Memorandum on Fusel Oil

Nov., 1886.] WARDEN ON FUSEL OIL. 321

(Joinmuuiafioits. containing amy lie alcohol, appears to consist ?rifliital chiefly of butyl alcohol. 6. Fusel oil is to MEMORANDUM ON FUSEL OIL. stated by Wagner* be formed in when fermen- By C. J. H. WARDEN, Esq., large quantities only tation takes at a in a Chemical Examiner to Government of Bengal. place high temperature concentrated saccharine solution while no tar- 1. As the of Fusel in subject country liquor taric acid is present. A fluid which ferments lias the attention of the Excise Com- engaged ? a . at low temperature and is very dilute, does the note be of mission, following may perhaps not yield fusel oil, at least no amylic alcohol, As far as I have able to ascer- interest. been which also is never formed in such wines as no of amount tain, quantitative estimations the have been fermented when tartaric acid has of fusel oil in Indian present country liquors been present in the fluid. hitherto been while fermenting have made; the published 7. Not only does eacli alcohol of the homo- determinations of fusel oil in quantitative logous series differ from the preceding one by and are few. This English foreign liquors may containing an additional atom of carbon and two be due to the fact that mere perhaps the detec- of hydrogen, but these alcohols also differ ill tion of fusel oil is se sufficient to condemn per their physical properties. Thus:?? a beverage, and the estimation of the amount Ethyl alcohol boils at ...... 78-4? C actually present consequently of comparatively Propyl ? ? 97-5? ? little moment. ? 7 j 116? ? 2. Fusel or fousel oil is a term ' ...... 137? generally Amyl ? ? ? to but fusel applied amylio alcohol, practically Hexyl ? ? 157? ? oil is a mixture of several alcohols ; homologous The alcohols therefore which go to make up an in homologous being expression employed fusel oil have all points than to denote a series of com- higher boiling organic chemistry alcohol, and upon this fact the each member of which differs from the ethyl depends pounds rectification or of of wine one an addition of purification spirits preceding by CH2. from fusel oil. When a mixture of 3. The fermentation of liquids, pure sugar yields whose boiling points differ, is subjected to dis- alcohol, of and ethyl ordinary spirits wine, tillation, the more volatile i.e., the one succinic and carbonic acids. But liquid, glycerine, with the lowest boiling point, distils over first,' when are used, derived from fruits or sugars but as the temperature rises the vapour in addition to ordinary alcohol, one or trrain, of the higher boiling point liquid also com- more of the of ethyl alcohol higher homologues mences to pass over, consequently one distill- are as well as ethereal salts and acids. yielded fatty ation or rectification is never sufficient to com- 4. alcohol means of wine Popularly, spirits remove all fusel from a from vinous but chemi- pletely spirit. Roscoef obtained fermentation, which indicates how of wine is a member of a givesanexample imperfectly* cally spirits merely even bodies whose points do not lie class of alcohols. an illustration boiling large Taking close together can be separated by one dis-: from the series, we have as the first homologous tillation. He for the experiment a member:? employed mixture of equal volumes of spirits of wine alcohol or wood a of Methyl spirit, product with a boiling point of 78'4?C and amylic alcohol the destructive distillation of wood, and having with a boiling point of 132?C. The mixture- a formula then alcohol or CH, OH; ethyl was distilled with certain and the of wine OH then alcohol precautions spirits C2H5 ; propyl distillate collected in seven fractions. Ou an- OH, an alcohol found in the of 02 H7 products alysis the following results were obtained :? the distillation of as well as of grain spirits, Spirits of wine Amjlic alcohol French brandies. Then alcohol per cent. per ceut. butyl C4Hg 1st Fraction I alcohol and alcohol boiling OH; amy C5HnOH; hexyl point ... 80?? 90? C 88 1 H'9

