H2 Chemistry 9729 Chemical Energetics

Anglo-Chinese Junior College

Department of Chemistry

CHEMICAL ENERGETICS
Prepared by ACJC Chemistry Department

SectionContent
1Enthalpy
1.1 Standard Conditions
2 Enthalpy change
2.1 List of enthalpy changes
2.1.1 Enthalpy Change of Reaction
2.1.2 Standard Enthalpy Change of Formation
2.1.3 Standard Enthalpy Change of Combustion
2.1.4 Standard Enthalpy Change of Neutralisation
Learning Outcomes 2.1.5 Standard Enthalpy Change of Atomisation
2.1.6 Bond Energy
2.1.7 Lattice Energy
2.1.8 Standard Enthalpy Change of Hydration
2.1.9 Standard Enthalpy Change of Solution
2.1.10 Ionisation Energy
2.1.11 Electron Affinity
2.2 Determination of Enthalpy Changes Using Experimental Results
2.3 Determination of Enthalpy Changes Using Hess’ Law
2.3.1 Relationship between Hr , Hr (reactants) and Hr (products)
2.3.2 Relationship between Hr , Hc (reactants) and Hc (products)
2.3.3 Relationship between Lattice Energy, Hhyd and Hsol
2.3.4 Usage of Bond Energies to calculate Hr
2.4 BornHaber Cycle
2.4.1 Born-Haber Cycle – Energy Cycle
2.4.2 Born-Haber Cycle – Energy Level Diagram
2.5 Algebraic Method
3 Entropy
3.1 Factors affecting Entropy (and Entropy Change)
3.1.1 Change in Temperature
3.1.2 Change in Phase
3.1.3 Change in Number of Particles
3.1.4 Mixing of Particles
4 Gibbs Free Energy
4.1 Standard Gibbs Free Energy Change and its relation to spontaneity
4.2 Limitations in the use of G o
4.3 Effect of Temperature on the spontaneity of a reaction
5 Extra Reading
5.1 Derivation of Gibbs Free Energy Formula
5.2 Energy Crisis
5.3 Difference between G and G o

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No. References
1 M. Clugston, R. Flemming, Advanced Chemistry, 1st Edition, UK, 2000
2 Chris Conoley, Phil Hills, Chemistry, 2nd Edition, UK, 2002
3 Peter Cann, Peter Hughes, Chemistry for Advanced level, UK, 2002
4 M.S. Silberberg, Chemistry: The Molecular Nature of Matter and Change, 4th Edition, NY,
2006

Learning Outcomes Section

Candidates should be able to:
(a) explain that most chemical reactions are accompanied by energy changes, 1 and 2
principally in the form of heat usually associated with the breaking and forming
of chemical bonds; the reaction can be exothermic (∆H, negative) or
endothermic (∆H, positive)
(b) construct and interpret an energy profile diagram, in terms of the enthalpy 1
change of the reaction and of activation energy
(c) explain and use the terms:
(i) enthalpy change of reaction and standard conditions, with particular 2.1
reference to: formation; combustion; hydration; solution; neutralisation;
atomisation
(ii) bond energy (∆H positive, i.e. bond breaking) 2.1.6
(iii) lattice energy (∆H negative, i.e. gaseous ions to solid lattice) 2.1.7
(d) calculate enthalpy changes from appropriate experimental results, including the 2.2
use of the relationship: heat change = mc∆T
(e) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the 2.1.7
numerical magnitude of a lattice energy
(f) apply Hess’ Law to construct simple energy cycles, e.g. Born-Haber cycle, and 2.4
carry out calculations involving such cycles and relevant energy terms (including
ionisation energy and electron affinity), with particular reference to:
(i) determining enthalpy changes that cannot be found by direct experiment, 2.3.2
e.g. an enthalpy change of formation from enthalpy changes of combustion
(ii) the formation of a simple ionic solid and of its aqueous solution 2.3.3
(iii) average bond energies 2.3.4
(g) explain and use the term entropy 3
(h) discuss the effects on the entropy of a chemical system by the following:
(i) change in temperature 3.1.1
(ii) change in phase 3.1.2
(iii) change in the number of particles (especially for gaseous systems) 3.1.3
(iv) mixing of particles 3.1.4
[quantitative treatment is not required]
(i) predict whether the entropy change for a given process or reaction is positive or 3.1
negative
(j) state and use the equation involving standard Gibbs free energy change of 4.1
reaction, ∆Gϴ: ∆Gϴ = ∆Hϴ − T∆Sϴ
[the calculation of standard entropy change, ∆Sϴ, for a reaction using standard
entropies, Sϴ, is not required]
(k) state whether a reaction or process will be spontaneous by using the sign of 4.1
∆Gϴ
(l) understand the limitations in the use of ∆Gϴ to predict the spontaneity of a 4.2
reaction
(m) predict the effect of temperature change on the spontaneity of a reaction, given 4.3
standard enthalpy and entropy changes

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H2 Chemistry 9729 Chemical Energetics

Introduction

Matter changes result in energy shifts. Fuels release heat when burned, while crops convert solar
energy to chemical energy. Chemical Energetics studies these energy changes

Learning Outcome:
(a) Explain that most chemical reactions are accompanied by energy changes, principally in the form of heat usually associated
with the breaking and forming of chemical bonds; the reaction can be exothermic (∆H, negative) or endothermic (∆H,
positive)

(b) Construct and interpret an energy profile diagram, in terms of the enthalpy change of the reaction and of activation energy

1 Enthalpy (H)

Enthalpy indicates a system's energy content and reflects its stability. We focus on enthalpy change,
∆H, the energy change in a reaction from initial (reactants) to final (products), involving associated heat.

∆H refers to the amount of heat change of a process at constant pressure. A commonly used unit
is kJ mol−1.

∆H = Hproducts − Hreactants

Endothermic reaction Exothermic reaction

(Hproducts > Hreactants) (Hproducts < Hreactants)

enthalpy enthalpy

Ea
products Ea

reactants
∆H > 0 ∆H < 0

reactants
products

reaction pathway reaction pathway

A positive sign for ∆ H indicates heat is A negative sign for ∆ H indicates heat is
absorbed from the surroundings to the system. evolved from the system to the surroundings.

Temperature of surroundings decreases. Temperature of surroundings increases.

Reactants are energetically more stable than Reactants are energetically less stable than
products. products.

Note:
The system comprises the reactants and products in a reaction mixture. Everything else other than
the system is known as the surroundings.

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1.1 Standard Conditions

The energy content of a substance is influenced by its temperature, pressure, and volume. Chemists
focus on enthalpy changes during reactions or processes, and hence standard conditions are needed
for the accuracy and consistency in these values.

The standard conditions (denoted by o) are defined as follows:

1) Temperature of the reaction is 298 K (25 oC)
2) Pressure of the reaction is carried out at 1 bar
3) Concentration of any solutions used is 1 mol dm−3

∆Hϴ (standard enthalpy change) is the enthalpy change at standard conditions.

