Atkins Physical Chemistry, 9th Edition

Chapter 4

Chapter 4
Physical Transformations of
Pure Substances
http://gncpl.hanyang.ac.kr
( 113-2)

Tel. 2220-2329, E-mail. ywsuh@hanyang.ac.kr

1

Chapter 4

Atkins Physical Chemistry, 9th Edition

Physical Transformation of Pure Substances

Objectives:

Phase diagrams
3.1 The stabilities of phases

See a type of phase diagram that is a map of the

pressures and temperatures at which each
phase of a substance is the most stable
Deduce the phase rule that summarizes the
constraints on the equilibria between phases for
systems of more than one component
Consider the factors that determine the
positions and shapes of the boundaries
between the regions on a phase diagram
Vapor pressure as a function of temperature
Melting point as a function of pressure

Deal with the chemical potential, a property that

will be at the centre of our discussions of
mixtures and chemical reactions

3.2 Phase boundaries

3.3 Three representative
phase diagrams
Thermodynamic aspects of
phase transitions
4.4 The dependence of stability
on the conditions
4.5 The location of phase
boundaries
4.6 The Ehrenfest classification
of phase transitions

Atkins Physical Chemistry, 9th Edition

Chapter 4

Physical Transformations of Pure Substances

Physical transformation
Changes of phase without change of chemical composition
Example: vaporization, melting (fusion), the conversion of graphite to diamond
Phase: a form of matter that is uniform throughout in chemical composition
and physical state
Example: solid, liquid, and gas phases of a substance
How do we know the phase of a substance at a given P and T?
The Gibbs free energy can give us the answer to this question because
spontaneous processes have negative changes in Gibbs free energy.
Example: if we want to know the most stable phase of water at a given P and T,
we can calculate the Gibbs free energies of each phases, compare them and
pick the lowest one.
Chemical potentials are equivalent to molar Gibbs energies of pure
substances, so the phase with the lowest chemical potential will be the most
stable phase.
3

Chapter 4

Atkins Physical Chemistry, 9th Edition

The Number of Phases (P)

Solid
Various phases [e.g. crystal structures (diamond; graphite)]
Alloys (sometimes its difficult to tell this microscopic examination may be
necessary {dispersions uniform on macroscopic scale})
Miscible one phase (P=1)
Immisible multiple phases (P>1)
Liquid
Miscible liquids are one phase
Immiscible liquids are multiple phases (P>1)

Example:
CaCO3(s) CaO(s) + CO2(g)
Phases: P = 2 solid + 1 gas = 3

Gas
Systems consisting of gases can have only one phase
Shape or degree of subdivision irrelevant
Heterogeneous and homogeneous systems
Systems with one phase are homogeneous.
Systems with more than one phase are heterogeneous.
4

Atkins Physical Chemistry, 9th Edition

Chapter 4

Phase Transitions
Phase transition = the spontaneous conversion of one
phase into another phase which occurs at a
characteristic temperature for a given pressure
Example: water at 1 atm,
Ice = the stable phase of water below 0C (below 0C the
Gibbs energy decreases as liquid water changes into ice)
Water = the stable phase above 0C (above 0C the Gibbs
energy decreases as ice changes into liquid water)

Transition temperature (Ttrs)

the temperature at which the two phases are in equilibrium
and the Gibbs energy of the system is minimized at the
prevailing pressure.
Techniques for detecting a phase transition
Thermal analysis: the transition is detected by noting that the
temperature does not change even though heat is being
supplied or removed from the sample (Figure 4.2)
X-ray diffraction: the occurrence of a phase transition in a solid,
for different structures are found on either side of the transition
temperature

Fig. 4.2 A cooling curve at

constant pressure. The halt
corresponds to the pause in
the fall of temperature while
the first-order exothermic
transition (freezing) occurs.
This pause enables Tf to be
located even if the transition
cannot be observed visually.

