INTERNATIONAL ADVANCED LEVEL

CHEMISTRY
EDEXCEL INTERNATIONAL GCSE

ECONOMICS
TOPIC GUIDE
ENERGETICS:
SPECIFICATION
ENERGY
Edexcel International GCSE in Economics (9-1) (4ET0)

AND ENTROPY
First examination June

Pearson Edexcel International Advanced Subsidiary in Chemistry (XCH11)

Pearson Edexcel International Advanced Level in Chemistry (YCH11)
First teaching September 2018
First examination from January 2019
First certification from August 2019 (International Advanced Subsidiary) and
August 2020 (International Advanced Level)
Contents
Introduction 3
Enthalpy 4
First principles 4
Definitions 4
Hess’s Law 6
Effect of temperature on the value of H 7
Born-Haber cycles 8
Entropy, S 10
Total entropy change 11
Spontaneity 14
Effect of temperature on entropy values 16
Entropy changes on dissolving 16
Gibbs Free Energy, G 17
Feasibility in terms of G 18
Calculation of Gθ for a reaction 18

Equilibrium, Stotal and rGθ 19

In terms of Stotal 19
In terms of rGθ 20
Effect of temperature on the value of K 20
Points to remember 20

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Introduction
This guide is intended to help support teachers new to this specification and to provide some
background information on the parts of the topic that are new – both from a teacher’s perspective to
ensure clarity of what is expected, and from a student’s perspective when discussing transition from
International GCSE/GCSE and addressing misconceptions.

This guide can be used as a reference document for teachers, and parts of it (such as the worked
examples) could work as revision material for students.

Included in this guide are:

 some ideas on how to address common misconceptions in both new and previously included
content
 possible teaching sequences for key specification points where there is new or challenging content
 worked examples which teachers could use to support students in developing their understanding.

George Facer

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Enthalpy
First principles

A reaction vessel can be regarded as a thermodynamic system. If the amount of heat flowing in or out
of the vessel during a chemical reaction is q, then q is negative if heat has left the system and has
gone to the surroundings. This happens in an exothermic reaction. Likewise if q is positive, the system
has gained heat from the surroundings and the reaction is endothermic.

Exothermic reaction: the system increases in temperature, so heat flows to the cooler
surroundings. The system loses heat energy to the surroundings, so q is negative.
Endothermic reaction: the system gets colder, so heat flows from the warmer
surroundings into the system. The system gains heat energy from the surroundings, so q is
positive.

There are two distinct set of conditions – the reaction happening at constant pressure or at constant
volume. In A level chemistry only changes that take place at constant pressure are considered. The
heat change at constant pressure is called the enthalpy change, H.

Exothermic reaction: H is negative

Endothermic reaction: H is positive

Any enthalpy change can be represented by

H = Hproducts - Hreactants

where  stands for ‘the sum of’. This applies to chemical or physical changes.

Definitions

All standard enthalpy changes must be quoted at 100 kPa pressure and a constant temperature, which
is usually 298K (25°C). These conditions must be included in all definitions. You should be able to find
a list of definitions of the enthalpy changes needed for A level chemistry in your textbook.
The definitions that students often get wrong are:

Enthalpy of combustion (of organic compounds), cHθ

It is the enthalpy change when 1 mol of a substance is burnt in excess oxygen at
100 kPa pressure and a stated temperature (usually 298K). The equation representing this for ethane
is:
C2H6(g) + 3½O2(g)  2CO2(g) + 3H2O(l)

Note the following points:

Only 1 mol of the substance being burnt is on the left of the equation. This may, as here,
result in a fractional number of oxygen molecules – don’t double the equation in order to
get whole numbers.

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Water is in the liquid state, because at 298K and 100 kPa it is the stable form of water.
When the experiment is carried out in the laboratory, water is normally produced as a
gas, so the cH value obtained will be quite different from any data book’s value.

