Popular Science Monthly/Volume 55/May 1899/Liquid Air

 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.

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 hjdrate. 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
 Fig. 1.—Laboratory Liquefaction Apparatus of Dewar for the Production of Liquid Oxygen, etc. A, air or oxygen inlet; B, carbon-dioxide inlet; C, carbon-dioxide valve; D, regenerator coils; F, air or oxygen expansion valve; G, vacuum vessel with liquid oxygen; H, carbon-dioxide and air outlet; ${\displaystyle \circ }$, air coil; ${\displaystyle \bullet }$, carbon-dioxide coil.
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.

Fig. 2.—Diagram showing Working of Compression Apparatus for making Liquid Air.

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. A1, A2, A3 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, B1, which is surrounded by water of the ordinary temperature. This compressed and cooled air is then further compressed in the second pump, A2, 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 B2. Once more the air is compressed, this time in the cylinder A3, 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 B3. 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.

When the liquid is poured out of a vessel in the air it is rapidly converted into gas. The great lowering in the temperature causes a condensation of the moisture of the air in the form of a cloud. The same thing is seen when the cover is removed from a can containing the liquid. Of course, this liquid does not wet things as water does. When, however, as happened in New York, the lecturer deliberately pours a dipperful of the liquid upon a priceless Worth gown, he may expect to hear expressions of horror from the owner. This experiment passed off most successfully. Every trace of the liquid air was converted into invisible gases before the fleeting agony of the sympathetic audience had passed away.

The effects of very low temperature upon a number of substances have been studied, and some of them can easily be shown. Paraffin, resin, and rubber immersed in liquid air soon become very brittle, and the color of the resin is completely changed. A beefsteak or an onion also becomes brittle, and can be broken into small fragments by the blow of a hammer. A similar effect is produced in the case of some metals. Tin and iron, for example, become brittle, and the tenacity of the iron is greatly increased. A copper wire, however, retains its flexibility. At low temperatures the electric conductivity of all metals is increased. In general, the lower the temperature the greater the conductivity. If a copper wire could by any means be kept cold enough, electrical energy could be transmitted by it with but little loss—perhaps none. Mercury is easily frozen by surrounding it with liquid air, and the solid thus formed is very hard, though if it is cooled down sufficiently it becomes brittle.

Alcohol can be frozen without difficulty by means of liquid air. By the aid of the lowest temperatures hitherto attainable it has only been possible to convert alcohol into a pasty mass. The frozen alcohol is as hard as ice. When alcohol is dropped into liquid air the drops retain the globular form. When taken out on a platinum loop the flame of a Bunsen burner does not set fire to it.

Phosphorescence is greatly increased by cooling substances down to the temperature of liquid air. This has been shown by means of water, milk, paper, eggs, and feathers. An egg and a feather could be distinctly seen in a dark room.

Scarlet iodide of mercury is converted into the yellow variety when it is subjected to the temperature of liquid air. Some other colors are changed under the same circumstances, but not enough is known of this subject to warrant a general statement.

Attention has already been called to the fact that liquid air loses its nitrogen more rapidly than it does its oxygen, and that, after a time, the residue contains a large proportion of oxygen. As combustion is combination with oxygen, combustion or burning takes place more readily in contact with this liquid oxygen than it does in the air. If a lighted match is attached to the end of a steel watch spring, and this then plunged beneath the surface of liquid air, the spring will soon take fire and burn brilliantly, the sparks flying off for some distance in beautiful coruscations. Hair felt, which does not burn in the air, burns in a flash when soaked with liquid air. Finally, when liquid air is confined in any vessel not capable of sustaining an enormous pressure, say about ten thousand pounds to the square inch, the vaporization goes on until the vessel bursts or the stopper is forced out. It might therefore be used as an explosive without any addition, but its manipulation is not altogether simple.