Learning Outcome:
(c) Explain and use the terms:
(i) enthalpy change of reaction and standard conditions, with particular reference to:
formation; combustion; hydration; solution; neutralisation; atomisation
(ii) bond energy (∆H positive, i.e. bond breaking)
(iii) lattice energy (∆H negative, i.e. gaseous ions to solid lattice)

2 Enthalpy Changes (∆H)

The magnitude (value) of ∆H of a reaction depends on:

1) Amount of substance involved as written in the chemical equation

C (s) + ½O2 (g) → CO (g) ∆H = −110 kJ mol−1 --- equation (1)

2C (s) + O2 (g) → 2CO (g) ∆H = −220 kJ mol−1 --- equation (2)

1
Equation (1) reads as: 110 kJ of energy is released when 1 mol of C reacts with mol of O2 to give 1
2
mol of CO.

Equation (2) reads as: 220 kJ of energy is released when 2 mol of C react with 1 mol of O2 to give 2
mol of CO.

2) Phase (e.g. solid, liquid, gas or aqueous) of the reactants and products

2H2O2(aq) → H2O(l) + O2(g) −196 kJ mol−1

2H2O2(aq) → H2O(g) + O2(g) −108 kJ mol−1

The energy content of H2O(l) is lower than that H2O(g) and more energy is liberated when liquid H2O is
produced compared to gaseous H2O in a reaction.

Therefore, it is important to always include state symbols in a thermochemical equation.

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2.1 List of Enthalpy Changes

2.1.1 Enthalpy Change of Reaction (∆Hr)

Enthalpy change of reaction is the energy change of a given stoichiometric equation at the given
temperature and pressure.

4Cl2(g) + CH4(g) → CCl4(l) + 4HCl(g) ∆Hr = −433 kJ mol−1

The above equation is an example of a thermochemical equation.

 It is a balanced equation with state symbols of the reactants and products.
 The corresponding enthalpy change for the given equation is stated.

Enthalpy change of reaction can be obtained through:

 experimental method using calorimetry (Section 2.2)
 calculation using other enthalpy change data available (Section 2.3)

2.1.2 Standard Enthalpy Change of Formation (∆Hfϴ)

Standard enthalpy change of formation is the energy change when one mole of substance is
formed from its constituent elements in their standard states at 298 K and 1 bar.

Example:
C(s) + 2H2(g) + ½O2(g) → CH3OH(l) ∆Hfϴ (CH3OH) = −238 kJ mol−1

Note:
The standard state for carbon is graphite.

 The enthalpy change of formation of elements at their standard states is zero (0).
e.g. ∆Hfϴ (H2(g)) = ∆Hfϴ (O2(g)) = ∆Hfϴ (Na(s)) = 0 kJ mol−1

2.1.3 Standard Enthalpy Change of Combustion (∆Hcϴ)

Standard enthalpy change of combustion is the energy evolved when one mole of substance is
burnt completely in excess oxygen at 298 K and 1 bar.

Examples:

C(s) + O2(g) → CO2(g) ∆Hcϴ (graphite(s)) = −393.5 kJ mol−1

Mg(s) + ½O2(g) → MgO(s) ∆Hcϴ (Mg(s)) = −602 kJ mol−1

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2.1.4 Standard Enthalpy Change of Neutralisation (∆Hneuϴ)

Standard enthalpy change of neutralisation is the energy evolved when one mole of water is
formed in the reaction between an acid and an alkali at 298 K and 1 bar.

It is represented by the ionic equation:

H+(aq) + OH–(aq) → H2O(l) ∆Hneuϴ = −57.3 kJ mol−1

strong acid and strong Examples:

base HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
½H2SO4(aq) + NaOH(aq) → ½Na2SO4(aq) + H2O(l)
∆Hneu ϴ remains constant
at about −57.3 kJ mol−1
 strong acid and base is completely ionised in aqueous solution
Example:
CH3COOH (aq) + NaOH (aq) → CH3COONa (aq) + H2O (l)

 Neutralisation involves two stages:

Neutralisation reaction
1) CH3COOH (aq) H+ (aq) + CH3COO− (aq) ∆H1 > 0
involving either a weak
acid or a weak base
∆H1 involves O–H bond breaking and hydration of the resulting
ions. Energy is absorbed to dissociate CH3COOH
∆Hneu ϴ is less exothermic
completely.
than −57.3 kJ mol−1
2) H+ (aq) + OH– (aq) → H2O (l) ∆H2 = −57.3 kJ mol−1

 Since ∆Hneuϴ = ∆H1 + ∆H2, ∆Hneuϴ is thus less exothermic than

−57.3 kJ mol−1

2.1.5 Standard Enthalpy Change of Atomisation (∆Hatomϴ)

Standard enthalpy change of atomisation of an element is the energy absorbed when one mole
of gaseous atoms is formed from the element in its standard state at 298 K and 1 bar.

Example:
Na(s) → Na(g) ∆Hatomϴ (Na) = +107 kJ mol−1

Question
Write an equation that represents the ethalpy change of atomisation of chlorine.

∆Hatomϴ (Cl) = +122 kJ mol−1

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2.1.6 Bond Energy (BE)

Bond energy is the average energy absorbed when one mole of a given covalent bond in a
gaseous compound is broken into gaseous atoms.

Example:
Cl2(g) → 2Cl(g) BE (Cl–Cl) = +244 kJ mol−1

 The starting molecule, with the covalent bond, must be in gaseous state. The covalent bond is
broken homolytically, i.e. the bond is broken with each atom receiving one electron from the
covalent bond.

 Energy is absorbed to overcome the electrostatic forces of attraction between the shared electrons
and the nuclei in the covalent bond, resulting in an endothermic process.

 Bond energies which can be found in the Data Booklet are average values, as the strength of a
covalent bond is affected by its surrounding atoms. See example below.

Example
Carbon dioxide has two C=O bonds. The following thermochemical equation can be used to
illustrate the bond energy of the C=O bond in CO2.
1 1
CO2 (g) → C (g) + O (g) BE (C=O) = +805 kJ mol−1
2 2
However, the breaking of the two C=O bonds can be separated into two distinct steps, where the
value of BE 1 ≠ BE 2.

step 1: O=C=O (g) → C=O (g) + O (g) BE 1

step 2: C=O (g) → C(g) + O(g) BE 2
Summing up step 1 and 2 gives: O=C=O (g) → C=O (g) + O (g)
C=O (g) → C(g) + O(g)
CO2(g) → C(g) + 2O(g) 2 × BE (C=O)
BE 1 + BE 2
BE (C=O) =
2
= +805 kJ mol−1

 Despite this limitation, bond energies are still useful in comparing the strengths of different covalent
bonds in general.

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2.1.7 Lattice Energy (LE)

Lattice energy is the energy evolved when one mole of an ionic solid is formed from its constituent
gaseous ions (at infinite distance apart).

Examples:

Mg2+(g) + 2Cl–(g) → MgCl2(s) LE (MgCl2(s)) = −2526 kJ mol−1

2Na+(g) + O2–(g) → Na2O(s) LE (Na2O(s)) = −2476 kJ mol−1

 Strong electrostatic forces of attraction between the oppositely charged ions are formed in the solid,
resulting in an exothermic process that releases energy.

Learning Outcome:
(e) Explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a lattice energy

As we have learnt in Chemical Bonding, LE is a measure of the strength of electrostatic attraction

between oppositely charged ions in an ionic solid.
q q q+ = charge of cation q− = charge of anion
LE 
r  r r+ = ionic radius of cation r− = ionic radius of anion

Question
The lattice energy of lithium chloride is −860 kJ mol−1, while the lattice energy of sodium chloride is
−776 kJ mol−1.

