01 Energetics Notes 2022

1
Energetics 
altEnergetics
Bilal Hameed Energetics

A Level subject content
A Level subject
Physical content
chemistry
2
Physical
23
chemistry
Chemical energetics
23.1 Chemical
23 Lattice energy and Born-Haber cycles
energetics
Learning
23.1 outcomes
Lattice energy and Born-Haber cycles
Candidates should be able to:
alt
Learning outcomes
1 define and
Candidates use be
should theable
terms:
to:
(a) enthalpy change of atomisation, Hat
1 define and use the terms:
(b) lattice energy, H (the change from gas phase ions to solid lattice)
(a) enthalpy change oflattatomisation, Hat
2 (a) define and use the term first electron affinity, EA
(b) lattice energy, Hlatt (the change from gas phase ions to solid lattice)
(b) explain the factors affecting the electron affinities of elements
2 (a) define and use the term first electron affinity, EA
(c) describe and explain the trends in the electron affinities of the Group 16 and Group 17 elements
(b) explain the factors affecting the electron affinities of elements
3 construct and use Born–Haber cycles for ionic solids
(c) describe and explain the trends in the electron affinities of the Group 16 and Group 17 elements
(limited to +1 and +2 cations, –1 and –2 anions)
3 construct and use Born–Haber cycles for ionic solids
4 carry out calculations involving Born–Haber cycles
(limited to +1 and +2 cations, –1 and –2 anions)
5 explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a
4 carry out calculations involving Born–Haber cycles
lattice energy
5 explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of a
lattice energy
23.2 Enthalpies of solution and hydration
Learning
23.2 outcomes
Enthalpies of solution and hydration
Learning outcomes
1 define and
Candidates use be
should theable
termto:enthalpy change with reference to hydration, Hhyd, and solution, Hsol
2 construct and use an energy cycle involving enthalpy change of solution, lattice energy and enthalpy change
1 define and use the term enthalpy change with reference to hydration, Hhyd, and solution, Hsol
of hydration
2 construct and use an energy cycle involving enthalpy change of solution, lattice energy and enthalpy change
3 carry out calculations involving the energy cycles in 23.2.2
of hydration
4 explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of an
3 carry out calculations involving the energy cycles in 23.2.2
enthalpy change of hydration
4 explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical magnitude of an
23.3 Entropy change, S
Learning outcomes
  23.3 Entropy change, S
Learning outcomes
1 define the
Candidates termbe
should entropy,
able to:S, as the number of possible arrangements of the particles and their energy in a
given system
1 define the term entropy, S, as the number of possible arrangements of the particles and their energy in a
2 predict and explain the sign of the entropy changes that occur:
given system
(a) during a change in state, e.g. melting, boiling and dissolving (and their reverse)
2 predict and explain the sign of the entropy changes that occur:
(b) during a temperature change
(a) during a change in state, e.g. melting, boiling and dissolving (and their reverse)
(c) during a reaction in which there is a change in the number of gaseous molecules
(b) during a temperature change
3 calculate the entropy change for a reaction, S, given the standard entropies, S , of the reactants and
(c) during a reaction in which there is a change in the number of gaseous molecules
products, S = S (products) – S (reactants)
3 calculate the entropy change for a reaction, S, given the standard entropies, S , of the reactants and
(use of S = Ssurr + Ssys is not required)
products, S = S (products) – S (reactants)
(use of S = Ssurr + Ssys is not required)
Back to contents page www.cambridgeinternational.org/alevel 35

Back to contents page www.cambridgeinternational.org/alevel 35
Energetics Bilal Hameed

11
1
alt
Energetics of ionic bonding
1. 2 Energetics: Recap
We have already seen how to use Hess’s law to construct Hess’s cycles.
In this chapter we will return to Hess’s law and use it to investigate the
enthalpy changes when an ionic compound is formed.
The standard enthalpy of formation ΔHf is the enthalpy change when

one mole of a compound is formed from its constituent elements under
standard conditions, all reactants and products in their standard states.
1. 3 Skill Check 1
(a) Write an equation, including state symbols, for the process that has
an enthalpy change equal to the standard enthalpy of formation of
silver(I) fluoride.
(b) Write an equation, including state symbols, for the process that has
an enthalpy change equal to the standard enthalpy of formation of
calcium chloride.
Bilal Hameed
Bilal Hameed Marginalizer Energetics
energetics, states of matter, ionic usually 298 K.
bonding, and change of state The standard molar enthalpy of formation ∆fH is the enthalpy
studied in Chapter 3, Bonding, and change when one mole of a compound is formed from its constituent
Chapter 4, Energetics. elements under standard conditions, all reactants and products in
12standard states.
their
Hint 1
For example: H2(g) + 2 O2(g) ➝ H2O(l) ∆fH = −286 kJ mol−1
2
17
You may also refer to the enthalpy The standard enthalpy of formation of an element is, by definition, zero.
Thermodynamics
of atomisation of a compound.
The standard molar enthalpy change of combustion ∆cH is the
enthalpy change when one mole of substance is completely
Hint 1. 4 Atomisation burnt in oxygen.
17.1 Enthalpy change

Ionisation enthalpies are always For example: CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
alt
positive because energy has to The standard∆enthalpy
c
H = −890ofkJatomisation
mol−1 ΔHat is the enthalpy change
be put in to pull an electron away which
The accompanies
standard enthalpythe of
formation of one
atomisation ∆atHmole ofenthalpy
is the gaseouschange
atoms from
from the attraction of the positively
Learning objective:
charged nucleus of the atom. the which accompanies
Hess’sfrom
law
element in its the formation
standard state of one
under mole ofconditions.
standard gaseous atoms

the element in its standard state under standard conditions.

➔ List the enthalpy changes that You have already Mg(s)
For example: seen how to use Hess’s ∆law
➝ Mg(g) to construct enthalpy
−1
atH = +147.7 kJ mol
are relevant to the
Study tipformation of cycles and enthalpy1 diagrams. In this chapter you will return to Hess’s
Br (l) ➝ Br(g) ∆atH = +111.9 kJ mol−1
ionic compounds.
The second ionisation energy of law and use it to investigate
2 2 the enthalpy changes when an ionic
1
Specification sodium
reference: the energy change forcompound is formed.
is not3.1.8 Cl (g) ➝ Cl(g)
2 2
∆atH = +121.7 kJ mol−1
Na(g) ➝ Na2+(g) + 2e−
Definition of terms
This is given per mole of chlorine or bromine atoms and not per mole
It is the energy change for of chlorine or bromine molecules.
When you measure a heat change at constant pressure, you call it an
SynopticNalink
+(g) ➝ Na2+(g) + e−
First
enthalpy ionisation energy (first IE) ∆iH is the standard enthalpy
change.
change when one mole of gaseous atoms is converted into a
You will needHint
to know the Standard conditions chosen
mole of gaseous areeach
ions 100with
kPa aand a stated
single positivetemperature,
charge.
energetics, states of matter, ionic usually 298 K. +
For example: Mg(g) ➝ Mg (g) + e − ∆iH = + 738 kJ mol−1
Hess’s law states that the enthalpy
bonding, and change of state The standard molar enthalpy of formation is the
∆f=H+738
or first IE enthalpy
kJ mol −1
change for a chemical reaction is
studied in Chapter 3, Bonding, and
always the same, whatever route is change when one mole of a compound is formed from its constituent
The second ionisation energy (second IE) refers to the loss of a
Chapter 4, Energetics.
taken from reactants to products. elements under standard conditions,
of singly all reactants andions.
products in
1.mole
5 ofSkill Check
electrons 2
from a mole
their standard
positively
states.
charged
For example: Mg+(g) ➝ Mg2+(g) + e− ∆ H = + 1451 kJ mol−1
i
Hint (a) Write an
For example:
1
H2equation,
(g) + 2 O2including state
(g) ➝ H2O(l) symbols,
∆fH
or second for
IE ==+ thekJ
−286
1451 process
kJ −1−1that has
mol
mol
You may also refer to the enthalpy an enthalpy first
change equal to the∆ enthalpy
theof atomisation of sodium.
The standardThe electron

enthalpy affinity
of formation ofHaniselement
ea standard enthalpy
is, by definition, zero.
of atomisation of a compound. change when a mole of gaseous atoms is converted to a mole of
  standard molar enthalpy change of combustion ∆ H is the
The gaseous ions, each with a single negative charge.c
enthalpy change when one mole of substance is completely
Hint 264 burnt in oxygen.
(b) Write an equation, including state symbols, for the process that has
Ionisation enthalpies are always For example: CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
an enthalpy change equal to the enthalpy of atomisation of oxygen.
positive because energy has to ∆c H = −890 kJ mol−1

be put in to pull an electron away
The standard enthalpy of atomisation ∆atH is the enthalpy change
from the attraction of the positively which accompanies the formation of one mole of gaseous atoms
charged nucleus of the atom. from the element in its standard state under standard conditions.
For example: Mg(s) ➝ Mg(g) ∆atH = +147.7 kJ mol−1
Study tip 1
∆atH = +111.9 kJ mol−1
Br (l) ➝ Br(g)
2 2
The second ionisation energy of
1
sodium is not the energy change for Cl (g) ➝ Cl(g)
2 2
∆atH = +121.7 kJ mol−1
Na(g) ➝ Na2+(g) + 2e− This 1.
is 6
givenIonisation Energies
per mole of chlorine or bromine atoms and not per mole
It is the energy change for of chlorine or bromine molecules.
The first ionisation enthalpy is the enthalpy change when one mole of
Na+(g) ➝ Na2+(g) + e− First ionisation energy (first ∆iHof gaseous
electrons is removed from oneIE)
mole is the standard
atoms toenthalpy
form one mole
of gaseous ions with a single positive charge.
Hint mole of gaseous ions each with a single positive charge.

For example: Mg(g) ➝ Mg+(g) + e− ∆iH = + 738 kJ mol−1
Hess’s law states that the enthalpy
change for a chemical reaction is or first IE = +738 kJ mol−1
always the same, whatever route is The second ionisation energy (second IE) refers to the loss of a
taken from reactants to products. mole of electrons from a mole of singly positively charged ions.
For example: Mg+(g) ➝ Mg2+(g) + e− ∆iH = + 1451 kJ mol−1
or second IE = + 1451 kJ mol−1
The first electron affinity ∆eaH is the standard enthalpy
change when a mole of gaseous atoms is converted to a mole of
gaseous ions, each with a single negative charge.
264
Energetics Marginalizer Bilal Hameed

Bilal Hameed
For example: Mg(s) ➝ Mg(g) ∆atH = +147.7 kJ mol−1
1
Br (l) ➝ Br(g)
2 2
∆atH = +111.9 kJ mol−1
on energy of
1
nergy change for Cl (g) ➝ Cl(g)
2 2
13kJ mol−1
∆atH = +121.7
+ 2e− This is given per mole of chlorine or bromine atoms and not per mole
3
ange for of chlorine or bromine molecules.
+ e− First ionisation energy (first IE) ∆iH is the standard enthalpy
1. 7moleIonisation Energies
of gaseous ions each with a single positive charge.
For example: Mg(g) ➝ Mg+(g) + e− ∆iH = + 738 kJ mol−1
hat the enthalpy
alt
The second ionisation enthalpy is the enthalpy change
or first IE = +738 when
kJ mol−1 one mole
cal reaction is
whatever route is of electrons is removed from one mole of gaseous ions with a single
The second ionisation energy (second IE) refers to the loss of a
ts to products. positive charge to form one mole of gaseous ions with a 2+ charge.
mole of electrons from a mole of singly positively charged ions.

For example: Mg+(g) ➝ Mg2+(g) + e− ∆iH = + 1451 kJ mol−1
or second IE = + 1451 kJ mol−1
Chapter 19: Lattice energy

The first electron affinity ∆eaH is the standard enthalpy
The third ionisation enthalpy is the enthalpy change when one mole of
change when a mole of gaseous atoms is converted to a mole of
electrons is removed
gaseous ions, from
each one
withmole of gaseous
a single negativeions with a 2+ charge to
charge.
The standard
form one mole enthalpy
of gaseous ionschange
with aof3+
atomisation
charge. of chlorine
relates to the equation: The second electron affinity, ∆H —
ea2, is the enthalpy
O
_1 Cl (g) change when 1 mole of electrons is added to 1 mole of

2 2 Cl(g) ΔH —Oat = +122 kJ mol–1 gaseous 1– ions to form 1 mole of gaseous 2– ions under
standard conditions.
Values of ΔH —Oat are always positive (endothermic) because
energy must be supplied to break the bonds holding the
atoms in the element together. The equations representing the 1st and 2nd electron
1. 8 Skill Check 3 affinities of oxygen are:
QUESTION
1st electron affinity:
(a) Why are ionisation energies always endothermic?
2 a The bond energy of the chlorine molecule is O(g) + e– O–(g) ΔH —Oea1 = –141 kJ mol–1
  +244 kJ mol–1. Why is the standard enthalpy 2nd electron affinity:
change of atomisation half this value?
O–(g) + e– O2–(g) ΔH —Oea2 = +798 kJ mol–1
b Write equations, including state symbols, that
(b) Why is the second ionisation
represent energy
the enthalpy changeofofany elementof:more
atomisation Note that 2nd electron affinities are always endothermic
endothermic than its first ionisation energy?
i oxygen (ΔH —Oea2 is positive), and so are 3rd electron affinities.
ii barium The overall enthalpy change in forming an oxide ion,
iii bromine. O2–, from an oxygen atom is found by adding together the
c What is the numerical value of the enthalpy change 1st and 2nd electron affinities:
of atomisation of helium? Explain your answer.
O(g) + 2e– O2–(g)
ΔH —Oea1 + ΔH —Oea2 = (–141) + (+798) = +657 kJ mol–1

Electron affinity
259
The energy change occurring when a gaseous non-metal
atom accepts one electron is called the electron affinity. QUESTION
The symbol for electron affinity is ΔH —Oea.
3 a Suggest why the 2nd and 3rd electron affinities are
1. 9 Electron Affinity always endothermic.
The first electron affinity, ∆H —
ea1, is the enthalpy change
O
b The 1st electron affinity of sulfur is –200 kJ mol–1.
The energy change for the
when 1 mole formation
of electrons of a to
is added negative
1 mole of ion is called the The second electron affinity of sulfur is
electron affinity. The term ionisation energy is used
gaseous atoms to form 1 mole of gaseous 1– ionsonly for the formation +640 kJ mol–1. Calculate a value for the enthalpy
under
standard conditions. change S(g) + 2e– S2–(g)
of positive ions.
c Write equations representing:

When an electron is representing
Equations acquired bythe
anfirst
atom, energy
electron is released,
affinity of for i the 1st electron affinity of iodine
example:
chlorine and sulfur are: ii the 2nd electron affinity of sulfur.
Cl(g) + e– Cl–(g) ΔH —Oea1 = –348 kJ mol–1
S(g) + e– S–(g) ΔH —Oea1 = –200 kJ mol–1

Born–Haber cycles
Note that:
Components of the Born–Haber cycle
■ the change is from gaseous atoms to gaseous 1– ions
We have seen how we can apply Hess’s law in energy cycles
■ the enthalpy change for the first electron affinity, ∆H —
ea1 is
O
generally exothermic: ∆H —O
is negative.
to work out enthalpy changes (page 97). A Born–Haber
ea
cycle is a particular type of enthalpy cycle used to calculate
When an element forms an ion with more than one lattice energy. In simple terms it can be represented by
negative charge, we must use successive electron affinities Figure 19.2.
(this is rather like the successive ionisation energies we
used on page 34). The 1st, 2nd and 3rd electron affinities
have symbols ΔH —Oea1, ΔH —Oea2 and ΔH —Oea3.
Bilal Hameed
14
4
1. 10 First Electron Affinity
alt
The first electron affinity is the enthalpy change when 1 mole of
electrons is added to 1 mole of gaseous atoms to form 1 mole of 1—
gaseous ions under standard conditions.
O(g) + e ➞ O—(g) ΔH = –141 kJ mol–1

This refers to single atoms, not to oxygen molecules O2.
Most first electron affinities are exothermic. This is because energy is

released when the electron comes under the attraction of the nucleus.
1. 11 Second Electron Affinity

The second electron affinity is the enthalpy change when one mole of
electrons is added to one mole of gaseous 1− ions to form one mole of
gaseous 2− ions under standard conditions.
O—(g) + e ➞ O2— (g) ΔH = +791 kJmol–1

Subsequent electron affinities are always endothermic since the
repulsion between the negatively charged ion and the incoming electron
outweighs the energy released when the electron comes under the
attraction of the nucleus.
1. 12 Electron Affinities
The overall enthalpy change in forming an oxide ion, O2−, from an oxygen
atom is found by adding together the 1st and 2nd electron affinities.
O(g) + 2e ➞ O2— (g) ΔH = (–141 + 791) kJmol–1

Bilal Hameed
15
5
1. 13 Skill Check 4
alt
State whether the following enthalpy changes are always exothermic,
always endothermic or sometimes exothermic and sometimes
endothermic:
(a) First ionisation energy

(b) Second ionisation energy
(c) Enthalpy change of atomisation
(d) Enthalpy change of formation
(e) First electron affinity
(f) Second electron affinity
1. 14 Ionic Bonding & Structure

