July,
1920
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
PRESERVATIVES FOR FERMENTABLE BEVERAGE SAMPLES By J. S. McCune and A. N. Thurston DIVISION OB LABORATORIES,OHIO STATEDEPARTMENTOB HEALTH, COLUMBUS,OHIO Received October 27, 1919
Before prohibition went into effect, t h e Liquor Licensing Board in Ohio was collecting many samples of alcoholic beverages in connection with t h e licensing laws. These were analyzed a t t h e Department of Health Laboratory, where all state analytical work is now done. Some of t h e samples collected in territory which was dry because of local option were near beers and ciders. Argument arose about these samples as t o t h e possibility of fermentation before delivery t o t h e laboratory, b u t after t h e sale of t h e liquid. With near beers and particularly with ciders there was no d o u b t as t o this having occurred in some instances where delivery was unavoidably delayed. For t h e purpose of testing out t h e necessity of preservatives, a n d t h e chemicals best suited for this use, cooperation between t h e two departments was arranged. However, when prohibition became effective, t h e Liquor Licensing Board ceased t o exist, which has handicapped t h e work t o some extent. Sweet cider could not be obtained, and so t h e preliminary experiments have been made on near beer. The tests are of interest, however, and will be of value in court cases for t h e enforcement of dry laws in t h e state. The experiments made are listed below, and since lack of samples has prevented any extensive study, t h e conclusions are open t o revision. Information from any bureaus or departments engaged in control work would be welcome. EXPERIMENT I--(‘Bruin,” a near beer manufactured in Columbus, Ohio, and sold in bottles, was allowed t o s t a n d open a t room temperature. CONTENT: PER CENT BY VOLIJfiIE Original.. . . . . . . . . . . . . . None After 1 d a y . , . . . . . . . . . . None After 2 d a y s . , . . . . . . . . . None After 5 d a y s . . . . . . . . . . . 0 . 1 9 (heavy mold growth)
.4I,COHOL
Conclusion: The bottled beer would not ordinarily ferment, even when open. EXPERIMENT z-Same, with I cc. of a suspension of Pleischman’s yeast. CONTENT: PER CENT B Y VOLUME Original.. None After 1 d a y . . 1.47 After 5 d a y s . . 2 .OS
.4I,COHOL
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Conclusion: With yeast 2 . 0 0 per cent alcohol were (obtained, t h e large portion in 24 hrs. E X P E R I M E N T 3-Bruin and I cc. yeast as above, [but with varying preservatives, each added as 0 . 2 0 per cent. ALCOHOLCONTENT:PER
CENT BY VOLUME Mercuric Chloride Salicylic Acid After 1 d a y . . 0.20 0.20 After 4 days.. 0.13 0.10 Sodium Benzoate Sodium Bisulfite After 1 d a y . .................... 0.16 0.73 After 4 days.. . . . . . . . . . . . . . . . . . . 0.10 2.20
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Conclusion: Two-tenths per cent of mercuric chloride, salicylic acid, or sodium benzoate are satisfactory
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t o prevent fermentation. The same percentage of sodium bisulfite is unsatisfactory. EXPERIMENT 4-Same as Expt. 3, but beer was allowed t o ferment one day before adding preservative, t o determine whether started fermentation would be checked. ALCOHOI,CONTENT:PER CENT B Y VOLUME Mercuric Chloride Salicylic Acid After 1 day, without preservative, . . . . . . . . . 1.OS 1.04 Same, 3 days, after preservative a d d e d . , 1.04 1.02 Sodium Benzoate Sodium Bisulfie After 1 day, without preservative, 1.04 1.04 Same, 3 days, after preservative a d d e d . , , , 1.95 1.88
....
......... ..
Conclusion: Two-tenths per cent of mercuric chloride or of salicylic acid are satisfactory t o check started fermentation, b u t t h e same amount of sodium benzoate or sodium bisulfite is unsatisfactory. EXPERIMENT 5-Same as Expt. 4, b u t with sodium benzoate only, t o determine whether t h e sodium benzoate result could be confirmed. VOLUME Sodium Benzoate No. 1 No. 2 One day’s fermentation before adding benzoate. . . . 0 . 4 7 0.48 After 3 days additional with 0.20 per cent benzoate 1.94 1.95 ALCOHOLCONTENT:PER CENT
BY
Conclusion: Sodium benzoate ( 0 . 2 0 per cent) is unsatisfactory t o check fermentation. E X P E R I M E N T &Draft near beer, purchased from keg, with 0 . 2 0 per cent sodium benzoate and without, t o determine whether draft beer would ferment without added yeast and whether benzoate would prevent t h e fermentation. ALCOHOLCONTENT:PER CENT BY VOLUME Without With Preserva,0.20 Per cent tive Benzoate As purchased.. 0.43 0.43 After 1 d a y . . 1.18 0.47 1.43 0.43 After 3 d a y s . . After 8 days 0 . 4 3 (heavy mold growth)
......... .......... ......... .............
Conclusion: ( a ) Draft near beer would ferment rapidly as purchased; ( b ) sodium benzoate, 0 . 2 0 per cent, prevented this fermentation. EXPERIMENT 7-Draft near beer, without yeast, preservatives, 0 . 2 0 per cent, added on day of purchase. ALCOHOLCONTENT: PER CENT BY VOLUME Mercuric Chloride Sai!cylic Acid As purchased ...................... 0.63 63 After 3 days with preservative.. 0.63 60 Sodium Benzoate c Acid As purchased., .................... . O . 63 tJ.63 1.53 After 3 %dayswith preservative.. 0.75
.......
