Page:EB1911 - Volume 02.djvu/514

 convenient method devised by Vernon Harcourt, in which air charged with ammonia is passed over red-hot copper. Under the influence of the heat the atmospheric oxygen unites with the hydrogen of the ammonia, and when the excess of the latter is removed with sulphuric acid, the gas properly desiccated should be pure nitrogen, derived in part from the ammonia, but principally from the air. A few concordant determinations of density having been effected, the question was at first regarded as disposed of, until the thought occurred that it might be desirable to try also the more usual method of preparation in which the oxygen is removed by actual oxidation of copper without the aid of ammonia. Determinations made thus were equally concordant among themselves, but the resulting density was about part greater than that found by Harcourt’s method (Rayleigh, Nature, vol. xlvi. p. 512, 1892). Subsequently when oxygen was substituted for air in the first method, so that all (instead of about one-seventh part) of the nitrogen was derived from ammonia, the difference rose to %. Further experiment only brought out more clearly the diversity of the gases hitherto assumed to be identical. Whatever were the means employed to rid air of accompanying oxygen, a uniform value of the density was arrived at, and this value was % greater than that appertaining to nitrogen extracted from compounds such as nitrous oxide, ammonia and ammonium nitrite. No impurity, consisting of any known substance, could be discovered capable of explaining an excessive weight in the one case, or a deficiency in the other. Storage for eight months did not disturb the density of the chemically extracted gas, nor had the silent electric discharge any influence upon either quality. (“On an Anomaly encountered in determining the Density of Nitrogen Gas,” Proc. Roy. Soc., April 1894.)

At this stage it became clear that the complication depended upon some hitherto unknown body, and probability inclined to the existence of a gas in the atmosphere heavier than nitrogen, and remaining unacted upon during the removal of the oxygen—a conclusion afterwards fully established by Lord Rayleigh and Sir William Ramsay. The question which now pressed was as to the character of the evidence for the universally accepted view that the so-called nitrogen of the atmosphere was all of one kind, that the nitrogen of the air was the same as the nitrogen of nitre. Reference to Cavendish showed that he had already raised this question in the most distinct manner, and indeed, to a certain extent, resolved it. In his memoir of 1785 he writes:—

Although, as was natural, Cavendish was satisfied with his result, and does not decide whether the small residue was genuine, it is probable that his residue was really of a different kind from the main bulk of the “phlogisticated air,” and contained the gas afterwards named argon. The announcement to the British Association in 1894 by Rayleigh and Ramsay of a new gas in the atmosphere was received with a good deal of scepticism. Some doubted the discovery of a new gas altogether, while others denied that it was present in the atmosphere. Yet there was nothing inconsistent with any previously ascertained fact in the asserted presence of 1% of a non-oxidizable gas about half as heavy again as nitrogen. The nearest approach to a difficulty lay in the behaviour of liquid air, from which it was supposed, as the event proved erroneously, that such a constituent would separate itself in the solid form. The evidence of the existence of a new gas (named Argon on account of its chemical inertness), and a statement of many of its properties, were communicated to the Royal Society (see Phil. Trans. clxxxvi. p. 187) by the discoverers in January 1895. The isolation of the new substance by removal of nitrogen from air was effected by two distinct methods. Of these the first is merely a development of that of Cavendish. The gases were contained in a test-tube A (fig. 1) standing over a large quantity of weak alkali B, and the current was conveyed in wires insulated by U-shaped glass tubes CC passing through the liquid and round the mouth of the test-tube. The inner platinum ends DD of the wire may be sealed into the glass insulating tubes, but reliance should not be placed upon these sealings. In order to secure tightness in spite of cracks, mercury was placed in the bends. With a battery of five Grove cells and a Ruhmkorff coil of medium size, a somewhat short spark, or arc, of about 5 mm. was found to be more favourable than a longer one. When the mixed gases were in the right proportion, the rate of absorption was about 30 c.c. per hour, about thirty times as fast as Cavendish could work with the electrical machine of his day. Where it is available, an alternating electric current is much superior to a battery and break. This combination, introduced by W. Spottiswoode, allows the absorption in the apparatus of fig. 1 to be raised to about 80 c.c. per hour, and the method is very convenient for the purification of small quantities of argon and for determinations of the amount present in various samples of gas, e.g. in the gases expelled from solution in water. A convenient adjunct to this apparatus is a small voltameter, with the aid of which oxygen or hydrogen can be introduced at pleasure. The gradual elimination of the nitrogen is tested at a moment’s notice with a miniature spectroscope. For this purpose a small Leyden jar is connected as usual to the secondary terminals, and if necessary the force of the discharge is moderated by the insertion of resistance in the primary circuit. When with a fairly wide slit the yellow line is no longer visible, the residual nitrogen may be considered to have fallen below 2 or 3%. During this stage the oxygen should be in considerable excess. When the yellow line of nitrogen has disappeared, and no further contraction seems to be in progress, the oxygen maybe removed by cautious introduction of hydrogen. The spectrum may now be further examined with a more powerful instrument. The most conspicuous group in the argon spectrum at atmospheric pressure is that first recorded by A. Schuster (fig. 2). Water vapour and excess of oxygen in moderation do not interfere seriously with its visibility. It is of interest to note that the argon spectrum may be fully developed by operating upon a miniature scale, starting with only 5 c.c. of air (Phil. Mag. vol. i. p. 103, 1901).

The development of Cavendish’s method upon a large scale