July, 1925
I S D C S T R I d L S S D E-VGISEERISG CHEJfISTRY
Synthetic Methanol Is Poisonous Editor of Industrial and Engineering Chemistry: I have performed a number of experiments upon animals with the German (synthetic) methanol which you sent me. The results were the same (qualitatively and quantitatively) as those obtained with pure methyl alcohol obtained from wood distillates. The synthetic methanol showed the same characteristic differences from ethyl alcohol: when the two alcohols were given in equal doses the animals receiving a single (large) dose of ethyl alcohol were more profoundly affected-showing a greater degree of incoordination and a greater depth of narcosis-than did those that had received the methanol. When, however, these doses were repeated a few times a t 24-hour intervals the differences between the action of the two alcohols became very striking: the animals receiving the ethyl alcohol became less powerfully affected (tolerance) whereas those receiving the methanol became more deeply poisoned with each dose (cumulative action). Thus after the third or fourth administration of a comparatively large dose of methanol the animals passed into a state of coma, in which they died, whereas similar doses of ethyl alcohol had a progressively less effect and could apparently be continued indefinitely without obvious harm. -4lthough the lower animals can tolerate somewhat larger single doses of methyl than of ethyl alcohol, it is known that this is not true of man: the more highly developed nervous system of man is more seriously affected by methyl alcohol than is that of the lower animals and permanent blindness has often been reported from single, sometimes small, doses of methyl alcohol, whereas such results are unknown in the case of ethyl alcohol. I did not perform experiments to determine the effect of the synthetic methanol upon the eyes of the lower animals. Such experiments seemed unnecessary, for it was shown years ago that it is the methyl alcohol in wood alcohol which causes the injuries to the eye, and since synthetic methanol is simply methyl alcohol and has the characteristic physiological action of the hitter, there is no reason to suppose that it would spare the eye. It can confidently be predicted that the use of the synthetic methanol as a beverage or as an adulterant will be followed by the same disastrous effects to life and vision as have characterized such uses of wood alcohol. Those who are circulating the report that the synthetic methanol is not poisonous are not only stating an untruth but are assuming a grave responsibility, for death or blindness will inevitably be the fate of a number of those who may be misled by such statements and attempt t o use synthetic methanol as a beverage. R E r D HVNT HaRVARD MEDICAL SCHOOL BOSTON, Mass. June 8 , 1925
Synthetic Methanol and the Wood Distillers Editor of Indi~strialand Engineering Chemisiry: Most of the criticism which has been brought against the hardwood distillation industry in recent discussions of the German synthetic methanol invasion is based on wrong premises. The American hardwood distillers, it is argued, should have been carrying on research on the synthesis of methanol and beaten the Germans in the race. If that is the case, they should also have been conducting research on synthetic acetic acid and on fermentation processes for producing acetone, and perhaps even on synthetic guaiacol, creosol, methylethyl ketone, and higher ketones-all these being wood distillation products which may be synthesized. That would be rather a large order for one small industry t o undertake.
