5.2. Energy

OCR A Chemistry A-level
Module 5.2: Energy

Detailed Notes
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5.2.1 Lattice Enthalpy
Lattice Enthalpy
Lattice Enthalpy (∆LEH)

Lattice enthalpies are used for ionic substances. Lattice enthalpy is a measure of the strength
of ionic bonding in a giant ionic lattice.
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.
Lattice enthalpy cannot be measured directly. It is calculated using experimental values for
other enthalpy changes in a cycle called a Born-Haber cycle.
Atomisation Enthalpy (∆atH)

This is defined as:
The energy required for the formation of one mole of

gaseous atoms from an element under standard conditions.
Enthalpy of Electron Affinity (∆eaH)

This is defined as:
The enthalpy change when one mole of electrons is added to a mole of gaseous
atoms to form one mole of gaseous 1- ions under standard conditions.
Born-Haber and Related Enthalpy Cycles
Born-Haber cycles are similar to the cycles used with Hess’s Law. Note, Hess’s law states that
the enthalpy change of a reaction is independent of the route taken. Born-Haber cycles allow
enthalpy changes to be determined when they cannot be measured directly.
The different enthalpy changes can be combined to produce a Born-Haber cycle. In a similar
way to Hess’s Law, the arrows represent a reaction and they are treated like vectors. If the cycle
counters the direction of the arrow, the sign of the enthalpy change represented by that arrow
is reversed.
Example:
In this example, lattice enthalpy of formation (∆leH)

is calculated by following anticlockwise
rotation around the cycle: ∆le H = [-(-355)-(121)-(502)-(107)+(-411)] = -786 kJ mol-1
This cycle, derived from empirical data, will produce a different value for lattice enthalpy
compared with the theoretical value predicted using electrostatic theory. This 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

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 character.
Covalent character occurs in ions 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.
Example:
Enthalpies of Solution (∆solH) and Hydration (∆hydH)

Enthalpies of solution and hydration can be used as another way 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 ionic solid 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 ∂+ 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.
Example: Calculating the lattice dissociation enthalpy of sodium chloride
Factors Affecting Enthalpy of Hydration and Lattice Enthalpy

Enthalpy of hydration is a measure of the attraction between ions (that were in a lattice) and
water molecules in solution. Positive ions will be attracted to the δ- oxygen atoms, and
negative ions will be attracted to the δ+ hydrogen atoms.
Attractions are stronger with smaller ions and with ions of a greater charge. This explains why
hydration enthalpies decrease as you move down a group and why Na+ ions have a lower
enthalpy of hydration than Mg2+ ions.
Lattice dissociation enthalpy also increases in magnitude with decreasing ionic radius and
increasing charge. This is because the ions form stronger attractions and so the energy
required for dissociation is greater.
5.2.2 Enthalpy and Entropy
Entropy
In chemistry, things tend towards a state of disorder. Entropy, ∆S, is a measure of disorder. It
is a measure of the dispersal of energy in a system, which is greater the more disordered a
system is.
Some endothermic reactions are able to occur spontaneously at room temperature. This
shows how enthalpy is not the only driver of chemical reactions. Entropy is also key.
Entropy increases as temperature increases because the particles gain energy and move
faster and further apart. In other words, the particles become less ordered.
Gases have the greatest entropy compared to solids and liquids.
When a substance melts or evaporates, there is a sudden increase in entropy. The entropy
change of vaporisation is much greater than that of fusion as a gas is much more disordered
than a liquid or a solid.
Another case where there is a sudden increase in entropy is in a reaction when there are more
moles of gaseous product than reactants. In this case there is an increase in disorder.
When a lattice is dissolved in solution, there is an increase in entropy. This is because 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. This freedom of movement causes an increase in
disorder.
The overall entropy change for a reaction can be calculated. It is measured in J K-1 mol-1:
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:
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.
Generally, you will only calculate the entropy change within a system. However, it is important to
understand that the natural direction of change is towards a more disorderly state overall,
which is a positive change in entropy. An example of this is the natural and spontaneous
spreading of gas throughout a room, or the expansion of the universe.
Free Energy
Gibbs free-energy quantifies the balance between entropy and enthalpy in a system, acting as
an indicator of reaction feasibility. It also allows ∆S to be found without needing to measure
the effects on the surroundings:
Gibbs free-energy is measured in kJ mol-1 so it is important that ∆H and T∆S are used in the
same, standard units.
This equation also takes the form ‘y = mx + c’, meaning it can be represented graphically as a
straight line graph of ∆G (y-axis) against T (x-axis).
∆G is less than or equal to zero for all spontaneous reactions. The minimum temperature at
which a reaction is spontaneous can be found by putting ∆G equal to zero.
Changing the temperature or the type of reaction occurring will change the feasibility of the
reaction happening.
Since ∆G is dependent on both the enthalpy and the entropy, if the entropy change for a
reaction is positive and large enough, a reaction with a positive ∆H (endothermic reaction)
could still have an overall negative ∆G and occur spontaneously.
Kinetics vs. Thermodynamics