Predict and explain how the lattice energy of lithium chloride compares to that of sodium chloride.

2.1.8 Standard Enthalpy Change of Hydration (∆Hhyd)

Standard enthalpy change of hydration is the energy evolved when one mole of gaseous ions is
converted to one mole of aqueous ions at infinite dilution at 298 K and 1 bar.

Examples:

Mg2+(g) + aq → Mg2+(aq) ∆Hhyd (Mg2+) = −1926 kJ mol−1

F–(g) + aq → F–(aq) ∆Hhyd (F– ) = −524 kJ mol−1

 Ion-dipole interactions are formed between the gaseous ions and relevant dipoles of water
molecules, resulting in an exothermic process that releases energy.

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2.1.9 Standard Enthalpy Change of Solution (∆Hsol)

Standard enthalpy change of solution is the energy change when one mole of substance (in its
standard state) is completely dissolved in infinite dilution in an aqueous solution at 298K and 1
bar.

Examples:

Ionic compounds: MgCl2(s) + aq → Mg2+(aq) + 2Cl–(aq) ∆Hsol (MgCl2) = −155 kJ mol−1

NaCl(s) + aq → Na+(aq) + Cl–(aq) ∆Hsol (NaCl) = +5 kJ mol−1

Other solutes: C2H5OH(l) + aq → C2H5OH(aq) ∆Hsol (C2H5OH) = −11 kJ mol−1

2.1.10 Ionisation Energy (IE)

First ionisation energy is the energy required to remove one mole of electrons from one mole of
gaseous atoms of an element to form one mole of singly charged positive gaseous ions.

Second ionisation energy is the energy required to remove one mole of electrons from one mole
of singly charged positive gaseous ions of an element to form one mole of doubly charged
positive gaseous ions.

Examples:

Mg(g) → Mg+(g) + e– 1st IE (Mg) = +736 kJ mol−1

Mg+(g) → Mg2+(g) + e– 2nd IE (Mg) = +1450 kJ mol−1

2.1.11 Electron Affinity (EA)

First electron affinity is the energy change when one mole of gaseous atoms of an element gain
one mole of electrons to form one mole of singly charged negative gaseous ions.

Second electron affinity is the energy change when one mole of singly charged negative
gaseous ions of an element gain one mole of electrons to form one mole of doubly charged
negative gaseous ions.

Examples:

O(g) + e– → O–(g) 1st EA (O) = −141 kJ mol−1

O–(g) + e– → O2–(g) 2nd EA (O) = +780 kJ mol−1

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2.2 Determination of Enthalpy Changes Using Experimental Results

Calorimetry measures heat transfer between system and surroundings, following energy conservation.
A calorimeter gauges heat in physical or chemical processes. A basic one includes an insulated
container with a stirrer, thermometer, and loose lid to maintain atmospheric pressure.

lid

A bomb calorimeter A simplified calorimeter

Note:
When we measure the temperature change of a reaction mixture, we are measuring the change in
energy of the surroundings, not the system.

components of system components of surroundings

 medium in which reaction is carried out,
 reactants e.g. aqueous medium
 products  reaction vessel / calorimeter
 air present in vessel (if any)

Learning outcome:
(d) Calculate enthalpy changes from appropriate experimental data, including the use of the relationship:
heat change = mc∆T

To determine the heat change of a reaction conducted in the calorimeter, the following equation is used:

q is the heat change (J)

m is the mass of solution (g)
q = mc∆T where
c is the specific heat capacity of the solution (J g−1 K−1)
∆T is the change in temperature of the solution (K)

A few assumptions are applied when using the above equation to determine the heat change of a
reaction.

1) There is 100% transfer of heat from the reaction to the solution / no heat lost to
surroundings.

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Heat transfers are almost impossible to be 100% efficient as heat is also absorbed by the
calorimeter or the air present inside the calorimeter.

2) The heat capacity of the solution is approximated to that of water and has a value of
4.18 J g−1 K−1.

3) The density of the solution is approximated to that of water and has a value of 1 g cm−3.

Many chemical reactions are carried in the aqueous medium and the concentrations of these
solutions used in general are sufficiently low.

As such, their specific heat capacity can be approximated to that of water and the mass of the
solutes does not significantly affect the density of the solution.

q
The enthalpy change of the reaction (∆H) can be determined by the equation: H 
n

q q is the heat change (J)

H  where
n n is the amount of limiting reagent (mol)

When ∆T > 0 ⟹ Reaction is exothermic When ∆T < 0 ⟹ Reaction is endothermic

⟹ ∆H < 0 ⟹ ∆H > 0
 Include (−) sign for value of ∆H 1. Include (+) sign for value of ∆H
q mcT q mcT
H  =  H  = 
n n n n

Example 1: Determination of Enthalpy Change of Reaction, ∆Hr

In an experiment, 50 cm3 of 1.00 mol dm−3 silver nitrate solution was placed in a styrofoam cup. 100
cm3 of 1.00 mol dm−3 potassium chloride solution was then added and the mixture was stirred. Both
solutions were initially at the same temperature. After mixing, the temperature of the mixture was found
to have risen by 10 oC.

Calculate ∆Hr. You may assume the specific heat capacity of the solutions is 4.18 J g−1 K−1.

AgNO3(aq) + KCl(aq) → AgCl(s) + KNO3(aq)

Mass of solution, m = 100 + 50 = 150 g

Amount of AgNO3 = 50/1000 x 1.00 = 0.0500 mol

Amount of KCl = 100/1000 x 1.00 = 0.100 mol
Hence, AgNO3 is the limiting reagent.

Since temperature has risen, the reaction is exothermic.

Heat change, q = mc∆T =  (150)(4.18)(10) = 6270 J

q
∆Hr = = −6270 / 0.05 = −125400 J mol−1 = −125 kJ mol−1 (3 s.f.)
n

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Question: Determination of Enthalpy Change of Combustion, ∆Hc

Retort stand

Thermometer

Glass beaker
Tripod stand

Spirit lamp
Stand

When 1.60 g of ethanol was burned in the lamp, the temperature of 200 g of water in the beaker rose
from 28 oC to 50 oC. Given that 45 % of the energy released was absorbed by the water, calculate the
enthalpy change of combustion of ethanol.

Example 2: Determination of Enthalpy Change of Reaction, ∆Hr, Using Graphical Method

Consider the reaction between Zn and CuSO4 solution.

Zn(s) + CuSO4(aq) → Cu(s) + ZnSO4(aq)

Procedure
Weigh 0.95 g of Zn powder in a weighing bottle using an electronic balance. Pipette 25.0 cm3 of 0.500
mol dm−3 CuSO4 solution into a Styrofoam cup supported in a 250 cm3 beaker. Using a thermometer,
measure the temperature of the CuSO4 solution at constant intervals of 30 s. At the 3rd minute, add the
Zn powder, stir well and continue to measure the temperature of the mixture at intervals of 1 minute for
another 8 minutes.

Results

Temperature / oC Time / min

0.0
(continue measuring temperature 0.5
till the 11th minute) 1.0
...