... 18 all of which be 2nd ? 90??100? G 82 C6H13 OH, may produced duriug ? 3rd ... C Cl o 38-5 the ferment ation of saccharine ? ? 100??110? substances; amylic 47-9 4th ? ? ... 110??120? G 52-1 alcohol in 4 81*6 being especially yielded large quan- 5th ? ? k.. 120??130? C 18 o tities the ... C 4-5 9o by fermentation of sugar obtained Gth ? ? 130??131? .. 0 2 99-8 7th ? ? 131??132? G from potato starch. 8. In this the alcohols 5. Excluding methyl alcohol, which is not a experiment employed a between their product of saccharine fermentation, the result had difference of 53"6?C boiling but with mixtures of alcohol aud fusel of ordinary fermentation will be a mixture of points, the first of the distillate ethyl and other higher alcohols, together with oil, portions might contain a of fatty acids and ethereal salts. The homologues very probably larger percentage fusel oil than is indicated in the above as of ethyl alcohol with the ethers, &c., being table, not a definite designated fusel oil. The composition of the fusel oil has composition, but to the * fuseT oil differs according nature of the Chemical Technology. mash. Fusel oil from mhowa spirit, though f Jtoscoe and Schorlemmer, Organic Chemistry. 322 THE INDIAN MEDICAL GAZETTE. [Nov., 1886.

varies to the source of the saccharine according per cent, matter fermented. As bearing on this point some amy lie alcohol. conducted be No. 5 Mhowa liquor, 1st fraction of experiments recently may quoted: ... 1 ... '455 ,, was gallon One maund of inhowa mixed with 24 2nd of ? ? Mhowa liquor, fraction of the mixture to 6 ...... -'862 gallons water, allowed ferment gallon ,, 3rd fraction of and one gallon distilled. ? ? Mhowa liquor, ...... "450 G gallon ? The distillate had a strength of 30 under proof and contained *1553 per cent, of fusel oil. 11. In discussing the physiological action of The distillation was then continued, and a fusel oil, it will be convenient to first consider second fraction of six gallons collected; this its effects as a whole and then to indicate the had a strength of 42 under proof and contained action of two of its chief constituents?butyl *233 per cent, of fusel oil. and amyl alcohol. The physiological action of third fraction The consisted of six gallons the remaining alcohols does not appear to have with an alcoholic strength of 64 under proof been fully studied. and contained *162 per cent, of fusel oil. According to Monsieurs Dujardin, Beaumety, 9. In addition to the fusel oil determin- and Andige* the higher homologues of ethyl ations already quoted, the following estimations alcohol exert a still more distinct physiological have been made with country spirit supplied by action than common alcohol, and to these is es- the Excise Commission, Calcutta. to be ascribed the evil effects which Proof Fusel oil pecially spirit ensue from the use of common Their by volume, per cent. brandy. * lis. A. P. experiments indicate that the impurer the alcohol No. Chirkunda 1, (Khedaram used the more marked are symptoms Kalwar), price ... 0 4 0 30*64 *676 during Kamalia Man- life and the anatomical lesions detected after ? 2, (Gonesh dal), price ... 0 4 0 2S'13 '510 death. Thus rectified spirit caused marked mor- Chirkuuda Rasi ? 4, (Kheda- bid whilst ethyl alcohol rectified ten ram Kalwar), price ... 0 0 9 10'5 *0215 changes, times induced but few alterations. ? 5, Kumardubi Rasi, (Khe- daram Kalwar), price... 0 0 9 14'6 '064 Dr. 13. W. Richardson in the Cantor lectures Note,?The spirit was prepared from the rahowa flower. delivered before the Society of Arts in 1875, No particulars were communicated regarding describes the physiological action of butylie the material used in the preparation of the above alcohol as follows :? " liquors. The action of butylie alcohol on the animal 10. In 1876 Dr. Dupre read a paper before body is divisible into four stages, the same as the Society of Public Analysts in which he we have seen in respect to methylic spirit, but gave the results of some determinations of fusel the period required for producing the different oil in whisky, &c. Dr. Duprd found in a sample stages is greatly prolonged, and when the third of Scotch whisky, strength 54'5 per cent, by stage, that of complete insensibility, is reached, weight in volume *108 per cent, of amylic there is added a new phenomenon which does while same a alcohol, the spirit submitted to not belong to any of the lighter alcohols. In process of purification gave no trace of fusel oil. this third after the of the ' degree, temperature A sample of Cape Smoke,' strength 35*7ii per body is depressed to the minimum by the butylie cent, by weight in volume contained '089 per spirit, distinct tremors occur throughout the cent, of fusel oil. whole of the muscular system. These come 21*51 A sample of Samsho, strength per cent, on at regular intervals spontaneously, but they *04 cent, by weight in volume per amylic alcohol. cau be excited by a touch at any time, and in A sample of fine Samsho strength 24*49 per the intervals when they are absent there is volume contained *033 cent, by weight in per frequent twitching of the muscles. The tre- cent, of amylic alcohol. Tabulating the various mors themselves are not positively muscular and the results fusei oil determinations, statiug contractions, but are rather vibrations or wave- the ratio of fusel oil to 100 so as to indicate like motions through the muscles, and are attend- parts of absolute alcohol? ed with an extreme deficiency of true contrac- Scotch Whisky per 100 absolute tile power in the muscular fibre. An electrical ... ? "19 percent. alcohol current the muscles which would amylic alcohol. passed through ... ??? '24 in health throw into Cape Smoke ? them rigid contraction will ... ??? "18 Common Samsho ? now excite the tremors and them ??? keep proceed- ??? "13 Fine ... ,, but will not excite contraction. Indian country liquors? ing, complete as the No. 1 Chirkunda (Khedaram Rs.A.P. So long tremors are present, the temper- Kalwar), price ... 0 4 0 4*777 ? ature of the body is depressed, falling even half ,, 2 Kamalia Man- (Gonesh a but when the ... degree, cease, dal), price 0 4 0 3*923 ? they temperature 4 rises not to but to ,, Chirkuuda Rasi (Kheda- again, the natural standard, ram Kalwar), price 0 0 9 '446 ? or near that which existed before the tremors ? 5 Kumardubi Rasi (Khedaram Kalwar), price ...... 0 0 9 '956 ? * Comptes Rendus, LXXXI, para. 152. Nov., 1886.] WARDEN ON FUSEL OIL. 323

