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CHEN 310: CHEMICAL ENGINEERING

THERMODYNAMICS

MODULE 3

Prof. S. M. Waziri & Prof. M. S. Galadima

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THE FRAMEWORK OF SOLUTION

THERMODYNAMICS
 Learning Objectives
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Our objectives in this module 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 and 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; these are composition-dependent and
distinct from the molar properties of pure species.
■Develop property relations for the ideal-gas-state mixture, which provide the basis for treatment of real-gas
mixtures
■Define yet another useful property, the fugacity; related to the chemical potential, it proves useful for analyzing
both phase- and chemical-reaction-equilibrium problems
■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
■ Define activity coefficients and relate them to the excess Gibbs energy of a mixture
■ Introduce several excess Gibbs energy and activity coefficient models
 FUNDAMENTAL PROPERTY RELATION
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Recall that the following equation relate the total Gibbs energy of any closed system to its canonical
variables, temperature and pressure

Closed system

It applies 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.
 FUNDAMENTAL PROPERTY RELATION
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Consider a single-phase, open system (i.e. material can enter and leave the system)

where ni is the number of moles of species i

The total differential of nG:

subscript nj indicates that all mole numbers except the ith are held constant The chemical potential
of species i is defined as
The chemical potential 𝜇𝑖 provides the fundamental
criterion for phase equilibrium and chemical-
reaction equilibria.
 FUNDAMENTAL PROPERTY RELATION
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Fundamental property relation for single-phase fluid systems of variable mass and composition.

Open system

For the special case of one mole of solution, n = 1 and ni = xi:

The Gibbs energy expressed as a function of its canonical variables serves as a generating function,
allowing calculation of all other thermodynamic properties by simple mathematical operations
(differentiation and elementary algebra). It implicitly represents complete property information.
 PARTIAL PROPERTIES
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ഥ𝑖 of species i in solution is defined as

Partial molar property 𝑀

Sometimes called a response function, 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

Kinds of properties used in solution thermodynamics

Property Symbol Examples
Solution properties 𝑀 𝑉, 𝑈, 𝐻, 𝑆, 𝐺
Partial properties ഥ𝑖
𝑀 𝑉ത𝑖 , 𝑈 ഥ𝑖 , 𝑆𝑖ҧ , 𝐺ҧ𝑖
ഥ𝑖 , 𝐻
Pure-species properties 𝑀𝑖 𝑉𝑖 , 𝑈𝑖 , 𝐻𝑖 , 𝑆𝑖 , 𝐺𝑖
 Equations Relating Molar and Partial Molar Properties
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Total thermodynamic properties of a homogeneous phase are functions of T, P, and the numbers of
moles of the individual species that comprise the phase. Thus for property M we can write:

The total differential of nM is:

The above can be rewritten as

where subscript x denotes differentiation at constant composition

 Equations Relating Molar and Partial Molar Properties
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But

Thus

Collecting like terms together gives

Which implies Summability

and
 Limiting Values of Partial Properties
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• Partial properties, like solution properties, are functions of composition

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

• For a partial property of a species that approaches its infinite-dilution limit

(i.e., a partial property value of a species as its mole fraction approaches
zero)
 GIBBS/DUHEM EQUATION
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Since

Differentiation gives

But

Thus

• It must be satisfied for all changes occurring

in a homogeneous phase
• It shows that the partial properties of
Special case species making up a solution are not
independent of one another
 Partial Properties in Binary Solutions
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Consider a binary system (i =1,2)

Summability

Gibbs/Duhem equation
(Const T and P)
 Graphical Interpretation
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 Class Exercise
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The molar volume (cm3mol-1) of a binary liquid mixture at T and P is given by:
𝑉 = 120𝑥1 + 70𝑥2 + (15𝑥1 + 8𝑥2 )𝑥1 𝑥2
(a) Find expressions for the partial molar volumes of species 1 and 2 at T and P.
(b) Show that when these expressions are combined in accord with the summability relation the
given equation for V is recovered.
(c) Show that these expressions satisfy the Gibbs/Duhem equation.
ഥ1
𝑑𝑉 ഥ2
𝑑𝑉
(d) Show that = =0
𝑑𝑥1 𝑥 =1 𝑑𝑥1 𝑥 =0
1 1
(e) Plot values of V, 𝑉ത1 , and 𝑉ത2 calculated by the given equation for V and by the equations
developed in (a) vs. x1. Label points 𝑉ത1 , 𝑉ത2 , 𝑉ത1∞ , 𝑉ത2∞ and show their values.
 Relations Among Partial Properties
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Recall that

