INTERMOLECULAR FORCES

This chapter answers:

Lesson 7: How do intermolecular forces affect the properties
of molecular covalent substances?
Lesson 8: How do structures of synthetic polymers relate to their properties
and uses?

Iodine, 12, water, H2O, and carbon dioxide, CO2, are molecular
covalent substances At room temperature and ordinary sea level air pressure,
iodine is a solid, water is a liquid and carbon dioxide is a gas. At 0°C, water
freezes while the freezing temperature of carbon dioxide is -78.5°C.

All molecular substances will condense to a liquid at a sufficiently low

temperature and freeze at even lower temperatures. When a liquid is cooled,
the average energy of the molecules decreases, the molecules slow down.
When the temperature is sufficiently low, at the freezing point of the
substance, the attractive forces overcome the energy the molecules and draw
the molecules closer together. The attractive forces also cause them to
arrange themselves into the regular pattern that characterizes the solid.

This characteristic of molecular substances to condense to a liquid and

freeze to a solid at sufficiently reduced temperatures is an indication that
intermolecular forces, forces between molecules, exist between molecules.
Different substances freeze at different temperatures, an indication that the
strength of these forces vary among substances. This chapter consists of
lessons that will describe the different intermolecular forces and how they
affect the properties of molecular covalent substances and will describe the
structure and properties of polymer solids.

LESSON 7: How do intermolecular forces affect the properties of

molecular covalent substances?

The strength of interaction between molecules determines the

properties of a substance like its physical state at a given temperature. The
interaction between water is in the liquid state and iodine is a solid.

Indicators of Strength of Intermolecular Forces

Intermolecular forces (IMF) are forces of attraction that exist between

molecules in a compound. These attractive forces are weaker than the
intramolecular forces (covalent bonds). Intramolecular forces influence the
chemical properties of substances while intermolecular forces affect the
physical properties of substances.

Some substances tend to evaporate more readily than others. This

property is called volatility. For example, acetone, CH3COCH3, is more
volatile than ethanol, CH3CH2OH. In acetone the intermolecular forces are
weaker compared to those in ethanol, thus at the same temperature, more
acetone molecules in the liquid state are able to overcome the intermolecular
forces and go to the gaseous state.
 Have you noticed beads of water on some leaves after a rain? The
formation of these beads arise from the forces of attraction between water
molecules. In the bulk of a liquid, each molecule is surrounded by other
molecules and is attracted to all of them and is, therefore, pulled equally in all
directions by the surrounding molecules. At the surface of the liquid, however,
the water molecules experience an imbalance of forces because they are only
pulled inwards by the molecules underneath the surface. This imbalance of
forces at the surface layer of the liquid causes the liquid surface to contract
and to resist being stretched or broken. The surface is under tension hence
the term surface tension given to this property of liquids. This surface tension
results in the formation of beads of water on waxy surfaces like some leaves
or on a waxed floor or counter top. This surface tension also allows small
objects like an insect or a paper clip to float on the surface of water. When an
object is on the surface of the liquid, the surface under tension behaves like
an elastic membrane allowing some object to float.

Have you tried pouring condensed milk from its can? How about
evaporated milk? Condensed milk flows very slowly compared to evaporated
milk. The resistance to flow, to movement or to change in shape is called
viscosity. A liquid, like condensed milk, is more viscous when the
intermolecular forces of attraction are stronger within the liquid.

Types of Intermolecular Forces

There are three types of intermolecular forces that exist in neutral

molecules. They are collectively known as van der Waals forces, after the
Dutch physicist Johannes Diderik van der Waals (1837-1923) who made an
extensive investigation on the weak forces between molecules. The three
types of van der Waals forces are: London dispersion force; dipole-dipole
interaction; and hydrogen bonding.

Dipole-Dipole Interaction
Dipole-dipole interaction occurs between polar covalent molecules. A
polar molecule has a partial positive (8+) charge on one end and a partial
negative (8-) on the other, forming a dipole (having two electrically charged
poles). The partial positive charge on one molecule is attracted to the partial
negative charge on another molecule. Figure 7.1 illustrates dipole-dipole
interaction between molecules.

