4.

0 MATTER
4.4 PHASE DIAGRAMS
 PHASE DIAGRAMS
- A phase is a homogenous part of the system which
is physically distinct from the other parts of the
system
- A phase may be a solid, liquid, gas or even a
homogenous solution or a mixture of gases
- A phase diagrams summarises the relationship
between the solid, liquid and gaseous states of a
given substance as a function of pressure and
temperature
- A phase diagram has the following features:
a. Each region represents respectively the solid,
liquid and gaseous phase of the substance
b. The lines separating the regions represent the
phase transition curves. Any point along the line
specifies the conditions under which the 2 phases
exist in equilibrium
c. Triple point: Point where the 3 phase-transition
curves meet. This describes the conditions under
which all 3 phases coexist in equilibrium
d. Critical point: The phase boundary between liquid
and gas does not continue indefinitely. Instead, the
liquid-gas line ends at a point called the critical point
Critical temperature, Tc is the temperature above
which a gas will not liquefy by increase in pressure
Beyond the critical point, the liquid and gaseous
phases become indistinguishable, which is known as
a supercritical fluid
 PHASE DIAGRAM OF CARBON DIOXIDE

- The phase diagram for CO2 is typical of most

substances
- BO line: solid ↔ gas
It shows the sublimation point at different pressures
and temperatures
- OD line: solid ↔ liquid
It gives the melting (freezing) point of solid carbon
dioxide at different pressures. The positive gradient
indicates that the melting point of CO2 increases with
the increase in pressure. This is expected as a solid is
usually denser than a liquid. So an increase in
pressure favours the more compact solid phase
- OC line: liquid ↔ gas
It shows the boiling point of liquid carbon dioxide at
different pressures. It also gives the vapour pressure
of liquid carbon dioxide at different temperature
- Triple point, O (5 atm, -57oC)
At this point, solid CO2 exists in equilibrium together
with liquid and vapour of CO2
- Critical point, C (73 atm, 31oC)
At this point, the average kinetic energy of the
molecules is so high that the vapour cannot be
condensed no matter what pressure is applied
USES OF DRY ICE
- Solid carbon dioxide is known as dry ice because it
looks and feels like ice but not wet
- Dry ice is cheap, non-toxic and commonly used as
refrigerant for food stuff and to preserve and ship
biological samples
- It can maintain cold temperatures and does not
leave messy liquid as it sublimes
- In the entertainment industry the ‘fog’ used in
effects is made with dry ice. When dry ice is placed in
water, sublimation is accelerated, the cold CO2 gas
causes nearby water vapour to condense and form a
thick white fog
- Dry ice is used in cloud seeding to induce rainfall.
Sublimation of CO2 absorbs heat from the clouds,
lowers the clouds temperature, causing water vapour
to condense to water
 PHASE DIAGRAM OF WATER

- AB: solid ↔ gas

-DB: solid ↔ liquid
- BC: liquid ↔ gas
- O: triple point (0.01oC, 0.006 atm / 0.6 kPa)
- C: critical point (374oC, 218 atm / 22089 kPa)
- AO: supercooling, H2O exist in a metastable state
(exist as liquid below its freezing point)
ANOMALOUS BEHAVIOUR OF WATER
- For most solids, melting point increase as pressure
increases, but for water, the melting point line has a
negative gradient. This shows the melting point of
water decreases with the increase in pressure
- Intermolecular hydrogen bonds lead to an open
structure in ice. So ice has a lower density than liquid
water

Liquid water ↔ Solid ice

(higher density, smaller volume) (lower density, larger volume)

- Water expands on freezing. An increase in pressure

favours the higher density of liquid water
 EFFECT OF A NON-VOLATILE SOLUTE ON THE
VAPOUR PRESSURE OF A SOLVENT
LOWERING OF VAPOUR PRESSURE
- If a solute is non-volatile, the vapour pressure of its
solution is lower than that of the pure solvent
- When a solute dissolves in a solvent, part of the
surface of the solutions is occupied by the solute
particles. Less solvent particles can escape to form
vapour, so the vapour pressure is lowered
ELEVATION OF BOILING POINT
- Boiling point is the temperature at which the vapour
pressure of the liquid equals the exterrnal
atmospheric pressure
- As the vapour pressure of a solution is lowered, a
higher temperature is needed to raise the vapour
pressure of a solution to equal the external pressure.
Hence the boiling point is increased

DEPRESSION OF FREEZING POINT

- Freezing point is the temperature at which an
equilibrium exists between the liquid and solid
phases
- The presence of foreign molecules makes the
orderly arrangement more difficult to achieve.
Temperature has to be lowered further for freezing
to occur. Thus, freezing point is depressed
COLLIGATIVE PROPERTIES
- Colligative properties are properties of a solution
that depend on the number of solute particles in a
solution and not on the nature of the particles
- Colligative properties include lowering of vapour
pressure, boiling point elevation, freezing point
depression and osmotic pressure
-The magnitude of the change depends on the
concentration of solute particles and also dependent
on the nature of the solvent