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Introduction to Chemical
Engineering Thermodynamics

Dr Tajammal Munir
Email: [email protected]

Chapter 7: Phase Equilibria II:

Fugacity

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C: Class & L: Lab

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Learning outcomes

1. Define the following preliminary concepts (LO1)

• Introduction to fugacity and its application
• Fugacity in the vapor phase
• Fugacity in the liquid phase

2. Apply above concepts to formulate & solve engineering

problems (LO2)

Engineering and Chemical Thermodynamics

Milo D. Koretzky
Wiley, 2nd Edition

Preliminary concepts (LO1)

Fugacity?
• Definition: A thermodynamic property of a real gas which if
substituted for the pressure or partial pressure in the equations for
an ideal gas gives equations applicable to the real gas.

𝑃𝑉 = 𝑛𝑅𝑇 𝑓𝑉 = 𝑛𝑅𝑇
• Example: Nitrogen gas (N2) at 0 °C and a pressure of P = 100
atmospheres (atm) has a fugacity of f = 97.03 atm. The fugacity
coefficient is 97.03 atm/100 atm = 0.9703.

• Fugacity is closely related to the chemical potential μ. Fugacity is

also a measure of the chemical potential. Fugacity measures the
deviation from ideal gas behavior in terms of chemical potential (μ).

• It has the dimensions of pressure, and for an ideal gas, it is identical

to the pressure.

• Usage: Ideal gas equations can be used for real gases by

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substituting pressure or partial pressure with fugacity.
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Preliminary concepts (LO1)

Fugacity?
• Definition: A thermodynamic property of a real gas which if
substituted for the pressure or partial pressure in the equations for
an ideal gas gives equations applicable to the real gas.
• Mathematically:
𝑑𝐺 𝑑𝐺 𝑅𝑇 𝑅𝑇
𝑑𝜇 = = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃 𝑑𝜇 = = 𝑉𝑑𝑃 = 𝑑𝑃 𝑉=
𝑑𝑛 𝑑𝑛 𝑃 𝑃

𝜇 = 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙

𝑅𝑇 Setting the standard condition: 𝜇 −𝜇 = 𝑔 −𝑔

𝑑𝜇 = 𝑑𝑃
𝑃 (𝜇 , at T and 𝑃 )

𝑃 Abstract quantity (not measurable)

𝜇 − 𝜇 = 𝑅𝑇 ln
𝑃 Real quantity (measurable)
𝑝
𝜇 − 𝜇 = 𝑅𝑇 ln For ideal gases: 𝑝 = 𝑦𝑃 𝑝 = 𝑦𝑃
𝑝

𝑓
𝜇 − 𝜇 = 𝑅𝑇 ln 𝑓 = 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦 𝑓𝑜𝑟 𝑟𝑒𝑎𝑙 𝑔𝑎𝑠 𝑤𝑖𝑡ℎ𝑖𝑛 𝑎 𝑚𝑥𝑡𝑢𝑟𝑒
5 𝑓
𝑓 = 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦 𝑓𝑜𝑟 𝑝𝑢𝑟𝑒 𝑟𝑒𝑎𝑙 𝑔𝑎𝑠 C

Preliminary concepts (LO1)

Fugacity?
• Definition: A thermodynamic property of a real gas which if
substituted for the pressure or partial pressure in the equations for
an ideal gas gives equations applicable to the real gas.

• Fugacity has the same unit as pressure. It plays the same role in
real gases that partial pressure plays in ideal gases. It can be
thought as a corrected pressure.

• So, for an ideal gas: 𝑓 = 𝑝

• Fugacity can also be applied to the solid and liquid phase.

• By definition, the Fugacity coefficient is:

𝑓 𝑓 𝑓
𝜑 = = For ideal gas: 𝜑 = =1 𝑓 =𝑝 𝑓 =𝑓
𝑝 𝑦 𝑃 𝑝
𝜑 <1 Attractive forces are stronger than repulsive forces
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𝜑 >1 Attractive forces are weaker than repulsive forces C

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Preliminary concepts (LO1)

Chemical Potential Understanding?

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C

Preliminary concepts (LO1)

Criteria for Chemical Equilibrium in Fugacity?