Application of the criterion of exactness, yields the following relations:

For every equation that provides a linear
relation among thermodynamic properties
of a constant-composition solution, there
exists an identical equation connecting the
corresponding partial properties of each
species in the solution.

Analog
 THE IDEAL-GAS-STATE MIXTURE MODEL
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For the ideal-gas state at given T and P the partial molar volume, the pure-species molar
volume, and the mixture molar volume are identical

The partial pressure of species i in the ideal-gas-state mixture (pi) as the pressure that species i
would exert if it alone occupied the molar volume of the mixture
 THE IDEAL-GAS-STATE MIXTURE MODEL
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Because the ideal-gas-state mixture model presumes molecules of zero

volume that do not interact, the thermodynamic properties (other than
molar volume) of the constituent species are independent of one another,
and each species has its own set of private properties
Gibbs 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.

Mathematically for
 THE IDEAL-GAS-STATE MIXTURE MODEL
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Enthalpy

Integration from
Entropy pi to P gives

Gibbs free energy

 THE IDEAL-GAS-STATE MIXTURE MODEL
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Alternative expressions for Gibbs free energy

Recall that

For an ideal gas at constant T

Integration gives
 FUGACITY AND FUGACITY COEFFICIENT: PURE SPECIES
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Ideal gas state

Real fluid
𝑓𝑖
Fugacity of pure species i 𝑓𝑖 Fugacity coefficient 𝜙𝑖 ≡ 𝑃
𝑖𝑔
For the ideal gas state 𝑓𝑖 = 𝑃 𝐺𝑖 = 𝐺𝑖 For the ideal gas state 𝜙𝑖 = 1 𝐺𝑖𝑅 = 0
 FUGACITY AND FUGACITY COEFFICIENT: SPECIES IN SOLUTION
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Challenges with direct use of 𝜇𝑖 𝑜𝑟 𝐺ҧ𝑖 in phase and chemical reaction equilibrium calculations
• Because 𝜇𝑖 are related to U and S, their absolute values are unknown
• 𝜇𝑖 approaches negative infinity when either P or yi approaches zero

Ideal gas state

Real fluid
መ
𝑓
Fugacity of species i in solution 𝑓෡𝑖 Fugacity coefficient 𝜙෠𝑖 ≡ 𝑦 𝑖𝑃
𝑖

For the ideal gas state 𝑖𝑔 For the ideal gas state 𝜙෠𝑖 = 1
𝑓෡𝑖 = 𝑦𝑖 𝑃 𝐺ҧ𝑖 = 𝐺𝑖ҧ 𝐺ҧ𝑖𝑅 = 0

𝐺ҧ𝑖𝑅
= 𝑙𝑛𝜙෠𝑖
𝑅𝑇
 Fugacity Coefficients from the Virial Equation of State
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• Values of 𝜙෠ 𝑖 for species i in solution are readily obtained from equations

of state.
• Consider the two-term volume explicit virial equation of state written
for a gas mixture

• It can be shown that

 Summary of Fugacity Formulas
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 GENERALIZED CORRELATIONS FOR THE
FUGACITY COEFFICIENT
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Starting from the two-term volume explicit virial equation of state

NOTE: it is applicable to gases at low
to moderate pressures (Pr < 1)

Substituting the above into the following and integrating

or

Abbott equations

Lee/Kesler generalized correlation, Tables D.13 Three-parameter corresponding-states principle

to D.16 of App. D. (Smith et. al. textbook)
or
The Lee/Kesler Generalized-Correlation Tables
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The Lee/Kesler Generalized-Correlation Tables
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 THE IDEAL SOLUTION MODEL
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Ideal gas state

𝑖𝑔
A natural extension of the ideal gas state model replaces 𝐺𝑖 𝑇, 𝑃 with 𝐺𝑖 (T, P), the Gibbs energy of
pure i in its real physical state of gas, liquid, or solid.

