486 13 PHYSICAL CHEMISTRY

DIPOLE MOMENT
In a molecule such as HCl, the bonding electron pair is not shared equally between the hydrogen
atom and the chlorine atom. The chlorine atom with its greater electronegativity, pulls the electron
pair closer to it. This gives a slight positive charge (+q) to the hydrogen atom and a slight negative
charge (– q) to the chlorine atom.
+q –q
H Cl or H Cl
Such a molecule with a positive charge at one end and a negative charge at the other end is referred
to as an electric dipole or simply dipole. The degree of polarity of a polar molecule is measured by its
dipole moment, (Greek mu).
= r

+q q

Figure 13.1
An electric dipole of the magnitude = r.
The dipole moment of a polar molecule is given by the product of the charge at one end and the
distance between the opposite charges. Thus,
= q×r
The dipole moment ( ) is a vector quantity. It is represented by an arrow with a crossed tail. The
arrow points to the negative charge and its length indicates the magnitude of the dipole moment.
Thus a molecule of HCl may be represented as

H Cl
Unit of Dipole Moment
The CGS unit for dipole moment is the debye, symbolised by D, named after the physical chemist
Peter Debye (1884-1966). A debye is the magnitude of the dipole moment ( ) when the charge (q) is
1 × 10–10 esu (electrostatic units) and distance (r) is 1Å (10–8 cm).
= q × r = 1 × 10–10 × 10–8 = 1 × 10–18 esu cm
Thus 1 D = 1 × 10–18 esu cm
In SI system, the charge is stated in Coulombs (C) and distance in metres (m). Thus dipole
moment is expressed in Coulomb metres (Cm). The relation of debye to SI units is given by the
expression coulomb:
1 D = 3.336 × 10–30 Cm
Determination of Dipole Moment
Electric condenser. The dipole moment of a substance can be experimentally determined with
the help of an electric condenser (Fig. 13.2). The parallel plates of the condenser can be charged by
connecting them to a storage battery. When the condenser is charged, an electric field is set up with
field strength equal to the applied voltage (V) divided by the distance (d) between the plates.
Polar molecules are electric dipoles. The net charge of a dipole is zero. When placed between the
charged plates, it will neither move toward the positive plate nor the negative plate. On the other
hand, it will rotate and align with its negative end toward the positive plate and positive end toward
the negative plate. Thus all the polar molecules align themselves in the electric field. This orientation
of dipoles affects the electric field between the two plates as the field due to the dipoles is opposed
to that due to the charge on the plates.
 487

Storage
battery

Condenser
plate

Figure 13.2
Polar molecules rotate and align in electric field.

The plates are charged to a voltage, say V, prior to the introduction of the polar substance. These
are then disconnected from the battery. On introducing the polar substance between the plates, the
voltage will change to a lower value, V'. Just how much the voltage changes depends on the nature of
the substance. The ratio = V/V' is a characteristic property of a substance called the dielectric
constant. The experimentally determined value of dielectric constant is used to calculate the dipole
moment.
Use of Rotational Spectra
The rotational spectrum of a polar molecule is examined in the gas phase. It is found that the
spectral lines shift when the sample is exposed to a strong electric field. From the magnitude of this
effect (Stark effect), the dipole moment can be determined very accurately. The dipole moments of
some simple molecules are listed in Table 13.2.
TABLE 13.2. DIPOLE MOMENTS OF SOME SIMPLE MOLECULES IN THE VAPOUR PHASE
Formula (D) Formula (D)

H2 0 CO2 0
Cl2 0 CH4 0
HF 1.91 CH3Cl 1.87
HCl 1.08 CH2Cl2 1.55
HBr 1.80 CCl4 0
HI 0.42 NH3 1.47
BF3 0 H2O 1.85

BOND MOMENT
Any bond which has a degree of polarity has a dipole moment. This is called Bond moment. The
dipole moment of H—H bond is zero because it is nonpolar. The dipole moment of the H—Cl bond is
1.08 D because it is polar.
In a diatomic molecule, the bond moment corresponds to the dipole moment of the molecule. The
dipole moments of the halogen halides shown below also indicate their bond moments.
1.91D 1.08 D 1.80 D 0.42 D

H F H Cl H Br H I

The bond moment decreases with decreasing electronegativity of the halogen atom.
488 13 PHYSICAL CHEMISTRY
When a molecule contains three or more atoms, each bond has a dipole moment. For example,
0.4 D 1.5 D 1.5 D 1.3 D

C H C Cl H O H N

The net dipole moment of the molecule is the vector resultant of all the individual bond moments.
If a molecule is symmetrical having identical bonds, its dipole moment is zero. That is so because the
individual bond moments cancel each other out.

