Besides the absorption by liquids, the vapours of the metals also absorb selectively, and if a tube containing a piece of sodium and filled with hydrogen (so that the metal will not get oxidized) is placed in the path of the rays, and the sodium heated, the spectrum is at first unaffected, but as the sodium gets hot and its vapour comes off, we can mark its effect on the spectrum. We see a dark line beginning to appear in the yellow, finally the whole light of that particular colour is absorbed, and we have a dark line in its place. To sum up then:—
We get from solids, when heated, general radiation, and when they act as absorbers, we get general absorption; from gases and vapours we get selective radiation and selective absorption.
Fig. 183.—Spectroscope arranged for showing Absorption.
Now it at once strikes any one performing these experiments that the dark line of yellow sodium appears in the same place in the spectrum as the bright one, and this is so. When the absorption by sodium vapour is examined by the spectroscope, it is then seen to consist of two well-defined lines close together, and when the radiation is examined, it is found to consist of two bright ones, and the absorption and radiation lines, the dark and bright ones, are found to exactly agree in position in the spectrum, showing that the substance that emits a certain light is able to absorb that same light, so that it matters not whether a body is acting as an absorber or radiator, for still we recognize its characteristic lines. In 1814 Fraunhofer strongly suspected the coincidence of the two bright sodium lines with the dark lines in the sun; afterwards Brewster, Foucault, and Miller showed clearly the absolute coincidence; and Professor Stokes in 1852 came to the conclusion that the double line D, whether bright or dark, belonged to the metal sodium, and that it absorbed from light passing through it the very same rays which it is able, when incandescent, to emit. The phenomena rendered visible to us by the spectroscope have their origin, as we have said, in molecular vibration, and the reason of the identical position of the light and dark lines, and indeed the whole theory of spectrum analysis, may be shortly stated as follows:—
The spectroscope tells us that when we break a mass of matter down to its finest particles, or, as some people prefer to call them, ultimate molecules, the vibrations of these ultimate parts of each different kind of matter are absolutely distinct; so that if we get the ultimate particle, say of calcium, and observe its vibrations we find that the kind of vibration or unrest of one substance—of the calcium, for instance—is different from the kind of unrest or mode of vibration—which is the same thing—of another substance, let us say sodium. Mark well the expression, ultimate molecule, because the vibrations of the larger molecular aggregations are absolutely powerless to tell us anything about their chemical nature. When we bring down a substance to its finest state, and observe, by means of the prism, the vibrations it communicates to the ether, we find that, using a slit in the spectroscope and making these vibrations paint different images of the slit, we get at once just as distinct a series of images of the slit for each substance as we should get a distinct sequence of notes if we were playing different tunes on a piano.
Next, this important consideration comes into play—whenever any element finds itself in this state of fineness, and therefore competent to give rise to these phenomena, it will give rise to them in different degrees according to certain conditions. The intensest form is observed when we employ electricity. In a great many cases the vibrations may be rendered very intense by heat. The heat of a furnace or of gas will, for instance, in a great many cases, suffice to give us these phenomena; but to see them in all their magnificence—their most extreme cases—we want the highest possible temperatures, or better still, the most extreme electric energy. What we get is the vibration of these particles rendered visible to our eye by the bright images of the slit or by their bright “lines.”
But that is not the only means we have of studying these states of unrest. We can study them almost equally well if, instead of dealing with the radiation of light from the particles themselves, we interpose them between us and a light source of more complicated molecular structure, and hotter or more violently excited than the particles themselves. From such a source the light would come to us absolutely complete; that is to say, a perfectly complete gamut of waves of light, from extreme red to extreme violet. When we deal with these particles between us and a light-source competent to give us a continuous spectrum, then we find that the functions of these molecules are still the same, but that their effect upon our retinas is different. They are not vibrating strongly enough to give us effectively light of their own, but they are eager to vibrate, and, being so, they are employed, so to speak, in absorbing the light which otherwise would come to our eyes. So that whether we observe the bright spectrum of calcium or any other metal, or the absorption spectrum under the conditions above stated, we get lines exactly in the same part of the chromatic gamut, with the difference that when we are dealing with radiation we get bright lines, and when dealing with absorption we get dark ones.
It was such considerations as these by which the presence of sodium was determined in the sun. Soon followed the discovery of coincidence of other dark lines with the bright lines of numbers of our elements, and we had maps made by Kirchhoff, and Bunsen, and Ångström, in which almost every dark line is mapped with the greatest accuracy.
The dark lines in the spectra of the stars, and the light ones in nebulæ, comets, and meteorites have also yielded to us a knowledge more or less accurate of the elements of which these celestial bodies are built up.