Although a reaction may be thermodynamically feasible, it still may not be able to occur due to
kinetic factors. A reaction may be thermodynamically feasible but kinetic factors may lead it to
occur at such a slow rate that, in practice, it does not appear to occur at all.
Another example of this is activation energy. A reaction may require a large activation energy
that is not provided by the reaction conditions. Therefore, it will not occur spontaneously.
5.2.3 Redox and Electrode Potentials
Redox
Oxidation is the loss of electrons and reduction is the gain of electrons. This can be
remembered by the acronym OILRIG - Oxidation Is Loss, Reduction Is Gain.
Oxidation results in the oxidation number becoming more positive, whereas reduction results
in the oxidation number becoming more negative.
Blocks of the periodic table, such as the s-block and d-block, indicate the orbital of the outer
electron. During reactions, s-block, d-block and some p-block species tend to undergo
oxidation whereas most p-block elements (further to the right of the periodic table) tend to
undergo reduction.
The oxidation number of a species tells you the oxidation state that it is in. This is indicated by
roman numerals. Example:
Fe(II) = Fe²⁺
Fe(III) = Fe³⁺
Redox Titration Calculations
Method for balancing half equations:
1. Balance all atoms except for oxygen and hydrogen.

2. Add H2O to balance oxygens (if needed).
3. Add H+ ions to balance hydrogens (if needed).
4. Add e- to balance charges (if needed).
Example:
→ Fe3+
Write the full half equations for Fe2+ and Cr2O 2- 3+
7 → Cr and
then combine the half equations.
Step 1: Write the full half equation for iron.

Fe2+ → Fe3+
[The only thing that isn’t balanced are the charges.]
⇒ Fe2+ → Fe3+ + e-
Step 2: Write the full half equation for chromium.
Cr2O72- → Cr3+
[Balance chromium]
Cr2O72- → 2Cr3+
[Balance oxygen]
Cr2O72- → 2Cr3+ + 7H2O
[Balance hydrogen]
Cr2O72- + 14H+ → 2Cr3+ + 7H2O
[Balance charges]
⇒ Cr2O7 + 14H+ + 6e- → 2Cr3+ + 7H2O
2-
Step 3: Combine the two half equations.

⇒ Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
⇒ Fe2+ → Fe3+ + e-
[Balance electrons]
Fe2+ → Fe3+ + e- (x6) ⇒ 6Fe2+ → 6Fe3+ + 6e-
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
[Cancel the electrons]

⇒ 6Fe + Cr2O72- + 14H+ →
2+
6Fe3+ + 2Cr3+ + 7H2O
Redox Titrations
Reaction between Iron ions and Potassium Manganate

In the redox titration between iron ions and manganate ions, the iron ions are oxidised while
the manganate ions are reduced. Their half equations can be found using the method
described above.
Fe2+ → Fe3+ ⇒ Fe2+ → Fe3+ + e-

MnO4- → Mn2+ ⇒ MnO4- + 8H+ + 5e-→ Mn2+ + 4H2O
These half equations can be combined to give the overall redox equation:
MnO4- + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
The iron solution is measured into a conical flask using a pipette and pipette filler. The endpoint
of the titration is indicated when the solution in the conical flask has a permanent pale pink
colour. At this point there is an excess of manganate ions.
Reaction between Iodine and Sodium Thiosulphate

In the redox titration between iodine and thiosulphate ions, the thiosulphate ions are oxidised,
while the iodine is reduced. Their half equations can be found using the method described
above.
I2 → I- ⇒ I2 + 2e- → 2I-

2S2O32- → S4O62- ⇒ 2S2O32- → S4O62- + 2e-
These half equations can be combined to give the overall redox equation:
2S2O32- + I2 →
S4O62- + 2I-
The same principles can be applied to any redox system.
Electrode Potentials
Electrochemical Cells
Electrochemical cells use redox reactions since the electron transfer between products
creates a flow of electrons. This flow of charged particles is an electrical current that flows
between electrodes in the cell. A potential difference is produced between the two electrodes
which can be measured using a voltmeter.
Most electrochemical cells consist of two solutions, two metal electrodes and a salt bridge.
A salt bridge is a tube of unreactive ions that can move between the solutions to carry the flow
of charge, whilst not interfering with the reaction. The salt bridge is crucial as it creates a closed
loop for the circuit.
Example: Electrochemical cell setup - the position of the lamp is where the voltmeter can be
placed to measure the potential difference.
Each electrochemical cell contains two half-cells which make up the full chemical cell. These
half-cells each have a cell potential which indicates how it will react, either in an oxidation or
reduction reaction.
Cell Potentials (Eo)

