AN INTRODUCTION TO

FAJAN’S RULES
A guide for A level students

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 KNOCKHARDY PUBLISHING

FAJAN’S RULES
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 if an interactive white board is available.
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

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 INTRODUCTION

Observations Not all ionic compounds have high melting points.

Some covalently bonded compounds have higher than

expected boiling points due to dipoles in their structure

Reason in many substances bonding is not 100% ionic or covalent

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 INTRODUCTION

Observations Not all ionic compounds have high melting points.

Some covalently bonded compounds have higher than

expected boiling points due to dipoles in their structure

Reason in many substances bonding is not 100% ionic or covalent

Ideal ionic
compound completely separate, spherical ions
electron densities are apart from each other

However, if the positive ion has a high charge density it can distort the
negative ion by attracting the outer shell electrons to give an area of electron
density between the two species ... a bit like a covalent bond

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 INTRODUCTION

The feasibility of having some covalent character can be predicted using Fajan’s Rules.

A compound is more likely to be covalent if the ...

CATION SMALL SIZE it is “highly polarising” and attracts electrons in the anion
HIGH CHARGE

ANION LARGE SIZE it is “highly polarisable” and will be easily distorted

HIGH CHARGE

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 INTRODUCTION

The feasibility of having some covalent character can be predicted using Fajan’s Rules.

A compound is more likely to be covalent if the ...

CATION SMALL SIZE it is “highly polarising” and attracts electrons in the anion
HIGH CHARGE

ANION LARGE SIZE it is “highly polarisable” and will be easily distorted

HIGH CHARGE

N.B. Just because a substance is less likely to be covalent according to

Fajan’s Rules doesn’t mean it will be ionic; it will remain covalent
but have some ionic character (or vice versa).

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 EXTREMES OF CHEMICAL BONDING

IONIC BONDING
• 3-DIMENSIONAL GIANT IONIC LATTICE
• ALTERNATE POSITIVE AND NEGATIVE IONS
• HIGH MELTING POINT
• SOLUBLE IN WATER
• MOLTEN STATE CONDUCTS ELECTRICITY

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 EXTREMES OF CHEMICAL BONDING

IONIC BONDING
• 3-DIMENSIONAL GIANT IONIC LATTICE
• ALTERNATE POSITIVE AND NEGATIVE IONS
• HIGH MELTING POINT
• SOLUBLE IN WATER
• MOLTEN STATE CONDUCTS ELECTRICITY

ELECTRON DENSITY IS SEPARATED AND AROUND EACH SPECIES

The ideal ionic compound has completely separate, spherical

ions and the electron densities are apart from each other.
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 EXTREMES OF CHEMICAL BONDING

COVALENT BONDING
• MOLECULAR (SIMPLE OR MACRO)
• SIMPLE MOLECULES HAVE LOW MELTING PTS - WEAK INTERMOLECULAR FORCES
• USUALLY INSOLUBLE IN WATER BUT SOME ARE HYDROLYSED
• MOLECULES DON’T CONDUCT ELECTRICITY IN THE MOLTEN STATE

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 EXTREMES OF CHEMICAL BONDING

COVALENT BONDING
• MOLECULAR (SIMPLE OR MACRO)
• SIMPLE MOLECULES HAVE LOW MELTING PTS - WEAK INTERMOLECULAR FORCES
• USUALLY INSOLUBLE IN WATER BUT SOME ARE HYDROLYSED
• MOLECULES DON’T CONDUCT ELECTRICITY IN THE MOLTEN STATE

ELECTRON DENSITY IS BETWEEN EACH SPECIES

H H H:H

The ideal covalent compound has the electron

density exactly in between the species
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 BLACK AND WHITE OR SHADES OF GREY?

POLAR COVALENT BONDS

• IN MANY MOLECULES THERE ARE POLAR COVALENT BONDS
• MOLECULES TEND TO HAVE HIGHER MELTING/BOILING POINTS FOR THEIR MASS
• DIPOLE-DIPOLE INTERACTION OR HYDROGEN BONDING ARE PRESENT

+-
H : Cl H Cl
In some covalent compounds, the electron density
isn’t exactly in the centre between the species

• HYDROGEN CHLORIDE HAS SOME ‘IONIC CHARACTER’ - CHARGE SEPARATION

• HYDROGEN CHLORIDE REACTS WITH WATER

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 BLACK AND WHITE OR SHADES OF GREY?

IONIC COMPOUNDS WHICH ‘MISBEHAVE’

• LITHIUM CHLORIDE SHOULD BEHAVE LIKE A TYPICAL GROUP I CHLORIDE
• BUT… IT IS HYDROLYSED BY WATER AND HAS A ‘LOW’ MELTING POINT

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 BLACK AND WHITE OR SHADES OF GREY?

IONIC COMPOUNDS WHICH ‘MISBEHAVE’

• LITHIUM CHLORIDE SHOULD BEHAVE LIKE A TYPICAL GROUP I CHLORIDE
• BUT… IT IS HYDROLYSED BY WATER AND HAS A ‘LOW’ MELTING POINT

THE POSITIVE ION ATTRACTS

THE OUTER SHELL
ELECTRONS OF THE
NEGATIVE ION AND
DISTORTS THE SPHERICAL
IONIC SHAPE...
THERE IS NOW SOME
ELECTRON DENSITY
BETWEEN THE SPECIES

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 BLACK AND WHITE OR SHADES OF GREY?

IONIC COMPOUNDS WHICH ‘MISBEHAVE’

• LITHIUM CHLORIDE SHOULD BEHAVE LIKE A TYPICAL GROUP I CHLORIDE
• BUT… IT IS HYDROLYSED BY WATER AND HAS A ‘LOW’ MELTING POINT

THE POSITIVE ION ATTRACTS

THE OUTER SHELL
ELECTRONS OF THE
NEGATIVE ION AND
DISTORTS THE SPHERICAL
IONIC SHAPE...
THERE IS NOW SOME
ELECTRON DENSITY
BETWEEN THE SPECIES

SMALL CATION LARGE ANION

HIGH CHARGE DENSITY ELECTRONS FAR FROM NUCLEUS
HIGHLY POLARISING
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 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

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 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

MORE COVALENT
CHARACTER

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 FAJAN’S RULES

A COMPOUND IS MORE LIKELY TO HAVE

SOME COVALENT CHARACTER IF...

• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING

• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE

MORE COVALENT

MORE COVALENT
CHARACTER

CHARACTER
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 FAJAN’S RULES

PROOF
Chlorides can be used to demonstrate changes in bond type as the positive charge
density increases due to higher charge (across Period 3) or larger size (down Group 1)

‘charge’ ionic rad. m.pt./°C solubility bonding

GREATER POSITIVE
CHARGE DENSITY
Period 3 NaCl 1+ 0.095nm 808 soluble ionic
MgCl2 2+ 0.065nm 714 soluble ionic
AlCl3 3+ 0.050nm 180 hydrolysed covalent
SiCl4 4+ 0.041nm -70 hydrolysed covalent

GREATER POSITIVE
CHARGE DENSITY

Group 1 LiCl 1+ 0.060nm soluble cov. character

NaCl 1+ 0.095nm soluble ionic
KCl 1+ 0.133nm soluble ionic
RbCl 1+ 0.148nm soluble ionic

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 AN INTRODUCTION TO
FAJAN’S RULES
THE END

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