Physical

Transformations
of Pure
Substances
Chapter 4
 Stabilities of Phase
A phase of a substance is a form of
matter that is uniform throughout in
chemical composition and physical
state.
A phase transition is the spontaneous
conversion of one phase into another.
Phase transitions occur at a
characteristic temperature and
pressure.
 Stabilities of Phase
At 1 atm, < 0 C, ice is the stable
phase of H2O, but > 0 C, liquid water
is the stable phase.
The transition temperature, Ttrs, is the
temperature at which two phases are
in equilibrium.
So what happens to Gibbs energy?
 Stabilities of Phase
At 1 atm, < 0 C, ice is the stable phase of H 2O,
but > 0 C, liquid water is the stable phase.
The transition temperature, Ttrs, is the
temperature at which two phases are in
equilibrium.
So what happens to Gibbs energy?
< 0 C Gibbs energy decreases as liquid
solid.
> 0 C Gibbs energy decreases as solid
liquid.
 Stabilities of Phase
Thermodynamics does not provide
information regarding the rate of
phase change.
Diamond graphite
Thermodynamically unstable phases
that persist due to slow kinetics are
called metastable phases.
Phase Diagrams
Phase boundaries
show the values of p
and T at which two
phases coexist in
equilibrium.
Vapor Pressure
The pressure of a
vapor in equilibrium
with a liquid is called
the vapor pressure.
The pressure of a
vapor in equilibrium
with a solid is called
the sublimation
vapor pressure.
 Boiling Point
Liquid can vaporize from a liquid surface
below its boiling point as we learnt from
the Drinking Bird.
In an open vessel, the temperature at
which the vapor pressure equals the
external pressure, is called the boiling
temperature.
At 1 atm, its called the normal boiling
temperature, Tb.
At 1 bar, its called the standard boiling
point.
 Critical Point
In a closed rigid vessel, boiling does not
occur.
As the temperature is raised the density
of vapor increases and the density of the
liquid decreases.
When the density of the vapor and liquid
phases are equal the surface between the
two phases disappears.
The temperature at which this occurs is
called the critical temperature, Tc.
The vapor pressure at the critical
Critical Point
 Melting and Freezing
The temperature at which, under a specified
pressure, the liquid and solid phases of a
substance coexist in equilibrium is called them
melting temperature.
The freezing temperature is the same as the
melting point.
At 1 atm, the freezing temperature is called the
normal freezing point, Tf.
At 1 bar, its called the standard freezing point.
The difference is negligible in most cases.
The normal freezing point is also called the
normal melting point.
 Triple Point
There is a set of conditions under which
three different phases of a substance
(typically solid, liquid and vapor) all
simultaneously coexist in equilibrium.
This point is called the triple point.
For any pure substance the triple point
occurs only at single definite pressure and
temperature.
The triple point of water lies at 273.16 K
and 611 Pa.
Triple Point
The triple point
marks the lowest
pressure at which a
liquid phase can
exist.
Carbon Dioxide
Water
Helium
 Thermodynamics of
Phase Transitions
The molar Gibbs energy, Gm, is also called
chemical potential, . Phase transitions
will be investigated primarily considering
the change in
Thermodynamic definition of equilibrium:
At equilibrium the chemical potential of a
substance is the same throughout the
sample, regardless of how many phases
are present.
Thermodynamics of
Phase Transitions
 Thermodynamics of
Phase Transitions
At low temperatures, and provided the
pressure is not too low, the solid phase of
a substance has the lowest chemical
potential and is therefore the most stable.
Chemical potentials change with
temperature: this explains why different
phases exist.
Dependence of Phase
Transitions
Gm

= Sm = Sm
T p T
p

As temperature
increases, chemical

potential decreases.
Melting and Applied
Pressure
Gm

= Vm = Vm
p T p
T

Molar volume of
solid is smaller than
that of the liquid.
Melting and Applied
Pressure
Gm

= Vm = Vm
p T p
T

Molar volume of
solid is greater than
that of the liquid.
Melting and Applied
Pressure


