THE ANALYST. 405 ORGANIC ANALYSIS. Composition of Aleurites Seeds from Cochin China. Ballard. (Jounz. Pharm. Chim., 1908, 28, 162.)-The oil expressed from the seeds of various kinds of alezuites is now extensively used in the manufacture of soap. Two samples examined by the author had the following composition: Water, 4.40 and 4.90; nitrogenous substances, 21-80 and 24.30; fat, 58.7 and 52.50 ; extracted by water, 7.8 and 10.27 ; cellulose, 340 and 3.75; and ash, 3.90 and 4.26 per cent. I n the author’s opinion cases of poisoning attributed to alezLrites seeds are probably due to the presence of seeds of abrasin. C. A. M. Bang’s Method of Estimating Sugar. I. Bang. (Biochem. Zeits., 1908,11, 538-540.)-1n answer to the criticisms of Jessen-Hansen (ANALYST, 1908, 324), the author maintains the reliability of the pro‘cess described by him (ANALYST, 1907, 32, 180); the conditions of the method must, however, be adhered to.W. P. S. Some of the Constituents of Cigar Smoke. J. Habermann and R. Ehrenfeld. (Zeits. Physiol. Chem., 1908, 56, 3G3-372.)-The authors have estimated the amounts of nicotine, ammonia, and sulphur in the smoke of various brands of cigars sold in Austria. The cigars were smoked by means of an aspirator connected with a series of absorption vessels. I t was found that the average quantity of sulphur in the smoke of different kinds of cigars was 0.02 per cent., calculated on the weight of the air-dried cigar. A brand known as ‘‘ Specials ’’ yielded smoke con- taining 0.015 per cent. of sulphur, but, on the whole, the amount of sulphur varied so little that it could not be used as a means of differentiating one class of cigar from another.On the other hand, the quantities of ammonia varied greatly, the smoke from three cigars of the same brand contained 0.01, 0.12, and 0.72 per cent. of ammonia respectively, whilst in other cases the quantity varied from nothing to 0.49 per cent. The amount of nicotine found in the different smokes ranged from nothing to 0.15 per cent. calculated on the cigar ; the alkaloid was concentrated in the unsmoked stumps of the cigars, as these contained from 3.22 to 4.71 per cent., whilst the cigars themselves contained from 1.02 to 1-53 per cent. of the base. There was but little difference in the quantities of moisture and ash in the various brands.(See also ANALYST, 1904, 29, 166.) w. P. s. Analysis of Copal Lacquers. H. Rebs. (Lack and 3”nrbeuind, 1908,122-123 ; Chenz. Zeit. Rep., 1908, 32, 435.)-The analysis of lacquers containing copal and rosin is carried out in the following manner : Ten grams of the lacquer are freed from oil of turpentine by distillation, and the turpentine is weighed. Three gram8 of the406 THE ANALYST. ~ Method 11. residue are mixed with about 200 C.C. of light petroleum spirit, and shaken with about 5 C.C. of dilute acetic acid. The copal is precipitated, whilst the rosin and oil remain dissolved in the petroleum. The solution is filtered, and the rosin is precipitated by the addition of ammonia to the filtrate; alcohol is then added until the precipitate is re-dissolved.Two clear layers are thus formed, the lower, alcoholic- ammonia layer, containing the rosin, and the upper, petroleum layer, the oil. The oil is estimated by evaporating the petroleum from an aliquot portion of the upper layer, and the rosin is calculated by difference. J. F. B. Method 111. Estimation of Formic Acid in Glacial Acetic Acid. H. Ost and F. Klein. ( Chem. Beit., 1908, 32, 815-816.)