CHAPTER 1

Intermolecular Forces

DR NORSHAHIDATUL AKMAR MOHD SHOHAIMI

5/13/2019 CHM474 - Topic 3 1

 The aim of this lecture
 Able to define types of intermolecular forces

 Able to differentiate types of intermoleculer

forces.

5/13/2019 CHM474 - Topic 3 2

 • 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

5/13/2019 CHM474 - Topic 3 3

 Properties can be understood in terms of how tightly the
molecules are packed together and the strength of the
intermolecular attractions between them.
5/13/2019 CHM474 - Topic 3 4
 Let ask ourselves these questions….
 Why do some solids dissolve in water but others
do not?
 Why are some substances gases at room
temperature, but others are liquid or solid?
 What gives metals the ability to conduct
electricity, what makes non-metals brittle?
 The answers have to do with …

Intermolecular forces
5/13/2019 CHM474 - Topic 3 5
 Now, we’ll see what is We have already looked at
Intermolecular forces intramolecular bonds (ionic, polar,
(IMF) all about??? non-polar)!!!!!!!
IMF have to do with the attraction
between molecules (vs. the attraction
5/13/2019 CHM474 - Topic 3 between atoms in a molecule) 6
 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.

5/13/2019 CHM474 - Topic 3 7

 Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)

5/13/2019 CHM474 - Topic 3 8

INTERMOLECULAR FORCES

Hydrogen Van der Waals’ Fritz London

bonds forces
(1900−1954).
Johannes van der
Waals (1837−1923).

London Dispersion
Dipole-dipole forces
forces

5/13/2019 CHM474 - Topic 3 9

5/13/2019 CHM474 - Topic 3 10
 Comparison of Energies for Intermolecular Forces
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

5/13/2019 CHM474 - Topic 3 11

 Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction
between they 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 EN of
NH, OH, and HF
bonds cause these
to be strong
forces (about 5x
stronger than
normal dipole-
dipole forces)
2.1 4.0 2.1 3.5 2.1 3.0

5/13/2019 CHM474 - Topic 3 12

 Hydrogen Bond

11.2

5/13/2019 CHM474 - Topic 3 13

Reasons for abnormal strength of H-bond
1. the polarity of H–X bond is great when X is F , O , or
N.

2. H atom does not have inner electrons.

 its nucleus (proton) is partially exposed due

to unequal sharing of electron.

 The partial positive charge on H is so

concentrated that it can come very close
to the lone pair of a small & highly
electronegative atom (F, O or N)

 Abnormally strong dipole-dipole forces

5/13/2019 CHM474 - Topic 3 14

 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.

5/13/2019 CHM474 - Topic 3 15

Tendency of H-bond formation : -

EN 0.4 0.4 0.9 0.9 1.4 1.9

C – H < S – H < Cl – H < N – H < O – H < F – H

No lone N is smaller
pair on C than Cl
H can come
closer

5/13/2019 CHM474 - Topic 3 16

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

All are polar

B.p.  as molecular size  (dispersion > dipole-dipole)

However, H2O, HF and NH3 have abnormally high b.p.
There exist unusually strong dipole-dipole forces (H-bond)
B.p.  as molecular size 
Group 4 hydrides are non-polar, only dispersion forces exist
Dispersion forces  as molecular size .
5/13/2019 CHM474 - Topic 3 18
 H – bonding and boiling point
Predicted and actual boiling points
100
50 Group 4
Boiling point

Group 5
0
-50 Group 6
-100
Group 7
-150
2 3 4 5
-200
Period

 Why does BP as period , why are some BP high at period 2?

5/13/2019 CHM474 - Topic 3 19

  Boiling points increase down a group (as period increases)
for two reasons: 1) EN tends to increase and 2) size
increases. A larger size means greater London forces.

 Boiling points are very high for H2O, HF, and NH3 because
these are hydrogen bonds (high EN), creating large
intermolecular forces

5/13/2019 CHM474 - Topic 3 20

 Let’s try this….

Relative Boiling point

Substance
molecular mass (°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.

5/13/2019 CHM474 - Topic 3 21

 hydrogen bond

Each NH3 molecule has only ONE lone pair.

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

5/13/2019 CHM474 - Topic 3 22

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

5/13/2019 CHM474 - Topic 3 23

 hydrogen bond

Each H2O molecule has TWO hydrogen atoms and TWO

lone pairs.

