Raffles Institution

Year 5 H2 Chemistry 2022

Lecture Notes Sb - Chemical Energetics 2

Content

• Entropy
• Free energy change, spontaneity of reactions

Learning Outcomes AG=AH-TAS

Candidates should be able to:

(a) explain and use the term entropy

(b) discuss the effects on the entropy of a chemical system by the following:

(i) change in temperature

(ii) change in phase
(iii) change in the number of particles (especially for gaseous systems)
(iv) mixing of particles
[quantitative treatment is not required]

(c) predict whether the entropy change for a given process or reaction is positive or negative
(d) state and use the equation involving standard Gibbs free energy change of reaction, /iG6,
tiG6 = 1i,;e - Ttise [the calculation of standard entropy change, tise, for a reaction using
standard entropies, se, is not required)

(e) state whether a reaction or process will be spontaneous by using the sign of /iG6
(f) understand the limitations in the use of /J.Ge to predict the spontaneity of a reaction
(g) predict the effect of temperature change on the spontaneity of a reaction, given standard
enthalpy and entropy changes

Lecture Outline

1 Direction of chemical change

2 Entropy and Entropy Change
3 Gibbs Free Energy Change
4 Effect of Temperature on the Spontaneity of Reaction

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 '

1 Direction of Chemical Change

• When a piece of hot sodium metal and chlorine gas come In contact, a violent reaction occurs
and sodium chloride Is formed.

2Na(s) + C/i(g) --+ 2NaC/(s)

Why do sodium and chlorine react readily to form sodium chloride?

Why does sodium chloride not form sodium and chlorine on its own accord?

• Chemists are always interested in the direction of change. By understanding the factors that
make a reaction go in a particular direction, it is possible to predict the conditions which might
allow a reluctant reaction to go the way that is wanted.

1.1 Spontaneous Change

• What is a spontaneous process?

A spontaneous process Is one that, once started, will continue without any external assistance.

• Conversely, a non-spontaneous process will not occur unless some external assistance is
continuously applied.

• Examples of spontaneous processes: H2O(s) --+ H2O(I) at 298 Kand 1 atm

NaOH(aq) + HCl(aq)--+ NaCl(aq) + H2O(I)
CH4(g) + 202(9)--+ CO2(g) + 2H2O(I)

• If a process is spontaneous, the reverse process is non-spontaneous. Both spontaneous and

non-spontaneous processes are possible, but only spontaneous processes will occur without
intervention. Non-spontaneous processes require the system to be acted on by an external
agent.

• Note: The term "spontaneous" signifies nothing about how fast a process occurs and has
nothing to do with how long a process takes to occur. A spontaneous process can either be
slow or fast.

1.2 Criteria for Spontaneity

• In early days of physical chemistry, it was thought that systems reacted or changed so as to
minimize their energy. In the 19th century, Marcellin Berthelot suggested that all exothermic
reactions are spontaneous.

• However, things are not quite simple since many endothermic processes do take place
spontaneously. Examples include the following :

o NH4NQ3(s) + aq.--+ NH4NQ3(aq) lif-16 = +26 kJ moI· 1

o H2O(s)--+ H2O(I) lif-16 = +6.01 kJ moI·1

• Since some spontaneous reactions are exothermic and others are endothermic, enthalpy (H)
alone cannot account for the direction of spontaneous change; a second factor must be
involved. This second thermodynamic factor is termed entropy (S).

• There are two natural tendencies behind spontaneous processes:

o the tendency to achieve a lower energy state and
o the tendency toward a state of greater entropy.

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 2 Entropy and Entropy Change

2.1 What Is Entropy?

Candldate1 should able to:

(a) explain and me the tenn entropy

• Definition

The entropy (symbol: S) of a system is a measure of the disorder of matter and energy in
the system. The more ways matter in the system can be arranged, and the more ways energy
in the system can be dispersed, the more disordered the system is and the larger is its
entropy.

Simplified version:
The entropy (symbol: S) of a system is a measure of the disorder in the system. The more
disordered the system is, the larger is its entropy.

• The entropy of a system is related to the number of ways the particles (atoms, molecules or ions)
in the system can be arranged or distributed and also the number of ways the energy in the
system can be dispersed or spread out.

• Example: For any substance, the entropy increases as the substance changes from solid to
liquid to gas.

0 0 0
0 0o
0o
0 O oc
0 0
0 00 0
0 0 0
0 o 0
0 0
ooo o
00
oo 0 0

solid liquid gas

entropy increases

The solid state The liquid state The gaseous state

• has the lowest entropy • has a higher entropy than the solid • has the highest entropy
• is the least disordered state but lower than that of the gas • is the most disordered
• has a regular and • is more disordered than the solid • the particles in the gas have
ordered structure in state greater freedom of motion than
which the particles are • the particles have sufficient kinetic those in the liquid
only able to vibrate energy to undergo translational • more ways to arrange the
about fixed positions in motion to some extent particles
the lattice • more ways to arrange the particles • the particles in the gas are even
• has the least energy • the particles are more randomly more randomly arranged than
dispersed within it arranged than those in the solid those in the liquid
• more ways to disperse the greater • more ways to disperse the greater
amount of energy in the liquid amount of energy in the gas

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2.2 Some Entropv Values

• Using a variety of experimental methods, it is possible to work out the absolute entropy values
of elements and compounds under different conditions. The tables below list the standard
entropies, S0 , of some substances at 298 K.

