A-LEVEL YEAR 2

STUDENT GUIDE

AQA
Chemistry
Physical chemistry 2

Alyn G . McFarland
Nora Henry
Philip Allan, an imprint of Hodder Education, an Hachette UK company, Blenheim Court,
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© Alyn McFarland and Nora Henry 2016
ISBN 978-1-4718-5860-4
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Contents
Getting the most from this book . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
About this book . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Content Guidance
Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Rate equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Equilibrium constant Kp for homogeneous systems . . . . . . . . . . . 32
Electrode potentials and electrochemical cells . . . . . . . . . . . . . . 39
Acids and bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

Questions & Answers

Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Rate equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Equilibrium constant Kp for homogeneous systems . . . . . . . . . . . 81
Electrode potentials and electrochemical cells . . . . . . . . . . . . . . 84
Acids and bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

Knowledge check answers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
■ Getting the most from this book

Exam tips
Advice on key points in the text to
Knowledge check
help you learn and recall content, Rapid-fire questions throughout
avoid pitfalls, and polish your exam the Content Guidance section to
technique in order to boost your check your understanding .
grade .

Knowledge check answers Summaries

■■ Each core topic is rounded
1 Turn to the back of the book
off by a bullet-list summary
for the Knowledge check
answers. for quick-check reference of
what you need to know .

Exam-style questions Thermodynamics

(ii) Using the values in Table 2, comment on the bonding in each of the
compounds. (4 marks)

The bonding in potassium bromide is ionic. ✓

There is some covalent character to cadmium bromide. ✓
The values are close together for potassium bromide. ✓
The higher experimental value for cadmium bromide indicates some covalent
bonding. ✓

e A common question is to compare the experimental lattice enthalpy with the

theoretical one. The experimental lattice enthalpy is determined using the values
in a Born–Haber cycle. An experimental value that is higher than the theoretical
value suggests some additional bonding in the compound, which would suggest
some covalent character. If the theoretical value is similar to the experimental
value, then the compound is completely ionic.

Question 4
Silver(i) nitrate, AgNO3, decomposes on heating according to the equation
Commentary on sample
Sample student
2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g)

student answers
The standard enthalpies of formation and standard entropy values of the
reactants and products in this reaction are given in Table 3.

answers Table 3
Substance ΔfH⦵ (kJ mol−1) S⦵ (J K−1 mol−1)
AgNO3(s) −123 141 Find out how many marks
Practise the questions, then Ag(s)
NO2(g)
O2(g)
0
+33
0
43
To be calculated
205 each answer would be
look at the student answers (a) Calculate the standard enthalpy change of reaction.
(b) Explain why the standard enthalpies of formation of Ag(s) and O2(g) are zero.
(2 marks)

(1 mark) awarded in the exam and then

that follow. (c) Calculate the standard entropy of NO2(g) if the ΔS⦵ for the reaction is
+489 J K-1 mol-1. (2 marks)
read the comments (preceded
by the icon e ) following
(d) Determine the temperature, in kelvin, at which this decomposition becomes
feasible. (3 marks)

e This is a common type of synoptic question from AS and you need to revise this

each student answer showing

from the energetics section. The calculation in (a) can be done using Hess’s law.

exactly how and where marks

are gained or lost.
Physical chemistry 2 75

4 AQA Chemistry
■ About this book
This book will guide you through sections 3.1.8 to 3.1.12 of the AQA A-level
Chemistry specification. The sections covered are all physical chemistry. The year 1
physical sections 3.1 to 3.7 are covered in the first student guide of this series.
Paper 1 of A-level covers physical chemistry (3.1.1 to 3.1.12), except 3.1.5 Kinetics and
3.1.9 Rate equations, as well as all inorganic chemistry (3.2.1 to 3.2.6, which can be
found in the second and fourth student guides of this series).
Paper 2 of A-level covers organic chemistry (3.3.1 to 3.3.16, found in the second and
fourth student guides of this series) as well as 3.1.5 Kinetics and 3.1.9 Rate equations
which are covered in the first student guide of this series and this book respectively.
Paper 3 covers all content.
This book has two sections:
■■ The Content Guidance covers the A-level physical chemistry sections 3.1.8 to
3.1.12 and includes tips on how to approach revision and improve exam technique.
Do not skim over these tips as they provide important guidance. There are also
knowledge check questions throughout this section, with answers at the back of
the book. At the end of each section there is a summary of the key points covered.
Many topics in the physical chemistry sections covered in the first student guide of
this series form the basis of synoptic questions in A-level papers. There are three
required practicals related to the topics in this book and notes to highlight these
are included.
■■ The Questions & Answers section gives sample examination questions of the
types you will find in the exams on each topic, as well as worked answers and
comments on the common pitfalls to avoid. This section contains many different
examples of questions but you should also refer to past papers, which are available
online.
The Content Guidance and the Questions & Answers section are divided into the
topics outlined by the AQA A-level specification.

Physical chemistry 2 5
Content Guidance
■ Thermodynamics
Born–Haber cycles
A Born–Haber cycle is an extension of Hess’s law for the formation of an ionic
compound. It allows the calculation of lattice enthalpy values.
Lattice enthalpy is most often the enthalpy of lattice dissociation and it is the
enthalpy change when 1 mole of an ionic compound is converted into its constituent
Exam tip
gaseous ions. The enthalpy of lattice dissociation is an endothermic process. It is
represented by ΔL H⦵ or Δlatt H⦵. For all formations, the
elements are written
The enthalpy of lattice formation is an exothermic process and has the same in their standard
numerical value as the enthalpy of lattice dissociation, but it has a negative sign. states at 25°C and
Lattice enthalpy values may be calculated using a Born–Haber cycle. 1 atm pressure, so
K(s) and Cl 2(g) . The
Born–Haber cycle equation representing
The Born–Haber cycle is a technique for applying Hess’s law to the standard enthalpy the formation must
changes that occur when an ionic compound is formed. be written for the
formation of 1 mole of
The formation of an ionic compound, for example potassium chloride (KCl), may be the compound, in this
thought of as occurring in a series of steps, even though the reaction itself may not case KCl(s) . Always
follow this route. include state symbols .
For KCl, the equation representing the enthalpy change of formation is:
The standard enthalpy
K(s) + ½Cl2(g) → KCl(s)
change of formation is
The standard enthalpy change of formation is represented by ΔfH⦵. the enthalpy change
when 1 mole of a
The important energy change that we are often trying to determine is the
compound is formed
standard lattice enthalpy of an ionic compound. This value cannot be determined
from its elements
experimentally, so it must be calculated using the Born–Haber cycle.
in their standard
For KCl, the equation representing the enthalpy of lattice dissociation is: states under standard
conditions .
KCl(s) → K+(g) + Cl−(g)
The standard lattice enthalpy is represented by ΔL H⦵ or Δlatt H⦵. The standard lattice
enthalpy is the enthalpy
The Born–Haber cycle linking these enthalpy changes for KCl can be drawn simply change when 1 mole of
as shown in Figure 1. an ionic compound is
converted into gaseous
ions .

6 AQA Chemistry
 Thermodynamics

1 x
K(s) + 2
Cl2(g) K+(g) + Cl–(g)

f L

KCl(s)

Figure 1 Simple Born–Haber cycle for potassium chloride (KCl)

All enthalpy changes can be determined experimentally apart from the standard
lattice enthalpy. Δ x H⦵ is a combination of a few standard enthalpy changes which
change K(s) + ½Cl2(g) to K+(g) + Cl−(g).
Remember, as with any Hess’s law diagram, any unknown enthalpy change may be The standard enthalpy
calculated if all the other values are known. change of atomisation
Other enthalpy changes is the enthalpy change
when 1 mole of gaseous
The change K(s) + ½Cl2(g) → K+(g) + Cl−(g) is composed of the following steps:
atoms is formed from
Step 1 K(s) → K(g) the element in its
standard state under
This is the atomisation of potassium. The standard enthalpy change of atomisation
standard conditions .
of potassium is represented by Δa H⦵ or Δat H⦵.
Step 2 K(g) → K+(g) + e−
This is the first ionisation of potassium. The first ionisation energy (enthalpy) is Knowledge check 1
represented by ΔIE1H⦵. What is the definition
of standard enthalpy
Step 3 ½Cl2(g) → Cl(g)
change of atomisation?
This is the atomisation of chlorine. The same symbol is used for the standard enthalpy
change of atomisation as for step 1 for potassium and the definition is the same. The first ionisation
For diatomic elements such as chlorine, the bond dissociation enthalpy may be used. energy is the energy
required to remove
This enthalpy change is also half of the bond dissociation enthalpy (energy). For 1 mole of electrons
diatomic elements the bond dissociation enthalpy (sometimes called the bond from 1 mole of gaseous
enthalpy or bond energy) can be given. If only 1 mole of atoms is required the enthalpy atoms to form 1 mole of
change is half of the bond dissociation enthalpy. gaseous monopositive
For the change Cl2(g) → 2Cl(g), the enthalpy change is equal to the bond dissociation ions .
enthalpy or twice the standard enthalpy change of atomisation.
The bond dissociation enthalpy is represented by ΔBDEH⦵. The bond dissociation
enthalpy is the energy
Exam tip required to break
Remember that the bond dissociation enthalpy is twice the standard 1 mole of a covalent
enthalpy of atomisation for diatomic elements . You may need to use one bond under standard
times the standard enthalpy of atomisation (if 1 mole of atoms is required) conditions .
or two times the standard enthalpy of atomisation (if 2 moles of atoms are
required) . If 1 mole of atoms is required you will need to use half of the
bond dissociation enthalpy or if 2 moles of atoms are required use one
bond dissociation enthalpy .

Physical chemistry 2 7
Content Guidance

Step 4 Cl(g) + e− → Cl−(g)

This is the first electron affinity of chlorine. It is represented by ΔEA1H⦵. The first electron
affinity is the enthalpy
Exam tip change when 1 mole
For halides of group 2 elements, two atomisations and two first electrons of electrons is added
affinities are required . For example Cl 2(g) is converted to 2Cl(g) and 2Cl(g) to 1 mole of gaseous
is converted to 2Cl− (g) . atoms to form 1 mole of
gaseous mononegative
ions .
A typical Born–Haber cycle diagram
The Born–Haber diagram shown in Figure 2 is that for a typical group 1 halide. This
is the Born–Haber cycle for potassium chloride (KCl). Knowledge check 2
Write an equation
Metal single
K+(g) + Cl(g) + e–
with state symbols to
positive ions
and non-metal represent the enthalpy
gaseous atoms ∆EAl of lattice dissociation of
K+(g) + Cl–(g) calcium oxide .
∆a Gaseous ions

Metal single K+(g) + 12 Cl2(g) + e–

positive ion

∆IEI
Metal K(g) + 12 Cl2(g)
gaseous Exam tip
atoms
∆L Endothermic processes
∆a have upwards arrows
and exothermic
K(s) + 12 Cl2(g) processes have
Elements in
standard states downwards arrows .
There are different
∆f
forms of this type of
KCl(s) Solid
compound
diagram, but this is the
most common . You will
Figure 2 Born–Haber cycle for potassium chloride (KCl) most often be asked to
The values given in a calculation may be: complete the diagram
or to use it . Don’t forget
■■ enthalpy of formation of potassium chloride (Δ fH⦵) = −437 kJ mol−1
the electrons or the
■■ enthalpy of atomisation of potassium (Δa H⦵) = +89 kJ mol−1
state symbols . This
■■ fi rst ionisation energy of potassium (ΔIE1H⦵) = +420 kJ mol−1 type of diagram can be
■■ enthalpy of atomisation of chlorine (Δa H⦵) = +121 kJ mol−1 applied to any group 1
■■ fi rst electron affinity of chlorine (ΔEA1H⦵) = −364 kJ mol−1 halide or hydride .
ΔL H⦵ = –ΔfH⦵ + Δa H⦵ + ΔIE1H⦵ + Δa H⦵ + ΔEA1H⦵
(KCl) (K) (K) (Cl) (Cl)

= +437 +89 +420 +121 +(–364)

= +703 kJ mol−1

8 AQA Chemistry
 Thermodynamics

The cycle works from the beginning of the arrow for lattice enthalpy to the end of
the arrow. The alternative route gives the same energy changes as predicted by Hess’s
law. The alternative route must take into account the direction of the arrows. If the
direction is reversed, then the negative of the value must be used.

Exam tip
The enthalpy of atomisation of chlorine is sometimes given or the bond
dissociation enthalpy can be given . It is vital that you understand that for
diatomic elements like the halides, the bond dissociation enthalpy is twice
the enthalpy of atomisation . If 2 moles of halide ion are required as shown
in the next example, two enthalpies of atomisation of F are required (or one
bond dissociation enthalpy) followed by two first electron affinities . The
group 2 metal ion requires a first and a second ionisation energy .

This is a standard Born–Haber diagram for all group 1 halides. 1 mole of the group 1
metal, A, reacts with half a mole of the halide, ½X 2, to form 1 mole of the solid halide,
AX (s). You may be asked to label the species present at each level in a Born–Haber
cycle. Always think about the change that is happening and don’t forget to include
the electron(s). Note the 1 mole of electrons only appears on two levels for a group 1
halide.

Born–Haber cycle for group 2 halides

For group 2 halides, MX 2, the Born–Haber diagram is slightly extended. Figure 3
shows the Born–Haber cycle for calcium fluoride (CaF2).
Metal double
positive ions Ca2+(g) + 2F(g) + 2e–
and non-metal
Exam tip
2∆EAI
gaseous atoms 2∆a or ∆BDE The main difference
Ca2+(g) + 2F–(g) Gaseous
Metal double Ca2+(g) + F2(g) + 2e– ions to note here is that
positive ion the first and second
∆IE2 ionisation energies of
Metal single Ca+(g) + F2(g) + e– the group 2 metal, A,
positive ion are needed to form
∆IEI
Metal gaseous Ca(g) + F2(g)
M2+ . Two enthalpies
atoms
of atomisation of
the halide, X 2, are
∆a ∆L
needed (or one bond
dissociation enthalpy)
Elements in Ca(s) + F2(g) as well as two electron
standard states
affinities to form
2 moles of the halide
∆f
ion, X− . Don’t forget to
CaF2(s) include the electrons
Solid
compound or you will lose all the
marks for that level .
Figure 3 Born–Haber cycle for calcium fluoride (CaF2)

Physical chemistry 2 9
Content Guidance

Worked example
Calculate the lattice enthalpy of calcium fluoride (CaF2).
Answer
Lattice enthalpy can be calculated since we know the other values in the Born–
Haber cycle:
Enthalpy of formation of calcium fluoride (ΔfH⦵) = −1220 kJ mol−1
Enthalpy of atomisation of calcium (Δa H⦵) = +178 kJ mol−1
First ionisation energy of calcium (ΔIE1H⦵) = +590 kJ mol−1
Second ionisation energy of calcium (ΔIE2H⦵) = +1145 kJ mol−1
Bond dissociation enthalpy of fluorine (ΔBDEH⦵) = +158 kJ mol−1
First electron affinity of fluorine (ΔEA1H⦵) = −348 kJ mol−1
ΔL H⦵ = −ΔfH⦵ + Δa H⦵ + ΔIE1H⦵ + ΔIE2H⦵ + ΔBDEH⦵ + 2ΔEA1H⦵
(CaF2) (Ca) (Ca) (Ca) (F) (F)
= +1220 +178 +590 +1145 +158 +2(−348)
= +2595 kJ mol−1

Born–Haber cycle for oxides

When dealing with oxides, the oxygen requires a first and a second electron affinity.
The first electron affinity of oxygen is −142 kJ mol−1 and the second electron affinity
is +844 kJ mol−1. The second electron affinity is endothermic as the second electron is
being added to an already negative ion so there is repulsion between the O− and the e−.

Mg2+(g) + O2–(g)

Mg2+(g) + O(g) + 2e–

∆ EAIH –142 ∆ EA2H +844
∆a +248 Mg2+(g) + O–(g) + e–
1
Mg2+(g) + O (g)
2 2
+ 2e–

∆ IE2H +1450

1
Mg+(g) + O (g)
2 2
+ e–
∆ LH

∆ IE1H +736
1
Mg(g) + O (g)
2 2

1
∆ aH +150 Mg(s) + O (g)
2 2

∆f –602

MgO(s)

Figure 4 Born–Haber cycle for magnesium oxide (MgO)

10 AQA Chemistry
 Thermodynamics

For magnesium oxide (MgO): Exam tip

ΔL H⦵ = −Δf H⦵ + Δa H⦵ + ΔIE1 H⦵ + ΔIE2 H⦵ + ΔBDE H⦵ + ΔEA1 H⦵ + ΔEA2 H⦵ It is expected that the
(MgO) (Mg) (Mg) (Mg) (O) (O) (O) endothermic second
electron affinity is
= +602 +150 +736 +1450 +248 +(−142) +844 shown as endothermic
= +3888 kJ mol−1 in a Born–Haber cycle
so the arrow should go
Patterns in lattice enthalpies back up and above the
level of the Mg2+(g) +
The lattice enthalpy depends on the size of the ions and also the charge on the ions.
O(g) + 2e − .
Table 1 gives the lattice enthalpy values for the group 1 and group 2 halides and oxides.

Table 1 Enthalpy values for group 1 and group 2 halides and oxides
Anion
Cation F− Cl− Br− I− O2−
Li+ +1029 +849 +804 +753 +2808

Na+ +915 +771 +743 +699 +2481

K+ +813 +703 +679 +643 +2231

Mg2+ +2883 +2492 +2414 +2314 +3888

Ca2+ +2595 +2197 +2125 +2038 +3523

Looking at the halides of sodium the lattice enthalpy decreases as the size of the
halide ion increases (from F− to I−). The charge on the ions in these compounds
remains the same, but the size of the larger halide ion means the ions cannot pack as
closely together, so the attraction between them is not as strong.
A similar pattern is seen by examining the group 1 fluorides. Again the ions are all 1+
and 1−, but the increasing size of the group 1 ion (from Li+ to K+) causes the decrease
in the lattice enthalpy.
The lattice enthalpies of the group 2 halides shows similar patterns, but they are
significantly larger than the lattice enthalpies of the group 1 halides due to the greater
attraction between the 2+ ion and the halide ions. Similar patterns are seen for the
oxides. Comparing the oxides to the chlorides, the 2− charge on the small oxide ion
gives the oxides higher lattice enthalpy values than any of the corresponding halides.
The lattice enthalpy for MgO is very high (and hence it is very stable and has a very
high melting point) due to the 2+ and 2− charge on the small ions.

Perfect ionic model

Ionic compounds can show some covalent character. A theoretical value for the lattice
enthalpy can be calculated based on the attraction of the ions if the ions are thought
of as being perfect spheres with point charges and only electrostatic attraction
between the ions.

Physical chemistry 2 11
Content Guidance

The experimental value for the lattice enthalpy is determined from the Born–Haber
cycle.
If the experimental value and the theoretical value are almost the same the bonding
in the compound is ionic.
If the experimental value is greater than the theoretical value this would imply that
there is additional bonding in the compound, which would suggest that there is some
degree of covalent character.

Exam tip
These points about the perfect ionic model are often asked so it is important to
understand the idea that the ions are perfect spheres with point charges with
only electrostatic attraction between the ions . The perfect ionic model does not
assume any covalent character in the compound .

Worked example
The experimental lattice enthalpy for silver(I) chloride is +905 kJ mol−1, whereas the
theoretical value is +770 kJ mol−1. Explain the difference.
Answer
Silver(i) chloride has covalent character, so there is additional bonding in silver(I)
chloride and the theoretical value from the perfect ionic model underestimates the
lattice enthalpy.

Enthalpy of solution
When an ionic compound dissolves in water the lattice is disrupted and the water The enthalpy of solution
molecules form bonds with the ions. The enthalpy of solution can be calculated from is the enthalpy change
the lattice enthalpy and the enthalpy of hydration. when 1 mole of a solute
dissolves in water .
Hydration enthalpy
The hydration enthalpy
Hydration is an exothermic process as energy is released when the bonds form
is the enthalpy change
between the polar water molecules and the ions. The δ+ H atoms on water interact
when 1 mole of gaseous
with the negative ions and the δ− O atom interacts with the positive ions. Energy is
ions is converted into
released.
1 mole of aqueous ions .
Hydration enthalpies are per mole of the ion so the hydration enthalpy of magnesium
ions is represented by the equation: Mg2+(g) → Mg2+(aq). For chloride ions the
change would be: Cl−(g) → Cl−(aq).

12 AQA Chemistry
 Thermodynamics

The numerical value for the enthalpy of hydration depends on the size and charge of
the ions. Smaller ions with a higher charge have the highest numerical values for the
enthalpy of hydration.
For the halides, F− = −506 kJ mol−1; Cl− = −364 kJ mol−1; Br− = −351 kJ mol−1;
I− = −307 kJ mol−1. As the size of the ion increases, the enthalpy of hydration
decreases in numerical value.
A similar pattern is observed in groups 1 and 2.
Between groups 1 and 2, the group 2 ions have a much higher numerical value for
hydration enthalpy than the group 2 ions. For example:
Na+ = −407 kJ mol−1 Mg2+ = −1891 kJ mol−1.
Exam tip
The Mg2+ is smaller and has a higher charge than the Na+ ion.
2Δ hydH⦵ are required
Calculating enthalpy of solution for magnesium
chloride as there are
Enthalpy of solution = lattice enthalpy + sum of enthalpies of hydration
2 moles of chloride ions
For magnesium chloride: being hydrated . As with
all enthalpy changes,
ΔsolH = ΔL H⦵ + Δhyd H⦵ + 2Δhyd H⦵
check carefully the
(MgCl2) (MgCl2) (Mg2+) (Cl−) number of moles of the
ions being hydrated .
Hydration enthalpies are exothermic and lattice enthalpy is endothermic. It is the
balance between lattice enthalpy and the sum of all the hydration enthalpies which
will determine whether the enthalpy of solution is endothermic or exothermic overall.
Exam tip
These enthalpy changes fit together in the cycle shown in Figure 5.
It is important to show
Mg2+(g) + 2Cl–(g) the solution (Mg2+(aq)
+ 2Cl− (aq)) line below
the solid (MgCl 2(s))
∆hydH (Mg2+) = –1891 line if the process is
exothermic or above it
∆LH = +2492
if it is endothermic .
Mg2+(aq) + 2Cl–(g)

MgCl2(s)
Knowledge check 3
2∆hydH (Cl–) = 2(–364) Calculate the enthalpy
∆solH of solution of sodium
Mg2+(aq) + 2Cl–(aq)
iodide given that its
lattice enthalpy is
Figure 5 Born–Haber cycle for magnesium chloride (MgCl 2) +699 kJ mol−1 and the
hydration enthalpies
ΔsolH⦵ = (+2492) + (−1891) + 2(−364) = −127 kJ mol−1
of the sodium ion
It is clear that 127 kJ of energy are released when 1 mole of MgCl2 dissolves in water and the iodide ion
to form a solution. All of the hydration enthalpies may be combined into one arrow. are −407 kJ mol−1
and −307 kJ mol−1
respectively .

