4.

Phase Equilibria in Pure Substances

phase: uniform throughout in chemical composition
and physical state
Second Law =dG
T,P
0
equilibrium if and only if dG
T,P
=0
consider a system with two phases, say and :
G =n

+n

assume an amount dn goes from phase to phase

at constant T and P:
dG
T,P
=

(dn) +

dn
dG
T,P
=(

)dn
dG
T,P
<0 if

>

spontaneous transport of matter from regions of high

chemical potential to regions of low chemical poten-
tial
PChem I 4.1
phase with the lowest chemical potential (Gibbs
free energy) is stable
chemical potential of a sample is uniform, if the
sample is at equilibrium, regardless of how many
phases are present
_

T
_
P
=S
phase coexistence: dG
T,P
=0

(T, P) =

(T, P)
PChem I 4.2
=T =T(P) or P =P(T)
phase coexistence line or phase boundary in T-P-
plane
phase diagrams
[Figure: typical phase diagram for a PVT system, Fig. 4.1]
[Figure: phase diagram for water, Fig. 4.5]
[Figure: phase diagram for carbon dioxide, Fig. 4.4]
[Figure: phase diagram for helium-4, Fig. 4.7]
derive equation for phase boundary
move along phase boundary line from one equlibrium
point a = (T, P(T)) to another equilibrium point b =
(T +dT, (P +dP)(T +dT))
[Figure: phase boundary, Fig. 4.12]

+d

+d

=d

along P =P(T)
d=SdT +V dP
P =P(T) : S

dT +V

dP =S

dT +V

dP
PChem I 4.3
(S

)dT =(V

)dP
P =P(T) :
dP
dT
=
S

=
S
V
Clapeyron equation
S
trs
=
H
trs
T
trs
dP
dT

P=P(T)
=
H
TV
solid-liquid boundary
= solid, = liquid
dP
dT
=
H
fus
TV
fus
H
fus
>0,

V
fus

typically small
V
fus
usually >0 (not true for water)
=
dP
dT
typically large, usually positive
PChem I 4.4
if H
fus
=const and V
fus
=const, then
P
2
=P
1
+
H
fus
V
fus
ln
_
T
2
T
1
_
note: (T
1
, P
1
) and (T
2
, P
2
) are both points on the phase
boundary
T
2
T
1
=
T
1
+T
2
T
1
T
1
=1+
T
2
T
1
T
1
ln(1+x) =x +. . . for |x| 1
P
2
P
1
+
H
fus
T
1
V
fus

_
T
2
T
1
_
for

T
2
T
1

T
1
1
solid-gas or liquid-gas boundary
= solid or liquid, = gas
H =H
sub
or =H
vap
, V =V
sub
or =V
vap
dP
dT
=
H
TV
PChem I 4.5
V =V (g)V (s/l ) V (g) =RT/P (treating the gas as
ideal)
dP
dT
=
H
T
RT
P
=
H P
RT
2
1
P
dP
dT
=
H
RT
2
d lnP
dT
=
H
RT
2
Clausius-Clapeyron equation
if H =const, then
_
2
1
d lnP =
H
R
_
2
1
1
T
2
dT
lnP
2
lnP
1
=
H
R
_

1
T
2
+
1
T
1
_
ln
_
P
2
P
1
_
=
H
R
_
1
T
2

1
T
1
_
P
2
=P
1
exp
_

H
R
_
1
T
2

1
T
1
_
_
vapor pressure
PChem I 4.6
Troutons rule: S
vap
85J K
1
mol
1
=H
vap
T
boil
85J K
1
mol
1
(Troutons rule does not hold for compounds with H-
bonding)

l
(T, P) =
g
(T, P) P
l g
=P(T)

s
(T, P) =
l
(T, P) P
sl
=P(T)
_
intersect in
one point
(T
3
, P
3
) :
s
=
l
=
g
triple point, material property
Ehrenfest classication:
_

P
_
T

P
_
T
=V

=V =0
_

T
_
P

T
_
P
=S

+S

=S =
H
T
=0
rst derivatives of or G are discontinuous: rst-
order transition
C
P
=
_
H
T
_
P
=T
_
S
T
_
P
=T
_

2
G
T
2
_
P
=
PChem I 4.7
H is discontinuous at transition, derivative does not
exist: C
P
=
dq =C
P
dT, phase transition: dq =0, dT =0 =C
P
=

second-order transitions:
rst derivatives of are continuous, V =0 and S =
0, and second derivatives are discontinuos, C
P
=0
such transitions are rare
[Figure: Ehrenfest classication, Fig. 4.16]
more common:
V =0, S =0, C
P
logarithmically: critical point
critical point = second-order transition
[Figure: C
P
for critical point, Fig. 4.17]
PChem I 4.8