Topic

9 Chemical Reactions and

Energy

Unit 34 Energy changes in chemical reactions

Unit 35 Hess’s Law and its applications

Key
C o ncepts

Energy changes in chemical

reactions
• Nature of energy and internal energy
of a system
• Enthalpy changes of reactions
• Exothermic and endothermic reactions
• Standard enthalpy changes of
formation, combustion, neutralization
and solution
• Calorimetry

Chemical Reactions
and Energy

Hess’s Law and its applications

• Hess’s Law
• Enthalpy change cycle and enthalpy
level diagram
• Determining enthalpy changes
which cannot be easily obtained by
experiment
 Topic 9 Chemical Reactions and Energy Unit 34 Energy changes in chemical reactions 

34.1 – 34.20
Unit 34 Energy changes in chemical reactions
Summary
1 The specific heat capacity (symbol: c) of a substance is the amount of heat required
34.1 Heat-packs and cold-packs
to raise the temperature of 1 g of the substance by 1 K (or 1 °C).
34.2 What is energy?
Amount of heat required = specific heat capacity x mass x rise in temperature
34.3 Specific heat capacity
= c x m x ∆T
34.4 The system and the surroundings
where ∆T is the temperature change.
34.5 Internal energy of a system
2 An enthalpy change, ∆H, is the heat released or taken in during any change in a
34.6 Comparing the enthalpy change (ΔH) and internal energy system, provided that the system is kept at constant pressure.
change (ΔE) of a system during a reaction
3 In an exothermic reaction, heat is released to the surroundings.
34.7 Enthalpy change of an exothermic reaction
34.8 Enthalpy change of an endothermic reaction

Enthalpy (kJ mol–1)

reactants
34.9 Enthalpy changes during physical and chemical changes
34.10 Thermochemical equations ∆H < 0 (negative)
34.11 Explaining energy changes – breakage and formation of chemical
bonds products

34.12 Standard conditions for measuring enthalpy changes

34.13 Standard enthalpy change of reaction
4 In an endothermic reaction, heat is taken in from the surroundings.
34.14 Standard enthalpy change of formation

Enthalpy (kJ mol–1)

34.15 Standard enthalpy change of combustion products
34.16 Standard enthalpy change of neutralization
34.17 Standard enthalpy change of solution ∆H > 0 (positive)

34.18 Determining enthalpy changes of neutralization reactants

34.19 Determining enthalpy changes of combustion
34.20 An improved apparatus: the flame calorimeter
5 The standard enthalpy change of reaction, ∆HrO , is the enthalpy change when molar
quantities of reactants as stated in the specified equation react together under standard
conditions.
6 The standard enthalpy change of formation of a substance, ∆HfO , is the enthalpy
change when one mole of the substance is formed from its elements in their standard
states.
7 The standard enthalpy change of combustion of a substance, ∆HcO , is the enthalpy
change when one mole of the substance is completely burnt in oxygen under standard
conditions.
8 The standard enthalpy change of neutralization, ∆HnO , is the enthalpy change when an
acid reacts with an alkali to form one mole of water under standard conditions.
9 The standard enthalpy change of solution of a substance, ∆HsO , is the enthalpy
change when one mole of the substance dissolves in an infinite volume of solvent
(or enough solvent so that further dilution has no additional effect) under standard
conditions.
 Topic 9 Chemical Reactions and Energy Unit 35 Hess’s Law and its applications 

Exam tips ♦ The enthalpy change of an exothermic reaction has a –ve sign, while Unit 35 Hess’s Law and its applications
that of an endothermic reaction has a +ve sign. DO NOT confuse these
two.
♦ Students should be able to provide a concise definition for the term
‘standard enthalpy change of formation’. 35.1 Hess’s Law

♦ In calculations, read the question carefully to see whether it asks about 35.2 Enthalpy level diagram and enthalpy change cycle
the enthalpy change of reaction or the enthalpy change involved when 35.3 Using Hess’s Law to determine enthalpy changes that cannot
a certain amount of the reactants undergoes reaction. be easily obtained by experiment
35.4 Determining the enthalpy change of formation of magnesium
carbonate from enthalpy changes of other reactions
Example 35.5 Determining the standard enthalpy change of formation of a
An experiment was carried out to determine the enthalpy change of the following compound from standard enthalpy changes of combustion
reaction:
35.6 Determining the standard enthalpy change of a reaction from
2+
Mg(s) + Cu (aq) Cu(s) + Mg2+(aq) standard enthalpy changes of formation
3 –3
50.0 cm of 0.500 mol dm CuSO4(aq) were transferred to a polystyrene cup with
negligible heat capacity, and the temperature of the solution was recorded.
1.00 g of magnesium were added to the cup. The mixture was stirred and its highest
temperature was recorded. There was a temperature rise of 63.0 °C.
a) Show, by calculation, that CuSO4 is the limiting reactant. (2 marks)
–1 –1
b) Assuming that the specific heat capacity and the density of the mixture are 4.18 J g K
and 1.00 g cm–3 respectively, calculate the enthalpy change of this reaction, in kJ.
(Relative atomic mass: Mg = 24.3) (2 marks)

Answer
–3 50.0
a) Number of moles of CuSO4 = 0.500 mol dm x dm3
1 000
= 2.50 x 10–2 mol (0.5)
1.00 g
Number of moles of Mg =
24.3 g mol–1
= 4.12 x 10–2 mol (0.5)
According to the equation, 1 mole of Mg reacts with 1 mole of CuSO4. During the
reaction, 2.50 x 10–2 mole of CuSO4 reacted with 2.50 x 10–2 mole of Mg.
∴ CuSO4 is the limiting reagent. (1)
b) Amount of heat released during the reaction
–1 –1
= 50.0 g x 4.18 J g K x 63.0 K
= 13 200 J
= 13.2 kJ (1)
–13.2 kJ
Enthalpy change of reaction =
2.5 x 10–2
= –528 kJ (1)
∴ the enthalpy change of the reaction is –528 kJ.

