THE ANALYST. ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS. FOODS AND DRUGS ANALYSIS. The Estimation of Alcohol in Wine. M. Duboux and P. Dutoit. (dniL. tSc Chim. anal., 1908, 13, 4-'3.)-The determination of the critical temperature of solution affords a more rapid and sensitive method of estimating alcohol than the determination of the specific gravity. The liquids found to give the best results as solvents were : (A), a mixture of 5 volumes of aniline with 3 volumes of 95 per cent. alcohol; and (B), a mixture of 1 volume of nitrobenzene with 9 volumes of 95 per cent, alcohol. On mixing 15 C.C. of liquid A with 10 C.C. of an aqueous solution of alcohol, and heating the mixture, the critical temperature of solution varied propor- tionately with the amount of alcohol in the aqueous solution, at the rate of 2-35" C.for each 1 per ceut. Similarly in the case of liquid B each 1 per cent. of alcohol caused the critical temperature of solution to vary by 1.2" C. The apparatus required consists of a test-tube 3.5 cm. in diameter and about 15 cm. long, closed by EL cork, through which is passed a thermometer graduated in tenths of a degree, and ti glass stirring rod (bent to a circle at the end), which can move freely through another opening. Fifteen C.C. of the liquid A and 10 C.C. of the distillate from the wine are gently heated and stirred in the tube until the turbidity suddenly disappears. On now cooling the liquid the turbidity should reappear at the same temperature, and this is noted as the critical temperature of solution.The result may then be checked by a determination with liquid B in place of A. To establish the relation- ship between the critical temperature of solution and the proportion of alcohol, three solutions are prepared, containing approximately 8, 10, and 12 per cent. of alcohol, the exact quantities being found by determinations of the specific gravities. Then, by plotting a curve in which the percentages of alcohol form the ordinates andTHE ANALYST. 91 the respective critical temperatures of solution the abscissae, the percentage of alcohol corresponding to any given critical temperature of solution may be found. I n the case of the distillates from wines the percentage of alcohol found by determining the critical temperature of solution is invariably higher than that obtained from the specific gravity.The difference averages 0.1 per cent., and must be attributed to the fact that the distillate from wine contains, in addition to alcohol and water, traces of substances which have a greater influence on the critical temperature than upon the specific gravity. C. A. M. Kamr Beer. A. C. Chapman and F. G. S. Baker. (Joirwt. Inst. Brewing, 1907, 13, 638-643.)-Two samples of this product gave the following results on analysis : Total solid matter ... ... ... ... Reducing carbohydrates (as maltose) ... Absolute alcohol (by weight) ... . . . ( = Proof spirit ... ... ... . . . Fixed aciditv (as lactic acid) ... ... Volatile acidity (as acetic acid) ... ... Present gravity ... ... ... Insoluble matters ... ... ... ... Ash .I . . . . ... ... . . . ... ‘‘ Lcting.” Per Ceiit. 5.19 0.23 3.19 6-97 1% 0.48 1014.4O “ Kaffir 13ecr.” l’er Cent. 5.76 0.07 2-44 1.03 0.4 1 3-62 0.38 101 4.4’ 5.37) The samples were similar in appearance, and both contained suspended matters consisting chiefly of maize starch, many of the granules being ruptured. A. R. T. The Detection of Tartaric Acid in Cider. G. A. Le Roy. ( h ? z . de. Chinz. mZfl/., 1908, 13, 16-17.)-The method is based upon the colour reactions given by resorcinol or pyrogallol in sulphuric acid solution with different organic acids --viz., with tartaric acid, a carmine red colour ; with citric acid, no coloration ; with malic acid, a lemon-yellow colour, changing to orange on prolonged heating; and with lactic acid a similar yellow colour, but of a more orange shade at the beginning.The cider under examination is treated with an excess of basic lead acetate, the precipitate washed and decomposed with hydrogen sulphide, the filtrate from the lead sulphide boiled, neutralised with sodium bicarbonate, and evaporated to dryness on the water- bath, and the residue stirred and heated with a few drops of a 1 to 2 per cent. solu- tion of pyrogallol or resorcinol in pure sulphuric acid. The appearance of a violet coloration, masking the yellow colour due to the malic acid, indicates the presence of tartaric acid. C A. M. Estimation of Cineol in Eucalyptus Oil. C. T. Bennett. (Cl~ent. mzd Di*ugg,ist, 1908,72,55.)-The author finds that the resorcinol method for the determina- tion of cineol, recently described by Schimmel and Co.