304 ABSTRACTS OP CHEMICAL PAPERS ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS. FOOD AND DRUGS ANALYSIS. Composition of the Fruit of Cicer* Arietinzcln L. (Chick Pea). A. Zlataroff. (Zeztsch. Unters. Nahr. Genussrn., 1916,31, 180-183.)-The dry substance of the chick pea contains: Fat, 6.30; starch, 50.32; crude fibre, 3.62; total nitrogen, 3.34 ; protein nitrogen, 2.1 1 ; nuclein nitrogen, 0.10 ; ammonia nitrogen, 0.10 ; amide nitrogen, 0.01 ; amino-acid nitrogen, 0.12; total phosphoric acid (P,O,), 0.998 ; lecithin phosphoric acid, 0- 142 ; protein phosphoric acid, 0.486 ; inorganic phosphoric acid, 0.118; organic soluble phosphoric acid, 0.244; total ash, 2-87 per cent.Oxalic acid (0.007 per cent .), citric acid, betain and choline (0-02 per cent. together), adenine, inositol, and an isomer of phytosterol, are also present.This isomer, which is termed slanutosterol, is present in the fat to the extent of about 0.3 per cent.; it yields an acetate melting a t 128" C. w. P. s. Analysis of Rancid Fats. G. Issoglio. (Annali Chzm. AppZic., 1916, 6, 1-18.)--A method of estimating the degree of rancidity of oils and fats is based upon the proportion of aldehydes, etc., liberated on distillation with steam under constant conditions, and measured by titration with permanganate solution.From 20 to 25 grms. of the sample are mixed with 100 C.C. of water and distilled in a current of steam, so that 100 C.C. of distillate are collected in ten minutes. Ten C.C. of the homogeneous distillate are then mixed with 50 C.C. of water, 10 C.C.of 20 per cent. sulphuric acid, and 50 C.C. of r& potassium permanganate solution, the mixture heated to the boiling point and kept boiling for five minutes in a flask connected with a ground-in condenser. After cooling, the liquid is treated with 50 C.C. of .r& oxalic acid solution and titrated with & potassium permanagnate solution. If N represents the amount of permanganate required for the oxidation and n thatFOOD AND DRUGS ANALYSIS 305 required in a blank test, and P the weight of fat taken, the oxidisability value of the fat may be expressed by the equation X=(N-n) 80 .- __ P. Hence the oxidisability value represents the mgrms. of oxygen required to oxidise the organic compounds separated under constant conditions from the fat.Speaking generally, the oxidisability value of sound fresh fats varies from about 3 to 10, while rancid fats show much higher values. The acid value does not stand in any definite relationship to the oxidisability value. For example, fifteen samples of fresh sound olive oils of different origin gave acid values ranging from 1.88 to 8.59, and oxidisability values of 3.20 to 10.45; while six samples of rancid olive oil showed acid values of 6.51 to 18.56, and oxidisability values of 14.62 to 59.10.When the oxidisability value exceeds 15 i t will usually be found that the fat is rancid or has undergone some other change. C. A. M. Estimation of the Degree of Bolting of Flour. C. L. Spica. (Annali Chim. AppZic., 1916, 6, 26-28.)-Ten grms. of the dry fat-free flour are hydrolysed, the insolubie residue is distilled with iiydrocilioric: acid of sp.gr. 1-35, and the whole of the furfural is collected. The distillate is mixed with 95 per cent. alcohol, so as to obtain a solution containing 50 per cent. of alcohol, and this is treated with an acetic acid solution of aniline acetate. The coloration produced is compared with that of a solution of 0.05 grm.of furfural in 1,000 C.C. of 50 per cent. alcohol. Practical tests with flour bolted fo yield 60, 80, and 100 per cent. yielded solutions with colorations corresponding to 0.025,0.1520, and 0.225 grm. of furfural respectively. C. A. M. Ester Acids of Lemon Juice. L. Wolfrum and J. Pinnow. (Zeitsch. Unters. Nahr. Genussm., 1915, 30, 144-156.)