 On the average, each H2O molecule can form

TWO hydrogen bonds

5/13/2019 CHM474 - Topic 3 24

Hydrogen Bonding & Water

5/13/2019 CHM474 - Topic 3 25

One of the most remarkable consequences of H-bonding is found in
the lower density of ice in comparison to liquid water, so ice floats
on water. In most substances the molecules in the solid are more
densely packed than in the liquid. A given mass of ice occupies a
greater volume than that of liquid water. This is because of an
ordered open H-bonding arrangement in the solid (ice) in
comparison to continual forming & breaking H-bonds as a liquid.
Ice is less dense than water

5/13/2019 CHM474 - Topic 3 26

 Structure and bonding of ice
The lone pairs of
oxygen atom of each
a water water molecule forms
molecule hydrogen bonds with
two hydrogen atoms of
hydrogen nearby water molecules
bond

hydrogen atom
hydrogen
bond
oxygen atom

5/13/2019 CHM474 - Topic 3 27

 The two hydrogen atoms of
each water molecule also
form hydrogen bonds with
the lone pairs of oxygen
hydrogen atoms of nearby water
bond molecules.

hydrogen atom
hydrogen
bond oxygen atom

5/13/2019 CHM474 - Topic 3 28

 Each H2O molecule is bonded
tetrahedrally to four H2O molecules

1
4
2

5/13/2019 CHM474 - Topic 3 29

In solid ice, the tetrahedral arrangement repeats over and
over again, resulting in an open and regular network
structure of water molecules.

Open : the maximum number of

hydrogen bonds can be formed
Regular : all molecules are held in
positions by strong hydrogen
bonds

5/13/2019 CHM474 - Topic 3 30

In liquid state, water molecules pack together more closely
and randomly.

Hydrogen bonds are continuously

formed and broken.

Liquid water takes the shapes of the

containers

5/13/2019 CHM474 - Topic 3 31

 Energy is absorbed to break some of the hydrogen
bonds
Less H-bonds
 less stable
 Close & random

More H-bonds
 More stable
 Open & regular

5/13/2019 CHM474 - Topic 3 32

 Without hydrogen bond, life becomes impossible

hydrogen bonds

5/13/2019 CHM474 - Topic 3 33

 Explain the following.
Water is easily absorbed by tissue paper
rather than forming droplets on it.
Tissue paper is composed of cellulose which is a natural
polymer made of glucose molecules.
Thus, tissue paper can form extensive hydrogen bonds with
water molecules.

5/13/2019 CHM474 - Topic 3 34

 3 types of
dipoles

Permanent Instantaneous Induced

dipole dipole dipole

5/13/2019 CHM474 - Topic 3 35

Van der Waals’ Forces
Van der Waals’
forces

Dipole- Dipole- Instantaneous

Dipole Induced Dipole-
Interaction Dipole Induced Dipole
Interaction Interaction

London dispersion forces

5/13/2019 CHM474 - Topic 3 36

 Weaker Intermolecular Forces
(a) Ion-Dipole Forces
•An ion-dipole force is an attractive
force that results from the electrostatic
attraction between an ion and a neutral
molecule that has a dipole.

•Most commonly found in solutions.

•Especially important for solutions of

ionic compounds in polar liquids.

•A positive ion (cation) attracts the

partially negative end of a neutral polar
Ion-dipole attractions
molecule. become stronger as either
the charge on the ion
•A negative ion (anion) attracts the
partially positive end of a neutral polar
increases, or as the
molecule. magnitude of the dipole of
the polar molecule
5/13/2019 CHM474 - Topic 3 increases. 37
 Continued….
Attractive forces between an ion and a polar molecule

Ion-Dipole Interaction

11.2

5/13/2019 CHM474 - Topic 3 38

 11.2

5/13/2019 CHM474 - Topic 3 39

 (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

5/13/2019 CHM474 - Topic 3 40

Boiling points increase for polar molecules of similar mass, but
increasing dipole:
Molecular Mass Dipole moment, u
Boiling Point (°K)
Substance (amu) (D)

Propane 44 0.1 231

Dimethyl ether 46 1.3 248

Methyl chloride 50 2.0 249

Acetaldehyde 44 2.7 294

Acetonitrile 41 3.9 355

5/13/2019 CHM474 - Topic 3 41

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

Due to electron repulsion, a temporary dipole on

one atom can induce a similar dipole on a
neighbouring atom

Prof. Fritz London

5/13/2019 CHM474 - Topic 3 42

 Continued…
Instantaneous dipole: Induced dipole:

Eventually electrons are A dipole forms in one atom or

situated so that tiny dipoles molecule, inducing a dipole in the other
form

5/13/2019 CHM474 - Topic 3 43

Instantaneous dipole-induced dipole
interactions

5/13/2019 CHM474 - Topic 3 44

Dispersion Forces Continued……..

The ease with which an external electric field can induce a dipole (alter the
electron distribution) with a molecule is referred as the "polarizability" of
that molecule ……
The greater the polarizability of a molecule the easier it is to induce a
momentary dipole and the stronger the dispersion forces …..
Larger molecules tend to have greater polarizability
Their electrons are further away from the nucleus (any asymmetric
distribution produces a larger dipole due to larger charge separation)
The number of electrons is greater (higher probability of asymmetric
distribution)
Thus, dispersion forces tend to increase with increasing molecular
mass. Dispersion forces are also present between polar/non-polar and
polar/polar molecules (i.e. between all molecules)

5/13/2019 CHM474 - Topic 3 45

 Briefly…..
Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud

Dispersion forces
usually increase
with molar mass.

