Part 4

[F] Chantre, 1884; Hoernes, 1892; Bertrand and Reinach, 1894 a; Sergi, 1898 a; and Orsi (Bull. Paletnologia Italiana, xi, 1885, p. 1 _et seq._) are best authorities. See also Hallstatt in the subject index of our Bibliography, soon to be published as a Special Bulletin of the Boston Public Library.

[G] Hoernes, 1892, p. 529; Bertrand, 1876 a, second edition, pp. 207-216, fixes about 800 B. C.; but 1894 a, p. 80, carries it back to 1200-1300 B. C.

[H] Zuckerkandl, 1883, p. 96.

[I] Weisbach, 1897 b.

[J] This fact has been established beyond doubt by the recent great work of Studer and Bannwarth, Crania Helvetica Antiqua, 1894. _Vide_ p. 13. Sergi's attempt to interpret the data otherwise (1898 a, p. 67) is entirely erroneous. Gross's data apparently refer entirely to the later period of Teutonic invasions in the iron age (1883, p. 106). _Cf._ Munro, pp. 537 and 541.

[K] Popular Science Monthly, December, 1897, p. 151.

[L] From Montelius, 1897.

[M] _Cf._ maps and data in J. Geikie, 1894; Penck, 1884; and Niederle, 1893, p. 25.

[N] Bertrand, 1876 a and 1876 b, gives a full account of it. The best recent authorities upon Scandinavian culture are Sophus Mueller, 1897, and Montelius, 1895 b. Other works of reference are those of Worsaae, Nilsson, Hildebrand, Madsen and Rygh, full titles being given in our supplementary Bibliography of the Anthropology and Ethnology of Europe. Comprising nearly two thousand titles, it will be provided with a detailed subject index.

[O] Bertrand, 1876 b, p. 40.

[P] Reinach, 1892, pp. 72-78, for severe criticism of Penka's hypotheses.

LIQUID AIR.

BY IRA REMSEN,

PROFESSOR OF CHEMISTRY IN THE JOHNS HOPKINS UNIVERSITY.

Water, the substance most familiar to us, is known in the liquid, in the solid, and in the gaseous state. Everybody knows that by heating the solid it passes into the liquid state, and that by heating the liquid it passes into the form of gas or vapor. So also everybody knows that when the vapor of water is cooled it is liquefied, and that by cooling liquid water sufficiently it becomes solid or turns to ice. In the same way many of the substances that are known to us as liquids, such as alcohol and ether, can be converted into the form of gas or vapor by heat. In fact, this is true of most liquids. The temperature at which a solid passes into the liquid state is called its melting point, and the temperature at which a liquid passes into the gaseous state is called its boiling point. The boiling point of water, for example, is 100° C. (212° F.) in the open air. But the boiling point varies with the pressure exerted upon the surface. The pressure that we ordinarily have to deal with is that of the atmosphere. If the pressure is increased the boiling point is raised, and if the pressure is decreased the boiling point is lowered. In dealing, then, with the conversion of a gas into a liquid, or that of a liquid into a gas, both the temperature and the pressure have to be considered.

Just as water is most familiar to us in the liquid form, so there are substances that are most familiar to us in the gaseous form. In fact, the only gaseous substances that can be said to be familiar to everybody are the gases contained in the air. The principal constituents of the air are nitrogen and oxygen, which form respectively about four fifths and one fifth of its bulk. Besides these gases, however, the air contains water vapor, carbonic-acid gas, ammonia, argon in small quantities, and many other substances in still smaller quantities. For the purposes of this article it is only necessary to have in mind the nitrogen, oxygen, water vapor, and carbonic acid. Of these, the water vapor is easily converted into liquid, as, for example, in the formation of rain, while the other constituents are liquefied with difficulty. The name "liquid air" is applied to the substance that is obtained by converting the air as a whole into a liquid; but in this process the water and the carbonic acid become solid and can be filtered from the liquid so that the latter consists almost wholly of oxygen and nitrogen. A few years ago this liquid was obtainable in only very small quantities. To-day, thanks especially to the efforts of Mr. Charles E. Tripler, of New York, it can be produced in any desired quantity, and at moderate cost. In consequence of this, it has come to be talked about in a familiar way, and many persons have had the privilege of seeing and feeling it, and of learning something about its wonderful properties. The object of this article is to explain the method employed in the production of liquid air, to give an account of some of its properties, and to indicate some of the uses to which it may possibly be put.

