91

Entropy change, ΔS ⦵

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

alt
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, ΔS ⦵, given the standard entropies, S ⦵, of
the reactants and products

Gibbs free energy change, ΔG⦵

a define standard Gibbs free energy change of reaction by means of the equation ΔG⦵=
ΔH⦵ – TΔS⦵

b calculate ΔG⦵ for a reaction using the equation ΔG⦵ = ΔH⦵ – TΔS⦵

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

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

92

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

alt
Learning outcomes
Candidates should be able to:

5.1 Enthalpy change, ΔH

5.3 Entropy change, a)
a) explain
explainthat
thatchemical
entropyreactions are accompanied
is a measure by energy
of the ‘disorder’ changes,and
of a system,
ΔS ⦵ principally in the form of heat energy; the energy changes
that a system becomes more stable when its energy is spread can be out
exothermic (ΔH is negative)
in a more disordered stateor endothermic (ΔH is positive)
b)
b) explain
explainandtheuse the terms:
entropy changes that occur:
(i)
(i) enthalpy
during a change
changeofinreaction and(s)
state e.g. standard
→ (I); (I)conditions,
→ (g); (s) with
→ (aq)
particular reference to: formation, combustion, hydration, solution,
(ii) during a temperature change
neutralisation, atomisation
(iii) during a reaction in which there is a change in the number of
(ii) bond energy (ΔH positive, i.e. bond breaking)
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
or negative enthalpy changes from appropriate experimental results,
including the use of the relationship
d) calculate the entropy change for a reaction, ΔS , given the
⦵

standard entropies,enthalpyS , of the

⦵ change, ΔH =and
reactants ΔT
–mcproducts
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)

b) apply Hess’
calculate ΔGLaw
⦵
toaconstruct
for reactionsimple energy
using the cycles,Δand
equation G =carry
⦵
ΔH ⦵out
– TΔS
⦵

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

d) (i) determining
predict enthalpy
the effect changes that
of temperature cannot
change onbe found
the by direct of a
spontaneity
experiment,
reaction, given e.g. an enthalpy
standard change
enthalpy and of formation
entropy from enthalpy
changes
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

Entropy Bilal Hameed
 93

3.1 Entropy
The dissolving of sodium chloride (common salt) in water is an

alt
endothermic process that occurs spontaneously at room temperature.
The idea of an endothermic reaction occurring spontaneously goes
against our daily experiences that things do not seem to move
spontaneously from lower to higher energy states (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 energy changes involved

that can be used to predict whether a reaction occurs spontaneously.

3.2 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.

3.3 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:
H2O(l) ⟶ H2O(g) ∆Sϴ = +119 JK−1 mol−1.
The disorder of the system has increased, as the molecules of water in
the gas phase are moving around much more.

Bilal Hameed Entropy

 94

3.4 Entropy change

A negative value for ∆Sϴ indicates a decrease in entropy, i.e. a decrease

alt
in disorder. For example

NH3(g) + HCl(g) ⟶ NH4Cl(s) ∆Sϴ = —285 JK−1mol−1

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

in disorder, i.e. a decrease in entropy.

This is an approximate rule

thumb, which is useful whe
considering the same substa
different states or similar su
When considering very diff
substances, it must be used
3.5 Predict the sign of an entropy change caution. For instance, S fo
(NH4)2SO4(s) is 220 J K−1 m
Gases have higher entropy than liquids, which have higher entropy than whereas that for CCl4(l) is
solids.
214 J K−1 mol−1 and that for
is 187 J K−1 mol−1.
The table below shows the values of standard entropies for elements
across period 2 in
Table 5.4 the the
shows periodic table.
values of
entropies for elements across
standard
period 2 in the periodic table. Lithium to carbon are all solid elements
Lithiumand
tohave
carbon are solid
low entropy elements
values at 298 K,and have low
but nitrogen entropy
to neon are allvalues
gases at 298
K, but and
nitrogen to neon
have much higherare gases
entropy and have much higher entropy values.
values.

Increase in number of mo
of gas: ∆S +ve (entropy
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 number of m
important factor in determining whether a chemical reaction involves an
of gas: ∆S −ve (entropy
increase or decrease in entropy is whether there is an increase or decrease
decreases).
3.6 Predict
in the number ofthe
molessign of an
of gas (Table 5.5).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 JK−1mol−1, whereas that for CCl4(l)
is 214 JK−1mol−1 and that for HCl(g) is 187 JK−1mol−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)

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

Entropy Bilal Hameed

 95

3.7 Predict the sign of an entropy change

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

alt
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
This is an approximate rule of
involves an increase or decrease in entropy is whether there is an
thumb, which is useful when
increase or decrease in the number of moles of gas.

considering the same substance in

different states or similar substances.
When considering very different
Increase in number of moles of gas: ∆Sϴ +ve (entropy increases).
substances, it must be used
with
caution. For instance, S for
Decrease in number of moles of gas: ∆Sϴ −ve (entropy
(NH4)2SO decreases). −1
4(s) is 220 J K 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.

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.

3.8 Entropy changes for some reactions

Increase in number of moles
gas: ∆S +ve (entropy
If the number of moles of gas is the same on bothof sides
increases).
of an
To predict the sign of the entropy change in a reaction, we must
equation,
consider whether the
thereprediction
is an increase orcould
decrease be made
in disorder that
in the the entropy change for this
system.
As gases have significantly higher entropy than solids and liquids, the most
reaction would be approximately zero. For example:
important factor in determining whether a chemical reaction involves an
Decrease in number of moles
of gas: ∆S −ve (entropy
F2(g) + Cl2(g) ⟶ 2ClF(g)
increase or decrease in entropy is whether there is an increase or decrease
in the number of moles of gas (Table 5.5).
∆Sϴ decreases).
≈0

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.

3.9 Skill check 1

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)

Bilal Hameed Entropy

 4NH
4NH3(g) + 3O2(g) 3
(g) 2N
+ 3O 2(g)
2(g) + 6H22N2(g) + 6H2O(l)
O(l)

96

A −1−240 kJ mol−1
A −240 kJ mol C −1532 kJCmol−1532
−1 kJ mol−1
B −1−332 kJ mol−1
B −332 kJ mol D −1900 kJDmol−1900
−1 kJ mol−1
3.10 Skill check 2
8 Which of8theWhich of the following
has reactions has that
a ∆Sis negative?
value that is negative?

alt
following reactions a ∆S value
A 2H2O2(aq) A 2H 2O
2H 2(aq)+ O22H
2O(l) (g)2O(l) + O2(g)
B CaCO3(s)B CaCO CaO(s)3(s)
+ COCaO(s)
2(g) + CO2(g)
CaCO3(s) + 2HCl(aq)
C CaCO3(s)C+ 2HCl(aq) CaCl2(aq) + CO CaCl 2(aq)
2(g) + H+2O(l)
CO2(g) + H2O(l)
D 2C4H10(g) 2C4H
D+ 13O 2(g)
10(g) + 13O
8CO 2
2
(g)
(g) + 8CO
10H 2
(g)
O(l)
2 + 10H2O(l)

9 Which of9theWhich of the

following willfollowing
have the will have
largest the of
value largest value
lattice of lattice enthalpy?
enthalpy?
A NaCl A NaClB MgO B MgOC CaO C CaO D MgBr2 D MgBr2

Using
10data
10 Using the giventhe data given
below, below,
calculate the calculate the value
value of ∆G of ∆G
, for the , for the
following following
reaction reaction
at 298 K: at 298 K:
SO2(g)SO
SO2(g) + Cl2(g) + Cl2(g)
2Cl2(l)
SO2Cl2(l)
−1 −1 J K−1 mol−1
∆H = −97.3∆H = −1
kJ mol −97.3
and kJ
∆Smol= −254.4
and ∆SJ K−1
= mol
−254.4

A −21.5 kJ A −21.5 kJ mol−1

mol−1 C −173.1 kJCmol−173.1
−1 kJ mol−1
−1 714 kJ mol−1 −97.0 kJ mol−1
B 75 714 kJBmol75 D −97.0 kJ D
mol−1

3.11 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

Values of ∆S may be worked

3.12 Calculating entropy changes entropy change
= total entropy of produ
Calculate the standard entropy change for the following reaction:

∆S = ∑S product
N2(g) + 3H2(g) ⟶ 2NH3(g)

Calculate the standard entropy

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

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

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
Entropy Bilal
standard entropy change Hameed
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)
 97

3.13 Skill check 3

What is ∆Sϴ for the following reactions?

alt
(a) CaCO3(s) ⟶ CaO(s) + CO2(g)

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






(b) C2H4(g) + H2O(l) ⟶ C2H5OH(l)


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

3.14 Skill check 4

Substance Sϴ / J K−1
Use the entropy values in the table to calculate the CH4(g) mol−1186

standard entropy change in each of the following reactions:

O2(g) 103
CO2(g) 214
(a) CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l) 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

3.15 Skill check 4

Substance Sϴ / J K−1

(b) 2Cu(NO3)2(s) ⟶ 2CuO(s) + 4NO2(g) + O2(g)
 CH4(g) mol−1186

O2(g) 103

 CO2(g) 214

 H2O(l) 70
Cu(NO3)2(s)
193


CuO(s)
43
NO2(g) 240
BCl3(l)
206
(c) 4BCl3(l) + 3SF4(g) ⟶ 4BF3(g) + 3SCl2(g) + 3Cl2(g)
SF4(g)
292
BF3(g) 254
SCl2(g) 282
Cl2(g) 83

Bilal Hameed Entropy

 98

3.16 Spontaneity
Spontaneous reaction: one that occurs without any outside influence, i.e.

alt
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.

3.17 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.

3.18 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
(system & surroundings). The total entropy change is given by:

∆STotal = ∆Ssurroundings + ∆Ssystem

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

Entropy Bilal Hameed

 99

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

alt
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 = ∆Ssystem — ∆Hreaction
T

3.20 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

3.21 Gibbs free energy

∆G is called the change in Gibbs free energy, or just the free energy
change. 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 kJmol−1 and T must be in K. The subscripts are now
omitted, as both ∆H and ∆S refer to the system (the chemical reaction).

Bilal Hameed Entropy

 100

3.22 Calculating ∆G
We can calculate ∆G for C2H2(g) + 2H2(g) ⟶ C2H6(g) given the following

alt
information:

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


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

3.23 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

3.24 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.

Entropy Bilal Hameed

 101

3.25 Skill check 5

alt
3.26 Skill check 6

3.27 Skill check 7

Calculate the Gibbs free energy change for the decomposition of zinc
carbonate at 298 K.
ZnCO3(s) ⟶ ZnO(s) + CO2(g) ∆H = +71.0 kJmol–1
Values for ∆S in JK–1mol–1:

CO2(g) = +213.6, ZnCO3(s) = +82.4, ZnO(s) = +43.6

Answer: +18.9 kJmol–1

Bilal Hameed Entropy

 102

3.28 Changing temperature & ∆G

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

alt
∆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.Therefore, as the

temperature is increased, this reaction becomes more spontaneous.

3.29 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.

3.30 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.

Entropy Bilal Hameed

 6 Use the approximate enthalpy change of combustion values given in the table to calculate the enthalpy
change (in kJ mol−1) for the reaction:
C4H6(g) + 2H2(g) C4H10(g)
103

3.31 Changing
A 290 temperature
B −290 & ∆G
C −5 D 5

alt
7 Use the enthalpy change of formation values in the table to calculate the enthalpy change for the following
reaction: Reactions for which ∆S is positive
become more spontaneous as
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l)
temperature increases, but reactions
for which ∆S is negative become
less spontaneous as temperature
increases.
A −240 kJ mol−1 C −1532 kJ mol−1
B −332 kJ mol−1 D −1900 kJ mol−1

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

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)
26 Given
D 2Cthe4Hdata below,
10(g) + calculate
13O2(g) 8CO2∆G for2O(l)
(g) + 10H the 29 Calculate ∆G for the following reaction, given
following reaction at 298 K and state whether it the ∆G f values in the table:
9 Which of is
thespontaneous
following will or not:
have the largest value of lattice enthalpy? C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l)
C2H 4(g) + H2(g) B CMgO 2H6(g)
3.32 Skill A
check
NaCl
8
∆H = −137 kJ mol−1 and
C CaO D MgBr2

given=below,
10 Using the data∆S −55.3 J K−1 mol
calculate
−1
the value of ∆G , for the following reaction at 298 K:
SO27 Given
2(g) + Cl2(g) theSO
data
2Cl2below,
(l) calculate ∆G for the
−1
∆H =following
−97.3 kJ molreaction
and ∆Sand
= −254.4 J K−1 mol−1it is
state whether
spontaneous
A −21.5 kJor molnot
−1
at 298 K: C −173.1 kJ mol−1
B 75 714 kJ mol
C3H8(g) + 5O2(g)
−1
3CO2(g) + 4H2O(l)−97.0 kJ mol
D −1
Is the reaction spontaneous at 298 K?
11 a Explain what you understand by the term−1 ‘average bond enthalpy’. [2]
∆H = −2219 kJ mol and 30 Consider the decomposition of Pb(NO3)2(s):
b Use the average bond enthalpies given in the −1
table to calculate the enthalpy change for the
combustion of = −373.3
∆Sethanol J K−1 mol
vapour, according to the equation: 2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)
−1
28
C Calculate
2H5OH(g) ∆G 2CO
+ 3O2(g) for2(g)
the following
+ 3H 2O(g) reaction, given ∆H = +598[3]kJ mol ∆G = +333 kJ mol−1
the ∆G f values in the table: a Work out the value for ∆S at 298 K.
CaCO3(s) CaO(s) + CO2(g) b Assuming that ∆H and ∆S do not change
with temperature, calculate the temperature,
c Explain why bond enthalpies could not be used to work out the enthalpy change for the reaction:
in °C, above which this reaction will become
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) [2]
spontaneous.
d Consider the reaction:
N2O4(g) 2NO2(g) ∆H = +57 kJ mol−1
31 For each of the following reactions, predict
whether it becomes more or less spontaneous as
Draw an enthalpy level diagram for this reaction and explain whether NO2 or N2O4 is more stable. [3]
temperature increases:
a Define ‘standard enthalpy change of formation’. a N2O4(g) [2] 2NO2(g)
12
3. 33 Skill check 9 b N 2(g) + 3H (g)
2[2] 2NH3(g)
b Write a chemical equation for the standard enthalpy change of formation of propan-1-ol.
2KNO3(s)
c standard
c(a) Use the standard enthalpy change of combustion values given in the table to calculate the 2KNO2(s) + O2(g)
enthalpy change of formation of propan-1-ol. d 2AgNO3(s) [3] 2Ag(s) + 2NO2(s) + O2(g)

