Chapter 4 & 14:

Chemical Bonding
& Structure

Intermolecular
Forces
 Intermolecular Forces

The physical properties of molecular

substances result from different types of
forces between their molecules.
1. Intermolecular forces include London (dispersion) forces, dipole-dipole
forces and hydrogen bonding.

2. The relative strengths of these interactions are London (dispersion)

forces < dipole-dipole forces < hydrogen bonds.
 Covalent bonding &
structures
• Covalent bonding leads to the formation of separate (discrete)
molecules.
 Covalent bonds inside the molecules are strong.
 Forces between the molecules are weak.

• So what are the forces that exist between these molecules, the so-
called intermolecular forces?
 it depends on polarity & size of the molecules involved,
 intermolecular forces will vary for different molecules.
 Attractive forces
• In covalent structures, there are two types of attractive forces:
1. Strong covalent bonds (within the molecule)
 affects chemical properties of substance

2. Weak forces of attraction (between molecules)

 affects physical properties of substance

• The strength of intermolecular forces determines

the physical properties of a substance. E.g.

1. conductivity
2. melting /boiling point
3. solubility
4. surface tension
5. Volatility

All the above physical properties can all be predicted and explained
from knowledge of the nature of the forces between molecules.
 Types of intermolecular
forces

https://www.youtube.com
/watch?v=VdZ7drbufZQ

The relative strengths of these intermolecular forces:

London (dispersion) forces < dipole-induced dipole < dipole-dipole
forces < hydrogen bonds.
 Types of intermolecular
https://www.youtube.com
forces
/watch?v=pPnspQUyYXY
 London (dispersion) forces
1. London dispersion forces
– very weak, short range forces
– instantaneous (temporary) induced dipole – induced dipole
attractions
• Present between atoms of noble gases and non-polar molecules.
 These forces are also present in polar molecules with dipole-dipole
forces.

• Non-polar molecules such as Cl2, N2 have no permanent separation

of charge within their bonds because the shared electrons are pulled
equally by the two atoms  they do not have a permanent dipole.
 London (dispersion) forces
At any instant, the He atom B with
He atom B can a dipole formed
become polar  is now able to
an excess of influence an
electrons on the uneven electron
left side & less distribution in
He atom A He atom B electrons on the He atom A He atom B He atom A
right side. (polarization).

Instantaneous
dipole is formed Induced dipole is
on He atom B formed on He
atom A
He atom A He atom B He atom A He atom B

• As a result, weak forces of attraction, known as London (dispersion)

forces, will occur between opposite ends of these two temporary
dipoles in the He atoms.
• These are the weakest form of intermolecular force.
 London (dispersion) forces
• Factors that affect the strength of London (dispersion) forces:
1. Atomic /Molecular size (weight)
2. Shape of molecule

• The molecules increase in size  a greater number of electrons 

electrons are further away from the nucleus and hence are less strongly
attracted
 electron cloud can be distorted increasingly easily – polarizability of
the bond increases
 size of the induced dipole also increases.
 Stronger and more extensive London (dispersion) forces.
 boiling points increase down the group for group 17 & 18.
London (dispersion) forces
 London (dispersion) forces
• Below shows the different structures of the same organic molecule
(isomers), pentane (C5H12):

• All 3 structures (I, II & III) have the same molecular formula but
different boiling points. Why?
Shape is
(I) Shape is (II) (III)
linear & long
branched
& compact

• Shapes that are branched & compact  a smaller contact area for
adjacent molecules to interact whereas
• Shapes that are long & linear  greater contact area
• Greater contact (surface) area  stronger London (dispersion)
forces  Higher boiling point
London (dispersion) forces
 London (dispersion) forces
• London (dispersion) forces are
responsible for the soft and Weak London
slippery properties of graphite. (dispersion) forces
between layers

• London (dispersion) forces of

attraction also account for the
deviations of the noble gases &
the halogens from ideal gas
behaviour (Chapter 1).