-Commercial glacial acetic acid frequently contains appreciable quantities of formic acid which are not detected by the usual cold permanganate test unless the liquid be allowed to remain with the permanganate for forty-eight hours. The authors have ascertained that the following four methods are available for the quantitative estimation of formic mid in presence of acetic acid : (1) Ten C.C.of the glacial acetic acid are heated with 50 C.C. of concentrated sulphuric acid in an apparatus from which tho air has been expelled by a current of carbon dioxide. The carbon monoxide evolved by the decomposition of the formic acid is collected over potash in a nitrometer. One hour’s heating at the temperature of the water-bath is sufficient, but the method is not suitable for diluts acids, nor for solutions of the salts. (2) The liquid is made alkaline with sodium carbonate, heated on the water-bath and titrated with & permanganate, which acts rapidly in alkaline solution. (3) The acid is oxidised with potassium bichromate and sulphuric acid at the boiling temperature, and the excess of bichromate is titrated back with thiosulphate after the addition of potassium iodide. I t is necessary to oxidise in highly dilute solutions with at least eight times the theoretical quantity of bichromate ; the reaction is complete in half an hour on the water-bath.(4) The acid is diluted and treated with sodium acetate and excess of mercuric chloride. On heating, mercurous chloride is precipitated, and may be collected and weighed. This reaction also requires at least six times the calculated quantity of mercuric chloride, and several hours’ heating. I n the table below the authors set forth the results obtained by the different methods on six different samples of glacial acid : Saml’lc. Method I. 0.007 0 - - - 0.48 Percentage of Formic Acid. 0.009 0 0.48 0.012 0.52 0.46 Method I V 0.008 0 0 40 0.014 0.59 047THE ANALYST.407 Method I. is the best for glacial acetic acid. The most satisfactory method for obtaining pure acetic acid is by crystallisation and separation of the inother liquors by means of the centrifuge. J. F. B. “ The Hydrogen Number ” as a Means of Determining Unsaturated Organic Compounds in a manner similar to the Iodine Values of Hub1 and Wijs. S. Fokin. (Journ. Russ. Phys. Chenz. SOC., 1908, 40, 700-709; Journ. Chem. SOC. (abstract), 1908, 94, ii. 637.)-The ‘‘ hydrogen value ” of an organic compound is defined as the number of cubic centimetres of hydrogen (at 0” and 760 mm.) which are absorbed by 1 gram of the compound. For the test, an apparatus is devised consisting of a distillation flask (50 to 150 c.c.), having a small beaker fused inside on the bottom, and connected by means of the side-tube to a gas burette and a gasometer containing hydrogen.I n the small beaker are placed 0.1 to 0.2 gram of platinum, moistened with 0.25 to 10.5 C.C. of water, and active in the flask, the substance to be examined and 20 to 30 C.C. of alcohol free from dissolved oxygen. The flask is shaken by a machine. The following hydrogen values were obtained by the author, the figures in brackets being either the hydrogen values corresponding with Wijs’ iodine value, or, where indicated, the theoretical hydrogen values: Elaidic acid, 78.6 to 81-4 (78.8) ; oleic acid, 86.2 to 87.2 (86.2); fatty acids from sunflower oil, 119.6 to 120.8 (122.9); fatty acids from linseed oil, 164.9 to 166-3 (166.0); castor oil, 73.7 (75.5); Owton oil, 2609 (theoretical, 258.4) ; undecoic acid, 115.6 (114.1) ; erucic acid, 39.4 (65.6) ; maleio acid, 190.6 to 191.6 (theoretical, 191.0) ; aconitic acid, 131.0 (theoretical, 127.7) ; citraconic acid, 175.2 (theoretical, 171.1 ; cinnamic acid, 215.0 (150.1).Colophony, naphthalene, benzoic acid, resorcinol, quinol, catechol, pyrogallol, and cymene do not absorb hydrogen under the conditions of the test. Notes on Messinger and Vortmann’s Method of Estimating Phenols. Estimation of Salicylic Acid. J. Bougault. (Journ. Pharna. Chim., 1908, 28, 145-154.)