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 involves arrangements different from what would at first be expected. The transformer working from a public supply should give about 6000 volts on open circuit, although when the electric flame is established the voltage on the platinums is only from 1600 to 2000. No sufficient advantage is attained by raising the pressure of the gases above atmosphere, but a capacious vessel is necessary. This may consist of a glass sphere of 50 litres’ capacity, into the neck of which, presented downwards, the necessary tubes are fitted. The whole of the interior surface is washed with a fountain of alkali, kept in circulation by means of a small centrifugal pump. In this apparatus, and with about one horse-power utilized at the transformer, the absorption of gas is 21 litres per hour (“The Oxidation of Nitrogen Gas,” Trans. Chem. Soc., 1897).
In one experiment, specially undertaken for the sake of measurement, the total air employed was 9250 c.c., and the oxygen consumed, manipulated with the aid of partially de-aërated water, amounted to 10,820 c.c. The oxygen contained in the air would be 1942 c.c.; so that the quantities of atmospheric nitrogen and of total oxygen which enter into combination would be 7308 c.c. and 12,762 c.c. respectively. This corresponds to N + 1.75 O, the oxygen being decidedly in excess of the proportion required to form nitrous acid. The argon ultimately found was 75.0 c.c., or a little more than 1% of the atmospheric nitrogen used. A subsequent determination over mercury by A.M. Kellas (Proc. Roy. Soc. lix. p. 66, 1895) gave 1.186 c.c. as the amount of argon present in 100 c.c. of mixed atmospheric nitrogen and argon. In the earlier stages of the inquiry, when it was important to meet the doubts which had been expressed as to the presence of the new gas in the atmosphere, blank experiments were executed in which air was replaced by nitrogen from ammonium nitrite. The residual argon, derived doubtless from the water used to manipulate the gases, was but a small fraction of what would have been obtained from a corresponding quantity of air.
| Fig. 2. |
The other method by which nitrogen may be absorbed on a considerable scale is by the aid of magnesium. The metal in the form of thin turnings is charged into hard glass or iron tubes heated to a full red in a combustion furnace. Into this air, previously deprived of oxygen by red-hot copper and thoroughly dried, is led in a continuous stream. At this temperature the nitrogen combines with the magnesium, and thus the argon is concentrated. A still more potent absorption is afforded by calcium prepared in situ by heating a mixture of magnesium dust with thoroughly dehydrated quick-lime. The density of argon, prepared and purified by magnesium, was found by Sir William Ramsay to be 19.941 on the O = 16 scale. The volume actually weighed was 163 c.c. Subsequently large-scale operations with the same apparatus as had been used for the principal gases gave an almost identical result (19.940) for argon prepared with oxygen.
Argon is soluble in water at 12° C. to about 4.0%, that is, it is about 2½ times more soluble than nitrogen. We should thus expect to find it in increased proportion in the dissolved gases of rain-water. Experiment has confirmed this anticipation. The weight of a mixture of argon and nitrogen prepared from the dissolved gases showed an excess of 24 mg. over the weight of true nitrogen, the corresponding excess for the atmospheric mixture being only 11 mg. Argon is contained in the gases liberated by many thermal springs, but not in special quantity. The gas collected from the King’s Spring at Bath gave only ½%, i.e. half the atmospheric proportion.
The most remarkable physical property of argon relates to the constant known as the ratio of specific heats. When a gas is warmed one degree, the heat which must be supplied depends upon whether the operation is conducted at a constant volume or at a constant pressure, being greater in the latter case. The ratio of specific heats of the principal gases is 1.4, which, according to the kinetic theory, is an indication that an important fraction of the energy absorbed is devoted to rotation or vibration. If, as for Boscovitch points, the whole energy is translatory, the ratio of specific heats must be 1.67. This is precisely the number found from the velocity of sound in argon as determined by Kundt’s method, and it leaves no room for any sensible energy of rotatory or vibrational motion. The same value had previously been found for mercury vapour by Kundt and Warburg, and had been regarded as confirmatory of the monatomic character attributed on chemical grounds to the mercury molecule. It may be added that helium has the same character as argon in respect of specific heats (Ramsay, Proc. Roy. Soc. l. p. 86, 1895).
The refractivity of argon is .961 of that of air. This low refractivity is noteworthy as strongly antagonistic to the view at one time favoured by eminent chemists that argon was a condensed form of nitrogen represented by N3. The viscosity of argon is 1.21, referred to air, somewhat higher than for oxygen, which stands at the head of the list of the principal gases (“On some Physical Properties of Argon and Helium,” Proc. Roy. Soc. vol. lix. p. 198, 1896).
The spectrum shows remarkable peculiarities. According to circumstances, the colour of the light obtained from a Plücker vacuum tube changes “from red to a rich steel blue,” to use the words of Crookes, who first described the phenomenon. A third spectrum is distinguished by J.M. Eder and Edward Valenta. The red spectrum is obtained at moderately low pressures (5 mm.) by the use of a Ruhmkorff coil without a jar or air-gap. The red lines at 7056 and 6965 (Crookes) are characteristic. The blue spectrum is best seen at a somewhat lower pressure (1 mm. to 2.5 mm.), and usually requires a Leyden jar to be connected to the secondary terminals. In some conditions very small causes effect a transition from the one spectrum to the other. The course of electrical events attending the operation of a Ruhmkorff coil being extremely complicated, special interest attaches to some experiments conducted by John Trowbridge and T.W. Richards, in which the source of power was a secondary battery of 5000 cells. At a pressure of 1 mm. the red glow of argon was readily obtained with a voltage of 2000, but not with much less. After the discharge was once started, the difference of potentials at the terminals of the tube varied from 630 volts upwards.
The introduction of a capacity between the terminals of the Geissler tube, for example two plates of metal 1600 sq. cm. in area separated by a glass plate 1 cm. thick, made no difference in the red glow so long as the connexions were good and the condenser was quiet. As soon as a spark-gap was introduced, or the condenser began to emit the humming sound peculiar to it, the beautiful blue glow so characteristic of argon immediately appeared. (Phil. Mag. xliii. p. 77, 1897.)