In the excellent researches of Leslie, De la Provostaye and Detains, and Balfour Stewart, the same reciprocity, as regards solid bodies, has been variously illustrated; while the labours, theoretical and experimental, of Kirchhoff have given this subject a wonderful expansion, and enriched it by applications of the highest kind. To their results are now to be added the foregoing, whereby gases and vapours, which have been hitherto thought inaccessible to experiments with the thermo-electric pile, are proved by it to exhibit the indissoluble duality of radiation and absorption, the influence of chemical combination on both being exhibited in the most decisive and extraordinary way.
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[15. Influence of Vibrating Period and Molecular Form. Physical Analysis of the Human Breath.]
In the foregoing experiments with gases and vapours have employed throughout invisible rays, and found some of these bodies so impervious to radiant heat, that lengths of a few feet they intercept every ray as actually as a layer of pitch. The substances, however, which show themselves thus opaque to radiant heat perfectly transparent to light. Now the rays of light differ from those of invisible heat merely in point of period, the former failing to affect the retina because their periods of recurrence are too slow. Hence, in one way or other, the transparency of our gases and vapours depends upon the periods of the waves which impinge upon them. What is the nature of this dependence? The admirable researches of Kirchhoff help us an answer. The atoms and molecules of every gas have certain definite rates of oscillation, and those waves aether are most copiously absorbed whose periods recurrence synchronise with those of the atomic groups amongst which they pass. Thus, when we find invisible rays absorbed and the visible ones transmitted by a layer of gas, we conclude that the oscillating periods of the atoms constituting the gaseous molecules coincide with those of the invisible, and not with those of the visible spectrum.
It requires some discipline of the imagination to form a clear picture of this process. Such a picture is, however, possible, and ought to be obtained. When the waves of aether impinge upon molecules whose periods of vibration coincide with the recurrence of the undulations, the timed strokes of the waves augment the vibration of the molecules, as a heavy pendulum is set in motion by well-timed puffs of breath. Millions of millions of shocks are received every second from the calorific waves; and it is not difficult to see that as every wave arrives just in time to repeat the action of its predecessor, the molecules must finally be caused to swing through wider spaces than if the arrivals were not so timed. In fact, it is not difficult to see that an assemblage of molecules, operated upon by contending waves, might remain practically quiescent. This is actually the case when the waves of the visible spectrum pass through a transparent gas or vapour. There is here no sensible transference of motion from the aether to the molecules; in other words, there is no sensible absorption of heat.
One striking example of the influence of period may be here recorded. Carbonic acid gas is one of the feeblest absorbers of the radiant heat emitted by solid bodies. It is, for example, to a great extent transparent to the rays emitted by the heated copper plate already referred to. There are, however, certain rays, comparatively few in number, emitted by the copper, to which the carbonic acid is impervious; and could we obtain a source of heat emitting such rays only, we should find carbonic acid more opaque to the radiation from that source, than any other gas. Such a source is actually found in the flame of carbonic oxide, where hot carbonic acid constitutes the main radiating body. Of the rays emitted by our heated plate of copper, olefiant gas absorbs ten times the quantity absorbed by carbonic acid. Of the rays emitted by a carbonic oxide flame, carbonic acid absorbs twice as much as olefiant gas. This wonderful change in the power of the former, as an absorber, is simply due to the fact, that the periods of the hot and cold carbonic acid are identical, and that the waves from the flame freely transfer their motion to the molecules which synchronise with them. Thus it is that the tenth an atmosphere of carbonic acid, enclosed in a tube four feet long, absorbs 60 per cent. of the radiation from carbonic oxide flame, while one-thirtieth of an atmosphere absorbs 48 per cent. of the heat from the same source.
In fact, the presence of the minutest quantity of carbonic acid may be detected by its action on the rays from the carbonic oxide flame. Carrying, for example, the dried human breath into a tube four feet long, the absorption there effected by the carbonic acid of the breath amounts to 50 per cent. of the entire radiation. Radiant heat may indeed be employed as a means of determining practically the amount of carbonic acid expired from the lungs. My late assistant, Mr. Barrett, while under my direction, made this determination. The absorption produced by the breath freed from its moisture, but retaining its carbonic acid, was first determined. Carbonic acid, artificially prepared, was then mixed with dry air in such proportions that the action of the mixture upon the rays of heat was the same as that of the dried breath. The percentage of the former being known, immediately gave that of the latter. The same breath, analysed chemically by Dr. Frankland, and physically by Mr. Barrett, gave the following results :—
Percentage of Carbonic Acid in the Human Breath.
| Chemical analysis | Physical analysis |
| 4.66 | 4.56 |
| 5.33 | 5.22 |