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Until quite recently we have had no accurate method for the determination of fusel oil in alcohol or brandy. In 1837 Meurer suggested a solution of one part of silver nitrate in nine parts of water as a reagent for its detection, stating that when added to alcohol containing fusel oil, a reddish brown color is produced, and in case large quantities are present, a dark brown precipitate is formed. It was soon found, however, that other substances than amyl alcohol produce brown colored solutions with silver nitrate; and Bouvier1 observed that on adding potassium iodide to alcohol containing fusel oil, the solution is colored yellow, from the decomposition of the iodide. Subsequently Böttger2 proved that potassium iodide is not decomposed by pure amyl alcohol, and that the decomposition is due to the presence of acids contained in fusel oil. More accurate results are obtained by using a very dilute solution of potassium permanganate, which is decomposed by amyl alcohol much more rapidly than by ethyl alcohol.
Depré3 determines fusel oil by oxidizing a definite quantity of the alcohol in a closed vessel with potassium bichromate and sulphuric acid. after removal of excess of the oxidizing reagents, the organic acids are distilled, and, by repeated fractional distillation, the acetic acid is separated as completely as possible. The remaining acids are saturated with barium hydroxide, and the salts analyzed; a difference between the percentage of barium found and that of barium in barium acetate proves the presence of fusel oil, and the amount of difference gives some idea of its quantity. Betelli4 dilutes 5 c.c. of the alcohol to be tested with 6 to 7 volumes of water, and adds 15 to 20 drops of chloroform and shakes thoroughly. If fusel oil is present, its odor may be detected by evaporating the chloroform; or, by treatment with sulphuric acid and sodium acetate, the ether is obtained, which can be readily recognized. Jorissen5 tests for fusel oil by adding 10 drops of colorless aniline and 2 to 3 drops of hydrochloric acid to 10 c.c. of the alcohol. In the presence of fusel oil a red color is produced within a short time, which can be detected when not more than 0.1 per cent. is present.
But Foerster6 objects to this method because he finds the color to be due to the presence of furfurol, and that pure amyl alcohol gives no color with aniline and hydrochloric acid.
Hager7 detects fusel oil as follows: If the spirit contains more than 60 per cent. of alcohol, it is diluted with an equal volume of water and some glycerine added, pieces of filter paper are then saturated with the liquid and exposed to the After the evaporation of the alcohol, the odor of the fusel oil can be readily detected. For the quantitative determination he distills 100 c.c. of the alcohol in a flask of 150 to 200 c.c. capacity connected with a condenser, and so arranged that the apparatus does not extend more than 20 cm. above the water bath. This arrangement prevents the fusel oil from passing over. If the alcohol is stronger than 70 per cent., and the height of the distillation apparatus is not more than 17 cm., the residue in the flask may be weighed as fusel oil. With a weaker alcohol, or an apparatus which projects further out of the water bath, the residual fusel oil is mixed with water. It can, however, be separated by adding strong alcohol and redistilling, or by treating with ether, which dissolves the amyl alcohol, and distilling, the temperature being raised finally to 60°.
Marquardt,8 like Betelli, extracts the fusel oil from alcohol by means of chloroform, and by oxidation converts it into valeric acid. From the quantity of barium valerate found he calculates the amount of amyl alcohol present in the original solution; 150 c.c. of the spirit, which has been diluted so as to contain 12 to 15 per cent. of alcohol, are shaken up thoroughly with 50 c.c. of chloroform, the aqueous layer drawn off, and shaken with a fresh portion of chloroform. This treatment is repeated several times. The extracts are then united, and washed repeatedly with water. The chloroform, which is now free from alcohol and contains all the fusel oil, is treated with a solution of 5 grammes of potassium bichromate in 30 grammes of water and 2 grammes of sulphuric acid, and then heated in a closed flask for six hours on a water bath at 85°. The contents of the flask are then distilled, the distillate saturated with barium carbonate, and the chloroform distilled; the residue is evaporated to a small volume, the excess of barium carbonate filtered off, and the filtrate evaporated to dryness and weighed. The residue is dissolved in water, a few drops of nitric acid added, and the solution divided into two portions.
In the first portion the barium is determined; in the second the barium chloride. The total per cent. of barium minus that of barium chloride gives the amount present as barium valerate, from which is calculated the per cent. of amyl alcohol. By this process the author has determined one part of fusel oil in ten thousand of alcohol. To detect very minute quantities of fusel oil, the chloroform extracts are treated with several drops of sulphuric acid and enough potassium permanganate to keep the solution red for twenty-four hours. If allowed to stand in a test tube, the odor of valeric aldehyde will first be noticed, then that of amyl valerate, and lastly that of valeric acid. - Amer. Chem. Journal.
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Dingler's Polytech. Jour., ccxii., 516.
Pharm. J. Trans.  vi., 867.
Berichte d. Deutschen Chem. Gesellsch., viii., 72.
Pharm. Centralhalle, xxii., 3.
Berichte d. Deutsch. Chem. Gesellsch., xv., 230.
Pharm. Centralhalle, xxii., 236.
Berichte d. Deutsch. Chem. Gesellsch., xv., 1,370 and 1,663.