Element set J K·1 mol·1 set J K·1 mo1·1

H20(s) H20(I)
5.6 186
LlSe = seH20(1) - s eH20(s)
2.4 229
= +70-48
158 270 = +22 J mo1- 1 K-1
41 .6 127
155 198
131 214
205 48.0 C(g) C(graphite)
192 70.0 LlS8 = S6 C(graphlte) - S6 c(g)
203 189 = +5.6-158
223 72.1 = -152.4 J mo1-1 K-1
152 26.9
116 91 .7

• When comparing the same or similar substances, entropies of gases are much larger than those
for liquids, and entropies of liquids are larger than those for solids. For example, the standard
entropies of h(s), Br2(I) and C/2(g) are 116, 152 and 223 J K-1 moI·1 respectively.

• For a series of related compounds, entropy increases with increasing molecular complexity.

2.3 Entropy Change

• The entropy change (AS) for a reaction or a process is a measure of the change in disorder in a
system.

• This entropy change (iiS) depends only on the entropy of the initial state (S1n1t1a1) and entropy of
the final state (Snna1) of the system (its composition, volume, pressure, temperature).

• The entropy change (iiS) for a reaction can be worked out using tabulated standard entropy values
but this is not required as stated under learning outcome (d) in the syllabus.

• Note:
entropy change is positive entropy change is negative
(iiS > 0) (AS< 0)

=> final state is more disordered => final state is less disordered
than initial state than initial state

• A qualitative idea of the entropy change can be obtained by inspecting the equation for the
reaction, and taking note of the various factors affecting entropy as discussed in the next section.

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2.4 Factors Affecting the Entropy of a Chemical System

Candidates should be able to:

(bl di5CUSS the effects on the entropy of a chemical system by the following:
(I) change in temperature
(Ii) change In phase
(ill) change in the number of particles (especially for gaseous systems)
(iv) mixing of particles
[quantitative treatment is not required]
(c) predict whether the entropy change for a given process or reaction is positive or negative

• In general, the following factors affect entropy of a chemical system:

1 change in temperature
2 change in phase
3 change in the number of particles (especially for gaseous systems)
4 mixing of particles

(1) Change in Temperature

• The entropy of a system increases as the temperature increases.

• An increase in temperature increases the average kinetic energy of the particles in the system,
giving the particles more energy to move. For liquids and gases, the particles undergo more rapid
random motion causing greater disorder. Hence the entropy of the system increases. But this
explanation is not sufficient.

• Explanation wanted: When the temperature of a system is increased, the increase in entropy
comes about because in the broadening of the Boltzmann energy distribution, there are
more ways of arranging energy quanta in the hotter system.

• To understand the explanation, there is a need to know the Maxwell-Boltzmann distribution

curve of kinetic energies which is described briefly below.

• The kinetic energy of any Maxwell-Boltzmann Distribution of Kinetic Energies

particular molecule in a gas is
always changing. This is due to
collisions and the resultant
change in speed and hence number of
energy. molecules
with a given
• However, at any given instant, energy
due to the large number of
molecules involved, the
distribution of kinetic energies is 0
always the same at the same kinetic energy
temperature and it follows the
Maxwell-Boltzmann distribution • The area under the curve is equal to the total
diagram shown on the right. number of particles in the system.
• The peak in the curve corresponds to the number of
particles with the most probable energy.

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• The Maxwell-Boltzmann distribution diagram below shows the distribution of kinetic energies for
a given sample of molecules at different temperatures.

Note: T1 < T2 < T3

number of molecules
with a given energy

0
kinetic energy

As temperature increases from T, to T3 K,

1. the maximum of the curve is displaced to the_ r:'~ and is __b--'1..4.

c:.....av~
2. there is a greater spread of kinetic energies i.e. the distribution curve broadens

• As the temperature increases, there is a broadening of the energy distribution of the

particles. Thus, there are more possible energy states in which the particles can adopt at a
higher temperature. Hence, an increase in temperature leads to an increase in entropy.
or
• As the temperature increases, there is a broadening of the energy distribution of the
particles. Thus, there are more packets of energy available to spread out within the system,
resulting in more ways to spread out the larger number of packets of energy. Hence, an increase
in temperature will lead to an increase in entropy.

Variation of entropy with temperatlre

(2) Change in Phase
gas

• For a substance, the entropy increases in the following order

&quid
Ssolid < Suquid << Sgas

solid

Tm Tb temperature/ K
• Solid to Liquid Phase
When a solid melts into a liquid, the order in the solid is destroyed. Particles in a liquid are more
randomly arranged and more disordered than those in the solid, resulting in an increase in
entropy.

