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 conditions for the formation of these two compounds, by passing ammonia
over silver chloride, to which reference has already been made, will be
readily understood from the above tables. In the case of the triammonia
mono-chloride, the dissociation pressure becomes equal to atmospheric
pressure at a temperature of about 20°; above this temperature, therefore,
it cannot be formed by the action of ammonia at atmospheric pressure on
silver chloride. The triammonia dichloride can, however, be formed, for its
dissociation pressure at this temperature amounts to only 9 cm., and
becomes equal to the atmospheric pressure only at a temperature of about
68°; and this temperature, therefore, constitutes the limit above which no
combination can take place between silver chloride and ammonia under
atmospheric pressure.
Attention may be here drawn to the fact, to which reference will also be
made later, that _two_ solid phases are necessary in order that the
dissociation pressure at a given temperature shall be definite; _and for
the exact definition of this pressure it is necessary to know, not merely
what is the substance undergoing dissociation, but also what is the solid
product of dissociation formed_. For the definition of the equilibrium, the
latter is as important as the former. We shall presently find proof of this
in the case {85} of an analogous class of phenomena, viz. the dissociation
of salt hydrates.
Salts with Water of Crystallization.--In the case of the dehydration of
crystalline salts containing water of crystallization, we meet with
phenomena which are in all respects similar to those just studied. A salt
hydrate on being heated dissociates into a lower hydrate (or anhydrous
salt) and water vapour. Since we are dealing with two components--salt and
water[154]--in three phases, viz. hydrate _a_, hydrate _b_ (or anhydrous
salt), and vapour, the system is univariant, and to each temperature there
will correspond a certain, definite vapour pressure (the dissociation
pressure), which will be independent of the relative or absolute amounts of
the phases, _i.e._ of the amount of hydrate which has already undergone
dissociation or dehydration.
[Illustration: FIG. 19.]
The constancy of the dissociation pressure had been proved experimentally
by several investigators[155] a number of years before the theoretical
basis for its necessity had been given. In the case of salts capable of
forming more than one hydrate, we should obtain a series of dissociation
curves (_pt_-curves), as in the case of the different hydrates of copper
sulphate. In Fig. 19 there are represented diagrammatically the
vapour-pressure curves of the following univariant systems of copper
sulphate and water:--
Curve OA: CuSO_{4},5H_{2}O <--> CuSO_{4},3H_{2}O + 2H_{2}O.
Curve OB: CuSO_{4},3H_{2}O <--> CuSO_{4},H_{2}O + 2H_{2}O.
Curve OC: CuSO_{4},H_{2}O <--> CuSO_{4} + H_{2}O.
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