[4 bis] Lord Rayleigh in 1894, when determining the weight of a volume of carefully purified nitrogen by weighing it in one and the same globe, found that the gas obtained from air, by the action of incandescent copper (or iron or by removing the oxygen by ferrous oxide) was always 1⁄200 heavier than the nitrogen obtained from its compounds, for instance, from the oxide or suboxide of nitrogen, decomposed by incandescent pulverulent iron or from the ammonia salt of nitrous acid. For the nitrogen procured from air, he obtained, at 0° and 760·4 mm. pressure, a weight = 2·310 grms., while for the nitrogen obtained from its compounds, 2·299 grms. This difference of about 1⁄200 could not be explained by the nitrogen not having been well purified, or by inaccuracy of experiment, and was the means for the remarkable discovery of the presence of a heavy gas in air, which will be mentioned in Note [16 bis].
[5] See Chapter II. Note [29].
[6] The combination of boron with nitrogen is accompanied by the evolution of sufficient heat to raise the mass to redness; titanium combines so easily with nitrogen that it is difficult to obtain it free from that element; magnesium easily absorbs nitrogen at a red heat. It is a remarkable and instructive fact that these compounds of nitrogen are very stable and non-volatile. Carbon (C = 12) with nitrogen gives cyanogen, C2N2, which is gaseous and very unstable, and whose molecule is not large, whilst boron (B = 11) forms a nitrogenous compound which is solid, non-volatile, and very stable. Its composition, BN, is similar to that of cyanogen, but its molecular weight, BnNn, is probably greater. Its composition, like that of N2Mg3, NNa3, N2Hg3 and of many of the metallic nitrides, corresponds to ammonia with the substitution of all its hydrogen by a metal. In my opinion, a detailed study of the transformations of the nitrides now known, should lead to the discovery of many facts in the history of nitrogen.
[7] This reaction, so far as is known, does not proceed beyond a certain limit, probably because cyanogen, CN, itself breaks up into carbon and nitrogen.
[8] Frémy and Becquerel took dry air, and observed the formation of brown vapours of oxides of nitrogen on the passage of sparks.
[9] If a mixture of one volume of nitrogen and fourteen volumes of hydrogen be burnt, then water and a considerable quantity of nitric acid are formed. It may be partly due to this that a certain quantity of nitric acid is produced in the slow oxidation of nitrogenous substances in an excess of air. This is especially facilitated by the presence of an alkali with which the nitric acid formed can combine. If a galvanic current be passed through water containing the nitrogen and oxygen of the air in solution, then the hydrogen and oxygen set free combine with the nitrogen, forming ammonia and nitric acid.
When copper is oxidised at the expense of the air at the ordinary temperature in the presence of ammonia, oxygen is absorbed, not only for combination with the copper, but also for the formation of nitric acid.
The combination of nitrogen with oxygen, even, for example, by the action of electric sparks, is not accompanied by an explosion or rapid combination, as in the action of a spark on a mixture of oxygen and hydrogen. This is explained by the fact that heat is not evolved in the combination of nitrogen with oxygen, but is absorbed—an expenditure of energy is required, there is no evolution of energy. In fact, there will not be the transmission of heat from particle to particle which occurs in the explosion of detonating gas. Each spark will aid the formation of a certain quantity of the compound of oxygen and nitrogen, but will not excite the same in the neighbouring particles. In other words, the combination of hydrogen with oxygen is an exothermal reaction, and the combination of nitrogen with oxygen an endothermal reaction.
A condition particularly favourable for the oxidation of nitrogen is the explosion of detonating gas and air if the former be in excess. If a mixture of two volumes of detonating gas and one volume of air be exploded, then one-tenth of the air is converted into nitric acid, and consequently after the explosion has taken place there remain only nine-tenths of the volume of air originally taken. If a large proportion of air be taken—for instance, four volumes of air to two volumes of detonating gas—then the temperature of the explosion is lowered, the volume of air taken remains unchanged, and no nitric acid is formed. This gives a rule to be observed in making use of the eudiometer—namely that to weaken the force of the explosion not less than an equal volume of air should be added to the explosive mixture. On the other hand a large excess must not be taken as no explosion would then ensue (see Chapter III. Note [34]). Probably in the future means will be found for obtaining compounds of nitrogen on a large industrial scale by the aid of electric discharges, and by making use of the inexhaustible mass of nitrogen in the atmosphere.