-The authors have detected the presence of ethyl citric acid in lemon juice, the acid having been separated by fractional extrac- tion in it Partheil-Rose apparatus and then precipitated as its calcium salt.The acid was also prepared by boiling together alcohol and citric acid (without a catalyst), and using the above-mentioned means for its isolation; the acid obtained in this way was identical with that isolated from lemon juice.The calcium, lead, and silver salts of the acid are but slightly soluble, and the acid itself saponifies a t a very slow rate. The presence of an anhydride of the acid could not be detected. w. P. s. Estimation of Essential Oils (Essences) in Liqueurs. C. F. Muttelet. (Ann. Falsific., 1916, 9, 70-73 ; 134-143.)-The quantity of essential oil in peppermint liqueur is besB estirgated gravimetrically.The liqueur is distilled, the distillate saturated with sodium chloride, extracted with petroleum spirit, and the residue of essential oil weighed after the solvent has been evaporated a t ordinary temperature. The official (Prench) method, in which the quantity of essential oil is deduced from the iodine absorption of the sample, is not applicable to peppermint liqueur, since306 ABSTRACTS OF CHEMICAL PAPERS it will not indicate the presence of added menthol; the latter does not absorb iodine.If, however, the essential oils are separated by means of petroleum spirit a deter- mination of their iodine absorption will show whether or not added menthol is present. One grm. of oil of peppermint absorbs 0.450 grm.of iodine. The author has also estimated the essential oils in a number of other liqueurs by both the gravimetric and volumetric (iodine) methods; only in the cases of aniseed liqueur and carrawat liqueur (Kummel) were agreeing results obtained by the two methods. With Curagao, Bhkdictine, Chartreuse, Angostura, and other bitters, the volumetric (iodine) method yielded untrustworthy results, as it was impossible to fix an average iodine value for the various liqueurs.Some of the liqueurs were coloured with caramel, and this introduced an additional difficulty in applying the volumetric method; the caramel absorbed iodine, and even when the samples were distilled and the method applied to the distillate, the results obtained were inaccurate owing to the presence of unsaturated (furfuraldehydic) compounds formed from the caramel.w. P. s. Estimation of Essential Oils (Essences) in Liqueurs. X. Roeques. (Ann. Ir’aZsJic., 1916, 9, 127-134.)-Methods which have been proposed for the estimation of essential oils in liqueurs were investigated by a Commission appointed by the Soci6tk des Experts-Chimistes de France. The volumetric method, which depends on the iodine value of the distillate from the liqueur, was found to yield accurate results only in the case of aniseed and carraway (kummel) liqueurs; as determined by the Hub1 method, 1 grm.of aniseed oil absorbs 1.45 grms. of iodine, and 1 grm. of carraway oil 2.40 grms. of iodine. For all other liqueurs (Chartreuse, BBnbdictine, mint, Curapoa, orange bitters, etc.) the use of the gravimetric method is recommended ; in this method the distillate from the liqueur is saturated with sodium chloride, and the essential oil extracted with petroleum spirit and weighed after the solvent has been evaporated a t a low temperature. Well-known brands of liqueurs examined generally contained more than 0-5 grm.of total essential oil per litre, the maximum limit fixed by a recent French law; Curagoa liqueur contained more than 2 grms.per litre, but vermouth was found to be free from any appreciable quantity of essential oil. w. P. s. Estimation of Essential Oils (Essences) in Vermouth. L. Ronnet. ( A m . PaZs*iJic., 1916,9,144-145.)-Experiments carried out by the author show that ver- mouth is practically free from essential oils (see also ANALYST, 1916,SS).W. P. S. Analysis of Maple Products. ‘VII. J. F. Snell. ( J . Ind. and Eng. Chem., 1916, 8, 331.)