at the bottom, but more frequently is applied to an artificial channel of wood or other material for the diversion of a stream of water from a river for purposes of irrigation, for running a sawmill, or for various processes in the hydraulic method of gold-mining (see Aqueduct).
FLUMINI MAGGIORE, a town of the province of Cagliari,
Sardinia, 10 m. by road N. of Iglesias, and 5 m. from the W. coast.
Pop. (1901) town 3908; commune 9647. It is the centre of
a considerable lead and zinc mining district. Three miles to the
S. are the ruins of a temple erected probably in the time of
Commodus (Corpus inscr. Lat. x., Berlin, 1883, No. 7539).
They seem to mark the site of Metalla (mines), a station on the
coast road from Sulci to Tharros, and the centre of the mining
district in Roman times. At Flumini Maggiore itself were found
two ingots of lead, one bearing a stamp with Hadrian’s name.
FLUORANTHENE, C15H10, also known as idryl, a hydrocarbon
occurring with phenanthrene, pyrene, diphenyl, and other
substances in “Stupp” fat (the fat obtained in working up the
mercury ores in Idria), and also in the higher boiling fractions
of the coal tar distillate. It was discovered by R. Fittig in 1878,
who, with Gebhard and H. Liepmann, elucidated its constitution
(see Ann., 1879, 200, p. 1). The hydrocarbons are separated
from the “Stupp” by means of alcohol, the soluble portion on
distillation giving first phenanthrene and then a mixture of pyrene
and fluoranthene. From the tar distillate, the chrysene can be
fractionally precipitated, and the fluoranthene can be separated
from most of the pyrene by fractional distillation in a partial
vacuum. In either case the two hydrocarbons are finally
separated by fractional crystallization of their picrates, which
are then decomposed by ammonia. Fluoranthene crystallizes
in large slender needles or monoclinic tables, melting at 109–110°
C. and boiling at 250–251° C. (60 mm.). It is easily soluble in hot
alcohol, ether and carbon bisulphide. On oxidation with chromic
acid it forms a quinone, C15H8O2, and an α-diphenylene ketocarboxylic
acid
| C6H4 | ≥ | CO | . The picrate melts at 182–183° C. |
| C6H3 | CO2H |
FLUORENE (α-diphenylene methane), C13H10 or (C6H4)2CH2,
a hydrocarbon found in coal-tar. It is obtained from the higher
boiling fractions, after separation of naphthalene and anthracene,
by fractional distillation, the portion boiling between 290–340° C.
being taken. The fluorene is separated from this by placing it in
a freezing mixture, and is then redistilled or crystallized from
glacial acetic acid, or purified by means of its picrate. It may
be prepared by distilling diphenylene ketone over zinc dust,
or by heating it with hydriodic acid and phosphorus to 150–160°
C.; and also by passing the vapour of diphenyl methane through
a red hot tube. It crystallizes in colourless plates, possessing
a violet fluorescence, melting at 112–113° and boiling at 293–295°
C. By oxidation with chromic acid in glacial acetic acid solution,
it is converted into diphenylene ketone (C6H4)2·CO; whilst on
heating with hydriodic acid and phosphorus to 250–260° C. it
gives a hydro derivative of composition C18H22.
FLUORESCEIN, or Resorcin-Phthalein, C20H12O5, in
chemistry, a compound discovered in 1876 by A. v. Baeyer by
the condensation of phthalic anhydride with resorcin at 195–200°
C. (Ann., 1876, 183, p. 1). The two reacting substances are either
heated alone or with zinc chloride for some hours, and the melt
obtained is boiled out with water, washed by dilute alcohol,
extracted by means of sodium hydrate, and the solution so
obtained is precipitated by an acid. The precipitate is well
washed with water and then dried. By repeating this process
two or three times, the fluorescein may be obtained in a very pure
condition. It forms a yellow amorphous powder, insoluble in
water but soluble in alcohol, and crystallizing from the alcoholic
solution in small dark red nodules. It is readily soluble in solutions
of the caustic alkalis, the solution being of a dark red colour
and showing (especially when largely diluted with water) a
brilliant green fluorescence. It was so named on account of this
last character. By brominating fluorescein in glacial acetic acid
solution, eosin (tetrabromfluorescein) is obtained, the same
compound being formed by heating 3.5–dibrom-2.4–dioxybenzoylbenzoic
acid above its melting point (R. Meyer, Ber.,
1895, 28, p. 1576). It crystallizes from alcohol in yellowish red
needles, and dyes silk, wool, and mordanted cotton a fine pink
colour. When heated with caustic alkalis it yields dibromresorcin
and dibrommonoresorcin-phthalein. The corresponding
iodo compound is known as erythrosin. Fluorescein is readily
nitrated, yielding a di- or tetra-nitro compound according to
conditions. The entrance of the negative nitro group into the
molecule weakens the central pyrone ring in the fluorescein
nucleus and the di- and tetra-nitro compounds readily yield
hydrates (see J.T. Hewitt and B.W. Perkins, Jour. Chem. Soc.,
1900, p. 1326). By the action of ammonia or amines the di-nitro
fluoresceins are converted into yellow dyestuffs (F. Reverdin,
Ber., 1897, 30, p. 332). Other dyestuffs obtained from fluorescein
are safrosine or eosin scarlet (dibromdinitrofluorescein) and rose
Bengal (tetraiodotetrachlorfluorescein).
