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Physical Considerations Of Decomposition Of Light

( Originally Published 1905 )

I sought to determine the particular portion of the light which produced the foregoing effects. When, previous to entering the experimental tube, the beam was caused to pass through a red glass, the effect was greatly weakened, but not extinguished. This was also the case with various samples of yellow glass. A blue glass being introduced before the removal of the yellow or the red, on taking the latter away prompt precipitation occurred along the track of the blue beam. Hence, in this case, the more refrangible rays are the most chemically active. The color of the liquid nitrite of amyl indicates that this must be the case; it is a feeble but distinct yellow: in other words, the yellow portion of the beam is most freely transmitted. It is not, however, the transmitted portion of any beam which produces chemical action, but the absorbed portion. Blue, as the complementary color to yellow, is here absorbed, and hence the more energetic action of the blue rays.

This reasoning, however, assumes that the same rays are absorbed by the liquid and its vapor. The assumption is worth testing. A solution of the yellow chromate of potash, the color of which may be made almost, if not altogether, identical with that of the liquid nitrite of amyl, was found far more effective in stopping the chemical rays than either the red or the yellow glass. But of all substances the liquid nitrite itself is most potent in arresting the rays which act upon its vapor. A layer one-eighth of an inch in thickness, which scarcely perceptibly affected the luminous intensity, absorbed the entire chemical energy of the concentrated beam of the electric light.

The close relation subsisting between a liquid and its vapor, as regards their action upon radiant heat, has been already amply demonstrated.' As regards the nitrite of amyl, this relation is more specific than in the cases hitherto adduced; for here the special constituent of the beam, which provokes the decomposition of the vapor, is shown to be arrested by the liquid.

A question of extreme importance in molecular physics here arises : What is the real mechanism of this absorption, and where is its seat?' I figure, as others do, a molecule as a group of atoms, held together by their mutual forces, but still capable of motion among themselves. The vapor of the nitrite of amyl is to be regarded as an assemblage of such molecules. The question now before us is this : In the act of absorption, is it the molecules that are effective, or is it their constituent atoms? Is the vis viva of the intercepted light-waves transferred to the molecule as a whole, or to its constituent parts?

The molecule, as a whole, can only vibrate in virtue of the forces exerted between it and its neighbor molecules. The intensity of these forces, and consequently the rate of vibration, would, in this case, be a function of the distance between the molecules. Now the identical absorption of the liquid and of the vaporous nitrite of amyl indicates an identical vibrating period on the part of liquid and vapor, and this, to my mind, amounts to an experimental proof that the absorption occurs in the main within the molecule. For it can hardly be supposed, if the absorption were the act of the molecule as a whole, that it could continue to affect waves of the same period after the substance had passed from the vaporous to the liquid state.

In point of fact, the decomposition of the nitrite of amyl is itself to some extent an illustration of this internal molecular absorption; for were the absorption the act of the molecule as a whole, the relative motions of its constituent atoms would remain unchanged, and there would be no mechanical cause for their separation. It is probably the synchronism of the vibrations of one portion of the molecule with the incident waves that enables the amplitude of those vibrations to augment, until the chain which binds the parts of the molecule together is snapped asunder.

I anticipate wide, if not entire, generality for the fact-that a liquid and its vapor absorb the same rays. A cell of liquid chlorine would, I imagine, deprive light more effectually of its power of causing chlorine and hydrogen to combine than any other filter of the luminous rays. The rays which give chlorine its color have nothing to do with this combination, those that are absorbed by the chlorine being the really effective rays. A highly sensitive bulb, containing chlorine and hydrogen, in the exact proportions necessary for the formation of hydrochloric acid, was placed at one end of an experimental tube, the beam of the electric lamp being sent through it from the other. The bulb did not explode when the tube was filled with chlorine, while the explosion was violent and immediate when the tube was filled with air. I anticipate for the liquid chlorine an action similar to, but still more energetic than, that exhibited by the gas. If this should prove to be the case, it will favor the view that chlorine itself is molecular and not monatomic.

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