Figure 7.1 Dipole-dipole interaction (represented by dotted lines) in polar

molecules

van der Waals interaction: Induced dipoles caused by charge fluctuations

 Some examples of dipoles are HCl, NH3, and CHCl3. The structural
formulas of these molecules are represented below:

Can you identify where the negative end of each molecule is located?
You are correct! The negative end in each molecule is as follows: on the side
of Cl in HCl, on N in NH and in any of the Cl atoms in CHCl3.

Polar molecules are considered as permanent dipoles because the

polarity of the molecules are unchanging. The more polar the molecules, the
stronger are the dipole-dipole forces between them.

London Dispersion Forces

Hydrogen, oxygen, nitrogen, and helium are all gases at room
temperature. This means that their boiling points are very low and indicates
that the intermolecular forces in these substances are very weak. These
substances are nonpolar and therefore there are no dipole-dipole interactions
between the molecules of these substances. What is the nature of the
attractive force in these substances?

A nonpolar molecule, like the oxygen molecule, has no permanent

negative end and positive end. However, the electrons in the molecule are in
constant motion and at one instant more of them may be located at one end
of the molecule making that end more negative than the other end, forming
what is called an instantaneous dipole. At this instant, electrons in a
neighboring molecule will be induced to move closer to the positive end of the
neighboring molecule, creating an induced dipole (see Figure 7.2). An
instantaneous attraction between the molecules is formed. This instantaneous
dipole-induced dipole interaction is called London dispersion forces.
Figure 7.2: Dispersion forces in O, molecules (A) The molecules have
symmetrical charge distribution. (B) A temporary dipole in the second
molecule is formed due to random electron movement. (C) The temporary
dipole induces dipoles in other molecules. The attraction between induced
dipoles is the dispersion forces.

This interaction was first proposed by Fritz London (1900-1954), an

American physicist, in 1930. London suggested that the constant motion of
electrons in an atom or molecule can create an instantaneous dipole which
induces instantaneous dipoles in neighboring molecules. The interaction
between these instantaneous dipoles, the London dispersion forces, exist in
all substances, polar or nonpolar. In nonpolar substances, this is the only type
of intermolecular force present.

London dispersion forces are stronger, between bigger atoms or

molecules. Bigger atoms or molecules contain more electrons, making it
easier for them to form temporary dipoles and also resulting into more polar
instantaneous dipoles. Thus, dispersion forces with increasing molecular
mass as seen among the noble gases. Radon, with the highest molecular
mass has the strongest London forces and consequently the highest boiling
point in the series.

Table 7.2 Boiling point of noble gas

Figure 7.2: Dispersion forces in O, molecules (A) The molecules have

symmetrical charge distribution. (B) A temporary dipole in the second
molecule is formed due to random electron movement. (C) The temporary
dipole induces dipoles in other molecules. The attraction between induced
dipoles is the dispersion forces.

Neon gas consists of nonpolar atoms. Hydrogen fluoride consist of polar

molecules. gas The neon atom has ten electrons as does the hydrogen
fluoride molecule. Thus the strength of the London dispersion forces in the
two substances are about the same. Hydrogen fluoride, however, is polar and
therefore, in addition to London dispersion forces, there are dipole-dipole
forces between the molecules. The van der Waals forces, the total
intermolecular forces, therefore, between molecules in hydrogen fluoride are
stronger than those between the neon atoms. We expect hydrogen fluoride to
have a higher boiling point than neon. As observed, the boiling point of
hydrogen fluoride is 19.5 °C while that of neon is -246.1 °C.
Hydrogen bond
A hydrogen bond is a strong type of dipole-dipole interaction existing
between molecules containing hydrogen bonded to a highly electronegative
atom - nitrogen, oxygen, or fluorine. It is the strongest of the van der Waals
forces.
In order to show the strength of hydrogen bonds compared to ordinary
dipole-dipole interactions, consider Figures 7.3. It shows that the boiling
points of hydrides of Group 14 increase down the group, from CH4 to SnH4.
Since these substances are all nonpolar, only London dispersion forces are
present. London dispersion forces increase down the group, from CH4 to
SnH4, following the increase in molecular mass in this series.