In the older text-books of physics and of chemistry certain gases were classed as "permanent," under the impression that these could not be liquefied, and this impression was based upon the fact that all efforts to liquefy them had failed. A brief account of these efforts will be helpful.

Among the so-called permanent gases was chlorine. An English chemist, Northmore, first succeeded, early in this century, in liquefying chlorine. His work was, however, lost sight of, and in 1823 Faraday at the Royal Institution showed independently that this transformation of gaseous chlorine into the liquid can be effected comparatively easily. The method used by him is this: When chlorine gas is passed into cold water it forms with the water a solid product known as chlorine hydrate. If kept well cooled this hydrate can be dried. If then its temperature is raised even to the ordinary temperature of the room, the solid hydrate is decomposed into liquid water and gaseous chlorine. Faraday put some of the solid hydrate into a stout glass tube sealed at one end and bent at the middle. The other end of the tube was then closed. The tube was then suspended so that the two ends were turned downward. On gently warming the end in which was the solid hydrate, this was decomposed into chlorine and water. But the gas given off would under ordinary conditions have occupied a much larger space than the solid hydrate. Being prevented from expanding by the tube in which it was inclosed, it was under very considerable pressure. The end of the tube that was not warmed was cooled, and in this end, in consequence of the pressure and the comparatively low temperature, chlorine, which is gaseous under the ordinary pressure of the air, appeared as a liquid. The general method made use of by Faraday in this classical experiment is that which is always made use of for the purpose of liquefying gases, but for some gases pressures very much higher and temperatures very much lower are required. Faraday himself succeeded in liquefying all the gases then known except oxygen, hydrogen, nitrogen, nitric oxide, and marsh gas. He subjected oxygen to a pressure of about one thousand pounds to the square inch, or nearly seventy atmospheres, but it showed no signs of liquefaction. Later experimenters increased the pressure to four thousand pounds to the square inch, with no better results, so that it is not surprising that it came to be held that some gases are permanent.

Within comparatively recent years several gases have been liquefied on the large scale by means of pressure. These are ammonia, carbonic acid, nitrous oxide, and chlorine. Ammonia is used for producing low temperatures, as in breweries and in cold-storage plants and in the manufacture of ice; carbonic acid, for fire extinguishers and for charging beer with the gas; nitrous oxide, for producing anæsthesia; and chlorine in connection with several branches of chemical manufacture. The production of low temperatures by means of liquid ammonia and of liquid carbonic acid will be more fully dealt with further on, when the principles involved will be briefly presented. It is to be borne in mind that these substances are liquefied by means of pressure alone, at temperatures that are easily reached, so that it appears that by mechanical pressure it is possible to produce low temperatures. In 1869 an important fact was discovered by Andrews. It was that for every gas there is a temperature above which it is impossible to liquefy it by pressure. Thus, if chlorine is at any temperature above 146° C. (294° F.) it can not be liquefied. This temperature is called the "critical temperature" of chlorine. The pressure to which the gas must be subjected at the "critical temperature" in order that the gas may be liquefied is called the "critical pressure." In the case of chlorine this is 93.5 atmospheres. Now, the critical temperature of the gases that were called permanent gases are very low--lower than could be reached by the means at the command of earlier experimenters. The critical temperature of oxygen, for example, is -118.8° C. (-182° F.), while that of nitrogen is -146° C. (-230° F.). The critical pressures are 50.8 and 35 atmospheres respectively. As there is no difficulty in obtaining these pressures, the problem of liquefying oxygen and nitrogen and air resolves itself into finding a method of producing temperatures below the critical temperatures of these gases.

