Feb., 191.9
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
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Permanganate-formalin method. Dichromate-formalin method. . Bleach-formalin method
$2.29 1 ,14 0.39
A question t h a t naturally arises upon consideration of t h e d a t a given for t h e bleach-formalin method is, why not increase t h e proportion of bleach t o formalin? There are two answers t o this. First, t h e reaction becomes extremely violent b y t h e time t h e ratio of 5 parts b y weight of bleach t o j parts b y volume of formalin is reached; second, above this ratio notable quantities of chlorine compounds are set free along with t h e formaldehyde gas. It is better t o adhere t o t h e proportions recommended, which proportions both experiment and practical experience in fumigating rooms have demonstrated t o be unobjectionable. It is not advisable t o sacrifice satisfaction for t h e slight saving in cost t h a t could t h u s be realized. SUMMARY
T h e use of bleaching powder and formalin in fumigating rooms has been proposed in this paper. By the aid of a new a n d convenient apparatus, this new method has been compared quantitatively with t h e permanganate-formalin and with t h e dichromate-formalin methods. T h e comparison leads t o t h e conclusion t h a t b y using 620 g. bleaching powder a n d 800 cc. formalin for each 1000 cu. f t . t o be fumigated, as much formaldehyde gas will be thrown off into t h e room as b y t h e use of 2 5 0 g. permanganate a n d joo cc. formalin, a n d a t only one-sixth t h e cost. The bleach-formalin method is shown t o be only one-third as costly as t h e dichromate-formalin method. It has been shown t h a t t h e printed objections t o t h e bleach-formalin method are without foundation in fact and are contradicted both b y experiment a n d in practice. REFERENCES I-Relative t o the determination of the formaldehyde gas evolved, see Evans and Russell, 13th Report State Board of Health of Maine, p. 234. Also, 14th Report, p. 232. Frankforter and West, J . A m . Chem. Soc., 27, 714. Also, I b i d . , 28, 1234. Base, I b i d . , 28, 964. Doerr and Raubitschek, Wiener klin. Wochschr., 20, 7 19. Fendler and Stiibler, 2. angew. Chem., 21, 2018. Also, Z . H y g . 16. Infektionskrankh. 6 6 , 177. Fendler, Stabler, and Frank, Desinfektion, 4, 228. Auerbach and Plueddemann, .4rb. K a i s . Gesundh., S O , 195. Strunk, Ver6ffent.Geb. ilililitarsanitalswesens, 41, I, 3. Kalaehne and Strunk, Z . Hyg. u . Iitfektionskrankh., 63, 375 a n d 402. Lockermann and Croner, Desinfektion, 2, 1, 549, 59S, and 670. Also, Ibid., 4, 393. Dixon, J . A m . Med. Assoc., 1914, 1025. Hamilton, A m . J . Pub. Health, 7 , 282. 2-Rosenau, “Preventive Medicine and Hygiene,” 3rd Ed., p. 1134. Permanganate was proposed in 1902 by Johnson in a paper read before the Sioux Valley Medical Association: the files of this society have been destroyed by fire, and the origifal paper is not available. See articles by Evans and Russell and by Rase, cited in Reference 1. For bacteriological tests, see Russell, and also McClintic, Hygienic Laboi~atovyBulletin, U. S. Pub. Health and Mar. Hos. Service, No. 27. 3--IIasseltine, U. S. Public Heelth Reports, 30, 2058. 4--I)ixon, LOC. cit., Reference 1; cf. Rosenau, LOC.cit., Reference 2. 5-Walker, J . A m . Chem. SOC.,27, 227; cf. MacNutt, Manual for Health OfEcers, p. 578, who directs the use of the same chemicals in other proportions. &I,ockermann and Croner, Desinfektion, 2 , 724. 7--l’arkes, “Practical Hygiene,” 4th Ed., p. 580. 8-New York City Dept. of Health, quoted by MacXutt, L O C .cit. 9-lZomijn, Z . anal. Chem., 36, 18. Smith, J . Am. Chem. Soc., 26, 1028. Rase, L O G .cit., p 968. See also Evans, LOG.c i t . IO-McClintic, LOC.cit., p. 20. 11-Evans and Russell, LOC.cit,, 14th Report, p. 233. 12-Glycerin is added t o prevent polymerization. It had been used for this purpose in some of the early forms of autoclaves for fumigations. See, Newman, “Bacteriology and the Public Health,” 3rd Ed., p. 444. 13-Cf. Dixon, LOC.cit., “LaWall found the solution would be perfectly stable.”