Figure 7.3: Boiling points of hydrides of:

Group 14 (Carbon Family).
Group 15 (Oxygen Family),
Group 16 (Nitrogen Family).
Group 17 (Flourine Family)

The trend observed in the Group 14 compounds is not followed by the

hydrides of the elements in Groups 15, 16, and 17.
The boiling point of the hydride of the first element, the one with the
lowest molecular mass in the series, in each of the Groups 15, 16 and 17 is
very high. There is a strong intermolecular force in NH3, H2O, and HF that
makes their molecules harder to separate from each other. This strong
intermolecular force is the hydrogen bond. The electrical nature of molecules
of a substance determines the intermolecular forces existing between them.
To determine the type of interaction in a substance, the compo sition of the
substance should be considered. Figure 7.4 shows the flowchart which you
can use to determine the kind of interaction between particles in a substance.

Figure 7.4: Flowchart of the types of Intermolecular forces

Hydrogen Bonds and Properties of Substances

Hydrogen bonding strongly affects the properties of water. In fact,
hydrogen bonding gives water its unique properties. Oxygen is a very
electronegative atom. The unequal sharing of electrons in the bond between
hydrogen and oxygen creates a dipole with hydrogen having a partial positive
charge and oxygen a partial negative charge. The hydrogen of one molecule
is attracted to the electronegative oxygen of nearby water molecules. Figure
7.5 illustrates the hydrogen bonding in water molecules. The unique
properties of water attributed to hydrogen bonds between water molecules
include: high boiling point, low density of ice, and high surface tension. At sea
level, the boiling point of water is 100°C and for a small molecule (having a
low molecular weight), this is relatively high. The hydrogen bond between
water molecules makes it harder to separate the individual molecules from

each other, resulting in a higher boiling point.

Figure 7.5: Hydrogen bonds (represented by dotted lines) in water molecules
 The floating of ice on water is an indication that ice has lower density
than water. As water freezes, the strong hydrogen bonds between molecules
allow the molecules to form a rigid and stable open-cage structure (see Figure
7.6), and keeps the water molecules in ice at a greater distance from each
other compared to their distances in the liquid state. This structure results in
ice occupying a greater volume which in turn results in a lower density
compared to the liquid state.

Figure 7.6: Open-cage structure of ice

Some insects like the water stryder can float in water (see Figure 7.7)
due to the high surface tension in water as a result of the hydrogen bonds
present. Similarly the formation of beads on some waxy leaves is also due to
the strong surface tension of water arising from the strong hydrogen bonding
between molecules.
Figure 7.7: (a) An insect on the surface of the water (b) Water droplets on a
leaf as a result of surface tension

Hydrogen bonding plays a major role in the structure, and therefore the
function, of several of the most important classes of biological molecules like
proteins and nucleic acids. DNA (deoxyribonucleic acid), a very important
biological molecule which provide instructions for the construction of cell
components such as proteins, is a double-stranded molecule with
complementary units called base pairs. The strands carry four s of molecules
called bases. Hydrogen bonds between complementary bases hold types the
two strands together to form the helical structure of DNA (see Figure 7.8). Its
main function is to store genetic information. Hydrogen bonds form between
the bases C and G. and A and T. The huge number of hydrogen bonds hold
the strands together effectively and gives the DNA a helical shape. This
structure is known as the double helix.

Figure 7.8: Portion of DNA double helix showing the complementary

base pairs and the hydrogen bonding
 Proteins are made up of long chains of amino acids. Each protein must
have the correct sequence of amino acids and must be folded in a specific
three-dimensional structure in order to carry-out its function. The folding of the
proteins is due to hydro- gen bonding. Figure 7.9 shows the two secondary
structures of protein, the alpha helix and the beta-pleated sheet. Keratin, hair
protein, has large amounts of alpha helix while wool has plenty of beta-
pleated sheets.

Figure 7.9: Secondary structures of protein showing the hydrogen bonds

LESSON 8: How do structures of synthetic polymers relate to their

properties and uses?

Polymers are high molecular weight materials formed from smaller

units called monomers. These monomers are bonded to each other with
covalent bonds to form a polymer. They have high molecular weight and
consist over 10,000 atoms. The natural polymers found in living things include
nucleic acids, carbohydrates, and proteins. Deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA) define life. Starch and cellulose, called
polysaccharides, are polymers of glucose. Spider silk, hair, and horn are
protein polymers.

