- Transition temperature- two phases are in equilibrium and the
Gibbs free energy is minimized at the prevailing pressure.
Phase: uniform throughout in chemical composition and
physical state
Examples: gas, liquid and solid including allotropes of
solids, carbon or white black allotropes of phosphorus.
Simplest application of thermodynamic to discuss phase
transition of pure substances.
Involves phase diagram- a map of the pressure and
temperature showing the most stable phases.
Phase transition- the spontaneous conversion of one
phase into another phase at characteristic temperature fo a
given pressure.
e.g. H2O (Ice more stable T< 0oC; liquid water stable T >
0oC)
The transition temperature, Ttrs, - two phases are in equilibrium
and the Gibbs energy of the system is minimized at the prevailing
pressure.
Figure 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.
Detecting a phase transition ?
Thermal analysis-The transition is detected as the temperature does not
change even though heat is being supplied or removed from the sample
X-ray diffraction also reveals the occurrence of a phase transition in a solid, for
different structures are found on either side of the transition temperature.
- Spontaneous transition predicted by thermodynamic may
occur at a slow rate,
Diamond is thermodynamically unstable and kinetically stable
- Immeasurable slow process except at high temperature!
- Phase transition in gas and liquid is relatively faster as
mobilities of molecules allow
- Metastable phase- thermodynamically unstable phase
persists because the transition is hindered kinetically.
-Phase diagram shows the regions of the pressure and
temperature at which its various phases are
thermodynamically stable
-A substance is characterized by a variety of
parameters that can be identified on its phase
diagram.
-Lines separating the regions are phase boundaries,
show T and P values at which two phases coexisted in
equilibrium.
-The phase rule relates the number of variables that
may be changed while the phases of a system remain
in mutual equilibrium.
Liquid- vapour pressure (evaporation)
Solid- vapour pressure (sublimation)
At high T, more molecules escape giving
higher vapour pressure
 Boiling point- vapour pressure equals to atmospheric pressure;
vaporization occurs freely throughout the bulk of liquid and
vapour.
Tb- normal boiling temperature at P = 1 atm
Tstd standard boiling temperature at P = 1 bar (1 bar = 0.987atm)
Boiling does not occur in rigid, closed vessel ?
(i) density of vapour increases; density of liquid drops (why?)
(ii) subsequently., vapour = liquid and this leads to disappearance
of two phases at temperature which called Critical
temperature!!!!!
Vapour pressure at critical temperature known as Critical
Pressure, a single uniform phase (Supercritical fluid) fills the
container and no interface exists.
Vapour
Supercritical fluid at Tc and Pc
liquid
-Positive slope of solid-liquid boundary-
Tm increases as pressure rises
Ttriple 5.11 atm (> 1 atm) in which liquid
cannot exist at normal atmosphere pressures
whatever the temperature, hence sublimation
occurs
Cylinder carbon dioxide generally contain
liquid and compress gas.
Phase diagram of H2O
At T= 25oC, Pvap = 67 atm if gas and liquid are
in equilibrium
If gas squirts through throttle, it cools by the
Joule-Thomson effect , it emerges into a
region where P = 1 atm and condenses into a
Phase diagram of CO2
finely snow-like solid
Melting temperature- the liquid and solid phases of a substance coexist in
equilibrium under specified pressure.
Freezing temperature = melting temperature?
1 atm normal freezing point ; 1 bar = standard freezing point (analogous
to naming boiling point!)
Triple point - Three different phases of a substance coexist in equilibrium
simultaneously where three phase boundaries meet and this occurs at
definite pressure and temperature
Invariant point- 0 degree of freedom; lowest pressure and temperature for
liquid phase.
Example: Ttriple water is at 273.16 K and 611 Pa .
What does it mean?
Do you know?
Supercritical carbon dioxide- ideal solvent for food processing and
pharmaceutical industries.
Accessible at T = 304.2 K (but 72.9 atm) , good solubility towards
solutes, no noxious residues once evaporate!
Liquid-vapour boundary summarize variation of
vapour pressure with temperature and boiling
temperature with pressure
Solid-liquid boundary very steep slope
showing enormous pressure required to bring
drastic changes.
Negative slope, up to 2k bar indicates
Tm falls with increasing pressure
Due to decrease of volume upon melting (ice=
0.92 g/cm3 water = 1 g/cm3), ice has very
open structure similar to that of wurtzite.
O
H - Water molecules are held apart, as well as
together by the hydrogen bonds between
them but structure partly collapses on
melting, this gives liquid slightly denser
than the solid
 Solid-gas boundary never exists- not in
equilibrium however low the temperature
Phase diagram is under consideration of
He atoms are so light and vibrate with a thermodynamically but not kinetically.
large amplitude motion, shake itself apart
even at low temperatures.
= chemical potential; potential in which a
Solid He obtained only by applying substance has undergoing for change in a
pressure to hold them together. system
Two isotopes, 3He and 4He exist- Gm = molar Gibbs free energy ?
4He has two liquids normal and

