Chapter 5

Condensed Phases
 What is a phase?
• A phase is a distinct state of a substance

eg.
– liquid

– gas, or

– solid that is uniform throughout.

 What is a phase?
Each substance has
– one gas phase
– one liquid phase
– often several different crystalline phases
(called polymorphs).
Graphite and diamond are polymorphs of
carbon
 What is a phase?
• substances can change from one phase
to another if the
Temperature
and/or
Pressure is altered.
• more than one phase can coexist
 Phase Transitions

GAS

Condensation
Sublimation

Deposition Evaporation

Melting
SOLID LIQUID
Freezing
 Evaporation and Vapour Pressure
• Transition : liquid to gas
• Molecules in a liquid have a range of energies as
shown by the Boltzmann distribution curve.
– average kinetic energy of molecules is a function of
temperature.
– some molecules have enough energy to overcome the
attractive forces between molecules.
– if these molecules are at the surface, they escape or
evaporate.
– the higher the temperature the greater the proportiion of
molecules with enough KE to evaporate.
 Evaporation and Vapour Pressure
• Molecules in the vapour phase will strike the surface
of the liquid and be captured or condense.

• After a short time in a sealed container

rate of evaporation = rate of condensation.

• This is called phase equilibria and is a dynamic
process.
 Evaporation and Vapour Pressure
• The pressure of the vapour above a liquid -
vapour depends on

– bonding between molecules in liquid - stronger

intermolecular bonds - lower vapour pressure.

– temperature - higher temperature - higher

vapour pressure.
 Boiling
• As the temperature of a liquid increases the vapour
pressure increases.
• When vapour pressure = external pressure (usually
1 atm.) liquid boils.
– gas bubbles form in body of liquid
– bubbles rise to surface and gas escapes.

• If external pressure is reduced,(eg up a mountain),

liquid will boil at a lower temperature
• If external pressure is increased,(eg pressure cooker),
liquid will boil at a higher temperature.
 Phase Diagram

solid
liquid
Critical
Triple point
point
gas

T
The lines indicate the T and P at
which two phases are in
equilibrium
P

solid
liquid
Critical
Triple point
point
gas

T
 Reading a Phase Diagram
• Triple point = point where all 3 phases are
in equilibrium.
– Triple point of water = 273.16 K and 0.006 atm
(a single point on the P vs T diagram)

– vapour pressure of ice and water are the same

– lowest P at which liquid can exist and usually

lowest T (except water)
 Reading a Phase Diagram

• normal melting point is the melting point

at 100 kPa.
• normal boiling point is the boiling point
at 100 kPa.
• Substances can melt and boil at other
temperatures depending on the pressure.
 Critical Point
• The critical point is the point at which the liquid-
vapour line ends. Physical differences between
liquids and gases disappear at the critical point
and we speak of a single "fluid" state.
– Above this point ( at higher temperatures or
pressures) condensation will not take place.
– eg. CH4, Tc = 190 K  CH4 cannot be liquified
at room temperature, liquid can only be
obtained below 190 K.
 Carbon dioxide, CO2
P
Tc = 304 K
Pc = 7.3 Mpa
liquid = 73 atm
solid
Triple
point Critical
point
gas
1 atm

T
• The triple point for CO2 lies above 1 atm so solid CO2
sublimes at this pressure.
• The melting curve runs nearly vertical since very large
pressure changes are needed to modify a liquid's freezing
point.
• For most substances the melting curve is inclined to the
right. dP
is + ve
dT

• The freezing temperature usually rises at higher pressures.

Most liquids near their freezing point will freeze if P
increases.
Note: Application of pressure always leads to a phase of
higher density. Water is unusual - solid ice is less dense
than liquid water.
– Ice shows the opposite behaviour - it melts under
pressure (e.g ice skating)
 P

liquid
solid

100 kPa Triple

point Critical
point
gas

T
Example: 273 K 373 K

• What is the melting point of ice at the bottom of the ocean

where P = 100 MPa (1000 atm approx)?

Answer: The new melting point is T = 265.85K

 Example
• What happens to the pressure inside a closed container
containing water and steam if we cool it from 373 K
(the normal boiling point of water) to 298 K ? (no
other gases present).
• Answer: At 373 K P(H2O) = 100 kPa by
definition, ie the pressure of water inside the container
is approx 1 atmosphere.
• The water phase diagram shows that the vapour
pressure inside the container drops from 100 kPa to
3 kPa as the temperature falls to 298K.
Phase Diagram for Water
showing various solid phases.
 The Supercritical region

solid
liquid
Critical
Triple point
point
gas

T
 Critical Temperatures and
Pressures
• The super critical region is usually a region of high
pressure and temperature

Tc/KTP/atm
• Carbon Dioxide 304.2 72.8

Water 647.3 217.6

Ammonia 405.6 111.3

Ethylene 282.4 49.7

 Properties of supercritical fluids
• They are like high density gases and low density
liquids

• As a high density gas they can penetrate into solids

eg concrete, and undergo reactions interneally

• As a low density liquid they can dissolve other

compounds, eg. CO2 can act as a solvent for organic
compounds. This property can be used to clean up
circuit boards, oil contaminated systems or be a host
for organic systhesis.
 Properties of supercritical fluids
• Go to the Web and find some other uses for
supercritical fluids.

• There a couple of Web sites on the C1011A site to

get you started.
 What’s the use of CO2
• Putting out fires
• Dissolving oils
• Cleaning nuclear valve seals
• Removing adhesives
• Strengthening concrete
• Recycling propellants
 What’s the use of CO2
• Photosynthesis
• Heating up the Planet
• Making rocks (chalk)
• Getting a head on a beer
• Fizzing up a Coke