It is not only hydrocarbons which are subject to metalepsis. Certain other hydrogen compounds, under the action of chlorine, also give corresponding chlorine derivatives in exactly the same manner; for instance, ammonia, caustic potash, caustic lime, and a whole series of alkaline substances.29 In fact, just as the hydrogen in marsh gas can be replaced by chlorine and form methyl chloride, so the hydrogen in caustic potash, KHO, ammonia, NH3, and calcium hydroxide, CaH2O2 or Ca(OH)2, may be replaced by chlorine and give potassium hypochlorite, KClO, calcium hypochlorite, CaCl2O2, and the so-called chloride of nitrogen, NCl3. For not only is the correlation in composition the same as in the substitution in marsh gas, but the whole mechanism of the reaction is the same. Here also two atoms of chlorine act: one takes the place of the hydrogen whilst the other is evolved as hydrochloric acid, only in the former case the hydrochloric acid evolved remained free, and in the latter, in presence of alkaline substances, it reacts on them. Thus, in the action of chlorine on caustic potash, the hydrochloric acid formed acts on another quantity of caustic potash and gives potassium chloride and water, and therefore not only KHO + Cl2 = HCl + KClO, but also KHO + HCl = H2O + KCl, and the result of both simultaneous phases will be 2KHO + Cl2 = H2O + KCl + KClO. We will here discuss certain special cases.
The action of chlorine on ammonia may either result in the entire breaking up of the ammonia, with the evolution of gaseous nitrogen, or in a product of metalepsis (as with CH4). With an excess of chlorine and the aid of heat the ammonia is decomposed, with the disengagement of free nitrogen.30 This reaction evidently results in the formation of sal-ammoniac, 8NH3 + 3Cl2 = 6NH4Cl + N2. But if the ammonium salt be in excess, then the reaction takes the direction of the replacement of the hydrogen in the ammonia by chlorine. The principal result is that NH3 + 3Cl2 forms NCl3 + 3HCl.31 The resulting product of metalepsis, or chloride of nitrogen, NCl3, discovered by Dulong, is a liquid having the property of decomposing with excessive ease not only when heated, but even under the action of mechanical influences, as by a blow or by contact with certain solid substances. The explosion which accompanies the decomposition is due to the fact that the liquid chloride of nitrogen gives gaseous products, nitrogen and chlorine.32
Chloride of nitrogen is a yellow oily liquid of sp. gr. 1·65, which boils at 71°, and breaks up into N + Cl3 at 97°. The contact of phosphorus, turpentine, india-rubber, &c. causes an explosion, which is sometimes so violent that a small drop will pierce through a thick board. The great ease with which chloride of nitrogen decomposes is dependent upon the fact that it is formed with an absorption of heat, which it evolves when decomposed, to the amount of about 38,000 heat units for NCl3, as Deville and Hautefeuille determined.
Chlorine, when absorbed by a solution of caustic soda (and also of other alkalis) at the ordinary temperature, causes the replacement of the hydrogen in the caustic soda by the chlorine, with the formation of sodium chloride by the hydrochloric acid, so that the reaction may be represented in two phases, as described above. In this manner, sodium hypochlorite, NaClO, and sodium chloride are simultaneously formed: 2NaHO + Cl 2 = NaCl + NaClO + H 2 O. The resultant solution contains NaClO and is termed ‘eau de Javelle.’ An exactly similar reaction takes place when chlorine is passed over dry hydrate of lime at the ordinary temperature: 2Ca(HO) 2 + 2Cl 2 = CaCl 2 O 2 + CaCl 2 + 2H 2 O. A mixture of the product of metalepsis with calcium chloride is obtained. This mixture is employed in practice on a large scale, and is termed ‘bleaching powder,’ owing to its acting, especially when mixed with acids, as a bleaching agent on tissues, so that it resembles chlorine in this respect. It is however preferable to chlorine, because the destructive action of the chlorine can be moderated in this case, and because it is much more convenient to deal with a solid substance than with gaseous chlorine. Bleaching powder is also called chloride of lime , because it is obtained from