the colour and plane of polarization depending on the position of the crystal with respect to the incident beam, and, if polarized light is used, on the plane of polarization of the latter.
Stokes’s Law.—In all the substances examined by Stokes, the fluorescent light appeared to be of lower refrangibility than the light which excited it. Stokes considered it probable that this lowering of the refrangibility of the light was a general law which held for all substances. This is known as Stokes’s law. It has been shown, however, by E. Lommel and others, that this law does not hold generally. Lommel distinguishes two kinds of fluorescence. The bodies which exhibit the first kind are those which possess strong absorption bands, of which only one remains appreciable after great dilution. These bodies are always strongly coloured and show anomalous dispersion and (in solids) surface colour. In such cases, the maximum of intensity in the fluorescent spectrum corresponds to the maximum of absorption. Stokes’s law is not obeyed, for a fluorescent spectrum can be produced by means of homogeneous light of lower refrangibility than a great part of the fluorescent light. The second kind of fluorescence is the most common, and is exhibited by bodies which show absorption only in the upper part of the spectrum, i.e. they are usually yellow or brown or (if the absorption is in the ultra-violet) colourless. The absorption bands also are different from those of substances of the first kind, for they readily disappear on dilution. A third class of bodies is formed by those substances which exhibit both kinds of fluorescence.
Nature of Fluorescence.—No complete theory of fluorescence has yet been given, though various attempts have been made to explain the phenomenon. Fluorescence is closely allied to phosphorescence (q.v.), the difference consisting in the duration of the effect after the exciting cause is removed. Liquids which fluoresce only do so while the exciting light is falling on them, ceasing immediately the exciting light is cut off. In the case of solids, on the other hand, such as fluor-spar or uranium glass, the effect, though very brief, does not die away quite instantaneously, so that it is really a very brief phosphorescence. The property of phosphorescence has been generally attributed to some molecular change taking place in the bodies possessing it. That some such change takes place during fluorescence is rendered probable by the fact that the property depends upon the state of the sensitive substance; some bodies, such as barium platinocyanide, fluorescing in the solid state but not in solution, while others, such as fluorescein, only fluoresce in solution. Fluorescence is always associated with absorption, but many bodies are absorbent without showing fluorescence. A satisfactory theory would have to account for these facts as well as for the production of waves of one period by those of another, and the non-homogeneous character of the fluorescent light. Quite recently W. Voigt has sought to give a theory of fluorescence depending on the theory of electrons. Briefly, this theory assumes that the electrons which constitute the molecule of the sensitive body can exist in two or more different configurations simultaneously, and that these are in dynamical equilibrium, like the molecule in a partially dissociated gas. If the electrons have different periods of vibration in the different configurations, then it would happen that the electrons whose period nearly corresponded with that of the incident light would absorb the energy of the latter, and if they then underwent a transformation into a different configuration with a different period, this absorbed energy would be given out in waves of a period corresponding to that of the new configuration.
Applications of Fluorescence.—The phenomenon of fluorescence can be utilized for the purpose of illustrating the laws of reflection and refraction in lecture experiments since the path of a ray of light through a very dilute solution of a sensitive substance is rendered visible. The existence of the dark lines in the ultra-violet portion of the solar spectrum can also be demonstrated in a simple manner. In addition to the foregoing applications, Stokes made use of this property for studying the character of the ultra-violet spectrum of different sources of illumination and flames. He suggested also that the property would in some cases furnish a simple test for the presence of a small quantity of a sensitive substance in an organic mixture. Fluorescent screens are largely used in work with Röntgen rays. There appears to be some prospect of light being thrown on the question of molecular structure by experiments on the fluorescence of vapours. Some very interesting experiments in this direction have been performed by R. W. Wood on the fluorescence of sodium vapour.
References.—Sir G. G. Stokes, Mathematical and Physical Papers, vols. iii. and iv.; Müller-Pouillet, Lehrbuch der Physik, Bd. ii. (1897); A. Wullner, Lehrbuch der Experimentalphysik, Bd. iv. (1899); A. A. Winkelmann, Handbuch der Physik, Bd. vi. (1906); R. W. Wood, Physical Optics (1905). (J. R. C.)
FLUORINE (symbol F, atomic weight 19), a chemical element
of the halogen group. It is never found in the uncombined
condition, but in combination with calcium as fluor-spar CaF2
it is widely distributed; it is also found in cryolite Na3AlF6,
in fluor-apatite, CaF2·3Ca3P2O8, and in minute traces in sea-water,
in some mineral springs, and as a constituent of the enamel
of the teeth. It was first isolated by H. Moissan in 1886 by the
electrolysis of pure anhydrous hydrofluoric acid containing
dissolved potassium fluoride. The U-shaped electrolytic vessel
and the electrodes are made of an alloy of platinum-iridium,
the limbs of the tube being closed by stoppers made of fluor-spar,
and fitted with two lateral exit tubes for carrying off the gases
evolved. Whilst the electrolysis is proceeding, the apparatus
is kept at a constant temperature of −23° C. by means of liquid
methyl chloride. The fluorine, which is liberated as a gas at
the anode, is passed through a well cooled platinum vessel,
in order to free it from any acid fumes that may be carried over,
and finally through two platinum tubes containing sodium
fluoride to remove the last traces of hydrofluoric acid; it is
then collected in a platinum tube closed with fluor-spar plates.
B. Brauner (Jour. Chem. Soc., 1894, 65, p. 393) obtained fluorine
by heating potassium fluorplumbate 3KF·HF·PbF4. At 200° C.
this salt decomposes, giving off hydrofluoric acid, and between
230–250° C. fluorine is liberated.
Fluorine is a pale greenish-yellow gas with a very sharp smell; its specific gravity is 1.265 (H. Moissan); it has been liquefied, the liquid also being of a yellow colour and boiling at -187° C. It is the most active of all the chemical elements; in contact with hydrogen combination takes place between the two gases with explosive violence, even in the dark, and at as low a temperature as −210° C; finely divided carbon burns in the gas, forming carbon tetrafluoride; water is decomposed even at ordinary temperatures, with the formation of hydrofluoric acid and “ozonised” oxygen; iodine, sulphur and phosphorus melt and then inflame in the gas; it liberates chlorine from chlorides, and combines with most metals instantaneously to form fluorides; it does not, however, combine with oxygen. Organic compounds are rapidly attacked by the gas.
Only one compound of hydrogen and fluorine is known, namely hydrofluoric acid, HF or H2F2, which was first obtained by C. Scheele in 1771 by decomposing fluor-spar with concentrated sulphuric acid, a method still used for the commercial preparation of the aqueous solution of the acid, the mixture being distilled from leaden retorts and the acid stored in leaden or gutta-percha bottles. The perfectly anhydrous acid is a very volatile colourless liquid and is best obtained, according to G. Gore (Phil. Trans., 1869, p. 173) by decomposing the double fluoride of hydrogen and potassium, at a red heat in a platinum retort fitted with a platinum condenser surrounded by a freezing mixture, and having a platinum receiver luted on. It can also be prepared in the anhydrous condition by passing a current of hydrogen over dry silver fluoride. The pure acid thus obtained is a most dangerous substance to handle, its vapour even when highly diluted with air having an exceedingly injurious action on the respiratory organs, whilst inhalation of the pure vapour is followed by death. The anhydrous acid boils at 19°.5 C. (H. Moissan), and on cooling, sets to a solid mass at −102°.5 C, which melts at −92°.3 C. (K. Olszewski, Monats. für Chemie, 1886, 7, p. 371). Potassium and sodium readily dissolve in the anhydrous acid with evolution of hydrogen and formation of
