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H2 Chemistry Notes

H2 Chemistry (9729)
Lecture Notes 6B
Chemical Energetics II

Assessment Objectives:
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, ΔG θ, ΔGθ =
ΔHθ – TΔSθ [the calculation of standard entropy change, ΔSθ, for a reaction using standard
entropies, S⦵, is not required]
(e) state whether a reaction or process will be spontaneous by using the sign of ΔG⦵
(f) understand the limitations in the use of ΔG⦵ 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
Content:
1. Introduction
2. Entropy
3. Factors affecting entropy of a chemical system
4. Gibbs Free Energy
5. Important consideration for reactions to occur

Recommended Materials:
1) Cann, Peter and Hughes, Peter, Chapter 5, Page 110, Energy changes in Chemistry, Chemistry for
advanced level, 2002
2) A-Level Chemistry (4th Edition) by E N Ramsden, published by Oxford University Press
3) Advanced Study Guide Chemistry by C S Toh, published by Step-by-Step International Pte. Ltd.

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1. Introduction

System and Surroundings

- System – A well-defined part of the universe under investigation, e.g a sample of reacting chemicals in
a test tube.
- Surroundings – the portion of the universe which is outside the system, but is in contact with the
system and where there can be an exchange of energy or matter with the system.

1.1. Spontaneous Chemical Reactions

- One of the major objectives in studying chemical thermodynamics is to be able to predict whether or
not a reaction will occur spontaneously when reactants are brought together under a special set of
conditions (e.g. at a certain temperature, pressure and concentration).
- A spontaneous reaction is one that occurs by itself and is also known as a feasible reaction.
Examples:
1. Rusting of iron 4Fe(s) + 3O2(g) →2Fe2O3(s) ΔH = -826 kJmol-1
2. Melting of ice H2O(s)→ H2O(l) ΔH = +22 kJmol-1
3. Dissolving of sodium chloride in water at room temperature.
NaCl(s) + aq →Na+(aq) + Cl-(aq) ΔH = +4.3 kJ mol-1
Note: All the above reactions can occur spontaneously regardless of the nature of the enthalpy
change.
- Using the sign of ΔH alone cannot predict spontaneous change of a reaction. Spontaneous does
not mean instantaneous and has nothing to do with how long a process takes to occur. It just means
that given enough time, the process will happen by itself.
- Therefore, entropy change, ΔS and Gibbs Free Energy, G have to be considered in order to determine
the spontaneity of a reaction.
- Based on the common observations of spontaneous reactions, there is a tendency for matter to
change from a less disordered to a more disordered state, i.e. from a state with relatively few ways of
arranging the particles to one with more ways of doing so.
- In thermodynamic terms, a change in order is a change in the number of ways of arranging the
particles, and it is a key factor in determining the direction of a spontaneous process.

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2. Entropy, S
- The number of ways of arranging the components of a system without changing its energy is directly
related to the entropy (S). This is a quantity which measures the degree of disorder of a system.

2.1. Entropy change of the universe, ΔSuniverse or the total entropy change, ΔStotal
- When considering total entropy change, it is necessary to consider the entropy change of a system,
ΔSsystem and the entropy change of the surrounding, ΔSsurroundings.
ΔSuniverse = ΔSsystem + ΔSsurroundings
- A reaction is considered feasible or spontaneous if ΔStotal or ΔSuniverse is positive (> 0)
- The direction of a chemical change will be in the direction of increasing entropy of the universe.
ΔSuniverse = ΔSsystem + ΔSsurroundings > 0
- The greater the number of ways of arrangement, the greater the disorder in the system and the greater
the entropy.
- The fewer the number of ways of arrangement, the lower the disorder in the system and hence the
smaller the entropy.
- The unit for S is J mol-1 K-1.
- Examples:
i) Sgas >> Sliquid > Ssolid
ii) SNaCl(aq) > SNaCl(s)
E.g. Melting, vaporisation and dissolution processes, ΔS>0

Melting (endothermic)
Sliquid > Ssolid

Vaporisation (endothermic)
Sgas/vapour > Sliquid

Dissolution
(exothermic/endothermic)
Ssolution > (Ssolvent + Ssolute)

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2.2. Entropy change of a System, ΔSsystem

- When considering the entropy change of a system, both the entropies of the particles before the
reaction and after the reaction must be taken into consideration.
ΔSsystem = SFinal – Sinitial
- When a change results in an increase in disorder of a system, S Final > SInitial, the entropy change,
ΔSsystem = SFinal - SInitial > 0 (i.e. positive).
- If ΔSsystem > 0, the change results in an increase in disorder.
- When a change results in a decrease in disorder of a system, S Final < SInitial, the entropy change, ΔSsystem
= SFinal - SInitial < 0 (i.e. negative).
- If ΔSsystem < 0, the change result in a decrease in disorder.