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Data Treatment
1. Plot a graph of temperature (y-axis) against time (x-axis).

Temperature/oC
True maximum temperature reading
if there is no heat loss (Tmax)

Highest recorded temperature

∆T

Initial temperature at
time of mixing (Ti)
Initial Ti
Time of mixing reactant

0 3 time/min

2. Extrapolate the curve to the time when the reactants are first mixed.

(We use the extrapolated line to determine the maximum temperature upon adding Zn in a perfect
situation where no heat is lost to the surroundings during the reaction.)

Assume that from the graph, ∆T = Tmax – Ti = 7.2 oC

Amount of Zn used = 0.95 / 65.4 = 0.0145 mol
Amount of CuSO4 = 25.0/1000 x 0.500 = 0.0125 mol
Hence, CuSO4 is the limiting reagent.

Heat released = 25 x 4.18 x 7.2 = 752.4 J

∆Hr = q / n = 752.4 / 0.0125 = 60192 J mol-1 = 60.2 kJ mol-1 (3 s.f.)

This is an example of a cooling curve for an exothermic reaction.

Example 3: Determination of the End-Point of Titration and Enthalpy Change of Neutralisation

Using Thermometric Titration

In a thermometric titration, the end-point occurs when the maximum temperature change occurs. When
the end-point is reached, the reaction is complete and addition of excess reactants will no longer cause
an increase in temperature for an exothermic reaction.

Consider the following neutralisation reaction between NaOH(aq) and HCl(aq).

NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

Procedure
First, measure a fixed volume of aqueous NaOH into a polystyrene cup. Use a thermometer to measure
the initial temperature of the solution. Next, add a fixed incremental volume of HCl to the styrofoam cup
supported in a 250 cm3 beaker and measure the temperature each time HCl is added.

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Results

Volume of HCl added Temperature / oC ∆T / oC (Temperature - initial temp)

/ cm3
0.00 27.0 (initial temp) 0.0
3.00 (continue addition of HCl in fixed
6.00 portion of 3.00 cm3 till 48.00 cm3)
...

Data Treatment
1. Plot a graph of ∆T vs volume of HCl added.
2. Draw two best fit lines through the plotted points to find the end-point for the titration.

∆T/°C

∆T

3
End-point of titration Volume of HCl / cm

q = mc∆T = (mass of solution) (4.18) ∆T

∆Hneutralisation = q / n = mc∆T / number of moles of water formed

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2.3 Determination of Enthalpy Changes Using Hess’ Law

Learning Outcome:
(f) Apply Hess’ Law to construct simple energy cycles, e.g. Born-Haber cycle, and carry out calculations involving such cycles
and relevant energy terms (including ionisation energy and electron affinity), with particular reference to:
(i) determining enthalpy changes that cannot be found by direct experiment, e.g. an enthalpy change of formation
from enthalpy changes of combustion
(ii) the formation of a simple ionic solid and of its aqueous solution
(iii) average bond energies

Hess’ Law states that the enthalpy change for a reaction is the same whether the reaction takes
place in one step or in a series of steps and is determined by the initial and final states of the system.
This means the enthalpy change of a reaction is independent of the reaction pathway.

An energy cycle or an energy level diagram may be used to illustrate Hess’ Law.

Example: Three hypothetical thermochemical equations are given below.

equation (1): A→C ∆H1 = +5 kJ mol−1

equation (2): A→B ∆H2 = +2 kJ mol−1
equation (3): B→C ∆H3 = +3 kJ mol−1

Energy cycle

Step 1: Illustrate equation (1) in the following manner.

∆H1
A C

Step 2: Notice that A is a reactant in both equations (1) and (2). Link equation (2) to equation (1) using
A as shown below.
∆H1
A C

∆H2
B

Step 3: Notice that B is a reactant and C is a product in equation (3). Both species can be linked via
equation (3) accordingly.

∆H1
A C

∆H2 ∆H3
B

The energy cycle is now complete.

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Energy Level Diagram

Two characteristics of energy level diagrams are:

1. A vertical axis labelled energy that allows relative energy levels of various stages to be illustrated.
 Stages with more energy content are placed above stages with less energy content.

2. Vertical arrows labelled with enthalpy changes.

 ↑ represent endothermic processes.
 ↓ represent exothermic processes.

Step 1: Using equation (1), A is converted to C, with ∆H1 as the associated enthalpy change. This is an
endothermic reaction, so the energy level of C is 5 kJ mol−1 higher than that of A.
Energy

C
∆H1

Step 2: Using equation (2), A is converted to B, with ∆H2 as the associated enthalpy change. This is an
endothermic reaction, so the energy level of B is 2 kJ mol−1 higher than that of A.
Energy

C
∆H1
B

∆H2
A

Step 3: Using equation (3), B is converted to C, with ∆H3 as the associated enthalpy change. This is an
endothermic reaction, so the energy level of C is 3 kJ mol−1 higher than that of B.
Energy

∆H3 ∆H1
B

∆H2
A

Notice in both energy cycle and energy level diagram that there are 2 reaction pathways from A (initial
state) to C (final state).
Path 1: A → C
Path 2: A → B → C

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Path 2 sums equations (2) and (3). Similarly, the enthalpy changes of equations (2) and (3) can be
summed up as well. The enthalpy change for path 2 = ∆H2 + ∆H3

Applying Hess’ Law: enthalpy change for path 1 = enthalpy change for path 2
∆H1 = ∆H2 + ∆H3

The energy level diagram is now completed.

2.3.1 Relationship between ∆Hr, ∆Hf(reactants) and ∆Hf(products)

Calculate ∆Hr by constructing an energy cycle with the following equations.

equation (1) C2H4(g) + H2(g) → C2H6(g) ∆Hr

equation (2) 2C(s) + 2H2(g) → C2H4(g) ∆Hfϴ (C2H4(g)) = +52.3 kJ mol−1
equation (3) 2C(s) + 3H2(g) → C2H6(g) ∆Hfϴ (C2H6(g)) = −83.9 kJ mol−1

Step 1: Illustrate equation (1) as follows.

∆Hr
C2H4(g) + H2(g) C2H6(g)

Step 2: Notice that C2H4(g) appears in equation (2) as a product and equation (1) as a reactant. Both
equations can be linked using C2H4(g) in the following manner.
∆Hr
C2H4(g) + H2(g) C2H6(g)

∆Hfϴ (C2H4(g))
2C(s) + 2H2(g)

Step 3: Notice that there is 1 mole of H2(g) not accounted in equation (2) of step 2. Add this into equation
(2) to ensure that the atoms are balanced.
∆Hr
C2H4(g) + H2(g) C2H6(g)

∆Hfϴ (C2H4(g))
2C(s) + 3H2(g)

Step 4: Notice that 2C(s) + 3H2(g) are the reactants and C2H6(g) is the product of equation (3). Both
parts can be linked via equation (3) accordingly.
∆Hr
C2H4(g) + H2(g) C2H6(g)

∆Hfϴ (C2H4(g)) ∆Hfϴ (C2H6(g))

2C(s) + 3H2(g)

Applying Hess’ Law, ∆Hfϴ (C2H4 (g)) + ∆Hr = ∆Hfϴ (C2H6 (g))
∆Hr = ∆Hfϴ (C2H6 (g)) − ∆Hfϴ (C2H4 (g))
= (−83.9) – (+52.3)
= −136.2 kJ mol−1 = −136 kJ mol−1 (3 s.f.)