• Liquid to Gas or Solid to Gas Phase

The change from liquid to gas or solid to gas is accompanied by an even larger increase in
entropy. This is because the gaseous state is the most disordered since the gas particles can
move freely and are the most randomly arranged. This change of phase is also accompanied by a
large increase in volume.
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(3) Change In the number of particles (especially for gaseous systems)

• The entropy of a system increases as the number of particles in the system increases.

• With more particles, there are more ways to arrange the particles and more ways to distribute
the energy in the system, and hence creating greater disorder in the system.

• For processes that result in an increase in the number of moles of gaseous particles in a
system, the entropy of the system increases more significantly.

This is because the arrangement of molecules in a gas is the most disordered amongst the three
states of matter as the gas molecules move randomly in all directions.

• Some examples of such reactions include

• decomposition of CaC0J'. CaC03(s) Ca0(s} + C02(g}
• decomposition of N20: N20(g) N2(g) + ½02(9)
• combustion of propane (at 100 °C): C3Hs(g) + 502(9) 3C02(g) + 4H20(g)

(4) Mixing of Particles (without chemical reaction)

(a) Mixing of gas particles

(b) Mixing of liquid particles
(c) Dissolution of an ionic solid in water

(a) Mixing of gas particles

• Gases always mix completely to create a more disordered state.

@
• •• 0
G 00
8
Iii
Iii
• i
QI @
". 0
• Upon mixing, each gas expands to occupy the whole container. Hence there is an increase in
entropy as there are now more ways for the molecules to arrange themselves in the larger
volume.

(b) Mixing of liquid particles

• Liquids of similar polarities, e.g. benzene and hexane, mix together to form a solution in which
the molecules are randomly mixed. The solution has greater disorder than the liquids in their
unmixed state.

• There is an increase in entropy as there are now more ways for the molecules to arrange
themselves in the larger volume of the solution.

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(c) Dissolution of an Ionic solid In water

• The dissolution of an ionic solid in water can lead to a net increase or decrease in disorder
depending on the constituent ions of the ionic solid.

• Example 1: NaC/(s) + aq. Na•(aq) + Ct(aq)

• In this case, t\S > 0.

• The dissolving of sodium chloride in water involves the disruption of the crystal structure of
solid NaCl and hydration of the gaseous Na• and C, ions.

• The disruption of the crystal increases disorder, since the Na• and C, ions previously
rigidly held in the solid lattice are now free to move about.

NaC/(s) Na•(g) + Ct(g)

• The hydration process, however, decreases disorder (or increases order) about the Na•
and C, ions because it puts the hydrating water molecules into an orderly arrangement about
the Na• and C, ions.
Na•(g) + Ct(g) + aq. Na•(aq) + Ct(aq)

H"• H"• ion-dipole interaction

H(+"oI a/
o+
~,,,H
o+
o- o+\ li+ ·li-
o_ 0
g_ 6-
H '--....6- l H \ H H_./
1/ Ho• / ,Ho+
o+ ,,,O Na+ ..~, ;,,. + er,,,,,
H,, "
o- o-
0
·· , H H0 + o+o+ H0 +
0+1/0 o, "·+ I H
o-- H \
--.. . o&-
H I;,.. I • '-. H
H HOT
&-

• It turns out that in this case, the overall dissolution process results in a net increase in
disorder and entropy change is greater than zero i.e. ~S > 0.

• Example 2: CaS04(S) + aq. Ca 2•(aq) + SOl-(aq)

• In this case, t\S < 0

• For salts such as Ca$04, which contain more highly charged ions, more water molecules
are ordered about the ions, and the dissolution process often results in a net decrease in
entropy.

• In this case, the decrease in entropy in the hydration process outweighs the increase in
entropy due to the disruption of the crystal lattice.

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 Worked Example 1
For each of the following processes, state, giving a reason in each case, whether the change in
entropy of the system is positive or negative.

(a) C11H36(s) C11H36(1) (d) Na+(g) + Ct(g) NaC/(s)

AS>O AS<O

The entropy change is positive because The entropy change is negative because
the reaction produces a liquid from a solid. the reaction produces a solid from gaseous
The molecules in the liquid can move particles and results in a decrease in the
about and hence there are more ways to number of moles of gaseous particles in
arrange the molecules in the liquid state the system.
than in the solid state. This results in
greater disorder, and hence an increase in In this case, the gaseous ions that are free
the entropy of the system. to move randomly formed a solid in which
the ions are confined to fixed positions in
the lattice. Thus there is a decrease in
disorder and entropy decreases.

