5 Energetics

5.1 Exothermic and endothermic reactions

Learning objectives

Explain what is meant by

exothermic and endothermic
reactions
Draw enthalpy level diagrams
for exothermic and endothermic
reactions
Understand what is meant by
stability

temperature
goes down

Chemical reactions may be classified as either exothermic or endothermic.

An exothermic reaction gives out heat to the surroundings (Figure 5.1).
An endothermic reaction takes in heat from the surroundings (Figure 5.2).

temperature
goes up

HEAT

HEAT
HEAT

HEAT
HEAT

HEAT

Figure 5.2 The heat energy in an

endothermic reaction is converted to internal
energy (e.g. by breaking chemical bonds).

To be more precise, the enthalpy

change is the heat energy
exchanged with the surroundings
at constant pressure.
means a change in a quantity.

Figure 5.1 The heat energy in an exothermic reaction comes from the decrease in
internal energy (the total energy of all the particles) of the system (e.g. by making
chemical bonds).

Exothermic reactions: chemical reactions that result in the release

of heat to the surroundings the reaction vessel gets hotter.
Endothermic reactions: heat is taken in from the surroundings
the reaction vessel gets colder.
We talk about the enthalpy change of a system. The enthalpy change
is basically the amount of heat energy taken in/given out in a chemical
reaction. Enthalpy is given the symbol H and enthalpy change is H.
Note: it is not possible to measure the enthalpy (H) of a
system (related to the total energy of all the particles making up a
substance), only the enthalpy change (H) when the system moves
from an initial state to some final state.

H for an exothermic reaction is negative.

H for an endothermic reaction is positive.
180

This reaction is exothermic, as heat is given out to the surroundings.

Figure 5.3 shows the enthalpy change for an exothermic reaction such
as the combustion of methane. No scale is shown on the vertical axis, as we
cannot measure the initial enthalpy or final enthalpy of the system. We can,
however, measure the enthalpy change of a reaction as the amount of heat
given out, and this is shown by the red arrow. The reaction is exothermic,
and the enthalpy of the products is less than that of the reactants. The
negative sign for the enthalpy change indicates a decrease in enthalpy.
We more normally use an enthalpy level diagram to show the enthalpy
change of a reaction (Figure 5.4).

Enthalpy

H = 890 kJ mol1

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

enthalpy
change
H = 890 kJ mol 1

PRODUCTS

Consider a reaction such as methane burning in oxygen:

REACTANTS

Exothermic reactions

Figure 5.3 An exothermic reaction: H

negative.

CH4(g) + 2O2(g)

Enthalpy

reactants
H = 890 kJ mol 1

CO2(g) + 2H2O(I)
products

Figure 5.4 An enthalpy level diagram for the combustion of methane.

In an exothermic reaction the products are at a lower energy (enthalpy)

level than the reactants, and we say that the products are more stable than
the reactants.

Endothermic reactions
An example of an endothermic reaction is that between nitrogen and
oxygen to form nitrogen(II) oxide (nitric oxide):

products

H = +181 kJ mol1

Heat energy must be put into the system, as the products have greater
energy than the reactants. The sign of H is positive, indicating the
increase in enthalpy in an endothermic reaction.
The enthalpy level diagram for this reaction is shown in Figure 5.5.
The products have greater energy (enthalpy) and are less stable than the
reactants.

Enthalpy

N2(g) + O2(g) 2NO(g)

2NO(g)

H = +181 kJ mol 1
N2(g) + O2(g)
reactants

Figure 5.5 An enthalpy level diagram for an

endothermic reaction.

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181

Stability
If a reaction is exothermic it involves a decrease in the enthalpy of the
system and we will often talk about the products being more stable than
the reactants.
Enthalpy

diamond

H = 1.9 kJ mol1

Cdiamond Cgraphite
H = 1.9 kJ mol 1

graphite

Graphite is at a lower enthalpy level than diamond and is therefore

1.9 kJ mol1 more stable than diamond (Figure 5.6).
Methane and oxygen are unstable with respect to the combustion
products, carbon dioxide and water:
H= 890 kJ mol1

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

Figure 5.6 An enthalpy level diagram for
the reaction in which diamond is turned into
graphite.

It is important to make the distinction between thermodynamic

stability and kinetic stability. Although graphite is thermodynamically
more stable than diamond (at a lower energy level) and carbon dioxide and
water are thermodynamically stable with respect to methane and oxygen,
in both cases, under normal conditions, the reactants are kinetically stable
with respect to the products. This means that the reaction of diamond to
become graphite is very, very slow under normal conditions!
If a little bit of energy, in the form of a spark, is provided to the methane
oxygen mixture, the reaction proceeds very quickly. This suggests that there
is some energy barrier that must be overcome before reaction can occur.
This energy barrier is called the activation energy (Figure 5.7).

activation
energy

CH4(g) + 2O2(g)

Enthalpy

reactants

H = 890 kJ mol 1

CO2(g) + 2H2O(I)
products
Reaction coordinate

Figure 5.7 An enthalpy level diagram for an exothermic reaction showing the
activation energy.

The activation energy is the

minimum energy that colliding
particles must have before collision
results in a chemical reaction this
will be considered in more detail
on pages 246251.

182

In general, all other things being equal, the higher the activation energy,
the slower the reaction. Thus, although the products may be more stable
than the reactants, it is still perfectly possible to have a bottle of the reactants
on the shelf in the chemical store cupboard, and to keep them there for
several years, as long as the activation energy is sufficiently high that the
reaction does not occur at a measurable rate under normal conditions.

There is no connection between these two ideas. A chemical reaction

could be extremely exothermic and proceed very slowly, whereas in
another, very fast, reaction the products may be only slightly more stable
than the reactants.
How exo- or endothermic a reaction is does not tell us anything
about how quickly a reaction occurs. For example:
CCl4(l) + 2H2O(l) CO2(g) + 4HCl(g)

H = 52 kJ mol1

SiCl4(l) + 2H2O(l) SiO2(s) + 4HCl(g)

H = 16 kJ mol1

The lower reaction occurs rapidly; the upper one immeasurably

slowly.
The enthalpy level diagram for an endothermic reaction is shown in
Figure 5.8. It is a fairly good rule of thumb that exothermic reactions tend
to occur spontaneously, whereas endothermic reactions do not. This is often
explained using the analogy that water always flows downhill, i.e. a system
will always move to lower energy by giving out energy to the surroundings.

Enthalpy

activation
energy
products

H
reactants
Reaction coordinate

Figure 5.8 In an endothermic reaction, the products are less stable than the
reactants.

However, endothermic reactions do occur, and they are perhaps much

more common than we realise; ice melting at room temperature, salt
dissolving in water, and water evaporating are all endothermic processes
that seem to occur fairly readily.

5.2 Calculation of enthalpy changes from

experimental data
Measuring enthalpy changes
In this section we will consider how to measure enthalpy changes of
combustion reactions. In order to understand how this works, we will first
consider specific heat capacity.

This suggests that perhaps enthalpy

change is not the fundamental
process that drives a chemical
reaction. Another thermodynamic
function that is more fundamental
in determining whether a reaction
occurs spontaneously will be
considered in Section 5.8 (Higher
Level only).

Learning objectives

Understand the principle of

experimental methods for
determining enthalpy changes
Work out enthalpy changes from
experimental data

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183

Specific heat capacity has units

of J g1 K1 or J g1 C1. Units
that are also encountered are
kJ kg1 K1 or J kg1 K1.
1 K is the same as 1 C when
temperature changes are being
considered.

temperature increases
by 1 C

Specic heat capacity

In chemistry we usually take the definition of specific heat capacity (c) to be:
the energy required to raise the temperature of 1 g of substance
by 1 K (1 C). It can also be defined as the energy to raise the
temperature of 1 kg of substance by 1 K.
The specific heat capacity of aluminium is 0.90 J g1 C1. Therefore,
if 0.90 J of heat energy is put into 1 g of aluminium, the temperature is
raised by 1 C (Figure 5.9).
If 1.80 J of heat energy were put into this block of aluminium, the
temperature would go up by 2 C. If the 1 g block of aluminium were
replaced by a 2 g block of aluminium, then 1.80 J would be required to
raise the temperature by 1 C, as 0.90 J is required to raise the temperature
of each 1 g by 1 C. The amount of heat energy required is therefore
proportional to the mass and the temperature change. An equation can
thus be derived for how much heat energy (q) must be supplied to raise
the temperature of mass m by T C:
q = mcT

0.90 J
1 g of
aluminium

Figure 5.9 The specic heat capacity of

aluminium is 0.90 J g1 C1.

T is the change in temperature.

The specific heat capacity indicates how much energy is required to

heat up a substance, and therefore substances with higher specific heat
capacities are more difficult to heat up than substances with lower specific
heat capacities. For example, the specific heat capacity of iron is roughly
half that of aluminium; therefore if the same amount of heat energy is
supplied to 10 g of each metal, the temperature of the iron will go up by
twice the amount.
The specific heat capacity also applies when a substance cools; so, for
instance, when 1 g of aluminium cools from 21 C to 20 C, 0.90 J of
energy is given out. This can be used to calculate the specific heat capacity
of an unknown metal.

Worked example
40.0 g of an unknown metal is heated to 91.3 C and then plunged into 100.0 g of water at 21.3 C. The water and
the metal reach a common temperature of 28.4 C. Given that the specific heat capacity of water is 4.18 J g1 C1,
calculate the specific heat capacity of the metal.
The amount of heat energy supplied to the water is given by: q1 = mcT
so: q1 = 100.0 4.18 (28.4 21.3) = 2970 J

184

The energy given out when the metal block cools is given by:
q2 = 40.0 c (91.3 28.4) = 2516c
where c is the specific heat capacity of the metal. The heat energy supplied to heat the water comes from the
cooling of the block of metal, so q1 = q2
Therefore: 2970 = 2516c
and c = 1.18 J g1 C1

Measuring the enthalpy change of combustion

reactions
The basic technique is that the heat given out in a combustion reaction
is used to heat another substance of known specific heat capacity, such as
water. The equation q = mcT can be used to calculate the amount of heat
given out.
The experimental set-up shown in Figure 5.10 could be used to
determine the enthalpy change when 1 mole of a liquid substance is
burnt. The mass and temperature change of the water must be measured,
as well as the mass change of the alcohol.

thermometer

copper
can

water

Worked example
Use the following experimental data to determine the enthalpy change
when 1 mole of ethanol (C2H5OH) is burnt:
Mass of water = 150.00 g
Initial temperature of water = 19.5 C
Maximum temperature of water = 45.7 C
Initial mass of spirit burner = 121.67 g
Final mass of spirit burner = 120.62 g
The temperature change of the water = 45.7 19.5 = 26.2 C
The amount of heat energy supplied to the water is given by:
q = mcT
q = 150.00 4.18 26.2 = 16 400 J

spirit
burner
alcohol

Figure 5.10 An experiment to work out the

enthalpy change when 1 mole of an alcohol
is burnt.

Note the mass of water and not

the mass of ethanol is used here
it is the water that is being heated.

This amount of heat energy is supplied by the burning of the ethanol.

mass of ethanol burnt = 121.67 120.62 = 1.05 g
The number of moles of ethanol burnt is given by:
no. moles =

The specific heat capacity of water

is 4.18 J g1 C1.

mass
molar mass

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185

The molar mass of ethanol is 46.08 g mol1. Therefore:

no. moles ethanol burnt =

More than three significant figures

were carried through on the
calculator to give this final answer.
The value of the enthalpy change
is negative because the combustion
reaction is exothermic.

When we carry out

experiments to measure
enthalpy changes we
often get unexpected values.
What criteria do we use when
carrying out these experiments
to decide whether there are flaws
in the experiment or flaws in
the theory? This is an example
of a more general problem,
and it is sometimes too easy to
dismiss an anomalous result as
being due to systematic errors
in the experiment. The opposite
also occasionally happens, and
a new theory is put forward
from an experiment that is
possibly flawed cold fusion
is an example of this (originally
announced by Pons and
Fleischmann in 1989).

186

1.05
= 0.0228 mol
46.08

When 0.0228 mol ethanol are burnt, 16 400 J of heat energy are
produced. Therefore the amount of energy released when 1 mole is
burnt is given by:
energy =

16 400
= 721 000 J mol1
0.0228

The enthalpy change when 1 mole of ethanol is burnt is therefore:

H = 721 kJ mol1
The accepted literature value for the enthalpy change of combustion
of ethanol is 1371 kJ mol1, so it can be seen that this experiment does
not give a very accurate answer. There are several major flaws (systematic
errors) in the experimental set-up. The most major problem is that of heat
loss to the surroundings. Of the heat energy released when the ethanol
burns, only some of it goes into heating the water the rest goes into
heating the copper can and the surrounding air. The experiment could
have been improved by determining the specific heat capacity of the can
and taking this into account when doing the calculation, insulating the
can so that less heat is lost through the can to the surroundings, using
some sort of draught shields to reduce convection currents around the
experiment, etc.
Another major problem with the experiment is incomplete
combustion of the ethanol. When ethanol undergoes complete
combustion the equation for the reaction is:
C2H5OH + 3O2 2CO2 + 3H2O
However, if there is not a sufficient supply of oxygen to the flame, some
of the ethanol can burn to produce carbon monoxide and soot (carbon) as
well as water. This is called incomplete combustion and gives out less heat
than complete combustion. Incomplete combustion causes the flame to be
yellow/orange rather than blue because of the presence of soot particles,
and the soot can also be seen on the bottom of the copper can.
Other, more minor, problems with the experiment include evaporation
of the water and alcohol.
More accurate values for the enthalpy change of a combustion reaction
require the use of a bomb calorimeter. This is a heavily insulated piece
of apparatus in which the substance is ignited electronically in a plentiful
supply of oxygen.

Self-test 1

Test yourself
You may assume that the specific heat capacity of water is 4.18 J g1 C1.
1 Work out the specific heat capacities of each metal
from the data given:
a Gold the temperature of 2.00 g of gold is raised
by 11.7 C when 3.00 J of energy is supplied.
b Silver the temperature of 100.0 g of silver
is raised by 2.12 C when 50.0 J of energy is
supplied.
2 a When 1.20 g of hexane (C6H14) is burnt, the
temperature of 250.0 g of water is raised by
56.0 C. Calculate the enthalpy change when
1 mole of hexane is burnt.
b When 2.00 kg of octane (C8H18) is burnt, the
temperature of 500 kg of water is raised by
46.0 C. Calculate the enthalpy change when
1 mole of octane is burnt.

3 Use the following experimental data to determine

the enthalpy change when 1 mole of propan-1-ol
is burnt:
Mass of water = 200.00 g
Initial temperature of water = 18.2 C
Maximum temperature of water = 38.6 C
Initial mass of spirit burner = 185.51 g
Final mass of spirit burner = 184.56 g
4 The actual value for the enthalpy change when
1 mole of propan-1-ol is burnt is 2010 kJ mol1.
Account for any differences between this value
and the one calculated from the experimental data
in question 3.