Remarks*
Remarks
➤ Questions may NOT tell you which of the reagents is the limiting reactant.
Using the given number of moles of Mg when carrying out the calculation
in (b) will get a wrong answer. So be careful when the question gives the
quantities of both reagents.
 Topic 9 Chemical Reactions and Energy Unit 35 Hess’s Law and its applications 

35.1 – 35.6 The recordings of temperature are shown in the graph below:

33
Summary
1 Hess’s Law states: 32
The enthalpy change of a reaction depends on the initial and final states of the
reaction and is independent of the route by which the reaction may occur. 31
2 Overall reaction = Step 1 + Step 2 + Step 3

Temperature (°C)
then 30
the enthalpy change for the overall reaction
∆HO = ∆H1 + ∆H2 + ∆H3 29

This concept enables us to find enthalpy changes that cannot be easily obtained by
experiment. 28

3 ∆H [compound] = ∑ ∆H [constituent elements] – ∆H [compound]

O
f
O
c
O
c

4 ∆HrO = ∑ ∆HfO [products] – ∑ ∆HfO [reactants] 27

26

Exam tips ♦ The enthalpy changes of formation of many compounds (e.g. ethanol)
CANNOT be determined directly. 25
0 1 2 3 4 5 6 7 8 9
The enthalpy changes of formation of these compounds may Time (min)
be determined from ∆H c of the constituent elements and the
compound.
a) i) Deduce the greatest temperature change of the reaction mixture. (Show your
♦ Drawing an enthalpy change cycle relating the known enthalpy changes working on the graph.) (2 marks)
will help you calculate the unknown enthalpy change.
ii) Calculate the molar enthalpy change of reaction (1) under the conditions of the
Alternatively, you may calculate the required enthalpy change by experiment. (Assume that the heat capacity of the expanded polystyrene cup is
combining the enthalpy changes of appropriate processes as shown in negligible, and that the specific heat capacity and density of the solutions are
the next example. –1 –1 –3
4.18 J g K and 1.00 g cm respectively.) (3 marks)
(Relative atomic mass: Zn = 65.4)
b) Given that under the same conditions the molar enthalpy change of reaction (2) is
Example –1 –1
–84.0 kJ mol and the molar enthalpy change of formation of H2O(l) is –286 kJ mol ,
The enthalpy change of formation (∆Hf) of ZnO(s) can be determined indirectly from calculate ∆Hf of ZnO(s). (3 marks)
the enthalpy change of formation of H2O(l) and the enthalpy changes of reactions (1)
and (2) below.
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g) (1)
ZnO(s) + 2HCl(aq) ZnCl2(aq) + H2O(l) (2)
An experiment as outlined below was carried out to determine the enthalpy change
of reaction (1):
3 –3
30.0 cm of 1.20 mol dm HCl(aq) (excess) were placed in an expanded polystyrene
cup. The temperature of the acid in the cup was measured with a thermometer at
half-minute intervals.
Right at the third minute, 0.980 g of Zn(s) was added to the cup. The mixture in
the cup was then stirred with the thermometer and its temperature was measured for
an additional 8 minutes.
10 Topic 9 Chemical Reactions and Energy Unit 35 Hess’s Law and its applications 11

Answer Reverse the equation (2) to give equation (2)’. By combining equations as shown
below, followed by collecting like terms, we can obtain the equation for the formation
a) i) (Working on the graph to show temperatures at the third minute.) (1) of ZnO(s) from its constituent elements.
33 (1) Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g) ∆H = –48.5 kJ
(2)’ ZnCl2(aq) + H2O(l) ZnO(s) + 2HCl(aq) ∆H = +84.0 kJ
32 1
(3) H2(g) + O2(g) H2O(l) ∆H = –286 kJ
2

31 1
Zn(s) + O2(g) ZnO(s)
2
Temperature (°C)

By Hess’s Law,
30
∆Hf[ZnO(s)] = [(–48.5) + (+84.0) + (–286)] kJ mol–1 (1)
–1
29 = –251 kJ mol (1)

∆T = 5.8 °C ∴ the enthalpy change of formation of zinc oxide is –251 kJ mol–1.

28
Remarks*
Remarks
➤ For an experiment carried out to determine the enthalpy change of a
27
certain reaction, students often need to work out the maximum temperature
rise of the reaction mixture from the plot of temperature against time by
26 extrapolation of the curves.
➤ Be careful when reading the questions; either the specific heat capacity or
the heat capacity of a solution may be provided.
25
0 1 2 3 4 5 6 7 8 9 DO NOT confuse ‘specific heat capacity’ with ‘heat capacity’.
Time (min)

Calculated temperature change ∆T = 5.8 °C (1)

ii) Amount of heat released when Zn reacted with HCl(aq)
–1 –1
= 30.0 g x 4.18 J g K x 5.8 K
= 727 J (1)
0.980 g
Number of moles of Zn reacted =
65.4 g mol–1
= 0.0150 mol
–727 J
Enthalpy change of the reaction = (1)
0.0150 mol
–1
= –48.5 kJ mol (1)
b) ∆Hf[ZnO(s)] refers to the enthalpy change of the following process:
1
Zn(s) + O2(g) ZnO(s) (1)
2
∆H values for the following processes are known:
(1) Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g) ∆H = –48.5 kJ
(2) ZnO(s) + 2HCl(aq) ZnCl2(aq) + H2O(l) ∆H = –84.0 kJ
1
(3) H2(g) + O2(g) H2O(l) ∆H = –286 kJ
2