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)
This method, it will be remembered, was employed by Richards for the
determination of the transition point of sodium sulphate decahydrate
(p. 136). The following figures give the results obtained by Meyerhoffer in
the case of the transformation:--
CuK_{2}Cl_{4},2H_{2}O <--> CuKCl_{3} + KCl + 2H_{2}O
the temperature being noted from minute to minute: 95°, 93°, 91.8°, 91.7°,
92°, 92.3°, 92.4°, 92.2°, 92.2°, 92°, 90.5°, 89°, and then a rapid fall in
the temperature. From this we see that the transition point is about 92.2°.
It is also evident that a slight supercooling took place (91.7°), owing to
a delay in the transformation, but that then the temperature rose to the
transition point. This is analogous to the supercooling of a liquid.
A similar halt in the temperature would be observed on passing from lower
to higher temperatures; but owing to a lag in the transformation, the same
temperature is not always obtained.
{337}
V. Optical Method.--The transition point can sometimes be determined by
noting the temperature at which some alteration in the appearance of the
substance occurs, such as a change of colour or of the crystalline form.
Thus mercuric iodide changes colour from red to yellow, and the blue
quadratic crystals of copper calcium acetate change, on passing the
transition point, into green rhombs of copper acetate and white needles of
calcium acetate (p. 260). Or again, changes in the double refraction of the
crystals may be also employed to ascertain the temperature of the
transition point. These changes are best observed by means of a microscope.
For the purpose of regulating the temperature of the substance a small
copper air-bath is employed.[404]
VI. Electrical Methods.--Electrical methods for the determination of the
transition point are of two kinds, based on measurements of conductivity or
of electromotive force. Both methods are restricted in their application,
but where applicable give very exact results.
The former method, which has been employed in several cases, need not be
described here. The second method, however, is of considerable interest and
importance, and calls for special reference.[405]
If two pieces, say, of zinc, connected together by a conducting wire, are
placed in a solution of a zinc salt, _e.g._ zinc sulphate, the potential of
the two electrodes will be the same, and no current will be produced in the
connecting wire. If, however, the zinc electrodes are immersed in two
solutions of _different_ concentration contained in separate vessels, but
placed in connection with one another by means of a bent tube filled with a
conducting solution, the potentials at the electrodes will no longer be the
same, and a current will now flow through the connecting wire. The
direction of this current _in the cell_ will be from the weaker to the more
concentrated solution.
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