Chapter 4

Atkins Physical Chemistry, 9th Edition

Thermodynamic Criteria of Phase Stability

All considerations will be based on the Gibbs energy, particularly on its molar Gibbs energy.
For a one-component system, molar Gibbs energy = chemical potential
Gm
=

Chemical potential: a measure of the potential that a substance has for undergoing
change in a system
Chapter 4: the potential of a substance to undergo physical change
Chapter 5: a broader significance and a more general definition of chemical potential
Chapter 6: the potential of a substance to undergo chemical change
At equilibrium, the chemical potential of a substance
is the same throughout a sample, regardless of how
many phases are present.

phase

phase(1) phase(2) dn
= 1 + 2 <0
= 11 + 22
= (21) < 0

If 1 > 2, spontaneous change (<0)

If 1 = 2, =0 (i.e., equilibrium)

dn
phase
6

Atkins Physical Chemistry, 9th Edition

Chapter 4

Phase Diagram
The phase diagram of a pure substance shows
the regions of pressure and temperature at which
its various phases are thermodynamically stable.
Any two intensive variables may be used
(such as temperature and magnetic field; in
Chapter 5 mole fraction is another variable),
but in this chapter we concentrate on
pressure and temperature.
The lines separating the regions, which are called
phase boundaries (or coexistence curves), show
the values of p and T at which two phases coexist
in equilibrium and their chemical potentials are
equal.

Fig. 4.4 The general regions of pressure and temperature where solid, liquid, or gas is stable
(that is, has minimum molar Gibbs energy) are shown on this phase diagram. For example,
the solid phase is the most stable phase at low temperatures and high pressures.
7

Atkins Physical Chemistry, 9th Edition

Chapter 4

Vapor Pressure
Consider a liquid sample of a pure substance in a closed vessel.
Vapor pressure of the substance
= the pressure of a vapor in equilibrium with the liquid
(a dynamic equilibrium exists
between evaporation and condensation)

Liquidvapor phase boundary in a phase diagram

how the vapor pressure of the liquid varies with temperature.

Solidvapor phase boundary

shows the temperature variation of the sublimation vapor

pressure, the vapor pressure of the solid phase.
The vapor pressure of a substance increases with temperature
because at higher temperatures more molecules have sufficient energy
to escape from their neighbors.

Atkins Physical Chemistry, 9th Edition

Chapter 4

Boiling and Melting (= Freezing)

When a liquid is heated in an open vessel, the liquid vaporizes from its surface.
When the vapor pressure is equal to the external pressure, vaporization can occur
throughout the bulk of the liquid and the vapor can expand freely into the surroundings.
The condition of free vaporization throughout the liquid is called boiling.
The temperature at which the vapor pressure of a liquid is equal to the external pressure
is called the boiling temperature at that pressure.
Normal boiling point (Tb) = boiling temperature at an external pressure of 1 atm
Standard boiling point = boiling temperature at an external pressure of 1 bar
1 bar is slightly less than 1 atm (1.00 bar = 0.987 atm)
The standard boiling point of a liquid is slightly lower than its normal boiling point.
Water: normal boiling point = 100.0C; standard boiling point = 99.6C
Melting temperature = temperature at which the liquid and solid phases of
a substance coexist in equilibrium under a specified pressure
The melting temperature of a substance is the same as its freezing temperature
because a substance melts at exactly the same temperature as it freezes.
Normal freezing point (Tf) = freezing temperature when the pressure is 1 atm
Standard freezing point = freezing point when the pressure is 1 bar
The normal and standard freezing points are negligibly different for most purposes.
The normal freezing point is also called the normal melting point.

Atkins Physical Chemistry, 9th Edition

Chapter 4

Critical Temperature and Pressure

Boiling does not occur when a liquid is heated in a rigid, closed vessel.
a. A liquid in equilibrium with its vapor.
b. When a liquid is heated in a sealed container, the density of
the vapor phase increases and that of the liquid decreases
slightly as a result of its expansion.
c. There comes a stage, at which the two densities are equal
and the interface between the fluids disappears.
This disappearance occurs at the critical temperature.
Critical temperature (Tc) = the temperature at which the
surface disappears.
critical pressure (Pc) = The vapor pressure at Tc

The critical temperature of water is 374C and the vapor pressure is 218 atm.
At and above the critical temperature, a single uniform phase called a supercritical fluid
fills the container and an interface no longer exists. That is, above the critical temperature,
the liquid phase of the substance does not exist.
10

