BORN-HABER CYCLES

A guide for A level students

KNOCKHARDY PUBLISHING

2008
SPECIFICATIONS

BORN-HABER CYCLES
INTRODUCTION

This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching using an interactive white board. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... www.knockhardy.org.uk/sci.htm

Navigation is achieved by... either clicking on the grey arrows at the foot of each page

or

using the left and right arrow keys on the keyboard

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 Na+ K+ -780 -711 Br -742 -679 F -918 -817 O2-2478 -2232 -3791 Units: kJ mol-1

Rb+
Mg2+ Ca2+

-685
-2256 -2259

-656

-783

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 Na+ K+ -780 -711 Br -742 -679 F -918 -817 O2-2478 -2232 -3791

Rb+
Mg2+ Ca2+

-685
-2256 -2259

-656

-783

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 Enthalpy of sublimation of sodium Enthalpy of atomisation of chlorine Ist Ionisation Energy of sodium Electron Affinity of chlorine Na(s) + Cl2(g) > NaCl(s) Na(s) > Na(g) 411 + 108 + 121 + 500 364

Cl2(g) > Cl(g) Na(g) > Na+(g) + e Cl(g) + e > Cl(g)

Lattice Enthalpy of NaCl

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

Born-Haber Cycle - NaCl

1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >

NaCl(s)

Na(s) + Cl2(g)

This is an exothermic process so energy is released. Sodium chloride has a lower enthalpy than the elements which made it.
VALUE = - 411 kJ 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 is an endothermic process. Energy is needed to separate the atoms. Sublimation involves going directly from solid to gas.
VALUE = + 108 kJ 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)
3

>

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 covalent bonds is an endothermic process. Energy is needed to overcome the attraction the atomic nuclei have for the shared pair of electrons.
VALUE = + 121 kJ mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl

1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >

2

NaCl(s)

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >
4

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 Ionisation Energies are endothermic. Energy is needed to overcome the attraction the protons in the nucleus have for the electron being removed.
VALUE = + 500 kJ mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl

1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >

2

NaCl(s)

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

>

Na(g)

5
4
Na+(g) + Cl(g) Na(g) + Cl(g)

Enthalpy of atomisation of chlorine

Cl2(g) >
4

Cl(g)

Ist Ionisation Energy of sodium

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

5

3
Na(g) + Cl2(g)

Electron Affinity of chlorine

Cl(g) + e

>

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

Electron affinity is exothermic. Energy is released as the nucleus attracts an electron to the outer shell of a chlorine atom.
VALUE = - 364 kJ mol-1

1
NaCl(s)

Born-Haber Cycle - NaCl

1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >

2

NaCl(s)

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

>

Na(g)

5
4
Na+(g) + Cl(g) Na(g) + Cl(g)

Enthalpy of atomisation of chlorine

Cl2(g) >
4

Cl(g)

Ist Ionisation Energy of sodium

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

5

3
Na(g) + Cl2(g)

Electron Affinity of chlorine

Cl(g) + e
6

>

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

Lattice Enthalpy of NaCl

Na+(g) + Cl(g) > NaCl(s) Lattice Enthalpy is exothermic. Oppositely charged ions are attracted to each other.

1
NaCl(s)

Born-Haber Cycle - NaCl

CALCULATING THE LATTICE ENTHALPY Apply Hesss Law 6
Na+(g) + Cl(g)

= -

2 + 1

5
4
Na+(g) + Cl(g) Na(g) + Cl(g)

The minus shows you are going in the opposite direction to the definition

= - (-364) - (+500) - (+121) - (+108) + (-411) = - 776 kJ mol-1

3
Na(g) + Cl2(g)

2
Na(s) + Cl2(g)

1
NaCl(s)

Born-Haber Cycle - NaCl

CALCULATING THE LATTICE ENTHALPY Apply Hesss Law 6
Na+(g) + Cl(g)

= -

2 + 1

5
4
Na+(g) + Cl(g) Na(g) + Cl(g)

The minus shows you are going in the opposite direction to the definition

= - (-364) - (+500) - (+121) - (+108) + (-411) = - 776 kJ mol-1

OR Ignore the signs and just use the values;

3
Na(g) + Cl2(g)

2
Na(s) + Cl2(g)

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

1
NaCl(s)

= (364) - (500) - (121) - (108) - (411) = - 776 kJ mol-1

Born-Haber Cycle - MgCl2

1

Enthalpy of formation of MgCl2 Mg(s) + Cl2(g) > MgCl2(s) Enthalpy of sublimation of magnesium Mg(s) > Mg(g) Enthalpy of atomisation of chlorine Cl2(g) > Cl(g)

Mg2+(g) + 2Cl(g)

5 6
Mg+(g) + 2Cl(g)

x2
4
Mg(g) + 2Cl(g)

Ist Ionisation Energy of magnesium Mg(g) > Mg+(g) + e 2nd Ionisation Energy of magnesium Mg+(g) > Mg2+(g) + e Electron Affinity of chlorine

Mg2+(g) + 2Cl(g)

3
Mg(g) + Cl2(g)

Cl(g) + e
7

>

Cl(g)

x2

Mg(s) + Cl2(g)

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

1
MgCl2(s)

BORN-HABER CYCLES
THE END

KNOCKHARDY PUBLISHING