-In continuation of previous work (ANALYST, 1914, 39, 85; 1916, 207) the author describes the conductivity test in its application to over two hundred samples of genuine syrups covering five seasons. ,Conductivity values ranging from 96 to 230 have been met with in genuine syrups, but the limits of percentage variation of the conductivity value in such syrups are much narrower than those of the older analytical values, with the exception of the volumetrical lead number.Conductivity values above 200 have only been met with in theFOOD ASD DRUGS ANALYSIS 307 I 1 Reichert- ~ Meissl case of boiled syrups, while values below 110 have been found in genuine syrups of the year 1915, but not in the years 1911-1914.A new type of electrode (Van Zoeren, J . Amer. Chem. Xoc., 1916, 38, 652) is now employed, necessitating the use of 20 C.C. of syrup in place of the 15 C.C. previously employed; this is mixed with 40 C.C. of distilled water and the resistance measured a t 25' C. exactly with the dip electrode.The constant of the cell divided by the observed number of ohms and multiplied by 100,000 furnishes the conductivity number. H. F. E. H. I Polellske Saljonifica- Iodine tion Value Fat of Egyptian Buffalo Milk. G. Hogan and E. Grimths-Jones. (Egyptian Dept. Public Hmlth, Publication No. 5, 1916, 1-3.) - Results of the examination of sixty-nine samples of buffalo butter-fat are recorded.The milk from which the butter was prepared was the mixed milk of five or six buffaloes, the animals being milked dry. Twenty-eight samples were taken during 1913, and the remainder during 1915. The maximum, minimum, and average analytical values obtained were as follows : Value. Value. I Value. 1 ! I I (Hiihl). -----I---- -. .___ -1 + .. 1 . ! i 1.0 I 218 Maximum .- * . 1 37.0 ' 2-8 Minimum . . . . 24.5 31.4 I 31.2 , 1.5 , i * . ~ Average . . Refractometer Value at 40' C. - - . - 44.0 40.4 42.5 No seasonal variation was observed in any of the values (see also ANALTST, 1892, 17, 46; 1913, 38, 242). w. P. s. Cgmposition of Egyptian Buffalo Milk. A. Pappel and G. Hogan. (Egyptian Dept. Public Health, 1914, 1-12.)-Sixty-one samples taken from different herds were examined; each sample represented the mixed milk from six animals. The maximum, minimum, and average percentage results obtained are given below : Sp.gr. a t 15"/4" C. Total solids Fat (Adams' method) Solids-not-fat . . Lactose . . . . Proteins . . .. Ash .. .. Chlorine . . .. Minimum. 14294 15-81 6.05 9.42 4.65 3.57 0.70 0.04 Maximum. 1.0343 19.75 9-75 10.40 5.19 4-80 0.84 0.10 Average.1.0324 17.91 7.95 9.95 4-86 4-16 0.78 0.08 w. P. s.308 ABSTRACTS OF CHEMICAL PAPERS Method for Detectidg the Admixture of Goat’s Milk with Cow’s Milk. N. A. Brodrick-Pittari. (Schweix. Zentralbl. Milchw., 1915, 4, 413-414; 1916, 5, 3-4; through Int. Rev. of the Science and Practice of Agriculture, 1916, 7, 431-433.)- A method proposed by Steinegger is based on the fact that the casein of COW’S milk dissolves readily in ammonia a t 50” C., whilst the casein of goat’s milk remains insoluble; Gabathuler and Pritzker have improved the method by separating the insoluble casein of goat’s milk by centrifugal action.The author has investigated the method, and finds that-(1) The same amount of goat’s milk, when mixed in equal quantities with milk from different cows, produces variable quantities of sediment.(2) The amount of sediment formed in a mixture of goat’s milk and colloidal solutions decreases with a decrease in the concentration of the solution. (3) Decrease of the colloidal concentration of cow’s milk by the addition of water diminishes the amount of sediment which may be produced by the presence of goat’s milk.(4) When absolutely fresh goat’s milk is added, the increase in the albumin content of cow’s milk causes an increase in the amount of sediment of in- soluble casein. (5) The amount of sediment diminishes with the age of the goat’s milk. (6) Formaldehyde interferes with the formation of the sediment, whilst potassium bichromate promotes its formation and causes a marked separation of the sediment from the serum.(7) The formation of the sediment of insoluble casein is promoted by a complete skimming of the mixed milk under examination. On the basis of these results, the author recommends the following procedure in carrying out the test: 100 C.C. of the milk are-treated with 1.6 C.C. of saturated potassium bichromate solution and then skimmed completely; 20 C.C.of the skimmed milk are now placed in a tube, 2 C.C. of 20 per cent. ammonia are added, the mixture is heated at 50” C. for one hour, and then submitted to centrifugal action. The for- mation of a sediment is a certain indication that the sample contains goat’s milk. The minimum quantity of goat’s milk that can be detected by the test is about 10 per cent., but the absence of a sediment does not prove the entirc absence of goat’s milk.w. P. s. Methyl Red as an Indicator in the Esti.mation of Nicotine by Toth’s Method. P. Schick and G. Hatos. (Zeitsch. Unters. Nahr. Genussrrb., 1914, 28, 269-270.)