87

⦵
Entropy change, ∆S

a explain that entropy is a measure of the ‘disorder’ of a system, and that a system
becomes more stable when its energy is spread out in a more disordered state

b explain the entropy changes that occur:

i during a change in state e.g. (s) → (I); (I) → (g); (s) → (aq)

ii during a temperature change

iii during a reaction in which there is a change in the number of gaseous

molecules

c predict whether the entropy change for a given process is positive or negative

d ⦵
calculate the entropy change for a reaction, ∆S , given the standard entropies, S ,
⦵

of the reactants and products

⦵
Gibbs free energy change, ∆G

a define standard Gibbs free energy change of reaction by means of the equation
⦵ ⦵ ⦵
∆G = ∆H – T∆S

b ⦵ ⦵ ⦵ ⦵
calculate ∆G for a reaction using the equation ∆G = ∆H – T∆S

c ⦵
state whether a reaction or process will be spontaneous by using the sign of ∆G

d predict the effect of temperature change on the spontaneity of a reaction, given

standard enthalpy and entropy changes

ENTROPY

BILAL HAMEED ENTROPY

 Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

88

5 Chemical energetics
Enthalpy changes and entropy changes accompany chemical reactions. This topic demonstrates why
some reactions and processes are spontaneous and others are not.
Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

Learning outcomes
Candidates should be able to:

5.1 Enthalpy change, ΔH a) explain that chemical reactions are accompanied by energy changes,
5.3 Entropy change, a) explain that entropy is a measure of the ‘disorder’ of a system, and
principally in the form of heat energy; the energy changes can be
ΔS ⦵ that a system becomes more stable when its energy is spread out
exothermic (ΔH is negative) or endothermic (ΔH is positive)
in a more disordered state
b) explain and use the terms:
b) explain the entropy changes that occur:
(i) enthalpy change of reaction and standard conditions, with
(i) during a change in state e.g. (s) (I); (I) (g); (s) (aq)
particular reference to: formation, combustion, hydration, solution,
(ii) neutralisation,
during a temperature
atomisationchange
(iii) bond
(ii) during a reaction
energy in which
(ΔH positive, i.e.there
bondisbreaking)
a change in the number of
gaseous molecules
(iii) lattice energy (ΔH negative, i.e. gaseous ions to solid lattice)
c) predict whether the entropy change for a given process is positive
c) calculate enthalpy changes from appropriate experimental results,
or negative
including the use of the relationship
d) calculate the entropy change for a reaction, ΔS , given the
⦵

enthalpy change, ΔH = –mcΔT

standard entropies, S , of the reactants and products
⦵

d) explain, in qualitative terms, the effect of ionic charge and of ionic

radius on the numerical magnitude of a lattice energy
5.4 Gibbs free energy a) define standard Gibbs free energy change of reaction by means of
change, ΔG the equation ΔG = ΔH – TΔS
⦵ ⦵ ⦵ ⦵

5.2 Hess’ Law, including a) apply Hess’ Law to construct simple energy cycles, and carry ⦵out
b) calculate ΔG for a reaction using the equation ΔG = ΔH – TΔS
⦵ ⦵ ⦵

Born-Haber cycles calculations involving such cycles and relevant energy terms, with
c) particular
state whether a reaction
reference to: or process will be spontaneous by using
the sign of ΔG
⦵

(i) determining enthalpy changes that cannot be found by direct

d) predict the effect
experiment, e.g.ofan
temperature
enthalpy changechange on the spontaneity
of formation from enthalpyof a
reaction,
changesgiven standard enthalpy and entropy changes
of combustion
(ii) average bond energies
(iii) the formation of a simple ionic solid and of its aqueous solution
(iv) Born-Haber cycles (including ionisation energy and electron
affinity)
b) construct and interpret a reaction pathway diagram, in terms of the
enthalpy change of the reaction and of the activation energy

Back to contents page www.cie.org.uk/alevel 21

BILAL HAMEED ENTROPY
 89

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).

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.

ENTROPY
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.

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.

Entropy is given the symbol S. The units of entropy are JK−1mol−1.

2

BILAL HAMEED ENTROPY

 90

ENTROPY CHANGE
It is possible to work out values for standard entropies for substances;

for example, the standard entropy of H2(g) is 131 J K−1 mol−1, and the standard
entropy of NaCl(s) is 72.4 J K−1 mol−1.