(ANALYST, 1908, 15)) gives untrustworthy results. Although with artificial mixtures good results may be obtained, when eucalyptus: oil is examined other constituents, soluble in resorcinol solution, considerably affect the accuracy of the method. The author points out92 THE ANALYST. that the specific gravities of two eucalyptus oils examined by Schimmel and Go. (-9185 and ~9142) are corroborative evidence in favour of the results obtained by the phosphoric acid method (namely, 51, 62 ; and 40, 51 per cent. of cineol respectively) rather than of those given by the resorcinol process (71 and 81 per cent. respectively). In the author's opinion the phosphoric acid method, weighing the pressed cake of cineol phosphate, gives fair results when the proportion of cineol in the sample is not less than 60 per cent.; while washing the compound with petroleum-ether, as directed in the United States Pharmacopoeia met hod, invariably gives low results.Fractionation of eucalyptus oil is a valuable guide to the proportion of cineol present, the fraction distilling between 175' and 185' C. consisting mainly of cineol. A. R. T. A Study of the Changes taking place in Whisky stored in Wood. C. A. Crampton and L. M. Tolman. (Jown. Amer. Chem. SOC., 19G8, 30, 98-136.) -The investigation was commenced in the year 1898, when thirty-one barrels of new spirits were set aside in as many different warehouses and from as many different distilleries. Each year, for eight years, quart samples were drawn from the barrels and placed in glass receptacles, the barrels being resealed.By this arrangement the sample of new spirit was kept in glass for eight years, the one-year-old spirit was kept in wood for one year and seven years in glass, and so on. All the samples were examined chemically when the last had been collected, except that the alcoholic strength, solids, and colour were estimated at the time the samples were drawn. - The average results obtained on the analysis of the samples were figures expressing grams per 100 litres of 100 per cent. proof spirit : as under, the Age. f New 1 year 1 I 3 years \ I 3 years ( l 4 years I ( 5 years k G years t 7 years \ I I 8 years . Kind. Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Rye Bourbon Origiii a1 Proof.101.2 101.1 103.5 101-H 104.9 102.2 10'7.; 103.0 111.2 104.3 11i3.8 106.1 118.0 107.9 121.4 109.6 123.8 111.1 Colonr. Solids. 13.3 26.5 119.7 99.6 144.7 136.8 1'71.4 149.3 185.0 151 -9 206.5 173.3 333.1 185.1 242.2 200.9 256.0 210.3 Acids. 4.4 10.0 46.6 41.1 51.9 45.6 62.7 54.3 65.9 58.4 (57.6 66.3 '72.4 6'7-1 76.7 71.9 82.9 76.4 Esters. 16.3 18.4 37.0 28.6 54-0 40.0 61.5 48.1 69.3 33.5 75.0 55.9 80.4 64.0 84.2 63.3 89.1 65% Alde- hydes. 5.4 3.2 7.0 5.8 10.5 8.4 12.5 10-5 1 3 9 11.0 15.0 11.4 14.6 11.9 15.5 12.4 16.0 12.9 1.0 0.7 1.8 1.6 2.2 1.6 1.5 1.7 2.8 1.9 3.2 1.9 3.3 1.8 3.2 1.9 3.4 2.1 Fuse1 Oil. 90.4 100.9 111.5 110.1 112.4 108.9 112.7 112.4 125.1 123.9 128.1 125.3 145.5 135.3 145.2 137.2 154.2 143.5THE ANALYST4 93 The colour of the samples is given in degrees of the brewer’s scale of Lovibond’s tintometer, and the fuse1 oil was estimated by the Allen-Marquardt process.The results show that there is an important relationship between the acids, esters, colour, and solids in a properly aged whisky, which will differentiate it from artificial mixtures and from young spirit, All the constituents are undergoing changes as the ageing process proceeds, and it is evident that the matured whisky is the result of these changes. The amount of higher alcohols increases in the matured whisky only in proportion to the concentration; the latter was due to the passage of the spirit through the pores of the wooden barrels, and it was demonstrated that water passes through the wood with much greater rapidity than alcohol.The wood had a very decided selective action on the materials passing through it, It will be seen that the acids and esters reached an equilibrium which was maintained after about three or four years. The rye whiskies-that is, whisky in the manufacture of which rye is the principal cereal used-show a higher content of solids, acids, esters, etc., than do the Bourbon whiskies which are made from maize ; but this is explained by the fact that heated warehouses are almost universally used for the maturing of rye whiskies, and unheated warehouses for the maturing of Bourbon whiskies. The characteristic aroma of American whiskies is derived almost entirely from the charred barrels in which they are stored, and the improvement in flavour of whiskies in charred barrels after the fourth year is largely due to concentration. The oily appearance of a matured whisky is caused by material extracted from the, charred barrel, as this appearance is lacking in whiskies aged in uncharred barrels.The so-called ‘‘ body ” of a whisky is due to the solids extracted from the wood. w. P. s. Estimation of Gliadin in Flour. W. E. Mathewson. (r702W% Anzer. Chent. SOC., 1908, 30, 74-81.)