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)
We are dealing here, therefore, with reciprocal salt-pairs, the behaviour
of which has just been discussed in the preceding pages. The present case
is, however, simpler than that of the salt-pair Na_{2}SO_{4}.10H_{2}O +
KCl, inasmuch as under the conditions of experiment neither hydrates nor
double salts are formed. Since the study of the reaction is rendered more
difficult on account of the fact that ammonium bicarbonate in solution,
when under atmospheric pressure, undergoes decomposition at temperatures
above 15°, this temperature was the one chosen for the detailed
investigation of the conditions of equilibrium. Since, further, it has been
shown by Bodländer[394] that the bicarbonates possess a definite solubility
only when the pressure of carbon dioxide in the solution has a definite
value, the measurements were carried out in solutions saturated with this
gas. This, however, does not constitute another component, because we have
made the restriction that the sum of the partial pressures of carbon
dioxide and water vapour is equal to 1 atmosphere. The concentration of the
carbon dioxide is, therefore, not independently variable (p. 10).
[Illustration: FIG. 126.]
In order to obtain the data necessary for a discussion of the conditions of
soda formation by the ammonia-soda process, solubility determinations with
the four salts, NaCl, NH_{4}Cl, NH_{4}HCO_{3}, and NaHCO_{3} were made,
first with the single salts and then {321} with the salts in pairs. The
results obtained are represented graphically in Fig. 126, which is an
isothermal diagram similar to that given by Fig. 124. The points I., II.,
III., IV., represent the composition of solutions in equilibrium with two
solid salts. We have, however, seen (p. 314) that the transition point,
when the experiment is carried out under constant pressure (atmospheric
pressure), is the point of intersection of four solubility curves, each of
which represents the composition of solutions in equilibrium with three
salts, viz. one of the reciprocal salt-pairs along with a third salt.
Since, now, it was found that the stable salt-pair at temperatures between
0° and 30° is sodium bicarbonate and ammonium chloride, determinations were
made of the composition of solutions in equilibrium with NaHCO_{3} +
NH_{4}Cl + NH_{4}HCO_{3} and with NaHCO_{3} + NH_{4}Cl + NaCl as solid
phases. Under the {322} conditions of experiment (temperature = 15°) sodium
chloride and ammonium bicarbonate cannot coexist in contact with solution.
These determinations gave the data necessary for the construction of the
complete isothermal diagram (Fig. 127). The most important of these data
are given in the following table (temperature, 15°):--
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