-1n Toth’s method (ANALYST, 1902, 27, 12) the nicotine is extracted by means of a mixture of ether and pebroleum ether from the tobacco after the latter has been treated with sodium hydroxide; an aliquot portion of the ethereal solution is then titrated.The aut.hor finds that methyl red may be used as the indicator in this titration, and that it serves equally as well as the iodeosin recom- mended by Toth. w. P. s. Detection andEstimation of Nitrites and Nitrates in Meats,Sausages, etc. D. Acel. (Zeitsch. Unters. Nahr.Genassm., 1916,31,332-341 .)--Nitrites in meat prepara- tions may be detected and estimated eolorimetrically with the Griess-Ilosvay reagent ; nitrates may be estimated in the same way after they have been reduced to nitrites by means of zinc and acetic acid. The presence of soluble starch, salicylic acid, sugar. vinegar, formaldehyde, or boric acid, does not interfere with the reaction.FOOD AND DRUGS ANALYSIS 309 Nitrites are produced during the burning of wood, and nitrites may be thus introduced into smoked meats, but it is found that the quantit'y is too small to have any material effect on the results obtained by the above method.Attention is drawn to the fact that potassium nitrate in meat is reduced rapidly to nitrite; for instance, if meat treated with potassium nitrate is kept a t 10" C.for four days, about 50 per cent. of the quantity of nitrate present is reduced to nitrite. w. P. s. Oil from the Fruit of the Canadian Vine. S. Fachini and G. Dorta. (Annali Chim. AppZic., 1016, 6, 301-304.)-The pulp of the fruit of the Canadian vine (Parthenocissus quinquefolia) yielded 3.3 per cent. of oil, while the kernels yielded 11.8 per cent.The fruit oil was a semi-solid mass, with a green colour and an astringent taste. It had the following constants: Refractive index a t 15" C., 1.4722 ; saponification value, 192.3-193.3 ; iodine value, 90.3 ; Hehner value, 94.0 ; unsaponifiable matter, 1.67 per cent. Patty acids : Iodine value, 94-4-94.6; mole- cular equivalent, 278.8; and iodine value of liquid fatty acids, 110.2. The solid fatty acids (about 10 per cent.) consisted of palmitic acid, while the liquid fatty acids contained oleic and linolic acids.The oil from the seeds was greenish- yellow and had a pleasant odour and taste. Its constants were: Sp. gr. a t 15" C., 0.9215; refractive index a t 15" C., 1.4778; saponification value, 189.2; iodine value, 141.4; Hehner value, 93-97; unsaponifiable matter, 1.44 per cent.Patty acids: Iodine value, 144.6; molecular equivalent, 281.2; and iodine value cf liquid fatty acids, 148.8. The solid fatty acids consisted of palmitic acid, while the liquid fatty acids contained oleic and linolic acids. The seed oil belonged to the semi-drying class. C. A. M. Volatile Oil of Cnlyccxnthus Occidentalis. C. C.Scalione. ( J . Ind. and Eng. Chern., 1916, 8, 729-731.)-The leaves and twigs of the spice bush CuEy- canthus occidentalis, which grows in California and Oregon, yielded, when distilled with steam under pressure, from 0.15 to 0-37 per cent. of a greenish-yellow oil, with a bitter taste and an odour of camphor. It had the following constants: Sp. gr. at 25" C., 0.9295; optical rotation, + 7" 28'; refractive index a t 20" C., 1,4713; free acid, 0.05 per cent.; saponification value, 54.3; and acetyl value, 33.5.It was soluble in all proportions in 90 per cent. alcohol, and in 15 to 16 volumes of 70 per cent. alcohol. It had the following composition: Pinene (d and E ) , 8-30; cineol, 60.32; borneol, 9.21; and linalyl acetate, 18.99 per cent., with traces of camphor, methyl salicylate, and sesquiterpene alcohols. C.A. M. Detection of Saccharin and its Estimation. M. Klostermann and K. Scholta. (Zeitsch. Unters. Nahr. Genussm., 1916, 31, 67-78.)