Atkins Physical Chemistry, 9th Edition

Chapter 4

Triple Point ()
Triple point (T3)
A point at which the three phase boundaries meet
A set of conditions under which three different phases of a
substance (typically solid, liquid, and vapour) all
simultaneously coexist in equilibrium
The triple point of a pure substance occurs at a single definite
pressure and temperature characteristic of the substance.
T3 of water = 273.16 K and 611 Pa (6.11 mbar, 4.58 Torr)
the three phases of water (ice, liquid water, and water vapour)
coexist in equilibrium at no other combination of pressure and
temperature.
This invariance of the triple point is the basis of its use in the
definition of the thermodynamic temperature scale.
When the slope of the solidliquid phase boundary is shown in the diagram (common),
The triple point marks the lowest pressure at which a liquid phase of a substance can exist.
The triple point also marks the lowest temperature at which the liquid can exist.
The critical temperature is the upper limit.
11

Atkins Physical Chemistry, 9th Edition

Chapter 4

Gibbs Phase Rule

Phase rule (deduced by Gibbs)
= the number of parameters that can be varied independently (at least to a small
extent) while the number of phases in equilibrium is preserved.
= a general relation between the variance (or number of degrees of freedom), F,
the number of components, C, and the number of phases at equilibrium, P, for a
system of any composition

F = the number of intensive variables that can be changed independently without

disturbing the number of phases in equilibrium.
Constituent = a chemical species that is present.
Component = a chemically independent constituent of a system
C (number of components) = the minimum number of types of independent species (ions
or molecules) necessary to define the composition of all the phases present in the system.
Example

A mixture of ethanol and water two constituents

A solution of sodium chloride three constituentswater, Na+ ions, and Cl ionsbut only two
components because the numbers of Na+ and Cl ions are constrained to be equal by the
requirement of charge neutrality.

12

Chapter 4

Atkins Physical Chemistry, 9th Edition

Justification for F = C P + 2
Number of intensive variables

Number of intensive variables from EOS (equation

of state): 2 (P & T); (PV = nRT)
Composition for one phase; (C1) mole fractions (x1
+ x2 + + xc = 1)
For P phases: P(C-1)
Total number of intensive variables: P(C-1) + 2

At equilibrium (same chemical potential of

component J for all phases)

, = , = for P phase
component J (P-1) equation
C components C(P-1)

Phase rule : = () + ()
= +
For a one-component phase diagram,
Point: F = 0 / Line: F = 1 / Area: F = 2

Fig. 4.7 The typical regions of a onecomponent phase diagram. The lines
represent conditions under which the
two adjoining phases are in equilibrium.
A point represents the unique set of
conditions under which three phases
coexist in equilibrium. Four phases
cannot mutually coexist in equilibrium.

13

Atkins Physical Chemistry, 9th Edition

Chapter 4

Example for the Phase Rule

System of a single component and a single phase (C = 1, P = 1): F = 2

The pressure and temperature may be changed independently without changing the number of
phases.
Such a system is bivariant or it has two degrees of freedom.
A single phase is represented by an area on a phase diagram.

System of two phases in equilibrium (a liquid and its vapor, for instance) in a single
component (C = 1, P = 2): F = 1

The temperature (or the pressure) can be changed at will, but the change in temperature (or
pressure) demands an accompanying change in pressure (or temperature) to preserve the number
of phases in equilibrium.
The equilibrium of two phases is represented by a line in the phase diagram.
At a given temperature, a liquid has a characteristic vapor pressure.
At a given pressure, freezing (or any other phase transition) occurs at a definite T.

System of three phases in equilibrium: F = 0 (system invariant)

This special condition can be established only at a definite temperature and pressure that
is characteristic of the substance.
The equilibrium of three phases is represented by a point, the triple point, on a phase diagram.

Four phases cannot be in equilibrium in a one-component system because F cannot be

negative.
14

Atkins Physical Chemistry, 9th Edition

Chapter 4

Phase Diagram of CO2

Tc = 304.2 C
Pc = 72.9 atm

Positive slope (up from left to right) of the solid

liquid boundary the direction of this line is
characteristic of most substances.
This slope indicates that the melting temperature of
solid carbon dioxide rises as the pressure is
increased.
The triple point lies above 1 atm the liquid
cannot exist at normal atmospheric pressures
whatever the temperature. As a result, the solid
sublimes when left in the open (hence the name
dry ice).
To obtain the liquid, it is necessary to exert a
pressure of at least 5.11 atm.
Cylinders of carbon dioxide generally contain the
liquid or compressed gas; at 25C that implies a
vapor pressure of 67 atm if both gas and liquid are
present in equilibrium.
Carbon dioxide gas at 1 atm cannot be liquefied
except by applying high pressure reflects the
weakness of the intermolecular forces between the
nonpolar carbon dioxide molecules.

