If it is only desired to indicate the mutual relationships of the different components and the conditions for their coexistence (paragenesis), a simpler diagram than Fig. 124 can be employed. Thus if the boundary curves of Fig. 124 are so drawn that they cut one another at right angles, a figure such as Fig. 125 is obtained, the Roman numerals here corresponding with those in Fig. 124.
Ammonia-Soda Process.—One of the most important applications of the Phase Rule to systems of four components with reciprocal salt-pairs has recently been made by Fedotieff[[392]] in his investigations of the conditions for the formation of sodium carbonate by the so-called ammonia-soda (Solvay)
process.[[393]] This process consists, as is well known, in passing carbon dioxide through a solution of common salt saturated with ammonia.
Whatever differences of detail there may be in the process as carried out in different manufactories, the reaction which forms the basis of the process is that represented by the equation
NaCl + NH4HCO3 = NaHCO3 + NH4Cl
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 Na2SO4.10H2O + 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]).
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, NH4Cl, NH4HCO3, and NaHCO3 were made, first with the single salts and then
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 NaHCO3 + NH4Cl + NH4HCO3 and with NaHCO3 + NH4Cl + NaCl as solid phases. Under the
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°):—