Phase Diagrams

Chapter 11
 Chemical Systems
• Undergo three main processes that chang
e their energy
– Chemical reactions
– Heating/cooling
– Phase transitions
 Phase Diagrams
Phase diagrams display the state of a substance a
t various pressures and temperatures and the pla
ces where equilibria exist between phases.
 Phase Diagrams
• The AB line is the liquid-vapor interface.
• It starts at the triple point (A), the point at which
all three states are in equilibrium.
 Phase Diagrams
It ends at the critical point (B); above this critical
temperature and critical pressure the liquid and v
apor are indistinguishable from each other.
 Phase Diagrams
• Each point along this line is the boiling point of th
e substance at that pressure.
– Pressure = Force / area
– Increasing pressure causes the molecules to be conden
sed making the molecular arrangement closer
 Phase Diagrams
• The AD line is the interface between liquid and sol
id.
• The melting point at each pressure can be found
along this line.
 Phase Diagrams
• Below A the substance cannot exist in the liquid s
tate.
• Along the AC line the solid and gas phases are in e
quilibrium; the sublimation point at each pressure
is along this line.
 Phase Diagrams
• As temperature increases, the average kinetic ene
rgy of the substance increases causing the spacing
between the molecules to increase and eventuall
y change phase
Phase Diagram of Water
• Note the high critical temper
ature and critical pressure:
– These are due to the strong va
n der Waals forces between wa
ter molecules.
• London dispersion force
• Dipole-dipole forces
• Hydrogen bonding
– Increase the melting and boiling poin
t of water
Phase Diagram of Water
• The slope of the solid–liquid li
ne is negative.
– This means that as the pressur
e is increased at a temperature
just below the melting point, w
ater goes from a solid to a liqui
d.
Phase Diagram of Carbon Dioxide
Carbon dioxide cannot
exist in the liquid state
at pressures below 5.11
atm; CO2 sublimes at no
rmal pressures.
Phase Diagram of Carbon Dioxide
The low critical tempera
ture and critical pressur
e for CO2 make supercri
tical CO2 a good solvent
for extracting nonpolar
substances (such as caff
eine).
Intermolecular Forces and impa
ct on ideal behavior
• Presence of intermolecular forces among
gas particles (including noble gases) leads
to deviations from ideal behavior
– Therefore, at sufficiently low temperatures or
sufficiently high pressures, gases can conden
se
 Heating/Cooling
• Between phase changes
, all heat (energy) absor
bed or released change
s the average amount o
f KE (therefore, the T) of
the substance
– Areas on graph with a sl
ope
 Heating/Cooling
• There is no slope in are
as where a phase chang
e is occuring
– All energy is being used t
o change the phase of m
atter (rather than chang
e the temperature)
 Heating/Cooling
• Melting and Boiling
– Endothermic
• Freezing and Condensation
– Exothermic
• The amount of energy needed to vaporize
= amount of energy needed to condense
– Reverse phase changes have equal but oppo
site magnitudes of energy gained or released
– Same applies for melting and freezing