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]

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]
Defithe
12 ba Use ne ‘standard enthalpy
average bond change of
enthalpies formation’.
given in the table to calculate the enthalpy change for the [2]
b combustion of ethanol
Write a chemical vapour,
equation according
for the standardto the equation:
enthalpy change of formation of propan-1-ol. [2]
104
c Use H5OH(g)
C2the standard+enthalpy
3O2(g) change
2COof2(g) + 3H2O(g)values given in the table to calculate the standard
combustion [3]
enthalpy change of formation of propan-1-ol. [3]

c Explain why bond enthalpies could not be used to work out the enthalpy change for the reaction:
3.34 Skill
C2H5OH(l) check
+ 3O2(g) 2CO92(g)
-+continued
3H2O(l) [2]
d Consider the reaction:

alt
d Use the standard entropy values in the table below to calculate the entropy change for the complete
(b)
−1
N2O4(g) of propan-1-ol
combustion 2NO2(g) and ∆Hjustify
= +57 kJ mol
the sign of the entropy change. [3]
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]
c Use the standard enthalpy change of combustion values given in the table to calculate the standard
e enthalpy
Calculatechange of formation
the standard of propan-1-ol.
free energy change, ∆G , for the complete combustion of propan-1-ol and [3]
explain whether the reaction will be spontaneous at 25 °C. [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]

3.35 Skill check 9

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]

20 Further energy changes

Worked example
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.
20 Answer Further energy changes
∆G 1 = ∆H 1 − T∆S 1
At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
3.
∆S
36
1. −70
Worked
= Skill
800 check −110
example
= −239 J mol K−1
298
For1000
At
1
the reaction C2−96.7
K, ∆G 1 =
∆H = −96.7 kJ mol –1
andkJ∆G
= +142
(
H4 (g) +– HCl(g)
1000 →
−239
1000 –1
mol= −25.9 kJ mol .
1 -1
)
× C2H5Cl(g), at 298 K,

Calculate the value of ∆G 1 at 1000 K.

This shows that as the temperature increases, the addition reaction becomes less feasible.
Answer
∆G 1 = ∆H 1 − T∆S 1
Now
At try
298this
K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
−70 800 −1 −1
∆S 1.= the temperature
1 Calculate = −239 J at
mol K ∆G1 for the addition of HCl to ethene becomes
which
298
zero.
At 1000 K, ∆G = −96.7 – 1000 ×
2 When KNO3 dissolves
1

in water
= +142 kJ mol
( −239
-12981000
at
)
K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 = +0.3 kJ mol−1.
a Calculate ∆S . 1
This shows that as the temperature increases, the addition reaction becomes less feasible.
b Calculate ∆G1 at 320 K.
c Comment on the effect of temperature on the solubility of KNO3.
3 Heptane
Now try is converted
this into methylbenzene industrially:
C7H16(l) → C7H8(l) + 4H2(g)
1 300
Calculate
K, ∆Hthe
1 temperature –1
= +211 kJ mol at and ∆G∆1G= +110
which for the
kJaddition
mol−1. of HCl to ethene becomes
1
At
zero.
2 When∆G
Estimate KNOat:
1
−1
3 dissolves in water at 298 K, ∆H = +34.8 kJ mol
1
and ∆G1 = +0.3 kJ mol−1.
a 600 K
a Calculate ∆S 1.
Entropy Bilal Hameed
b 900 K
b Calculate ∆G1 at 320 K.
c Explain why your
c Comment estimated
on the effect ofvalues will be on
temperature unreliable.
the solubility of KNO3.
3 Heptane is converted into methylbenzene industrially:
 105

3.37 Skill check 11 Further energy changes

alt
Worked example
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.