An entropy change is represented by the symbol ∆Sϴ

A positive value for ∆Sϴ indicates an increase in entropy, i.e. an increase in disorder.

For example, ∆Sϴ for the process H2O(l) ⟶ H2O(g) is +119 J K−1 mol−1.

The disorder of the system has increased, as the molecules of water in the gas
phase are moving around much more.

ENTROPY CHANGE
A negative value for ∆Sϴ indicates an decrease in entropy, i.e. an
decrease in disorder.

For example, ∆Sϴ for the process NH3(g) + HCl ⟶ NH4Cl is —285 J
K−1 mol−1.

Two molecules of gas being converted into a solid results in a decrease in

disorder, i.e. a decrease in entropy.

BILAL HAMEED ENTROPY

 This is an appr
91 thumb, which
considering th
different states
When conside
PREDICT THE SIGN OF AN ENTROPY CHANGE substances, it m
caution. For in
Gases have higher entropy than liquids, which have higher entropy than (NH4)2SO4(s)
whereas that fo
solids. 214 J K−1 mol−
is 187 J K−1 mo
The table below shows the values of standard entropies for elements
across period 2 in the periodic table.
Table 5.4 shows the values of standard entropies for elements across
Lithiumperiod 2 in the
to carbon periodic
are table.
all solid Lithium and
elements to carbon
haveare all entropy
low solid elements
values at 298
and have low entropy values at 298 K, but nitrogen to neon are all gases
K, but nitrogen to neon
and have much areentropy
higher all gases and have much higher entropy values.
values.

5
Increase in nu
of gas: ∆S +ve
increases).
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
Decrease in n
important factor in determining whether a chemical reaction involves an
of gas: ∆S −ve
increase or decrease in entropy is whether there is an increase or decrease
decreases).
in the number of moles of gas (Table 5.5).
PREDICT THE SIGN OF AN ENTROPY CHANGE
Gases have higher entropy than liquids, which have higher entropy than
solids.

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, Sϴ for (NH4)2SO4(s) is 220 J K−1 mol−1, whereas that for CCl4(l)
is 214 J K−1 mol−1 and that for HCl(g) is 187 J K−1 mol−1.
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)

6

the prediction could be made that the entropy change for this reaction
would be approximately zero.

BILAL HAMEED ENTROPY

 92

PREDICT THE SIGN OF AN ENTROPY CHANGE

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 isThis
anis increase orrule of
an approximate
thumb, which is useful when
decrease in the number of moles of gas. considering the same substance in
different states or similar substances.
Increase in number of moles of gas: ∆Sϴ +ve (entropyWhen
increases).
considering very different
substances, it must be used with
caution. For instance, S for
Decrease in number of moles of gas: ∆Sϴ −ve (entropy decreases).
(NH4)2SO4(s) is 220 J K−1 mol−1,
whereas that for CCl4(l) is
7
214 J K−1 mol−1 and that for HCl(g)
is 187 J K−1 mol−1.

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.

ENTROPY CHANGES FOR SOME REACTIONS

Increase in number of moles
If the number of moles of gas is the same on both sides of anofequation, gas: ∆S +veas in this one:
(entropy
increases).
To predict the sign of the entropy change in a +reaction,
F2(g) Cl2(g) we⟶ must 2ClF(g)
consider whether there is an increase or decrease in disorder in the system.
As the
gasesprediction
have significantly
couldhigher
beentropy
madethanthatsolids
the and liquids,change
entropy the most for this reaction would be
Decrease in number of moles
important factor in determining whether a chemical reaction involves an
of gas: ∆S −ve (entropy
approximately
increase or decrease inzero.
entropy is whether there is an increase or decrease
decreases).
in the number of moles of gas (Table 5.5).

