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TOTAL . ...
. . . 2:8
28 Oil of sp. gr. '915 at 60° F. . . . . . 51.7 46:6 Pitch . . . . . . . . . ...
514 TOTAL : ...
Experiments on the manufacture of patent fuel, from Chitteedand (Salt-range) Coal No, zia, Khatan Petroleum, and pitch made from the petroleum (in experiment No. 1)
At the conclusion of his paper on the Khatan oil-field, Mr. Townsend says (loc,
cit., p. 210): “It has occurred to me as a tenable theory On the origin of the origin of the
that the petroleum of
that the petroleum of this locality may be produced by the benzenes.
action of sulphurous acid waters, combined with alkalies, all at a moderately high degree of heat acting chemically upon a deep depasit of coal, or lignite, under confinement, and it may be that all petroleum has a similar origin.”
The author has failed to point out the precise chemical changes whereby “sulphurous acid waters combined with alkalies” convert coal or lignite into petroleum. ' As he has given no clue to the nature of the organic compounds in the Khatan oil, it is difficult to see the steps by which he has been led to such a generalization.
In studying the evidence which bears on the subject of the origin of petroleum most writers have been in the habit of dealing with generalities too vague to be corrected by subsequently discovered facts. The large number of hydrocarbons of which nearly all mineral oils are composed are often lumped together as possible products of destructive distillation of organized matter, and as mutually convertible; whereas the organic compound, as well as the inorganic body, possesses a distinct individuality and only a possible set of conditions for existence. If ever the solution of the complicated problem of the origin of petroleum be accomplished it can only be by a careful and accurate detailed study of the characters of the individual organic bodies of which it is composed, together with the geological conditions of its occurrence.
I propose here only to point out some of the points in the chemical characters of the benzols which seem to have an important bearing on the subject, many of which have not, so far as I am aware, been hitherto considered in discussing the origin of petroleum, and which may be of service to field-workers who are making a special study of the geological conditions under which the Baluchistan oil occurs.
I have already quoted a sufficient number of authors to show that, notwithstanding the remarks of Pelouze and Cahours, the presence of the benzene series in crude petroleums seems to be true for an increasing number of localities.
Some of the many explanations for the formation of mineral oil which have been proposed have been concisely reviewed in a previous volume of the Records by the late Director, Mr. H. B. Medlicott.
Since Faraday's discovery in 1825 of benzene, a large number of its homologues, and members of the parallel series and derivatives, have been found in the products of the destructive distillation of organic bodies; and this fact has been in a general way used in support of the theory for the organic origin of petroleum. But a long series of researches have revealed the presence of many aromatic compounds occurring also as natural constituents of both animal and vegetable matter.
Catechol (orthodihydroxylbenzene), whose properties have been investigated successively by Reinsch, Zwenger and Wagner, occurs in the extracts of nearly all plants which contain tannic acid. It is found in the juice of Pterocarpus, Eucalyptus and Butea, in the bilberry plant, and in the autumnal leaves of the Virginia creeper.3 Resorcinol (or metadihydroxylbenzene, C.H.(HO),) occurs in many
1 Rec. G. S. I., vol. xix (1886), p. 187. 2 Phil. Trans., 1825, p. 440. 3 Flückiger : Ber. Deutsch. Chem. Ges., vol. v, p. 1.
resins and in Asafætida, Acaroid and Saga penum, Quercitol (CH (HO);) was found by Bracconot in the acorn, and again by Dessaignes in the leaves of the Fan palin (Chamærops humilis).
But of the members of the aromatic group probably the natural occurrence of phenol is the most interesting in the present instance. The existence of phenol (C. H:HO, or carbolic acid) has long been known as a product of the destructive dis. tillation of wood and other organic bodies. So long ago as 1834 it was found by Runge in coal-tar.3 The researches of Städler,4 Baumann, Salkowski,6 and Munk? have established its presence in various excretory products of mammals. Wöhler has shown its existence in castoreum, a substance secreted by the præputial glands of the beaver.8 Its occurrence also in some plants has been recorded.'
The occurrence of phenol in both animals and plants has a most significant bearing upon the question of the organic origin of the aromatic hydrocarbons in petroleum, for, by the simplest change, this compound is reduced to the hydrocarbon benzene (CH). In fact, it was Baeyer's experiments 10 on the reduction of the oxidized aromatic compounds to their corresponding hydrocarbons that led to the discovery of artificial alizarin, the colouring matter of madder.