Enthalpy changes in solution

A general method for measuring enthalpy changes involving solutions in
the laboratory is to measure out known amounts of reagents, record their
initial temperatures, mix together the reagents in a polystyrene cup and
record the maximum/minimum temperature observed. The specific heat
capacity of the final solution is assumed to be the same as water. Before
we look at some examples of how to do this, we must consider a couple
of definitions.
Enthalpy change of neutralisation (Hn) is the enthalpy
change when 1 mole of H2O molecules are formed when an acid
(H+) reacts with an alkali (OH) under standard conditions:

The enthalpy change of

neutralisation is always
exothermic.

H+(aq) + OH(aq) H2O(l)

Enthalpy change of solution (Hsol) is the enthalpy change when
1 mol of solute is dissolved in excess solvent to form a solution of
infinite dilution under standard conditions, e.g.:
excess H2O

NH4NO3(s) NH4+(aq) + NO3(aq)

Hsol = +25.7 kJ mol1

Infinite dilution means that any

further dilution of the solution
produces no further enthalpy
change, i.e. the solute particles are
assumed not to interact with each
other in the solution.
The enthalpy change of solution
may be exothermic
or endothermic.

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187

Worked examples
Consider the following experiment: 100.0 cm3 of 1.00 mol dm3 potassium hydroxide solution was measured
out and poured into a polystyrene cup and the temperature of the potassium hydroxide solution was taken; then
120.0 cm3 of 1.00 mol dm3 hydrochloric acid was measured out and the initial temperature was taken. The
hydrochloric acid was in excess to make sure that all the potassium hydroxide reacted. The hydrochloric acid was
then poured into the polystyrene cup and the mixture stirred rapidly. The maximum temperature was recorded.
The results of this experiment:
Initial temperature of potassium hydroxide
solution = 19.7 C
Initial temperature of hydrochloric acid = 19.7 C
Maximum temperature reached = 25.9 C
Temperature change of the mixture = 6.2 C
Total volume of the reaction mixture = 220.0 cm3
We will assume that the density of the mixture is the same as that of water, and so 220.0 cm3
of solution has a mass of 220.0 g.
Assumption: the density of the potassium hydroxide and hydrochloric acid
solutions are the same as water, so 1 cm3 of solution has a mass of 1 g.
We can work out how much heat (q) has been released in this reaction by looking at the temperature change
of the mixture.
q = mcT = 220 4.18 6.2 = 5700 J
Assumption: the specific heat capacity of the mixture is the same as that of water.
This is a fairly reasonable assumption, as the reaction mixture is mostly water.
To work out the enthalpy change of neutralisation, we need to know how many moles of water have been formed.
The equation for the reaction is:
KOH + HCl KCl + H2O
no. moles KOH = concentration volume in dm3
no. moles KOH = 1.00
no. moles HCl = 1.00

100
= 0.100 mol
1000

120
= 0.120 mol
1000

The HCl is in excess and the number of moles of water produced is 0.100 mol. Therefore 5700 J of energy is
released when 0.100 mol of water is formed.

188

The definition of enthalpy change of neutralisation is the enthalpy change when 1 mole of water
is produced. Therefore, for 1 mole of water formed:
heat energy released =

1
5700 = 57 000 J mol1
0.100

Therefore, the enthalpy change of neutralisation, Hn = 57.0 kJ mol1.

This is negative, as the

reaction is exothermic.

The accepted literature value for the heat of neutralisation of KOH with HCl is 57.2 kJ mol1.
Possible errors in this experiment are heat loss to the surroundings and the assumptions that have
been made about the specific heat capacities and the density of the solutions.
a 100.0 cm3 of 1.00 mol dm3 potassium hydroxide solution was reacted with 100.0 cm3 of 1.00 mol dm3
hydrochloric acid. The temperature rise was 6.82 C. Calculate the enthalpy change of neutralisation.
b The experiment in part a was repeated with 50.0 cm3 of 1.00 mol dm3 potassium hydroxide solution and
50.0 cm3 of 1.00 mol dm3 hydrochloric acid. Calculate the temperature change of the reaction mixture.
a We can use the method used in the previous example to calculate the enthalpy change of neutralisation:
q = mcT = 200 4.18 6.82 = 5700 J
The number of moles of KOH and HCl in this case are the same, both 0.100 mol. Therefore 0.100 mol of water
are formed.
heat energy released =

1
5700 = 57 000 J mol1
0.100

Therefore the enthalpy change of neutralisation, Hn = 57.0 kJ mol1.

b A shortcut can be used to answer this part. The volume of each solution is half that in part a but the
concentrations are the same. Therefore we can deduce that the number of moles of water formed will be half
as much as in part a. This means that half as much heat energy will be given out in the neutralisation reaction.
However, the total volume of reaction mixture that is being heated is half the original volume; therefore only
half as much heat energy will be required to heat it to the same temperature. The temperature change in this
experiment is thus the same as in part a, i.e. 6.82 C.
Consider the following experiment: 100.0 cm3 of water was measured out and poured into a polystyrene cup and
the temperature of the water was taken; 5.20 g of ammonium chloride was measured out. The ammonium chloride
was added to the water and the solution stirred vigorously until all the ammonium chloride had dissolved. The
minimum temperature was recorded.
The results of this experiment:
Initial temperature of water = 18.3 C
Minimum temperature = 15.1 C

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189

Temperature change of the mixture = 3.2 C

We will assume that the density of the solution is the same as that of water, and so 100.0 cm3 of solution has a mass
of 100.0 g. We can work out how much heat has been absorbed in this reaction by looking at the temperature
change of the mixture:
q = mcT = 100.0 4.18 3.2 = 1340 J

Assumption: the specific heat capacity of

the solution is the same as that of water.

To work out the enthalpy change of solution, we need to

know how many moles of ammonium chloride dissolved.
no. moles NH4Cl =

mass
molar mass

molar mass of NH4Cl = 53.50 g mol1

Therefore, the number of moles of NH4Cl that dissolve =

5.20
= 0.0972 mol.
53.50

Therefore 1340 J of energy is absorbed when 0.0972 mol NH4Cl dissolve.

The definition of enthalpy change of solution is the enthalpy change when 1 mole of substance dissolves.
Therefore, for 1 mole of NH4Cl dissolving:
heat energy absorbed =

1
1340 = 13 800 J mol1
0.0972

This is positive, as the

reaction is endothermic.

Therefore the enthalpy change of solution, Hsol = +13.8 kJ mol1.

The accepted value for the enthalpy change of solution of ammonium chloride is 15.2 kJ mol1. Errors in this
experiment include absorption of heat from the surroundings and the assumptions about the specific heat capacity
of the solution being the same as that of water. The mass of the ammonium chloride was also not taken into
account when working out the heat energy released in the experiment (i.e. it was not included in the mass of
the solution). The results from this experiment are greatly improved by vigorous stirring of the solution, as the
ammonium chloride does not dissolve instantaneously. If it is allowed to dissolve slowly, there is more time for
heat to be absorbed from the surroundings and the temperature drop is not as large as expected. This effect can be
reduced by using the technique of the next experiment.
The following experiment may be used to determine the enthalpy change of reaction for:
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
30

Temperature / C

50.0 cm3 of 0.200 mol dm3 copper(II)

sulfate solution was placed in a polystyrene
cup. The temperature was recorded every
30 seconds for two minutes. At 2 minutes
30 seconds, 1.20 g of powdered zinc was
added. The mixture was stirred vigorously
and the temperature recorded every half
minute for several minutes. The results
obtained were then plotted to give the
graph shown in Figure 5.11.

line extrapolated

25
temperature
change

20

zinc added

15
10

10
Time / min

15

Figure 5.11 Temperature against time for the reaction of zinc with copper
sulfate solution.

190

20

The problem with this reaction is that it does not occur instantaneously, and so, although heat is being given out in
the reaction, at the same time the reaction mixture is also cooling down by losing heat to the surroundings. From
the graph it can be seen that there is an initial rise in temperature, where heat being given out by the reaction is
the major factor, but after that the reaction mixture cools. By extrapolating the line back from this cooling part of
the curve, we can estimate the temperature from which the mixture appears to be cooling. If we look at the value
of the temperature on this curve at 2 minutes 30 seconds, the point at which the zinc was added, we should get an
estimate of the temperature rise if the reaction had occurred instantaneously. It can be seen that this temperature
rise is greater than the temperature rise actually measured in the experiment.
From the graph we estimate the temperature change as 10.3 C.
The heat given out in the reaction is given by:

Assumption: the density of copper sulfate

solution is the same as that of water.

q = mcT = 50.0 4.18 10.3 = 2150 J

To work out the enthalpy change of reaction, we need to know how many moles of copper sulfate reacted
(the zinc was in excess).
no. moles of CuSO4 = concentration volume in dm3
no. moles of CuSO4 = 0.200

50.0
= 0.010 mol
1000

Therefore 2150 J of energy is released when 0.010 mol of copper sulfate reacts.
For the reaction of 1 mole of copper sulfate:
heat energy released =

1
2150 = 215 000 J mol1
0.010

Therefore the enthalpy change of reaction = 215 kJ mol1.

This is negative, as the reaction is exothermic.

The extrapolation of the line is very much a matter of judgement and could introduce errors into the calculation.
Self-test 2

Test yourself
5 a 200.0 cm3 of 0.150 mol dm3 hydrochloric acid
is mixed with 100.0 cm3 of 0.300 mol dm3
sodium hydroxide solution. The temperature
rose by 1.36 C. If both solutions were
originally at the same temperature, calculate the
enthalpy change of neutralisation.
b Predict the temperature rise if the experiment
in part a is repeated using:
i 400.0 cm3 of 0.150 mol dm3 hydrochloric
acid and 200.0 cm3 of 0.300 mol dm3
sodium hydroxide solution
ii 200.0 cm3 of 0.300 mol dm3 hydrochloric
acid and 100.0 cm3 of 0.600 mol dm3
sodium hydroxide solution

iii 50.0 cm3 of 0.300 mol dm3 hydrochloric

acid and 25.0 cm3 of 0.600 mol dm3 sodium
hydroxide solution.
6 a When 1.00 g of magnesium chloride is dissolved
in 50.0 cm3 of water the temperature goes up
from 21.5 C to 29.1 C. Calculate the enthalpy
change of solution of magnesium chloride.
b Predict the temperature change when 2.00 g of
magnesium chloride is dissolved in 100 cm3 of
water.
c Predict the temperature change when 2.00 g of
magnesium chloride is dissolved in 50.0 cm3 of
water.

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191

Learning objectives

5.3 Hesss law

Hesss law

Use Hesss law to calculate

enthalpy changes

Hr

direct route

H1

in

dir

e ct rou

te

It is not always possible to design experiments to measure certain enthalpy

changes, and so we often have to use data from reactions in which the
enthalpy change can be measured to work out the enthalpy change for a
particular reaction in which it cannot be measured directly. In order to do
this, we use Hesss law.
The enthalpy change accompanying a chemical reaction is
independent of the pathway between the initial and final states.

H2

What this basically means is that, if we consider the conversion of A into

B, the enthalpy change for the reaction is the same if we go directly from
A to B or indirectly via other reactions and intermediates (Figure 5.12).
Thus, if we know the value for H1 (for the conversion of A to C)
and H2 (for the conversion of C to B) we can work out the value of
the enthalpy change Hr for the conversion of A into B using this cycle.
Hesss law states that the enthalpy change for the direct conversion of
A to B is exactly the same as the enthalpy change for the indirect route
between A and B. Therefore, in this case:

Figure 5.12 An enthalpy cycle.

Extension
This is basically just a question of
vectors:

AB = AC + CB

Hr = H1 + H2
Hr

direct route

H1

in

dir

e ct rou

te

Let us consider a slightly different situation in which the enthalpy changes

we know are:
A C = H1

H2

Figure 5.13 If we know the enthalpy

change for the conversion B C rather than
C B, the arrow between B and C is the
other way around.

This produces a slightly different cycle, in which the arrow for H2 is

the other way around, because the reaction we know is from B to C
(Figure 5.13). Now, the enthalpy change from A to B is given by: Hr =
H1 H2. We have H2 in this case, as the conversion C B on the
indirect route (A C B) goes in the opposite direction to the arrow
we have drawn.
Another possible situation is one in which we know:
C A = H1

Hr

direct route

H1

in

dir

e ct rou

te

H2

Figure 5.14 If we know the enthalpy

change for the conversion C A rather than
A C, the arrow between A and C is the
other way around.

192

B C = H2

C B = H2

This is shown in Figure 5.14. Here the enthalpy change for the direct
route is given by: Hr = H1 + H2. In going from A C B, we go
the wrong way along the H1 arrow (therefore the sign is negative) but
the right way along the H2 arrow (therefore the sign is positive).

Why Hesss law works

The reason Hesss law works can be understood from Figure 5.15.

Enthalpy

enthalpy
change

Figure 5.15 Enthalpy is basically a property of a substance under a certain set

of conditions. This means that the enthalpy depends on the substance and the
conditions. Thus A has a certain amount of enthalpy and B has a certain amount of
enthalpy, and these are xed for a particular set of conditions. The route that is taken
between A and B cannot affect the amount of enthalpy A or B have, and therefore
the difference in enthalpy between A and B is constant.

Extension
Enthalpy is a state function.

Some denitions
Enthalpy changes have different values, depending on the conditions
under which they are measured; therefore, to make them transferable, they
are all quoted for the same set of conditions, which is called standard
conditions. If an enthalpy change is not measured under standard
conditions, its value is corrected to standard conditions. An enthalpy
change under standard conditions is called a standard enthalpy change
and has the symbol H , where the symbol means under standard
conditions.
Standard enthalpy change of reaction (H r ) is the enthalpy
change (heat given out or taken in) when molar amounts of
reactants as shown in the stoichiometric equation react together
under standard conditions to give products.
For example, for the reaction N2(g) + 3H2(g) 2NH3(g), the enthalpy
change of reaction is 92 kJ mol1. This means that 92 kJ of heat energy
are given out when 1 mol N2 reacts with 3 mol N2 to form 2 mol NH3.
If the equation is written as:
1
3
2N2(g) + 2H2(g)

NH3(g)

Standard conditions:
Pressure = 1.01 105 Pa
(1 atmosphere)
Temperature = 298 K (25 C)

Extension
For this course we assume that
standard conditions refers to a
temperature of 298 K. For more
advanced work, the temperature
should always be stated for a standard
enthalpy change. This is often written
as H 298 of H (298 K).

H r = 46 kJ mol1

then the enthalpy change of reaction is for 0.5 mol N2 reacting, and the
enthalpy change is half as much.

Working out enthalpy changes

We are not always able to determine enthalpy changes directly from
experiments and Hesss law can then be used to work out unknown
enthalpy changes from ones that are known.
5 ENERGETICS

193

Worked examples
Given the following enthalpy changes below, calculate the enthalpy change for the reaction:
2CO(g) + O2(g) 2CO2(g)
2C(s) + O2(g) 2CO(g)
C(s) + O2(g) CO2(g)

H = 222 kJ mol1
H = 394 kJ mol1

H1
H2

Reaction 1
Reaction 2

Three methods will be considered for working out the enthalpy change.