Enthalpy of atomisation, atHθ (of an element)

This is the enthalpy change under standard conditions of 100 kPa pressure and a temperature of 298K
when 1 mol of gaseous atoms is formed from the element in its standard state. The equation
representing this for bromine is:

Br2(l)  Br(g)

The common errors are to start with the gaseous form of a liquid element or having
1 mol of a diatomic substance on the left of the equation. So it is not for

Br2(g)  Br(g)

nor for
Cl2(g)  2Cl(g)

Enthalpy of reaction, rHθ

This is the enthalpy change under standard conditions of 100 kPa and 298K when the moles as in the
equation written completely react.

For: SO2(g) + ½O2(g)  SO3(g) rHθ = -129 kJ mol-1

But for: 2SO2(g) + O2(g)  2SO3(g) rHθ = -258 kJ mol-1

This means that all enthalpy of reaction data must be linked to an equation.

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Hess’s Law

The enthalpy of formation of almost all organic compounds cannot be measured directly – ethanol
cannot be directly made from carbon, hydrogen and oxygen. However a table of such data is essential
for calculating many enthalpies of reaction. Where a change cannot take place directly, then rHθ must
be calculated by an indirect method. This uses Hess’s Law.

Hess’s Law: When reactants are converted into products, the enthalpy change is the same
whether the reaction takes place in one step or in a series of steps.

The enthalpy of formation of ethanol can thus be calculated knowing the enthalpies of combustion of
ethanol, carbon and hydrogen. (Note that the enthalpies of combustion of these two elements are the
same as the enthalpies of formation of water and carbon dioxide)

Figure 1
fH of C2H5OH(l)
2C(s) + 3H2(g) + O2 C2H5OH(l) + 3O2(g)

2 × cH of C(s) 3 × cH of H2(g) cH of C2H5OH(l)

2CO2(g) + 3H2O

fH of C2H5OH(l) = 2 × cH of C(s) + 3 × cH of H2 – cH of C2H5OH

The arrow for the combustion of ethanol could be drawn from 2CO2 + 3H2O towards C2H5OH but then
the label would be – cH of C2H5OH(l).
It is essential to have the arrows properly labelled, either as in Figure 1 or with their numerical values.

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Effect of temperature on the value of H

It is assumed, at A level, that a change in temperature will not alter the value of an enthalpy change.
This is an oversimplification as can be seen from a Hess’s Law diagram.

Figure 2

CO(g) + O2(g) H2 CO2(g) at 398K

H3 H4 H5

CO(g) + O2(g) H1 CO2(g) at 398K

H1 is the enthalpy change of the reaction at 298K

H2 is the enthalpy change of the reaction at 398K
H3 is the heat change when 1 mol of CO is heated from 298 to 398K
= 100 × molar heat capacity of CO = +2860 J
H4 is the heat change when  mol of O2 is heated from 298 to 398K
= 100 × ½ × molar heat capacity of O2 = +1470 J
H5 is the heat change when 1 mol of CO2 is cooled from 398 to 298K
= -100 × molar heat capacity of CO2 = -3710 J

H1 = H3 + H4 + H2 + H5

H1 – H2 = +2860 + 1470 – 3710 = +670 J or 0.7 kJ

The conversion of CO to CO2 is exothermic, but the value at 398K is 0.670 kJ more exothermic per
mole of CO reacting. The value at 298K = -283.0 kJ mol-1 whereas that at 398K is -283.7 kJ mol_1.
Thus it is fair, at A level, to regard an enthalpy change as being independent of temperature, unless
the change in temperature results in a change of state.

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Born-Haber cycles

These are specific examples of Hess’s Law and relate the enthalpy of formation of an ionic compound
with a number of other quantities. It assumes that the alternative pathway is:

element in normal state  gaseous atoms  gaseous ions  solid ionic compound

The example below is the cycle for calcium chloride.

Figure 3
Ca2+(g) + 2Cl(g)

H4

H3 Ca2+(g) + 2Cl-(g)

Ca2+(g) + Cl2(g)

H2 H5

Ca(g) + Cl2(g)

H1

Ca(s) + Cl2(g)

rH

CaCl2(s)

rH = H1 + H2 + H3 + H4 + H5 where

H1 = enthalpy of atomisation of calcium
H2 = 1st + 2nd ionisation energies of calcium
H3 = 2 × enthalpy of atomisation of chlorine
H4 = 2 × electron affinity of chlorine
H5 = the lattice energy of calcium chloride.

