The Phase Rule and Its ApplicationsFindlay, Alexander
Science
The Phase Rule and Its Applications
Findlay, Alexander
Chemistry, Physical and theoretical; Phase rule and equilibrium; Solution (Chemistry)
The Phase Rule.--The Phase Rule of Gibbs, which defines the condition of
equilibrium by the relation between the number of coexisting phases and the
components, may be stated as follows: A system consisting of n components
can exist in _n_ + 2 phases only when the temperature, pressure, and
concentration have fixed and definite values; if there are _n_ components
in _n_ + 1 phases, equilibrium can exist while one of the factors varies,
and if there are only _n_ phases, two of the varying factors may be
arbitrarily fixed. This rule, the application of which, it is hoped, will
become clear in the sequel, may be very concisely and conveniently
summarized in the form of the equation--
P + F = C + 2, or F = C + 2 - P
where P denotes the number of the phases, F the degrees of freedom, and C
the number of components. From the second form of the equation it can be
readily seen that the greater the number of the phases, the fewer are the
degrees of freedom. With increase in the number of the phases, therefore,
the {17} condition of the system becomes more and more defined, or less and
less variable.
Classification of Systems according to the Phase Rule.--We have already
learned in the introductory chapter that systems which are apparently quite
different in character may behave in a very similar manner. Thus it was
stated that the laws which govern the equilibrium between water and its
vapour are quite analogous to those which are obeyed by the dissociation of
calcium carbonate into carbon dioxide and calcium oxide; in each case a
certain temperature is associated with a definite pressure, no matter what
the relative or absolute amounts of the respective substances are. And
other examples were given of systems which were apparently similar in
character, but which nevertheless behaved in a different manner. The
relations between the various systems, however, become perfectly clear and
intelligible in the light of the Phase Rule. In the case first mentioned,
that of water in equilibrium with its vapour, we have one
component--water--present in two phases, _i.e._ in two physically distinct
forms, viz. liquid and vapour. According to the Phase Rule, therefore,
since C = 1, and P = 2, the degree of freedom F is equal to 1 + 2 - 2 = 1;
the system possesses one degree of freedom, as has already been stated. But
in the case of the second system mentioned above there are two components,
viz. calcium oxide and carbon dioxide (p. 12), and three phases, viz. two
solid phases, CaO and CaCO_{3}, and the gaseous phase, CO_{2}. The number
of degrees of freedom of the system, therefore, is 2 + 2 - 3 = 1; this
system, therefore, also possesses one degree of freedom. We can now
understand why these two systems behave in a similar manner; both are
univariant, or possess only one degree of freedom. We shall therefore
expect a similar behaviour in the case of all univariant systems, no matter
how dissimilar the systems may outwardly appear. Similarly, all bivariant
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