-Many of the tests which have been proposed for the detection and identification of saccharin are rendered useless when applied to food substances owing to the interfering action of other substances which may be present.For inst'ance, clove oil, cinnamon oil, salicylaldehyde, gum benzoin, tannin, benzaldehyde, and vanillin, all give a re- action with the phenol-sulphuric acid test (formation of a red coloration when the310 A BSTltAC'TS OF CI-IEMICA L PAPERS substance is heated with phenol and sulphuric acid, and then treated with sodium hydroxide): The following method is suggested with the object of overcoming these difficulties. The material to be tested is rendered acid and the saccharin extracted with a mixture of ether and petroleum spirit; the solvent is evaporated, the residue obtained is boiled for ten minutes with 10 per cent.hydrochloric acid, and the solution again evaporated to dryness. If the residue now obtained has an odour of vanillin it is washed several times with a mixture of equal volumes of ether and chloroform; saccharin is insoluble in this mixture.The residue is now trested with liquid phenol a d the solution poured on to phosphoric anhydride. If saccharin is present the mixture exhibitjs a red colour which, on the addition of water, changes to yellow; this yellow solution gives a blue-red coloration when rendered alkaline, and the colour is discharged by ammonium sulphide. Besides vanillin (which is eliminated as described), benzsldehyde is the only other substance which gives a reaction similar to saccharin, and this aldehyde is expelled during heating with hydrochloric acid or it is converted into benzoic acid, which does not interfere.In methods for the estimation of saccharin, and which depend on the estimation of the sulphur content, the substance should be hydrolysed with hydro- chloric acid and extracted with a mixture of ether and chloroform, in order to re- move any p-benzoic sulphinide; otherwise, the sulphur contained in the latter would be included in the quantity yielded by the saccharin.w. P. s. Analysis of Soap Powders. L.Rosenberg and V. Lenher. ( J . Ind. and Eng. Chem., 1916, 8, 716-719.)--Moisture: 2 grms. of the sample are dried in a vacuum oven a t 65" C. until constant in weight (about twenty hours). Fat: The residue from the moisture estimation is extracted with petroleum spirit, the solvent evaporated, and the residue dried a t 110" C. Soap and free alkali : The fat-free residue containing the soap and mineral constituents is extracted for thirty minutes with 95 per cent.alcohol, which dissolves the soap and free alkali. The alcoholic extract is titrated with -:G acid, with phenolphthale'in as indicator, and the amount of caustic alkali found calculated as Na,O. The solution is then diluted with a large aniount of water, the alcohol expelled by evaporation, and the liquid boiled with a measured excess of An addition of 4 grms.of stearic acid is made, the liquid again boiled, then cooled, and the cake of fatty acids and added stearic acid separated and weighed. The excess of acid in the solution is titrated back with sodium hydroxide solution, and the amount of acid which had been used calculated into the amount of sodium oxide in combination in the soap.Mineral constituents and insoluble matter : The residue from the alcoholic extraction may contain sodium carbonate, chloride, silicate, sulphate or borate, starch, etc. It is dissolved in hot water, and any insoluble residue of starch, etc., separated and weighed. The solution is divided into five equal portions, and one of each taken for the estimation of the different salts of sodium by the usual methods. The recent introduction of continuous drying apparatus by the larger manufacturers has changed the relative composition of these powders.Commercial samples typical of those on the market gave the following results: nitric acid.FOOD AND DRUGS ANALYSIS 311 - 1 2 3 4 6 7 - - Moist 11 re. l'er Cent. 37.82 22-06 23.75 20.86 18.52 43.38 30.40 Fatty \ t i hy d ride Per Cent.18.39 19.44 21.63 18-93 20.34 16.74 121.46 Per Ceri t. 2.63 3.58 2.7 1 2-66 2.68 2.23 2.86 Total Soall. Per Cellt. 