INORGANIC CHEMISTRY I

CHM474

Electronegativity, Bond Polarity &

Dipole Moment
(Silberberg: Chapters 8 & 9)

Outline:
Trends of Electronegativity
How to determine bond polarity
How to identify dipole moment

Electronegativity is the ability of an atom to attract

toward itself the electrons in a chemical bond.
Electron Affinity - measurable, Cl is highest
X (g) + e-

X-(g)

Electronegativity - relative, F is highest

Electronegativity is defined as the ability of an atom

in a molecule to attract electrons to itself

Electronegativity is a function of two properties of
isolated atoms;
The atoms ionization energy (how strongly an atom
holds onto its own electrons)
The atoms electron affinity (how strongly the atom
attracts other electrons)
For example, an element which has:
A large (negative) electron affinity
A high ionization (always endothermic, or
positive for neutral atoms)

Prof. Linus Pauling

Nobel Prize for Chemistry 1954
Nobel Prize for Peace 1962

Will: Attract electrons from other atoms and Resist having electrons attracted
away

Such atoms will be highly electronegative

Electronegativity generally
decreases increases
down a left
group
to right
for
representative
across
a periodelements
.
.

 When two identical atoms form a covalent

bond each atom has an equal share of the
bonds electron pair
When different kinds of atoms combine, one of
the nuclei usually attracts the electrons in the
bond more strongly

(a) The electron density of the electron

pair in the bond is spread evenly
between the two H atoms in H2,
which gives a nonpolar covalent
bond.

(b) The electron density of the bond in

HCl is pulled more tightly around
the Cl end of the molecule giving a
partial separation of charge and a
polar covalent bond.

Covalent bonding with equal sharing of

electrons occurs in diatomic molecules
formed from one element.

hydrogen

chlorine

iodine

A dash may replace a pair of dots.

nitrogen

 If the two atoms that constitute a

covalent bond are identical, then there
is equal sharing of electrons.

This is called nonpolar covalent

bonding.
Ionic bonding and nonpolar covalent
bonding represent two extremes.

 If the two atoms that constitute a

covalent bond are not identical, then
there is unequal sharing of electrons.

This is called polar covalent bonding.

One atom assumes a partial positive
charge and the other atom assumes a
partial negative charge.
This charge difference is a result of the
unequal attractions the atoms have for
their shared electron pair.

Partial positivePartial
charge
negative charge
on hydrogen. on chlorine.

Polar Covalent Bonding in HCl

:
:
H Cl

Chlorine
hasthat
a greater
attraction
forelement
the
Shared
Theof
shared
electron
electron
pair. pair
The attractive
force
an atom
an
has
shared electron pair than is
hydrogen.
to chlorine than
for shared electrons in a molecule closer
or a polyatomic
ion
to hydrogen.
is known as its electronegativity.

The polarity of a bond is determined by the

difference in electronegativity values of the
atoms forming the bond.

Linus Pauling devised a method for calculating

electronegativities of elements.
Pauling's electronegativity values for representative
elements are given in the following figure.
However, the transition metals do not follow these
trends.
Nonmetals are the most electronegative elements and
metals are the least electronegative (they are
electropositive)

H
2.1
Li
1.0

Be
1.5

B
2.0

C
2.5

N
3.0

O
3.5

F
4.0

Na
0.9

Mg
1.2

Al
1.5

Si
1.8

P
2.1

S
2.5

Cl
3.0

K
0.8

Ca
1.0

Pauling's electronegativity values of the first twenty

elements.

The difference in the electronegativity values of two

bonded atoms gives an estimation of the polarity to
be expected in a bond.
Electronegativity values are useful in determining if
a bond is to be classified as nonpolar covalent,
polar covalent or ionic.
What you should do is look only at the two atoms
in a given bond. Calculate the difference between
their electronegativity values. Only the absolute
difference is important.

The three major types of intramolecular bond can be described by

the electronegativity difference:

Non-Polar Covalent Bonds which occur between atoms with

little or no electronegativity difference (less than 0.5).

Polar Covalent Bonds which occur between atoms with a

definite electronegativity difference (between 0.5 and 2.0).

Ionic Bonds which occur between atoms with a large

electronegativity difference (2.0 or greater), where electron transfer
can occur.
E.g.
F-F (4.0 4.0 = 0) is non-polar covalent
H-F (4.0 2.1 = 1.9) is polar covalent
LiF (4.0 1.0 = 3.0) is ionic

I. Nonpolar Covalent:
This type of bond occurs when there is equal sharing (between the
two atoms) of the electrons in the bond. Molecules such as Cl 2, H2
and F2 are the usual examples.
Textbooks typically use a maximum difference of 0.2 - 0.5 to
indicate nonpolar covalent. Since textbooks vary, let us use 0.5.
One interesting example molecule is CS2. This molecule has
nonpolar bonds. Since the electronegativities of C and S are both
2.5, you have a nonpolar bond.

