IAL Edexcel Chemistry Unit 4 (WCH14):

Rates, Equilibria and Further Organic Chemistry

(Part 2/5)
REALLYACADEMICS
Preface
● This series will be divided into 5 parts corresponding to the 5 topics in the 2018
specification
○ PART 1 - TOPIC 11: Kinetics
○ PART 2 - TOPIC 12: Entropy and Energetics
○ PART 3 - TOPIC 13: Chemical Equilibria
○ PART 4 - TOPIC 14: Acid-base Equilibria
○ PART 5 - TOPIC 15: Organic Chemistry: Carbonyls, Carboxylic Acids and Chirality
● This series will provide you with a means of last minute revision on [WCH14] IAL
Edexcel Chemistry Unit 4
● This series will aim to provide you with an revision in under 50 MINS
● All information here is a summary of the New Specification Book
● This series will not serve as a primary study material but as an adjunct to help you
recall and prepare as a last minute revision
● YOU CAN ALSO SUPPLEMENT THIS WITH MY OTHER VIDEOS ON FREQUENTLY ASKED
QUESTIONS OF UNIT 4
Syllabus
● Section A - Entropy
1. Understand that, since endothermic reactions can occur spontaneously at room temperature, enthalpy changes alone
do not control whether reactions occur
2. Understand entropy as a measure of disorder of a system in terms of the random dispersal of molecules and of
energy quanta between molecules
3. Understand that the entropy of a substance increases with temperature, that entropy increases as solid → liquid →
gas and that perfect crystals at zero kelvin have zero entropy
4. Be able to interpret the natural direction of change as being in the direction of increasing total entropy (positive
entropy change), including gases spread spontaneously through a room
5. Understand why entropy changes occur during:
a. Changes of state
b. Dissolving of a solid ionic lattice
c. Reactions in which there is a change in the number of moles from reactants to products
6. Understand that the total entropy change of any reaction is the sum of the entropy change of the system and the
entropy change of the surroundings, summarised by the expression: ∆S total = ∆Ssystem + ∆Ssurroundings
7. Be able to calculate the entropy change of the system for a reaction, ∆Ssystem, given the entropies of the reactants
and products
8. Be able to calculate the entropy change in the surroundings, and hence ∆Stotal
9. Understand that the feasibility of a reaction depends on:
a. The balance between ∆Ssystem and ∆Ssurroundings, so that even endothermic reactions can occur spontaneously at room temperature
b. Temperature, as higher temperatures decrease the magnitude of ∆Ssurroundings so its contribution to ∆Stotal is less
10. Understand that reactions can occur as long as ∆Stotal is positive even if one of the other entropy changes is negative
11. Understand and distinguish between the concepts of thermodynamic stability and kinetic stability
Syllabus
● Section B - Lattice Energy
1. Be able to define the terms:
a. Standard enthalpy change of atomisation, ∆atH
b. Electron affinity
c. Lattice energy (as the exothermic process for the formation of one mole of an ionic solid from its gaseous ions)
2. Be able to construct Born-Haber cycles and carry out related calculations
3. Understand that a comparison of the experimental lattice energy value (from a Born-Haber cycle) with the
theoretical value (obtained from electrostatic theory) in a particular compound indicates the degree of
covalent bonding
4. Understand that polarisation of anions by cations leads to some covalency in an ionic bond, based on
evidence from the Born-Haber cycle
5. Be able to define the terms ‘enthalpy change of solution, ∆solH’ and ‘enthalpy change of hydration, ∆hydH of
an ion’
6. Be able to use energy cycles and energy level diagrams to calculate the enthalpy change of solution of an
ionic compound, using enthalpy change of hydration and lattice energy
7. Understand the effect of ionic charge and ionic radius on the values of enthalpy change of hydration and
the lattice energy of an ionic compound
8. Be able to use entropy and enthalpy changes of solution values to predict the solubility of ionic
compounds and discuss trends in the solubility of ionic compounds covered in Unit 2
Section A - Entropy
Entropy, ΔS
● Endothermic reactions can also occur spontaneously at room
temperature because there is entropy that governs the reaction.
● Entropy, ΔS, is the measure of a disorder in a system. It is stated that all
systems tend to move towards a state of disorder
○ Entropy increases as temperature increases because the particles get the extra energy to
move further away from each other to become more disorders
○ Hence, we can state that gases have the greatest entropy compared to solids and liquids.
● A perfect crystal at absolute zero would have an entropy of zero,
because there would be no movement, and therefore no disorder.
Entropy, ΔS (Continued…)
● Situations when there is an increase in entropy:
○ When a substance melts or evaporates
■ The entropy change of vaporization is much greater than that of fusion as a gas is
much more disordered than a liquid or a solid.
○ When there are more moles of product than reactants, there will be a sudden increase
in entropy because of the increased disorder.
○ When a lattice is dissolved in solution there is an increase in entropy.
■ The ions that make up the lattice are dissociated and can move in the solution, as
opposed to being held in their position by strong bonds.
Entropy, ΔS (Continued…)
● The overall entropy change for a reaction can be calculated as follows. It is
measured in JK-1 mol-1:

