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CHAPTER 4

LIQUIDS AND SOLIDS

SUBTOPICS
4.1 Liquids
4.2 Solids
4.3 Phase Diagram
4.4 Vapour Pressure of Solution

4.1 LIQUID
4.1.1 The Liquid State
In liquids, the particle (atoms, molecules or ions)
are very closely packed as compared with the
gaseous state.
Condensation of a gas to liquid occurs when the
intermolecular forces between the particles are
strong enough to overcome the kinetic energy of
the particles.
The liquid particles are held together in small
clusters with little space between them.

The Liquid State

Empty space

Cluster of liquid particle

4.1.2 Vapour Pressure


Some

particles at the surface of the liquid can


undergo evaporation to become a gas.

In

an open container, evaporation will


continue until there is no liquid left.

If

the liquid is in a closed container, the particles in the


vapour state will be trapped in the container and collide
with the walls of the container and exert a pressure called
the vapour pressure.

Some particles after colliding with the walls of the


container or with one another might re-enter the
body of the liquid. This is known as condensation.

Initially

the rate of vaporisation is higher than the


rate of condensation (because there are fewer
vapour particles).
Hence the vapour pressure increases with time.
However a time is reached when the rate of
vaporisation becomes equal to the rate of
condensation.
After this, the total number of particles in the
vapour state remains constant, and the vapour
pressure attains a maximum value.
This maximum vapour pressure is known as the
saturated vapour pressure.

vapour
pressure

Saturated vapour pressure


Evaporation= condensation

Evaporation > condensation

time

Liquids

with higher vapour pressure have lower


boiling points.
The graph below shows the variation of saturated
vapour pressure with temperature for three liquids.

4.1.3 Boiling
When a liquid is heated in an open container, its saturated
vapour pressure increases.
When the saturated vapour pressure becomes equal to
atmospheric pressure, bubbles of vapour will form in the
liquid and escape into the atmosphere because the vapour
pressure is high enough to overcome the external pressure.
The liquid boils.
The boiling point of a liquid is the temperature at which
its saturated vapour pressure is equal to the external
pressure.
The higher the external pressure, the higher is the boiling
point.

The

more volatile a liquid, the lower is its boiling


point.

4.1.4 Freezing
When

the temperature of a liquid is lowered, the


kinetic energy of the particles decreases.
A point is reached when the intermolecular forces
are strong enough to hold the particles together in
a fixed, orderly arrangement. The liquid freezes to
solid.
The freezing point is the temperature at which a
solid is in equiblibrium with its liquid under a
pressure of 1 atm. This happen at 0C for water.

4.2 SOLIDS
4.2.1 Lattice Structure and Unit Cell
Most solids are crystalline. In crystalline solids the
particles (atoms, molecular or ions) are arranged in
an orderly fashion.
The particles are held rigidly together by strong
attractive forces in a three dimensional structure
called the lattice structure.
In amorphous solids, the particles are not arranged
in an orderly fashion.

The

basic repeating unit of a crystalline solids is


called a unit cell.
The diagram below shows a solid lattice and its
unit cell.

4.2.2 Basic Crystalline System


All solid crystal lattice can be classified under
seven basic crystalline systems.
They are:
i.
The cubic system
ii. The hexagonal system
iii. The monoclinic system
iv. The orthorhombic system
v. The rhombohedron system
vi. The tetragonal system
vii. The triclinic system

However

each crystalline system mentioned above


consistes of several different structures.
For example, the cubic system consists of the
following structures:
simple cube
body-centered cube
face-centered cube
All in all there are 32 crystalline structures.

Triclinic

Hexagonal

Simple
monoclinic

Tetragonal

Orthorhombic

Cubic

Tetragonal

4.2.2 The Cubic System


There are three important structures in the cubic
system.
The arrangment of the lattice particles for the
three cubic structures is shown below.
a. Simple cubic structure (Ex: KCl)

b)

Body-centered system (Ex: NaCl)

c.

