Chapter 4.

Real Materials + 1 Component

Physical Transformations of Pure Substances
The Stability of Phases
Basic Principle:
The tendency of systems slides down to lower chemical potential.
The principle of uniform chemical potential applies.
However, many phases can be in equilibrium.

Temperature dependence of phase stability

m (s), m (l), m (g): the chemical potentials of the solids, liquids, and gas
phases.
 G   Gm   m 
   S ,       Sm
 T  p  T  p  T  p
As T rises, the chemical potential falls because Sm is always positive.
The gradient is steeper for gases than for liquids (Sm(g) > Sm(l)), and
steeper for a liquid than the solid (Sm(l) > Sm(s)).
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 The schematic temperature dependence of
Pure Substance the chemical potential of the solid, liquid,
and gas phases of a substance.
constant P
The lines should be curved.
× curvature
Chemical potential, m

The phase with the lowest chemical

Solid
× potential at the specified T and P is the
most stable.
Liquid
The transition temperatures, the melting
Gas and boiling temperatures, are the
temperatures at which the chemical
=G × potentials of two phases are equal.

Solid
stable
Liquid
stable
Gas
stable ----------
The chemical potentials of
Tf Tb
two phases
Temperature, T are equal in multicomponents:
mLia = mLib
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mSia = mSib 2
 Figure 4A.4

The general regions of pressure and

Critical
temperature where solid, liquid, or gas is
Solid point
Pressure, p

stable (that has the lowest chemical

s l Liquid
potential).

The solid phase is the most stable phase

Triple at low temperatures and high pressures.
point
Vapor

T3
v Tc
Temperature, T

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 Uniform Chemical Potential Only 1 Component

In Equilibrium
Figure 4A.3
The vapor pressure of a liquid or
solid is the pressure exerted by the
Vapor vapor in equilibrium with the
H2O condensed (L or S) phase.
atom in v

↓ ↑
atom in l

Liquid
H2O -------------
T < Tmelting 300 K with Ar at 1 atm
In general, Au (materials) and air (or pure nitrogen).
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 Only 1 Component

*** When two or more phases are in

equilibrium,
V
Chemical potential of a component

↓ ↑ __ is

the same in each phase, and is the same

L at all points in each phase.

P = equilibrium vapor pressure

ΔG = 0

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 Only 1 Component
T < Tc T > Tc
P < Pc P > Pc (a) A liquid in equilibrium with its vapor.

(b) When a liquid is heated in a sealed

container, the fraction of vapor phase
increases and that of liquid decreases
slightly.
V V (c) There comes a stage at which the two
densities are equal, and the interface
V=L between the fluids disappears.

The container needs to be strong: the

L L critical temperature of water is 374˚C and
the vapor pressure is then 218 atm.

Example:
continuous heating (constant volume)
T + P going up
Figure 4A.6
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 with Ar (or air) for the desired pressure
CO2 Phase diagram for carbon dioxide.
As the triple point lies at pressures well
above atmospheric, liquid carbon dioxide
does not exist under normal conditions

A pressure of at least 5.11 atm must be

 
applied.

5.11 atm

1 atm ~300 K

Dry ice
- Baskin Robbins (ice cream)
- chemistry department
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 8000 H2O + Many Metastable Ice Phases
Ice VI

6000
Ice V
Figure 4A.9
Liquid
(water)
Equilibrium Phase Diagram for
4000
water showing the different solid
p/atm

Ice III
phases of ice.
Ice II
2000
Ice I Critical


point


218.3

2
Normal
Ice I freezing
point
Vapor
1 Normal (steam)
Triple boiling
point point

0.006
200 300 400 500 600 700
273.15 273.16 373.15
(Tf) (T3) (Tb) Temperature, T/K 647.30
(Tc)
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 _
He Figure 4A.11
The phase diagram for helium (4He).

The l-line marks the conditions under which

the two liquid phases are in equilibrium.

Helium-II is the superfluid phase.

_ Note that a pressure of over 20 bar must be

exerted before solid helium can be obtained.

Different solid phases:

hcp: hexagonal close packing
bcc: body-centered cubic

~2 K

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 m = Gm
4B.1(b). Chemical Potential Dependence on Pressure Pure Substances

 m 
   Vm
 p T
An increase in pressure raises the chemical potential (because V is certainly
positive), and increases it much more for gases than either liquids or solids.
The molar volume of gas is ~1000 times larger than that of liquid or solid.
An increase in pressure increases the chemical potential of a liquid slightly more
than the potential of a solid, resulting in the raising of the freezing point.
m ~5×1022 atoms/cm3

P + DP
P + DP

P
l P + DP
Figure 4B.2

s
Melting point
P
The pressure dependence of the chemical
potential, and its effect on the melting and
raised boiling point boiling points.
raised P

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Tf T´f Tb v T´b
1 mole of gas (6×1023 atoms or molecules) in 22.4 liter 10
Figure 4B.2  m  Tm
Tm    Vm S L ←
→  p T
general Si
S
Water
Tm S-L L

-
The pressure dependence of the chemical potential depends on the molar volume of the
phase. In nature, the lines should be curved.