(b) N2(g) + 02(9) 2NO(g) (e) Ch(g) 2C/(g)

&s~o AS>O
(very small, can be positive or
negative) The entropy change is positive because
the reaction results in an increase in the
The entropy change is close to zero number of moles of gaseous particles in
because the reaction does not cause any the system.
change in the number of moles of
gaseous molecules in the system. With more particles, there are more ways to
arrange the particles and more ways to
Hence there is little change in the disorder distribute the energy in the system, and
in the system and the entropy of the hence creating greater disorder and higher
system remains almost the same. entropy in the system.

(c) 2H2O(I) 2H2(g) + 02(9) (f) Mg(s) + ZnO(s) MgO(s) + Zn(s)

S>O &s~o
(very small, can be positive or
The entropy change is positive because negative)
the reaction produces gases from a liquid
and results in an increase in the number The entropy change is close to zero
of moles of gaseous molecules in the because the reaction does not cause any
system (from Oto 3 moles). change in the number of moles of
particles in the system and also there is no
With more gaseous molecules which can phase change in any substance.
move more randomly, there are more
ways to arrange them. Thus, disorder There is little change in the number of ways
increases and hence entropy increases. to arrange the particles in the system and
the entropy of the system remains. almost
the same.

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 3 Gibbs Free Energy Change

Candidates !lhould be able to:

(di state and 1M the equation involving standard Gibbs free energy change of reaction, tiG", tiG" • AH" - TllS" (the
calculation of stand.an! entropy change, llS", for a reaction using standard entropies, S", Is not required]
(e) state v.tlether a reaction or process will be spontaneous by using the sign of tiG"
(f) undentand the limitations In the use of llG" to predict the spontaneity of a reaction

• There are two natural tendencies behind spontaneous processes:

• the tendency to achieve a lower energy state and

• the tendency toward a state of greater entropy.

• For a process or reaction, neither tiH nor tiS alone can be used to predict whether the process
or reaction is spontaneous or not. Both tiH and tiS affect the spontaneity of a reaction or
process.

• How can 6H and tiS be considered together to predict whether a reaction or a process is
spontaneous? This problem was first solved by J. Willard Gibbs, who introduced a new quantity,
now called the Gibbs free energy (or just free energy) and given the symbol G.

3.1 Standard Gibbs Free Energy Change

• The Standard Gibbs Free Energy change, tiG8, of a reaction is given by the equation:

AG8=M/8-TAS8

• Standard conditions:
• .!lG6 is obtained at a pressure of 1 bar and at a specified temperature, which is
commonly 298 K.
• The reactants and products are in their standard states.

• Generally, we can assume that t,.~ and t,.$6 do not vary significantly with temperature i.e.
t,.~ and t,.$6 can be assumed to be constant unless there is a phase change.

• Similarly, at constant temperature and pressure, the Gibbs Free Energy change, t,.G, of a
reaction is given by the equation:

t,.G= Ml- TAS

• Note

AG6 AH6 AS8

or AG orAH T orAS
Units commonly used kJ mo1- 1 kJ mo1- 1 K J mo1- 1 K-1

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3.2 Relationship between 6c;e and the Spontaneity of a Reaction

• The sign of 6c;e can be used to deduce whether a reaction or process is spontaneous under
standard conditions (i.e. 1 bar and a specified temperature, usually 298 K).

6c;e< 0 the forward reaction is spontaneous

or 6c;e Is negative (or thermodynamically feasible)
or the reaction/process is exergonic under standard conditions

6c;e > 0 the forward reaction is not spontaneous

or 6c;e is positive (or not thermodynamically feasible)
or the reaction/process is endergonic under standard conditions

• Similarly, the sign of 6G can be used to deduce whether a reaction or process is spontaneous
under non-standard condijions (i.e. at a particular temperature and pressure).
!iG= Ml- T!iS

6.G<O • the forward reaction is spontaneous

or 6G is negative (or thermodynamically feasible)
or the reaction is exeraonic
AG>O • the forward reaction is not spontaneous
or 6G is positive (or not thermodynamically feasible)
or the reaction is endergonic
AG=O* • the system is at equilibrium
• there is no net chanae
* This part will be discussed in the topic on Chemical Equilibrium.

6
3.3 Limitations of the use of /iG

• /iG6 indicates the thermodynamic feasibility (spontaneity) of a reaction i.e. whether it can occur
under standard conditions. -
• It gives no information about the kinetic feasibility (whether the reaction proceeds at an
observable rate). The kinetic feasibility of a reaction depends on the activation energy of the
reaction.
• In practice, a reaction with tJ.G6 < 0 may not occur due to the very high activation energy of the
reaction.
• Note: The same limitations apply to the use of AG under non-standard conditions.

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3.4 Calculations Involving Standard Gibbs Free Energy Change, ti.G6

Worked Example 2
Calculate t,.G6 al 500 K for each of the following Note: There is a need to convert t:.S'> from
reactions and hence predict whether the J moI- 1 K-1 to kJ moI-1 K- 1 when doing the
reaction is spontaneous at 500 K. calculations.

