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BORN-HABER

CYCLES

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

Example

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.
Na+(g)

Cl(g)

Na+(g) + Cl(g)

NaCl(s)

Na+ Cl(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

Example

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.
Na+ Cl(s)

Na+(g)

Na+(g) + Cl(g)

NaCl(s)

Cl(g)

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

O2-

Na+

-780

-742

-918

-2478

K+

-711

-679

-817

-2232

Rb+

-685

-656

-783

Mg2+

-2256

Ca2+

-2259

-3791
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

O2-

Na+

-780

-742

-918

-2478

K+

-711

-679

-817

-2232

Rb+

-685

-656

-783

Mg2+

-2256

Ca2+

-2259

-3791

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) + Cl2(g) > NaCl(s)

411

Enthalpy of sublimation of sodium

Na(s)

+ 108

Enthalpy of atomisation of chlorine

Cl2(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

Na+(g) + Cl(g) > NaCl(s)

Lattice Enthalpy of NaCl

> Na(g)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >

NaCl(s)

Na(s) + Cl2(g)

This
Thisisisan
anexothermic
exothermicprocess
processso
so
energy
is
released.
Sodium
energy is released. Sodium
chloride
chloridehas
hasaalower
lowerenthalpy
enthalpy
than
the
elements
which
than the elements whichmade
madeit.it.
-1
VALUE
VALUE==- -411
411kJ
kJmol
mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

NaCl(s)

Enthalpy of sublimation of sodium

Na(s)

>

Na(g)

Na(g) + Cl2(g)

2
Na(s) + Cl2(g)

This
Thisisisan
anendothermic
endothermicprocess.
process.
Energy
is
needed
to
separate
Energy is needed to separatethe
the
atoms.
Sublimation
involves
atoms. Sublimation involves
going
goingdirectly
directlyfrom
fromsolid
solidtotogas.
gas.
-1
VALUE
VALUE==++108
108kJ
kJmol
mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

Enthalpy of sublimation of sodium

Na(s)
3

NaCl(s)

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >

Cl(g)
Na(g) + Cl(g)

3
Na(g) + Cl2(g)

2
Na(s) + Cl2(g)

Breaking
Breakingcovalent
covalentbonds
bondsisisan
an
endothermic
process.
Energy
endothermic process. Energyisis
needed
neededtotoovercome
overcomethe
the
attraction
the
atomic
nuclei
attraction the atomic nucleihave
have
for
forthe
theshared
sharedpair
pairofofelectrons.
electrons.
-1
VALUE
VALUE==++121
121kJ
kJmol
mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

NaCl(s)

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >

Cl(g)
Na(g) + Cl(g)

Ist Ionisation Energy of sodium

Na(g) > Na+(g) + e


Na(g) + Cl2(g)

2
Na(s) + Cl2(g)

All
AllIonisation
IonisationEnergies
Energiesare
are
endothermic.
Energy
is
endothermic. Energy isneeded
needed
totoovercome
the
attraction
overcome the attractionthe
the
protons
in
the
nucleus
have
protons in the nucleus havefor
for
the
theelectron
electronbeing
beingremoved.
removed.
-1
VALUE
VALUE==++500
500kJ
kJmol
mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

NaCl(s)

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >

Na+(g) + Cl(g)

Cl(g)
Na(g) + Cl(g)

Ist Ionisation Energy of sodium

Na(g) > Na+(g) + e


5

Na(g) + Cl2(g)

Electron Affinity of chlorine

Cl(g) + e

>

Cl(g)
Na(s) + Cl2(g)

Electron
Electronaffinity
affinityisisexothermic.
exothermic.
Energy
is
released
Energy is releasedas
asthe
thenucleus
nucleus
attracts
an
electron
to
the
outer
attracts an electron to the outer
shell
shellofofaachlorine
chlorineatom.
atom.
-1
VALUE
VALUE==- -364
364kJ
kJmol
mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

NaCl(s)

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >

Na+(g) + Cl(g)

Cl(g)
Na(g) + Cl(g)

Ist Ionisation Energy of sodium

Na(g) > Na+(g) + e


5

Na(g) + Cl2(g)

Electron Affinity of chlorine

Cl(g) + e
6

>

Cl(g)

Lattice Enthalpy of NaCl

Na(s) + Cl2(g)

Na+(g) + Cl(g) > NaCl(s)


Lattice
LatticeEnthalpy
Enthalpyisis exothermic.
exothermic.
Oppositely
Oppositelycharged
chargedions
ionsare
are
attracted
to
each
other.
attracted to each other.

1
NaCl(s)

Born-Haber Cycle - NaCl


CALCULATING THE LATTICE ENTHALPY

Na+(g) + Cl(g)

Apply Hesss Law


6

= -

+ 1

The minus shows you are going in the


opposite direction to the definition
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol-1

Na+(g) + Cl(g)
Na(g) + Cl(g)

3
Na(g) + Cl2(g)

Na(s) + Cl2(g)

1
NaCl(s)

Born-Haber Cycle - NaCl


CALCULATING THE LATTICE ENTHALPY

Na+(g) + Cl(g)

Apply Hesss Law


6

= -

+ 1

The minus shows you are going in the


opposite direction to the definition
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol-1

Na+(g) + Cl(g)
Na(g) + Cl(g)

3
Na(g) + Cl2(g)

OR

Ignore the signs and just use the values;


If you go up you add, if you come down
you subtract the value
6

Na(s) + Cl2(g)

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


= - 776 kJ mol-1

NaCl(s)

Born-Haber Cycle - MgCl2


1

Enthalpy of formation of MgCl2


Mg(s) + Cl2(g) >

Enthalpy of sublimation of magnesium


Mg(s)

>

Enthalpy of atomisation of chlorine

Ist Ionisation Energy of magnesium

Mg2+(g) + 2Cl(g)

Mg(g) + 2Cl(g)

3
Mg(g) + Cl2(g)

Electron Affinity of chlorine


Cl(g) + e

2nd Ionisation Energy of magnesium


Mg+(g) > Mg2+(g) + e

Mg (g) + 2Cl(g)
+

x2

Cl(g)

Mg(g) > Mg+(g) + e


5

Mg(g)

Cl2(g) >
4

Mg2+(g) + 2Cl(g)

MgCl2(s)

>

Cl(g)

x2

Mg(s) + Cl2(g)

1
Lattice Enthalpy of MgCl2
Mg2+(g) + 2Cl(g) > MgCl2(s)

MgCl2(s)

BORN-HABER
CYCLES
THE END