were excited. After the tremors are once estab- " Amylic alcohol, when it is introduced as an lished, they continue without further adminis- adulterant, is an extremely dangerous addition tration of the alcohol for ten and twelve hours, to ordinary alcohol, in whatever form it is so do that re- and slowly they decline, they may presented, whether as wine or spirit. Its ac- a even hours. main in slight degree,for thirty-six tion on the body is the same as that of butylic remission of and They subside by intensity pro- alcohol. It produces three stages of insensi- interval of recurrence. One fact longation of bility, ending in the profoundest narcotism or attaches itself to these of singular significance coma, followed by reduction of temperature tremors. are the tremors which muscular They and by muscular tremors. These tremors recur occur in man during the stage of alcoholic dis- with the most perfect regularity of themselves, there is set that to which ease, when up malady but they can be excited at any moment by we the name of delirium tremens. An ordi- give touching the body, or blowing upon it, or even intoxication with a alcohol is in- a nary lighter by sharp noise, such as the snap of the finger. to this of sufficient produce extreme perversion In all other respects the phenomena induced nervous and muscular but the introduc- power, are the same as are observed from butylic tion of one of these heavier or it alcohols, may alcohol, except that they are much more pro- excessive saturation of with a be the the body longed from two to three days being some- lighter spirit?for on this point I am not sure?is times required for the complete restoration of to cause the tremulous motion. What sufficient the animal temperature. The reason of this what the nature of these muscular movements is, prolongation of action lies in the greater weight betweeu the unnatural relationships exist and the greater insolubility of this spirit; nervous the muscles and the blood to system, that is to say, the force required to decompose are In- lead to them, questions still unsolved. it or mechanically lift it out of the body when voluntarily developed even against the will, ex- it has once entered it, is so much greater than cited by an external touch, attended with great is required for the lighter spirits, which diffuse reduction of temperature, and remaining as long more readily through the secretions, volatilise as the temperature is reduced, they indicate an by the breath or possibly undergo rapid decom- extreme depression of animal force; a condition position. The odour of the substauce remains in all the to which force of life that remains has for many hours iu the animal tissues." be expended on the mere organic acts of life, on Blyth* gives a resume, of the investigations the support of the motions of the heart, the of Eulenberg, Rabuteau, Cross, and others. muscles of respiration and the functions of secret- " Eulenberg allowed 30 grains of amyl alcohol ing glands. The voluntary systems of nerve to evaporate iu hot saud in a zinc box in which and muscle are indeed well-nigh dead, and the a kitten was confined. After half the quautity rests 011 of recovery entirely the maintenance had been put in, the symptoms immediately nervous will the organic power. Still recovery commenced, and in an hour the animal lay take place if the body be sustained by external partly insensible, breathing with difficulty, and internal nourishment. heat and by There was, however, no full narco- " shivering. In the extreme stage of intoxication from sis, and it recovered in four days. In another butylic alcohol, the red blood in the arteries experiment, in which 40 drops of amyl alcohol loses its rich colour, and the blood from the had been administered to a kitten, after seven- veius, which flows with difficulty, is of a dirty teen minutes there was palpitation of the heart, hue. The blood coagulates readily, but the irregular breathing, and relaxation of the limbs, clot is loose, and the fibrine, of which it is coin- and in twenty-two minutes there was full posed, separates in a coarse network or mesh. atucsthesia. The animal recovered after a The little corpuscles of the blood run into each short time, the heart's action remaining more other, forming rolls or columns. Indeed, it is frequent than usual until the next day. Cross wonderful how the blood circulates through the observed similar symptoms iu pigeons and kit- structures it should nourish. The vascular tens ; in the latter, the was stertorous. membrane respiration of the brain are found charged Rabuteau states that one of amylic alcohol with this tarry blood ; the brain structure is in 500 of water causes ansesthesia in frogs in softened and gives the odour of the poison, and twenty minutes; the heart's action becomes muscles the when divided by the knife cut with- slower, and the skin dark, and in about two out firmness, yielding from numerous points the hours death occurs, the cardiac pulsations same tai-like blood. The vascular organs, gradually ceasing. Dr. Frust of Berlin killed livei% are spleen, lungs, kidneys, equally a rabbit with about 7*6 grammes injected into and in a similar changed manner. Their fine the stomach ; another, however, recovered from are structures infiltrated with the deteriorated the same dose." which was vascular fluid intended for their main- Blyth also states that, "men engaged in the tenance, and even the secretions and cavities manufacture of potato spirit suffer from headache of the body are perverted by being charged with fluid derived from the unnatural blood.? * Composition of foods, 1882. 324 THE INDIAN MEDICAL GAZETTE. [Nov., 1886.