-The results recordeJ demonstrate the unreliability of the usual methods for estimating gliadin. From 8 to 17 per cent. more nitrogenous matter is extracted from flour when 4 grams of the latter are treated with 100 C.C. of 70 per cent. alcohol than when 16 grams of the flour are taken. After drying for six hours in a water-oven, from 10 to 20 per cent.less gliadin is obtained on extracting with cold alcohol; with hot solvent, the figures were nearly the same, being slightly lower. No tendency for glutenin to remove gliadin from its alcoholic solution could be detected. The use of 70 per cent. propyl alcohol gives results which are equally untrustworthy. It was also found that, whilst anhydrous phenol dissolves a, high percentage of protein matter from flour, the dissolved matter is not pure gliadin ; nor does it appear to be even gliadin mixed with but one other protein. w. P. s. The Unsaponiflable Constituents of Cacao Butter. H. Matthes and 0. Rohdich. (Ber. deut. Chem. Ges., 1908, 41, 19-23.)-1n the course of an investigation carried out on 13 kilos of cacao butter, the authors failed to isolate any constituent to which the peculiar flavour of the cacao could be attributed.The unsaponifiable matter from this quantity of fat amounted to 28 grams, consisting of a pleasant-smelling oil, with an odour of hyacinth and 22 grams of “ crude phytos- terol.” From the latter were isolated a hydrocarbon, C30H4S, identioal with amyrilene,94 THE ANALYST. a phytosterol which combines with 2 atoms of bromine by addition, identical with the stigmasterol prepared from Calabar beans by Windaus, and a phytosterol which combines with 1 atom of bromine, identical with the sitosterol of Calabar beans. This phytosterol possessed the properties of the ordinary ‘‘ phytosterol,” which forms the unsaponifiable residue of most vegetable fats. COLOUR REACTIONS OF THE PRODUCTS OBTAINED.Hydrocarbon . . . ‘‘ Stigmasterol ” . . . ‘‘ Phytosterol ” . . , Phy tos terol acetate Phytosterol acetate dibromide Phytosterol acetate tetrabromide Tsc hougaje 11”s Reagent (Trichloracetic Acid) and Zinc Chloride. First pale pink, First pale pink, then orange-red. then red. Red. Pink. Impure red, soon faded. T,ieherniann- RurcharC Test. First blue, then green. 7 , Very faint green after some time. Sal kow sk i Test. Not tried. Chloroform, first yellow, then violet. Sulphuric acid, greenish fluores- cence. 9 7 7 , Not tried. J. F. B. The Effect of Nitrogen Peroxide on Wheat Flour. F. J. Alway and R. M. Pinckney. (Jozmz. Anze~. Cliem. SOC., 1908, 30, 81-85.)-Continuing their investigation on bleached flours (cj. ANALYST, 1907, 32, 418), the authors find that the yellow colour of flour is due to a very minute quantity of coloured substance contained in the fat.When the fat is removed, high-grade flours become colourless. Exposure to sunlight, or treatment with nitrogen peroxide, changes the coloured compound into one or more colourless substances. The fat from bleached flour is practioally colourless, but the use of an excessive quantity of the bleaching agent causes both the flour and the fat obtained from it to assume a, yellow to brownish- yellow colour. Unless used in excess, nitrogen peroxide does not increase the acidity of the flour or affect the expansion of the gluten. Bread made from bleached flours does not differ in weight, texture, odour, or taste from that made from unbleached flour ; it is in all cases whiter where high-grade flours are used.Low-grade flours, however, when bleached produce bread possessing an uninviting colour. Whilst bread prepared from bleached flour sometimes contains nitrites, the quantity of the latter is always smaller than that present in the flour. The authors consider that many of the conflicting opinions recorded regarding the effect of nitrogen peroxide on flour are to be attributed to the probability that the flours examined had been over- treated with the bleaching agent. w. P. s.THE ANALYST. 95 The Composition of 6 6 Noodles ” (Nudeln) prepared with Milk and Eggs. W. Plucker. (Zeit. C’?ztcrsuch. Nahr. Genzissm., 1907, 14, 748-754.)