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.
BILAL HAMEED ENTROPY
 93

6 Use the approximate

6 Use the approximate enthalpy changeenthalpy change of values
of SKILL
combustion combustion
given values givento
in the table incalculate
the tablethe
to calculate
enthalpy the
−1 CHECK
change (in kJchange
mol−1) (in
for kJ
themol ) for the reaction:
reaction:
C H (g)Work
4 6
out
+ 2HC4(g)
H6(g)
2
whether
+
C 2H
4
eachCof4Hthe
H 2(g)
(g)
10
following processes involves an increase or
10(g)
decrease in entropy:

(a) C2H2(g) + 2H2(g) ⟶ C2H6(g)

(b) 2C2H6(g) + 7O2(g) ⟶ 4CO2(g) + 6H2O(l)

2902(g) A 290 B −290 B −290C −5 C −5 D 5 D 5

(c)ACOCl ⟶ CO(g) + Cl2(g)

7 (d)Use
7 Use the enthalpy the enthalpy
change
2C(s) + of (g)change
⟶ of
O2formation formation
values
2CO(g) in the values
table toincalculate
the tablethe
to calculate
enthalpy the enthalpy
change change
for the for t
following
reaction: reaction:

4NH (g) + 3O 4NH(g)3(g) +

2N3O(g)
2(g)
+ 6H 2N 2(g) + 6H2O(l)
O(l)
3 2 2 2 9

A −1
A −240 kJ mol −240 kJ mol−1 C −1532 kJCmol−1532
−1 kJ mol−1
B −1
B −332 kJ mol −332 kJ mol−1 D −1900 kJDmol−1900
−1 kJ mol−1
SKILL CHECK
8 Which of8theWhich of the
following following
reactions has reactions has that
a ∆S value a ∆Sis negative?
value that is negative?
A 2H2O2(aq) 2H O(l) + O2(g)
A 2H2O2(aq) 2H2O(l) + O2(g)2
B CaCO3(s) CaO(s) + CO2(g)
B CaCO3(s) CaO(s) + CO2(g)
C CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
C CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
D 2C4H10(g) + 13O2(g) 8CO2(g) + 10H2O(l)
D 2C4H10(g) + 13O2(g) 8CO2(g) + 10H2O(l)

9 Which of the following will have the largest value of lattice enthalpy?
9 Which of the following will have the largest value of lattice enthalpy?
A NaCl B MgO C CaO D MgBr2
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:
10 Using the data given below, calculate the value of ∆G , for the following reaction at 298 K:
SO (g) + Cl2(g) SO2Cl2(l)
SO2(g) + Cl2(g) 2 SO2Cl 2(l) 10
∆H = −1 −97.3 kJ mol−1 and ∆S = −1 −254.4 J K−1 mol−1
∆H = −97.3 kJ mol and ∆S = −254.4 J K mol−1
A −21.5 kJ mol−1 C −173.1 kJ mol−1
A −21.5 kJ mol−1 C −173.1 kJ mol −1
B 75 714 kJ mol−1 D −97.0 kJ mol−1
B 75 714 kJ mol−1 D −97.0 kJ mol−1

BILAL HAMEED ENTROPY

 94

CALCULATING ENTROPY CHANGES

Values of ∆Sϴ may be worked out from standard entropies, Sϴ:

entropy change = total entropy of products — total entropy of reactants

∆Sϴ = ΣSproducts — ΣSreactants

11

Values of ∆S may be
CALCULATING ENTROPY CHANGES
entropy change
Calculate the standard entropy change for the following reaction: = total entropy

N2(g) + 3H2(g) ⟶ 2NH3(g) ∆S =

Calculate the standard

N2(g) + 3H2(g) 2

∆S = (2 × 193) − [1
The standard entropy values are
multiplied by the appropriate ∆S = −199 J K−1 m
∆Sϴ = (2 × 193) — [192 + (3 × 131)]
 coefficients in the equation.
That there is a decreas
∆Sϴ = —199 J K−1 mol−1 above based on the nu

12 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
BILAL HAMEED reactions: ENTROPY
a CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
b 2Cu(NO3)2(s) 2CuO(s) + 4NO2(g) + O2(g)
 95

SKILL CHECK
What is ∆Sϴ for the following reactions?

