• Le Chatlier’s principle

• Phase transitions
• Van der Waals gas and stability
Le Chatlier’s Principle
The criterion for stability is that any inhomogeneity that somehow develops in
a system should induce a process that tends to eradicate the inhomogeneity.

Local inhomogeneities always occur in physical systems even in absence of

external perturbations. For example, in a gas individual molecules move at
random and by pure chance this motion can produce regions of high density
and other regions of low density. Stability conditions cause compressibility to
be positive which ensures that regions of increased density and hence
increased pressure expand and regions of low density contract thereby
restoring a homogenous density in the system.
Thermodynamics of phase transitions
A phase is a state that has a particular composition and definite, characteristic physical and chemical properties.
We may have several different phases that are identical in composition but different in physical properties. A
phase can be in the solid, liquid or gas state. In addition, there may exist more than one distinct crystalline
phase. This is termed polymorphism, and each crystalline phase represents a distinct polymorph of the
substance.

If different phases of the same substance, such as solid, liquid, and gas, are in contact, particles can migrate
from one phase to the other across the phase boundary. In this case the phase with a higher chemical
potential recedes and the phase with a lower chemical potential grows. The phase boundary moves across
the sample until the receding phase disappears completely.

If, for example, the values of T and P correspond to the stable phase being a gas, then a rapid quench of the
temperature to a value such that the liquid phase becomes stable, might lead to the gas phase becoming
metastable . In this case we say that the gas is supercooled . The system will remain in the gas phase for some
time until spontaneous density fluctuations drive the system to the stable liquid phase.

In many systems, two phases can coexist. For example, liquid water in equilibrium with its vapor inside a closed
container is an example of two-phase coexistence.
 Conditions for Two-phase equilibrium
Consider a liquid phase in equilibrium with vapor phase at
constant temperature and under constant pressure
Gibbs free energy for 𝐺 = 𝑛1 𝑔1 + 𝑛2 𝑔2
the system
𝑔𝑖 is Gibbs free energy/mole of phase 𝑖 and 𝑛𝑖 is
number of moles of phase 𝑖

Atoms would traverse interface between liquid and vapor phases in such a way that net rate of
transfer is zero at equilibrium
𝑑𝑛 = 𝑑𝑛1 + 𝑑𝑛2 = 0
At equilibrium G has a minimum value and therefore,
𝑑𝐺 = 0 𝑔1 𝑑𝑛1 + 𝑔2 𝑑𝑛2 = 0
𝑔1 = 𝑔2 𝜇1 = 𝜇2
In basic thermodynamic systems, the
chemical potentials of the phases
𝜇𝑖 depend on P and T; so that for a
given set (P, T) the phase with lowest
chemical potential will be realized.

Figure on the right shows chemical

potential of two phases (liquid and gas)
as function of pressure at a given
temperature

The phase with lower chemical potential at a given pressure and temperature is thermodynamically stable,
while the other is metastable. If the pressure exerted on the system is increased past the coexistence
pressure, at constant temperature, a phase transition from gas (phase 1) to liquid (phase 2) occurs.
 Classification of phase transitions
First order phase transitions: Phase transitions with
discontinuous first derivatives of Gibbs free energy
(taken with respect to T and P) are called first order
phase transitions. For example, vapor-liquid, vapor-
solid and liquid-solid transitions.
Entropy=

Specific Heat=

First Order Phase Transition

 Classification of phase transitions
Second Order Phase
Continuous phase transitions: Phase transitions with Transition
continuous first derivatives of Gibbs free energy (taken 𝐺
with respect to T and P) but discontinuous higher order
derivatives are called continuous transitions.
Ehrenfrest had introduced the terminology “nth order
phase transition” to indicate a phase transition for
which the nth derivative of G was the first 𝜕𝐺
𝑆=
discontinuous derivative. 𝜕𝑇

Ginzburg and Landau developed a general theory of

continuous phase transitions which involves an
analytic expansion of the free energy in terms of the 𝜕2𝐺
𝐶=
order parameter. 𝜕𝑇 2
 Simple Phase Diagram
The lines represent the phase coexistence curves between
the solid and liquid phases, the solid and vapor phases, and
the liquid and vapor phases. On these curves, the chemical
potentials of the two phases are equal.
Suppose that a fraction x of the particles is in phase A and a
fraction 1−x of the particles is in phase B at some point along the
phase coexistence line where 𝑔𝐴 = 𝑔𝐵 . Then, total Gibbs free
energy is equal to 𝐺 = 𝑥𝑁𝑔𝐴 + 1 − 𝑥 𝑁𝑔𝐵 = 𝑁𝑔𝐴 = 𝑁𝑔𝐵 ,
which is independent of x. Hence for values of P and T on the
phase boundary, the two phases can coexist in equilibrium in any
proportion.
The condition 𝜇𝐴 = 𝜇𝐵 = 𝜇𝐶 for the coexistence of all three phases leads to a unique temperature and pressure
that defines the triple point .
 Simple Phase Diagram
A system can cross the phase boundary from its solid
phase directly to its vapor without passing through the
liquid phase, a transformation known as sublimation.
Extensively used in freeze drying.