Compounds of metals with non-metals, such as sodium chloride and
magnesium oxide, are composed of ions. When such compounds form,
the metal atoms lose electrons and form positive ions. At the same time,
the non-metal atoms gain electrons and form negative ions.
For example, when sodium reacts with chlorine, each sodium atom loses
its one outer electron forming a sodium ion, Na+. Chlorine atoms gain
these electrons and form chloride ions, Cl−
1. 15 Ionic crystals
Ionic crystals consist of giant lattices containing billions of positive and
negative ions packed together in a regular pattern. In the lattice, each
Na+ ion is surrounded by Cl− ions, and each Cl− ion is surrounded by Na+
ions. The oppositely charged ions attract each other.
At the same time, the chloride ions repel other chloride ions and sodium
ions repel other sodium ions, but overall there are strong net electrostatic
attractions between ions in all directions throughout the lattice. These
electrostatic attractions between oppositely charged ions are described
as ionic bonding.
Bilal Hameed
● a pressure of 1 × 10 Pa = 100 kPa (this is very close to standard atmospheric Figure 13.1.5 An energy leve
pressure at sea level, which is 101.3 kPa) the formation of sodium chlor
● all reactants and products in their standard (stable) states at 25 °C and
1 atmosphere pressure
any solutions at −3
●
16a concentration of 1 mol dm .
The symbol for these standard enthalpy changes is Δ H 1, and Δf H 1 for
standard enthalpy changes of6formation.
The enthalpy change shown in Figure 13.1.5 relates to the formation of
one mole of sodium chloride from its elements sodium and chlorine. If the
measurements have been made at 25 °C (298 K) and 1 atmosphere pressure
1. 16 Standard
the result isenthalpy change
described at the standardof formation
enthalpy change of NaCl of
of formation Tip
sodium chloride. This can be written either as:
The superscript sign in ΔH1
alt
1
Na(s) + 2 Cl 2(g) → Na+Cl−(s) ΔfH 1 = −411 kJ mol−1 that the value quoted is for

or as: Δf H 1[NaCl(s)] = −411 kJ mol−1 conditions. The symbol is pr

The above is the standard enthalpy of formation of NaCl. Its a simplified ‘delta H standard’.
equation that hides a few facts. As far as sodium is concerned, it “ignores”
the following:
Key term
• Sodium starts as a giant

The standard lattice
enthalpy of metal
change atoms.
of formation of Energy is required
a compound, Δ f H1, is thetoenthalpy
separate the sodium
change when atoms
one moleinofthe giant lattice
the compound formstofrom
produce gaseous
its elements atoms.
under standard
conditions with the elements and the compound in their standard (stable) states.
• Energy is also required to remove one electron from each gaseous
sodium atom to form positive sodium ions, Na+.
Test yourself
7 Why does Δ f H1 = 0 kJ mol−1 for an element?
8 Why are values for the standard enthalpy changes of formation of
compounds containing carbon based on graphite and not diamond?
9 Write an equation for the reaction for which the enthalpy change is the
standard enthalpy change of formation of calcium iodide.
1. 17 Standard enthalpy change of formation of NaCl
As far as chlorine is concerned, it “ignores” the following facts:
• Chlorine consists of Cl2 molecules. Energy is required to break the

13.1.2 Energy changes and ionic bon
bonds between Cl atoms in the Cl2 molecules and form separate
gaseous Cl atoms.
• An469983_13.1_Chem_Y1-2_349-366.indd
energy change also occurs 351
when one electron is added to each
gaseous Cl atom forming chloride ions, Cl−. The energy change for this
process is called the first electron affinity of chlorine.
1. 18 Standard enthalpy change of formation of NaCl

Finally, and equally importantly, the equation “ignores” the fact that
energy is given out when gaseous Na+ and Cl− ions come together
forming a giant ionic lattice of sodium chloride, Na+Cl− (s).
The energy change for this process is called the lattice energy of
sodium chloride.

Bilal Hameed
The first electron affinity of an element is the energy change when each atom in one
mole of gaseous atoms gains one electron to form one mole of gaseous ions with a
single negative charge.
The following two equations define the first and second electron affinities for oxygen:
17
O(g) + e− → O−(g) 1st EA = −141 kJ mol−1
O−(g) + e− → O2−(g) 7 kJ mol−1
2nd EA = +798
The gain of the first electron is exothermic, but adding a second electron to a
negatively charged ion is endothermic.
1. 19Lattice
Lattice energy
energies
alt
The lattice
The lattice energyenergy of a compound
of a compound is defined
is defined as the
as the energy
energy changewhen
change when
one mole of an ionic compound is formed from free gaseous ions. For sodium
one mole of an ionic compound is formed from free gaseous ions.
chloride, this is summarised by the equation:

Na+(g) + Cl−(g) → Na+Cl−(s) ΔlattH 1[NaCl(s)] = −787 kJ mol−1

This is the lattice energy for the process shown diagrammatically in Figure
Lattice energies are important because they can be used as a measure
13.1.6.
of theLattice
strength of theare
energies ionic bonding
important in different
because compounds.
they can
be used as a measure of the

strength of
The strength of ionic
the ionic bonding
bonds, in different
measured compounds.
as lattice energies in kJmol−1,
arisesThe
fromstrength of ionic
the energy bonds,
given outmeasured
as billionsas upon
latticebillions kJ mol−1,and
energiesofinpositive arises
from the energy given out as billions upon billions of positive and negative Na+ Cl–
negative ions come together to form a crystal lattice.
ions come together to form a crystal lattice. Figure 13.1.6 Lattice energy is the energy
The overall force of attraction between the ions is stronger and this results in that would be given out to the surroundings
a more exothermic lattice energy if: (red arrows) if one mole of an ionic
compound could be formed directly from
● the charges on the ions are large free gaseous ions coming together (black
● the ionic radii are small, allowing the ions to get closer to each other. arrows) and arranging themselves into a
1. 20It isSkill Check
important to distinguish between the lattice energy of an ionic compound crystal lattice.
and its standard enthalpy change of formation. The lattice energy relates to the
Write formation
equationsoffor
onethe
mole of a compound
following from its free gaseous ions, whereas the
processes.
standard enthalpy change of formation relates to the formation of one mole of
(a) The enthalpyfrom
the compound change of formation
its elements of magnesium
in their stable states underchloride.
standard conditions.
(b) During
The the early
lattice energypartofofmagnesium
the twentiethchloride.
century, scientists found ways in which
to measure enthalpy changes of formation and atomisation, ionisation energies Key term
(c) The second affinities
and electron ionisationof energy
various of magnesium.
elements. This led two German scientists,
The lattice energy of an ionic
Max Born (1882–1970) and Fritz Haber (1868–1934), to analyse the energy
The enthalpy compound is the energy change when
(d) changes in the change
formationofofatomisation of compounds.
different ionic magnesium. Their work resulted
one mole of the compound forms from
in Born–Haber cycles, which are thermochemical cycles for calculating lattice
(e) The first electron affinity of chlorine.
energies and for investigating the stability and bonding in ionic compounds.
free gaseous ions.
13.1.3 Enthalpy changes when ions form 353
469983_13.1_Chem_Y1-2_349-366.indd 353 13/04/19 10:06 PM

1. 21 Born–Haber cycles
The enthalpy change for this direct one-step formation reaction of NaCl
will, by Hess’s law, be equal to the sum of the enthalpy changes involved
if the reaction were to take place in several steps.
Born and Haber were the first to think of the formation of an ionic
compound in this way.
Bilal Hameed
The force of attraction between the ions is stronger, and this results in a of formation of
more exothermic lattice enthalpy, if: magnesium chloride.
b) The lattice energy of
● the charges on the ions are large magnesium chloride.
● the ionic radii are small, allowing the ions to get closer to each other. c) The second ionisation en
18 magnesium.
It is important to distinguish between the lattice enthalpy of an ionic
d) The enthalpy change of
compound and its standard enthalpy 8change of formation. The lattice
atomisation of magnesiu
enthalpy relates to the formation of 1 mole of a compound from its free e) The first electron affinity
gaseous ions, whereas the standard enthalpy change of formation relates to the chlorine.
formation of 1 mole of the compound from its elements in their normal states
Cambridge International A Level Chemistry
under standard conditions.
5 Draw an enthalpy profile diag
the formation of aluminium o
1. 22DuringHess’s cycle
the early part of for ion compound
the twentieth formations
century, scientists found ways of ∆H f [Al2O3(s)] = −1676 kJ
measuring enthalpy changes of formation and atomisation, ionisation energies 6 Why should the state of wat
and electron affinities of various elements. This led the German scientists standard enthalpy changes r
alt
Max Born (1882–1970) and Fritz Haber (1868–1934) to analyse the energy H2O(l) and not H2O(g)?
changes inions
theinformation oflattice energy,
different ∆Hcompounds.
ionic latt ionic
Their work resulted in Step
7 Why2 isConvertthe standard gaseous
enthalp
Born–Haber cycles ions:change
the ofenthalpy
formation of copp
chang
gaseous statewhich are thermochemical cyclescompound
for calculating lattice
equal to zero?
enthalpies and for investigating the stability and bonding in ionic compounds.
energy
8 Why isof thelithium,
first electronΔH —
O
affin
i1
chlorine exothermic, but its s
13.4 ∆H
Born–Haber
1 cycles standard electron affinity endothermic
Li(g) Li+(g) + e
9 Why are ionisation energies
enthalpy change
Born–Haber cycles are an application of Hess’s law (Section 16.5 in endothermic?
OCR Chemistry for AS). They provide a model for the formation, ∆H f
ofdetermination Tutorial
elements in their
Step
10 Why3 isConvert
the secondfluorine
ionisation
of lattice enthalpies which cannot be measured experimentally. They of any element more endoth
standard
also enable chemists to test the ionicstates
model of bonding in different thethan enthalpy changeenerg
its first ionisation req
substances. atomisation of fluorine,
11 Why does the lattice enthalp
A Born–Haber cycle identifies all the enthalpy changes that contribute to lithium fluoride indicate that
Figure 19.2 A simple enthalpy cycle that can be used to
the standard enthalpy change of formation of a compound. These changes, bonding in lithium fluoride is
_1stronger
calculate
shown in Figurelattice energy. The dashed line shows the two-step
13.7, involve: 2 F2(g) than that F(g)
in sodium
— — —
O chloride?
route: using Hess’s law, ∆H 1 + ∆Htolattcreate
O
● the energy (enthalpy changes) required
= ∆Hfree
O
f . gaseous ions by (∆H lattice [LiF(s)] = −1031 kJ m
atomising and then ionising the elements Step ∆H 4 Convert gaseous
lattice [NaCl(s)] = −780 kJ m
● the
Weenergy
can given out (thethe
determine lattice enthalpy)
lattice energywhen
of athecompound
ions come together
if to ions: the enthalpy chang
1. 23form
General
we know: Born-Haber cycle
a crystal lattice. affinity of fluorine, ΔH —Oe
—
■ its enthalpy changegaseous
of formation,
ions ∆H Of F(g) + e– F–(g)
■ the enthalpy changes involved in changing the elements
fromtotal
their standard states to their gaseous ions, ∆H —
enthalpy
1.
O
Step 5 By adding all th
change for atomising
and ionising the
According to Hess’s law, Figure 19.2 shows that: for ΔH —O1 .
two elements
lattice The enthalpy change
ΔH —O1 + ΔH —Olatt = ΔH —Of enthalpy
–617 kJ mol–1. We now h
metal element and
non-metal element calculate the lattice ener
Rearranging this equation we get:
enthalpy change
of formation
ΔH —Olatt = ΔH —Of – ΔH —
O of Calculating lattic
the compound
1 compound
260 Applying Hess’s law to fi
The enthalpy change ΔH 1 involves several steps.
—
O
fluoride:
Figure 13.7 !
Taking
The overall structurelithium fluoride
of a Born–Haber as an example, the relevant
cycle.
enthalpy cycle can be written to show these steps ΔH —Olatt = ΔH —Of – ΔH —O1
(Figure 19.3).
We know that:
1. 24 Born–Haber cycle for NaCl
∆ H latt
Li+(g) + F –(g) LiF(s) ΔH —O1 = ΔH —Oat [Li] + Δ
In the case of NaCl, the steps are:
step 4 atoms into gaseous atoms
● turning solid sodium So

Li+(g) + F(g) + e–
● splitting gaseous chlorine molecules into gaseous atoms
step 3
ΔH —Olatt
∆H 1 an electron Li
● removing from 1
each
+(g) + gaseous
– ∆H
f
sodium atom = ΔH —Of – {ΔH —Oat [Li] +
2 F2(g) + e
● adding an electron to step
each2 gaseous chlorine atom
Putting in the figures:
Li(g) + 12 F2(g)
● bringing the ions together into an ionic lattice
step 1 ΔH —Olatt = (–617) – {(+16
Li(s) + 12 F2(g)
ΔH —Olatt = (–617) – (+43
Figure 19.3 An enthalpy cycle that can be used to calculate
the lattice energy of lithium fluoride. The dashed line shows Note: take care to accou
the two-step route. changes. The values of t
and the electron affinity
The enthalpy changes needed to calculate ΔH —O1 are as follows.
Step 1 Convert solid lithium to gaseous lithium atoms:
the enthalpy change required is the enthalpy change of Bilal Hameed
atomisation of lithium, ΔH —Oat.
Li(s) Li(g) ΔH —Oat = +161 kJ mol–1
19
9
● removing an electron from each gaseous sodium atom

● adding an electron to each gaseous chlorine atom 5.12 Enthalpy changes and ionic bonding
● bringing the ions together into an ionic lattice
These processes are shown in Figure 3.1: QUESTIONS
Answer
alt
1 Write the equation+ showing all the atoms and bonds in the molecules. 16 Using bond energies from
Na (g) + Cl−(g)
H H Table 5.2, calculate the enthalpy
\ / Step 4 change for the reaction shown
N − N + 2F − F → N ≡ N + 4H − F
EA(Cl)
/ \ in Figure 5.16.
H Na+(g)H + e− + Cl(g) 17 Write equations to explain that
2 Count the number bonds broken and bonds formed. Step 5
D (H − H) = 2 × ΔH at (H(g))
Step 3
∆Hlatt(NaCl)
Bonds broken1st IE(Na)kJ mol –1 Bonds formed kJ mol –1 18 a Calculate the bond energy
one N − N +160
Na(g) N≡2N
one Step –994 for the O − H bond in water
∆Ha(Cl)
four N − H +(4 × 390) four H − F –(4 × 562) from the data below.
Step 1
two F − F ∆Ha(Na) +(2 × 158) ∆Hf (NaCl(s)) H2O(g) → HO(g) + H(g)
1
Na(s)
3 Calculate the enthalpy change+ knowing
2 Cl2(g) NaCl(s)
that this is the difference between ΔH = 498 kJ mol–1
the energyFigure
needed
3.1to break bonds and the energy released as bonds form. HO(g) → H(g) + O(g)
So ΔHr = +160 + (4 × 390) + (2 × 158) – 994 – (4 × 562) ΔH = 428 kJ mol–1
Step 1: =the enthalpy of atomisation of sodium, ∆Ha(Na)
+2036 – 3242 = –1206 kJ mol–1
(+109 kJ molb−1)Why is your answer to part a
Step 2: the enthalpy of atomisation of chlorine, ∆Ha(Cl) (+121 kJ mol−1)not the same as the average
O − H bond energy in
3: the
Step the
For most reactions, first of
values ionisation energy
ΔH estimated of sodium,
from IE(Na)
average bond 1st −1
energies (+494 kJ mol )Table 5.2.
agree quite closely
Stepwith experimental
4: the first electronvalues.
usefulness of bond energies.
affinityThis has further
of chlorine, established the(−364 kJ mol
EA(Cl)
Chemical energetics
−1) the data in Table 5.2 to
19 Use
estimate the enthalpy change
−1
Step 5: the lattice energy of sodium chloride, ∆H latt(NaCl) (−771 kJ molfor) the following reactions.
We canhowever,
Sometimes, break downthere the process into
are differences three changes calculated from
in enthalpy
2(g) → 2NH3(g)
a N2(g) + •3HThen,
average bond energies compared withofthose determined forbysteps
experiment. These the removal of one electron from each gase

