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 greater the difference in the concentration of the solutions with
respect to zinc, the greater will be the difference of the potential at the
two electrodes, or the greater will be the E.M.F. of the cell. When the
concentration of the two solutions becomes the same, the E.M.F. will become
zero, and no current will pass.
It will be understood now how this method can be made use of {338} for
determining the transition point of a salt, when we bear in mind that at
the transition point the solubility of the two forms becomes identical.
Thus, for example, the transition point of zinc sulphate heptahydrate into
hexahydrate could be determined in the following manner. Tube A (Fig. 134)
contains, say, a saturated solution of the heptahydrate along with some of
the solid salt; tube B, a saturated solution of the hexahydrate along with
the solid salt. The tube C is a connecting tube bent downwards so as to
prevent the mixing of the solutions by convection currents. ZZ are two zinc
electrodes immersed in the solution; the cell is placed in a thermostat and
the zinc electrodes connected with a galvanometer. Since, now, at
temperatures below the transition point the solubility of the hexahydrate
(the metastable form) is greater than that of the heptahydrate, a current
will be produced, flowing in the cell from heptahydrate to hexahydrate. As
the temperature is raised towards the transition point, the solubilities of
the two hydrates also approach, and the current produced will therefore
become weaker, because the E.M.F. of the cell becomes less; and when the
transition point is attained, the E.M.F. becomes zero, and the current
ceases. If the temperature is raised above this, the solubility of the
heptahydrate becomes greater than that of the hexahydrate, and a current
will again be produced, but in the opposite direction. By noting the
temperature, therefore, at which the current ceases, or the E.M.F. becomes
zero, the transition temperature can be ascertained.[406]
[Illustration: FIG. 134.]
In the case just described, the electrodes consisted of the same metal as
was contained in the salt. But in some cases, _e.g._ sodium sulphate,
electrodes of the metal contained in the salt cannot be employed.
Nevertheless, the above electrical method can be used {339} even in those
cases, if a suitable non-polarizable mercury electrode is employed.[407]
Although, as we saw, no current was produced when two pieces of zinc were
immersed in the same solution of zinc salt, a current will be obtained if
two different metals, or even two different modifications of the same
metal, are employed. Thus an E.M.F. will be established when electrodes of
grey and of white tin are immersed in the same solution of zinc salt, but
at the transition point this E.M.F. will become zero. By this method Cohen
determined the transition point of grey and white tin (p. 42).
* * * * *
{340}
NAME INDEX
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