Method A (using a cycle)

The enthalpy changes given are used to construct a cycle.
The enthalpy change that we have to find is put at the top
of the cycle.
Only the first reaction has been added here. Reaction 1 is
highlighted in yellow and shows the reaction of 2C and 1 O2
to form 2CO. The other O2, highlighted in orange, remains
unchanged, and there is no enthalpy change for this. This means
that the total enthalpy change along the red arrow is H1.
If Reaction 2 is now added to complete the cycle, it must
be multiplied by 2, as we need to form 2 mol CO2. The
enthalpy change must also be multiplied by 2, hence 2H2:
2C(s) + 2O2(g) 2CO2(g)

2H2

2CO(g) + O2(g)

2CO2(g)

H1
2C(s) + O2(g) + O2(g)
This O2 does
not change

2CO(g) + O2(g)
H1

2CO2(g)
2H2

2C(s) + O2(g) + O2(g)

Reaction 2 is highlighted in green.

The values can now be put into the cycle:
2CO(g) + O2(g)

222 kJ mol1

in

H
direct route

2CO2(g)

te

2 394 kJ mol1

dir

e ct rou

2C(s) + O2(g) + O2(g)

The overall enthalpy change is given by

H = H1 + 2H2
H = (222) + (2 394) = 566 kJ mol1

194

This is worked out from Hesss law: the enthalpy change

for the direct route is the same as that for the indirect
route. As the direction of the indirect route arrow
is opposite to that of the red arrow, the sign of the
quantity on the red arrow is reversed.

Method B (manipulating the equations)

In this method we rearrange the equations for the data given to give the equation for the reaction corresponding
to the enthalpy change we have to find.
First, Reaction 1 is reversed to give 2CO on the left-hand side, as in the overall equation:
2CO(g) 2C(s) + O2(g)

H = +222 kJ mol1

sign changed

Now Reaction 2 is multiplied by 2 to give 2CO2 on the right-hand side, as in the overall equation:
2C(s) + 2O2(g) 2CO2(g)

H = 788 kJ mol1

enthalpy change multiplied by 2

We now have 2CO on the left-hand side and 2CO2 on the right-hand side, as in the overall equations. The two
equations and their enthalpy changes are now added together and common terms cancelled to produce the overall
equation and its enthalpy change:
2CO(g) 2C(s) + O2(g)
2C(s) + 2O2(g) 2CO2(g)
2CO(g) + O2(g) 2CO2(g)

H = +222 kJ mol1
H = 788 kJ mol1
H = 566 kJ mol1

Method C (using an enthalpy level diagram)

2C(s) + O2(g) + O2(g)

indirect route

2CO(g) + O2(g)

H r

2 394 kJ mol 1

222 kJ mol 1

Enthalpy

Figure 5.17 shows an enthalpy level diagram

for this reaction.
The total difference in enthalpy between
the top and bottom on both sides must be the
same, because the diagram starts at a certain
enthalpy level (that of 2C + 2O2) and ends at a
certain level (that of 2CO2).
The total enthalpy difference on the lefthand side is 222 + Hr. The total enthalpy
difference on the right-hand side is 2 394,
i.e. 788 kJ mol1. The difference in enthalpy
on the two sides are equal; therefore
788 = 222 + Hr. Rearranging this we
get Hr = 566 kJ mol1.

2CO2(g)

Figure 5.17 Exothermic processes are shown as downward arrows and

endothermic processes would be shown as upward arrows.

Using this method for working out the enthalpy change from an enthalpy level diagram can sometimes run
into trouble when the arrows of the enthalpy changes do not all go in the same direction on one particular side,
and therefore an alternative method for working out the enthalpy change is generally preferred. This uses the same
approach as for the cycle, where the enthalpy change for the direct route between reactants and products (shown as
H r ) is equated to the enthalpy change for the indirect route.
Thus we can write:
H r = +222 + 2 394 = 566 kJ mol1

The sign of 222 is changed to positive

because the indirect route takes us in the
opposite direction to this arrow.

5 ENERGETICS

195

Use the enthalpy change data given below to work out the enthalpy change for the process:
H2O(l) H2O(g)
2H2(g) + O2(g) 2H2O(l)
2H2(g) + O2(g) 2H2O(g)

H1 = 572 kJ mol1
H2 = 484 kJ mol1

Reaction 1
Reaction 2

Method A (enthalpy cycle)

Each enthalpy change given should be divided by 2, as the enthalpy change for the reaction we have to find just
involves 1 H2O:
H2(g) + 12O2(g) H2O(l)

H3 = 286 kJ mol1

H2(g) + 12O2(g) H2O(g)

H4 = 242 kJ mol1

A cycle can be constructed.

H
direct route

H2O(I)

The enthalpy change for the direct route is the same as that
for the indirect route:
H = H3 + H4
The indirect route goes in the opposite direction to the
H3 arrow, so the sign is negative.

H3

in

dir

e ct rou

te

H2O(g)

H4

H2(g) + 2 O2(g)

Substituting in values we get:

H = (286) + (242) = +44 kJ mol1

Method B (manipulating equations)

Divide each equation by 2 to get 1 H2O in each:
H2(g) + 12O2(g) H2O(l)

H = 286 kJ mol1

H2(g) + 12O2(g) H2O(g)

H = 242 kJ mol1

Equation 1 must be reversed so that H2O(l) is on the left-hand side, as in the overall equation:
H2O(l) H2(g) + 12O2(g)

H = +286 kJ mol1

We now have the correct numbers of H2O on the correct sides and can add the two equations together:
H2O(l) H2(g) + 12O2(g)
H2(g) + 12O2(g) H2O(g)
H2O(l) H2O(g)

H = +286 kJ mol1
H = 242 kJ mol1
H = +44 kJ mol1

Method C (enthalpy level diagram)

Each enthalpy change given should be divided by 2 as the enthalpy change for the reaction we have to find just
involves 1 H2O:

196

H2(g) + 12O2(g) H2O(l)

H3 = 286 kJ mol1

H2(g) + 12O2(g) H2O(g)

H4 = 242 kJ mol1

We can construct an enthalpy level diagram:

H2(g) + 12O2(g)

The enthalpy change for the direct route is

the same as that for the indirect route:
H = H3 + H4
Enthalpy

indirect route

H4

The indirect route goes in the opposite

direction to the H3 arrow, so the sign
is negative.

H2O(g)

H3

Substituting in values we get:

H = (286) + (242) = +44 kJ mol1

H2O(I)

A more complicated enthalpy change calculation can be attempted if we consider the reaction:
C2H4(g) + H2O(g) C2H5OH(l)
Use the following information to work out the enthalpy change for this reaction:
H2O(l) H2O(g)
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)

H1 = +44 kJ mol1
H2 = 1371 kJ mol1
H3 = 1409 kJ mol1

Reaction 1
Reaction 2
Reaction 3

Method A (enthalpy cycle)

The following cycle can be constructed:
H

C2H4(g) + H2O(g) (+3O2(g))

C2H5OH(I) (+3O2(g))

H3
2CO2(g) + 2H2O(I) + H2O(g)

H2

H1

3O2(g) has been added to each

side of the original equation, but
as the same thing has been added
to both sides, this does not affect
the overall enthalpy change.

2CO2(g) + 2H2O(I) + H2O(I)

This cycle shows the individual enthalpy changes involved. All arrows are drawn in the same direction as the
equations given. The values can be substituted into the cycle:
H

C2H4(g) + H2O(g) (+3O2(g))

direct route

C2H5OH(I) (+3O2(g))

1409 kJ mol1
2CO2(g) + 2H2O(I) + H2O(g)
+44 kJ mol1

in

dir

e ct rou

te

1371 kJ mol1

The arrow for the indirect route

goes in the opposite direction
to the arrow for the enthalpy
changes H1 and H2.

2CO2(g) + 2H2O(I) + H2O(I)

5 ENERGETICS

197

The enthalpy change for the direct route is the same as that for the indirect route.
H = 1409 (+44) (1371) = 82 kJ mol1

The cycle could have been simplified by reversing

the enthalpy change H1 and incorporating H1
and H3 into one step, but care must be then taken
with the sign of H1.

Method B (manipulating equations)

Reactions 1 and 2 are reversed to give H2O(g) and C2H5OH on the correct sides:
H1 = 44 kJ mol1
H2 = +1371 kJ mol1

H2O(g) H2O(l)
2CO2(g) + 3H2O(l) C2H5OH(l) + 3O2(g)

All the species are now on the correct sides, as in the overall equation. These equations are now added and
common species cancelled:
H1 = 44 kJ mol1
H2 = +1371 kJ mol1
H3 = 1409 kJ mol1
H = 82 kJ mol1

H2O(g) H2O(l)
2CO2(g) + 3H2O(l) C2H5OH(l) + 3O2(g)
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)
C2H4(g) + H2O(g) C2H5OH(l)

Method C (enthalpy level diagram)

C2H4(g) + H2O(g) (+ 3O2(g))

H2O(g) does not

change in this reaction

indirect route

1409 kJ mol1

Enthalpy

C2H5OH(I) (+ 3O2(g))

1371 kJ mol1

2CO2(g) + 2H2O(I) + H2O(g)

44 kJ mol1
the only change here
is H2O(I) is converted
to H2O(g)

2CO2(g) + 2H2O(I) + H2O(I)

3O2 is added to both sides of the equation, as this is required for the combustion reactions, but this does not
change the enthalpy change that we are calculating, as it is exactly the same on both sides.
Because the arrows on the left-hand side go in opposite directions, it is much easier to work out the enthalpy
change in terms of the direct and indirect route between reactants and products.
H = 1409 44 + 1371 = 82 kJ mol1
The signs of two of the enthalpy changes were
reversed, as the indirect route arrow goes in the
opposite direction to those two arrows.

198

Examiners tip
Only one of these methods needs to be
understood. Find a method that you are
happy with and ignore the others!

Self-test 3

Test yourself
7 a Use the data below to calculate the enthalpy change for the process:
C2H5OH(l) C2H5OH(g)
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
C2H5OH(g) + 3O2(g) 2CO2(g) + 3H2O(l)
b Use the data below to calculate the enthalpy change for the process:
C6H6(l) C6H6(g)
2C6H6(l) + 15O2(g) 12CO2(g) + 6H2O(l)
2C6H6(g) + 15O2(g) 12CO2(g) + 6H2O(l)

H = 1371 kJ mol1
H = 1415 kJ mol1

H = 6544 kJ mol1
H = 6606 kJ mol1

8 a Use the data below to calculate the enthalpy change for the reaction:
BrF(g) + 2F2(g) BrF5(l)
BrF(g) + F2(g) BrF3(l)
BrF3(l) + F2(g) BrF5(l)
b Use the data below to calculate the enthalpy change for the reaction:
ClF3(g) + F2(g) ClF5(g)
Cl2(g) + 3F2(g) 2ClF3(g)
Cl2(g) + 5F2(g) 2ClF5(g)

H = 328 kJ mol1
H = 510 kJ mol1

9 Use the data below to work out an enthalpy change for the reaction:
C2H2(g) + 2H2(g) C2H6(g)
C2H2(g) + 212O2(g) 2CO2(g) + H2O(l)
H2(g) + 12O2(g) H2O(l)
C2H6(g) + 312O2(g) 2CO2(g) + 3H2O(l)

H = 1300 kJ mol1
H = 286 kJ mol1
H = 1560 kJ mol1

5.4 Bond enthalpies

H = 242 kJ mol1
H = 158 kJ mol1

Learning objectives

Enthalpy changes for reactions in the gas phase can be worked out if we
know the amount of energy required/released when bonds are broken/
made. To be able to do this we must first consider the definition of bond
enthalpy (also just called bond energy):

Define average bond enthalpy

Use bond energies to calculate
enthalpy changes

bond enthalpy is the enthalpy change when 1 mole of covalent

bonds, in a gaseous molecule, are broken under standard
conditions.
For example, the HH bond enthalpy is 436 kJ mol1, which can be
represented by the equation:
H2(g) 2H(g)

H = +436 kJ mol1

1 mole of H2 molecules is broken apart to give 2 moles of gaseous

hydrogen atoms.

5 ENERGETICS

199

Examiners tip
HCl(g) 12H2(g) + 12Cl2(g)
does not represent the bond
enthalpy of HCl. 12H2(g)
represents half a mole of H2
molecules and is not the same
as H(g), which is 1 mole of
gaseous H atoms.

The HCl bond enthalpy is 431 kJ mol1, which is represented by:

H = +431 kJ mol1

HCl(g) H(g) + Cl(g)

Bond enthalpies can be calculated only for substances in the

gaseous state.
If we consider the process:
H = +224 kJ mol1

Br2(l) 2Br(g)

This does not represent the bond enthalpy of the BrBr bond, as this
reaction can be broken down into two processes:
The BrBr bond enthalpy is
193 kJ mol1, and the enthalpy
change of vaporisation (for
formation of 1 mol gaseous
molecules) is 31 kJ mol1.

Br2(I)

2 Hat

Hvap
enthalpy change
of vaporisation

2Br(g)

BrBr bond
enthalpy
Br2(g)

H at is the enthalpy change for

formation of 1 mole of gaseous
atoms.

Bond breaking requires energy

(endothermic): H positive.
Bond making releases energy
(exothermic): H negative.

The process Br2(l) 2Br(g) is called atomisation, and energy must

be supplied to break the van der Waals forces between the bromine
molecules as well as to break the BrBr bonds. The enthalpy change for
this process is twice the enthalpy change of atomisation (Hat).
Energy must be supplied to break apart two atoms in a molecule
against the attractive force holding them together. Therefore, the process of
breaking bonds must be endothermic, i.e. the enthalpy change is positive.
Energy is released when two atoms come together to form a bond.
Therefore, the process of making bonds is exothermic, i.e. the enthalpy
change is negative.
Bond enthalpies are defined in terms of breaking bonds and,
therefore, have positive values.
Some average bond enthalpies are shown in Table 5.1.
The bond energies given in tables are average values. For example,
the CH bond energy is slightly different in ethane (C2H6) from that
in benzene (C6H6), so the value quoted in the tables is an average value,
averaged over the values for the CH bond in many compounds. This can
introduce some inaccuracies into calculations involving bond energies.
Bond energy calculations are therefore most accurate when they involve
only breaking/making a few bonds.

200

Bond

Bond
enthalpy
/kJ mol1

Bond Bond
enthalpy
/kJ mol1

Bond Bond
enthalpy
/kJ mol1

Bond Bond
enthalpy
/kJ mol1

HH

436

CH

412

OO

146

CO

360

CC

348

SiH

318

O=O

496

C=O

743
1070

C=C

612

NH

388

SiO

374

C=O

C=C

837

PH

322

FF

158

CN

305

SiSi

226

OH

463

ClCl

242

C=N

613
890

NN

163

SH

338

BrBr

193

C=N

N=N

409

FH

562

II

151

CF

484

N=N

944

ClH

431

NCl

200

CCl

338

PP

172

BrH

366

SiF

590

CBr

276

SS

264

IH

299

NF

278

CI

238

Table 5.1 Average bond enthalpies.