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Points to note are:
Lattice energies are defined as the energy change when the gaseous ions (infinitely far apart) form a
mole of ionic solid, and so is exothermic and hence is a negative number.
H2 is the sum of the 1st and 2nd ionisation energies, not just the 2nd ionisation energy of calcium.
The enthalpy of atomisation is that for the formation of 1 mol of gaseous atoms not the enthalpy
change for the atomisation of 1 mol of the diatomic molecule, thus
H3 = 2 × atH of chlorine.
The change from Ca(g) to Ca2+(g) is often written as two separate steps.

This cycle is used to find the experimental lattice energy of an ionic compound. The theoretical value
can be worked out. The energy change when one ion pair is formed can be calculated from Coulomb’s
Law and using integral calculus and is:

the product of the charges on the ions

Energy 
the distance between the centre of the ions

This theoretical value assumes that the solid is 100% ionic. In many ionic compounds this is not true
as the cation polarises the anion to some extent. The difference between the theoretical and the
experimental values depends on the extent of polarisation. The process representing the actual
(experimental) lattice energy can be regarded as:

Gaseous ions step 1

100% ionic solid step 2
Polarised ionic solid

Step 1 is the exothermic process of bringing the gaseous ions together to form a perfect lattice and is
equal to the theoretical lattice energy. Step 2 is moving the electron cloud around the anion closer to
the polarising cation and is also exothermic. The sum of steps 1 and 2 is the experimental lattice
energy. As each step is exothermic the experimental lattice energy will be more exothermic than the
theoretical value. The greater the difference, the more the anion has been polarised.
Cations with a 2+ charge are more polarising than those with a 1+ charge and those with a smaller
ionic radius are more polarising. Likewise anions with a 2- charge are more polarisable than those with
a 1- charge and larger anions are more polarisable than smaller anions – see Table 1.

Table 1
● Substance ● Radius of ● Radius of ● Difference between
cation / anion / experimental and theoretical
nm nm lattice energies
● / kJ mol-1
NaCl 0.095 0.181 10
NaI 0.095 0.216 18
CsCl 0.169 0.181 18
CsI 0.169 0.216 21
MgCl2 0.065 0.181 100
MgI2 0.065 0.216 383

The extent of polarisation is sometimes called the extent of covalency.

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Entropy, S
The first law of thermodynamics states that energy cannot be created or destroyed. This concept was
encountered earlier in both Hess’s Law and Born-Haber cycles.
In chemical and physical changes there is almost always a change in enthalpy, but some endothermic
changes happen and some exothermic ones do not. When solid ammonium carbonate is added to liquid
ethanoic acid, the reaction is rapid with the evolution of carbon dioxide but the mixture becomes much
colder. So this endothermic reaction is spontaneous. Water at 25°C does not spontaneously freeze
even though the process of a liquid turning to a solid is exothermic.

Entropy is a measure of disorder

It is the second law that predicts whether a change is spontaneous or not.

A spontaneous change is one that has a natural tendency to occur without the needing to
be driven by an external factor.

The second law of thermodynamics states that every natural thermodynamic process
proceeds in the direction in which the total entropy is increased.

Examples of changes which result in an increase in entropy are:

The increase in temperature of a gas. This can be seen by looking at the Maxwell-Boltzmann
distribution of a gas at two or more temperatures. The spread of energies is much greater at a
higher temperature meaning that the disorder or randomness of the hot gas is greater than that of
the cooler gas.

