Dipole Moment

Special reference to Alkyl Halides

Submitted To:
Dr. Shazia Naheed
Submitted By:
Muhammad Usman
Reg. No:
UW-17-CHM-BS-128
Date:
 Dipole Moment
A diatomic molecule such as A2 has a covalent bond, which contains two electrons of
opposite spin. Two A atoms, each with a single electron, combine to form this bond. Since each
A atom contributes one electron, a neutral A2 atom must have an electron density equal to unity.
The two electrons in the covalent bond are shared equally, the electron density is the same at
each atom, and the molecule is nonpolar.

But in a diatomic molecule like A-B where B is more electronegative than A the two
bonding electrons are not shared equally. The electron density at A is less than unity where as the
electron density at B is greater. In this molecule there exists a region which is relatively positive
and a region that is relatively negative; such a molecule is polar.

So in the molecule containing atoms of different electronegativity the electron density is

higher near more electronegative atoms and lower near the less electronegative atoms. While the
molecule is as a whole neutral, there is a point within the molecule about which the positive
charge centers and a point about which the negative charge centers. If these two centers do not
coincide, the molecule will have electric dipole moment.

Dipole moments occur when there is a separation of charge. They can occur between two ions
in an ionic bond or between atoms in a covalent bond; dipole moments arise from differences in
electronegativity. The larger the difference in electronegativity, the larger the dipole moment.
The distance between the charge separations is also a deciding factor into the size of the dipole
moment. The dipole moment is a measure of the polarity of the molecule.

When atoms in a molecule share electrons unequally, they create what is called a dipole
moment. This occurs when one atom is more electronegative than another, resulting in that atom
pulling more tightly on the shared pair of electrons, or when one atom has a lone pair of
electrons and the difference of electronegativity vector points in the same way. One of the most
common examples is the water molecule, made up of one oxygen atom and two hydrogen
atoms. The differences in electronegativity and lone pairs give oxygen a partial negative charge
and each hydrogen a partial positive charge.

Dipole Moment
“When two electrical charges, of opposite sign and equal magnitude, are separated
by a distance, an electric dipole is established.”

OR

“Dipole moment is defined as the product of the magnitude of charge on any one of
the atoms and the distance between them.”

Dipole moment is represented by a Greek letter µ.

It can be expressed mathematically, as

µ=qxd

where, e = charge on any one of the atoms

d = distance between the atoms.

For example, dipole moment of HCl is 1.03 x10-18Cm and is expressed as 1.03 D.

Dipole moment can be determined experimentally and its value can give an idea of the polar
character of a molecule. It is a vector quantity as it has a direction as well as magnitude.

The direction of dipole moment is usually represented by an arrow à pointing from positive end
towards the negative end. The dipole moment is expressed by symbol

The direction of a dipole

The vector points from positive to negative, on both the molecular (net) dipole moment and the
individual bond dipoles.

Units:

In SI units, q is expressed in coulombs and d in meters, so μ has the dimensions of C-m. If one
entire electron charge is displaced by 100 pm (a typical bond length), then

μ = (1.6022 × 10–19 C) × (10–10 m) = 1.6 × 10–29 C-m = 4.8 D

The quantity denoted by D, the Debye unit, is still commonly used to express dipole moments.

Dipole moment is measured in Debye units, which is equal to the distance between the charges
multiplied by the charge.

(1 Debye = 3.34×10−30Cm.)
DIPOLE MOMENT AND MOLECULAR STRUCTURE:

Diatomic molecule:
A diatomic molecule has two atoms bonded to each other by covalent bond. In such a
molecule the dipole moment of the bond also gives the dipole moment of the molecule. For
example, dipole moment of HCl molecule is the same as that of H-Cl bond (µ. = 1.03 D).

Greater the electronegativity difference between the atoms more will be the dipole moment of
such molecules. For example, the dipole moment of HF is 1.91D while that of HCl is 1.03D
(F is more electronegative than Cl).

Polyatomic molecule:

A polyatomic molecule has more than two atoms bonded by covalent bonds. In such cases the
idea of a dipole can be applied to individual bonds within the molecule. The dipole moment of
individual bond in a polyatomic molecule is referred to as bond dipole. The dipole moment of
the molecule depends upon the orientations of various bond dipoles.

For example, carbon dioxide (C02) and water (H2O) are both triatomic molecules but dipole
moment of carbon dioxide is zero whereas that of water is 1.83 D.

