pyrogenetic relationships of hydrocarbons, these compounds only liberate carbon by a process of the continual coalescence of hydrocarbon molecules with the elimination of hydrogen, until there is left the limiting solid hydrocarbon hardly distinguishable from carbon itself and constituting the glowing soot of flames.
V. B. Lewes, on the other hand, basing his conclusions on a study of the thermal decomposition of hydrocarbons, on temperature measurements of flames and analysis of their gases, has more recently developed a theory of flame luminosity in which the formation and sudden exothermic decomposition of acetylene are regarded as the essential incidents productive of carbon separation and luminosity. Smithells has disputed the evidence on which this theory is based and it appears to have gained no adherence from those who have worked in the same field; but as it has not been formally disavowed by the author and has found its way into some text-books, it is mentioned here.
W. A. Bone and H. F. Coward (Journ. Chem. Soc., 1908) published the results of a very careful study of the decomposition of hydrocarbons when heated in a stationary condition and when continually circulated through hot vessels. Their results disclose once more the great difficulty of tracing the processes of decomposition and of arriving at a generalization of wide applicability, but they appear to be conclusive against the views both of Berthelot and of Lewes.
They do not think that the decomposition of hydrocarbons can be adequately represented by ordinary chemical equations owing to the complexity of the changes which really take place. Methane, which is the most stable of the hydrocarbons, appears to be resolved at high temperatures directly into carbon and hydrogen, but the phenomenon is dependent mainly on surface action; ethane, ethylene and acetylene undergo decomposition throughout the body of the gas (loc. cit. p. 1197 et seq.).
“In the cases of ethane and ethylene it may be supposed that the primary effect of high temperature is to cause an elimination of hydrogen with a simultaneous loosening or dissolution of the bond between the carbon atoms, giving rise to (in the event of dissolution) residues such as : CH2 and ∶ CH. These residues, which can only have a very fugitive separate existence, may either (a) form H2C : CH2 and HC ∶ CH, as the result of encounters with other similar residues, or (b) break down directly into carbon and hydrogen, or (c) be directly hydrogenized to methane in an atmosphere rich in hydrogen. These three possibilities may all be realized simultaneously in the same decomposing gas in proportions dependent on the temperature, pressure and amount of hydrogen present. The whole process may be represented by the following scheme, the dotted line indicating the tendency to dissolve a bond between the carbon atoms which becomes actually effective at higher temperatures:—
“In the ease of acetylene, the main primary change may be either one of polymerization or of dissolution according to the temperature, and if the latter, it may be supposed that the molecule breaks down across the triple bond between the carbon atoms, giving rise to 2(∶ CH), and that these residues are subsequently either resolved into carbon and hydrogen or “hydrogenized” according to circumstances, thus:—
“Acetylene is, moreover, distinguished by its power of polymerization at moderate temperatures so that whether it is the gas initially heated or whether it is a prominent product of the decomposition of another hydrocarbon polymerization will occur to an extent dependent on temperature.”
We may describe briefly the view to which we are led as to the genesis of an ordinary luminous hydrocarbon flame:—
The gaseous hydrocarbon issues from the burner or wick, let us suppose, in a cylindrical column. This column is not sharply marked off from the air but is so penetrated by it that we must suppose a gradual transition from the pure hydrocarbon in the centre of column to the pure air on the outside. Let us take a thin transverse slice of the flame, near the lower part of the wick or close to the burner tube. At what lateral distance from the centre will combustion begin? Clearly, where enough oxygen has penetrated the column to give such partial combustion as takes place in the inner cone of a Bunsen burner. This then defines the blue region. Outside this the combustion of the carbon monoxide, hydrogen and any hydrocarbons which pass from the blue region takes place in a faintly luminous fringe. These two layers form a sheath of active combustion, surrounding and intensely heating the enclosed hydrocarbons in the middle of the column. These heated hydrocarbons rise and are heated to a higher temperature as they ascend. They are accordingly decomposed with separation of carbon in the higher parts of the flame, giving the region of bright yellow luminosity. There remains a central core in which neither is there any oxygen for combustion nor a sufficiently high temperature to cause carbon separation. This constitutes the dark interior region of the flame. We thus account for the different parts of the flame. It is to be noted, however, that the bright blue layer only surrounds the lower part of the flame, whilst the pale, faintly-luminous fringe surrounds the whole flame. The flame also is conical and not cylindrical. The foregoing explanation is therefore not quite complete. Let us suppose that the changes have gone on in the small section of the flame exactly as described and consider how the processes will differ in parts above this section. The central core of unburned gases will pass upwards and we may treat it as a new cylindrical column which will undergo changes just as the original one, leaving, however, a smaller core of unburned gases, or, in other words, each succeeding section of the flame will be of smaller diameter. This gives us the conical form of the flame. Again, the higher we ascend the flame the greater proportionally is the amount of separated carbon, for we have not only the heat of laterally outlying combustion to effect decomposition, but also that of the lower parts of the flame. The lower part of a luminous flame accordingly contains less separated carbon than the upper. Where the hydrocarbon is largely decomposed before combustion we have no longer the conditions of the Bunsen flame, and so in the upper parts of a luminous flame the bright blue part fades away. The luminous fringe would, however, be continued, for the separated hydrogen has still to burn. In this way then we may reasonably account for the existence, position and relative sizes of the four regions of an ordinary luminous flame. (A. S.)
FLAMEL, NICOLAS (c. 1330–1418), reputed French alchemist
and scrivener to the university of Paris, was born in Paris or
Pontoise about 1330, and died in Paris in 1418, bequeathing the
bulk of his property to the church of Saint-Jacques-la-Boucherie,
where he was buried. During his life he contributed freely to
charitable and religious purposes from the considerable wealth
he amassed either by the practice of his craft, or, as some surmise
without definite proof, by fortunate speculation or money
lending, or, as legend has it, by alchemy. According to a document
purporting to be written by himself in 1413 (printed in
Waite’s Lives of the Alchemystical Philosophers, London, 1888),
there fell into his hands in 1357, at the cost of two florins, a book
on alchemy by Abraham the Jew, which taught in plain words
the transmutation of metals. It did not, however, explain the
materia prima, but merely figured or depicted it, and for more
than 20 years Flamel strove in vain to find out the secret. Then,
returning from a journey to Spain, he fell in with a Christian
Jew, named Canches, who gave him the explanation, and after
three more years’ work he succeeded in preparing the materia
prima, thus being enabled in 1382 to transmute mercury into
both silver and gold. But this fantastic story was disposed
of by the facts, derived from parish records, set forth in Vilain’s
Essai sur l’histoire de Saint-Jacques-la-Boucherie, 1758, and his
Histoire critique de Nicolas Flamel et de Pernelle sa femme,
recueillie d’actes anciens qui justifient l’origine et la médiocrité de
leur fortune contre les imputations des alchimistes, 1761.
A book on alchemy in the Paris Bibliothèque, Le Trésor de philosophie, professing to be written and illuminated by Flamel with his