● The entropy of the surroundings is dependent on enthalpy change and

temperature:

● The entropy change for a reaction within a system can be calculated by

finding the difference between the standard entropies of the products
and the reactants:
Entropy, ΔS (Continued…)
● If the entropy change for a reaction is positive, the products are more
disordered than the reactants.
● If the entropy change for a reaction is negative, the products are less
disordered than the reactants
● The natural direction of change is towards a more disorderly state
overall, which is a positive change in entropy.
Entropy, ΔS (Continued…)
● Summary:
○ ΔStotal will be positive if:
■ Both ΔSsurroundings and ΔSsystem are positive
■ ΔSSurroundings is positive and ΔSsystem is negative, but the magnitude of ΔSsurroundings >
the magnitude of ΔSsystem
■ ΔSSurroundings is negative and ΔSsysstem is positive, but the magnitude of ΔSsurroundings
< the magnitude of ΔSsystem
Thermodynamic and Kinetic Stability
● If you look at this equation between methane and oxygen,

● The total entropy change has a positive value but the reaction doesn’t
take place until the reaction mixture is ignited, usually with a flame. Why
is that the case?
○ The added heat energy gives the reactant energy to overcome the high activation energy
of the reaction
○ So a reaction mixture with a high activation energy, where a reaction will not take place
spontaneously at room temperature, is said to be kinetically stable
○ Hence, we can say that this equation is thermodynamically unstable but kinetically
stable.
Why does water freeze?
● Ice has lower entropy than liquid water, so ΔSsystem is negative
● The process is exothermic, so ΔSsurroundings is positive
● If the magnitude of ΔSsurroundings > the magnitude of ΔSsystem, then ΔStotal is
positive and the water will freeze
Example Question 1
1. Use the values in the table to calculate
ΔSsystem for the following reaction:
Substance Entropy S/J K-1 mol-1
CaCO3(s) —> CaO(s) + CO2(g)
CaCO3 92.9

CaO 39.7

CO2 213.6
Example Question 1: Answer
1. Use the values in the table to calculate
ΔSsystem for the following reaction:
Substance Entropy S/J K-1 mol-1
CaCO3(s) —> CaO(s) + CO2(g)
CaCO3 92.9

CaO 39.7

CO2 213.6
Example Question 2
1. Use the values in the table to calculate
ΔSsystem for the following reaction:
Entropy S/J K-1 mol-1
N2(g) + 3H2(g) —> 2NH3(g) Substance

N2 191.6

H2 130.6

NH3 192.3
Example Question 2: Answer
1. Use the values in the table to calculate
ΔSsystem for the following reaction:
Entropy S/J K-1 mol-1
N2(g) + 3H2(g) —> 2NH3(g) Substance

N2 191.6

H2 130.6

NH3 192.3
Example Question 3
1. Calculate the ΔSsurroundings at 298K when one mole of hydrogen gas is
burned in oxygen.
Example Question 3: Answer
1. Calculate the ΔSsurroundings at 298K when one mole of hydrogen gas is
burned in oxygen.
Example Question 4
1. Using the information in the table, calculate the total entropy change at
298K for the following reaction:

Substance Entropy S/J K-1 mol-1

O2 205.0

H2 130.6

H2O 69.9
Example Question 4: Answer
1. Using the information in the table, calculate the total entropy change at
298K for the following reaction:

Substance Entropy S/J K-1 mol-1

O2 205.0

H2 130.6

H2O 69.9
Gibbs Free-Energy (ΔG)
● Gibbs free-energy quantifies the balance between entropy and enthalpy in a
system, acting as an indicator of reaction feasibility. It also allows ΔS to be found
without needing to measure the effects on the surroundings:

● Free-energy is measured in kJ mol-1 so it is important that ΔH and ΔS are used in

the same, standard units.
● The equation also takes the form ‘y=mx + c‘ meaning it can be represented
graphically as a straight line graph of ΔG on the y axis and T on the x axis
Gibbs Free-Energy (ΔG) (Continued…)
● ΔG is nonpositive for all spontaneous reactions.
● The minimum temperature at which a reaction is spontaneous can be
found by putting ΔG equal to zero.
Gibbs Free-Energy (ΔG) (Continued…)
ΔG ΔH TΔS Result

- - + Energetically favorable
Entropically favorable
Always spontaneous

+ + - Energetically unfavorable
Entropically unfavourable
Never spontaneous

+/- + + Energetically unfavorable

Entropically favourable
Spontaneous at high Temperature

+/- - - Energetically favourable

Entropically unfavourable
Spontaneous at low Temperature
Section B - Lattice Energy
Key terms
● Lattice Enthalpy (ΔLEH)
○ Lattice enthalpies are used for ionic substances.
■ Lattice dissociation enthalpy is defined as:
● The enthalpy change when one mole of a solid ionic compound is completely
dissociated into its gaseous constituent ions under standard conditions.
● This is an endothermic process
■ Lattice formation enthalpy is defined as:
● The enthalpy change when one mole of a solid ionic compound is formed from
its gaseous constituent ions under standard conditions
● This is an exothermic process
Factors affecting the magnitude of lattice energy
● The larger the charge of the positive ion, the larger the lattice energy
(more negative)
● The more cation-to-anion interactions, the larger the lattice energy (more
negative)
● The smaller the distance between the centres of the cations and their
neighbouring anions, the larger the lattice energy (more negative)
Key Terms
● Atomisation Enthalpy (ΔatH)
○ The energy required for the formation of one mole of gaseous atoms from an element
under standard conditions.
○ Some examples include:

● Enthalpy of Electron Affinity (ΔeaH)

○ The enthalpy change when one mole of electrons is added to one mole of gaseous atoms
to form one mole of gaseous 1-ions under standard conditions
○ Some example include:
Born-Haber Cycles
● They allow enthalpy changes to be determined indirectly
● The different enthalpy changes can be combined to produce a
Born-Haber cycle.
● Example on the next slide:
 Born-Haber Cycles (Continued…)
● In this example, lattice enthalpy of
formation (ΔleH) is calculated by following
anticlockwise around cycle:
ΔleH = [-(-355)-(121)-(502)-107+(-411)] = -786 kJmol -1
Born-Haber Cycles (Continued…)
● This cycle, derived from empirical data, will produce a different value for
lattice enthalpy compared with the theoretical value predicted using
electrostatic theory.
● Electrostatic theory assumes a ’perfect ionic model’.
○ Therefore, experimentally derived lattice enthalpies can be used as indicators of the
degree of covalent bonding in a lattice
Perfect Ionic Model
● Hydration enthalpy is heavily influenced by the size and charge of the molecules
being dissolved. Therefore, it is often assumed that the ions are ‘perfectly ionic’.
● The perfect ionic model assumes that:
○ All the ions are perfectly spherical
○ Charge is distributed evenly throughout the ion
○ The ions display no covalent characteristic
● Covalent character occurs in compounds when two bonded ions have varying
sizes or charges, meaning the distribution of charge is not even. This
polarisation of anions by cations creates covalent character.
Extent of covalent character: polarisation of the anion
● Fajan’s Rules:
○ Polarisation will be increased by:
■ A high charge and small size of the cation (i.e. A high charge density of the cation)
■ A high charge and large size of the anion
Enthalpies of Solution (ΔsolH) and Hydration (ΔhydH)
● Enthalpies of solution and hydration can be used as another means of
measuring lattice enthalpies indirectly. They are combined using a similar idea
to Hess’s Law.
● Enthalpy of solution is defined as:
○ The enthalpy change when one mole of solute is dissolved in water to infinite dilution so that the
ions no longer interact under standard conditions.
● Enthalpy of hydration is defined as:
○ The enthalpy change when one mole of gaseous ions is dissolved in water to form one mole of
aqueous ions under standard conditions.
● Enthalpy of hydration is nearly always negative as water molecules have 𝛿+
regions that naturally attract negative ions.
● The enthalpy of solution and the enthalpy of hydration are combined in the
following way to form an energy cycle.
Enthalpies of Solution (ΔsolH) and Hydration (ΔhydH)
(Continued…)
1. Calculating the lattice dissociation
enthalpy of sodium chloride.
Factors affecting Enthalpy of hydration and lattice energy