(a) 2CO(g) + 2NH3(g) C2Hs(g) + 2NO(g) (a) t,.c;e = Mr - Tt,.$6

fi.H0 = +409.0 kJ moI-1
ti.se = -129.1 J moI-1K-1

Note:
The units of t:.H3 and
ti.se are different.
(b) 2NO(g) + 02(9) 2NO2(g) (b) t,.c;e = Mr - Tti.S'>
1
fi.H0 = -114.1 kJ moI-
ti.se = -146.2 J moI-1 K- 1

Worked Example 3

Substance
6Gt6 I kJ moI-1

(a) Use the t:.G,e data given and the formula, 6G6 = Im6G16 (products) - IMG16 (reactants),
to calculate the standard free energy change, 6G6, for the reaction below.

MgCO3(s) MgO(s) + CO2(g) Note: The tJ.G6 of a

reaction can be
Will the above reaction take place spontaneously? calculated in a similar
way (via formula or
(b) Given that the 6/-fJ of the above reaction is +101 kJ moI-1 , and the energy cycle) to that of
6.56 for the reaction is +159 J moI-1 K- 1, determine the temperature the M-16 of a reaction,
above which the reaction will take place spontaneously. using tJ.G16 data
L - - - -- - - - - - - - -- - - - -- -----------l instead of !l.H16 data.

Solution
(a) 6G6 =- =
569 - 394-(-1012) +49 kJ mo1- 1
Since 6G6 > 0, the reaction will not take place spontaneously.

(b)

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 Worked Example 4

I Substance l C2He(q) I H20m I C02(a) I

I !1Gr"' I kJ mo1-1 I -32.9 I -237.2 I -394.4 I
With the aid of the given data and an energy cycle, calculate /1GG for the combustion
of ethane, C2He(Q).
Note: The tJ.G6 of a
reaction can be
Solution calculated in a similar
way (via formula or
7
2COz(g) + 3Hz0(1) energy cycle) to that of
C2H&(g) + Oz(g)
2 the M-16 of a reaction,
using tJ.G,e data
instead of tJ.H1e data.

Worked Example 5

For the reaction, C2H4(Q) + HC/(g) C2HsC/(g), at 298 K,

M~ = -96. 7 kJ mo1-1 and /1GG = -25.9 kJ mo1-1 .

Determine by calculation, whether the reaction is feasible at 1000 K.

Solution

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 4 Effect of Temperature on the Spontaneity of a Reactlon

Candidates should be able to:

(!II predict the effect of temperature change on the spontaneity of a reaction, given standard enthalpy and entropy
changes

• Consider dG =Mt- TdS.

• dG is dependent on temperature, T. So, for some reactions, the spontaneity depends on

temperature.
• Mt and dS change comparatively little with temperature as long as no phase changes occur.
As an approximation, both terms can be assumed to be temperature independent as long as
no phase changes occur.
• By comparing the signs and the magnitude of Mt and - HS for a reaction, the sign of dG
for the reaction can be determined, and hence the spontaneity of the reaction can be
predicted.
• There ari 4 scenarios to consider.

·~
AS
AH<O AH>O
AS>O AS>O
Spontaneous at all Spontaneous at
temperatures high temperatures
AH ...

AH<O AH>O
AS<O AS<O
Spontaneous at Non-spontaneous at
low temperatures all temperatures

4.1 The 4 Scenarios

(a) Scenario 1: AH < 0 and AS > 0

AG< 0 at all temperatures Explanation:

These reactions are spontaneous (i.e t:.G = t:.H - Tt:.S

thermodynamically feasible) at all temperatures. Comparing the signs of AH and -TAS:
Examples of such processes include:
• t:.H<O
I
decomposition of ozone and dinitrogen monoxide • t:.S > 0 - Tt:.S < 0
I
organic combustion
I
combustion of explosives Since both t:.H and -Tt:.S are negative,
AG< 0 for all values of T.

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(b) Scenario 2: Mi> 0 and AS< 0

&G > 0 at all temperatures Explanation:

These reactions are not spontaneous at 6G=Afl-T6S

all temperatures. Comparing the signs of Mi and -T6S:
Thus these reactions have to be driven • 6H>0
continuously with external assistance. • 6S < 0 -T6S > 0
Since both 6H and -T6S are positive,
Examples of such processes include:
• photosynthesis &G > 0 for all values of T.
• formation of ozone from oxygen
(c) Scenario 3: Mi> 0 and AS> 0

llH Explanation:
6G > 0 at low temperatures (T <
65)
6G=Afl-T6S
6G < 0 at high temperatures (T > :; ) Comparing the signs of Mi and -T&S:
• 6H>0
These reactions are • 6S > 0 -T6S < 0
• not spontaneous at low temperatures, AtlowT,
and
• the sign of 6G is determined by the sign of 6H
• spontaneous at high temperatures . • the positive 6H outweighs the negative -T!J.S
• !J.G> 0

Examples of such processes include: At high T,

• melting and boiling • the sign of 6G is determined by the sign of - T6S
• most decomposition reactions • the negative -T6S outweighs the positive 6H
• electrolysis • AG<O
• dissolving (for certain solids)