result either from variations in values
∆Hf(NaCl(s)) = sum the ∆H 1–5 + –
Na Cl (s)
stages.
small differences the strength of one particular b H2C = CH2gaseous, positive
(g) + H2(g) → sodium ions. This is the first ion
bond in different molecules, or=when∆Ha(Na) + ∆H
one of the (Cl) + 1stor
areactants IE(Na) + EA(Cl)
products is Stage
not +3∆H latt(NaCl)
in CH CH (Section 2.6).
(g)
the Stage
gaseous1:state,
Formation of gaseous Na+ ions
3 3
as bond energy calculations
= +109 + 121 +assume.
494 + (−364) + (−771) Na+= + ClkJ–(g)
(g)−411 mol−1 Na(g) → Na+(g) + e– ΔH
Stage 2: Formation of gaseous
The enthalpy Cl— ions
∆H , of an element is the enthalpy change
of atomisation, a 2 The formation of gaseous chloride ions, Cl–(g)
elementCl(g)
Na(g)
5.12
when 1 mol of gaseous atoms is made Stage
from1 an Stage
in its 2
standard
Stage 3: Formation of solid sodium chloride This stage also involves two separate processes.
state. It is always endothermic.
Enthalpy changes and ionic bonding
Na(s) + 12 Cl2 (g)
The first electron affinity of an element is the energy change when 1 mol • First, the formation of gaseous chlorine atoms by
Cl2 molecules. This process is the enthalpy change
of gaseous 1− ions is formed from 1Figmol 5.17 of
Keygaseous atoms.
stages in the Itofissodium
formation always
chloride from its elements (Section 5.5).
exothermic.
When sodium reacts with chlorine, a very exothermic reaction occurs. Sodium In this section you will learn to:12Cl2(g) → Cl(g) Δ
chloride is produced,The heatsecond electron
is lost affinity is the
to the surroundings andenergy change
the enthalpy when an •electron
of the is
State that the formation of
• Then, the addition of one electron to each Cl atom
Tip system falls. Thisadded
can be to a gaseousby1−
summarised theion, forming a 2− ion. It is always endothermic.
equation: sodium chloride from its This process is called the electron af
ions, Cl–(g).
Na(s) 1
For +example,
Cl (g) →the enthalpy
Na + –
Cl (s)of ΔH
atomisation
= – of:
411kJ mol –1 elements is exothermic
The first electron 2 2
Cl(g) + e– → Cl–(g)
affinity is alwaysAlthough this equation 1 • Describe in steps how elements
● chlorine is for the change Cl 2(g) → Cl(g)
identifies the formation of sodium chloride as an ionic
negative (exothermic). 2 are ‘atomised’
3 The, ‘ionised’ and of solid sodium chloride, Na+
formation
solid, it simplifies the process in many ways. This has prompted chemists to look + ‘formation’
1 then combined Naby (g) and Cl–(g) ions
The second is always
at the formation ● of ionic compounds in moreBr detail and identify three key stages
bromine is for the change 2 2(l) → Br(g)
1. 27 Stage 1: Formation of gaseous Na ions
(Figure 5.17). In practice, these stages overlap with one another because+some
positive (endothermic)
ions will be completing the final stage while 1 others are starting the first stage.
• Define ‘lattice
compare data
Stageenergy’
of lattice
ionic common
and gaseous Na+ and Cl– ions coming to
3 involves
ionicsodium chloride. The process is
of solid
as a negative electron ● sulfur is for the change 8S8(s) → S(g)
solids of sodium chloride, ΔHlatt(Na+Cl–(s). In some textboo
is brought towards a
1 TheThis stageFor
formation involves
of gaseous two processes.
sodium ions,
Na+(g), from sodium metal, Na(s)
example, the first electron affinity for oxygen is for the change O(g) + e− → O−(g)
negative ion. lattice energies are called lattice enthalpies. The latti
and
This stage involves the
twosecond
separateelectron affinity
processes. is for the change O −(g) + e− → O2−(g). is the standard enthalpy change when one mole of t
First, the separation of gaseous sodium atoms from sodium Na+ atoms in the
from free gaseous ions under standard conditions. F
• First, the separation of gaseous sodium atoms from
giant metallic solid. This process involves the enthalpy change sodium atoms Cl– in the of summarised in the equation:
giant metallic solid. This process involves the enthalpy change of atomisation
atomisation of sodium, ΔH at(Na(g))
Fig 5.18 Lattice energy is the heat (red arrows) Na+(g) + Cl–(g) → Na+Cl–(s)
60 3 Energetics II (TopicΔH
of sodium, 13)at(Na(g)) (Section 5.5). that would be given out to the surroundings if
Na(s) → Na(g) ΔH at(Na(g)) one mole kJ
= +107 of amol
crystalline
–1

ionic compound could This is a very exothermic process because of the stro
be formed directly from free gaseous ions
oppositely charged Na+ and Cl– ions. A diagram show
– • Then, Then, the removal
the removal of oneof one electron
electron from each from eachsodium
gaseous gaseousatomsodium
to form atom to form the lattice energy process is shown in Figure 5.18.
(s)
DEFINITIONS
gaseous, positive sodium ions. This is the first ionisation energy of sodium 107
gaseous, The lattice energies of some ionic solids are listed in
e3 (Section
07435_03_Edexcel_GF_Chem_059-095.indd 60 2.6). positive sodium ions. This is the first ionisation energy of sodium
The electron affinity of an 20/05/15 6:02 pm

Lattice energies are always negative because they ar
ΔH i1(Na(g)) element is mol
the –1
enthalpy change
–
Cl (g) Na(g) → Na+(g) + e– = +494 kJ
when each atom in one mole of of oppositely charged ions come together and form
gaseous atoms gains one electron provide a measure of the strength of ionic bonds in
Cl(g) Stage 2 2 The formation of gaseous chloride ions, Cl–(g), from chlorine gas, Cl2(g)
to form one mole of gaseous ions and can be compared with bond energies which pro
This stage also involves two separate processes. with a single negative charge. strength of covalent bonds.
Cl2 (g) • First, the formation of gaseous chlorine atoms by breaking the As the force of attraction between ions increases, w
Thebond between
lattice energy of an ionic
e formation of sodium
Cl2 molecules. This process is the enthalpy change of atomisation of chlorine
compound is the standard to get stronger and become more exothermic. So, la
s (Section 5.5). enthalpy change when one mole negative as:
1
2Cl2(g) → Cl(g) ΔH at(Cl(g)) of
= the
+122 compound
kJ mol–1 is formed from • charges on the ions increase,
free gaseous ions.
• Then, the addition of one electron to each Cl atom forming gaseous chloride • ionic radii decrease, allowing the ions to get close
ions, Cl–(g). This process is called the electron affinity of chlorine. Make sure you understand the difference between t
Table 5.3 The lattice energies of some ionic
Bilal Hameed Cl(g) + e– → Cl–(g)
Bilal Hameed Ea(Cl(g)) = –349 kJ mol–1 Marginalizer the enthalpy change of formation of an ionic compo
Energetics
solids
+ –
involves the formation of 1 mole of a compound fro
3 The formation of solid sodium chloride, Na Cl (s), from gaseous Lattice energy / kJ mol–1
Compound whereas the enthalpy change of formation involves
Na+(g) and Cl–(g) ions
NaF –918 the compound from its elements in their normal sta
Stage 3 involves gaseous Na+ and Cl– ions coming together toNaCl form a giant –776 Although the concept of lattice energies is helpful in
ionic lattice of solid sodium chloride. The process is called the lattice energy
20
Chemical energetics
Chemical energetics 10
Na+Cl–(s) • Then, the removal of one electron from each gaseous sodium atom to form
Na+Cl–(s)
gaseous,
• Then, thepositive
removal sodium
of oneions. This from
electron is the each
first ionisation energyatom
gaseous sodium of sodium
to form
Stage 3 (Section 2.6).
gaseous, positive sodium ions. This is the first ionisation energy of sodium
Stage 3Cl–(g)
Na+(g) + 1.2.6).
(Section 28 Stage Na(g) 2:
→Formation
Na+(g) + e– of gaseous
ΔH (Na(g)) = +494 Cl — ions
kJ mol –1
i1
Na+(g) + Cl–(g) Na(g) → Na+(g) + e– ΔH i1(Na(g)) = +494 kJ mol–1
alt
Na(g) Cl(g)
This stageofalso
2 The formation involves
gaseous two ions,
chloride separate processes.
Cl–(g),
from chlorine gas, Cl2(g)

Stage 1 Stage 2
–
Cl(g) 2This
The formation
stage also of gaseous
involves two chloride
separate ions, Cl (g), from chlorine gas, Cl2(g)
processes.
Stage 1 Na(g)
Chemical energetics Stage 2 First, the formation of gaseous chlorine atoms by breaking the bond
Na(s) + 2 Cl2 (g)
1
This stage
• First, thealso
between involves
Cl2 of
formation two separate
molecules.
gaseous Thisprocesses.
chlorineprocess
atoms byisbreaking
the enthalpy change
the bond of
between
Na(s) + 2 Cl2formation
1
(g) Cl
• First,molecules.
the This
formation process
of is
gaseous the enthalpy
chlorine change
atoms by of atomisation
breaking the of chlorine
bond between
Fig 5.17 Key stages in the
Na+Cl–(s)
of sodium 2
atomisation
• Then,
(Section 5.5).
of chlorine.
the removal of one electron from each gaseous sodium atom to form
chloride from its elements Cl
Fig 5.17 Key stages in the formation of sodium 2 molecules. This process
gaseous, positive sodium is the
ions.enthalpy change
This is the of atomisation
first ionisation of of
energy chlorine
sodium
(Section 5.5). 1
chloride from its elementsStage 3 (Section 2.6). 2Cl2(g) → Cl(g) ΔH at(Cl(g)) = +122 kJ mol–1

1
Na+(g) + Cl–(g) • Then, the addition 2of Clone
2(g) →→ Cl(g)
electron
Na(g) toNa (g) + e– ΔHforming
each
+ Cl atom
ΔH(Cl(g)) = +122
gaseous kJ mol–1 –1
chloride
i1(Na(g)) = +494 kJ mol
at
Then, the addition of one electron to each Cl
ions, Cl (g). This process is called the electron affinity of chlorine.
– atom forming gaseous
• Then, the addition of one electron to each Cl atom forming gaseous chloride
Na(g) Cl(g) ions, chloride
2 The
Cl–
(g). Thisions,
formation +Clegaseous
of
process
Cl(g)
––(g).
is→ This
called process
Clchloride is called
ions,
(g) electron
–the –
ClE(g),
affinitythefrom
a(Cl(g))
electron
of –349affinity
= chlorine
chlorine. gas,
kJ mol ofClchlorine.
–1 2(g)
Stage 1 Stage 2
3 The This stage alsoCl(g)
formation involves
of solid two
→separate
+ e– sodium (g) processes.
Cl–chloride, a(Cl(g))
Na+ClE–(s), –349 kJ mol–1
from=gaseous
+ –
Na(s) + Cl2 (g) 1 Na (g)
• First,and Cl (g)
the formation ions
2 3 The formation of solidofsodiumgaseous chloride,
chlorine atoms
Na+Clby – breaking the bond between
(s), from gaseous
+3Cl molecules. – This process
+ is– the enthalpy change of atomisation of chlorine
Fig 5.17 Key stages in the formation of sodium Na
Stage (g) 2 and Cl
involves (g)
gaseousions Na and Cl ions coming together to form a giant
chloride from its elements (Section 5.5).
ionic lattice of solid sodium chloride.+ –
The process is called the lattice energy
Stage 3 involves gaseous Na + and Cl ions coming together to form a giant
of sodium chloride, ΔHlatt(Na 1 Cl–(s). In some textbooks you will find that
2(g) → The
Clchloride. Cl(g) ΔH atthe
(Cl(g)) = +122 kJ mol–1
ionic
latticelattice of solid
energies sodium
are called 2lattice enthalpies. process is called
The lattice energy oflattice energy
a compound
of sodium
is the Then, chloride,
• standard the ΔHlattchange
addition
enthalpy (Na + –
Cl when
of one (s). Inone
electron some textbooks
tomole
eachofClthe
atom you will find
forming
compound that chloride
isgaseous
formed
Na+ lattice energies – are called lattice enthalpies. The lattice energy of a compound
Cl–
from free
is 1. 29
ions, Cl
gaseous
the standard
summarised
Stage
(g). This
ions
enthalpy
in the
under
equation:
3: formation
process
change
is
when one moleof
called
standard the
conditions.
of solid
electron
For affinity
sodium
the compoundsodium
of chlorine.
chloride, chloride
this
is formed
is
Na+ from free gaseous ionsCl(g) e → Cl
–
under+ standard
–
(g)
conditions. Ea(Cl(g))
For sodium = –349
chloride, kJismol–1
this
Fig 5.18 Lattice
Cl– energy is the heat (red arrows)
summarised StageNa 3
+
involves
(g) + Cl
in the equation:
–
(g) gaseous
→ Na Na
+ –+
Cl (s)and Cl– ions
ΔH coming
= ΔH together
(Na + –
Cl (s))to form a
that would be given out to the surroundings if 3 The formation of solid sodium chloride, Na+Cl–(s),lattfrom gaseous
one
Fig mole
5.18 of a crystalline
Lattice energy isionic compound
the heat could
(red arrows) This is Na a giant
very
+
(g)Na ionic
(g) +lattice
exothermic
and Cl
+ – – process
(g)(g)
Cl of→
ions solid Nasodium
because Cl (s) chloride.
+ – of the strong ΔH The = process
attraction (Na+is
ΔH lattbetween Clcalled
– the the
(s))
be would
that formedbe
directly
given from
out tofree
thegaseous ions if
surroundings +
oppositely charged
lattice Na
ethalpy and
of Cl– ions.
sodium +
A diagram
chloride,– ΔHshowing
latt(Na +what
Cl happens
–(s)).
during
one mole of a crystalline ionic compound could This Stage
is a very
the lattice
3 involves
energyexothermic gaseous
process is processNa and
shownbecause
Cl ions
in Figure of 5.18.
thecoming
strongtogether
attraction to form
between a giant
the
be formed directly from free gaseous ions ionic lattice of solid+ sodium – chloride. The process is called the lattice energy
oppositely The charged
lattice Na
energyand Cl
of(Naions.
a compoundA diagram showing
is the standardwhat happens during
youenthalpy
will find change when
DEFINITIONS Thelattice
the lattice
of sodiumenergies
energy of
chloride,
processsomeΔH ionic
islatt
shown
+solids
–
Clin (s).areIn listed
Figure some5.18. in Table
textbooks 5.3. that
The electron affinity of an latticeone mole
energies ofarethe compound
called lattice is formed
enthalpies. Thefrom free
lattice gaseous
energy of aions under
compound
DEFINITIONS
element is the enthalpy change Lattice
The energies
lattice energies are always
of somenegativeionic because
solids areone they arise
listed in Tableas billions
5.3. upon billions
is the
of oppositely standard
standard charged enthalpy
conditions.
ions come change
For when
sodium
together andchloride,
formmole ofthis
ionic the compound
is
bonds. summarised is formed
Lattice energies in the
The
whenelectron
eachNa +affinity
atom in one ofmole
an of
Lattice
providefrom a free
energies
measuregaseous
are of theions
always under of
negative
strength standard
because
ionic conditions.
bondsthey in arise For
as
different sodium
billions
ionic chloride,
upon
compounds this is
billions
element is
gaseous atoms the enthalpy change
Cl– gains one electron equation:
summarised in
the equation:
when
to form eachone atom
moleinofone mole ions
gaseous of of
and oppositely
can be charged
compared ions
with come
bond together
energies and
which form
provide ionic a bonds.
measure Lattice
of the energies
Fig a5.18 Lattice energy ischarge.
the heat (red arrows)provide
strengthaofmeasure covalent Naof the+ strength
+bonds.
(g) Cl–(g) → of ionicNa+Cl bonds
–
(s) in different ΔH ionic
= ΔHcompounds + –
gaseous
with atoms
single gains
negative one electron latt(Na Cl (s))
that would be given out to the surroundings if and can be compared with bond energies which provide a measure of the
to form
one oneofmole
mole a of gaseous
crystalline ionic ions couldAs the force of attraction between ions increases, we would expect ionic bonds
compound
The lattice energy of an ionic strengthThis of is acovalent
very exothermic
bonds. process because of the strong attraction between the
with beaformed
singledirectly
negative charge.
from free gaseous ions to get stronger and become
compound is the standard oppositely charged Na+ more
and Clexothermic.
–
ions. A diagram So, latticeshowingenergieswhat become
happens moreduring
The latticechange
enthalpy energy when of an one mole
ionic negative
As the
theforceas: of energy
lattice attraction between
process is shownions increases,
in Figure 5.18. we would expect ionic bonds
of the
compound compound
DEFINITIONS is formed from
is the standard to get stronger and become more exothermic. So, lattice energies become more
• charges on the
The lattice ions increase,
energies of some ionic solids are listed in Table 5.3.
freeThe
enthalpygaseouschange ions.when one mole negative as:
electron affinity of an • ionic radii decrease, allowing the ions to get closer.
of the compound
element is theisenthalpy
formed from change Lattice energies
• charges on the ions increase, are always negative because they arise as billions upon billions
free gaseous
when ions. Make of sure you
oppositely understand
charged the difference
ions come together between and theformlattice
ionicenergy
bonds. and Lattice energies
The each
latticeatom
energies inofone somemole
ionicof •theionic radii decrease, ofallowing the of ions to get closer.
Table 5.3
enthalpy
provide achange measure formation
of the strength anof ionicionic compound. The lattice
bonds in different energy
ionic compounds
solids gaseous
toThe
form
atoms
oneenergies
gains
mole of
one electron
involves
Make andsure1.
can 30
theyou formation
be General
compared
understand of 1with
mole
the Born-Haber
of a compound
bond
difference energies between from
which cycle
the itslattice
free gaseous
provide a measure
energy ions,
and of the
Table 5.3 lattice of gaseous
some ionic ions
whereas the enthalpy
Compound Lattice energy / kJ mol ofchange of formation involves the formation of 1energy
mole of
–1
with a single negative charge. the strength
enthalpy of covalent
change bonds.
formation of an ionic compound. The lattice
solids the compound from its elements
NaF –918 involves the formation of 1 molein oftheir normalgaseous
anon-metal
compound states.
from its atomfree gaseous ions,
The lattice energy of an ionic As the force of attraction between ions increases, we would expect ionic bonds
Compound
NaCl Lattice energy
–776 / kJ mol –1
whereas
Although the
the enthalpy
concept change
ofbecome of formation
lattice energies involves
is helpful inSo, the formation
studying of 1 mole of
the strength
compound is the–918 standard to get stronger and more exothermic. lattice energies become more
NaF
NaBr –742 the compound
of ionic bonds, from
it is its elements
impossible to in their
measure ∆H normal
lattice states.
energies directly.
∆H However,
enthalpy change when one mole negative as: at of non-metal E.A. of non-metal
NaCl during thethe early part
metalofofthe 20thenergies
gaseous century,
ion isscientists developed
studyingmethods of
NaI
of the compound–776 –705
is formed from Although • charges
concept
on the ions
lattice
increase,
helpful in the strength
NaBr
MgCl2 free gaseous ions. –742
–2526
measuring
of ionic bonds, atomisation energies,
it is impossible toionisation
measure lattice energies, electron
energies affinities
non-metal
directly. and
gaseous
However, ion
•
enthalpy ionic radii
changes decrease,
of formation. allowing
And the
this∆H ions
enabled
during the early part of the 20th century, scientists developed methods ofI.E.of to
metalget closer.
scientists to prepare energy
NaI
MgO –705
–3791
measuring metal gaseous
atomisation energies,atom ionisation energies, electron affinities and
MgCl2 –2526 Make sure you understand the difference between the lattice energy and
108 Table 5.3 The lattice energies of some ionic enthalpy changes change of formation. And this enabled scientists to prepare energy
MgO solids –3791
the enthalpy of formation of an ionic compound. The lattice energy
involves the formation of 1 mole of ∆H aatcompound
of metal from Lattice Enthalpy
its free gaseous ions,
108 Compound Lattice energy / kJ mol–1 whereas the enthalpy change
metal + non-metal of formation involves the formation of 1 mole of
NaF –918 the compound from its elements in their normal states.
∆Hf
NaCl –776 Although the concept of lattice energies is helpful in studying the strength
ionic compound
NaBr –742 of ionic bonds, it is impossible to measure lattice energies directly. However,
NaI –705 during the early part of the 20th century, scientists developed methods of
MgCl2 –2526
measuring atomisation energies, ionisation energies, electron affinities and
enthalpy changes of formation. And this enabled scientists to prepare energy
MgO –3791
108