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We see that ∆Hr = ∆Hfϴ (C2H6(g)) − ∆Hfϴ (C2H4(g)) Note: ∆Hfϴ (H2(g)) = 0
∆Hfϴ (product) ∆Hfϴ (reactant)

Given the enthalpy change of formation (∆Hfϴ) of the reactants and products of a reaction, the
enthalpy change of the reaction (∆Hrϴ) can be determined by:

∆Hr = ∑m∆Hfϴ (products) – ∑n∆Hfϴ (reactants)

where m = stoichiometric coefficients of the respective products

n = stoichiometric coefficients of the respective reactants

Question
Tetrachloroethene is commonly used as degreasing agent. The standard enthalpy change for the
following reaction is −878.5 kJ mol−1.

C2H4(g) + 4HCl(g) + 2O2(g) → C2Cl4(l) + 4H2O(l)

Using the following information, calculate the standard enthalpy change of formation of
tetrachloroethene in kJ mol−1.

Compound C2H4(g) HCl(g) H2O(l)

∆Hfϴ / kJ mol −1
+52.3 −92.3 −285.8

2.3.2 Relationship between ∆Hr, ∆Hc(reactants) and ∆Hc(products)

Calculate ∆Hr by constructing an energy cycle with the following equations.

1. C4H6(g) + 2H2(g) → C4H10(g) ∆Hr

2. C4H6(g) + 5½O2(g) → 4CO2(g) + 3H2O(l) ∆Hcϴ (C4H6(g)) = −2540 kJ mol−1
3. C4H10(g) + 6½O2(g) → 4CO2(g) + 5H2O(l) ∆Hcϴ (C4H10(g)) = −2878 kJ mol−1
4. H2(g) + ½O2(g) → H2O(l) ∆Hcϴ (H2(g)) = −286 kJ mol−1

∆Hr
C4H6(g) + 2H2(g) C4H10(g)
+ O2(g)
+ 5½ O2(g) + 6½ O2(g)
2 x ∆Hc ϴ (H2(g))
∆Hc (C4H6(g))
ϴ
∆Hc ϴ (C4H10(g))

4CO2(g) + 5H2O(l)

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Applying Hess’ Law,

∆Hr = [∆Hcϴ (C4H6(g)) + 2∆Hcϴ (H2(g))] – ∆Hcϴ (C4H10(g))
= [(–2540) + 2(–286)] – [–2878] = –234 kJ mol–1

We see that ∆Hr = ∆Hcϴ (C4H6(g)) + 2∆Hcϴ (H2(g)) − ∆Hcϴ (C4H10(g))

∆Hcϴ (reactants) ∆Hcϴ (product)

Given the enthalpy change of combustion (∆Hcϴ) of the reactants and products, the enthalpy change of
the reaction (∆Hrϴ) can be determined by:

∆Hr = ∑n∆Hcϴ (reactants) – ∑m∆Hcϴ (products)

where m = stoichiometric coefficients of the respective products

n = stoichiometric coefficients of the respective reactants

2.3.3 Relationship between Lattice Energy, ∆Hhyd and ∆Hsol

An energy cycle is also useful in illustrating the relationship of the processes involved in the dissolution
of an ionic solid in water.

MgF2(s) + aq → Mg2+(aq) + 2F–(aq) ∆Hsol

2+ 2+
Mg (g) + aq → Mg (aq) ∆Hhyd (Mg2+) = −1926 kJ mol−1
– –
F (g) + aq → F (aq) ∆Hhyd (F−) = −524 kJ mol−1
2+ –
Mg (g) + 2F (g) → MgF2(s) LE = −2962 kJ mol−1

∆Hsol
MgF2(s) Mg2+(aq) + 2F–(aq)
∆Hhyd(Mg2+) +
LE
2∆Hhyd(F−)
Mg2+(g) + 2F–(g)
Applying Hess’ Law,
∆Hsol (MgF2) = [∆Hhyd (Mg2+) + 2∆Hhyd (F–)] – LE (MgF2)
= [(−1926) + 2(−524)] – (−2962) = −12.0 kJ mol−1

∆Hsol = Σ∆Hhyd – LE

Comparing the magnitudes of LE and ∆Hhyd

| LE | < | ∆Hhyd | | LE | > | ∆Hhyd |
∆Hsol < 0 ∆Hsol > 0
Note:
When ∆Hsol < 0, the ionic solid is likely to be soluble in water. A more accurate indicator of the solid’s
solubility is its value of the change in Gibbs free energy.

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2.3.4 Usage of Bond Energies to calculate ∆Hr

Determine the enthalpy change of reaction for the following equation.

CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Step 1 Draw out the full structural formulae for each species to show all the bonds.

Step 2 Identify the type and number of bonds that are broken and formed.

Bonds Broken Bonds Formed

4 BE (C−H) 2 BE (C=O)
2 BE (O=O) 4 BE (O−H)

∆Hr + 2BE(C=O) + 4BE(O−H) = 2BE(O=O) + 4BE(C−H)

Step 3 Select relevant bond energy values from the Data Booklet.

Bonds Broken Bonds Formed

4 BE (C−H) 4 × 410 2 BE (C=O) 2 × 805
2 BE (O=O) 2 × 496 4 BE (O−H) 4 × 460
2632 3450

Step 4 Determine ∆Hr

∆Hr = 2632 – 3450 = −818 kJ mol−1

Using bond energies, the enthalpy change of a reaction can be determined by:

∆Hr = ∑BE (bonds broken) – ∑n BE (bonds formed)

Note:
The use of bond energies to determine the enthalpy change of reaction is most appropriate for reactions
involving only gaseous reactants and products.

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Question
Hydrazine (N2H4) is often used as a rocket fuel. It reacts very exothermically with oxygen forming purely
gaseous products as shown below.

N2H4(g) + O2(g) → N2(g) + 2H2O(g) ∆Hr = −622 kJ mol−1

Besides its reaction with oxygen, another suggestion is to react hydrazine with fluorine instead. N2(g)
and HF(g) are formed in the reaction.

N2H4(g) + 2F2(g) → N2(g) + 4HF(g)

(a) Determine the enthalpy change for this reaction.

Use of the Data Booklet is relevant to this question.

(b) Based on your answer to (a), comment whether a mixture of hydrazine and fluorine is a better rocket
fuel than a mixture of hydrazine and oxygen.

2.4 Born-Haber Cycle

Born-Haber cycles are energy cycles concerned with the formation of ionic substances. It allows for the
determination of lattice energy. The following enthalpy changes are involved:

1. Enthalpy change of formation of the ionic solid

2. Enthalpy change of atomisation of the constituent elements
3. Ionisation energies and electron affinities of the respective gaseous atoms
4. Lattice energy of the ionic solid

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2.4.1 Born-Haber Cycle – Energy cycle

Draw a Born-Haber cycle, using the data provided below, to calculate the lattice energy of calcium
oxide.