At high temperatures phenol is, according to Krämer's experiments, broken up into benzene (CpH), toluene (C,Hz), xylene (Cg Hjo), naphthalene (C10Hz), and phenanthrene (C14H10). 11
It is thus seen that phenol, which occurs as a constituent of some organic bodies, is converted by heat alone, or with reducing agents, into hydrocarbons which are being found now in most mineral oils, and this fact points to the organic origin of petroleum, a conclusion which seems in no way discordant with the geological conditions under which the crude oil occurs. Of the presence of de-oxidizing agents in the Baluchistan area sufficient evidence is obtained from Mr. Townsend's account of the presence of pyrites, sulphur and “sulphurous acid waters."'1% I have also found sulphites in the water accompanying the oil collected by Mr. Oldham.
The heat evolved during the crumpling and contortion of the rocks accounts for that factor in the decomposition of the phenol. Moreover, Mr. Townsend quotes
2 Comptes Rendus, vol. xxxiii, pp. 308 and 462.
• Mr. A. H. Allen, in his Commercial Organic Analysis, 2nd edition (1886), vol. ii, p. 536, says, “ Phenol is alleged to exist in the leaves, stem and cones of Pinus sylvestris." Since writing the above I have found an article by Dr. A. B. Griffiths describing his discovery of “ the occurrence of phenol in the stem, leaves and cones of Pinus sylvestris” (Chem. News, vol. xlix (1884), p. 95). The author has also suggested this as the source of the phenol found in mineral oil by Freund and Pebal.
10 Ann. Chem, u. Pharm., vol. cxl, p. 295. 11 Ibid., vol. clxxxix, p. 129.
?? Loc. cit., pp. 208, 209 and 210. I presume by "sulphurous,” the author means water in which shulphurous anhydride (S0,) is dissolved, not sulphates or sulphuric anhydride (SO3).
more direct evidence in the actual high temperature of one of the springs in the Khatan field, which has a temperature of 109° F., at the point of overflow.?
The occurrence of phenol itself in mineral oil from Galicia has been recorded by Pebal and Freund in the memoir to which reference has already been made from the Caucasus by Markownikoff and Oglobini, and from Hanoverian oil by Krämer and Böttcher.
In tracing here the simple series of changes chemically and geologically feasible for the production of the ait matic hydrocarbons and alcchols from organic sources, I am not suggesting that this is the only manner in which these compounds are produced in petroleum. Much confusion has arisen, not only from considering the organic compounds as one group with common properties, but also by supposing that any particular hypothesis is capable of general and exclusive application. Hydrocarbons of this series have been artificia ly prepared by processes purely inorganic by a large number of researchers, notably Berthelot (in 1866 and subsequently), Byasson (in 1871), Friedel and Crafts (in 1877), Mendeljeff (in 1877), Claz (in 1877) and by Landolph (in 1878; but it has been disputed by some (as well as supported by others) that the conditions of production in many, or most, of these cases are to be found in nature.
Although I am not justified in discussing points in these theories which have already been so concisely reviewed by Mr. Medlicott in the paper quoted above (ante, p. 93), I may call attention to an interesting series of results laid before the Chemical Society on June 19th, 1884, by Drs. Armstrong and Miller. These authors carefully investigated the effect of high temperatures on petroleum-hydrocarbons, and one of the conclusions 10 which they arrived was that the benzenes are products in a direct line of the action of heat upon the paraffins and not, as hitherto supposed, built up from hydıocarbons of the acetylene series. This conclusion bears most directly upon the conclusions of Berthelot and his successors.
A further point upon which recent researches have thrown a great deal of light might also be noticed here. The impermeability of clays, limestones and other rocks has been urged, by Sterry Hunt and others, as an argument in favour of the indigenous origin of petroleum. Mr. Medlicott, in noticing this point, says (loc. cit., p. 191), “When we find geodes filled with successive layers of minerals in the midst of compact basalt, it is difficult to place limits upon the possibilities of permeation,'' an objection which has been greatly confirmed by other and more conclusive evidences in the recent studies of rock-metamorphism. In 1885, and since that year, Professor Judd has accumulated a large amount of evidence from experiment and observation to prove that, in deep-seated rock-masses, liquids can both penetrate and, along certain definite directions, effect the solution of minerals, with the production of isolated or connected negative crystals, which become afterwards infilled by various solids to produce the schiller appearances now being widely recognized in crystals. A most striking case of this nature occurs in the well
? Loc. cit., p. 208.