Examples:
Predict whether ΔSsystem is positive or negative in each of the following processes:
(a) Warming of nitrogen gas from -50°C to -20°C ΔS > 0
(b) HCl(g) + NH3(g) → NH4Cl(s) ΔS << 0
(c) 2SO2(g) + O2(g) → 2SO3(g) ΔS < 0

General Rule:
- If the total number of gas molecules increases (i.e. gases are formed) during a reaction, ΔS system is
positive as there is an increase in the number of ways of arrangement.
- If there is no net change in the total number of gas molecules, then ΔSsystem may be positive or
negative, but will be relatively small numerically.
- For the following reaction:
m1A + m2B → n1C + n2D
The standard entropy change of the system, ΔSθsystem, is given by:
ΔSθsystem = ΣnSθ(products) - ΔmSθ(reactants)
where Sθ values are the standard molar entropies of the products or reactants (measured under
standard conditions of 1 atm pressure and 298K), and m and n are the stoichiometric coefficients in
the chemical equation.
- The unit of ΔSθ is J mol-1 K-1.

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3. Factors which affect entropy of a chemical system

3.1. Change in Temperature
- The temperature increase represents an increase in average kinetic energy of the particles.
- There are more ways to distribute the energy of the substance at the higher temperature, so the
entropy of the substance goes up.
- For a given substance, entropy increases as the temperature rises.
- E.g. Typical Values for Cu metal:
T (K) 273 295 298
Sθ 31.0 32.9 33.2

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

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 molecules can adopt at a higher
temperature. Hence, an increase in temperature leads to an increase in entropy.

3.2. Change in Phase (Physical State)

- Examples: Melting and vaporisation
- Both processes lead to a more disordered system and the
particles have more ways to distribute their energies.
- H2O(s) → H2O(l) → H2O(g)
- (least disordered) (more disordered) (most disordered)
- When a phase changes to become more disordered, the entropy change is positive (ΔS>0).
- Examples:
Na H2O C (graphite)
Sθ (solid or liquid) 51.4 (solid) 69.9 (liquid) 5.7 (solid)
Sθ (gas) 153.6 188.7 158.0

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- For a given substance, Sθ increases as the substance changes from a solid to a liquid to a gas.
The solid is relatively ordered and has the lowest entropy, with its particles vibrating about their
fixed positions.
- As the temperature rises,
o The solid melts. The particles begin to move freely between and around each other in
liquid state, so there is an abrupt increase in entropy.
o Further heating increases the speed of the particles in the liquid, and the entropy
increase gradually. Finally, when freed from intermolecular forces, the particles undergo
another abrupt entropy increase and move randomly as a gas.
- The increase in entropy from liquid to a gas is much higher than from solid to liquid.
3.3. Change in Number of Particles
- When there is an increase in the number of particles in a chemical reaction, there is an
increase in entropy, since there are now more particles moving randomly and more ways to
distribute energy.
- Example – Some decomposition reactions, ΔS > 0
2NH3(g) → N2(g) + 3H2(g)
There is an increase in the number of gaseous particles. Hence, there is an increase in the
disorderliness in the system. ΔS is positive.
- When there is a decrease in the number of particles in a chemical reaction, there is a
decrease in entropy, ΔS < 0.
- Examples:
o Combination reactions
In combination reactions, entropy change is negative as there is often a reduction in the
number of molecules of gases.
E.g. N2(g) + 3H2(g) → 2NH3(g)
o Precipitation reactions
In precipitation reactions, entropy change is negative as there is often an increase in the
orderliness of the system.
E.g. Ca2+(aq) + CO32-(aq) → CaCO3(s)
3.4. Mixing of Particles
(a) Mixing of Gases
- When mixing 2 or more gases with an increase in volume, entropy increases as there is more room
for the gases to move and more ways in their arrangements.

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(b) Dissolution of a solid or liquid

- The entropy change accompanying the dissolution of a salt has two contributions:
o A positive contribution as the crystal separates into ions, dispersed by the pure liquid (more
random, hence S>0)
o A negative contribution as solvent molecules becomes organised around each ion. (S<0)
Case 1- Dissolution of sodium chloride in water
- When an ionic solid dissolves in water, the highly ordered crystal mixes with the pure liquid and
becomes separated, hydrated ions dispersed randomly in a solution (recall enthalpy of solution,
hydration and lattice energy).
- We expect the entropy of the ions themselves to be greater in the solution than in crystal.
- However, note that the water molecules surrounding the ions have become more orderly and hence
may make a negative contribution to the entropy, as the entropy of water molecules decreases.

- Positive entropy change, ΔSsystem >0.

- The increase in entropy of the ions outweighs the decrease in entropy for water molecules.
Case 2 – Dissolution of silver chloride in water
- In fact, for small, multiple-charged ions (recall high charge density and hydration energy), the water
molecules (solvent) become so highly organised around each ion that this negative contribution can
dominate and lead to negative Sθ values for the ion in solution.