15

Atkins Physical Chemistry, 9th Edition

Chapter 4

Phase Diagram of H2O

(Ordinary
ice)

Water has one liquid phase but many different

solid phases other than ordinary ice (ice I).
Ice VII, for instance, melts at 100C but exists
only above 25 kbar. Two further phases, Ice XIII
and XIV, were identified at 160C but have not
yet been allocated in the phase diagram.
Many triple points occur in the diagram other
than the one where vapor, liquid, and ice I
coexist.
The solid phases of ice differ in the arrangement
of the water molecules: under the influence of
very high pressures, hydrogen bonds buckle
and the H2O molecules adopt different
arrangements.

The solid-liquid line has a steep negative slope.

As P , melting point decrease in volume on melting
Hydrogen bonding open structure of ice
Hydrogenbonded structure partially collapses on melting.
The liquid is denser than the solid.

16

Atkins Physical Chemistry, 9th Edition

Chapter 4

Phase Diagram of 4He

Helium behaves unusually at low temperatures
because the mass of its atoms is so low and their
small number of electrons results in them interacting
only very weakly with their neighbors.

For instance, the solid and gas phases of helium are

never in equilibrium however low the temperature: the
atoms are so light that they vibrate with a large
amplitude motion even at very low temperatures and
the solid simply shakes itself apart.
Solid helium can be obtained, but only by holding the
atoms together by applying pressure.
Pure helium-4 has two liquid phases. The phase
marked He-I in the diagram behaves like a normal
liquid; the other phase, He-II, is a superfluid; it is so
called because it flows without viscosity.
Helium is the only known substance with a liquidliquid
boundary, shown as the -line (lambda line).

17

Chapter 4

Atkins Physical Chemistry, 9th Edition

Supercritical CO2
(31.0C)

The critical temperature and pressure are readily accessible, it is cheap, and can
readily be recycled. The density of scCO2 at its critical point is 0.45 g cm3.
A great advantage of scCO2: no noxious residues once the solvent has been
allowed to evaporate. So, coupled with its low critical temperature, scCO2 is
ideally suited to food processing and the production of pharmaceuticals.
The low critical temperature and
critical pressure for CO2 make
supercritical CO2 a good solvent
for extracting nonpolar
substances (like caffeine)

18

Atkins Physical Chemistry, 9th Edition

Chapter 4

Thermodynamic Aspects of Phase Transitions

For a one-component system, the chemical potential = the molar Gibbs energy
As we already know how the Gibbs energy varies with temperature and pressure
(Section 3.9), we can expect to be able to deduce how phase equilibria vary as the
conditions are changed.

dG = d ( H TS ) = dH TdS SdT
G
G

dp
dT
+
=
= TdS + Vdp TdS SdT = SdT + Vdp

T p
p T
G
S
G
V

,
=

=
S
V

T
p
T

p
p

T
T
At very low temperatures and if the pressure is not too low, the solid phase of a
substance has the lowest chemical potential and is therefore the most stable phase.
However, the chemical potentials of different phases change with temperature in
different ways, and above a certain temperature the chemical potential of another
phase (another solid phase, a liquid, or a gas) may turn out to be the lowest.
19

Atkins Physical Chemistry, 9th Edition

Chapter 4

Temperature Dependence of Phase Stability

Gm

G
S
=

= Sm

T p
T p T p
As the temperature is raised,
the chemical potential of a pure substance decreases ( Sm > 0)
the slope of a plot of against T is negative.
Because Sm(g) > Sm(l), the slope of a plot of against
temperature is steeper for gases than for liquids.
Because Sm(l) > Sm(s), the slope is also steeper for a
liquid than the corresponding solid.
The steep negative slope of (l) results in it falling below
(s) when the temperature is high enough, and then the
liquid becomes the stable phase: the solid melts.
The chemical potential of the gas phase plunges steeply
downwards as the temperature is raised (because the
molar entropy of the vapour is so high), and there comes
a temperature at which it lies lowest. Then the gas is the
stable phase and vaporization is spontaneous.
20