Figure 4

The blue line is for a lower temperature than the red line and the green line represents the distribution
at a much higher temperature.
A solid melting or a liquid boiling. The ordered arrangement of molecules in the solid become random
as it melts. The close packed molecules in the liquid become dispersed in the gas phase.
Sice = 43 J K-1 mol-: Swater = 70 J K-1 mol-1: Svapour = 189 J K-1 mol-
A reaction in which a gas is produced from a solid and a liquid

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 (NH4)2CO3(s) + 2CH3COOH(l)  2CH3COONH4(s) + CO2(g) + H2O(l)
Ssystem > 0
A reaction in which there is an increase in the number of moles in the same physical state.
Cu(H2O)6]2+(aq) + 3NH2CH2CH2NH2(aq)  [Cu(NH2CH2CH2NH2)3]2+(aq) + 6H2O(l)
The change is from four moles to seven moles, so Ssystem > 0.

Total entropy change

The total entropy involved in a change, Stotal, is made up of the entropy change of the system, Ssystem
and that of the surroundings, Ssurroundings.

Stotal = Ssystem + Ssurroundings

At A level, the system is normally considered to be the substances reacting; and the surroundings the
air in the room in which the reaction is taking place.

For a spontaneous change, Stotal must be positive.

Thus it is possible for either Ssystem or Ssurroundings to be negative, as long as their sum is positive.

Entropy change of the system, Ssystem

This is equal to the sum of all the molar entropies of the products – the sum of those of the reactants.

Ssystem = Sproducts – Sreactants

So for the reaction

N2(g) + 3H2(g)  2NH3(g)
it is
Ssystem = 2 × SNH3 – ( SN2 +3 × SH2 )

Calculation of Ssystem requires a table of entropies. At A level, these will always be standard entropies
which is the entropy value at a pressure of 100 kPa and a temperature of 298K (25°C). The units are J
K-1 mol-1.

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Table 2 Standard entropies of some substances

● Physical ● Substance ● Standard

state entropy, Sθ / J
K-1 mol-1
Solid Calcium carbonate, CaCO3 93
Calcium oxide, CaO 40
Magnesium carbonate, MgCO3 66
Liquid Ethanol, C2H5OH 161
Propan-1-ol, C2H5CH2OH 197
Benzene, C6H6 173
Gas Hydrogen, H2 131
Nitrogen, N2 192
Ammonia, NH3 193
Carbon monoxide, CO 191
Carbon dioxide, CO2 214
Hydrogen chloride, HCl 187
Chlorine, Cl2 223
Ethene, C2H4 219
Ethane, C2H6 230
Propane, C3H8 270

Notice the following things:

1 The entropies of gases, except for the simplest gases, are generally larger than those of liquids
which are larger than those of solids: Sgas > Sliquid > Ssolid
The more atoms there are in a species (in a given physical state), the larger the entropy: S(CaCO3(s))
> S (CaO(s)) and S(C6H6(l)) > S(C2H5OH(l))
For species with a similar number of atoms, the larger the number of electrons, the larger the entropy:
S (CaCO3(s)) > S (MgCO3(s)) and S(Cl2(g)) > S(CO(g))
Points 2 and 3 can be summarised as: the more complex the substance, the larger is its entropy.
It is often stated that the entropy of gases are always bigger than those of a liquid. This is an
oversimplification as liquid benzene has a higher entropy than gaseous hydrogen. The reason is that
benzene has many more atoms in a molecule and so more ways of arranging energy in terms of
vibration and rotation.

Example 1
1 Use Table 2 to calculate Ssystem for:
2 (a) CaCO3(s)  CaO(s) + CO2(g)
3
4 (b) N2(g) + 3H2(g)  2NH3(g)
5
6 (c) H2(g) + Cl2(g)  2HCl(g)

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 Answers for Example 1
7 (a) Ssystem = 40 + 214 – 93 = +161 J K-1 mol-1
8
9 (b) Ssystem = 2 × 193 – (192 + 3 × 131) = -199 J K-1 mol-1
10
11 (c) Ssystem = 2 × 187 – (131 + 223) = + 20 J K-1 mol-1

These Ssystem values show the following general rules:

If there are more gas moles on the right than on the left of an equation, Ssystem will be positive and
large
If there are fewer gas moles on the right than on the left of an equation, Ssystem will be a large
negative number
If there are the same number of gas moles on each side, Ssystem may be positive or negative and will
be small.