• They are also partly responsible

for the solubility of covalent
compounds, especially organic
compounds, in organic solvents.
 Dipole – dipole forces
2. Dipole – dipole forces of attraction
• occurs between polar molecules with permanent dipoles. It is also known
as permanent dipole-dipole forces.

• Polar molecules such as hydrogen chloride (HCl), have a permanent

separation of charge within their bonds  difference in electronegativity
between the bonded atoms (H & Cl).

• One end of the molecule is electron deficient with a partial positive charge
(+), while the other end is electron rich with a partial negative charge (–) 
known as a permanent dipole.
 opposite charges on neighbouring molecules attract each other,
generating a force known as a dipole–dipole attraction.
 Dipole – dipole forces
• Dipole–dipole forces are only effective when the polar molecules are
very close together, in the solid and liquid states.

• They are very weak in comparison to ionic or covalent bonds.

• The strength of a dipole–dipole force depends on the size of the

dipole moment of the molecule involved.
 The larger the dipole moment, the more polar the molecules
 greater the strength of the dipole–dipole force.
 Higher boiling point
Dipole – dipole forces
All the molecules
have similar Mr
 Dipole – dipole forces
Polar molecules have both London (dispersion) & dipole-dipole forces.
Which Have a Greater Effect: Dipole-Dipole or London (dispersion) forces?

1. If two polar molecules are of comparable size & shape,

 dipole-dipole forces will likely be the dominating force.

2. If one polar molecule is much larger than the other,

 London (dispersion) forces will likely determine its physical
properties.
• HCl molecule is the most polar as Cl is most electronegative
 Boiling point should be highest
 But its b.p. is the lowest. Why?
• HCl is the smallest molecule weakest London forces
• London forces > significant than dipole-dipole forces
 Dipole – dipole forces
How to explain the trend in boiling points of
the 2 groups of molecules shown on the left?

1. Group of (CH4, SiH4, GeH4, SnH4)

• Hydrides of Group 14 elements
• Non-polar molecules
• London (dispersion) forces ↑
as molecular size ↑
 Boiling point ↑

2. Group of (H2O, H2S, H2Se, H2Te)

• Hydrides of Group 16 elements
• Polar molecules
• Molecular sizes are different
*b.p. of H2O is exceptionally high • London (dispersion) forces ↑
Why? as molecular size ↑
 Boiling point ↑ Electronegativity
values
 Hydrogen bonding
• When a molecule contains hydrogen covalently
bonded to a very electronegative atom (fluorine,
nitrogen, or oxygen), these molecules are attracted to
Electronegativity values of each other by a particularly strong type of
some common elements: intermolecular force called a hydrogen bond.

• hydrogen bond is a particular case of dipole–dipole

attraction.

 The large electronegativity difference between H

& the bonded F, O & N results in the shared
electron pair being pulled away from the H.
 H atom in the molecule now exerts a strong
attractive force on a lone pair in the
electronegative atom of a neighbouring molecule
 This is the hydrogen bond.

• Hydrogen bonds are the strongest form of

intermolecular attraction
 Hydrogen bonding

*When drawing hydrogen bonding, it is important to show:

1. the lone pairs of electrons on the electronegative atom (F, O, N)
2. The H bonds drawn with dotted lines NOT solid lines.
 Hydrogen bonding
https://www.youtube.com/watch?v=m-v5G8C70pc

Each H2O molecule forms 2 H-

bonds with 2 other H2O
molecules  forms a network
of tetrahedral structure.

