646
T H E J O U R N A L OF INDL-STRIAL A N D EKGINEERING CHEMISTRY. Amount from the 6 liters of juice. Names of acids. Grams. Sulphuric acid (as SOs), total not determined, ..................... 0.0305 Phosphoric acid (as P20j). . . . . . . . . 0 . 1 8 8 7 Oxalic acid.. . . . . . . . . . . . . . . . . . . . . 0.0027 Tartaric a c i d . . . . . . . . . . . . . . . . . . . . none 0.0461 Malic acid.. ..................... Succinic acid. . . . . . . . . . . . . . . . . . . . none Aconitic acid, not determined b u t indications of about. . . . . . . . . . . . 3 . 0 none Citric acid.. ..................... Total determined or indicated
3 ,2680
Gram acid per 100 cc juice. 0.00051 0.00314 0.00004 none O.OOOi7 none 0.05
none 0.05447
Remarks.-If we compare the total of acids accounted for in this summary, equivalent to 6 0 . 2 cc. normal solution, with the amount of acidity found in the residue of acids after their separation from the juice b y means of the lead salts and hydrogen sulphide, viz., 1 2 5 . I cc. normal solution, we find that about half of the acids there present are unaccounted for. Doubtless part of this was acetic acid from lead acetate not completely washed out of the precipitate. Lactic acid was not looked for. If present it would have been left as a calcium salt in the 85 per cent. alcohol which was discarded. Nor was any account taken of tricarballylic acid, which v. LippmannI found in sugar beets, along with citric acid and aconitic acid. Some work started on the volatile acids was interrupted before it was finished and no report of interest can a t present be made on these nor on such other acids as may be present which are not precipitated with lead acetate. I t seems clear from the work thus far accomplished t h a t aconitic acid is the predominating one among those precipitated with lead salts in a neutral 50 per cent. alcohol mixture. The only others thus far identified that are present in significant amounts are phosphoric and sulphuric acids. Oxalic, tartaric, succinic, citric, and malic acids are either completely absent or are present in such small quantities as t o have no practical significance to the manufacturer. These facts may have important significance to the sugar chemist and manufacturer, who is seeking t o improve the sugar house and refinery operations so as to secure more complete exhaustion of the molasses or t o prevent the formation of scale in the evaporation apparatus. This relatively high percentage of aconitic acid is a special characteristic of sugar cane juice and its unpurified products. The suggestion that i t occasions the peculiar cane flavor in these products, however, finds no support in the taste of the purified acid, nor in odor or taste developed in heating aconitic acid or its salts, or mixtures of these, with sugar. The free acid facilitates the browning of sugar upon heating, as do also other acids, e . g., tartaric, citric or malic. The phosphoric acid is doubtless removed in part in the clarification process if the juice is limed t o neutrality. Such of the phosphate and the sulphate of lime as remains in the clarified juice may become the cause of the formation of scale. With reference t o the extraction of sucrose from the molasses, it would ’ B e r . d . chem. Ges , 11, i o 7 ( 1 8 7 S j ; 12, 1649-(1879).
Sept., 1 9 1 1
values” of the aconitic acid and its several salts, i. e . , their power of preventing or facilitating the crystallization of sucrose. The high solubility of the lime salt of aconitic acid, even in the hot solution, makes it improbable that any notable quantity of the aconitic acid is removed in the clarification process in which lime is used, or that it is deposited as a scale or sediment during the evaporation in the “effects” or th‘e “ p a n , ” unless the presence of sugars to the point of saturation materially reduces the solubility of the calcium aconitate. The aconitic acid therefore accumulates in the molasses, where it is usually present in extraordinary large amounts. BUREAUOF CHEMISTRY.
D.c.
~ASHIIUGTON,
THE OCCURRENCE O F LEVAN IN SUGAR. B y W. G. TAGGART Received July 3 , 1911
Greig Smith and Thomas SteeleI obtained from sucrose solutions inoculated with Bac. levaniformans a new gum which they named levan, and of which they made a complete chemical study. In conjunction with W. L. Owen, bacteriologist for the Louisiana Sugar Experiment Station, in his work on “The Bacterial Deterioration of Sugars”’ it became necessary to study this same gum. The results agree with Smith and Steele in t h a t levan hydrolyzes quantitatively into levulose according to the reaction (C6Hlo05),a n(H,O) = “(C,H,,O,) ; t h a t its specific rotary power is about [ a 1 ] , = -40; that it melts a t z o o o C.; does not reduce Fehling’s solution; and is not precipitated by lead subacetate. Although Smith and Steele found the gum-forming organism to be present in nearly pure cultures and believed t h a t the organism is responsible for .the greater part of the deterioration of sugars in storage, they were unable t o show by analysis that levan is formed in sugars. Comparison of results obtained by analyses made monthly of a large number of raw sugars proved t h a t the relation between the fall in single polarization and in sucrose (Clerget) could not be accounted for by inversion. In some cases, while the single polarization was found t o decrease the sucrose (Clerget) would slightly increase. Bacteriological examination showed all of these sugars to contain large numbers of the gum-forming organism, and i t may readily be seen that should levan be present in a sugar the single polarization would be decreased 0.6’ v. for every I per cent. gum, and a t the same time the sucrose (Clerget) would be increased 0.67’ v. by the levan hydrolyzing t o levulose during inversion. To prove t h a t levan was responsible for the unusual changes found t o take place in these sugars, attempts were made to separate the gum from solutions of these sugars by precipitating it with alcohol made slightly alkaline with sodium hydroxide. This method, however, brought down so much of the other gummy matter that it was found impossible to separate small
+
J . SOC.Chem. Ind.,Xov. 29, 1902. 2
Louisiana Bulletin, No. 125.
