 𝒎𝒐𝒍𝒅𝒎−𝟑 .
(i) Given that colour changes when [𝑰𝒏− ] = [𝑯𝑰𝒏], calculate the pH at which Congo red begins to
change colour.
(ii) State the acid-base titrations for which Congo red would be a suitable indicator.
(iii) Calculate the pH of 𝟎. 𝟐𝟎 𝒎𝒐𝒍𝒅𝒎−𝟑 solution of Congo red.
(iv) If an indicator contributes to the pH of a solution, suggestion a reason why the pH of a titration
mixture is not affected by the indicator used.
(5)
(d) The pH changes during the titration of acid 𝑯𝑨 against base 𝑯𝑩 are shown in Table 1.
Volume of base 𝑯𝑩 / 𝒄𝒎𝟑 0 5 10 15 20 22 25 30
pH 0.8 1.0 1.6 2.4 3.6 8.0 9.0 9.6
Table 1
(i) Plot a graph of pH against volume of base HB.
(ii) Use your graph to deduce the pH at end point.
(4)
[Total 12 marks]
[© ZIMSEC 9189/1 N2014]
–2 –3
58. A student titrated the 1.50 × 10 mol dm methanoic acid with aqueous sodium hydroxide.
3
A 25.00 cm sample of the 𝐻𝐶𝑂𝑂𝐻(𝑎𝑞) was placed in a conical flask and the 𝑁𝑎𝑂𝐻(𝑎𝑞) was added
from a burette until the pH no longer changed.
(i) Write a balanced equation for the reaction between 𝐻𝐶𝑂𝑂𝐻(𝑎𝑞) and 𝑁𝑎𝑂𝐻(𝑎𝑞).
(ii) Part of the pH curve for this titration is shown below.
14
13
12
11
10
9
8
pH 7
6
5
4
3
2
1
0
0 5 10 15 20 25 30 35 40 45 50
volume NaOH(aq) added cm 3
–3
Calculate the concentration, in mol dm , of the aqueous sodium hydroxide.
[3]
–14 –3
(iii) Calculate the pH of the aqueous sodium hydroxide. [Kw = 1.00 × 10 mol dm
[2]
(iv) The pH ranges in which colour changes for three acid-base indicators are shown below.
indicator pH range
metacresol purple 7.4 – 9.0