Entropy change of the surroundings, Ssurroundings

In an exothermic reaction heat is transferred to the surroundings. This increases the variety of
energies of the surrounding air molecules and so increases their disorder. This is clearly shown in the
Maxwell-Boltzmann curves at different temperatures (see page 9). The result is that the transfer of
heat to the surroundings causes Ssurroundings to increase. Conversely if heat is transferred from the
surroundings to the reaction vessel, Ssurroundings will decrease.

Exothermic: Ssurroundings positive Endothermic: Ssurroundings negative

The magnitude of Ssurroundings depends upon two factors:

2 The enthalpy or reaction, rH
If the value of rH for an exothermic reaction is large, there will be a large increase in the disorder
of the surrounding air molecules and so the value of Ssurroundings will also be large.
Ssurroundings is proportional to -rH and is positive for an exothermic reaction.
The temperature, T
If the temperature in the surrounding air is high, the air molecules will already be in a high state of
disorder and so an input of heat energy will only make a small difference to its extent of disorder.
This means that Ssurroundings only increases by a small amount. However if the temperature is low,
an input of energy will cause a much bigger increase in disorder and so Ssurroundings will increase to
a greater extent.
Ssurroundings is inversely proportional to an increase in temperature.

When these two are combined the following relationship is obtained:

rH
Ssurroundings = -
T

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Spontaneity

Stotal = Ssystem + Ssurroundings

rH
= Ssystem -
T

For a spontaneous change Stotal must be positive.

Table 3

● Ssystem ● Enthalpy change ● Spontaneity

rH
Positive Negative (so - positive) At all temperatures
T
rH
Negative Negative Only if - > Ssystem
T
rH rH
Positive Positive (so - negative) Only if Ssystem> -
T T

Negative Positive Never

Example 2
12 Calculate whether the following changes are spontaneous or not at a temperature
of 298K.
13
14 (a) N2(g) + 3H2(g)  2NH3(g)
15
rH = -92.2 kJ mol-1 Ssystem = -199 J K-1 mol-1
16

17 (b) CaCO3(s)  CaO(s) + CO2(g)

18
rH = +178 kJ mol-1 Ssystem = +164 J K-1 mol-1
19
20 Note that Ssystem is measured in J units whereas rH is measured in kJ
units, so the latter has to be multiplied by 1000 so as to get both in joules.

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 Answers for Example 2
rH
21
(a) Stotal = Ssystem - = -199 – (-92200 ÷ 298) = +110 J K-1 mol-1
T
22
23 This is positive so the reaction is spontaneous at a temperature of 298 K.
rH
24 The favourable Ssurroundings (- ) outweighs the unfavourable Ssystem.
T
25 This reaction is thermodynamically spontaneous but a mixture of nitrogen and
hydrogen can be left for years and there will be no sign of any ammonia. The reason is that
the reaction has a very high activation energy and so is said to be kinetically stable. For this
reason the word ‘feasible’ or the phrase ‘thermodynamically spontaneous’ is sometimes
used in place of ‘spontaneous’, the latter implying that it happens automatically.
26
27
(b) Stotal = +164 – (+178000 ÷ 298) = -433 J K-1 mol-1
28
29 This is negative, so the reaction is not spontaneous at a temperature
of 298K.
rH
30 The unfavourable Ssurroundings (- ) outweighs the favourable Ssystem.
T

Change in spontaneity
For reactions where Ssystem and Ssurroundings have different signs, there will be a unique temperature at
which the reaction changes from being spontaneous to be non-spontaneous or vice versa. This
happens at the temperature when Stotal = zero.
rH
Stotal = Ssystem – =0
T
rH
Ssystem =
T

The temperature at which this happens is given by

rH
T=
S system

Example 3
31 Use the data from Example 2 (b) to calculate the temperature at which the
decomposition of calcium carbonate becomes thermodynamically feasible.

