CHM 361

Chapter 1: Intermolecular Forces In

Covalent Compounds

Outlines

Van der Waals

Hydrogen Bonding
Dipole-Dipole Interaction
Ion-Dipole Interaction
Instantaneous Dipole-Dipole Interaction

INTRODUCTION
The attractions
between molecules
Intermolecular
are not nearly as
strong as the
forces ??
intramolecular
attractions that hold
compounds together
These
intermolecular
forces as a group
are referred to as
play important roles
van der Waals
in determining the
Forces that holding
forces.
properties
of
a
molecules together
substances (boiling
and melting
points, vapor
pressures, and
viscosities.)

VAN DER WAALS

Named after the Dutch physicist
Johannes van der Waals
1.

2.He had studied the effects of intermolecular forces on the behavior of

real gas
3. Several types of intermolecular
forces (Van der Waals ) such as:
Hydrogen bonding
Dipole-dipole
interaction

Ion-dipole
interaction
Dispersion forces

London Dispersion Forces

Instantaneous dipole-dipole
attraction

1)Known as :

Dispersion forces
2)These forces are
present in all molecules,
whether they
are polar or nonpolar.

3)In nonpolar molecules, this is the only

intermolecular
forces that operates
4)Dispersion forces result from temporary
dipoles
induced in atoms or molecules

London Dispersion
Forces
What is temporary/instantaneous dipole and
induced dipole?
1) Movement of atoms/molecules,
together with their electrons, may
result in the electrons gathering at
one side of the molecule

2)This will result in

temporary/instantaneous dipole for
the molecule

3) If this molecule is close enough

with another molecule, it will induce
a dipole with its neighbour
4)Due to random movement, a
different temporary dipole is created
the next moment, which will induce
the dipole from its neighbours

5) the arrangement keep on changing

as the molecules are moving

London Dispersion
Forces
The likelihood of induced dipole depends on
the polarisability of the atom or molecule
Polarisability the ease with which the
distribution of electron cloud can be distorted
The larger the electron cloud (or the
higher number of electrons), the easier it
is to be polarised
Polarisability increased with increase of
molar mass

London Dispersion Forces

1) As you can see in
this table, the
melting point
increase with the
increase of molar
mass of the
molecules
2) The increase of
melting point shows
increase in
intermolecular
forces in this case,
London dispersion
forces

Dipole-dipole interaction

Dipole-dipole forces attractiv

forces between polar molecules

Dipole-dipole forces exist betw

molecules that have dipole mom
The larger the dipole moment,
the greater the force
Polar molecules align in a way
maximises the attractive
interaction

Dipole-dipole interaction

The more polar the molecule, the higher is its boiling point

Which Have a Greater Effect:

Dipole-Dipole Interactions or Dispersion
Forces?

1. If two molecules are of comparable

size and shape, dipole-dipole
interactions will likely be the
dominating force.
2. If one molecule is much larger than
another, dispersion forces will likely
determine its physical properties

Hydrogen Bonding
1. The dipole-dipole interactions experienced
when H is bonded to N, O, or F are
unusually strong.
2. We call these interactions hydrogen bonds
3. The hydrogen must also be chemically
bonded
with either one of the three element
4. Note that N, O and F all have at least one
lone
or
A H B
A H A
pair to interact with H atom in other
A & B are N, O, or F
molecules

Hydrogen Bonding
Hydrogen
bonding arises in
part from the
high
electronegativity
of nitrogen,
oxygen, and
fluorine.
Also, when hydrogen is bonded to one
of those very electronegative
elements, the hydrogen nucleus is
exposed.

Hydrogen Bonding
The strength of
hydrogen bond
depends on the
interaction of the
lone pair electrons
with hydrogen
Example: The
boiling point of HF
Although F is more elecronegative
is lower
than O, but H2O can form
4 than H2O
intermolecular hydrogen bonds. HF
can only form 2 hydrogen bonds, as
shown in this figure

Ion-dipole forces
Ion-dipole forces are attraction between an
ion and a polar molecule
The strength of this interaction depends on
the charge of the ion, the dipole moment of
the molecule & the size of both
A cation interacts more with dipoles than
anion with the same magnitude
The strength of these forces are what make
it possible for ionic substances to dissolve in
polar solvents

Ion-dipole forces
Hydration is an example
of common ion-dipole
interaction
The ion-dipole
interaction of 2 different
ions, Na+ and Mg2+ is
shown here
Mg2+ ion, with higher
charge and smaller,
interacts strongly with
water

Ion-dipole forces
In aqueous
solutions, metal
ions are usually
surrounded by
water molecules in
octahedral
arrangement

Summary
In general, the strength of intermolecular forces
increase in this order:
dispersion < dipole-dipole < hydrogen bond <
ion-dipole
Dispersion forces operates on all molecules and
depend only on molecular mass
Dipole-dipole operates on polar molecules, but
compete with dispersion
The contribution of dipole-dipole forces in polar
molecules is usually smaller than dispersion forces
However, if hydrogen bond is present, it makes a
significant contribution to intermolecular
interaction between molecules

Summary
weights
&
shapes,

similar
in
differences is due to different polarity
of molecules the higher polarity
will have greater intermolecular
forces

How to compare
strength of
intermolecular
interaction??
molecules differ widely in
weights, dispersion forces
will determine the strengths
of intermolecular forces
the higher molecular weight
will have greater

Summary

Sample problem
For each pair of substances, identify the key
intermolecular forces(s) in each substance,
and select the substance with the higher
boiling point:
a) CH3NH2 or CH3F
b) CH3OH or CH3CH2OH
c) MgCl2

or PCl3

Plan
1) we examine the formulas and picture the structure
difference to identify the key difference
2)Are ions present? Polar or nonpolar? Is N, O, F
bonded
to H?
3)do the molecules have different masses or shape?
Remember that :
Bonding forces are stronger than intermolecular forces
Hydrogen bonding is a strong type of dipole-dipole
force.
Dispersion are always present, but they are decisive
when the
differences is molar mass or molecular shape

Solution
(a)CH3NH2 and CH3F both consist of polar molecules of about
the same molar mass, CH3NH2 has N-H bonds, so it can
form H bonds. But, CH3F contain C-F bond but no H-F
bond, so dipole-dipole forces occur but not H bonds.
Therefore CH3NH2 has the higher boiling point.
(b) CH3OH and CH3CH2OH molecules both have O-H bond,
so the can form H bond, CH3CH2OH have additional
CH2- group and the larger molecular mass, which
correlates with stronger dispersion forces, therefore
have the higher boiling points
(c) MgCl2 =ionic bonding PCl3 = dipole-dipole
moment,the forces of MgCl2 > PCl3. so it has a higher
boiling point.