SOLUTION THERMODYNAMICS:

THEORY
FUNDAMENTAL PROPERTY
RELATIONS
2.1 Fundamental Property Relation

• Total Gibbs energy of any closed system as a function of temperature and pressure

𝑑 𝑛𝐺 = 𝑛𝑉 𝑑𝑃 − 𝑛𝑆 𝑑𝑇

where : n=total number of moles in the system

𝜕 𝑛𝐺 𝜕 𝑛𝐺
= 𝑛𝑉 𝑎𝑛𝑑 = −𝑛𝑆
𝜕𝑃 𝑇,𝑛
𝜕𝑃 𝑃,𝑛
Subscript n indicates that the no. of moles of all chemical species are held constant.

• The chemical potential of species in the mixture is :

𝜕 𝑛𝐺
𝜇𝑖 = (2.1)
𝜕𝑛𝑖 𝑃,𝑇,𝑛
The preceding equation becomes :
𝜕 𝑛𝐺
𝑑 𝑛𝐺 = 𝑛𝑉 𝑑𝑃 − 𝑛𝑆 𝑑𝑇 + σ𝑖 (2.2)
𝜕𝑛𝑖 𝑃,𝑇,𝑛

Eq. (2.2) is the fundamental property relation for single-phase fluid systems of variable mass and composition.
• For the special case of one mole of solution, 𝑛 = 1 𝑎𝑛𝑑 𝑛𝑖 = 𝑥𝑖 .
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + σ𝑖 𝜇𝐼 𝑥𝑖
For σ𝑖 𝑥𝑖 = 1,
𝜕𝐺 𝜕𝐺
𝑉= 𝑎𝑛𝑑 𝑆 = −
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
From Enthalpy 𝐻 = 𝐺 + 𝑇𝑆
𝜕𝐺
𝐻 =𝐺−𝑇
𝜕𝑇 𝑃,𝑥

• When the Gibbs energy is expressed as a function of its canonical variables, it plays the role of a generating function.
THE CHEMICAL POTENTIAL AND
PHASE EQUILIBRIA
2.2 The Chemical Potential and Phase Equilibria

• For a closed system,

𝑑(𝑛𝐺)𝛼 = 𝑛𝑉 𝛼
𝑑𝑃 − 𝑛𝑆 𝛼
𝑑𝑇 + ෍ 𝜇𝑖𝛼 𝑑𝑛𝑖𝛼
𝑖

𝑑(𝑛𝐺)𝛽 = 𝑛𝑉 𝛽
𝑑𝑃 − 𝑛𝑆 𝛽
𝑑𝑇 + σ𝑖 𝜇𝑖𝛽 𝑑𝑛𝑖𝛽
Where 𝛼 and 𝛽 are the two phases in equilibrium
𝛽
𝜇𝑖𝛼 = 𝜇𝑖

• Multiple phases at the same T and P are in equilibrium when the chemical potential of each species is the same in all phases.
PARTIAL PROPERTIES
2.3 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 and pressure.

• Partial molar property 𝑀𝑖 of species 𝑖 in solution as:

𝜕 𝑛𝑀
ഥ𝑖 =
𝑀
𝜕𝑛𝑖 𝑃,𝑇,𝑛
• Three kinds of properties used in solution thermodynamics :
• Solution properties 𝑀, for example : V, U, H, S, G
ഥ𝑖 , 𝑈𝑖 , 𝐻𝑖 , 𝑆ഥ𝑖 , 𝐺ഥ𝑖
• Partial properties 𝑀𝑖 , for example : 𝑉
• Pure-species properties 𝑀𝑖 , , for example : 𝑉𝑖 , 𝑈𝑖 , 𝐻𝑖 , 𝑆𝑖 , 𝐺𝑖
Differential form of thermodynamics of potentials
Equations Relating Molar and Partial Molar Properties

• Partial molar property provides the means for calculation of partial properties from solution-property data.
𝜕𝑀 𝜕𝑀
𝑑 𝑛𝑀 = 𝑑𝑃 + 𝑛 𝑑𝑇 + ෍ 𝑀𝑖 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑥
𝜕𝑇 𝑃,𝑥 𝑖
where subscript x denotes differentiation at const. composition, 𝑛𝑖 = 𝑥𝑖 𝑛
𝑑𝑛𝑖 = 𝑥𝑖 𝑑𝑛 + 𝑛𝑑𝑥𝑖
𝑑 𝑛𝑀 = 𝑛𝑑𝑀 + 𝑀𝑑𝑛
Thus n and dn are independent and arbitrary,

