Published on PNG 520: Phase Behavior of Natural Gas and Condensate Fluids (https:/www.e-
education psu.edu/png520)
Home > Gouree Ouline > Thermodyname Tools Il) > Fugacity
Fugacity
We have seen that, for a closed system, the Gibbs energy is related to pressure and temperature as
follows:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.15)
For a constant temperature process,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.16)
For an ideal gas,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.17)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.18)
This expression by itself is strictly applicable to ideal gases. However, Lewis, in 1905, suggested
extending the applicability of this expression to all substances by defining a new thermodynamic
property called fugacity, f, such that
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.19)
This definition implies that for ideal gases, f must be equal to 'P’. For mixtures, this expression is
written as:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.20)
where
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
are the partial molar Gibbs energy and fugacity of the i-th component, respectively. Fugacity can be
readily related to chemical potential because of the one-to-one relationship of Gibbs energy to
chemical potential, which we have discussed previously. Therefore, the definition of fugacity in
terms of chemical potential becomes:
For a pure substance,This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.21a)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.21b)
For a component in a mixture,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.22c)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.224)
The fugacity coefficient (
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
is defined as the ratio of fugacity to its value at the ideal state. Hence, for pure substances
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)
and for a component in a mixture,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.23b)
The fugacity coefficient takes a value of unity when the substance behaves like an ideal gas.
Therefore, the fugacity coefficient is also regarded as a measure of non-ideality, the closer the value
of the fugacity coefficient is to unity, the closer we are to the ideal state.
Fugacity turns out to be an auxiliary function to chemical potential. Even though the concept of
thermodynamic equilibrium which we discussed in the previous section is given in terms of chemical
potentials, above definitions allow us to restate the same principle in terms of fugacity. To do this,
previous expressions can be integrated for the change of state from liquid to vapor at saturation
conditions to obtain:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.24a)
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.24b)
For equilibrium,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
shence,
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.(16.24)
Therefore:
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers.
(16.25)
For equilibrium, fugacities must be the same as well! This is, for a system to be in equilibrium, both
the fugacity and the chemical potential of each component in each of the phases must be equal.
Conditions (16.14) and (16.25) are equivalent. Once one of them is satisfied, the other is satisfied
immediately. Using
This equation is not rendering properly due to an incompatible browser. See Technical
Requirements in the Orientation for a list of compatible browsers
to describe equilibrium is a matter of choice, but generally the fugacity approach is preferred.
‘Source URL: htips:/www.e-education.psu.edulpng520/m16_p4.html