Fig. 13.—Calorimetric Apparatus.
The apparatus (fig. 13) consists of a large vacuum vessel A, of 2 or 3 litres’ capacity, containing liquid air, in which is inserted a smaller vacuum vessel B, of 25-30 c.c. capacity, having sealed to it a long narrow tube G that projects above the mouth of A and is held in place by some loosely packed cotton wool. To the top of this tube the test tube C, containing the material under investigation, is connected by a piece of flexible rubber tubing D; this enables C to be tilted so as to throw a piece or pieces of the contained material into the calorimeter. An improved form of this receptacle, attached to B by a flexible tube at D′, is shown at C′. In this P is a wire movable through a cork Q and having at its end a hook by which a piece of the substance under examination can be pulled up and dropped into B. In the absence of other arrangements the substance is at the temperature of the room, but when lower initial temperatures are desired a vacuum vessel H containing solid carbonic acid, liquid ethylene, air or other gas, can be placed to envelop C or C′, or higher temperatures may be obtained by filling the surrounding vessel with vapour of water or other liquids. The gas volatilized in B is conveyed by a side tube E to be collected in a graduated receiver F over water, oil or other liquid. If liquid hydrogen is to be used as the calorimetric substance the instrument must be so modified as to prevent the ordinary atmosphere from entering G, and to that end a current of hydrogen supplied from a Kipp apparatus is arranged to flow continuously through D and E until the moment of making the experiment, when it is cut off by a suitable stop-cock. In this case the outer vessel must contain liquid hydrogen instead of liquid air.
Table X.
| Substance. | 18° to −78° C., or, at −30° C. | −78° to −188° C., or, at −133° C. | −188° to −252° C., or, at −220° C. |
| Diamond | 0.0794 | 0.0190 | 0.0043 |
| Graphite | 0.1341 | 0.0599 | 0.0133 |
| Ice | 0.463* | 0.285 | 0.146 |
* This is from −18° to −78° in the ice experiment.
Dewar used pure metallic lead for the purpose of conveying
definite amounts of heat to liquid gas calorimeters of this kind,
that metal being selected on the ground of the small variation in
its specific heat at low temperatures. He was thus able to
determine the latent heats of evaporation of liquid oxygen,
nitrogen and hydrogen directly at their boiling points, and he
also ascertained the specific heats of a large number of inorganic
and organic bodies, and of some gases in the solid state, such as
carbon dioxide, sulphurous acid and ammonia. Perhaps his
most interesting results were those which showed the variation
in the specific heats of diamond, graphite and ice as typical
bodies (table X.). With Professor Curie he used both the liquid
oxygen and the liquid hydrogen calorimeter for preliminary
measurements of the rate at which radium bromide gives out
energy at low temperatures. The quantity of the salt available
was 0.42 gram, and the thermal evolutions were as follows:—
| Gas evolved per minute. | Calories per hour. | ||
| Liquid oxygen | 5.5 cc. | 22.8 | Crystals. |
| Liquid hydrogen | 51.0 ” | 31.6 | |
| Melting ice | .. | 24.1 | |
| Liquid oxygen | 2.0 ” | 8.3 | After fusion. |
| Liquid oxygen | 2.5 ” | 10.3 | Emanation condensed. |
The apparent increase of heat evolution at the temperature of liquid hydrogen was probably due to the calorimeter being too small; hydrogen spray was thus carried away with the gas, making the volume of gas too great and inferentially also the heat evolved.
Liquid air and liquid hydrogen calorimeters open up an almost unlimited field of research in the determination of specific heats and other thermal constants, and are certain to become common laboratory instruments for such purposes.
Chemical Action.—By extreme cold chemical action is enormously reduced, though it may not in all cases be entirely abolished even at the lowest temperatures yet attained; one reason for this diminution of activity may doubtless be sought in the fact that in such conditions most substances are solid, that is, in the state least favourable to chemical combination. Thus an electric pile of sodium and carbon ceases to yield a current when immersed in liquid oxygen. Sulphur, iron and other substances can be made to burn under the surface of liquid oxygen if the combustion is properly established before the sample is immersed, and the same is true of a fragment of diamond. Nitric oxide in the gaseous condition combines instantly with free oxygen, producing the highly-coloured gas, nitric peroxide, but in the solid condition it may be placed in contact with liquid oxygen without showing any signs of chemical action. If the combination of a portion of the mixture is started by elevation of temperature, then detonation may take place throughout the cooled mass. The stability of endothermic bodies like nitric oxide and ozone at low temperatures requires further investigation. The behaviour of fluorine, which may be regarded as the most active of the elements, is instructive in this respect. As a gas, cooled to −180° C. it loses the power of attacking glass; similarly silicon, borax, carbon, sulphur and phosphorus at the same temperature do not become incandescent in an atmosphere of the gas. Passed into liquid oxygen, the gas dissolves and imparts a yellowish tint to the liquid; if the oxygen has been exposed to the air for some hours, the fluorine produces a white flocculent precipitate, which if separated by filtering deflagrates with violence as the temperature rises. It appears to be a hydrate of fluorine. As a liquid at −210° fluorine attacks turpentine also cooled to that temperature with explosive force and the evolution of light, while the direction of a jet of hydrogen upon its surface is immediately followed by combination and a flash of flame. Even when the point of a tube containing solid fluorine is broken off under liquid hydrogen, a violent explosion ensues.
Photographic Action.—The action of light on photographic plates, though greatly diminished at −180°, is far from being in abeyance; an Eastman film, for instance, remains fairly sensitive at −210°. At the still lower temperature of liquid hydrogen the photographic activity is reduced to about half what it is at that of liquid air; in other words, about 10% of the original sensitivity remains. Experiments carried out with an incandescent lamp, a Röntgen bulb and the ultra-violet spark from magnesium and cadmium, to discover at what distances from the source of light the plates must be placed in order to receive an equal photographic impression, yielded the results shown in table XI.
Table XI.
| Source of Light. | Cooled Plate. | Uncooled Plate. | Ratio of Intensities at Balance. |
| 16 C.P. lamp | 20 in. | 50 in. | 1 to 6 |
| Röntgen bulb | 10 in. | 2434 in. | 1 to 6 |
| Ultra-violet spark | 2212 in. | 90 in. | 1 to 16 |
It appears that the photographic action of both the incandescent lamp and the Röntgen rays is reduced by the temperature of liquid air to 17% of that exerted at ordinary temperatures, while ultra-violet radiation retains only 6%. It is possible that the greater dissipation of the latter by the photographic film at low temperatures than at ordinary ones is due to its
