ILYDLTSTRIALAn'D EA*Gl-VEERING CHEMISTRY
September, 1923
position of which will be dependent upon the relative intensities of the two groups of wave lengths involved, and upon the temperature. Usually, photochemical reactions are sensitive to a comparatively narrow band in the spectrum. If a wide band is used, energy is therefore wasted, and an undesirable result may be produced. Now that light is playing an increasingly important role in the photosynthesis of many compounds, it becomes more important that sources of very intense monochromatic illumination be developed. The prebent practice is either to secure approximately monochromatic light by dispersion of light through a prism, letting the desired wave length fall upon a slit behind which the reacting system is placed, or by the use of filters designed to filter out the wave lengths not desired. I n eit)her case, the intensitj of the resulting illuminating beam is not great, particularly if it is anywhere near monochromatic. I n order that reactions may be carried out on anything like a commercial scale, better means of producing powerful, intense sources of such light must be developed. sPSTIIESIS O F CARBOHYDRATE AKD PROTEIN M a T E R I A L
Much interest has lately been aroused in the synthesis of carbohydrates and protein material, particularly as a result of the fine investigations of Baly and his eo-workers in England and Baudisch in this country. As a result of these investigations the mechanisms of these photochemical processes are better understood, and while the work of the two groups is not entirely confirmatory, at least much progress
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has been made. It is believed that because nature seems to use chlorophyll for the synthesis of carbohydrates, it does not necessarily follow that this is the best of all possible catalysts, and it is the hope of the photo chemist that new and more effective catalysts may be found for this important photochemical process.
UTILIZATION OF RADJAKT ENERGY OF SUN Another photochemical problem of great interest, and one which has excited the imagination of the scientists of many generations, is the possible utilization of the enormous quantities of radiant energy coming from the sun. Waste places, now useless for any purpose, may eventually become the sites of great manufacturing plants, once the secret of transforming radiant energy into chemical energy is solved. Here we have an unlimited and almost constant source of energy of enormous magnitude, and one which by its successful utilization will tend to neutralize in a large measure the effect of our diminishing coal and oil supply. While the coal and oil problem may not be a serious one for the present generation, surely the time will come when other sources of energy supply must be found and utilized if civilization is not to perish. Knowing that hundreds of billions of horse power of radiant energy are constantly coming to the earth from the sun, it is not strange that the photo chemist casts a speculative eye toward the possible utilization of this enormous amount of energy, a very considerable portion of which is now entirely wasted.
Occurrence of Levo-Menthone in Pine Oil' By Augustus H. Gill I V f A S S A C H U S E T T S I N S T I T U T E OF
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HE pine oil known as "Spinol" was manufactured by dry distillation of wood, the heat being controlled by a circulating oil bath, the three fractions being turpentine, pine oil, and impure resin oils known as tar oils. This had been redistilled so as to free it from the turpentine fraction; it had stood for about fourteen years, giving ample opportuiiity for resinification. The physical characteristics of the sample were: Specific Gravity a t 15.5'' C. 0.9856
Refractive Index a t 20' C. 1 4868
Optical Rotation a t 26" C -70 20'
The oil mas distilled under 4 mm. pressure, a t first small quantjtios of water and terpenes distilled over, and a large portion, about 60 per cent, distilled over between 74" and 79" C. Fraction between 79" and 100" C. was 10 per cent. By repeated fractional distillation of the first fraction a t atmospheric pressure, two distinct fractions were isolated, one boiling a t 202' to 203" C. which constituted 8 per cent of the original oil, while the other had a boiling point of 208.5" to 209.5" C. and constituted 20 per cent of the oil. The fraction boiling between 79" to 100" C. at 4 mm. was gluey to the touch and was suspected to contain terpineol; attempts to convert it into terpin hydrate by the method of Tieniann and Schmidt2were in vain; hence, the oil contained no terpineol, thus differing in its most important constituent from the pine oils so far studied. The fraction boiling at 202" to 203" C. was thought to be fenchyl alcohol. It was optically inactive. It was oxidized to its corresponding ketone fenchone by nitric acid.s The inactire Eenchone thus obtained had a boiling point of 193" C. and an odor resembling camphor. The inactive fenchone 1 2
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Recexved July 10, 1923. Be7 , 28, 1781 (1895). A n n , 263, 131, 146 (1S91).
TECHNOLOGY, CAMBRIDGE,
MASS.
was next converted into semicarbazone with semicarbazide hydrochloride, having a melting point of 173" C., differing from the active form which has a melting point of 182' to 183" C. Thus, the presence of inactive fenchyl alcohol was conclusively proved. The second fraction, which was levo-rotatory, having an optical rotation -20" 28', was identified as I-menthone by converting it into semicarbazone, melting point 184O C. This was the first time that I-menthone was isolated from oils of the Pinus family. A study of the resinous matter in the oil was made by steam distilling the oil, when the first half, which distils over, contains all the fenchyl alcohol and Z-menthone, and an appreciable quantity of resinous matter. The other half, which remains in the flask, consists of a viscid liquid, an examination of which showed an acid value of 2.7, saponification value of 17.2, and an iodine value to be 65.6. These values are in very close agreement with those found for rosin oil, except for the fact that the rosin oils so far studied are strongly dextro-rotatory, the value varying from 30 to 50, while this sample under examination was levo-rotatory, having a value of about -14". It is possible that some of the menthone in the oil may have polymerized or resinified, thus giving a levo-rotation. It gave the Renard, Liebermann-Storch, and Halphen reactions for rosin oil. This pine oil differs from others in its high menthone content and absence of terpineol; besides fenchyl alcohol it probably contains small quantities of terpenes and sesquiterpenes, which have changed into the resinous body, the remainder constituting a large percentage of the rosin oil, with small quantities of rosin spirit and colophony. Acknowledgment is due 11. J. Karasji by whom some of the work was performed.