Bilal Hameed
a Why does the lattice energy become less exothermic along the series
NaF, NaCl, NaBr, NaI?
b Why do you think the lattice energy of MgO is about four times more
exothermic than that of NaF?
21
5.13
11
Born–Haber cycles
1. 31 Figure
Born–Haber cycle for NaCl
5.19 shows the Born–Haber cycle for sodium chloride. In this section you will learn to:
• Recognise a Born–Haber cycle
Na+(g) + e– + Cl(g) • Clarify thermochemical
alt
reactions as being more or less
ΔHat(Cl(g)) = +122 kJ mol–1 exothermic and use arrows
Na+(g) + e– + 1/2Cl2(g) appropriately in the cycle
Ea(Cl(g)) = –349 kJ mol–1
• Apply Hess’ law to calculate the
lattice energy of a salt
Na+(g) + Cl–(g)
ΔHi1(Na(g)) = +494 kJ mol –1
Na(g) + 1/2Cl2(g) NOTES

In comparing lattice energies
ΔHat(Na(g)) = +107 kJ mol–1 which are always negative, it
ΔHlatt(Na+Cl–(s)) = ?
Na(s) + 1/2Cl2(g) is ambiguous to use the words
‘larger’ or ‘smaller’. It is better Chapter 19: Lattice energy
to describe one lattice energy
ΔHf (Na+Cl–(s)) = –411 kJ mol–1 as ‘more exothermic’ or ‘less
exothermic’ than another.
Na+ Cl–(s)
To draw
An exothermic thein
change cycle
oneyou:
QUESTION
Fig 5.19 The Born–Haber cycle for sodium chloride direction becomes endothermic
■ start by putting down the elements in their standard state
with the opposite sign if it is
Notice that: 4 a Write equations to represent: on the left-hand side
reversed.
i the 1st ionisation energy of caesium ■ add the other enthalpy changes in the order of steps 1 to 4
• It contains all the enthalpy changes identified in Section 5.12 and in shown in Figure 19.4
Figure 5.17 that contribute to the enthalpyii change
the 3rdof
ionisation
formationenergy of aluminium
of sodium
■ complete the cycle by adding the enthalpy change of
chloride. iii the enthalpy change of formation of
1. 32 Example 2: LiF calcium oxide
formation and lattice energy.
iv the enthalpy change of formation of iron(III) Note that the arrows 109
going upwards represent an
chloride.
Calculate the lattice enthalpy of lithium fluoride increase in energy (ΔH —O is positive) and the arrows
b Calculate the lattice energy for sodium chloride, going downwards represent a decrease in energy (ΔH —O
given that: is negative).
Enthalpy of atomisation of Li +161
— kJ =mol
∆H Of [NaCl]
–1
–411 kJ mol–1
Bond energy of F +158

∆H — kJ =mol
at [Na]
O
+107–1
kJ mol–1 QUESTION
First ionisation energy of Li +520

∆H at [Cl]kJ mol
—
O
kJ mol–1
= +122–1 5 a Draw a fully labelled Born–Haber cycle for
potassium bromide, naming each step.
∆H —
i1 [Na]
O
kJ mol–1
= +496–1
Electron affinity of F – 328 kJ mol b State the name of the enthalpy changes
∆H —
O
[Cl] = –348 kJ mol–1 represented by the following equations:
enthalpy change of formation of LiF – 617
ea1
kJ mol–1
i I2(s) I(g)
ii N(g) + e– N–(g)
The Born–Haber cycle as an energy iii Sr(s) + Cl2(g) SrCl2(s)
level diagram iv Cd2+(g) + 2Cl–(g) CdCl2(s)
We can show the Born–Haber cycle as an energy level
diagram (Figure 19.4). This is the best, and clearest, type
of diagram for a Born–Haber cycle. You should therefore
choose to draw this type of diagram to show a Born– The Born–Haber cycle for
Haber cycle. magnesium chloride
The Born–Haber cycle for magnesium chloride is shown in
Li+(g) + F(g)+ e– Figure 19.5.
1. 33 LiF step 3 Li+(g) + 1–2 F2(g)+ e–
step 4 Mg2+(g) + 2Cl(g)+ 2e–
2∆H at Mg2+(g) + Cl2(g)+ 2e–
Li+(g) + F–(g)
step 2 2∆H ea1
Mg2+(g) + 2Cl–(g)
1–
Li(g) + 2 F2(g) ∆H i2
step 1 1
Li(s) + –2 F2(g)
step 5 ∆H latt Mg+(g) + Cl2(g) + e–
∆H latt
∆H f ∆H i1
Mg(g) + Cl2(g)
∆H at Mg(s) + Cl2(g)
LiF (s)
∆Hf
Figure 19.4 Born–Haber cycle for lithium fluoride. MgCl2(s)
Figure 19.5 Born–Haber cycle for magnesium chloride.
Bilal Hameed
To draw the cycle you:

QUESTION 22
■ start by putting down the elements in their standard state
4 a Write equations to represent: on the left-hand side
i the 1st ionisation energy of caesium ■
12the other enthalpy changes in the order of steps 1 to 4
add
ii the 3rd ionisation energy of aluminium shown in Figure 19.4
■ complete the cycle by adding the enthalpy change of
iii the enthalpy change of formation of
formation and lattice energy.
calcium oxide
iv the enthalpy change of formation of iron(III) Note that the arrows going upwards represent an
chloride. 1. 34 Example 3: MgClincrease
2 in energy (ΔH —
O
is positive) and the arrows
b Calculate the lattice energy for sodium chloride, going downwards represent a decrease in energy (ΔH —O
alt
given that:Calculate the lattice enthalpy of MgCl 2 chloride given the following data:
is negative).
—
∆H Of [NaCl] = –411 kJ mol–1
∆H —
at [Na] = +107 kJ mol
O –1 QUESTION
—
∆H at [Cl]
O Enthalpy of atomisation of Mg
= +122 kJ mol–1
+148 kJmol–1
5 a Draw a fully labelled Born–Haber cycle for

∆H —
i1 [Na]
O Enthalpy
= +496 kJ mol–1 of atomisation of Cl +122
potassium kJmol
bromide, –1
each step.
naming
b State the name of the enthalpy changes
FirstkJionisation
∆H ea1 [Cl] = –348
—
O
mol–1 energy of Mg +736
represented kJmol
by the following
equations:
–1
i I2(s) I(g)
Second energy of ionisation of Mg +1450 kJmol–1
ii N(g) + e– N–(g)
The Born–HaberElectron
cycle asaffinity
an energyof Cl iii Sr(s) —349
+ Cl2(g) kJmol
–1
SrCl2(s)
level diagram
Standard enthalpy of formation of MgCl2 —641 kJmol–1 2(s)
We can show the Born–Haber cycle as an energy level
iv Cd 2+(g) + 2Cl–(g) CdCl
diagram (Figure 19.4). This is the best, and clearest, type 261

of diagram for a Born–Haber cycle. You should therefore
choose to draw this type of diagram to show a Born– The Born–Haber cycle for
Haber cycle. magnesium chloride
The Born–Haber cycle for magnesium chloride is shown in
Li+(g) + F(g)+ e– Figure 19.5.
step 3 Li+(g) + 1–2 F2(g)+ e–
Mg2+(g) + 2Cl(g)+ 2e–
1. 35 MgCl
step 4
2 2∆H at Mg2+(g) + Cl2(g)+ 2e–
Li+(g) + F–(g)
step 2 2∆H ea1
Mg2+(g) + 2Cl–(g)
1–
Li(g) + 2 F2(g) ∆H i2
step 1 1
Li(s) + –2 F2(g)
step 5 ∆H latt Mg+(g) + Cl2(g) + e–
∆H latt
∆H f ∆H i1
Mg(g) + Cl2(g)
∆H at Mg(s) + Cl2(g)
LiF (s)
∆Hf
Figure 19.4 Born–Haber cycle for lithium fluoride. MgCl2(s)
Figure 19.5 Born–Haber cycle for magnesium chloride.
1. 36 Example 4: Na2O
Calculate the lattice energy of sodium oxide from the following data:
Enthalpy of atomisation of Na +107 kJmol—1
Enthalpy of atomisation of oxygen +249 kJmol—1
First ionisation energy of Na +496 kJmol—1
First Electron affinity of oxygen —141 kJmol—1
Second Electron affinity of oxygen +798 kJmol—1
Enthalpy of formation of sodium oxide —414 kJmol—1

Bilal Hameed
23
Lattice enthalpy and Born–Haber cycles
13
A Born–Haber cycle is usually set out like an enthalpy profile diagram, with
enthalpy changes one after another. All the processes in the cycle can be
measured experimentally except the lattice enthalpy. So, by using Hess’s law it
is possible to calculate the lattice enthalpy.
Figure 13.8 shows the Born–Haber cycle for sodium oxide, Na2O.
1. 37 Na2O
alt
Sum of the first and second
2Na+(g) + O2–(g)
electron affinities of O(g)
Eaff.1 + Eaff.2 = –141 + 798
Eaff.1 + Eaff.2 = +657 kJ mol–1 2Na+(g) + 2e– + O(g)
Atomisation to form 1 mol O(g) 2Na+(g) + 2e– + 12 O2(g)

∆Hat = +249 kJ mol–1
Ionisation of 2 mol Na(g)

2 × ∆Hi1 = +992 kJ mol–1 Lattice enthalpy of
2Na(g) + 12 O2(g) sodium oxide,
∆Hlattice[Na2O(s)] = ?
Atomisation to form 2 mol Na(g) 2Na(s) + 12 O2(g)
2 × ∆Hat = +214 kJ mol–1
Standard enthalpy change

of formation of Na2O(s)
∆Hf [Na2O(s)] = –414 kJ mol–1
Na2O(s)
Figure 13.8!
5 The Born–Haber cycle
The Born–Haber forforthe
cycle hypothetical
sodium oxide. compound MgCl3 suggests
that Δ fH Starting
[MgCl3with(s)] the
= +3950
elementskJsodium
mol−1and . oxygen, the measured value for the
standard enthalpy change of formation of sodium oxide has been written
a) Whatdownwards
does theonvalue of Δ H
the cycle, showing
f
[MgCl (s)] tell you about the stability of
that3it is exothermic. Above that, the terms
1. 38 MgCl Born-Haber
3
(s)?
and values for the cycles
atomisation and then ionisation of sodium are written
upwards as endothermic processes.
b) Suggest why the value of
Notice also that the amount
Δ H [MgCl (s)] is so endothermic.
f of sodium3 required is 2 mol because there are 2
If 6
theThe
cycles are
estimated
moles examined
oflattice
sodium in 1 it
enthalpywillofbe
mole seen
of MgCl
sodium that:
(s)
oxide. is −5440 kJ mol−1.
3
These terms and values for sodium are followed by those required for the
• the a) largest
Writeconversion
an equation
single to summarise
contributions
of
the
in each
half a mole of oxygen
lattice
cycle
molecules, 1 enthalpy of MgCl3.
are made by lattice
2 O2(g), to one mole of oxide
b) Why ions,
energy and is theO2−lattice
(g). Thisenthalpy
ionization
involves the
energy ofatomisation
and MgCl3 more
these exothermic
of oxygen
two are
followed bythan that
its first
alwaysvalues,
opposite
and of
which in
MgClsecond
we
(s)? electron affinities. From the experimentally determined
2 now have in the cycle, it is possible to calculate the lattice enthalpy.
sign
• Worked
the magnitude of example
the enthalpy of formation depends on the relative
Calculate the lattice enthalpy of sodium oxide, ∆H lattice [Na2O(s)] using the
values
Test of data
theinlattice
yourself energy and the ionisation energy
Figure 13.8.
Note
Notes on the method
• 4ifdefined,
Lattice enthalpies, as usually ionisation
Write energy
equations
Apply isthe
forlaw
Hess’s toothehigh
cycle to
to following be supplied
processes:
in Figure by lattice
13.8 remembering that anenergy then
exothermic
are negative. This means that the the change
enthalpy in one
changedirection
of becomes
formation an endothermic
of calciumchange
oxide with the opposite
such a compound will not form ionically
a)
descriptions ‘larger’ and ‘smaller’ can sign in the reverse direction.
be ambiguous in comparing lattice b) the lattice energy of calcium oxide
enthalpies. For this reason, it is better Answer
to describe one lattice enthalpyc) as the second ionisation energy of calcium
∆H lattice [Na2O(s)] = (− 657 − 249 − 992 − 214 − 414) kJ mol−1
being more exothermic or less d) the enthalpy change of atomisation
exothermic than another. = −2526 kJ mol−1 of calcium
e) the second electron affinity of oxygen.
176
5 Why does the lattice enthalpy of lithium fluoride indicate that the ionic
bonding in lithium fluoride is stronger than that in sodium chloride?
1. 39 Skill
(Δ lattice Check
H ° [LiF(s)] 5 kJ mol−1; Δlattice H ° [NaCl(s)] = −780 kJ mol−1)
= −1031
6 Use Table 4.3 to construct a Born–Haber cycle to determine the lattice
Useenthalpy
the following tablefluoride.
of calcium to construct a Born–Haber cycle to determine the
lattice
Tableenthalpy
4.3 of calcium fluoride.
Enthalpy of formation of calcium fluoride −1219.6 kJ mol−1

Enthalpy of atomisation of calcium + 178.2 kJ mol−1
Enthalpy of atomisation of fluorine + 79.0 kJ mol−1
1st ionisation enthalpy of calcium + 590.0 kJ mol−1
2 ionisation enthalpy of calcium
nd
+ 1145.0 kJ mol−1
Electron affinity of fluorine −328.0 kJ mol−1
y changes of hydration and solubility

The concept of a Born–Haber cycle can be extended to provide a partial
explanation of the solubility of substances in water. To understand this,
hange of hydration another enthalpy term must be introduced. This is the enthalpy change of
hydration of an ion.
on is the enthalpy
ccurs when 1 mole δ–
Bilal Hameed
on is completely
δ+
ater. It is, therefore,
δ–
hange for the δ+ δ– δ+ δ+
δ+ δ– δ+
δ–
24
14
1. 40 Skill Check 5
alt
1. 41 Lattice energy
Lattice enthalpy is the energy
that would be given out to the
surroundings
Successive (red arrows)
ionisation if one
energies for the same element measure the energy needed to
mole ofremove
a compound could
a second, third, beelectron, and so on. For example, the third ionisation
fourth
formedenergy of sodium
directly fromrelates
free to the process:
gaseousNa ions
2+ → Na (g)together
(g)coming 3+ + e−
(black arrows) and arranging
The first electron affinity of an element is the energy change when each atom in one
mole of gaseous
themselves into a crystal atoms gains one electron to form one mole of gaseous ions with a
lattice.
single negative charge.
The following two equations define the first and second electron affinities for oxygen:
O(g) + e− → O−(g) 1st EA = −141 kJ mol−1
O−(g) + e− → O2−(g) 2nd EA = +798 kJ mol−1
The gain of the first electron is exothermic, but adding a second electron to a
negatively charged ion is endothermic.
1. 42Lattice
Lattice energy
energies
The lattice
The lattice energyenergy of a compound
of a compound is defined
is defined as the
as the energy
energy changewhen
change when
one mole of an ionic compound is formed from free gaseous ions. For sodium
one mole of an ionic compound is formed from free gaseous ions.
chloride, this is summarised by the equation:

Na+(g) + Cl−(g) → Na+Cl−(s) ΔlattH 1[NaCl(s)] = −787 kJ mol−1

This is the lattice energy for the process shown diagrammatically in Figure
Lattice energies are important because they can be used as a measure
13.1.6.
of theLattice
strength of theare
energies ionic bonding
important in different
because compounds.
they can
be used as a measure of the

strength of
The strength of ionic
the ionic bonding
bonds, in different
measured compounds.
as lattice energies in kJmol−1,
arisesThe
fromstrength of ionic
the energy bonds,
given outmeasured
as billionsas upon
latticebillions kJ mol−1,and
energiesofinpositive arises
from the energy given out as billions upon billions of positive and negative Na+ Cl–
negative ions come together to form a crystal lattice.
ions come together to form a crystal lattice. Figure 13.1.6 Lattice energy is the
The overall force of attraction between the ions is stronger and this results in that would be given out to the surro
a more exothermic lattice energy if: (red arrows) if one mole of an ionic
compound could be formed directly
● the charges on the ions are large free gaseous ions coming together
● the ionic radii are small, allowing the ions to get closer to each other. arrows) and arranging themselves i
It is important to distinguish between the lattice energy of an ionic compound crystal lattice.
and its standard enthalpy change of formation. The lattice energy relates to the
formation of one mole of a compound from its free gaseous ions, whereas the
Energetics Marginalizer
standard enthalpy change of formation relates to the formation of one Bilal
moleHameed
of
Bilal Hameed
the compound from its elements in their stable states under standard conditions.
During the early part of the twentieth century, scientists found ways in which
to measure enthalpy changes of formation and atomisation, ionisation energies Key term
and electron affinities of various elements. This led two German scientists,
25
15
1. 43 Lattice energy example
alt
Gaseous ion ➞ ionic solid
Ca2+(g) + 2Cl—(g) ➞ CaCl2(s) ∆Hreaction = ∆Hlatt
Ionic solid ➞ Gaseous ion
CaCl2(s) ➞ Ca2+(g) + 2Cl—(g) ∆Hreaction = — ∆Hlatt

Lattice enthalpy is a measure of the strength of the forces between the
ions in an ionic solid. The greater the lattice enthalpy, the stronger the
forces.
Lattice energy is the energy change
(liberated) when 1 mole of solid
lattice is formed from its constituent
gaseous ions under standard
conditions (at 298K and 1 atm).
The value of ∆H is always negative

because lattice enthalpy is always
exothermic
M+(g) + X—(g) ➞ M+X—(s) ∆H = —x kJ mol–1 (Lattice energy)
The magnitude of Lattice energy depends on the force of electrostatic
attraction between the ions: This force of attraction is stronger, and the
lattice enthalpy is more exothermic, if:
• the charges on the ions are large
• the ionic radii are small, allowing the ions to get closer to each other.
Bilal Hameed
26
16
1. 46 Trends in lattice enthalpies
Lattice enthalpy
Table 4.2 Table of approximate lattice enthalpies.
Tip
alt
When referring to lattice O2− Cl− Br− I−
enthalpies, you must choose Na +
−2478 −780 −742 −705
words carefully. For example, Mg2+ −3791 −2526 −2440 −2327
when comparing the lattice Al3+ −15 900
enthalpies of aluminium oxide
Ca2+ −3401 −2258 −2176 −2074
(−15 900 kJ mol−1) and magnesium
Sr2+ −3223 −2156 −2075 −1963
oxide (−3971 kJ mol ), it is very
−1
tempting to say that the lattice

Table 4.2 illustrates two clear trends in the size of the lattice energies of
enthalpy of Al2O3(s) is ‘greaterThe above
ionic table illustrates
compounds relating two
to: clear trends in the size of the lattice
than’ that for MgO(s), but
this would be incorrect as the
energies
● of ionic
ionic compounds relating to ionic charge and ionic radius.
charge
numbers are negative. It is best ● ionic radius.
to avoid words like ‘greater than’
or ‘bigger than’, instead stating
Ionic charge
that the lattice enthalpy of Al2O3
As the charge on an ion increases, the lattice enthalpy becomes more
(s) is ‘more negative’ or ‘more
exothermic. (That is more energy is released when the lattice is formed
exothermic’ than the lattice and, hence, more energy is required to break the lattice.)
enthalpy of MgO(s).
If you compare the value of the lattice enthalpy for sodium chloride with
that of magnesium oxide, you will see that the magnesium oxide lattice is
1. 47 Ionic charge and lattice enthalpy
stronger (more energy is released when it is formed from its gaseous ions)
than that of sodium chloride. This is a result of the stronger forces that
As the exist
chargewithin the crystal, because the charge on the oxide ion (O2−) is higher
on an ion increases, the lattice enthalpy becomes
than the charge on the chloride ion (Cl−).
more exothermic. (That is more energy is released when the lattice is
Likewise, if you compare the lattice enthalpies of the series Na2O
formed(−2478
and, hence,
kJ mol−1), more energy
MgO (−3791 is required
kJ mol −1
to3 (−15
) and Al 2O break900the lattice.)
kJ mol −1
), the
lattices become progressively stronger as the charge on the cation

If you compare
increases. the value of the lattice enthalpy for sodium chloride with
that of magnesium oxide, you will see that the magnesium oxide lattice is
Ionic radii
stronger (more
If ions haveexothermic) than
the same charge, that
then of sodium
smaller chloride.
ions will form
a stronger
lattice. That is, the numerical value of the lattice enthalpy increases. If you
This is compare
a resultthe
of the stronger
values forces
of the lattice that exist
enthalpies of CaO within
(−3401the crystal,
kJ mol−1
), SrO because
(−3223 kJ mol−1
) and BaO (−3054 kJ mol−1
), you will see that the
the charge on the oxide ion (O ) is higher than the charge on the chloride
2− lattices
become progressively weaker as the size of the cation increases. This is
ion (Cl−because
). the centres of the cation and anion are not as close, so the force
of attraction between them is less. Ionic radius does not have such a
pronounced effect as that caused by a difference in the charge of the ions,
but it does make some difference.
You can see the same pattern when comparing the lattice strengths of the
group(II) chlorides or the other halides of a group(II) metal.
Taken together, these factors have their most obvious effect on the melting
1. 48 points
Ionic charge
of compounds. and the
In general,
the higher the melting point.
lattice enthalpy
more negative the lattice enthalpy,
Likewise, if you compare the lattice enthalpies of the series
Na2O (−2478 kJ mol−1),  

MgO (−3791 kJ mol−1) and  
Al2O3 (−15 900 kJ mol−1),  
61
the lattices become progressively stronger as the charge on the cation
increases.

Bilal Hameed
27
17
1. 49 Skill Check 6
alt
The lattice energy of CsF is -744 kJ mol , whereas that of BaO is -3029
-1
kJ mol . Explain this large difference in lattice energy.

-1
1. 50 Ionic radii and lattice enthalpy

If ions have the same charge, then smaller ions will form a stronger
lattice. That is, the numerical value of the lattice enthalpy increases
(becomes more exothermic).
If you compare the values of the lattice enthalpies of  

CaO (−3401 kJmol−1), SrO (−3223 kJmol−1) and BaO (−3054 kJmol−1),
you will see that the lattices become progressively weaker (less
exothermic) as the size of the cation increases. This is because the
centres of the cation and anion are not as close, so the force of attraction
between them is less.
1. 51 Skill Check 7
Rubidium iodide has a lattice energy of -617 kJ mol , while potassium
-1
bromide has a lattice energy of -671 kJ mol .
-1
Why is the lattice energy of potassium bromide more exothermic than

the lattice energy of rubidium iodide?
Bilal Hameed
28
18
1. 52 Ionic radii and lattice enthalpy
alt
Ionic radius does not have such a pronounced effect as that caused by a
difference in the charge of the ions, but it does make some difference.
Taken together, these factors have their most obvious effect on the
melting points of compounds. In general, the more negative the lattice
enthalpy, the higher the melting point.
The enthalpy of lattice dissociation
lattice formation would be exotherm
but be a negative enthalpy change.
1
1000
lattice enthalpy/kJ mol

800 Comparison of lattice enthalp
600 The value of the lattice enthalpy giv
400 bond and this depends on the char
200 The greater the value of the lattice e
0 Smaller ions and higher charge ion
NaF NaCI NaBr NaI
Figure 18.17 The bar chart shows the ● Smaller ions are more closely pa
effect of ion size on lattice enthalpy of
attracted to each other.
sodium halides as Group 7 is descended.
The negative ions get bigger and so ● Ions with a high charge are more
the distance between the centres of ● For example, the lattice enthalpy
the oppositely charged ions is greater NaF is +915 kJ mol−1.
and the attraction less, resulting in a ● The ions have the same + and −
decrease in lattice enthalpy. Cl− ion so the ions in NaF can p
1. 53 Lattice energy: trends summary lattice enthalpy is greater as the
NaF compared to NaCl.
4000
Hence, the magnitude of Lattice energy:
● The lattice enthalpy for MgO is +
lattice enthalpy/kJ mol−1

3500
3000
+3888 kJ mol−1.
•
● The lattice enthalpy for MgO is g
Increases as the charges on the ions 2500
2000 2− charge on the O2− ion compar
increase 1500 O2− ion is also smaller than the C
1000 between Mg2+ and O2− ions than
The the
enthalpy of latticefor
disso
•
500 ● Note lattice enthalpy MgO
Decreases as the sizes of the ions 0 lattice
and has formation
a very high would
meltingbe e
poin
MgCl2 MgO
increase. Figure 18.18 The larger the charge on
small
but beions.
a negative enthalpy c
1
the1000
ion, the stronger the electrostatic The balance of enthalpy values in a B
lattice enthalpy/kJ mol
force of attraction between the ions

800 mayComparison of lattice
be asked to comment on the en
di
which results in high lattice enthalpy.
600 other enthalpy
The value values
of theinlattice
the cycle.
enthaF
400 it is bond
the halogen bonddepends
and this enthalpyon value
th
200 The greater the value of the
TEST 0 YOURSELF 3
NaF NaCI NaBr NaI Smaller ions and higher char
1 The enthalpy changes below can be used to a) Explain t
Figure 18.17 The
calculate thebar chart shows
enthalpy thedissociation
of lattice ● Smaller
of ions are more clo
of lattice
effect of ion size on
rubidium chloride.lattice enthalpy of (calculate
attracted to each other.
sodium halides as Group 7 is descended. enthalpy
The negative ions get bigger and so ● Ions with a high charge ar
Step Process ∆H 1/kJ mol−1 chloride.
the distance between the centres of ● For example, the lattice en
b) The
−1.enth
1
the oppositely Rb(s) + 12 Clions
charged 2 (g) → RbCl(s) −435
is greater NaF is +915 kJ mol is −437 kJ
and the
2 attraction
Rb(s)less,
→ Rb(g) resulting in a +81 ● The ions have theofsame potass+
decrease in lattice enthalpy. − ionisation
Cl ion so the ions in NaF
1. 54 Skill Check 8
+ 3 − Rb(g) → Rb (g) + e +403
lattice enthalpy isand
4
the d
greater
1 Cl (g) → Cl(g) +121
NaF 3 The
2 2
compared to bond dis
NaCl.
5
4000 Cl(g) + → −364 e− Cl− (g)
+158 kJ mol−
Consider each of the following pairs and explain which compound you ● The lattice enthalpy for M
a) Write an
lattice enthalpy/kJ mol−1
3500
a) Name the enthalpy change represented+3888 by −1
kJ mol . represen
would expect to have the greater lattice enthalpy. 3000step 1.
● The lattice enthalpy
b) What forisMm
b) Calculate the enthalpy of lattice dissociation
2500 of
2− charge on the O 2− ion c
fluorine.
(a) KCl or KI 2000rubidium chloride.
O2− ion is also c) The first
smaller tha
2 1500
The enthalpy of lattice dissociation of potassium
chloride is +715 kJ mol−1.
1000 between Mg2+ and−348 O2−kJion
m
(b) MgO or MgS 500 the proce
● Note the lattice enthalpy f
0 and has a very high meltin
(c) BaO or MgO MgCl2 MgO
small ions.
Figure 18.18 The larger the charge on
(d) LiF or CsF the ion, the stronger the electrostatic The balance of enthalpy value
force of attraction between the ions
469839_18_AQA_Chem_363-387.indd 379 may be asked to comment on
which results in high lattice enthalpy.
(e) KCl or CaCl2 other enthalpy values in the c
it is the halogen bond enthalp
TEST YOURSELF 3
1 The enthalpy changes below can be used to a) Ex
calculate the enthalpy of lattice dissociation of of
rubidium chloride. (ca
en
Step Process ∆H 1/kJ mol−1 ch
b) Th
1 Rb(s) + 12 Cl 2(g) → RbCl(s) −435
is
2 Rb(s) → Rb(g) +81 of
3 Rb(g) → Rb+(g) + e− +403 ion
an
Energetics Marginalizer 4 Bilal Hameed
1 Cl (g) → Cl(g) +121
Bilal Hameed
2 2 3 The b
5 Cl(g) + e − → Cl− (g) −364 +158 k
a) Name the enthalpy change represented by a) Wr
step 1. re
b) Calculate the enthalpy of lattice dissociation of b) Wh
flu
29
19
1. 55 Skill Check 9
alt
Arrange the following in order of increasing magnitude of lattice
energy:
a) LiBr KI CaO 

 
b) CaO KBr KCl SrO 

 
c) BaCl2 LiF ZnS
1. 56 Skill check 10
a) Explain the term lattice energy.
b) Write a balanced equation including state symbols to represent the

lattice energy
Lattice enthalpy of magnesium
and Born–Haber chloride.
cycles
c) Describe how, and explain why, the lattice enthalpy of magnesium

Activity
fluoride differs from that of calcium chloride.
The stability of ionic compounds

d) How would you expect the magnitude of lattice energy of magnesium
Almost all the compounds of metals with non-metals are regarded
oxide
as ionic,to
andcompare with have
these compounds thatstandard
of sodium
enthalpyoxide?
changes Explain
of your reasoning.
formation which are exothermic. This means that the compounds
are at a lower energy level and therefore more stable than their
elements.
If you look at the Born–Haber cycles in Figures 13.8 and 13.9, you
will see that an ionic compound will have an exothermic standard
enthalpy of formation if its negative lattice enthalpy outweighs the
total energy needed to produce gaseous ions from the elements.
Using a Born–Haber cycle with a theoretically calculated value for
the lattice enthalpy, it is possible to estimate the standard enthalpy
change of formation for compounds which do not normally exist. For
1. 57 The stability of ionic compounds
example, consider the Born–Haber cycle for the hypothetical
compound MgCl in Figure 13.12.
Mg+(g) + e– + Cl(g)
∆Ha t [ 12 C l 2 ( g ) ] = +122 kJ mol–1 Mg+(g) + e– + 1 Cl (g)

Ea ff [ C l ] = –349 kJ mol–1
2 2
Mg+(g) + Cl–(g)
∆Hi.1 [ M g ] = +738 kJ mol–1
Mg(g) + 12 Cl2(g) Theoretical

∆Hl a tti c e [ M g C l ( s ) ] = –753 kJ mol–1
–1
∆Ha t [ M g ( g ) ] = +148 kJ mol Mg(s) + 12 Cl2(g)
∆Hf [ M g C l ( s ) ]
MgCl(s)

1 Use Figure 13.12 to calculate a value for the standard enthalpy Figure 13.12!
(a) Use theofabove
change cycle
formation to calculate a value for the ΔHf MgCl(s).
of MgCl(s). A Born–Haber cycle for the
hypothetical compound MgCl.
2 What does your answer to question 1 suggest about the stability
of MgCl(s)?
3 Using the Hess cycle in Figure 13.13, calculate the standard
enthalpy change for the reaction
2MgCl(s) → MgCl2(s) + Mg(s)
knowing that ∆H f [MgCl2(s)] = −641 kJ mol−1.
Figure 13.13"
2MgCl(s) MgCl2(s) + Mg(s) A Hess cycle for the reaction
2MgCl(s) → MgCl2(s) + Mg(s).
Bilal Hameed
2Mg(s) + Cl2(g)
180
Mg(g) + 2 Cl2(g)
∆Hl a tti c e [ M g C l ( s ) ] = –753 kJ mol–1
∆Ha t [Mg( g) ] = +148 kJ mol–1 1
Mg(s) + Cl2(g)
2
30 ∆Hf [ MgCl ( s ) ]
MgCl(s)
1 Use Figure 13.12 to20

calculate a value for the standard enthalpy Figure 13.12!
change of formation of MgCl(s). A Born–Haber cycle for the
hypothetical compound MgCl.
2 What does your answer to question 1 suggest about the stability
of MgCl(s)?
1. 58 The stability
3 Using theof ionic
Hess cycle incompounds
Figure 13.13, calculate the standard
enthalpy change for the reaction
alt
(b) What does your answer to (a) suggest about the stability of MgCl(s)?
2MgCl(s) → MgCl2(s) + Mg(s)

(c) Using the Hess cycle below, calculate the standard enthalpy change for
knowing that ∆H [MgCl (s)] = −641 kJ mol−1.
the reaction 2MgCl(s) → MgClf 2(s) +2Mg(s)
Figure 13.13"
2MgCl(s) MgCl2(s) + Mg(s) A Hess cycle for the reaction
2MgCl(s) → MgCl2(s) + Mg(s).
2Mg(s) + Cl2(g)

180
knowing that ΔHf[MgCl2(s)] = −641 kJ mol—1.

