CHEMICAL KABANDA

STEPHEN
ENERGETICS
LATTICE
ENERGY AND
BORN-HABER
CYCLES
 ▪ The standard enthalpy change of formation is
the enthalpy change when one mole of a
Standard enthalpy compound is formed from its elements under
change of standard conditions
formation, ΔHθf ▪ The reactants and products must be in their
standard states
 ▪ The standard enthalpy change of atomisation,
is the enthalpy change when one mole of
gaseous atoms is formed from its element
Standard enthalpy under standard conditions
change of ▪ Values of ΔHθat are always positive
atomisation, ΔHθat (endothermic) because energy must be
supplied to break the bonds holding the atoms
in the element together
 ▪ First electron affinity, EA1: is the enthalpy change when 1
First electron mole of electrons is added to 1 mole of gaseous atoms to
affinity, EA1 form 1 mole of gaseous ions with a single negative charge
under standard conditions
▪ Equations representing the first electron affinity of chlorine
and sulfur are:

▪ Note that:
▪ the change is from gaseous atoms to gaseous 1− ions
▪ the enthalpy change for the first electron affinity, EA1 is
generally exothermic: EA1 is negative
 ▪ Second electron affinity, EA2: is the enthalpy change when
Second electron 1 mole of electrons is added to 1 mole of gaseous 1– ions to
affinity, EA2 form 1 mole of gaseous 2– ions under standard conditions
▪ The equations representing the 1st and 2nd electron
affinities of oxygen are:

▪ Note that:
▪ Second electron affinities are always endothermic
(EA2 is positive), and so are third electron affinities
Factors affecting the electron affinities of
elements
▪ The value of the first electron affinity depends on the attraction between the added electron and
the positively charged nucleus. The stronger the attraction, the greater the amount of energy
released
▪ Nuclear charge: The greater the nuclear charge, the greater the attractive force between the
nucleus and the outer electrons. So, chlorine, with a greater nuclear charge than sulfur, will
tend to attract an electron more readily
▪ Atomic radius: The further away the outer shell electrons are from the positive nuclear charge,
the less the attractive force between the nucleus and the outer shell electrons is
▪ Sheilding effect: The greater the number of electron shells, the greater the power of inner
shell electrons to shield the outer shell electrons from the nuclear charge
Trends in the electron affinities of the group 16
and group 17 elements
▪ Generally, electron affinities for non-metal atoms get more negative (more exothermic) across a
period with a maximum at Group 17 but the pattern is not always clear
▪ For Groups 16 and 17, there is a trend to less negative (less exothermic) electron affinities as you go
down the group, apart from the first member in the group
 ▪ Lattice energy is the enthalpy change when 1 mole of an
Lattice energy, ionic compound is formed from its gaseous ions under
ΔHθlatt standard conditions

▪ Note that:
▪ it is the gaseous ions that combine to form the ionic
solid
▪ the lattice energy is always exothermic: the value of
ΔHθlatt is always negative, because the definition
specifies the bonding together of ions, not the
separation of ions
 ▪ It is impossible to determine the lattice energy of a
Lattice energy, compound by a single direct experiment
ΔHθlatt ▪ We can, however, calculate a value for ΔHθlatt using several
experimental values and an energy cycle called a
Born–Haber cycle
 ▪ A Born–Haber cycle is a particular type of enthalpy cycle
used to calculate lattice energy
▪ In simple terms it can be represented by

Born–Haber
cycles
 ▪ We can determine the lattice energy of a compound if
we know:
▪ its enthalpy change of formation ΔHθf
▪ the enthalpy changes involved in changing the
elements from their standard states to their gaseous
Born–Haber ions ΔHθ1

cycles ▪ According to Hess’s law

▪ Rearranging this equation, we get:

 Born–Haber
cycle for lithium
fluoride
 ▪ Taking lithium fluoride as an example, the relevant enthalpy
cycle can be written to show these steps
▪ Step 1 Convert solid lithium to gaseous lithium atoms: the
enthalpy change required is the enthalpy change of
Born–Haber atomisation of lithium, ΔHθat
cycles: example
LiF ▪ Step 2 Convert gaseous lithium atoms to gaseous lithium
ions: the enthalpy change required is the 1st ionization
energy of lithium, IE1

