Chapter 11

SOLUTION THERMODYNAMICS: THEORY

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CONTENT

SOLUTION THERMODYNAMICS: THEORY

11.1 Fundamental Property Relation
11.2 The Chemical Potential and Equilibria
11.3 Partial Properties
11.4 Ideal-Gas-Mixture
11.5 Fugacity and Fugacity Coefficient: Pure Species
11.6 Fugacity and Fugacity Coefficient: Species in Solution
11.7 Generalized Correlations for the Fugacity Coefficient
11.8 The Ideal-Solution Model
11.9 Excess Properties

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Course Learning Outcomes (CLO):
Upon successful completion of this course, you will be able to:

1. Define thermodynamic principles to formulate & solve problems

involving open & closed systems. [SO(1)]
2. Determine properties of nonideal gas using residual properties [SO(1)]
3. Demonstrate the requirements for phase equilibrium for both ideal &
non-ideal solutions. [SO(1)]
4. Calculate fugacity & activity coefficient to describe nonideal behaviors.
[SO(1)]
5. Calculate the equilibrium conversion as a function of temperature,
pressure & initial concentrations for single & multi-reaction systems.
[SO(1)]

SO(1)
An ability to identify, formulate, & solve complex engineering
problems by applying principles of engineering, science, &
mathematics.

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Objectives
The objectives of this chapter are to:
Develop a fundamental property relation that is applicable to open phases of
variable composition.

Define the chemical potential, a fundamental new property that facilitates

treatment of phase & chemical-reaction equilibria.

Introduce partial properties, a class of thermodynamic properties defined

mathematically to distribute total mixture properties among individual species
as they exist in a mixture.

Develop property relations for the ideal-gas-state mixture, which provide the
basis for treatment of real-gas mixtures.

Define another useful property, the fugacity.

Introduce a useful class of solution properties, known as excess properties, in

conjunction with an idealization of solution behavior called the ideal-solution
model, which serves as a reference for real-solution behavior.

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Introduction
A mixture is a combination of two or more substances that are not
chemically united & do not exist in fixed proportions to each other. Most
natural substances are mixtures.
e.g. Salt-water

A solution is a mixture of two or more substances in a

single phase. At least two substances must be mixed in
order to have a solution.
• The substance in the smallest amount & the one that
dissolves or disperses is called the solute.
• The substance in the larger amount is called the
solvent. Dye solution
In most common instances water is the solvent. The gases, liquids,
or solids dissolved in water are the solutes.

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Introduction
We will consider:

Single phase system &

Multicomponent:
This means there is interaction among species inside the
system.
Reaction interaction will not considered.
Example: Mixing ethanol & water

Total solution properties (Property of a mixture)

Property of a pure species
Partial property in a mixture

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Introduction
Example: Mixing ethanol & water
# no of moles are
the same by the
volume is not.
Partial Properties

Partial volume of
V= Ethanol in the mixture.

Properties of Property of a mixture

pure species (Total solution property)

50 ml ethanol + 20 ml water = 67 NOT 70 ml ∆ The shrinking in volume is due to the

interaction between ethanol & water

෍ 𝐏𝐮𝐫𝐞 𝐬𝐩𝐞𝐜𝐢𝐞𝐬 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬 ≠ 𝐓𝐨𝐭𝐚𝐥 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬 Because of

interaction.
෍ 𝐏𝐚𝐫𝐭𝐢𝐚𝐥 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬 = 𝐓𝐨𝐭𝐚𝐥 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬

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Introduction

Consider a closed volume which contains two phases,

denoted by a & b.
Phase a
For the entire system, the total volume, (nV), the n1 n2
total number of moles, n, & the number of moles
of each component, ni, are fixed, but the amount
Phase b
attributed to each phase is not.
Therefore the total system is a closed system, n1 n2
but each individual phase is an open system.
Closedcontainer
Closed Container

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11.1 Fundamental Property Relation
The total Gibbs energy of any closed system:

(6.7) (G is related to T & P)

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

The subscript n indicates that the numbers of moles of all chemical species are held
constant.
Consider a case of a single-phase, open system, material may pass into
& out of the system, & nG becomes a function of the numbers of moles of
the chemical species present.

It remains a function of T & P, thus,

where ni is the number of moles of species i.

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11.1 Fundamental Property Relation
(6.6)
The total differential of nG is then:
Chemical potential
nV -nS

The summation is over all species present, & subscript nj indicates that all mole
numbers except the ith are held constant.
The definition of the chemical potential of species i in the mixture is:

(11.1)

Fundamental property
relation for single-
phase fluid systems of (11.2)
variable mass &
composition. It is the foundation upon which the structure of
solution thermodynamics is built.