supercritical separated by -line (liquid-

Second Law applies-
liquid boundary)

Phase diagram of Helium He-II supercritical liquid flows without Chemical potential of a sample is uniform, if the sample
viscosity . is at equilibrium, regardless of how many phases are
3He
present
is unusual entropy solid > entropy
liquid; melting is exothermic.

- Second Law dGT,P 0 ; Chemical potential of a sample is uniform, if the sample

- Equilibrium if and only if dGT,P = 0 is at equilibrium, regardless of how many phases are present
-Consider a system with two phases, and

- Assume an amount dn goes from

phase to phase at constant T and P:

- spontaneous transport of matter from regions of high chemical

potential to regions of low chemical potential
- phase with the lowest chemical potential (Gibbs free energy) is
stable phase coexistence line or phase boundary in T-P plane
 The dependence of stability on the conditions
(a) The chemical potential of a substance
- At low temperature and not too low pressure, solid
substance has the lowest chemical potential, -
decreases with increasing temperature at a
most stable! rate determined by its molar entropy.
of different phases (another solid, liquid or gas) (b) The chemical potential of a substance
vary with different temperature, turn to be lowest increases with increasing pressure at a rate
and this transition to second phase is determined by its molar volume.
spontaneous and kinetically feasible. (c) When pressure is applied to a condensed
phase, its vapour pressure rises.
i. Temperature dependence of phase stability
ii. Response of melting to applied pressure
iii. Effect of applied pressure to vapour pressure

i. Temperature dependence of phase stability

Temperature dependence is expressed in term of entropy of the Most substances melt at a higher temperature when subjected to
system, (G/T)p = S. Chemical potential just another expression pressure.
of molar Gibbs energy Pressure, P ,prevents formation of less dense liquid phase.
(preferably, solid phase with higher density)

S > O, hence, decreases with increasing Exception case, water whereby its liquid has higher density than solid
temperatures. phase (Ice).
- Application of pressure- encourages formation of liquid phase; water
S(liq.) S(vap); hence, slope is steeper freezes at low temperature when it is under pressure.
for vapour than liquid.