’
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Conclusion: Mercuric chloride, or salicylic acid per cent), satisfactory t o prevent fermentation; sodium benzoate ( 0 . 2 0 per cent), doubtful; boric acid (0.20 per cent), unsatisfactory. EXPERIMENT 8-Draft near beer as in Expt. 7, b u t preservatives added after one day’s standing. (0.20
ALCOHOLCONTENT:PER CENT BY VOLUME Mercuric Chloride Salicylie Acid As purchased 0.63 0.63 After 1 d a y without preservative.. ........... 1.35 1.35 After 3 days additional with preservative. ..... 1.30 1.36 Sodium Benzoate Boric Acid As purchased 0.63 0.63 After 1 d a y without preservative.. ........... 1.35 1.35 After 3 days additional with preservative.. .... 1.50 1 56
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T H E J O U R N A L OF I N D U S T R I A L A N D EATGINEERING C H E M I S T R Y
Conclusion: Fermentation nearly complete in one day, b u t results in general checked conclusions of Expt. 7. G E N E R A L CONCLUSIONS
These experiments show t h e efficiency of t h e above preservatives used in untreated draft beer and bottled beer treated with Fleischman’s yeast. Sodium benzoate, 0 . 2 0 per cent, is unreliable as a preservative. Sodium bisulfite and boric acid, 0 . 2 0 per cent, are worthless. Mercuric chloride and salicylic acid, 0 . 2 0 per cent, are satisfactory preservatives. Due t o t h e poisonous nature and higher cost of mercuric chloride, salicylic acid, 0 . 2 0 per cent, is recommended as t h e preservative t o be used when fermentable samples are t o be tested for alcohol content and when immediate delivery t o t h e laboratory is not possible. A SIMPLE ALCOHOL-TESTING DEVICE‘ By Sigmund Waldbott THELLOYDCHEMICAL RESEARCHLABORATORY, CINCIINATI,OHIO Received December 16, 1919
A simple device has been developed which readily differentiates between a beverage of low alcohol cont e n t , e. g., 0.5 per cent, and one containing more, e. g., 3 per cent alcohol. It is not intended t o replace t h e exact methods of alcohol determination, b u t rather t o aid them, by giving preliminary information as t o alcoholic contents. Its principle is t o boil out t h e alcohol, separate i t from t h e water vapor b y means of a simple fractionating device, and demonstrate t h e alcohol vapor by ignition. T h e apparatus consists of a copper flask and a fractionating attachment as shown in t h e sketch, made of glass or metal. T h e fractionating medium consists of glass beads which fill t h e receptacle of t h e attachment. The bend in t h e exit t u b e has some advantage in t h e demonstration. In heating the, flask b y a Bunsen burner, or b y a n 1 Presented at a meeting of the Cincinnati Section, American Chemical Society, October 15, 1919.
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alcohol lamp, use a n asbestos plate with a I-in. opening i n t h e center. Fifty cc. of t h e fluid, e . g., beer, are p u t i n t o t h e flask, and heated over a medium-sized Bunsen flame to boiling, regulating t h e flame according t o apparent needs. When using a glass attachment, t h e Drom-ess . - of condensation is easily observed. I n t h e case of metal, t h e 1%‘ sense of touch will tell, When t h e alcohol vapor appears a t t h e orifice, ignite i t with a burning match or candle. If t h e beer contains 3 per cent alcohol, a semiluminous, blue flame about 3 in. long will continue t o burn for 1 2 0 t o 1 5 0 sec. depending on t h e size of t h e Bunsen flame. -- 6” When t h e beer contains only 0.5 per cent alcohol, t h e flame of t h e same length lasts about 2 0 t o 2 5 sec. under t h e same conditions of heating t h e bulb. Thus t h e duration of t h e flame is approximately proportional t o t h e alcohol contents. T o -A ” this extent, €he apparatus permits even approximate Y quantitative estimations. T h e apparatus may serve as a lecture experiment, and may prove useful as a legal instrument in t h e hands of government officials charged with t h e enforcement of laws relating t o alcoholic contents of beverages. ~
ADDRESSES AND CONTRIBUTED ARTICLES A PLAN FOR INCENTIVE TO RESEARCH IN PURE AND APPLIED CHEMISTRY1 By William J. Hale Dow CHEMICAL C o . , MIDGAND, MICHIGAN
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In these post-bellum days of industrial reconstruction we cannot fail to note the prominence gained by American chemists. Those with adequate training and experience meet with little difficulty in their forward progress, but far too many realize more and more that lack of broader training in their early academic career. Only those young men thoroughly grounded in the fundamentals of their science and well versed in engineering and mathematics can ever expect t o gain the prominence they seek. Colleges everywhere must recognize this situation 1 Read at the 59th Meeting of the American Chemical Society, Division of Industrial and Engineering Chemistry, St. Louis, Mo., April 12 to 16, 1920. A committee has been appointed b y this Division to study the questions herein presented and t o draw up a definite plan for actiod
and strengthen decidedly their prescribed chemical training. For the university man who is soon t o enter actively the chemical profession it has thus appeared as most reasonable to recommend the further pursuit of the science for a year or more on some problem of research, and under competent guidance; to this end a number of industries have endeavored to lend encouragement through the offer of material aid. This aid usually follows some plan more or less in keeping with precedent at the particular university and beyond this much is left t o the goodwill of all concerned. Though the best of motives may have prompted this action on the part of the industries, I feel that they have not sufficiently weighed the outcome of their well-intended efforts. In other words, I believe that a far better plan for the furtherance of chemical research lies open to us. You may characterize my plan as daring, but I shall choose to call it the plan of incentive, and in order to draw sup-
