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# 17.7: Chemical Potential, Pressure, Fugacity

• • Contributed by Jeremy Tatum
• Emeritus Professor (Physics & Astronomy) at University of Victoria

Equation 12.9.11 told us how to calculate the change in the Gibbs function of a mole of an ideal gas going from one state to another. For N moles it would be

$\Delta G=N \int C_{P} d T-N T_{2} \int C_{P} d(\ln T)+N R T_{2} \ln \left(\dfrac{P_{2}}{P_{1}}\right)-N S\left(T_{2}-T_{1}\right),$

where CP and S are molar, and G is total.

Since we know now how to calculate the absolute entropy and also know that the entropy at T = 0 is zero, this can be written

$G(T, P)=N(R T \ln P+\text { constant }) \label{17.7.2}$

The “constant” here depends on the temperature, but is not a function of the pressure, being in fact the value of the molar Gibbs function extrapolated to the limit of zero pressure. Sometimes it is convenient to write Equation \ref{17.7.2} in the form

$G=N R T(\ln P+\phi)$

where $$φ$$ is a function of temperature.

If we have a mixture of several components, the total Gibbs function is

$G(T, P)=\sum_{i} N_{i}\left(R T \ln p_{i}+\text { constant }\right)$

We can now write this in terms of the partial molar Gibbs function of the component i – that is to say, the chemical potential of the component i, which is given by $$\mu_{i}=\left(\partial G / \partial N_{i}\right)_{P, T, N_{j \neq 1}}$$, and the partial pressure of component i. Thus we obtain

$\mu_{i} =\mu_{i}^{0}(T)+R T \ln p_{i}$

and

$\mu_{i} =R T\left(\ln p_{i}+\phi_{i}\right)$

Here I have written the “constant” as 0 µi0 (T), or as RTφi. The constant µi0 (T) is the value of the chemical potential at temperature $$T$$ extrapolated to the limit of zero pressure. If the system consists of a mixture of ideal gases, the partial pressure of the ith component is related to the total pressure simply by Dalton’s law of partial pressures:

$p_{i}=n_{i} P,$

where ni is the mole fraction of the ith component. In that case, equation 17.7.4 becomes

$\mu_{i}=\mu_{i}^{0}(T)+R T \ln n_{i}+R T \ln P.$

and equation 17.7.5 becomes

$\mu_{i}=R T\left(\ln n_{i}+\ln P+\phi_{i}\right).$

However, in a common deviation from ideality, volumes in a mixture are not simply additive, and we write equation 17.7.4 in the form

$\mu_{i}=\mu_{i}^{0}(T)+R T \ln f_{i},$

or equation 17.7.5 in the form

$\mu_{i}=R T\left(\ln f_{i}+\phi_{i}\right).$

where fi is the fugacity of component i.