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- Negative entropy change, ΔSsystem <0

- The decrease in entropy of the water molecules outweighs the increase in entropy of the ions.
Case 3 – Mixing of methanol and water
- For molecular solutes, the increase in entropy upon dissolving is typically much smaller than for
ionic solutes.
- For a solid, such as glucose, there is no separation into ions, and for a liquid, such as ethanol, the
breakdown of a crystal structure is absent as well.
- Furthermore, in pure ethanol and in pure water, the molecules form many hydrogen bonds among
themselves, so there is relatively little change in their freedom of movement when they are mixed.
- The small increase in the disorder of the dissolved ethanol arises from the random mixing of the two
types of molecules.
- The relative magnitude of these positive and negative entropies determines the overall entropy
change.
- In most cases, the entropy of the solution is greater than that of the ionic solid and solvent.
Case 1: NaCl(s) Case 2: AlCl3 (s) Case 3: CH3OH (l)
Sθ (solid or liquid) 72.1 167 127
Sθ (aqueous) 115.1 -148 132

3.5. Prediction of entropy change for a given process

Example:
Predict the entropy change (positive or negative) for the following process.
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
Solution:
Since 6 moles of gas yields 3 moles of gas, entropy will decrease, i.e. less disorder. ΔSθrxn < 0.
(Actual calculated value of ΔSθrxn = -374 J K-1 mol-1).

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Exercise:
Predict the sign of the entropy change for the following processes.
1) Alcohol evaporating (ΔS>0)

2) Perfume vapours diffusing through a room (ΔS>0)

3) 2K(s) + F2(g) → 2KF(s) (ΔS<0)

4) NH3(g) + HBr(g) → NH4Br(s) (ΔS<0)

5) NaClO3(s) → Na+(aq) + ClO3-(aq) (ΔS>0)

6) CaCO3(s) + 2HCl (aq) → CaCl2(aq) + H2O(l) + CO2(g) (ΔS>0)

7) 2NO(g) + O2(g) → 2NO2(g) (ΔS<0)

8) 2KClO3(s) → 2KCl (s) + 3O2(g) (ΔS>0)

For the following reactions, predict whether there is entropy change for the system and for each
of the reaction, deduce whether the entropy change is positive or negative.

(a) Ag+(aq) + Cl-(aq) → AgCl (s) (ΔS<0)

(b) NH4Cl (s) → NH3(g) + HCl (g) (ΔS>0)

(c) H2(g) + Br2(g) → 2HBr(g) (ΔS~0)

(d) 2Zn(s) + O2(g) → 2ZnO(s) (ΔS<0)

(e) N2(g) + O2(g) → 2NO(g) (ΔS~0)

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3.6. Spontaneous Exothermic and Endothermic Reactions (Self Read)

We can now understand why both exothermic and endothermic spontaneous reactions occur. Regardless
of the enthalpy change, a spontaneous reaction may occur if the total entropy of the reacting system
and its surroundings increases significantly.
Exercise:
Why does ice still freeze at 0°C although the particles in water have a greater degree of
randomness than the particles in ice?

Solution:
Entropy of the system, Ssystem decreases since particles in solid ice have less random distribution than the
particles in water, i.e. ΔSsystem < 0.

However, when ice freezes, latent heat of fusion is given out into the surroundings. This causes the
entropy of the air particles in the surroundings to increase, i.e. ΔSsurroundings > 0.
Since ΔSsurroundings is greater than ΔS system, the total entropy change, ΔS total is greater than zero, resulting in
the reaction having positive entropy change. The reaction is therefore spontaneous.

4. Gibbs free energy change of reaction, G

- The Gibbs free energy, or simply free energy (G), is a function that combines the system’s
enthalpy and entropy, i.e. G = H – TS
What is Gibbs free energy?
- When a chemical reaction occurs, the change in energy may be given off solely as heat e.g. a
combustion reaction occurring in a bomb calorimeter or it may be used to produce electricity in
an electrochemical cell when a lot of work is produced.
- The proportion of heat to work depends on how the reaction is carried out. Under special
conditions a reaction can be carried out to produce the maximum amount of work and the
minimum amount of heat.
- This maximum amount of work is called free energy, G
4.1. Standard Gibbs free energy change (ΔGθ)
ΔGθ= ΔHθ-TΔSθ

- Units for ΔGθ is kJ mol-1

Standard free energy change (ΔGθ) is the maximum amount of work that can be obtained from a
reaction under standard conditions. The relationship between free energy, enthalpy and entropy is
given in the equation above.