The first synthetic manufactured polymer was Bakelite, created in 1909

for telephone casing and electrical components. The first manufactured
polymeric fiber was Rayon, from cellulose, in 1910. Nylon was invented in
1935 while pursuing a synthetic spider silk.
The terms polymer and plastic are sometimes used interchangeably but there
is a fine distinction between them. A polymer can be either natural or
synthetic. Plastics are synthetic, man-made materials that incorporate a
polymer in its composition. Synthetic plastics, DNA, cellulose from wood and
other natural products are all polymers. "Plas- tic" infers plasticity and gets its
name from the Greek words "plastikos" and "plastos." meaning "fit for
molding" and "molded." Some common plastics are PET (polyethylene
terephthalate) used in soda bottles, HDPE (high density polyethylene) used in
deter- gent bottles, yogurt tubs, hard hats, PVC (polyvinyl chloride) used in
plastic pipes, out- door furniture and PS (polystyrene) used in meat trays, to-
go "clam-shell" containers.

Biomaterials
Biomaterials are natural or synthetic materials that make up whole or
part of a living structure or biomedical devices that perform, augment, or
replace natural functions of a living system. They are used in many blood-
contacting devices like artificial heart valves, synthetic vascular grafts, drug-
release systems, orthopedic implants, a wide range of invasive treatments
and diagnostic systems.

Figure 8.1: Examples of biomaterial

The most common classes of biomaterials are polymers, metals, and

ceramics. They are used singly or in combination to form the biomaterials that
are being used today. There are a large number of polymers that have
assumed an important role in med- ical application this is due to their unique
properties such as flexibility, resistance to biochemical attack, good
biocompatibility (acceptance of an artificial implant by the surrounding tissues
and by the body as a whole), lightweight, available in a wide variety of
compositions having adequate physical and mechanical properties, and ease
in man- ufacturing the products with desired shape. One of the major classes
of polymer used as biomaterial is polytetrafluoroethylene (PTFE),
commercially known as Teflon. It has a carbon backbone chain where each
carbon has two fluorine atoms attached to it, as shown in the structure below.
Figure 8.2: Chemical structure of PTFE

Due to the nonpolar character of PTFE molecules they are hydrophobic

(water-hating). The molecules have strong carbon-fluorine bond making them
biologically inert (chemically stable). They are nonbiodegradable, highly
crystalline and slippery; and have low friction characteristics, low modulus of
elasticity, low tensile strength but with very high density. PTFE can be
produced in various forms such as pastes, rubes, strands, and sheets. PTFE
can be woven into porous fabric like mesh, making it ideal for medical devices
like vascular grafts. Once implanted in the body, the mesh allows the tissue to
grow into its pores. However, PTFE has relatively low wear resistance and
under under compression or in solutions where abrasion can occur, it can
form wear particles. This can lead to chronic imlammatory reaction.

Polyethylene (PE) is chemically the simplest of all polymers used as

biomaterial and a homochain polymer. It is essentially stable and appropriate
for long-time implantation: relatively inexpensive; and has good general
mechanical properties making it a versatile biomaterial for catheters and joint
replacement.

Another biomaterial polymer is the polymethylmethacrylate (PMMA). It

is hard, brittle polymer that appears to be unsuitable for most medical
applications although possesses important characteristics such as its
readiness to be prepared under ambient conditions, making it manipulable in
the operating area or dental clinic which explains its use in dentures and bone
cement. The disadvantages of PMMA are the toxicity of methylmethacrylate,
its ability to produce heat during polymerization, and its fracture toughness.
Despite these disadvantages, there is no better material that has been
developed to replace it.

There are many different biomaterials, but there is no single biomaterial

that is best for all implants and all patients. There are specific requirements of
an implant material depending on how it will be used and who will use it. For
example, during daily ac tivities an orthopedic implant may encounter
mechanical forces that tend to push on it, pull on it, bend it, scrape it, or wear
againts it. These forces can cause an implant to break or wear out after some
time. An implant inside the human body is also exposed to different chemicals
that could cause it to corrode. Thus, an implant must be able to withstand the
forces and chemical environment in the patient in order for it to perform its
function.
Composites
Composite materials, or composites, are made by combining two
materials - fibers fragments of one material called reinforcement and a binder
of the fibers called matrix-having different properties to give the resulting
product unique properties. The combining materials in a composite do not
dissolve or blend together and retain their distinct properties (see Figure 8.3).

Table 8.3: Materials that make-up composites

Table 8.4: Distinct properties of each combining materials

Composites, also called reinforced plastics, are modified plastics that

contain fibers of another substance (glass, graphite, synthetic polymers, or
ceramics) embedded in a matrix of polymers (usually a thermosetting
condensation polymer). The strongest form for a solid is a wire or a fiber, and
the use of a polymer matrix prevents the fiber from bending and buckling. This
results in a reinforced plastic that is stronger than steel on a weight basis.
Composites have low density and non-corroding materials.

The low density, high strength, and high chemical resistance of

composites make them ideal automobile and airplane parts. Composites are
also widely used in construction and sporting goods industries.

Fiberglass is an example of a composite. It is widely used for boat

hulls, sports equipment, building panels and many car bodies. In fiberglass,
the matrix is a plastic and the reinforcement is glass of fine threads woven
into a cloth-like material. The reinforcement glass is very strong but brittle and
it will break if bent sharply. To protect this reinforcement from damage, the
plastic matrix holds the glass fibers together and shares out the forces acting
on them.

Some advanced composites are now produced by replacing glass with

carbon fibers. These materials are lighter and stronger than fiberglass but
producing them is more expensive. These materials are used in aircraft
structures and sports equipment like golf clubs.

The Airbus A380 (see Figure 8.4) is the world's largest passenger
airliner. More than 20% of this aircraft is made of composite materials, mainly
plastic reinforced with carbon fibers. The design uses glass-fiber-reinforced
aluminum, a new composite that is 25% stronger than conventional airframe
aluminum but 20% lighter.

Figure 8.5: Airbus A380 uses modern composites in its design

Silicones
Silicones, or polysiloxane, are polymers whose chains are composed
of alternating sil icon and oxygen atoms. They can be linear, cyclic, or cross-
linked networks. Below is the representation of the structure of simple
silicones, the R represents a hydrocarbon group such as methyl, ethyl,
ethenyl, etc.
Figure 8.5

Silicones are heat-stable. They are resistant to most chemicals and

have excellent waterproofing characteristics. The physical form and uses of
the silicones depend on the structure of their polymers. There are four classes
of silicones: silicone fluids, silicone gels, silicone elastomers (rubbers), and
silicone resins. Silicones are used for synthetic human body parts like artificial
ears, nose, fingger joints, and eye sockets. Most cookwares are also made of
silicones. Silicone fluids are usually straight chains of polydimethylsiloxane
and the repeating structure is

at the end of the chain they have trimethylsilyl group, Si(CH3)3 as

shown in Figure 8.6 (Structure of a silicone fluid)

Poly(dimethyl) siloxane

Silicone fluids are short-chained silicones and have a constant

viscosity over a wide range of temperatures (around -73 to 177°C). They have
unique surface properties be- cause they have low surface tension making
them useful as lubricant in polishes and paints, and for water-proofing fabrics,
paper and leather. The anti-foaming properties of silicone fluids make them
useful in suppressing the foaming of detergents in sewage disposal plants.
Their properties of low enthalpy of vaporization, and a smooth and silky feel
make silicone fluids good components of personal care products like antiper-
spirants and skin lotions.

Silicone gels are composed of polydimethylsiloxane chains but with few

cross-links between the chain resulting in a very open three-dimensional
network. Silicone gels prepared by combining silicone fluid and a reactive
group in a mould and then warmed or catalyzed to allow cross-linking
between the polymer chains. Silicone gels are for protecting electronic
equipment from damage from vibration and act as insulator. Shock absorbers
in high-performance trainers and running shoes are made from pads
containing silicone gel.