Physical chemistry 2 13
Content Guidance

Summary
■■ Lattice enthalpy is the enthalpy of the breaking of ■■ Second electron affinities are endothermic (ΔH is
1 mole of the ionic lattice into gaseous ions and is positive) .
endothermic (ΔH is positive) . ■■ The perfect ionic model allows the calculation of
■■ A Born–Haber cycle allows us to calculate the a theoretical value for lattice enthalpy .
lattice enthalpy from atomisation enthalpy ■■ Ionic compounds which have a theoretical value for
values, ionisation enthalpy values, bond lattice enthalpy less than the experimental value
dissociation enthalpy values, electron affinities from a Born–Haber cycle have some covalent
and enthalpy of formation values . character .
■■ The bond dissociation enthalpy values for ■■ Enthalpy of solution is the total of the lattice
halogens is twice the value of the enthalpy of enthalpy and the enthalpies of hydration of
atomisation . all the ions .

Gibbs free energy change, ΔG⦵ and entropy

change, ΔS⦵
Endothermic reactions are not energetically favourable in terms of the intake of
energy, so for them to occur spontaneously or to be feasible, they show an increase in
entropy. Entropy is a measure of disorder.

Estimating a change in entropy

Reaction 1: KI(s) → K+(aq) + I−(aq) ΔH⦵ = +31 kJ mol−1
Reaction 2: NH4Cl(s) → NH3(g) + HCl(g) ΔH⦵ = +176 kJ mol−1
Reaction 3: H2O(s) → H2O(l) ΔH⦵ = +6 kJ mol−1
In general, gases are more disordered than liquids and solutions, which are more
disordered than solids. This means that the entropy of solids is low. The more ordered
the structure of the solid, the lower the entropy. Gases are highly disordered.
The change in entropy in a reaction can be estimated from the state of the substances
in a reaction as described previously or from the number of moles of substances
should they all be in the same state. Also in general for gases, the higher the Mr of the
gas the higher its entropy.
All three reactions above show an increase in entropy.
■■ Reaction 1 has 1 mole of solid forming 1 mole of each of the ions in the solution.
■■ Reaction 2 has 1 mole of solid forming 2 moles of gas.
■■ Reaction 3 has 1 mole of solid forming 1 mole of liquid.

Entropy of changes of state

Changes of state show a change in entropy. This can be shown on a graph of entropy
plotted against temperature (Figure 6).

14 AQA Chemistry
 Thermodynamics

250
Solid Liquid Gas
200

150
Boiling

100

Melting
50

0
273 373
Temperature/K

Figure 6 Change in entropy

The four points below are common questions about this type of graph:
■■ At zero kelvin (0 K) all substance should have an entropy value of zero. This is because
at zero kelvin (K) the particles should not be moving and should have perfect order.
■■ As temperature increases, entropy increases as the substance becomes more
disordered as the particles gain energy and movement increases.
■■ The vertical sections on the graph show the changes in state where there is a large
increase in entropy as the temperature remains constant. Entropy is a measure
■■ The vertical section on boiling is longer than the one for melting because there is a
of disorder or
very large increase in entropy when a substance changes into a gas as gases are very randomness in a
disordered. system .

Entropy values
Entropy is given the symbol S and so standard entropy is S⦵. Change in entropy is
represented by ΔS⦵. An increase in the disorder of a system has a positive ΔS⦵ value.
Entropy is measured in J K−1 mol−1.
Some entropy (S⦵) values are given in Table 2 in order of increasing entropy.

Table 2 Entropy of various substances

Substance State S⦵ (J K−1 mol−1)
C (diamond) Solid 2 .4
Si(s) Solid 19
Mg(s) Solid 32 .7
CaO(s) Solid 39 .7
H2O(s) Solid 48
H2O(l) Liquid 70
CaCO3(s) Solid 93
NaCl(aq) Aqueous 116
C2H5OH(l) Liquid 161
H2O(g) Gas 189
O2(g) Gas 205
CO2(g) Gas 214

Physical chemistry 2 15
Content Guidance

The pattern is not perfect because CaCO3(s) has a higher entropy value than water. Exam tip
Water has an ordered structure for a liquid owing to hydrogen bonds, and CaCO3
Make sure that the
is not a well-ordered ionic solid owing to the size of the carbonate ion and the
+ or − sign is always
polarisation of this ion by the calcium ion.
used when giving
In general, highly ordered structures such as macromolecular, metallic and ionic changes in entropy,
crystalline structures have low enthalpy values. for example ΔS ⦵ =
+22 .5 J K−1 mol−1 or ΔS ⦵
Change in entropy, ΔS⦵ = −17 .4 J K−1 mol−1 . It is
The change in entropy (ΔS⦵) in a reaction can be estimated from the state of the also very important
substances in a reaction as described previously. ΔS⦵ can be calculated from standard to remember that the
entropy values for a given chemical reaction. A positive value for ΔS⦵ indicates that units of S ⦵ and ΔS ⦵ are
there is an increase in entropy and a negative value indicates that there is a decrease J K−1 mol−1 .
in entropy.
ΔS⦵ = sum of S⦵ for the products − sum of S⦵ for the reactants Knowledge check 4
What does ΔS⦵ mean
Worked example 1
and what are its units?
Calculate the change in entropy (ΔS⦵) for the reaction:
2SO2(g) + O2(g) → 2SO3(g)
Exam tip
given the standard entropies, in J K−1mol−1, of SO2(g), O2(g) and SO3(g) are For all ΔS calculations
248, 205 and 257 respectively. the ‘per mole’ in the
Answer equation must be taken
into account . If 2 moles
ΔS⦵ = sum of S⦵ for the products – sum of S⦵ for the reactants of a reactant are used,
then 2 moles of the
ΔS⦵ = 2 × 257 − (2 × 248 + 205) = −187 J K−1 mol−1 entropy value for this
substance are used .

Worked example 2
Calculate the entropy value for H2(g) in the following reaction:
CH4(g) + 2H2O(g) → CO2(g) + 4H2(g)

if ΔS⦵ = +174 J K−1 mol−1 and the standard entropies of CH4(g) = 186 J K−1 mol−1,
H2O(g) = 189 J K−1 mol−1 and CO2(g) = 214 J K−1 mol−1.
Answer
ΔS⦵ = sum of S⦵ for the products − sum of S⦵ for the reactants
Exam tip
Let x = standard entropy of hydrogen in J K−1mol−1:
This is a slightly
+174 = (214 + 4x) − (186 + 2 × 189) different type of
+174 = −350 + 4x calculation, but uses
the same expression
4x = 524 to calculate an entropy
x = 131 J K−1 mol−1 value from a change in
entropy .

16 AQA Chemistry
 Thermodynamics

Gibbs free energy, ΔG⦵ Exam tip

Gibbs free energy is represented by ΔG⦵ and is calculated using the expression ΔG⦵ The most important
= ΔH⦵ – TΔS⦵, where ΔH⦵ is the standard enthalpy change for the reaction measured thing to remember
in kJ mol−1; T is the temperature measured in kelvin (K) and ΔS⦵ is the standard when calculating a
enthalpy change measured in kJ K−1 mol−1. ΔG has units of kJ mol−1. value for ΔG ⦵ is that
the ΔS ⦵ value quoted
In order for a reaction to be feasible ΔG⦵ must be zero or negative. You can calculate
in J K−1 mol−1 must
whether a reaction is feasible at a certain temperature by calculating ΔG⦵. You can
be divided by 1000 to
also calculate the temperature at which a reaction becomes feasible using ΔG⦵ and
convert to kJ K−1 mol−1
ΔH⦵, assuming that ΔG⦵ = 0 for a feasible reaction.
before being used in
the expression . This is
Worked example
the most common error
Show that the thermal decomposition of silver(i) nitrate is not feasible at 600 K and in these questions .
determine the temperature at which the reaction becomes feasible.
2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g) ΔH⦵ = +312 kJ mol−1
Knowledge check 5
given the following standard entropy values: What are the units
Substance S⦵ (J K−1 mol−1) of ΔG?
AgNO 3(s) 141
Ag(s) 43
NO2(g) 240
O2(g) 205

Exam tip
Answer
To determine the
First ΔS⦵ is calculated as before using: temperature for a
ΔS⦵ = sum of S⦵ for the products – sum of S⦵ for the reactants reaction to become
feasible, divide ΔH by
ΔS⦵ = (2 × 43 + 2 × 240 + 205) – (2 × 141) = + 489 J K−1 mol−1 ΔS, but remember to
make sure ΔS is in
Then ΔG is calculated using ΔG⦵ = ΔH⦵ − TΔS⦵ with the values below: kJ K−1 mol−1 .
ΔH⦵ = +312 kJ mol−1, T = 600 K and ΔS⦵ = +0.489 kJ K−1 mol−1 You should also revise
Hess’s law calculations
ΔG⦵ = +312 – 600(+0.489) = +18.6 kJ mol−1 from the Energetics
section of AS . These
ΔG⦵ is positive at 600 K, so the reaction is not feasible at this temperature. often form part of
At what temperature does it become feasible? an entropy question
at A-level because
To find the temperature at which the reaction becomes feasible, we need to work out you may have to use
the temperature at which ΔG⦵ = 0. standard enthalpies of
When ΔG⦵ = 0, T = ΔH⦵/ΔS⦵, where ΔS⦵ should be in units of kJ K−1 mol−1. formation to determine
the enthalpy change
T = 312 = 638 K
0.489 using Hess’s law .

Physical chemistry 2 17
Content Guidance

Physical changes related to ΔG⦵

During a physical change of state ΔG⦵ = 0 as the system is at equilibrium. This
means that ΔH⦵ = TΔS⦵. This can be used to work out the enthalpy change for this
particular change in state or the melting point or boiling point may be determined. Exam tip
Worked example The enthalpy change of
vaporisation of bromine
The standard entropy values of bromine as a liquid and a gas are 152 and could have been given
245 J K−1 mol−1. The boiling point of bromine is 332 K. Determine the enthalpy change in this question and the
of vaporisation of bromine, Br2(l) → Br2(g). Give your answer to 3 significant figures. boiling point calculated .
Answer Try this calculation to
ensure you get ‘around’
ΔS⦵ = sum of S⦵ for the products – sum of S⦵ for the reactants 332 K . Rounding may
affect the answer . At
ΔS⦵ = 245 – 152 = + 93 J K−1 mol−1 temperatures below
the boiling point the
As this is a change in state, ΔG⦵ = 0. So ΔH⦵ = TΔS⦵. So: value for ΔG⦵ will be
ΔH⦵ = 332 × 0.093 = +30.9 kJ mol−1 positive .

As expected, the enthalpy of vaporisation is endothermic.

Knowledge check 6
Calculate the boiling
Factors affecting feasibility of a reaction point of ethanol if the
The feasibility of a reaction depends on whether a reaction is endothermic or change
exothermic and also on whether there is an increase in entropy or a decrease in C2H5OH(l) →C2H5OH(g)
entropy. Table 3 shows how these factors affect ΔG⦵ and the feasibility of a reaction. ΔS⦵ = +110 J K−1 mol−1
and ΔH⦵ = +38 .6 kJ mol−1 .
Table 3 Feasibility of a reaction Give your answer to
ΔH⦵ ΔS⦵ ΔG⦵ Feasibility 3 significant figures .

May be positive or Feasible below certain

Negative Negative
negative temperatures
Feasible at any Exam tip
Negative Positive Always negative
temperature
The most often used
Not feasible at any
Positive Negative Always positive reactions are the ones
temperature
May be positive or Feasible above certain which are endothermic
Positive Positive and which have an
negative temperatures
increase in entropy
■■ An exothermic reaction with an increase in entropy is feasible at any temperature. as they allow for
■■ An endothermic reaction with a decrease in entropy is not feasible at any the calculation of a
temperature. temperature at which
the endothermic
reaction becomes
feasible . This can be
applied to any reaction
including physical
changes like dissolving .

18 AQA Chemistry
 Thermodynamics

Graphs of ΔG⦵ against T

ΔG⦵ varies with temperature. If a graph of ΔG⦵ in kJ mol−1 is plotted against T in K,
the graph will be a straight line in the form y = mx + c, where the gradient (m) is
−ΔS⦵ and the intercept (c) with the ΔG⦵ axis is ΔH⦵. ΔS⦵ = − gradient, but the value
will be in kJ K−1 mol−1, so would be multiplied by 1000 to convert to J K−1 mol−1.
There are two possible graphs based on the gradient being positive or negative (Figure 7).
The gradient of this
line is –∆S . A positive
∆G gradient like this one
The intercept The gradient of this
means a negative
of the line on ∆G line is –∆S . A negative
value of ∆S
the ∆G axis gradient like this one The intercept
gives the means a positive of the line
value of ∆H value of ∆S on the ∆G
0 axis gives the 0
T/K value of ∆H T/K

This is the temperature at which This is the temperature at which

∆G = zero. This is the minimum ∆G = zero. This is the maximum
temperature for the reaction to be temperature for the reaction to be
feasible. At all temperatures feasible. At all temperatures below
above this the reaction is feasible. this the reaction is feasible.

Figure 7 Variation of ΔG⦵ with temperature

You would be expected to analyse a graph and calculate a gradient (−ΔS⦵) and
intercept (ΔH⦵) from the graph. A suitable range would be allowed. Figure 8 shows a
plot of ΔG⦵ against T.
600
∆G /kJ mol–1

500

400

300

200 420

100
750
0
300 600 900 1200
–100 T/K

–200

–300

–400

Figure 8 Graph of ΔG⦵ against temperature

Physical chemistry 2 19
Content Guidance

Exam tip
From the graph, the line intercepts with the ΔG⦵ axis at +420 kJ mol−1, so this
is the value of ΔH⦵ for this reaction . The gradient is determined by dividing
rise over run, which is 420/750 = −0 .56 kJ K−1 mol−1 . The gradient is negative as
the line slopes down . ΔS⦵ = +560 J K−1 mol−1 . The gradient is –ΔS⦵ and has to
be multiplied by 1000 to convert the units from kJ K−1 mol−1 to J K−1 mol−1 . The
temperature at which the reaction becomes feasible is the intercept on the
T axis, as this is the temperature at which ΔG⦵ = 0 . Above this temperature ΔG⦵
will be negative, so from this temperature upwards the reaction is feasible .
This could be checked by calculation using ΔG⦵ = ΔH⦵ − TΔS⦵ .

Summary
■■ Standard entropy (S⦵) is measured in J K−1 mol−1 . ■■ ΔS⦵ is in J K−1 mol−1 and it must be divided by 1000
Entropy is a measure of disorder . to convert to kJ K−1 mol−1 for use in the expression
■■ ΔS⦵ = sum of the standard entropy values of the ΔG⦵ = ΔH⦵ − TΔS⦵ .
products − sum of the standard entropy values of ■■ For a reaction to be feasible ΔG⦵ must be less
the reactants . than or equal to zero .
■■ ΔG⦵ is Gibbs free energy and is measured in ■■ For a change in state ΔG⦵ = 0 .
kJ mol−1 . ■■ For a graph of ΔG⦵ against T, the gradient is −ΔS⦵
■■ ΔG⦵ = ΔH⦵ − TΔS⦵, where T is the temperature in (in kJ K−1 mol−1) and the intercept with the ΔG⦵
kelvin, ΔS⦵ is the standard entropy change and axis is equal to ΔH⦵ .
ΔH⦵ is the enthalpy change of the reaction .

■ Rate equations
■■ A rate equation expresses the link between the rate of a chemical reaction and the
concentration of the reactants.
■■ The rate of a reaction can be measured based on how fast the concentration of a
reactant is decreasing or how fast the concentration of a product is increasing.
■■ The units of rate are concentration per unit time, for example, mol dm−3 s−1 (mol per
dm3 per second).
■■ Square brackets [ ] as for Kc at AS indicate concentration of the substance inside
the brackets. This is always measured in mol dm−3 (mol per dm3). For example:
[H+] = concentration of hydrogen ions measured in mol dm−3
[I2] = concentration of iodine measured in mol dm−3

The rate equation

The rate equation is an expression showing how the rate of reaction is linked to the
concentration of the reactants. Rate is equal to the rate constant (k) multiplied by the
concentration of each reactant raised to certain whole number powers (called orders).
The rate equation for the general reaction P + Q → R + S is:
rate = k[P]x [Q]y

20 AQA Chemistry
 Rate equations

where x is the order of reaction with respect to reactant P, y is the order of reaction The order of reaction
with respect to reactant Q and k is the rate constant. with respect to a
particular reactant is
The overall order of the reaction is the sum of all the orders in the rate equation. For
the power to which the
this reaction the overall order of reaction would be x + y.
concentration of this
reactant is raised in the
Units of the rate constant rate equation .
Rate has units of mol dm−3 s−1.
Concentration has units of mol dm−3. The rate constant is
the proportionality
The units of the rate constant, k, depend on overall order of reaction and the units constant which links
can be calculated as shown: the rate of reaction
For a general rate equation: to the concentrations in
the rate equation .
rate = k[P][Q]
the overall order is 2 (1 + 1) The overall order of a
reaction is the sum of
rate = k × (concentration)2 the powers to which the
Putting in the units: concentration terms
are raised in the rate
mol dm−3 s−1 = k(mol dm−3)2 equation .
Rearranging to find k:
mol dm −3 s −1 mol dm −3 s −1 Exam tip
k= =
(mol dm −3 )2 mol2 dm −6 As the order increases
Treat each term separately: mol/mol2 = mol−1 and dm−3/dm−6 = dm−3−(−6) = dm3. by 1 an extra mol−1 dm3
is multiplied into the
Units of the rate constant k = mol−1 dm3 s−1 units .
Table 4 shows the units of the rate constant for some overall orders.

Table 4 Units of the rate constant Knowledge check 7

Overall order Units of What are the units of
of reaction rate constant, k the rate constant for
1 s−1 the reaction
2 mol−1 dm3 s−1 2A + B → C + 3D
3 mol−2 dm6 s−1
with the rate equation
rate = k[A][B]2?
4 mol−3 dm9 s−1

Exam tip
Determining and using orders of reaction The constant
The order of reaction with respect to the reactants may be determined from temperature is
experimental data at a constant temperature. Often these data are tabulated. important as changes
There may be values missing in the table, which have to be calculated once the orders in temperature affect
of reaction have been determined. the rate of the reaction
as well .

Physical chemistry 2 21
Content Guidance

Worked example 1
For the reaction between two compounds A and B, the following information was
obtained from rate experiments at a constant temperature.

Initial rate of
Initial concentration Initial concentration
Experiment reaction
of A (mol dm−3) of B (mol dm−3)
(mol dm−3 s−1)
1 1 .20 × 10 −4 2 .40 × 10 −4 1 .60 × 10 −5
2 1 .80 ×10 −4 3 .60 ×10 −4 3 .60 × 10 −5
3 1 .80 × 10 −4 5 .40 × 10 −4 8 .10 × 10 −5

a Determine the orders of reaction with respect to A and B.

b Write a rate equation for this reaction.
c Deduce a value of the rate constant, k, at this temperature and state its units.
Give your answer to three significant figures.
Answer (a)
The key to determining rate is often looking for two experiments in which the
concentration of one of the reactants does not change. In this example the
concentration of A does not change between experiments 2 and 3. This would be
good practice as it allows the effect of the change in concentration of B on the rate
to be examined. We then use the factors by which the rate and the concentration
have change to determine the order with respect to B.
8.10 × 10−5
The rate increased by a factor of = 2.25 (factor r — r meaning rate)
3.60 × 10−5
5.40 × 10−4
The concentration of B increased by a factor of = 1.5 (factor b — b
3.60 × 10−4
meaning concentration of B)
The power to which factor b is raised to equal factor r is the order with respect to B
(we are using x to represent the order with respect to B).
1.5x = 2.25 so x must be 2. The order with respect to B is 2.
Now we know the order with respect to one reactant we can determine the order
with respect to the other.
The order with respect to A can only be determined using experiments 1 and 2 as
this is where the concentration of A is changing. However, the concentration of B is Exam tip
also changing. Remember that the
3.60 × 10−5 orders should be 0, 1 or
The rate increased by a factor of = 2.25 (factor r — r meaning rate)
1.60 × 10−5 2 . Try the numbers in
1.80 × 10−4
The concentration of A increased by a factor of = 1.5 (factor a — a your calculator to make
1.20 × 10−4 sure you can work out
meaning concentration of A)
➜ that the order is 2 .

22 AQA Chemistry
 Rate equations

3.60 × 10−4
The concentration of B increased by a factor of = 1.5 (factor b — b
2.40 × 10−4
meaning concentration of B)
As both are changing, the order with respect to B (we are using y this time as the
order) is calculated as shown below:
(factor a)y(factor b)2 = factor r

We know the order with respect to B is 2. So

(1.5)y(1.5)2 = 2.25 Exam tip
Any number raised to
(1.5)y(2.25) = 2.25 the power of 0 is equal
to 1 . Try this on your
(1.5)y = 2.25 = 1 calculator to make sure
2.25
you understand .
So y = 0.
Answer (b)
The rate equation for this reaction is: rate = k[B]2
As A has zero order it is not in the rate equation for the reaction. It could be
included as in rate = k[A]0[B]2, but it is not necessary as any value to the power of 0
is equal to 1. Zero order reactants can be left out of the rate equation.
Answer (c)
You may use any of the experiments in the table, but sometimes you will be directed
to use the results of a particular experiment.
Using experiment 1:
rate = k[B]2

1.60 × 10 −5 = k(2.40 × 10 −4)2

1.60 × 10−5 1.60 × 10−5
k= −4 2 =
= 278 mol−1 dm3 s−1
(2.40 × 10 ) 5.76 × 10−8

Physical chemistry 2 23
Content Guidance

Worked example 2
Sometimes a value is missing from the table that has to be completed.
In the reaction between X and Y, the following rate measurements were made. The
rate equation for the reaction is rate = k[X]2[Y].

