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)
systems will exhibit analogous behaviour; and generally, systems possessing
the same degree of freedom will show a like behaviour. In accordance with
the Phase Rule, therefore, we may classify the different systems which may
be found into invariant, univariant, bivariant, multivariant, {18}
according to the relation which obtains between the number of the
components and the number of coexisting phases; and we shall expect that in
each case the members of any particular group will exhibit a uniform
behaviour. By this means we are enabled to obtain an insight into the
general behaviour of any system, so soon as we have determined the number
of the components and the number of the coexisting phases.
The adoption of the Phase Rule for the purposes of classification has been
of great importance in studying changes in the equilibrium existing between
different substances; for not only does it render possible the grouping
together of a large number of isolated phenomena, but the guidance it
affords has led to the discovery of new substances, has given the clue to
the conditions under which these substances can exist, and has led to the
recognition of otherwise unobserved resemblances existing between different
systems.
Deduction of the Phase Rule.--In the preceding pages we have restricted
ourselves to the statement of the Phase Rule, without giving any indication
of how it has been deduced. At the close of this chapter, therefore, the
mathematical deduction of the generalization will be given, but in brief
outline only, the reader being referred to works on Thermodynamics for a
fuller treatment of the subject.[21]
All forms of energy can be resolved into two factors, the _capacity_ factor
and the _intensity_ factor; but for the production of equilibrium, only the
intensity factor is of importance. Thus, if two bodies having the same
temperature are brought in contact with each other, they will be in
equilibrium as regards heat energy, no matter what may be the amounts of
heat (capacity factor) contained in either, because the intensity
factor--the temperature--is the same. But if the temperature of the two
bodies is different, _i.e._ if the intensity factor of heat energy is
different, the two bodies will no longer be in equilibrium; but heat will
pass from the hotter to the colder until both have the same temperature.
As with heat energy, so with chemical energy. If we have a substance
existing in two different states, or in two different {19} phases of a
system, equilibrium can occur only when the intensity factor of chemical
energy is the same. This intensity factor may be called the _chemical
potential_; and we can therefore say that a system will be in equilibrium
when the chemical potential of each component is the same in all the phases
in which the component occurs. Thus, for example, ice, water, and vapour
have, at the triple point, the same chemical potential.
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