It is well known that a temperature somewhat below the freezing point of water can be produced artificially by mixing ice and salt. The ordinary ice-cream freezer is a familiar application of this method of producing cold. Other freezing mixtures that are sometimes used consist of calcium chloride and snow, that gives the temperature -48° C. (-54.4° F.), and solid carbonic acid and ether, that is capable of lowering the temperature to -100° C. (-148° F.). But even with the latter mixture it is not possible to reach the critical temperature of oxygen or that of nitrogen. How, then, is it possible to reach these extremely low temperatures?

In order to answer this question it will be necessary to take into consideration certain temperature changes that are observed when solids are melted and liquids are boiled, as well as when gases are liquefied and liquids are frozen. When heat is applied to a mass of ice at its melting point it melts and forms a mass of water having the same temperature. Heat disappears in the operation. It is stored up in the water. This disappearance of heat that accompanies the melting of ice can be shown in a very striking way by mixing a certain weight of ice with the same weight of water that has been heated to 80° C. (176° F.). The ice will melt and all the water obtained will be found to have the temperature of the melting ice--that is, 0° C. (32° F.). The water of 80° C. is thus cooled down to 0° by the melting of the ice. Again, when heat is applied to water its temperature rises until the boiling point is reached. Then it is converted into vapor, but this vapor has the temperature of the boiling water. During the process of boiling there is no rise in the temperature of the water or of the vapor. Heat disappears, therefore, or is used up in the process of vaporization. Similar phenomena are observed whenever a solid is melted or a liquid is boiled. When, however, a gas is liquefied it gives up again the heat that is absorbed by it when it is formed from a liquid; and so also when a liquid solidifies it gives up the heat it absorbs when it is formed from a solid.

But it is not necessary that a gas should be converted into a liquid in order that it should give up heat. Whenever it is compressed it becomes warmer. Some of the heat stored up in it is, as it were, squeezed out of it. Conversely, whenever a gas expands, it takes up heat and, of course, surrounding objects from which the heat is taken become colder. Now, it is a comparatively simple matter to compress air. Every wheelman knows that, and he also knows that the process causes a rise in temperature; at least he knows it if he uses a small hand pump. With large pumps run by steam any desired pressure can be reached. This is simply a question of securing the proper engines, and vessels sufficiently strong to stand the pressure. It has already been pointed out that several gases are now liquefied on the large scale by means of pressure. It is to be noted that low temperatures can be produced by converting certain gases, such as ammonia and carbonic acid, into liquids, and by compressing certain gases, as, for example, air. When liquefied gases are used it is only necessary to allow them to pass rapidly into the gaseous state, when more or less heat is absorbed. This is the basis for the use of liquid ammonia in the manufacture of ice. A vessel containing the liquid ammonia is placed in another containing water. The inner vessel being opened, the liquid ammonia is rapidly converted into the gas; heat is absorbed from the water; it freezes. When a vessel containing liquid carbonic acid is opened so that the gas that is formed escapes through a small valve, so much heat is absorbed that a part of the liquid carbonic acid is itself frozen. In this case the substance is present in all three states of aggregation--the solid, the liquid, and the gaseous. The use of a mixture of ether and solid carbonic acid as a freezing mixture has already been referred to. Its value depends, of course, principally upon the fact that solid carbonic acid is liquefied, and the liquid then converted into gas, both of which operations involve absorption of heat.