∆H / kJ mol−1 equation
first ionisation energy of +590
(from Data Booklet) Ca(g) → Ca+(g) + e−
calcium
second ionisation energy of +1150
(from Data Booklet) Ca+(g) → Ca2+(g) + e−
calcium
enthalpy change of
+178 Ca(s) → Ca(g)
atomisation of calcium
enthalpy change of 1
+248 O2(g) → O(g)
atomisation of oxygen 2
1st electron affinity of
−141 O(g) + e− → O−(g)
oxygen
2nd electron affinity of
+780 O−(g) + e− → O2−(g)
oxygen
enthalpy change of 1
−636 Ca(s) + O2(g) → CaO(s)
formation of calcium oxide 2
1
Note: The enthalpy change of atomisation of oxygen = BE (O=O). This is true for all homonuclear diatomic
2
molecules in the gaseous state.
1st EA of O
2+ − 2+ −
Ca (g) + O(g) + 2e Ca (g) + O (g) + e−
st nd
1 + 2 IE of Ca
2nd EA of O
Ca(g) + O(g) Ca2+(g) + O2−(g)

∆Hatom (O) LE of CaO

Ca(g) + O2(g) CaO(s)

∆Hatom (Ca)
∆Hf(CaO)

Ca(s) + O2(g)
Applying Hess’ Law,
∆Hfϴ (CaO) = ∆Hatomϴ (Ca) + ∆Hatomϴ (O) + (1st & 2nd IE of Ca) + (1st & 2nd EA of O) + LE (CaO)

−636 = (+178) + (+248) + [(+590) + (+1150)] + [(−141) + (+780)] + LE of CaO

LE (CaO) = −3441 kJ mol−1 = −3440 kJ mol−1 (3 s.f.)

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2.4.2 Born-Haber Cycle − Energy Level Diagram

The Born-Haber Cycle can be represented as an energy level diagram and is drawn relative to a datum
line, which is the arbitrary zero enthalpy of any pure element.

Using the same data in 2.4.1, an energy level diagram was constructed to calculate the lattice energy
of calcium oxide. Fill in the boxes with appropriate labels.

Enthalpy
(kJ mol−1)
Ca2+(g) + O2−(g)

2nd EA (O)

Ca2+(g) + O(g) + 2e–

1st EA (O)
Ca2+(g) + O–(g) + e–

2nd IE (Ca)

Ca+(g) + O(g) + e–

1st IE (Ca)

Ca(g) + O(g)
LE (CaO)
∆Hatom (O)
Ca(g) + ½ O2(g)

∆Hatom (Ca)
Ca(s) + ½ O2(g)

∆Hfϴ (CaO)

CaO(s)

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Applying Hess’ Law,

∆Hfϴ (CaO) = ∆Hatomϴ (Ca) + ∆Hatomϴ (O) + (1st & 2nd IE of Ca) + (1st & 2nd EA of O) + LE (CaO)

−636 = (+178) + (+248) + [(+590) + (+1150)] + [(−141) + (+780)] + LE of CaO

LE (CaO) = −3441 kJ mol−1 = −3440 kJ mol−1

2.5 Algebraic Method

Not all questions require the drawing of an energy cycle, Born-Haber cycle or energy level diagram. In
such a case, it may be faster to use simple algebra.

Example: In a blast furnace, carbon or carbon monoxide can be used to reduce iron(III) oxide.

2Fe2O3(s) + 3C(s) → 4Fe(s) + 3CO2(g) ∆H1 = +46.8 kJ mol−1

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) ∆H2 = −24.8 kJ mol−1

Carbon monoxide can be formed according to the equation shown below.

C(s) + CO2(g) → 2CO(g) ∆H3

Calculate the value of ∆H3 in kJ mol−1.

Step 1: Recognise species (C(s), CO2(g), CO(g)) that are found in intended equation. Recognise that
Fe2O3(s) and Fe(s) do not appear in intended equation.

Step 2: Manipulate given equations to give intended equation accordingly.

2Fe2O3(s) + 3C(s) → 4Fe(s) + 3CO2(g) ∆H1

4Fe(s) + 6CO2(g) → 2Fe2O3(s) + 6CO(g) −2∆H2

Step 3: Sum equations and cancel species which appear on both sides of equation.

2Fe2O3(s) + 3C(s) → 4Fe(s) + 3CO2(g)

4Fe(s) + 6CO2(g) → 2Fe2O3(s) + 6CO(g)

3CO2(g)

3C(s) + 3CO2(g) → 6CO(g) ∆H1 + (−2∆H2)

Step 4: Sum enthalpy changes and determine ∆H3.

H1  2H2
∆H3 = = +31.1 kJ mol−1
3

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3 Entropy (S)

Learning Outcome:
(g) Explain and use the term entropy

Enthalpy changes help identify feasible, exothermic reactions, but they don't explain endothermic
reactions. The spontaneity of a reaction, indicating its natural tendency, considers the system's entropy.

Entropy is a measure of the disorder in the system and may be understood as the number of ways in
which:

1. The particles are arranged in a system.

2. The energy in a system is dispersed.

These characteristics result in disorder within the system.

Entropy increases with greater particle and energy arrangements in a system. Systems naturally favour
higher entropy, which involves increased disorder. Hence, systems favour changes that lead to higher
entropy.

Example: Consider an experiment with two types of gases at the same pressure and temperature
separated by a divider. When the divider between the two gases is removed, the two gases will mix
spontaneously.

Note:
It may be helpful to see the system as being made up of particles and the possible number of different
arrangements of these particles will give us an indication of the system’s entropy.

Question
State whether the 2−particle or 3−particle system has greater disorder.

Arrangement 1 Arrangement 2

Arrangement 1 Arrangement 2 Arrangement 3

Since changes in entropy are present in chemical reactions, we must be able to predict the entropy
change, ∆S, of a system.

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3.1 Factors Affecting Entropy (and Entropy Change ∆S)

Learning Outcome:
(h) 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]
(i) predict whether the entropy change for a given process or reaction is positive or negative

Entropy change is a measure of the change in disorder of a system, by considering the change in
entropy between the initial (reactants) and final (products) state of the system.

∆S sign of ∆S significance
>0 (+)  final state is more disordered than initial state
<0 (−)  final state is less disordered than initial state

3.1.1 Change in Temperature

Increasing the temperature of the system causes the following:

 broadening of the Boltzmann energy distribution;
 there are more ways of dispersing energy in the system (or more energy states);
 the system becomes more disorderly.

Boltzmann Distribution

low temperature

number
of
high temperature
particles

energy

As such, entropy increases when temperature increases as:

1. there are more ways of arrangement for the particles;
2. there is a broadening of the energy distribution, leading to more energy states which the
particles can adopt (more ways of dispersing energy in the system).

Example:
Heating solid copper metal from 273K to 373K which leads to an increase in entropy (∆S > 0).

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3.1.2 Change in Phase

Changing of phase (e.g. solid to liquid) is a physical phenomenon and not a chemical reaction. Particles are ordered differently in each
phase and the entropy present in these phases is different.