(a) CaCO3(s) ⟶ CaO(s) + CO2(g)


[∆Sϴ /J mol–1 K–1: CaCO3(s) 92.9; CaO(s) 39.7; CO2(g) 213.6]






(b) C2H4(g) + H2O(l) ⟶ C2H5OH(l)


[∆Sϴ /J mol–1 K–1: H2O(l) 69.9; C2H5OH(l) 160.7; C2H4(g) 219.5]

13

SKILL CHECK
(c) N2(g) + 3H2(g) ⟶ 2NH3(g)

[∆Sϴ /J mol–1 K–1: H2(g) 130.6; N2(g) 191.6; NH3(g) 192.3]

14

BILAL HAMEED ENTROPY

 96

SKILL CHECK
Substance Sϴ / J K−1 mol−1
Use the entropy values in the table to calculate the
CH4(g) 186
standard entropy change in each of the following reactions: O2(g) 103

(a) CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l) 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
15

SKILL CHECK - CONTINUED

Substance Sϴ / J K−1 mol−1
(b) 2Cu(NO3)2(s) ⟶ 2CuO(s) + 4NO2(g) + O2(g)

CH4(g) 186

 O2(g) 103


 CO2(g) 214


 H2O(l) 70
Cu(NO3)2(s) 193
CuO(s) 43
(c) 4BCl3(l) + 3SF4(g) ⟶ 4BF3(g) + 3SCl2(g) + NO2(g) 240
BCl3(l) 206
3Cl2(g)
SF4(g) 292
BF3(g) 254
SCl2(g) 282
Cl2(g) 83
16

BILAL HAMEED ENTROPY

 97

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

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:

4Na(s) + O2(g) ⟶ 2Na2O(s)

This reaction will occur by itself – nothing has to be done to make the reaction
occur.

This is an example of a spontaneous reaction.

17

SPONTANEITY
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!

A spontaneous reaction does not have to happen quickly.

18

BILAL HAMEED ENTROPY

 98

SPONTANEITY
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.

The total entropy change (of the Universe) is given by:

∆STotal = ∆Ssurroundings + ∆Ssystem

If the value of ∆STotal is positive, the total entropy increases and the reaction occurs
spontaneously.
19

SPONTANEITY
The total entropy change is given by: ∆Stotal = ∆Ssurroundings + ∆Ssystem

The entropy change of the system is given by: ∆Ssystem = ΣSproducts — ΣSreactants

The entropy change of the surroundings is given by:

∆Ssurroundings = —∆Hreaction
T

∆Stotal = ∆Ssurroundings — ∆Hreaction

T

20

BILAL HAMEED ENTROPY

 99

GIBBS FREE ENERGY

There is a more straightforward way in which we can take account of both system
and surroundings.

It involves a quantity called Gibbs free energy or, more simply, free energy.

The Gibbs free energy change is given by the relationship:

∆G = —T∆Stotal

∆Stotal = ∆Ssurroundings + ∆Ssystem

— ∆G = —∆Hreaction + ∆Ssystem
T T
∆G = ∆H —T∆S
21

GIBBS FREE ENERGY

∆G is called the change in Gibbs free energy, or just the free energy change.
Or, under standard conditions, we have ∆Gϴ, which is the standard free energy
change.

∆G is related to the entropy change of the Universe, and for a reaction to be

spontaneous, ∆G for the reaction must be negative.

∆G = ∆H —T∆S

The units of ∆G are kJ mol−1 and T must be in K.

The subscripts are now omitted, as both ∆H and ∆S refer to the system, i.e. the
chemical reaction.
22

BILAL HAMEED ENTROPY

 100

CALCULATING ∆G
We can calculate ∆G for C2H2(g) + 2H2(g) ⟶ C2H6(g) given the
following information:

∆H = —313 kJ mol−1 and ∆S = −233JK−1 mol−1


∆G = —313 — 298 × (233/1000) = —244 kJmol−1

23

CALCULATING ∆G: EXAMPLE

Consider the decomposition of Mg(NO3)2(s):

2Mg(NO3)2(s) ⟶ 2MgO(s) + 4NO2(g) + O2(g)

Mg(NO3)2(s) MgO(s) NO2(g) O2(g)

∆H f /kJmol −1 —790 —602 34 0

Sϴ / J K−1 mol−1 164 27 240 205

24

BILAL HAMEED ENTROPY

 101

CALCULATING ∆G: EXAMPLE

To calculate the enthalpy change, we have been given ∆Hf and so can use:

∆H = [(2 × —602) + (4 × 34) + 0] — [(2 × —790)] = 512 kJmol−1

To calculate the entropy change we use:

∆Sϴ = ΣSproducts — ΣSreactants

∆S = [(2 × 27) + (4 × 240) + 205] — [(2 × 164)] = 891 JK−1 mol−1

∆G = ∆H —T∆S

∆G = 512 — 298 × (891/1000) = 246 kJmol−1

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

25

SKILL CHECK

26

BILAL HAMEED ENTROPY

 102

SKILL CHECK

27

SKILL CHECK
Calculate the Gibbs free energy change for the decomposition of zinc carbonate at 298 K.