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 For the special case of one mole of solution, n = 1 & ni = xi: xi = ni/nT
Functional relationship of
the molar Gibbs energy
to its variables, here: T, (11.3)
P, & {xi}:

(11.4) (11.5)

Other solution properties come from definitions; e.g., the enthalpy,

from H = G + TS. Thus, by Eq. (10.5),

When the Gibbs energy is expressed as a function of its canonical

variables, it serves as a generating function, providing the means for the
calculation of all other thermodynamic properties by simple mathematical
operations (differentiation & elementary algebra), & it implicitly represents
complete property information.

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11.2. THE CHEMICAL POTENTIAL & EQUILIBRIUM

The total system is a closed system,

but each individual phase is an open system.
α
Phase a

Apply Eqn (11.2) applies separately to each phase:

(11.2)
β
Phase b

Closed Container
+
where superscripts α & β identify the phases.
The change in the total Gibbs energy of the two-phase system is the
sum of the equations for the separate phases:

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 Because the two-phase system is closed, Eq. (6.7) is also valid.
Comparison of the two equations shows that at equilibrium:

The changes result from mass transfer between the

phases; mass conservation therefore requires: Because the 𝑛𝑖𝛼 are
independent variables,
the eqn must hold for
and any choice of values for
𝑑𝑛𝑖𝛼 .

where N is the number of

species present in the system.
For multiple phases (π phases):

(11.6)

Thus, multiple phases at the same T & P are in equilibrium when

the chemical potential of each species is the same in all phases.

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11.3. Partial Properties
A partial molar property is a thermodynamic quantity which
indicates how an extensive property of a solution or mixture varies
with changes in the molar composition of the mixture at constant
temperature & pressure.

Notation for Mixtures:

Symbol Description Examples

𝑴 Bulk solution property 𝐺, 𝐻, 𝑉, …
ഥ𝒊
𝑴 Partial molar property of species i in 𝐺ҧ𝑖 , 𝐻
ഥ𝑖 , 𝑉ത𝑖 , …
the solution

𝑴𝒊 Molar property of substance i 𝐺𝑖 , 𝐻𝑖 , 𝑉𝑖 , …

as a pure material

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11.3. Partial Properties
The chemical potential: (11.1)

ഥ𝑖 of species i in solution as:

The partial molar property 𝑀

(11.7)

Always in term Always hold the The number of moles of all

of ni intensive properties species except i are hold
T & P constant constant (nj ≠ i)

Comparison of Eq. (11.1) with Eq. (11.7) written for the Gibbs energy
shows that the chemical potential & the partial molar Gibbs energy are
identical; i.e.,
(11.8)

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Equations Relating Molar & Partial Molar Properties

Thus for property M, we can write nM as a function which we could

call 𝕄:

The total differential of nM is:

n = constant n = constant ഥ𝑖
𝑀

(11.9)

where subscript x denotes differentiation at constant composition.

Because ni = xin,

Moreover:

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 When dni & d(nM) are replaced in Eq. (11.9), it becomes:

The terms containing n are collected & separated from those containing dn to
yield:

Each term in brackets can be zero:

(11.10)

Thus, if the partial molar properties

are known, the mixture properties
are known. (11.11)
Multiply by n:
(11.12)

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 Differentiation of Eq. (11.11):

Combining this eqn with Eq. (11.10) yields the Gibbs/Duhem eqn:

Gibbs/Duhem
(11.13)
Equation

This equation must be satisfied for all changes occurring in a

homogeneous phase.

For the important special case of changes in composition at constant T

& P:

(constant T , P) (11.14)

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A Rationale for Partial Properties

Central to applied solution thermodynamics, the partial-property

concept implies that a solution property represents a “whole,”
ഥ𝑖
i.e., the sum of its parts as represented by partial properties 𝑀
of the constituent species.

Partial properties, like solution properties, are functions of composition.

ഥi
In the limit as a solution becomes pure in species i, both M & M
approach the pure-species property Mi.

For a species that approach its infinite-dilution limit, i.e., the value as
its mole fraction approaches zero:

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Summary:
The essential equations of this section are thus summarized as follows:

Definition: (11.7)

which yields partial properties from total properties.

(11.11)
Summability:

which yields total properties from partial properties.

Gibbs/Duhem: (11.13)

which shows that the partial properties of species making up a

solution are not independent of one another.

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Worked Example:
Label the volumes depicted in following Figure according to the different
types of thermodynamic properties depicted in this section.

Mixing of ethanol + =
and water.

(e) (w)

+ =

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Partial Properties in Binary Solutions
An eqn for a partial property as a function of composition can
always be derived from an eqn for the solution property by direct
application of Eq. (11.7).
(11.7).
For a special case of a binary system:
(A)
Differentiate:
(B)

When M is known as a function of x1 at constant T & P, the Gibbs-Duhem

at constant T & P:

(C)

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Eliminating dx2 in favor of dx1 in Eq. (B) & combining the result with
Eq. (C) gives:
(D)

Two equivalent forms of Eq. (A) ( )result from the

elimination separately of x1 & x2: x1 + x2 =1

In combination with Eq. (D) these become:

(11.15) (11.16)

Thus for binary systems, the partial properties are readily calculated
directly from an expression for the solution property as a function of
composition at constant T & P.

