Published on PNG 520: Phase Behavior of Natural Gas and Condensate Fluids (https://www.e-
education psu.edu/png520)
Home > Course Ouline > Thermodyranvc Tool) > Expression for Fugly Calulaton
Expressions for Fugacity Calculation
It is clear that, if we want to take advantage of the fugacity criteria to perform equilibrium
calculations, we need to have a means of calculating it. Let us develop a general expression for
fugacity calculations. Let us begin with the definition of fugacity in terms of chemical potential for a
pure component shown in (16.214):
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.26)
The Maxwell's Relationships presented in equation (15.27¢) is written for a pure component system
as:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.27)
Consequently,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.28)
Substituting (16.28) into (16.26),
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.29)
Introducing the concept of fugacity coefficient given in equation (16.23a),
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.23a)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.30)
We end up with:This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.31a)
or equivalently,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.31b)
Integrating expression (16.31b),
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.32)
Itis convenient to define the lower limit of integration as the ideal state, for which the values of
fugacity coefficient, volume, and compressibility factor are known.
At the ideal state, in the limit
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.33)
Substituting into (16.32),
E
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.34)
Equation (16.34) is the expression of fugacity coefficient as a function of pressure, temperature, and
volume. Notice that this expression can be readily rewritten in terms of compressibility factor:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.35)
Let us also derive the expression for the fugacity coefficient for a component in a multicomponent
mixture. Following a pattern similar to that which we have presented, beginning with the definition of
fugacity for a component in terms of chemical potential:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.36)This time, it is more convenient to use the Maxwell's Relationships presented in equation (15.274):
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.37)
After you introduce the definitions of fugacity coefficient and compressibility factor:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.38a)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.38b)
and recalling that our lower limit of integration is the ideal state, for which, at the limit
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.39¢)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.39)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.39)
it can be proven that:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.40)
The multi-component mixture counterpart of equation (16.35) becomes:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.41)
where:This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.41b)
Equations (16.34), (16.35), (16.40), and (16.41) are very important for us. Basically, they show that
fugacity, or the fugacity coefficient, is a function of pressure, temperature and volume:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
This tells us that if we are able to come up with a PVT relationship for the volumetric behavior of a
substance, we can calculate its fugacity by solving such expressions. It is becoming clear why we
have studied equations of state — they are just what we need right now: PVT relationships for
various substances. Once we have chosen the equation of state that we want to work with, we can
calculate the fugacity of each component in the mixture by applying the above expression. Now that
we know how to calculate fugacity, we are ready to apply the criteria for equilibrium that we just
studied! That is the goal of the next module.
‘Source URL: htips:/www.e-education.psu.edulpngS20/m16_p§.html