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154
HEAT
[DIATHERMANCY


although the spiral is undoubtedly at a lower temperature than the flame. The explanation is that the spiral is a fairly good radiator of the visible rays to which the glass is transparent, but a bad radiator of the invisible rays absorbed by the glass which constitute the greater portion of the heat-radiation from the feebly luminous flame.

Fig. 6.—Tyndall’s Apparatus for observing absorption of heat by gas and vapours.

Assuming that the radiation from the source under investigation is qualitatively determinate, like that of a black body at a given temperature, the proportion transmitted by plates of various substances may easily be measured and tabulated for given plates and sources. But owing to the highly selective character of the radiation and absorption, it is impossible to give any general relation between the thickness of the absorbing plate or layer and the proportion of the total energy absorbed. For these reasons the relative diathermancies of different materials do not admit of any simple numerical statement as physical constants, though many of the qualitative results obtained are very striking. Among the most interesting experiments were those of Tyndall, on the absorptive powers of gases and vapours, which led to a good deal of controversy at the time, owing to the difficulty of the experiments, and the contradictory results obtained by other observers. The arrangement employed by Tyndall for these measurements is shown in Fig. 6. A brass tube AB, polished inside, and closed with plates of highly diathermanous rocksalt at either end, was fitted with stopcocks C and D for exhausting and admitting air or other gases or vapours. The source of heat S was usually a plate of copper heated by a Bunsen burner, or a Leslie cube containing boiling water as shown at E. To obtain greater sensitiveness for differential measurements, the radiation through the tube AB incident on one face of the pile P was balanced against the radiation from a Leslie cube on the other face of the pile by means of an adjustable screen H. The radiation on the two faces of the pile being thus balanced with the tube exhausted, Tyndall found that the admission of dry air into the tube produced practically no absorption of the radiation, whereas compound gases such as carbonic acid, ethylene or ammonia absorbed 20 to 90%, and a trace of aqueous vapour in the air increased its absorption 50 to 100 times. H. G. Magnus, on the other hand, employing a thermopile and a source of heat, both of which were enclosed in the same exhausted receiver, in order to avoid interposing any rocksalt or other plates between the source and the pile, found an absorption of 11% on admitting dry air, but could not detect any difference whether the air were dry or moist. Tyndall suggested that the apparent absorption observed by Magnus may have been due to the cooling of his radiating surface by convection, which is a very probable source of error in this method of experiment. Magnus considered that the remarkable effect of aqueous vapour observed by Tyndall might have been caused by condensation on the polished internal walls of his experimental tube, or on the rocksalt plates at either end.[1] The question of the relative diathermancy of air and aqueous vapour for radiation from the sun to the earth and from the earth into space is one of great interest and importance in meteorology. Assuming with Magnus that at least 10% of the heat from a source at 100° C. is absorbed in passing through a single foot of air, a very moderate thickness of atmosphere should suffice to absorb practically all the heat radiated from the earth into space. This could not be reconciled with well-known facts in regard to terrestrial radiation, and it was generally recognized that the result found by Magnus must be erroneous. Tyndall’s experiment on the great diathermancy of dry air agreed much better with meteorological phenomena, but he appears to have exaggerated the effect of aqueous vapour. He concluded from his experiments that the water vapour present in the air absorbs at least 10% of the heat radiated from the earth within 10 ft. of its surface, and that the absorptive power of the vapour is about 17,000 times that of air at the same pressure. If the absorption of aqueous vapour were really of this order of magnitude, it would exert a far greater effect in modifying climate than is actually observed to be the case. Radiation is observed to take place freely through the atmosphere at times when the proportion of aqueous vapour is such as would practically stop all radiation if Tyndall’s results were correct. The very careful experiments of E. Lecher and J. Pernter (Phil. Mag., Jan. 1881) confirmed Tyndall’s observations on the absorptive powers of gases and vapours satisfactorily in nearly all cases with the single exception of aqueous vapour. They found that there was no appreciable absorption of heat from a source at 100° C. in passing through 1 ft. of air (whether dry or moist), but that CO and CO2 at atmospheric pressure absorbed about 8%, and ethylene (olefiant gas) about 50% in the same distance; the vapours of alcohol and ether showed absorptive powers of the same order as that of ethylene. They confirmed Tyndall’s important result that the absorption does not diminish in proportion to the pressure, being much greater in proportion for smaller pressures in consequence of the selective character of the effect. They also supported his conclusion that absorptive power increases with the complexity of the molecule. But they could not detect any absorption by water vapour at a pressure of 7 mm., though alcohol at the same pressure absorbed 3% and acetic acid 10%. Later researches, especially those of S. P. Langley with the spectro-bolometer on the infra-red spectrum of sunlight, demonstrated the existence of marked absorption bands, some of which are due to water vapour. From the character of these bands and the manner in which they vary with the state of the air and the thickness traversed, it may be inferred that absorption by water vapour plays an important part in meteorology, but that it is too small to be

  1. In reference to this objection, Tyndall remarks (Phil. Mag., 1862, p. 422; Heat, p. 385); “In the first place the plate of salt nearest the source of heat is never moistened, unless the experiments are of the roughest character. Its proximity to the source enables the heat to chase away every trace of humidity from its surface.” He therefore took precautions to dry only the circumferential portions of the plate nearest the pile, assuming that the flux of heat through the central portions would suffice to keep them dry. This reasoning is not at all satisfactory, because rocksalt is very hygroscopic and becomes wet, even in unsaturated air, if the vapour pressure is greater than that of a saturated solution of salt at the temperature of the plate. Assuming that the vapour pressure of the saturated salt solution is only half that of pure water, it would require an elevation of temperature of 10° C. to dry the rocksalt plates in saturated air at 15° C. It is only fair to say that the laws of the vapour pressures of solutions were unknown in Tyndall’s time, and that it was usual to assume that the plates would not become wetted until the dew-point was reached. The writer has repeated Tyndall’s experiments with a facsimile of one of Tyndall’s tubes in the possession of the Royal College of Science, fitted with plates of rocksalt cut from the same block as Tyndall’s, and therefore of the same hygroscopic quality. Employing a reflecting galvanometer in conjunction with a differential bolometer, which is quicker in its action than Tyndall’s pile, there appears to be hardly any difference between dry and moist air, provided that the latter is not more than half saturated. Using saturated air with a Leslie cube as source of heat, both rocksalt plates invariably become wet in a minute or two and the absorption rises to 10 or 20% according to the thickness of the film of deposited moisture. Employing the open tube method as described by Tyndall, without the rocksalt plates, the absorption is certainly less than 1% in 3 ft. of air saturated at 20° C., unless condensation is induced on the walls of the tube. It is possible that the walls of Tyndall’s tube may have become covered with a very hygroscopic film from the powder of the calcium chloride which he was in the habit of introducing near one end. Such a film would be exceedingly difficult to remove, and would account for the excessive precautions which he found necessary in drying the air in order to obtain the same transmitting power as a vacuum. It is probable that Tyndall’s experiments on aqueous vapour were effected by experimental errors of this character.