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)
Illustration.--In order to illustrate the application of the principles of
the Phase Rule to the study of systems formed by a volatile and a
non-volatile component, a brief description may be given of the behaviour
of sulphur dioxide and potassium iodide, which has formed the subject of a
recent investigation. After it had been found[236] that liquid sulphur
dioxide has the property of dissolving potassium iodide, and that the
solutions thus obtained present certain peculiarities of behaviour, the
question arose as to whether or not compounds are formed between the
sulphur dioxide and the potassium iodide, and if so, what these compounds
are. To find an answer to this question, Walden and Centnerszwer[237] made
a complete investigation of the solubility curves (equilibrium curves) of
these two components, the investigation extending from the freezing point
to the critical point of sulphur dioxide. For convenience of reference, the
results which they obtained are represented diagrammatically in Fig. 41.
The freezing point (A) of pure sulphur dioxide was found to be -72.7°.
Addition of potassium iodide lowered the freezing point, but the maximum
depression obtained was very small, and was reached when the concentration
of the potassium iodide in the solution was only 0.336 mols. per cent.
Beyond this point, an increase in the concentration of the iodide was
accompanied by an elevation of the freezing point, the change of the
freezing point with the concentration being represented by the curve BC.
The solid {159} which separated from the solutions represented by BC was a
bright _yellow_ crystalline substance. At the point C (-23.4°) a
temperature-maximum was reached; and as the concentration of the potassium
iodide was continuously increased, the temperature of equilibrium first
fell and then slowly rose, until at +0.26° (E) a second temperature-maximum
was registered. On passing the point D, the solid which was deposited from
the solution was a _red_ crystalline substance. On withdrawing sulphur
dioxide from the system, the solution became turbid, and the temperature
remained constant. The investigation was not pursued farther at this point,
the attention being then directed to the equilibria at higher temperatures.
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