If measured under standard conditions, cell potentials are measured compared to the
Standard Hydrogen Electrode (SHE) to give a numerical value for the half-cell potential. SHE
is an electrode used for reference on all half-cell potentials, so, by definition it has a standard
electrode potential of zero.
Positive potentials mean the substances are more easily reduced and will gain electrons.
Negative potentials mean the substances are more easily oxidised and will lose electrons to
become more stable.
Standard Hydrogen Electrode (SHE)

The standard hydrogen electrode is the measuring standard for half-cell potentials. It has a
cell potential of 0.00V, measured under standard conditions. These conditions are:
● Solutions of 1.0 mol dm-3 concentration

● A temperature of 298K
● 100 kPa pressure
The cell consists of hydrochloric acid solution, hydrogen gas and platinum electrodes.
Platinum electrodes are chosen as they are metallic, so will conduct electricity, but inert, so will
not interfere with the reaction.
Example:
Conventional Cell Representation

Cells are represented in a simplified way so that they don’t have to be drawn out each time. This
representation has specific rules to help show the reactions that occur:
● The half-cell with the most negative potential goes on the left.
● The most oxidised species from each half-cell goes next to the salt bridge.
● A salt bridge is shown using a double line.
● State symbols are always included.
ompared to copper, zinc has the most negative potential so is placed on the left and
Example: C
undergoes oxidation.
Calculating Cell Emf
Standard cell potential values are used to calculate the overall cell emf. This is always
calculated as the potential of the right of the cell minus the potential of the left of the cell,
when looking at the conventional cell representation.
It can also be remembered as the most positive potential minus the most negative
potential.
If the overall cell potential is a positive value, the reaction taking place is spontaneous and
favourable. The more positive the potential, the more favourable the reaction.
The cell emf can be calculated for electrochemical cells containing different metals or
non-metals in contact with their ions, or alternatively, for electrochemical cells involving two half
cells containing the same element but in different oxidation states.
For example, a Fe2+ half cell and a Fe3+ half cell could be combined to make up an
electrochemical cell.
Eөcell and Entropy

The standard emf of a cell is directly proportional to both ln(K), where K is the equilibrium
constant of the reaction, and the total entropy change, (ΔStotal). This means that a positive
Eөcell value will have an overall positive entropy change.
Limitations
There are limitations to both calculating a standard cell potential using the SHE and using the
calculated value to determine reaction feasibility.
Although the cell emf value will tell you if a reaction is thermodynamically feasible or not, it does
not take into account the kinetics of the reaction. Even if a reaction is feasible, it may occur at
such a slow rate that, in practice, it does not actually occur.
The standard cell potential relies on conditions being standard throughout the experiment,
when in reality, the system may deviate from standard conditions.
Oxidising and Reducing Agents
Standard electrode potentials can also be referred

to as standard reduction potentials and can be
ordered into a series known as the
electrochemical series. In this series, all half
reactions are written in the reduction direction.
Electrode potentials that are very positive are

better oxidising agents and will oxidise those
species more negative than themselves.
Species that are very negative are better

reducing agents and will reduce those species
less negative than themselves.
Disproportionation
In a disproportionation reaction, a species is both oxidised and r educed. This is indicated by
both an increase and decrease in the oxidation number for that species.
Electrode potentials can be used to assess whether a species will undergo disproportionation. If
the overall Eөcell value is positive, then the disproportionation reaction is feasible.
Example:
Will Cu+ ions undergo disproportionation into Cu2+ ions and copper?
Reaction Eөcell
Cu2+ + 2e- ⇌ Cu +0.34
Cu2+ + e- ⇌ Cu+ +0.15
Cu+ + e- ⇌ Cu +0.52
The disproportionation of Cu+ ions involves the second and third half reactions.
E θ cell = +0.52 - (+0.15) = +0.37V
This value is positive, therefore the reaction is thermodynamically feasible.
Storage and Fuel Cells
Commercial Cells
Electrochemical cells can be a useful source of energy for commercial use. They can be
produced to be non-rechargeable, rechargeable or fuel cells.
Fuel Cells
Fuel cells are a type of electrochemical cell which
continuously produces a voltage when supplied with a
fuel and oxygen. The fuel donates electrons at one
electrode and oxygen gains electrons at the other
electrode. The energy released is used to generate a
voltage.
The most common type of fuel cell is the hydrogen