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4.2. Calculations using ΔGθ= ΔHθ-TΔSθ

Example
Given that the ΔSθ of the reaction is -36.8 J mol -1 K-1 and the ΔHfθ values, calculate the ΔGθ for the following
reaction at 25°C
4 KClO3(s) → 3KClO4(s) + KCl(s)
(ΔHfθ: KClO3 = -397.7kJ mol-1 ; KClO4 = -432.8 kJ mol-1; KCl = -436.7 kJ mol-1)
Solution:
ΔHrxn = ΣHf (products) - ΣHf (reactants)
= [(3) (-432.8) + (1) (-436.7)] – [(4) (-397.7)]
= -144.3 kJ mol-1
ΔGθ = ΔHθ-TΔSθ
= -144.3 – [(298K) (-36.8/1000)]
= -133 kJ mol-1
Exercise:
Determine the standard free energy change at 298K for the reaction
2 NO(g) + O2(g) → 2NO2(g)
Given: ΔSrxnθ = -146.5 J mol-1 K-1; ΔHfθ: NO = +90.3 kJ mol-1; NO2 = +33.2 kJ mol-1
Ans:- 70.5 kJ mol-1
ΔHrxn = 2(33.2) – 2(90.3)
= -114.2 kJ mol-1
ΔG = ΔH – TΔS
= (-114.2) – (298) (-146.5 / 1000)
= -70.5 kJ mol-1

4.3. Prediction of spontaneity of reactions using the sign of ΔGθ

ΔG < 0 for a spontaneous process
ΔG > 0 for a non-spontaneous process
ΔG = 0 for a process at equilibrium

- The free energy of a reaction tells us whether it proceeds spontaneously.
- The temperature at which a reaction occurs influences the magnitude of the TΔS θ term, thus overall
spontaneity depends on the temperature for many cases.
Exercise 4:
Question 1
Given that the enthalpy change of vaporisation of benzene is +31 kJ mol -1 and the entropy change of
vaporisation is +88 J mol-1 K-1. Calculate the temperature at which benzene boils.
Solution:
ΔG = ΔH – T ΔS

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0 = (+31) – [T(+88/1000)]
T = 352 K
Question 2
What are some other processes in which ΔG = 0?
melting, freezing, boiling, condensing

- Since ΔG = ΔH – TΔS, the signs and magnitudes of both ΔH and ΔS for the reaction affect the
spontaneity of the reaction.
- As ΔH and ΔS can each be positive or negative, there are 4 possibilities shown below.
- Reaction spontaneity and the signs of ΔH, ΔS and ΔG
Cas
ΔS ΔH TΔS ΔG Description
e
1 + - + - Spontaneous at all T Independent of
2 - + - + Non spontaneous at all T Temperature
Spontaneous at higher T; non
3 + + + + or -
spontaneous at lower T Dependent on
Spontaneous at lower T; non Temperature
4 - - - + or -
spontaneous at higher T

Temperature-Independent Examples
Reaction ΔH TΔS ΔG Spontaneity
C8H18(g) + 12½O2(g)→8CO2(g) + 9H2O(g) Spontaneous at all T
ΔH = -5109 kJ mol-1 - + <0
ΔS = +238 J mol-1 K-1
3O2(g)→2O3(g) Non spontaneous at all T
ΔH = +286 kJ mol-1 (can occur only if enough energy is
+ - >0
ΔS = -137 J mol-1 K-1 supplied to drive it, and usually takes
place in several steps)
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Temperature-Dependent Examples
Reaction ΔH TΔS ΔG Spontaneity
2 N2O(g) + O2(g) → 4 NO(g) Spontaneous at high T when |TΔS| > |
ΔH = -197.1 kJ mol-1 ΔH|, for ΔG<0 (For this example:
ΔS = +198.2 J mol-1 K-1 + + <0 T>994K);
Or
Non spontaneous at low T
2 Na(s) + Cl2(g) → 2 NaCl(s) Spontaneous at low T when |TΔS| < |ΔH|,
ΔH <0 for ΔG<0
- - >0
ΔS = -181.7 J mol-1 K-1 Or
Non spontaneous at high T

5. Important consideration for reactions to occur

Energetics tells us if a reaction is feasible and spontaneous. However, it says nothing about the rate /
kinetics of the reaction. A reaction can be highly spontaneous and exothermic but the rate can be
immeasurably slow. In such cases, we say that the reactants are kinetically stable with respect to the
products.
e.g. C(diamond) → C(graphite) ΔH = -2 kJ mol-1
Diamonds do not become graphite in real life though the reaction is exothermic because the rate of this
reaction is immeasurably slow (plus we have to take into account entropy factor). Hence we can say
that diamond is energetically unstable with respect to graphite because of the negative enthalpy, but
kinetically stable with respect to graphite.

6. Limitations of the use of ΔGθ

ΔGθ indicates the thermodynamic feasibility (spontaneity) of a reaction i.e. whether it can occur.
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.

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