Dipole Moment in Alkyl Halide:

The haloalkanes, also known as alkyl halides, are a group of chemical compounds comprised of
an alkane with one or more hydrogens replaced by a halogen atom (fluorine, chlorine, bromine,
or iodine).
There is a fairly large distinction between the structural and physical properties of haloalkanes
and the structural and physical properties of alkanes. The structural differences are due to the
replacement of one or more hydrogens with a halogen atom. The differences in physical
properties are a result of factors such as electronegativity, bond length, bond strength, and
molecular size.

Halogens (F, Cl and Br) are more electronegative than carbon. Consequently, carbon atoms that
carry halogens are charged partially positive while the halogen is charged partially negative. The
polarity of the C-X bond causes a measureable dipole moment. As a result of the partial positive
charge, the carbon atom displays an electrophilic character. The chemical behavior of alkyl
halides is determined mainly by the electrophilicity of the carbon.

The polar nature of C-X bond is expected to increase with increase in the electronegativity
difference between carbon and halogen atom.

Hence the expected order of polarity of C-X bond will be: C-F > C-Cl > C-Br >> C-I.

Actually, based on EN difference, C-I bond should be considered as non-polar since both carbon
and iodine atoms have same EN i.e. 2.50.

Dipole moments of organohalogen compounds depend on the polarity of the bond and also on
the bond length.
It is expected that organofluorides possess highest dipole moment values since the C-F bond is
more polar. However, usually organochlorides possess greater dipole moment values. It is due to
cumulative result of polarity and longer bond length of C-Cl compared to C-F.

E.g. the dipole moments of methyl halides vary as follows.

Bond length and bond Strength:

The bond length of C-X bond depends on the nature of halogen as well as the hybridization of
carbon atom.

 The bond length increases with increase in the size of halogen atom. The C-X bond
weakens with increase in the bond length and decrease in the overlap of atomic orbitals.

Order of bond length: C-F < C-Cl < C-Br < C-I

Order of bond strength (bond energy): C-F > C-Cl > C-Br > C-I

 The sp3 C-X bonds of alkyl halides are longer than sp2 C-X bonds of vinyl and aryl
halides. In the latter case, the C-X bond has partial double bond character that arises due
to delocalization of π electrons. Hence the bond strength also increases with increase in
double bond character.

Polar C-X bonds cause most haloalkanes to have molecular dipoles and the magnitude of their
dipole moments depends on X.
Since electronegativity values of X increase in the order

I<Br< Cl <F

We might expect haloalkanes dipole moments to also increase in this order. While this is true for
dipole moments of trihaloalkanes (CHX3) and dihaloalkanes (CH2X2), you can see that it is not
generally true for monohaloalkanes (CH3X). As we would expect, the dipole moment for CH3I
has the lowest value, but those for CH3F, CH3Cl, and CH3Br are all about the same even though
the electronegativity values of F, Cl, and Br are quite different from each other. This
inconsistency occurs because dipole moments depend not only on the amount of charge
separated at the two ends of the dipole, but also the distance of that separation. The bond lengths
of the C-X bonds determine the distance of this charge separation and we will see below that
these bond lengths are significantly different for the four halogens.

EXAMPLE 1

Dipole moment of Cl substituted Alkanes:

CH3Cl>CH2Cl2>CHCl3>CCl4

In case of CCl4, tetrahedral symmetry exists. Therefore, the dipole moment of three C-Cl bonds
on one side, gives a resultant moment that is equal and opposite to the dipole moment of the
single C-Cl bond on the opposite side. So, μ=0.

This explains CHCl3>CCl4.

Again, in case of CHCl3, the three C-Cl bonds point to one side, so a moment equal to C-Cl bond
is generated as a result. A moment of C-H bond is added to it. In CH2Cl2, the moment of two C-
Cl bond is added at 1090X(approx.) so the resultant is greater than on C-Cl bond.
This explains CH2Cl2>CCl4

In case of CH3Cl, the dipole moment of one C-Cl bond is added with moment of one C-H bond
(resultant of three C-H bonds).

Methyl chloride has higher dipole moment than other methyl halides:

REASON:
As dipole moment is a product of charges and distance between charges, in case of Methyl
Chloride the bond length is greater although charges are less, the product of charges and bond
length is greater than that of Methyl Fluoride.

EXAMPLE 2

Dipole moment of CBr4, CHBr3, CH2Br2 and CH3Br:

All the structure have tetrahedral geometry, So the vector addition in CBr4 will be equally
nullified hence it has 0 dipole moment, CHBr3 has one H which has lesser force hence it has
greater dipole moment, similarly CH2Br2 will have even more dipole moment, finally CHBr3 has
greatest dipole moment.(the red arrows indicate dipole moment of individual bonds).

Br is more electronegative than a sp3 Carbon atom while H is less electronegative than the same,
hence direction of the dipole moment they produce individually is different.