THE ANALYST. 361 ORGANiC ANALYSIS. (zeit. phpiol. Chem., 1902, xxxvi., 51 ; Chem. Rev. Fett-u. Ham-lnd., 1902, ix., 232.)-According to the results of the author's analyses, normal adult human fat consists in the main of glycerides of oleic, palmitic, and stearic acids, with traces of lower fatty'acids. The fat of EL The Composition of Human Fat. H. Jaeckle.362 THE ANALYST. child during the first few months shows pronounced differences from the adult fat, being characterized by a high proportion of lower fatty acids and a small proportion of oleic acid. It was not found possible to trace any influence of the food of different individuals upon the composition of the fat. In pathological cases the fat may undergo very great changes (cf. ANALYST, xxi., 171). C . A. M. The Molecular Equivalent of Insoluble Fatty Acids.M. Tortelli and A. Pergami. (Chm. Rev. Fett-a. Haw-Ind., 1902, ix., 182-184, 204, 205.)-The ordinary process of determining the molecular equivalent of fatty acids consists of dissolving a weighed quantity in alcohol and titrating the solution with & alkali. It has usually been assumed that the acid value thus found is identical with the saponification value. The authors, however, point out that there is a great dis- crepancy between the recorded molecular equivalents of the fatty acids of different oils and their known composition. The cause of this source of error, which is clearly shown in the following examples, is to be attributed to the presence of lactones : Oil or Fat. Almond oil : 2 i years old ...... 2+ years old ... ... 2 years old . . . ... 24 years old ... ... 3 years old ... ... 2 years old ... . . L Fresh, rendered by heat Lard : 2 years old ... ... Fresh, rendered by heat Palmitic acid , , . ... Stearic acid ... ... Oleic acid, from olive oil.. . Fresh, cold-drawn . . . Cotton-seed oil : Fresh, cold-drawn . . . Colxa, oil : Fresh, cold-drawn . . . Castor oil : Fresh, cold-drawn . . , Linseed oil : Fresh, cold-drawn . . . o x tallow : Oil or Fat. - Acid Value. I. 1 -50 0.70 0.19 3.80 3.7 0.55 3.29 1.9 2.70 0.30 4.3 1.4 0.2 5-9 - - - Saponi- fication Value. 11. 193.6 193.6 195.2 198.3 172.2 174-9 - 181-3 192.6 189-8 199.6 200 -0 196.8 196.8 - - - Insoluble Fatty Acids. Acid Value. 111. 196.0 195% 194.3 200.9 178.3 176.6 183-1 187.0 191.5 194.6 205.4 205.7 2034 205-0 202.7 198.7 199.5 Saponi- fication Value.IV. 202.2 203.2 204.5 203-1 182.5 181.2 189.0 191.1 205.4 201-8 207.1 209-9 203 *1 204.8 218.7 198 *9 201-4 Mean Molecular Equivalent of Fatty I Acids. - % 3alculated Crom Acid Value. V. 286.2 286-5 288.7 279.2 314.6 317.7 306.4 300.0 292.8 288.2 273.1 272.7 275.8 273.4 276.5 282.3 281.2 Calculated from Saponifica ,ion Value. VI. 277.5 278.3 274.3 276-2 307.4 309.6 296.7 294.3 273.2 277.9 270.8 267.2 276.2 273.9 256.4 282.0 278-5 Differ- ence. v. -VI. 8.7 8.2 14-4 3.0 7.2 8.1 9.7 5.7 19.6 10.3 2.3 5-5 0.4 0.5 20.1 0.3 2-7THE ANALYST. 363 To obviate this error, the authors hydrate the lactones by boiling the fatty acids with an excess of alkali and titrate the excess, just as in the determination of the saponification value by Koettstorfer’s method.C. A. M. Some Colour Reactions of Fatty Oils. H. Ereis. (Chem. Zeit., 1902, XXVi., 1014.)-This is essentially a continuation of the author’s previous article (ANALYST, xxvii., 330). It is known that Bishop’s reaction-a green colour on shaking with 1.19 hydrochloric acid-only occurs with such sesame oils as have been bleached by insolation or otherwise. It is also known that, if a sesame oil that does not give Bishop’s reaction is mixed with some other insolated or bleached oil, the whole gives a strong green or blue colour when treated similarly. Moreover, ~t list of oils was contained in the former paper which no longer yielded the Bellier test, but which behaved with sesame as above. For convenience this reaction may be termed the Bishop-Kreis test.It is now found that oils which yield tho Bishop-Kreis reaction also give colourFs with resorcinol and with