Vapor-liquid and Liquid-Liquid equilibrium

Introduction:
The experiment is concerned with the principles behind vapor-liquid and liquid-liquid
equilibrium. For a binary vapor-liquid mixture, separation process is governed by concept of relative
volatility. Enrichment of more volatile vapors from mixture is responsible for separation of vapors from
vapor-liquid mixture. VLE data can be plotted in Txy or Pxy form and relative mole fractions of liquid and
vapor are determined at desired temperature and pressure conditions.

For liquid-liquid equilibrium calculations are based on K values other than Txy and Pxy plots. If
mixture exhibits non-ideal behavior than calculations need component material balances coupled with
K-value expressions and an energy balance if heat transfer occurs.

Background:
Separation process in chemical industries is mainly based on vapor-liquid and liquid-liquid
equilibrium principles. Distillation involves the concepts of vapor-liquid equilibrium behind separation of
two or more components. Similarly, liquid-liquid extraction being another major industrial process
involves separation of liquid-liquid mixture based on their relative solubility and liquid-liquid
equilibrium.

The first major concept behind vapor-liquid equilibrium was introduced by Dalton who said that
the total pressure is equal to the summation of the partial pressures. Since in an ideal gas or vapor the
partial pressure is proportional to the mole fraction of the constituent, then:

PA=yAP

The idea was extended by Roult. For an ideal mixture, the partial pressure is related to the
concentration in the liquid phase by Raoult’s law which may be written by:

PA = P◦AxA

where P◦A is the vapor pressure of pure A at the same temperature. This relation is usually found to be
true only for high values of xA, or correspondingly low values of xB, although mixtures of organic isomers
and some hydrocarbons follow the law closely. For low values of xA, a linear relation between PA and xA
again exists, although the proportionality factor is Henry’s constant H, and not the vapor pressure P0A of
the pure material. For a liquid solute A in a solvent liquid B, Henry’s law takes the form:

PA =HxA

Liquid liquid equilibrium condition for the distribution of one solute between two liquid phases
is conveniently considered in terms of the distribution law. Thus, at equilibrium, the ratio of the
concentrations of the solute in the two phases is given by CE/CR = K, where K is the distribution
constant. This relation will apply accurately only if both solvents are immiscible, and if there is no
association or dissociation of the solute. If the solute forms molecules of different molecular weights,
then the distribution law holds for each molecular species. Where the concentrations are small, the
distribution law usually holds provided no chemical reaction occurs.

References:

[1] Coulson and Richardson, Chemical Engineering, Volume 2, Edition 5th

[2] Philip C.Wankat, Separation Process Engineering, Edition 3rd.