-The following are the average results obtained on the analysis of specimens of this article of food, and they are recorded with the object of affording some data as regards the detection of the presence or absence of eggs in the product.The “noodles ” were prepared by the author himself : Flour used (10 samples) ‘‘ Noodles ” made with water and 1 egg per pound of flour (5 sam- Ditto, with 2 eggs per pound of flour (5 samples) Ditto, with milk and 1 egg per pound of flour (5 samples) ... Ditto, with 2 eggs per pound of flour (5 samples) Ditto, with milk but no eggs (5 samples) ... ples) ... ... Water. Per* Cent. 13-05 12-37 11.84 12.30 10.48 11-22 Ash. Per Ceut. 0.60 0.77 0.73 0.87 I -09 1.05 Total ’hosphoric Acid (1’206). Per Cent. 0.277 0 *37 5 0-355 0.448 0.483 0.473 Lecithiii- ’hosphoric Acid (P,O,). Per Cent. 0.028 0.051 0.078 0.048 0.071 0.028 Ether E xtrsct .Per Ccnt. 1.29 2.09 3.52 3.13 4.19 3.04 Iodine Pat. 17tLiue 104.71 84-99 81.07 65.01 69-65 62-26 Iteich ert- Meisd Value of Fat. 3.79 3-81 3-65 12.53 12.20 18.53 With the exception of the water and ash, the results are calculated on the dry I t was found that the iodine value decreased with the age of the substance. “ noodles ” (see also ANALYST, 1905, 30, 245). w. P. s. Estimation of the Tannin of Hops. A. C. Chapman. ( J o w n . Inst. Brewing, 1907, 13, 646-652.)-The author has applied the method of precipitation of tannin by means of an alkaloid to the estimation of the tannin in hops, Cin- chonine was found to be preferable to quinine and strychnine, a saturated aqueous solution of the sulphate immediately precipitating the hop-tannin as a yellow flocculent compound only slightly soluble in water, and practically insoluble in cin- chonine sulphate solution.Experirnentfi with pure gallotannic acid (C,,H,,,O,.SH,O) showed that 0.1 gram gave 0.146 gram of the cinchonine compound prepared by the method to be described, corresponding to a content of 63 per cent. of gallotannic acid. The compound of hop-tannin contained 4 per cent. of nitrogen-equivalent to 42 per cent. of cinchonine-and 58 per cent. of tannin, and was thus similar in96 THE ANALYST. composition to the gallotannic acid compound. For calculation purposes, 60 per cent. of hop-tannin in the dry alkaloidal precipitate may be taken as an average figure. For the estimation, 10 grams of hops are placed in a flask marked at 508 c.c., 400 C.C.of boiling water added, and the flask immersed in a boiling water-bath for two hours. During the extraction the hops are macerated with a glass rod. After cooling the contents of the flask to 15" C., water is added to the containing mark. The liquid is filtered, and 50 C.C. of the filtrate evaporated to about 15 c.c., and, when cool, 50 C.C. of a saturated aqueous solution of cinchonine sulphate are added, the liquid set aside for one to two hours in a cool place, and then filtered on to asbestos in a Gooch crucible. The precipitate is washed several times with a diluted cin- chonine sulphate solution, prepared by mixing equal volumes of the saturated solution and water, and then dried to constant weight at 100" C. The Gooch crucible before weighing should be treated with a little of this washing solution, and dried at 100" C.The weight of the cinchonine compound, multiplied by 0-6, gives the amou3t of hop-tannin in 1 gram of the sample. The following results were obtained : Description of Hop. Choice Bohemian, 1907 . . . Choicest Hallertau, 1907 Choice Hallertau, 1906 ... Choice Bavarian, 1907 . .. Alsace, 1907 East Kent Goldings, 19Oi" Kent Fuggles, 1906 ... Choice Worcester, 1905 ... East Kent, 1907 , . . ... Moisture. Per Cent. 11-48 10.76 10.96 10*00 10-14 15.10 11.82 10.76 14-24 T\' oigh t of Cinchoiiinc Prccipitate. Gram. 0.068; 0,066 0.069 0.054; 0.055 0.058; 0.055 0-048 0.035; 0,038 0.039 0,035; 0.035 0.032; 0.034 Tarinin per Cent. on- ( I ) Sample. 4.02 4.14 3.30 3.42 2-88 2.28 2.34 2.10 2 .oo ( 2 ) Dry Hop 4-54 4-64 3.70 3.80 3.20 268 2-65 2.35 2-32 The Estimation of Tannin in White Wines.M. Koebner. A. R. T. (Chenz. Xeit., 1908, 32, 77.)-The following simple colorimetric method is stated to give good results: Ten C.C. of the wine are mixed successively with 10 C.C. of tartaric acid solution (1 : lo), 3 drops of ferric cbloride solution (I : lo), and ammonia in excess, and the whole diluted to 50 C.C. The depth of coloiir of the clear solution thus obtained is proportional to the amount of tannin, and may be matched with that given under the s&me conditions by different quantities of a solution containing 1 gram of tannin (dried at 100" C.) and 50 grams of concentrated hydrochloric in 1,000 C.C. of water. C. A. M.THE ANALYST. 97 Estimation of Water in Foods and Other Substances.W. Thorner. (Zeit. angezo. Chem., 1908, 21, 148-151.)