2,4,6-trinitrotoluene 11.5 – 13.0
ethyl orange 3.4 – 4.8
Explain which of the three indicators is suitable for this titration.
[2]
[Total 8 marks]
59. (a) (i) What is meant by the term buffer solution?
[2]
(ii) Write equations to show how the hydrogencarbonate ion, 𝐻𝐶𝑂3− , controls the pH of blood.
[2]
(iii) A solution containing both 𝑁𝑎2 𝐻𝑃𝑂4 and 𝑁𝑎2 𝐻2 𝑃𝑂4 is commonly used as a buffer solution.
The following equilibrium is present in the solution.
𝑯𝟐 𝑷𝑶−𝟒 (𝒂𝒒) 𝑯𝑷𝑶𝟐− +
𝟒 (𝒂𝒒) + 𝑯 (𝒂𝒒) 𝐾𝑎 = 6.2 𝑥 10−8 𝑚𝑜𝑙𝑑𝑚−3
Calculate the pH of a buffer solution made by mixing 100 𝑐𝑚3 of 0.5 𝑚𝑜𝑙𝑑𝑚−3 𝑁𝑎2 𝐻𝑃𝑂4 and
100 𝑐𝑚3 of 0.3 𝑚𝑜𝑙𝑑𝑚 −3 𝑁𝑎2 𝐻2 𝑃𝑂4 .
[2]
(b) Silver phosphate, 𝐴𝑔3 𝑃𝑂4 , is sparingly soluble in water.
(i) Write an expression for the solubility product, 𝐾𝑠𝑝 , of 𝐴𝑔3 𝑃𝑂4 , and state its units.
(ii) The numerical value of 𝐾𝑠𝑝 is 1.25 𝑥 10−20 at 298 𝐾. Use this value to calculate[𝑨𝒈+ (𝑎𝑞)] in a
saturated solution of 𝐴𝑔3 𝑃𝑂4 .
[4]
(c) The half-equation for the redox reaction between phosphoric (III) acid and phosphoric (V) acid is
shown.
𝑯𝟑 𝑷𝑶𝟒 (𝒂𝒒) + 𝟐𝑯+ (𝒂𝒒) + 𝟐𝒆− 𝑯𝟑 𝑷𝑶𝟑 (𝒂𝒒) + 𝑯𝟐 𝑶(𝒍) 𝑬𝜽 = −𝟎. 𝟐𝟖𝑽
Find suitable data from the Data Booklet to write an equation for the reaction between 𝐻3 𝑃𝑂3 and
𝐹𝑒 3+ (𝑎𝑞) ions, and calculate the 𝐸𝑐𝑒𝑙𝑙
𝜃
for the reaction.
[2]
[Total 12 marks]
[© UCLES 2015 9701/42/M/J/15]
60. (a) Hydrazine, 𝑁𝐻2 𝑁𝐻2 , is used as a rocket fuel and it reacts with fluorine as shown in the equation:
𝑵𝑯𝟐 𝑵𝑯𝟐 (𝒈) + 𝟐𝑭𝟐 (𝒈) 𝑵𝟐 (𝒈) + 𝟒𝑯𝑭(𝒈)
(i) Use bond energy values from the Data Booklet to calculate the enthalpy change for the reaction.
(ii) Suggest a reason why hydrazine is used as a rocket fuel.
[3]
(b) Fig. 1 shows a fuel-cell Breathalyzer used by the police to measure the amount of ethanol,
𝐶𝐻3 𝐶𝐻2 𝑂𝐻, in the blood stream of a person suspected of driving under the influence of alcohol. The
cell is similar to a hydrogen-oxygen fuel cell.
(i) Give two ion-electron half equations that take place at each electrode.
(ii) Explain how the fuel cell is used to measure the amount of ethanol in the breath of a person.
[5]
(c) (i) Define the term solubility product with reference to silver carbonate, 𝐴𝑔2 𝐶𝑂3 .
(ii) The solubility of silver carbonate in water is 0.0035 𝑔 𝑝𝑒𝑟 100 𝑐𝑚3 at 25 ℃.
Calculate the solubility product of 𝐴𝑔2 𝐶𝑂3 in water at this temperature.
[4]
[Total 12 marks]
[© ZIMSEC 9189/1 N2011]
61. (a) Liquid ammonia and aqueous ammonia dissociate to give ammonium ions, the dissociation reaching
equilibrium.
(i) Construct equations for the dissociation of each of the two substances.
(ii) Write the equilibrium constant expression, 𝑲𝒃 , for the dissociation of aqueous ammonia.
(iii) Calculate the 𝑲𝒃 value of aqueous ammonia given that 𝟎. 𝟎𝟏 𝒎𝒐𝒍𝒅𝒎−𝟑 of the solution yield
equilibrium concentration of 𝟒. 𝟑𝟎 𝒎𝒐𝒍𝒅𝒎−𝟑 for each product, stating any assumption you have
made.
[5]
(b) Mixtures of aqueous solutions of ammonia and ammonium chloride act as buffers.
(i) Name the type of buffer made by these solutions.
(ii) Write equations to show how the ammonia/ammonium chloride buffer system works.
(iii) Use your 𝑲𝒃 value in (a) (iii) to calculate the pH of the buffer solution that would be formed
when 1.0 g of ammonium chloride is added to 𝟏. 𝟎 𝒅𝒎𝟑 of 𝟎. 𝟎𝟏 𝒎𝒐𝒍𝒅𝒎−𝟑 ammonia solution.
[7]
[Total 12 marks]
[© ZIMSEC 9189/1 N2012]

