A History of Science — Volume 5

by Henry Smith Williams; Edward Huntington Williams

Now after this statement, it is clear that what the low-temperature worker does when he would liquefy a gas is to become the champion of the force of cohesion. He cannot directly aid it, for so far as is known it is an unalterable quantity, like gravitation. But he can accomplish the same thing indirectly by weakening the power of the rival force. Thus, if he encloses a portion of gas in a cylinder and drives a piston down against it, he is virtually aiding cohesion by forcing the molecules closer together, so that the hold of cohesion, acting through a less distance, is stronger. What he accomplishes here is not all gain, however, for the bounding molecules, thus jammed together, come in collision with one another more and more frequently, and thus their average activity of vibration is increased and not diminished; in other words, the temperature of the gas has risen in virtue of the compression. Compression alone, then, will not avail to enable cohesion to win the battle.

But the physicist has another resource. He may place the cylinder of gas in a cold medium, so that the heat vibrations sent into it will be less vigorous than those it sends out. That is a blow the molecule cannot withstand. It is quite impotent to cease sending out the impulses however little comes in return; hence the aggregate motion becomes less and less active, until finally the molecule is moving so sluggishly that when it collides with its fellow cohesion is able to hold it there. Cohesion, then, has won the battle, and the gas has become a liquid.

Such, stated in terms of the mechanical theory of heat, is what is brought to pass when a gas is liquefied in the laboratory of the physicist. It remains only to note that different chemical substances show the widest diversity as to the exact point of temperature at which this balance of the expansive and cohesive tendencies is affected, but that the point, under uniform conditions of pressure, is always the same for the same substance. This diversity has to do pretty clearly with the size of the individual molecules involved; but its exact explanation is not yet forthcoming, and, except in a general way, the physicist would not be able to predict the "critical temperature" of any new gas presented to him. But once this has been determined by experiment, he always knows just what to expect of any given substance. He knows, for example, that in a mixture of gases hydrogen would still remain gaseous after all the others had assumed the liquid state, and most of them the solid state as well.

These mechanical conceptions well in mind, it is clear that what the would-be liquefier of gases has all along sought to attain is merely the insulation of the portion of matter with which he worked against the access of heat-impulse from its environment. It is clear that were any texture known which would permit a heat-impulse to pass through it in one direction only, nothing more would be necessary than to place a portion of gas in such a receptacle of this substance, so faced as to permit egress but not entrance of the heat, and the gas thus enclosed, were it hydrogen itself, would very soon become liquid and solid, through spontaneous giving off of its energy, without any manipulation whatever. Contrariwise, were the faces of the receptacle reversed, a piece of iron placed within it would be made red-hot and melted though the receptacle were kept packed in salt and ice and no heat applied except such as came from this freezing mixture. One could cook a beefsteak with a cake of ice had he but such a material as this with which to make his stove. Not even Rumford or our modern Edward Atkinson ever dreamed of such economy of fuel as that.

But, unfortunately, no such substance as this is known, nor, indeed, any substance that will fully prevent the passage of heat-impulses in either direction. Hence one of the greatest tasks of the experimenters has been to find a receptacle that would insulate a cooled substance even partially from the incessant bombardment of heat-impulses from without. It is obvious that unless such an insulating receptacle could be provided none of the more resistent gases, such as oxygen, could be long kept liquid, even when once brought to that condition, since an environment of requisite frigidity could not practicably be provided.

But now another phase of the problem presents itself to the experimenter. Oxygen has assumed the quiescent liquid state, to be sure, but in so doing it has fallen below the temperature of its cooling medium; hence it is now receiving from that medium more energy of vibration than it gives, and unless this is prevented very soon its particles will again have power to kick themselves apart and resume the gaseous state. Something, then, must be done to insulate the liquefied gas, else it will retain the liquid state for too short a time to be much experimented with. How might such insulation be accomplished?