Now for the inevitable question: Of what use is liquid air likely to be? This is a perfectly proper question, and yet, if scientific workers always stopped to ask it, and would not work unless they could find a favorable answer, progress would, to say the least, be much slower than it is. Most great practical discoveries have necessarily passed through the plaything stage. Some of the most important discoveries have not even furnished playthings, and have found no practical applications as this expression is commonly understood. But the production of liquid air, while furnishing mankind with a beautiful and instructive plaything, seems likely to find practical applications. We may look for these in four directions, to each of which a short paragraph may be devoted:

First, as a cooling agent. Low temperature is marketable. To be sure, the demand for the extremely low temperature that can be produced by liquid air does not exist to-day, but this concentrated low temperature can be diluted to suit conditions. The only question to be answered in this connection is, then, What is the cost of cold produced by liquid air? It is impossible for any one to answer this question at all satisfactorily at present. It can only be said that this is what experimenters are trying to find out. It appears, however, that they are on the way to cheap liquid air, and that as the processes are improved the price will become lower and lower.

Second, for the construction of motors. There is no doubt that liquid air with its enormous power of expansion can be used as a source of motive power just as compressed air is. In the case of steam it is necessary to heat the water in order to convert it into steam, and to heat the steam to give it the power of expansion. The cost is, in the first instance, that of the fuel. Given a certain amount of heat, and a certain amount of work is obtained. If liquid air is used, the problem is much the same. Engines must be run in order to compress the air which is to be liquefied. Every gallon of liquid air has been produced at the expense of work of some kind, low, the question arises at once. What proportion of the work that was put in that gallon of liquid air in the course of its production can be got out of it again? It is certain that all of it can not be got out unless all that we have ever learned about such matters goes for nothing. In dealing with the problem of the application of liquid air as a source of motive power we are therefore doubly handicapped. In the first place, we do not know the cost of the liquid when produced on the large scale; and, in the second place, we do not know the probable efficiency of a liquid-air motor. I say "we do not know." Perhaps Mr. Tripler and the others engaged in the experiments on this subject do know approximately. We certainly can not blame them for not telling us all they know at this stage of the work. It is unfortunate, however, that such a statement as was recently published in a popular magazine should be allowed to gain currency—apparently with the sanction of Mr. Tripler. The statement referred to is to the effect that ten gallons of liquid air have been made by the use of three gallons of liquid air in the engine. If that means that the ten gallons of liquid air are made from air at the ordinary pressure, the statement is in direct conflict with well-established principles. If it means that the ten gallons of liquid air are made from air that has already been partly compressed, we must know how much work has been done before the liquid-air engine began. Leaving out of consideration the question of cost, it may be pointed out that liquid-air engines would have the advantage of compactness, though they would necessarily be heavy, as they would have to be strong enough to stand the great pressure to which they would be subjected.

The third application of liquid air that has been suggested is in the preparation of an explosive. In fact, an explosive has been made and used for some time in which liquid air is one of the constituents. When the liquid from which a part of the nitrogen has boiled off is mixed with powdered charcoal, the mixture burns with great rapidity and great explosive force. "To make this explosive. Dr. Linde pours the liquid containing about forty or fifty per cent of oxygen on fragments of wood charcoal, two or four cubic millimetres in size. These are kept from scattering under the ebullition of the liquid by mixing them into a sort of sponge with about one third of their weight of cotton wool." Of course, this explosive must be made at or near the place where it is used. It has been in use in the way of a practical test in a coal mine at Pensberg, near Munich. It is claimed that the results were satisfactory. The chief advantage of the explosive is its cheapness, and the fact that it soon loses its power of exploding.

Finally, the fourth application of liquid air is for the purpose of getting oxygen from the air. This can be accomplished by chemical means, but the chemical method is somewhat expensive. Oxygen has commercial value, and cheap oxygen would be a decided advantage in a number of branches of industry. It will be observed that it is the liquid oxygen that makes possible the preparation of the explosive described in the last paragraph. Oxygen as such in the form of gas is of value in Deacon's process for the manufacture of chlorine. In this process air and hydrochloric acid are caused to act upon each other so as to form water and chlorine. The nitrogen takes no part in the act, and it would be an advantage if it could be left out. It is only the oxygen that is wanted. There are many other possible uses for oxygen either in the liquid or in the gaseous form, but these need no mention here.

In conclusion it may safely be said that it is highly probable that liquid air will be found to be a useful substance, but it is impossible at present to speak with any confidence of the particular uses that will be made of it. As work with it is being carried on energetically in at least three countries, we may confidently expect important developments in the near future.