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The absurdity of such criticism is further shown when we consider for a moment that the wood distillation industry has never been and never can be manufacturers of synthetic chemicals. They are, primarily, distillers of wood, with large investments in timber lands and wood distillation apparatus; and even if they had researched and discovered methods for making one or more of their products synthetically, they would have been where they seem to be now-with large investments in timber and apparatus on their hands, practically worthless. To be sure, they might have held the patents for the synthetic processes without using them, but such suppression is costly, since continued research is necessary under these conditions to keep the outsider from developing another and possibly a better process. It is unreasonable to expect the wood distiller t o undertake expensive investigations on the synthesis of his products. It might with just as much logic be demanded that the dairy farmer finance research on artificial butter, or that the sugar planter finance Balg’s work on photosynthesis of carbohydrates. Because the hardwood distilling industry ought not t o be taken t o task for neglecting research on synthetics is, however, no reason why it may not properly be criticized for neglect of research on its own processes for the purpose of making them more efficient against competition from synthetics Many opportunities for such studies have presented themselves in the past, and just now there is news of a process for recovering acetic acid direct from crude pyroligneous acid (instead of the former roundabout method through acetate of lime), which, if it turns out a success, may reprieve or save the industry. This is the kind of research that the wood distillers should have been financing for a long time-research on the process and its by-products, not research on the synthesis of its finished products. Perhaps American chemistry in general ought to be criticized for not beating the Germans to synthetic methanol, but critics should not place the entire onus on the wood distillation industry. L. F. HAWLEY FORESTPRODUCTS LABORATORY MADISON, WIS. May 29, 1925
Coke Yields b y Low- and HighTemperature Carbonization Editor of Industrial and Engineering Chemistry: I n an article by Morrell and Egloff, THISJOURNAL, 17, 473 (1925), a comparison (Table 11) is made of the yield from one ton of average coal by various carbonization processes. Some of the figures quoted for carbonization in coke ovens are utterly ridiculous to anyone who is a t all acquainted with American practice. The table is copied from an article by a British writer and can refer only t o the results obtained in the antiquated British by-product coke oven industry. hloreover, the figures are doubtless based on British units of measurement-viz., the long ton and the Imperial gallon. Yet these figures are quoted by Morrell and Egloff in such a way that an ordinary reader would take them tu be based on American units and applicable t o American practice. I n America the amount of coal which is being carbonized in byproduct coke ovens per year is more than 66,000,000 tons. This is more than three times the amount annually carbonized in England. There is not a single modern by-product coke plant in America which is making gas as low as 450 B. t. u. per cubic foot. The usual heating value is about 550 B. t. u. per cubic foot, and many plants are regularly producing gas of still higher heating value. The fact that the American gas industry is rapidly adopting the by-product coke oven instead of the retort as the standard type of carbonization apparatus should be very convincing in disproving the absurd assertion that coke-oven gas is of “poor quality.”
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INDUSTRIAL AND ENGINEERING CHESUSTRY
The yield of tar is ordinarily about 10 to 11 U. S. gallons per net ton of coal, but in some of the new plants the yield is in excess of 12 gallons. F. W. SPERR, JR. T H EKOPPERS COMPANY LABORATORIES MELLON JNSTITUTE, PITTSBURGH. PA. May 11, 1925
. . . . . . . . .. Editor of Industrial and Engineering Chemistry: Mr. Sperr’s criticism of the table which Morrell and Egloff quoted from Tupholme is somewhat inconsistent. He states that the ordinary reader would be misled in assuming that the figures quoted applied to American practice. Mr. Sperr, who had no difficulty in ascertaining that the figures quoted were based on British practice, does not give the ordinary reader credit for sufficient intelligence to do likewise. Reference t o the article quoted by the writers shows this immediately. Tupholme’s work was quoted because it represents a direct comparison of low- and high-temperature carbonization based upon commercial practice by one and the same worker. The criticism of Tupholme’s results, for which the writers are not responsible, should be directed to the proper source. While it is true that the calorific value of the coke-oven gas obtained by Tupholme is low, Tupholme states that it is “poor quality cokeoven gas,” and not, as Mr. Sperr implies, “that coke-oven gas is of poor quality.” So far as the present writers’ comparison of gas produced from low-temperature carbonization and high-temperature carbonization is concerned, the low value given by Tupholme for cokeoven gas (450 B. t. u.’s per cubic foot) makes no difference. He has likewise shown a relatively low calorific value for the gas produced by low-temperature carbonization (average 725 B. t . u.’s per cubic foot), according to very recent