𝑀 = ෍ 𝑥𝑖 𝑀𝑖
𝑖
Another general equation for dM, yields the Gibbs-Duhem equation:
𝜕𝑀 𝜕𝑀
𝑑𝑃 + ഥ𝑖 = 0
𝑑𝑇 − ෍ 𝑥𝑖 𝑑𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖
Partial Properties in Binary Solutions
• For binary systems, an alternative procedure may be more convenient.
Relations among Partial Properties
THE IDEAL GAS MIXTURE MODEL
2.4 The Ideal-Gas Mixture Model
• The ideal-gas mixture model provides a conceptual basis upon which to build the structure of solution thermodynamics is a
useful property model because it:
 Has a molecular basis
 Approximate reality in the well-defined limit of zero pressure
 Is analytically simple
 𝑃𝑉 𝑡 = 𝑛𝑅𝑇
𝑃𝑖 𝑉 𝑡 = 𝑛𝑖 𝑅𝑇
Partial pressure 𝑃𝑖 = 𝑦𝑖 𝑃
• Partial molar volume

• Enthalpy ( not function of P)

• Internal Energy (not function of P)

• Entropy (depend on P)

• Gibbs free energy

FUGACITY AND FUGACITY
COEFFICIENTS
Pure Species
2.5 Fugacity and Fugacity Coefficients : Pure Species

For a real fluid

𝐺𝑖 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖

𝑖𝑔
• 𝑓𝑖 =𝑃
2.5 Fugacity and Fugacity Coefficients : Pure Species

Residual Gibbs Energy 𝐺𝑖 𝑅

𝐺𝑖 𝑅 = 𝑅𝑇 ln 𝜙𝑖

𝑓𝑖
• Fugacity coefficient: 𝜙𝑖 =
𝑃
2.5 Fugacity and Fugacity Coefficients : Pure Species

At constant Temperature:
𝑃
𝑑𝑃
ln 𝜙𝑖 = න 𝑍𝑖 − 1
0 𝑃

𝑓𝑖
• Fugacity coefficient: 𝜙𝑖 =
𝑃
Fugacity Coefficients from Generic Cubic Equation of
State

ln 𝜙𝑖 = 𝑍𝑖 − 1 − ln 𝑍𝑖 − 𝐵𝑖 − 𝑞𝑖 𝐼𝑖
Vapor/Liquid Equilibrium for Pure Species

• The fugacity of pure species i, may be written for species i as a saturated

vapor and as a saturated liquid at the same temperature.

𝐺𝑖 𝑣 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖 𝑣
𝐺𝑖 𝑙 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖 𝑙

𝑓𝑖 𝑣
𝐺𝑖 𝑣 − 𝐺𝑖 𝑙 = 𝑅𝑇 ln
𝑓𝑖 𝑙
Vapor/Liquid Equilibrium for Pure Species

𝐺𝑖 𝑣 − 𝐺𝑖 𝑙 = 0
Therefore:
𝑓𝑖 𝑣 = 𝑓𝑖 𝑙 = 𝑓𝑖 𝑠𝑎𝑡
• For a pure species coexisting liquid and vapor phases are in equilibrium
when they have the same temperature, pressure, and fugacity.
𝑠𝑎𝑡
𝑓𝑖
𝜙𝑖 𝑠𝑎𝑡 = 𝑠𝑎𝑡
𝑃𝑖
𝜙𝑖 𝑣 = 𝜙𝑖 𝑙 = 𝜙𝑖 𝑠𝑎𝑡
Fugacity of a Pure Liquid

• A – vapor phase fugacity coefficient of pure vapor i at its vapor/liquid

saturation pressure
• B – unity
• C – reflects the effect of pressure in the fugacity of pure liquid i
FUGACITY AND FUGACITY
COEFFICIENTS
Species in Solution
2.6 Fugacity and Fugacity Coefficients: Species in
Solution
• Ideal-gas:
𝜇𝑖 = Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓መ𝑖
• 𝑓መ𝑖 - fugacity if species of i in the solution