Average bond enthalpy is the average amount of energy

required to break 1 mole of covalent bonds, in a gaseous molecule
under standard conditions. Average refers to the fact that the
bond enthalpy is different in different molecules and therefore the
value quoted is the average amount of energy to break a particular
bond in a range of molecules.

Extension
Why is bond making exothermic?
When two atoms are a long way apart,
the electrical potential energy of the
two together is a maximum (consider
separating the two atoms from where
they are bonded together to where
they are an infinite distance apart
work must be done against the force
holding them together, so the potential
energy increases). As they approach
closer together, owing to the attractive
force between them, the potential
energy decreases and this energy is
released as heat. This can be likened to
a ball falling to Earth as the ball and
the Earth come together, the potential
energy of the system is first of all
converted to kinetic energy and then
to heat as the two collide.

Using bond enthalpies to work out enthalpy

changes for reactions
Example
Consider the reaction between ethene and bromine to produce
1,2-dibromoethane:
C2H4(g) + Br2(g) C2H4Br2(g)
What is the enthalpy change for this reaction?
If the species are drawn as structural formulas, then all the bonds can be
seen clearly:
H

H
C

C + Br Br
H

Br

Br

Bromine and 1,2-dibromoethane

are both liquids under standard
conditions. The equation here is for
the reaction in the gas phase, and
the enthalpy change will not be the
same as for the reaction involving
liquid bromine to form C2H4Br2(l).

5 ENERGETICS

201

This is not how the reaction

occurs, it is just a way of allowing
us to work out the enthalpy change.

We imagine the reaction happening with all the bonds in the reactant
being broken:
H

break
bonds

C + Br Br

Br

H Br

gaseous
atoms

Then new bonds form to make the products:

H
C

Br

H Br

make
bonds

gaseous
atoms

Br

Br

The bond energies can then be added up to work out the enthalpy
change:
Bond broken

Bond energy /
kJ mol1

Number of
bonds

Total energy /
kJ mol1

CH

412

1648

C=C

612

612

BrBr

193

193

Total energy to break all bonds

2453

The total enthalpy change when all the bonds are broken is
+2453 kJ mol1. This is positive, as breaking bonds is an endothermic
process.
Bond made

Bond energy /
kJ mol1

Number of
bonds

Total energy /
kJ mol1

CH

412

1648

CC

348

348

CBr

276

552

Total energy released when bonds made

2548

The total enthalpy change when all the bonds are made is
2548 kJ mol1. This is negative, as making bonds is an exothermic
process.
If we add up these enthalpy changes, we get the overall enthalpy change
for the reaction:
H = 2453 2548 = 95 kJ mol1
The overall process is sometimes summarised as:
Hr = (bonds broken) (bonds made)
202

where the bond energies are taken directly from the bond energies table
and no signs changed, i.e. all values are put in as positive.
This approach would give:
H = [(4 412) + (1 612) + (1 193)] [(4 412) + (1 348) + (2 276)]
A shortcut to do this question would be to realise that there are four
CH bonds in ethene and four CH bonds in 1,2-dibromoethane, and
therefore there is no need to make or break these bonds:
H

H
C

C + Br Br

H
C

Br
Br

Br

Br

If the enthalpy change for

C2H4(g) + Br2(g) C2H4Br2(g)
is calculated using enthalpy changes of formation (see Higher Level
section on page 207), the value obtained is 121 kJ mol1, which is
different from the value of 95 kJ mol1 obtained through bond enthalpy
calculations. The value obtained from the enthalpy changes of formation
is expected to be more reliable, as the enthalpy changes of formation
are specific to the particular substances, whereas the bond enthalpies are
average values. The CH bond energies in C2H4 and C2H4Br2 would not
be expected to be the same, and the values used for the C=C and CC
bonds are not necessarily the actual bond energies in these compounds.

Extension
The hybridisation of the C atom can
significantly affect the CH bond
enthalpy.

Using a cycle in calculations involving bond

enthalpies
Example
Using bond enthalpies given in the table, we can calculate the enthalpy
change for the reaction:
H2(g) + 12O2(g)

H2O(g)

A cycle can be drawn:

HH(g) +

1
2

1
2

O=O(g)

HH bond enthalpy
+
O=O bond enthalpy

H r
direct route

in

dir

e ct rou

te

2H(g) + O(g)

Bond

Bond enthalpy / kJ mol1

HH

436

O=O

496

OH

463

O
H

H(g)

2 OH bond enthalpy

gaseous atoms

A reaction in the gas phase will

be endothermic if less energy is
released when bonds are formed
(exothermic) than is required to
break bonds (endothermic). This
could be the case if stronger/
more bonds are broken than are
formed.

5 ENERGETICS

203

A reaction in the gas phase will

be exothermic if more energy is
released when bonds are formed
(exothermic) than is required to
break bonds (endothermic). This
could be the case if stronger/
more bonds are made than are
broken.

The values can be substituted into the cycle:

O
HH(g) +

1
2

H r

O=O(g)

direct route

436 kJ mol1
+
1
1
2 496 kJ mol

in

dir

e ct rou

H(g)

2 463 kJ mol1

te

2H(g) + O(g)

The enthalpy change for the direct route is the same as that for the
indirect route. The direction of the arrow for the indirect route is opposite
to that of the red arrow, and therefore the sign of this enthalpy change
must be reversed.
H r = (436 + 12 496) (2 463) = 242 kJ mol1
If we wanted to find the enthalpy change for the formation of liquid
water from its elements, i.e. for the process:
H2(g) + 12O2(g) H2O(l)
we would also have to know the enthalpy change of vaporisation of water,
i.e. the enthalpy change for the process:
Hvap = +41 kJ mol1

H2O(l) H2O(g)
This can be incorporated in to the cycle above as:

HH(g) +

1
2

H r
direct route

O=O(g)

HH bond enthalpy
+
1
2 O=O bond enthalpy

in
1

(684 kJ mol )

dir

e ct rou

liquid water
converted to
gaseous water

Hvap
(41 kJ mol1)
O

te

2H(g) + O(g)

H(l)

H(g)

2 OH bond enthalpy
(926 kJ mol1)

The enthalpy change for the reaction is:

H r = 684 926 41 = 283 kJ mol1

Working out a bond enthalpy from an enthalpy

change of reaction
Example
Using the bond enthalpies for the FF and BrBr bonds and the enthalpy
change of reaction given, we can calculate the mean BrF bond energy
in BrF3:
Br2(g) + 3F2(g) 2BrF3(g)
204

H = 545 kJ mol1

This is most easily done using the equation:

Hr = (bonds broken) (bonds made)
545 = [193 + (3 158)] [6 BrF]
Rearranging this we get:
6 BrF = 193 + (3 158) + 545
6 BrF = 1212
Therefore the BrF bond enthalpy is

1212
, i.e. 202 kJ mol1.
6

Using bond enthalpies and enthalpies of

atomisation
In order to use bond enthalpies, the substances must be in the gas
phase. This is because intermolecular forces must also be taken into
account in the liquid and solid states. Thus, in order to use bond enthalpies
with solids and liquids we must first generate gaseous species. This can
either be done as above, using the enthalpy change of vaporisation or,
more directly, using the standard enthalpy change of atomisation.
Standard enthalpy change of atomisation (Hat ) is the
enthalpy change when 1 mole of gaseous atoms is formed from
the element under standard conditions.
For example:
1
2H2(g) H(g)
1
2Cl2(g) Cl(g)

Na(s) Na(g)

H at = +218 kJ mol
H at = +121 kJ mol1
H at = +109 kJ mol1

The use of the enthalpy change of atomisation can most easily be seen
with an example.

Example
We can calculate the enthalpy change for the process:
3C(s) + 4H2(g) C3H8(g)
using the data in the table and the enthalpy change of atomisation of
carbon:
C(s) C(g)

H at = 715 kJ mol

Note: formation of 1 mole of

atoms.
Hat is endothermic
The values for the enthalpy
changes of atomisation of hydrogen
and chlorine are half the bond
enthalpy values in Table 5.1 on
page 201. The bond enthalpy for
Cl2 refers to breaking 1 mole of
covalent bonds to produce 2 moles
of gaseous atoms, whereas the
enthalpy change of atomisation for
chlorine refers to breaking half a
mole of covalent bonds to produce
1 mole of gaseous atoms.

Bond

Bond enthalpy / kJ mol1

CH

412

HH

436

CC

348

5 ENERGETICS

205

A cycle can be used to work out the overall enthalpy change:

H r
direct route

3C(s) + 4H2(g)
3 H at(C(s))
+
4 HH bond enthalpy

in

dir

e ct rou

te

3C(g) + 8H(g)

H(g)

8 CH bond enthalpy
+
2 CC bond enthalpy
gaseous atoms

In the left-hand process, represented by the blue arrow, the enthalpy

change of atomisation is used to convert carbon into gaseous atoms. The
values can be substituted into the cycle:

3C(s) + 4H2(g)
3 715 kJ mol1
+
4 436 kJ mol1

The published value for this

enthalpy change is 104 kJ mol1;
so, in this case, there is fairly good
agreement between data worked
out using bond enthalpies and in
other ways.

H r

direct route

in

dir

e ct rou

te

8 412 kJ mol
+
2 348 kJ mol1

H(g)

3C(g) + 8H(g)

The value of the unknown enthalpy change is given by:

H = ((3 715) + (4 436)) ((8 412) + (2 348))
H = 103 kJ mol1

Self-test 4

Test yourself
10 Use the bond enthalpies in Table 5.1 on
page 201 to work out the enthalpy changes
for the following reactions:
a CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
b C2H2(g) + 2H2(g) C2H6(g)
c CO(g) + Cl2(g) COCl2(g)
11 Calculate the mean ClF bond enthalpy, given
the following data:
Cl2(g) + 3F2(g) 2ClF3(g) H = 164 kJ mol1
and the ClCl and FF bond enthalpies in
Table 5.1 (page 201).
Both ClF3 and ClF5 just contain single bonds
between Cl and F.

206

12 Calculate the mean ClF bond energy, given the

following data:
H = 91 kJ mol1
ClF3(g) + F2(g) ClF5(g)
and the FF bond enthalpy in Table 5.1 (page 201).
13 Work out the enthalpy change for the following
reaction:
S(s) + F2(g) SF2(g)
Enthalpy change of atomisation of
sulfur / kJ mol1

223

SF bond energy / kJ mol1

327

158

FF bond energy / kJ mol

5.5 Calculating enthalpy changes

HL

Some more denitions

Standard enthalpy change of combustion (H c ) is the
enthalpy change when 1 mole of a substance is completely burnt
in oxygen under standard conditions.
The standard enthalpy change of combustion is always negative, as
combustion is always an exothermic process. For example:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

Learning objectives

H c = 890 kJ mol1

Standard enthalpy change of formation (H f ) is the

enthalpy change when 1 mole of the substance is formed from its
elements in their standard states under standard conditions.
The equation that represents the enthalpy change of formation of
methane is:
C(s) + 2H2(g) CH4(g)

Calculate enthalpy changes,

given standard enthalpy changes
of formation or combustion

Examiners tip
Although this section is Higher
Level only, Standard Level
students may also find a study
of the examples useful practice
in solving problems involving
enthalpy changes.

The carbon here is graphite, which

is the most stable form of carbon.

Or, for ammonia, the enthalpy change of formation is for the reaction:
1
3
2N2(g) + 2H2(g)

NH3(g)

which shows the formation of 1 mole of ammonia.

The standard state of nitrogen is N2(g), whereas that of iodine is I2(s).
These are the states in which these substances exist at 25 C and
1 atmosphere pressure.
The standard enthalpy change of formation of any element in its
standard state is zero because, by definition, no heat energy is taken in or
given out when 1 mole of element in its standard state is formed from
1 mole of element in its standard state.
I2(s) I2(s)

H f = 0

The standard enthalpy change of formation may be exothermic or

endothermic, depending on the substance.
In the next sections we will look at how to use given values for
enthalpy changes to work out other enthalpy changes.

Using standard enthalpy change of combustion

data to calculate enthalpy changes

Standard state is the physical state

in which a substance exists under
standard conditions. More precisely,
it is the state in which the pure
substance exists at 1 atm and a
specified temperature (assume
298 K).
H f for any element in its
standard state is zero.
Note: state symbols must always be
included in equations for enthalpy
changes, as the enthalpy change
will be different depending on the
state of a substance. For example,
the standard enthalpy change of
formation of I2(g) is not zero.

Given the following enthalpy changes of combustion, we can work out

the enthalpy change for the reaction:
C2H4(g) + H2(g) C2H6(g)
5 ENERGETICS

207

H c / kJ mol1
C2H4(g)
H2(g)
C2H6(g)

1409
286
1560

HL We are given enthalpy change of combustion data, so we know the

enthalpy changes for the following reactions:

C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)

H c = 1409 kJ mol1

H2(g) + 12O2(g) H2O(l)

H c = 286 kJ mol1

C2H6(g) + 312O2(g) 2CO2(g) + 3H2O(l)

H c = 1560 kJ mol1

Four different methods for doing this type of question will be looked at.
The processes on the left-hand
(blue) arrow are the combustion
of the reactants to form carbon
dioxide and water. The process
on the right-hand (red) arrow is
the combustion of the product to
form exactly the same combustion
products as the reactants. 312O2 is
added to both sides of the original
equation, as oxygen is needed
for the combustion reactions.
However, as the same amount of
oxygen is added to both sides, this
makes no difference to the overall
enthalpy change.

This is worked out from Hesss law:

the enthalpy change for the direct
route is the same as that for the
indirect route. As the direction of
the indirect route arrow is opposite
to that of the red arrow, the sign
of the quantity on the red arrow is
reversed.

Method 1
An enthalpy cycle can be constructed:
C2H4(g) + H2(g) (+ 3 12 O2(g))

H r
direct route

C2H6(g) (+ 3 12 O2(g))

Hc [C2H4(g)]
in
+
te
dir
e ct rou
Hc [H2(g)]

Hc [C2H6(g)]

2CO2(g) + 3H2O(I)

Hc[C2H4(g)] + Hc[H2(g)] = 1409 286 = 1695 kJ mol1

The values can be substituted into the cycle:
C2H4(g) + H2(g) (+ 3 12 O2(g))

1695 kJ mol1

H r
direct route

in

dir

e ct rou

te

C2H6(g) (+ 3 12 O2(g))

1560 kJ mol1

2CO2(g) + 3H2O(I)

H r = 1695 (1560) = 135 kJ mol1

The standard enthalpy change for this reaction is 135 kJ mol1.
Note: at no point is any carbon dioxide or water formed in this
reaction. The cycle represents a way of working out the enthalpy
change it does not indicate how the reaction actually occurred.

Method 2
The reaction(s) for the combustion
of the product(s) is/are always
reversed.

208

The equations given above must be rearranged to give the overall

equations related to the enthalpy change we are trying to find. In order to
do this, the third enthalpy change is reversed, so that C2H6 appears on the
right-hand side, as in the overall reaction.
Substances that are the same on both sides are cancelled out, and that
leaves the overall equation. The enthalpy changes are simply added up to
give the enthalpy change of reaction.

