Definitions of the Chemical Potential

2.2 The Chemical Potential and Phase Equilibria

 Vapor-Liquid Equilibrium for Pure Species

Consider a closed system containing , )

a single species that can transform

from one phase () to another ()
 

Vapor     

    

    0
At equilibrium, P & T are uniform
Liquid
  or  
 Fugacity

 used to represent equilibrium because fugacity is directly related to G.

 In an equilibrium between two phases, the G’s of component i in both phases are the same.
 A thermodynamic property for real fluids. Physically, it is the tendency of the molecules
from one phase to escape into the other.

For a condensed phase (liquid or solid) in A

equilibrium with its vapor phase, the chemical
potential is equal to that of the vapor, and B
therefore the fugacity is equal to the fugacity of
the vapor. This fugacity is approximately equal to
the vapor pressure when the vapor pressure is
not too high.
 Fugacity of Pure Species

Gibbs energy for ideal

gas at pressure P
Change in pressure
from Po=1 atm to P
Molar Gibbs energy for ideal gas 𝑜
based on standard Gibbs energy
Chemical potential ideal gas based  𝑜
on standard chemical potential
Chemical potential of REAL gas based  𝑜 Fugacity of a pure species
on standard chemical potential
Preferred state is the lower fugacity
Generating Functions

This function can enable us to

evaluate other thermodynamic
design experiments to generate a
thermodynamic diagram.

Ex. What can we measure in order

to generate the S-T curve for a
pure substance?
Equation of State to Calculate
Residual Properties of Pure Species
Phase Diagram

Substances Substances
P that expand that contract Recognize that different
on freezing on freezing components of the
Melting Critical diagram and their
point
LIQUID physical significance
SOLID Vaporization Illustrate processes in
VAPOR phase diagrams
Sublimation

T
Problem Set
Learning Objectives
o Define the conditions for phase
equilibrium of pure species
o Estimate the conditions for phase
equilibrium of pure species
o Define fugacity of a pure species Derivation
o Calculate fugacities of pure
species
o Use fugacity to determine phase
equilibrium of pure species
Problem Set / Examples
Describe phase equilibrium
physically and mathematically
Dew or bubble point calculations
Given subcooled liquid at some
temperature T1 at which the vapor
pressure is P1sat and molar volume is
V1sat. Estimate the fugacity at T1
and some low pressure P1.
Determination of equilibrium
compositions
Fundamental Property Relations for Open Systems
with Variable Amounts and Composition
NATURAL
VARIABLES
S&V

T&V

S&P

T&P
 Fundamental Property Relation for a Mixture
whose mass and composition may change

CLOSED SYSTEM:

, ,

OPEN SYSTEM:

1 2 )
For maximum learning, try to generate on your own the exact
differential [d(nG)] for the open system.
 Fundamental Property Relation for Mixtures
( ) ( ) ( ) ( ) ( )
…
, , , , , , , ,

, , , ,

Definition of Chemical Potential for Mixtures

, ,
Chemical Potential for Species in a Mixture

Mass transfer in the direction

of increasing concentration?

How can mass transfer continue in the direction

of increasing concentration?
Equilibrium Criterion in terms of Chemical Potential

Non-equilibrium

Equilibrium
Mathematical Derivation of Equilibrium
Criterion in terms of Chemical Potential

 For the Vapor () phase:

𝑥 𝑥
Vapor

 For the Liquid () phase:

𝑥 𝑥

Liquid
 For the whole two-phase system:
 For the Vapor () phase:

𝑥 𝑥
 For the Liquid () phase: Vapor

 For the whole two-phase system:

𝑥 𝑥

Liquid
 Total System Property,

 Change in Total System Property = Sum of Changes in Phase

Properties
Criterion for equilibrium in terms
of the chemical potential

 

 

  
Chemical Potential in a Mixture: Some Relations

For an ideal gas mixture:

 
For a gas mixture
 
For a liquid mixture

 
Chemical Potential Fundamental Property Relations

, ,

, ,

, ,

, ,
 Chemical Potential at Reference State

Under standard conditions

(298K, 101.kPa), the chemical 
potential scale is defined by:

For the stable form of the elements (except Phosphorous)




 Chemical Reaction

Ca(OH)2 + CO2  CaCO3 + H2O

, kJ/mol:  897  394  1129  237

LHS =  1291 kJ/mol RHS =  1388 kJ/mol

What is Chemical Potential? (Multi-Component System

https://www.youtube.com/watch?v=sNsWABMT0As
 Introduction to Partial Molar Properties

You had been accepted in an Scenario: In a project team

engineering design firm ……. meeting you had been asked:
“Can you handle the preliminary
design of the distillation unit?

You go to your process simulator and find that

the mixture to be separated is not in the
database, but you found an article and patent
information that provides a few VLE data
points for the particular mixture of interest.
Partial Molar Property

The chemical potential of a pure component is an intensive property

The chemical potential of a species in a mixture is a partial molar property

, ,
Partial Molar Volume – virtual partitioning of
the mixture volume by species

For a mixture containing N components,

Volume of
mixture +
per mole

Partial Partial Partial Partial

molar molar molar molar
volume volume volume volume
Comp. 1 Comp. 2 Comp. i Comp. N
 X1=0.60 Add 0.001 mole
X10.60
X2=0.40 of component 1
X2  0.40
V=1.000L V=1.015L
liquid liquid

( )
=
, , .
General definition of partial molar property

Partial molar property of a specie i in a mixture

, ,

Solution Properties M V,U,H,S,G,A

Pure Species Properties , ,

Partial Properties
Equations Relating Molar and Partial Molar Properties

, , , ,

, ,

, ,
Partial Molar Enthalpy

Eqn. (1) Eqn. (2)

, ,

Write the equivalent expressions of Eqns. (1) and (2)

for the following thermodynamic properties:

 Internal energy, U
 Entropy, S
 Helmholtz free energy, A
Equations Relating Molar and Partial Molar Properties

, , , ,

, ,

, ,
Experimental Measurement
Solution Enthalpy at Different Compositions

@ multiple
temperatures
 Calculating the Partial Molar Enthalpy

The enthalpy of a binary solution changes with

composition in the manner described by:

Given the expression shown for the enthalpy of a

binary solution as a function of mole fractions x1
and x2,
1. What would be the expression for the partial
molar property of specie 1?
2. What would be the expression for the partial
molar property of specie 2?