Solution Thermodynamics

26-05-2022
ChE 3107
Chemical Engineering
Thermodynamics
(Solution Thermodynamics: Theory)
Instructor:
Shuvashish Mondal
Lecturer,
Department of Chemical Engineering, KUET
Khulna-9203
Introduction
Why we have to study solution thermodynamics?
✓ To develop the theoretical foundation for applications of
thermodynamics to gas mixtures and liquid solutions.
✓ To predict the existence of equilibrium between phases
✓ To understand the dependence of properties of
multicomponent system on composition
26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 2
© Shuvashish Mondal, Lecturer, Department

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26-05-2022
Fundamental Property Relation

Gibbs energy to the temperature and pressure in any closed
system:
where n is the total number of moles of the system. This equation

may be applied to a single-phase fluid in a closed system wherein
no chemical reactions occur. For such a system the composition is
necessarily constant, and therefore:
The subscript n indicates that the numbers of moles of all

chemical species are held constant.
For the more general case of a single phase, open system,
material may pass into and out of the system, and nG becomes a
function of the numbers of moles of the chemical species present.
Thus,
where ni is the number of moles of species i.
Fundamental Property Relation

The total differential of nG is then:
The derivative in the final term is given its own symbol and name.
Thus, by definition the chemical potential of species i in the
mixture is:
With this definition and with the first two partial derivatives
replaced by (nV) and −(nS), the preceding equation becomes:
(11.2)
Equation (11.2) is the fundamental property relation for single-
phase fluid systems of constant or variable mass and constant or
variable composition, and is the foundation equation upon which
the structure of solution thermodynamics is built.
For the special case of one mole of solution, n = 1 and ni = xi:

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The Chemical potential
(11.2)
6.6
The Chemical potential
• Chemical potential ()

➢ is an extensive property,
➢ provides a measure of the work of a system is capable when a change in
mole numbers occurs e.g. chemical reaction or a transfer of mass

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Partial properties
ഥ𝑖 of species i in solution is defined as:
• Partial molar property 𝑀
(11.7)
It is a response function, i.e., it is a measure of the response of total

property nM to the addition of an infinitesimal amount of species i to a
finite amount of solution, at constant T and P.
Comparison of Eq. (11.1) with Eq. (11.7) written for the Gibbs energy shows
that the chemical potential and the partial molar Gibbs energy are identical;
i.e.,
Thus, the partial molar Gibbs energy is the chemical potential.

Partial Molar Properties

The definition of a partial molar property, Eq. (11.7), provides the
means for calculation of partial properties from solution-property
data. Implicit in this definition is another, equally important,
equation that allows the reverse, i.e., calculation of solution
properties from knowledge of the partial properties.
Because the first two partial derivatives on the right are evaluated
at constant n and because the partial derivative of the last term is
given by Eq. (11.7), this equation has the simpler form:
(11.9)

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11.9
Differentiate Eq. (11.11)

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(11.13)
(11.14)
Partial Properties in Binary Solutions

Notation
Written for a binary solution, the summability relation, Eq. (11.11),

becomes:
(11.11)

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Partial Properties in Binary Solutions

11.14
(11.15) (11.16)
Example 11.2 (10.2 in 8th ed)

Describe a graphical interpretation of Eqs. (11.15) and (11.16).
(11.15) (11.16)
Solution 10.2 :
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ഥ1∞ → the partial property of species 1, when it is present at infinite

𝑀
dilution (x1 = 0)

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Example 11.3 (10.3 8th ed)
Solution 10.3:
Solution 10.3

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Solution 10.3
Example 11.4
Solution 10.4

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Example 11.4
Example 11.4
A numerical value for H1 results by substitution of x1 = 1 in either Eq.

(A) or (B).
H1 = 400 J·mol–1
Similarly, H2 is found from either Eq. (A) or (C) when x1 = 0.
H2 = 600 J·mol–1
The infinite-dilution values 𝐻

ഥ1∞ and 𝐻
ഥ2∞ are found from Eqs. (B) and (C)
when x1 = 0 in Eq. (B) and x1 = 1 in Eq. (C).

of ChE 11
26-05-2022
ChE 3107
Thermodynamics
Instructor:
Shuvashish Mondal
Lecturer,
Khulna-9203
Date: 22-05-2022
Relations among Partial Properties

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Similarly,

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The Ideal-gas-state Mixture Model

Dalton’s Law of partial pressure:

Amagat’s Law of partial volumes:
the total volume of a gas mixture is equal to the sum of the partial
volumes each gas would occupy if it existed alone at the temperature and
pressure of the mixture .
vt =σi vi and vi =yivt
the partial molar volume of a substance X in a mixture is the change

in volume per mole of X added to the mixture

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A partial molar property (other than volume) of a constituent
species in an ideal-gas-state mixture is equal to the corresponding
molar property of the species in the pure ideal-gas state at the
mixture temperature but at a pressure equal to its partial
pressure in the mixture.
Since 1/ yi > 1, this quantity is always

positive, in agreement with the second law

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Problem 11.1
Solution:
Fugacity And Fugacity Coefficient: Pure Species