● Attractions are stronger with smaller ions and ions with greater charge.
This explains why hydration enthalpies decreases as you move down a
group and why Na+ ions have a lower enthalpy of hydration than Mg2+
ions.
● Lattice dissociation enthalpy also increases with decreasing ionic radius
and increasing charge, again because the ions form stronger attractions
and so the energy required for dissociation is greater
● Entropy, along the enthalpy changes of solution, can be used to predict
the solubility of ionic compounds. Generally, the less exothermic (more
endothermic) the enthalpy of solution, the less soluble the ionic
compound is.
Section C - Example Questions
Example Question 1
1. The Born-Haber cycle shown below
can be used to calculate the lattice
energy for magnesium oxide.
a. Give the name of each of the enthalpy
changes labelled ΔH1, ΔH2 and ΔH3
b. Write the missing formulae from the top
of the Born-Haber cycle. Include state
symbols.
c. The equations for the first and second
electron affinities of oxygen are:

d. Use the data in the Born-Haber cycle to

calculate the lattice energy of
magnesium oxide.
Example Question 1: Answer
A. Give the name of each of the
enthalpy changes labelled ΔH1,
ΔH2 and ΔH3
Answer:
● ΔH1 is the first ionisation
energy of magnesium
● ΔH2 is the enthalpy change of
atomisation of magnesium
● ΔH3 is the enthalpy change of
formation of magnesium oxide
Example Question 1: Answer
B. Write the missing formulae from
the top of the Born-Haber cycle.
Include state symbols.

Answer:

● Mg2+ (g) + O2- (g)

Example Question 1: Answer
C. The equations for the first and
second electron affinities of oxygen
are:

Answer:
● Energy is required to
overcome the repulsion
between the O- ion and the
electron being added
Example Question 1: Answer
D. Use the data in the Born-Haber
cycle to calculate the lattice energy
of magnesium oxide.
 Example Question 2
1. The equation for the combustion of
hydrogen is:
a. Calculate the standard entropy change of
the system at 298K, ΔSsystem, for the
combustion of hydrogen.
b. Calculate the standard entropy change of
the surroundings at 298K, ΔSsurroundings, for
the combustion of hydrogen
Substance H2(g) O2(g) H2O(l) c. Calculate the total standard entropy
change at 298K, ΔStotal, for the combustion
of one mole of hydrogen. Give your answer
S /J K-1 mol-1 131.0 205.0 69.9 to an appropriate number of sig. fig.
2. Explain why hydrogen does not react
with oxygen unless the mixture is
ignited.
 Example Question 2: Answer
1. The equation for the combustion of
hydrogen is:
a. Calculate the standard entropy change of the
system at 298K, ΔSsystem, for the combustion of
hydrogen.
b. Calculate the standard entropy change of the
surroundings at 298K, ΔSsurroundings, for the
combustion of hydrogen
c. Calculate the total standard entropy change at
Substance H2(g) O2(g) H2O(l) 298K, ΔStotal, for the combustion of one mole of
hydrogen. Give your answer to an appropriate
number of sig. fig.
S /J K-1 mol-1 131.0 205.0 69.9
 Example Question 2: Answer
2. Explain why hydrogen does not
react with oxygen unless the mixture
is ignited.

Answer: The activation energy of the

Substance H2(g) O2(g) H2O(l) reaction is high
S /J K-1 mol-1 131.0 205.0 69.9
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