The most successful attack upon this important problem has been made by Professor Dewar. He invented a receptacle for holding liquefied gases which, while not fulfilling the ideal conditions referred to above, yet accomplishes a very remarkable degree of heat insulation. In consists of a glass vessel with double walls, the space between which is rendered a vacuum of the highest practicable degree. This vacuum, containing practically no particles of matter, cannot, of course, convey heat-impulses to or from the matter in the receptacle with any degree of rapidity. Thus one of the two possible means of heat transfer is shut off and a degree of insulation afforded the liquefied substance. But of course the other channel, ether radiation, remains. Even this may be blocked to a large extent, however, by leaving a trace of mercury vapor in the vacuum space, which will be deposited as a fine mirror on the inner surface of the chamber. This mirror serves as an admirable reflector of the heat-rays that traverse the vacuum, sending more than half of them back again. So, by the combined action of vacuum and mirror, the amount of heat that can penetrate to the interior of the receptacle is reduced to about one-thirtieth of what would enter an ordinary vessel. In other words, a quantity of liquefied gas which would evaporate in one minute from an ordinary vessel will last half an hour in one of Professor Dewar's best vacuum vessels. Thus in one of these vessels a quantity of liquefied air, for example, can be kept for a considerable time in an atmosphere at ordinary temperature, and will only volatilize at the surface, like water under the same conditions, though of course more rapidly; whereas the same liquid in an ordinary vessel would boil briskly away, like water over a fire. Only, be it remembered, the air in "boiling" is at a temperature of about one hundred and eighty degrees below zero, so that it would instantly freeze almost any substance placed into it. A portion of alcohol poured on its surface will be changed quickly into a globule of ice, which will rattle about the sides of the vessel like a marble. That is not what one ordinarily thinks of as a "boiling" temperature.

If the vacuum vessel containing a liquefied gas be kept in a cold medium, and particularly if two vacuum tubes be placed together, so that no exposed surface of liquid remains, a portion of liquefied air, for example, may be kept almost indefinitely. Thus it becomes possible to utilize the liquefied gas for experimental investigation of the properties of matter at low temperatures that otherwise would be quite impracticable. Great numbers of such experiments have been performed in the past decade or so by all the workers with low temperatures already mentioned, and by various others, including, fittingly enough, the holder of the Rumford professorship of experimental physics at Harvard, Professor Trowbridge. The work of Professor Dewar has perhaps been the most comprehensive and varied, but the researches of Pictet, Wroblewski, and Olzewski have also been important, and it is not always possible to apportion credit for the various discoveries accurately, since the authorities themselves are in unfortunate disagreement in several questions of priority. But in any event, such questions of exact priority have no great interest for any one but the persons directly involved. We may quite disregard them here, confining attention to the results themselves, which are full of interest.

The questions investigated have to do with the physical properties, such as electrical conductivity, magnetic condition, light-absorption, cohesion, and chemical affinities of matter at excessively low temperatures. It is found that in all these regards most substances are profoundly modified when excessively cooled. Thus if a piece of any pure metal is placed in an electric circuit and plunged into liquid air, its resistance to the passage of the electricity steadily decreases as the metal cools, until at the temperature of the liquid it is very trifling indeed. The conclusion seems to be justified that if the metal could be still further cooled until it reached the theoretical "absolute zero," or absolutely heatless condition, the electrical resistance would also be nil. So it appears that the heat vibrations of the molecules of a pure metal interfere with the electrical current. The thought suggests itself that this may be because the ether waves set up by the vibrating molecules conflict with the ether strain which is regarded by some theorists as constituting the electrical "current." But this simple explanation falters before further experiments which show, paradoxically enough, that the electrical resistance of carbon exactly reverses what has just been said of pure metals, becoming greater and greater as the carbon is cooled. If an hypothesis were invented to cover this case there would still remain a puzzle in the fact that alloys of metals do not act at all like the pure metals themselves, the electrical resistance of such alloys being, for the most part, unaffected by changed temperature. On the whole, then, the facts of electrical conduction at low temperatures are quite beyond the reach of present explanation. They must await a fuller knowledge of molecular conditions in general than is at present available—a knowledge to which the low-temperature work itself seems one of the surest channels.

Even further beyond the reach of present explanation are the facts as to magnetic conditions at low temperatures. Even as to the facts themselves different experimenters have differed somewhat, but the final conclusion of Professor Dewar is that, after a period of fluctuation, the power of a magnet repeatedly subjected to a liquid-air bath becomes permanently increased. Various substances not markedly magnetic at ordinary temperatures become so when cooled. Among these, as Professor Dewar discovered, is liquid oxygen itself. Thus if a portion of liquid air be further cooled until it assumes a semi-solid condition, the oxygen may be drawn from the mass by a magnet, leaving a pure nitrogen jelly. These facts are curious enough, and full of suggestion, but like all other questions having to do with magnetism, they hold for the present generation the double fascination of insoluble mystery. To be sure, one may readily enough suggest that if magnetism be really a whirl in the ether, this whirl is apparently interfered with by the waves of radiant heat; or, again, that magnetism is presumably due to molecular motions which are apparently interfered with by another kind of molecular motions which we call heat vibrations; but there is a vagueness about the terms of such guesses that leaves them clearly within the category of explanations that do not explain.