-The method described is similar to that recommended by Aschrnan and Arend (ANALYST, 1907, 32, 21); the substance in which the water is to be estimated is heated with ordinary petroleum in a flask, and the distillate is collected in a burette surrounded by a water-jacket. The delivery-tube from the flask reaches well into the top of the burette, and it is stated that the water separates rapidly from the petroleum which also distils over. From 10 to 20 grams of the substance are taken for the estimation; the quantity of petroleum employed is about 50 c.c., and a few pieces of pumice-stone are added to prevent the contents of the flask from “ bumping.” I n the case of liquids, such as milk, etc., which are liable to froth on heating, a little tannin may be added to the distillation flask.The results of estimations of water in butter, sausages, meals, meats, spices, soap, cocoa, inorganic salts, etc., are given, the figures agreeing with those obtained by estimating the water gravimetrically. w. P. s. BACTERIOLOGICAL, PHYSIOLOGICAL, ETC. Quantitative Estimation of Pentoses in Urine. A. Jolles. (Xeits. a d . them., 1907, 46, 764-771.)-1n a previous paper (Biochewt. Zeits., 2, 243) the author described a method for the detection of pentoses in urine which consisted in forming the osazone from 15 C.C. of the urine, washing the precipitate, and distilling it with a small quantity of hydrochloric acid. The distillate was then' tested with Bial's reagent, which would give a distinct green colour if only 0.05 per cent.of pentose were present in the sample. The author has now applied his volumetric method for the estimation of furfural by means of sodium bisulphite (ANALYST, 1906, 31, 116) to the estimation of pentoses in urine. One hundred C.C. of urine are placed in a flask of about 1-5 litre capacity together with 150 C.C. of hydrochloric acid of 1-06 specific gravity. In a second flask are placed 900 C.C. of water, and the steam generated by boiling this water is paased through the liquid in the first flask. The distillate con- taining the furfural is collected, an aliquot portion of it is carefully neutralised with 20 per cent. sodium hydroxide solution in presence of methyl orange, and 10 C.C. of standardised bisulphite solution are added, the excess of bisulphite being titrated back after two hours with -& iodine solution.The author has proved by a large number of analyses that, in the absence of pentoses, neither healthy nor patho- logical urines yield any appreciable quantity of substances capable of combining with bisulphite when treated in this manner. The highest; error due to substances other than pentoses amounted to 0.032 per cent. (calculated aa pentose), and was caused by the presence of large quantities of glycuronic acid derivatives. I n cases of pentosuria, however, the quantities of pentose found range from 0.1 per cent, upwards. The error mtty be still further reduced by previously boiling the urine with dilute acetic acid. J. F. B. them., 1907, 764-771.)-1n a previous paper 243) the author described method for the detection of pentoses in urine which consisted in forming the osazone from C.C.of the urine, washing the precipitate, and distilling it with a small quantity of hydrochloric acid. The distillate was then' tested with Bial's reagent, which would a distinct green colour if only 0.05 per cent. of pentose were present in the sample. The author has now applied his volumetric method for the estimation of furfural by means of sodium bisulphite 116) to the estimation of pentoses in urine. One hundred C.C. of urine are placed in flask about litre capacity together with C.C. of hydrochloric acid of specific gravity. In a second flask are placed C.C. of water, and the steam generated by boiling this water is paased through the liquid in the first flask. The distillate con- taining the furfural is collected, aliquot portion it is carefully neutralised with per cent. sodium hydroxide solution in presence of methyl orange, and C.C. of standardised bisulphite solution are added, the excess of bisulphite being titrated back after two hours with iodine solution. The author has proved by a large number of analyses that, in the absence of pentoses, neither healthy nor patho- logical urines yield appreciable quantity of substances capable of combining with bisulphite when treated in this manner. The highest; error due to substances other than pentoses amounted to 0.032 per cent. (calculated pentose), and was caused by the presence large quantities of glycuronic acid derivatives. I n cases of pentosuria, however, the quantities of pentose found range from per cent, upwards. The error mtty be still further reduced by previously boiling the urine with dilute acetic acid.