FEC: Liquid-phase Fugacity

Liquid-Phase Fugacity

$\mu_i - \mu_i^o = RT \ln \left [\frac{\hat f_i}{f_i^o} \right ]$

For a liquid, a reference state ($f_i^o$) of an ideal gas is a poor choice. Instead, we choose what is called an ideal solution.

Definition:

An ideal solution is a solution where all of the intermolecular interactions are essentially the same. The two ways that this could be accomplished is:

  • having any composition of mixture with components that are molecularly similar
  • having a very dilute (or very concentrated) solution

In both of these cases the intermolecular interactions are the same.

Outcome:

Identify conditions when a liquid or solid mixture would form an ideal solution.

The two choices of reference state for the liquid phase fugacity are therefore:

Outcome:

Explain when Lewis-Randall versus Henry ideal solution reference states are appropriate.

Lewis-Randall

For an a-a dominant ideal solution (Lewis-Randall solution), the proper choice of reference state is the pure-species fugacity $\hat f_i^o = x_if_i$ (Note the lack of a hat.) As we will see, under certain conditions this can reduce to the saturation pressure of the pure substance.

$\mu_i - \mu_i^o = RT \ln \left [\frac{\hat f_i}{x_if_i} \right ]$

Henry

For an a-b dominant ideal solution (Henry solution), the proper choice of reference state is the so-called Henry's constant for the species $\hat f_i^o = x_i \mathcal{H}_i$. This quantity can be found tabulated in a variety of places.

$\mu_i - \mu_i^o = RT \ln \left [\frac{\hat f_i}{x_i \mathcal{H}_i} \right ]$

For both reference states, it is convenient to define a new quantity ...

Definition:

The activity coefficient, $\gamma_i$ is defined as the ratio of the species fugacity in the liquid mixture to the ideal solution reference state fugacity:

$\gamma_i = \frac{\hat f_i}{\hat f_i^o}$

L-R: $\gamma_i = \frac{\hat f_i}{x_if_i}$

Henry: $\gamma_i = \frac{\hat f_i}{x_i \mathcal{H}_i}$

Outcome:

Use the activity coefficient to calculate the liquid (or solid) phase fugacity.