BORN-HABER

CYCLES
A guide for A level students

KNOCKHARDY PUBLISHING
2008
SPECIFICATIONS
 BORN-HABER CYCLES
INTRODUCTION

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BORN-HABER CYCLES

CONTENTS
• Lattice Enthalpy
• Definition of enthalpy changes
• Born-Haber cycle for sodium chloride
• Calculation of Lattice Enthalpy
• Born-Haber cycle for magnesium chloride
 Lattice Enthalpy Definition(s)
THERE ARE TWO DEFINITIONS OF LATTICE ENTHALPY

1. Lattice Formation Enthalpy

‘The enthalpy change when ONE MOLE of an ionic lattice
is formed from its isolated gaseous ions.’

Example Na+(g) + Cl¯(g) Na+ Cl¯(s)

2. Lattice Dissociation Enthalpy

‘The enthalpy change when ONE MOLE of an ionic lattice
dissociates into isolated gaseous ions.’

Example Na+ Cl¯(s) Na+(g) + Cl¯(g)

MAKE SURE YOU CHECK WHICH IS BEING USED

 Lattice Enthalpy Definition(s)
1. Lattice Formation Enthalpy
‘The enthalpy change when ONE MOLE of an ionic lattice
is formed from its isolated gaseous ions.’

Values highly EXOTHERMIC

strong electrostatic attraction between oppositely charged ions
a lot of energy is released as the bond is formed
relative values are governed by the charge density of the ions.

Example Na+(g) + Cl¯(g) Na+ Cl¯(s)

Na+(g) + Cl–(g)

NaCl(s)
 Lattice Enthalpy Definition(s)
2. Lattice Dissociation Enthalpy
‘The enthalpy change when ONE MOLE of an ionic lattice
dissociates into isolated gaseous ions.’

Values highly ENDOTHERMIC

strong electrostatic attraction between oppositely charged ions
a lot of energy must be put in to overcome the attraction
relative values are governed by the charge density of the ions.

Example Na+ Cl¯(s) Na+(g) + Cl¯(g)

Na+(g) + Cl–(g)

NaCl(s)
 Calculating Lattice Enthalpy
SPECIAL POINTS

you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY

it is CALCULATED USING A BORN-HABER CYCLE

 Calculating Lattice Enthalpy
SPECIAL POINTS

you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY

it is CALCULATED USING A BORN-HABER CYCLE

greater charge
densities of ions = greater attraction
= larger lattice enthalpy
 Calculating Lattice Enthalpy
SPECIAL POINTS

you CANNOT MEASURE LATTICE ENTHALPY DIRECTLY

it is CALCULATED USING A BORN-HABER CYCLE

greater charge
densities of ions = greater attraction
= larger lattice enthalpy

Effects

Melting point the higher the lattice enthalpy,

the higher the melting point of an ionic compound

Solubility solubility of ionic compounds is affected by the relative

values of Lattice and Hydration Enthalpies
 Lattice Enthalpy Values
Cl¯ Br¯ F¯ O2-
Na+ -780 -742 -918 -2478
K+ -711 -679 -817 -2232
Rb+ -685 -656 -783
Mg2+ -2256 -3791
Ca2+ -2259 Units: kJ mol-1

Smaller ions will have a greater attraction for each other because of their
higher charge density. They will have larger Lattice Enthalpies and larger
melting points because of the extra energy which must be put in to separate
the oppositely charged ions.
 Lattice Enthalpy Values
Cl¯ Br¯ F¯ O2-
Na+ -780 -742 -918 -2478
K+ -711 -679 -817 -2232
Rb+ -685 -656 -783
Mg2+ -2256 -3791
Ca2+ -2259

Smaller ions will have a greater attraction for each other because of their
higher charge density. They will have larger Lattice Enthalpies and larger
melting points because of the extra energy which must be put in to separate
the oppositely charged ions.

Na+ Cl¯ K+ Cl¯

The sodium ion has the same charge as a potassium ion but is smaller. It has a higher
charge density so will have a more effective attraction for the chloride ion. More energy
will be released when they come together.
 Born-Haber Cycle For Sodium Chloride

kJ mol-1
Enthalpy of formation of NaCl Na(s) + ½Cl2(g) ——> NaCl(s) – 411

Enthalpy of sublimation of sodium Na(s) ——> Na(g) + 108

Enthalpy of atomisation of chlorine ½Cl2(g) ——> Cl(g) + 121

Ist Ionisation Energy of sodium Na(g) ——> Na+(g) + e¯ + 500

Electron Affinity of chlorine Cl(g) + e¯ ——> Cl¯(g) – 364

Lattice Enthalpy of NaCl Na+(g) + Cl¯(g) ——> NaCl(s) ?

 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s)

Na(s) + ½Cl2(g)

This
Thisisisan
anexothermic
exothermicprocess
processso
so 1
energy is released. Sodium
energy is released. Sodium
chloride
chloridehashasaalower
lowerenthalpy
enthalpy
than
than the elements whichmade
the elements which madeit.it. NaCl(s)
VALUE
VALUE==- -411
411kJ
kJmol
-1
mol-1
 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s)

2
Enthalpy of sublimation of sodium
Na(s) ——> Na(g)

Na(g) + ½Cl2(g)

Na(s) + ½Cl2(g)

This
Thisisisan
anendothermic
endothermicprocess.
process. 1
Energy
Energy is needed to separatethe
is needed to separate the
atoms. Sublimation involves
atoms. Sublimation involves
going
goingdirectly
directlyfrom
fromsolid
solidtotogas.
gas. NaCl(s)
VALUE
VALUE==++108
108kJ
kJmol
-1
mol-1
 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s)

2
Enthalpy of sublimation of sodium
Na(s) ——> Na(g)

3 Enthalpy of atomisation of chlorine

½Cl2(g) ——> Cl(g)
Na(g) + Cl(g)