(d) Scenario 4: Mi< 0 and AS< 0

6.H Explanation:
AG< Oat low temperatures (T < - )
6.S
!J.G=!J.H-T!J.S
6.H
AG> Oat high temperatures (T > AS) Comparing the signs of AH and -TAS:
• !J.H< 0 and
These reactions are • !J.S < 0 - T!J.S > 0
• spontaneous at low temperatures, AtlowT,
and
• the sign of AG is determined by the sign of AH
• not spontaneous at high temperatures . • the negative AH outweighs the positive -TAS
• AG<O
.
Examples of such processes include:
condensation and freezing At high T,
\

.
• addition and combination reactions
electrochemical cells
• the sign of AG is determined by the sign of -T6S
• the positive - T6S outweighs the negative 6H
• precipitation
•6G>O

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4.2 Worked Examples

Worked Example 6
For the following reaction, explain why !:!,Ji and AS have the signs
as shown and comment on the feasibility.
AH<O, AS> 0

Solution
AS>O
The entropy change is positive because the reaction produces a gas (and a liquid) from a liquid, and
results in an increase in the number of moles of gaseous molecules (from O mole to 0.5 moles) in the
system. Wrth more gaseous molecules which can move more randomly, there are more ways to arrange the
molecules and hence creating greater disorder and higher entropy in the system.

AH<O
The enthalpy change is negative because H2O(I) and 02(9) are energetically more stable compared to
H2O2(I) or the bonds in H2O(I) and 02(9) are overall stronger compared to those in H2O2(I).

Comment on feasibility (i.e. comment on sign of AG)

t!.G=llH-Tt!.S
t!.H < 0, t!.S > 0 -Tt!.S < 0
Since t!.H and -Tt!.S are both negative, AG< 0 at all temperatures.
Thus, the reaction is spontaneous (i.e. thermodynamically feasible) at all temperatures.

Worked Example 7

For the following process, explain why AH and AS have the signs as shown
and comment on the thermodynamic feasibility.
NH4NO3(s) NH/(aq) + NO3-(aq) AH> 0, AS> 0

Solution
AS>O
The entropy change is positive because the increase in disorder due to the breaking up of the solid
ionic lattice into mobile ions outweighs the decrease in disorder due to the ordering of water molecules
around the ions via ion-dipole interactions.

AH> 0 Recall: AHsoln = "fii.Hhyd - LE

In this case, t!.H is flHso1n[NH4NO3(S)] and it is positive because the lattice energy of NH4NO3 is more
negative than the sum of AHhyd[NH4+(9)] and flHhyd(NO3-(g)].

Comment on feasibility (i.e. comment on sign of AG)

AG= AH - TAS
AH> 0, AS> 0 -TAS < 0

At low temperatures (i.e. T < : ), AG> 0 because the positive AH outweighs the negative -TAS.
The reaction is not spontaneous (i.e. not thermodynamically feasible) at low temperatures .

At high temperatures (i.e. T > : ), AG< 0 because the negative -TAS outweighs the positive AH.
The reaction is spontaneous (i.e. thermodynamically feasible) at high temperatures.

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 Worked Example 8
For the following reaction, explain why Ml and 6S have the signs
as shown and comment on the feasibility of the reaction.
C2H,(g) + H2(g) C2Ha(g) /lH < 0, !iS < 0

Solution
&S < o The entropy change is negative because the reaction results in decrease in the number of mo)es
of gaseous molecules in the system. With fewer molecules, there are fewer ways of arranging
the molecules and fewer ways of distributing the energy in the system, and hence creating less
disorder and lower entropy in the system.

Mf < 0 The enthalpy change is negative because the energy consumed to break bonds in the reactant
molecules is less than the energy released from bonds formed in the product molecules.

Note: Bonds broken: 1 C=C bond and 1 H-H bond Bonds formed: 1 C-C bond and 2 C-H bonds
1
t:.H = +610 + 436- 350-(2)(410) = -124 kJ mo1- < 0

Comment on feasibility (i.e. comment on sign of flG)

t:.G=t:.H-Tt:.S
t:.H< 0, t:.S< 0 0

At low temperatures (i.e. T < : ), AG< Obecause the negative Mf outweighs the positive -T6S.
The reaction is spontaneous (i.e. thermodynamically feasible) at low temperatures.

At high temperatures (i.e. T > : ), AG > 0 because the positive -TAS outweighs the negative AH.
The reaction is not spontaneous (i.e. not thermodynamically feasible) at high temperatures.

Worked Example 9
A reaction is non-spontaneous at room temperature but is spontaneous at -40 °C. What can you
say about the signs of /lH and /iS?

Solution
t:.H is negative and t:.S is negative.
At a low temperature of -40 °C, t:.G < 0 (i.e. the reaction is spontaneous) because the negative t:.H
outweighs the positive -Tt:.S.
At a higher temperature of room temperature, t:.G > 0 (i.e. the reaction is non-spontaneous) because the
positive - HS outweighs the negative t:.H.