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
Vol. 15, s o . 9
Research for the Petroleum Industry By Raymond F. Bacon 50 EAST41sT ST., NEWYORK,N. Y
HERE is no industry of anything like the magnitude formed are probably ring compounds. Still, so far as the of the petroleum industry which has such a dearth writer’s observation goes, these ring compounds formed in of fundamental chemical knowledge on which to base this way are not of the same character as the naphthenes, as its operations. The reasons for this fact are twofold: One they do not show the same resistance toward chemical agents is that petroleum refining as conducted in the past has been as the true naphthenes. largely -by physical seiarations rather ELECTRICAL WAVESI N CRACKING than by chemical processes. The other PROCESSES is that a study of the structure and reactions of petroleum hydrocarbons inIn the patent literature on cracking volves very great difficulties. The inprocesses claims are made by various industry in the past has separated the ventors of the efficacy of electrical waves, petroleum into certain of its original of the impact of ions, and even of meparts and has marketed these parts as chanical impact itself in causing the gasoline, kerosene, lubricating oil, fuel breaking down of hydrocarbons containoil, paraffin, etc. The time has now ing many carbon atoms into those concome when commercially successful petaining a lesser number. Scientific worktroleum refining means the manufacture ers would find here an interesting and from the oil of substances which do perhaps profitable field of investigation, not exist in the crude petroleum as such, for it is, of course, known that under but are formed by chemical transmutaproper conditions electrical waves of tions from other compounds present as suitable character can cause profound constituents of the petroleum. For examchanges in chemical compounds. It is also ple, the time has come when not all the known that electrons meeting molecules at kerosene hydrocarbons which exist natusufficient velocity can cause the disinterally in crude petroleum can be advangration of those molecules, thus forming Bachraich tageouslv sold as kerosene. Ideal refinRAYMOND F. BACON new compounds. Furthermore, impact ing means production from the crude of sufficiently violent character does cause oil of only those products which can be most profitably the breaking down of many types of compounds-as, for marketed a t a particular time. This means chemical change instance, explosives. The scientific study of reactions of this of many of the compounds contained in petroleum into other type should yield most valuable results which might also chemical individuals. possibly prove to be’ of great practical value. The industry is meeting this situation, as the thousand and LUBRICATION more patents relating to cracking processes for making gasoWhen one considers the subject in all its ramifications, line would indicate. The industry, however, could work out its salvation much faster and on sounder lines if more were there is hardly anything in the world quite so important as known regarding the nature and properties of the individual lubrication. The world’s consumption of lubricants does hydrocarbons constituting petroleum. One can read in not rank with its consumption of many other products, but scientific literature pages and pages describing the properties without the lubricants all machinery stops. There is no and chemical reactions of hydrocarbons of which a t most a doubt that one of the greatest sources of worry of the German few hundred grams may have existed in the whole world, General Staff in the war was as to whether they could mainwhile tons and thousands of tons of hydrocarbons are being tain a sufficient supply of lubricants in a shut-in Germany. produced daily of which we know absolutely nothing regard- Yet, with the subject so important, what do we know about ing their chemical properties, their reactions, and their the scientific nature of lubrication or the chemical or physical structure. There is almost no field of research open to the structure of a substance which makes it a good lubricant? pure scientist which offers such fascination in its difficulty, Our ignorance is really appalling. The writer well remembers nor such promise, if its difficulties are overcome, of opening the fascination with which he heard Dr. Mabery tell about up a whole new field of chemistry, as the study of these how he had fractioned a certain petroleum into various narrow unknown petroleum hydrocarbons. The action of heat alone fractions and had found that one of these fractions made a on these hydrocarbons, under all possible conditions, is an most excellent oil for lubricating watches, while a nearby alluring field of study, and on this heat action (pyrolysis) fraction was of such a character that it stopped the watch. most of the processes of gasoline manufacture are founded, It is well known to all who are conversant with the subject but largely on an empirical basis. As an example of interest- that there are no chemical or physical tests which can be made ing relations of this character, the Burton and other similar on a new product which will prove definitely whether or not pressure distillation processes of cracking give gasoline which, it will serve as a good lubricant for a particular piece of maconsidering its saturated constituents,’ is apparently of much chinery. The only test that is of real value is to try it on the same character as the gasoline hydrocarbons found natu- the machine to be lubricated. I n this connection, there is another subject which offers rally occurring in petroleums. On the other hand, when heavy petroleum oils are cracked under the conditions of the Ramage great promise for investigation, and that is the relation of process, the gasoline hydrocarbons obtained have for similar those hydrocarbons which go to make up what we call “petboiling points a much higher specific gravity and a much rolatum” to other hydrocarbons, possibly with the same higher refractive index, indicating that the hydrocarbons number of carbon atoms, which are either liquid oils or are
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