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)
In the case of a solution of common salt, however, we may have ice in
contact with the solution at different temperatures and pressures. Further,
it is possible to have a solution in equilibrium not only with anhydrous
salt (NaCl), but also with the hydrated salt (NaCl, 2H_{2}O), as well as
with ice, and the question, therefore, arises: Is it possible to state in a
general manner the conditions under which such different systems can exist
in equilibrium; or to obtain some insight {3} into the relations which
exist between pure liquids and solutions? As we shall learn, the Phase Rule
enables us to give an answer to this question.
The preceding examples belong to the class of so-called "physical"
equilibria, or equilibria depending on changes in the physical state. More
than a hundred years ago, however, it was shown by Wenzel and Berthollet
that "chemical" equilibria can also exist; that chemical reactions do not
always take place completely in one direction as indicated by the usual
chemical equation, but that before the reacting substances are all used up
the reaction ceases, and there is a condition of equilibrium between the
reacting substances and the products of reaction. As an example of this,
there may be taken the process of lime-burning, which depends on the fact
that when calcium carbonate is heated, carbon dioxide is given off and
quicklime is produced. If the carbonate is heated in a closed vessel it
will be found, however, not to undergo entire decomposition. When the
pressure of the carbon dioxide reaches a certain value (which is found to
depend on the temperature), decomposition ceases, and calcium carbonate
exists side by side with calcium oxide and carbon dioxide. Moreover, at any
given temperature the pressure is constant and independent of the amount of
carbonate or oxide present, or of the volume of the gas; _nor does the
addition of either of the products of dissociation, carbon dioxide or
calcium oxide, cause any change in the equilibrium_. Here, then, we see
that, although there are three different substances present, and although
the equilibrium is no longer due to physical, but to chemical change, it
nevertheless obeys the same law as the vapour pressure of a pure volatile
liquid, such as water.
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