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Fugacity

This document discusses fugacity, which is a measure of the chemical potential of a real, non-ideal gas or liquid. It defines fugacity for pure substances and mixtures. For pure gases, fugacity is a function of pressure that accounts for non-ideality. For mixtures, the fugacity of a species is related to its mole fraction and the fugacities in the reference states. Fugacity, not pressure, must be equal between phases at vapor-liquid equilibrium. The document also briefly mentions vapor-liquid equilibria and residual properties.

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Anubhav Singh
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81 views37 pages

Fugacity

This document discusses fugacity, which is a measure of the chemical potential of a real, non-ideal gas or liquid. It defines fugacity for pure substances and mixtures. For pure gases, fugacity is a function of pressure that accounts for non-ideality. For mixtures, the fugacity of a species is related to its mole fraction and the fugacities in the reference states. Fugacity, not pressure, must be equal between phases at vapor-liquid equilibrium. The document also briefly mentions vapor-liquid equilibria and residual properties.

Uploaded by

Anubhav Singh
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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FUGACITY

Pure Gas

The total differential of Gibb’s Free energy for a pure fluid is given by:

dG = V dp − SdT = μdN (1)

Dividing this extensive property by the moles of pure fluid, we have the total differential of the molar Gibb’s
Free Energy or the chemical potential:

For constant temperature, this reduces to:

For an ideal gas, the molar volume is:


Equation 4 for an ideal gas to introduce a new function, the fugacity of pure species ”i” which will contain all the
non-ideality of the fluid.

Note that fugacity is not pressure


• Fugacity is a function of pressure
• Fugacity is a direct measure of the chemical potential of a real, non-ideal fluid! Fugacity is chemical potential!
• Equivalence of a species’ chemical potentials in various phases at equilibrium coexistence is the same as the
equivalence of fugacities in various phases at equilibrium coexistence.

Now, for an ideal gas the chemical potential at a particular temperature, T, and pressure, p, relative to some
reference state chemical potential, at a reference state pressure of
We can compute the same for the real gas, rg:

Taking the difference between Equations 7 and 6 gives:

If we take the reference state to be an ideal gas state (low pressure reference state), the first two terms on the
right hand side of Equation 8 cancel one another, and
this leads to

Equation 9 allows us to define the fugacity coefficient for a pure species as:
Fugacity coefficient of a pure species at a temperature, T, and pressure, P is defined as

We can thus rewrite Equation 9 as:

If we now reference the ideal gas chemical potential to a reference state with pressure = 1 bar, we can rewrite
the previous equation as :

Finally, we can combine the second and third terms on the right-hand side of equation 12 to obtain
the following relation which we will return to later in our discussion of activity.
Gas Mixtures

For an ideal gas species ”i” in an ideal gas mixture (mixture of ideal gases) at a temperature, T, and pressure, P,
relative to a pure gas reference state at pref and the same temperature, we can write the chemical potential as:

For a real (non-ideal) gas (superscripted as rg in the following) species in a non-ideal gas mixture, we can write
analogously, making use of our definition of fugacity as presented in the section on pure gases, as:

Here, is the fugacity of species in the non-ideal gas mixture. Again, the reference state is a pure fluid state; thus
we omit the hat on the fugacity of species in the denominator of fraction of which we take the natural log.
Taking the reference state to be an ideal gas state, we can make the simplifications as for the pure gas case to
obtain:

This allows us to write Equation 18 as:

The chemical potential of the ideal gas species at temperature T and total pressure p can be written in terms of
the chemical potential of the pure ideal gas at a reference pressure p0 as we did before:
which can be written as:
• We have defined the fugacity for pure gases and liquids, as well as for species ”i” in a gas and liquid mixture.
• Fugacity is a direct measure of the chemical potential of a species in a mixture.
VAPOR-LIQUID EQUILIBRIA
Residual Properties

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