Fugacity in Liquids

Fugacity in liquids is not as simple as the fugacity concept of gases and vapour. first
of all, we need to define what is a “liquid”, a liquid is a state of matter where, unlike
solid, moves freely but not as freely as gas or vapour, in fact, the boundaries liquids
have are the containers where they’re in. Some liquids flow more rapidly than others,
and this is because of the viscosity, that is the liquid’s relative resistance. [1]

Now, fugacity, as it was mentioned before, is a complex concept in this case. For
liquids as for gases, for the calculation of this term it’s needed a reference state, we
can’t apply the same criteria because a liquid is mainly composed by intermolecular
forces, which are the forces between molecules. these are the responsible of making
the condensed phases possible; without these, only the entropically favored gas
phase would exist. Therefore, for fugacity in liquids, there are two options for the
reference state: the Lewis/Randall rule and Henry’s law. The choice depends on the
system.

Figure 1. Representation of Intermolecular and intramolecular forces.[2]

So, what makes an ideal solution can be defined as a solution where all the mixing
rules are the same as for an ideal gas and needs to follow these rules:
ΔV(idealmix)=0
Δh(idealmix)=0
Δg(idealmix)=RT∑xiLnxi

So, to decide if it’s more convenient use Lewis/Randall Rule or Henry’s Law, you
need to verify this:
Figure 2. Lewis/Randall Rule and Henry’s Law conditions

“In Lewis/Randall Rule there are all a-a interactions. The characteristic of this
intermolecular interaction is given by the pure species fugacity, fa. Consequently,
one choice of reference state is the pure species fugacity of species a.” (Koretsky,
2012, p.415).

“Consider now the case when a is very dilute in b. As far as a molecule of a is

concerned, it essentially sees only species b in solution. Thus, again, we have an
ideal solution because all the intermolecular interactions species a has are the same.
In this case, however, it is the a-b interaction that is characteristic of the ideal
solution. This provides another choice on reference state based on a-b interactions,
which we call Henry’s law.” (Koretsky,M. 2012, p.415).

The lower the fugacity of the liquid, the lower its partial pressure in the vapor phase.
Having a lower partial pressure in the vapor phase means that that phase will “trap”
the molecules, therefore, the intermolecular interactions are stronger. So the
stronger interaction, the lower the fugacity.
Figure 3. Interactions a-a and a-b. [3]

So:

Figure 4.Thermodynamics of solutions.

And:
Figure 5. Thermodynamics of solutions and activity coefficient.

**Note: The notation “x” refers to liquids/solids and “y” to vapour or gas. It’s important
to mention that for the fugacity in solids it also applies these kind of rules mentioned
before and the calculation of fugacity is similar.

References:
[1] (2013). 6.11 Expression for Fugacity of a Pure Liquid. Retrieved 25/06/2018, from
http://nptel.ac.in/courses/103101004/48.
[2]KhanAcademy.(s.f.).Intramolecular and intermolecular forces.Retrieved 25/06/2018, from
https://www.khanacademy.org/test-prep/mcat/chemical-processes/covalent-bonds/a/intramolecular-
and-intermolecular-forces
[3]Koretsky, M. (2012).Engineering and Chemical Thermodynamics, 2nd Edition.