INTERMOLECULAR

FORCES

DR AMALINA MOHD TAJUDDIN

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Outlines

q Van der Waals

q Hydrogen Bonding
q Dipole-Dipole Interaction
q Ion-Dipole Interaction
q Instantaneous Dipole-Induced Dipole Interaction
q Ion induced dipole interaction

2
 Intermolecular Attractions and the
Properties of Liquids and Solids
• There are important differences between gases,
solids, and liquids:

Gases - expand to fill their container

Liquids - retain volume, but not shape
Solids - retain volume and shape

3
Properties can be understood in terms of how tightly the
molecules are packed together and the strength of the
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intermolecular attractions between them.
Intramolecular forces are always stronger than intermolecular forces
5
• Strong intramolecular attractions exist between H and Cl
within HCl molecules. These attractions control the chemical
properties of HCl.

• Weaker intermolecular attractions exist between neighbouring

HCl molecules. Intermolecular attractions control the physical
properties of this substance.
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Interaction Forces Approximate Energy
Intermolecular
London 1 – 10 kJ
Dipole-dipole 3 – 4 kJ
Ion-dipole 5 – 50 kJ
Hydrogen bonding 10– 40 kJ
Chemical bonding
Ionic 100 – 1000 kJ
Covalent 100 – 1000 kJ
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INTERMOLECULAR FORCES

Hydrogen Van der Waals

bonds forces

Ion-dipole Dipole-dipole London

interaction Forces Dispersion forces

Ion- Dipole- Instantaneous

Induced Dipole Induced Dipole Dipole-
Interaction Interaction Induced Dipole
Interaction

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 Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction between
hydrogen atom in a polar N-H, O-H, or F-H bond and an
electronegative O, N, or F atom.

A H…B or A H…A
A & B are N, O, or F

The high DEN of NH,

OH, and HF bonds
cause these to be
strong forces (about 5x
stronger than normal
2.1 4.0 2.1 3.5 2.1 3.0 dipole-dipole forces)

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Two essential requirements for the formation of a hydrogen
bond:

• One molecule must contain at least one H atom attached

to a highly electronegative atom (i.e. F, O or N).

• The other molecule must contain an F, O or N atom

that provides the lone pair of electrons.

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 Why is the hydrogen bond considered a “special”
dipole-dipole interaction?

All are polar

B.p. ­ as molecular size ­

However, H2O, HF and NH3 have abnormally high b.p.
There exist unusually strong dipole-dipole forces (H-bond)
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 Let’s try this….

Relative Boiling
Substance
molecular mass point (°C)
NH3 17 -33.3
HF 20 19.5
H2O 18 100 ????

H2O > HF because

H2O can form H-bonds more extensively, regardless of the
fact that H-F bond is more polar than H-O bond.

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 hydrogen bond

Each NH3 molecule has only ONE lone pair.

Þ On the average, each NH3 molecule can form only ONE
hydrogen bond

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Each HF molecule has only ONE hydrogen atom.
Þ On the average, each HF molecule can form only ONE
hydrogen bond

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 hydrogen bond

Each H2O molecule has TWO hydrogen atoms and TWO lone
pairs.

Þ On the average, each H2O molecule can form TWO

hydrogen bonds

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Hydrogen Bonding & Water

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 INTERMOLECULAR FORCES

van der Waals

forces

Ion-dipole Dipole-dipole London

interaction Forces Dispersion forces

Ion- Dipole- Instantaneous

Induced Dipole Induced Dipole Dipole-
Interaction Interaction Induced Dipole
Interaction

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 (a) Ion-Dipole Forces

• An ion-dipole force is an attractive force that results from the

electrostatic attraction between an ion and polar molecule

• Most commonly found in solutions

• Especially important for solutions of ionic compounds in polar

liquids

• The strength of this interaction depends on the charge of the

ion, the dipole moment of the molecule

• The strength of these forces are what make it possible for ionic
substances to dissolve in polar solvents

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 Attractive forces between an ion and a polar molecule
Ion-Dipole Interaction

A positive ion (cation) attracts the partially negative end of

a neutral polar molecule.

A negative ion (anion) attracts the partially positive end of a

neutral polar molecule.
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• Ion-dipole attractions become stronger as either the charge on
the ion increases, or as the magnitude of the dipole of the polar
molecule increases

• Mg2+ ion, with higher charge and smaller, interacts strongly

with water
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 Ion-dipole forces

• Hydration is an example of
common ion-dipole
interaction

• In aqueous solutions, metal

ions are usually surrounded
by water molecules in
octahedral arrangement
• e.g: [Cr(H2O)6]3+

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 (b) Dipole-dipole Attractive Forces
Orientation of Polar Molecules in a Solid

• A dipole-dipole force exists between neutral polar molecules

• Polar molecules attract one another when the partial positive charge on
one molecule is near the partial negative charge on the other molecule

• The polar molecules must be in close proximity for the dipole-dipole

forces to be significant

• Dipole-dipole forces are characteristically weaker than ion-dipole forces

• Dipole-dipole forces increase with an increase in the polarity of the

molecule (The larger the dipole moment, the greater the force) 22
• The more polar the molecule, the higher is its boiling point

• For polar molecules of similar mass, boiling points increase

with increasing dipole

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(c) London Dispersion Forces – significant only when molecules
are close to each other

• These forces are present in all molecules, whether they are

polar or nonpolar

• Due to electron repulsion, a temporary dipole on one atom can

induce a similar dipole on a neighbouring atom

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• London forces
• The (very) weak attractions between nonpolar molecules
• Arise from the interactions of instantaneous dipoles on
neighboring molecules