Equilibria by Xhex

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7

7.1 Chemical Equilibria

7.1 Chemical Equilibria

 A reversible reaction is one which

 As the reaction proceeds, the rate

Characteristics of Dynamic Equilibrium

 If the concentration of 𝐴 or 𝐵 is increased, the rate of 𝑨 + 𝑩 𝑪 + 𝑫

 If the concentration of a product (𝐶 or 𝐷) is increased, 𝑨 + 𝑩 𝑪 + 𝑫

Le Chatelier's Principle predicts that:

 If the pressure of a system at equilibrium is

 Example 1: 𝟐𝑺𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈) 𝟐𝑺𝑶𝟑 (𝒈)

 Example 2: 𝟐𝑯𝟐 𝑺(𝒈) + 𝑺𝑶𝟐 (𝒈) 𝟑𝑺(𝐬) + 𝟐𝑯𝟐 𝑶(𝒈)

 Example 3: 𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)

 An increase in temperature will 𝑨 + 𝑩 𝑪 + 𝑫, ∆𝑯 = −250 kJmol−1

 If ∆𝐻 = 0, then a change in temperature will have no effect on the position of equilibrium.

 Example 1: 𝑵𝟐 (𝒈) + 𝟑𝑯𝟐 (𝒈) 𝟐𝑵𝑯𝟑 (𝒈), ∆𝐇 < 𝟎

 Example 2: 𝑪𝒂𝑪𝑶𝟑 (𝒔) 𝑪𝒂𝑶(𝒔) + 𝑪𝑶𝟐 (𝒈), ∆𝐇 > 𝟎

Chemical Equilibria in the Chemical Industry

a) The Contact Process

 But such conditions are not used because:

Fig.7.2 Flow diagram for the manufacture of sulphur trioxide

b) The Haber Process

 But such conditions are not used because:

Fig.7.3 Flow diagram for the manufacture of ammonia

 For the reversible reaction

Units: 𝒎𝒐𝒍−𝟐 𝒅𝒎𝟔 Units: 𝑷𝒂−𝟐

Factors Affecting Equilibrium Constants

 Pressure, concentration and use of catalyst have no effect on an equilibrium constant.

Effect on equilibrium Effect on equilibrium

𝑵𝟐 (g) + 𝟑𝑯𝟐 (g) 𝟐𝑵𝑯𝟑 (g),

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚

0.60 1.80 0.80

𝑪𝑶𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝑪𝑶(𝒈) + 𝑯𝟐 𝑶(𝒈)

[𝐶𝑂][𝐻2 𝑂] (0.24 + 𝑥)2

Taking a square root of both sides:

2. For the reaction

6. Methanol can be produced by the following:

7. Consider the following equilibrium:

8. Which of the factors below is not a condition necessary for equilibrium?

9. Consider the following equilibrium system:

10. Consider the following equilibrium:

 A base is a proton (𝐻 + ) acceptor. An example is ammonia:

 The general equation for a Brønsted-Lowry acid-base reaction is:

Example 1: 𝑯𝟐 𝑶 + 𝑵𝑯𝟑 𝑵𝑯𝟒+ + 𝑶𝑯−

Example 2: 𝑯𝑪𝒍 + 𝑯𝟐 𝑶 𝑯𝟑 𝑶+ + 𝑪𝒍−

 The 𝐻𝑆𝑂4− ion is also amphoteric:

Strong and Weak Acids and Bases

pH and Hydrogen Ion Concentration

The Ionic Product of Water, 𝐾𝑤

 The equilibrium expression for this reaction can be written:

 The value of 𝐾𝑤 varies with temperature,

(b) A solution of a strong acid was found to have a pH of 0.5.

(b) (i) [𝐻 + ] = 10−𝑝𝐻 = 10−0.5 = 0.316 𝑚𝑜𝑙𝑑𝑚−3

(ii) [𝐻 + ] at pH = 0.7 is 10−0.7 = 0.199 𝑚𝑜𝑙𝑑𝑚 −3

Fig. 7.4 pH of some common substances

The Acid Dissociation Constant, 𝐾𝑎

𝒑𝑲𝒂 = −𝑙𝑜𝑔10 (𝑲𝒂 )

(a) Calculating pH of Strong Acids

p c) Calculating the pH of Weak Acids and Weak Bases