ZnCO3(s) ⟶ ZnO(s) + CO2(g) ∆H = +71.0 kJ mol–1

Values for ∆S in J K–1 mol–1: CO2(g) = +213.6, ZnCO3(s) = +82.4, ZnO(s) = +43.6

Answer: +18.9 kJ mol–1

28

BILAL HAMEED ENTROPY

 103

CHANGING TEMPERATURE & ∆G

Consider a reaction for which ∆H is positive and ∆S is positive:

∆G = ∆H —T∆S

In this case, at low temperatures, the reaction is not spontaneous, as T∆S is smaller
than ∆H, so ∆G is positive.

As the temperature is raised, T∆S becomes larger, and as this is being subtracted
from ∆H, ∆G becomes smaller.

When T∆S is larger than ∆H, ∆G is negative, and the reaction becomes spontaneous.

Therefore, as the temperature is increased, this reaction becomes more

spontaneous.

29

CHANGING TEMPERATURE & ∆G

∆G = ∆H —T∆S

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 —T∆S in the equation is positive, and this

means that the value of ∆G will increase as the temperature is increased.

The consequence of —T∆S being positive is that this reaction will never be
spontaneous.

30

BILAL HAMEED ENTROPY

 104

CHANGING TEMPERATURE & ∆G

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.

And if an exothermic reaction involves an increase in entropy (∆S positive)

then −T∆S will be negative. As ∆H is also negative, ∆G will always be
negative, and the reaction will always be spontaneous.
31

CHANGING TEMPERATURE & ∆G

Reactions
become m
temperatur
for which
less sponta
increases.

32

26 Given the data below, calculate ∆G for the 29 Calculate ∆G for the follo
following reaction at 298 K and state whether it the ∆G f values in the table:
is spontaneous or not: C5H12(l) + 8O2(g) 5C
C2H4(g) + H2(g) C2H6(g)
BILAL HAMEED −1 ENTROPY
∆H = −137 kJ mol and
∆S = −55.3 J K−1 mol−1
 A 2H2O2(aq) 2H2O(l) + O2(g)
B CaCO3(s) CaO(s) + CO2(g)
C CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
D 2C4H10(g) + 13O2(g) 105
8CO2(g) + 10H2O(l)

9 Which of the following will have the largest value of lattice enthalpy?
A NaCl B MgO CaO D MgBr2
SKILL CHECKC
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 mol−1 and ∆S = −254.4 J K−1 mol−1
A −21.5 kJ mol−1 C −173.1 kJ mol−1
B 75 714 kJ mol−1 D −97.0 kJ mol−1

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) [3]

c Explain why bond enthalpies could not be used

33 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 mol−1
Draw an enthalpy level diagram for this reaction and explain whether NO2 or N2O4 is more stable. [3]

12 a Define ‘standard enthalpy change of formation’. [2]

b
SKILL CHECK
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
(a)
enthalpy change of formation of propan-1-ol. [3]

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. [3]

34

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. [3]

BILAL HAMEED ENTROPY

 11 a Explain what you understand by the term ‘average bond enthalpy’. [2]
b Write a chemical equation for the standard enthalpy change of formation of propan-1-ol. [2]
b Use the average bond enthalpies given in the table to calculate the enthalpy change for the
c Use the standard enthalpy change of combustion values given in the table to calculate the standard
combustion of ethanol vapour, according to106
the equation:
enthalpy change of formation of propan-1-ol. [3]
C2H5OH(g) + 3O2(g) 2CO2(g) + 3H2O(g) [3]

SKILL CHECK
c Explain why bond enthalpies could not be used to work out the enthalpy change for the reaction:
d UseCthe
(b) 2H5standard
OH(l) + 3O 2(g) values
entropy 2COin2(g)
the+table
3H2O(l)
below to calculate the entropy change for the complete [2]
combustion of propan-1-ol
d Consider the reaction: and justify the sign of the entropy change. [3]