Thus water in solid

state (ice) has a cage-
like “open” structure
due to H-bonds.
 Hydrogen bonding

• From the graph, water, ammonia & hydrogen fluoride have

abnormally high boiling points.
 strong forces must exist between molecules of these
substances
 hydrogen bonds (very strong permanent dipole-dipole forces)
 Hydrogen bonding
• Alcohols e.g. ethanol, propanol can also form hydrogen
bonds with each other. Thus it has a higher boiling point
than other organic molecules of the same molecular mass.
substance Molecular mass Boiling point /oC Main forces of attraction
Ethanal (C2H4O) 44 20.8 Dipole-dipole forces
Ethanol (C2H5OH) 46 78.0 Hydrogen bonding

Ethanol Ethanal

H atom of one ethanol Hydrogen atom of the ethanal

molecule can form a H- molecule CANNOT form a H-
bond with the O atom of bond as it is NOT directly
another ethanol molecule bonded to the electronegative
O atom.
 Hydrogen bonding

• Comparing boiling points of ethanol and methanoic acid.

substance Molecular mass Boiling point /oC Main forces of attraction

Ethanol (C2H5OH) 46 78.0 Hydrogen bonding
methanoic acid 46.03 101 Hydrogen bonding
(HCOOH) (stronger)

• The hydrogen bonding between the methanoic Electrons are

drawn towards
molecules is relatively strong owing to the the double
bonded oxygen
electron-withdrawing effect of the carbonyl
group (C=O)  increases the size of the positive
charge on the hydrogen atom of the −OH group.
• This effect is not present in alcohols and hence
carboxylic acids form stronger hydrogen bonds
Methanolc acid
compared to alcohols (of similar molar mass).
 Hydrogen bonding

• Carboxylic acids (organic acids) can also form

hydrogen bonds with each other. Each molecule can
form 2 hydrogen bonds with each other  forming a
dimer.

Hydrogen bond is formed

between a partially positive
H atom & a lone pair on the
partially negative O atom.

• The dimer formed with 2 carboxylic acids joined together is very stable.
 Hydrogen bonding
Effect of hydrogen bonding on the solubility of simple covalent
compounds:

• In general, simple covalent compounds are insoluble in water.

• However, ammonia (NH3), amines (R–NH2), alcohol (R–OH, e.g.
ethanol) & carboxylic acids (R–COOH, e.g. ethanoic acid) are soluble
in water because these molecules can form hydrogen bonds with
water molecules.

polar bond
Hydrogen bonding
• Carboxylic acids (organic acids) form H-bonds
with many water molecules.

• Carboxylic acids with 1–4 carbon atoms are very

soluble in water.

• As no. of C atoms ↑, solubility ↓.

 Hydrogen bonding
1. Intramolecular hydrogen bonding
 hydrogen bonds formed within the molecule

2. Intermolecular hydrogen bonding

 Hydrogen bonds
formed between
molecules.
 Hydrogen bonding in
biological molecules
• Hydrogen bonding can occur between many biological molecules
and water.

• Hydrogen bonding can also occur between two biological

molecules or within the biological molecule.

• E.g. DNA relies on

H-bonding to hold
the double helix
together.
 Hydrogen bonding in
biological molecules
• Primary structure of proteins
consists of a long chain of amino
acids joined together
(polypeptides)

• Secondary structures of proteins

e.g. α helix & β pleated sheet are
produced due to hydrogen bonds
formed between the amine
group (-NH2) and carboxyl group
(-COOH) of the protein molecule.

• polypeptides turn or fold upon

itself as a result of hydrogen
bonding. This results in a more
stable and robust structure than
a straight chain.
 Ion – dipole forces
• Ion-Dipole forces are intermolecular forces that occur between an ion
and a polar molecule (containing a dipole moment).

• They are attractive forces between the opposite charges of the ion and
the polar molecule.

• The strength of ion-dipole forces depends on:

1. magnitude of the polar molecule or
2. strength of the charge of the ion
 Ion – dipole forces
• Ion – dipole forces are mostly found in solutions. It is important for
solutions of ionic compounds in polar liquids (water).

• The strength of these forces is what makes it possible for ionic

compounds to dissolve in polar solvents.

• When ionic compound e.g NaCl dissolves in water,

its ions separate  water molecules (polar, with
dipoles) attract the ions (ion-dipole forces) more
than ions attract each other.
 “shells of water molecules” cluster around the
ions (solvation spheres)
 Induced dipole forces
Other intermolecular forces include:
3. Ion-induced dipole
 is a weak attraction between an ion and a non-polar molecule
/atom
 the approach of an ion induces a dipole in a non-polar molecule
/atom

4. Dipole-induced dipole
 is a weak attraction between a polar molecule & a non-polar
molecule
 Van der Waals forces
• The umbrella term van der Waals’ forces is used to include:

1. London dispersion forces

2. dipole–dipole attractions
3. dipole–induced dipole.

