Gibbs Phase Rule

Let's try to motivate the Gibbs phase rule. Consider a typical onecomponent
phase diagram.

In the onephase regions one can vary either the temperature, or the
pressure, or both (within limits) without crossing a phase line. We say that in
these regions there is a variance of 2. We have indicated in the solid, liquid,
and gas regions that there is one phase and the variance is two. Along a
phase line we have two phases in equilibrium with each other, so on a phase
line the number of phases is 2. However, if we want to stay on a phase line,
we can't change the temperature and pressure arbitrarily. If we change the
temperature and keep two phases then the pressure must change also to
keep us on the phase line. Otherwise we go off the line and we no longer
have two phases in equilibrium. So on a phase line the number of phases is 2,
but the variance is 1. At the triple point there are three phases in equilibrium,
but there is only one point on the diagram where we can have three phases
in equilibrium with each other. Therefore, at the triple point the variance is
zero. Notice that the variance seems to be related to the number of phases,
such as,

v = 3 p, or
v = 2 + 1 p.

(1)
(2)

(You will see why we wrote it this way in a minute.)

Now let's look at another example. Consider the boiling diagram of a
twocomponent ideal liquidliquid solution.

In the onephase regions (liquid or vapor) we have a variance of three

because we can change the temperature, the composition, X, and the
pressure (by moving in and out of the plane of the screen). In the two phase

region the variance is only two because if we change the temperature the
compositions of both the liquid and vapor phases must track as indicated by
the tielines connecting the liquid and vapor composition lines. Here it looks
like the variance satisfies,

v = 4 p, or
v = 2 + 2 p.

(3)
(4)

Notice that equations 2 and 4 are the same except for the second term. In
Equation 2 there is one component and the second term is 1. In Equation 4
there are two components and the second term in Equation 4 is a 2. It looks
like the second term may indicate the number of components in the system.
We might guess that the general form for Equations 2 and 4 might be,
v = 2 + c p.
We shall see below whether or not our guess is correct.
Before we try to derive a general form for the variance of a system in
equilibrium we need to take a look as some mathematical principles.

Take a system where we have three variables, x, y, and z. Let's look at five
cases:

Case 1. There is no equation connecting the variables. Then we can pick the
values of all three variables to be anything we wish, independently of each
other. There are no restrictions on the values of the variables and the
variance is 3.

Case 2. There is one equation connecting the variables,

. (5)
In this case we can select the values any two of the variables, but when we
do, the value of the third is fixed by the equation. The number of equations is
one and the variance is 2.

Case 3. There are two equations connecting the variables,

(6a, b)
In this case we can select the value of any one variable at random, but then
the values of the other two are fixed by the two equations. (Two equations in
two unknowns is a soluble problem.) The number of equations is two and the
variance is 1.
Case 4. There are three equations connecting the variables,

(7a, b, c)
In this case we can not select any of the variables arbitrarily. The values of
the variables are fixed because a system of three unknowns and three
(linearly independent) equations has a unique solution.
(8a, b, c)
The number of equations is three and the variance is zero.
Case 5. There are four linearly independent equations connecting the
variables.

(9,a, b, c, d)
This system does not have a solution. There are no values of the three
variables which will satisfy all four equations. We conclude that we cannot
have a variance less than zero.
The principle we extract here is that

variance = number of variables number of equations 0.

(10)

Let us now apply this principle to phase equilibrium. Consider a system which
is composed of c components. That is,
c = number of components.

(11)

(We define the number of components as the minimum number of

independent substances (compounds and/or elements) required to form the
system. If you can make one substance out of the others you can't count it!

For example, a system containing CO2, CaO, and CaCO3 has two components
because you can form the CaCO3 by reacting the other two. There is,
however, a special case. If our system contains exactly the same number of
moles of CaO and CO2 it is a one component system because it can be made
starting with just pure CaCO3. That is, you can heat the CaCO3 to generate
the other two in equal molar amounts.)
Number the components 1, 2, 3, . . . c.

Let

p = number of phases.

(12)

(We will have to be careful to distinguish between the number of phases and
the pressure since we are using the same symbol.)
Enumerate the phases by lower case Greek letters, , , , , . . . . Let's
now count the number of variables and the number of equations. We will get
the variance from
v = variables equations.

(13)

Our variables are T, p , (pressure) and the mole fractions of the components
in each phase.
(14)
Notice that there are p columns and c rows in the array of mole fraction
variables. That is, there are cp mole fraction variables. This gives a total of 2
+ cp variables.
Now let's count the equations. First of all the mole fractions in each phase
must sum to unity. That is

(15)
Since there is one such equation for each phase this gives p equations. Next,
the chemical potential of each component must be the same in every phase.
(In the following we designate as the last phase, that is the phases are
denoted , , , . . . , .)
(16)

(Note that there is no row of the form 1 = 1, etc. Equations of this

form are not linearly independent because they can be deduced from the
other p 1 equations.) So for this array of chemical potential equations there
are c columns and p 1 rows, which yields c(p 1) equations. The total
number of equations is then p + c(p 1). If, as we have argued above, the
variance is given by
v = variables equations,

(13)

we get,
v = 2 + cp p c(p 1)
v = 2 + c p.

(16)

(17)

Equation 17 is called the Gibbs phase rule and it is a generally valid

thermodynamic equation. That is, it contains no approximations. If you go
back and check it against the (motivational) examples we started with you
will see that it agrees exactly with our initial observations.
The Gibbs phase rule is an important tool in the analysis of systems with
several phases and one or more components. It is used not only in chemistry,
but also in geology and geophysics.

WRS

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Copyright 2004, W. R. Salzman

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Last updated 22 Oct 04
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