If T is high enough, liquid becomes Slope of a plot of against T equals to the molar volume of
stable phase if compared to solid: the substance.
melting P (because Vm > 0)
Tm ? Applied pressure?
plunges steeply as molar entropy of
vapour is so high : liquid gas
 In most case, molar volume Vm(l) > Vm(s), this predicts
increase in pressure increases the chemical potential of the
liquid more than that of the solid.
Effect of pressure in (a) increases the
freezing temperature, Tf slightly
The pressure dependence of the chemical
potential of a substance depends on the
molar volume of the phase!!!!!!
However, for water Vm(s) > Vm(l), increase of
pressure increases the chemical potential of
solid than that of liquid. Tm decreases slightly
Calculate the effect of an increase in pressure of 1.00 bar on the
liquid and solid phases of carbon dioxide (of molar mass 44.0 g
mol1) in equilibrium with densities 2.35 g cm3 and 2.50 g cm3,
respectively.
[(l) = +1.87 J mol1, (s) = +1.76 J mol1; solid forms]
Example: Calculate the effect on the chemical potentials of ice and water of
increasing the pressure from 1.00 bar to 2.00 bar at 0oC. The density of ice is
0.917 gcm-3 and that of liquid water is 0.999 gcm-3 under these conditions. (1 bar
= 1x 105 Pa or Nm-2)
Solution:
= Vm P ; hence we need to determine the molar volume first.
Vm = M / (molar mass divided by molar density); P = (2.00 bar -1.00 bar)
= (M P) /
Vm (ice) = 18.00 gmol-1/ 0.917 gcm-3 =19.63 cm3mol-1
= 1.963 x 10-5 m3mol-1
(ice)= Vm P = 1.963 x 10 m mol-1 x 1x105 Nm-2
-5 3
= 1.963 Nm mol-1 or Jmol-1
Vm (water) = 18.00 gmol-1/ 0.999 gcm-3 =18.02 cm3mol-1
= 1.802 x 10-5 m3mol-1
(water)= Vm P = 1.802 x 10-5 m3mol-1 x 1x105 Nm-2
= 1.802 Nm mol-1 or Jmol-1
Hint: The chemical potential of ice rises more sharply than that of water
so, if they are initially in equilibrium at 1 bar, then there will be a tendency
for the ice to melt at 2 bar.
iii. The vapour pressure of a liquid subjected to pressure
When pressure is applied to a condensed phase, its vapour
pressure rises: in effect, molecules escape as a gas.
How pressure exerted? (i)Mechanically or (ii) injecting inert gas
Case (ii)-The vapour pressure is the partial pressure of the vapour
in equilibrium with the condensed phase.
Possible complications:
a. if the condensed phase is a liquid, then the pressurizing gas
might dissolve and change the properties of the liquid.
b. Gas phase molecules might attract molecules out of the liquid
by the process of gas solvation, the attachment of molecules
to gas-phase species.
 The quantitative relation between the vapour pressure, p and the
vapour pressure, p*, of the liquid in the absence of an additional Deriving eq. 4.4.
pressure is At equilibrium, the chemical potentials of the liquid and its
vapour are equal: (l) = (g).
For any change that preserves equilibrium,
d(g) = d(l).
P Applied pressure
p* - Vapour Pressure of the liquid (without additional pressure) When the pressure P on the liquid is increased by dP, the
chemical potential of the liquid changes by
This shows how the vapour pressure increases when the pressure d(l) = Vm(l)dP.
acting on the condensed phase is increased. The chemical potential of the vapour changes by
d(g) = Vm(g)dp But dp????

If the vapour assumed as perfect gas, the molar volume can be

replaced by Vm(g) = RT/p, and

Then, d(g) = RTdp/p.

Equate both changes in chemical potentials of the vapour and the liquid: Dividing both sides by RT and assume that the molar volume of the liquid
Remiains constant throughout the small range of pressures involved:

If no additional pressure acting on the liquid, P (the pressure experienced

by the liquid) equals to the normal vapour pressure p*,
so when P = p*, p = p* too. Integrating and hence

When there is an additional pressure P on the liquid, with the result that
P = p + P, the vapour pressure is p(the value we want to find).
Rearrange and this gives eq.4.4 Recall : eln x = x
Provided the effect of pressure on the vapour pressure is small, a good
approximation is to replace the p in p + P by p* itself, and to set the
upper limit of the integral to p* + P. For water, which has density 0.997 g cm3 at 25C and therefore molar
volume 18.1 cm3 mol1, when the pressure is increased by 10 bar (that
The integrations required are therefore as follows: is, P = 1.0 106 Pa)

where we have used 1 J = 1 Pa m3. It follows that p

= 1.0073p*, an increase of 0.73 per cent.