4.3 Summary of Effect of Temperature on the Spontaneity of a Reaction

AG
t:.H !iS -Tt:.S
At/ow T I At high T
Always< O
1 Temperature- <O >O <O
(Spontaneous at all T)
- independent Always> O
2 cases >O <O >O
(Non-sPontaneous at alln
>O <O
3 Temperature- >O >O <O
(Non-spontaneous) (Spontaneous)
dependent <O >O
4 cases <O <O >O
(Spontaneous) (Non-spontaneous)

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4.4 Graph of 6.GO against temperature T

• M,
From the preceding sections, it should be clear that 6 is strongly dependent on temperature.
A graph of t:,.G6 for a reaction against temperature T is sometimes plotted.

t:,.G8 = (-t:,.$6) T + t:,.H9

y = mx + c

• Note that a graph of t,,,G6 against temperature T is a straight line with a gradient of -fl.Sf' and a
y-intercept (at OK) of t!,,Ji6.

• The plot below shows the variation of t:,.G6 with T for the following reaction:

,....
"=s +100

i
t<l 0

T(I<)
Example 10
In 1944, T. Ellingham published plots of 1:,~ against temperature T
for a number of reactions. Today, such plots are called Ellingham
diagrams.
An Ellingham diagram for three reactions involving the oxidation of
C and CO is shown below.

0 ---------------·
I
L...
0
E
-,
.x

UI

50D 2000
Temperature, TI K
Which of the following shows correctly the three reactions
corresponding to I, II and III in the above Ellingham diagram?
If Ill
A 2CO + 02 2C02 C + 02 CO2 2C + 0 2 2CO

B 2C + 02 2CO 2CO + 02 2C02 C+ 02 CO 2

C C + 02 CO2 2CO + 02 2C02 2C + 0 2 2CO

D 2CO + 02 2C02 2C + 02 2CO C+ 02 CO 2

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 i RAFFLES INSTITUTION
Year 5 H2 CHEMISTRY 2022
Tutorial Sb - Chemical Energetics 2

Self-Check Qp~sti9t!_S

1. The reaction, NH3(g) + HC/(g) NH4C/(s), proceeds spontaneously at 25 °C even though

there is a decrease in disorder in the system.

I Substance I NH3(g) HC/(g) NH4C/(s)

I fl.H,e/ kJ moI- 1 I -46.2 -92.3 -314.4 I
Given that t:.S8 is -284.6 J moI- 1 K- 1, explain with relevant calculations why the reaction is
spontaneous at 25 °C.

2. For each of the following reactions, predict conditions in temperature, if any, in which the
reaction will be spontaneous.

(a) X(s) Y(s) + Z(g) tJ.H8 = +250 kJ moI-1

(b) 2X(g) + Y(g) 2Z(g) tJ.H8 = -100 kJ moI-1

(c) X(I) Y(I) + Z(g) tJ.H8 = -200 kJ moI-1

(d) 2X(s) + 2Y(g) Z(g) tJ.H8 = +50 kJ moI- 1

3. One suggestion for the reduction of greenhouse gas emissions from coal-fired power stations
is to separate the CO2 from the flue gases and pump it into the sea bed, where it will dissolve
in water under pressure.
CO2(g) + nH2O(I) -= CO2(aq)
During this process, hydrogen bonds are formed between CO2 and H20 molecules.

What will be the signs of llH and !lS for th is equilibrium for the forward reaction?

fl.H 11S
A - -
B - +
C + -
D + +

4. When SOC/z is added to Ba(OH)z, a vigorous reaction occurs and the temperature falls from
25 °C to 0 °C.
What are the correct signs of fl.G and fl.S for this reaction?

fl.G 11S
A - -
B - +
C + -
D + +
5. At temperatures below 13 °c, shiny, ductile metallic tin, known as 'white tin', changes slowly
into a grey powder which is brittle.

Data for each form of tin are given in the table.

6Hr8 / kJ moI-1 $6/ J K- 1moI-1

white 0 51.4
grey -2.09 44.1

What is the expression for t1G6, in J moI-1, for the formation of grey tin from white tin at 12 °C?

A tl.G8 = -2.09 - 285 (-7.3)

B tl.G8 = -2.09-12 (+7.3)
C tl.G8 = -2090 -12 (+7.3)
D tl.G8 = -2090 - 285 (-7.3)

Practice Questions

6. Describe and explain how the entropy of each of the following systems will change during the
stated process. Assume the pressure of each system remains at 1 bar throughout.

(a) 1 mol of Ch(g) at 298 K is added to 1 mol of N2(g) at 298 K.

(b) 1 mol of Ch(g) at 298 K is heated to 373 K.