(a) In general, the molar volume of solid is less than that of the liquid, and m (s)
increases less than m (l). As a result, the freezing temperature rises.

(b) The molar volume is greater for the solid than the liquid (as for Si or water):
m (s) increases more strongly than m (l).
The freezing temperature is lowered.

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4B.2. The Location of Figure 4B.4
Phase Boundaries

solid - liquid
liquid - vapor
solid - vapor
a phase - b phase

When pressure is applied to a system in which two phases are in equilibrium (at a),
the equilibrium is disturbed.

It can be restored by changing the temperature, so moving the state of the system to b.
It follows that there is a relation between dp and dT that ensures that the system
remains in equilibrium as either variable is changed.

-Wed/Apr/06/22
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 Boundary of a Phase – b Phase
4B.2(a). Phase Diagrams
The boundaries between two phases lie at the values of p and T
where the two phases can exist.
phase a  -  phase b Ga = Gb at Ttr & Ptr
m (a ; p, T )  m ( b ; p, T )
________________________ (1)
dG   SdT  Vdp
dGm  dm   S m dT  Vm dp (2)

Combining Eqs. (1) and (2), we know

___________________
 S (a )dT  V (a )dp  S (b )dT  V (b )dp (3)
m m m m

Vm (a ) Vm (b )dp  Sm (a )  Sm (b )dT

dptr DSm

_____
dTtr DVm Clapeyron equation
French: [klapɛʁɔ̃]
(4)
(4B.5a)

where DSm  Sm (a )  Sm (b ), DVm  Vm (a ) Vm (b )

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 dPtr DH tr
Solid-Liquid Boundary 
dTtr Ttr DVtr
_________
At the melting point Tf

___________
DG  DHm T DS  0
melt , m f m Gs = Gl at Tm

The molar entropy change of melting

DH melt ,m
DS m 
Tf
dp DS m
From eq (4) 
dT DVm
(5) (4B.6)
dp DH melt ,m

dT T f DVm
melting = fusion

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 dPtr DH tr

_______
dTtr Ttr DVtr
On integrating eq (5), the equation of the solid-liquid equilibrium curve

DH melt ,m T (assuming latent heat (6)

p  p* ln
DVm T* independent of P and T)

where p* and T* are the pressure and temperature on some point of

the equilibrium line.

When T is close to T*, the logarithm can be approximated using

T   T T * T T *
ln   ln1  
T *  T*  T*

 DH melt ,m 
 p  p *  T  T *
 T * DV m 

(4B.8)
which is linear in T.
T * DT  T p * Dp  p
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 dPtr DH tr

dT Ttr DVtr
_________
tr

 DH melt ,m 
p  p *  T  T *
 T * DVm 

Figure 4B.5
A typical solid-liquid phase boundary slopes steeply upwards.
This slope implies that, as the pressure is raised, the melting temperature rises.
Most substances behave in this way.

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 Note that water freezes 0oC at 1 atm.
Example:
What is the freezing point of water under a pressure of 1500 atm?
DH melt ,m  6.01kJ / mol ~0.5 eV/atom in Si
(assuming independent of P and T)
DVmelt ,m  1.7cm / mol
3

Solution:
DH melt ,m

 

T  T exp p  p DVmelt ,m / DH melt ,m   p p  

DVm
T
ln 
T
 
 1500 1 1.013105 Nm  2  1.7cm 3 / mol 
 273.15K exp 

 6.01kJ / mol 
 273.15K exp 0.043
 261.7 K
DT  T  T   _________
11.50 C

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 4B.2(c). The Liquid-Gas Boundary dPtr DH tr

________
dTtr Ttr DVtr
DHvap,m : the molar enthalpy of vaporization
DVvap,m : the molar volume change on vaporization

dp DHvap ,m dp DH melt ,m
 the Clapeyron equation 
dT TDVvap ,m dT Ttr DVmelt ,m
DHvap ,m  0, DVvap ,m

dp
 is much smaller than in the case of solid-liquid equilibrium.
dT

The slope depends on DVvap,m, and the volume of the gas is sensitive to P.
Increasing pressure decreases V(g) and therefore DVvap,m also.
The slope  dp  increases as p increases, and this is why the line drawn in Figure 4B.7 curls upwards.
 dT 

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(skip) (skip)

Assuming that the gas behaves ideally, Vm(g) may be replaced by

dp DH vap ,m pDH vap ,m
  DVvap ,m  Vm g   Vm l   Vm g 
dT  RT  RT 2
T  
 p 
On rewriting,
d ln p  DH vap ,m (4B.10)
 Clausius - Clapeyron equation (7)
dT RT 2
Assuming that DHvap,m does not depend on the temperature,

   DH vap ,m  1 1  (4B.11)
p  p exp      Ideal Gas +
 R  T T  Negligible Volume of Liquid

where p* is the pressure at some temperature T*.

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(skip) (skip)
Figure 4B.5

dPtr DH tr

dTtr Ttr DVtr
   DH vap ,m  1 1 
p  p exp     
 R  T T 
Ideal Gas +
Negligible Volume of Liquid

A typical liquid-vapor phase boundary.

The boundary can be regarded as a plot of the vapor pressure against T.
The phase boundary terminates at the critical point (not shown).

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4B.2(c). Solid-Vapor dPtr DStr DH tr
 
Boundary ____________
dTtr DVtr Ttr DVtr
DHsub,m: the molar enthalpy of sublimation
Similarly,

  DH sub,m  1 1    DH vap ,m  1 1 
p  p exp
*
  *  p  p exp 
*
  * 
 R  T T   R  T T 

______
usu. DHsub,m > DHvap,m
dp
The slope is steeper for sublimation than for vaporization. (See Fig. 4B.8)
dT
________________________________________________________________________

The Solid-Liquid-Gas Equilibrium

Triple Point: A point where solid, liquid, and gas can all coexist in
equilibrium. It is given by the values of p and T for
which all three chemical potentials are equal.

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4B.3. More Remarks about Phase Transitions
At the transition point, DS at Ttr
 Dm   m b    m a   
DH m  TDSm  T    T        0
 T p  T p  T p 
 Dm   m b    m a   DV at Ptr
DVm           0
 p T  p T  p T
 m   m 
Since both DVm and DHm are non-zero, it follows that   and 

 can
 p T  T p
be different on either side of the transition. In other words, the
derivatives of Gibbs free energy can be discontinuous. This is
the basis of the term the First-Order Phase Transition.
The case in which the first derivative of G is continuous, but the second
derivative is discontinuous.
→ the Second-Order Phase Transition.
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 True, In general,
all the time. but not all the time.

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 Second-Order Phase Transition
A continuous slope of m implies that the entropy and volume (and
hence the enthalpy) do not change at the transition.

The heat capacity is discontinuous at the transition but does not

become infinite.

The type of 2nd-order transition may include:

Order-Disorder Transition
DS at Ttr
Ferromagnetic Transition DV at Ptr
Ferroelectric Transition
Fluid-Superfluid Transition
.....

http://bp.snu.ac.kr Ttr Tc 24
  Dm   m b    m a   
 
DH m  TDS m  T    T     0
 T  p  T  p  T  p 
 

×
***
_
Ttr ×
~3kB/atom

Tc
× _
~3kB/atom

V H G S Cp
Figure 4B.9
(a) first-order and (b) second-order phase transitions.
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 c

a
abc abc
b slow
Equal
rates

Phase
Fast transition Equal
rates
Fast Equal
Tetragonal rates
Cubic
phase
phase

(a) (b)
Fig. 4B.11 One version of a second-order phase transition in which (a) a tetragonal phase
expands more rapidly in two directions than a third, and hence becomes a cubic phase, which (b)
expands uniformly in three directions as the temperature is raised.
There is no major rearrangement of atoms at the transition temperature, and hence the
enthalpy of transition may become zero.
Example: Perovskite Semiconductor
Formamidinium
Methylammonium [Cs0.05[{CH(NH2)2}0.83{CH3NH3}0.17]0.95]Pb(I0.83Br0.17)3 = ABX3
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 A B A B A B A B A B A B
Figure 4B.12
Order-Disorder Transition
(a) At T = 0, there is perfect order, with
different kinds of atoms occupying alternate
T=0K sites.
A B A B A B A B A AA B (b) As the temperature is increased, atoms
exchange locations and islands of each kind
of atom form in regions of the solid. Some
of the original order survives.
(c) At and above the transition temperature, the
islands occur at random throughout the
T < Tc T < Ttr sample.
A B B B AA B B A B B B
A and B atoms like each other,
compared to the A-A or B-B atoms.

T > Tc T > Ttr

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 Problems from Chap. 4
4A.4
4A.2(b)
4B.2 4B.4
4B.5(b)
4B.6 4B.12

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