Topic 7: Intermolecular Forces

Table of Contents
LEARNING OUTCOMES ................................................................................................................................. 1

7.0 INTRODUCTION ................................................................................................................................ 2

7.1 TYPES OF INTERMOLECULAR FORCES ........................................................................................... 2

7.1.1 ION – DIPOLE INTERACTION ........................................................................................................... 2

7.1.2 DIPOLE – DIPOLE .............................................................................................................................. 3

7.1.3 HYDROGEN BONDS ........................................................................................................................... 3

7.1.4 ION – INDUCED DIPOLE INTERACTION .......................................................................................... 4

7.1.5 DIPOLE – INDUCED DIPOLE INTERACTION ................................................................................... 5

7.1.6 LONDON FORCES OR DISPERSION FORCES .................................................................................... 6

Self-Test 7.1.................................................................................................................................................... 8

7.2 EFFECT OF INTERMOLECULAR FORCES ON MELTING AND BOILING POINTS OF MOLECULAR

COVALENT MOLECULE ................................................................................................................................. 8

Self-Test 7.2.................................................................................................................................................... 9

7.3 SUMMARY .......................................................................................................................................... 9

7.4 ADDITIONAL SUPPORTING MATERIALS ...................................................................................... 10

7.5 ANSWERS TO SELF-TESTQUESTIONS ........................................................................................... 10

Learning Outcomes
At the completion of this topic you should be able to:

 Determine the type of intermolecular forces operating between given molecules

 Discuss the relative strength of intermolecular forces
 Differentiate between dipole-dipole and hydrogen bonding
 Explain the mechanics of London forces and relate the strength of London forces to
molecular sizes.
 Explain the effect of intermolecular forces on physical properties such as melting
point and boiling point.

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7.0 Introduction
All matter is held together by force. The force between atoms within molecule is a chemical
or intermolecular force. The force between molecules is a physical or intermolecular force.
The intermolecular forces (forces between molecules) are weaker than intramolecular
forces (the chemical bonds within an individual molecule).

7.1 Types of Intermolecular Forces

Intermolecular forces come in six forms:

1. Ion - dipole
2. Dipole -dipole
3. H-bonding
4. Ion –induced dipole
5. Dipole – induced dipole
6. London forces

7.1.1 Ion – dipole interaction

This is an interaction between an ion and a polar molecule as shown below:

Figure 7.1a: Ion –dipole interation experienced between Na+ and water molecule

Figure 7.1b The ion –dipole interaction with the magnitude of the intermolecular force given.

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7.1.2 Dipole – Dipole
Only polar covalent molecules have the ability to form dipole-dipole attractions between
molecules. Polar covalent molecules acts like little magnets; they have positive ends and
negative ends which attract each other. For example, dipole-dipole interactions occur
between CH3OH and CHCl3 as shown below. The partial positive charge on one molecule is
electrostatically attracted to the partial negative charge on a neighbouring molecule (See
Figure 7.3 and 7.4 respectively).

Figure 7.2: Dipole – Dipole interaction between ICl molecules.

Figure 7.3: Dipole – Dipole interaction between two polar molecules such as CH3OH and CHCl3.

7.1.3 Hydrogen Bonds

It is a special kind of dipole – dipole interaction. If the permanent net dipole within the polar
molecules results from a covalent bond between a hydrogen atom and either fluorine,
oxygen or nitrogen, the resulting intermolecular force is referred to as a hydrogen bond. For
example, hydrogen bonds operate between water (H2O) molecules, ammonia (NH3),
hydrogen fluoride (HF) molecules, hydrogen peroxide (H2O2) molecules, alkanols (alcohols)
such as methanol (CH3OH) molecules, and between alkanoic (carboxylic) acids such as
ethanoic (acetic) (CH3COOH) and between organic organic amines such as methanamine
(methyl amine, CH3NH2).These hydrogen bonds are important in biological systems like
shown in Figure 7.5.

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 Figure 7.4: An illustration of hydrogen bond in DNA molecules.

H-bonding is a special type of dipole -dipole attraction that is very strong, about 5x stronger
than normal dipole-dipole forces. Hydrogen nucleus is extremely small and positively
charged and fluorine, oxygen, and nitrogen being very electronegative so that the electron,
on hydrogen atom is strongly attracted to fluorine, oxygen or nitrogen atom, leaving a
highly localized positive charge on the hydrogen atom and highly negative charge localized
on the fluorine, oxygen, or nitrogen atom. This means the electrostatic attraction between
these molecules will be greater than for the polar molecules that do not have hydrogen
covalently bonded to fluorine, oxygen or nitrogen.

7.1.4 Ion – Induced Dipole Interaction

This intermolecular force exists between an ion and non-polar molecule, whereby the
charge or ion is capable of distorting the electron cloud density of the non-polar molecule
and inducing a dipole moment as shown in Figure 7.6.

Figure 7.5: An illustration of interaction between an ion and non-polar molecule

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 Figure 7.6: An illustration of a charge polarizing a non-polar molecule to induce a dipole moment.

7.1.5 Dipole – induced dipole Interaction

This interaction is similar to ion to induced dipole interaction only it exists between a polar
and non-polar molecule. When the existing dipole moment in the polar molecule
approaches the non-polar molecule then it polarizes the electron cloud and induces a dipole
moment as shown in Figure 7.8 and Figure 7.9:

Figure 7.7: An iluustration of Dipole – induced dipole interaction between a polar and a non-polar
molecule.

Figure 7.8: An illustration of how a dipole in a polar molecule induces a dipole moment in a non-polar
molecule.