C2H4(g) + 3O2(g)
1

H2(g) + 2 O2(g)

H c = 1409 kJ mol1

H2O(I)

H c = 286 kJ mol1

HL

C2H6(g) + 3 2 O2(g) H c = +1560 kJ mol1

2CO2(g) + 3H2O(I)
C2H4(g) + H2(g)

2CO2(g) + 2H2O(I)

H r = 135 kJ mol1

C2H6(g)

Let us look at this technique in more detail:

2CO2(g) cancelled
on each side

3 12 O2(g) cancelled
on each side

2CO2(g) + 2H2O(I) H c = 1409 kJ mol1

C2H4(g) + 3O2(g)
1

H2(g) + 2 O2(g)

H c = 286 kJ mol1

H2O(I)
1

2CO2(g) + 3H2O(I)

C2H6(g) + 3 2 O2(g) H c = +1560 kJ mol1

C2H4(g) + H2(g)

C2H6(g)

H r = 135 kJ mol1

3H2O(I) cancelled from

each side

sign changed
add these up
to get the overall
enthalpy change

Method 3
In this method we will use an enthalpy level diagram to calculate the
enthalpy change:

Hr

Hc [C2H4(g)]

C2H6(g)

Hc [H2(g)]

+ 12 O2(g)

2CO2(g) + 2H2O(I) + H2(g)

+ 312 O2(g)

+3O2(g)

Enthalpy

C2H4(g) + H2(g)

Hc [C2H6(g)]

2CO2(g) + 3H2O(I)

A downward arrow in the diagram represents an exothermic process

and an upward arrow represents an endothermic process.

5 ENERGETICS

209

The values can be substituted into the diagram:

HL

Hr

286 kJ mol1

+ 12 O2(g)

2CO2(g) + 2H2O(I) + H2(g)

C2H6(g)

+ 312 O2(g)

1409 kJ mol1

indirect route

Enthalpy

+3O2(g)

C2H4(g) + H2(g)

1560 kJ mol1

2CO2(g) + 3H2O(I)

Because the arrows on individual

sides all go in the same direction,
we could have also equated the total
enthalpy change on the left-hand
side to that on the right-hand side.

The enthalpy change for the direct route (marked as H r ) is equal to

that for the indirect route. We can therefore write:
H r = 1409 286 + 1560
The sign of the enthalpy change marked in blue is reversed, as the indirect
route goes in the opposite direction to this arrow.
Therefore:
H r = 135 kJ mol1

means sum of

Method 4
The last method uses an equation:

Examiners tip
You only need to use one of
the methods to solve problems.
Find a method that you are
happy with and use that in
each case.

Hr = Hc(reactants) Hc(products)
So:
Hr = [1409 + (286)] [1560] = 1695 + 1560
Hr = 135 kJ mol1

Worked example
Given the following enthalpy changes of combustion, work out the enthalpy change of formation
of benzoic acid (C6H5COOH(s)).
H c / kJ mol1
C(s)

394

H2(g)

286

C6H5COOH(s)

3227

The equation for the enthalpy change of formation is:

7C(s) + 3H2(g) + O2(g) C6H5COOH(s)

210

Enthalpy change of formation:

formation of 1 mole of substance
from its constituent elements in
their standard states.

As in the previous example, the data that we have been given are enthalpy changes of combustion,
so the methods used will be the same as above.

Method 1 (cycle)
The information given is:
C(s) + O2(g) CO2(g)

H c = 394 kJ mol1

H2(g) + 12O2(g) H2O(l)

H c = 286 kJ mol1

C6H5COOH(s) + 712O2(g) 7CO2(g) + 3H2O(l)

H c = 3227 kJ mol1

This can be used to construct an enthalpy cycle. The quantity we need to find is written along the top,
and the arrows from both sides go down to the combustion products:
Hf

7C(s) + 3H2(g) + O2(g) + 7 2 O2(g)

C6H5COOH(s) + 7 2 O2(g)

direct route

7Hc [C(s)]
+

in

3Hc [H2(g)]

dir

e ct rou

te

Hc [C6H5COOH(s)]

7CO2(g) + 3H2O(I)

The enthalpy change of combustion of C must be multiplied by 7, as there are 7 moles of C on the
left-hand side of the equation. Similarly, the enthalpy change of combustion of H2 is multiplied by 3.
Total enthalpy change for combustion of reactants:
(7 394) + (3 286) = 3616 kJ mol

The values can be put into the cycle:

Hf

7C(s) + 3H2(g) + O2(g) + 7 2 O2(g)

3616 kJ mol1

direct route

in

dir

e ct rou

There is no enthalpy change of combustion for oxygen,

as oxygen does not burn in oxygen! The O2 on the lefthand side is incorporated into the CO2 and H2O of the
combustion products.

te

C6H5COOH(s) + 7 2 O2(g)

3227 kJ mol1

The indirect route goes in the

opposite direction to the red arrow,
therefore the sign of this enthalpy
change is reversed.

7CO2(g) + 3H2O(I)

The enthalpy change for the direct route is equal to the enthalpy change for the indirect route:
H f = 3616 (3227)
Therefore the standard enthalpy change of formation of benzoic acid is 389 kJ mol1.

Method 2 (manipulating equations)

C(s) + O2(g) CO2(g)
H2(g) + 12O2(g) H2O(l)
C6H5COOH(s) + 712O2(g) 7CO2(g) + 3H2O(l)

H c = 394 kJ mol1
H c = 286 kJ mol1
H c = 3227 kJ mol1

Equation 1
Equation 2
Equation 3

5 ENERGETICS

211

These equations have to be rearranged to give the overall equation:

7C(s) + 3H2(g) + O2(g) C6H5COOH(s)
Equation 1 must be multiplied by 7 to give 7C(s), and Equation 2 must be multiplied by 3 to give 3H2(g).
The enthalpy changes are then also multiplied by these numbers:
H = 2758 kJ mol1
H = 858 kJ mol1

7C(s) + 7O2(g) 7CO2(g)

3H2(g) + 112O2(g) 3H2O(l)

Equation 3 must then be reversed so that C6H5COOH(s) is on the products side, as in the overall equation:
7CO2(g) + 3H2O(l) C6H5COOH(s) + 712O2(g)

H = +3227 kJ mol1

The sign of the enthalpy change for Equation 3 has changed, as the enthalpy change is now for the reverse
reaction.
The equations are now added together and terms that are the same on both sides are cancelled, which should
produce the overall equation for the enthalpy change we are trying to find:
7C(s) + 7O2(g) 7CO2(g)
3H2(g) + 112O2(g) 3H2O(l)
7CO2(g) + 3H2O(l) C6H5COOH(s) + 712O2(g)
7C(s) + 3H2(g) + O2(g) C6H5COOH(s)

H
H
H
H

= 2758 kJ mol1
= 858 kJ mol1
= +3227 kJ mol1
= 389 kJ mol1

Note: only 712O2(g) out of the 812O2(g) are cancelled from the left-hand side,
as there are only 712O2(g) on the right-hand side.
Therefore the standard enthalpy change of formation of C6H5COOH(s) is 389 kJ mol1.

Method 3 (enthalpy level diagram)

In the enthalpy level diagram showing the overall process and the enthalpy changes of combustion, we have
assumed that the enthalpy change of formation of CH3COOH(s) is exothermic and have drawn the arrow
downwards. We have no real way of knowing this before doing the calculations, but it doesnt matter if we have
drawn it the wrong way round, as it will still work out correctly in the calculation.

Hf

7Hc [C(s)]

+7 2 O2(g)

C6H5COOH(s)

3Hc [H2(g)]

7CO2(g) + 3H2(g)
+112 O2(g)

+6O2(g)

Enthalpy

7C(s) + 3H2(g) + O2(g)

7CO2(g) + 3H2O(I)

212

Hc [C6H5COOH(s)]

The values for the enthalpy changes

are put in:

Hf

+1 12 O2(g)

7CO2(g) + 3H2(g)

C6H5COOH(s)

+7 2 O2(g)

7 394 kJ mol1

indirect route

+6O2(g)

Enthalpy

7C(s) + 3H2(g) + O2(g)

3227 kJ mol1

3 286 kJ mol1

7CO2(g) + 3H2O(I)

The enthalpy change for the direct route is equated to that for the indirect route:
H f = (7 394) + (3 286) + 3227
The sign of the enthalpy change marked in red in the diagram is reversed, as the indirect route goes
in the opposite direction to this arrow.
H f = 389 kJ mol1

Method 4 (equation)
Hr = Hc(reactants) Hc(products)
H c / kJ mol1

So:

C(s)

394

H f = [(7 394) + (3 286)] [3227] = 3616 + 3227

H2(g)

286

H f = 389 kJ mol1

C6H5COOH(s)

3227

Using enthalpy change of formation data to

calculate other enthalpy changes
We will use similar methods to before, but there are some changes, as
we have different data (enthalpy change of formation instead of enthalpy
change of combustion). The technique we use is determined by the data
we are given (not what we are trying to find).
Given the enthalpy changes of formation in the table, calculate the
standard enthalpy change for the reaction:
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)

Method 5
We will set up an enthalpy change cycle. The equations of the reactions
for which we know the enthalpy changes are:
2Fe(s) + 32O2(g) Fe2O3(s)

H f = 822 kJ mol1

C(s) + 12O2(g) CO(g)

H f = 111 kJ mol1

C(s) + O2(g) CO2(g)

H f = 394 kJ mol1

H f / kJ mol1
Fe2O3(s)

822

CO(g)

111

CO2(g)

394

Enthalpy change of formation:

formation of 1 mole of substance
from its constituent elements in
their standard states.

5 ENERGETICS

213

This reaction is important in the

extraction of iron from its ore.

HL These can be used to construct a cycle, in which the equation for the

reaction of the enthalpy change we want to find is along the top and the
enthalpy changes we know are from the elements to the substances in this
equation:
H r

Fe2O3(s) + 3CO(g)

2Fe(s) + 3CO2(g)

direct route

Hf [Fe2O3(s)]
+
3Hf [CO(g)]

in

dir

e ct rou

te

3Hf [CO2(g)]

2Fe(s) + 3C(s) + 3O2(g)

Arrows go up from elements.

elements in their
standard states

The total enthalpy change for the formation of the reactants (Fe2O3(s) and
3CO(g)) from their elements is:
H f [Fe2O3(s)] + 3H f [CO(g)] = 822 + 3 (111) = 1155 kJ mol1
The standard enthalpy change of
formation of Fe(s) is 0, as it is an
element in its standard state.

The total enthalpy change for the formation of the products (2Fe(s) and
3CO2(g)) from their elements is:
2H f [Fe(s)] + 3H f [CO2(g)] = 0 + 3 (394) = 1182 kJ mol1
These values can be added to the cycle:
H r

Fe2O3(s) + 3CO(g)

2Fe(s) + 3CO2(g)

direct route

in

1155 kJ mol1

dir

e ct rou

te

1182 kJ mol1

2Fe(s) + 3C(s) + 3O2(g)

The enthalpy change for the direct route is the same as the enthalpy
change for the indirect route. The indirect route goes in the opposite
direction to the blue arrow and therefore the sign of this enthalpy change
is reversed:
H r = (1155) + (1182) = 27 kJ mol1
Therefore the enthalpy change of reaction is 27 kJ mol1.

Method 6
In this method, the equations are rearranged to give the equation for the
reaction corresponding to the enthalpy change we have to find.
The equations for the reactions we have been given are:

214

2Fe(s) + 32O2(g) Fe2O3(s)

H f = 822 kJ mol1

Equation 1

C(s) + 12O2(g) CO(g)

H f = 111 kJ mol1

Equation 2

C(s) + O2(g) CO2(g)

H f = 394 kJ mol1

Equation 3

The equation for the reaction we have to find is:

HL

Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)

Equations 1 and 2 must be reversed to give Fe2O3 and CO on the lefthand (reactants) side:
Fe2O3(s) 2Fe(s) + 32O2(g)
CO(g)

H = +822 kJ mol1

C(s) + 12O2(g)

Note sign change.

H = +111 kJ mol

Equations 2 and 3 must be multiplied by 3 to give 3CO and 3CO2,

respectively:
3CO(g) 3C(s) + 32O2(g)

H = +333 kJ mol1

3C(s) + 3O2(g) 3CO2(g)

H = 1182 kJ mol1

The correct reactants and products are now on each side. The equations
are added together and species that are the same are cancelled from each
side:
Fe2O3(s) 2Fe(s) + 32O2(g)
3CO(g) 3C(s) + 32O2(g)
3C(s) + 3O2(g) 3CO2(g)
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)

H
H
H
H

= +822 kJ mol1
= +333 kJ mol1
= 1182 kJ mol1
= 27 kJ mol1

As the equations are multiplied by

3, the enthalpy changes must also
be multiplied by 3.

The equations involving the

formation of the reactants are
always the ones that are reversed
when enthalpy changes of
formation have been given.

Therefore the enthalpy change of reaction is 27 kJ mol1.

Method 7
In this method we will draw an enthalpy level diagram:
2Fe(s) + 3C(s) + 3O2(s) elements

Enthalpy

Hf [Fe2O3(s)]
3Hf [CO2(g)]

Fe2O3(s) + 3C(s) + 2 O2(g)

3Hf [CO(g)]
Fe2O3(s) + 3CO(g)
Hr
2Fe(s) + 3CO2(g)

5 ENERGETICS

215

HL The values can then be substituted into the diagram:

2Fe(s) + 3C(s) + 3O2(g)

3 394 kJ mol1

indirect route

Enthalpy

822 kJ mol1

Fe2O3(s) + 3C(s) + 2 O2(g)

3 111 kJ mol1
Fe2O3(s) + 3CO(g)
Hr

2Fe(s) + 3CO2(g)

The enthalpy change for the direct route is equated to that for the indirect
route:
The signs of two of the enthalpy
changes are reversed, as the
direction of the indirect route
arrow goes in the opposite
direction to these two arrows.

H r = (3 111) (822) + (3 394)

H r = +333 + 822 1182
H r = 27 kJ mol1

Method 8
In this method we use an equation. In this case, where we have been
given standard enthalpy changes of formation, the equation is:
H f / kJ mol1
Fe2O3(s)

822

CO(g)

111

CO2(g)

394

Hr = Hf(products) Hf(reactants)
Therefore, in this case, for the equation:
Fe2O3(s) + 3CO(g) 2Fe(s) + 3CO2(g)
H r = [(2 0) + (3 394)] [(822) + (3 111)]
H r = (1182) (1155)
Therefore the enthalpy change of reaction is 27 kJ mol1.

Determining an enthalpy change of formation

from an enthalpy change of reaction
If we are given an enthalpy change of reaction and some enthalpy changes of
formation it is possible to work out a missing enthalpy change of formation.

Example
Given that the standard enthalpy change of formation of ethane (C2H6(g))
is 85 kJ mol1, and given the equation below, work out the enthalpy
change of formation of ethyne (C2H2(g)).
C2H2(g) + 2H2(g) C2H6(g)
216

H = 311 kJ mol1

This is probably most easily done by using the equation from method 8
above (although the other methods could be used instead):

HL

H r = H f (products) H f (reactants)
311 = 85 [H f (C2H2(g)) + 2 0]
Rearranging the equation gives:
H f (C2H2(g)) = 85 + 311
Therefore the standard enthalpy change of formation of ethyne is
+226 kJ mol1.