Experiment Initial concentration Initial concentration Initial rate of reaction

of X (mol dm−3) of Y (mol dm−3) (mol dm−3 s−1)
1 2 .50 × 10 −2 3 .00 × 10 −3 1 .45 × 10 −3
2 2 .50 × 10 −2 to be calculated 4 .36 × 10 −3
3 5 .00 × 10 −2 4 .50 × 10 −3 to be calculated

The rate equation states that the rate of the reaction is proportional to the
concentration of X squared and the concentration of Y. This allows for the
calculation of the unknown values in the table.
a Calculate the initial concentration of Y when the rate is 4.36 × 10−3 mol dm−3 s−1.
b Calculate the rate of reaction when the concentration of Y is 4.50 × 10−3 mol dm−3.
Answer (a)
Between experiment 1 and 2 the concentration of X stays the same so it has no effect
on the rate. The rate changes by a factor of 4.36 × 10−3 = 3 (factor r).
−3

1.45 × 10
As the order with respect to Y is 1, Y also increases by a factor of 3.
The concentration of Y in experiment 2 is 3.00 × 10−3 × 3 = 9.00 × 10−3 mol dm−3.
Answer (b)
From experiment 1 to experiment 3:
5.00 × 10−2
X increases by a factor of = 2 (factor x).
2.50 × 10−2
−3
4.50 × 10
Y increases by a factor of = 1.5 (factor y).
3.00 × 10−3
rate = k[X]2[Y]

factor r = (factor x)2(factor y)

factor r = (2)2(1.5) = 6
Exam tip
Alternatively the
The rate will increase by a factor of 6. rate constant k could
be calculated using
rate = 1.45 × 10−3 × 6 = 8.70 × 10−3 mol dm−3 s−1
experiment 1
(k = 773 mol−2 dm6 s−1) .
Factors affecting rate This could be used to
calculate the rate for
Rate is directly dependent on concentration of reactants as shown in the rate equation. experiment 3 using
rate ∝ concentration (rate is proportional to concentration) the rate equation: rate
= 773 × (5 .00×10 −2)2 ×
Rate is also dependent on temperature and activation energy, but these factors are (4 .50 × 10−3) = 8 .70 × 10−3
not seen in the rate equation. The activation energy is affected by the presence of a mol dm−3 s−1
catalyst. The rate constant, k, is dependent on temperature and activation energy.
24 AQA Chemistry
 Rate equations

Figure 9 shows the effect of temperature on the rate constant.

Figure 9 Effect of temperature on the rate constant

Methods of determining rate of reaction

The rate of a chemical reaction may be an initial rate monitoring of reaction or it
may be continuous rate monitoring for measurements taken during the reaction.
■■ The initial rate is often referred to as the rate at time zero seconds (or t = 0 s)
when the reaction has just started. At this point the rate is dependent on the
concentrations of the reactants added at t = 0 s.
■■ Continuous rate measurements are taken as the reaction proceeds. The rate of
reaction decreases as the reaction proceeds, as the reactants are used up.
■■ Methods of measuring initial rate values relate these to the concentration of the
reactant at t = 0 s.
■■ Progressive rate methods can measure the rate at certain points during the reaction
and relate this directly to the concentration of reactants at these times.
■■ This may seem more complex, but it simply relies on being able to measure the
concentration of a reactant directly during the reaction.
Exam tip
Rate measurements When colorimetry is
being used to measure
Rate measurements are based on a measurable concentration of a reactant or product.
the rate of a reaction, a
The methods depend on the chosen reactant or product. All are measured against
calibration curve using
time, as their change in concentration against time gives a measure of rate of reaction.
known concentrations
The following methods can be used to measure the concentration of a substance
of the coloured
against time.
substance should
■■ If the substance is coloured, a colorimeter can be used to measure its
always be included in
concentration. Often a calibration curve is used. This is a previously drawn
the answer .
curve relating absorbance value on the colorimeter to the concentration of known
solutions of the coloured substance. It shows a directly proportional relationship.
Any absorbance values can be directly converted to a concentration value using the Exam tip
calibration curve.
Substances that can
■■ If a gas is released, a gas syringe can be used to measure gas volume (which is the
be titrated include
same as gas concentration), or the change in mass can be recorded.
acid (using a standard
■■ If a substance can be titrated, a sample of the reaction can be taken and quenched
solution of alkali) and
and titrated to determine concentration. Quenching may be chemical (removing alkali (using a standard
another reactant) or by cooling the reaction rapidly to stop the reaction at the time solution of acid) .
when the sample is taken.

Physical chemistry 2 25
Content Guidance

■■ If H+ or OH− ions are a reactant or a product, the change in pH can be measured

using a pH meter (this can also be titrated with a standard solution of alkali for H+
ions or a standard solution of acid for OH−). Exam tip
Initial rate monitoring You will be measuring
Choose a property that is measurable (this could be gas volume of a product, colour of the rate of reaction
a product, pH values for a product or a property that can be determined by titration). relative to this
reactant, as this is
For one reactant, choose a range of concentrations of this reactant and set up a series the only variable you
of experiments with a range of concentrations of this reactant. are changing . So any
Plot graphs of measurable quantity against time. This could be gas volume against time, change in the rate of
absorbance against time, pH against time or concentration against time determined by reaction is caused
titration. Determine the initial gradient to determine initial rate at t = 0 s by drawing a by the change in
tangent at t = 0 s and determine its gradient. This is the initial rate of reaction. concentration of this
reactant .
Initial rate of a reaction from a gas volume–time graph
A gas syringe is a ground glass syringe which is attached to a sealed reaction vessel
and measures the volume of gas produced (Figure 10).

Gas syringe

Conical flask

Reaction mixture

Figure 10 A gas syringe

The volume of gas produced is measured against time and a graph of gas volume
against time is plotted (Figure 11).
The initial gradient gives a measure of the initial rate of reaction.

As reaction nears completion

gradient of tangent approaches 0
Gas volume/cm3

Gradient of tangent taken at

t = 40 is less than at t = 0

Gradient of tangent taken at t = 0 is greater than

gradients at later times — this gives the initial rate

0 20 40 60 80 100 120 140 160

Time/s

Figure 11 Example of a gas volume–time graph

26 AQA Chemistry
 Rate equations

A reaction in which a gas is produced may also be monitored by measuring the mass
over a period of time. The graph decreases and the initial tangent gives a measure of
rate of reaction (Figure 12).
Mass/g

Time/s

Figure 12 Example of a graph showing change in mass against time

Repeat the experiment for the other concentrations of this reactant. This will give you
initial rate values for different concentrations of the reactant you have chosen when
you take tangents at t = 0 s. Then plot a graph of initial rate against concentration of
this reactant. The shape of the graph of rate against concentration gives the order with
respect to this reactant.
Figure 13 shows the graphs expected for order 0, 1 and 2 for the reactant investigated.
Rate
Rate

Rate

Zero order First order Second order

Exam tip
Concentration Concentration Concentration
You should be able
For a zero order reactant For a first order reactant For a second order reactant to recognise and
the graph of rate will be the graph of rate will be a the graph of rate will be a sketch rate versus
a straight line where straight line where as the curved line where as the
concentration of the concentration graphs
concentration has no effect concentration of the
on the rate of reaction. reactant doubles the rate reactant doubles the rate for these orders of
of reaction also doubles. of reaction quadruples (×4). reaction .
Figure 13 Graphs of rate against concentration

Continuous rate monitoring

For this method work out whether the concentration of a reactant can be determined
directly. For example:
■■ Hydrogen ions (H+) are determined directly from pH measurements. Make sure no
other ions would interfere, such as OH− ions or a different acidic or alkaline product.
■■ Coloured reactant is determined from colorimeter readings using a calibration curve.
■■ A specific reactant may be titrated.

Allow the reaction to progress and take readings (colorimeter/pH) or take samples
at various times (samples should be quenched to stop the reaction and titrated —
quenching can be carried out by rapid cooling or adding large quantities of cold water or
Physical chemistry 2 27
Content Guidance

chemical quenching). Plot a graph of concentration against time for this reactant. The
shape of graph gives the order with respect to this reactant (Figure 14).
Concentration

Concentration

Concentration
Zero order First order Second order

Time Time Time

Figure 14 Graphs of concentration against time

The gradient at various points may be taken to determine the rate of reaction. The
slope of these graphs (Figure 14) gives the rate (change in concentration against time).
Using a graph of concentration against time
For a coloured reactant we can use continuous rate monitoring. This means one
experiment is carried out and the colorimeter readings are converted to concentration
using the calibration curve. A graph of concentration against time is drawn and
often the shape of this curve can give the order with respect to the coloured reactant
(Figure 15). A gradient of a tangent at any concentration on the graph is a measure
of rate at that concentration. The rate can then be related to the concentration and
the order determined as shown before, or a graph of rate against concentration can
be drawn. The shape of this graph gives the order of reaction with respect to the
changing reactant concentration.
Concentration/mol dm−3

The gradient of this line is the rate

0.04 of reaction when the concentration
is 0.04 mol dm–3

The gradient of this line is the rate

of reaction when the concentration
is 0.02 mol dm–3
0.02
The gradient of this line is
the rate of reaction when the
0.01 concentration is 0.01 mol dm–3

Time

Figure 15 Using a graph of concentration against time

28 AQA Chemistry
 Rate equations

Rate against concentration graphs may be plotted for a clearer order. The values
determined from the gradient at different concentrations are used. The graphs
of rate against concentration are as shown in initial rate methods and this allows
determination of order.

Arrhenius equation
The Arrhenius equation links the rate constant (k) with the activation energy (Ea)
and the temperature (T) measured in kelvin. A is the Arrhenius constant and e is a
mathematical constant (2.71828).
k = Ae − Ea RT
R is the gas constant (8.31 J K−1 mol−1) and the activation energy is measured in J mol−1
in this expression. The Arrhenius constant has the same units as the rate constant.
Worked example
A reaction has an activation energy of 105 kJ mol−1 at 300 K. The Arrhenius constant
A = 1.27 × 1010 s−1, R = 8.31 J K−1 mol−1, e = 2.71828. Calculate the value of the rate
constant k to 3 significant figures.
Answer
Ea
= 105000 = 42.12
RT 8.31 × 300
k = Ae − Ea RT

k = 1.27 × 1010 × e–42.12

k = 6.48 × 10−9 s−1

Exam tip
Natural log is the log
The units of the rate constant are the same as the units of the Arrhenius constant.
to the base of e . This
means that the log is
the power to which e
Graphical analysis has to be raised to be
equal to the number . So
The Arrhenius equation can be analysed graphically by plotting a graph of ln k
ln e = 1, as e would be
against 1/T.
raised to the power of
E
ln k = − a + ln A 1 to be equal to e . ex is
RT
A graph of ln k against 1/T yields a straight line in the form y = mx + c, where the the reverse process of
E ln, so taking a natural
intercept on the ln k axis is ln A and the gradient of the line is − a . log of ex is x .
R

Physical chemistry 2 29
Content Guidance

Worked example
In a reaction the values of k were determined at different temperatures. The units of
k are s−1. A graph of ln k against 1/T was drawn (Figure 16).
50

ln k
40

30

20
30
10
0.0025
0
0 0.001 0.002 0.003
1/T

Figure 16

From this graph, the intercept on the ln k axis is 30. This means that ln A is 30.
So A = e30 = 1.07 × 1013 s−1.
The units of A are the same as the units of k.
E 30
The gradient is − a . The calculated gradient = − = −12000.
R 0.0025
Ea
= 12 000 (R = 8.31 J K−1 mol−1)
R Knowledge check 8
Ea = 12 000 × 8.31 = 99 720 J mol−1 What are the units of
Ea in the Arrhenius
Ea = 99.7 kJ mol−1 equation?

Order linked to mechanism

The rate determining step in the mechanism for a reaction is the slowest step in the
reaction.
Reactants which do not take part in the rate determining step have zero order.
Reactants which do take part in the rate determining step have order of 1 or 2.

30 AQA Chemistry
 Rate equations

Worked example
The reaction between X and Y is shown overall by the equation X + 2Y → 3Z.
The rate equation for the reaction is:
rate = k[X]2

Which one of the following is a suitable mechanism for the reaction?

A X → Y (slow step) 3Y → 3Z (fast step)
B X + Y → A (slow step) A + Y → 3Z (fast step)
C 2Y → B (slow step) B + X → 3Z (fast step)
D X + Y → (slow step) Y + Z → 4Z (fast step)
Answer
As X is the only reactant in the overall equation that is not zero order, only X can be
a reactant in the rate determining step, which is the slowest step in the mechanism.
The answer is A, as all other slow steps include Y as a reactant.

Required practical 7
Measuring the rate of reaction
Students will be required to measure the rate of reaction by an initial method
such as measuring gas volume or by a continuous rate method such as titration
or colorimetry . To carry out this practical you must be familiar with the content
on pages 25 to 29 .

Summary
■■ The rate law states that the rate is proportional ■■ The overall order of reaction is the sum of the
to the concentration of the reactants raised to the individual order of reactions .
power of the orders of reaction with respect to ■■ Zero-order reactants do not take part in the rate
each reactant . determining step .
■■ The rate constant is k and it links the rate of ■■ The Arrhenius equation links the rate constant (k)
reaction to the concentration of the reactants in with the activation energy (Ea) and temperature (T) .
the rate equation . ■■ A graph of ln k against 1/T gives a straight line
■■ The order of reaction with respect to a specific with a gradient of –Ea /R and an intercept on the
reactant is determined experimentally by ln k axis of ln A .
measuring the rate of reaction against known
concentrations of this reactant .

Physical chemistry 2 31
Content Guidance

■ Equilibrium constant Kp for Exam tip

homogeneous systems Kp can be determined
Kp is an equilibrium constant calculated from partial pressure of reactants and for homogeneous
products (measured in pressure units) for homogeneous gaseous reactions. gaseous reactions
since the concentration
All equilibrium constants are only constant at constant temperature. The temperature of a gas can be
should be quoted when the value of any equilibrium constant is given. If temperature calculated as the
remains constant, the equilibrium constant will not change. If any other factor is number of moles of the
varied, such as pressure or concentration of reactants, the value of Kp remains constant. gas in a certain volume
(in dm3) .
Kp expressions and units of Kp
For the reaction:
aA(g) + bB(g)  cC(g) + dD(g) Exam tip
The position of
( pC)c ( pD)d
Kp = equilibrium may
( pA)a ( pB)b
vary when external
where pC represents the partial pressure of C in the equilibrium mixture and c is the factors are changed,
balancing number for C in the equation for the reaction. The same applies to A, B and but only changes
D. The partial pressures of all products are on the top line of the expression raised to in temperature will
the power of their balancing numbers and the partial pressures of all reactants are on affect the value of the
the bottom line again raised to the power of their balancing numbers. equilibrium constant .
(pressure unit)( c+ d ) This is a common
units of Kp = question .
(pressure unit)( a+ b)
The units of Kp are expressed in the same units as the units of the total pressure.
If c + d = a + b, then Kp will have no units.

Worked example
Write an expression for Kp for the reaction:
N2(g) + 3H2(g)  2NH3(g)

and calculate its units when the total pressure is measured in Pa.
Answer Knowledge check 9
( pNH3 )2
Kp = Write a Kp expression
( pN2 )( pH2 )3
for the reaction:
(Pa)2 N2O4(g)  2NO2(g)
units of Kp = = Pa−2
(Pa)4

Mole fractions and partial pressures

The mole fraction is the number of moles of that particular gas at equilibrium divided
by the total number of moles of all gases at equilibrium.
number of moles of particular gas at equilibrium
mole fraction =
total number of moles of gas at equilibrium
32 AQA Chemistry
 Equilibrium constant Kp for homogeneous systems

The partial pressure is the mole fraction of a gas in the equilibrium mixture Exam tip
multiplied by the total pressure of the system.
The total of all the mole
partial pressure = mole fraction × total pressure fractions should add
The units of the partial pressure are the same as units of the overall pressure. up to 1 . The total of
the partial pressures
For homogeneous gaseous reactions partial pressures may be used to calculate a value should add up to the
for Kp. total pressure . This is a
Where P is the overall pressure, partial pressures are calculated as shown from the handy check if you are
mole fraction. asked to calculate the
mole fractions and then
A lower case p followed by the substance is used to represent the partial pressure. For the partial pressures .
example, the partial pressure of A is pA; the partial pressure of N2 is pN2.
For the reaction A + B  C + D: Exam tip
( pC)( pD)
Kp = Again remember that
( pA)( pB)
the total of the partial
(pressure)2 pressures must add to
units = = no units
(pressure)2 the total pressure . In
this general example:
Calculating Kp and using Kp pA + pB + pC + pD = P

The calculations involving Kp may involve calculating Kp or using Kp to calculate an

equilibrium number of moles, a partial pressure, the total pressure on a system or an Exam tip
initial number of moles (Table 5). Again, remember that if
Kp has no units, then Kp
Table 5 Blank table for calculations involving Kp
can be calculated from
A + B  C + D mole fractions instead
of partial pressures .
Initial moles ← Put initial
values in here Exam tip
Reacting moles ← These must Initial masses of
be in ratio gases present or
of balancing even masses of gases
number in
equation present at equilibrium
Equilibrium ← Put final mole may be given . Simply
moles values in here divide the mass of
these gases by the Mr
Mole fraction ← Calculated of the gas to determine
from total the initial moles or
moles
equilibrium moles
Partial pressure ← mole fraction
× overall and fill them into the
pressure correct position in the
table . Watch out for the
If Kp is given, then the above expression table is filled in using x as the number of diatomic gases because
moles of x which react (for example, −x in the reacting moles box for A as explained in you have to use the Mr
the section on using Kc at AS). If Kp is given, the equilibrium moles may be in terms of the diatomic gas: for
of x when Kp has no units. If you are expected to calculate the total pressure, it can be example, 32 for O2 .

Physical chemistry 2 33
Content Guidance

written as P and the partial pressures will be in terms of P. These can be substituted
into the Kp expression and solved for P.

Calculating Kp
Worked example
Calculate a value for Kp for the equilibrium:
2SO2(g) + O2(g)  2SO3(g)

if an original mixture of 16.0 g of sulfur dioxide and 4.0 g of oxygen yields 16.0 g of
sulfur trioxide at equilibrium, at a total pressure of 1.1 × 106 Pa at 450°C.
Answer
(pSO3 )2
Kp =
(pSO2 )2 (pO2 )
(Pa)2 1
units of Kp = = = Pa −1
(Pa)2 (Pa) (Pa)
From the masses:
Initial moles of SO2 = 16.0 = 0.250 mol
64.1
4.00
Initial moles of O2 = = 0.125 mol
32.0
16.0
Equilibrium moles of SO3 = = 0.200 mol
80.1
Completing the table with the given data:
2SO2 + O2  2SO3

Initial moles 0 .250 0 .125 0

Reacting moles
Equilibrium moles 0 .200
Mole fraction
Partial pressure

If 0.200 moles of SO3 are present at equilibrium, then 0.200 moles of SO2 and
0.100 moles of O2 must have reacted to form 0.200 moles of SO3.
➜

34 AQA Chemistry
 Equilibrium constant Kp for homogeneous systems

The table now looks like the one below:

2SO2 + O2  2SO3
Initial moles 0 .250 0 .125 0
Reacting moles −0 .200 −0 .100 +0 .200
Equilibrium moles 0 .050 0 .025 0 .200
Mole fraction
Partial pressure

The mole fraction is calculated from the total equilibrium moles of gas = 0.050 +
0.025 + 0.200 = 0.275.

The moles fractions are calculated as shown in the table below:

2SO2 + O2  2SO3

Initial moles 0 .250 0 .125 0

Reacting moles −0 .200 −0 .100 +0 .200
Equilibrium moles 0 .050 0 .025 0 .200
Mole fraction 0.050 0.025 0.200
0.275 0.275 0.275
Partial pressure
0.050 0.025 0.200
× 1.1 × 106 × 1.1 × 106 × 1.1 × 106
0.275 0.275 0.275
= 2 .00 × 105 Pa = 1 .00 × 105 Pa = 8 .00 × 105 Pa

( pSO3 )2 (8.00 × 105 )2

Kp = = = 1.60 × 10−4 Pa−1
( pSO2 ) ( pO2 ) (2.00 × 105 )2 × (1.00 × 105 )
2

Exam tip
This is the first type of equilibrium calculation, which has two numbers
Knowledge check 10
multiplied on the bottom line . As a rule for Kp expressions, always
calculate the top line and bottom line separately and then divide, as this What is the sum of all
avoids common calculator errors . Unless you are very proficient with a the mole fractions in a
calculator and the use of brackets you will make mistakes . Check the gaseous reaction?
answer twice .

Physical chemistry 2 35
Content Guidance

Calculations using Kp
For the equilibrium H2(g) + I2(g)  2HI(g), Kp = 2.00 at 1500 K. Initially there is
1.00 mole of H2 and 1.00 mole of I2. Calculate the number of moles of HI present at
equilibrium.
( pHI)2
Kp =
( pH2 )( pI2 )
(pressure)2
units of Kp = = no units
(pressure)2
As there is 1.00 mole of H2 and 1.00 mole of I2 present initially, the table can be
completed as shown up to the equilibrium moles.
H2 + I2  2HI
Initial moles 1 .00 1 .00 0
Reacting moles −x −x +2x
Equilibrium moles 1 .00 – x 1 .00 − x 2x
Mole fraction
Partial pressure

The total equilibrium moles of gas are determined = (1.00 − x) + (1.00 − x) + 2x = 2.

The total equilibrium moles of gas are not given in terms of x and this is common in
this style of question where Kp has no units. The total pressure is taken as P.
H2 + I2  2HI
Initial moles 1 .00 1 .00 0
Reacting moles −x −x +2x
Equilibrium moles 1 .00 – x 1 .00 − x 2x
Mole fraction 1.00 − x 1.00 − x 2x
2 2 2
Partial pressure 1.00 − x × P 1.00 − x 2x × P
×P
2 2 2

The mole fractions can be used in place of the partial pressures in the Kp expression
as there are no units of Kp. The total pressure, P, would cancel out in the equilibrium
expression.

36 AQA Chemistry
 Equilibrium constant Kp for homogeneous systems

( 22x ) Exam tip

2
(2 x)2
(pHI) 2
4 (2 x)2 4 This seems
Kp = = = 2 = ×
(pH2 )(pI2 )
( ) (1.00 − x) 4 (1.00 − x)2
2
1.00 − x complicated maths
2 4 but it is basically

( )
2
(2 x)2
2x fractions and indices
= =
(1.00 − x)2 1.00 − x and you will be become
more proficient with
Kp = 2.00 practice . Remember
that a fraction divided
So:
by another fraction
( )
2
2x = 2.00 is simply the top
1.00 − x
fraction multiplied by
Taking a square root of both sides: the bottom fraction

( ) 2x
1− x
= 2.00
upside down . And if
both quantities in a
So: fraction are squared
(top and bottom) then it
2x
= 1.41 is a simple fraction all
1− x
squared .
2x = 1.41(1 – x) = 1.41 – 1.41x
3.41x = 1.41, which gives:
1.41
x= = 0.414
3.41
Once the value of x is calculated it can be filled into the values in the table to
determine mole fractions. If the total pressure was given, the partial pressure can be
determined.
H2 + I2  2HI
Initial moles 1 .00 – x 1 .00 − x 2x
When x = 0 .414 0 .586 0 .586 0 .828

These are the mole fractions. So the answer to the question is that the number of
moles of HI present at equilibrium is 0.828.

Exam tip
When you have determined the value of x, always check the question to
see exactly which quantity you are being asked to determine . It may be
1 − x or in this case it is 2x . Many candidates think they have finished the
question when they determine the value of x, but the answer may involve
using x further .

