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)
Since, from the method of investigation, the temperatures of the eutectic
curves will depend on the melting point of the third component (A), it is
possible, by employing substances with widely differing melting points, to
investigate the interaction of the two components (_e.g._ two optical
antipodes) B and C over a range of temperature; and thus determine the
range of stability of the compound, if one is formed. Since, in some cases,
two substances which at one temperature form mixed crystals combine at
another temperature to form a definite compound, the relationships which
have just been described can be employed, and indeed, have been employed,
to determine the temperature at which this change occurs.[334] By means of
this method, Adriani found that below 103° _i_-camphoroxime exists as a
racemic compound, while above {258} that temperature it occurs as a racemic
mixed crystal[335] (_cf._ p. 219).
B. Equilibria at Higher Temperatures. Formation of Double Salts.--After
having studied the relationships which are found in the neighbourhood of
the freezing points of the components, we now pass to the discussion of the
equilibria which are met with at higher temperatures. In this connection we
shall confine the discussion entirely to the systems formed of two salts
and water, dealing more particularly with those cases in which the water is
present in relatively large amount and acts as solvent. Further, in
studying these systems, one restriction must be made, viz. that the single
salts are salts either of the same base or of the same acid; or are, in
other words, capable of yielding a common ion in solution. Such a
restriction is necessary, because otherwise the system would be one not of
three but of four components.[336]
Transition Point.--As is very well known, there exist a number of hydrated
salts which, on being heated, undergo apparent partial fusion; and in
Chapter V. the behaviour of such hydrates was more fully studied in the
light of the Phase Rule. Glauber's salt, or sodium sulphate decahydrate,
for example, on being heated to a temperature of about 32.5°, partially
liquefies, owing to the fact that the water of crystallization is split off
and anhydrous sodium sulphate formed, as shown by the equation--
Na_{2}SO_{4},10H_{2}O = Na_{2}SO_{4} + 10H_{2}O
The temperature of 32.5°, it was learned, constituted a _transition point_
for the decahydrate and anhydrous salt plus water; decomposition of the
hydrated salt occurring above this temperature, combination of the
anhydrous salt and water below it.
Analogous phenomena are met with in systems constituted of two salts and
water in which the formation of double salts can take place. Thus, for
example, if _d_-sodium potassium {259} tartrate is heated to above 55°,
apparent partial fusion occurs, and the two single salts, _d_-sodium
tartrate and _d_-potassium tartrate, are deposited, the change which occurs
being represented by the equation--
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