INTERMOLECULAR FORCES

These bonding are usually described as

1. Non-bonding interactions
2. Intermolecular as they exist between molecules

Types of Intermolecular forces

1. London forces (dispersion forces) (instantaneous dipole – induced dipole interaction)

How they arise:
i. Normally electron cloud is symmetrically distributed around a molecule
ii. But electron density fluctuates and becomes unsymmetrical.
iii. Instantaneous dipoles are generated.
iv. It induces dipoles in the neighboring molecule as well.
v. Electrostatic forces of attraction between instantaneous dipole and induced
dipole is called London forces.

Factors which determine the strength of London Force

1. The strength of the London forces depends on the number of electrons a molecule
has; greater the number of electrons, stronger the London forces.
Ex: In halogens London force becomes stronger down the group.
 2. Strength of the London forces depends on the size and the shape of the Molecule.
More point of contact there are between the molecule, stronger the London force.
Ex: straight chain molecule has stronger London force than branched molecule with
the same molecular mass.
3. London forces arise always between any molecules.

PERMANENT DIPOLE- PERMANENT DIPOLE INTERACTION

When molecules have permanent dipoles, they have these interactions.

But molecules do not always align themselves to produce a favorable interaction.

HYDROGEN BOND

• Hydrogen bonds are formed when hydrogen atom is bonded to more electronegative
atom such as F, O and N.
• The interaction between hydrogen atom bonded to more electronegative atom of one
molecule and the lone pair of electrons on more electronegative atom of other
molecule is called hydrogen bonding.
 • The angle between hydrogen atom and oxygen atom in the hydrogen bond should be
180o because hydrogen bond formation is considered to be partial bond formation.
Hence, two bonds around H atom arrange in a linear shape.

Question 1: Draw hydrogen bond formation between ethanol molecules.

Hydrogen bonding through Nitrogen

Hydrogen bonding through Fluorine

Question 2: Explain how it is possible for a hydrogen bond to form between propanone and
trichloromethane.

propanone

trichloromethane
Question 3: Draw a diagram to show hydrogen bonds are formed between two molecules of
ethanoic acid.

Intermolecular interactions and physical properties

1. Boiling point of alkanes increases as the number of carbon atoms increases.

Explanation:
a) As the molecular mass increases, the number of electrons per molecule increases.
So, the instantaneous and induced dipoles also increase.
 b) As the length of the carbon chain increases, the number of points of contact
between the molecules, also increases, thus the greater the overall intermolecular
forces of attraction.

Question 4 : Explain the trend shown in the table.

Gas Helium Neon Argon Krypton Xenon Radon

Boiling 4.3 27.1 87.4 121 165 211
point/K

2. Branched chain alkanes have lower boiling temperatures than their unbranched
isomers.

When a molecule has more branching, fewer points of contact between adjacent molecules
occur, resulting lower intermolecular forces of attraction between molecules.
Question 5: Explain why the fluorine is more electronegative than oxygen and forms stronger
hydrogen bond, water has greater boiling point than HF.

ALCOHOL

Formula Number of Boiling Formula of alkane Number of Boiling

electrons in a temperature electrons in temperatur
molecule /K molecule e/K
CH3OH 18 338 CH3CH3 18 184
CH3CHOH 26 352 CH3CH2CH3 26 231
CH3CH2CH2OH 34 370 CH3CH2CH2CH3 34 267
CH3CH2CH2 CH2OH 42 390 CH3CH2CH2CH2CH3 42 309

When considering two molecules with the same number of electrons, alcohol has greater
boiling point than alkanes.

• For two molecules with the same number of electrons they would have identical London
forces.
• In addition, Alcohol has oxygen attached to hydrogen, hence they have extra hydrogen
bond between molecules.
• A large amount of energy would need to break hydrogen bonds and boiling point
becomes greater.

Question 6: Explain why the boiling point increases with increasing number of carbon atoms.
Enthalpy change of vaporization

A measure of the amount of energy required to completely separate the molecules of a liquid
and convert it into a gas at the same temperature.