(d) What does your result for part (c) tell you about the stability of
MgCl(s)?
(e) The Born–Haber cycle for the hypothetical compound MgCl3
suggests that ΔHf [MgCl3(s)] = +3950 kJ mol−1.
(i) What does the value of ΔHf [MgCl3(s)] tell you about the stability of
MgCl3(s)?
(ii) Suggest why the value of ΔHf [MgCl3(s)] is so endothermic

(f) The estimated lattice enthalpy of MgCl3(s) is −5440 kJ mol−1.
(i) Write an equation to summarise the lattice enthalpy of MgCl3.
(ii) Why is the lattice enthalpy of MgCl3 more exothermic than that of
MgCl2(s)?

Bilal Hameed
31
21
alt
Enthalpy changes in solution
Enthalpy changes in solution QUESTION

When an ionic solid dissolves in water, the crystal lattice
1. 62 Enthalpy
breaks changes
up and the ions during
separate. It requires dissolving
a large amount
12 a Write equations to represent the enthalpy change of
solution of:
of energy to overcome the attractive forces between the i are
potassium sulfate
Why do ionic crystals dissolve in water, even though ions in the lattice
ions. How does this happen, even when the water is not
strongly attracted to eachthis
other?
in this section. ii zinc chloride.
heated? We will answer question
b The enthalpies of solution of some metal halides are
An ionic compound
Enthalpy change suchof as solution
sodium chloride does not dissolve in non- given below. What do these values tell you about the
polar solvents like hexane, but it will dissolve in a polar solvent like water. relative solubilities of these four compounds?
sodium chloride, ∆H — –1
sol = +3.9 kJ mol
O
When one mole of sodium chloride dissolves —
in excess water to produce
The enthalpy change of solution, ∆H sol, is the energy
O
–1
a very absorbed
dilute solution under
whenstandard conditions,
ionic solid there is an enthalpy
silver chloride, ∆H — sol = +65.7 kJ mol
O
Enthalpy
change of +3.8inkJ
dissolves changes
or released
mol−1water
sufficient in asolution
1 mole of an
.
to form very dilute solution. QUESTION –1
sodium bromide, ∆H — sol = –0.6 kJ mol
O
When an ionic solid dissolves in water, the crystal lattice

12 a Write equations to represent the enthalpy change of
of bromide, ∆H sol = +84.5 kJ mol–1
—
Thisbreaks
enthalpy change
up and the ionsisseparate.
described as thea standard
It requires enthalpy change
large amount silver O
solution of:
The enthalpy
of energy
solution, ΔH to changesofthe
overcome
solution, ofsodium
solution forforces
attractive magnesium
chloride. betweenchloride
the i potassium sulfate
and
ions.sodium chloride
How does are described
this happen, by the
even when the equations
water is notbelow:
heated? We will answer this question in this—section. ‘Soluble’ii and
zinc‘insoluble’
chloride. are only relative terms.
MgCl2(s) + aq MgCl2(aq) ΔH Osol = –55 kJ mol–1 b
Magnesium carbonate
The enthalpies is regarded
of solution as being
of some insoluble
metal halides are
Enthalpy change of solution becausegiven
only below.
0.6 g What
of the do these
salt values
dissolves tell
in you
everyabout
dm the
3 of
or relative solubilities of these four compounds?
water. No metallic salts are absolutely insoluble in water.
2+ sodium ∆H —
chloride,whichO
= regarded –1
+3.9 kJ molas
MgCl2(s) + aq Mg (aq) + 2Cl –(aq) Even lead carbonate, solis insoluble,
The enthalpy change of solution, ∆H — sol, is the
O
energy dissolves to achloride,
very small∆H extent: 0.000 17 g–1dissolves in
1. 63 absorbed
Enthalpy change
when 1 mole of
of ansolution
—
–1 silver O
= +65.7 kJ mol
or released ΔH —
O
= –55 kJ mol
ionicsolsolid sol
dissolves in sufficient water to form a very dilute solution. every dm3 of water. If salts—Owere completely insoluble they
sodium bromide, ∆H sol = — –0.6 kJ mol–1
NaCl(s) +changes
The enthalpy aq NaCl(aq)
of solution for ΔH sodium
—
O
= +3.9 kJ mol
chloride –1
and could not have a value for ΔH Osol.
magnesium 265
sol — –1
silver bromide, O
∆H sol = +84.5 kJ mol
chloride are described
The enthalpy bysolution
changes of the equations below:
for magnesium
chloride Enthalpy change of hydration

or
and sodium chloride are described by the equations below: The lattice energy for sodium chloride is –788 kJ mol–1.
NaCl(s) + aq Na+(aq) + Cl–(aq) ΔH —sol O
= +3.9 kJ mol–1 ‘Soluble’ and ‘insoluble’ are only relative terms.
This means that we need to supply (at least) +788 kJ mol–1
MgCl2(s) + aq MgCl2(aq) ΔH —Osol = –55 kJ mol–1
Magnesium carbonate is regarded as being insoluble
Note that: to overcome the forces of attraction between the ions. But
because
ΔH —O only[NaCl] 0.6is
g of the+3.9
only salt kJ
dissolves dm3the
in everydoes
mol–1. Where of energy
or
■ the symbol for enthalpy change of solution is ∆H sol
—
O
water. solNo metallic salts are absolutely insoluble in water.
2+ needed to separate the ions come from? The answer is that
the symbol
■ MgCl ‘aq’ represents
2(s) + aq Mg (aq) the very
+ 2Cl –(aq)
large amount of water Even lead carbonate, which is regarded as insoluble,
it comes from the strong attraction between the ions and
used dissolves to a very small extent: 0.000 17 g dissolves in
ΔH —Osol = –55 kJ mol–1 the water molecules.
■ enthalpy changes of solution can be positive (endothermic) every dm3 of water. If salts were completely insoluble they
or negative (exothermic) When an ionic solid dissolves in water, bonds are
NaCl(s) + aq NaCl(aq) ΔH —Osol = +3.9 kJ mol –1 could not have a value for ΔH —Osol. 265
■ a compound is likely to be soluble in water only if ∆H sol is
—O formed between water molecules and the ions. These
positive value; substances with large Enthalpy bonds are called change ion–dipole bonds. Water is a polar
of hydration
or negative or has a small
positive values of ∆H — O
sol are relatively insoluble. molecule. The δ– oxygen
The lattice energy for sodium chloride atoms in water
is –788molecules
kJ mol–1. are
NaCl(s) + aq Na+(aq) + Cl–(aq) ΔH —sol O
= +3.9 kJ mol–1
This means that we need to supply (at least) +788 kJ mol–1 The
attracted to the positive ions in the ionic compound.
Note that: to δ+ hydrogen
overcome theatoms
forces in water molecules
of attraction between arethe
attracted
ions. Butto the
ΔH negative
—O
[NaCl]ionsis in
onlythe ionic
+3.9 kJ compound
mol –1. Where(Figure 19.9).
does the energy
— sol
O
needed to separate the ions come from? The answer is that
■ the symbol ‘aq’ represents the very large amount of water
a used b δ+ it comes from the strong attraction between the ions and
bond between bond forming δ+H δ– H the water molecules.
■ enthalpy changes of solution can be positive (endothermic)
O
new bonds
ions weakens Hδ+ When an ionic solid dissolves in water, bonds are
or negative (exothermic) Hδ+ H O formed
Bilal Hameed
Bilal Hameed δ– δ+ δ– + formed betweenMarginalizer
water molecules and the ions. These Energetics
■ a compound is likely to O beδ+ soluble in water only if δ– —
∆H O
δ+is
– + – + δ+H O O sol
H
negative or has a small positive value; substances
δ– with
H
large bonds are called ion–dipole bonds. Water is a polar
+ – + – δ+
positive values of ∆H — sol are relatively insoluble.
O
Hδ+ H molecule. The δ– oxygen atoms in water molecules are
– + – + δ+ δ+
δ– δ–
attracted
H to Hthe positive
δ–
ions in19.9
Figure the ionic compound.
a Water molecules The
O O – O
+ – + –
δ+ δ+ δ+ hydrogen atoms in water molecules are attracted
forming ion–dipole bonds with an to the
ionic
H
32
22
1. 64 Skill Check 11
alt
Write equations to represent the enthalpy change of solution of:
i potassium sulfate  
ii zinc chloride.  
The enthalpies of solution of some metal halides are given below. What
do these values tell you about the relative solubilities of these four
compounds?
sodium chloride, ∆Hsol = +3.9kJmol–1
silver chloride, ∆Hsol = +65.7 kJ mol–1
sodium bromide, ∆Hsol = —0.6 kJmol–1
silver bromide, ∆Hsol = +84.5 kJ mol–1
1. 66 Enthalpy changes during dissolving

When an ionic solid dissolves in water, the crystal lattice breaks up and
the ions separate. It requires a large amount of energy to overcome the
attractive forces between the ions.
The lattice energy for sodium chloride is –788 kJ mol–1. This means that
we need to supply (at least) +788 kJ mol–1 to overcome the forces of
attraction between the ions. But the ∆Hsol [NaCl] is only +3.9kJmol–1.
Where does this energy come from?

Bilal Hameed
12 a Write equations Thechange
— to represent the enthalpy of energy for sodium chloride is –788 kJ mol–1.
lattice
NaCl(s)
breaks up and the ions separate. It requires a large +amount
aq Na+(aq) + Clsolution
–(aq) ΔH O = +3.9 kJ mol–1
of: sol This means that we need to supply (at least) +788 kJ mol–1
of energy to overcome the attractive forces between the i potassium sulfate
ions. How does this happen, even whenNote that:is not
the water to overcome the forces of attraction between the ions. But
ii zinc chloride. ΔH —Osol [NaCl] is only +3.9 kJ mol–1. Where does the energy
heated? We will answer this question in■thisthe
section.
symbol for enthalpy change of solution is ∆H —
O
b The33enthalpies of solution
sol of some metalneeded
halides are
to separate the ions come from? The answer is that
Enthalpy change of solution■ the symbol ‘aq’ represents thegiven very large
below.amount
What doof water
these values tell you about the
used 23 relative solubilities of these four compounds?
the water molecules.
■ enthalpy changes of solution can be positive
sodium chloride,(endothermic)
∆H — –1
sol = +3.9 kJ mol
O
The enthalpy change of solution, ∆H — O

, is or
thenegative
energy (exothermic) When an ionic solid dissolves in water, bonds are
sol silver chloride, ∆H — sol =—
O
+65.7 kJ mol–1formed between water molecules and the ions. These
absorbed or released when 1 mole of an■ionic solid
a compound is likely to be soluble in water only if ∆H sol is O
dissolves in sufficient water to form a very dilute solution.

negative or has a small positivesodium
value;bromide,
substances∆H — O
= –0.6
with
sol kJ mol–1 bonds are called ion–dipole bonds. Water is a polar
large
1. 67 Enthalpy changes during
positive values —
dissolving
of ∆H sol are
O
relatively insoluble.∆H —O = +84.5 kJ mol–1molecule. The δ– oxygen atoms in water molecules are
silver bromide, sol
The enthalpy changes of solution for magnesium chloride attracted to the positive ions in the ionic compound. The
alt
When an ionic solid dissolves
and sodium chloride are described by the equations below: in water, bonds are formed between water δ+ hydrogen atoms in water molecules are attracted to the
‘Soluble’ and ‘insoluble’ are only relative terms. negative ions in the ionic compound (Figure 19.9).
MgCl2(s) + aq
moleculesMgCl
and the ions. These bonds are called ion–dipole bonds. Water
ΔH —Osol = –55 kJ mol–1
2(aq) Magnesium carbonate is regarded as being insoluble
is a polar molecule.
because only 0.6 g of the salt dissolves in every dm3 of
or a b δ+
water. No metallic salts are
δ+H δ– absolutely
H insoluble in water.
2+ bond between bond forming
MgCl2(s) + aq Mg (aq) + 2Cl–(aq) Even lead carbonate, which O is regarded as insoluble,
ions weakens H new bonds
δ+ H O δ+
dissolves
δ– H to a very small extent: 0.000 17 gformed
δ+ δ– dissolves in
ΔH —Osol = –55 kJ mol–1 +
δ– completely
– + – + every
O dm3 of water.
δ+
δ+H O
If salts were
O —
δ+ insoluble they
H H
NaCl(s) + aq NaCl(aq) + ––1
ΔH —Osol = ++3.9– kJ mol could not have a valueδ–for ΔHδ+Osol. 265
Hδ+ H
δ+ δ+
or
– + – +
Enthalpy
O
δ– change of hydrationδ– H H
δ– Figure 19.9 a Water molecules
+ – + – O –1 – O
The
δ+ latticeδ+ energy for sodium chloride is –788 kJ H mol . H forming ion–dipole bonds with an ionic
NaCl(s) + aq Na+(aq) + Cl–(aq) ΔH sol = +3.9 kJ mol–1 H H
—
O
δ+kJ mol–1 δ+
lattice of ions This means that we need to supply (at least) +788 compound. b Hydrated ions in solution.
Note that: to overcome the forces of attraction between the ions. But
—
ΔH —Osol [NaCl] is only +3.9 kJ mol–1. Where does the energy
O
needed to separate the ions come from? The answer is that
■ the symbol ‘aq’ represents the very large amount of water
used
the water molecules.
■ enthalpy changes of solution can be positive (endothermic)
or negative (exothermic) When an ionic solid dissolves in water, bonds are
—
■ a compound is likely to be soluble in water only if ∆H sol is
O formed between water molecules and the ions. These
negative or has a small positive value; substances with large bonds are called ion–dipole bonds. Water is a polar
positive values of ∆H —
sol are relatively insoluble.
O molecule. The δ– oxygen atoms in water molecules are
The δ– oxygen atoms in water molecules attracted are attracted to theions
to the positive positive
in the ionic compound. The
δ+ hydrogen atoms in water molecules are attracted to the
ions in the ionic compound. The δ+ hydrogen atoms in water molecules
negative ions in the ionic compound (Figure 19.9).
are attracted to the negative ions in the ionic compound.
Enthalpy changes during dissolving

Enthalpy changes during dissolving
a b δ+ Figure 13.16!
bond between bond forming δ+H δ– H δ– Figure 13.16!
δ–
O Sodium and chloride ions are hydrated
ions weakens Hδ+ new δ+
bonds Sodium and chloride ions are hydrated when sodium chloride dissolves in water.
δ+ δ+ H O formed δ–
when sodium chloride dissolves in water. Polar water molecules are attracted to
δ– H δ+ δ– + δ– δ+ δ– δ+ δ+
Polar water molecules
δ+ are attracted to both cations and anions.
δ– Oδ– δ+ δ+ δ+ δ–
O δ+ δ+
– +δ+ – +
δ– H δ+ δ+H O δ– δ+ H δ–
δ–
both cations and anions.
δ– Na+ Cl– δ+
+ – + δ–– δ+ δ+
Na + Hδ+ H Cl– δ–
δ+ δ–
δ+ δ+
– + – + δ+ H
δ– δ– δ– H Figure 19.9 δ+ δ–
a Water molecules
O δ+ δ– δ– δ+
O
δ– δ–
+ – + – δ– δ+ O δ– –
δ+
δ+ δ+ H forming ion–dipole bonds with an ionic
δ+ H H δ– H
δ+ δ+ δ+
lattice of ions b Hydrated ions in solution.
compound. δ–
δ+
δ–
Test yourself
Test yourself
18 Look at the data sheet on the Dynamic Learning Student website headed
Data
‘Enthalpy changes of hydration’.
Data
18 Look at the data sheet on the Dynamic Learning Studenta)website
How isheaded
the enthalpy change of hydration affected by increasing ionic charge?
‘Enthalpy changes of hydration’. b) List an appropriate series of ions and their enthalpy changes of hydration to
illustrateionic
a) How is the enthalpy change of hydration affected by increasing conclusion in part a).
your charge?
19 changes
b) List an appropriate series of ions and their enthalpy Look at Table 13.2 showing
of hydration to the radii of some ions, and the data sheet headed
illustrate your conclusion in part a). ‘Enthalpy changes of hydration’.