Exam tip
Answers to these questions, and those in which we use Kp, can be
checked, if time permits, by putting your answers into the expression for
the equilibrium constant . For example, in the above example:
(0.828)2
Kp = = 2 .00
(0.586)(0.586)
Physical chemistry 2 37
Content Guidance

Calculating the total pressure

Often P is used for the total P where it has to be determined. You will be given
enough information in the question to determine P from the Kp value or sometimes
from a partial pressure.

Worked example
If sulfur dioxide and oxygen are mixed in a 2.00 moles SO2 to 1.00 mole O2 ratio and
heated to 1050 K, they reach equilibrium according to the equation:
2SO2(g) + O2(g)  2SO3(g) Kp = 1.25 × 10−4 Pa−1

A 50% conversion of sulfur dioxide to sulfur trioxide occurred. Determine the total
pressure on the system.
Answer
(pSO3 )2 If 50% of SO2 is
Kp = = 1.25 × 10−4 Pa−1
(pSO2 )2 (pO2 ) converted into SO3
then 1 .00 mole out
2SO2 + O2  2SO3 of the 2 .00 moles
of SO2 reacts
Initial moles 2 .00 1 .00 0
Reacting moles −1 .00 −0 .500 +1 .00
Equilibrium moles 1 .00 0 .500 1 .00 Total equilibrium
moles = 2 .50
Mole fraction 1.00 0.500 1.00
= 0.400 = 0.200 = 0.400
2.50 2.50 2.50
Partial pressure 0 .400P 0 .200P 0 .400P

Kp = (0.400P)2
=
1 = 1.25 × 10−4 Pa−1 Exam tip
(0.400P)2 (0.200P) 0.200P
At this stage (0 .400P)2
So: cancels down to 1 in
1 = 0.200P × 1.25 × 10−4 = 2.5 × 10−5P the expression, leaving
1/0 .200P . You can
1 still multiply out the
P= = 40000 Pa
2.5 × 10−5 (0 .400P)2 to get 0 .160P2,
but remember that
both the 0 .400 and the
P need to be squared .

38 AQA Chemistry
 Electrode potentials and electrochemical cells

Position of equilibrium and the equilibrium Exam tip

constant The one to remember
is that a change in
The position of equilibrium and Kc were studied earlier in the course. The position of
pressure has no effect
equilibrium may be affected by changes in temperature, pressure and concentration
on the value of Kp .
(this should be revised from AS), but only a change in temperature affects the value
The value of Kp is only
of Kc. The same applies to Kp.
affected by changes in
Only a change in temperature will affect the value of Kp. temperature .
■■ For an exothermic forward reaction, an increase in temperature will decrease the
value of Kp.
Knowledge check 11
■■ For an endothermic reaction, an increase in temperature will increase the
value of Kp. What effect, if any,
does increasing the
This can be used to predict whether a reaction is endothermic or exothermic with pressure have on the
given values of Kp. position of equilibrium
Summary and the value Kp for the
reaction:
(pC)c (pD)d ■■ The sum of the mole fractions is 1 . N2(g) + 3H2(g)  2NH3(g)
■■ Kp = for the gaseous
(pA)a (pB)b ■■ The sum of the partial pressures is where ΔH = −92 .2kJ mol−1?
equilibrium aA + bB  cC + dD . the total pressure .
■■ Kp is constant at constant ■■ The units of Kp are pressure
temperature; its value is units and there may be no units
not affected by changes in depending on a, b, c and d .
concentration, volume or pressure . ■■ For an equilibrium which has no
■■ pA represents the partial pressure units of Kp, the equilibrium moles or
of gas A in the mixture and is mole fractions may be used in the
calculated from the mole fraction × Kp expression to calculate a value
total pressure . for Kp .
■■ The mole fraction is calculated
from the equilibrium moles of
a substance divided by the total
equilibrium moles .

■ Electrode potentials and

electrochemical cells
When a metal is placed in a solution of its ions, an equilibrium is established between
the ions in the solution and the metal atoms.
The equilibrium can be represented by a half-equation:
Mn+(aq) + ne− → M(s)
for example:
Zn2+(aq) + 2e− → Zn(s)
Fe2+(aq) + 2e− → Fe(s)

Physical chemistry 2 39
Content Guidance

The ions are aqueous and the metal is solid.

■■ The half-equations are written as reduction reactions (gain of electrons).
■■ The metal dipping into a solution of its ions is called a half cell.
■■ Two half cells combined are called a cell.
■■ In one of the half cells an oxidation must occur and in the other a reduction must
occur.
■■ In any electrochemical reaction, there must be a reduction and an oxidation.
■■ Often normal arrows are used to represent the reactions occurring in the half cell.

Standard electrode potentials

The electrode potential is a relative measure of the feasibility of the reduction The standard electrode
occurring. potential is the
electrode potential of
Electrode potentials are represented by E⦵ and are measured in volts (V).
a standard electrode
The electrode potential must be stated with a sign and the units V. with ion concentration
of 1 .00 mol dm−3 at
For example:
298 K connected
Fe2+(aq) + 2e− → Fe(s) E⦵ = −0.44 V to a standard
Zn2+(aq) + 2e− → Zn(s) E⦵ = −0.76 V hydrogen electrode
(1 .00 mol dm−3 H+(aq),
A negative electrode potential indicates that the reduction reaction is not feasible 298 K and 100 kPa H2(g))
unless a more feasible oxidation takes place. using a high resistance
The reduction of iron(ii) ions to iron is not feasible, but if iron(ii) ions were mixed with voltmeter and a salt
zinc metal, the zinc metal would oxidise: bridge .

Zn(s) → Zn2+(aq) + 2e− +0.76 V

Exam tip
and the iron(ii) would be reduced to iron: Standard electrode
Fe2+(aq) + 2e− → Fe(s) −0.44 V potentials are not
measured per mole of
Electromotive force (emf) anything, as they are
all carried out under
The electromotive force (emf) of a complete cell is the total value of the oxidation
standard solution
and reduction standard electrode potentials when the two half cells are combined.
conditions . It does
■■ A positive emf indicates a feasible reaction.
not matter how many
■■ A negative emf indicates an unfeasible reaction.
moles of each reactant
■■ The emf always relates to the overall redox reaction (oxidation and reduction react .
combined).
The overall electromotive force (emf) of this cell is +0.76 − 0.44 = +0.32 V.
The electromotive force
So this overall reaction is feasible. A positive emf indicates that the reaction is (emf) is the potential
feasible. difference measured
The E⦵ values given are actually standard electrode potentials. The standard means when two half cells are
they have been compared to a standard, which is the standard hydrogen electrode. combined .

40 AQA Chemistry
 Electrode potentials and electrochemical cells

Features of standard hydrogen electrode

Figure 17 shows the features of the standard hydrogen electrode:
■■ platinum electrode
■■ 1.00 mol dm−3 hydrogen ions in solution
■■ H2 gas at 100 kPa pressure
■■ the temperature should be 298 K
■■ the standard electrode potential of the standard hydrogen electrode is 0.00 V

Temperature = 298 K

Hydrogen gas at
100 kPa pressure
Platinum wire
Knowledge check 12
What conditions
Platinum foil covered are required for the
in porous platinum standard hydrogen
electrode?
[H+] = 1.00 mol dm–3

Figure 17 The standard hydrogen electrode

Combination of half cells

Two half cells can be combined using a salt bridge and an external circuit containing
a high resistance voltmeter to produce a cell.

Exam tip
A high resistance voltmeter is used to measure the emf of the cell, but
Exam tip
does not allow current to flow in the circuit . Any flow of current would
change the concentration of ions in the solutions and the cell would no Potassium chloride
longer be under standard conditions . may be used in place
of potassium nitrate
The salt bridge is usually filter paper soaked in saturated potassium nitrate solution for the salt bridge, but
which dips into both half cell solutions. The salt bridge allows electrical connection this may interfere with
between the half cells without allowing them to mix. the cell, as Cl− ions can
■■ The left-hand half cell (by convention) is the one in which oxidation occurs. This is
form complexes with
the negative electrode of the cell. transition metal ions so
it is to be avoided with
■■ The right-hand half cell (by convention) is the one in which reduction occurs. This
cells containing these
is the positive electrode of the cell.
ions .
Figure 18 shows the combination of a standard hydrogen half cell or electrode on the
left with a zinc half cell or electrode on the right.

Physical chemistry 2 41
Content Guidance

High resistance
Temperature = 298 K voltmeter
V
Hydrogen at
100 kPa pressure
Salt bridge
Zinc
Platinum wire

Platinum foil covered

in porous platinum

[H+] = 1.00 mol dm–3 [Zn2+] = 1.00 mol dm–3

Figure 18 Standard hydrogen half cell and zinc half cell

Exam tip
A common question can be to sketch the right-hand cell attached to the
standard hydrogen electrode . You would not usually be expected to draw
the standard hydrogen electrode . Sketch the diagram from the voltmeter
through the labelled right-hand cell to the salt bridge connecting to the
standard hydrogen electrode .

Left-hand cell or right-hand cell

For the two standard electrode potentials given below:
Zn2+(aq) + 2e− → Zn(s) E⦵ = −0.76 V
Cd2+(aq) + 2e− → Cd(s) E⦵ = −0.40 V
There are several ways to approach working out which is the left-hand cell and Exam tip
which is the right-hand cell but the easiest idea to keep in your head is that the most
NEGATOX is a good way
negative one, or the one closest to negative if they are both positive, is the oxidation
of remembering which
half cell and should be on the left. It will form the negative electrode.
electrode is negative as
So the zinc half cell is on the left and the cadmium half cell is on the right. The the negative electrode
overall ionic equation for the reaction would be: is the one at which
Zn + Cd2+ → Zn2+ + Cd oxidation occurs .

Exam tip
You worked through balancing half-equations at AS . Simply reverse the
more negative equation (change Zn2+ + 2e − → Zn to Zn → Zn2+ + 2e −) . The
electrons are balanced (2e − in each equation) and combine them to cancel
out the electrons .

The emf of this cell is found by adding together the E⦵ values with the sign of the
left-hand one changed. In this example it is + 0.76 − 0.44 = + 0.32 V. The + 0.76 is
E⦵ value for the zinc half cell with its sign changed. A diagram of the cell is shown in
Figure 19.

42 AQA Chemistry
 Electrode potentials and electrochemical cells

V
Exam tip
Indicating the direction
Zn Salt bridge Cd
of flow of electrons can
be a common question .
The electrons are
flowing from the left-
hand side (as they are
given up by Zn → Zn2+
Zn2+(aq) Cd2+(aq) + 2e −) to the right-hand
side (where they are
Figure 19 Zinc and cadmium cell used as Cd2+ + 2e − →
Cd) .
Non-standard conditions in a cell
Two identical cells or two cells with the same electrode potential will show no overall
voltage. However, two identical cells with different concentration of solution will show
a reduction where the ion in solution is at a greater concentration.
The left-hand cell in Figure 20 will show a reduction (Cu2+ + 2e− → Cu), as the Cu2+
ions are at higher concentration.

Copper Salt bridge Copper

1.00 mol dm–3 0.200 mol dm–3

CuSO4(aq) CuSO4(aq)

Figure 20 Two copper half cells

Note that the ammeter between the cells allows current to flow. A voltmeter is not
used here as you are not trying to measure the emf of the cell.
The mass of the left-hand electrode will increase as copper is deposited on it and
the mass of the right-hand one will decreases as Cu → Cu2+ + 2e−, so copper in the
electrode is being used up.

Conventional cell representation

Cells are written as oxidation at left-hand half cell || reduction at right-hand half cell.
State symbols are not absolutely necessary in cell notation but should be included if
asked for in a question.
For example:
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
|| represents the salt bridge.
Zn(s) | Zn2+(aq) represents the oxidation reaction Zn → Zn2+ + 2e−
Physical chemistry 2 43
Content Guidance

Cu2+(aq) | Cu(s) represents the reduction reaction Cu2+ + 2e− → Cu Exam tip
The overall emf of the cell can be calculated using the expression: Erhs⦵ − Elhs⦵ This is a fast way
(right-hand side − left-hand side). of doing it from cell
For Zn2+ + 2e− → Zn: E⦵ = −0.76 V notations but again the
sign of the oxidation
For Cu2+ + 2e− → Cu: E⦵ = +0.34 V side is changed, hence
Therefore for the cell Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s). −Elhs⦵ . The − changes
the sign .
emf = +0.34 – (−0.76) = +1.10 V
This can be written more simply without state symbols as: Zn | Zn2+ || Cu2+ | Cu. This
is common.
This reaction is feasible as the overall emf is positive.

Phase boundaries
The | used in cell representation is called a phase boundary and should be used when the
two species in a half cell are in different phases or states. For example, Zn(s) | Zn2+(aq).
However, if the two species are in the same phase a comma should be used between
them. For example, Fe3+(aq), Fe2+(aq).
Pt should be included if it is used as the electrode for gas electrodes and also for those
with two ions in solution.

Worked example
The two half cells
Fe3+(aq) + e− → Fe2+(aq) E⦵ = +0.77 V

Cl2(g) + 2e− → 2Cl−(aq) E⦵ = +1.36 V

Write the equation for the overall cell reaction. Give the conventional cell
representation for this cell, identify the positive electrode and calculate the emf of
the cell.
Answer
First, the more negative one is the one that will be reversed. Both have positive E⦵,
but the more negative is the Fe half cell as it is closer to being negative. This will be
the oxidation half cell and will be on the left.
The overall equation requires the Fe half cell to be reversed and multiplied by 2 to
balance the electrons.
2Fe2+ → 2Fe3+ + 2e−

Cl2 + 2e− → 2Cl−

The overall equation is: 2Fe2+ + Cl2 → 2Fe3+ + 2Cl−

➜

44 AQA Chemistry
 Electrode potentials and electrochemical cells

The cell representation is: Pt | Fe2+, Fe3+ || Cl2 | Cl− | Pt

■ Note that Pt has to be included at either end as it is used as the electrode in both
half cells and it should be separated by a |.
■ The comma between Fe2+ and Fe3+ is there as they are both in solution, both (aq),
so in the same phase.
■ 2Cl− is not needed as it is just the species that is needed.
■ A | is required between Cl2 and Cl− as Cl2 is a gas and Cl− ions are in solution.

Using NEGATOX, the negative electrode is the one at which oxidation occurs.
Oxidation occurs at the iron electrode, so it is negative, which means that the
chlorine electrode is the positive electrode.
The emf is +1.36 − (−0.77) = +2.13 V.

Feasibility of reactions
A positive emf for an electrochemical cell is an indication that the reaction between
the species would occur under standard conditions. This can be used to predict the
feasibility of normal chemical reactions.
From the following standard electrode potentials:
Zn2+ + 2e− → Zn E⦵ = −0.76 V
Cu2+ + 2e− → Cu E⦵ = +0.34 V
Mg2+ + 2e− → Mg E⦵ = −2.37 V
Fe2+ + 2e− → Fe E⦵ = −0.44 V
Consider the reaction between zinc and iron(ii) ions in solution. The ionic equation
for the reaction is:
Zn + Fe2+ → Zn2+ + Fe
When a piece of zinc is placed in a solution containing iron(ii) ions, a displacement
reaction occurs. From GCSE we would explain that this is due to zinc being more
reactive than iron, but it is more accurately explained using the electrode potentials.
A positive emf for the electrochemical cell containing these two half cells indicates a
feasible reaction. The answers are usually presented in one of two ways:
1 Explain that a reaction occurs by considering that the E⦵ value for the
reduction of Fe2+ to Fe is greater than the E⦵ value for the reduction of
Zn2+ to Zn. This would mean that the reduction of Fe2+ to Fe is more
favourable, so Zn reacts with Fe2+ ions in solution. This is often simply
written in mark schemes as E⦵ (Fe2+ | Fe) > E⦵ (Zn2+ | Zn).
2 It can also be explained by calculating the emf of the cell.
Zn2+ + 2e− → Zn E⦵ = −0.76 V
Fe2+ + 2e− → Fe E⦵ = −0.44 V

Physical chemistry 2 45
Content Guidance

The more negative one changes direction and becomes the oxidation. So: Knowledge check 13
Zn → Zn2+ + 2e− +0.76 V In the cell
Fe2+ + 2e− → Fe −0.44 V Zn | Zn2+ || Cu2+ | Cu
which is the negative
emf = +0.32 V electrode?
The positive emf indicates that this is a feasible reaction. So zinc will reduce iron(ii)
ions to iron.

Link to reactivity
Extending the series we had above:
Zn2+ + 2e− → Zn E⦵ = −0.76 V
Cu2+ + 2e− → Cu E⦵ = +0.34 V
Mg2+ + 2e− → Mg E⦵ = −2.37 V
Fe2+ + 2e− → Fe E⦵ = −0.44 V
I2 + 2e− → 2I− E⦵ = +0.54 V
Br2 + 2e− → 2Br− E⦵ = +1.07 V
Cl2 + 2e− → 2Cl− E⦵ = +1.36 V
The electrode potential for the reverse oxidation reaction gives a measure of the
reactivity of the metal, as the most reactive metal will form its ions most easily.
From these values, it is clear that it is most feasible for Mg to form its ions (+2.37 V)
followed by Zn (+0.76 V), followed by Fe (+0.44 V) and least of all Cu (−0.44 V).
This explains the order of reactivity of the metals.
The non-metals are reduced and it is most feasible for chlorine to be reduced
(+1.36 V) compared to bromine (+1.07 V) and then iodine (+0.54 V). This explains why
the reactivity of the halogens decreases down group 7. Exam tip
Look to the left of the
Oxidising agents and reducing agents half-equations for the
Oxidising agents are easily reduced and reducing agents are easily oxidised. oxidising agents, as
E⦵/V these species will gain
electrons and so cause
Mg2+ + 2e− → Mg −2.37 an oxidation to occur
Zn2+ + 2e− → Zn −0.76 as some other species
loses electrons . Look
Fe2+ + 2e− → Fe −0.44 to the right of the
Cu2+ + 2e− → Cu +0.34 half-equations for the
reducing agents, as
I2 + 2e− → 2I− +0.54
these species will lose
Cl2 + 2e− → 2Cl− +1.36 electrons and so cause
an oxidation to occur
The best reducing agent in the above set of half-equations is magnesium, as it is most
as some other species
easily oxidised (Mg → Mg2+ + 2e− is + 2.37 V). The best oxidising agent is chlorine
gains electrons .
(Cl2 + 2e− → 2Cl− is + 1.36 V).
46 AQA Chemistry
 Electrode potentials and electrochemical cells

Electrode potentials applied to vanadium

chemistry
Transition metals have variable oxidation states and this will be studied in the
next book. However, electrode potentials may be used to explain the oxidation and
reduction processes. Vanadium compounds exist with vanadium in the +5, +4, +3
and +2 oxidation states. The half-equations below show the sequential reduction of
vanadium.
Oxidation states Half-equation Electrode potential
+5 to +4 VO2+ + 2H+ + e− → VO2+ + H2O E⦵ = +1.00 V
+4 to +3 VO2+ + 2H+ + e− → V3+ + H2O E⦵ = +0.32 V
+3 to +2 V3+ + e− → V2+ E⦵ = −0.26 V

Worked example
Which reducing agent will reduce vanadium from the +5 oxidation state to the
+3 oxidation state but not to the +2 oxidation state?
A iodine
B iron
C sulfur dioxide
D zinc
given the following standard redox potentials:
E⦵/V
Zn2+(aq) + 2e− → Zn(s) −0.76
Fe2+(aq) + 2e− → Fe(s) −0.44
SO42−(aq) + 2H+(aq) + 2e− → 2H2O(l) + SO2(g) +0.17
I2(aq) + 2e− → 2I−(aq) +0.54

Answer
The choice has to be from the right of these half-equations, as a substance which is
to be oxidised (i.e. lose electrons) must be chosen. If any substance is given which
is on the left of one of these equations (for example, iodine) then it can be ruled
out, as it would be reduced.
Each reaction is taken in turn with each stage of the reduction of vanadium.
Try the oxidation of Fe to Fe2+, which has a potential of +0.44 V:
VO2+ + 2H+ + e− → VO2+ + H2O +1.00 V
Fe2+ + 2e− → Fe −0.44 V
(Reverse second equation) emf = +1.44 V feasible
➜

Physical chemistry 2 47
Content Guidance

or E⦵ (VO2+/VO2+) > E⦵ (Fe2+/Fe), so vanadium is reduced from +5 to +4 by the

oxidation of iron:
VO2+ + 2H+ + e− → V3+ + H2O +0.32 V
Fe2+ + 2e− → Fe −0.44 V
(Reverse second equation) emf = +0.76 V feasible

or E⦵ (VO2+/V3+) > E⦵ (Fe2+/Fe), so vanadium is reduced from +4 to +3 by the

oxidation of iron:
V3+ + e− → V2+ −0.26 V
Fe2+ + 2e− → Fe −0.44 V
(Reverse second equation) emf = +0.18 V feasible

or E⦵ (V3+/V2+) > E⦵ (Fe2+/Fe), so vanadium is reduced from +3 to +2 by the

oxidation of iron.
Fe cannot be the answer because it will reduce vanadium from +5 to +2.
Try the oxidation of sulfur dioxide to sulfate:
VO2+ + 2H+ + e− → VO2+ + H2O +1.00 V
SO42− + 4H+ + 2e− → SO2 + 2H2O +0.17 V
(Reverse second equation) emf = +0.83 V feasible

or E⦵ ( VO2+/VO2+) > E⦵ (SO42−/SO2), so vanadium is reduced from +5 to +4 by the

oxidation of sulfur dioxide:
VO2+ + 2H+ + e− → V3+ + H2O +0.32 V
SO42− + 4H+ + 2e− → SO2 + 2H2O +0.17 V
(Reverse second equation) emf = +0.15 V feasible

or E⦵ (VO2+/V3+) > E⦵ (SO42−/SO2), so vanadium is reduced from +4 to +3 by the

oxidation of sulfur dioxide:
V3+ + e− → V2+ −0.26 V
SO42−+ 4H+ + 2e− → SO2 + 2H2O +0.17 V
(Reverse second equation) emf = −0.43 V not feasible

or E⦵ (V3+/V2+) < E⦵ (SO42−/SO2), so vanadium is not reduced from +3 to +2 by the

oxidation of sulfur dioxide.
Sulfur dioxide (SO2) is the answer, as it will reduce vanadium from +5 to +3, but will
not reduce vanadium from +3 to +2.
Zinc will reduce vanadium from +5 to +2 and iodide ions (which were not given in
the question) will reduce vanadium from +5 to +4 but no further.

48 AQA Chemistry
 Electrode potentials and electrochemical cells

Required practical 8
Measuring the emf of an electrochemical cell
Students should be able to measure the emf of a simple cell, such as Zn | Zn2+ ||
Cu2+ | Cu, using a high resistance voltmeter .

Commercial application of cells

The emf of an electrochemical cell can be used as a commercial source of electrical
energy. These are commonly called cells or batteries. There are three main types:
1 Primary cells — these are single use and non-rechargeable.
2 Secondary cells — these can be recharged.
3 Fuel cells — these continuously produce an electrical current as long as
they are supplied with a fuel.