II. Polar Covalent:

This type of bond occurs when there is unequal sharing (between the
two atoms) of the electrons in the bond. Molecules such as NH 3 and
H2O are the usual examples.
The typical rule is that bonds with an electronegativity difference less
than 1.6 are considered polar. (Some textbooks or web sites use 1.7.)
Obviously there is a wide range in bond polarity, with the differences in
the C-H bonds in CH4 being 0.4 to the difference the H-O bonds in
water being 1.4.
III. Ionic:
This type of bond occurs when there is complete transfer (between
the two atoms) of the electrons in the bond. Substances such as NaCl
and MgCl2 are the usual examples.
The rule is that when the electronegativity difference is greater than
2.0, the bond is considered ionic.

So, let's review the rules:

1.If the electronegativity difference (usually called EN) is less than 0.5, then
the bond is nonpolar covalent.
2.If the EN is between 0.5 and 1.6, the bond is considered polar covalent
3.If the EN is greater than 2.0, the the bond is ionic.
That, of course, leaves us with a problem. What about the gap between 1.6
and 2.0? So, rule #4 is:
4.If the EN is between 1.6 and 2.0 and if a metal is involved, then the bond
is considered ionic. If only nonmetals are involved, the bond is considered
polar covalent.
So, that means compounds like HF and SiO2 are considered to be polar
covalent, even though there is a large electronegativity difference.
A warning: rule #4 may not exist in your textbook. Often, the 1.6 value is
used and the 1.6-2.0 range is lumped into the ionic category. (Steven
Zumdahl in his "World of Chemistry" textbook, makes the rule be 2.0 instead
of 1.6 for polar covalent. This allows him to include HF as polar covalent.)

Classification of bonds by difference in electronegativity

Difference
0
2
0 < and <2

Bond Type
Covalent
Ionic
Polar Covalent

Increasing difference in electronegativity

Covalent

Polar Covalent

share e-

partial transfer of e-

Ionic
transfer e-

Boundary ranges for classifying ionic character

of chemical bonds.
3.0

EN
2.0

0.0

If the electronegativities are the same, the bond

is nonpolar covalent and the electrons are shared
equally.
The molecule is
nonpolar covalent.

Electronegativity
Difference = 0.0

Electronegativity
2.1

Hydrogen Molecule

11.10

Electronegativity
2.1

If the electronegativities are the same, the bond

is nonpolar covalent and the electrons are shared
equally.
The molecule is
nonpolar covalent.

Cl
Electronegativity
3.0

Cl

Electronegativity
Difference = 0.0

Electronegativity
3.0

Chlorine Molecule
11.10

If the electronegativities are not the same, the

bond is polar covalent and the electrons are
shared unequally.
The molecule is
polar covalent.

Electronegativity
2.1

Cl

Electronegativity
Difference = 0.9

Electronegativity
3.0

Hydrogen Chloride Molecule

11.10

If the electronegativities are very different, the

bond is ionic and the electrons are transferred to
the more electronegative atom.
No molecule exists.
The bond is ionic.
Electronegativity
Difference = 2.1

Na+
Electronegativity
0.9

ClElectronegativity
3.0

Sodium Chloride
11.10

A dipole is a molecule that is

electrically asymmetrical, causing it
to be oppositely charged at two
points.

A dipole can be written as

An arrow can be used to indicate a dipole.

The arrow points to the negative end of the

dipole.
Molecules of HCl, HBr and H2O are polar .

Cl

Br

A molecule containing different kinds of

atoms may or may not be polar depending
on its shape.

The carbon dioxide molecule is nonpolar

because its carbon-oxygen dipoles cancel
each other by acting in opposite directions.

 The magnitude of the polarity is expressed

in terms of the dipole moment
dipole moment q r
q amount of charge
r distance between charges

Dipole moments are frequently reported in

units of Debye (D)

1 D 3.34 10

-30

Cm
Prof. Peter Debye
Noble Prize 1936

 The dipole moments and bond lengths

for some diatomic molecules are:
Dipole

Bond

Compound Moment(D) Length(pm)

HF

1.83

91.7

HCl

1.09

127

HBr

0.82

141

HI

0.45

161

CO

0.11

113

NO

0.16

115

Relating Bond Type to

Electronegativity Difference.

11.11

 The difference in electronegativity

provides an estimate for the degree of
polarity (or sometimes referred to as the
ionic character) of the bond
There is no sharp dividing line between
ionic and covalent bonding: ionic
bonding and nonpolar covalent bonding
represent the extremes
A bond is mostly ionic when the
electronegativity difference between the
two atoms is large

 The degree of polarity, or ionic character,

varies continuously with the electronegativity
difference
Each atom in a bond has
a partial charge of about
+0.5 or 0.5 units when
the electronegativity
difference is 1.7.

In general, electronegativity increases bottom

to top in a group and left to right in a period

Which of the following molecules have a dipole moment?

H2O, CO2, SO2, and CH4

O
H

dipole moment
polar molecule

S
O

dipole moment
polar molecule

no dipole moment
nonpolar molecule

H
no dipole moment
nonpolar molecule