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Example 10.2
Describe a graphical interpretation of Eqs. (11.15) & (11.16).

(11.15) (11.16)

The tangent line shown extends across the figure,

intersecting the edges (at x1 = 1 & x1 = 0) at points
labeled I1 & I2.
and ഥ1
𝑀
Tangent line
and
Comparisons of these expressions with Eqs. ഥ2
𝑀
(11.16) and (11.15) show that:

Thus, the tangent intercepts give directly the x1

values of the two partial properties. Fig. 11.1: (a) Plot of M vs. x for a binary
system.
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These intercepts of course shift as the
point of tangency moves along the
curve, as shown in Fig. 11.1(b).

For the tangent line

drawn at x1= 0
(pure species 2),

& at the opposite intercept,

Figure 11.1: (b) Infinite-dilution values of

partial properties.
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Example 11.3

Partial molar Molar volumes of

volumes pure components

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Solution:
(11.11),

Mixture’s molar volumes

Total number of moles

Moles of each component

Volumes of each component

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Example 11.4

Q: How to plot H vs. x for this binary system?

Solution:

(11.15),

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Solution cont.:

(11.16),

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Solution cont.:

X1 = 0

X1 = 1

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 Problem:

[i]

[ii] What is the partial molar volume of species (1) at T and P when x1 = 0.40?

[iii] What is the pure molar volume of species (1) at T and P?

[iv] What is the pure molar volume of species (2) at T and P?

[v]

[vi]

[i]

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 Problem:

[i]
[ii]

[iii]

[i]

[ii]

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11.4 THE IDEAL-GAS-STATE MIXTURE MODEL

The ideal-gas-state mixture model provides a conceptual basis upon

which to build the structure of solution thermodynamics.
It is a useful property model because it:
Has a molecular basis.
Approximates reality in the well-defined limit of zero pressure.
Is analytically simple.

At the molecular level, the ideal-gas state

represents a collection of molecules that
do not interact & occupy no volume. This
idealization is approached for real
molecules in the limit of zero pressure.

Although they do not interact with one another, molecules in the ideal-gas
state do have internal structure; it is differences in molecular structure
that give rise to differences in ideal-gas-state heat capacities, enthalpies,
entropies, and other properties.
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Molar volumes in the ideal-gas state are (ig = ideal-gas state)

The partial molar volume of species i in the ideal-gas-state mixture

applied to the volume:

𝑗 ≠𝑖 𝑗 ≠𝑖 𝑗 ≠𝑖

𝑛 = 𝑛𝑖 + ෍ 𝑛𝑗
𝑗

Because there is no interaction (11.20)

between molecules.
The partial pressure of species i in the ideal-gas state mixture:

where yi is the mole fraction of species i.

The partial pressures SUM to the total pressure.

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The ideal-gas-state mixture model presumes molecules of zero volume
that do not interact.
Thus, the thermodynamic properties (other than molar volume) of the
constituent species are independent of one another, & each species has
its own set of private properties.

This is the basis for the following statement of Gibbs’s theorem:

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.
(other than volume)

(11.21)

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Enthalpy in the ideal-gas state is independent of pressure;

or (11.22)
𝑖𝑔
where 𝐻𝑖 is the pure-species value at the mixture T & P.
Applying the summability relation:

(11.23)

An analogous eqn applies for Uig & other properties that are
independent of P.

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Entropy in the ideal-gas state does depend on pressure, restricted
to constant temperature:

(6.24)

The entropy difference between a gas at its partial pressure in the mixture
& at the total pressure of the mixture & integration from Pi to P gives:

Hence,
Summability relation
Comparing with Eqn 11.21( )

or, (11.24)
𝑖𝑔
where 𝑆𝑖 is the pure-species value at the mixture T & P.
By the summability relation: (11.25)

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For the Gibbs energy in the ideal-gas-state mixture,
the parallel relation for partial properties is:

But and

or,
(11.26)

𝑖𝑔
𝜇𝑖 is the chemical potential.
𝑖𝑔
An alternative expression for the chemical potential is obtained when 𝐺𝑖
is eliminated from Eqn 11.6:
(6.11)

Integration:

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 (11.27)

Where the integration constant at constant T.

Now Eqn (11.26) can be written as:
(11.28)

Applying the summability relation:

(11.29)

These equations, remarkable in their simplicity, provide a full description

of ideal-gas-state behavior.

Because T, P, & {yi} are the canonical variables for the Gibbs energy, all
other thermodynamic properties for the ideal-gas model can be
generated from them.

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Summary

Summability relations

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 Reference

Smith J.M., Van Ness H.C., & Abbott M. M., Introduction to Chemical Engineering
Thermodynamics, 7th Edition, McGraw Hill, New York, 2001.

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