Face-centered cube (Ex: I2)

4.2.4 Number of Particles in a Unit Cell


There are four types of particles in a cubic unit
cell depending on the positions they occupy.
They are:
a. Particle at the corner of a cube
b. Particle at the edge of face
c. Particle at the centre of a face
d. Particle at the centre of the cube

Type of particle

Fraction of particle
perunit cell

Corner

1/8

Along the edge

1/4

Centre of a face

1/2

In the centre of the cube

4.2.5 Allotropy
Some elements can exists in more than one crystalline
form. These elements are said to exhibit allotropy. The
differents forms of the sema element are called
alotropes.
Examples are carbon, sulphur and oxygen.
4.2.6 Allotropes of Carbon
a.
Diamond
In diamond, each carbon atom is bonded to four other
carbon atoms through strong covalent bonds in
atetrahedral arrangment.

The

strong covalent bonds in the three dimensional


structure make diamond the hardest material known
and account for its high melting point (3823 K).
All the four valence electrons of the carbon atoms
are involved in the formation of covalent bonds,
therefore there are no free electrons. Diamond is
anon-conductor of electricity.
The high refractive index of diamond makes it a
good material for ornaments.

b.

Graphite
Graphite is an example of a layeed structure in
the hexagonal crystalline system.
In the layers, each carbon atom is covalentrly
bonded to three other carbon atoms to form a
hexagonal ring.
The layers are held together by weak van der
Waals forces.
The more open structure of graphite as compared
with diamond, make graphite less dense than
diamond (density diamond: 3.50 g.cm3; graphite:
2.25 g/cm3)

c.

Each carbon atom, makes use of three of the four


valence electrons to form covalent bonds. Thus there is a
free electron which can move throughout the solid
lattice.
Hence graphite is a good conductor of electricity.
Fullerene
Fullerene with a molecular formula of C60 is the third
allotrope of carbon discovered in 1985.
Fulleene is spherical.
The C60 molecule is made up of 60 carbon atoms
joinded by covalent bonds to form a spherical structure
just like a football.
Consists of 32 hexagonal and 12 pentagonal rings.

Each

carbon atom in fullerene undergoes sp2


hybridisation.
Fullerene is also used as lubricants, semi-conductor
and catalyst.
4.2.7 Allotrope of Sulphur
There are several allotropic forms of sulphur, the
most important being the rhombic and the
monoclinic forms.
Both forms consists of S8 molecules arranged in
different fashions.

In rhombic form, the S8 molecules arrange themselves in


the form of a octahedron while in the monoclinic form,
they are arranged to form log, thin needles.
The rhombic form is the stable form at room temperature.
When the rhombic form is heated slowly, it change s to the
monoclinic form at temperature above 95.6C.
When cooled, the monoclinic form reverst back to the
rhombic form when the temperature falls below 95.6 C.
95.6 C is known as the transition temperature.

S(rhombic) S(monoclinic)

The

table below lists some properies of rhombic


sulphur and monoclinic sulphur.
Property

S(rhombic)

S(monoclinic)

Molecular formula

S8

S8

Structure

Octahedron

Long, thin
needles

Density

2.06 g/cm3

1.96 g/cm3

Stability
Melting point (C)

Stable at temp. Stable at temp. >


< 95.6 C
95.6 C
113
119

Solubility

Soluble

Insoluble

4.3 PHASE DIAGRAM


Most

matter can exist in three physical phases, i.e.


solid, liquid and gas.
At 85 C and 1 atm, water exists in liquid form.
But at 85 C and 0.4 atm, water exists in the form
of gas.
The tranformation between the physical states of a
substance is best reperensented by a phase
diagram.
The phase diagram is a graphical plot from
experimental results.

4.3.1 Phase Diagram of Water


The phase diagram of water is shown below.
The graph is divided into three areas.
Each ares represents a single phase as given in the
table below.
Area

Phase

ATC

Ice, H2O(s)

ATB

Vapour, H2O(g)

CTB

Water, H2O(l)

T
A

The
-

Curve TB (liquid/vapour line)


This curve shows the variation of the saturated
vapour pressure of liquid water with temperature.
It also the boiling ppint of water at different
pressures