We are now prepared to understand the important experiments of Cailletet and of Pictet, the results of which were published in 1877. It should be said that they worked independently of each other--Cailletet in Paris and Pictet in Geneva. Pictet liquefied carbonic acid and sulphur dioxide by pressure. The liquid carbonic acid was passed through a tube that was surrounded by liquid sulphur dioxide boiling in a partial vacuum. The liquid carbonic acid thus cooled was then boiled under diminished pressure in a jacket surrounding a tube in which the gas to be liquefied was contained under high pressure. When this gas was allowed to escape from a small opening its temperature was so reduced by the expansion that a part of it was liquefied in the tube and passed off as a liquid. Cailletet worked in essentially the same way, but on a smaller scale. Neither of these experimenters liquefied oxygen or nitrogen on the large scale, but they pointed out the way that must be followed in order that success may be attained. They destroyed the belief in "permanent" gases.

Later experimenters in this field are Wroblewski, Olszewski, and Dewar, who have been interested mainly in the purely scientific side of the problem, while Linde in Germany, Hampson in England, and Tripler in the United States have their minds on the practical side. Notwithstanding the low temperatures involved in the experiments, a number of heated discussions have been carried on in the scientific journals touching the question of priority. To the unprejudiced observer it appears that all of those named above are entitled to credit. They have all helped the cause along, but just how to apportion the credit no one knows. In a general way, however, some of the results obtained by each in turn should be given. Wroblewski and Olszewski have carried on the work begun by Cailletet and Pictet, and have produced lower temperatures. In the latest form of apparatus used by Olszewski, liquid ethylene is used as the cooling agent. Its boiling point is -102° C. (-151.6° F.). By causing it to boil rapidly under diminished pressure a temperature below the critical temperature of oxygen can be reached. As early as 1891 Olszewski obtained as much as two hundred cubic centimetres of liquid air by this method. Dewar has also made use of liquid ethylene. This was passed through a spiral copper tube surrounded by solid carbonic acid and ether. It was then passed into a cylinder surrounded by another cylinder containing solid carbonic acid and ether. A spiral copper tube, which runs through the outer cylinder and also through the inner cylinder in which the ethylene was boiling under diminished pressure, carried the air. This was liquefied and then collected in a vacuum vessel below. Later he found that air can be liquefied by using liquid carbonic acid alone as the cooling agent. A sectional drawing of his apparatus described in 1896 is given herewith. As he remarks: "With this simple machine, one hundred cubic centimetres of liquid oxygen can readily be obtained, the cooling agent being carbon dioxide, at the temperature of -79°. If liquid air has to be made by this apparatus, then the carbonic acid must be kept under exhaustion of about one inch of mercury pressure, so as to begin with a temperature of -115°."

The introduction of the vacuum vessel by Dewar has been of great service in all the work on liquefied gases. A vacuum vessel is a double-walled glass vessel, as shown in Fig. 1, G. The space between the inner and outer walls of the vessel is exhausted by means of an air pump before it is closed. The vessel is therefore surrounded by a vacuum. As heat is not conducted by a vacuum, it is possible to keep specimens of liquefied gases in such vessels for a surprisingly long time. Heat enough can not pass through the vacuum to vaporize the liquid rapidly. The most common form of these vessels is that of a globe. Such a vessel is known as a Dewar globe or bulb.

It has been found that liquid air can be kept very well by putting it in a tin or galvanized iron vessel, which in turn is placed in a larger one, and then filling the space between the two with felt. Under these conditions vaporization takes place quite slowly, and it is possible to transport the liquid comparatively long distances. It has, for example, been transported from New York to Baltimore and Washington. In one case with which the writer is familiar two cans were taken from Mr. Tripler's laboratory in the morning, delivered at the Johns Hopkins University in the afternoon, and used to illustrate a lecture in the evening. After the lecture there was enough left for certain experiments that were carried on during the rest of the night.

