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 preceding examples, in which decomposition of the double salt was
effected by a rise of temperature, were chosen for first consideration as
being more analogous to the case of Glauber's salt; but not a few examples
are known where the reverse change takes place, formation of the double
salt occurring _above_ the transition point, and decomposition into the
constituent salts below it. Instances of this behaviour are found in the
case of the formation of astracanite from sodium and magnesium sulphates,
and of sodium ammonium racemate from the two sodium ammonium tartrates, to
which reference will be made later. Between these various systems, however,
there is no essential difference; and whether decomposition or formation of
the double salt occurs at temperatures above the transition point, will of
course depend on the heat of change at that point. For, in accordance with
van't Hoff's law of movable equilibrium (p. 58), that change will take
place at the higher temperature which is accompanied by an absorption of
heat. If, therefore, the formation of the double salt from the single salts
is accompanied by an absorption of heat, the double salt will be formed
from the single salts on raising the temperature; but if the reverse is the
case, then the double salt on being heated will decompose into the
constituent salts.[340]
In those cases, now, which have so far been studied, the change at the
transition point is accompanied by a taking up or a splitting off of water;
and _in such cases the general rule can be given, that if the water of
crystallization of the two constituent {261} salts together is greater than
that of the double salt, the latter will be produced from the former on
raising the temperature_ (_e.g._ astracanite from sodium and magnesium
sulphates); _but if the double salt contains more water of crystallization
than the two single salts, increase of temperature will effect the
decomposition of the double salt_. When we seek for the connection between
this rule and the law of van't Hoff, it is found in the fact that the heat
effect involved in the hydration or dehydration of the salts is much
greater than that of the other changes which occur, and determines,
therefore, the sign of the total heat effect.[341]
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