Basic electrochemistry of cells

A cell has a positive electrode (labelled +) and a negative electrode (labelled −).
The electrons flow from the negative electrode to the positive electrode when the cell Exam tip
is being used.
Remember NEGATOX
At the negative electrode, an oxidation reaction occurs; electrons are lost and as this still applies .
oxidation number increases. The negative electrode
At the positive electrode, a reduction reaction occurs; electrons are gained and is where an oxidation
oxidation number decreases. reaction is occurring .

Primary cells
A typical primary cell is shown in Figure 21.
+
Cover

Carbon rod

MnO2 paste

Porous separator
Zinc
ZnCl2 paste
–

Figure 21 A typical non-rechargeable cell

At the negative electrode (oxidation occurs):

Zn → Zn2+ + 2e−
At the positive electrode (reduction occurs):
MnO2 + H2O + e− → MnO(OH) + OH−
Physical chemistry 2 49
Content Guidance

The half-equation for the reaction at the positive electrode is more unusual and Knowledge check 14
should be learned. These types of reactions are common and you should copy them
What is the oxidation
out until you know them and understand the changes in oxidation state.
state of manganese in
In this half-equation, manganese is reduced from +4 to +3. MnO(OH)?
+4 in MnO2 and +3 in MnO(OH) as the O is −2 and the OH− is overall −1,
so Mn is +3.
You should also be able to combine half-equations to write an overall ionic equation
Exam tip
for the reaction in the cell. The overall equation for this cell is: This was worked out
by multiplying the
Zn + 2MnO2 + 2H2O → Zn2+ + 2MnO(OH) + 2OH−
reduction equation by
This reaction is non-reversible, so the cell, once discharged, cannot be used again. 2 to balance electrons
and adding them
Secondary cells together .
There are several types of secondary cells.

Nickel cadmium cell

At the negative electrode (oxidation occurs):
Cd + 2OH− → Cd(OH)2 + 2e−
At the positive electrode (reduction occurs):
NiO(OH) + H2O + e− → Ni(OH)2 + OH−
The overall equation is:
Cd + 2NiO(OH) + 2H2O → Cd(OH)2 + 2Ni(OH)2
When any secondary cell is recharged, the equation above is simply reversed.
Sometimes the standard electrode potentials may be given and this allows the emf to
be calculated, which is the voltage delivered by the cell or battery. Knowledge check 15
Cd(OH)2 + 2e− → Cd + 2OH− E⦵ = −0.88 V Explain in terms of
oxidation states how
NiO(OH) + H2O + e− → Ni(OH)2 + OH− E⦵ = +0.52 V
nickel is reduced in
The top half-equation is reversed in the cell so the emf = +0.52 + 0.88 = +1.40 V this cell .

Lead–acid cell
This is the type of cell used in cars.
At the negative electrode (oxidation occurs):
Pb + HSO4− → PbSO4 + H+ + 2e−
At the positive electrode (reduction occurs):
PbO2 + 3H+ + HSO4− + 2e− → PbSO4 + 2H2O
The overall equation is:
PbO2 + 2H+ + 2HSO4− + Pb → 2PbSO4 + 2H2O

50 AQA Chemistry
 Electrode potentials and electrochemical cells

Lead(ii) sulfate is insoluble, so if the cell is not recharged for a long period of time
the lead(ii) sulfate builds up and the cell cannot be recharged. Again this equation is
reversed as the cell is recharged.

Lithium ion cell

Lithium ion cells are the most commonly used cells in portable electronic devices
such as mobile phones, tablets and laptops.
At the negative electrode (oxidation occurs):
Li → Li+ + e−
At the positive electrode (reduction occurs):
Li+ + CoO2 + e− → Li+[CoO2]−
The overall equation is:
Li + CoO2 → Li+[CoO2]−
Graphite powder is used for the support medium in this type of cell, as water would
react with lithium. Again the reaction is reversed when the cell is recharged.
The conventional cell representation for this cell is: Li | Li+ || Li+, CoO2 | LiCoO2 | Pt.
Lithium is oxidised from 0 to +1 and cobalt is reduced from +4 in CoO2 to +3 in
LiCoO2.

Fuel cells
Fuel cells convert chemical energy into electrical energy. There are several types of
fuel cells.

Hydrogen fuel cell

A hydrogen fuel cell operates in acidic or alkaline conditions. The alkaline one is
considered here.
At the negative electrode (oxidation occurs):
H2 + 2OH− → 2H2O + 2e−
At the positive electrode (reduction occurs):
O2 + 2H2O + 4e− → 4OH−
The overall equation is:
2H2 + O2 → 2H2O
The conventional cell representation for an alkaline hydrogen fuel cell is:
Pt | H2 | OH−, H2O || O2 | H2O, OH− | Pt
Platinum is used for the electrodes. All species undergoing any redox change are
included.
The overall equation in the hydrogen fuel cell is always the same and the emf is
always +1.23 V, whether it is in alkaline or acidic conditions.

Physical chemistry 2 51
Content Guidance

The current from a fuel cell should remain constant as long as the fuel is continuously Exam tip
supplied. The current from a primary or secondary cell will fall over time.
In acidic conditions
the oxidation reaction
Risks and benefits is H2 → 2H+ + 2e −, the
Primary cells generate waste and although some parts may be recycled they are reduction equation is
generally just thrown away. Secondary cells can be recharged many times, but O2 + 4H+ + 4e − → 2H2O .
again they have a lifetime. Fuel cells continuously produce current as long as the The overall emf is
fuel is supplied. Cells allow us to have portable electrical devices away from main +1 .23 V and as H2 → 2H+
electricity. However, they do contain metals, which are in ever-decreasing supply + 2e − has E⦵ = 0 .00 V by
and should be recycled. Hydrogen fuel cells require a steady supply of hydrogen gas, definition, the E⦵ for
which is flammable and so difficult to contain safely. Ethanol fuel cells are a possible the reduction reaction
alternative, as the ethanol may be produced by fermentation and so can be considered is +1 .23 V .
a carbon-neutral fuel since the CO2 released by combustion is offset by the CO2
taken in by photosynthesis.

Summary
■■ Standard electrode potentials give a measure in ■■ The strongest oxidising agent (oxidant) is the one
volts (V) of the feasibility of a half cell reaction . which is most easily reduced .
■■ The emf (electromotive force) is the combination ■■ A cell shows the reduction as the left-hand half
of the standard electrode potentials for the two cell and the reduction as the right-hand half cell .
half cell reactions . ■■ The negative electrode is where an oxidation
■■ A positive emf indicates a feasible reaction, reaction occurs (NEGATOX) .
whereas a negative emf indicates a reaction ■■ Conventional cell representation shows the
which is not feasible . cell in terms of the oxidation on the left and
■■ The standard hydrogen electrode is measured at the reduction on the right, using | as a phase
100 kPa pressure of H2, 1 mol dm−3 of H+ ions and boundary and || to show the salt bridge .
298 K . ■■ Commercial electrochemical cells are either
■■ The strongest reducing agent (reductant) is the primary cells (non-rechargeable), secondary
one which is most easily oxidised . cells (rechargeable) or fuel cells .

■ Acids and bases

Brønsted–Lowry theory of acids and bases
The chemistry of acids and bases depends on protons. The terms proton and hydrogen
ion are interchangeable, but proton is most often used.
In the reaction:
NH3 + H2O → NH4+ + OH− A Brønsted–Lowry base
■■ NH3 accepts a proton to become NH4+. NH3 acts as a Brønsted–Lowry base. is a proton acceptor .
■■ H2O donates a proton. H2O acts as a Brønsted–Lowry acid. A Brønsted–Lowry acid
In the following reaction: CH3COOH + H2O → CH3COO− + H3O+ is a proton donor .
■■ H2O accepts a proton to become H3O+. H2O acts as a Brønsted–Lowry base.
■■ CH3COOH donates a proton. CH3COOH acts as a Brønsted–Lowry acid.

52 AQA Chemistry
 Acids and bases

Exam tip Knowledge check 16

Water can act as both a Brønsted–Lowry acid and base . H3O+ is the In the equation
hydronium ion or hydroxonium ion or oxonium ion . It is the ion formed HCO3 − + H2O →
when acids react with water . All three names are acceptable . CO32− + H3O+
what is acting as a
Brønsted–Lowry acid?
Classification of acids and bases
Acids (and bases) may be classified as strong or weak.
A strong acid is completely dissociated into its ions in solution.
Common strong acids are hydrochloric acid (HCl), sulfuric acid (H2SO4) and nitric
acid (HNO3). For strong acids, all of the acid molecules in solution are dissociated
into ions.
For example: HCl → H+ + Cl−
H2SO4 → 2H+ + SO42−
HNO3 → H+ + NO3−
HCl and HNO3 are described as monoprotic acids. H2SO4 is a diprotic acid. Monoprotic acids are
acid molecules that
Exam tip donate one proton (H+)
per molecule of acid .
The equations for the dissociation of strong acids use a full arrow (→)
to show that the acid is fully dissociated . The dissociation equations can
be written as the reaction of the acid, with water on the left forming the
anion and H3O+ . For example, HCl + H2O → H3O+ + Cl− .

A weak acid is slightly dissociated into its ions in solution.

Common weak acids are carbonic acid (H2CO3), most carboxylic acids such as Exam tip
ethanoic acid (CH3COOH), hydrocyanic acid (HCN), nitrous acid (HNO2) and Most of the weak acids
sulfurous acid (H2SO3). you will encounter are
For example: monoprotic acids and
any calculations will
CH3COOH  H+ + CH3COO− make that assumption .
HNO2  H+ + NO2− The reversible arrow
( ) is used to show
Generally this can be represented as: the slight dissociation .
HA  H+ + A− Again the dissociation
equation can be written
where HA is the undissociated monoprotic weak acid.
as the reaction of the
Strong bases are completely dissociated into their ions in solution, whereas weak bases acid with water forming
are slightly dissociated into their ions in solution. the anion and H3O+ . For
example: H3COOH + H2O
Group 1 hydroxides are strong bases, for example, sodium hydroxide (NaOH) and
 CH3COO− + H3O+ .
potassium hydroxide (KOH). Ammonia is the most common example of a weak base.

Physical chemistry 2 53
Content Guidance

NaOH → Na+ + OH−

KOH → K+ + OH−
NH3 + H2O  NH4+ + OH−
Soluble bases are called alkalis and they form hydroxide ions in solution.

Calculating pH
pH (always written with a small p and a capital H) is a logarithmic scale which gives a
measure of the H+ concentration in a solution.
pH = −log10[H+]
where [H+] represents the concentration of H+ ions in solution measured in mol dm−3.
To calculate the hydrogen ion concentration from the pH, reverse the calculation
[H+] = 10(−pH)
A hydrogen ion concentration of 1.00 × 10−2 mol dm−3 (= 0.0100 mol dm−3) will give a
pH of 2.00.
A solution with a pH of 8.00 has hydrogen ion concentration of 10−8.00 (= 1.00 ×
10−8 mol dm−3).
pH is usually quoted to 2 decimal places.
Knowledge check 17
pH of strong acids Define pH .
Figure 22 links the concentration of the acid in mol dm−3 shown as [acid] with the
concentration of hydrogen ions shown as [H+] and the pH.
× proticity of acid pH = –log10[H+]
[Acid] [H+] pH
÷ proticity of acid [H+] = 10(–pH)

Figure 22 Determining pH of a strong acid

Worked example 1
Calculate the pH of 0.128 mol dm−3 hydrochloric acid. Give your answer to 2 decimal
places.
Answer
HCl is monoprotic, so [H+] = [acid].
[H+] = 0.128 mol dm−3
pH = −log10[H+] = −log10(0.128) = 0.89

54 AQA Chemistry
 Acids and bases

Worked example 2 Exam tip

Calculate the pH of 1.05 mol dm−3 sulfuric acid. Give your answer to 2 decimal When the concentration
places. of hydrogen ions is
above 1 .00 mol dm−3,
Answer the pH will be negative .
H2SO4 is diprotic, so [H+] = 2 × [H2SO4]. If [H+] = 1 .00 mol dm−3,
the pH will be 0 . The
[H+] = 2 × 1.05 = 2.10 mol dm−3
above processes may
pH = −log10[H+] = −log10(2.10) = −0.32 be reversed . Check you
can do these on your
calculator .
Worked example 3
Calculate the concentration of a solution of sulfuric acid with a pH of 2.49. Give
your answer to 3 significant figures.
Answer
[H+] = 10−2.49 = 0.00324 mol dm−3
H2SO4 is diprotic, so [H+] = 2 × [H2SO4]

[H2SO4] =
[H+ ] = 0.0324 = 0.00162 mol dm−3
2 2

Exam tip Knowledge check 18

The same answer to 3 significant figures is obtained if the calculation is Calculate the pH of
carried out completely on a calculator . However, as long as you show your 2 .54 mol dm−3 sulfuric
working out for these questions, any rounding errors can be avoided . acid .
Work to 3 or 4 significant figures throughout the calculation, but give the
answer to the required level of accuracy at the end .

Ionic product of water

Water slightly dissociates into hydrogen ions and hydroxide ions.
H2O  H+ + OH−
■■ Kw is the ionic product of water and Kw = [H+][OH−].
■■ Units of Kw are always mol2 dm−6.
■■ At 25.0°C, Kw = 1.00 × 10−14 mol2 dm−6.

Physical chemistry 2 55
Content Guidance

Calculating the pH of water

In water [H+] = [OH−], so Kw = [H+]2.
Worked example
At 50°C Kw = 5.48 × 10−14 mol2 dm−6. Calculate the pH of water at 40°C. Give your
answer to 2 decimal places.
Answer
Kw = 5.48 × 10−14 = [H+]2 [H+] = 5.48 × 10 −14 = 2.34 × 10−7 mol dm−3

pH = −log10[H+] = –log10(2.34 × 10−7) = 6.63

Exam tip
We have become accustomed to think that the pH of pure water is 7,
but this is only true at 25°C . As temperature increases above 25°C, the
pH of water drops below 7 . Kw increases as temperature increases,
which indicates that the dissociation of water into H+ and OH− ions is
endothermic, as the equilibrium is moving to the right (more H+) as
temperature increases .

pH of strong alkalis
Alkalis contain hydrogen ions, OH−, in solution. If the concentration of OH− ions is
known, this can be converted to the concentration of H+ ions using the Kw expression
at a given temperature.
Figure 23 shows the connections between concentration of the alkali, [alkali],
concentration of hydroxide ions, [OH−], concentration of hydrogen ions, [H+], and pH
for a strong alkali.
× number of moles
of OH– produced
by 1 mole of the Kw
[H+] = ——–
base in solution [OH–] pH = –log10[H+]
[Alkali] [OH–] [H+] pH
÷ number of moles Kw [H+] = 10(–pH)
[OH–] = ——–
of OH– produced [H+]
by 1 mole of the
base in solution

Figure 23 Determining pH of a strong alkali

56 AQA Chemistry
 Acids and bases

Worked example 1
Calculate the pH of a 0.644 mol dm−3 solution of sodium hydroxide (Kw = 1.00 ×
10−14 mol2 dm−6). Give your answer to 2 decimal places.
Answer
[NaOH] = 0.644 mol dm−3

[OH−] = 0.644 mol dm−3 (as 1 OH− per NaOH)

Kw 1.00 ×10−14
[H+] = = = 1.55 × 10−14 mol dm−3
[OH ]− 0.644
pH = −log10[H+] = −log10(1.55 × 10−14) = 13.81

Worked example 2
Calculate the concentration of potassium hydroxide solution, in mol dm−3, at
40°C, which has a pH of 13.64. Kw at 40°C is 2.92 × 10−14 mol2 dm−6. Give your
answer to 3 significant figures.
Answer
[H+] = 10−13.64 = 2.29 × 10−14 mol dm−3
Kw 2.92 × 10−14
[OH−] = = = 1.28 mol dm−3
[H+ ] 2.29 × 10−14
[KOH] = [OH−]

So:
[KOH] = 1.28 mol dm−3

Exam tip
The majority of strong bases (alkalis) you will encounter will have 1 mole of
OH− ions per mole of the base . However, sometimes a question is set on a
group 2 hydroxide where you are asked to assume that the base is strong
and so the number of moles of OH− per mole of base for Ca(OH)2 is 2 .
Check the second calculation the other way round if you have time . Make
sure you get a pH of 13 .64 using a concentration of 1 .28 mol dm −3 and the
Kw at that temperature . The answer may be approximate, but this may be
to do with rounding .

pH of weak acids
Weak acids are slightly dissociated in solution. This is represented using a reversible
arrow (). The equilibrium constant for the acid dissociation is represented by Ka.
For the general weak acid dissociation equation, HA  H+ + A−.

Physical chemistry 2 57
Content Guidance

Ka =
[H+ ][ A − ] for the species present at equilibrium.
[HA ]
Ka always has units of mol dm−3.

Worked example
Write an expression for Ka for ethanoic acid, CH3COOH.
Answer
Ka =
[H+ ][CH3COO− ]
[CH3COOH]

Exam tip
HA is the undissociated acid . Remember that the undissociated acid
Knowledge check 19
does not cause it to be acidic . It is the concentration of H+ that causes
acidity when the acid dissociates . HA is not acidic until it dissociates . It is Write a Ka expression
important to be able to write Ka expressions for weak acids . It is always for methanoic acid,
the [anion] and [H+] on the top and [undissociated acid] on the bottom . HCOOH .

The value of Ka gives a measure of the strength of the acid. A higher Ka value
indicates a ‘stronger’ weak acid. For example, ethanoic acid has a Ka value of 1.8 ×
10−5 mol dm−3, whereas hydrocyanic acid has a Ka of 4.9 × 10−10 mol dm−3. Ethanoic
acid is a ‘stronger’ acid than hydrocyanic acid.
For a weak acid, [H+] is calculated from the concentration of the acid and the Ka value
using the expression:
[H+] = Ka × initial concentration of acid
The pH is calculated using pH = −log10[H+]. This is summarised in Figure 24.

[H+] = √ Ka × [weak acid] pH = –log10[H+]

[Weak acid] [H+] pH
[H+]2 [H+] = 10(–pH)
[Weak acid] = ——–
Ka

Figure 24 Determining pH of a weak acid

pKa
The pKa of a weak acid may be given in place of its Ka. pKa = −log10 Ka. To convert
between a pKa value and Ka use the following: Ka = 10(−pKa).
The higher the pKa value, the weaker the acid. A lower pKa indicates a ‘stronger’ acid.

58 AQA Chemistry
 Acids and bases

Worked example 1
Ka for methanoic acid (CH3COOH) is 1.60 × 10−4 mol dm−3. Calculate the pH of a
0.128 mol dm−3 solution of methanoic acid. Give your answer to 2 decimal places.
Answer
[H+] = Ka × [weak acid]

[H+] = 1.60 × 10 −4 × 0.128 = 2.048 × 10 −5 = 4.525 × 10−3 mol dm−3

pH = −log10[H+] = −log10(4.525 × 10−3) = 2.34

Worked example 2
Calculate the pH of a solution if 0.0253 moles of a weak acid is dissolved in 500 cm3
of water (pKa for the acid = 2.85). Give your answer to 2 decimal places.
Answer
Concentration of the weak acid in mol dm−3 = 0.0253 × 2 = 0.0506 mol dm−3.
Ka = 10(−pKa) = 10(−2.85) = 1.41 × 10−3 mol dm−3

[H+] = Ka × [weak acid]

[H+] = 1.41 × 10 −3 × 0.0506 = 7.13 × 10 −5 = 8.45 × 10−3 mol dm−3

pH = −log10[H+] = −log10(8.45 × 10−3) = 2.07

The acid dissociation constant, Ka, may be calculated from pH and the concentration
of the weak acid. [H+] is determined from pH in the usual way and the acid
dissociation constant can be calculated using Ka = [H+]2/[weak acid].

Worked example 1
A 0.0244 mol dm−3 solution of a weak acid has a pH of 3.24. Calculate a value for the
acid dissociation constant, Ka, for this weak acid. Give your answer to 3 significant
figures.
Answer
[H+] = 10−3.24 = 5.75 × 10−4 mol dm−3
[H+ ]2 (5.75 × 10 −4 )2
Ka = = = 1.36 × 10−5 mol dm−3.
[weak acid] 0.0244
The concentration of the weak acid may be determined from the pH and the Ka
using the expression [weak acid] = [H+]2/Ka.

Physical chemistry 2 59
Content Guidance

Worked example 2
The pKa for nitrous acid, HNO2, is 3.25. A solution of nitrous acid has a pH of 2.35.
Calculate the concentration of the solution of nitrous acid. Give your answer to
3 significant figures.
Knowledge check 20
Answer
Calculate the pH
[H+] = 10−2.35 = 4.47 × 10−3 mol dm−3 of a weak acid
of concentration
Ka = 10−pKa = 10−3.25 = 5.62 × 10−4 mol dm−3 0 .0145 mol dm−3,
+ 2 (4.47 × 10−3 )2 where Ka = 1 .44 ×
[weak acid] = [H ] = = 0.0356 mol dm−3 10 −4 mol dm−3 .
Ka 5.62 × 10−4

Dilutions
Diluting a solution of a strong acid or a strong base will change the pH as the
concentration of H+ or OH− ions will change.
The main expression to remember is the one below as this allows the concentration of
the diluted solution to be determined.
moles of solute
concentration of diluted solution (mol dm−3) = × 1000
volume of new solution (cm3 )
Dilutions of strong acids
Worked example
17.2 cm3 of a 1.24 mol dm−3 solution of nitric acid are dilute to 150 cm3. Calculate
the pH of the solution formed. Give your answer to 2 decimal places.
Answer
17.2 × 1.24
Moles of HNO3 added = = 0.0213 mol
1000
New volume = 150 cm3

Concentration of new solution = 0.0213 × 1000 = 0.142 mol dm−3

150 Exam tip
Nitric acid is monoprotic. So [H+] = [HNO3]: If the acid was diprotic
[H+] = 0.142 mol dm−3 like H2 SO4:
[H+] = 2 × [H2 SO4]
pH = −log10[H+] = −log10(0.142) = 0.85

The volume of water added or the total volume of the solution may also be calculated
for a given pH of a diluted solution.

60 AQA Chemistry
 Acids and bases

Worked example
Calculate the volume of water added to 40.0 cm3 of a 0.0278 mol dm−3 solution of
sulfuric acid so that the pH of the resulting solution is 1.88. Give your answer to
3 significant figures.
Answer
Moles of H2SO4 in original solution = 40.0 × 0.0278 = 1.11 × 10−3 mol
1000
Moles of H+ in original solution = 2.22 × 10−3 mol

New [H+] = 10−1.88 = 0.0132 mol dm−3

moles of H+
New [H+] = × 1000
volume of new solution (cm3 )
moles of H+
Volume of new solution = × 1000
new [H+ ]
2.22 × 10−3
Volume of new solution = × 1000 = 168 cm3
0.0132
Volume of water added = 168 – 40.0 = 128 cm3

Dilution of solutions of strong bases

For a solution of a strong base, Kw is required to determine the pH.