Which method to choose

We have looked at eight different methods for working out enthalpy
changes. Methods 1, 2, 3 and 4 are entirely equivalent, and when enthalpy
change of combustion data are given, any of these four methods may be
used. Similarly, when enthalpy change of formation data are given, any
one of methods 5, 6, 7 and 8 may be used. The key point is, however,
to choose a method based on the data that are given and not on
what has to be found. For instance, if you are asked to determine an
enthalpy change of combustion and have been given enthalpy change of
formation data, then you would choose one of methods 5, 6, 7 and 8, as
these are the methods to use when enthalpy change of formation data has
been given.
If you look closely at the methods above, method 1 is very similar to
method 5, and method 2 is basically the same as method 6, etc. Once you
have understood the basic principles of the methods, there is no need for
any artificial distinctions between them.
Self-test 5

Test yourself
14 Write equations for the enthalpy change of
formation of the following:
a HF(g)
b CH3Cl(g)
c H2O(l)
d C5H11OH(l)
15 Calculate the enthalpy change for the following
reaction, given the data in the table:
C4H8(g) + H2(g) C4H10(g)

16 Calculate the enthalpy change of formation of

propanone (CH3COCH3(l)), given the following
data:
H c / kJ mol1
CH3COCH3(l)

1817

C(s)

394

H2(g)

286

H c / kJ mol1
C4H8(g)

2717

C4H10(g)

2877

H2(g)

286

5 ENERGETICS

217

17 Calculate the enthalpy change for the following

reaction, given the enthalpy changes of
formation in the table:
S2Cl2(l) + Cl2(g) 2SCl2(g)
1

SCl2(g)

427
19.7

SF4(g)

775

S2Cl2(l)

59.4

BF3(g)

1137

SCl2(g)

19.7

Learning objectives

BCl3(l)

H f / kJ mol

18 Calculate the enthalpy change for the following

reaction, given the enthalpy changes of
formation in the table:
4BCl3(l) + 3SF4(g)
4BF3(g) + 3SCl2(g) + 3Cl2(g)

H f / kJ mol1

Understand how to draw a

BornHaber cycle
Understand the factors that
affect the value of lattice
enthalpy

All ionisation energies are

endothermic
The (g) symbol is essential in these
equations.

HL

19 Calculate the enthalpy change of formation of

NO2(g) from the following data:
2Pb(NO3)2(s) 4NO2(g) + 2PbO(s) + O2(g)
H = +602 kJ mol1
H f / kJ mol1
Pb(NO3)2(s)

452

PbO(s)

217

5.6 Enthalpy changes for ionic

compounds
So far the energy cycles we have drawn have been for covalent substances. In
this section we will consider an enthalpy level diagram for ionic substances.
Before we look at this diagram we must consider some definitions.
First ionisation energy is the enthalpy change when one
electron is removed from each atom in 1 mole of gaseous atoms
under standard conditions:
M(g) M+(g) + e
Second ionisation energy is the enthalpy change for the
process:
M+(g) M2+(g) + e

The first electron affinity is

exothermic for virtually all
elements; it is a favourable process
to bring an electron from infinity
to where it feels the attractive force
of the nucleus in an atom.

218

First electron affinity is the enthalpy change when one electron

is added to each atom in 1 mole of gaseous atoms under standard
conditions:
X(g) + e X(g)

Second electron affinity is enthalpy change for the process:

X(g) + e X2(g)
Lattice enthalpy (Hlatt) is the enthalpy change when 1 mole
of an ionic compound is broken apart into its constituent gaseous
ions under standard conditions.
For example, for NaCl:
NaCl(s) Na+(g) + Cl(g)

H latt = +771 kJ mol1

Note, for ammonium nitrate the equation is:

NH4NO3(s) NH4+(g) + NO3(g)

BornHaber cycles
A BornHaber cycle is an enthalpy level diagram breaking down the
formation of an ionic compound into a series of simpler steps. For
example, for sodium chloride, we will show the stages in construction of
the cycle. The first step we put in is the equation for the enthalpy change
of formation:

The second electron affinity is

always endothermic. It is an
unfavourable process to add
an electron to an ion which is
already negatively charged, due to
repulsion between the negative
charges.
Look carefully to determine
whether lattice enthalpy is
exothermic or endothermic, as it
can be defined in either direction,
i.e. as the making or breaking of
the lattice. Here it is defined as the
breaking of the lattice and is an
endothermic process: energy must
be supplied to separate the ions
against the attractive forces holding
them in the lattice.

The enthalpy change of formation

for NaCl(s) is exothermic, and the
arrow is shown in the downward,
negative, direction.

Na(s) + 2 CI2(g)
Enthalpy

HL

Hf
NaCI(s)

The cycle gives us an alternative route between the elements (Na(s) +

and the ionic compound (NaCl(s)). NaCl(s) can be broken apart
into its constituent gaseous ions this is the lattice enthalpy:
1
2Cl2(g))

Enthalpy

Na+(g) + CI (g)

The BornHaber cycle was

developed by two Nobel-prizewinning German scientists: Fritz
Haber (18681934) and Max
Born (18821970). Max Born
was the grandfather of the singer
Olivia Newton-John, star of the
film Grease.

Hlatt

Na(s) + 2 CI2(g)

The arrow for Hlatt goes upwards,

indicating an endothermic process.

Hf
NaCI(s)

This step gives us an idea of what we are aiming at so, to complete the
cycle, Na(s) and 12Cl2(g) must be converted into gaseous ions.

5 ENERGETICS

219

The Na(s) is first converted into Na+(g) in two steps:

HL

Na+(g) + CI (g)

Enthalpy

Na(g) + 2 CI2(g)
Hat(Na)

Hlatt

Na(s) + 2 CI2(g)
Hf
NaCI(s)

The sodium must be converted to gaseous atoms before it can be

ionised, as the definition of ionisation energy is removal of an electron
from a gaseous atom.
electron removed
from Na
1

Na+(g) + e + 2 CI2(g)
_

Enthalpy

1st ionisation
energy of Na

Na+(g) + CI (g)

Na(g) + 2 CI2(g)
Hat(Na)

Hlatt

Na(s) + 2 CI2(g)
Hf

NaCI(s)

The sodium has been converted into the required species (Na+(g)), and
now we must do the same with the chlorine. The first stage is atomisation
of chlorine:
Na+(g) + e + CI(g)
1

Na+(g) + e + 2CI2(g)

Hat(CI2)

Enthalpy

1st ionisation
energy of Na

Na+(g) + CI (g)

Na(g) + 2 CI2(g)
Hat(Na)

Hlatt

Na(s) + 2 CI2(g)
Hf

NaCI(s)

220

standard enthalpy change of atomisation

is for formation of 1 mole of atoms

The cycle can now be connected and completed by adding the electron HL
removed from the sodium atom to the chlorine atom (Figure 5.18). This
process is the first electron affinity of chlorine and is exothermic, therefore
the arrow goes downwards.
Na+(g) + e + CI(g)

Na+(g) + e + 12 CI2(g)

Hat (CI2 )

1st electron affinity

of CI

Enthalpy

1st ionisation
energy of Na

Na+(g) + CI(g)

Na(g) +12 CI2(g)

Hat (Na)

Hlatt

Na(s) +12 CI2(g)

Hf

NaCI(s)

Figure 5.18 The BornHaber cycle for NaCl. Upward arrows represent endothermic
processes, whereas downward arrows represent exothermic processes.

If all the quantities in the cycle except one are known, then application
of Hesss law allows the last quantity to be worked out. For example, let us
calculate the lattice enthalpy of sodium chloride.
The values can be put into the diagram:
Na+(g) + e + CI(g)
1

Na+(g) + e + 2 CI2(g)

121 kJ mol1

109 kJ mol1

Hat (Cl2(g))

121 kJ mol1

rst ionisation energy

(Na)

494 kJ mol1

rst electron afnity (Cl)

364 kJ mol1

Hf (NaCl(s))

411 kJ mol1

364 kJ mol1
_

Na+(g) + CI (g)

494 kJ mol1
Enthalpy

Hat (Na(s))

Na(g) + 2 CI2(g)
109 kJ mol1

Na(s) + 2 CI2(g)

Hlatt

411 kJ mol1

NaCI(s)

5 ENERGETICS

221

HL

Hesss law is used. The enthalpy change for the direct route is the same
as that for the indirect route.
Na+(g) + e + CI(g)
121 kJ mol1

364 kJ mol1

Na+(g) + e + 2 CI2(g)

Na+(g) + CI (g)

Enthalpy

494 kJ mol1

Na(s) + 2 CI2(g)

direct route

109 kJ mol1

indirect route

Na(g) + 2 CI2(g)
Hlatt

411 kJ mol1

NaCI(s)

The sign of 411 was reversed as

the direction of the indirect route
arrow goes against the direction of
this arrow.

Therefore:
H latt = 411 + 109 + 494 + 121 364
H latt = 771 kJ mol1

Worked example
Draw a BornHaber cycle for magnesium oxide and use it to work out the second electron affinity of oxygen.
Enthalpy term

222

Enthalpy change / kJ mol1

H at [Mg(s)]

150

H at [O2(g)]

248

rst ionisation energy (Mg)

736

second ionisation energy (Mg)

1450

rst electron afnity (O)

142

H f (MgO)

602

H latt (MgO)

3889

The Born Haber cycle is shown in

Figure 5.18.

Mg2+(g) + O2(g)

2nd electron affinity

of O
Mg2+(g) + O(g) + 2e

Enthalpy

Hat (O2)
Mg2+(g) + 12O2(g) + 2e
2nd ionisation
energy of Mg

1st electron affinity

of O
Mg2+(g) + O(g) + e

Mg+(g) + 12O2(g) + e

Hlatt

1st ionisation
energy of Mg
Mg(g) + 12 O2(g)
Hat (Mg)
Mg(s) + 12 O2(g)
Hf [MgO(s) ]

MgO(s)

Figure 5.18 A BornHaber cycle for MgO. The rst electron afnity for O(g) is
negative, but the second electron afnity is positive.

The second electron affinity of O is

worked out most easily by applying
Hesss law and looking at the
enthalpy change for the direct route
and the indirect route (Figure 5.19).
Mg2+(g) + O(g) + 2e

1450 kJ

142 kJ mol1
Mg2+(g) + O(g) + e
3889 kJ mol1

248 kJ mol1
Mg2+(g) + 12O2(g) + 2e

direct route

2nd electron affinity

of O

Enthalpy

The signs of the enthalpy changes

highlighted in Figure 5.19 are
reversed, as the direction of the
indirect route was in the opposite
direction to the arrows on the
diagram. The enthalpy change
for the direct route is the same as
that for the indirect route: second
electron affinity of O = 142 248
1450 736 150 602 + 3889
= 845 kJ mol1.

Mg2+(g) + O2(g)

mol1

Mg+(g) + 12O2(g) + e
736 kJ mol1
Mg(g) + 12O2(g)
150 kJ mol1
Mg(s) + 12O2(g)
602 kJ mol1

i n d i re c t r o u t e
MgO(s)

Figure 5.19 The BornHaber cycle for MgO, showing the enthalpy changes for
which the sign must be changed to work out the second electron afnity of oxygen.

5 ENERGETICS

223

HL

Magnesium chloride
The BornHaber cycle for MgCl2 is shown in Figure 5.20.
Mg2+(g) + 2CI(g) + 2e
2 Hat (CI2)

2 1st electron affinity

of CI
Mg2+(g) + 2CI(g)

Mg2+(g) + CI2(g) + 2e
2nd ionisation
energy of Mg

Enthalpy

Mg+(g) + CI2(g) + e
1st ionisation
energy of Mg
Mg(g) + CI2(g)

Hlatt

Hat (Mg)
Mg(s) + CI2(g)
Hf [MgCI2(s) ]

MgCI2(s)

Figure 5.20 A BornHaber cycle for MgCl2.

The only difference here from the other BornHaber cycles considered
above is that the enthalpy change of atomisation and the electron affinity
of chlorine are both multiplied by 2. Remember that the definition of
the enthalpy change of atomisation refers to the formation of 1 mole of
gaseous atoms and not the breaking of 1 mole of covalent bonds.

Comparison of lattice enthalpies

Some lattice enthalpies are shown in Table 5.2.
Substance

NaCl

MgCl2

MgO

lattice enthalpy / kJ mol

+771

+2526

+3791

charges on ions

1+

radius of metal ion / pm

95

65

65

Substance

CsCl

BaCl2

BaO

lattice enthalpy / kJ mol1

+645

+2056

+3054

charges on ions

1+

radius of metal ion / pm

169

2+

2+
135

2+

2+

135

Table 5.2 Some lattice enthalpies.

The electrostatic attraction

between ions depends on the
charge on the ions and the size
of the ions (ionic radii).
224

Lattice enthalpy is the result of electrostatic attractions between

oppositely charged ions in the giant lattice. The greater the electrostatic
attraction between the ions, the more energy has to be supplied to break
apart the lattice.

The effect of charge

HL

MgCl2 has a higher lattice enthalpy than NaCl (Figure 5.21).

The higher the charge on the ions, the more strongly they will
attract each other and therefore the greater the lattice enthalpy.
The force between ions is proportional to the product of the charges, so
the force of attraction increases along the series:

2+

2+

2+

2+

greater
electrostatic
attraction

Figure 5.21 NaCl contains 1+ and 1 ions,

whereas MgCl2 contains 2+ and 1 ions.

1+/1 < 1+/2 < 2+/2

The effect of size

CsCl has a smaller lattice enthalpy than NaCl.
Ions act like point charges, i.e. a positive ion such as Na+ behaves as if
its ionic charge all acts at its centre and a negative ion such as Cl behaves
as if a 1 charge exists at its centre.The greater the ionic radii, the greater
the distance between the centres of the ions and, therefore, the smaller the
attraction between the ions and the smaller the lattice enthalpy (Figure 5.22).

+
+

Lattice enthalpy is larger for

smaller ions.

smaller
electrostatic
attraction
larger
distance

Figure 5.22 Smaller ions have a greater attraction between them.

Thus we can see that MgCl2 has a larger lattice enthalpy than NaCl,
not just because the Mg2+ ion has a higher charge than the Na+ ion, but
also because the Mg2+ ion is smaller.

Examiners tip
The greatest lattice enthalpy
is obtained for small, highly
charged ions. When comparing
different compounds, the
effect of charge causes a larger
change in lattice enthalpy than
do size variations.

Worked example
Arrange the following compounds in order of increasing lattice enthalpy:
BaCl2

LiF

ZnS

The most important factor in determining the lattice enthalpy is the charge on the ions. ZnS contains 2+ and 2
ions, BaCl2 contains 2+ and 1 ions and LiF contains 1+ and 1 ions. The order of increasing lattice enthalpy is thus:
LiF < BaCl2 < ZnS
The attraction between 2+/2 ions in ZnS is greater than that between 2+/1 ions in BaCl2, which is greater
than between 1+/1 ions in LiF.
Because the melting point of an ionic substance depends on the force
of attraction between ions, a substance with a high lattice enthalpy would
also be expected to have a high melting point (Table 5.3).
5 ENERGETICS

225

HL

Substance

Lattice enthalpy / kJ mol1

Melting point / C

NaCl

+771

801

MgO

+3791

2852

KCl

+711

770

CaO

+3401

2614

CsCl

+645

645

BaO

+3054

1918

Table 5.3 The lattice enthalpies and melting points of some substances.