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7.1.6 London forces or Dispersion forces
This is the only force of attraction operating between nonpolar - nonpolar molecule.
Dispersion forces exist because the electron clouds of molecules can be distorted. Each
molecule contains positive nuclei surrounded by a cloud of negative electrons. As two
molecules approach, the nucleus of one molecule attracts the electron cloud of the other
(See Figure 7.10 and Figure 7.11).It is also known as Van der Waals or London Forces.

Figure 7.9 An illustration of cloud distortion that results in establishment of temporary dipole
moments that is the basis for weak intermolecular forces.

Figure 7.10: An illustration of weak van der waals forces.

The electron cloud is always constant motion and there is a possibility that at one time the
electrons could be pulled to one side of the atom due to the polarising power of the nucleus
of the adjacent atom. This will cause a temporary dipole moment that is capable of inducing
the dipole moment in the next molecule. This induced dipole – induced dipole interaction
gives rise to the London or dispersion forces (see Figure 7.12). This interaction is momentary
and when the electron cloud move again it breaks this interaction and a new induced dipole
- induced dipole is formed and as a result the dispersion forces are very weak.

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 Figure 7.11: Process involved in the formation of weak van der waals forces between two non-polar
molecules.

The magnitude or the strength of the dispersion forces depends on how easy it is to distort
the electron cloud of a molecule. This ease of distortion is called the polarisability because
distortion of an electron cloud generates a temporary polarity, called an instantaneous
dipole. The periodic trends in polarizability are as follows:

 increases down a group (outer electrons further away)

 decreases across a period (higher Zeff, more tightly held)
 anions are more polarizable than parent neutral atom (lower Zeff)
 cations are less polarizable than parent atom (higher Zeff)

As a general rule of thumb the strength of the dispersion forces increases with number of
electrons present in the molecule. The larger the molecule, the more easily its electron
cloud is distorted to give rise to induce dipole to induced dipole interaction.

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 Self-Test 7.1

Identify the Intermolecular forces operating between the molecules of:

a) CO2
b) HCl
c) HF
d) NH3
e) CH3Cl
f) Cl2
g) H2O and F2

7.2 Effect of Intermolecular forces on melting and boiling points

of molecular covalent molecule
The melting or boiling point of a covalent molecule depends on the progressive weakening
of the attractive forces between the molecules. With the increase in attractive
intermolecular force the boiling and melting point will also increase. Hence the strength of
the intermolecular attraction determines the boiling points. The general trend in the
strength of the intermolecular forces is as follows:

Dispersion forces < dipole-dipole interactions < hydrogen bonds

If only dispersion forces are present, then the more electrons the molecule has (and
consequently the more mass it has) the stronger the dispersion forces will be, so the higher
the melting and biling points will be. Consider the hydrides of Group 14, all of which are
nonpolar molecules, so only dispersion forces act between the molecules. CH 4 (Mr = 16
g/mol), SiH4(Mr = 32 g/mol), GeH4(Mr = 77 g/mol) and SnH4(Mr = 123 g/mol) can all be
considered non-polar covalent molecules. As the mass of the molecules increases, so does
the strength of the dispersion force acting between the molecules, so more energy is
required to weaken the attraction between the molecules resulting in higher boiling points.

If a covalent molecule has a permanent net dipole then the force of attraction between
these molecules will be stronger than if only dispersion forces were present between the
molecules. As a consequence, this substance will have a higher melting or boiling point than
similar molecules that are non-polar in nature.

Consider the boiling points of the hydrides of Group IV elements. All of the molecules HF
(Mr = 20 g/mol), HCl (Mr = 37 g/mol), HBr (Mr = 81 g/mol) and HI (Mr = 128 g/mol) are
polar, the hydrogen atom having a partial positive charge (Hδ+) and the halogen atom having
a partial negative charge (Fδ-, Cl δ-, Br δ-, I δ-). As a consequence, the stronger dipole
interactions acting between the hydride molecules of Group VII elements results in higher
boiling points than for the hydrides of Group IV elements as seen above. With the exception

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of HF, as he molecular mass increases, the boiling point of the hydrides increases. HF is an
exception because of the stronger force of attraction between HF molecules resulting from
hydrogen bonds acting between the HF molecules. Weaker dipole- dipole interaction act
between the molecules of HCl, Hbr and HI. So HF has a higher boiling point than the other
molecules in this series. Although these molecules are polar but as the size of the molecule
increases.

Self-Test 7.2

Which substance has the lower boling point? Explain

a) LiCl or HCl
b) NH3 or PH3
c) Xe or I2

7.3 Summary
 Given below is the summary of all the intermolecular and intramolecular forces
studied in this course and its relative strength of the interaction.

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  The magnitude or the strength of the dispersion forces depends on how easy it is to
distort the electron cloud of a molecule. As a general rule of thumb the strength of
the dispersion forces increases with number of electrons present in the molecule.
The larger the molecule, the more easily its electron cloud is distorted to give rise to
induce dipole to induced dipole interaction.
 The melting or boiling point of a covalent molecule depends on the progressive
weakening of the attractive forces between the molecules. With the increase in
attractive intermolecular force the boiling and melting point will also increase.

7.4 Additional Supporting Materials

1. [Link]
2. [Link]
affect-boiling-points/
3. [Link]

7.5 Answers to Self-TestQuestions

Answer to Self-Test 7.1:

a) Van der Waals forces

b) Dipole – Dipole interaction
c) Hydrogen bonding
d) Hydrogen bonding
e) Dipole – Dipole interaction
f) Van der waals forces
g) Dipole – induced dipole interaction

Answer to Self-Test 7.2:

a) HCl: it has dipole – dipole forces, and there stronger ionic bonds in LiCl.
b) PH3: it has eaker intermolecular forces (dipole-dipole) than NH3 (hydrogen bonding).
c) Xe; it exhibits weaker dispersion forces since its smaller in size resulting in lower
polarizibility than the larger I2 molecules.

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