Tripler, Linde, and Hampson have all succeeded in devising forms of apparatus by means of which air can be liquefied without the aid of other cooling agents than the expanding air. In principle the methods employed by these three workers are essentially the same. It appears from the published statements that at the present time Tripler's plant is the most efficient. While a few years ago a half pint or so of liquid air is said to have cost five hundred dollars, now five gallons can be made for about twenty dollars, and probably much less. The general working of Tripler's apparatus can be made clear by the aid of the accompanying drawing, Fig. 2. A^1, A^2, A^3 represent steam compression pumps. Air is taken through I from above the roof of the laboratory. In the first pump it is compressed to sixty-five pounds to the square inch. It, of course, becomes heated as it is compressed. In order to cool it down again it is passed through a coil, B^1, which is surrounded by water of the ordinary temperature. This compressed and cooled air is then further compressed in the second pump, A^2, to four hundred pounds to the square inch. Again it is cooled in the same way as before by means of water which circulates around the coil B^2. Once more the air is compressed, this time in the cylinder A^3, in which it is subjected to a pressure of two thousand to twenty-five hundred pounds to the square inch; and then this compressed air is brought down to the ordinary temperature in the cooler B^3. The air under this great pressure is now passed through the purifier C, where it is freed from particles of dust and to a great extent from moisture. From C the air passes into the inner bent tube, about thirty feet in length, until it reaches D. This may be called the critical point of the apparatus. Here is situated a needle valve from which the air is allowed to escape. It, of course, expands enormously, and is correspondingly cooled. This very cold air passes into the space between the inner and outer tubes, and finally escapes at F. The result of this is that the compressed air in the inner tube is soon cooled down so far that a considerable part of the air that escapes at D appears in the liquid form. This collects in the lower part of the jacket, and on opening the stopcock at E the liquid escapes in a stream the size of one's finger.

In Mr. Tripler's laboratory the liquid is collected in the cans already referred to. Although for the reasons mentioned the evaporation of the liquid is comparatively slow, it is constantly going on, and as the gas formed occupies a very much larger volume under the pressure of the atmosphere than the liquid from which it is formed, it is necessary to leave the cans loosely covered. Otherwise the pressure would increase to such an extent as to burst any but the strongest vessels. One cubic foot of liquid air gives at atmospheric pressure eight hundred cubic feet of gaseous air.

Liquid air obtained as described is a turbid, colorless liquid. The turbidity is due to the presence of solid water and solid carbonic acid. By passing the liquid through a paper filter the solids are removed, and a transparent liquid is thus obtained. This, as already stated, consists mostly of nitrogen and oxygen in the proportion of about four fifths of the former to one fifth of the latter. Though it should not be forgotten that this liquid contains argon in small quantity, besides three or four other substances in still smaller quantities, as has recently been shown by Professor Ramsay, we may disregard everything except the nitrogen and oxygen. Liquid air is a _mixture_ of these two substances. They are not chemically combined as hydrogen and oxygen are, for example, in water. This mixture boils at -191° C. (-312° F.), which is the temperature of the liquid as it is in the cans. As the nitrogen boils at a lower temperature (-194° C. or 318° F.) than oxygen (-183° C. or 297° F.), more nitrogen is converted into gas in a given time than oxygen, and after a time the liquid that is left is much richer in oxygen than ordinary air. When liquid air is poured upon water it, being a little lighter than the water, floats, not quietly, to be sure, but in a very troubled way. Soon, however, the liquid sinks to the bottom because the nitrogen, which is the lighter constituent, passes into the gaseous state, and the liquid oxygen which is left is a little heavier than water. The experiment is a very beautiful one. A scientific poet could alone do justice to it. The beauty is enhanced by the fact that while liquid air is colorless, or practically so, liquid oxygen is distinctly blue.

Although liquid air has the temperature -191° C. (-312° F.), one can without danger pass the hand through it rapidly. The sensation is a new one, but it is evanescent. Very serious results would follow if the hand were allowed to remain in the liquid even for a short time. The tissues would be killed. So also, it is possible to pass the hand rapidly through molten lead without injury. In the latter case the moisture on the hand is converted into vapor which forms a protecting cushion between the hand and the hot liquid; while, in the former case, the heat of the hand converts the liquid air immediately surrounding it into gas which prevents the liquid from coming in contact with the hand.