Worked example
14.8 cm3 of 0.884 mol dm−3 sodium hydroxide solution were diluted to 200 cm3.
Calculate the pH of the new solution at 25°C. Give your answer to 2 decimal places.
Answer
Kw = 1.00 × 10−14 mol2 dm−6 at 25°C.
14.8 × 0.884
Moles of NaOH = = 0.0131 mol
1000
New [NaOH] = 0.0131 × 1000 = 0.0655 mol dm−3
200
[NaOH] = [OH−] = 0.0655 mol dm−3
Kw 1.00 × 10−14
[H+] = − =
= 1.53 × 10−13 mol dm−3
[OH ] 0.0655
pH = −log10[H+] = −log10(1.53 × 10−13) = 12.82

Neutralisations
Adding acid to base or vice versa will mean some of the acid or base has been
neutralised and this will also change the pH. In this type of question it is important to
be able to calculate the amount, in moles, of the acid or base that is left over.
Physical chemistry 2 61
Content Guidance

Worked example 1
19.2 cm3 of 0.322 mol dm−3 hydrochloric acid were added to 15.0 cm3 of
0.350 mol dm−3 solution of sodium hydroxide. Calculate the pH of the resulting
solution. Give your answer to 2 decimal places.
Answer
NaOH + HCl → NaCl + H2O

NaOH and HCl react in a 1:1 ratio.

15.0 × 0.350
Initial moles of NaOH = = 5.25 × 10−3 mol
1000
19.2 × 0.322
Initial moles of HCl = = 6.18 × 10−3 mol
1000
HCl is in excess. Moles of HCl remaining = 6.18 × 10−3 − 5.25 × 10−3 = 9.30 × 10−4 mol
New total volume of solution = 19.2 + 15.0 = 34.2 cm3
moles of reactant in excess
New concentration of reactant in excess = × 1000
volume of new solution (cm3 )

New concentration of reactant (HCl) in excess = 9.30 × 10 × 1000

−4

34.2
= 0.0272 mol dm−3

HCl is monoprotic. So [H+] = [HCl]:

[H+] = 0.0272 mol dm−3

pH = −log10[H+] = −log10(0.0272) = 1.57

Be careful with 1:2 or 2:1 ratios of acid:base.

Worked example 2
22.5 cm3 of 0.0228 mol dm−3 sulfuric acid is reacted with 27.4 cm3 of
0.0544 mol dm−3 potassium hydroxide solution. Calculate the pH of the solution
formed at 25°C. Give your answer to 2 decimal places. Kw = 1.00 × 10−14 mol2 dm−6
at 25°C.
Answer
27.4 × 0.0544
Initial moles of KOH = = 1.49 × 10−3 mol
1000
Initial moles of H2SO4 = 22.5 × 0.0228 = 5.13 × 10−4 mol
1000
2KOH + H2SO4 → K 2SO4 + 2H2O
➜

62 AQA Chemistry
 Acids and bases

KOH reacts with H2SO4 in a 2:1 ratio.

2 × 5.13 × 10−4 = 1.03 × 10−3 mol

so KOH is in excess.
Moles of KOH in excess = 1.49 × 10−3 − 1.03 × 10−3 = 4.60 × 10−4

Total volume = 22.5 + 27.4 = 49.9 cm3

moles of reactant in excess
New concentration of KOH = × 1000
volume of new solution (cm3 )
4.60 × 10−4
New [KOH] = = 9.22 ×10−3 mol dm−3
49.9
As KOH has one OH−, [OH−] = [KOH] = 9.22 × 10−3:
Kw 1.00 × 10−14
[H+] = − = = 1.08 × 10−12 mol dm−3
[OH ] 9.22 × 10−3
pH = −log10[H+] = −log10(1.08 × 10−12) = 11.97 Knowledge check 21
Calculate the pH of the
solution obtained from
Exam tip
diluting 10 .0 cm3 of a
All values in these calculations were stated to 3 significant figures as that 0 .145 mol dm−3 solution
is the level of accuracy stated throughout . However, even doing all the of sulfuric acid to
calculations on a calculator gives the same pH . 500 .0 cm3 .

pH curves
A pH curve is a graph of pH against volume of alkali or acid added. It is obtained
using a pH meter or probe during a titration.
■■ A typical curve shows the initial pH of the acid or alkali in the conical flask and
the vertical region of the curve occurs at a volume where neutralisation occurs.
■■ The shape of the curve shows the type of titration. The vertical region occurs when
one drop is added from the burette, which neutralises the substance in the conical
flask.
■■ The pH changes rapidly and any indicator chosen for the titration must have a
range of pH, which changes completely in the pH range of this vertical region so
that the full colour change of the indicator is shown.
Four types of sample titration curves are shown in Figure 25 with some notes below
each one as to the starting pH and the shape of the curve including the pH range of
the vertical region.

Physical chemistry 2 63
Content Guidance
pH

13

pH
Titration 13 Titration
11 curve 1 11 curve 2

9 Strong acid- 9 Weak acid-

strong base strong base
7 titration 7 titration
5 5
3 3
1 1
0 0
0 25.0 0 25.0
Volume of base added/cm3 Volume of base added/cm3

■■ Vertical region from pH 3 to pH 10. ■■ Vertical region from pH 6 to pH 10.

■■ Initial pH is 1, so a strong acid in the ■■ Initial pH is 3, so a weak acid in the
conical flask at the start. conical flask at the start.
■■ 25.0 cm3 of the base solution are ■■ 25.0 cm3 of the base solution are
required to neutralise the acid. required to neutralise the acid.
■■ This is the curve for a strong acid– ■■ This is the curve for a weak acid–
strong base titration. strong base titration.
pH

13
pH

Titration 13 Titration
11 curve 3 11 curve 4

9 9
7 7
Strong acid- Weak acid-
5 weak base 5 weak base
titration titration
3 3 Exam tip
1 1 The information on the
0 0
0 25.0 0 25.0 shapes of the curves
Volume of base added/cm3 Volume of base added/cm3 is important, as the
■■ Vertical region from pH 3 to pH 8. ■■ No clear vertical region. shape of the curve
depends on the type
■■ Initial pH is 1, so a strong acid in the ■■ Initial pH is greater than 3, so a weak
(strong or weak) of acid
conical flask at the start. acid in the conical flask at the start.
or base (alkali) used in
■■ 25.0 cm3 of the base solution are ■■ It is not clear what volume of the base
the titration . It would
required to neutralise the acid. solution is required to neutralise the
be very unusual for it
■■ This is the curve for a strong acid– acid.
to be a weak acid–weak
weak base titration. ■■ This is the curve for a weak acid– base (alkali) titration .
weak base titration. The sketch is just that
Figure 25 Titration curves — a rough sketch of the
shape — so follow the
Sketching titration curves (rough) guidelines as
If you are asked to sketch a titration curve you may be given: to where the inflection
point (vertical section)
■■ An initial calculation for the pH of the strong or weak acid — this is the starting
occurs, i .e . between
pH for the curve where the volume of alkali added is equal to 0.00 cm3.
what approximate pH
■■ The names of the acid and base used — this will determine the shape of the
values .
titration curve including the length of the point of inflection.

64 AQA Chemistry
 Acids and bases

■■ The concentrations of the acid and base (alkali) used — the volume at which
the point of inflection occurs can be calculated from the volume of base (alkali)
required to neutralise the acid.

Worked example
In a titration 0.175 mol dm−3 sodium hydroxide solution is added to 25.0 cm³ of
0.123 mol dm−3 hydrochloric acid. Sketch the titration curve you would expect to obtain.
Answer
Initial pH:
HCl is a monobasic acid. So [H+] = 0.123 mol dm−3.
Initial pH = −log10[H+] = −log10(0.123) = 0.91.
Shape:
Strong acid–strong base titration. So curve shaped like curve 1 — equivalence point
with a change between approximately pH 3 and 10.
Volume of base:
25.0 × 0.123
Moles of HCl present = = 3.08 × 10−3 mol
1000
NaOH + HCl → NaCl + H2O

1 mole of NaOH reacts with 1 mole of HCl.

Moles of NaOH = 3.08 × 10−3 mol
3.08 × 10−3 × 1000
Volume of NaOH = = 17.6 cm3
0.175
The titration curve for this neutralisation looks like Figure 26.
14

12

Shape of
Exam tip
10
curve The titration curve
indicates
8
strong may be for a volume
pH

acid- of acid added to a

6 strong volume of alkali . Work
base
4
out the initial pH of
titration
the strong alkali —
Initial pH
2 this is the initial pH;
of 0.91
the volume required
0 for neutralisation is
0 5 10 15 20 25 30
determined in the
Volume of NaOH (cm3) 17.6cm3 of 0.175 mol dm–3
NaOH solution required for same way; the shape of
neutralisation curve is the same but
reversed .
Figure 26

Physical chemistry 2 65
Content Guidance

Indicators for titrations Exam tip

The colour change pH range of the indicator must be completely within the vertical Methyl orange and
region of the titration curve (Table 6). phenolphthalein are
Table 6 Some indicators and their colour change pH ranges the main indicators of
choice . Both may be
Indicator pH range of colour change Suitable for titrations between used for strong acid–
strong acid–strong base
strong base titrations .
Methyl orange 3 .1 – 4 .4 Methyl orange is used
strong acid–weak base
strong acid–strong base for strong acid–weak
Methyl red 4 .4 – 6 .2
strong acid–weak base base (alkali) titrations .
strong acid–strong base Phenolphthalein is
Phenolphthalein 8 .3 – 10 .0
weak acid–strong base used for weak acid–
Table 7 Colours of common indicators strong base (alkali)
titrations .
Colour change when adding Colour when adding alkali to
Indicator
acid to alkali acid
Exam tip
Methyl orange Yellow to red Red to yellow
Phenolphthalein Pink to colourless Colourless to pink A pH meter must be
used for weak acid–
weak base (alkali)
Required practical 9 titrations as there is no
vertical region to the
Investigating pH changes pH curve .
Students should monitor pH using a pH meter or a pH probe in the reaction
between a weak acid and a strong base and between a strong acid and a weak base .
Knowledge check 22
State the colour of
phenolphthalein in a
Buffers solution of pH 12 .00 .
Buffers are solutions that maintain almost constant pH despite dilution or the
addition of small amounts of acid or base.
■■ An acidic buffer is a solution formed from a weak acid and its salt.
■■ A typical acidic buffer would be a solution containing ethanoic acid and the
ethanoate ion.
■■ A basic buffer is a solution of a weak base and its salt.
■■ A typical basic buffer would be a solution containing ammonia and the
ammonium ion.
Dilution of a buffer changes the concentration of the ions to the same degree and this
has little effect on the pH of the buffer.

Action of buffers
Buffers maintain an almost constant pH by being able to remove small quantities of
H+ ions or OH− ions added to them.

66 AQA Chemistry
 Acids and bases

Acidic buffers Exam tip

The anion (A−) and the undissociated weak acid can react with added H+ and OH− If the weak acid and its
ions respectively to maintain an almost constant pH. salt are named, then
Explanation of buffering action use the correct anion
and weak acid . For
Addition of acid: extra H+ added:
example, if the buffer
A− reacts with H+ to form HA (A− + H+ → HA). is made from ethanoic
acid and ethanoate
This removes the added H+.
ions, the equation
Addition of base: extra OH− ions added: should read CH3COO − +
H+ → CH3COOH to show
HA reacts with OH−, forming A− and H2O:
the removal of the
(HA + H2O → A− + H2O) added H+ ions .
This removes the added OH−.
Exam tip
Basic buffers
Again if the weak
The weak base Y and its ion YH+ can react with added H+ and OH− ions respectively acid and its salt are
to maintain an almost constant pH. named, then use the
Addition of acid: extra H+ ions added: correct weak acid and
anion . For example,
Y reacts with H+ to form YH+: if the buffer is made
(Y + H+ → YH+) from hydrocyanic
acid and cyanide ions,
This removes the added H+. the equation should
Addition of base: extra OH− ions added: read HCN + OH− →
CN− + H2O to show the
YH+ reacts with OH− to form Y and H2O:
removal of the added
(YH+ + OH− → Y + H2O) OH− ions .

This removes the added OH−.

Exam tip
Again use the given base . For example, if the basic buffer is made from
ammonia (NH3) and ammonium ions (NH4+), use these in place of Y and
YH+ in the equations above . Amines are weak bases and can also be
used to form a basic buffer, for example, methylamine (CH3NH2) and the
methylammonium ion (CH3NH3 +) .

Preparation of an acidic buffer

There are several ways to prepare an acidic buffer, but all of them produce a solution
containing a weak acid and its anion, for example, ethanoic acid and the ethanoate ion.
Methods include:
■■ adding solid salt of a weak acid to a solution of the weak acid
■■ mixing a solution of a weak acid with a solution of its salt
■■ mixing a strong base solution with an excess of a solution of a weak acid

Physical chemistry 2 67
Content Guidance

Calculating pH of a buffer
To calculate the pH of a buffer you must determine the concentration of the anion
[A−] (this equals the concentration of the salt) and the concentration of the weak acid
[HA] from the information given in the method used to prepare the buffer.
[H+] is calculated from the Ka expression and pH is then calculated in the usual way.

Worked example 1
0.0185 mol of sodium ethanoate were dissolved in 150 cm3 of 0.0242 mol dm−3
ethanoic acid (Ka = 1.74 × 10−5 mol dm−3). Calculate the pH of this buffer solution.
Give your answer to 2 decimal places.
Answer
Concentration of weak acid [CH3COOH] = 0.0242 mol dm−3

Exam tip
Remember to always try to calculate the concentration of the weak acid
and its salt . The calculation always follows a similar pattern once you
have calculated these concentrations . In this example the concentration
of the weak acid is unchanged as solid is added . So there is no dilution of
the weak acid solution .

Exam tip
Concentration of salt [CH3COONa] = 0.0185 × 1000 = 0.123 mol dm−3 The concentration of
150 the anion in mol dm−3 is
Concentration of anion [CH3COO−] = 0.123 mol dm−3 determined by dividing
the number of moles of
[CH3COO− ][H+ ] salt (the solute) by the
Ka = = 1.74 × 10−5 mol dm−3
[CH3COOH] volume of the solution
and multiplying by
[H+] = Ka × [CH3COOH] =
1.74 × 10−5 × 0.0242 = 3.42 × 10−6 mol dm−3
[CH3COO ]−
0.123 1000 to convert to the
number of moles per
pH = −log10[H+] = −log10(3.42 × 10−6) = 5.47
1 dm3 (1000 cm3) .

Exam tip
All methods of determining the pH of a buffer end in the same way —
using the concentration of the acid [HA] and the concentration of the anion
[A−] to determine [H+] from Ka . pH is calculated from [H+] .

68 AQA Chemistry
 Acids and bases

Worked example 2
14.2 cm3 of a 0.224 mol dm−3 solution of the salt of a weak acid, NaX, is added to
50.0 cm3 of a 0.482 mol dm−3 solution of the weak acid, HX. The pKa for HX is 4.23.
Calculate the pH of the buffer formed. Give your answer to 2 decimal places.
Answer
14.2 × 0.224 Exam tip
Moles of NaX added = = 3.18 × 10−3 mol
1000
3.18 × 10−3 The pKa is converted
[NaX] = [X−] = × 1000 = 0.0495 mol dm−3 into a Ka using Ka = 10(−pKa) .
64.2
50.0 × 0.482 The new concentrations
Moles of HX added = = 0.0241 mol in mol dm−3 are
1000
determined using the
[HX] = 0.0241 × 1000 = 0.375 mol dm−3
64.2 number of moles of
solute in the new total
Ka = 10−pKa = 10−4.23 = 5.89 × 10−5 mol dm−3
volume of 64 .2 cm3
− +
Ka = [X ][H ] = 5.89 × 10−5 mol dm−3 (50 .0 + 14 .2) converted
[HX] to 1 dm3 (1000 cm3) .
Ka × [HX] 5.89 × 10−5 × 0.375
[H+] = = = 4.47 × 10−4 mol dm−3
[X − ] 0.0495
pH = −log10[H+] = −log10(4.47 × 10−4) = 3.35

Worked example 3
45.0 cm3 of 0.0500 mol dm−3 methanoic acid were mixed with 55.0 cm3 of
0.0270 mol dm−3 sodium hydroxide solution. The Ka for methanoic acid is 1.60 ×
10−4 mol dm−3. Calculate the pH of the resulting buffer solution. Give your answer
to 2 decimal places.
Answer Exam tip
Moles of methanoic acid added (HCOOH) = 45.0 × 0.0500 = 2.25 × 10−3 mol Again both solutions
1000
dilute each other and
Moles of sodium hydroxide added (NaOH) = 55.0 × 0.0270 = 1.49 × 10−3 mol
the sodium hydroxide
1000
reacts with some of
The equation for the reaction between methanoic acid and sodium hydroxide the methanoic acid to
solution is: form the salt, sodium
HCOOH + NaOH → HCOONa + H2O methanoate (HCOONa) .
The new total volume in
Moles of HCOOH after reaction = 2.25 × 10−3 − 1.49 × 10−3 = 7.60 × 10−4 mol this example is 100 cm3
and this will be used
Moles of HCOONa after reaction = 1.49 × 10−3 mol to calculate the new
concentrations of the
7.60 × 10−3
[HCOOH] = × 1000 = 0.0760 mol dm−3 weak acid and its salt .
100
➜

Physical chemistry 2 69
Content Guidance

Exam tip
1.49 × 10−3
[HCOONa] = [HCOO−] = × 1000 = 0.0149 mol dm−3 All of the sodium
100
hydroxide has been
[HCOO− ][H+ ]
Ka = = 1.60 × 10−4 mol dm−3 used up, leaving only
[HCOOH]
some moles of the
Ka × [HCOOH] 1.60 × 10−4 × 0.0760 weak acid (HCOOH) and
[H+] = = = 8.16 × 10−4 mol dm−3
[HCOO− ] 0.0149 some moles of the salt
pH = −log10[H+] = −log10(8.16 × 10−4) = 3.09 (HCOONa) in solution .
The water formed is in
the solution .
Henderson–Hasselbalch equation
The Henderson–Hasselbalch equation may also be used to calculate the pH of a Exam tip
buffer. pH = pKa + log10([A−]/[HA]), where [A−] is the concentration of the anion and
[HA] is the concentration of the acid. In some cases the
concentration of the
The example above is calculated as: weak acid and its salt
pKa = −log10Ka = −log10(1.60 × 10−4) = 3.80 may be the same . In
this case [H+] = Ka .
[A−] = [HCOO−] = 0.0149 mol dm−3
[HA] = [HCOOH] = 0.0760 mol dm−3
Knowledge check 23
pH = 3.80 + log10 ( 0.0149
0.0760)= 3.80 – 0.71 = 3.09
What is a buffer?

Addition of acid or alkali to a buffer

A buffer maintains an approximately constant pH when small amounts of acid or base
are added to it. The new pH of the buffer may be calculated by calculating the change
in the concentration of the anion and the weak acid.
When acid is added to an acidic buffer, the anion reacts with the H+ ions that have
been added to remove them:
A− + H+ → HA
This means that the amount of A− decreases by the same amount as the moles of H+
added and the amount of HA increases by the same amount. These new amounts can
be used to recalculate the pH of the buffer.

Worked example
a A buffer was prepared by mixing 0.0258 moles of ethanoic acid with 0.0370 moles
of sodium ethanoate in 200 cm3. Ka for ethanoic acid is 1.74 × 10−5 mol dm−3.
Calculate the pH of the buffer. Give your answer to 2 decimal places.
b 0.00172 moles of hydrochloric acid were added to the buffer in a. Calculate the
new pH of the buffer. Give your answer to 2 decimal places.
➜

70 AQA Chemistry
 Acids and bases

Answer
a [CH3COOH] = 0.0258 × 1000 = 0.129 mol dm−3
200
−
[CH3COO ] = 0.0370 × 1000 = 0.185 mol dm−3
200
[CHCOO− ][H+ ]
Ka = = 1.74 × 10−5 mol dm−3
[CHCOOH]
Ka × [CHCOOH] 1.74 × 10−5 × 0.129
[H+] = = = 1.21 × 10−5 mol dm−3
[CHCOO− ] 0.185
pH = −log10[H+] = −log10(1.21 × 10−5) = 4.92
b HCl is monoprotic, so 0.00172 mol of H+ added. Exam tip
CH3COO− decreases by 0.00172, so new CH3COO− = 0.0370 − 0.00172 = The calculation is
0.0353 mol virtually the same for
CH3COOH increases by 0.00172, so new CH3COOH = 0.0258 + 0.00172 = the addition of alkali
0.0275 mol except the equation HA
+ OH− → A− + H2O is
[CH3COOH] = 0.0275 × 1000 = 0.138 mol dm−3 used . The amount of HA
200
0.0353 decreases by the same
[CH3COO−] = × 1000 = 0.177 mol dm−3 amount as the amount
200
K × [CHCOOH] 1.74 × 10−5 × 0.138 of OH− ions added
[H+] = a = = 1.36 × 10−5 mol dm−3 and the amount of A−
[CHCOO− ] 0.177
increases by the same
pH = −log10[H+] = −log10(1.36 × 10−5) = 4.87 amount . The rest of the
calculation is identical .
So the pH only changes from 4.92 to 4.87 on the addition of the hydrochloric acid.

Summary
■■ An acid is a proton donor; a base is a proton ■■ The indicator in a titration depends on the pH
acceptor; a proton is a hydrogen ion (H+) . range of the vertical region in the pH curve .
■■ pH = −log10[H+], where [H+] represents the ■■ A buffer is a solution which maintains almost
concentration of H+ in mol dm−3 . constant pH when small amounts of acid or alkali
■■ The pH of a strong acid can be calculated from are added .
[H+] = concentration of the acid × proticity of the ■■ An acidic buffer is a solution containing a weak
acid . Then pH = −log10[H+] . acid and its salt; a basic buffer is a solution
■■ Kw = [H+][OH−] = 1 .00 ×10 −14 mol−2 dm6 at 25°C . containing a weak base and its salt .
■■ The pH of strong bases is calculated using ■■ The pH of an acidic buffer is calculated by
Kw . H+ = Kw/[OH−], where [OH−] is equal to the determining the concentration of the weak acid
concentration of the base × number of moles of and its anion in the solution and using the Ka
OH− produced by 1 mole of the base in solution . expression to calculate [H+] .
■■ For a weak acid [H+] = K a × [weak acid] .

Physical chemistry 2 71
Questions & Answers
This section contains a mix of multiple-choice and structured questions similar to
those you can expect to find in the A-level papers.

