The Principles of Chemistry, Volume IMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume I
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
Although in the majority of cases the solubility of solids increases
with the temperature, yet there are some solid substances whose
solubilities decrease on heating. Glauber's salt, or sodium sulphate,
forms a particularly instructive example of the case in question.
If this salt be taken in an ignited state (deprived of its water of
crystallisation), then its solubility in 100 parts of water varies with
the temperature in the following manner: at 0°, 5 parts of the salt
form a saturated solution; at 20°, 20 parts of the salt, at 33° more
than 50 parts. The solubility, as will be seen, increases with the
temperature, as is the case with nearly all salts; but starting from 33°
it suddenly diminishes, and at a temperature of 40°, less than 50 parts
of the salt dissolve, at 60° only 45 parts of the salt, and at 100°
about 43 parts of the salt in 100 parts of water. This phenomenon may
be traced to the following facts: Firstly, that this salt forms various
compounds with water, as will be afterwards explained; secondly, that
at 33° the compound Na_{2}SO_{4} + 10H_{2}O formed from the solution
at lower temperatures, melts; and thirdly, that on evaporation at a
temperature above 33° an anhydrous salt, Na_{2}SO_{4} separates out. It
will be seen from this example how complicated such an apparently simple
phenomenon as solution really is; and all data concerning solutions lead
to the same conclusion. This complexity becomes evident in investigating
the _heat of solution_. If solution consisted of a physical change
only, then in the solution of gases there would be evolved--and in the
solution of solids, there would be absorbed--just that amount of heat
corresponding to the change of state; but in reality a large amount of
heat is always evolved in solution, depending on the fact that in the
process of solution chemical combination takes place accompanied by an
evolution of heat. Seventeen grams of ammonia (this weight corresponds
with its formula NH_{3}), in passing from a gaseous into a liquid state,
evolve 4,400 units of heat (latent heat); that is, the quantity of heat
necessary to raise the temperature of 4,400 grams of water 1°. The
same quantity of ammonia, in dissolving in an excess of water, evolves
twice as much heat--namely 8,800 units--showing that the combination
with water is accompanied by the evolution of 4,400 units of heat.
Further, the chief part of this heat is separated in dissolving in small
quantities of water, so that 17 grams of ammonia, in dissolving in 18
grams of water (this weight corresponds with its composition H_{2}O),
evolve 7,535 units of heat, and therefore the formation of the solution
NH_{3} + H_{2}O evolves 3,135 units of heat beyond that due to the
change of state. As in the solution of gases, the heat of liquefaction
(of physical change of state) and of chemical combination with water
are both positive (+), therefore in the _solution of gases_ in water a
_heat effect_ is always observed.
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