N2O4(g) 2NO2(g) ∆H = +57 kJ mol−1

Draw an enthalpy level diagram for this reaction and explain whether NO2 or N2O4 is more stable. [3]

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]
e Calculate the standard free energy change, ∆G , for the complete combustion of propan-1-ol and
c Use the standard enthalpy change of combustion values given in the table to calculate the standard
explain whether the reaction will be spontaneous at 25 °C. [3]
enthalpy change of formation of propan-1-ol. [3]

35

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. [3]

SKILL CHECK
e Calculate the standard free energy change, ∆G , for the complete combustion of propan-1-ol and
(c)
explain whether the reaction will be spontaneous at 25 °C. [3]

36

BILAL HAMEED ENTROPY

 For the reaction C2H4 (g) + HCl(g) → C2H5Cl(g), at 298 K,
∆H 1 = −96.7 kJ mol –1 and ∆G 1 = −25.9 kJ mol –1.
Calculate the value of ∆G 1 at 1000 K. 107
Further energy changes
Answer
∆G 1 = ∆H 1 − T∆S 1
At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
Worked example SKILL CHECK
1. −70 800 −1 −1
∆S = = −239 J mol K
298 C2H4 (g) + HCl(g) → C2H5Cl(g), at 298 K,
For the reaction
∆H1000
At 1 K, ∆G
= −96.7 = −96.7
kJ1mol –1

= +142
Calculate the value
(
and –∆G1000
of ∆GkJ
1
1

mol -1
at 1000
−239
1000
K.
)
× kJ mol –1.
= −25.9

ThisAnswer
shows that as the temperature increases, the addition reaction becomes less feasible.

∆G 1 = ∆H 1 − T∆S 1
At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
Now try this
−70 800
∆S 1.= = −239 J mol−1 K−1
298
1 Calculate the temperature
(
at which ∆−239
At 1000 K, ∆G 1 = −96.7 – 1000 ×
zero.
= +142 kJ mol-1
1000 )
G1 for the addition of HCl to ethene becomes

2 When KNO3 dissolves in water at 298 K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 = +0.3 kJ mol−1.
This shows that
a Calculate ∆S 1as
. the temperature increases, the addition reaction becomes less feasible.
b Calculate ∆G at 320 K.
1

c Comment on the effect of temperature on the solubility of KNO3.

Now try this
3 Heptane is converted into methylbenzene37industrially:
C7H16(l) →
1 Calculate theC7temperature
H8(l) + 4H2(g)
at which ∆G1 for the addition of HCl to ethene becomes
zero.K, ∆H = +211 kJ mol and ∆G1 = +110 kJ mol−1.
At 300 1 –1
−1 −1
2 When ∆G 1 3 dissolves in water at 298 K, ∆H = +34.8 kJ mol and ∆G = +0.3 kJ mol .
KNO 1 1
Estimate at: 1
a Calculate
a 600 K ∆S .
b Calculate
b 900 K ∆G1 at 320 K.
c Comment on the effect of temperature on the solubility of KNO3.
c Explain why your estimated values will be unreliable.
3 Heptane is converted into methylbenzene
SKILL CHECK industrially:
C7H16(l) → C7H8(l) + 4H2(g)
Applying free
At 300 K, ∆H 1
energy
= +211 kJ mol–1 andchanges
∆G1 = +110 kJ mol−1.
Estimate
The free ∆Gof at:
energy
1
a reaction tells us whether the reaction proceeds spontaneously
a 600 K
and this depends on the signs and magnitudes of both ∆H 1 and ∆S 1 for the reaction.
b 900 K 1
As ∆Hc1 Explain
and ∆Swhycan each be positive or negative, there are four possibilities.
your estimated values will be unreliable.