Comparison of theoretical and experimental

lattice enthalpy values

Extension
Equations that can be used to do this
are the BornLand, BornMayer
and Kapustinskii equations. These are
complicated and involve terms for the
structure and the size of the ions and
their charge, as well as other terms.

Assuming a totally ionic model in which the bonding is solely due to

the attraction between oppositely charged ions, a theoretical value for
the lattice enthalpy can be calculated using various equations.
The BornHaber cycle gives us an experimental value for the lattice
enthalpy, and by comparing the theoretical and experimental values we
can get an idea of how ionic the bonding in a particular compound is.
If the values are exactly the same, that would suggest complete ionic
bonding; however, if there is a significant difference between the values,
then it suggests that the bonding has a significant degree of covalency.
For instance, for NaCl:
Theoretical value / kJ mol1

This close agreement between the

two values indicates a very high
degree of ionic character in NaCl.

766

736

purely ionic

226

2+

polarisation of
ion = covalent
character

771

If the theoretical and experimental values for silver iodide are

compared, it can be seen that there is a much larger difference between
the two values, and this indicates a larger degree of covalent character
in the bonding. In this case, a purely ionic model for the bonding is not
entirely appropriate.
Theoretical value / kJ mol1

2+

Experimental value / kJ mol1

Experimental value / kJ mol1

876

Covalent character in the bonding can result from polarisation of the

negative ion by the positive one. A small highly charged cation such
as Mg2+ is able to polarise neighbouring negative ions. This effect is
especially large if the anion is large, such as I.
Consider MgI2: the Mg2+ ion polarises the I ion, i.e. pulls electron
density away from it. There is now shared electron density between the
two nuclei (some covalent character in the bonding). The difference
between the experimental and theoretical lattice enthalpies for MgI2 is
almost 400 kJ mol1, and the bonding includes a significant contribution
from covalent bonding.

This is an example of using a mathematical

model to describe a scientific system.
A mathematical equation/system of
equations is developed to approximate as closely as
possible the behaviour or properties of a real system.
The BornLand, BornMayer and Kapustinskii
equations represent equations with different levels of
sophistication, taking different factors into account to
predict values for lattice energies.

Scientists use mathematical modelling to try to

predict the possible effects of climate change. A model
is developed, tested against climate data from the
past and, if there is good agreement, used to make
predictions about what may happen in the future.
Does complete agreement of theoretical values from a
mathematical model with experimental values indicate
that the model provides a true description of reality?

Self-test 6

Test yourself
20 Use the data in the table to calculate the first
electron affinity of Br.
/ kJ mol1
Hat [K(s)]

90

Hat [Br2(l)]

112

rst ionisation energy (K)

418

Hlatt (KBr)

670

Hf (KBr(s))

394

21 Use the data in the table to calculate the lattice

enthalpy of BaF2.
/ kJ mol1
Hat [Ba(s)]

176

Hat [F2(g)]

79

rst ionisation energy (Ba)

502

second ionisation energy (Ba)

966

rst electron afnity (F)

Hf (BaF2(s))

22 Arrange the following in order of increasing

lattice enthalpy (smallest first):
LiF
KCl
CaO
CaS
CaCl2
23 State whether the following enthalpy changes
are always exothermic, always endothermic
or sometimes exothermic and sometimes
endothermic:
a first ionisation energy
b second ionisation energy
c enthalpy change of atomisation
d enthalpy change of formation
e first electron affinity
f second electron affinity

348
1201

5.7 Entropy
The dissolving of sodium chloride (common salt) in water is an example
of an endothermic process that occurs spontaneously at room temperature.
The idea of an endothermic reaction occurring spontaneously goes
against our experience from everyday life that things do not seem to
move spontaneously from a lower to a higher energy state (a book does
not jump from a lower shelf to a higher one but will fall to a lower shelf
if the shelf it is on breaks). Endothermic processes such as the melting of

HL

Learning objectives

Understand what is meant by

entropy
Predict the sign of the entropy
change for a given reaction
Work out entropy changes from
standard entropy values

5 ENERGETICS

227

Entropy is a measure of the

randomness or disorder of a
system.

HL ice at room temperature and water evaporating are relatively common,

however, and this suggests that it is not just a consideration of the energy
changes involved that can be used to predict whether a reaction occurs
spontaneously. The examples of endothermic processes mentioned here all
have one thing in common: they all involve an increase in disorder. In a
sodium chloride solution the Na+ and Cl ions are dispersed throughout
the solution and are moving around, which is a much more disordered,
or random, arrangement than a separate crystal of sodium chloride and a
beaker of pure water. Similarly, liquid water is much more disordered than
a solid lump of ice, as in the liquid form all the molecules are moving
around each other randomly. This property of disorder is called entropy,
and it is possible to assign values to the entropy of a system and the
entropy change for a reaction. An endothermic reaction can only occur if
it involves an increase in entropy.

Note: not kJ.

Entropy is given the symbol S. The units of entropy are J K1 mol1.

Actual values of entropy can be

calculated from experimental data,
as opposed to enthalpy, for which
only an enthalpy change can be
measured.

S is called the standard entropy. It is possible to work out values

for standard entropies for substances; for example, the standard
entropy of H2(g) is 131 J K1 mol1, and the standard entropy of
NaCl(s) is 72.4 J K1 mol1.
An entropy change is represented by the symbol S .

The Austrian physicist Ludwig

Boltzmann (18441906)
developed a statistical approach
to entropy. His famous equation,
S = k log W, is inscribed on his
gravestone.

A positive value for S indicates an increase in entropy, i.e. an

increase in disorder.
For example, S for the process H2O(l) H2O(g) is +119 J K1 mol1.
The disorder of the system has increased, as the molecules of water in the
gas phase are moving around much more.
A negative value for S indicates a decrease in entropy, i.e. an
decrease in disorder.
For example, S for the process NH3(g) + HCl(g) NH4Cl(s) is
285 J K1 mol1. Two molecules of gas being converted into a solid
results in a decrease in disorder, i.e. a decrease in entropy.

How to predict the sign of an entropy change

Gases have higher entropy than liquids, which have higher entropy than
solids (Figure 5.23).

228

increasing entropy

solid

HL

liquid

gas

Figure 5.23 In a solid, the particles vibrate about mean positions; in a liquid, the
particles move around each other; in a gas, the particles move at high speeds in all
directions.

This is an approximate rule of

thumb, which is useful when
considering the same substance in
different states or similar substances.
When considering very different
substances, it must be used with
caution. For instance, S for
(NH4)2SO4(s) is 220 J K1 mol1,
whereas that for CCl4(l) is
214 J K1 mol1 and that for HCl(g)
is 187 J K1 mol1.

Table 5.4 shows the values of standard entropies for elements across
period 2 in the periodic table. Lithium to carbon are all solid elements
and have low entropy values at 298 K, but nitrogen to neon are all gases
and have much higher entropy values.
Element
State
1

S / J K mol

Li

Be

N2

O2

F2

Ne

solid

solid

solid

solid

gas

gas

gas

gas

29

10

192

205

203

146

Table 5.4 Standard entropies for elements across period 2.

To predict the sign of the entropy change in a reaction, we must

consider whether there is an increase or decrease in disorder in the system.
As gases have significantly higher entropy than solids and liquids, the most
important factor in determining whether a chemical reaction involves an
increase or decrease in entropy is whether there is an increase or decrease
in the number of moles of gas (Table 5.5).

Increase in number of moles

of gas: S +ve (entropy
increases).

Decrease in number of moles

of gas: S ve (entropy
decreases).

Reaction

Entropy

Explanation

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

decrease

4 moles of gas on the left-hand side converted to 2 moles of gas

on the right-hand side; a decrease in the number of moles of gas
suggests a decrease in disorder and therefore a decrease in entropy

CaCO3(s) CaO(s) + CO2(g)

increase

1 mole of solid becomes 1 mole of solid and 1 mole of gas;

therefore the number of moles of gas increases

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

decrease

3 moles of gas converted to 1 mole of gas

C2H4(g) + H2(g) C2H6(g)

decrease

2 moles of gas converted to 1 mole of gas

Table 5.5 Entropy changes for some reactions.

If the number of moles of gas is the same on both sides of an equation,

as in this one:
F2(g) + Cl2(g) 2ClF(g)
the prediction could be made that the entropy change for this reaction
would be approximately zero.
5 ENERGETICS

229

HL

Calculating an entropy change for a reaction

Values of S may be worked out from standard entropies, S :
entropy change
= total entropy of products total entropy of reactants
S = S products S reactants

S / J K mol
N2

192

Example

H2

131

Calculate the standard entropy change for the following reaction:

NH3

193

The standard entropy values are

multiplied by the appropriate
coefficients in the equation.
Self-test 7

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

S = (2 193) [192 + (3 131)]
S = 199 J K1 mol1
That there is a decrease in entropy corresponds to the prediction made
above based on the number of moles of gas.

Test yourself
24 Work out whether each of the following processes
involves an increase or decrease in entropy:
a C2H2(g) + 2H2(g) C2H6(g)
b 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l)
c COCl2(g) CO(g) + Cl2(g)
d 2C(s) + O2(g) 2CO(g)
25 Use the entropy values in the table to calculate the
standard entropy change in each of the following
reactions:
a CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
b 2Cu(NO3)2(s) 2CuO(s) + 4NO2(g) + O2(g)
c 4BCl3(l) + 3SF4(g) 4BF3(g) + 3SCl2(g) + 3Cl2(g)

Learning objectives

230

Calculate values of G for a

reaction
Work out whether a reaction is
spontaneous from the sign of G
Predict how the spontaneity of a
reaction varies with temperature

Substance

S / J K1 mol1

CH4(g)

186

O2(g)

103

CO2(g)

214

H2O(l)

70

Cu(NO3)2(s)

193

CuO(s)

43

NO2(g)

240

BCl3(l)

206

SF4(g)

292

BF3(g)

254

SCl2(g)

282

Cl2(g)

83

5.8 Spontaneity
Spontaneous reaction: one that occurs without any outside
influence, i.e. no input of energy.

Predicting whether a reaction will be spontaneous

HL

If sodium and oxygen are put together in an isolated container (one

with no connection to the outside world) at 25 C, they will react
spontaneously to produce sodium oxide:

O2

4Na(s) + O2(g) 2Na2O(s)

If the value of SUniverse is positive, the entropy of the Universe increases

and the reaction occurs spontaneously.
When heat is given out in a chemical reaction, the surroundings get
hotter, the particles move around more, and therefore the entropy of the
surroundings increases. The entropy change of the surroundings can thus
be related to the enthalpy change of the system. A new equation can be
derived from the equation of the entropy change of the Universe given
above. The new equation is:
G = H TS
G is called the change in Gibbs free energy, or just the free energy
change. Or, under standard conditions, we have G , which is the
standard free energy change.
G is related to the entropy change of the Universe, and from the
condition that for a reaction to occur spontaneously the entropy of the
Universe must increase we can derive the condition:
for a reaction to be spontaneous, G for the reaction must be
negative.

A spontaneous reaction does not

have to happen quickly.
The first law of thermodynamics
is basically a statement of the
principle of conservation of energy:
the energy of the Universe remains
constant.

undin
o
r
r

gs

SUniverse = Ssurroundings + Ssystem

Na

su

This reaction will occur by itself nothing has to be done to make the
reaction occur. This is an example of a spontaneous reaction.
If methane and oxygen are put into an isolated container at 25 C,
they will react together spontaneously to form carbon dioxide and water.
This reaction, although it is spontaneous, is not a very fast reaction at
room temperature (unless a spark is supplied) and would have to be
left for a very long time before a significant amount of carbon dioxide
and water could be detected. Similarly, the conversion of diamond to
graphite at room temperature is a spontaneous process, but luckily occurs
immeasurably slowly!
Whether a reaction will be spontaneous or not under a certain
set of conditions can be deduced by looking at how the entropy
of the Universe changes as the reaction occurs. The second law of
thermodynamics states that for a process to occur spontaneously it must
result in an increase in the entropy of the Universe.
The Universe may be regarded as being composed of the system (the
chemical reaction) and the surroundings (Figure 5.24).
The entropy change of the Universe is given by:

system
(the chemical
reaction)

Figure 5.24 The Universe!

The units of G are usually

kJ mol1.

T must be in K.

The subscripts are now omitted,

as both H and S refer to the
system, i.e. the chemical reaction.

5 ENERGETICS

231

Extension

HL

The entropy change of the

surroundings depends on the
temperature and is given by:
Hsystem
Ssurroundings =
T
(H because an exothermic reaction
(H negative) causes the entropy
of the surroundings to increase
(Ssurroundings positive))
SUniverse = Ssurroundings + Ssystem
SUniverse = Hsystem + Ssystem
T
TSUniverse = Hsystem TSsystem

Calculating G
The standard free energy change for a reaction can be calculated in two
ways.

Method 1
Using G = H TS to calculate G .
Example
We can calculate G at 298 K for:

C2H2(g) + 2H2(g) C2H6(g)

given the following information:
S = 233 J K1 mol1
H = 313 J K1 mol1
H is in kJ but S is in J, and in order to combine them they must
be converted so they are both in kJ or J. As G is usually quoted in kJ,
S will be converted to kJ. Therefore:

TSUniverse is given the symbol G.

S =
This is under standard conditions,
so we use the symbol G .

233
= 0.233 kJ K1 mol1
1000

G = 313 298 (0.233) = 244 kJ mol1

As the value of G is negative, the reaction is spontaneous.

Note: temperature must be in

kelvin.

Method 2
Using the standard free energy of formation to calculate G :

G = G f (products) G f (reactants)
Examiners tip
If you are asked to calculate a
standard free energy change
and no temperature is given,
you can assume that the
temperature is 298 K.

Standard free energy of formation is the free energy change for

the formation of 1 mole of substance from its elements in their
standard states and under standard conditions.
Example
Given the data in the table, we can calculate the standard free energy
change for the reaction:

2SO2(g) + O2(g) 2SO3(g)

G f / kJ mol1
SO2(g)

300

SO3(g)

370

J. Willard Gibbs (18391903) was

an American mathematician and
scientist.

232

Using the formula for G given above:

G = [2 370] [(2 300) + 0] = 140 kJ mol1
This reaction is spontaneous, as G is negative.
The G f for oxygen is zero, as it is an element in its standard state.

Worked example
Consider the decomposition of Mg(NO3)2(s):
2Mg(NO3)2(s) 2MgO(s) + 4NO2(g) + O2(g)
Use the following data to work out G and thus
whether the reaction will be spontaneous at 25 C.

