4A.

Phase Diagrams of Pure Substances

4A.1a The number of phases
Phase is a form of matter that is uniform throughout in chemical composition and physical state.
Allotrope is a particular molecular form of an element (such as O2 and O3 ) and may be solid,
liquid, or gas.
Polymorph is one of a number of solid phases of an element or compound.

4A.1b Phase transitions

Phase transition is the spontaneous conversion of one phase into another phase, occurs at
characteristic temperature for a given pressure.
Transition temperature (Ttrs) is the temperature at which the two phases are in equilibrium and
the Gibbs energy of the system is minimized at the prevailing pressure.
Thermal analysis detects phase transitions by nothing that the temperature does not change even
though heat is being supplied or removed from sample.
Metastable phases are thermodynamically unstable phases that persist because the transition is
kinetically hindered.
4A.1c Thermodynamic criteria of phase stability
Chemical potential is a measure of the potential that a substance has for undergoing change in a
system. For a one component system molar Gibbs energy and chemical potential are synonyms.
Criterion of phase equilibrium
At equilibrium, the chemical potential of a substance is the same throughout a sample, regardless
of how many phases are present.
Only if 1 = 2 is there no change in G , and only then is the system at equilibrium.
4A.2a Phase boundaries
Phase diagram of a pure substance shows the regions of pressure and temperature at which its
various phases are thermodynamically stable.
Phase boundaries are the lines separating the regions, they show the values of T and p at which
two phases coexist in equilibrium and their chemical potentials are equal.
Vapor pressure is the pressure of a vapor in equilibrium with the liquid.

Sublimation vapor pressure is the vapor pressure of the solid phase.

Boiling is the coniditon of free vaporization through the liquid.
Boiling temperature is the temperature at which the vapor pressure of a liquid is equal to the
external pressure.
Normal boiling point (Tb) or normal freezing/melting point (Tf) is when the external pressure
is 1 atm.
Standard boiling point or standard freezing point is when the external pressure is standard
pressure (1 bar)
Critical temperature (Tc) is the temperature at which the surface disappears. Above the critical
temperature, the liquid phase of the substance does not exist.
Critical pressure (Pc) is the vapor pressure at the critical temperature.
Supercritical fluid is a single uniform phase found at and above the critical temperature.
Melting/freezing temperature is the temperature at which, under specified pressure, the liquid
and solid phases of a substance coexist in equilibrium.
Triple point is the point at which the 3 phase boundaries meet.
Vapor pressure increases with higher temperatures, because at higher temperatures more
molecules have sufficient energy to escape from their neighbors.
When liquid is heated in open vessel, the liquid vaporizes form its surface. When vapor pressure is
equal to external pressure, vaporization can occur throughout the bulk of liquid.
Boiling does not occur when liquid is heated in rigid closed vessel. When the density of the vapor
is equal to that of the remaining liquid, the surfaces between the two phases disappear.
4A.2b The phase rule
Phase rule gives the number of parameters that can be varied independently.
Component is a chemically independent constituent of a system.
Constituent means chemical species that is present in the system.
Variance (or number of degrees of freedom, F) of a system is the number of intensive variables
that can be changed independently without disturbing the number of phases in equilibrium.
Bivariant F=2
4A.1 Phase rule

F=2+C P

Carbon dioxide phase diagram. Positive slope for solid-liquid boundary indicates melting temperature of
solid rises as pressure is increased.

Water phase diagram. Steep solid-liquid boundary steep slope indicates enormous pressures are
needed to bring about significant change to melting temperature. Negative slope means that melting
temperature falls as the pressure is increased (decrease in volume occurs on melting, more favorable for
solid to transform into liquid as pressure is raised)

4B Thermodynamic aspects of phase transitions

4B.1
At very low temperatures and provided pressure is not too low, solid phase of substance has lowest
chemical potential and therefore most stable phase.
4b.1a Temperature dependence of phase stability

4b.1

=Sm
T P

Variance of chemical potential with temperature

As the temperature is raised the chemical potential of a pure substance decreases.
S(g)>S(l) the slope of a plot of chemical potential vs. temperature is steeper for gasses than for liquids.
S(l)>S(s) almost always, the slope is steeper for liquid than for solid.
4B.1B The response of melting to applied pressure
Most substances melt at higher temperature when subjected to pressure.
4b.2