∆H 1 and ∆S 1 both positive

TheseApplying
reactions arefree
said toenergy
be entropy changes
driven. These endothermic reactions, which
may not be feasible at room temperature, become feasible if the temperature is raised
The free energy of a reaction tells us whether the reaction proceeds spontaneously
(Le Chatelier’s Principle). The following are some examples:1
and this depends on the signs and magnitudes of both ∆H and ∆S 1 for the reaction.
As ∆H 1and
● melting ∆S 1 can each be positive or negative, there are four possibilities.
andboiling
● decomposition reactions
∆H 1 and ∆S 1 both positive
● electrolysis
38
These reactions
● dissolving are cases).
(in some said to be entropy driven. These endothermic reactions, which
may not be feasible at room temperature, become feasible if the temperature is raised
It is(Le
easy to see why
Chatelier’s both ∆H
Principle). The and
1
∆S 1 are
following arepositive for melting and boiling (see
some examples:
Figure 20.10). The change is endothermic because intermolecular bonds are being
● melting and boiling
broken. There is an increase in the entropy because disorder increases from solid to
● decomposition reactions
liquid to gas.
● electrolysis
BILALMost
HAMEEDdecomposition reactions (for example, the cracking of alkanes and theENTROPY
● dissolving (in some cases).
thermal decomposition of calcium carbonate) are endothermic because the total bond
enthalpy in the
It is easy products
to see why both ∆H than
is less 1
∆S 1inare
andthat thepositive
reactants. The energy
for melting required
and boiling to
(see
 (
At 1000 K, ∆G = −96.7 – 1000 ×
= +142 kJ mol-1
1000 )
This shows that as the temperature increases, the addition reaction becomes less feasible.
108

Now try this

SKILL
1 Calculate the temperature at which ∆G1 forCHECK
the addition of HCl to ethene becomes
zero.
Chapter
2 When KNO3 dissolves in water at 298 K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 =23: Entropy
+0.3 kJ mol−1and
. Gibbs free ener
a Calculate ∆S .
1

b Calculate ∆G1 at 320 K.

c Comment on the effect of temperature on the solubility of KNO3.
3 Heptane is converted into methylbenzene industrially:
■ Standard
C7H16(l)Gibbs
→ Cfree energy of reaction is the Gibbs
7H8(l) + 4H2(g)
the enthalpy change of reaction and entropy
free energy change when the amounts of reactants change of the system by the relationship
At 300 K, ∆H 1 = +211 kJ mol–1 and ∆G1 = +110 kJ mol−1. —
O —
O —
O
shown in the stoichiometric equation react under ∆G reaction = ∆G products – ∆G reactants
standard∆G
Estimate at: to form the products.
1
conditions ■ The Gibbs free energy change of formation of an
a 600 K
■ Gibbs free energy is related to the enthalpy change element is zero.
b 900 K
of reaction and entropy change of the system by the
c Explain why your
—
O estimated
—
O values
—
O will be unreliable.■ Spontaneous (feasible) chemical changes involve a
relationship ∆G = ∆H reaction – T∆S system decrease in Gibbs free energy (∆G is negative).
■ The Gibbs free energy change of a reaction can ■ Chemical reactions tend not to be spontaneous if there
Applying free energy changes
be calculated from Gibbs free energy changes
39
is an increase in Gibbs free energy (∆G is positive).
of formation using the relationship is related to
The free energy of a reaction tells us whether the reaction proceeds spontaneously
and this depends on the signs and magnitudes of both ∆H 1 and ∆S 1 for the reaction.
As ∆H 1 and ∆S 1 can each be positive or negative, there are four possibilities.

∆H 1 and ∆S 1 both positive

These reactions are said to be entropy driven. These endothermic reactions, which
may not be feasible at room temperature, become feasible if the temperature is raised
End-of-chapter questions SKILL CHECK
(Le Chatelier’s Principle). The following are some examples:
1 Graphite and diamond are both forms of carbon. Their standard molar entropies are:
● melting and boiling
● ∆S —
O
decomposition K–1 mol–1, ∆S —
graphite = 5.70 Jreactions
–1
diamond = 2.40 J K mol
O –1