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14-For proportion, see Rosenau, LOC.cit., p. 1137. 15-Am. J . Pub. Health, 7 , 282. 16-Fendler*and Stubler, Z . angew. Chem., 21, 2021. Evans, L O C . cit., 14th Report, p. 227. I7--Ber., 89, 1327. IS-These costs weie calculated for the original paper, read December 29, 1917. The prices were from the New York Journal of Commevce and Commercial Bulletin and were the minimum prices listed for December 24, 1917. I have not recalculated a t later prices as confusion might result, since these costs appeared in the A m . J . Pub. Health, 8 , 161.
PRIVATE LABORATORY B R Y N M A W R , PENNSYLVANIA
THE PRESENCE OF ACETYLMETHYLCARBINOL IN SACCHARINE SORGHUM SILAGE By W. G. FRIGDEXANN AND C. T. DOWELL Received May 28, 1918
I n t h e course of t h e determination of t h e alcohols i n some saccharine sorghum silage b y t h e Duclaux method, t h a t is, b y t h e distillation of t h e alcohols from a neutral solution, oxidation of t h e distillate with potassium dichromate and sulfuric acid, redistilling, and determining t h e acids b y t h e Duclaux method in t h e second distillate, it was observed b y one of us (Friedemann) t h a t a n unusually large amount of acetic acid was present. This led us t o make a further examination of this substance and i t was found t h a t t h e distillate had reducing properties and t h a t i t would form a n osazone. N o further work was done on this until recently when another sample of saccharine sorghum silage was being studied and it was decided t o determine what this reducing substance might be. T h e work of Balcom‘ on t h e volatile reducing substance in cider vinegar was recalled in this connection, and t h e conditions under which t h e silage was formed and t h e f a c t t h a t it was formed from a cane having a very large amount of sugar led us t o suspect t h a t t h e reducing substance was acetylmethylcarbinol which was found b y Balcom t o be present in cider vinegar. It was thought desirable t o compare t h e reducing power of t h e distillate with t h e reducing power of t h e original extract from t h e silage. For this purpcse 2 5 cc. of t h e juice were clarified b y treating with lead subacetate and sodium carbonate a n d centrifuging. T h e reducing power of t h e clarified juice was then determined b y Fehling’s solution a n d subsequent oxidation and weighing oE t h e copper as cupric oxide. I t was found in this way t h a t t h e reducing power of I O O cc. of t h e silage extract was represented b y 1.26 g. of metallic copper. I n order t o get t h e reducing power of t h e distillate, 500 cc. of water were added t o I O O cc. of t h e silage extract and 300 cc. were distilled off; then another 2 0 0 cc. of water were added and t h e distillation continued until t h e total distillate amounted t o 500 cc. T h e purpose of adding t h e 2 0 0 cc. of water was t o avoid t h e concentration of t h e acid becoming great enough t o act on t h e pentosans t o form furfural. T h e reducing power of t h e distillate was determined b y taking 2 j cc. and proceeding as in t h e case of t h e silage extract. It was found t h a t t h e reducing power of t h e total distillate of 500 cc. was represented b y 0.9660 g. of metallic copper. It was 1
J . A m . Chem. Soc., 39 (1917), 309.
