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)
Cryohydrates.[195]--On cooling a solution of common salt in water to a
temperature of -3°, Guthrie observed that the hydrate NaCl,2H_{2}O
separated out. This salt continued to be deposited until at a temperature
of -22° opaque crystals made their appearance, and the liquid passed into
the solid state without change of temperature. A similar behaviour was
found by Guthrie in the case of a large number of other salts, a
temperature below that of the melting point of ice being reached at which
on continued withdrawal of heat, the solution solidified at a constant
temperature. When the system had attained this minimum temperature, it was
found that the composition of the solid and the liquid phases was the same,
and remained unchanged throughout the period of solidification. This is
shown by the following figures, which give the composition of different
samples of the solid phase deposited from the solution at constant
temperature.[196]
{118}
---------------------------------
No. | Temperature of | NaCl.
| solidification. | Per cent.
----|-----------------|----------
1 | -21° to -22° | 23.72
2 | -22° | 23.66
3 | -22° | 23.73
4 | -23° | 23.82
5 | -23° | 23.34
6 | -23° | 23.35
---------------------------------
Mean 23.6
---------------------------------
Conversely, a mixture of ice and salt containing 23.6 per cent. of sodium
chloride will melt at a definite and constant temperature, and exhibit,
therefore, a behaviour supposed to be characteristic of a pure chemical
compound. This, then, combined with the fact that the solid which was
deposited was crystalline, and that the same constant temperature was
attained, no matter with what proportions of water and salt one started,
led Guthrie to the belief that the solids which thus separated at constant
temperature were definite chemical compounds, to which he gave the general
name _cryohydrate_. A large number of such cryohydrates were prepared and
analysed by Guthrie, and a few of these are given in the following table,
together with the temperature of the cryohydric point:[197]--
CRYOHYDRATES.
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