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ثرمو محاضرة 2 مرحلة 3
ثرمو محاضرة 2 مرحلة 3
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
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;
….. (4)
where
….. (5)
….. (6)
….. (7)
….. (8)
and
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
Solution
Virial Coefficient
A useful generalized correlation for InФ results when the simplest form of the virial equation
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
Where
This is the choice made here, and Tables E.13 through E.16
1-First, the fugacity coefficient of saturated vapor ϕisat= ϕiv: evaluated at P = Pisat .
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)
….. (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)
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.