in order to predict the concentration of a solute in each of two phases in

equilibrium, experimental equilibrium data must be available. Also, if the two

phases are not at equilibrium, the rate of mass transfer is proportional to the
driving force, which is the departure from equilibrium. In all cases involving
equilibria, two phses are involved, such as gas-liquid or liquid-liquid. The
important variables affecting the equilibrium of a solute are temperature,
pressure and concentration.

The equilibrium between two phases in a given situation is restricted by the

phase rule :

F=C-P+2............ (10.2-1)

Where P is the number of phases at equilibrium, C the number of total

components in the two phases when no chemical reactions are occuring and F
the number of variants or degrees of feedom of the system. For example, for the
gas-liquid system of CO2 air-water, there are two phases and three components
(considering air as one inert component) Then by Eq (10.2-1)

F=C-P+2=3-2+2=3

This means that there are 3 degrees of freedom. If the total pressure and the
temperature are set only one variable is left that can be arbitrarily set. If the
mole fraction composition X4 OF co2 (A) in the liquid phase is set, the mole
fraction composition YA or pressure pA in the gas phase is automatically
determined.

The phase rule does not tell us the partial pressure P A in equilibrium with the
selected XA. The value of PA must be determined experimentally. The two phases
can, of course, be gas-liquid, liquid-solid, and so on. For example, the equilibrium
distribution of acetic acid between a water phase and isopropyl ether phase has
been determined experimentally for various conditions.

10.2 B

1. gas-liquid equilibrium data

To ilustrate the obtaining of experimental gas-liquid equilibrium data., the system

SO2-air-water will be considered. An amount of gaseous SO 2, air, and water are
put in a closed container and shaken repeatedly at a given temperature until
equilibrium is reached. Samples of the gas and liquid are analyzed to give the
partial pressure pA in atm of SO2 (A) in the gas and mole fraction X A in the liquid.
Figure 10.2-1 shows a plot of data from appendix A.3 of the partial pressure P A of
SO2 in the vapor in equilibrium with the mole fraction x A of so2 in the liquid at 293
K (20 C)

2. Henrys Law

Often the equilibrium relation between P A in the gas phase and XA can be
expressed by a straight-line Henrys law equation at low concentrations.
 PA=HXA

Where H is the Henry,s law constant in atm/mole fraction for the given system. If
both sides of eq (10.2-2)are divided by total pressure P in atm.

YA= HXA

Where H is the Henrys law constant in mole fraction gas/mole fraction liquid
and is equal to H/P. Note that H depends on total pressure, where as H does not.

In figure 10.2-1 the data folow Henrys law up to a concentration x A of about

0,005, whwre H=29,6 atm/mol fraction. In general, up to a total pressure of
about 5x105 Pa(5 atm) the value of H is independent of P. Data for some common
gases with water are given in appendix A.3