Mg(NO3)2(s)
H f / kJ mol1
1

S / J K mol

MgO(s) NO2(g)

O2(g)

790

602

34

164

27

240

205

To calculate the enthalpy change, we have been given Hf and so can use:
H = Hf (products) Hf (reactants)
H = [(2 602) + (4 34) + 0] [(2 790)] = 512 kJ mol1
To calculate the entropy change we use:
S = S(products) S(reactants)
S = [(2 27) + (4 240) + 205] [(2 164)] = 891 J K1 mol1
At 298 K:
G = H TS
G = 512 298

891
= 246 kJ mol1
1000

S is divided by 1000 to convert to kJ.

Thus, at 298 K the reaction is not spontaneous because G is positive.

Because S is positive, as the temperature is increased TS will become larger until it is eventually bigger than H
and the reaction will be spontaneous.
We can estimate the temperature at which this reaction is
going to become spontaneous. As the temperature is increased,
G will become less and less positive, until it becomes
zero, and then it will be negative. Thus, if we work out the
temperature at which G becomes zero, the reaction will be
spontaneous at any temperature above that.

When G = 0, this means that the

reaction has no tendency to proceed in
either direction, and so the system is in
equilibrium.

Using
G = H TS
0 = 512 T

891
1000

This calculation is only approximate, as

the values of H and S change with
temperature, and we have used H
and S , i.e. the values at 298 K.

Rearranging the equation gives:

T = 575 K
This means that this reaction is likely to become spontaneous above 575 K (302 C).

5 ENERGETICS

233

HL

Extension
Actually the situation has been
oversimplified here, and reactions that
appear to have a positive value of G
can occur. Consider the Haber process
for the production of ammonia:
N2(g) + 3H2(g)

2NH3(g)

Equilibrium can be attained from

either direction, i.e. starting with
either nitrogen and hydrogen or with
pure ammonia. The reaction has a
positive value of G in one direction
and a negative value in the other,
but this is for complete conversion
of 1 mole of nitrogen and 3 moles
of hydrogen to 2 moles of ammonia.
However, the equilibrium state has a
lower Gibbs free energy than either
pure nitrogen and hydrogen or pure
ammonia, and therefore the reaction
from pure reactants or products to the
equilibrium mixture has a negative
G value.

Non-spontaneous reactions
If a reaction is non-spontaneous it does not mean that it can never
happen, it just means that it will not happen without external influence.
For instance, in the above worked example we can increase the
temperature to make the reaction spontaneous.
Consider the following reaction:
2H2O(l) 2H2(g) + O2(g)

G = +474 kJ mol1

This reaction is not spontaneous at 25 C, but it can be made to happen

at this temperature by the continuous passage of an electric current
(electrolysis).

The effect of changing temperature on the

spontaneity of a reaction
Consider a reaction for which H is positive and S is positive:
G = H TS
In this case, at low temperatures, the reaction is not spontaneous, as TS
is smaller than H, so G is positive. As the temperature is raised, TS
becomes larger, and as this is being subtracted from H, G becomes
smaller. When TS is larger than H, G is negative, and the reaction
becomes spontaneous. Therefore, as the temperature is increased, this
reaction becomes more spontaneous.
Now consider a reaction for which H is positive and S is negative. In
this case, at low temperatures, the reaction is not spontaneous. However,
as S is negative TS in the equation is positive, and this means that the
value of G will increase as the temperature is increased. The consequence
of TS being positive is that this reaction will never be spontaneous.
Both the reactions considered here so far have been endothermic
reactions and it can be seen that:
an endothermic reaction can only occur spontaneously if it
involves an increase in entropy (and the temperature is sufficiently
high).
An exothermic reaction (H negative) will always be spontaneous at some
temperature. If the reaction involves an increase in entropy (S positive)
then TS will be negative. As H is also negative, G will always be
negative, and the reaction will always be spontaneous.
If the reaction involves a decrease in entropy (S negative), the reaction
will be spontaneous at lower temperatures, when H is more negative
than TS is positive. It will, however, become less spontaneous as the
temperature increases (as TS is positive and becomes more positive as
the temperature increases). At higher temperatures TS will be more
positive than H is negative, and therefore G will be positive and the
reaction will be non-spontaneous at higher temperatures.

234

HL

H S

TS G

Spontaneous?

negative

at all temperatures

becomes more negative as

temperature increases

becomes more spontaneous

as temperature increases

becomes less negative as

temperature increases

becomes less spontaneous

as temperature increases

positive

never

Reactions for which S is positive

become more spontaneous as
temperature increases, but reactions
for which S is negative become
less spontaneous as temperature
increases.

Self-test 8 & Application 1

Test yourself
26 Given the data below, calculate G for the
following reaction at 298 K and state whether it
is spontaneous or not:
C2H4(g) + H2(g) C2H6(g)
H = 137 kJ mol1 and
S = 55.3 J K1 mol1
27 Given the data below, calculate G for the
following reaction and state whether it is
spontaneous or not at 298 K:
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
H = 2219 kJ mol1 and
S = 373.3 J K1 mol1
28 Calculate G for the following reaction, given
the G f values in the table:
CaCO3(s) CaO(s) + CO2(g)
Substance
CaCO3(s)

G f /kJ mol1
1129

CaO(s)

604

CO2(g)

395

29 Calculate G for the following reaction, given

the G f values in the table:
C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l)
Substance
C5H12(l)

G f /kJ mol1
9.2

H2O(l)

237.2

CO2(g)

395

Is the reaction spontaneous at 298 K?

30 Consider the decomposition of Pb(NO3)2(s):
2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)
H = +598 kJ mol1 G = +333 kJ mol1
a Work out the value for S at 298 K.
b Assuming that H and S do not change
with temperature, calculate the temperature,
in C, above which this reaction will become
spontaneous.
31 For each of the following reactions, predict
whether it becomes more or less spontaneous as
temperature increases:
a N2O4(g) 2NO2(g)
b N2(g) + 3H2(g) 2NH3(g)
c 2KNO3(s) 2KNO2(s) + O2(g)
d 2AgNO3(s) 2Ag(s) + 2NO2(s) + O2(g)

5 ENERGETICS

235

Exam-style questions
1 The specific heat capacity of a liquid is 4.00 J g1 K1; 2000 J of heat energy is supplied to 100.0 g of the liquid.
By how much would the temperature of the liquid increase?
A 278 K

B 5K

C 80 K

D 20 K

2 Which of the following is correct about endothermic reactions?

A
B
C
D

Heat energy is taken in and the temperature increases.

Heat energy is given out and the temperature increases.
Heat energy is taken in and the temperature decreases.
Heat energy is given out and the temperature decreases.

3 Use the following information:

H = 572 kJ mol1
H = 484 kJ mol1

2H2(g) + O2(g) 2H2O(l)

2H2(g) + O2(g) 2H2O(g)

to calculate the enthalpy change for the process:

H2O(g) H2O(l)
A 88 kJ mol1
B 44 kJ mol1

C +88 kJ mol1
D +44 kJ mol1

4 Use the bond enthalpies in the table to calculate the enthalpy change (in kJ mol1) for the reaction:
CH4(g) + 2Cl2(g) CH2Cl2(g) + 2HCl(g)
Bond

Bond enthalpy / kJ mol1

CH

410

ClCl

240

CCl

340

HCl

430

A 720

B +240

C +620

D 240

HL 5 Which of the following processes is exothermic?

A Br2(l) 2Br(g)
B Na(g) Na+(g) + e

236

C CaF2(s) Ca2+(g) + 2F(g)

D Cl(g) + e Cl(g)

HL

6 Use the approximate enthalpy change of combustion values given in the table to calculate the enthalpy
change (in kJ mol1) for the reaction:
C4H6(g) + 2H2(g) C4H10(g)
H c / kJ mol1

Substance
C4H6(g)

2595

C4H10(g)

2875

H2(g)

285

A 290

B 290

C 5

D 5

7 Use the enthalpy change of formation values in the table to calculate the enthalpy change for the following
reaction:
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l)
H f / kJ mol1

Substance
NH3(g)

46

H2O(l)

286

A 240 kJ mol1
B 332 kJ mol1

C 1532 kJ mol1
D 1900 kJ mol1

8 Which of the following reactions has a S value that is negative?

A
B
C
D

2H2O2(aq) 2H2O(l) + O2(g)

CaCO3(s) CaO(s) + CO2(g)
CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
2C4H10(g) + 13O2(g) 8CO2(g) + 10H2O(l)

9 Which of the following will have the largest value of lattice enthalpy?
A NaCl

B MgO

C CaO

D MgBr2

10 Using the data given below, calculate the value of G , for the following reaction at 298 K:
SO2(g) + Cl2(g) SO2Cl2(l)
H = 97.3 kJ mol1 and S = 254.4 J K1 mol1
A 21.5 kJ mol1
B 75 714 kJ mol1

C 173.1 kJ mol1
D 97.0 kJ mol1

5 ENERGETICS

237

11 a Explain what you understand by the term average bond enthalpy.

[2]

b Use the average bond enthalpies given in the table to calculate the enthalpy change for the
combustion of ethanol vapour, according to the equation:
C2H5OH(g) + 3O2(g) 2CO2(g) + 3H2O(g)
Bond
1

Bond enthalpy / kJ mol

[3]

CH

CC

CO

OH

O=O

C=O

412

348

360

463

496

743

c Explain why bond enthalpies could not be used to work out the enthalpy change for the reaction:
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)

[2]

d Consider the reaction:

N2O4(g) 2NO2(g)

H = +57 kJ mol1

Draw an enthalpy level diagram for this reaction and explain whether NO2 or N2O4 is more stable.
HL 12 a Define standard enthalpy change of formation.

[2]

b Write a chemical equation for the standard enthalpy change of formation of propan-1-ol.

[2]

c Use the standard enthalpy change of combustion values given in the table to calculate the standard
enthalpy change of formation of propan-1-ol.

[3]

Substance
CH3CH2CH2OH(l)

H c / kJ mol1
2010

C(s)

394

H2(g)

286

d Use the standard entropy values in the table below to calculate the entropy change for the complete
combustion of propan-1-ol and justify the sign of the entropy change.
Substance

196.6

CO2(g)

214

O2(g)

[3]

S / J K1 mol1

CH3CH2CH2OH(l)
H2O(l)

69.9
205

e Calculate the standard free energy change, G , for the complete combustion of propan-1-ol and
explain whether the reaction will be spontaneous at 25 C.

238

[3]

[3]

HL 13 Hydrazine, N2H4, has been used as a rocket fuel.

a Draw a Lewis structure for hydrazine.

[1]

b Write a chemical equation to represent the enthalpy change of formation of gaseous hydrazine.

[2]

c Use bond enthalpies from the table to calculate the enthalpy change of formation of gaseous hydrazine.

[3]

Bond
1

Bond enthalpy / kJ mol

N=N

N=N

NN

HH

NH

944

409

163

436

388

d The equation for the combustion of liquid hydrazine is:

N2H4(l) + O2(g) N2(g) + 2H2O(l)

H = 622 kJ mol1

The enthalpy change of formation of H2O(l) is 286 kJ mol1.

Use these data to calculate the enthalpy change of formation of liquid hydrazine.

[3]

e Calculate the enthalpy change for the process:

N2H4(l) N2H4(g)

[2]

14 a Define lattice enthalpy.

[2]

b Write chemical equations to represent the following enthalpy changes:

i the lattice enthalpy of potassium chloride
ii the first electron affinity of chlorine
iii the first ionisation energy of potassium

[3]

c Construct a BornHaber cycle for the formation of potassium chloride and use it and the values
in the table to calculate the lattice enthalpy of potassium chloride.
Process
Hat (K(s))

[5]

Enthalpy change / kJ mol1

90

Hat (Cl2(g))

121

rst ionisation energy (K)

418

rst electron afnity (Cl)

364

Hf (KCl(s))

436

d Explain why the value of the lattice enthalpy for calcium chloride is substantially greater than that for
potassium chloride.

[2]

5 ENERGETICS

239

Summary
ENERGETICS

exothermic
reaction

gives out heat to

surroundings

Products have lower energy than reactants,

so are more stable.

endothermic
reaction

takes in heat from

surroundings

Products have higher energy than reactants,

so are less stable.

To ENTROPY on
next page
enthalpy
change, H

heat energy exchanged

with surroundings at
constant pressure

To IONIC COMPOUNDS
on next page

standard enthalpy change:

enthalpy change for molar
amounts of substance under
standard conditions

To SPONTANEOUS
REACTIONS on
next page

indicated by the symbol

negative for exothermic reaction
positive for endothermic reaction

types of enthalpy
change

enthalpy change of solution (Hsol):

heat given out or taken in when
1 mole of a solute is dissolved into
excess solvent to form an innite
dilution
enthalpy change of reaction (Hr):
heat given out or taken in when molar
amounts of reactants react together

q = mcT

tools for enthalpy

calculations

enthalpy change of atomisation

(Hat):
heat taken in when 1 mole of
gaseous atoms are formed from the
element

enthalpy change of neutralisation

(Hn):
heat given out when 1 mole of H2O
molecules are formed from H+ and OH

HL

Hesss law:
the enthalpy change
accompanying a reaction is
independent of the pathway
taken from reactants to products
H r = H c (reactants) H c (products)

enthalpy change of formation

(Hf):
heat given out or taken in when
1 mole of substance is formed from
its elements in their standard states

H r = H f (products) H f (reactants)
The standard state of an element is
its (most stable) state under standard
conditions.
For an element in its standard state:
H f = 0

bond breaking is endothermic

bond making is exothermic

240

specic heat capacity:

energy required to raise
the temperature of 1 g of
substance by 1 K

enthalpy change of combustion

(Hc):
heat given out when 1 mole of
substance is completely burnt in
oxygen

bond enthalpy:
heat taken in when 1 mole of
covalent bonds, in a gaseous
molecule, is broken

bond enthalpy values

for a given type of bond
are averaged over many
compounds

standard conditions:
P = 1.01 105 Pa (1 atm)
T = 298 K (25 C)

Hr = (bonds broken) (bonds made)

HL
IONIC COMPOUNDS

types of enthalpy
change

1st electron afnity:

heat given out (in very few
cases taken in) when 1
electron is added to each atom
in 1 mole of gaseous atoms

ENTROPY, S

BornHaber cycle

tools for enthalpy calculations

1st ionisation energy:

heat taken in when 1 electron
is removed from each atom in
1 mole of gaseous atoms

The greater the difference between the

theoretical and experimental values, the greater
is the covalent character of the bonding.

lattice enthalpy (Hlatt):

heat taken in when 1 mole of
an ionic compound is broken
apart into gaseous ions

Is the result of electrostatic interactions

between the ions.
Higher charge/smaller ions
higher lattice enthalpy

measure of the amount

of disorder in a system

gas > liquid > solid

units: J K1 mol1

S = S (products) S (reactants)

if number of gas molecules

increases: S = +ve
if number of gas molecules
decreases: S = ve

SPONTANEOUS
REACTIONS

occur without any outside

inuence, i.e. with no input
of energy

if G = H TS = ve
(or G = G f (products) G f (reactants) = ve)

If S is positive, the reaction becomes

more spontaneous as T increases.
If S is negative, the reaction becomes
less spontaneous as T increases.

G = Gibbs free energy change

5 ENERGETICS

241