21.02 23.02 24.34 21.58 23.02 18-07 24-32 Sodium hrbonate Per Cent. 39.37 53.53 50.35 55-38 56-45 36.30 40.00 Sodium Silicate. Per Ccii t 0.45 0.99 0-72 0.90 0-36 0.72 0.99 Sotliiini Chloride Per Ceri t, 0.55 0.75 0.35 0.86 1-32 0.34 0.72 Unsa1)on i tied Matter.Per Cont. 0.69 0.24 0.85 0.45 0-74 0.87 0.79 Total. Per Cctit. 99.90 100.59 100.36 100.03 100.41 100.58 97.22 Estimations of sugcr, resin, glycerol, fluorides, and sodium bicarbonate, are not included in this scheme of cna'lysk. are of simple compc sltion. In the aut'hors' experience these powders C. A. M. Studies of Soap Solutions. V. Lenher and M.V. R. Buell. ( J . Ind. and Eng. Ghem., 1916,8, 701-703.)--Xurface tension ; Pure sodium oleate solutions were delivered from a modification of Traube's stalagmometer provided with a device to regulate the pressure. The surface tension towards air at 25" C. expressed in dynes per cm. feil from 28-20 with &- solutions to 24-17 with & solutioiis, and then rose to 24.91 with &c solutions and 41.28 with i2& solutions.Under the same con- ditions water gave 71.78 towards air. Frothing of the soap was most pronounced In .the concentrations between ;'& and &. Emubifying action : The emulsification of soap solution and immiscible liquid was effected by means of a thin metal paddle containing nuinercus perforations, which was driven by an electric motor.The liquids were a,gitated for five minutes and an emulsion regarded as satisfactory if it did not sepmate within five minutes. A difference of 0.1 C.C. of 2\ sodium oleate solution (=O.OOlr> grm.) could be detected by this method. The following results were obtained with Fure water a t Z O O C. : Subs tancc. Sodium Oleate required for Water. Eiiiulsification.c. c. Turpentine, 50 C.C. . . . . . . 60 Carbon tetrachloride, 50 C.C. . . . . 50 Chloroform, 50 C.C. . . . . . . 50 Benzene, 50 . . . . . . . . 50 Vaseline, 2.5 grms. . . . . . . 50 gyms. 0.633 1 0.1140 0.7824 0.9804 1.5200 Weak solutions of sodium oleate were more economical in the emulsification of turpentine and water. At higher temperatures a definite quantity of sodium oleate was able to emulsify greater amounts of the immiscible liquids, but the emulsifications were less stable than those made a t lower temperatures.The emulsifying power of sodium oleate solutions was only very slightly reduced by the hydrolysis which had taken place after four and a half months. Hence a soap solution which has312 ABSTRACTS OF CHEMICAL PAPERS stood for a long time appears to be as effective for washing purposes as a freshly made solution. At 100" C. sodium palmitate emulsified olive oil much more efficiently than did sodium oleate or stearate. Xuspensions .- Sifted ferric oxide and manganese dioxide were shaken with sodium oleate solutions of concentrations from ;G to iTgG, and the mixtures allowed to stand for five days to three weeks. The maximum suspension invariably occurred with solutions of about 3& strength. C. A. M. Colorimetric Method for the Detection of Potato Starch. G. Blunck. (Zeitsch. Unters. Nahr. Genussm., 1915, 29, 246-247.)-Potato starch and cell tissues are coloured a bright golden-yellow by the dye called " metachrome red G Agfa," whilst cereal starches are not coloured. The presence of potato starch in ordinary flour may be detected by treating a portion of the sample on a microscope slide with a drop of water, drying it, adding a drop of the dye solution, washing off the excess of the latter, and examining the slide under the microscope. The dye solu- tion is prepared by saturating boiling 30 per cent. alcohol with the dye, filtering the cooled solution, and diluting it with 25 per cent. of its volume of water. When i t is desired to apply the test to bread, a quantity of the crumb must be treated with dilute alkali solution and then washed before the dye solution is added. The treatment with alkali removes any acidity, and is an essential procedure, since in the presence of acids the dye colours wheat starch as well as potato starch. w. I?. s.