DIPOLE MOMENT AND MOLECULAR STRUCTURE

Dipole moment can provide important information about the geometry of molecular structure. If
there are two or more possible structures for a molecule, the correct one can be identified from a
study of its dipole moment.
(1) H2O has a Bent Structure
Water molecule (H2O) can have a linear or bent structure.

Net dipole
moment

H O H H O

H
(a) (b)

The dipole moments of the two O—H bonds in structure (a) being equal in magnitude and
opposite in direction will cancel out. The net dipole moment ( ) would be zero. In structure (b) the
bond moment will add vectorially to give a definite net dipole moment. Since water actually has a
dipole moment (1.85 D); its linear structure is ruled out. Thus water has a bent structure as shown
in (b).
(2) CO2 has a Linear Structure and SO2 a Bent Structure
Carbon dioxide has no dipole moment ( = 0). This is possible only if the molecule has a linear
structure and the bond moments of the two C = O units cancel each other.

Net dipole
moment
S
O C O
=0 O O
= 1.63 D

On the other hand, SO2 has a dipole moment ( = 1.63). Evidently, here the individual dipole
moments of the two S = 0 bonds are not cancelled. Thus the molecule has a bent structure. The vector
addition of the bond moments of the two S = 0 units gives the net dipole moment 1.63 D.
(3) BF3 has a Planar and NH3 a Pyramid Structure
The dipole moment of boron trifluoride molecule is zero. This is possible if the three B—F bonds
are arranged symmetrically around the boron atom in the same plane. The bond moments of the three
B—F bonds cancel each others effect and the net = 0.
 489

F
Lone pair

B N
H H Net dipole
F F
moment
H
Boron trifluoride, BF3 Ammonia, NH3
( = 0) ( = 1.47 D)
Ammonia molecule (NH3) has a dipole moment ( = 1.47 D). This is explained by its pyramidal
structure. The three H atoms lie in one plane symmetrically with N atom at the apex of the regular
pyramid. The dipole moments of the three N—H bonds on vector addition contribute to the net
dipole moment. In addition, there is a lone pair of electrons on the N atom. Since it has no atom
attached to it to neutralise its negative charge, the lone pair makes a large contribution to the net
dipole moment. Thus the overall dipole moment of ammonia molecule is the resultant of the bond
moments of three N—H bonds and that due to lone-pair.
It may be recalled that the high dipole moment of water (H2O) can also be explained by the
presence of two lone-pairs of electrons on the oxygen atom.
H H

0.4 D
o
109.5
C C
H H H o H
70.5

H
H
0.4 D
(a) (b)
Figure 13.3
Dipole moment of methane molecule.
(4) CH4 has Tetrahedral Structure
Methane (CH4) has zero dipole moment, despite the fact that each C—H bond possesses a
dipole moment of 0.4 D. This can be explained if the molecule has a symmetrical tetrahedral structure
(Fig. 13.3).
1
Each C—H bond in the pyramidal CH3 group contributes ( cos 70.5) to the resultant
3
dipole moment. Thus the net dipole moment of CH3 group is equal to . This acts in a direction
opposite to that of the fourth C—H bond moment, thereby cancelling each other.
(5) Identification of cis and trans Isomers
The dipole moment can be used to distinguish between the cis and trans isomers. The cis isomer
has a definite dipole moment, while the trans isomer has no dipole moment ( = 0). For example,
H H H Cl