1. An instantaneous dipole on
one molecule can produce
and induced dipole on
another.
2. The net interaction of these
over time is attractive.
¢ 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

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3) If this molecule is close enough with another molecule, it will induce
a dipole with its neighbouring molecule

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

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– The likelihood of induced dipole depends on the
polarizability of the atom or molecule

– Polarizability is a measure of the ease with which the

electron cloud on a particle is distorted

– It tends to increase as the electron cloud volume increases

• The larger the electron cloud (or the higher number of
electrons), the easier it is to be polarized
• Polarizability increased with increase of molar mass
 Large electron clouds are
Large electrondeformed
more easily clouds arethan
more
of the resulting
small ones. The partial charge
magnitude
is
of also
the larger. Thepartial
resulting larger
molecules
charge is experience
also larger.larger
The
London forces than small
larger molecules
molecules.
experience larger London
forces than small
molecules.

• The boiling point of the halogens and noble gases

demonstrate this:
BP( o C) BP( o C) BP( o C) BP( o C)
F2 - 188.1 Br2 58.8 He - 268.6 Ar - 185.7
Cl 2 - 34.6 I2 184.4 Ne - 245.9 Xe - 107.1
Rn - 61.8
 Conclusions
Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud

Dispersion forces
usually increase with
molar mass.

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 Strength of van der Waals forces

Depends on three factors (in decreasing order of importance):

1. Size of molecule
2. Surface area of molecule
3. Polarity of molecule

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1. Size of Molecule
Molecule Boiling point Size
Rel. of molecule
molecular mass­ ­
(oC)
Helium -269
Neon -246
Size of electron cloud ­
Argon -186
Fluorine -188
Chlorine -34.7
Bromine 58.8 Polarizability ­
Methane -162
Ethane -88.6
Propane -42.2 Dispersion forces ­
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 What type(s) of intermolecular forces exist
between each of the following molecules?

HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.

CH4
CH4 is nonpolar: dispersion forces.

SO2
S O
O
SO2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules.
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2. Surface area of molecule

The van der Waals’ forces also increase with

the surface area of the molecule.

∵ van der Waals' forces are short-ranged forces

Atoms or molecules must come close together for significant

induction of dipoles.

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–Molecular shape affects the strength of London forces
• More compact molecules tend to have lower London forces than
longer chain-like molecules
• An example is between neopentane and n-pentane

Both are non-polar

Same number of
electrons

§ Space filling models of two molecules with formula C5H12.

§ The H atoms in the more compact neopentane cannot
interact as well with neighbouring molecules as the H atoms
in the more chain-like n-pentane.
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3. Polarity of molecules

• For molecules with comparable molecular sizes

and shapes, dispersion forces are approximately
equal.
• Then, strength of van der Waals’ forces depends
on the polarity of molecules involved

Polar/polar > polar/non-polar > non-polar/non-polar

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• Acetone is a polar molecule and experiences dipole-dipole and London
forces

• Ethylene glycol, which also has ten atoms, in addition to London

dispersion forces, also participates in hydrogen-bonding.

• Therefore, the viscosity of ethylene glycol is higher than the viscosity of

acetone.

• Likewise the boiling point of ethylene glycol is higher than acetone

because of the presence of hydrogen bonds. 37
 H3C Dipole-dipole H3C
d+ d- forces d+ d-
C O C O
+
H3C Dispersion forces H C
3

RMM = 58.0,
b.p. = 56°C

Dispersion forces

+
RMM = 58.0, H-bonding
b.p. = 197°C

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 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
similar in weights & shapes, differences is due to
different polarity of molecules à 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 à the higher molecular
weight will have greater intermolecular forces
Summary
 Let’s see this….
CH3Cl < CH3Br < CH3I

b.p./°C -24.2 3.56 42.4

• The strength of dispersion forces increases with
molecular size/mass.

• Thus, b.p. increases with molecular size/mass

• Although chloromethane is more polar, the effect of

dispersion forces outweights that of dipole-dipole
forces.

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Let’s see this….
NO < C2H6

b.p./°C -151 -89

RMM 28.0 28.0

C2H6 > NO. It is because

1. C2H6 has a greater molecular size and contact surface
area than NO and thus has stronger dispersion forces
than NO.
2. Although NO is polar, the effect of dispersion forces
outweights that of dipole-dipole forces.

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So far we have discussed 4 kinds of intermolecular
forces: ionic, dipole-dipole, hydrogen bonding, and
London forces.
What kind(s) of intermolecular forces are present in
the following substances:

a) NH3, b) SF6, c) PCl3, d) LiCl, e) HBr, f) CO2

(hint: consider DEN and molecular shape/polarity)

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a) NH3: Hydrogen bonding (H + N), London.
b) SF6: London only (it is symmetrical).
c) PCl3: DEN = 2.9-2.1. Dipole-dipole, London.
d) LiCl: DEN = 2.9-1.0. Ionic, (London).
e) HBr: DEN = 2.8-2.1. Dipole-dipole, London.
f) CO2: London only (it is symmetrical)

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For each of the following pairs, choose the substance with the
higher boiling point. Justify your choice.

i) Pentane, C5H12, or 2,2-dimethylpropane, C5H12.

(3 marks)

ii) Sulphur dioxide, SO2, or carbon dioxide CO2.

(3 marks)

iii) Ammonia, NH3, or phosphine, PH3.

(3 marks)

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