fuel cell, which uses a continuous supply of
hydrogen and oxygen from the air to generate a
continuous current. Other common fuels include
hydrogen-rich compounds like methane.
The reaction that takes place in a hydrogen fuel cell

produces water as the only waste product, so the
hydrogen fuel cell is seen as being relatively environmentally friendly.
The downsides to hydrogen fuel cells include the high flammability of hydrogen and that they
are expensive to produce, meaning they are not yet commonly used.
The hydrogen fuel cell can be carried out with either an acidic or an alkaline electrolyte. The
overall equation in both systems is the same:
In an acidic electrolyte, such as H2SO4, there are H+ ions in solution. The half equations are as
follows:
In an alkaline electrolyte, there are OH- ions in solution. The half equations are as follows:
Lithium ion batteries are a commonly used example of an electrochemical cell. They are
rechargeable, however, their benefits are counteracted by risks of toxicity and fire.

5.2. Energy

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OCR A Chemistry A-level

Module 5.2: Energy

This work by PMT Education is licensed under https://bit.ly/pmt-cc

Lattice Enthalpy (∆​LE​H)

Lattice ​dissociation​ enthalpy is defined as:

This is an ​endothermic process.

Lattice ​formation​ enthalpy is defined as:

This is an ​exothermic process.

Atomisation Enthalpy (∆​at​H)

The energy required for the formation of one mole of

Enthalpy of Electron Affinity (∆​ea​H)

In this example, lattice enthalpy of formation (∆​leH)

Perfect Ionic Model

The perfect ionic model assumes that:

● All the ions are ​perfectly spherical​.

Enthalpies of Solution (∆​sol​H) and Hydration (∆​hyd​H)

Enthalpy of ​solution​ is defined as:

Enthalpy of ​hydration​ is defined as:

The enthalpy change when one mole of gaseous ions is dissolved in

Factors Affecting Enthalpy of Hydration and Lattice Enthalpy

5.2.2 Enthalpy and Entropy

Gases​ have the ​greatest entropy​ compared to solids and liquids.

Kinetics vs. Thermodynamics

5.2.3 Redox and Electrode Potentials

Redox Titration Calculations

Method for balancing half equations:

1. Balance all atoms except for oxygen and hydrogen.

Step 1: Write the full half equation for iron.

Step 3: Combine the two half equations.

Reaction between Iron ions and Potassium Manganate

Fe​2+​ → Fe​3+ ⇒ Fe​2+​ → Fe​3+​ + e​-

MnO​4​-​ + 8H​+​ + 5Fe​2+​ → Mn​2+​ + 5Fe​3+​ + 4H​2​O

Reaction between Iodine and Sodium Thiosulphate

I​2​ → I​- ⇒ I​2​ + 2e​-​ → 2I​-

The same principles can be applied to any redox system.

Cell Potentials (E​o​)

Standard Hydrogen Electrode (SHE)

● Solutions of ​1.0 mol dm​-3​ concentration

Conventional Cell Representation

E​ө​cell​ and Entropy

Standard electrode potentials can also be referred

Electrode potentials that are very ​positive​ are

Species that are very ​negative​ are better

Cu​2+​ + 2e​-​ ⇌ Cu +0.34

Cu​2+​ + e​-​ ⇌ Cu​+ +0.15

Cu​+​ + e​-​ ⇌ Cu +0.52

This value is positive, therefore the reaction is ​thermodynamically feasible​.

The most common type of fuel cell is the​ hydrogen

The reaction that takes place in a hydrogen fuel cell

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Lattice Enthalpy (∆LEH)

Lattice dissociation enthalpy is defined as:

This is an endothermic process.

Lattice formation enthalpy is defined as:

This is an exothermic process.

Atomisation Enthalpy (∆atH)

Enthalpy of Electron Affinity (∆eaH)

In this example, lattice enthalpy of formation (∆leH)

● All the ions are perfectly spherical.

Enthalpies of Solution (∆solH) and Hydration (∆hydH)

Enthalpy of solution is defined as:

Enthalpy of hydration is defined as:

Gases have the greatest entropy compared to solids and liquids.

Fe2+ → Fe3+ ⇒ Fe2+ → Fe3+ + e-

MnO4- + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O

I2 → I- ⇒ I2 + 2e- → 2I-

Cell Potentials (Eo)

● Solutions of 1.0 mol dm-3 concentration

Eөcell and Entropy

Electrode potentials that are very positive are

Species that are very negative are better

Cu2+ + 2e- ⇌ Cu +0.34

Cu2+ + e- ⇌ Cu+ +0.15

Cu+ + e- ⇌ Cu +0.52

This value is positive, therefore the reaction is thermodynamically feasible.

The most common type of fuel cell is the hydrogen