C C C C

Cl Cl Cl H
cis-Dichloroethylene trans-Dichloroethylene
( = 2.96 D) ( = 0)
In the cis isomer, the bond moments add vectorially to give a net dipole moment. The trans
isomer is symmetrical and the effects of opposite bond moments cancel so that = 0.
490 13 PHYSICAL CHEMISTRY
(6) Identification of ortho, meta and para Isomers
Benzene has a dipole moment zero. Thus it is a planar regular hexagon. Let us examine the dipole
moments of the three isomeric dichlorobenzenes (C6H4Cl2). Since the benzene ring is flat, the angle
between the bond moments of the two C—Cl bonds is 60° for ortho, 120° for meta and 180° for para.
On vector addition of the bond moments in each case, the calculated dipole moments are ortho 2.6 D,
meta 1.5 D and para 0 D. These calculated values tally with the experimental values. Thus the above
structures of o-, m - and p-isomers stand confirmed. In general, a para disubstituted benzene has zero
dipole moment, while that of the ortho isomer is higher than of meta isomer. This provides a method
for distinguishing between the isomeric ortho, meta and para disubstituted benzene derivatives.

Cl Cl Cl

Cl
o
60 o
120
o
180
Cl

Cl
= 2.6 D = 1.5 D =0
Figure 13.4
Dipole moments of ortho, meta and para dichlorobenzenes.
Dipole Moment and Ionic Character
The magnitude of the dipole moment of a diatomic molecule determines its ionic character. Let us
consider an HBr molecule whose measured dipole moment ( exp) is 0.79 D and bond distance
(r) = 1.41Å.
If the molecule were completely ionic (H+Br–), each of the ions will bear a unit electronic charge,
e (4.8 × 10–10 esu). Thus the dipole moment of the ionic molecule ( ionic) can be calculated.
–10 esu) (1.41 × 10–8 cm)
ionic = e × r = (4.8 × 10
= 6.77 D
But the experimental dipole moment ( exp) of H +—Br –, which determines its actual fractional
ionic character, is 0.79 D. Therefore,

expt
% ionic character of HBr 100
ionic

0.79 D
100 11.6
6.77 D
Hence HBr is 12% ionic in character.
MOLAR REFRACTION AND CONSTITUTION
The molar refraction (RM) is an additive and constitutive property. The molar refraction of a
molecule is thus a sum of the contributions of the atoms (atomic refractions) and bonds (bond
 491

refractions) present. From the observed values of RM of appropriate known compounds, the atomic
refractions of different elements and bonds have been worked out. Some of these are listed in Table 13.3.
TABLE 13.3. SOME ATOMIC AND BOND REFRACTIONS IN cm3 mol–1 FOR D LINE (VOGEL 1948)
Atom Ratomic Bond Rbond

C 2.591 C–H 1.676

H 1.028 C=C 4.166
O (in C = O) 2.010 C C 1.977
O (in –O–) 1.643 6C ring – 0.15
O (in –O–H) 1.518 5C ring – 0.10
Cl 5.844 4C ring 0.317
Br 8.741

The molar refraction of the proposed structure of a molecule can be computed from the known
atomic and bond refractions. If this value comes out to be the same as the experimental value, the
structure stands confirmed. Some examples are given below for illustrating the use of molar refractions
in elucidating molecular structure.
(1) Acetic acid. The accepted structural formula of acetic acid is
H O

H C C O H

H
The molar refraction (RM) may be computed from the atomic refractions of the constituent atoms
as
2C 2 × 2.591 = 5.182
4H 4 × 1.028 = 4.112
l O (in OH) 1 × 1.518 = 1.518
l O (in C = O) 1 × 2.010 = 2.010
Total RM = 12.822 cm3 mol–1
The value of molar refraction of acetic acid found by determination of its refractive index is 13.3
cm3 mol–1. There is a fairly good agreement between the calculated and experimental values. It
confirms the accepted formula of acetic acid.
(2) Benzene. The molar refraction of benzene (C6H6) on the basis of the much disputed Kekule
formula may be calculated as :
H 6C 6 × 2.591 = 15.546
C
HC CH 6H 6 × 1.028 = 6.168