phloroglucinol, the test being preferably made by mixing 2 C.C. of 1.19 HCl with 2 C.C. of oil and 2 C.C. of a cold saturated solution of resorcinol in benzene, or of a solution of 1 part of phloroglucinol in 1,000 parts of ether. After a short time-or rapidly on the water-bath-fine violet or red tints appear in the acid, which are not affected by the addition of water. Hitherto this reaction has been observed with olive, arachis, sesam6, cotton, poppy, and walnut oils, also with two samples of butter which had become tallowy. A sample of arachis, which gave the Bellier test powerfully, but failed to yield the Bishop-Kreis test, was exposed to sunlight for eight (September) days; it then failed to give the Bellier, but gave a notable green with the Bishop-Kreis, and also yielded bright colours with resorcinol or phloroglucinol and HCI.The acid value (4.4) was not affected by the insolation. F. H. L. Detection of Sesame Oil in Earth-Nut Oil. J. Schnell. (Zed. fGr Untersuch. der Nahr. und Genussmittel, 1902, v., 961-963.)-Soltrsien’s reaction is recommended, the test being carried out as follows : The oil is mixed with an equal volume of stannous chloride (German Pharmacopceia strength) and shaken vigorously, but not repeatedly. The test-tube containing the mixture is then placed in boiling water until separation takes place. A red coloration appears should sesame oil be present, whilst pure earth-nut oil gives no coloration. Less than 1 per cent.of sesame oil can be detected, but attention is drawn to the fact that sometimes the same press is used for sesame seeds as for earth-nuts, and the oil from the latter may, for this reason, show indications of the presence of traces of sesame oil. It may be mentioned that the stannous chloride reaction is particularly applicable to butters and margarines artificially coloured with coal-tar dyes. The colours are reduced and rendered colourless when the test is applied, and their previous extrac- tion with dilute hydrochloric acid is unnecessary. Several samples of earth-nut oil from West Africa examined by the author gave iodine numbers as low as 84.4 to 85.7. Others, from the East Indies, gave higher364 THE ANALYST.numbers than usual-from 89.7 to 95.0. As these numbers are higher than that for pure olein, other unsaturated acids besides oleic are probably present in these samples. w. P. s. Halphen's Reaction for Cotton-Seed Oil. B. Sjollema and J. E. Tulleken. (Zeit. fiir Untersuch. der Nahr. und Genussmittel, 1902, v., 914-916.)-Butter obtained from cows which have been fed on cotton-seed meal gives with Halphen's test exactly the same coloration as does cotton-seed oil itself. On spectroscopically examining the colour produced in this test the authors found that, at a low temperature (550 C.), cotton-seed oil yielded an absorption band in the yellow with a maximum at X 550, a thicker layer showing a maximum more to the left at X 570. By long heating or by employing a higher temperature a second band was produced at h 490, which gradually increased in intensity.A thicker layer, without dilution, caused the right half of the spectrum to become so dark that observations were rendered impossible. On considerably diluting with amyl alcohol, the band had a distinct maximum at X 490, but the band in the yellow had lost muah of its intensity. w. P. s. Notes on Some Essential Oils. (Schimmel and Co.'s Half-Yearly Report, October, 1902 ; through Chem. Zeit., 1902, xxvi., 1005.) Camphor Oils.-Method s of manufacture having been somewhat altered, these oils are rather different from what they formerly were. The light oil has a yellowish colour and a specific gravity of about 0.900; the dark oil is green, and its density is 0.930.A third product is now prepared, viscid, and of a fine blue colour ; it is used in porcelain painting. It boils between 280" and 300" C., has a specific gravity of 0.95 to 0.96 at 15" C., and is dextrorotatory, one sample showing a value of + 3 2 O 55. Apparently it consists for the most part of an alcoholic body, for on treatment with acetic anhydride it yields a considerable saponification value. In spite of its colour, it does not tint soap, and it is therefore employed as a fixing agent for ordinary soap perfumes. Little is yet known of the constituents of camphor oil which are soluble in alkali. On distillation aldehydes and acids are obtained, but the latter have not been identified. A comparatively small quantity of eugenol is present in the higher fractions, In the highest acid fractions eugenol and carvacrol have been found; the latter boils at 86" to 88" C.at a pressure of 2 millimetres. Apparently a second product, boiling at 94" to 99" (3 millimetres), is also present. About 3 per cent. of the portion soluble in alkali dissolves in dilute sodium carbonate; it consists of a mixture of the carboxylic acids of the fatty series, caprylic wid being predominant. Through its easily soluble calcium salt a liquid acid boiling at 1 1 4 O to 115" (4 milli- metres) has been recovered from the crude acids; analysis of its silver compound leads to the formula C,H,,O,; it probably belongs to the oleic series. Oil of Bergamot.-S. Gulli has published an account of this oil. It is only dis- tilled between February and April, when the trees are pruned and stripped ; the yield is quite small, 100 kilos of leaves giving but 150 grammes of oil; probably not more than 20 or 25 kilos are made in any year.The pure oil has a specific gravity of about 0.870 to 0.873, its rotatory power is +25O to +26O, and it is soluble in an equalTHE ANALYST. 365 volume of 90 per cent. alcohol. It contains about 32 to 34 per cent. of esters reckoned as linalyl acetate, part being the methyl ester of anthranilic acid. Oil of Lemon.-Although a large number of bodies have been identified in this oil-d-limonene, cymol (?), phellandrene, citral, citronellal, geranyl acetate, a sesquiter- pene, octyl- and nonyl-aldehyde, and pinene-it is not possible by artificially mixing these substances together to produce a useful lemon oil.This is due to the fact that several important odour-giving constituents have been overlooked. Recently in Schimmel's laboratory methylheptenone has been obtained from the distillate of lemon oil, and tierpineol (melting at 35", A-Terpene-8-01) recovered from the residue. OiE of Lemn-grass.-Owing to the lack of prosperity in the sugar industry of the West Indies, it would seem that attempts are being made to cultivate the lemon- grasses in those islands. The superintendent of the botanical gardens in Trinidad has published an account of some investigations made in the Government laboratory at Antigua on this subject. The oil of Andropogon Nardus var. has been found to 15.5" have a, specific gravity of 0.9084 at lm; a specific rotatory power of + 0" 1'; an aldehyde content of 15.5 per cent.; saponification value, 23; and saponi- fication value after acetyliaation, 168.6, corresponding with about 53 per cent. of total alcohols. The oil of Andropogon Schomanthus gave : Specific gravity, 0.9315 at 15.5" 15.5" ; rotatory power, + 3" ; aldehyde content, 48-2 per cent. ; saponification value, 31.1 ; after acetylization, 69.6, corresponding gith 20.2 per cent. of C,,H,,O. Apart from its slight dextrorotatory power, the former oil resembles Ceylon citro- nella oil, for it is not soluble in 10 volumes of 70 per cent. alcohol, but dissolves in the same volume of 80 per cent. spirit ; but the latter has very different properties from Palmarosa oil, with which it appears to be botanically identical.Palmarosa oil, however, is not a lemon-grass oil, for it contains too little aldehydes, assuming, that is, that its aldehyde is really citral. Liquid Oil of Musk.-Ordinary oil of musk is solid at ordinary temperatures, owing most probably to the presence of palmitic acid. This being inconvenient in practice, Schimmel and Co. have removed the solid constituent, and have introduced a, liquid oil. The new material remains fluid at all temperatures, and is equivalent to six times its quantity of the usual product. The liquid oil has a, specific gravity of 0.909, a rotatory power of + 1" lo', an acid value of 2.4, an ester number of 180.5, and it is soluble in 5 to 6 volumes of 80 per cent. alcohol. Oil of Neroli.-A recent investigation has shown that oil of neroli contains, besides the constituents hitherto recognised, the following bodies : I-pinene, Z-cam- phene (?), dipentene, decyl-aldehyde (?), an alcohol C,,H,,O (probably I-linalool), phenylethyl alcohol (free, or as ester), d-terpineol (melting-point, 3 5 O ) , phenylacetic acid, and benzoic acid.Oil of Petit-grain.-A specimen of genuine oil from Paraguay has been found to have a specific gravity of 0.8912, and to contain furfurol, I-pinene (?), I-camphene (?), dipenteae, an alcohol C,,H,,Q (Z-linalool), d-terpineol (melting-point, 35"), geraniol, geranyl acetate, and traces of a basic substance. Italian Oil of Peppermint.-A sample of this oil, distilled in Piedmont, had366 THE ANALYST. a pale greenish-yellow colour and an odour somewhat resembling pennyroyal.Its constants were : specific gravity at 15", 0.9122 ; rotatory power, - 16" 21' ; solubility, 7 volumes of 70 per cent., 1.1 volume of 80 per cent. alcohol ; total menthol content, 52.5 per cent., 7.89 per cent. thereof existing as esters. The sample, accordingly, did not solidify in a freezing mixture. The menthone, on the contrary, was high-vie., 22 per cent. With larger quantities of alcohol than those mentioned the oil gave a transient opalescence. After removing the bulk of the anethol, the sample had a rotatory power of - 3" 15'. Besides the con- stituents already known-pinene, phellandrene, methylchavicol, the ethyl ester of quinol, anisaldehyde, and anisic acid-Tardy found anisic ketone, a sesquiterpene having a laworotatory power of 5", and a body melting at 212", which is probably identical with the substance melting at 213' C.isolated from oil of fennel. Tardy also considers that oil of aniseed contains terpineol, but beyond quoting the boiling- point of 216' to 218" he gives no proof of its existence. Oil of Bystropogon 0riganifolius.-This is a new material introduced by the firm of L. Riga1 in Teneriffe. It is prepared from a shrub of the Labiate species which grows largely in the Canary Islands. It forms a bright yellow oil with an odour recalling that of pennyroyal. Its constants are: specific gravity at 15", 0.9248; rotatory power, + 2" 57 ; acid value, 0; saponification value, 11.1; after acetylization, 58.83 ; coefficient of refraction, 1.48229 ; solubility, 2.5 volumes of 70 per cent., 0.7 volume of 80 per cent.alcohol. The oil distils mainly between 162" and 234' C. Its chief constituents are pulegone and menthone ; it contains but little limonene. F. H. L. Oil of Aniseed.-Tardy has recently investigated this oil. Detection of Carbazol and Phenanthrene in Anthracene. H. Behrens. (Rec. trav. chim. des Pays-Bas et de la Belge, 1902, xxi., 252; through Clzem. Zeit. Rep., 1902, 266.)-To detect carbazol, anthracene is extracted with cold acetic ether and the liquid evaporated to dryness. The residue is again taken up in a few drops of the same solvent, and allowed to evaporate on a watch-glass. The carbazol separates out at the edges, the anthracene in the middle of the mass. A little of the former portion is removed with a needle, and treated with a small drop of nitro- benzene in which a few little crystals of phenanthrene-quinone have been suspended.In the presence of only 0.5 per cent. of carbazol copper-coloured crystalline plates are produced, pure anthracene giving no reaction. To detect phenanthrene, the anthracene is extracted with benzene and the solid portion of the extract treated with nitrobenzene oontaining some a-dinitrophenanthrene-quinone. If the original anthracene contained only 1 per cent. of phenanthrene, the existence of the latter will be shown by the formation of the characteristic brown rod-like crystals of the condensation product. F. H. L. The Extraction of Alkaloids from AlkQline Solutions. E. Springer, (Pharm. Zeit., 1902, xlvii., 82, 83; through Zeit. fiir Untersuch. der Nahr. und Genussmittel, 1902, v., 935, 936.)-By employing an apparatus in which aqueouaTHE ANALYST.367 solutions may be extracted continuously with immiscible solvents (see ANALYST, 1892, p. 44), it was found that the whole of the commonly occurring alkaloids can be quantitatively extracted with chloroform in this manner. Morphine, not being readily soluble in pure chloroform, is best extracted with chloroform containing 10 per cent. of alcohol, after first liberating the morphine by ammonia or sodium hydrogen carbonate, as sodium hydroxide is not suitable. In the case of veratrine, codeine or cocaine, an excess of alkali is to be avoided. Sodium hydrogen carbonate should be employed to liberate codeine from its salts, as sodium hydroxide is liable to cause the retention of small traces of the alkaloid in the aqueous solution.Strychnine is rapidly extracted from solutions containing sodium hydroxide? and in traces even from acid solutions. Cocaine is also readily extracted, but it should be noted that it is liabIe to decomposition at moderately low temperature; chloroform extracts traces of this alkaloid from acid solutions. Traces of atropine and narcotine are also obtained from acid solutions, whilst the extraction is rapid when the solution is alkaline. Coniine and nicotine must be extracted at quite low temperatures. Other solvents, such as isobutyl alcohol, amyl alcohol, benzene, toluene, carbon tetrachloride, and petroleum may, in certain cases, be used instead of chloroform, w. P. s. The Extraction of Alkaloids from Acid Solutions and Salts of the Alkaloids from Aqueous Solutions.(Apoth. Zeit., 1902, xvii., 225, 226.)- Chloroform was found to extract alkaloids most readily from solutions rendered acid with hydrochloric acid as compared with other acid solutions, and it follows that the hydrochlorides are comparatively more soluble than other salts of the alkaloids. In testing for traces of alkaloids hydrochloric acid solutions should not be shaken out with chloroform, unless these extracts are tested for alkaloids as well as the alkaline extractions. From sulphuric acid and phosphoric acid solutions less alkaloid is removed by chloroform, and in the case of solutions acidified with tartaric acid very little. Only aconitine and narcotine salts are appreciably soluble in chloroform. Codeine, cocaine, quinine, morphine, coniine, and nicotine salts are practically insoluble? and strychnine, atropine, and veratrine only yield a minute trace of soluble salt.Morphine is not dissolved by pure chloroform from acid solutions, but is to some extent soluble in chloroform containing 10 per cent. of alcohol. Morphine hydrochloride, morphine sulphate, and quinine sulphate are not dis- solved by chloroform from neutral solutions ; cocaine hydrochloride gives traces of the free base. All the other alkaloids are extracted from neutral solutions, the soluble portion consisting partly of the salt and partly of free base. The more concentrated the solutions are, the more is dissolved by the chloroform. The presence of glycerol, saponin, etc., has no influence on the solubilities.W. P. S. E. Springer. Detection of Blood Colodring-Matters in Urine. 0. Rossel. (Schweig. Wochschr. Chern. Plzarm., 1901, xxxix., 557, 558 ; through Zeit. fiir Untersuch. der Nahr. und Genussmittel, 1902, v., 942.)-The urine is strongly acidified with acetic acid and shaken out with an equal volume of ether, A drop of water is added to the368 THE ANALYST. ethereal extract, and then 15 to 30 drops of old oil of turpentine or 5 to 6 drops of fresh hydrogen peroxide. After shaking, 10 to 20 drops of a freshly-prepared 2 per cent. solution of Barbadoes aloin in alcohol (70-90 per cent.) are added, and the mixture is again well shaken. In the presence of minute traces of blood-too small to be detected spectroscopically-the aqueous layer becomes distinctly red in colour within three minutes.After ten minutes the colour turns to bright cherry red. w. P. s. A New Colorimetric Method of determining Mercury in Urine, Schu- macher and W. Jung. (Zeit. anal. Chem., 1902, xli., 461-484.)-As a rule, 500 C.C. of the urine are taken, but if subsequently no coloration is given with hydrogen sulphide, the amount of mercury, if present, cannot exceed 0.6 milligramme per litre; and in such cases a litre or more of the urine should be concentrated on the water-bath, with the addition of a few grammes of sodium chloride to prevent any mercuric chloride volatilizing. The 500 C.C. of urine are heated to the boiling-point with 50 C.C. of concentrated hydrochloric acid and about 5 grammes of potassium chlorate, after which the contents of the flask are cooled to about 80" C., and treated with 12 grrtmmes of pure zinc filings.Eventpually an additional 3 grammes of zinc are added, and the flask set aside for two hours. The supernatant liquid is then decanted from the deposit of zinc particles (which will have combined with all the mercury present), and this deposit washed twice with water, then treated for a few minutes with a dilute solution of sodium hydroxide, and again washed twice with water. The residue is now mixed with 50 C.C. of dilute hydrochloric acid and a little potassium chlorate, and heated gently over a small flame until everything has dissolved, more potassium chlorate being added from time to time. The solution is cooled to 70" to 80' C., mixed with about 5 C.C.of alcohol, again boiled, cooled, and transferred to a 100 C.C. flask. The liquid is mixed with a few C.C. of hydrogen sulphide water and made up to the mark, and the colour compared with that given by a freshly-prepared standard solution of mercuric chloride. The authors state that this is the most rapid and simple method known, and they show by the results of test experiments that it is extremely accurate, whilst being capable of determining 0.1 milligramme of mercury per litre after concentrating the original urine from 3 litres to I litre. C. A. M. The Examination of Civet. A. HBbert. (BUZZ. SOC. Chim., 1902, xxvii., 997- 1000.)-The samples of guaranteed purity examined by the author melted a t 36" to 37" C. The principal constituent of civet is soluble in ether, benzene, chloroform, and petroleum spirit, but is only soluble with difficulty in alcohol, methyl alcohol, and acetone at the ordinary temperature.The residue left on treating civet with organic solvents consists of accidental impurities, hair, etc., In three samples examined by the author it ranged from 3-6 to 5-3 per cent. The ash varied from 0.8 to 1.2 per cent., and consisted of sulphates (in largeTHE ANALYST. 369 quantity), carbonates, phosphates, and other salts of iron, aluminium, calcium, magnesium, potassium, and sodium. Chlorides were almost entirely absent. The rotatory power of a filtered solution in a mixture of alcohol and ether was prac- tically nil. When civet is distilled in a current of steam nearly the whole of the malodorous part (skatole) passes over, whilst the residue has a musk-like odour, and resembles fat in appearance. Civet is not readily saponified, and the boiling with alcoholic alkali must be continued for a very long time. When the saponification product is taken up with warm water an opalescent solution is obtained, and on acidulating this with sulphuric acid a layer of fatty acids rises to the surface. In the three samples examined by the author these melted a t 39" C., and amounted to from 51 to 70 per cent. of the original material. The composition of civet can be considerably influenced by the method of extraction. In some cases the instrument used for the incision is smeared with honey, and the civet then reduces Fehling's solution, and has a rotatory power. Fat is also commonly used to smear the instrument, and in the author's opinion this was the case with the samples examined by him. C. A. M.