Electronegativity, Bond Polarity

& Dipole Moment

DR AMALINA MOHD TAJUDDIN

(Silberberg: Chapters 8 & 9)

1
 Outline

•Trends of Electronegativity

•How to determine bond polarity

•How to identify dipole moment

2
Electronegativity (EN) is the ability of an atom to
attract the bonding electrons toward itself in a chemical
bond.
Remember the definition …

Electron Affinity - measurable, Cl is highest

X (g) + e- X-(g)

It is the energy change when 1 mole of e- is

gained by 1 mole of gaseous atom

Electronegativity - relative, F is highest

3
Electronegativity is a function of two properties of isolated
atoms;
• The atom’s ionization energy (how strongly an atom holds
onto its own electrons)
• The atom’s 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)

Will: Attract electrons from other atoms and resist having

electrons attracted away
Such atoms will be highly electronegative
4
Pauling’s electronegativity scale
The higher the value, the more electronegative the
element

Atoms with high electronegativity values (EN’s) are the

best electron attractors and atoms with low
electronegativity values (EN’s) are the worst electron
attractors.

Fluorine is the most electronegative element

It has an electronegativity value of 4.0

5
Electronegativity decreases down a group for representative
elements.

Electronegativity generally increases left to right across a

period.

6
 Types of Chemical Bonds
• Ionic bond – transfer of electrons (metal with
non-metal)

• Covalent bond – sharing of electrons

• When two identical atoms form a covalent
bond each atom has an equal share of the
bond’s electron pair

• When different kinds of atoms combine, one

of the nuclei usually attracts the electrons in
the bond more strongly
7
(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

8
Covalent bonding with equal sharing of
electrons occurs in diatomic molecules formed
from one element.

hydrogen chlorine iodine nitrogen

A dash may replace a pair of dots.

9
• 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.
10
• 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.

11
 Partial positive charge Partial negative charge
on hydrogen. on chlorine.

d+ : d-
:
H Cl The attractive force that an atom of
an element has for shared electrons
in a molecule or a polyatomic ion
Chlorine has a greater is known as its electronegativity.
attraction for the
shared electron pair
than hydrogen. The shared electron pair is
closer to chlorine than to
hydrogen.
12
 BOND POLARITY
How it is determined???????

•The polarity of a bond is determined by the

difference in electronegativity values of
the atoms forming the bonds

13
• Linus Pauling devised a method for calculating electronegativities
of elements

Pauling's electronegativity values for representative elements are

given in the following figure

H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca
0.8 1.0

• However, the transition metals do not follow these trends.

Nonmetals are the most electronegative elements and metals are

the least electronegative (they are electropositive)
14
•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

15
 Electronegativity Values
Calculating the difference between their electronegativity values (the
absolute value).
• I. Pure/Non Polar Covalent:
• equal sharing (between the two atoms) of the electrons in the bond.
• Ex: Molecules such as Cl2, H2 and F2
• a maximum difference of 0.2 - 0.5 H H

• II. Polar Covalent:

• unequal sharing (between the two atoms) of the electrons in the bond.
• Ex: Molecules such as NH3 and H2O
• difference less than 1.6 d+
H Cl
d-

• III. Ionic:
• complete transfer (between the two atoms) of the electrons in the bond.
• Ex: Substances such as NaCl and MgCl2.
N C
• the electronegativity difference is greater than 2.0, a l
+ 16
Sodium Chloride
 SUMMARY
Electronegativity Difference Type of Bond
(DEN)
less than 0.5 pure covalent/non polar covalent
between 0.5 and 1.6 polar covalent
≥2.0 ionic

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

d+ d-
H F
If the DEN 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

The polarity of bond gives partial ionic character

17
 Classification of bonds by difference in electronegativity
Increasing difference in electronegativity

Covalent Polar Covalent Ionic

share e- partial transfer of e- transfer e-

18
 Determining Bond Polarity from EN Values

(a) Use a polar arrow to indicate the polarity of each bond: N-H, F-N, I-Cl.
(b) Rank the following bonds in order of increasing polarity: H-N, H-O, H-C.

PLAN: (a) Use Figure 1 to find EN values; the arrow should point
toward the negative end.
(b) Polarity increases across a period.

SOLUTION: (a) The EN of N = 3.0, H = 2.1; F = 4.0; I = 2.5, Cl = 3.0

N-H F-N I - Cl

(b) The order of increasing EN is C < N < O; all have an EN larger

than that of H.
H-C < H-N < H-O

19
• The magnitude of the polarity is expressed in terms of the
dipole moment

A dipole is a molecule that is electrically asymmetrical,

causing it to be oppositely charged at two points.

A dipole can be written as + -

Use an arrow to represent a dipole moment.
§Point to the negative charge center with the tail of the
arrow indicating the positive center of charge

20
The magnitude of the polarity is expressed in
terms of the dipole moment

µ =q´d
q = amount of charge
d = distance between charges

1 Debye (D) = 3.336´10-30 Coulomb meter

21
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

Electronegativity : C : 2.5
O : 3.5

Bond polarity : 3.5-2.5 = 1.0 (C-O bond is polar)

Dipole moment: 1.0-1.0 = 0.0 (CO molecule is NOT polar as it
symmetrical, thus no dipole moment) 22
The overall dipole moment of a molecule is the vector
sum of dipole moments of individual bonds and lone
pairs.

F Cl Net dipole moment

(the vector sum) is zero
C
B Cl
Cl ® Non-polar
F F Cl

S S
O O O O
Non-polar Polar
23
 F F
Xe
F F
Dipole moments of the two lone
Symmetrical ® Non-polar pairs point in opposite directions –
non polar

H H

C C

H H
Symmetrical ® Non-polar

24
 Non-polar molecules
Shape Molecule Cancelling out of dipole
moments
Linear

Trigonal planar

Tetrahedral

Trigonal
bipyramidal

Octahedral

25
 Polar molecules
Shape Molecule Dipole Net resultant
moment of dipole moment
individual polar
bonds

V-shaped
( or bent)

Trigonal
pyramidal

Tetrahedral

26
 Example
The C-Cl bond is polar but CCl4 molecule is non-polar. Explain.

Solution: 2.5 3.0

Ø The C-Cl bond is polar because the chlorine atom being more
electronegative pulls the shared electron pair towards itself.
Ø In CCl4, there are four C-Cl bonds.

Ø Since these polar bonds are symmetrically arranged, the polarities of

individual bonds cancel each other resulting in a zero dipole moment
for the molecule.
Ø The net result is that CCl4 molecule is non-polar.

27
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4

O S
H O
H O
dipole moment dipole moment
polar molecule polar molecule

H C H
O C O

H
no dipole moment
nonpolar molecule no dipole moment
nonpolar molecule

28