and nervous unless the general indisposition present in the second fraction. On t.lie other are An vapours conducted away from them. hand, the last six gallons of the distillate con- experiment by Cross 011 himself showed that the tain less fusel oil than the second fraction. caused intense and heaviness vapour aching These results may at first appear not to be in of the head, and other unpleasant symptoms. accord with the experiments described by Iios- It has also been shown that 20 centigrammes coe, in which the amy lie alcohol steadily increas- of taken amylic alcohol internally produce ed as the distillation proceeded. It must be slight symptoms, the action being first stimu- remembered that lloscoe's experiment was made then lating, depressing." with a mixture of pure ethylic and amy lie alco- 12. Regarding the chronic effects of very hols, and that the fractions collected were small. small doses of amylic alcohol, nothing definite In the inhowa liquor experiment, only three is known. Three to be the low- grains appear fractions were collected, the alcohol was dilute, est amount with which can be distinct effects and fusel oil present only in comparatively small but one produced, any liquor containing amount. The dilute alcohol had a boiling point, grain and a half of amylic alcohol per fluid at the commencement of the experiment, suffi- ounce must be considered injurious to health. ciently high to vapourize some of the fusel oil, (Blytli.) and a certain amount was found in the first frac- 13. In the following table is shown the tion. As the alcohol distilled over, the boiling amount of one fusel oil contained in ounce of point of the still contents rose, and a larger each of :? the samples examined amount of fusel oil distilled over. But as the amount of fusel oil was limited, and most of it had Scotch *48 of fusel oil ounce. Whisky grains per already distilled over, in the third fraction a Smoke ... -43 Cape ? ,, smaller amount was found than in the second Samsho ... *19 ? ? fraction. In the distillation of a mhowa mash, Fine Samsho ... -14 ? ? in which a certain is 1. from only quantity distilled, Country liquor after the whole of the alcohol has distilled over Mhowa ... *72 ? ? occurs after about 25 2. Ditto ... 1*10 ? ? (which distilling per cent.) still is a ... the in the mixture 3. Ditto -78 ,, ? liquid remaining a ... of a amount of with 1. Chirkunda 3-21 ? ? very large water, very ... 2'44 small of fusel and each succeed- 2. Kamalia ,, ? percentage oil,

