COURSE INFORMATION
Course Name: Chemical Engineering Thermodynamics
Course Code: ChEg3202
Lesson Title: Solutions Thermodynamics
Instructor Name: Ms. Fana T.
Peer Reviewers
1, Desta
Getachew 1
Content Outline
4 Solutions Thermodynamics
4.1 Fundamental Property Relation
4.2 Chemical potential and phase equilibria
4.3 Partial properties
4.4 Ideal gas mixtures
4.5 Fugacity and fugacity coefficient: pure species & Fugacity and
fugacity coefficient: species in solution
4.6 The ideal solution models & Excess properties 2
Lesson Objective
In this chapter we will learn to answer the following questions.
How do we determine the thermodynamic properties of
solution?
How do individual species behave in a solution?
What is chemical potential? And why it is important?
What is a fugacity and activity coefficient?
3
4.1 Fundamental Property Relation
The definition of the chemical potential of
species i in the mixture of any closed system:
nG
i
ni P ,T ,n j
the Gibbs energy which is the function
of temperature, pressure and number of moles
of the chemical species present.
4.2 The Chemical Potential and Phase
Equilibria
For a closed system consists of 2 phase in
equilibrium, the mass transfer between phases
may occur.
At the same P and T, the chemical potential of
each species of multiple phases in equilibrium
is the same for all species.
.......
i
i i
4.3 Partial Properties in Solution
Pure-species properties, M V , H , S ,G
i i i i i
In a mixture solution:
1) A solution properties, M V , H , S , G
2) The partial properties base on components
in a solution, M V , H , S , G
i i i i i
Partial molar property M
ofi species i in solution:
nM
Mi
ni P ,T ,n j
In a solution of liquids, its properties:
M i xi M i M V , H , S,G
M i Vi , H i , S i , Gi
For a binary solution, its properties:
M x1 M 1 x2 M 2
Similarly, for separate x1 and x2;
M M 1 x2 M 1 M 2 M x1 M 1 M 2 M 2
Example 1
The need arises in a laboratory for 2000 cm 3 of an antifreeze
solution consisting of 30 mol-% methanol in water. What
volumes of pure methanol and of pure water at 25°C must be
mixed to form the 2000 cm3 of antifreeze, also at 25°C? Partial
molar volumes for methanol and water in a 30 mol-% methanol
solution and their pure-species molar volumes, both at 25°C,
are:
Solution
The mole fractions and partial molar volumes:
4.4 Ideal Gas Mixture
In a ideal gas mixture, partial molar properties
of a species (except volume) is equal to its
molar properties of the species as a pure ideal
gas when the temperature is the mixture
temperature and the pressure equal to its
partial pressure in the mixture.
M ig
T , P M T , p
ig
i i
Partial pressure of a species i in ideal-gas
mixture: y RT
pi i
yi P
V ig
Hence, for enthalpy; H ig
i yi H i
ig
For entropy; S i yi S i R i yi ln yi
ig ig
For Gibbs energy; integration constant
G i yi i T RT i yi ln yi P
ig
4.5 Fugacity and Fugacity Coefficient:
Pure Species and Species in Gas
Mixture or Solution of Liquids
For pure species in ideal-gas state;
Gi i T RT ln P
ig
For pure species in real-gas state;
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.
where integration is at constant Tr.
Substitution for Zi
CONT……
where for simplicity subscript i is omitted. This
equation may be written in alternative form:
may also be written,
For species i in a mixture of real gases or in a
solution of liquids, in equilibrium;
ˆ ˆ ˆ
f i f i .... f i
The fugacity of each species is the same in
all phases.
For vapor-liquid equilibrium,
ˆf i v fˆi l
Example 2
Estimate a value for the fugacity of 1-butene vapor
at 200°C and 70 bar
Solution
For species in gas mixture or solution of liquids,
Fugacity coefficient of species i in gas mixture;
ˆi
f
ˆi
yi P
Fugacity coefficient of species i in solution;
fˆi
ˆi
xi P
For species i in ideal-gas mixture, ˆ
i 1
ig
4.6 Ideal Solution and Excess Properties
M is defined as the difference between the
E
actual value of solution and value from ideal
solution;
M M M
E id
Quiz 2
The need arises in a laboratory for 2000 cm 3 of an antifreeze
solution consisting of 70 mol-% methanol in water. What
volumes of pure methanol and of pure water at 25°C must be
mixed to form the 2000 cm3 of antifreeze, also at 25°C?
Partial molar volumes for methanol and water in a 50 mol-%
methanol solution and their pure-species molar volumes,
both at 25°C, are: