THE ANALYST. ABSTRACTS OF PAPERS PUBLISHED - 467 IN OTHER JOURNALS. FOODS AND DRUGS ANALYSIS. The Estimation of Alkaloids in Extracts of Belladonna and Hyoscyamus. E. Rupp. Chem. Zeit. Rep., 1908, 32, 529.)-Three grams of belladonna extract or 5 grams of hyoscyamus extract are dissolved in 5 (or 8) C.C. of hot water, and the cold solution shaken for fifteen minutes with 90 C.C. of ether and 1 C.C. of ammonia solution, and then allowed to stand for fifteen minutes. Sixty C.C. of the ethereal layer are then filtered through cotton- rvool into an Erlenmeyer flask, and the ether evaporated on the water-bath. The cotton filter is washed with three portions of 5 C.C. each of ether, and the washing evaporated each time in the flask. The residue is dissolved in a few C.C. of warm alcohol, and the solution mixed with 20 C.C.of & acid and about the same amount of water. Should the solution be coloured, it is shaken with 5 to 10 C.C. of ether in a separating funnel, the aqueous layer drawn off, the ether shaken twice with portions of 10 to 15 C.C. of water, and the aqueous washings added to the main liquid. The latter is now covered with a layer of about 1 cm. in depth of ether, and titrated brtck, with i$u. alkali solution, after the addition of 5 to 10 drops of iodeosin solution as indicator. The proportion of alkaloids should not be less than 1 per cent. in belladonna extract, nor less than 0.5 per cent in hyoscyamus extract. (Pharm. Xeit., 1908, 53, 738. C. A. M. The Colorimetric Estimation of Benzaldehyde in Almond Essences. A.G. Woodman and E. F. Lyford. (Jown. Amel.. Chem SOC., 1908, 30, 1607- 1611.)-It is shown that benzaldehyde may be estimated in almond essences by means of fuchsin-sulphurous acid (SchiE’s reagent) if care be taken in the preparation of the reagent and in the removal of all aldehyde from the alcohol used in diluting the test solutions. The reagent is propared by dissolving 0.5 gram of pure fuchsin in 100 C.C. of water, adding a solution of sulphurous acid containing 20 grams of sulphur dioxide, and diluting the whole with water to a volume of 1 litre. The solution may be used for ten days after being made; owing to the sulphuric acid formed by oxidation of the sulphur dioxide the sensitiveness of the reagent is so diminished that it then becomes useless. To remove aldehyde from ordinary alcohol, it is recommended that the latter be treated with silver oxide and distilled; to the distillate are then added 25 grams of m-phenylenediamine per litre, and a fairly rapid current of air is drawn through the mixture for three hours.The alcohol is next; distilled, the first 100 C.C. being rejected. A standard solution of benzaldehyde is prepared by dissolving such a, quantity of the freshly distilled aldehyde in the purified alcohol that each C.C. contains 0.001 gram of benzaldehyde. As each C.C. of com- tnercial almond essence contains approximately 0.009 gram of bensaldehyde, an amount of the essence containing enough benzaldehyde to give the colour best suited for comparison would be too small for convenient measurement. Consequently, 10 grams of the essence are diluted to 50 C.C.with aldehyde-free alcohol. Two C.C. of468 THE ANALYST. the solution are placed in a colorimeter tube, and diluted to 20 C.C. with alcohol; three standard solutions are then made up containing, say, 0.002, 0.004 and 0.006 gram of benzaldehyde, and placed in similar tubes. All the tubes are placed in a water-bath at a temperature of 1 5 O C. ; when the contents of the tubes have reached this temperature, 20 C.C. of the reagent (also at 15' C.) are added to each tube, and, after thorough mixing, the tubes are allowed to stand for ten minutes. The colora- tion in the sample tube is then compared with those of the other tubes. Within the above limits the depth of colour is proportional to the concentration of benzaldehyde.w. P. s. The Analysis of Cacao Butter. G. Halphen. (Jo?(r1z. Pharm. Cllim., 1908, 28, 345-346.)-A method of detecting certain vegetable fats, such as bcurrc w i - t and other preparations of cocoanut oil in cacao butter, is based upon the difference in solubility of the respective bromine derivatives. A solution of the fat in twice its volume of carbon tetrachloride is treated gradually with an excess of a highly con- centrated solution of bromine in the same solvent, the liquid filtered through a mixture of equal parts of sand and starch, and the filtrate mixed with four to five times its volume of petroleum spirit, and cooled for two hours in water at 15" C. I n the case of pure cacao butter the liquid will remain perfectly clear, whereas an abundant precipitate will be formed by beurw vert, or by a mixture of cacao butter with 10 per cent.or more of that fat. If, instead of diluting the liquid with four to five times its volume of petroleum spirit, only two to three times the volume be used, it is possible to detect as little as 5 per cent. of the adulterant, especially if com- parative tests be made with pure cacao butter. For the detection of beuwe vert in chocolate the fat is extracted in the ordinary way and dissolved in carbon tetrachloride in the proportion of 2 C.C. per gram, and the solution boiled with animal charcoal under a, reflux condenser, and then cooled and filtered. One C.C. of the colourless filtrate is treated drop by drop with a solution of bromine in carbon tetrachloride until the liquid remains red.After standing for about two minutes the liquid is mixed with 3 C.C. of petroleum spirit of specific gravity 0.700, and the tube closed and allowed to stand over-night. With pure cacao butter the liquid remains clear, while in the presence of even 5 per cent. of beurre u c ~ t there is a slight deposit, and a pronounced precipitate with larger proportions of the adulterant. C. A. M. A New Adulterant of Fennel Seed. C. Arragon. (Zcits. U&rsPich. Nahr. Gemssm., 1908, 16, 400-402.)-The author has examined a sample of fennel seeds which contained 72.8 per cent. of true fennel seed, 16.7 per cent. of foreign seeds (mostly sea-damaged wheat grains, together with a few poppy and vetch seeds), and 10-5 per cent. of small stones. The latter were of particular interese, as they consisted of small fragments of marble coloured with iron ochre.Even the fennel seeds themselves were not of good quality, many of the seeds being quite tasteless, and had evidently been extracted or exhausted previously. The portion of the sample, consisting of good and bad fennel seeds, gave the following results on analysis: Aqueous extract, 16.5 per cent. ; alcoholic extract, 5.6 per cent. ; fat,THE ANALYSTo 469 5.2 per cent. ; ethereal oil, 1-5 per cent. ; total ash, 7.4 per cent. (cf. ANALYST, 1899, 24, 127). w. P. s. The Deterioration and Commercial Preservation of Flesh Foods. Experiments on Frozen Beef. W. D. Richardson and E. Scherubel. ( J o z m . Amer. Chem. Soc., 1908, 30, 1515-1564.)-The chemical work recorded in this paper was begun with the object of determining whether or not there was progressive change in the chemical constituents of the meat, such as would result in an increase of the soluble constituents due to the autodigestion of insoluble proteins, and also an increase of the Nearly all the experiments were carried out on the portion of meat known to butchers as the knuckle,” and the lean part of the meat was used as far as possible, The fresh samples varied in age from 0 to 7 days, and from the time of slaughter were stored in a temperature which varied from 2’ to 4” C.The frozen samples varied from 33 to 554 days in age, and were stored, while frozen, in a room whose temperature ranged from - 9” to - 12” C. The following is a summary of the results obtained : ammoniacal nitrogen.” Ammoniacal Nitrogen.Age. Days. Moisturc. Total Nitrogen. Ash. Fat. I. 11. 77.27 7’5.26 76.35 77.11 75.32 76.39 1.31 1.11 1-23 1.29 1.16 1.23 3.34 0.78 1-43 2.12 1.17 1.65 3.65 3.34 3-49 3.65 3.31 3-51 0.033 0.022 0.029 0-031 0.024 0.028 0.011 0.009 0.010 0.013 0.009 0.01 1 Maximum Average ... Maximum 7 0 3.7 554 33 353 COLD-WATER EXTRACT. Coagu. lable Nitro- gen. Albu- mose Nitro- gen. Meat- base Nitro- gen. Acidity as Lactic Acid. Total Nitro- gen. Organic E s trac- tives. Total Solids. Ash. 6.24 5.55 6.01 6.27 5.56 5.94 1.27 0 95 1.14 1.21 0.96 1.14 5.27 4.42 4.87 5.18 4.40 4 -80 0.854 0.742 0 *806 0.861 0.730 0.795 0,034 0.014 0,024 0.026 0.021 0.023 0.398 0.360 0,355 0-379 0-337 0.357 0.82 0.63 0.68 0.92 0.66 0.79 Maximum Fresh meat Minimum Average... Maximum Average . . . { 0,452 0.358 0.413 0,468 0.353 0-413 The figures represent percentages calculated on the original meat. The ammoniacal nitrogen ‘ 4 I.” was obtained by distilling the meat with magnesium oxide, whilst the ammoniacal nitrogen ‘‘ 11.” was found by extracting the meat with 60 per cent. alcohol, and distilling the extract with magnesium oxide. The cold-470 THE ANALYST. water extracts were obtained by digesting 100 grams of the meat with successive quantities of cold water until the united extracts amounted to 1 litre. A general inspection of the tables shows that there is very little difference between the analyses of the fresh and the frozen samples, The slight variations noticeable do not tend definitely in one direction in the frozen samples, and the ammoniacal nitrogen, the coagulable nitrogen, and the albuniose nitrogen figures do not show a positive tendency to increase or decrease.No importance is attached by the authors to the slight differences in the acid figureB. No difference in flarow could be detected between fresh and frozen meat, On the whole, the results of the various lines of work given in this paper-chemical, histological, and bacteriological -all go to indicate that cold storage, at temperatures below -0.9" C. at least, is an adequate and satisfactory method of preserving beef for a period of 554 days, and probably for a much longer time. w. P. s. The Lead Value of' Maple Products. A. P. Sy. (JOZLWZ.. Anzer. Chem. Soc., 1908, 30, 1611-1616.)-By the lead value is meant the amount of lead precipitated on adding lead acetate solution to 100 grams of sugar or 100 C.C.of syrup ; this value decreases in adulterated samples as the quantity of cane-sugar increases (cj. ANALYST, 1906, 31, 411). As many different ways of obtaining the value have been proposed, all more or less trustworthy, for differentiating between pure and badly adulterated samples, the author thinks it desirable to record a method which will give con- cordant results on the same sample by the same or different analysts. The details of this method are as follows : Fifty C.C. of syrup or 50 grams of sugar are diluted with 200 C.C. of water, heated to boiling, treated with 20 C.C. of 10 per cent. neutral lead acetate solution, again boiled, and allowed to cool.The precipitate is collected on a filter and washed with water at a temperature of 20" C. The filter and pre- cipitate are then heated with 15 C.C. of concentrated nitric acid and 10 c.c.-of concentrated hydrochloric acid until the filter is disintegrated ; 10 C.C. of concentrated sulphuric acid are next added to the cooled mixture, and the heating is continued uutil sulphuric acid fumes are given off. If the resulting liquid is black, 5 C.C. of nitric acid are added, and the heating is repeated. After cooling, 50 C.C. of water and 100 C.C. of alcohol are added, and, at the end of six hours, the lead sulphate is collected on a filter, washed, dried, and weighed. The weight of lead sulphate multiplied by 1,366 gives the weight of lead precipitated by 100 c.c., or 100 grams, of the sample.The lead value of a pure maple product should not be less than 0.250, and is usually over 0.300. Six samples of maple-sugar of known purity gave values between 0.376 and 1.024. w. P. s. The Lecithin-Content of' Various Milks. J. Nerking and E. Haensel. (BI3ioehcm. Zcits., 1908, 13, 348-353,)-1n view of the conflicting statements which have beeu recorded as to the quantity of lecithin present in milk, one observer, owing to faulty wethods of extraction, having come to the conclusion that milk doesTHE ANALYST 471 not contain lecithin, the authors give the results of a number of estimations of this substance in various milks. The highest, lowest, and average results obtained were as follows : Percentage of Lecithin. Kind of Milk.Highest. Lowest . Average. Human, ten samples ... * . . ... Cows), seventeen samples ... Asses), six samples ... ... ... ... Sheep's, four samples ... ... ... ... Goats', eleven samples ... ... Mares', eight samples ... ... ... ... ... ... ... ... 0.080 0.1 16 0.039 0.167 0.075 0.174 0.024 0,036 0.006 0.051 0.036 0.007 0.050 0.063 0.016 0.083 0.049 0.011 The method employed for estimating the lecithin consisted in adding 200 C.C. of alcohol to 100 C.C. of the milk, the mixture being stirred during the addition; when the precipitate had settled, the liquid portion was passed through a filter, and the precipitate, together with the filter paper, was extracted in a Soxhlet apparatus with chloroform for thirty hours. Meanwhile, the alcoholic filtrate was evaporated at a temperature of from 50" to 60" C., and the residue extracted thoroughly with chloroform, The two chloroform solutions were then united, evaporated in a, platinum basin, and the residue, after the addition of sodium carbonate and potassium nitrate, was ignited. The phosphoric acid in the ash was next separated by means of molybdic acid and weighed as magnesium pyrophosphate.No attempt was made to separate the lecithin from the cephalin, the main object of the investigation being the estimation of the total phosphatides present in the milks. w. P. s. The Constituents of Expressed Oil of Nutmeg. F. B. Power and A. H. Salway. ('rrans. Chem. SOL, 1908, 93, 1653-1659.)-As the result of their investigation the authors find that the approximate composition of genuine expressed oil of nutmeg (nutmeg butter) is as follows : Per Cent.Essential oil ... ... ... ... ... 12.5 Olein ... ... ... ... ... ... 3.0 Linolein ... ... ... ... ... 0.5 Resinous matters ... ... ... ... 2-0 Trimyristin ... ... ... ... ... 73.0 Formic, acetio, and cerotic acids ... ... (very small amounts) Unsaponifiable matters ... ... ... 8.5 The unsaponifiable matter consisted of a new compound, C,8H,,0, (amounting to about 5 per cent. of the expressed oil), together with some myristicin, CllH1208, and a very small amount of phytosterol. Although the myristicin is a constituent of the essential oil, it was not practicable to effect its complete removal by the preliminary treatment of the fat with steam. The oil employed in the investigation472 THE ANALYST.was obtained from a portion of the same lot of Ceylon nutmegs as that from which the essential oil previously examined had been distilled (cf. ANALYST, 1908, 52). Some of the Constituents of Saffron and a Method for the Valuation of Saffron. B. Pfyl and W. Scheitz (Zeits. Unterszdz. Nnh-. Genussm., 1908, 16, 337-352.)-Three crystalline substances were isolated from the petroleum spirit and chloroform extracts of pure saffron. The substance which was extracted by means of chloroform was similar to the picrocrocin described previously by Kayser, in that it yielded a sugar and an ethereal oil on hydrolysis; this sugar was lzvo-rotatory, and gave an osazone corresponding to that of dextrose or laevulose, but did not yield dextrose-P-naphthylhydrazone. The picrocrocin obtained by the method given by Kayser (Berich, 1884, 35, 2228) could not be crystallised.Extraction of the saffron with absolute alcohol (after treatment with petroleum spirit and chloroform) resulted in a sugar being obtained having the same properties as the above- mentioned sugar, and a glucoside, which on hydrolysis furnished a further quantity of the same sugar, together with an ethereal oil. The authors consider that this sugar is llievulose. The method proposed for the valuation of saffron depends on the estimation of the reducing sugars present in the drug. The sample under examination is dried in the water-oven, powdered, and again dried. Five grams of the dried powder are then extracted for one hour in a Soxhlet apparatus with petroleum spirit.The cartridge containing the powder is next carefully heated until all the petroleum spirit has been removed, and the powder is then extracted for two hours with chloroform. The chloroform extract is evaporated, the brown residue is taken up with hot acetone, and the solution is poured into 25 C.C. of water contained in a small beaker. The mixture is boiled until the acetone has been driven off, and the heating is continued after the addition of 5 C.C. of hydrochloric acid for a further fifteen minutes, any loss by evaporation being made up by the addition of a little water from time to time. When cold, the solution is filtered; the filtrate is neutralised by the addition of alkali solution, and added to a boiling mixture of 50 C.C. of Fehling's solution and 25 C.C.of water. The whole is boiled for a further two minutes, and the precipitated cuprous oxide is collected, washed, and weighed as metallic copper. Genuine saffron (Crocus Gatiizuis electus) yields about 0.209 gram of metallic copper when examined in this way : samples containing an undue proportion of pistils, or adulterated in other ways, yield smaller amounts of copper. The usual adulterants of saffron-namely, safflower (Carthamus tinctoriz~s), marigold (Cnleizdzda oficinalzs), sandal-wood, turmeric, logwood, peony petals, etc.