= Vm
p T
= Vm p

 Melting and Applied
Pressure
Calculate the effect on the chemical
potentials of ice and water of
increasing pressure from 1.00 to
2.00 bar at 0 C. The density of ice is
0.917 g cm-3 and that of liquid water
is 0.999
M g cm -3
. Mp
Vm = =

M = 18.02gmol1 = 0.01802kgmol1
p = 1bar = 10 5 Pa
ice = 917kgm3 water = 999kgm3
 Melting and Applied
Pressure
Calculate the effect on the chemical
potentials of ice and water of
increasing pressure from 1.00 to
2.00 bar at 0 C. The density of ice is
0.917 g cm-3 and that of liquid water
1
(0.01802kgmol
is 0.999 g cm .-3 ) (1.00Pa)
u(ice) = 3
= +1.97Jmol 1

917kgm
(0.01802kgmol 1 ) (1.00Pa) 1
u(liquid) = = +1.80Jmol
999kgm 3
 Vapor Pressure and
Applied Pressure
When pressure is applied to a
condensed phase, its vapor pressure
rises.
This is interpreted as molecules get
squeezed out of the condensed phase
* V (l )P RT
and pescape
=pe m

as a gas.
p = vaporpressure
p* = vaporpressureofcondensedphase
intheabsenceofanadditionalpressure
P = pressureapplied
Vapor Pressure and
Applied Pressure
 Location of Phase
Boundaries
Locations of phase boundaries
pressures and temperatures - can be
located precisely by making use of
the fact that at when two phases are
in equilibrium, their chemical
potentials must be equal
( p,T) = ( p,T)
Location of Phase
Boundaries
dG = Vdp SdT
d = Vm dp Sm dT
V,m dp S,m dT = V ,m dp S ,m dT
(S ,m S,m )dT = (V ,m V,m )dp
trsS dp
= Clapeyronequation
trsV dT
Location of Phase
Boundaries
Solid-liquid boundary
trsS dp
= Clapeyronequation
trsV dT
trsH
trsS =
T
dp fusH
=
dT T trsV
Solid-liquid boundary
Solid-liquid boundary
dp fusH
=
dT T fusV
fusH dT
dp =
fusV T
p T fusH dT
p* dp = T * V T
fus

p fusH TdT
p* dp V T * T
trs

fusH ?T ?
pp +*
ln? * ?
fusV ?T ?
 Solid-liquid boundary

fusH ?T ?
pp +*
ln? * ?
fusV ?T ?
WhenTandT* donotdiffermuch
fusH
pp + *
*
(T T * )
T fusV
Liquid-vapor boundary
trsS dp
= Clapeyronequation
trsV dT
trsH
trsS =
T
dp vap H
=
dT T vapV
Liquid-vapor boundary

dp
"small"
dT
dT
"large"
dp

 Liquid-vapor boundary

dp vap H
= vapV Vm (g)
dT T vapV
dp vap H
=
dT T(RT p)
d ln p vap H
= Clausius Clapeyronequation
dT RT 2

 Liquid-vapor boundary
d ln p vap H
=
dT RT 2
vap H
d ln p = 2
dT
RT
ln p T vap H
ln p* d ln p = T * RT 2 dT
ln p vap H T dT vap H 1 1
ln p* d ln p = R T * T 2 = R T T *
* vap H 1 1
ln( p p ) = *
R T T
p vap H 1 1
*
= e
= *
p R T T
p = p*e
 Liquid-vapor boundary
d ln p vap H
=
dT RT 2
vap H
d ln p = 2
dT
RT
ln p T vap H
ln p* d ln p = T * RT 2 dT
ln p vap H T dT vap H 1 1
ln p* d ln p = R T * T 2 = R T T *
* vap H 1 1
ln( p p ) = *
R T T
p vap H 1 1
*
= e
= *
p R T T
p = p*e
 Solid-gas boundary

sub H 1 1
*
p= p e = *
R T T