HC CH
3C=C 3 × 1.575 = 4.725
C 16 C ring = – 0.150
H
Kekule formula
for benzene
Total RM = 26.289 cm3 mol–1
The observed values of RM for benzene is 25.93. This is in good agreement with the calculated
value. Hence the Kekule formula for benzene is supported.
492 13 PHYSICAL CHEMISTRY
(3) Optical Exaltation. A compound containing conjugated double bonds (C=C—C=C) has a
higher observed RM than that calculated from atomic and bond refractions. The molar refraction is
thus said to be exalted (raised) by the presence of a conjugated double bond and the phenomenon
is called optical exaltation. For example, for hexatriene,
CH2=CH—CH=CH—CH=CH2
the observed value of RM is 30.58 cm3 mol–1 as against the calculated value 28.28 cm3 mol–1.
If present in a closed structure as benzene, the conjugated double bonds do not cause exaltation.
OPTICAL ACTIVITY AND CHEMICAL CONSTITUTION
Optical activity is a purely constitutive property. This is shown by a molecule which is
dissymmetric or chiral (pronounced ky-ral). A chiral molecule has no plane of symmetry and cannot
be superimposed on its mirror image. One such molecule is lactic acid, CH3CHOHCOOH. Assuming
that carbon has a tetrahedral structure, lactic acid can be represented by two models I and II.

COOH COOH

C C

H OH HO H
CH3 CH3

Model I Model II
Mirror
(+)-Lactic acid ( )-Lactic acid

Figure 13.5
Two chiral models of lactic acid.
If you try to place model II on model I so that any two similar groups coincide, the remaining two will
clash. Suppose you try to coincide COOH and H by rotating model II, the groups OH and CH3 will go
in opposite positions. The fact that model II cannot be superimposed on model I shows that they
represent different molecules. The molecules that are nonsuperimposable mirror images, are called
enantiomers.
Lactic acid is actually known to exist in two enantiomeric forms (optical isomers). They have the
same specific rotation but with sign changed.
(+)-Lactic acid [ ]25
D = +3.8°
(–)-Lactic acid [ ]25
D = –3.8°
A third variety of lactic acid is obtained by laboratory synthesis. It is, in fact, a mixture of
equimolar amounts of (+)- and (–)-lactic acid. It is represented as ( )-lactic acid and is termed
racemate or racemic mixture. Evidently, a racemic mixture has zero optical rotation.
COOH COOH

C C

OH
H OH H
CH3 CH3

OH
H OH H
CH3 CH3
Figure 13.6
The interaction of polarized light with the opposite orientation of groups
produces opposite rotatory powers in two enantiomers of lactic acid.
 493

What Makes a Molecule Optically Active ?

Lactic acid molecule is chiral because it contains a carbon joined to four different groups H, OH,
CH3, COOH. A carbon bearing four different groups is called an asymmetric or chiral carbon. It may
be noticed that the arrangement of groups about the asymmetric carbon is either clockwise or
anticlockwise. It is the interaction of polarized light with these opposite arrangements of groups
which is responsible for the opposite rotatory powers of (+)- and (–)-lactic acids.
Presence of Chiral Carbons, Not a Necessary Condition for Optical Activity
A molecule containing two or more chiral (or asymmetric) carbons may not be optically active. It
is, in fact, the chirality of a molecule that makes it optically active.
Let us consider the example of tartaric acid which contains two chiral carbon atoms. It exists in
three stereoisomeric forms.

COOH COOH COOH

H OH HO H H OH

C C C

C C C

H OH
OH
H H OH
COOH COOH COOH
I II III

Enantiomers Meso
The forms I and II are nonsuperimposable mirror images. They represent an enantiomeric pair.
The form III has a plane of symmetry and divides the molecule into two identical halves. The
arrangement of groups about the two chiral carbons is opposite to each other. The optical rotation
due to the upper half of the molecule is cancelled by the rotation of the lower half. Thus the form III
although containing two chiral carbons, is optically inactive. This is called the meso form.
Tartaric acid is actually known to exist in three stereoisomeric forms :
(+)-Tartaric acid [ ]20
D = +12.7°
(–)-Tartaric acid [ ]20
D = –12.7°
meso-Tartaric acid [ ]20
D = 0°

COOH

H C OH
Plane of
symmetry
H C OH

COOH

An equimolar mixture of (+)-tartaric acid and (–)-tartaric acid is referred to as racemic tartaric
acid or ( )-tartaric acid.