The table below provides a summary.

phase solid liquid gas

submicroscopic
representation

arrangement of fixed positions and particles particles are mobile and slide particles are in constant random
particles vibrate about their positions across each other motion, with spaces in between

number of ways to in between that present in

few many
arrange particles solids and gases

in between that present in

entropy low high
solids and gases

Examples:

1. Melting: solid to liquid (∆S > 0) as Ssolid < Sliquid

2. Boiling: liquid to gas (∆S > 0) as Sliquid ≪ Sgas

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3.1.3 Change in Number of Particles

Increasing the number of gaseous particles of a system causes the following:

 an increase in number of ways to arrange the particles;
 an increase in entropy (change in entropy is positive).

Examples:
N2O(g) → N2(g) + ½O2(g)
H2O2(aq) → H2O(l) + ½O2(g)

3.1.4 Mixing of Particles

Mixing of different types of particles causes the following:

 an increase in number of ways to arrange the particles;
 an increase in entropy (change in entropy is positive).

Before mixing, there is only one After mixing, there are

possible arrangement of the two many more ways to
different types of particles. arrange the particles.

Examples:
 A solid dissolving in a liquid solvent, e.g. solid sodium chloride in water
o Dissolution of a solid in water may not always be ∆S > 0
 Solid particles mixing in gas, e.g. dust and soot in air, giving rise to haze

Question:
State and explain the change in entropy of the following changes:
(i) 3H2(g) + N2(g) → 2NH3(g)
Since there is a decrease in the amount of gas particles from four moles to two moles, there is a
decrease in disorder of the system with fewer ways to arrange the particles. Hence there is a decrease
in entropy.

(ii) Na(s) → Na(l)

Sodium is converted from the solid to liquid state. There is an increase in the number of arrangements
for the Na atoms in the liquid, since they now can slide across each other. Hence there is an increase
in entropy.

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4 Gibbs Free Energy (G)

Learning Outcome:
(j) State and use the equation involving standard Gibbs free energy change of reaction, ∆Gϴ: ∆Gϴ = ∆Hϴ - T∆Sϴ
[the calculation of standard entropy change, ∆Sϴ , for a reaction using standard entropies, Sϴ , is not required]
(k) State whether a reaction or process will be spontaneous by using the sign of ∆Gϴ
(l) Understand the limitations in the use of ∆Gϴ to predict the spontaneity of a reaction

Systems tend to prefer lower enthalpy and higher entropy, leading to spontaneous reactions. However,
some spontaneous reactions are endothermic or decrease entropy.

The change in the reaction’s Gibbs Free Energy provides us an indication of its spontaneity. Gibbs Free
Energy is a function that relates a reaction’s enthalpy and entropy terms to its spontaneity.

4.1 Standard Gibbs Free Energy change Gϴ & its relation to spontaneity

The Standard Gibbs Free Energy change, ∆Go, is given by the equation:

∆Go: change in standard Gibbs free energy (kJ mol−1)

∆Ho: standard enthalpy change of the system (kJ mol−1)
∆Go = ∆Ho – T∆So where
∆So: standard entropy change of the system (J mol−1 K−1)
T: temperature of the system (in K)

 When ∆Go < 0, the chemical reaction is spontaneous.

 When ∆Go > 0, the chemical reaction is non-spontaneous.
Note:
When ∆G = 0, the chemical reaction is said to be at dynamic equilibrium. Do not confuse ∆Go and ∆G.
See 5.3 for details.

4.2 Limitations in the use of Gϴ

∆Go allows us to predict the spontaneity of a reaction as it gives an indication of the reaction’s
thermodynamic feasibility (i.e. based on energy consideration).

However, thermodynamic feasibility does not predict the kinetics of a reaction, such as its rate
and the reaction may not take place because of a high activation energy barrier.

Example:
SOCl2(l) + H2O(l)  SO2(g) + 2HCl(g)

Given that Ho is +49.4 kJ mol−1 and So is +336.1 J mol−1 K−1, predict whether the reaction is
spontaneous at 298 K.

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4.3 Effect of temperature on the spontaneity of a reaction

Learning Outcome:
(m) Predict the effect of temperature change on the spontaneity of a reaction, given standard enthalpy and entropy
changes

Assuming ∆H and ∆S do not change with temperature, we can see that changing the temperature can potentially cause the sign of
∆Go to change from positive (> 0) to negative (< 0) or vice versa. The table below serves as a useful guide to see how ∆G value will
change with temperature and thus potentially affecting the spontaneity of a reaction / process.

∆Ho ∆So example explanation conclusion

∆G = ∆H – T∆S
 Reaction is spontaneous at all
(−) (+)
− + temperatures
∆G < 0 at all temperatures
∆G = ∆H – T∆S
(–) (–)

 Freezing At low temperatures:  Reaction is spontaneous at low

− −
 Condensation |T∆S| < |∆H| ⟹ ∆G < 0 temperatures

At high temperatures:  Reaction is non – spontaneous

|T∆S| > |∆H| ⟹ ∆G > 0 at high temperatures
∆G = ∆H – T∆S
(+) (+)

 Melting At low temperatures:  Reaction is non – spontaneous

+ +
 Boiling |T∆S| < |∆H| ⟹ ∆G > 0 at low temperatures

At high temperatures:  Reaction is spontaneous at

|T∆S| > |∆H| ⟹ ∆G < 0 high temperatures
∆G = ∆H – T∆S
+ −
(+) (−)  Reaction is non-spontaneous
at all temperatures
∆G > 0 at all temperatures

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Question

One alternative fuel technology involves the conversion of liquid methanol into hydrogen gas as shown by the equation below.

CH3OH(g) → H2(g) + 2CO(g) H ϴ = +129 kJ mol−1

S ϴ = +332 J K−1mol−1

(i) Calculate ΔGϴ at 298K. Comment on the value obtained.

(ii) Calculate the minimum temperature above which this reaction is spontaneous. State any assumptions made in your
calculation.

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5 Extra Reading

5.1 Derivation of Gibbs Free Energy Formula

The 2nd Law of Thermodynamics states that for a process (including chemical reactions) to be
spontaneous, ∆Suniverse > 0 (or ∆Stotal > 0). To have a particular change to occur in a particular direction,
the total entropy change must be increased. The heat transfer between the system and the
surroundings will result in a change in the entropy of both the system and the surroundings. Essentially,
it is insufficient to simply investigate the system to see if a reaction is spontaneous. We have to examine
both the system and the surroundings.

Since heat (q) from the system is transferred to the surroundings, the change in entropy of the
surroundings is given as follows.

∆Ssurroundings = qsurroundings / T = -qsystem / T (T = temperature in K)

We can derive Gibbs Free Equation from entropy using the 2nd Law,

Suniverse = ∆Ssystem + ∆Ssurroundings

Suniverse = ∆Ssystem – (qsystem / T)

Since at constant pressure, ∆H = q,

∆Suniverse = ∆Ssystem + ∆Ssurroundings

= ∆Ssystem + (-qsystem/T)
= ∆Ssystem + (-∆Hsystem/T)
-T∆Suniverse = ∆Hsystem – T∆Ssystem

Let ∆G = -T∆Suniverse,

∆G = ∆H – T∆S

where ∆G = change in Gibbs free energy

∆H = enthalpy change of the system
∆S = entropy change of the system
T = temperature of the system (in K)

∆G = ∆H – T∆S = -T∆Suniverse

Given that a chemical reaction is spontaneous when ∆Suniverse > 0 by the 2nd Law of Thermodynamics,

 When ∆Go < 0, the chemical reaction is spontaneous.

