Argon

Argon (from the Gr. ἀ-, privative, and ἒργον, work; hence meaning “inert”), a gaseous constituent of atmospheric air. For more than a hundred years before 1894 it had been supposed that the composition of the atmosphere was thoroughly known. Beyond variable quantities of moisture and traces of carbonic acid, hydrogen, ammonia, &c., the only constituents recognized were nitrogen and oxygen. The analysis of air was conducted by determining the amount of oxygen present and assuming the remainder to be nitrogen. Since the time of Henry Cavendish no one seemed even to have asked the question whether the residue was, in truth, all capable of conversion into nitric acid.

The manner in which this condition of complacent ignorance came to be disturbed is instructive. Observations undertaken mainly in the interest of Prout’s law, and extending over many years, had been conducted to determine afresh the densities of the principal gases—hydrogen, oxygen and nitrogen. In the latter case, the first preparations were according to the 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 1⁄1000 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 ½%. 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 ½% 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:—

“As far as the experiments hitherto published extend, we scarcely know more of the phlogisticated part of our atmosphere than that it is not diminished by lime-water, caustic alkalies, or nitrous air; that it is unfit to support fire or maintain life in animals; and that its specific gravity is not much less than that of common air; so that, though the nitrous acid, by being united to phlogiston, is converted into air possessed of these properties, and consequently, though it was reasonable to suppose, that part at least of the phlogisticated air of the atmosphere consists of this acid united to phlogiston, yet it may fairly be doubted whether the whole is of this kind, or whether there are not in reality many different substances confounded together by us under the name of phlogisticated air. I therefore made an experiment to determine whether the whole of a given portion of the phlogisticated air of the atmosphere could be reduced to nitrous acid, or whether there was not a part of a different nature to the rest which would refuse to undergo that change. The foregoing experiments indeed, in some measure, decided this point, as much the greatest part of air let up into the tube lost its elasticity; yet, as some remained unabsorbed, it did not appear for certain whether that was of the same nature as the rest or not. For this purpose I diminished a similar mixture of dephlogisticated [oxygen] and common air, in the same manner as before [by sparks over alkali], till it was reduced to a small part of its original bulk. I then, in order to decompound as much as I could of the phlogisticated air [nitrogen] which remained in the tube, added some dephlogisticated air to it and continued the spark until no further diminution took place. Having by these means condensed as much as I could of the phlogisticated air, I let up some solution of liver of sulphur to absorb the dephlogisticated air; after which only a small bubble of air remained unabsorbed, which certainly was not more than 1⁄120 of the bulk of the dephlogisticated air let up into the tube; so that, if there be any part of the dephlogisticated air of our atmosphere which differs from the rest, and cannot be reduced to nitrous acid, we may safely conclude that it is not more than 1⁄120 part of the whole.”

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.  
  
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Fig. 1.  
  
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.  
  
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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.)

The behaviour of argon at low temperatures was investigated by K.S. Olszewski (Phil. Trans., 1895, p. 253). The following results are extracted from the table given by him:—

Name. | Critical  
Temperature,  
Cent. | Critical  
Pressure,  
Atmos. | Boiling  
Point  
Cent. | Freezing  
Point,  
Cent.  
---|---|---|---|---  
Nitrogen | −146.0 | 35.0 | −194.4 | −214.0  
Argon | −121.0 | 50.6 | −187.0 | −189.6  
Oxygen | −118.8 | 50.8 | −182.7 | ?  
  
The smallness of the interval between the boiling and freezing points is noteworthy.

From the manner of its preparation it was clear at an early stage that argon would not combine with magnesium or calcium at a red heat, nor under the influence of the electric discharge with oxygen, hydrogen or nitrogen. Numerous other, attempts to induce combination also failed. Nor does it appear that any well-defined compound of argon has yet been prepared. It was found, however, by M.P.E. Berthelot that under the influence of the silent electric discharge, a mixture of benzene vapour and argon underwent contraction, with formation of a gummy product from which the argon could be recovered.

The facts detailed in the original memoir led to the conclusion that argon was an element or a mixture of elements, but the question between these alternatives was left open. The behaviour on liquefaction, however, seemed to prove that in the latter case either the proportion of the subordinate constituents was small, or else that the various constituents were but little contrasted. An attempt, somewhat later, by Ramsay and J. Norman Collie to separate argon by diffusion into two parts, which should have different densities or refractivities, led to no distinct effect. More recently Ramsay and M.W. Travers have obtained evidence of the existence in the atmosphere of three new gases, besides helium, to which have been assigned the names of neon, krypton and xenon. These gases agree with argon in respect of the ratio of the specific heats and in being non-oxidizable under the electric spark. As originally defined, argon included small proportions of these gases, but it is now preferable to limit the name to the principal constituent and to regard the newer gases as “companions of argon.” The physical constants associated with the name will scarcely be changed, since the proportion of the “companions” is so small. Sir William Ramsay considers that probably the volume of all of them taken together does not exceed 1⁄400th part of that of the argon. The physical properties of these gases are given in the following table (Proc. Roy. Soc. lxvii. p. 331, 1900):—

  | Helium. | Neon. | Argon. | Krypton. | Xenon.  
---|---|---|---|---|---  
Refractivities (air = 1) |  .1238 |  .2345 |  .968 |  1.449 |  2.364  
Densities (O = 16) | 1.98 |  9.97 |  19.96 |  40.88 |  64  
Boiling points at 760 mm. | c. 6°1 abs. | ? | 86.9° abs. | 121.33° abs. | 163.9° abs.  
Critical temperatures | ? | below 68° abs. | 155.6° abs. | 210.5° abs. | 287.7° abs.  
Critical pressures | ? | ? |  40.2 metres. |  41.24 metres. |  43.5 metres.  
Weight of 1 c.c. of liquid | ? | ? |  1.212 gm. |  2.155 gm. |  3.52 gm.  
  
The glow obtained in vacuum tubes is highly characteristic, whether as seen directly or as analysed by the spectroscope.

Now that liquid air is available in many laboratories, it forms an advantageous starting-point in the preparation of argon. Being less volatile than nitrogen, argon accumulates relatively as liquid air evaporates. That the proportion of oxygen increases at the same time is little or no drawback. The following analyses (Rayleigh, Phil. Mag., June 1903) of the vapour arising from liquid air at various stages of the evaporation will give an idea of the course of events:—

Percentage of  
Oxygen. | Percentage of  
Argon. | Argon as a Percentage  
of the Nitrogen and  
Argon.  
---|---|---  
30 | 1.3 |  1.9  
43 | 2.0 |  3.5  
64 | 2.0 |  5.6  
75 | 2.1 |  8.4  
90 | 2.0 | 20.0  
  
(R.)

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1 Sir James Dewar, Compt. Rend. (1904), 139, 261 and 241.

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