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Phase Equilibrium in One Component System

1. This document discusses phase equilibria in one-component systems using water as an example. It explores the relationships between temperature, pressure, and phase stability/transitions. 2. Equilibrium occurs when the chemical potential of a species is equal across phases. A gradient in chemical potential drives diffusion between phases. Equilibrium minimizes the Gibbs free energy of the system. 3. Solid-liquid and vapor-liquid equilibria are examined using concepts like the Clausius-Clapeyron equation, Gibbs free energy diagrams, and experimental data on substances like water and iron. Phase diagrams are used to represent phase boundaries and transitions.

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103 views

Phase Equilibrium in One Component System

1. This document discusses phase equilibria in one-component systems using water as an example. It explores the relationships between temperature, pressure, and phase stability/transitions. 2. Equilibrium occurs when the chemical potential of a species is equal across phases. A gradient in chemical potential drives diffusion between phases. Equilibrium minimizes the Gibbs free energy of the system. 3. Solid-liquid and vapor-liquid equilibria are examined using concepts like the Clausius-Clapeyron equation, Gibbs free energy diagrams, and experimental data on substances like water and iron. Phase diagrams are used to represent phase boundaries and transitions.

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© © All Rights Reserved
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Phase Equilibrium in One Component

System
Introduction
• Example: H2O: Solid, Liquid and Gas
• Though the entire discussion is centred
around H2O, but it works for ANY one
component system
• Either stability of a single phase(S/L/G) or
Equilibrium of any two or three
• Function of Temperature (T) and Pressure
(P)
• But not the composition
On Chemical Potential
• The chemical potential of the species i in a phase is a
measure of the tendency of the species i to leave the phase
• It is thus a measure of the chemical pressure exerted by i in
the phase
• If the chemical potential of i has different values in
different phases of the system, which are at the same
temperature and pressure
• As the escaping tendencies differ, the species i will tend to
move from the phases in which it occurs at the higher
chemical potential to the phases in which it occurs at the
lower chemical potential
• A gradient in chemical potential is the driving force for
chemical diffusion
• Equilibrium is attained when the species i is distributed
throughout the various phases in the system such that its
chemical potential has the same value in all phases
Criteria for Equilibrium
• In a closed system of fixed composition, e.g., a
one-component system
• Equilibrium, at the temperature T and the
pressure, P, occurs when the system exists in
that state which has the minimum value of G’
• The equilibrium state can thus be determined
by means of an examination of dependence of
G on pressure and temperature
The Variation of Gibbs Free Energy with
Temperature

SL
LG
SG
Solid- Liquid Equilibrium: Effect of Temp at
Constant Pressure
Solid- Liquid Equilibrium: Effect of Temp at
Constant Pressure
Variations of the molar Gibbs free energies of
ice and water with temperature at constant
pressure
Variation of the molar Gibbs free energy of
melting of ice with temperature at constant
pressure
Calculating ∆GS=>L
The variations, with temperature, of the molar
enthalpies of ice and water at 1 atm pressure
Variations, with temperature, of the molar
entropies of ice and water at 1 atm pressure
Variation, with temperature, of TS for solid and
liquid water at 1 atm pressure
Variations, with temperature, of the molar
Gibbs free energy of melting, the molar
enthalpy of melting, and T*the molar entropy
of melting of water at 1 atm pressure
Variation of Gibbs Free Energy of ice and
water with Pressure at Constant Temperature
Variations of the molar Gibbs free energies of
ice and water with pressure at constant
temperature
Condition of SL equilibrium: Clapeyron
Equation

• At equilibrium ΔG=0,
and hence Δ H=TΔ S
• At an increase in pressure
decreases the equilibrium
melting temperature
Schematic representation of the equilibrium
surfaces of the solid and liquid phases of
H2O in G-T-P space
Equilibrium of Gas with Condense Phase:
Clausius-Clapeyron equation
Simplification of the Clausius-Clapeyron
equation
• If ΔH is independent of temperature, i.e., if
Cp(vapor)=Cp(condensed phase):
Simplification of the Clausius-Clapeyron
equation
• If ΔCp for the evaporation or sublimation is not
zero, but is independent of temperature
Application of Clausius-Clapeyron Equation
for Water-Vapour Equilibrium
Application of Clausius-Clapeyron Equation
for Water-Vapour Equilibrium
Comparing the results with experiments:
Water-Vapour Equilibrium
• Fitting the
Experimental
Data
Vapor pressures of several elements as
functions of temperature
Schematic representation of part of the phase
diagram for H2O
Gibbs phase rule
Solid-Solid Equilibria: Case Study of Fe
Solid-Solid Equilibria: Case Study of Fe
Schematic phase diagram for zirconia, ZrO2

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