5 Quart. Journ. Geol. Soc., vol. xli (1885), pp 371.389; Mineralogical Magazine, vol. vi (1986), p 81, and subsequent papers.
known“ Apatitbringer," of Oedegaarden, near Bamle, in which Professor Judd showed that plagioclase-crystals, by a process to which in the same year he gave the name of statical metamorphism, become first infested in this way with sodium chloride solution, and then by dynamic action become transformed into scapolite. I have only quoted these cases as examples of many proofs (by numerous other authors as well) to show that the so called impermeability of deep-seated rocks by liquids lends no support to the notion that petroleum is indigenous to the rocks in which it is found.
APPENDIX. Bibliography of the Petroleum resources of the Punjab and Baluchistan area.3 1835. PIDDINGTON, J.-Examination of a mineral exudation from Ghazni. Journ. As. Soc.
Beng., Vol. IV, p. 696. 1836.
Bibl. Univer., Geneva, p. 173. 1841. Wood, J.-A personal narrative of a journey to the source of the River Oxus by the
route of the Indus, Kabul and Badakshan, performed under sanction of the Supreme Government of India in the years 1836, 1837, and 1838.
London, 1841, 144 pp. (and new edition, 1872, 91 pp.). 1842. Vigne, G. T.- Rock-oil near Derabund, Kabul, p. 61, » »
Travels in Kashmir, Ladak, Iskardo, the countries adjoining the mountain-course of the Indus, and the Himalaya, north of the Punjab,
Vol. II, p. 305. 1843. Jameson, W.-General observations on the Punjab and on the Geology of the Salt-Range
and part of Afghanistan. Fourn. As. Soc., Beng., Vol. XII, p. 193. 1846. Hutton, T.-Notes on the geology and mineralogy of Afghanistan. Cal. Four. Nat.
Hist., Vol. VI, pp. 564 and 601. 1847. ABBOTT, J.-Extracts from a letter descriptive of geological and mineralogical observa
tions in the Huzaree district, ( amp Puhli, in Huzaree, 19th June, 1847.
Fourn. As. Soc., Beng., Vol. XVI, p. 1137. 1848. FLEMMINO, A.- Report on the Salt-Range and on its coal and other minerals. Fourn.
As. Soc., Beng., Vol. XVII, pt. II, p. 517. 1853. „ Report on the geological structure and mineral wealth of the Salt-Range in
the Punjab. Fourn. As. Soc., Beng., Vol. XXII, pp. 265 and 347 1854. TheobaLD, W.-Notes on the geology of the Punjab Salt-Range. Fourn. As. Soc.
Beng., Vol. XXIII, p. 669. 1857. THORNTON, E.-Gazetteer of India - Kohat, p. 509. 1862. MACLAGAN, R.- Government Gazette, Feb., pp. 23 and 28. 1866. FENNER, A.--Punjab oil, Proc., Punj. Govt., P. W. D., June 19th. 1867. BROWN, DR.- Supp. Punj. Govt. Gaz., 7th Feb. Oldham, T.- Memorandum on the results of a cursory examination of the Salt-Range
and parts of the districts of Bunnoo and Kohat with a special view to the mineral resources of those districts. Sel., Rec., Govt. Ind., Vol. LXIV, p. 780.
i Geol. Mag., dec. iii, vol. vi (1889), pp. 243-249.
3 In compiling the bibliography the petroleum-resources of this area, which is now being more thoroughly surveyed, I have sought especially to bring together original observations which may be of value to present workers in the field. At the same time, for the general traveller or commercial adventurer I have given a large number of references which are principally abstracts or summaries of original publications, and which may in some cases be the only literature available, an occurrence not infrequent in this country.
For the sake of uniformity, I have followed the abbreviations used in Mr. R. D. Oldham's excellent “ Bibliography of Indian Geology" (Calcutta, 1888). References not occurring in that work are given sufficiently clearly to dispense with explanation.