Chemical Engineering Department

The third stage

Dr. Mohammad N. Fares

FUGACITY AND FUGACITY

COEFFICIENT
 FUGACITY AND FUGACITY
COEFFICIENT

FUGACITY ( f )
It is simply a measure of molar Gibbs energy of a real gas .

effective pressure”.
The fugacity is an “effective pressure The fugacity has the units of pressure.
zero, the real gas approach the ideal gas behavior
As the pressure approaches zero
and f approaches the pressure P

It directly relates to the tendency of a substance to prefer one phase (liquid, solid, gas) over
another.
 As an engineering tool for predicting the final phase and reaction state of multi-component
mixtures at various temperatures and pressures without doing the actual lab test.
 Can be calculated through measurements of volume as a function of pressure at constant
temperature.
 The Gibbs energy,( G )

Differentiation gives:
This fundamental property relation are general equation for a homogeneous fluid
of constant composition.
At constant temperature

For ideal gas

Integration gives
where Γ (T), the integration constant at constant T
•For pure species in ideal-gas state; ….. (1)

….. (2)
•For pure species in real-gas state;

pressure P is replaced by a new property fi

Subtraction
….. (3)

According to the definition of Eq.

Gi - Giig is the residual Gibbs energy, GiR
The dimensionless ratio fi / P is fugacity coefficient, given the symbol Фi.

….. (4)

where
 ….. (5)

….. (6)

….. (7)

….. (8)

and

To be rewritten: ….. (9)

Fugacity coefficients for pure gases are evaluated by this equation from
P V T data or from equation of state.
 Evaluation of fugacity from equations of state
Vander Waals

From the compressibility factor Z of a Van der waals:

 Example 1
Given that the Van der Walals constants of nitrogen are: a = 1.408 L2atm.mol-2 and
b=0.03913L.mol-1. Calculate the fugacity of nitrogen gas at 50 bar and 298K.

Solution
 Virial Coefficient
A useful generalized correlation for InФ results when the simplest form of the virial equation

Together, these two equations become:

Substitution in Eq.

Integration yield
Example -1
Estimate the fugacity of one of the following liquids at its normal-boiling-point
temperature and 200 bar:
(a) n-Pentane
(b) Isobutylene
(c) 1-Butene.
Redlich-Kwong:
 GENERALIZED CORRELATIONS
FOR THE FUGACITY COEFFICIENT

Equation (9) is put into generalized form by substitution of the relations,

where integration is at constant T.

Pitzer Correlations for the Compressibility Factor

Where ω acentric factor.

Substitution for Zi by Eq. Z = Z0 + ωZ1 yields:

This equation may be written in alternative form:

Where

Lee and Kesler

We have the option of providing correlations for ϕ0 and ϕl

This is the choice made here, and Tables E.13 through E.16

This correlation as functions of Tr and Pr thus providing a three parameter

generalized correlation for fugacity coefficients. Tables E.13 and E.15.
Reduced temperatures , Tr
 Example
For SO2 at 600K and 300bar, determine good estimates of the fugacity and of G/RT
Example

Estimate the fugacity of one of the following:

(a) Cyclopentane at 383.15 K (110°C) and 275 bar. At 383.15 K (110°C) the vapor pressure
of cyclopentane is 5.267 bar.
(b) 1-Butene at 393.15 K (120°C) and 34 bar. At 393.15 K (120°C) the vapor pressure of
1-butene is 25.83 bar.
 Fugacity of a Pure Liquid.

The fugacity of pure species i as a compressed liquid is calculated in two steps:

1-First, the fugacity coefficient of saturated vapor ϕisat= ϕiv: evaluated at P = Pisat .

Then fisat = ϕisat . Pisat

2-Second is the calculation of the fugacity change resulting from the pressure
increase ,Pisat to P, that changes the state from saturated liquid to compressed liquid.

For the second step, an isothermal change of pressure

isothermal
… (10)
Another expression for the difference on the left side is obtained by writing Eq.(2)
twice, for both Gi and Gisat . Subtraction yields:

….. (11)

The two expressions for Gi - Gisat are set equal:

….. (12)

Since Vi, the liquid-phase molar volume, is a very weak function of P at temperatures
well below TC , then Vi, is assumed constant at the value for saturated liquid, Vli

….. (13)
Substituting fisat = ϕisat Pisat and solving for fi , gives:

….. (14)

The exponential is known as a poynting factor.

GENERALIZED CORRELATIONS FOR LIQUIDS

Example 5:
Determine the fugacity of liquid water at 30oC and at the saturation pressure, 10 bar,
and 100 bar.

Solution
Example

From data in the steam tables, determine a good estimate for f/ f sat for liquid water
at 423.15 K (150°C) and 150 bar, where f sat is the fugacity of saturated liquid at
423.15 K (150°C).
Question
Determine the fugacity (MPa) for acetylene at: (a) 250K and 1 bar; (b) 250K and 2 bar.
Use the Second Virial Coefficient.