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Page:Popular Science Monthly Volume 19.djvu/490

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THE POPULAR SCIENCE MONTHLY.

fied in concluding that also in other cases, where no such change of density has yet been observed, it yet takes place; and it is not a very daring generalization to believe that a change in spectra is always due to a change in molecular arrangement, and generally, perhaps always, accompanied by a change in the number of atoms which are bound together into one molecule.

With regard to the well-known statement that solids and liquids give continuous spectra, while gases give line-spectra, it must be remarked that metallic vapors show in nearly all cases a continuous spectrum before they condense. Oxygen gives a continuous spectrum at the lowest temperature at which it is luminous. Examining liquids and solids by the method of absorption, we find that many of them show discontinuous spectra, presenting fairly narrow bands. It is not denied that the nearness of molecules does not affect the spectrum. It may render the bands more wide and indistinct at their edges, but its influence is more of a nature which in gas spectra is sometimes observed at high pressures when the lines widen, and does not consist of an alteration in type. Though in a solid or liquid body the molecules are much nearer together, they are less mobile; and hence the number of actual collisions need not be necessarily much increased. The fact that a crystal may show a difference in the absorption spectrum according as the vibrations of the transmitted light take place along or across the axis, shows, I think, that mutual impacts can not much affect the vibrations, but that each molecule, at least in a crystal, must be kept pretty well in its place.

We have divided spectra into three types, but in all attempts at classification we are met by the same difficulty. The boundaries between the different types are not in all cases very well marked. Every one will be able to distinguish a well-defined band-spectrum from a line-spectrum, but there are spectra taking up intermediate positions both between the line-and band-spectra and between band-spectra and continuous spectra. With regard to these it may be difficult to tell to which type the spectrum really belongs. It may happen that a change of spectrum takes place, the spectrum retaining its type; but in these cases, as a rule, the more complex molecule will have a spectrum approaching the lower type, although it may not actually belong to that lower type. To be perfectly general, we may say that a combination of atoms always produces an alteration in the spectrum in the direction of the change from the line-spectrum, through the band spectrum to the discontinuous spectrum.

If we accept the now generally received opinion as to the cause of the different types of spectra, we may obtain information on molecular arrangement and complexity where our ordinary methods fail. At high temperatures, or under much diminished pressure, measures of density become difficult or impossible; and it is just in these cases that the spectroscope furnishes us with the most valuable information.