Sept., 191I
T H E J O U R A ’ A L OF I N D U S T R I A L AA’D E L Y G I K E E R I A : G C H E M I S T R Y .
quantities of levan from such sugars, even where i t had been added. By adopting special methods, however, a separation of the levan from inoculated sugars was affected, thus bringing the deterioration process of sugars in line with t h a t found t o take place in sugar solutions. For this work inoculated Peruvian crystals were used. Two solutions of 14 per cent. sugar of j liters each were thoroughly sterilized, and then incculated with yeast and allowed to ferment. When most of the sugar had fermented, the solutions were filtered and evaporated to I liter. The gum was precipitated from the concentrate by adding 3 liters of alcohol made alkaline with sodium hydroxide. After the gum had been dissolved and precipitated four times, a small quantity was obtained which was polarized, hydrolyzed, and the resulting levulose polarized:
Polarization of gum. . . . . . . . . . . . . , . Polarization of hydrolyzed product Theoretical polarization., , , , . . . , . . .
S o . I.
No. 11.
-0 35 -0.72 -0 i 8
-11.24 -0.51 -11 53
Control 99.8 sugar. 00.0 00.0 00 0
Attempts have been made to find a means of avoiding the error in analysis which is caused by the presence of levan. The invertase method was tried and found unsatisfactory, and likewise the Andrlik urea method. I n making the direct polarimetric reading in acid and urea solutions i t was found t h a t the rate a t which the gum hydrolyzed was slower than the rate of sucrose inversion. THE DETECTION O F SUBSTITUTION OF SPIRITS FOR AGED DATA A DISCUSS1oN OF THE PRESENTED I N THE TRIAL O F U. S. vs. NINE BARRELS O F WHISKEY.‘ By A
B
a4DAIfS,
Chief Chemist, Internal Revende Bureau
Received A D n l 24, 1911
I n this country when i t is intended to age new whiskey, it is, as a rule, placed in Government Bonded Warehouses for the purpose. When it enters the warehouse i t is stamped with what is called the “warehouse stamp” which bears the date of inspection and gauge. When the owner desires t o withdraw the package, the t a x is paid and a tax-paid stamp placed upon the stamp head, denoting the fact, stating also the time of t a x payment and number of gallons content. This is called a “double stamped package.” The integrity of the stamp and the Government marks and brands is guaranteed by law, or rather, the Statutes provide a heavy fine and imprisonment for changing the contents of a package, unless the marks and brands are destroyed. For many years it has been a common custom among certain dealers to take such a double stamped package, dispose of a portion, or all of its contents, and then refill the package with either an inferior grade of whiskey or alcohol diluted t o the proper proof and artificially colored and flavored. This is a violation, as stated above, of Section 3455 R.S. The past several years the Commissioner of Internal Revenue has claimed t h a t the substitution of Published by authority of the Commissioner of Internal Revenue.
647
other spirits in a double stamped package could be ascertained by chemical examination. This claim was vigorously disputed by the attorneys who represented the Wholesale Liquor Dealers’ Association before the Bureau of Internal Revenue, it being claimed by them t h a t packages of whiskey varied too much from one another in their chemical constituents t o make such a comparison reliable. At their request it was arranged t h a t a case be tried before a jury, and from the many packages under seizure thirteen barrels were selected for trial. These had been seized on the premises of ---- TVholesale Liquor Dealers, Cincinnati. As four of the packages were libeled later than the others they became two cases, namely, “U. S. vs. Yine Barrels of Whiskey” and “U. S. vs. Four Barrels of Whiskey.” The libel alleged that the barrels were substituted, or did contain other spirits than those tax-paid therein. The first part of the libel read as follows: “First: That said --- doing business under the firm name of -- Co., did then and there receive and have in their possession with intent to defraud, the said nine distillers’ original packages (barrels) of whiskey, which said packages had then and there contained distilled spirits other than the contents which were therein when such packages (barrels) were labeled, stamped, branded and marked b y a duly appointed officer of the Internal Revenue.” ,4s the thirteen barrels were owned and claimed b y the same parties, for convenience sake, the cases were combined for trial and heard as one case. The thirteen packages under seizure, according to the marks and brands, contained whiskey which had been produced by two reputable distillers a t different periods, stored in the respective U. S. Bonded Warehouses for different periods, in order to properly age the whiskey. SOTE -It must be understood t h a t the Government had absolutely no suspicion t h a t the distillers had tampered with the packages The proceedings n e r e v h a t are called ‘in r e m ” , t h a t IS, the suit was for the forfeiture of the packages and not a criminal action, the Government making no allegation as to who changed the contents of the barrels
For several years the Division of Chemistry of the Bureau of Internal Revenue had been collecting analytical data on whiskey, in order to see if the chemical experts of the office were justified in deciding that a package of whiskey found on the market was not the identical whiskey indicated b y the marks and brands. The method of procedure was as follows: Upon the receipt, in the laboratory, of the sample of whiskey suspected by a Revenue officer of being other spirits than those indicated b y the marks and brands on the package, orders would be sent t o the Government officer a t the bonded warehouse of the distillery, whose marks and brands were on the suspected package, t o obtain from the bonded warehouse one or two samples as near as possible t o the same date of inspection as the suspected sample The suspected and genuine would then be analyzed and the comparison of the different chemical constituents made. If the results were fairly close the sample was reported as genuine. if there was a marked
