<Phase diagrams>

Figure 6.1-1 phase diagrams of H2O and CO2

<Gibbs Phase Rule>

When two phases are brought into contact with each other, a redistribution of the components of each
phase normally takes place-species evaporate, condense, dissolve, or precipitate until a state of equilibrium
is reached in which the temperatures and pressures of both phases are the same and the compositions of
each phase no longer change with time.
Suppose you have a closed vessel containing three components A, B, and C distributed between gas and
liquid phases, and you wish to describe this system to someone else in sufficient detail so that person could
duplicate it exactly. Specifying the system temperature and pressure, the masses of each phase, and two
mass or mole fractions for each phase would certainly be sufficient; however, these variables are not all
independent-once some of them are specified, others may be calculated from physical properties of the
system components.
The variables that describe the condition of a process system fall into two categories: extensive variables,
which depend on the size of the system, and intensive variables, which do not. Mass and volume are
examples of extensive variables; intensive variables include temperature, pressure, density and specific
volume, and mass and mole fractions of individual system components.

<Gibbs Phase Rule>

The number of intensive variables that can be specified independently for a system at equilibrium is
called the number of degrees of freedom of the system. Let
= the number of phases in a system
m = the number of chemical species
F = the number of degrees of freedom
The relationship among F, , and m is given by the Gibbs phase rule.
If no relations occur among the system components, the phase rule is
F=2+m
If r independent reactions occur among the system components and the reactions proceed to equilibrium,
then the value of m in this equation must be reduced by r. (Note: Perrys Chemical Engineers Handbook,
p.4-78, presents a proof of the phase rule and outlines a method for determining how many independent
reactions may occur among the components of a system.)
The example that follows illustrates the application of the phase rule to several systems. The reminder of
the chapter presents the equilibrium relationships that are need to determine the remaining intensive
system variables once the allowed number of these variables has been specified.

<Gibbs Phase Rule>

- SAMPLE Specify the number of degrees of freedom of each of the following equilibrium systems:
1. Pure liquid water(l)
One phase ( = 1), one component (m = 1)

F=2+1 1=2
Two intensive variables (for example, T and P) can therefore be specified arbitrarily (recognizing,
however, that only within certain ranges of T and P can water exist as a liquid).
2. A mixture of ice(s) and liquid water(l)
= 2,

m=1

F=2+1 2=1

Thus only one variable (T or P) can be specified. If (say) a value of T is chosen, the value of P may be
uniquely determined. (It can be read from the solid-liquid equilibrium curve on the H2O phase diagram.)
3. Pure liquid acetone in equilibrium with acetone vapor(lg) and nitrogen(g)
= 2,

m=2

F=2+2 2=2

Two variables can therefore be specified: T and P, or a gas-phase mass or mole fraction (of either
acetone or N2) and either T or P, and the third may then be determined.