▪ Step 3 Convert fluorine molecules to fluorine atoms: the

enthalpy change required is the enthalpy change of
atomisation of fluorine, ΔHθat
 ▪ Step 4 Convert gaseous fluorine atoms to gaseous fluoride
ions: the enthalpy change required is the 1st electron affinity
of fluorine, EA1
Born–Haber
cycles: example ▪ Step 5 By adding all these values together, we get a value for
LiF ΔHθ1
▪ The enthalpy change of formation of lithium fluoride is
–617 kJ mol–1
 ▪ Applying Hess’s law to find the lattice energy of lithium
fluoride:

Born–Haber
cycles: example
LiF
 The Born–
Haber cycle for
magnesium
chloride
 ▪ There are a few minor differences between this cycle and
the one for lithium fluoride

The Born–Haber
cycle for magnesium
chloride
 ▪ In order to calculate the lattice energy, we need some
additional information:

The Born–Haber
cycle for magnesium
chloride
 ▪ October/November 2002 9701/4 qn2
▪ May/June 2004 9701/04 qn1
▪ October/November 2005 9701/04 qn1
Questions ▪ May/June 2007 9701/04 qn1
▪ October/November 2009 9701/42 qn1
 ❑Ionic radius
▪ As the size of the ion increases, the lattice energy
becomes less exothermic
▪ This applies to both anions and cations
▪ Ions with the same ionic charge have a lower
Factors affecting the charge density if their radius is larger
value of lattice ▪ A lower charge density results in weaker
energy electrostatic forces of attraction in the ionic lattice
▪ Sodium fluoride has a less exothermic lattice
energy than lithium fluoride. This reflects the
lower charge density on sodium ions compared
with lithium ions
 Lattice
enthalpies of
the Group 1
halides
 ❑Charge on the ions
▪ The lattice energy becomes more exothermic as the
ionic charge increases
▪ For ions of similar size, the greater the ionic charge,
the higher the charge density
▪ This results in stronger ionic bonds being formed
Factors affecting the ▪ compare lithium fluoride, LiF, with magnesium oxide,
value of lattice MgO. The cations Li+ and Mg2+ have similar sizes. The
energy anions F – and O2– are fairly similar in size
▪ Magnesium oxide has a greater lattice energy than
lithium fluoride
▪ The doubly charged Mg2+ and O2– ions in magnesium
oxide attract each other more strongly than the singly
charged ions of the same size in LiF
Enthalpies of solution and
hydration
 ▪ The enthalpy change of solution, ΔHθsol, is the
Enthalpy change of energy absorbed or released when 1 mole of
an ionic solid dissolves in sufficient water to
solution form a very dilute solution
 ▪ The enthalpy changes of solution for magnesium
chloride and sodium chloride are described by the
equations below:

Enthalpy change of
solution
Enthalpy change of
solution
a) Water molecules
forming ion–dipole bonds
with an ionic compound
b) Hydrated ions in solution
Question
Enthalpy change of ▪ The enthalpy change of hydration, ΔHθhyd, is
the enthalpy change when 1 mole of a
hydration specified gaseous ion dissolves in sufficient
water to form a very dilute solution
 ▪ The enthalpy changes of hydration for calcium ions and
chloride ions are described by the equations below:

Enthalpy change of
hydration
 ▪ We can calculate the enthalpy change of solution or the
enthalpy change of hydration by constructing an
enthalpy cycle and using Hess’s law

Calculating enthalpy
changes in solution
 ▪ Step 1: Draw the energy cycle

Worked example
 ▪ Step 2: Rearrange the equation and substitute the
figures to find ΔHθsol