Ideal solution
 The Lewis/Randall Rule
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Recall that

For the special case of an ideal solution

Lewis/Randall rule
Division by Pxi

It shows that the fugacity of each species in an ideal solution is proportional to its mole fraction; the
proportionality constant is the fugacity of pure species i in the same physical state as the solution and
at the same T and P.
 EXCESS PROPERTIES
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The generic excess property is defined by

where M and Mid are actual and ideal-solution properties at the same T, P and composition. They
represent molar values for any extensive thermodynamic property, e.g., V, U, H, S, or G

Examples:

Relation between ME and MR

Partial-property relation

Fundamental excess-property relation

Note that excess properties (unlike residual properties) have no meaning for pure species.
 EXCESS GIBBS ENERGY AND ACTIVITY COEFFICIENTS
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Ideal solution

Real solution

𝑓መ𝑖
Activity coefficient 𝛾𝑖 ≡ For an ideal solution 𝛾𝑖 = 1 𝐺ҧ𝑖𝐸 = 0
𝑥𝑖 𝑓𝑖

Fundamental excess-property relation

𝐺ҧ𝑖𝐸
= 𝑙𝑛𝛾𝑖
𝑅𝑇
 EXCESS GIBBS ENERGY AND ACTIVITY COEFFICIENTS
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More useful forms in practice

Partial property analogs

Summability and Gibbs/Duhem equation

Fundamental residual-property relation derives its usefulness from its direct relation to experimental
PVT data and equations of state. The fundamental excess-property relation is useful because activity
coefficients are found from VLE data while VE and HE values come from mixing experiments.
 EXCESS PROPERTIES
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 CORRELATIONS FOR LIQUID-PHASE ACTIVITY COEFFICIENTS
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 In general, GE∕RT is a function of T, P, and composition, but for liquids at low to moderate pressures
it is a very weak function of P.
 Therefore
𝐺𝐸
= 𝑔(𝑥1 , 𝑥2 , ⋯ 𝑥𝑁 ) (const T)
𝑅𝑇

 Redlich/Kister expansion (binary system)

𝐺𝐸 2
𝑥1 𝑥2 𝑅𝑇
= 𝐴 + 𝐵(𝑥1 − 𝑥2 )+ C 𝑥1 − 𝑥2 +⋯

𝐺𝐸
If A=B=C= ⋯ =0 =0 𝑙𝑛𝛾1 = 0 𝑙𝑛𝛾2 = 0 𝛾1 = 𝛾2 =1
𝑥1 𝑥2 𝑅𝑇
𝐺𝐸
If B=C= ⋯ =0 =𝐴 𝑙𝑛𝛾1 = 𝐴𝑥22 𝑙𝑛𝛾2 = 𝐴𝑥12 𝑙𝑛𝛾1∞ = 𝑙𝑛𝛾2∞ = 𝐴
𝑥1 𝑥2 𝑅𝑇
 CORRELATIONS FOR LIQUID-PHASE ACTIVITY COEFFICIENTS
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 Margules Equation (for binary system)

𝐺ҧ𝑖𝐸
= 𝑙𝑛𝛾𝑖
𝑅𝑇

 Among the simplest models that can reasonably fit low-pressure VLE involving moderately nonideal
liquid-phase behavior
 For the limiting conditions of infinite dilution

NOTE
 CORRELATIONS FOR LIQUID-PHASE ACTIVITY COEFFICIENTS
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 The van Laar Equation (for binary system)

𝐺ҧ𝑖𝐸
= 𝑙𝑛𝛾𝑖
𝑅𝑇

 For the limiting conditions of infinite dilution

 Wilson Equation (for binary system)

 CORRELATIONS FOR LIQUID-PHASE ACTIVITY COEFFICIENTS
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 NRTL Equation (binary system)

𝐺ҧ𝑖𝐸
= 𝑙𝑛𝛾𝑖
𝑅𝑇

 Other Models
 UNIFAC
 UNIQUAC
 There are multicomponent versions of the activity coefficient models