Chapter 4

Atkins Physical Chemistry, 9th Edition

Melting Response to Applied Pressure

= V
= Vm
p T
p T
The slope of a plot of chemical
potential against pressure is equal
to the molar volume of the
substance.
An increase in pressure raises the chemical potential of any pure substance (because Vm > 0).
(a) In most cases, Vm(l) > Vm(s) and the equation predicts that an increase in pressure
increases the chemical potential of the liquid more than that of the solid. As shown in Fig.
4.13a, the effect of pressure in such a case is to raise the melting temperature slightly.
(b) For water, however, Vm(l) < Vm(s), and an increase in pressure increases the chemical
potential of the solid more than that of the liquid. In this case, the melting temperature is
lowered slightly (Fig. 4.13b).

21

Chapter 4

Atkins Physical Chemistry, 9th Edition

Vapor Pressure Response to Applied Pressure

Quantitative relation between the vapor pressure, p, when a

pressure P is applied and the vapor pressure, p*, of the liquid in

the absence of an additional pressure

At equilibrium : () = ()
By pressurizing with inert gas ; () = ()
For liquid, p p + dp, () = Vm(l)dp
For vapor, () = Vm(g)dp (dp: change in the vapor pressure)

dp
= d (l ) = Vm (l )dp
p
p*+ p
p dp
V (l )
V (l )
p
=
= m p p = p * exp( m p )
RT
Vm (l )dp ln
p* p
p*
p*
RT
RT

d ( g ) = RT
Fig. 4.14 Pressure may be
applied to a condensed
phases either (a) by
compressing the condensed
phase or (b) by subjecting it to
an inert pressurizing gas.
When pressure is applied, the
vapor pressure of the
condensed phase increases.

if

p = p * (1 +

Vm (l )
1
p << 1, e x = 1 + x + x 2 + 1 + x
RT
2

Vm (l )
p p * Vm (l )
p ) or
=
p
RT
p*
RT

22

Atkins Physical Chemistry, 9th Edition

Chapter 4

Example for Increase of Vapor Pressure

At 25 C, the density of water is 0.997 g/cm3, what is the extent of vapor
pressure increase when water is subjected to an applied pressure of 10 bar?
Vm (l )
p )
RT
V (l )
p p * Vm (l )
p = p * (1 + m p ) or
=
p
RT
p*
RT
p = p * exp(

18.015 g
1cm 3
= 18.1cm 3 mol 1

Vm (l ) =
1mol
0.997 g
Vm (l )
(18.1 10 6 m 3 mol 1 )(1 10 6 Pa )
= 7.3 10 3
p =
1
1
(8.314 JK mol )(298 K )
RT
V (l )
p p * Vm (l )
=
p = 7.3 10 3
p = p * (1 + m p ) or
RT
p*
RT

An increase of vapor pressure for water = 0.73%

23

Chapter 4

Atkins Physical Chemistry, 9th Edition

Location of Phase Boundaries

We can find the precise locations of the phase boundariesthe pressures and
temperatures at which two phases can coexistby making use of the fact that, when
two phases are in equilibrium, their chemical potentials must be equal.
Where the phases and are in equilibrium, (; p,T) =(; p,T)
By solving this equation for p in terms of T, we get an equation for the phase boundary.

The slopes of the phase boundaries

d ( ) = d ( ) S m ( )dT + Vm ( )dp = S m ( )dT + Vm ( )dp
[Vm ( ) Vm ( )]dp = [ S m ( ) S m ( )]dT
dp [ S m ( ) S m ( )] S m ( ) trs S
=
=
=
dT [Vm ( ) Vm ( )] Vm ( ) trsV

The Clapeyron equation is an exact expression for the slope

of the tangent to the boundary at any point and applies to
any phase equilibrium of any pure substance.
Fig. 4.15 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.

24

Chapter 4

Atkins Physical Chemistry, 9th Edition

Slope of SolidLiquid Boundary

Recall that T does not change during a phase transition.