Answer for Example 3

32
rH = + 178 kJ mol-1 Ssystem = +164 J K-1 mol-1
rH  178000J mol1
33 T= = = 1085K = 812°C
S system  164 J K -1 mol1

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Effect of temperature on entropy values

As a solid is heated, the motion of its molecules increases and so its entropy increases. This is a
gradual process until the melting temperature is reached, when a large increase in entropy occurs.
There is a further gradual increase in entropy as the liquid is heated and then a large increase as the
liquid boils. Finally there is another gradual increase in entropy as the gas is heated. This happens with
all substances.

For a reaction in a given physical state

AB
both S(A) and S(B) increase as the temperature is increased. It is an acceptable approximation to
state that both S(A) and S(B) increase by the same amount and so Ssystem will not change in value if
the temperature is altered.
This is not true if the temperature change causes a change of physical state. Consider the combustion
of hydrogen. At 25°C the product water is a liquid but at 125°C it is a gas. Ssystem at 125°C is much
greater than Ssystem at 25°C but very similar to Ssystem at 225°C.
It is also assumed that rH is also independent on temperature (see page 6). It is a fair assumption
that neither Ssystem nor rH varies with temperature, but Stotal will alter as the temperature is changed
because Stotal = Ssystem - rH / T. This is an important point when considering how the equilibrium
constant changes with temperature (page 19).

Entropy changes on dissolving

It is often thought that the dissolving of an ionic solid always results in an increase of Ssystem. This is
true for solids with singly charged cations such as Na+ and NH4+. But with doubly and triply charged
anions this is not the case.
When an anhydrous ionic solid dissolves in water there are two contributions to Ssystem:
3 The increased disorder caused by the highly ordered solid spreading out into the solvent. The
entropy change here is always positive.
The ions, and especially the cations, become hydrated. In magnesium chloride, the magnesium ions
gather six water molecules around them.
Mg2+ + 6H2O  [Mg(H2O)6]2+
These hydrated ions then gather a second sphere of water molecules around them, thus the water
solvent becomes significantly ordered. In this process the entropy change is negative and often
outweighs the positive entropy change caused by the solid becoming dispersed through the solvent.
For small and highly charged cations this decrease in entropy can be quite large and the solid will
only dissolve if Hsolution is highly exothermic.

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Gibbs Free Energy, G
Not that the Gibbs free energy is not expected by the IAL specification, but is included here as teachers
may wish to used it as an alternative approach to entropy.

The free energy measured at constant pressure is called the Gibbs free energy (or
Gibbs function), symbol G, and is named after the American scientist J. Willard
Gibbs. It is a measure of the chemical potential, μ, that a mole of a substance has
when on its own. It is the energy that is available to do work in the same way that water at a higher
potential energy can run downhill and drive a machine.

Gibbs free energy is defined as:

G = H − TS
where H is the enthalpy of the substance and S its entropy. T is the temperature, measured in kelvin.
The Gibbs free energy can be thought of as the enthalpy content minus TS which represents the
substance’s energy that is already disordered. This difference is the energy that is available to become
disordered by doing work.
When 1 mol of substance A reacts to form 1 mol of substance B, the change in free energy is given by:
rGθ = GBθ – GAθ = (HBθ – TSBθ) – (HAθ – TSAθ)

Thus rGθ = rHθ – TSθ

As all these quantities refer to the system, the subscript system need not be used for the entropy
change.

The expression for the total entropy change has been seen earlier.

  rH 
Stotal = S system –
T
If this is multiplied by –T, it becomes
 
-T Stotal = rHθ – T S system

This is identical to the expression for Go, so the relationship between Gθ and Stotal is


rGo = - T Stotal

 rG θ
or S total =-
T

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Feasibility in terms of G
The criterion for a process being thermodynamically spontaneous is that Stotal must be positive. This
means that G must be negative for a spontaneous change.
A reaction changes spontaneity at a temperature such that G = 0.
G = H – TS = 0
H
T =
S
This is identical to the expression on page 14.

Calculation of Gθ for a reaction

This calculation is similar to that for calculating rH given a table of standard enthalpies of formation.
rGθ = (fGθ of products) – (fGθ or reactants)
(Taking into account the number of moles of each substance in the equation.)