... 4. Chirkunda *096 ,, ? ingO fraction will contain less fusel oil,' because ( t t ... -288 amount oil is 5. Kumardubi ,, ? the of fusel progressively dimin- ishing as the distillation proceeds. A mixture The worst of Indian thus sample liquor contains of a small quantity of fusel oil with a very large nearly seven times as much fusel oil per fluid amount of water thus behaving like a mixture ounce as Dr. Dupre's sample of unrectified of ordinary alcohol and water, in which each Scotch whisky, while the least contaminated succeeding fraction contains a smaller amount contains.rather less than half the amount found of alcohol. On the other hand, if the fusel oil in fine " Samsho," Judged, therefore, by the be equal in amount to the water, the liquid amount of fusel oil fluid sam- per ounce, certain distils like a mixture of ethylic and amy lie of Indian ples country liquor would appear to be alcohols in which each succeeding fraction con- than less injurious beverages Scotch whisky, &c. tains a larger amount of the higher boiling point This method of indicating the relative purity of alcohol. the is correct as as we the spirits long compare 15. In distilling country liquor the last por- of the various But low class the are volumes liquors. tions of distillate frequently rejected as of take it for the effects which consumers liquor being unfit for potable purposes. It is unlike- An ounce of Chirkunda at nine it produces. ly, for the reasons already indicated, that this not an of pie per bottle does equal ounce, say, can be due to a large excess of fusel oil beino- or "Samsho" in alcoholic Scotch whisky present. Acetic and butyric acids are products strength. To institute, therefore, a comparison of the fermentation of inhowa, and the following between Indian and the was to country liquors spirits experiment instituted ascertain the pei> ratio which examined by Dr. Dupre, the the fusel centage of acid in various portions of the distil- alcohol must be the oil bears to the ethylic late. I lie experiment was made with mhowa the least contamin- standard, and by this standard mash, prepared with mhowa 1 maund, water contains ated of the Indian country liquors 21 gallons, spirit wash 6 gallons, and was allowed twice the amount of fusel oil present in Cape to ferment 4 days. Smoke. The distillation was conducted in a metal 14. As regards thecomparafive purity ofliquors still; and every precaution taken to condense the of and low alcoholic the high strength, experi- whole of the vapour. One gallon of mash waft ment detailed in paragraph 8 very clearly indi- distilled and the distillate collected in 6 frac- cates that from the strong spirit obtained the first tions of 20 ounces each, leaving therefore in runnings contains far less fusel oil than that the still 40 ounces. Nov., 1886.] WARDEN ON FUSEL OIL. 325

Proof cali- spirit fidas bassia is, when much like cent. carefully distilled, perr ace

* Calculated as P. S. these 4 fractions of a gallon contain 28-73 oz. of P. S. Assuming that one maund of mhowa mixed with 27 gallons of water, yields 27 gallons of mash, the yield of P. S. from that quantity would be 816 gallons. It has been stated that in England 6" 16 gallons P. S. were obtained from 1 cwt. mhowa, this would be equivalent to about 4-4 gallons P. S. per maund of 82 lbs. The amount which of spirit the flowers can yield obviously depends upon the amount of saccharine matter present, and this varies. The fact that the flowers absorb moisture must also be taken into account, and lastly, the nature of the still and mode of condensing the vapour are important factors. An analysis of Mhowa flowers in their air-dried condition was recently reported by Church (Nature 33, 343-341) 100 parts contained:? Cane sugar g.2 Invert sugar Other matters soluble in water 7-2 Cellulose 2-4 Albuminoids ..: 2-2 Ash 1 Water at 100?C J. It. on the uses of some Jackson, of the Indian spe- Undetermined .... 12-0 cies of Bassia.?J. Pharm. Soc.,. 1878.