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Thermodynamics
Chapter 5
Solution of Thermodynamics:
Theory and applications
Chapter Outline
5.1 Fundamental Property Relation
5.2 The Chemical Potential and Phase Equilibria
5.3 Partial Properties of Solution
5.4 Ideal Gas Mixture
5.5 Fugacity and Fugacity Coefficient: Pure
Species and Species in Mixture/Solution
5.6 Fugacity Coefficient of Gas Mixture from the
Virial Equation of State
5.7 Ideal Solution and Excess Properties
5.8 Liquid Phase Properties from VLE data
5.9 Property Changes of Mixing
5.10 Heat Effects of Mixing Process
Multi-component gases and liquids commonly
undergoes composition changes by separation
and mixing processes.
nG
i
ni P ,T ,n j
M M 1 x2 M 1 M 2 M x1 M 1 M 2 M 2
M ig T , P M iig T , pi
Partial pressure of a species i in ideal-gas
mixture: yi RT
pi ig yi P
V
Hence, for enthalpy; H
ig
i yi H i
ig
For entropy; S yi S i R yi ln yi
ig ig
i i
G i yi i T RT i yi ln yi P
ig
5.5 Fugacity and Fugacity Coefficient:
Pure Species and Species in Gas
Mixture or Solution of Liquids
Gi i T RT ln f i
fi
Gi Gi RT ln Gi
ig R
P
where fi
i
P
is called fugacity coefficient of pure species.
For species i in a mixture of real gases or in a
solution of liquids, in equilibrium;
0.422 0.172
Bij0 0.083 Bij1 0.139
Trij1.6 Trij4.2
ij Vcij
2 2
Z ci Z cj Z cij RTcij
Z cij Pcij
2 Vcij
5.7 Ideal Solution and Excess Properties
M is defined as the difference between the
E
ˆf i l fˆi v yi P
Problem 11.19
Problem 11.37
Problem 12.32
Problem 12.46
Problem 12.59
Assignment 5
Smith et al., (2006)
Problem 11.18
Problem 11.25
Problem 11.40
Problem 12.30
Problem 12.33