Silicone elastomers (rubbers) are made from long chains of

polysiloxanes with more crosslinking into the linear chain polymers. The
structure of silicone rubber is somewhat similar to natural rubber. Silicone
rubbers are more stable at both low temperatures (-73°C) and high
temperatures (177 to 327°C). They are also resistant to chemical attack. The
addition of silica as filler makes the elastomer stronger. Silicone elastomers
are used in automotive industry, electrical applications, food and personal
hygiene (see Figure 8.7).
 Figure 8.7 Examples of products more from alcone alostomers

Another group of silicones that are heavily crosslinked, with three-

dimensional structure of highly branched siloxane polymers, and require
curing at elevated tem- peratures are the silicone resins. The atoms in silicone
resins are arranged tetrahedrally about the silicon atoms. Silicone resins are
made up largely of tri-functional groups or tetrafunctional groups (see Figure
8.8). They do not usually contain silica fillers. They possess silicone reactivity
in the form of silanol (SiOH) and may be designed also to possess organic
reactivity.

Figure 8.8: Structural units of silicone resins

Generally, silicone resins enhance gloss and color retention, and

resistance to corro- sion, moisture, weather, and heat in high-performance
coatings, whereas, in specialty chemical formulations, silicone resins improve
weather ability, water repellency, physi- cal strength, and release properties.

The kind and amount of the R group in the chain of the silicone resins
determine the properties of the material. Silicone resins with only methyl
content possess flexibility, water repellency, low temperature flexibility, fast
cure, arc resistance, gloss retention, heat/shock resistance, and UV stability.
This kind of silicone resins produces little resi- due when heated; releases
minimal amount of heat; and has low odor even in high tem- perature
conditions. These characteristics make methyl silicone resins useful as
binders, and vehicle parts that require heat resistant materials.

Silicone resins that contain methyl and phenyl groups as substituents

have excellent heat resistance. They do not easily decompose even at 250°C
and have high mechanical strength which make them good materials in the
production of heat resistant paints, lustrous coatings, and electrical insulation
coatings.
Silicone resins can be tailored to suit many uses by changing the ratio
of branched and linear siloxanes in their composition and by attaching various
functional groups to the silicon. Silicon resins can combine with many different
organic polymers to produce organic resin-modified silicone resins, a hybrid
material with high mechanical strength and high chemical resistance. Thus, it
is easy to optimize certain properties such as cure characteristics, flexibility,
adhesion, weather resistance, and other properties that would give a wide
range of performance options by just adding different organic polymers to the
silicone resins.
A very good application of silicone resin is found in London eye and
some buildings, the windows of the capsules of the London eye (see Figure
8.9) are made of reinforced glass using polyvinyl butyral (the laminate) which
is anchored to the metal frame using a silicone resin. This silicone resin is
prepared in situ using silicone with alkoxy groups as one of the components
which provide the cross-linking needed to produce the resin. Using this
material, the capsule can withstand winds of 280 km/h.

The same procedure is used in buildings that are considered to be

vulnerable 10 terrorists attacks. In these buildings, the glass which is resistant
to bomb blasts and bullets, will keep in place since it is strongly bonded to the
metal frames.

Summary:
 Intermolecular forces are forces of attraction existing between molecules
of a substance. They are also known as van der Waals forces.
 The basic types of intermolecular forces are London dispersion forces,
dipole-dipole interaction, and hydrogen bond.
a) London dispersion forces or instantaneous dipole-induced dipole
interaction are the weakest intermolecular forces that exist in all
types of molecules. They are formed from the distortion of the
electron clouds due to the constant motion of molecules.

b) Dipole-dipole interaction occurs between polar molecules. The

interaction is formed when the partial positive end of the molecule
is attracted to the partial negative end of another molecule.

c) Hydrogen bond is a strong type of dipole-dipole interaction and

exists when the molecules have a hydrogen bonded to a highly
electronegative atom such as nitrogen, oxygen, and fluorine.

 High boiling point, low density of ice, and high surface tension are the
properties of water that can be explained by the strong hydrogen bonding
between water molecules.
 Biomaterials are natural or synthetic materials that make up whole or part
of a living structure or biomedical devices that perform, augment, or
replace natural functions of a living system.
 Composites are modified plastics that contain fibers of another substance
embedded in a matrix of polymers.
 Silicones are polymers whose chains are composed of alternating silicon
and oxygen atoms.