5/13/2019 CHM474 - Topic 3 46

  London forces depend on the number of atoms in the
molecule
• The boiling point of hydrocarbons demonstrates this trend

Formula BP at 1 atm ( o C) Formula BP at 1 atm ( o C)

CH 4 - 161.5 C 5 H 12 36.1
C2H6 - 88.6 C 6 H 14 68.7
C3H8 - 42.1  
C 4 H 10 - 0.5 C 22 H 46 327

5/13/2019 CHM474 - Topic 3 47

 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

5/13/2019 CHM474 - Topic 3 48

1. Size of Molecule Sometimes !
Molecule Boiling point Rel.
Sizemolecular
of molecule
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 
5/13/2019 CHM474 - Topic 3 49
 • Hexane, C6H14, (right) has a BP of 68.7oC while the
BP propane, C3H8, (left) is –42.1oC because hexane
has more sites (marked with *) along its chain where
attraction to other molecules can occur.

5/13/2019 CHM474 - Topic 3 50

 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

SO2 is a polar molecule: dipole-dipole forces. There are

also dispersion forces between SO2 molecules.
5/13/2019 CHM474 - Topic 3 51
  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
• Presumably this is because the hydrogen on
neopentane cannot interact as well as those on n-
pentane with neighbouring molecules

5/13/2019 CHM474 - Topic 3 52

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.

5/13/2019 CHM474 - Topic 3 53

 Both are non-
polar
Same no. of
electrons

 For example the more compact neopentane molecule

(CH3)4C has a lower boiling point than n-pentane,
CH3CH2CH2CH2CH3

 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.

5/13/2019 CHM474 - Topic 3 54

 rod-shaped spherical in shape

pentane molecules
larger contact area 2,2-dimethylpropane molecules
smaller contact area
5/13/2019 CHM474 - Topic 3 55
Pentane (C5H12)

Boiling point
= 36.1C

Larger contact surface area

 Higher chance of forming induced dipoles
 stronger dispersion forces

5/13/2019 CHM474 - Topic 3 56

2,2-dimethylpropane
(C5H12)
Boiling point
= 9.5C

Smaller contact surface area

 lower chance of forming induced dipoles
 weaker dispersion forces

5/13/2019 CHM474 - Topic 3 57

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

5/13/2019 CHM474 - Topic 3 58

 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.

5/13/2019 CHM474 - Topic 3 59

 H3C Dipole-dipole H3C
+  forces + 
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

5/13/2019 CHM474 - Topic 3 60

  The boiling point of a liquid can be defined as the
temperature at which the vapor pressure of the liquid is equal
to the prevailing atmospheric pressure
 The normal boiling point is the temperature at which the
vapor pressure is 1 atm
 Molecules with higher intermolecular forces have higher
boiling points

5/13/2019 CHM474 - Topic 3 61

 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.

5/13/2019 CHM474 - Topic 3 62

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.

5/13/2019 CHM474 - Topic 3 63

 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)
Oh my
GOD……

5/13/2019 CHM474 - Topic 3 64

5/13/2019 CHM474 - Topic 3 65
 1. a) Which would have a lower boiling point: O2 or F2? Explain.
b) Which would have a lower boiling point: NO or O2? Explain.

2. Which would you expect to have the higher melting point (or
boiling point): C8H18 or C4H10? Explain.

3. 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 EN and molecular shape/polarity)

4. Ethanol (CH3CH2OH) and dimethyl ether (CH3OCH3) have the

same formula (C2H6O). Ethanol boils at 78 C, whereas
dimethyl ether boils at -24 C. Explain why the boiling point of
the ether is so much lower than the boiling point of ethanol.
5/13/2019 CHM474 - Topic 3 66
1. (a) F2 would be lower because it is smaller. Larger atoms/molecules
can have their electron clouds more easily deformed and thus have
stronger London attractions and higher melting/boiling points.
(b) O2 because it has only London forces. NO has a small EN, giving
it small dipoles.
2. C8H18 would have the higher melting/boiling point. This is a result of
the many more sites available for London forces to form.
3. a) NH3: Hydrogen bonding (H + N), London.
b) SF6: London only (it is symmetrical).
c) PCl3: EN=2.9-2.1. Dipole-dipole, London.
d) LiCl: EN=2.9-1.0. Ionic, (London).
e) HBr: EN=2.8-2.1. Dipole-dipole, London.
f) CO2: London only (it is symmetrical)
4. In ethanol, H and O are bonded (the large EN results in H-bonding).
In dimethyl ether the O is bonded to C (a smaller EN results in a
dipole-dipole attraction rather than hydrogen bonding).
5/13/2019 CHM474 - Topic 3 67
 The world
gave u
problems
Becoz u r the
only 1 who
can solve it..

5/13/2019 CHM361 - Topic 1 68

 Any
questions???

5/13/2019 CHM474
CHM361
- Topic
- Topic
3 1 69