-The author concludes, from experiments here described, that the two hypoiodous esters described by Messinger and Vortmann (ANALYST, 1891, 16, 75)- viz., di-iodophenol iodide, C,HsT,OI, and the potassium salt of the hypoiodous ester of an iodo-salicylic acid, C,H,I(OI)CO,K-were not chemical entities, but mixtures.Ths final product of the action of iodine, in the presence of alkalies or alkali carbonates. upon phenol, salicylic acid, or p-oxybenzoic acid, is one and the same compound, identical with Lautemann’s ‘‘ red body,” and named by Benzinger and Kamrnerer tetraiododiphenylene - quinone or tetraiododiphenylene dioxide (C,H,I,O),. This compound is so insoluble that it can be used in the gravimetric estimation of salicylic acid, and for the separation of that acid from acids which do not react with iodine under the same conditions. Phenol and p-oxybenzoic acid may also be estimated in the same way. In the author’s opinion, the aristol of thymol is probably an iodine derivative of a quinone compound closely related in constitution to Lautemann’s (‘ red body.” Estimation of Salicylic Acid.-In separating 0.1 gram of salicylic acid from 0.3 gram of cinnamic acid, the mixture is treated with 1 gram of dry sodiuu408 THE ANALYST.carbonate, and dissolved in 50 C.C. of water. The solution is heated on the water- bath, treated with an excess of a solution of iodine in potassium iodide solution, the heating continued for thirty minutes on the water-bath, and the liquid finally boiled for ten minutes under a reflux condenser. A few drops of sodium sulphite solution are now added to destroy the excess of iodine, and the red precipitate collected in a tared Gooch's crucible containing asbestos, washed, dried at 100" C., and weighed.The weight multiplied by the factor 0.4012 gives the corresponding amount of salicylic acid, The cinnamic acid in the filtrate and washings may be recovered by extraction with ether from the liquid after acidification with hydrochloric acid. In the test experiments quoted, the amounts of salicylic acid taken and found agree within a fraction of a milligram. C. A. 14. The Detection of Saponin. J. Ruhle. (Zeits. Uutersuch. Nahy. Gemssm., 1908,16, 165-171.)-The method proposed by the author as giving trustworthy results is a modification of the process described originally by Brunner, in which the saponin is extracted by means of phenol; the phenolic solution is then shaken with water and ether, and the aqueous portion containing the saponin is separated and evapo- rated.I n dealing with the separation of saponin from beverages such as aerated waters, etc., certain dotails of procedure, which are given below, have to be observed in order to obtain the saponin in a sufficiently pure state to give its characteristic reactions. One hundred C.C. of the sample under examination are neutralised by the addition of magnesium carbonate, 20 grams of ammonium sulphate are added, and the mixture is vigorously shaken in a separating funnel with 9 C.C. of pure phenol. After removing the aqueous layer, the phenol is shaken with about 50 C.C. of water and 100 C.C. of ether, about 4 C.C. of alcohol being added, if necessary, to break down the emulsion. When the layers have separated, which usually takes from twelve to fourteen hours, and the layer of emulsion between the ethereal and aqueous portions has diminished to a thickness of from 1 to 2 mm., the aqueous portion is drawn off' and evaporated. The residue, after being dried in a desiccator, is treated with about 10 C.C. of acetone, allowed to stand for twenty hours, and the acetone is then poured off; after a second similar treatment with acetone the residue is dried in the water- oven, at a temperature of looo C ., weighed, and tested for saponin. I n the case of liquids containing dextrin, 100 C.C. of the sample are evaporated 60 a volume of about 20 c.c., and 150 C.C. of 96 per cent. alcohol are then added. After the lapse of thirty minutes the mixture is heated until the alcohol just boils, and filtered immediately. The alcoholic filtrate is evaporated, after the addition of water, until all the alcohol has been removed, the residual solution is diluted to a volume of 100 c.c., and the process is then carried out as described above. Results of experiments are given in which known quantities of saponin were added to various solutions containing saccharose, invert sugar, dextrin, glycerol, tartaric acid, etc., from which it is seen that from 70 to 90 per cent. of the saponin can be recovered by the method. w. P. s.