Thermal Equilibrium

8 Chemical Equilibrium
Mechanical Equilibrium C

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Preliminary concepts (LO1)

Fugacity calculation in various phases and types?

• Main difference: The difference in the expression for fugacity
between vapor and condensed phases typically lies in the choice of
reference state.

Pure
component
In vapor
phase
Mixture (Ideal
& real)
Fugacity
calculation
Pure
component
In liquid phase
Solution (Ideal
& real)

Calculation of fugacity in various phases and types

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C

Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒊 ) of Pure Gases:
• The first step is to identify an appropriate reference state.

• An obvious choice of reference state for gases: a low enough

pressure that the gas behaves as an ideal gas.

• With this choice, we got:

𝑓 →𝑃 𝜑 →1 𝑇 = 𝑇 𝑃 = 𝑃

• Fugacity of pure gas species: For fugacity calculation

𝑓 𝒇𝒗𝒊
𝜇 − 𝜇 = 𝑔 − 𝑔 = 𝑅𝑇𝑙𝑛
𝑓
→ 𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘

For fugacity coefficient calculation

𝒇𝒗𝒊
𝝋𝒗𝒊 =
10 𝑷𝒍𝒐𝒘
C

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Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒊 ) of Pure Gases:
For fugacity calculation

𝑓 𝒇𝒗𝒊
𝜇 − 𝜇 = 𝑔 − 𝑔 = 𝑅𝑇𝑙𝑛
𝑓
→ 𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘

For fugacity coefficient calculation

𝒇𝒗𝒊
𝝋𝒗𝒊 =
𝑷𝒍𝒐𝒘

• The fugacity (𝒇𝒊 ) of a real gas can be obtained using three

possible sources of data for pure gases:
1. Tables (e.g. steam tables, etc.)
2. Equations of state (e.g. van der Waals, etc.)
3. Generalized correlations

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C

Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• The fugacity (𝒇𝒊 ) of a real gas can be obtained using three
possible sources of data for pure gases:
1. Tables (e.g. steam tables, etc.)
2. Equations of state (e.g. van der Waals, etc.)
3. Generalized correlations
For fugacity calculation

𝒇𝒗𝒊
𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘

Using steam tables: (Table B.4) find ℎ, 𝑎𝑛𝑑 𝑠̂  calculate 𝑔 = ℎ − 𝑇𝑠̂

Reference state:
𝑔 −𝑔 - T is given
𝑓 = 𝑃 exp - Lowest pressure from the
𝑅𝑇
steam table for the given T

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C

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Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• The fugacity (𝒇𝒊 ) of a real gas can be obtained using three
possible sources of data for pure gases:
1. Tables (e.g. steam tables, etc.)
2. Equations of state (e.g. van der Waals, etc.)
3. Generalized correlations
For fugacity calculation

𝒇𝒗𝒊
𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘

Using equations of state:

𝑓 If IGL is not applicable, any other

𝜇 −𝜇 = 𝑣 𝑑𝑃 = 𝑅𝑇 ln equation can be used (SRK, SK, PR,
𝑃
2-PCS, Virial…

Example: van der Waals EOS

𝑅𝑇 𝑎
𝑃= −
13 𝑣−𝑏 𝑣
C

Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• The fugacity (𝒇𝒊 ) of a real gas can be obtained using three
possible sources of data for pure gases:
1. Tables (e.g. steam tables, etc.)
2. Equations of state (e.g. van der Waals, etc.)
3. Generalized correlations
For fugacity calculation

𝒇𝒗𝒊
𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘

Using generalized correlations:

( ) ( ) Figures 7.1 and 7.2; page 401

log 𝜑 = log 𝜑 + 𝜔 log 𝜑
Tables C.7 and C.8; pages 672-674

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Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

Using generalized correlations:

( ) ( ) Figures 7.1 and 7.2; page 401

log 𝜑 = log 𝜑 + 𝜔 log 𝜑
Tables C.7 and C.8; pages 672-674

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C

Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for gases

Using steam table
Example 7.1:

Solution:

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Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for gases

Using steam table
Example 7.1:

Solution:

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C&L

Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒗𝒊 ) of Gas mixtures:

Low pressure
Gas can be considered as ideal
High temperature

Lewis fugacity rules: The rules to approximate the fugacity and

fugacity coefficient of species i in a mixture.