If we move along the liquid-gas coexistence curve toward

higher temperatures, the two phases become more and
more alike. At the critical point, the liquid-gas coexistence
curve ends, and there is no longer a distinction between
a gas and a liquid. For temperatures and pressures above
the critical point it is not possible to distinguish between
a gas and a liquid, and the substance is known as a
supercritical fluid.
Common Phase Diagrams
Carbon Dioxide Water
Gibbs Phase Rule: How many phases can coexist, for a system in
thermodynamic equilibrium
Coexisting phases are in thermal and mechanical equilibrium with each other and can exchange matter. That is,
temperature, pressure and chemical potential of the two phases are equal.
Consider, a system which is pure (composed of one kind of atoms/molecules/particles). For a pure system, two
phases, 𝐼 and 𝐼𝐼 can coexist at a fixed value of P and T if their respective chemical potentials are equal.
𝜇𝐼 (𝑃, 𝑇) = 𝜇𝐼𝐼 (𝑃, 𝑇)
This equation gives us a relation between values of P and T for which phases can coexist, P=P(T) and in the P-T
plane it defines a coexistence curve/line for the two phases.
If the pure system has three phases, then the three coexisting phases must satisfy
𝜇𝐼 𝑃, 𝑇 = 𝜇𝐼𝐼 𝑃, 𝑇 = 𝜇𝐼𝐼𝐼 𝑃, 𝑇 .
Here, we have two equations and two unknowns, the three phases can only coexist at a single point in P-T plane
(triple point).
For a pure system, four phases cannot coexist because we would then have 3 equations and 2 unknowns which
would mean no solution.
For a mixture of 𝑙 different types of particles, at most 𝑙 + 2 phases can coexist
Clausius-Clapeyron equation: The slope of the phase coexistence curve

Consider two points on the phase coexistence curve, for

example, one point at 𝑇, 𝑃 and a nearby point at 𝑇 +
Δ𝑇 and 𝑃 + Δ𝑃

The condition for equilibrium implies,

𝑔𝐴 𝑇, 𝑃 = 𝑔𝐵 𝑇, 𝑃 and
𝑔𝐴 𝑇 + Δ𝑇, 𝑃 + Δ𝑃 = 𝑔𝐵 𝑇 + Δ𝑇, 𝑃 + Δ𝑃 .

𝑔𝑖 𝑇 + Δ𝑇, 𝑃 + Δ𝑃 = 𝑔𝑖 𝑇, 𝑃 + Δ𝑔𝑖
Δ𝑔𝐴 = Δ𝑔𝐵
−𝑠𝐴 Δ𝑇 + 𝑣𝐴 Δ𝑃 = −𝑠𝐵 Δ𝑇 + 𝑣𝐵 Δ𝑃

where 𝑠𝑖 is the entropy per particle and 𝑣𝑖 is the volume per particle in phase 𝑖 .
𝑑𝑃 𝑠𝐵 − 𝑠𝐴 Δ𝑠 Thus, the slope of the coexistence curve at any point on the curve is equal to the ratio of
= =
𝑑𝑇 𝑣𝐵 − 𝑣𝐴 Δ𝑣 entropy difference to the volume difference as the curve is crossed at that point.
 𝑑𝑃 𝑠𝐵 − 𝑠𝐴 Δ𝑠
= =
𝑑𝑇 𝑣𝐵 − 𝑣𝐴 Δ𝑣

Latent heat (heat released/absorbed) 𝑙 = 𝑇 Δ𝑠

during phase transition,
𝑑𝑃 𝑙
=
𝑑𝑇 TΔ𝑣
For most substances the slope of the solid-liquid coexistence curve is positive. The Clausius- Clapeyron equation
shows that this positive slope is due to the fact that most substances expand on melting and therefore have Δ𝑣 > 0.
Water is an important exception and contracts when it melts.
Using Clausius-Clapeyron equation: Liquid-gas coexistence curve
The Clausius-Clapeyron equation for the vapor pressure curve can be approximated by neglecting the specific
volume of the liquid in comparison to the gas, Δ𝑣 = 𝑣𝑔𝑎𝑠 − 𝑣𝑙𝑖𝑞𝑢𝑖𝑑 ≈ 𝑣𝑔𝑎𝑠

If we assume that the vapor behaves like an ideal gas, then 𝑣𝑔𝑎𝑠 = 𝑅𝑇/𝑃 for one mole of the gas.

𝑑𝑃 𝑙𝑃
=
𝑑𝑇 RT 2
𝑑𝑃 𝑙 𝑑𝑇
=
𝑃 RT 2
−𝑙
𝑃(𝑇) = 𝑃0 𝑒 𝑅𝑇 Where where P0 is a constant.
Using Clausius-Clapeyron equation: Liquid-solid coexistence curve
Assume that the temperature dependence of latent heat and Δ𝑣 can be neglected.