The examinations
The A-level examination consists of three examinations of 2 hours each. Papers 1 and
2 comprise short and long structured questions with a total mark of 105 each. Paper 3
covers the entire specification and contains practical and data analysis questions as
well as multiple-choice questions worth 30 marks. For each multiple-choice question
there is one correct answer and at least one clear distractor.
A-level paper 1 contains topics of physical chemistry (except 3.1.5 and 3.1.9) and
includes inorganic chemistry (3.2). A-level paper 2 covers organic chemistry (3.3) and
all the physical chemistry except 3.1.1, 3.1.7 and 3.1.8). A-level paper 3 covers the
entire specification. The questions in this section are on physical chemistry sections
3.8 to 3.12 but also draw on sections 3.1 to 3.7 covered in the first student guide of
this series.

About this section

Answers to questions are followed by comments, preceded by the icon e . Try the
questions first to see how you get on and then check the answers and comments.

General tips
■■ Be accurate with your learning at this level — examiners will penalise incorrect
wording.
■■ At least 20% of the marks in assessments for chemistry will require the use of
mathematical skills. For any calculation, always follow it through to the end even if
you feel you have made a mistake — there are marks for the correct method even if
the final answer is incorrect.
■■ Always attempt to answer a multiple-choice question even if it is a guess (you have
a 25% chance of getting it right).
The uniform mark you receive for each of paper 1 and paper 2 will be out of 105. The
uniform mark for paper 3 is out of 90. The total marks for A-level Chemistry are 300.

72 AQA Chemistry
 Thermodynamics

■ Thermodynamics
Question 1
Which one of the following is exothermic?
A Enthalpy of atomisation
B First electron affinity
C First ionisation enthalpy
D Enthalpy of lattice dissociation (1 mark)

The answer is B ✓

e This type of question tests your knowledge of Born–Haber cycles and the
associated enthalpy changes . Remember that the only enthalpy changes that are
exothermic in a normal cycle are generally the enthalpy change of formation and
the first electron affinity . Some enthalpy changes of formation are endothermic
but this is unusual for ionic compounds as most are exothermic .

Question 2
Which one of the following reactions will show a decrease in entropy?
A CaCO3(s) → CaO(s) + CO2(g)
B CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
C NH3(g) + HCl(g) → NH4Cl(s)
D 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) (1 mark)

The answer is C ✓

e Remember that entropy is a measure of disorder, so solids have lower

enthalpy than liquids (and solutions), which have lower entropy than gases . Any
reaction such as those in A and B that produce a gas from solids and solutions
show an increase in entropy . Totally gaseous mixtures where the number of
moles of gas increases also show an increase in entropy . Two gases mixing to
form a solid as in C show a decrease in entropy . Remember that an increase in a
single state — for example moles of a substance in solution increasing — causes
an increase in entropy .

Physical chemistry 2 73
Questions & Answers

Question 3
Some enthalpy changes are given in Table 1.
Table 1
Equation ΔH⦵ (kJ mol−1)
Cd(s) → Cd(g) +113
Cd(g) → Cd+(g) + e − +870
Cd+(g) → Cd2+(g) + e − +1600
Cl 2(g) → 2Cl(g) +242
Cl(g) + e − → Cl− (g) −348
Cd(s) + Cl 2(g) → CdCl 2(s) −392

(a) Use the data in Table 1 to calculate a value for the lattice dissociation
enthalpy for cadmium chloride. (3 marks)

Δ LH = +392 + 113 + 870 + 1600 + 242 + 2(−348) ✓✓

= + 2521 kJ mol−1 ✓

e The most common error with this type of 2+ metal ion halide is to forget
to multiply the electron affinity of chlorine by 2 . This would give an answer of
+2869 kJ mol−1, which would be worth 2 marks instead of 3 .

(b) Table 2 gives the experimental and theoretical lattice enthalpies for cadmium
bromide and potassium bromide. The theoretical values are calculated using
the perfect ionic model.
Table 2

Cadmium bromide Potassium bromide

Δ LH (theoretical) +2481 +679
Δ LH (experimental) +2725 +678

(i) Explain what is meant by the perfect ionic model. (1 mark)

Ions are point charges/ions are perfect spheres/only electrostatic interactions

between the ions/only ionic bonding with no covalent bonding/no polarisation of
ions ✓

e Any of the above points can be used to explain the use of the perfect ionic
model to calculate the theoretical value for the lattice enthalpy . This assumes
that the ions are simply a perfect sphere with a point charge, so there are only
ionic attractions between them . Polarisation of the ions can lead to some covalent
character in the compound .

74 AQA Chemistry
 Thermodynamics

(ii) Using the values in Table 2, comment on the bonding in each of the
compounds. (4 marks)

The bonding in potassium bromide is ionic . ✓

There is some covalent character to cadmium bromide . ✓
The values are close together for potassium bromide . ✓
The higher experimental value for cadmium bromide indicates some covalent
bonding . ✓

e A common question is to compare the experimental lattice enthalpy with the

theoretical one . The experimental lattice enthalpy is determined using the values
in a Born–Haber cycle . An experimental value that is higher than the theoretical
value suggests some additional bonding in the compound, which would suggest
some covalent character . If the theoretical value is similar to the experimental
value, then the compound is completely ionic .

Question 4
Silver(i) nitrate, AgNO3, decomposes on heating according to the equation
2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g)
The standard enthalpies of formation and standard entropy values of the
reactants and products in this reaction are given in Table 3.
Table 3
Substance ΔfH⦵ (kJ mol−1) S⦵ (J K−1 mol−1)
AgNO3(s) −123 141
Ag(s) 0 43
NO2(g) +33 To be calculated
O2(g) 0 205

(a) Calculate the standard enthalpy change of reaction. (2 marks)

(b) Explain why the standard enthalpies of formation of Ag(s) and O2(g) are zero. (1 mark)

(c) Calculate the standard entropy of NO2(g) if the ΔS⦵ for the reaction is
+489 J K-1 mol-1. (2 marks)

(d) Determine the temperature, in kelvin, at which this decomposition becomes

feasible. (3 marks)

e This is a common type of synoptic question from AS and you need to revise this
from the energetics section . The calculation in (a) can be done using Hess’s law .

Physical chemistry 2 75
Questions & Answers

(a) Using enthalpies of formation the enthalpy change for the reaction ΔH is
calculated using:

ΔH = ΣΔfH⦵products – ΣΔfH⦵reactants

ΔH = 2(+33) − 2(–123) ✓ = +312 kJ mol−1 ✓

(b) Ag(s) and O2(g) are elements in their standard states . ✓

(c) ΔS⦵ = ΣS⦵products – ΣS⦵reactants

+489 = 2(43) + 2(x) + 205 − 2(141) ✓

2x = 480 ⇐ x = 240 ✓

(d) For the reaction to be feasible ΔG⦵ ≤ 0, so using ΔG⦵ = 0:

ΔG⦵ = ΔH⦵ –TΔS⦵

ΔH⦵ = TΔS⦵
Δ H⦵ 312
T= ✓ ✓ = 638 K ✓
Δ S⦵ 0.489

e In (d), remember to change the standard entropy change from J K−1 mol−1 to
kJ K−1 mol−1 by dividing by 1000 because all the other units in the expression are in
kJ mol−1 .

Question 5
The vaporisation of methanol is represented by the equation:
CH3OH(l)  CH3OH(g) ΔH⦵ = +35.3 kJ mol−1
The standard entropy of CH3OH(l) is 127 J K−1 mol−1. Given that the reaction
becomes feasible at 338 K, calculate the standard entropy of CH3OH(g). (6 marks)

ΔG⦵ = 0, so ΔH⦵ = TΔS⦵ ✓

+35 .3 = 338 × ΔS⦵ ✓

35.3
ΔS⦵ = = +0 .104 kJ K−1 mol−1 ✓
338
ΔS⦵ = +104 J K−1 mol−1 ✓

ΔS⦵ = S⦵products − S⦵reactants

+104 = S⦵products − 127 ✓

Entropy of CH3OH(g) = 104 + 127 = 231 J K−1 mol−1 ✓

e For a system in equilibrium, ΔG = 0 . A change of state is considered a system

in equilibrium .

76 AQA Chemistry
 Thermodynamics

Question 6
A graph of ΔG⦵ against T is shown in Figure 1.
700

/kJ mol –1 600

500
∆

400

300

200

100
340
0
300 600 900 1200
–100 T/K
–280
–200

–300

–400

Figure 1

(a) From the graph state the value of ΔH⦵ for this reaction. State the units. (1 mark)

ΔH⦵ = –280 kJ mol−1 ✓

e The value of ΔH⦵ is equal to the value of ΔG⦵ where the line hits the axis .

(b) From the graph calculate the value for ΔS⦵ for this reaction. State the units. (3 marks)

280
gradient = –ΔH⦵ = = 0 .824 kJ K−1 mol−1 ✓
340
ΔS⦵ = –824 ✓ J K−1 mol−1 ✓

e From the graph the gradient is −ΔS⦵ . The gradient of this graph is positive and
the value is in kJ K−1 mol−1 . The sign must be changed to calculate ΔS⦵ and also
multiplied by 1000 to convert to J K−1 mol−1 .

(c) From the graph state the temperature below which the reaction is feasible. (1 mark)

T = 340 K ✓

e The point on the T axis where the line crosses is the temperature where a
reaction changes from being feasible to not feasible — in this example as ΔG⦵
becomes positive .

Physical chemistry 2 77
Questions & Answers

■ Rate equations
Question 1
The rate equation for the reaction A + 2B  3C + D
rate = k[A]2
What are the units of the rate constant k?
A s−1 C mol−1 dm3 s−1
B mol dm−3 s−1 D mol−2 dm6 s−1 (1 mark)

The answer is C ✓

e The units of rate are mol dm−3 s−1 . This is the reason for answer B . The overall
order of reaction (total of the orders) is 2 . Dividing mol dm−3 s−1 by (mol dm−3)2
gives mol(1 − 2) dm(−3 − (−6)) s−1 = mol−1 dm3 s−1 . A would be the answer where the
overall order of reaction is 1 and D where the overall order of reaction is 3 .

Question 2
A graph of ln k against 1/T gave a gradient of −7142.9 and the graph intercepted
the ln k axis at 20. The gas constant, R = 8.31 J K−1 mol−1.
What is the activation energy for the reaction in kJ mol−1 to 3 significant figures?
A 0.166 C 59400
B 59.4 D 4.85 × 108 (1 mark)

The answer is B ✓

e The Arrhenius equation may be plotted graphically as ln k = Ea/RT + ln A . The

vertical axis is ln k and the horizontal axis is 1/T . The gradient of the line is −Ea /R
and the intercept with the ln k axis is ln A . So the activation energy is determined
from the gradient . −Ea /R = −7142 .9 . Ea = 7142 .9 × R = 7142 .9 × 8 .31 = 59 357 .5 J mol−1 .
It is important to remember that this value is J mol−1 and so dividing by 1000
gives 59 .4 kJ mol−1 . Answer A would be obtained by confusing the intercept and
the gradient and simply multiplying by R and dividing by 1000 . Answer C has
no dividing by 1000 step and answer D is e20 which is the method of calculating
A from ln A from the intercept . Distractors will always be seemingly sensible
processing of the numbers, so take care .

78 AQA Chemistry
 Rate equations

Question 3
A reacts with B to form C. A + 2B → C. The data in Table 4 are from some
experiments into the rate of reaction.
Table 4
Initial [A] Initial [B] Initial rate
Experiment
(mol dm−3) (mol dm−3) (× 10 −4 mol dm−3 s−1)
1 0 .127 0 .240 1 .99
2 0 .127 0 .480 7 .99
3 0 .254 0 .240 4 .00

(a) Determine the order of reaction with respect to A and B. (2 marks)

(b) Write a rate equation for the reaction. (1 mark)

(c) Using experiment 3, calculate the value of the rate constant and state its units.
Give your answer to 3 significant figures. (3 marks)

(a) Order of reaction with respect to A = 1 ✓

Order of reaction with respect to B = 2 ✓

e As concentration of A doubles (experiment 1 to experiment 3) the rate doubles .

So order of reaction with respect to A is 1 . As the concentration of B doubles
(experiment 1 to experiment 2) the rate quadruples (×4) . So the order of reaction
with respect to B is 2 .

(b) rate = k[A][B]2 ✓

e The rate equation simply gives the relationship between the concentrations of
the reactants and the rate . Don’t forget to include the rate constant, k . This should
be a lower case k, not to be confused with an equilibrium constant, capital K .

4.00 × 10−4
(c) 4 .00 × 10 –4 = k(0 .254)(0 .240)2k = ✓ = 0 .0274 ✓ mol−2 dm6 s−1 ✓
0.0146

e Any experiment may be used to calculate a value for the rate constant, but if
one is suggested, use it . Also make sure you take into account the orders when
using the concentrations in the rate equation . The units are based on the overall
order . Rate always has units of mol dm−3 s−1, so dividing these units by mol 3 dm−9
gives mol−2 dm6 s−1 . 0 .0273 is obtained if the entire calculation is carried out on
your calculator . This would also be accepted . Show all steps clearly .

Physical chemistry 2 79
Questions & Answers

Question 4
The reaction between P and Q is shown by the equation:
2P + Q → R + 3S
The rate equation is determined to be rate = k[P]2
Table 5 gives data from a series of experiments into the rate of this reaction.
Table 5
[P] [Q] Rate of reaction
Experiment
(mol dm−3) (mol dm−3) (mol dm−3 s−1)
1 1 .54 × 10 −3 2 .10 × 10 −3 1 .44 × 10 −4
2 2 .31 × 10 −3 3 .15 × 10 −3 to be calculated
3 to be calculated 5 .25 × 10 −3 9 .00 × 10 −4

(a) Calculate the rate of reaction in experiment 2. (1 mark)

From experiment 1 to experiment 2: [P] increases by a factor of 1 .5 and [Q]

increases by a factor of 1 .5
Rate = k[P]2, so change in [Q] has no effect .
As [P] increases ×1 .5, rate increases ×1 .52 = rate ×2 .25 .
So new rate is 1 .44 × 10 −4 × 2 .25 = 3 .24 × 10 −4 ✓

e It is important to be able to manipulate these powers . When a concentration

is multiplied by a factor — call it factor p in this case — for the ×1 .5 increase in [P],
the rate increases by that factor raised to the order of the reactant . As P has order 2,
(1 .5)2 = 2 .25, so the rate increases by a factor of 2 .25 . It is important to note that
as Q is zero order, any change in Q has no effect on the rate of reaction .

(b) Calculate the concentration of P in experiment 3. (1 mark)

From experiment 1 to experiment 3 the rate increases by a factor of 6 .25

(9 .00 × 10 −4 /1 .44 × 10 −4) .
[P] increases by the factor which is the square root of this, which is 6.25 = 2 .5 .
So [P] from experiment 1 to 3 should be ×2 .5 .
1 .54 × 10 −3 × 2 .5 = 3 .85 × 10 −3 ✓

e Again [Q] has no effect on the rate of this reaction .

(c) Use experiment 1 to calculate a value for the rate constant and state its
units. Give your answer to 3 significant figures. (3 marks)

1 .44 × 10 −4 = k(1 .54 × 10 −3)2

1.44 × 10−4
k= ✓ = 60 .7 ✓ mol−1 dm3 s−1 ✓
(1.54 × 10−3 )2

80 AQA Chemistry
 Equilibrium constant Kp for homogeneous systems

(d) Use the Arrhenius equation to calculate a value for the Arrhenius constant A
given that the activation energy for the reaction is +84.6 kJ mol−1 at 300 K and
the gas constant R = 8.31 J K−1 mol−1. Give your answer to 3 significant figures. (2 marks)

Ea
−
k = Ae RT

84600
− ✓
60.7 = Ae 8.31 × 300
60 .7 = A(1 .83 × 10 −15)
60.7
A= = 3 .32 × 1016 ✓
1.83 × 10−15

e Again remember to convert Ea to J mol−1 for use in the expression . The clue is
that R is given in J K−1 mol−1, so this leaves the power unitless if Ea is in J mol−1 . Use
A to check the calculation back to ensure you obtain a value of around 60 .7 for k .

■ Equilibrium constant Kp for

homogeneous systems
Question 1
A gaseous mixture at equilibrium contains 0.250 moles of hydrogen and
0.175 moles of nitrogen and 0.345 moles of ammonia. The total pressure is 110 kPa.
N2(g) + 3H2(g)  2NH3(g)
What is the partial pressure of ammonia in this mixture?
A 25.0 kPa
B 35.7 kPa
C 49.3 kPa
D 89.6 kPa (1 mark)

The answer is C ✓

e Mole fractions are determined by dividing the moles at equilibrium by the

total equilibrium moles (0 .250 + 0 .175 + 0 .345 = 0 .770) . The partial pressure is
calculated by multiplying the mole fraction by the total pressure (110 kPa) . A is
the partial pressure of nitrogen, B is the partial pressure of hydrogen and D is the
answer which would be obtained if the 2 in the equation for ammonia were to be
used incorrectly . When amounts, in moles, at equilibrium are given, there is no
need to consider the balancing numbers in the equation .

Physical chemistry 2 81
Questions & Answers

Question 2
For the reaction:
N2O4(g)  2NO2(g)
1.00 moles of N2O4 are allowed to reach equilibrium at 500 K. At equilibrium
0.240 moles of N2O4 remain. The total pressure is 200 kPa.
(a) Calculate the mole fractions of N2O4 and NO2 at equilibrium. Give your
answer to 3 significant figures. (4 marks)

Moles of N2O4 at equilibrium = 0 .240 mol

Moles of NO2 at equilibrium = 1 .52 mol ✓

Total equilibrium moles = 0 .24 + 1 .52 = 1 .76 mol ✓

Mole fraction of N2O4 = 0 .240/1 .76 = 0 .136 ✓

Mole fraction of NO2 = 1 .52/1 .76 = 0 .864 ✓

e The moles at equilibrium are calculated using the initial 0 .240 moles of N2O4 .
The amount, in moles, of NO2 present at equilibrium is 2 × 0 .760 = 1 .52 mol based
on the balancing numbers in the equation for the reaction . The total equilibrium
moles is 0 .240 + 1 .52 = 1 .76 moles . Mole fractions are calculated by dividing the
moles by the total equilibrium moles .

(b) Calculate the partial pressures of N2O4 and NO2 at equilibrium. Give your
answer to 3 significant figures. (2 marks)

Partial pressure of N2O4 = 0 .136 × 200 = 27 .2 kPa ✓

Partial pressure of NO2 = 0 .864 × 200 = 173 kPa ✓

e The partial pressures are calculated by multiplying the moles fractions by the
total pressure .

(c) Calculate a value for Kp at 500 K. State its units. Give your answer to
3 significant figures. (3 marks)

(pNO2 )2 (173)2
Kp = ✓= = 1100 ✓ kPa ✓
(pN2O4 ) (27.2)

e The calculation of the Kp is from partial pressures . If Kp has no units, then

equilibrium moles or mole fractions may be used to calculate Kp .

82 AQA Chemistry
 Equilibrium constant Kp for homogeneous systems

Question 3
Hydrogen iodide decomposes into hydrogen and iodine according to the equilibrium:
2HI(g) H2(g) + I2(g)
0.0248 moles of hydrogen iodide were placed in a sealed container at 350 K.
Calculate a value for Kp at 350 K if 0.0220 moles of hydrogen iodide are present in
the equilibrium mixture. Give your answer to 3 significant figures. (4 marks)

Moles of HI which react = 2 .80 × 10 −3 mol ✓

Moles of H2 and I2 formed = 1 .40 × 10 −3 mol ✓

(pH2 )(pI2 ) (1.40 × 10−3 )2
Kp = = ✓■= 4 .05 × 10 −3 ✓
(p HI)2 (0.0220)2
or, using mole fractions:

Total equilibrium moles = 0 .0220 + 1 .40 × 10 −3 + 1 .40 × 10 −3 = 0 .0248 mol

0.0220
Mole fraction of HI = = 0 .887 ✓
0.0248
1.4 × 10−3
Mole fraction of H2 = mole fraction of I2 = = 0 .0565 ✓
0.0248
(pH2 )(pI2 ) (0.0565) 2
Kp = = ✓■= 4 .06 × 10 −3 ✓
(pHI)2 (0.887)2

e As Kp has no units, either equilibrium moles or mole fractions may be used to

calculate the value of Kp . Note that if the question requires you to calculate mole
fractions, you should do this . Also some texts will show P as the total pressure
multiplied by the mole fractions to calculate the partial pressures, but the P will
cancel out in the Kp expression . The slight difference in the answers is due to
rounding in the mole fractions .

Question 4
Sulfur dioxide reacts with oxygen to form sulfur trioxide according to the equation:
2SO2(g) + O2(g)  2SO3(g)
0.115 moles of sulfur dioxide were mixed with 0.210 moles of oxygen in a
container at 700 K. At equilibrium 68% of the sulfur dioxide had reacted. Kp for
the reaction at 700 K is 0.0651 kPa−1. Calculate the total pressure in this reaction
and state its units. Give your answer to 3 significant figures. (5 marks)

Physical chemistry 2 83
Questions & Answers

2SO2 + O2  2SO 3

Initial moles 0 .115 0 .210 0

Reacting moles −0 .0782 −0 .0391 +0 .0782
(68% of 0 .115)
Equilibrium moles 0 .0368 0 .171 0 .0782
Mole fraction 0.0368 0.171 0.0782
= 0 .129 = 0 .598 = 0 .273
0.286 0.286 0.286
Partial pressure 0 .129P ✓ 0 .598P ✓ 0 .273P ✓

Total equilibrium moles = 0 .286

(pSO3 )2 (0.273P )2
Kp = = ✓
(pSO2 ) (pO2 ) (0.129P )2 (0.598P )
2

0.0745P 2
=
9.95 × 10−3 P 3
0.0745
So = 0 .0651 kPa−1
9.95 × 10−3 P
0.0745
P= = 115 kPa ✓
9.95 × 10−3 × 0.0651

e This is a complex calculation which takes time . If you have time, you can put
the 115 kPa answer back into the calculation to make sure you get the same value
for Kp .

■ Electrode potentials and

electrochemical cells
Question 1
Using the standard electrode potentials below, choose the oxidising agent
capable of oxidising vanadium from the +2 to the +4 oxidation state but not to the
+5 oxidation state.
E⦵/V
− −
Cl2(aq) + 2e  Cl (aq) +1.36
I2(aq) + 2e −  2I−(aq) +0.54
SO42−(aq) + 2H+(aq) + 2e −  2H2O(l) + SO2(g) +0.17
VO2+(aq) + 2H+(aq) + e −  V3+(aq) + H2O(l) +0.32
+ + − 2+
VO2 (aq) + 2H (aq) + e  VO (aq) + H2O(l) +1.00
V3+(aq) + e −  V2+(aq) −0.26
Sn2+(aq) + 2e −  Sn(s) −0.15
A chlorine C iodine
B Sn2+ ions D sulfate ions (1 mark)

84 AQA Chemistry
 Electrode potentials and electrochemical cells

The answer is C ✓

e It is important to be able to recognise vanadium in its various oxidation states:

VO2+ represents vanadium in the +5 oxidation state; VO2+ represent vanadium in
its +4 oxidation state; V 3+ and V2+ speak for themselves in the +3 and +2 oxidation
states respectively . The electrode potentials are all stated as reduction reactions .
The strongest oxidising agent will be found on the left-hand side of these half-
equations . Iodine reduces to iodide with a potential of +0 .54 V .