Table 4 Standard free energy of formation, fGo, of some substances

● Substance ● fGθ / kJ mol-1
Nitrogen, N2(g) 0
Hydrogen, H2(g) 0
Ammonia, NH3(g) -27
Ethanoic acid, CH3COOH(l) -390
Ethanol, C2H5OH(l) -175
Ethyl ethanoate, CH3COOC2H5(l) -326
Water, H2O(l) -237

Note that, as with fH data, the standard free energy of formation of elements in their standard states
is zero. This means that fHθ and fGθ data for elements will not be given in an A level question.
Example 4
34 Calculate the standard free energy change for the following reactions:
35 (a) N2(g) + 3H2(g)  2NH3(g)
36
37 (b) CH3COOH(l) + C2H5OH(l)  CH3COOC2H5(l) + H2O(l)

Answers for Example 4

38 (a) rGθ = 2 × -27 – (0 + 0) = -54 kJ mol-1
39 As this value is negative, the reaction is (thermodynamically)
spontaneous at 298K.
40
41 (b) rGθ = -326 + (-237) – (-390 – 175) = +2 kJ mol-1
42 As this value is positive, the reaction is (just) non-spontaneous at 298K.
43

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Equilibrium, Stotal and rGθ
θ
In terms of Stotal
As an equilibrium reaction proceeds from reactants towards products, the total entropy of the mixture
increases, reaching a maximum when equilibrium is reached. This is shown in Figure 5 for the
equilibrium reaction
A⇌B
Figure 5

θ
The relationship between the total entropy change, Stotal , and the equilibrium constant, K, is given by
the expression
θ
Stotal = RlnK

In this expression Kp must be used for gaseous equilibria and Kc for equilibria in solution. Also partial
pressures must be in atm. The reason for this is that the partial pressure term of A(g) in the
expression for Kp is really the partial pressure of A(g) divided by the standard pressure. So for a gas
with a mole fraction of 0.25 at 1 atm, the value that should be substituted into the expression for Kp is
0.25 atm ÷ 1 atm = 0.25. If kPa had been used the value should be 0.25 × 100 kPa ÷ 100 kPa = 0.25.
The resulting value will be the same as long as the partial pressures are divided by the standard
pressure.

For this reason Edexcel will always use atm as the unit for pressure in all Kp questions, so that failure
to divide by 1 will not alter the value of Kp.

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In terms of rGθ

The relationship between rGo and Stotal is

rGo = - T Stotal
So the relationship between rGo and K is

rGo = RTlnK

Effect of temperature on the value of K

For an exothermic reaction, it is usual to state that, because rH is negative, an increase in
temperature will cause the value of K to decrease. This, in turn, lowers the equilibrium yield (drives the
position of equilibrium to the left). This can be explained in terms of the total entropy change.

θ θ θ r H θ
Stotal = RlnK and Stotal = Ssystem –
T
θ
θ
S total Ssystem  Hθ
lnK = = – r
R R RT
r H θ
For an exothermic reaction rH is negative and so - is positive.
RT
An increase in temperature will cause this positive number to decrease in value making lnK a smaller
number. This means that K will also be a smaller number.
θ
Note that this assumes that neither Ssystem nor rHθ change in value as the temperature is altered
(see page 15).
It also can be explained in terms of rGθ.
rGθ = -RT lnK
r Gθ = rHθ – T Ssystem
θ

θ θ
 rG θ TSsystem  Hθ Ssystem  Hθ
lnK = = – r = – r
RT RT RT R RT

θ
This is the same expression as that derived from Stotal and so the reasoning for the change in the
θ
value of K is the same as that from Stotal .

Points to remember
Entropies and the gas constant R are always quoted in joules, whereas free energy and enthalpy
values are quoted in kilojoules.
θ
A positive value for Stotal means that the forward reaction is thermodynamically feasible and so there
will be more product than reactant in the equilibrium mixture.
A negative value for rGθ also means that the forward reaction is thermodynamically feasible and so
there will be more product than reactant in the equilibrium mixture.
The temperature at which feasibility changes is given by the expression
r H θ
T= θ
S system

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