As an example of this, we may first consider the well-known case of the dissociation of calcium carbonate. This substance on being heated dissociates into calcium oxide, or quick-lime, and carbon dioxide, as shown by the equation CaCO3
The dissociation pressure of calcium carbonate was first studied by Debray,[[149]] but more exact measurements have been made by Le Chatelier,[[150]] who found the following corresponding values of temperature and pressure:—
| Temperature. | Pressure in cm. mercury. |
| 547° | 2.7 |
| 610° | 4.6 |
| 625° | 5.6 |
| 740° | 25.5 |
| 745° | 28.9 |
| 810° | 67.8 |
| 812° | 76.3 |
| 865° | 133.3 |
From this table we see that it is only at a temperature of about 812° that the pressure of the carbon dioxide becomes equal to atmospheric pressure. In a vessel open to
the air, therefore, the complete decomposition of the calcium carbonate would not take place below this temperature by the mere heating of the carbonate. If, however, the carbon dioxide is removed as quickly as it is formed, say by a current of air, then the entire decomposition can be made to take place at a much lower temperature. For the dissociation equilibrium of the carbonate depends only on the partial pressure of the carbon dioxide, and if this is kept small, then the decomposition can proceed, even at a temperature below that at which the pressure of the carbon dioxide is less than atmospheric pressure.
Ammonia Compounds of Metal Chlorides.—Ammonia possesses the property of combining with various substances, chiefly the halides of metals, to form compounds which again yield up the ammonia on being heated. Thus, for example, on passing ammonia over silver chloride, absorption of the gas takes place with formation of the substances AgCl,3NH3 and 2AgCl,3NH3, according to the conditions of the experiment. These were the first known substances belonging to this class, and were employed by Faraday in his experiments on the liquefaction of ammonia. Similar compounds have also been obtained by the action of ammonia on silver bromide, iodide, cyanide, and nitrate; and with the halogen compounds of calcium, zinc, and magnesium, as well as with other salts. The behaviour of the ammonia compounds of silver chloride is typical for the compounds of this class, and may be briefly considered here.
It was found by Isambert[[151]] that at temperatures below 15°, silver chloride combined with ammonia to form the compound AgCl,3NH3, while at temperatures above 20° the compound 2AgCl,3NH3 was produced. On heating these substances, ammonia was evolved, and the pressure of this gas was found in the case of both compounds to be constant at a given temperature, but was greater in the case of the former than in the case of the latter substance; the pressure, further, was independent of the amount decomposed. The behaviour of these two substances is, therefore, exactly analogous to that shown by calcium carbonate, and the explanation is also similar.
Regarded from the point of view of the Phase Rule, we see that we are here dealing with two components, AgCl and NH3. On being heated, the compounds decompose according to the equations:—