Oxidation state Oxidation Cl2 → 2Cl− Sn2+ → Sn I2 → 2I− SO42− → SO2

change of V potential (V) (+1.36) (−0.15) (+0.54) (+0.17)
1 +2 → +3 +0 .26 ✓ ✓ ✓ ✓
2 +3 → +4 −0 .32 ✓ ✗ ✓ ✗
3 +4 → +5 −1 .00 ✓ ✗ ✗ ✗

A ✓ in the table shows a positive emf, a ✗ shows a negative emf . The only
reduction reaction that will make the emf for the first and second reactions
positive is I2 → 2I− (+0 .54 V) . Chlorine would oxidise vanadium from +2 to +5 . Sn2+
and sulfate ions would oxidise vanadium from +2 to +3 but no further .

Question 2
Figure 2 shows an electrochemical cell.

Co(s) Platinum

Platinum

Solution containing Solution containing

1.00 mol dm–3 1.00 mol dm–3 Fe2+ ions and
CO2+ ions 1.00 mol dm–3 Fe3+ ions

Figure 2

The half-equations and electrode potentials are:

Co2+(aq) + 2e − → Co(s) −0.28 V
Fe3+(aq) + e − → Fe2+(aq) to be determined
(a) Write the conventional cell representation for this cell. (2 marks)

Co | Co2+ || Fe3+, Fe 2+ | Pt ✓✓

Physical chemistry 2 85
Questions & Answers

e The conventional cell representation is sometimes called cell notation and

has the oxidation on the left and the reduction on the right . The || in the middle
represents the salt bridge . Any substances in different phases (states) are
separated by a phase boundary line (|) . Substance such as Fe3+ and Fe2+ are in the
same state and so are separated by a comma . Pt is included as the electrode in
the iron half cell at the right, again separated by a phase boundary line as it is a
solid and the other ions are in solution .

(b) Write an overall equation for the reaction occurring. (2 marks)

Co2+ + 2Fe3+ → Co + 2Fe2+ ✓✓

e Combining the oxidation and reduction half-equations requires the balancing

of the electrons . So first reverse the cobalt half-equation to make it the oxidation
and multiply the reduction iron half-equation by 2 . Then simply add them together
and cancel out the 2e − on each side .

(c) The emf of the cell is 1.05 V. Calculate the standard electrode potential for
the half-equation Fe3+(aq) + e − → Fe2+(aq) (2 marks)

1 .05 = x – (–0 .28) ✓

x = 1 .05 – 0 .28 = +0 .77 V ✓

e The skill here is remembering that the emf is determined by adding together
the reduction and oxidation potentials . One of the potentials has its sign changed .
In this example the cobalt is oxidised, so the iron potential we are calculating is
the reduction one . This can also be achieved by using emf = Erhs − Elhs as the − Elhs
changes the sign of the oxidation reaction for you . This is the method used in the
answer .

(d) What direction do the electrons flow in the cell? (1 mark)

From left to right/cobalt electrode to iron electrode ✓

e Electrons are released when the cobalt is oxidised . These electrons flow
around the circuit to the iron half cell and the Fe3+ is reduced to Fe2+ . So the
electrons always flow from the oxidation half cell to the reduction half cell .

(e) What change, if any, would be observed in the mass of the cobalt? (1 mark)

Decrease ✓

e As cobalt is oxidised the reaction which occurs in the left-hand cell is

Co → Co2+ + 2e − . The cobalt will go into solution and so the mass of the cobalt
will decrease .

86 AQA Chemistry
 Electrode potentials and electrochemical cells

(f) Identify the negative electrode. (1 mark)

Cobalt electrode ✓

e NEGATOX is used to identify the negative electrode . The negative electrode is

where an oxidation reaction occurs . The oxidation occurs at the cobalt electrode .

Question 3
Use the standard electrode potentials given in Table 6 for this question.
Table 6
Half reaction E/V
F2(g) + 2e − → 2F− (aq) +2 .87
Cl 2(g) + 2e − → 2Cl(aq) +1 .36
Br2(l) + 2e − → 2Br– (aq) +1 .07
Fe3+(aq) + e − → Fe2+(aq) +0 .77
I2(s) + 2e − → 2I− (aq) +0 .54
Cu2+(aq) + 2e − → Cu(s) +0 .34
Sn4+(aq) + 2e − → Sn2+(aq) +0 .14
2H+(aq) + 2e − → H2(g) 0 .00
Pb2+(aq) + 2e − → Pb(s) −0 .13
Fe2+(aq) + 2e − → Fe(s) −0 .44
Zn2+(aq) + 2e − → Zn(s) −0 .76

(a) Explain why a reaction occurs between chlorine and iron(ii) ions in solution
but not between iodine and iron(ii) ions. (2 marks)

E⦵ (Cl 2 /Cl−) > E⦵ (Fe3+/Fe2+) or emf is +0 .59 V ✓

E⦵ (I2 /I−) < E⦵ (Fe3+/Fe2+) or emf is −0 .23 V ✓

e Calculation of the emf for the reaction between Cl 2 and Fe2+ ions gives a
positive value or you can state that the reduction of Cl 2 has a greater electrode
potential than the reduction of Fe3+ to Fe2+, so Cl 2 will oxidise Fe2+ to Fe3+ .
However, a negative emf is calculated for the reaction of I2 with Fe2+, or the
potential for the reduction of Fe3+ to Fe2+ is greater than the potential for the
reduction of I2 to I− .

(b) Identify the strongest oxidising agent from Table 6. (1 mark)

F2 /fluorine ✓

Physical chemistry 2 87
Questions & Answers

e Fluorine is the species in the table that is most easily reduced, because it has
the most positive value for its reduction to fluoride ions . Zinc is the strongest
reducing agent in the table, because it is most easily oxidised since it has the most
positive value for its oxidation if the half-equations were reversed and the signs
changed .

(c) A conventional cell representation is Pb | Pb2+ || Cu2+ | Cu.

(i) Calculate the emf of the cell. (1 mark)

0 .47 V ✓

e Again this type of calculation can be done by simply reversing one of the
equations (in this case the lead one) and changing the sign of the electrode
potential and adding them together . Alternatively the equation below can be used:
emf = Erhs − Elhs
emf = +0 .34 – (−0 .13) = +0 .47 V
(ii) Identify the positive electrode. (1 mark)

Copper electrode ✓

e Using NEGATOX the negative electrode is the one where oxidation occurs, so
the positive electrode is the one where reduction occurs . The reduction electrode
is the copper electrode .

Question 4
The half-equations for the lithium ion cell are given below:
Li+ + e − → Li E⦵ = −3.03 V
+ − +
Li + CoO2 + e → Li [CoO2] − E⦵ = +0.67 V
(a) What is the change in oxidation state of the cobalt in the second half-equation? (2 marks)

+4 ✓ to +3 ✓

e The oxidation state of oxygen is −2, so Co in CoO2 is +4, whereas in CoO2−

cobalt has an oxidation state of +3 .

(b) Write an overall equation for the reaction that occurs. (2 mark)

Li + CoO2 → Li+[CoO2]− ✓✓

e Again combining the equations by reversing the top one and adding them
together . The Li+ and e − can be cancelled out .

88 AQA Chemistry
 Acids and bases

(c) Calculate the voltage that can be supplied by the cell. (1 mark)

3 .70 V ✓

e As the top equation becomes the oxidation one, the overall emf of the cell,
which is the same as the voltage supplied, is 3 .03 + 0 .67 = 3 .70 V .

(d) Suggest why water is not used as the solvent in this type of cell. (1 mark)

Lithium reacts with water ✓

e This type of ‘suggest’ question tests your ability to think outside the topic and
apply knowledge .

■ Acids and bases

Question 1
Which one of the pH curves in Figure 3 would show the change in pH when
0.100 mol dm−3 sodium hydroxide solution is added to 25.0 cm3 of 0.100 mol dm−3
hydrochloric acid? (1 mark)
A B
14 14
pH

pH

12 12
10 10
8 8
6 6
4 4
2 2
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Volume/cm3 Volume/cm3

C D
14 14
pH

pH

12 12
10 10
8 8
6 6
4 4
2 2
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Volume/cm3 Volume/cm3

Figure 3

The answer is B ✓

Physical chemistry 2 89
Questions & Answers

e The pH curve must go from low to high pH . As it is a strong acid–strong base

titration, the vertical region should go from around pH 3 to 10 . The volume at
neutralisation will be 25 .0 cm3 . Curve A would be for the addition of a strong base
to a weak acid; curve C would be for the addition of a weak base to a strong acid;
curve D would be for the addition of a weak acid to a strong base .

Question 2
What is the pH of a solution of ethanoic acid (Ka = 1.74 × 10 −5 mol dm−3) of
concentration 0.224 mol dm−3? (1 mark)

A 0.65 C 4.76
B 2.71 D 5.41

The answer is B ✓

e The [H+] of a weak acid = K a × [weak acid] . The pH is determined using pH

= −log10 [H+] . [H+] for this acid = 1.74 × 10−5 × 0.224 = 1 .97 × 10 −3 mol dm−3 .
pH = −log10(1 .97 × 10 −3) = 2 .71 . Answer A is obtained if the concentration of [H+] is
taken as 0 .224 mol dm−3; answer C is obtained if −log10 Ka is calculated; answer D
is obtained if the square root is not taken .

Question 3
Hydrochloric acid and sulfuric acid are strong acids. In this question give
all values of pH to 2 decimal places and all volumes and concentrations to
3 significant figures.
(a) Write an expression for the term pH. (1 mark)

pH = −log10[H+] ✓

(b) Calculate the pH of 0.125 mol dm−3 hydrochloric acid. (2 marks)

[H+] = 0 .125 mol dm−3 ✓ pH = −log10[H+] = −log10(0 .125) = 0 .90 ✓

e Hydrochloric acid is a strong acid and monoprotic, so the concentration of H+

is the same as the concentration of HCl .

(c) Calculate the concentration of sulfuric acid with a pH of 0.50. (2 marks)

[H+] = 10 −0 .50 = 0 .316 mol dm−3 ✓ [H2 SO4] = 0 .158 mol dm−3 ✓

e The concentration of [H+] is calculated using the pH as [H+]= 10 −pH . As H2 SO4

is a strong diprotic acid the concentration of the acid is half the concentration of
hydrogen ions .

90 AQA Chemistry
 Acids and bases

(d) Calculate the volume of water that would be added to 25.0 cm3 of
0.125 mol dm−3 hydrochloric acid to give a solution with pH 1.54. (4 marks)

(25.0 × 0.125)
moles of H+ in original solution = = 3 .125 × 10 −3 mol ✓
1000
[H+] in new solution = 10 −1 .54 = 0 .0288 mol dm−3 ✓
3.125 × 10−3
× 1000 = 0 .0288, where V is new total volume of solution
V
3.125 × 10−3
V= × 1000 = 108 .5 cm3 ✓
0.0288
volume of water added = 108 .5 − 25 = 83 .5 cm3 ✓

e Answers in the range 83 .0 cm3 to 83 .7 cm3 would be acceptable due to

rounding to 3 significant figures during the calculation . It is acceptable to work
to 4 significant figures during a calculation as long as the answer is given to the
required number of significant figures . The dilution of the number of moles of
H+ to a new concentration can be determined by dividing the moles of H+ in the
original solution by the volume of the solution and multiplying by 1000 .

(e) 30.0 cm3 of 0.170 mol dm−3 sodium hydroxide solution is added to 25.0 cm3 of
0.125 mol dm−3 sulfuric acid. Calculate the pH of the solution formed. (6 marks)

30.0 × 0.170
Moles of NaOH = = 5 .10 × 10 −3 mol ✓
1000
25.0 × 0.125
Moles of H2 SO4 = = 3 .125 × 10 −3 mol ✓
1000
Ratio of NaOH:H2 SO4 = 2:1

Moles of H2 SO4 in excess = 5 .75 × 10 −4 mol ✓

Total volume = 55 .0 cm3

5.75 × 10−4
New [H2 SO4] = × 1000 = 0 .0105 mol dm−3 ✓
55.0
[H+] = 2 × [H2 SO4] = 0 .0210 mol dm−3 ✓

pH = −log10[H+] = −log10(0 .0210) = 1 .68 ✓

e This is a complex calculation due to the 2:1 ratio of NaOH to H2SO4 . Dividing
5 .10 × 10 −3 by 2 gives 2 .55 × 10 −3 and this is subtracted from the moles of H2 SO4
(3 .125 × 10 −3) to determine the moles of H2 SO4 in excess . The total volume is
55 .0 cm3 as this is the total volume of the two solutions when mixed . This allows
the concentration of H2 SO4 to be calculated . As H2 SO4 is a strong diprotic acid, [H+]
= 2 × [H2 SO4] . The pH is calculated in the normal way using pH = −log10[H+] . Watch
out for calculations where the base is in excess, as Kw is required to calculate [H+] .

Physical chemistry 2 91
Questions & Answers

Question 4
(a) 20.0 cm3 of 0.0500 mol dm−3 sodium hydroxide solution were added to 30.0 cm3
of 0.0500 mol dm−3 ethanoic acid (Ka = 1.74 × 10 −5 mol dm−3). Calculate the pH
of the buffer solution formed. Give your answer to 2 decimal places. (6 marks)

30.0 × 0.0500
Moles of CH3COOH = = 1 .50 × 10 −3 mol
1000
20.0 × 0.0500
Moles of NaOH = = 1 .00 × 10 −3 mol
1000
CH3COOH + NaOH → CH3COONa + H2O

Moles of ethanoic acid remaining = 1 .50 × 10 −3 − 1 .00 × 10 −3 = 5 .00 × 10 −4 mol ✓

Moles of sodium ethanoate formed = 1 .00 × 10 −3 mol ✓

Total volume of solution = 50 .0 cm3

5.00 × 10−4
New [CH3COOH] = × 1000 = 0 .0100 mol dm−3 ✓
50.0
1.00 × 10−3
New [CH3COO –] = × 1000 = 0 .0200 mol dm−3 ✓
50.0
[H+ ][CH3COO− ] K [CH3COOH]
Ka = [H+] = a
[CH3COOH] [CH3COO− ]
1.74 × 10−5 × 0.0100
[H+] = = 8 .70 × 10 −6 mol dm−3 ✓
0.0200
pH = −log10[H+] = −log10(8 .70 × 10 −6) = 5 .06 ✓

e Buffer calculations are never easy, but it is important that you aim to discover
the new concentration of the weak acid and its anion in the solution, taking into
account the new total volume of the solution .

(b) 5.0 cm3 of a 0.0105 mol dm−3 solution of hydrochloric acid are added to the
buffer solution in (a). Calculate the pH of the buffer solution after the addition
of the acid. (6 marks)

5.00 × 0.0105
Moles of H+ added = = 5 .25 × 10 −5 mol ✓
1000
New moles of CH3COOH = 5 .00 × 10 −4 + 5 .25 × 10 −5 = 5 .525 × 10 −4 mol ✓

New moles of CH3COO − = 1 .00 × 10 −3 – 5 .25 × 10 −5 = 9 .475 × 10 −4 mol ✓

New total volume = 50 + 5 = 55 cm3

5.525 × 10−4
New [CH3COOH] = × 1000 = 0 .0100 mol dm−3 ✓
55.0
9.475 × 10−4
New [CH3COO –] = × 1000 = 0 .0172 mol dm−3 ✓
55.0

92 AQA Chemistry
 Knowledge check answers

[H+ ][CH3COO− ] K a [CH3COOH]

Ka = [H+] =
[CH3COOH] [CH3COO− ]
1.74 × 10−5 × 0.0100
[H+] = = 1 .01 × 10 −5 mol dm−3 ✓
0.0172
pH = −log10[H+] = −log10(3 .68 × 10 −5) = 4 .99 ✓

e A buffer maintains an almost constant pH on the addition of small quantities of

an acid or a base . The pH of the buffer should not be very different on the addition
of the acid or the base . Remember that added H+ increases the HA and decreases
the A−, but the addition of a base decreases the HA and increases the A− . The total
volume should be taken into account, though using the moles of HA and A− will
give the same answer .

Knowledge check answers 10 1

11 Position of equilibrium moves to right
1 The standard enthalpy change of atomisation is the No change for Kp
enthalpy change when 1 mole of gaseous atoms is 12 100 kPa, 298 K, any solutions 1.00 mol dm−3
formed from the element in its standard state under 13 Zinc
standard conditions. 14 +3
2 CaO(s) → Ca2+(g) + O2− (g) 15 Ni +3 to +2
3 −15 kJ mol−1 16 HCO 3 −
4 Standard change in entropy and J K−1 mol−1 17 pH = −log10[H+]
5 kJ mol−1 18 −0.71
6 350.9 K [HCOO −][H+]
7 mol−2 dm6 s−1 19 Ka =
8 J mol−1 [HCOOH]
(pNO2) 2 20 2.84
9 Kp = 21 2.24
(pN2O 4) 22 Pink
23 Maintains an almost constant pH on addition of small
amounts of acid or base

Physical chemistry 2 93
Index

Note: page numbers in bold E F

indicate key term definitions. electrochemical cells feasibility of reactions 45–46
basic electrochemistry of 49 factors affecting 18
A commercial application 49 Gibbs free energy, ΔG⦵ 17
acid dissociation constant (Ka) 59
fuel cells 51–52 and positive emf 40, 45–46
acids and bases 52–71
positive emf and feasibility of and temperature 18–20
Brønsted–Lowry theory 52–53 reaction 45–46 first electron affinity 8
buffers 66–71 primary cells 49–50 first ionisation energy 7
classification of 53–54 risks and benefits 52 fuel cells 51–52
dilutions 60–61 secondary cells 50–51
ionic product of water 55–56 electrode potential 40 G
neutralisations 61–63 electrode potentials 39–48 gas syringes 26
pH of strong acids 54–55 applied to vanadium chemistry gas volume–time graphs 26–27
pH of strong alkalis 56–57 47–48 Gibbs free energy change (ΔG⦵)
pH of weak acids 57–60 feasibility of reactions 45–46 14, 17
pH calculation 54 oxidising agents and reducing and feasibility of a reaction 18
pH curves 63–66 agents 46 graphs of ΔG⦵ against
questions and answers 89–93 questions and answers 84–89 temperature 19–20
activation energy (Ea) reactivity order 46 physical changes related to 18
Arrhenius equation 29 standard electrode potentials group 1 halides, Born–Haber cycle
40–45 8–9
and rate of reaction 24
electromotive force (emf) 40 group 2 halides, Born–Haber cycle
Arrhenius equation 29–30
calculation 44 9–10
B positive emf and feasibility of
batteries (cells) 49–52 reaction 40, 45–46
H
half cells 40
bond dissociation enthalpy 7 enthalpy of solution 12
combination of 41–42
Born–Haber cycles 6–11, 13 calculating 13
conventional representation
Brønsted–Lowry acid 52 hydration enthalpy 12–13
43–44
Brønsted–Lowry base 52 entropy change (ΔS⦵) 14–16
left-hand cell or right-hand cell
buffers 66–71 calculations 16 42–43
acidic 67 changes of state 14–15 non-standard conditions 43
action of 66–67 entropy (S) 15 phase boundaries 44–45
addition of acid or alkali to 70–71 values for various substances Henderson–Hasselbalch equation 70
basic 67 15–16 Hess’s law 6, 7, 9
calculating pH of 68–70 equilibrium constant (Kp) for hydration enthalpy 12–13
preparation of acidic 67 homogeneous systems 32–39
hydrogen fuel cells 51, 52
calculating and using 33–37
C expressions and units of 32 I
changes of state, entropy of 14–15 mole fractions and partial indicators 66
concentration against time graphs, pressures 32–33 initial rate monitoring, rate of
reaction rates 28–29 questions and answers 81–84 reaction 26–27
continuous rate monitoring, rate of temperature affecting value ionic product of water 55–56
reaction 27–29 of 39
total pressure calculation 38 K
D experimental value for lattice Ka (acid dissociation constant)
dilutions, strong acids and bases 60–61 enthalpy 11–12 57–58, 68
94 AQA Chemistry
 Index

Kp see equilibrium constant for phase boundaries 44 phase boundaries 44–45

homogeneous systems phenolphthalein 66 standard hydrogen electrode 41
Kw (ionic product of water) pKa 58–60 standard enthalpy change of
55–57, 61 position of equilibrium and Kc 39 atomisation 7
potassium chloride (KCl), standard enthalpy change of
L Born–Haber cycle 6–7 formation 6
lattice enthalpies
primary cells 49–50 standard entropy (S⦵) 15
patterns 11
standard hydrogen electrode 41
theoretical and experimental R standard lattice enthalpy 6
values 11–12 rate of reaction, methods of strong acids 53
lead–acid cell 50–51 determining 25–29 dilutions of 60–61
lithium ion cells 51 continuous rate monitoring 27–29 pH of 54–55
initial rate monitoring 26–27
M strong alkalis, pH of 56–57
rate measurements 25–26
methyl orange 66
methyl red 66
rate constant (k) 20–21 T
Arrhenius equation 29–30 temperature
mole fractions 32–33
factors affecting 24–25 effect on value of Kp 39
calculations 35, 36–37
units of 21 graphs of ΔG⦵ against
N rate determining step 30–31 19–20
NEGATOX mnemonic 49 rate equations 20–31 and rate constant 24–25
neutralisations 61–63 questions and answers 78–81 theoretical value for lattice
nickel cadmium cell 50 reactivity–feasibility link 46 enthalpy 11–12
reducing agents 46 thermodynamics 6–20
O required practicals Born–Haber cycles 6–14
order of reaction 21 investigating pH changes 66 Gibbs free energy and entropy
determining and using 21–24 measuring emf of electrochemical 14–20
linked to mechanism 30–31 cell 49 questions and answers 73–77
overall order of reaction 21 measuring rate of reaction 31 titration 63–64
oxides, Born–Haber cycle 10–11 curves, sketching 64–65
oxidising agents 46 S indicators for 66
secondary cells 50–51 total pressure calculation 38
P standard electrode potential 40
partial pressures 32–33 standard electrode potentials V
calculations 33–34, 37 40–45 vanadium chemistry, electrode
perfect ionic model 11–12 combination of half cells 41–42 potentials applied to 47–48
pH of strong acids 54–55 conventional cell representation
pH of strong alkalis 56–57 43–44 W
pH of water 56 left-hand cell or right-hand water, calculating pH of 56
pH of weak acids 57–60 cell 42–43 weak acids 53–54
pH calculation 54 non-standard conditions in a and buffers 67–69
pH curves 63–66 cell 43 pH and pKa 57–60

Physical chemistry 2 95