S trs

H trs
=
Ttrs

fus H
dp trs S
=
=
dT trsV T fusV

Transition
= fusion

(P, T)

Assume that fusH and fusV change so

little with temperature and pressure that
they can be treated as constant.

p*

dp =

fus H

dT
fusV T * T

p = p*+

fus H
fusV

ln

T
T*

the equation of a steep

straight line when p is
plotted against T

T
T T *
T T *
= ln(1 +
)=
)
T*
T*
T*
fus H T T *
fus H
p p*
p = p*+

=
fusV T *
T T * T * fusV

(ln

(P*,T*)

25

Chapter 4

Atkins Physical Chemistry, 9th Edition

Slope of LiquidVapor Boundary

vap H
dp trs S
=
=
dT trsV T vapV
The enthalpy of vaporization is positive; vapV is large and positive.
Therefore, dp/dT is positive, but it is much smaller than for the solidliquid boundary.
dT/dp is large, meaning that the boiling temperature (Tb) is more responsive to
pressure than the freezing temperature (Tf).

Because the molar volume of a gas is so much greater than the molar volume of a
liquid, we can write vapV Vm(g).
Moreover, if the gas behaves perfectly, Vm(g) = RT/p.
vap H
1 dp d ln p vap H
dp
=

=
=
dT T ( RT / p )
p dT
dT
RT 2
ln p
vap H T dT
vap H 1
1
ln
d
p
=
=

ln p*
R T * T 2
R T T *
vap H 1
1
p = p * exp( ), =

R T T *

for the variation of vapor

pressure with temperature

26

Atkins Physical Chemistry, 9th Edition

Chapter 4

Examples
Estimate the typical size of the effect of increasing pressure on the boiling point of a
liquid.
vap H
vap S =

= 85 JK 1mol 1 (Trouton ' s constant )

RT (0.082dm 3 atmK 1mol 1 )(298 K )

vapV = Vm ( g ) Vm (l ) Vm ( g ) =
=
25 dm 3 mol 1
(1atm)
p
vap H
85 JK 1mol 1
85 JK 1mol 1
dp
=
=
=
= 3.4 103 Pa K 1 = 0.034 atm K 1
3
3
3
1
1
25 dm mol
25 10 m mol
dT T vapV
dT
29 K atm 1 A change of pressure of +0.1 atm can be expected to change a boiling
dp
temperature by about +3 K.

Estimate the vapour pressure of a liquid at any temperature from its normal boiling
point, the temperature at which the vapour pressure is 1.00 atm (101 kPa).
The normal boiling point of benzene is 80C (353 K) and vapH = 30.8 kJ mol1.
To calculate the vapor pressure at 20C (293 K),

vap H 1
1 30.8 103 Jmol 1
1
1
=
(

) = 2.15
=

R T T * 8.3145 JK 1mol 1 293K 353K
p = p * exp( ) = (101kPa) exp(2.15) 12 kPa
27

Chapter 4

Atkins Physical Chemistry, 9th Edition

Application of ClausiusClapeyron Equation

d ln p vap H
=
dT
RT 2
vap H
ln p =
+C
RT

ln p1 =

vap H
RT1

+ C , ln p2 =

vap H
p
ln 2 =
R
p1

vap H
RT2

+C

1 1

T2 T1

p=
(equilibrium) vapor pressure

ln p

m = Hvap/R

1/T

28

Chapter 4

Atkins Physical Chemistry, 9th Edition

Slope of SolidVapor Boundary

vap H
dp trs S
=
=
dT trsV T vapV

Triple point (T3)

vap H
dp
=
dT T vapV

for liquid-vapor boundary

H
dp
= sub
dT T subV

for solid-vapor boundary

sub H > vap H ( sub H = fus H + vap H )

Because the enthalpy of sublimation is greater than the enthalpy of vaporization,

the equation predicts a steeper slope for the sublimation curve than for the
vaporization curve at similar temperatures, which is near where they meet at the
triple point.

29

Chapter 4

Atkins Physical Chemistry, 9th Edition

Ehrenfest Classification of Phase Transitions

Many different types of phase transition
Familiar examples: fusion and vaporization
Less familiar examples: solid-solid, conducting-superconducting, fluid-superfluid transitions

Use thermodynamic properties of substances, and in particular the behavior

of the chemical potential, to classify phase transitions into different types.
The classification scheme was originally proposed by Paul Ehrenfest, and is known as the
Ehrenfest classification.

