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16.4: Expressions for Fugacity Calculation

  • Page ID
    568
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    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 (16.21a):

    \[d \mu=R T d \operatorname{In} f @ \text { const } \mathrm{T}\]

    The Maxwell's Relationships presented in equation (15.27c) is written for a pure component system as:

    \[\left(\dfrac{\partial \mu}{\partial P}\right)_r=\bar{V}=\tilde{v}\]

    Consequently,

    \[d \mu=\tilde{v} d P @ \text { const T }\]

    Substituting (16.28) into (16.26),
    \(R T d \operatorname{In} f=\tilde{v} d P\) @ const T

    Introducing the concept of fugacity coefficient given in equation (16.23a),

    \[\begin{array}{c}
    \phi=\dfrac{f}{P} \\[4pt]
    \ln \phi=\ln \mathrm{f}-\ln P
    \end{array}\]

    We end up with:

    \[R T d \ln \phi=\tilde{v} d P-R T d \ln P\]

    or equivalently,

    \[R T d \ln \phi=\tilde{v} d P-R T \dfrac{d P}{P}\]

    Integrating expression (16.31b),

    \[\int_{\ln \phi^m}^{\ln \phi} d \ln \phi=\int_{P^m}^P\left\{\dfrac{\tilde{v}}{R T}-\dfrac{1}{P}\right\} d P\]

    It is convenient to define the lower limit of integration as the ideal state, for which the values of fugac coefficient, volume, and compressibility factor are known.

    At the ideal state, in the limit \(P->0\),

    \[\phi^*->1 \therefore \ln \phi^*->0\]

    Substituting into (16.32),

    \[\ln \phi=\int_0^P\left\{\dfrac{\tilde{v}}{R T}-\dfrac{1}{P}\right\} d P\]

    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:

    \[\ln \phi=\int_0^P\left(\dfrac{\dfrac{P \tilde{v}}{R T}-1}{P}\right) d P=\int_0^P\left\{\dfrac{Z-1}{P}\right\} d P\]

    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:

    \[d \mu_i=R T d \ln f_i @ \text { const } \mathrm{T}\]

    This time, it is more convenient to use the Maxwell's Relationships presented in equation (15.27d):

    \[\left(\dfrac{\partial \mu_i}{\partial V}\right)_{T, n}=-\left(\dfrac{\partial P}{\partial n_i}\right)_{T, V, n_{i \neq 1}}\]

    After you introduce the definitions of fugacity coefficient and compressibility factor:

    \[\phi_i=\dfrac{f_i}{y_i P}\]

    \[
    P=\dfrac{Z n R T}{V}\]

    and recalling that our lower limit of integration is the ideal state, for which, at the limit \(P->0\) :

    \[V^*->\infty\]

    \(\phi i^*->1\) and hence \(\ln \phi \mathrm{i}^*->0\)

    \(z^*->1\) and hence \(\ln Z^*->0\)

    it can be proven that:

    \[\ln \phi_i=\dfrac{1}{R T} \int_{\infty}^v\left\{\dfrac{R T}{V}-\left(\dfrac{\partial P}{\partial n_i}\right)_{T, V, n_{i \neq 1}}\right\} d V-\ln Z\]

    The multi-component mixture counterpart of equation (16.35) becomes:

    \[\ln \phi_i=\int_0^P\left\{\bar{Z}_i-1\right\} \dfrac{d P}{P}\]

    where:

    \[\bar{Z}_i=\left(\dfrac{\partial Z}{\partial n_i}\right)_{P, T, n_{i \neq 1}}=\dfrac{P}{R T}\left(\dfrac{\partial V}{\partial n_i}\right)_{P, T, n_{i \neq 1}}=\dfrac{P \overline{\bar{V}_i}}{R T}\]

    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:

    \[f=f(P, V, T)\]

    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.

    Contributors and Attributions

    • Prof. Michael Adewumi (The Pennsylvania State University). Some or all of the content of this module was taken from Penn State's College of Earth and Mineral Sciences' OER Initiative.


    This page titled 16.4: Expressions for Fugacity Calculation is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Michael Adewumi (John A. Dutton: e-Education Institute) via source content that was edited to the style and standards of the LibreTexts platform.

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