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 might be supposed, now, that this behaviour would be shown by other
dissociating substances, _e.g._ ammonium chloride. When this substance is
heated it dissociates into ammonia and hydrogen chloride, and at any given
temperature the pressure of these gases is constant,[3] and is independent
of the amounts of solid and gas present. So far, therefore, ammonium
chloride behaves like calcium carbonate. If, however, one of the {4}
products of dissociation be added to the system, it is found that the
pressure is no longer constant at a given temperature, but varies with the
amount of gas, ammonia or hydrogen chloride, which is added. In the case of
certain dissociating substances, therefore, addition of one of the products
of dissociation alters the equilibrium, while in other cases it does not.
With the help of the Phase Rule, however, a general interpretation of this
difference of behaviour can be given--an interpretation which can be
applied not only to the two cases cited, but to all cases of dissociation.
Again, it is well known that sulphur exists in two different crystalline
forms, octahedral and prismatic, each of which melts at a different
temperature. The problem here is, therefore, more complicated than in the
case of ice, for there is now a possibility not only of one solid form, but
of two different forms of the same substance existing in contact with
liquid. What are the conditions under which these two forms can exist in
contact with liquid, either singly or together, and under what conditions
can the two solid forms exist together without the presence of liquid
sulphur? To these questions an answer can also be given with the help of
the Phase Rule.
These cases are, however, comparatively simple; but when we come, for
instance, to study the conditions under which solutions are formed, and
especially when we inquire into the solubility relations of salts capable
of forming, perhaps, a series of crystalline hydrates; and when we seek to
determine the conditions under which these different forms can exist in
contact with the solution, the problem becomes more complicated, and the
necessity of some general guide to the elucidation of the behaviour of
these different systems becomes more urgent.
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