At the transition from a phase to another phase ,

G
= Vm

= V
p T
p T
( )
( )
= Vm ( ) Vm ( ) = trsV 0

p
p
T

G
= Sm

= S

T
T
p
p

The slopes of the chemical potential

plotted against either p or T are different
on either side of the transition. In other
words, the first derivatives of the
chemical potentials with respect to
pressure and temperature are
discontinuous at the transition.

H
( )
( )

= S m ( ) + S m ( ) = trs S = trs 0
Ttrs
T p T p

30

Atkins Physical Chemistry, 9th Edition

Chapter 4

First-order Phase Transition

First-order phase transition: a transition for which the first derivative of the
chemical potential with respect to temperature is discontinuous
Slope of a plot of H with respect to T: constant-pressure heat capacity (Cp)
At a first-order phase transition, H changes by a finite amount for an infinitesimal
change of temperature. Therefore, at the transition the heat capacity is infinite.
The physical reason is that heating drives the transition rather than raising the
temperature. For example, boiling water stays at the same temperature even
though heat is being supplied.

Fig. 4.19(a)
The changes in thermodynamic properties accompanying a 1st-order phase transition

31

Atkins Physical Chemistry, 9th Edition

Chapter 4

Second-order Phase Transition

Second-order phase transition: a transition in which the first derivative of with
respect to temperature is continuous but its second derivative is discontinuous
A continuous slope of (a graph with the same slope on either side of the
transition) implies that the volume and entropy (and hence the enthalpy) do not
change at the transition.
Cp is discontinuous at the transition but does not become infinite there.
Example: Conductingsuperconducting transition in metals at low temperatures
(phase transition of tetragonal to cubic phase)

Fig. 4.19(b)
The changes in thermodynamic properties accompanying a 2nd-order phase transition

32

Atkins Physical Chemistry, 9th Edition

Chapter 4

-Transition
-transition: a phase transition that is not first-order but
has infinite heat capacity at the transition temperature
The heat capacity increase well before the transition.
This occurs in:
Orderdisorder transitions in alloys
Onset of ferromagnetism
Fluidsuperfluid transition of liquid He

Example:
Orderdisorder transition in -brass (CuZn)
(a) At T = 0: perfect order with different kinds of
atoms occupying alternate sites
(b) As T 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 sample.

The shape of the heat

capacity curve
resembles the Greek
letter lambda.

33

Chapter 4

Atkins Physical Chemistry, 9th Edition

Checklist of Key Equations in Chap. 4

Property

Equation

Comment

Chemical potential

= Gm

For a pure substance

Phase rule

F=CP+2

Variation of with T

(/T)p = Sm

Variation of with p

(/p)T = Vm

Vapor pressure
p = p*exp(VmP/RT)
in the presence of applied pressure
Clapeyron equation

dp/dT = trsS/trsV

ClausiusClapeyron
Equation

d lnp/dT = vapH/RT2

P = Papplied p*

Assumes Vm(g) >> Vm(l)

and vapor is a perfect gas
34

Atkins Physical Chemistry, 9th Edition

Chapter 4

Road Map for Physical Equilibria (Chap. 4 & 5)

Chapter 5
35

Atkins Physical Chemistry, 9th Edition

Chapter 4

Homework for Chapter 4

Exercise 4.9(b) The vapor pressure of a substance at 20.0C is 58.0 kPa and its
enthalpy of vaporization is 32.7 kJ mol1. Estimate the temperature at which its
vapor pressure is 66.0 kPa.
Exercise 4.10(b) The vapor pressure of a liquid in the temperature range 200 K to
260 K was found to fit the expression ln(p/Torr) = 18.361 3036.8/(T/K). What is
the enthalpy of vaporization of the liquid?
Problem 4.7 50.0 dm3 of dry air was slowly bubbled through a thermally insulated
beaker containing 250 g of water initially at 25C. Calculate the final temperature.
(The vapor pressure of water is approximately constant at 3.17 kPa throughout, and
its heat capacity is 75.5 J K1 mol1. Assume that the air is not heated or cooled and
that water vapor is a perfect gas.)
Problem 4.10 Construct the phase diagram for benzene near its triple point at 36
Torr and 5.50C using the following data: fusH = 10.6 kJ mol1, vapH = 30.8 kJ
mol1, (s) = 0.891 g cm3, (l) = 0.879 g cm3.
36