Answer
∆G 1 = ∆H 1 − T∆S 1
At 298 K, −T∆S 1 = −25.9 − (−96.7) = +70.8 kJ mol–1
−70 800
∆S 1.= = −239 J mol−1 K−1
298
At 1000 K, ∆G 1 = −96.7 – 1000 ×
= +142 kJ mol -1
( −239
1000 )
This shows that as the temperature increases, the addition reaction becomes less feasible.

Now try this

3.38 Skill check 12
1 Calculate the temperature at which ∆G1 for the addition of HCl to ethene becomes
zero. Chapter 23: Entropy and Gibbs free energy
2 When KNO3 dissolves in water at 298 K, ∆H 1 = +34.8 kJ mol−1 and ∆G1 = +0.3 kJ mol−1.
a Calculate ∆S 1.
b Calculate ∆G1 at 320 K.
c Comment on the effect of temperature on the solubility of KNO3.
StandardisGibbs
3■ Heptane free energy
converted of reaction is theindustrially:
into methylbenzene Gibbs the enthalpy change of reaction and entropy
free energy change when the amounts of reactants change of the system by the relationship
C7H16(l) → C7H8(l) + 4H2(g) —
O —
O —
O
shown in the stoichiometric equation react under ∆G reaction = ∆G products – ∆G reactants
–1 −1
At 300 K, ∆H 1
= +211 kJ mol and ∆G
standard conditions to form the products.
1
= +110 kJ mol .
■ The Gibbs free energy change of formation of an

■
Estimate ∆G
Gibbs free
1
at: is related to the enthalpy change
energy element is zero.
aof600 K and entropy change of the system by the
reaction ■ Spontaneous (feasible) chemical changes involve a
brelationship
900 K —
O —
O —
O
∆G = ∆H reaction – T∆S system decrease in Gibbs free energy (∆G is negative).
c Explain why your estimated values will be unreliable.
■ 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
Applying free energy changes
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

3.39
These Skill
reactions
End-of-chapter check
are said 13 driven. These endothermic reactions, which
to be entropy
questions
may not be feasible at room temperature, become feasible if the temperature is raised
1 Graphite
(Le and Principle).
Chatelier’s diamond areThe
bothfollowing
forms of carbon. Their examples:
are some standard molar entropies are:
∆S —
O
graphite = 5.70 J K–1 mol–1, ∆S —
O
diamond = 2.40 J K–1 mol–1
● melting and boiling
a i Suggest why the standard molar entropy of graphite is greater than that of diamond. [2] 363
● decomposition reactions
● ii Calculate the entropy change of the process Cgraphite
electrolysis Cdiamond at 298 K [1]
● iii Explain
dissolving (in why
someyoucases).
would be unlikely to make diamonds from graphite at atmospheric
temperature and pressure. [1]
It isbeasy to see why both ∆H 1 and ∆S 1 are positive Cfor melting
The standard molar enthalpy change for Cgraphite
and boiling
–1 (see
diamond is +2.00 kJ mol .
Figure i20.10). The change is endothermic because intermolecular
Calculate the total entropy change for this reaction at 25.0 ºC.
bonds are being [4]
broken. ii There
Explainiswhy
an you
increase
would inbe the entropy
unlikely because
to make diamonds disorder increases
from graphite from solid to
at atmospheric
liquid to gas.
temperature and pressure. [1]
Most decomposition
c Graphite reacts withreactions
oxygen to (for
formexample, the cracking
carbon dioxide. Would youofexpect
alkanes and theof the
the entropy
thermalproducts to be greater
decomposition of or less than
calcium the entropyare
carbonate) of the reactants? Explain
endothermic becauseyourthe
answer.
total bond [1]
enthalpy in the products is less than that in the reactants. The energy required to Total = 10
break relatively strong bonds is not recovered by the formation of fewer or weaker
2 3268 kJ are required to change 1 mole of ethanol into its gaseous atoms.
bonds. Decomposition reactions are accompanied by an increase in entropy because
2H5OH(g)
the Cchange 2C(g) of
in number + 6H(g) + O(g) ∆n, is positive.
molecules,
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]
Bilal Hameed 339 Entropy
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
 ii Calculate the entropy change of the process 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 106
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]
3.40 Skill check 14 Total = 10

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

alt
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

Entropy Bilal Hameed