3
Na(g) + ½Cl2(g)

Na(s) + ½Cl2(g)

Breaking
Breakingcovalent
covalentbonds
bondsisisan an 1
endothermic
endothermic process. Energyisis
process. Energy
needed
neededtotoovercome
overcomethe the
attraction
attraction the atomic nucleihave
the atomic nuclei have NaCl(s)
for
forthe
theshared
sharedpair
pairofofelectrons.
electrons.
VALUE
VALUE==++121
121kJ
kJmol
-1
mol-1
 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s) Na+(g) + Cl(g)

2
Enthalpy of sublimation of sodium
Na(s) ——> Na(g) 4
3 Enthalpy of atomisation of chlorine
½Cl2(g) ——> Cl(g)
Na(g) + Cl(g)
4
Ist Ionisation Energy of sodium
3
Na(g) ——> Na+(g) + e¯
Na(g) + ½Cl2(g)

Na(s) + ½Cl2(g)

All
AllIonisation
IonisationEnergies
Energiesare are 1
endothermic.
endothermic. Energy isneeded
Energy is needed
totoovercome
overcome the attractionthe
the attraction the
protons
protons in the nucleus havefor
in the nucleus have for NaCl(s)
the
theelectron
electronbeing
beingremoved.
removed.
VALUE
VALUE==++500
500kJ
kJmol
-1
mol-1
 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s) Na+(g) + Cl(g)

2
Enthalpy of sublimation of sodium
5
Na(s) ——> Na(g) 4
3 Enthalpy of atomisation of chlorine
Na+(g) + Cl–(g)
½Cl2(g) ——> Cl(g)
Na(g) + Cl(g)
4
Ist Ionisation Energy of sodium
3
Na(g) ——> Na+(g) + e¯
Na(g) + ½Cl2(g)
5
Electron Affinity of chlorine
Cl(g) + e¯ ——> Cl¯(g) 2

Na(s) + ½Cl2(g)

Electron
Electronaffinity
affinityisisexothermic.
exothermic. 1
Energy
Energy is releasedas
is released asthe
thenucleus
nucleus
attracts an electron to the
attracts an electron to the outerouter
shell
shellofofaachlorine
chlorineatom.
atom. NaCl(s)
VALUE
VALUE==- -364
364kJ
kJmol
-1
mol-1
 Born-Haber Cycle - NaCl
1 Enthalpy of formation of NaCl
Na(s) + ½Cl2(g) ——> NaCl(s) Na+(g) + Cl(g)

2
Enthalpy of sublimation of sodium
5
Na(s) ——> Na(g) 4
3 Enthalpy of atomisation of chlorine
Na+(g) + Cl–(g)
½Cl2(g) ——> Cl(g)
Na(g) + Cl(g)
4
Ist Ionisation Energy of sodium
3
Na(g) ——> Na+(g) + e¯
Na(g) + ½Cl2(g)
5
Electron Affinity of chlorine
Cl(g) + e¯ ——> Cl¯(g) 2 6

6 Na(s) + ½Cl2(g)
Lattice Enthalpy of NaCl
Na+(g) + Cl¯(g) ——> NaCl(s) 1

Lattice
LatticeEnthalpy
Enthalpyisis exothermic.
exothermic. NaCl(s)
Oppositely
Oppositelycharged
chargedions
ionsare
are
attracted to each other.
attracted to each other.
 Born-Haber Cycle - NaCl

CALCULATING THE LATTICE ENTHALPY Na+(g) + Cl(g)

Apply Hess’s Law

6 = - 5 - 4 - 3 - 2 + 1 5
4
The minus shows you are going in the
opposite direction to the definition
Na+(g) + Cl–(g)

Na(g) + Cl(g)
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol-1 3
Na(g) + ½Cl2(g)

2 6

Na(s) + ½Cl2(g)

NaCl(s)
 Born-Haber Cycle - NaCl

CALCULATING THE LATTICE ENTHALPY Na+(g) + Cl(g)

Apply Hess’s Law

6 = - 5 - 4 - 3 - 2 + 1 5
4
The minus shows you are going in the
opposite direction to the definition
Na+(g) + Cl–(g)

Na(g) + Cl(g)
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol-1 3
Na(g) + ½Cl2(g)
OR…
Ignore the signs and just use the values; 2 6

If you go up you add, if you come down Na(s) + ½Cl2(g)

you subtract the value
1
6 = 5 - 4 - 3 - 2 - 1

= (364) - (500) - (121) - (108) - (411) NaCl(s)

= - 776 kJ mol-1
 Born-Haber Cycle - MgCl2
Enthalpy
1 of formation of MgCl2
Mg(s) + Cl2(g) ——> MgCl2(s) Mg2+(g) + 2Cl(g)

2
Enthalpy of sublimation of magnesium
Mg(s) ——> Mg(g) 5
6
3 Mg (g) + 2Cl(g)
+
Enthalpy of atomisation of chlorine
½Cl2(g) ——> Cl(g) x2
4
4
Ist Ionisation Energy of magnesium Mg2+(g) + 2Cl–(g)
Mg(g) + 2Cl(g)
Mg(g) ——> Mg+(g) + e¯

5 3
2nd Ionisation Energy of magnesium
Mg(g) + Cl2(g)
Mg+(g) ——> Mg2+(g) + e¯
6
2 7
Electron Affinity of chlorine Mg(s) + Cl2(g)
Cl(g) + e¯ ——> Cl¯(g) x2
1
7
Lattice Enthalpy of MgCl2
Mg2+(g) + 2Cl¯(g) ——> MgCl2(s) MgCl2(s)
BORN-HABER
CYCLES
THE END

KNOCKHARDY PUBLISHING