Question 7: Suggest why enthalpy change of vaporization increases when the change length
increases in alcohol.

Formula Enthalpy Formula of alkane Enthalpy Approximate

change of change of percentage of
vaporization/ vaporization contribution of
kJ/mol /kJ/mol hydrogen bonding in
alcohol
CH3OH 38.6 CH3CH3 15.7

CH3CHOH 47.5 CH3CH2CH3 21.0

CH3CH2CH2OH 52.4 CH3CH2CH2CH3 26.4

CH3CH2CH2 57.0 CH3CH2CH2CH2CH3 31.6

CH2OH

The calculation above indicates that the predominate bonding in alcohol is always not the
hydrogen bonding. When the chain length increases, London forces become more dominant.
BOILING TEMPERATURE OF THE HYDROGEN HALIDES

• HF has exceptionally high boiling point because of extra hydrogen bond present. A large
amount of energy is needed to break those hydrogen bonds.
• From HCl to HI boiling point increases because number of electrons increases and
henceforth, London forces become stronger.

Question 8: sketch the graph of boiling point against the hydrogen compounds of first four
group 6 elements.
ANOMALOUS PROPERTIES OF WATER

1. It has a relatively high melting and boiling temperatures for a molecule with so few
electrons because the hydrogen bond between water molecules are fairly stronger than
other hydrogen bonds.

Comparison of hydrogen bonds

Molecule Boiling temperature Number of electrons per Strength of hydrogen

molecule bonding/kJ/mol
H2O 373 10 22
NH3 240 10 17
HF 293 10 29

The hydrogen bond strength for HF is greater than hydrogen bond strength for H2O. But its
boiling temperature is lower than that of water molecule.

A. HF can form two hydrogen bonds per molecule whereas H2O can form four hydrogen
bonds per molecule. This means that the hydrogen bonding is much more extensive in
water.
B. Not all of hydrogen bonds in HF are broken on vaporization. HF is substantially
polymerized.
C. Ammonia has the lowest boiling temperature of three molecules. Nitrogen atom has
only one lone pair. There are not enough lone pairs to satisfy all the hydrogen atoms.

2. The density of ice at 0 oC is less than that of water at 0 oC.

The density of solid (ice) is less than the density of liquid water at 0 oC. The molecules of ice
are arranged in rings of six, held together by hydrogen bonds.
ION – DIPOLE INTERACTION

When a salt is dissolved in water,

1. First, energy is absorbed to break the forces of attraction between ions.

2. Then, the new interactions are formed between water molecules and ions. These are
called ion-dipole interactions. Energy is released when these interactions are formed.

For a salt to dissolve, the energy released when ion-dipole interactions formed between
ions and water must be greater than the energy absorbed when ionic bonds are broken in
salt.
Water Solubility Of Alcohols

Alcohol have hydrogen attached to oxygen atom. Therefore, alcohol can form hydrogen
bonds with water.

Solubility of alcohols in water decreases as the chain length increases. Hydrocarbon chain
can not form hydrogen bonds with water. Therefore, required amount of energy cannot
be released to break hydrogen bonds between water molecules and London forces
between alcohol molecules.
Water Solubility Of Non-Polar Molecules

Non-polar molecules cannot form hydrogen bonds with water. Therefore, required amount of
energy cannot be released to break hydrogen bonds between water molecules and London
forces between non-polar molecules

Answer the following questions

1. The hydrides of Group 4 exist as tetrahedral molecules. Explain the following trend in
boiling temperature.
CH4 (112 k)
SiH4 (161 K)
GeH4 (185 K)
SnH4 (221 K)

2. Suggest why water has relatively high surface tension for a molecule of such low
molecular mass.
3. Suggest why magnesium chloride is soluble in water even though the energy required to
break up the lattice is 2494 kJ/mol.

4. Propanone molecule (CH3OCH3) has 32 electrons. A butane molecule (CH3CH2CH2CH3)

has 34 electrons. Explain why propanone has a much higher boiling temperature than
butane.