19 Look at Table 13.2 showing the radii of some ions, and the
‘Enthalpy changes of hydration’.
a) data
How sheet
is the enthalpy
headed change of hydration affected by increasing ionic radius?
b) List an appropriate series of ions, their radii and their enthalpy changes of
hydration to illustrate your conclusion in part a).
a) How is the enthalpy change of hydration affected by increasing ionic radius?
b) List an appropriate series of ions, their radii and their enthalpy changes of
The energy
hydration released
to illustrate in forming
your conclusion in part a). ion–dipole bonds is sufficient to
The effect of ionic charge on enthalpy change of hydration
compensate for the energy thatand must beenthalpy
lattice put in to separate the anions
The effect of ionic charge on enthalpy change Enthalpy ofchanges of hydration and lattice enthalpies both involve
hydration
and cations
and lattice enthalpy
that are bonded together
electrostaticin the crystal
attractions lattice.
between opposite
Because of these
charges.
attractions, both processes are exothermic.
Enthalpy changes of hydration and lattice enthalpies both involve both processes become more exothermic as the charges on the
Furthermore,
The energy
electrostatic released
attractions when
between opposite gaseous
charges. Because ions
of these
ions increase dissolve
because the charge indensity
water of anis
ioncalled
increases the
and therefore its
attractions, both processes are exothermic. attraction for any opposite charge increases.
enthalpyboth
Furthermore, change of hydration.
processes become
Thisasisthe
more exothermic chargesvery
illustrated on the
well by the enthalpy changes of hydration for Na+
ions increase because the charge density of an ion increases
and Mg2+and andtherefore
the latticeitsenthalpies of NaF and MgO in Table 13.3.
attraction for any opposite charge increases.
This is illustrated very well by the enthalpy changes of hydration for Na+
Enthalpy change of hydration /kJ mol−1 Lattice enthalpy /kJ mol−1
Table 13.3!
and Mg2+ and the lattice enthalpies of NaF and MgO in Table 13.3. Comparing enthalpy changes of
Na+ −444 NaF −918 hydration and lattice enthalpies.
Mg2+ −2003 Table 13.3! MgO −3791

Enthalpy change of hydration /kJ mol−1 Lattice enthalpy /kJ mol−1
Comparing enthalpy changes of
Li+ −559 LiF −1031
Na+ −444 NaF −918 hydration and lattice enthalpies.
K+ −361 KF −817
Mg2+ −2003 MgO −3791
Li+ −559 LiF −1031
The effect of ionic radius on enthalpy change of hydration and
K+ −361 KF −817
lattice enthalpy
As the radius of an ion increases, its charge density decreases. This results in a
weaker attraction for oppositely charged ions and for the δ+ or δ− charges on
The effect of ionic radius on enthalpy change of hydration
polar molecules such as and
water. So, an increase in ionic radius leads to less
lattice enthalpy exothermic values for enthalpy changes of hydration and lattice enthalpies.
This point This
As the radius of an ion increases, its charge density decreases. is neatly in a by the enthalpy changes of hydration for Li+
illustrated
results
weaker attraction for oppositely charged ions and forand
theKδ+and
+
or the
δ− lattice
chargesenthalpies
on of LiF and KF in Table 13.3.
polar molecules such as water. So, an increase in ionic radius leads to less
exothermic values for enthalpy changes of hydration and lattice enthalpies. 183
This point is neatly illustrated by the enthalpy changes of hydration for Li+
Bilal
andHameed
K+ and the lattice enthalpies of LiF and KF in Table 13.3.
183
The energy released in forming ion–dipole bonds is Calculating enthalpy changes in
sufficient to compensate for the energy that must be put We can calculate the enthalpy change of solu
in to separate the 34
anions and cations that are bonded enthalpy change of hydration by constructin
together in the crystal lattice. cycle and using Hess’s law (Figure 19.10).
The energy released when24 gaseous ions dissolve in
water is called the enthalpy change of hydration. lattice energy
gaseous ions ionic
∆H latt
The enthalpy change of hydration, ∆H — enthalpy change of enth

hyd, is the enthalpy
O
1. 70 Enthalpy change
change when of hydration
1 mole of a specified gaseous ion dissolves hydration of cation
and anion, ∆H hyd
of so
∆H s
in sufficient water to form a very dilute solution.
alt
The enthalpy change of hydration is the enthalpy change when one ions in aqueous
solution
Chemical energetics mole of gaseous ions dissolve
The enthalpy changes ofinhydration
water toforgive an infinitely
calcium ions and dilute solution.
the symbolchloride
for enthalpy
ions arechange ofby
described hydration is ∆H
the equations hyd
below: Figure 19.10 An enthalpy cycle involving lattice

enthalpy change of hydration and enthalpy chan
5.15
Ca2+(g) + aq Ca2+(aq) ΔH —Ohyd = –1650 kJ mol–1
Enthalpy changes when ionic We can see from this enthalpy cycle that:
Cl–(g) + aq Cl–(aq)
substances dissolve ΔH hyd = –364 kJ mol–1 —
O
ΔH —Olatt + ΔH —Osol = ΔH —Ohyd

Note that:
Enthalpy change of hydration is always exothermic.
or absorbed.Note
Whythat the ΔH hyd values for both anions a
—
O
—
In this section you will learn to: When ionic the symbol
■ solids for in
dissolve enthalpy
water,change
heat isofusually
hydration is ∆H Ohyd
evolved
• Define and describe the is this? In ■
order
theto answerchange
enthalpy the question, we isneed
of hydration to exothermic
always consider the enthalpy added together to get the total value of ΔH —Ohy
‘standard enthalpy change of changes which
■ the take place
value of ∆Hwhen
—
O ionic compounds dissolve.
hyd is more exothermic for ions with the
We can use this energy cycle to calculate:
—
solution (ΔH soln)’ same charge but smaller ionic
When one mole of sodium chloride dissolves in water radii, e.g. ∆H O
is more
hydto produce a solution
—
■ the value of ∆H sol
O
• Define and describe the containing

266 exothermic
1 mol for Li+standard
dm–3 under than for Na +
conditions, the enthalpy of the system —
■ the value of ∆H hyd.
O
‘standard enthalpy change of increases by■ 4the
kJ.value
This of ∆H —O
enthalpyhyd is change
more exothermic
is called for
theions with
standard enthalpy
hydration (ΔH hyd)’ the sameofradii
change of solution but a larger
sodium charge,
chloride, ΔH soln ∆H —
e.g.(NaCl(s)).
hyd is more
O
The process can be
• Calculate hydration energies summarised as: exothermic for Mg2+ than for Li+.
WORKED EXAMPLES
with use of a Born–Haber cycle Na+Cl–(s) + aq → Na+(aq) + Cl–(aq) ΔH soln = + 4 kJ mol–1
• Describe the effect of ionic
charge and size of ionic radius
1. 71 Enthalpy changes during dissolving NaCl
QUESTIONS
In the equation ‘aq’ means ‘addition of water’.
1 Determine the enthalpy change of solution
fluoride using the following data:
on lattice energies and ΔHhyd Sodium chloride13 and
a Whymanyis the enthalpy
other changedissolve
substances of hydration
easilyalways
in water even though■ lattice energy = –902 kJ mol–1
When sodiumare
the processes chloride dissolves
endothermic.
exothermic? This isinfurther
water,evidence
the overall
that ΔHprocess cannot
values are be
■ enthalpy change of hydration of sodiu
pictured in two stages:
a reliable guide to the likelihood of a process

b Write equations to represent: or reaction taking place. In these
ions = –406 kJ mol–1
cases, the increase in disorder (entropy) of the system drives the process forward
DEFINITIONS i the hydration of a sodium ion
Stage 1: Na+spaced
as regularly and Clions ions
— in themust
crystalbe separated
lattice from
dissolve to formthe solid
freely NaClions in enthalpy change of–1hydration of fluori
moving ■
The standard enthalpy change solution. ii the hydration of a chloride ion. ions = –506 kJ mol
of solution is the enthalpy crystals to form well-spaced
c Draw
ions
diagrams
in the gaseous state, Na+(g) and Cl—(g).
to show:
change when one mole of a In order to understand the enthalpy change when ionic solids like sodium Step 1: draw the enthalpy cycle (Figure 1
This is the reverse of
chloride dissolve, the
the lattice
i overall
4 water energy
molecules
process
and labelled
canhydrating
−ΔHstages
a magnesium
be divided latt=+787kJmol−1
into two ion as shown in

compound dissolves in water to
Figure 5.22. In fact, the stages overlap with one another because some ions will
ii +2 water molecules hydrating a bromide ion. ∆Hlatt = –902 kJ mol–1
produce a solution containing Stage 2: Gaseous Na (g)stage
and while
Cl—(g)others
ions are
areonly
hydrated by water Na+(g) + F –(g)
1 mol dm–3 under standard be completing the second
Show the dipole on each water molecule.starting the first.
+
conditions. molecules formingions
• In the first stage,
a dilute
in the
solution
solid
of sodium chloride, Na+(aq) + Cl—(aq).
O Na+Cl–(s), are separated into free,
∆Hhyd [Na ] = –406 kJ mol–1
d Explain why the ionic
value lattice,
of ∆H —hyd for magnesium
+aq
The standard enthalpy change Thiswell-spaced
is the sumgaseous
of the
ionsstandard
ions, Na+(g)
is much enthalpy
more Cl–(g).changes
andexothermicThis is the
than of hydration
reverse
∆H —
hyd for
O of Na+(g) ∆Hhyd [F –] = –506 kJ mol–1
of the lattice
of hydration (hydration energy
and Cl (g).
— process. potassium ions.
Na+(aq) + F –(aq)
energy) is the enthalpy change 14NaName
Cl (s) → Na (g) + Cl–(g)
+ – the changes+associated with the equations
–ΔHlatt = + 776 kJ mol–1
when one mole of gaseous ions below: + –
dissolves in water to form a solution • In the second stage, the gaseous Na (g) and Cl (g) ions are hydrated by polar Figure 19.11 An enthalpy cycle to determine
water moleculesa to
KBr(s) KBr(aq)
form+ aaqsolution (for 1 chloride,
of sodium mole of KBr)
Na+(aq) + Cl–(aq).of NaF.
containing 1 mol dm–3 of the ions
under standard conditions, e.g. for K+(g) + aq this second
Under standardb conditions, K+(aq) stage(forinvolves K+ ions)
1 mole ofthe standard enthalpy
sodium ions: change of hydration of both Na +
(g) and Cl–
(g), ΔH hyd(Na +
) + ΔH hyd(Cl–). Step 2: rearrange— the equation and subst
c K+(g) + Br–(g) + KBr(s) –(for 1 mole of KBr) figures to find ∆H Osol
Na+(g) + aq → Na+(aq) Na (g) + Cl (g) + (aq) → Na (aq) + Cl (aq)
+ –
Δhyd(Na+) = –391 kJ mol–1 1. 72 Enthalpy changes during dissolving NaCl

ΔH (Na+) + ΔH
hyd
d Br–(Cl
hyd
Br–mol
(g)–)+ =aq–772 kJ (aq) –1 (for 1 mole of Br– ions) ∆H — — —
latt + ∆H sol = ∆H hyd
O O O
Na+(g) + Cl–(g) + (aq)
ΔHhyd (Na+) + ΔHhyd (Cl–) = –772 kJ mol–1

+ – –1
– ΔHlatt (Na Cl (s)) = +776 kJ mol
Na+(aq) + Cl–(aq)
ΔHsoln(Na+Cl– (s)) = +4 kJ mol–1

Na+Cl– (s) + (aq)
Fig 5.22 A Born–Haber cycle connecting the enthalpy change of solution, the enthalpy changes of
hydration and lattice energy
112

Bilal Hameed
35
25
1. 73 Enthalpy changes during dissolving NaCl
alt
The enthalpy change of solution is the difference between the energy
needed to separate the ions from the crystal lattice (the reverse of the
lattice energy) and the energy given out as the ions are hydrated (the sum
Step 1:
of the hydration enthalpies).
NaCl(s) → Na+(g) + Cl−(g) ∆H = −∆H latt
Step 2:
HO
Na+(g) ⎯⎯→
2
Na+(aq) ∆H = ∆Hhyd(Na+)
H 2O
Cl−(g) ⎯⎯→ Cl−(aq) ∆H = ∆Hhyd(Cl−)
On addition, the gaseous ions cancel, giving:
HO
NaCl(s) ⎯⎯→
2
Na+(aq) + Cl−(aq) ∆Hsoln = −∆H latt + ∆Hhyd(Na+) + ∆Hhyd(Cl−)
This can be shown as a Hess’s law cycle (Figure 3.6).
(g) + Cl (g) + −
1. 74 Enthalpy changes Na
during dissolving
• −∆Hlatt(NaCl) Σ∆H + −
The more exothermic the lattice energy, the more hyd(Na and Cl the
endothermic )
enthalpy of solution
NaCl(s) Na+(aq) + Cl−(aq)

• The more exothermic either of the hydration
∆Hsoln enthalpies, the more
exothermic the enthalpy of solution.
Figure 3.6
Tip The sign of the enthalpy of solution is determined by the difference in

magnitude between the ∆H soln =energy
lattice −∆H lattand
+ ∆H
thehyd
sum(Naof+)the
+ ∆H −
hyd(Cl )
hydration
Remember that the lattice
energies.
energy is defined in the From this equation, it can be seen that:
exothermic direction. ● the more exothermic the lattice energy, the more endothermic the enthalpy of
It is the energy change solution
when 1 mol of an ionic ● the more exothermic either of the hydration enthalpies, the more exothermic the
solid is formed from its enthalpy of solution
constituent gaseous ions
infinitely far apart. The sign of the enthalpy of solution is determined by the difference in magnitude
between the lattice energy and the sum of the hydration energies (Figure 3.7).
1. 75 Exothermic dissolving
Exothermic dissolving Endothermic dissolving
Gaseous ions Gaseous ions
−∆Hlatt Σ∆Hhyd
Σ∆Hhyd −∆Hlatt
Solid Solution
Solution Solid

Figure
If the magnitude of the 3.7 enthalpy is less than the sum of the
lattice
hydration enthalpies of the two ions, dissolving will be exothermic.
If the magnitude of the lattice enthalpy (blue arrow) is less than the sum of the
hydration enthalpies of the two ions (red arrow), dissolving will be exothermic.
If the magnitude of the lattice enthalpy is greater than the sum of the hydration
enthalpies of the two ions, dissolving will be endothermic.
A general relationship can be deduced from Figure 3.7:
∆Hsoln = −lattice energy + the sum of the hydration energies of all the ions
Bilal Hameed
66 3 Energetics II (Topic 13)
energy is defined in the From this equation, it can be seen that:
exothermic direction. ● the more exothermic the lattice energy, the more endothermic the enthalpy of
It is the energy change solution
when 1 mol of an ionic 36
● the more exothermic either of the hydration enthalpies, the more exothermic the
solid is formed from its enthalpy of solution 26
infinitely far apart. The sign of the enthalpy of solution is determined by the difference in magnitude
between the lattice energy and the sum of the hydration energies (Figure 3.7).
1. 76 Endothermic dissolving
alt
Solid Solution
Solution Solid

Figure 3.7
If the magnitude of the lattice enthalpy is greater than the sum of the
hydration enthalpies of the two ions, dissolving will be endothermic.
If the magnitude
Cambridge International
Cambridge of
A Level Chemistry
International A Level lattice enthalpy is greater than the sum of the hydration
the Chemistry
1. 77 Calculating enthalpy changes in solution
The energy released in forming ion–dipole bonds is Calculating enthalpy changes in solution
sufficient to compensate for the energy that must beCalculating enthalpy changes inofsolution
The energy released in forming ion–dipole bonds is
put
sufficient to compensate ∆H
for the
soln =
energy−lattice
that must energy
be put
in to separate the anions and cations that are bonded
+ the sum ofWethe
We can calculate
hydration
can calculate
the enthalpy
energies
the enthalpy
change
changeof
of solution
allor the
solution
the
or ions
the
We can calculate the enthalpy change
of by constructing
solution or the anenthalpy
enthalpy change
in to separate the anions
togetherand cations
in the crystalthat are bonded
lattice. enthalpy change of hydration
cycle and using Hess’sby constructing
law (Figure 19.10).an enthalpy
together in the crystalThe
lattice.
energy released when of hydration
gaseous byin
ions dissolve constructing
cycle an enthalpy
and using Hess’s cycle and using Hess’s law.
law (Figure 19.10).
66 3 Energetics II (Topic
The energy 13)
released
water iswhen
calledgaseous ions dissolve
the enthalpy change of inhydration. lattice energy
gaseous ions ionic solid
water is called the enthalpy change of hydration. lattice energy ∆H latt
gaseous ions ionic solid
The enthalpy change of hydration, ∆H — enthalpy change of∆H latt enthalpy change
hyd, is the enthalpy
O
change when 1 mole of hydration of cation

a specified gaseous ion dissolves enthalpy change of solution
The enthalpy change of hydration, ∆H —
O
, is the enthalpy andof
anion, ∆H hyd enthalpy∆Hchange
sol
in sufficient water to form
hyd a very dilute solution.
change when 1 mole of a specified gaseous ion dissolves hydration of cation of solution
ions in aqueous
and anion, ∆H hyd ∆H sol
in sufficient water to form a very dilute solution. solution
xcel_GF_Chem_059-095.indd 66 The enthalpy changes of hydration for calcium ions and ions in aqueous 20/05/15 6:02 pm
chloride ions are described by the equations below: Figure 19.10 An enthalpy cycle
solution involving lattice energy,
The enthalpy changes of hydration for calcium ions and enthalpy change of hydration and enthalpy change of
solution.
Ca2+(g) +byaqthe equations
chloride ions are described Ca2+(aq)below:ΔH —Ohyd = –1650 kJ mol–119.10 An enthalpy cycle involving lattice energy,
Figure
enthalpy We can see from this enthalpy cycle that:
Cl–(g) + aq Cl–(aq) ΔH —Ohyd = –364 kJ mol–1 change of hydration and enthalpy change of solution.
Ca2+(g) + aq Ca2+(aq) ΔH hyd = –1650 kJ mol–1
—O
ΔH —Olatt + ΔH —Osol = ΔH —Ohyd
Note that: We can see from this enthalpy cycle that:
Cl–(g) + aq ■
Cl–(aq) ΔH —Ochange
the symbol for enthalpy hyd
= –364 kJ mol–1 O
of hydration is ∆H — Note that the ΔH —Ohyd values for both anions and cations are
hyd
the enthalpy change of hydration is always exothermicΔH latt + added ΔH soltogether
= ΔH hyd
—
O —
O —
O
■ to get the total value of ΔH hyd. —
O
Note that: — We can use this energy cycle to calculate:

■ the value of ∆H hyd is more exothermic for ions with the
O
■ the symbol for enthalpy changebut

same charge of smaller
hydration ∆H —
ionicisradii,
O
e.g. ∆H —
hyd
Note that the
hyd is more
O ΔH hyd values
—
O
■ the value
Ofor both anions and cations are
of ∆H —
sol
■ the enthalpy
266 changeexothermic
of hydration
+ than for Na+
for Liis always exothermic added together to get the total
— value of ΔH —Ohyd.
— ■ the value of ∆H hyd.
O
■ the value of ∆H hyd is more exothermic for ions with We can use this energy cycle to calculate:
O
—
■ the value of ∆H hyd is more exothermic for ions with the —
O
same charge but smaller ionic radii,2+e.g. ∆H —

exothermic for Mg than
O
hyd
for
1. 78 Example
the same radii but a larger charge,
Li+is
.
e.g. ∆H O is more
more hyd —
■ the value of ∆H sol
O
+ +
exothermic for Li than for Na WORKED EXAMPLES
266 —
■ the value of ∆H hyd.
O
■ the value of ∆H —
hyd is more exothermic for ions
O
QUESTIONS —
Determine
with the enthalpy change
1 Determine ofthe
solution of sodium
enthalpy change fluoride
of solution of sodium using the
the same radii but a larger charge, e.g. ∆H hyd is more
O
exothermic for Mg2+13than for Li+. following data:
a Why is the enthalpy change of hydration always WORKED EXAMPLES

■ lattice energy = –902 kJ mol–1
exothermic?
lattice
b Write equations to represent: energy = –902 kJ mol■ –1 enthalpy
1 Determine theions
enthalpy
change of hydration of sodium
QUESTIONS kJ mol–1of solution of sodium
= –406change
i the hydration of a enthalpy
sodium ion change offluoride
hydration
using offollowing
■ the sodium
enthalpy change ofions
data: = –406
hydration kJ mol–1  
of fluoride
13 a Why is the enthalpy
ii change of hydration
the hydration always
of a chloride ion. ions==––902
■ lattice energy 506 kJ –1
mol–1
kJmol
exothermic? c Draw diagrams to show: enthalpy change of hydration of fluoride ions = –506 kJ mol–1
■ enthalpy change
Step 1: drawof hydration
the enthalpyofcycle
sodium
(Figure 19.11)
b Write equations toirepresent:
4 water molecules hydrating a magnesium ion ions = –406 kJ mol–1
ii a 2sodium
water molecules hydrating a bromide ion. ∆Hlatt = –902 kJ mol–1
i the hydration of ion ■ enthalpy changeNaof+(g) hydration
+ F –(g) of fluoride NaF(s)
Show
ii the hydration of the dipole
a chloride ion.on each water molecule. ions = –∆H
506 kJ+mol –1
hyd [Na ] = –406 kJ mol–1
d Explain why the value of ∆H —
hyd for magnesium
O +aq ∆Hsol
c Draw diagrams to show: Step 1: draw the
∆Hhydenthalpy cycle
[F –] = –506 kJ mol–1(Figure 19.11)
ions is much more exothermic than ∆H —hyd for
O
i 4 water molecules hydrating

potassium ions.a magnesium ion
–1 + F –(aq)
+(aq)
ii 2 water molecules hydrating a bromidewith
ion.the equations ∆Hlatt = –902 kJNamol
14 Name the changes associated Na+(g) + F –(g) NaF(s)
Show the dipolebelow:
on each water molecule.
∆Hhyd [Na+Figure
] = –40619.11
—
kJ mol–1An enthalpy cycle to determine ∆H sol
O
a KBr(s) + aq KBr(aq) (for 1 mole of KBr) of NaF.
d Explain why the value of ∆H —hyd for magnesium
O +aq ∆Hsol
+(g) + aq –
b Kexothermic
ions is much more K+(aq)
than ∆H —O (for 1 mole of K+ ions) ∆Hhyd [F ] = –506 kJ mol–1
hyd for Step 2: rearrange the equation and substitute the
potassium ions.c K+(g) + Br–(g) KBr(s) (for 1 mole of KBr) —
figures to find ∆HNa
O
+(aq) + F –(aq)
sol
14 Name the changes associated with the–equations ∆H — — —
O O O
d Br–(g) + aq Br (aq) (for 1 mole of Br– ions)
below:
Figure 19.11 An enthalpy cycle to determine ∆H —
O
sol
a KBr(s) + aq KBr(aq) (for 1 mole of KBr) of NaF.
b K+(g) + aq K+(aq) (for 1 mole of K+ ions)
Step 2: rearrange the equation and substitute the
c K+(g) + Br–(g) KBr(s) (for 1 mole of KBr) figures to find ∆H —
O
Energetics Marginalizer sol Bilal Hameed

Bilal Hameed
d Br–(g) + aq Br–(aq) (for 1 mole of Br– ions) ∆H — —
O —
O O
1 Determine the enthalpy change of solution of sodium
hydration always lattice energy = –902 kJ mol–1
■ 37
■ enthalpy change of hydration of sodium
ions = –406 kJ mol–1 27
on ■ enthalpy change of hydration of fluoride
ion. ions = –506 kJ mol–1
1. 79 Example
Step 1: draw the enthalpy cycle (Figure 19.11)
ng a magnesium ion
alt
ng a bromide ion. ∆Hlatt = –902 kJ mol–1
Na+(g) + F –(g) NaF(s)
r molecule. +
∆Hhyd [Na ] = –406 kJ mol–1
d for magnesium
+aq ∆Hsol
than ∆H — ∆Hhyd [F –] = –506 kJ mol–1
hyd for
O
Na+(aq) + F –(aq)
h the equations
Figure 19.11 An enthalpy cycle to determine ∆H —

O
sol
1 mole of KBr) of NaF.
1 mole of K+ ions)
Step 2: rearrange the equation and substitute the
1 mole of KBr) figures to find ∆H —
O
sol
1 mole of Br– ions) ∆H —

O —
O —
O
1. 80 Enthalpy of solution - Example

Draw a simple energy cycle & calculate the enthalpy of solution of
sodium chloride from the following data
• Lattice energy of sodium chloride = —787 kJ mol-1
• Hydration energy of Na+(g) = —406 kJ mol-1
• Hydration energy of Cl—(g) = —364 kJ mol-1
1. 81 Calculating enthalpy changes in solution
Ionic solid Aqueous ions

+ H2O
NaCl(s) Na+(aq) + Cl—(aq)
∆Hsoln NaCl
∆H
+
Na
Cl
-
L
yd
E
Hh
Na
∆ hy
d
∆H ∆HLE NaCl + ∆Hsoln NaCl
Cl
= ∆Hhyd Na+ + ∆Hhyd Cl- 

Na+(g) + Cl—(g) ∆HLE + ∆Hsoln = ∆Hhyd
Gaseous ions ∆Hsoln = —∆HLE + ∆Hhyd
Bilal Hameed
soln
Figure 3.6
Tip ∆Hsoln = −∆H latt + ∆Hhyd(Na+) + ∆Hhyd(Cl−)

energy is defined in the From this equation, it can be seen that: 38
exothermic direction. the more exothermic the lattice energy, the more
It is the energy change
●
28endothermic the enthalpy of
solution
when 1 mol of an ionic ● the more exothermic either of the hydration enthalpies, the more exothermic the
solid is formed from its enthalpy of solution
The sign of the enthalpy of solution is determined by the difference in magnitude
infinitely far apart.
1.lattice
between the 82 Calculating
energy and the sum enthalpy
of the hydrationchanges in3.7).
energies (Figure solution
alt
You can also use a Born-Haber cycle to calculate ∆Hsol and ∆Hhyd

Solid Solution
Solution Solid

Figure 3.7
∆Hsol = —∆Hlatt + ∆Hhyd
If the magnitude of the lattice enthalpy is greater than the sum of the hydration
∆Hsoln = −lattice energy + the sum of the hydration energies of all the ions
1. 83 Enthalpy of solution - Example
66 3 Energetics II (Topic 13)
Na+(g) + Cl—(g)
807435_03_Edexcel_GF_Chem_059-095.indd 66
—∆Hlattice = ∆Hhyd = ∆Hhyd [Na+] + ∆Hhyd [Cl20/05/15
—] 6:02 pm
—(—787) = (—406)+ (—364)
Na+(aq) + Cl—(aq)
∆Hsolution
NaCl(s)
Draw a diagram to calculate the enthalpy of solution of potassium
bromide using the information below. 
∆Hlattice (KBr) = −679 kJ mol-1
∆Hhyd (K+) = −322 kJ mol-1
∆Hhyd (Br-) = −335 kJ mol−1

Bilal Hameed
39
29
alt
When calcium chloride dissolves in water, the process can be represented by
the equation:
Ca2+(Cl−)2(s) + aq → Ca2+(aq) + 2Cl−(aq)
lattice enthalpy of calcium chloride = −2258 kJ mol−1
enthalpy change of hydration of Ca2+(g) = −1657 kJ mol−1
enthalpy change of hydration of Cl−(g) = −340 kJ mol−1
Draw and label the Born–Haber cycle linking the enthalpy change of solution of
calcium chloride with the enthalpy changes in the data above and use it to
calculate the enthalpy change of solution of calcium chloride.
Use the following data to determine the enthalpy change of solution of
copper(II) chloride.
Enthalpy of hydration of Cu2+(g) = —2161 kJ mol—1
Enthalpy of hydration of Cl— (g) = —338 kJ mol—1
Lattice enthalpy of copper(II) chloride = —2811 kJ mol—1
Determine the enthalpy change of hydration of the chloride ion using the
following data.
lattice energy of lithium chloride = –846 kJ mol–1  

enthalpy change of solution of lithium chloride = –37 kJ mol–1  
enthalpy change of hydration of lithium ion = –519 kJ mol–1 
Bilal Hameed
40
30
alt
Calculate the enthalpy of hydration of magnesium ions given that:
∆Hlatt[MgCl2] = –2592 kJ mol–1
∆Hsol[MgCl2] = –55kJ mol–1
∆Hhyd[Cl–] = –364 kJ mol–1
a) What is meant by the term enthalpy change of hydration, ∆Hhyd? 
b) Write an equation that represents the of the ∆Hhyd Mg2+ ion.  
c) Suggest why ∆Hhyd of the Mg2+ ion is greater than of the Ca2+ ion.  
d) Suggest why it is impossible to determine the enthalpy change of

hydration of the oxide ion, O2–.
1. 90 Solubility
If the magnitude of the energy of hydration of ions is:
• Greater than the lattice energy the compound dissolves exothermically
• much lower than the lattice energy of the ions the compound will not
dissolve
• slightly less than the lattice energy, the little extra energy required for the
breakdown of the lattice is obtained from the thermal energy of the solvent.
Hence the process is endothermic resulting in a drop in temperature
Most salts dissolve endothermically. Hence an increase of temperature favors

the equilibrium point to shift forwards resulting in an increase in the solubility.

Bilal Hameed
41
31
alt
By constructing relevant thermochemical cycles, use the following data
to calculate a value for ∆Hsol (MgCl2(s)):
Enthalpy change Value/kJ mol–1
∆Hf (MgCl2(s)) —641
∆Hf (MgCl2(aq)) —801
1. 92 Skill check 19 - Solution
MgCl2 (s) x MgCl2 (aq)
—641 —801
Mg(s) + Cl2(g)
—641 + x = —801
x = —160 kJmol—1
ENERGETICS
1. 93 SkillENERGETICS
20 A2 A2 WS 2
check 3 WS 2 For
3 For Examiner’s
1(b) Iron(III) chloride readily dissolves in water. Examiner’s Use
1(b) 10Iron(III) chloride readily dissolves in water.
Use
10
FeCl (s) Fe3+(aq) + 3Cl –(aq)
FeCl 3(s) 3 Fe3+(aq) + 3Cl –(aq)
(i) Use the following data to calculate the standard enthalpy change for this process.
(i) Use the following data to calculate the standard enthalpy change for this process.
species
species DH o / kJ mol–1
DH o / kJ f –1
mol
f
FeCl 3FeCl
(s) 3(s) –399.5–399.5
Fe3+(aq)
Fe3+(aq) –48.5 –48.5
Cl –(aq)
Cl –(aq) –167.2–167.2
Bilal Hameed
Bilal Hameed
DH o =D.........................................kJ mol–1 Marginalizer
H o = .........................................kJ mol–1 Energetics
(ii) (ii)
A solution of iron(
A solution ofIII ) chloride
iron( is usedis to
III) chloride dissolve
used unwanted
to dissolve copper copper
unwanted from printed
from printed
circuitcircuit
boards.boards.
When a copper-coated printed circuit board is immersed in FeCl 3(aq), the solution
When a copper-coated printed circuit board is immersed in FeCl 3(aq), the solution
turns pale blue.
42
32
1. 94 Skill check 20 - Solution
alt
x
FeCl3 (s) Fe3+(aq) + 3Cl— (aq)
—399.5 (— 48.5) + 3(—167.2)
Fe (s) + 1.5Cl2 (g)

(— 48.5) + 3(—167.2) = —399.5 + x
x = —150.6
(a) Use the data below to draw a Born–Haber cycle and hence
calculate the lattice energy of magnesium fluoride, MgF2.  
 
ΔHat for magnesium = +150 kJ mol−1  
ΔHat for fluorine = +79 kJ mol−1  
1st ionisation energy for magnesium = +736 kJ mol−1  
2nd ionisation energy = +1450 kJ mol−1  
electron affinity for fluorine = −328 kJ mol−1  
ΔHf for MgF2(s) = −1102 kJ mol−1
(b) Use your answer to (a) and the data below to calculate the enthalpy
of solution of MgF2.  
 
ΔHhydration of Mg2+(g) = −1920 kJ mol−1  
ΔHhydration of F−(g) = −506 kJ mol−1  
 
(c) What does your answer to (b) tell you about the solubility of
magnesium fluoride?

Bilal Hameed

01 Energetics Notes 2022

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1

Bilal Hameed Energetics

Back to contents page www.cambridgeinternational.org/alevel 35

Energetics Bilal Hameed

The standard enthalpy of formation ΔHf is the enthalpy change when

17.1 Enthalpy change

the element in its standard state under standard conditions.

The standardThe electron

positive because energy has to ∆c H = −890 kJ mol−1

Hint mole of gaseous ions each with a single positive charge.

Energetics Marginalizer Bilal Hameed

mole of electrons from a mole of singly positively charged ions.

Chapter 19: Lattice energy

_1 Cl (g) change when 1 mole of electrons is added to 1 mole of

ΔH —Oea1 + ΔH —Oea2 = (–141) + (+798) = +657 kJ mol–1

c Write equations representing:

Cl(g) + e– Cl–(g) ΔH —Oea1 = –348 kJ mol–1

S(g) + e– S–(g) ΔH —Oea1 = –200 kJ mol–1

1. 10 First Electron Affinity

O(g) + e ➞ O—(g) ΔH = –141 kJ mol–1

Most first electron affinities are exothermic. This is because energy is

1. 11 Second Electron Affinity

O—(g) + e ➞ O2— (g) ΔH = +791 kJmol–1

O(g) + 2e ➞ O2— (g) ΔH = (–141 + 791) kJmol–1

Energetics Marginalizer Bilal Hameed

(a) First ionisation energy

1. 14 Ionic Bonding & Structure

or as: Δf H 1[NaCl(s)] = −411 kJ mol−1 conditions. The symbol is pr

• Sodium starts as a giant

• Chlorine consists of Cl2 molecules. Energy is required to break the

1. 18 Standard enthalpy change of formation of NaCl

Energetics Marginalizer Bilal Hameed

chloride, this is summarised by the equation:

be used as a measure of the

13.1.3 Enthalpy changes when ions form 353

469983_13.1_Chem_Y1-2_349-366.indd 353 13/04/19 10:06 PM

step 4 atoms into gaseous atoms

● turning solid sodium So

● removing an electron from each gaseous sodium atom

The electron affinity of an 20/05/15 6:02 pm

from chlorine gas, Cl2(g)

Energetics Marginalizer Bilal Hameed

Na(g) + 1/2Cl2(g) NOTES

Bond energy of F +158

First ionisation energy of Li +520

Figure 19.4 Born–Haber cycle for lithium fluoride. MgCl2(s)

Figure 19.5 Born–Haber cycle for magnesium chloride.

To draw the cycle you:

5 a Draw a fully labelled Born–Haber cycle for

diagram (Figure 19.4). This is the best, and clearest, type 261

Figure 19.4 Born–Haber cycle for lithium fluoride. MgCl2(s)

Figure 19.5 Born–Haber cycle for magnesium chloride.

Enthalpy of atomisation of Na +107 kJmol—1

Enthalpy of atomisation of oxygen +249 kJmol—1

First ionisation energy of Na +496 kJmol—1

First Electron affinity of oxygen —141 kJmol—1

Second Electron affinity of oxygen +798 kJmol—1

Enthalpy of formation of sodium oxide —414 kJmol—1

Energetics Marginalizer Bilal Hameed

Atomisation to form 1 mol O(g) 2Na+(g) + 2e– + 12 O2(g)

Ionisation of 2 mol Na(g)

Standard enthalpy change

Enthalpy of formation of calcium fluoride −1219.6 kJ mol−1

Na2O (−2478 kJ mol−1),  

If you compare the values of the lattice enthalpies of  

a) LiBr KI CaO 

b) CaO KBr KCl SrO 