figures given by Porter [ J . Franklin Inst., 199, 386 (1925)], who cites values of from 800 t o 950 B. t. u.’s per cubic foot for low-temperature carbonization. The ratio of calorific values for gas from low-temperature and high-temperature carbonization given by Tupholme is 1.61. Porter’s figures show a ratio of 1.54. Using Sperr’s value of 550 B. t. u.’s per cubic foot for high-temperature carbonization, and Porter’s average value of 875 B. t. u.’s per cubic foot for low-temperature carbonization, the ratio becomes 1.59. The relative values then shown by Tupholme are not so far amiss. Presuming that Mr. Sperr is correct in his assumption that British units of measurements were used by Tupholme, which is entirely reasonable, the ratio of U. S. gallons of tar produced by low-temperature carbonization as against that produced by hightemperature carbonization is 2.36. The specific gravity of the low-temperature coal tar was taken as 1.074, while that for the high-temperature tar was 1.184 in arriving a t the figures shown. Here again it is believed that Tupholme’s figures for tar yield by low-temperature carbonization are relatively as low as his figures shown for high-temperature carbonization. The writers in their article assumed a yield of 25 gallons per ton for low-temperature carbonization. Morgan and Soule [Chem. Met., 26, 924 (1922)] have shown yields of 11.3 per cent by weight of the coal which from the data shown by them indicates a yield slightly in excess of 25 gallons per ton. Porter (loc. cit.) shows a yield of 20 t o 25 gallons per ton, while others have shown yields in excess of 30 gallons per ton. Taking Sperr’s average figure of 10.5 gallons of tar per ton for high-temperature carbonization and 25 gallons per ton for lowtemperature carbonization, the ratio becomes 2.37. The relative values shown between low- and high-temperature carbonization when properly interpreted, and all the data and references are given for such interpretation, check quite well with American practice. These figures are shown t o indicate that for comparative purposes there is some value in quoting from British writers
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on the subject, especially when such work is of a comprehensive nature. Most of Mr. Sperr’s discussion is entirely irrelevant to the main contents of the article and the broad purpose of the work presented therein by Morrell and Egloff. His belated criticism of Tupholme’s results and British practice, while of interest, does not concern the present writers. His criticism of the present writers might well have been boiled down t o a single sentence, indicating that no doubts would have been left in the mind of the casual reader, despite the references shown to Tupholme, if the table were labeled “British practice.” JACQUE C. MOIZRELL UNIVERSAL OIL PRODUCTS Co. GUSTAVEGLOFF CHICAGO, ILL. May 22, 1925
Properties of Dogfish Liver Oil Editor of Industrial and Engineering Chemistry: On page 310 of the March issue of THISJOURNAL is a paper by A. D. Holmes and Madeleine G. Pigott on the vitamin A potency of dogfish liver oil. As I have already published the results of some work on this oil, and as no reference is made t o this in their communication, I would like t o point out that in Analyst, 43, 156 (1918), I dealt with the chemical properties of this oil. In a later paper dealing with the liver oil of the tope, Galeus galeus, [Analyst, 47, 203 (1922)] is a definite statement that the dogfish liver oil had been examined physiologically, and that it was found that “as a source of the fat-soluble, growth-promoting accessory substance, it was equal to medicinal “cod liver oil.” The full details of the physiological experiments summarized in this statement are, of course, in my possession. My examination of the liver oil was made incidentally in the course of an investigation dealing with the more or less complete utilization of the dogfish. A. CHASTON CHAPMAN 8 DUKE ST., ALDGATE LONDON, E. C. 3 March 16, 1925
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Editor of Industrial and Engineering Chemistry: Referring t o Mr. Chapman’s criticism, I would say that our paper was devoted primarily t o ‘ a discussion of the vitamin A potency of dogfish liver oil. Our only object in publishing data concerning the chemical and physical characteristics of dogfish liver oil was t o supply sufficient information in this regard so that the readers would have some general idea of the nature of the oil on which we were reporting t h e vitamin A potency. Concerning Mr. Chapman’s comment relative to the information that he had contributed to the subject of the vitamin potency of dogfish liver oil, it may be noted that the paper to which he refers was devoted to a discussion of the physical and chemical characteristics of liver oil obtained from tope, Galeus galeus. Mr. Chapman concludes this paper as follows: I do not know what medicinal or dietetic qualities this oil possesses, but in 1917 Dr. Drummond was good enough to make a t my request an examination of the dogfish liver oil on which I was then working, and found that as a source of the fat-soluble, growth-promoting accessory substances, it was equal to medicinal cod liver oil. Probably tope liver oil would have a similar dietetic value. Thus, his sole contribution t o the subject of the vitamin potency of dogfish liver oil constitutes only a portion of a sentence included in a paper devoted t o a discussion of the chemical and physical characteristics of tope liver oil. ARTHURD. HOLMES THE E. L.PATCH COMPANY BOSTON, MASS. May 19, 1925