Key Points
(a) The Clapeyron equation is an expression for the slope of a
phase boundary.
(b) The Clapeyron equation gives an expression for the slope of
the solidliquid phase boundary in terms of the enthalpy of
fusion.
(c) The ClausiusClapeyron equation is an approximation that
relates the slope of the liquidvapour boundary to the enthalpy
of vaporization.
(d) The slope of the solidvapour boundary is similarly related
to the enthalpy of sublimation.
Let p and T be changed infinitesimally, but in such a way that
the two phases and remain in equilibrium.
Chemical potentials of the two phases must be equal
d() = d().
Recall equation, dG = Vdp SdT
Then, d = SmdT +Vmdp
where Sm() and Sm() are the molar entropies of the phases
and Vm() and Vm() are their molar volumes. Hence
{Vm() Vm()}dp = {Sm() Sm()}dT
The precise locations of the phase boundariesthe pressures and
temperatures at which two phases can coexist
The chemical potentials of phases and must be equal at equilibrium
Solving this equation for p in terms of T, equation for the phase boundary
is obtained
(a) The slopes of the phase boundaries
At point a, equilibrium is disturbed if
pressure is applied, but it can be
restored by changing the temperature
(states shifts to point b)
Slope dp/dT
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.
It implies that the thermodynamic data are used to
predict the appearance of phase diagrams and to
understand their form.
A more practical application is to the prediction of the
response of freezing and boiling points to the application
of pressure.

Melting (fusion) is accompanied by a molar enthalpy change fusH
and occurs at a temperature T.
The molar entropy of melting at T is therefore fusH/T and the
Clapeyron equation becomes
Assuming fus H and fus V remained constant if only little change
with temperature and pressure
If the melting temperature is T* when the pressure is p*, and T
when the pressure is p,

The equation of the solid-liquid boundary is

A typical solid-
liquid phase
fusV is the change in molar volume that boundary slopes
occurs on melting. steeply upwards.
The enthalpy of melting is positive and Simplify the (In T/ T*) term using Thomson-James
Pressure Tm
the volume change is usually positive and
always small. approximation and T is close to T*, hence,
The slope dp/dT is steep and usually
positive (Fig. 4.16).

The entropy of vaporization at a temperature T is equal to vapH/T Method

The Clapeyron equation for the liquid-vapour boundary is therefore
To use eqn 4.10 we need to estimate the right-hand side.
At the boiling point, the term vapH/T is Troutons constant (Section 3.3b).
Because the molar volume of a gas is so much greater than the molar volume of a
liquid,
vapV = Vm(g) Vm(l) Vm(g)

The enthalpy of vaporization is positive; vap V is large and positive.
Therefore, dp/dT is positive, (but it is much smaller than for the
solid-liquid boundary).
It follows that dT/dp is large, and hence that the boiling temperature
is more responsive to pressure than the freezing temperature.
Also assumeVm(g) the molar volume of a perfect gas (at low pressures, at least).
Answer
Troutons constant has the value 85 J K1 mol1. The molar volume of a perfect gas
is about 25 dm3 mol1 at 1 atm and near but above room temperature. Therefore,
We have used 1 J = 1 Pa m3.

This value corresponds to 0.034 atm K1 and hence to dT/dp = 29 K atm1.