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T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
thought possible t h a t even with this large amount of distillate not all of t h e volatile substance had been carried over a n d in order t o dqcide this point another I O O cc. of water were added t o t h e distillation flask and IOO cc. distilled over. The reducing power of this I O O cc. distillate was found t o be represented b y 0.0796 g. of metallic copper. This shows t h a t there was still considerable of t h e volatile reducing substance left in t h e distillation flask. It is interesting t o note t h a t t h e total reducing power of t h e 600 cc. of distillate was represented b y 1.0456 g. of metallic copper and t h e total reducing power of t h e silage extract, as stated above, was represented b y 1.26 g. of metallic copper. When it is remembered t h a t probably part of t h e volatile reducing substance was still i n t h e distillation flask, i t is seen t h a t very little of t h e reducing power of t h e extract was due t o sugar and other reducing substances, and this in spite of t h e fact t h a t t h e total sugars in t h e cane when it was made into silage ran 13.35 per cent a n d t h e reducing sugars (as dextrose) r a n 7.62 per cent. P a r t of t h e distillate was treated as directed’by Balcom for t h e formation of t h e osazone and after heating on t h e water bath for 2 hrs., a considerable quantity of a lemon-colored precipitate was formed. It was found when we tried t o filter off this precipitate t h a t a considerable amount of i t had stuck t o t h e bottom of t h e flask. There was no apparent reason why i t should adhere in this way since t h e precipitate up in the liquid seemed t o be more or less pulverulent. When i t was attempted t o remove t h e precipitate from the flask with astirring rod, it was found t h a t it stuck t o t h e rod, indicating t h a t there was some glue- or oil-like substance holding t h e precipitate together. No a t t e m p t was made t o determine what this oily substance was b u t t h e precipitate +as recrystallized twice from 95 per cent alcohol, when a lemon-colored powder was obtained. T h e melting point of this precipitate was determined and found t o be 2 4 3 ’ t o 244’ C. This was t h e melting point found b y Balcom for t h e osazone of t h e compound acetylmethylcarbinol so t h a t there is no doubt t h a t this is t h e volatile reducing substance t h a t is present in t h e saccharine silage. A nitrogen determination was not made on t h e substance on account of t h e fact t h a t t h e department has b u t a small supply of phenylhydrazine hydrochloride and has not been able t o buy i t on t h e market, and for this reason we did not care t o use much of it. Furthermore, i t was thought t h a t sufficient work was done t o prove t h a t t h e substance was actually acetylmethylcarbinol without its being necessary t o make t h e nitrogen determination. Extracts from Sudan grass, corn, and feterita silage were distilled and tested for volatile reducing substances without finding t h e m t o be present. Neither was furfural found t o be present in a n y of these distillates. One would expect, however, t h a t since t h e composition of these substances is very similar t o t h a t of t h e saccharine sorghum, the greatest difference being in t h e per cent of sugars present, t h a t acetylmethylcarbinol would be present in t h e fresh silage
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formed from these substances. This point will be tested out this next Fall. It is very important t o determine whether or not this substance i s present in these silages since, if it is present, it will be necessary t o modify t h e method for t h e determination of sugars and also t h e method for t h e determination of t h e alcohols in silage. It is quite probable, as pointed out b y Balcom, t h a t when acetylmethylcarbinol is oxidized, acetic acid is formed, and hence in t h e Duclaux method for t h e determination of t h e alcohols, as outlined above, if t h e ethyl alcohol is calculated on t h e basis of t h e amount of acetic acid found, it is seen t h a t this method is totally unreliable for t h e determination of ethyl alcohol in saccharine sorghum silage. It should be added here t h a t t h e saccharine sorghum silage is t h e only one in which we have found formic acid t o be present and this is quite likely due t o t h e fact t h a t formic acid is one of t h e oxidation products of acetylmethylcarbinol. As stated above, a further test will be made on t h e fresh silages this Fall t o determine whether or not acetylmethylcarbinol is present in the fresh silage made from field crops t h a t are usually used for this purpose. OKLAHOMA EXPERIMBNT STATION STILLWATER, OKL.4HOMA
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COURSE OF REACTION IN EXPLOSIONS OF DILUTE CSrAIR MIXTURES By G R . STEWART AND
JOHN
S BURD
Received June 29, 1918
T h e enormous destructiveness of ground squirrels, and t h e great practical benefits resulting from a n y improvement in methods of coping with these pests, recenily led us t o undertake field and laboratory studies on t h e effects of various gases believed t o be effective as killing agents. T h e results of this work are, for t h e most part, printed elsewhere,l t h e present paper being confined t o t h a t phase of our experiments which may be of technical interest t o chemists. Carbon disulfide, t h e compound which we have t o consider, is extensively used in attempts t o exterminate ground squirrels. Two general procedures are commonly followed in its application. One of these is t o p u m p t h e vaporized carbon disulfide into t h e burrow; t h e other method consists in saturating an absorbent cloth with liquid carbon disulfide, placing t h e same within t h e mouth of t h e burrow and igniting. Considerable difference of opinion exists among practical men as t o t h e relative efficiencies of t h e two methods. This is doubtless due t o t h e fact t h a t conditions vary so much in t h e field t h a t one method may be superior under a given set of conditions and quite inferior under other circumstances. It seems clear, however, t h a t t h e effectiveness of both procedures depends upon two factors, toxicity of t h e disulfide or its combustion products, and t h e rate of dissemination of t h e toxic gases into t h e subterranean passages of the burrow. Any comprehensive s t u d y 1 Stewart and Burd. “Control of Ground Squirrels by Fumigation Methods,” Bzdlelzn, Ccl. A g Y . Espt. Stclzon, 1918. I n preparation