𝜑 =𝜑 Only 𝑖 − 𝑖 interactions

𝑓 =𝑦𝜑 𝑃 𝑖 − 𝑗 interactions

𝑓 =𝑦𝜑𝑃 Lewis fugacity rule (𝑖 − 𝑖 interactions)

𝑓 =𝑦𝑃 Ideal gas (no interactions)

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Preliminary concepts (LO1)

Fugacity calculation in vapor phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒗𝒊 ) of Gas mixtures:

Low pressure
Gas can be considered as ideal
High temperature

Lewis fugacity rules: The rules to approximate the fugacity and

fugacity coefficient of species i in a mixture.
Lewis fugacity rule can be applied at the following conditions:

Low pressure
High temperature
(ideal gas approximation is valid)

One component of the mixture is in the huge excess

𝑦 ≫𝑦
𝑦 →0

Chemical properties of all species are similar

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C

Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for gases

Using EOS
Fugacity and Fugacity Coefficient Using EOS:

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C&L

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Preliminary concepts (LO1)

Fugacity calculation in liquid phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒊 ) of Pure Liquids:
• It is difficult to measure fugacity in a liquid phase directly

• But, if, the liquid phase is saturated (in equilibrium with the
vapor phase), the chemical potentials of the two phases are
equal (𝜇 =𝜇 )

• The fugacity of a liquid is defined the same way as for a gas:

𝑓 𝑑𝐺
𝜇 − 𝜇 = 𝑔 − 𝑔 = 𝑅𝑇𝑙𝑛 𝑑𝜇 = = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 = 𝑉𝑑𝑃
𝑓 𝑑𝑛
For gas fugacity calculation

𝒇𝒗𝒊 𝑔 −𝑔 𝑉(𝑃 − 𝑃 )
𝒈𝒊 − 𝒈𝟎𝒊 = 𝑹𝑻𝒍𝒏
𝑷𝒍𝒐𝒘
𝑓 = 𝑃 exp
𝑅𝑇 → 𝑓 =𝜑 𝑃 exp
𝑅𝑇

For gas fugacity coefficient calculation

𝑣
𝒇𝒗𝒊 𝑓 =𝜑 𝑃 exp 𝑑𝑃
𝝋𝒗𝒊 = 𝑅𝑇
21 𝑷𝒍𝒐𝒘
C

Preliminary concepts (LO1)

Fugacity calculation in liquid phase?

• Fugacity (𝒇𝒊 ) and Fugacity Coefficient (𝝋𝒊 ) of Pure Liquids:
• The fugacity of a liquid is defined the same way as for a gas:

𝑉(𝑃 − 𝑃 ) 𝑣
𝑓 =𝜑 𝑃 exp 𝑓 =𝜑 𝑃 exp 𝑑𝑃
𝑅𝑇 𝑅𝑇

𝑣
For low and moderate pressures 𝑃 < 100 𝑏𝑎𝑟, 𝑃. 𝐶. ≈ 1 exp 𝑑𝑃 Poynting correction
𝑅𝑇

For low P and 𝑃 :

𝑓 =𝑃

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Applications of preliminary concepts (LO2)

Assessing conceptual context of thermodynamic concepts

Problem 7.11:

Solution:

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L

Applications of preliminary concepts (LO2)

Assessing conceptual context of thermodynamic concepts

Problem 7.13:

Solution:

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Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for gases

Problem 7.14:

Solution:

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L

Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for gases

Problem 7.14:

Solution:

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L

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Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for liquids

Problem 7.50:

Solution:

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Applications of preliminary concepts (LO2)

Assessing application of Fugacity and Fugacity Coefficient for liquids

Problem 7.50:

Solution:

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L

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Summary

1. Define the following preliminary concepts (LO1)

• Introduction to fugacity and its application
• Fugacity in the vapor phase
• Fugacity in the liquid phase

2. Apply above concepts to formulate & solve engineering

problems (LO2)

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C&L

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