Worked example
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ENTROPY
CHANGE, ΔS
 ▪ This is the number of possible arrangements of
the particles and their energy in a given system
Or
Entropy
▪ Measure (degree) of disorder or randomness of
a system
Comparing entropy
values
▪ Gases generally have much higher entropy
values than liquids, and liquids have higher
entropy values than solids
▪ Simpler substances with fewer atoms have
lower entropy values than more complex
substances with a greater number of atoms.
For example, for calcium oxide, CaO,
Sθ = 39.7 J K–1 mol–1 but for calcium carbonate,
CaCO3, Sθ = 92.9 J K–1 mol–1
 ▪ For a given substance the entropy increases as
a solid melts and then changes to a vapour. For
example, the molar entropy of ice just below its
melting point is 48.0 J K–1 mol–1; the molar
entropy for water is 69.9 J K–1 mol–1, but just
Entropy changes above its boiling point, the value increases to
during a change in 188.7 J K–1 mol–1
state and ▪ There is a gradual increase in entropy as the
temperature temperature of a substance is increased.
Increasing the temperature of a liquid or gas
increases the entropy because it increases the
disorder of the particles
Entropy changes during a change in state and temperature
 ▪ If there is a change in the number of gaseous molecules in a
reaction, there is likely to be a significant entropy change
▪ This is because high values of entropy are associated with
gases
❑Example 1:
▪ There is an increase in entropy of the system because a gas
Entropy changes in is being produced (high entropy) but the reactant, calcium
carbonate, is a solid (low entropy). So, the entropy change
reactions of the system is positive
❑Example 2:
▪ There is a decrease in the entropy of the system because
there is a reduction in the number of gas molecules as the
reaction proceeds. So, the entropy change of the system is
negative
Question
 ▪ In order to calculate the entropy change of the
system we use the relationship:

Calculating the
entropy change of Note:
the system ▪ Take into account the stoichiometry of the
equation
Worked example

▪ The negative value for the entropy change shows that

the entropy of the system has decreased
Worked example

▪ The negative value for the entropy change shows that

the entropy of the system has decreased
Question
 ▪ In determining whether a chemical reaction is likely to
be spontaneous we use the quantity Gibbs free energy
Gibbs free energy change, ΔG
change, ΔG ▪ The Gibbs free energy change is given by the
relationship:
 ▪ The value of T is always positive on the absolute (kelvin)
temperature scale
Gibbs free energy ▪ So, applying these signs to the relationship ΔGθ = –TΔSθ,
and spontaneous the value of ΔG must be negative for a reaction to be
reactions spontaneous
 ❑The Gibbs free energy change for a reaction can be
calculated if we know:
▪ the entropy change of the system in J K–1 mol–1
▪ the enthalpy change of the system in J mol–1;
Applying the equation we have to multiply the value of the enthalpy
ΔGθ = ΔHθ– TΔSθsystem change by 1000 because the entropy change is
in joules per kelvin per mol
▪ the temperature; under standard conditions,
this is 298 K
Worked example
Question
Question
 ▪ For a reaction to be spontaneous, ΔG must be negative
▪ The temperature can influence the spontaneity of a
reaction
▪ We can deduce this by considering the Gibbs free energy
Temperature as a combination of two terms in the relationship
change and reaction
spontaneity

▪ Assuming that the value of ΔH reaction does not change

much with temperature, we can see that the value of
TΔSsystem may influence the value of ΔG
 ❑For an exothermic reaction, the first term (ΔHreaction) has a
negative value
▪ If the value of ΔSsystem is positive, the second term (–TΔSsystem) is
Temperature change negative and the reaction will be spontaneous because both
ΔHreaction and –TΔSsystem are negative. So ΔG is negative
and reaction ▪ If the value of ΔSsystem is negative, the second term is positive.
spontaneity The reaction is likely to be spontaneous if the temperature is
low because ΔHreaction is more likely to have a greater negative
value than the positive value of the second term. So ΔG is
negative
▪ If the temperature is very high, the second term may be positive
enough to overcome the negative value of ΔHreaction and make
ΔG positive. So, the reaction is less likely to be spontaneous at a
higher temperature
 ❑For an endothermic reaction, the first term (ΔHreaction) has a
positive value
▪ If the value of ΔSsystem is negative, the second term is positive.
Temperature change The reaction will not occur because both terms are positive,
making the value of ΔG positive
and reaction ▪ If the value of ΔSsystem is positive, the second term is negative.
spontaneity The reaction is unlikely to be spontaneous if the temperature is
low because ΔHreaction is more likely to have a greater positive
value than the negative value of the second term. So ΔG is
positive
▪ If the temperature is very high, the second term may be
negative enough to overcome the positive value of ΔHreaction and
make ΔG negative. So, the reaction is more likely to be
spontaneous at a higher temperature
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