=V m
p T

Variance of chemical potential with pressure

An increase in pressure raises the chemical potential of any pure substance because Vm>0.
Most cases Vm(l)>Vm(s), increase ini pressure increases chemical potential of liquid more than that of
solid.
For water, because V(s)>V(l) increase in pressure increases chemical potential of solid more than that of
liquid, because of this, melting temperature is lowered slightly.
4B.1C The vapor pressure of a liquid subjected to pressure
If pressure is applied to condensed phase, vapor pressure rises (molecules squeezed out of phase and escape
as gas)
Partial vapor pressure is partial pressure of vapor in equilibrium with the condensed phase.
Gas solvation gas phase molecules might attract molecules out of liquid, the attachment of molecules to
gas-phase species.
4B.3 p= p eV m (l ) P / RT
Effect of applied pressure

P on vapor pressure p

4B.2a The slopes of the phase boundaries

4B.5a

dp trs S
=
dT trs V

Clapeyron equation is exact expression for slope of tangent to boundary at any point and applies to any
phase equilibrium of any pure substance.
4B.5b

dT trs V
=
dp trs S

4B.2b the solid-liquid boundary

The molar entropy of melting at T is

4B.6

fus H /T

dp fus H
=
dT T fus V

Slope of solid-liquid boundary

Enthalpy of melting is positive
Change in volume is usually positive and always small
Slope dp/dT is steep and usually positive.
Assuming fus H and fus V change little with temperature and pressure, they can be treated as a
constant. After integration of equation 4B.6
4B.7

p= p +

fus H T
ln
fus V T

The approximate equation of the solid-liquid boundary

4B.2C The liquid-vapor boundary
4B.9

dp vap H
=
dT T vap V

Slope of liquid-vapor boundary

Enthalpy of vaporization is positive. Vvap is large and positive
dp/dT is positive, but much smaller than for solid-liquid boundary.
dT/dp is large, hence boiling temperature is more responsive to pressure than freezing temperature.
Vm(g)>>>>Vm(l) we can write deltaVvap~~~Vm(g), if gas is perfect Vm(g)=RT/p
4B.10

d ln p vap H
=
dT
R T2

Clausius-Clapeyron equation (if vapor is a perfect gas)

After integration equation 4B.10 becomes
4B.11

p= p ex , where x=

vap H 1 1
( )
R
T T

4B.2D The solid-vapor boundary

Enthalpy of sublimation is greater than enthalpy of vaporization, equation predicts steeper slope for
sublimation curve than for vaporization curve at similar temperatures.
4B.3 The Ehrenfest classification of phase transitions
Ehrenfest classification classifies phase transitions into different types.
4B.3a The Thermodynamic Basis

( )
=V m ( )V m ( )= trs V
p T
4B.12a
( )

p T

4B.12b

trs H
( )
p =S m ( ) + Sm ( )= trs S=
T
T trs
()

T p

First-order phase transition the first derivative of the chemical potential with respect to temperature is
discontinuous.

5AThe thermodynamic description of mixtures

Binary mixtures are mixtures of 2 components, A and B.

x A + x B=1

c J ) is the amount of solute divided by the volume of the

solution. c =mol d m (units :mol d m3 mol L1)
Molality (b) is amount of solute divided by the mass of solvent. b =mol k g1
Molar concentration (molarity, [J], or
3

a) Partial molar volume

Partial molar volume

6A The equilibrium constant

There is a tendency of a mixture of reactants to undergo a reaction until the Gibbs energy of the mixture has
reached a minimum: that state corresponds to a state of chemical equilibrium.
a) The reaction Gibbs energy
Extent of reaction measure of how much reaction has gone to completion
Reaction Gibbs energy is the slope of the graph of the Gibbs energy plotted against the extent of reaction.

G
p ,T
6A.1
, where r G=B A
r G=
Reaction Gibbs energy

The reaction is at equilibrium and spontaneous in neither direction when

6A.3 r G=0
b) Exergonic and endergonic reactions
Spontaneity of a reaction at constant temperature and pressure can be expressed in terms of the reaction
Gibbs energy:
r G< 0 , forward reaction is spontaneous. Exergonic reactions can be used to drive another

process.
r G> 0 , reverse reaction is spontaneous. Endergonic reactions can be made to occur only

by doing work on it.

r G=0 , reaction is at equilibrium

6A.2 The description of equilibrium

a) perfect gas equilibria
6A.4

B + RTln pB
r G=B A =

Q is a reaction quotient, ranges from 0 (when pB=0, pure A) to infinity (pA=0, pure B)