-yield no chloroform-soluble substance which reduces Fehling's solution. As the quantity of cuprous oxide precipitated is not proportional to the amount of sugar present, but varies with the concentration of the latter, it is necessary, in calculating the percentage of genuine saffron in an adulterated sample, to make use of the following table, which gives the quantities of copper corresponding with different weights of pure saffron : (;ran~s.Gral~~s, Grams. Graiiis. Grams. Grams. (;rams. Grams. Grams. Weight of sample take11 5.0 4.5 4'0 3.5 3.0 2.5 2.1 1'2 1.0 Copper ... ... .,. 0'2090 0*1870 0.1619 0.1120 0'0828 0'0614 0.0476 0'0264 0'0230THE ANALYST 473 Suppose 5 grams of a sample yield 0.0661 gram of copper : this number is not given in the table, but the next lowest number is 0.0614, corresponding with 2.5 earns of saffron. The actual quantity of saffron present is then obtained by interpolation, and the percentage is calculated. Analyses of test mixtures are given ahowing that the mothod is trustworthy.w. P. s. The Examination of Alcohol-free Wines. J. M. Krasser. (Zeits. Untersuch. Nahr. Genussnt., 1908, 16, 398-400.)-The following results were obtained on the analysis of six samples of alcohol-free wine, the figures expressing grams per 100 C.C. : Traminer (red) ... Kalterer (red) ... Terlaner (white) Mailbergel (white) Moorer (white) Villanjer (red) ... Specific Gravity 1.0230 1.0298 1-0263 1.0220 1.0294 1.0273 Alcohol, 0.37 0.21 0.21 0.16 0.21 0.26 Total solids 647 8.35 6.77 5.71 8.16 7-88 Ash. 0.17 0.17 0.13 0.13 0.16 0.15 Total. Acid (as Tar. taric). 0.59 0.55 0.68 0.66 0.75 0.61 Volatilc Acid Ace tic). ("9 0.1 5 0.08 0.06 0.05 0 -05 0.05 Gly- cerol. 0.20 0.23 0.14 0.10 0.28 0.29 Pot,assium Hydrogen Tartrate. 0.21 0.20 0-26 0.26 0.28 0.19 Invert Sugar.1 -00 0.91 4-75 4.19 3.06 1.33 Sucrose. 4-52 6.37 0.53 0-61 2.59 4.62 All the samples were free from coal-tar dyes and preservatives. They had been mixed with carbonated mineral water, and had evidently not been fully fermented before the alcohol was removed. The question is discussed whether alcohol-free wines, when sold as such, should not be wine from which the alcohol has been removed, and not simply sterilised grape juices or musts. w. P. s. The Identification of Thqjone in Liqueurs. L. Duparc and A. Monnier. (Ann. de Chem. Anal. AppZ., 1908, 13, 378-382.)-Legal's nitro-prusside reagent may be used for the detection of thujone (tanacetone) in certain liqueurs, as was shown by Cuniasse in the case of absinthe (ANALYST, 1907, 32, 119); but the coloration is fugitive and not sufficiently characteristic in the presence of carvone and essential oils of ketonic nature.These drawbacks are obviated by adding to the liquid under examination a few drops of a solution of zinc sulphate before the sodium nitro-prusside, a gooseberry-red precipitate being then obtained instead of the fugitive red coloration. The reaction is still unmistakable in a solution containing i part of thujone in 5,000. Other essential oils give more or less pronounced precipitates, but of a light colour, usually yellowish-white. Thus, oil of carvi gives tt white precipitate; carvone, a yellow precipitate; eau-de-vie de marc, a white precipitate ; and acetone, a yellow precipitate. The only substance that would474 THE ANALYST, interfere with the detection of thujone is citral, which gives an orange-red precipitate, and that could he eliminated by condensation with aniline phosphate. In applying the test, 10 C.C. of the solution (e.g., 0.2 per cent.) of the essential oil in 60 per cent, alcohol are treated with 2 C.C. of a 10 per cent. solution of zinc sulphate, followed by 0.5 C.C. of a 10 per cent. solution of nitro-prusside. After the mixture has been shaken, 4 C.C. of a 5 per cent. solution of sodium hydroxide (free from carbonate) are slowly added, the tube allowed to stand for a minute without shaking, and from 2 to 3 C.C. of glacial acetic acid then added. After a few minutes a flocculent precipitate will form. In the case of liqueurs the test is applied to 10 C.C. of the distillate. Thujone may be detected in the presence of citral, not only by condensing the latter by means of aniline phosphate, but also by shaking with ether the red liquid given by citral in the test. The liquid is immediately decolorised, while the ether becomes yellow, and in the presence of thujone LZ red precipitate is at once formed at the zone of contact of the two liquids. This treatment with ether may also be used for the detection of traces of thujone in liqueurs that do not contain citral. C. A. M.