𝑙 𝑑𝑇
𝑑𝑃 = Can be integrated to yield
TΔ𝑣

𝑙 𝑇 where 𝑇0 , 𝑃0 is a point on the phase coexistence curve

𝑃 = 𝑃0 + 𝑙𝑛
Δ𝑣 𝑇0

The volume change Δ𝑣 between the liquid and the solid is small and the entropy change is large, the slope of the
coexistence curve in the P -T plane is very steep
Van der Waal’s equation of state and stability
𝑅𝑇 𝑎
𝑃= − 2
𝑣−𝑏 𝑣
Many of the isotherms do not satisfy the criterion of
intrinsic stability everywhere. The criterion being 𝜅 𝑇 > 0
𝜕𝑃
which is equivalent to <0
𝜕𝑉 𝑇

For example, the stability criterion is not satisfied in the

region marked FKM. That is, this region is unphysical and must
be superseded by a phase transition. The isotherms become S
shaped below a critical temperature. Critical isotherm does
not have a maximum or minimum but has an inflection point.
 Law of corresponding states
Find the temperature TC , pressure PC and Volume VC at the critical point of the van der
𝑃𝑐 𝑉𝑐
Waals gas and calculate ration of
𝑅𝑇𝑐

Use whiteboard
 𝑃 𝑉 𝑇
𝑃෨ ≡ 𝑉෨ ≡ 𝑇෨ ≡
𝑃𝑐 𝑉𝑐 𝑇𝑐

8 𝑇෨ 3
𝑃෨ = − 2
(3𝑣෤ − 1) 𝑣෤

෨ 𝑣,
The equation of state in terms of the dimensionless variables 𝑃, ෤ 𝑇෨ does not depend explicitly on the material dependent
parameters a and b.

One of the features of the van der Waals equation of state is that it predicts the law of corresponding states, which states
that the equations of state of all fluids are identical if they are expressed in terms of dimensionless variables relative to
their value at the critical point. This prediction holds only approximately in reality, but it is exact for the van der Waals
equation of state; that is, dimensionless form of Van der Waals equation of state is independent of the material
parameters a and b.
Maxwell Construction
The S-shaped region tells us that for a given temperature, the
system separates into two phases at two different densities,
indicated by two specific volumes at the same pressure. But
how can we determine the pressure 𝑃𝑒 at which there is
equilibrium between the two phases representing liquid and
gas?
We know from Gibbs Dunhem equation,

𝜕𝜇
=𝑣
𝜕𝑃 𝑇
𝑓 𝑓
න 𝑑𝜇 = න 𝑣𝑑𝑃
𝑖 𝑖
𝑓 𝑓
𝜇𝑓 − 𝜇𝑖 = න 𝑑 𝑃𝑣 − න 𝑃𝑑𝑣
𝑖 𝑖
 𝑓 𝑓
𝜇𝑓 − 𝜇𝑖 = න 𝑑 𝑃𝑣 − න 𝑃𝑑𝑣
𝑖 𝑖

We consider states with specific volumes 𝑣𝑓 and 𝑣𝑖 that coexist and so by definition have equal chemical so that LHS=0

Also the pressure 𝑃𝑒 of the coexisting phases must be same, so that

𝑓 𝑓
න 𝑑 𝑃𝑣 = 𝑃𝑒 න 𝑑𝑣
𝑖 𝑖

𝑓
0 = න (𝑃 𝑣 − 𝑃𝑒 )𝑑𝑣
𝑖

Geometric interpretation: The coexistence pressure and associated coexistence specific volumes of the phases
are determined by a condition of equality between the two areas defined by three intersections between the p-
V curve provided by the equation of state and the horizontal line at P=Pe
 Lever Rule
The system with volume per particle between vi and vf will consist of an appropriate mixture of the two coexisting phases.
Consider a point Z on the isotherm

Total volume, 𝑉𝑍 = 𝑛𝑔 𝑣𝑖 + 𝑛𝑙 𝑣𝑓 and total mole number 𝑛 = 𝑛𝑔 + 𝑛𝑙

Total molar volume is given by 𝑣𝑍 = 𝑥𝑔 𝑣𝑖 + 𝑥𝑙 𝑣𝑓 where 𝑥𝑔 = 𝑛𝑔 /(𝑛𝑔 + 𝑛𝑙 ) and 𝑥𝑙 = 𝑛𝑙 /(𝑛𝑔 + 𝑛𝑙 )

𝑣𝑍 = 𝑥𝑔 𝑣𝑖 + 𝑥𝑙 𝑣𝑓

𝑣𝑍 = 𝑥𝑔 𝑣𝑖 + (1 − 𝑥𝑔 )𝑣𝑓

𝑣𝑍 − 𝑣𝑓
𝑥𝑔 =
𝑣𝑖 − 𝑣𝑓 An intermediate point on the flat portion of the isotherm implies a mole fraction of each phase
𝑣𝑖 − 𝑣𝑍 that is equal to fractional distance of that point from opposite end of flat region. At point Z, there
𝑥𝑙 =
𝑣𝑖 − 𝑣𝑓 exists a mixed liquid gas system with a mole fraction of liquid phase equal to length ZD divided by
length OD.