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