• Multiple phases at the same T and P are in equilibrium when the fugacity of
each constituent species is the same in all phases.
2.6 Fugacity and Fugacity Coefficients: Species in
Solution
• Residual Property:
𝑀𝑅 ≡ 𝑀 − 𝑀𝑖𝑔
• M – molar (or unit-mass) value of a thermodynamic property
• 𝑀𝑖𝑔 - value that the property would have for an ideal gas of the same
composition at the same T and P.
2.6 Fugacity and Fugacity Coefficients: Species in
Solution

• Residual Gibbs Energy:

𝑅 𝑖𝑔
𝐺෠𝑖 = 𝐺෠𝑖 − 𝐺෠𝑖
2.6 Fugacity and Fugacity Coefficients: Species in
Solution
𝑅
𝐺෠𝑖 = 𝑅𝑇 ln 𝜙෠ 𝑖
𝑓መ𝑖
𝜙෠ 𝑖 ≡
𝑦𝑖 𝑃
෠ 𝑖 - fugacity of coefficient of species i in solution
•𝜙

For ideal gas:

𝑖𝑔
መ
𝑓𝑖 = 𝑦𝑖 𝑃
Fundamental Residual-Property Relation
𝑛𝐺 𝑛𝑉 𝑛𝐻 𝐺෠𝑖
𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖

• Fundamental Residual Property Relation:

𝑛𝐺 𝑅 𝑛𝑉 𝑅 𝑛𝐻 𝑅
𝑑 = 𝑑𝑃 − 2
𝑑𝑇 + ෍ ln 𝜙෠ 𝑖 𝑑𝑛𝑖
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑖
GENERALIZED CORRELATIONS
FOR THE FUGACITY COEFFICIENT
2.7 Generalized Correlations for the Fugacity Coefficient
𝑃𝑟
𝑑𝑃𝑟
ln 𝜙𝑖 = න 𝑍𝑖 − 1
0 𝑃𝑟
THE IDEAL SOLUTION MODEL
2.8 The Ideal Solution Model
• The chemical potential as given by the ideal-gas mixture, contains the final
term that gives it the simples possible composition dependence: indeed, one
that could reasonably serve for dense gases and liquids.
𝑖𝑔
𝜇𝑖 ≡ 𝐺𝑖 = 𝐺𝑖 𝑖𝑔 𝑇, 𝑃 + 𝑅𝑇 ln 𝑦𝑖
𝑖𝑔 ෘ
• Ideal solution:
𝑖𝑑
𝜇𝑖 𝑖𝑑 ෘ
≡ 𝐺𝑖 = 𝐺𝑖 𝑇, 𝑃 + 𝑅𝑇 ln 𝑥𝑖

𝑖𝑑
ҧ
𝑆𝑖 = 𝑆𝑖 − 𝑅 ln 𝑥𝑖
ഥ𝑖 𝑖𝑑 = 𝐻𝑖
𝐻
2.8 The Ideal Solution Model
• The summability relation:
𝑖𝑑
𝑀 𝑖𝑑 ഥ
= ෍ 𝑥𝑖 𝑀𝑖
𝑖

𝐺 𝑖𝑑 = ෍ 𝑥𝑖 𝐺𝑖 + 𝑅𝑇 ෍ 𝑥𝑖 ln 𝑥𝑖
𝑖 𝑖

𝑆 𝑖𝑑 = ෍ 𝑥𝑖 𝑆𝑖 + 𝑅 ෍ 𝑥𝑖 ln 𝑥𝑖
𝑖 𝑖
𝑉 𝑖𝑑 = σ𝑖 𝑥𝑖 𝑉𝑖 𝐻 𝑖𝑑 = σ𝑖 𝑥𝑖 𝐻𝑖
Lewis/Randall Rule
• The composition dependence of the fugacity of a species in an ideal solution
is particularly simple.

𝜇𝑖 ≡ Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓መ𝑖
𝐺𝑖 ≡ Γ𝑖 𝑇 + 𝑅𝑇 ln 𝑓𝑖

• Lewis Randall Rule:

𝑖𝑑
መ
𝑓𝑖 = 𝑥𝑖 𝑓𝑖