 When ∆Go > 0, the chemical reaction is non-spontaneous.
 When ∆G = 0, the chemical reaction is at equilibrium.

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5.2 Energy Crisis

What is Energy Crisis?

The energy crisis arises from the increasing demand for limited natural resources, which take hundreds
of thousands of years to replenish. Governments and individuals prioritize renewable resources and
conservation to address this issue. Despite efforts, the crisis persists due to a lack of broad
understanding of its causes and solutions, leading to ongoing deterioration.

According to Wikipedia,
“An energy crisis is any great bottleneck (or price rise) in the supply of energy resources to an economy.
In popular literature though, it often refers to one of the energy sources used at a certain time and place,
particularly those that supply national electricity grids or serve as fuel for vehicles.”

How Real is Energy Crisis?

During election years, debates arise over the validity of the energy crisis. One side questions it as
political or based on faulty science, while the other accuses them of neglecting future concerns.
Ultimately, the issue revolves around responsibility for future generations: the crisis is real if one cares
about their future, but not if they disregard it.

Causes of Energy Crisis

It would be easy to point a finger at one practice or industry and lay the blame for the entire energy
crisis at their door, but that would be a very naive and unrealistic interpretation of the cause of the crisis.

1. Overconsumption: The energy crisis is a result of many different strains on our natural resources,
not just one. There is a strain on fossil fuels such as oil, gas and coal due to overconsumption – which
in turn can put a strain on our water and oxygen resources by causing pollution.

2. Overpopulation: Another cause of the crisis has been the steady increase in the world’s
population and its demands for fuel and products. No matter what type of food or products you choose
to use – from fair trade and organic to those made from petroleum products in a sweatshop – not one
of them is made or transported without a significant drain on our energy resources.

3. Poor Infrastructure: Aging infrastructure of power generating equipment is yet another reason for
energy shortage. Most of the energy producing firms keep on using outdated equipment that restricts
the production of energy. It is the responsibility of utilities to keep on upgrading the infrastructure and
set a high standard of performance.

4. Unexplored Renewable Energy Options: Renewable energy still remained unused is common in
most of the countries. Most of the energy comes from non-renewable sources like coal. It still remains
the top choice to produce energy. Unless we give renewable energy a serious thought, the problem of
energy crisis cannot be solved. Renewable energy sources can reduce our dependence on fossil fuel
sand also helps to reduce greenhouse gas emissions.

5. Delay in Commissioning of Power Plants: In few countries, there is a significant delay in

commissioning new power plants that can fill the gap between demand and supply of energy. Old plants
can come under huge stress to meet daily demand of power. When supply does not match demand, it
results in load shedding and breakdown.

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6. Wastage of Energy: In most parts of the world, people do not realize the importance of conserving
energy. It is only limited to books, internet, newspaper ads, lip service and seminars. Unless we give it
a serious thought, things are not going to change anytime sooner. Simple things like switching off fans
and lights when not in use, using maximum daylight, walking instead of driving for short distances, using
CFL instead of traditional bulbs, proper insulation for leakage of energy can go a long way in saving
energy.

7. Poor Distribution System: Frequent tripping and breakdown are result of a poor distribution system.

8. Major Accidents and Natural Calamities: Major accidents like pipeline burst and natural calamities
like eruption of volcanoes, floods, earthquakes can also cause interruptions to energy supplies. The
huge gap between supply and demand of energy can raise the price of essential items which can give
rise to inflation.

9. Wars and Attacks: Wars between countries can also hamper supply of energy especially if it
happens in Middle East countries like Saudi Arabia, Iraq, Iran, Kuwait, UAE or Qatar. That’s what
happened during 1990 Gulf war when price of oil reached its peak causing global shortages and created
major problem for energy consumers.

10. Miscellaneous Factors: Tax hikes, strikes, military coup, political events, severe hot summers or
cold winters can cause sudden increase in demand of energy and can choke supply. A strike by unions
in an oil producing firm can cause an energy crisis.

Possible Solutions to Energy Crisis

1. Move Towards Renewable Resources: The best possible solution is to reduce the world’s
dependence on non-renewable resources and to improve overall conservation efforts. Much of
the industrial age was created using fossil fuels, but there is also known technology that uses
other types of renewable energies – such as steam, solar and wind. The major concern isn’t so
much that we will run out of gas or oil, but that the use of coal is going to continue to pollute the
atmosphere and destroy other natural resources in the process of mining the coal that it has to
be replaced as an energy source. This isn’t easy as many of the leading industries use coal, not
gas or oil, as their primary source of power for manufacturing.

2. Buy Energy Efficient Products: Replace traditional bulbs with CFL’s and LED’s. They use
less watts of electricity and last longer. If millions of people across the globe use LED’s and
CFL’s for residential and commercial purposes, the demand for energy can go down and an
energy crisis can be averted.

3. Lighting Controls: There are a number of new technologies out there that make lighting
controls that much more interesting and they help to save a lot of energy and cash in the long
run. Preset lighting controls, slide lighting, touch dimmers, integrated lighting controls are few of
the lighting controls that can help to conserve energy and reduce overall lighting costs.

4. Easier Grid Access: People who use different options to generate power must be given
permission to plug into the grid and getting credit for power you feed into it. The hassles of
getting credit of supplying surplus power back into the grid should be removed. Apart from that,
subsidy on solar panels should be given to encourage more people to explore renewable
options.

5. Energy Simulation: Energy simulation software can be used by big corporates and
corporations to redesign building unit and reduce running business energy cost. Engineers,

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architects and designers could use this design to come with most energy efficient building and
reduce carbon footprint.

6. Perform Energy Audit: Energy audit is a process that helps you to identify the areas where
your home or office is losing energy and what steps you can take to improve energy
efficiency. Energy audit when done by a professional can help you to reduce your carbon
footprint, save energy and money and avoid energy crisis.

7. Common Stand on Climate Change: Both developed and developing countries should adopt
a common stand on climate change. They should focus on reducing greenhouse gas emissions
through an effective cross border mechanism. With current population growth and over
consumption of resources, the consequences of global warming and climate change cannot be
ruled out. Both developed and developing countries must focus on emissions cuts to cut their
emission levels to half from current levels by 2050.

What is Being Done Today?

Global initiatives are tackling the energy crisis through stricter carbon emission regulations, promoting
eco-friendly manufacturing, funding hybrid and sustainable technology research, and more.
Communities are also embracing local resource management with initiatives like community gardens,
parks, and farmer’s markets, not just for sustainability but also for public education on resource
importance.

Adapted from:
[Link]

5.3 Difference between ∆G and ∆Go

What is the difference between G and G?

Consider a reaction of A to give B,

A⇌B GA and GB are the Gibbs free energy of pure A
and pure B respectively.
G = GB – GA < 0

G = GA
Gibbs free energy

G = GB – GA and represents the difference

in free energy of pure A and pure B. We can use
this difference to predict whether the complete
G = GB conversion of A to B is thermodynamically
G = gradient < 0 feasible.
G = gradient > 0
G = gradient
=0 G is the instantaneous gradient at any point
along the curve. Its significance will be discussed
pure A pure B in greater detail in Chemical Equilibrium.

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