● electrolysis
a i Suggest why the standard molar entropy of graphite is greater than that of diamond. [2]
● dissolving (in some cases).
ii Calculate the entropy change of the process C C at 298 K [1]
graphite diamond
iii Explain
It is easy to see why
whyyou would
both ∆Hbe1 unlikely 1
and ∆S toaremake diamonds
positive forfrom graphite
melting andatboiling
atmospheric
(see
temperature and pressure.
Figure 20.10). The change is endothermic because intermolecular bonds are being [1]
b The standard –1.
broken. There is anmolar enthalpy
increase change
in the for Cgraphite
entropy Cdiamond isincreases
because disorder +2.00 kJ molfrom solid to
i Calculate
liquid to gas. the total entropy change for this reaction at 25.0 ºC. [4]
Mostii decomposition
Explain why youreactions
would be unlikely to make diamonds
(for example, the crackingfromofgraphite
alkanesat atmospheric
and the
temperature and pressure. [1]
thermal decomposition of calcium carbonate) are endothermic because the total bond
c Graphite reacts with oxygen to form carbon dioxide. Would you expect the entropy of the
enthalpy in the products is less than that in the reactants. The energy required to
products to be greater or less than the entropy of the reactants? Explain your answer. [1]
break relatively strong bonds is not recovered by the formation of fewer or weaker
bonds. Decomposition reactions are accompanied by an increase in entropy because Total = 10
40
the change
2 3268 inrequired
kJ are numbertoof molecules,
change ∆n,
1 mole of is positive.
ethanol into its gaseous atoms.

C2H5OH(g) 2C(g) + 6H(g) + O(g)

a Calculate the entropy change of the surroundings during this process when it is carried339
out at 150 °C. [3]
b Explain why the total entropy change of this reaction is likely to be negative. [2]
c When ethanol undergoes combustion, carbon dioxide and water are formed.
BILAL HAMEED –1 ENTROPY
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) reaction = –1367 kJ mol
∆H —
O

10/10/14 9:31 PM
Calculate the total standard entropy change for this reaction.
 ■ Standard Gibbs free energy of reaction is the Gibbs the enthalpy change of reaction and entropy
free energy change when the amounts of reactants
109 change of the system by the relationship
—
O —
O —
O
shown in the stoichiometric equation react under ∆G reaction = ∆G products – ∆G reactants
standard conditions to form the products. ■ The Gibbs free energy change of formation of an
■ Gibbs free energy is related to the enthalpy change element is zero.
of reaction and entropy change of the system by the ■ Spontaneous (feasible) chemical changes involve a
—
O —
O —
O
relationship ∆G = ∆H reaction – T∆S system decrease in Gibbs free energy (∆G is negative).
■ The Gibbs free energy change of a reaction can ■ Chemical reactions tend not to be spontaneous if there
be calculated from Gibbs free energy changes is an increase in Gibbs free energy (∆G is positive).
of formation using the relationship is related to

End-of-chapter questions
1 Graphite and diamond are both forms of carbon. Their standard molar entropies are:
∆S — –1 –1 — –1 –1
graphite = 5.70 J K mol , ∆S diamond = 2.40 J K mol
O O

a i Suggest why the standard molar entropy of graphite is greater than that of diamond. [2]
ii Calculate the entropy change of the process 41
Cgraphite Cdiamond at 298 K [1]
iii Explain why you would be unlikely to make diamonds from graphite at atmospheric
temperature and pressure. [1]
b The standard molar enthalpy change for Cgraphite Cdiamond is +2.00 kJ mol–1.
i Calculate the total entropy change for this reaction at 25.0 ºC. [4]
ii Explain why you would be unlikely to make diamonds from graphite at atmospheric
temperature and pressure. [1]
c Graphite reacts with oxygen to form carbon dioxide. Would you expect the entropy of the
products to be greater or less than the entropy of the reactants? Explain your answer. [1]
SKILL CHECK Total = 10

2 3268 kJ are required to change 1 mole of ethanol into its gaseous atoms.

C2H5OH(g) 2C(g) + 6H(g) + O(g)

a Calculate the entropy change of the surroundings during this process when it is carried out at 150 °C. [3]
b Explain why the total entropy change of this reaction is likely to be negative. [2]
c When ethanol undergoes combustion, carbon dioxide and water are formed.
–1
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) reaction = –1367 kJ mol
∆H —
O

Calculate the total standard entropy change for this reaction.

(Values for S —
O
in J K–1 mol–1: C2H5OH(l) = 160.7, CO2 =213.6, H2O(l) = 69.90, O2(g) = 205.0) [6]
Total = 11

42

BILAL HAMEED ENTROPY