• In other words, van der Waals’ forces refers to all forces between
molecules that do not involve electrostatic attractions between
ions or bond formation.

• We can summarize this as follows:

 Strengths of types of
intermolecular forces
Relative strength of the various types of bonds &
intermolecular forces:

strongest Chemical Bonds

(covalent/ionic/metallic)

Hydrogen Bonds

Dipole-Dipole Forces

weakest London (Dispersion) Forces

Summary
 Summary

Non-polar
Polar molecules
Polar molecules molecules
with N, O, F atoms
with water
molecules

Hydrogen bonding
 Explaining physical
properties – Solubility
1. Solubility
• Polar substances & ionic compounds are soluble in
polar solvents
• non-polar substances are soluble in non-polar
solvents  like dissolves like.
Energy is needed to
overcome the forces
of attraction • The process of dissolving is related to the forces of
between particles in attraction between the solute & solvent particles.
the solute & solvent

1. Forces between the solute particles are

overcome. (energy absorbed)

But energy is 2. Intermolecular forces between the solvent

released when particles are also overcome. (energy absorbed)
water
molecules are
attracted to
3. Attraction occurs between the particles of the
these solute solute & solvent  particles are rearranged to
particles form a homogeneous solution. (energy
released)
 Explaining physical
properties – Solubility
1. Solutes (ionic compounds /polar molecules) dissolving in water

2. Solutes (ionic compounds /polar molecules) 3. Solutes (non-polar molecules) mixing with
mixing with non-polar solvent polar solvent
 Explaining physical
properties – Solubility
a) Solubility of ionic compounds in water:
• most ionic compounds are soluble in water.

• due to ion-dipole forces formed between ions & the polar water
molecules.

• The greater the charge /& smaller the size of the ions, the
greater electrostatic forces of attraction between the oppositely
charged ions in the ionic compounds, solubility decreases.

https://www.youtube.com/
watch?v=NIuf0bFrFY8
 Explaining physical
properties – Solubility
Non-polar b) Solubility of polar covalent compounds in water:
• E.g. HCl, NH3, C2H5OH, CH3COOH

• due to hydrogen bonding formed between

polar molecules & water molecules  able to
overcome the dipole-dipole forces between
the polar molecules.

• For organic polar molecules like alcohols &

carboxylic acids, the bigger the non-polar part
of the molecule, the lower the solubility.
 Explaining physical
properties – Solubility
c) Solubility of non-polar covalent compounds in
non-polar solvents:
• Non-polar covalent compounds are not
soluble in polar solvents e.g. water but are
soluble in non-polar solvents.

• Non-polar solute dissolves in non-polar

solvents due to London (dispersion) forces
formed between them can overcome the
weak intermolecular forces of attraction
between the non-polar solute.
The interface between water
& tetrachloromethane
*water &
tetrachloromethane
are immiscible
 Explaining physical properties
– Melting /boiling point
2. Melting & boiling points
• Strengths of intermolecular forces of attraction affect melting &
boiling points of simple covalent structures.

• For melting /boiling to occur, intermolecular forces of attractions

must be overcome.
 the stronger the forces of attraction, the greater the amount of
energy absorbed to overcome the forces
 the higher the melting & boiling point.
 Explaining physical properties
– Melting /boiling point

C5H12

C5H12

C5H12

C2 H 6 O

C2 H 6 O

Non-polar

Polar

Polar
 Explaining physical
properties – Viscosity
3. Viscosity
• Resistance of a liquid to flow is called viscosity.

• It is related to the ease with which molecules can

move past each other.

• Viscosity increases with stronger intermolecular

forces (larger molecules) & decreases with higher
temperature.
Summary of physical
properties