Phase Equilibrium: One Component System
•Introduction
•Unary phase diagrams
•Equilibrium Between Liquid and Solid Phases
•Clapeyron equation
•Gibbs phase rule
•Driving force for a phase transition
•First order and second-order phase transitions
•Summary
P-T Phase Diagram (PD) for a Pure Material
The solid lines (phase boundary lines) on the phase
diagram show the conditions where different phases
coexist in equilibrium: Gphase1 = Gphase2
The Relationship between P and V for Pure Substance
➢As pressure is increased at T1, the volume of the gas decreases.
➢When the pressure reaches a certain value, the volume suddenly reduces as the
gas liquefies
➢A further increase in pressure causes little further reduction in volume as liquid is
generally not compressible to a large extent.
➢When the P-V relationship is examined at different T, one may
obtain the results shown in the diagram below:
At the point A the liquid and vapor are
A T5 indistinguishable and their densities are identical.
T4
Tc
T2 T1
All gases exhibit this type of behavior, but values of critical pressure
and critical temperature vary from one substance to another.
Equilibrium Between Liquid and Solid Phases
dG = -SdT +VdP
As we can see from this fundamental equation, the free energy of a phase increases with pressure:
This means that if the two phases have different molar volumes, their free energies will
increase by different amounts when pressure changes at a fixed T. Since V(l)-V(s) is negative,
the ice melts when pressure is increased to value greater than 1 atm.
Vl < Vs for water
Vl > Vs for most materials
What is the curvature of the G(P) at const. T?
Ths is called isothermal
copressibility
This is the Bulk modulus.
Equilibrium Between Two Phases
•We have seen that if two phases in equilibrium have different molar volumes,
their free energies will increase by different amounts when P changes at certain T.
•The equilibrium, therefore will be disturbed by the change in pressure.
•The only way to maintain equilibrium at different pressures is to change
temperature as well.
For two phases (say liquid and solid) in equilibrium Gl = Gs and dGl =
dGs for infinitesimal change in T and P (so that the system remains in
equilibrium):
We know that at equilibrium ∆G = 0 ⇒ ∆H – T ∆S = 0 ∴ ∆S = ∆H/T
Clapeyron equation: it gives the relationship
⇒ between the variations of P and T required to maintain the
equilibrium between two phases.
G as Function of T and P for Two Phases
Schematic representation of the
equilibrium surfaces of the solid and
liquid phases of water in G-T-P
space.
The planes show the free energies of liquid and solid
phases, the intersections of the planes correspond to
the (P, T) conditions needed for maintaining
equilibrium between the phases, Gl = Gs
Clapeyron’s Equation – Example 1
For liquid to gas transition:
∆V = Vg - Vl >> 0
∆H = Hg - Hl > 0
i.e. we have to add heat to convert liquid to gas.
⇒
A typical phase diagram
for a pure material
For liquid to solid transition:
∆V = Vs - Vl < 0 → for most materials
∆H = Hs - Hl < 0 The slope of the equilibrium lines in a P-T phase
i.e. heat is released upon crystallization. diagram of a pure material reflects the relative
⇒ densities of the two phases.
For some materials, however, ∆V = Vs - Vl > 0
⇒
This is the case for H2O (ice floats in liquid water), Ga, Ge, diamond
Unary System - Density
Which is denser liquid or solid?
Liquid
Note what happens along the isotherm when you
Solid
increase the pressure.
Pressure
Vapor
Solid2
Liquid
Temperature
Solid1
Pressure
Liquid
Solid Vapor
Pressure
Temperature
Vapor
Temperature
Dr. M. Medraj
Example 2: Gibbs Phase Rule
The following is the phase diagram for a pure substance.
Calculate the number of degrees of freedom at the triple point A
Gibbs phase rule: F= C– P + 2
This special condition is established only at definite T and P
which are characteristic of the substance and outside our control.
Example 3: Gibbs Phase Rule
Calculate the number of degrees of freedom at the triple point c
Gibbs phase rule:
F=C–P+2
1
(liquid=vapor)
The vapor–liquid critical point denotes the
conditions above which distinct liquid and gas
phases do not exist.
The critical point is ………....
Vapor–Liquid Critical Point for Pure Substances
Clapeyron’s Equation – Example 4
Some materials may exist in more than one crystal structure, this is called
Polymorphism If the material is an elemental solid, it is called allotropic
Close-packed FCC γ-Fe has a
smaller molar volume than BCC
α-Fe:
∆V = Vγ - Vα < 0
And at the same time ∆H = Hγ - Hα > 0
⇒
The effect of increasing P is to increase the area of the
PD over which the phases of the smaller molar V
(higher density) are stable.
Phase Diagrams of One-Component Materials
graphite
From the phase diagram, what phase has higher
density near two-phase equilibrium conditions:
-Diamond or graphite?
-Diamond or liquid carbon?
-Graphite or liquid carbon?
diamond
The Driving Force for the Phase Transformation
•If solid and liquid are in equilibrium, Gs = Gl and a slow addition of
heat leads to the melting of some part of the solid, but does not change
the total G of the system: G = nl Gl + ns Gs = const, where nl and ns are the
numbers of moles of liquid and solid phases, and Gl and Gs are the molar Gibbs free energies.
•However, if energy is added or removed quickly, the system can be
brought out of equilibrium (overheated or undercooled), the
melting/freezing process is spontaneous/irreversible and G is decreasing.
For small undercooling ∆T, we can neglect the The driving force
difference in Cp of liquid and solid phases and assume forsolidification
that ∆H and ∆S are independent of T.
First-Order and Second-Order Phase Transitions
The classification of phase transitions proposed by Ehrenfest is based on the behavior of G near the
phase transformation.
First-order phase transition: first derivatives of G are discontinuous.
Second-order phase transition: first derivatives of G are continuous, but second derivatives
of G are discontinuous.
First-Order and Second-Order Phase Transitions
Summary
• The various solid/liquid/gas transitions are classified as first-order transitions
because they involve a discontinuous change in density, which is the first
derivative of the free energy with respect to chemical potential.
•Just knowing the internal energy U of a system with a constant volume and
temperature is not enough to tell us what the equilibrium configuration will be.
•There could be many macrostates with the same U. That is why just minimizing U
(or H) is not good enough, we have to minimize A = U - TS or G = H - TS to find
the equilibrium configuration of the system.
•Of all the macrostates possible for a given U (or H) the one with the largest
entropy at the given temperature will be the one that the system will adopt.
•Equilibrium occurs when the balance between a small energy and a large entropy
is achieved. High entropies often mean small energies and vice versa - both
quantities are opposed to each other.
