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)
It is, however, only in the case of systems of more than one component that
any difficulty will be found; for only in this case will a choice of
components be possible. Take, for instance, the dissociation of calcium
carbonate into calcium oxide and carbon dioxide. At each temperature, as we
have seen, there is a definite state of equilibrium. When equilibrium has
been established, there are three different substances present--calcium
carbonate, calcium oxide, and carbon dioxide; and these are the
constituents of the system between which equilibrium exists. Now, although
these constituents take part in the equilibrium, they are not all to be
regarded as components, for they are not mutually independent. On the
contrary, the different phases are related to one another, and if two of
these are taken, the composition of the third is defined by the equation
CaCO_{3} = CaO + CO_{2}
{12} Now, in deciding the number of components in any given system, not
only must the constituents chosen be capable of independent variation, but
a further restriction is imposed, and we obtain the following rule: _As the
components of a system there are to be chosen the_ smallest number _of
independently variable constituents by means of which the composition of
each phase participating in the state of equilibrium can be expressed in
the form of a chemical equation._
Applying this rule to the case under consideration, we see that of the
three constituents present when the system is in a state of equilibrium,
only two, as already stated, are independently variable. It will further be
seen that in order to express the composition of each phase present, two of
these constituents are necessary. The system is, therefore, one of _two
components_, or a system of the second order.
When, now, we proceed to the actual choice of components, it is evident
that any two of the constituents can be selected. Thus, if we choose as
components CaCO_{3} and CaO, the composition of each phase can be expressed
by the following equations:--
CaCO_{3} = CaCO_{3} + 0CaO
CaO = CaO + 0CaCO_{3}
CO_{2} = CaCO_{3} - CaO
As we see, then, both zero and negative quantities of the components have
been introduced; and similar expressions would be obtained if CaCO_{3} and
CO_{2} were chosen as components. The matter can, however, be simplified
and the use of negative quantities avoided if CaO and CO_{2} are chosen;
and it is, therefore, customary to select these as the components.
While it is possible in the case of systems of the second order to choose
the two components in such a way that the composition of each phase can be
expressed by positive quantities of these, such a choice is not always
possible when dealing with systems of a higher order (containing three or
four components).
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