(c) 1 mol of Ch(g) at 298 K is reacted with iodine according to the following equation:

1 2
Ch(g) + 3 h(s)
3IC/3(1)
(d) 1 mol of Ch(g) at 1000 K is photolysed according to the following equation:

Ch(g) 2C/• (g)

7. The standard enthalpy change of formation, t1H18 , and the standard free energy of formation,
t1G18 , of CO(g) and CO2(g) are given in the table below.

CO(q) COia)
t1H18 / kJ moI-1 -110.5 -393.5
t1G,8/ kJ mo1- 1 -137.2 -394.4

(a) (i) Calculate the standard entropy change of formation, 11st, of CO(g) and CO2(g).
(ii) Explain why the two values in (a)(i) are so different.

(b) Use the formula t1G6(reaction) = :Emt1G18 (products) - :EMG18 (reactants) to calculate
t1G6 for the reaction
C(s) + 2CO(g)

and hence, show that the reaction is not feasible at 298 K but feasible at 1000 K.

2
8. Vaporisation and transport of tungsten normally limit the life of the tungsten filament lamp.
The quartz-iodine lamp contains small quantities of iodine which react with deposited tungsten:

W(s) + h(g) Wh(g) (on quartz envelope)

Substance h(g) Wh(g)

t:.H,0 1kJ moI- 1 +62.43 -8.37

(a) Given that t:,.$8 for the above reaction is -43.1 J mor-1 K-1, calculate t:.G8 at 350 °C, the
0 0
normal temperature of the quartz envelope. Assume that t:.H and t:.S are independent
of temperature.
(b) The Wh vapour then decomposes and deposits tungsten on the filament. The iodine is
then liberated for further scavenging. Find the temperature of the filament above which
Wl2 will decompose.
[(a) LlG112JK = -43.9 kJ mo, ;(b) T = 1643 KJ
1

9. (a) Bromine and fluorine react together to give bromine trifluoride.

Br2(I) + 3F2(g) 2BrF3(I)

(i) Construct a fully labelled energy cycle relating the reactants and products of this
reaction to their gas phase atoms. Use your cycle to calculate the average bond
energy of the Br-F bond in 8F3.

Your cycle should include relevant data from the Data Booklet together with the
following data.

standard enthalpy change of formation of BrF3(I) = -301 kJ moI- 1

enthalpy change of vaporisation of Br2(I) = +31 kJ moI-1
enthalpy change of vaporisation of BrF3(I) = +44 kJ moI-1

(ii) The standard Gibbs free energy of formation, t:.G?, of BrF3(I) is -241 kJ moI-1.
Calculate tS? and comment on its sign with respect to the reaction.

(b) Chlorine dioxide readily decomposes to its elements.

2 O=C/=O(g) C/2(9) + 202(9) t:.H8 = -204 kJ moI-1

(i) Construct a suitable energy cycle using this equation and use data from the Data
Booklet and your cycle to calculate the Cl=O bond energy in C/O2.

(ii) Explain how the value and sign of t:.G8 would compare to the value and sign of t:,.H8
for the decomposition of C/O2.

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10. When fuel consisting of 2,3,4-trlmethylpentane, C8H,8. is combusted In a car engine, it can
form either CO2or CO, according to the following equations.
25
CaH,e(I) + ¥02(9) 8CO2(g) + 9H2O(I) - - -- - (1)

17
CeH,e(I) + i02(g) 8CO(g) + 9H2O(I) ----(2)

The following data are available:

Reaction Af-16 I kJ mo1- 1 .1se / J moi--1 K-1

(1) -5465 -553
(2) -3261 +138

(a) Calculate 6.G6 for reactions (1) and (2). f- 5300 kJ mo,'; -3302 kJ mo,'J

(b) Hence, suggest which reaction predominantly takes place during the combustion of
CeH,e under standard conditions.

(c) On the axes provided below, sketch how AG6 for each reaction (1) and (2) will vary with
temperature. Label your sketches appropriately.

t:,,r;e I kJ mo11

Qi,-----------
T/K

(d) Comment on whether CO or CO2 will be produced when combustion takes place at very
high temperatures.

11. The following data relates to the energy changes which occur when sodium hydroxide, NaOH,
and magnesium hydroxide, Mg(OH)2, dissolve in water:

sodium maQnesium
Hydration enerav of metal ion / kJ moI-1 -390 -1890
Lattice eneraY of metal hydroxide / kJ moI- 1 -896 -2995
Enthalpy chanae of solution of metal hydroxide / kJ moI- 1 -44 X
Extent of hydration of metal ion 5 15
(AveraQe number of attached water molecules per metal ion)

(a) Explain why the hydration energy of Mg 2• is more negative than that of Na•.

(b) Use the data above, calculate x, the enthalpy change of solution of Mg(OH)2.
{x= +5 kJ mo, 1}

(c) Solubility is also controlled by the entropy change which accompanies dissolution. Use
the extent of hydration from the table to compare qualitatively the entropy changes of
solution of Mg(OH)2 and NaOH. -

(d) Suggest and explain one other factor which contributes to the total entropy change when
Mg(OH)2 dissolves in water.

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