On fusion with caustic alkali, fluorescein yields resorcin, C6H4(OH)2, and monoresorcin phthalein (dioxybenzoylbenzoic acid), (HO)2C6H3·CO·C H4·COOH. With zinc dust and caustic soda it yields fluorescin. By warming fluorescein with excess of phosphorus pentachloride it yields fluorescein chloride, C20H10O3Cl2 (A. Baeyer), which crystallizes from alcohol in small prisms, melting at 252° C. When heated with aniline and aniline hydrochloride, fluorescein yields a colourless anilide (O. Fischer and E. Hepp, Ber., 1893, 26, p. 2236), which is readily methylated by methyl iodide and potash to a fluoresceinanilidedimethyl ether, which when heated for six hours to 150° C. with acetic and hydrochloric acids, is hydrolysed and yields a colourless fluoresceindimethyl ether, which melts at 198° C. On the other hand, by heating fluorescein with caustic potash, methyl iodide and methyl alcohol, a coloured (yellow) dimethyl ether, melting at 208° C. is obtained (Fischer and Hepp). By heating the coloured dimethyl ether with caustic soda, the monomethyl ether is obtained (O. Fischer and E. Hepp, Ber., 1895, 28, p. 397); this crystallizes in triclinic tables, and melts at 262° C. It is to be noted that the colourless monomethyl ether fluoresces strongly in alkaline solution, the dimethyl ether of melting point 208° fluoresces only in neutral solution (e.g., in alcoholic solution), and the dimethyl ether of melting point 198° C. only in concentrated hydrochloric or sulphuric acid solution (Fischer and Hepp). Considerable discussion has taken place as to the position held by the hydroxyl groups in the fluorescein molecule, C. Graebe (Ber., 1895, 28, p. 28) asserting that they were in the ortho position to the linking carbon atom of the phthalic anhydride residue. G. Heller (Ber., 1895, 28, p. 312), however, showed that monoresorcin-phthalein when brominated in glacial acetic acid gives a dibrom derivative which, with fuming sulphuric acid, yields dibromxanthopurpurin (1.3-dioxy-2.4–dibromanthraquinone), a reaction which is only possible if the fluorescein (from which the monoresorcin-phthalein is derived) contains free hydroxyl groups in the para position to the linking carbon atom of the phthalic anhydride residue.
 |
| Fig. 1. |
FLUORESCENCE. In a paper read before the Royal Society of Edinburgh in 1833, Sir David Brewster described a remarkable phenomenon he had discovered to which he gave the name of “internal dispersion.” On admitting a beam of sunlight, condensed by a lens, into a solution of chlorophyll, the green colouring matter of leaves (see fig. 1), he was surprised to find that the path of the rays within the fluid was marked by a bright light of a blood-red colour, strangely contrasting with the beautiful green of the fluid when seen in moderate thickness. Brewster afterwards observed the same phenomenon in various vegetable solutions and essential oils, and in some solids, amongst which was fluor-spar. He believed this effect to be due to coloured particles held in suspension. A few years later, Sir John Herschel independently discovered that if a solution of quinine sulphate, which, viewed by transmitted light, appears colourless and transparent like water, were illuminated by a beam of ordinary daylight, a peculiar blue colour was seen in a thin stratum of the fluid adjacent to the surface by which the light entered. The blue light was unpolarized and passed freely through many inches of the fluid. The incident beam, after having passed through the stratum from which the blue light came, was not sensibly enfeebled or coloured, but yet it had lost the power of