Therefore, a change of pressure of + 0.1 atm can be expected to change a
boiling temperature by about + 3 K.
Because the molar volume of a gas is so much greater than the molar
volume of a liquid, we can write vap V Vm(g)
if the gas behaves perfectly, Vm(g) = RT/p. These two approximations
turn the exact Clapeyron equation into
Clausius-Clapeyron equation for the variation of vapour pressure
with temperature:
assume that the enthalpy of vaporization is independent of
temperature, this equation can be integrated as follows:
Recall: dx/x = d ln x
where p* is the vapour pressure when the temperature
is T* and p the vapour pressure when the temperature
is T.
Using Eq. 4.12 to 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 (from Table 2.3)
Therefore, to calculate the vapour pressure at 20C (293 K),
Subsitute this value into E.q. 4.12 with p* = 101 kPa. The result is
12 kPa. The experimental value is 10 kPa.
Therefore, because the integral on the left evaluates to
ln(p/p*), the two vapour pressures are related by
A typical liquid-vapour phase boundary. The
boundary can be regarded as a plot of the
vapour pressure against the temperature.
The phase boundary has the opposite
curvature (see Fig. 4.11). This phase
boundary terminates at the critical point
The only difference between this case and the last is the replacement
of the enthalpy of vaporization by the enthalpy of sublimation, sub H.
Because the enthalpy of sublimation is greater than the enthalpy of
vaporization (recall that sub H = fus H + vapH),
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 (Fig. 4.18).
Near the point where they coincide (at the
triple point), the solid-gas boundary has a
steeper slope than the liquid-gas boundary
because the sub H is greater than the vapH
The temperatures that occur in the Clausius-
Clapeyron equation for the slope have similar
values.
 (a) The thermodynamic basis
Many familiar phase transitions, like fusion and vaporization, are
(a) Different types of phase transition are identified by the accompanied by changes of enthalpy and volume.
behaviour of thermo-dynamic properties at the transition These changes have implications for the slopes of the chemical potentials
temperature. of the phases at either side of the phase transition.
(b) The classification reveals the type of molecular process Thus, at the transition from a phase to another phase ,
occurring at the phase transition.

It is possible to use thermodynamic properties of substances, and in

particular the behaviour of the chemical potential, to classify phase
transitions into different types. Known as Ehrenfest Classification

Because trs V and trs H are non-zero for melting and vaporization, it follows that
for such transitions the slopes of the chemical potential plotted against either A second-order phase transition in the Ehrenfest sense is one in which
pressure or temperature are different on either side of the transition (Fig. 4.19a). the first derivative of with respect to temperature is continuous but its
second derivative is discontinuous.
In other words, the first derivatives of the chemical potentials with respect to
pressure and temperature are discontinuous at the transition.
A continuous slope of (a graph with the same slope on either side of
The constant-pressure heat capacity, Cp, of a substance is the slope of a plot of the the transition) implies that the volume and entropy (and hence the
enthalpy with respect to temperature. enthalpy) do not change at the transition (Fig. 4.19b).
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
The heat capacity is discontinuous at the transition but does not become
physical reason is that heating drives the transition rather than raising the
temperature. e.g., boiling water stays at the same temperature even though heat is
infinite there. An example of a second-order transition is the
being supplied. conducting-superconducting transition in metals at low temperatures.2
The term -transition is applied to a
phase transition that is not first-order
yet the heat capacity becomes infinite at
the transition temperature.
Typically, the heat capacity of a system
that shows such a transition begins to
increase well before the transition
(Fig. 4.20), and the shape of the heat
capacity curve resembles the Greek letter
lambda.
First-order transitions typically involve the relocation of atoms,
molecules, or ions with a consequent change in the energies of their
interactions.
Thus, vaporization eliminates the attractions between molecules and a
first-order phase transition from one ionic polymorph to another
involves the adjustment of the relative positions of ions.
One type of second-order transition is associated with a change
in symmetry of the crystal structure of a solid

This type of transition includes order-
disorder transitions in alloys, the onset
of ferromagnetism, and the fluid-
superfluid transition of liquid helium.
Figure 4.21 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
(b) expands uniformly in three directions as the
temperature is raised. There is no rearrangement
of atoms at the transition temperature, and hence
no enthalpy of transition.

The order-disorder transition in -brass (CuZn) is an

example of a -transition.

The low-temperature phase is an orderly array of

alternating Cu and Zn atoms. The high-temperature
phase is a random array of the atoms (Fig. 4.22).

At T = 0 the order is perfect, but islands of disorder

appear as the temperature is raised. The islands form
because the transition is cooperative in the sense that,
once two atoms have exchanged locations, it is easier for
their neighbours to exchange their locations.

The islands grow in extent and merge throughout the

crystal at the transition temperature (742 K).

The heat capacity increases as the transition temperature

is approached because the cooperative nature of the
transition means that it is increasingly easy for the heat
supplied to drive the phase transition rather than to be
stored as thermal motion.