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Vapor/Liquid Equilibrium for Pure Species
Fugacity of a Pure Liquid

The fugacity of pure species i as a compressed (subcooled) liquid
can be calculated as the product of the saturation pressure with
three ratios that are each relatively easy to evaluate:
All terms are at the temperature of interest. Cancellation of

numerators and denominators produces a mathematical identity.
Writing the fugacity as a product of these three ratios is simply
done for convenience.
Ratio (A) is the vapor-phase fugacity coefficient of pure vapor i at
its vapor/liquid saturation pressure, designated 𝜙isat. It is given by
Eq. (11.35), written,

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As shown by Eq. (11.39), expressing the equality of liquid and
vapor fugacities at equilibrium, ratio (B) is unity. Ratio (C) reflects
the effect of pressure on the fugacity of pure liquid i. This effect is
generally small. The basis for its calculation is Eq. (6.10),
integrated at constant T to give:
Another expression for this difference results when Eq. (11.31) is

written for both Gi and Gisat; subtraction then yields:
(11.43)
(11.44)
(11.44)

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If Zvi is given by Eq. (3.38), the simplest form of the virial equation, then:
and Eq. (11.44) becomes:
(11.45)
ChE 3107
Thermodynamics
Instructor:
Shuvashish Mondal
Lecturer,
Khulna-9203
Date: 23-05-2022

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Example 11.5
Example 11.5
3030.8 J/g 6.4817 J/g.K
3030.8-3076.8
(6.4817-10.345) 8.1971
3630.4
3630.4 3630.4 3630.4

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Example 11.5 (cont’d)

3630.4
0.9076
45
Example 11.5
Figure 11.3

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Fugacity And Fugacity Coefficient: Species In Solution
Thus, multiple phases at the same T and P are in

equilibrium when the fugacity of each constituent species
is the same in all phases

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The Fundamental Residual-Property Relation

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Fugacity Coefficients from the Virial Equation of State

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ChE 3107
Thermodynamics
Instructor:
Shuvashish Mondal
Lecturer,
Khulna-9203
Date: 26-05-2022

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Example 11.7
26 May 2022 57
Generalized correlations for fugacity coefficient

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Generalized correlations for fugacity coefficient
Example 11.9

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Example 11.9
Homework

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The Ideal Solution
The Ideal Solution

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Excess Properties
Excess property ME is defined as the difference between
the actual property value of a solution and the value it
would have as an ideal solution at the same temperature,
pressure, and composition
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Excess Properties

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The Nature of the Excess Properties
67
The Nature of the Excess Properties

All excess properties become zero as either species
approaches purity.
Although the systems exhibit a diversity of behavior, they have

common features:
• Although GE vs. x1 is approximately parabolic in shape,
both HE and TSE exhibit individualistic composition
dependencies
• Excess properties are often strong functions of temperature,
but at normal temperatures they are not strongly influenced
by pressure
• When an excess property ME has a single sign (as does GE in
all six cases), the extreme value of ME (maximum or
minimum) often occurs near the equimolar composition.

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11.28.
11.28.

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11.28.
11.28.

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11.28.
11.28.

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Solution Thermodynamics

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26-05-2022

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 2

© Shuvashish Mondal, Lecturer, Department

Fundamental Property Relation

where n is the total number of moles of the system. This equation

The subscript n indicates that the numbers of moles of all

where ni is the number of moles of species i.

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 3

Fundamental Property Relation

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 4

© Shuvashish Mondal, Lecturer, Department

The Chemical potential

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 5

The Chemical potential

• Chemical potential ()

© Shuvashish Mondal, Lecturer, Department

It is a response function, i.e., it is a measure of the response of total

Thus, the partial molar Gibbs energy is the chemical potential.

Partial Molar Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 8

© Shuvashish Mondal, Lecturer, Department

Partial Molar Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 9

Partial Molar Properties

Differentiate Eq. (11.11)

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 10

© Shuvashish Mondal, Lecturer, Department

Partial Molar Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 11

Partial Properties in Binary Solutions

Written for a binary solution, the summability relation, Eq. (11.11),

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 12

© Shuvashish Mondal, Lecturer, Department

Partial Properties in Binary Solutions

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 13

Example 11.2 (10.2 in 8th ed)

© Shuvashish Mondal, Lecturer, Department

Example 11.2 (10.2 in 8th ed)

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 15

Example 11.2 (10.2 in 8th ed)

ഥ1∞ → the partial property of species 1, when it is present at infinite

© Shuvashish Mondal, Lecturer, Department

Example 11.3 (10.3 8th ed)

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26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 18

© Shuvashish Mondal, Lecturer, Department

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26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 20

© Shuvashish Mondal, Lecturer, Department

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 21

A numerical value for H1 results by substitution of x1 = 1 in either Eq.

The infinite-dilution values 𝐻

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 22

© Shuvashish Mondal, Lecturer, Department

Relations among Partial Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 24

© Shuvashish Mondal, Lecturer, Department

Relations among Partial Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 25

Relations among Partial Properties

26 May 2022 Shuvashish Mondal, Lecturer, Department of Chemical Engineering 26

© Shuvashish Mondal, Lecturer, Department

The Ideal-gas-state Mixture Model