336 THE ANALYST, ORGANIC ANALYSIS. Rose-Herzfeld and Sulphuric Acid Methods for Determination of Higher Alcohols. V. H. Veley. (Joz~rn. Sot. Chm. Ind. 1906 xxv. pp. 398-401.)-From a full examination of the two methods working with several of the higher alcohols, the Quthor concludes that by adopting all necessary precautions as to determination of specific gravity of the spirit calibration of the apparatus keeping the chloroform sheltered from the light etc. the R6se-Herzfeld method is sufficiently accurate for all commercial and legal purposes. The removal of aldehydes from the distillate from brandy or other spirit by heating for one hour with caustic soda under a reflu THE ANALYST. 337 condenser is considered more satisfactory than the sulphuric acid process and subse-quent destruction of the aldehydes by means of m-phenylene-diamine or preferably aniline phosphate.The line of demarcation between the chloroform and aqueous layer is more distinct if after shaking the chloroform is allowed to drop very slowly from the upper to the lower bulb and Griinheit's observation is confirmed that after the manipulation has been completed the chloroform slowly contracts sometimes requiring an hour before a constant level is reached. Though less accurate the su1phuri.c acid process gives valuable information. The risk of loss of higher alcohol before it is attacked by the sulphuric acid during the heating of the mixture in equal volumes of the sulphuric acid and alcohol solution may be obviated by using glass-stoppered bottles of about 50 C.C.capacity the stoppers of which are tightly tied down during the heating operation. A bath of saturated NH,C1 is suitable for this purpose a constant temperature of 109' to 110" C. being thereby readily maintained. The colour produced varies considerably with the temperature a difference of 2' or 3" causing a marked difference in the tint. It is better to cleanse the bottles prior to use with sulphuric acid only not using nitric acid also as the latter is SL source of danger. From the author's experience it seems probable that no reaction would take place if the higher alcohols and acid were both pure and the containing vessel quite clean. Unification of Reduction Methods of Sugar Analysis. L. S. Munson and P. H. Walker. (Journ. Amer. Chewz. Soc. 1906 xxviii.pp. 663-686.)-The use of one standard set of solutions is proposed for all reducing sugar determinations the precipitated cuprous oxide being weighed. The solutions recommended are one containing 34-639 grams of crystallized CuSO, which must not contain more than a trace of iron per 500 c.c. and the other containing 173 grams of Rochelle salt and 50 grams of sodium hydroxide per 500 C.C. For a determination 25 C.C. of each solution are placed in a 400 C.C. beaker and 50 C.C. of reducing sugar solution added or if less sugar solution is used the volume is made up to 100 C.C. with water. The beaker is covered with a watch-glass and heated on asbestos gauze over a Bunsen the flame being so regulated that boiling begins in four minutes. Boiling is continued for exactly two minutes and the cuprous oxide at once filtered without dilution on an asbestos felt in a Gooch crucible using suction the cuprous oxide being thoroughly washed with water at about 60" C.then with 10 C.C. of alcohol and finally with 10 C.C. of ether the ciucible transferred to a water-oven at 100' C. for thirty minutes cooled and weighed. The asbestos is best prepared by first digesting with 1 3 HC1 for two or three days, then washing free from acid and digesting for a similar period with soda solution, after which it is treated for a few hours with hot alkaline copper tartrate of the strength employed in the analyses. It is then washed free from alkali digested for several hours with HNO, and after a final washing is ready for use. The same felts may be used repeatedly the cuprous oxide being dissolved off each time with HNO,.A blank experiment should be made each day to determine the correction necessary for the slight spontaneous precipitation of cuprous oxide which takes place when copper tartrate is boiled and also for the slight loss of asbestos by solution in the alkaline liquid. The copper-reducing powers of 6-glucose invert sugar and two W. H. S 338 THE ANALYST. mixtures of invert sugar and sucrose have been determined and tables are given showing the equivalents for these of all quantities of cuprous oxide between 10 and 490 mgms. The results are summarized in the following formule where y=mgms. of cuprous oxide and x = mgms. of reducing sugar For &glucose y=0*5614+ 2.3484% - 0.001209~2; for invert sugar y = - 0,2460 + 2.27473 - 0.001077~~ ; for invert sugar and sucrose 0.400 gram total y = 6,3886 + 2.2279~ - 0*0009703x2 ; and for invert sugar and sucrose 2.000 grams total y = 20.6600 + 2.202133 - O-O00903Ox? W.H. S. The Determination of Sugar in Urines containing little Glucose. J. Blaise. (Ann. de Chinz. Ann. 1906 vol. 11 pp. 285-287.)-Most urines poor in glucose give when boiled with Fehling’s solution a yellowish-green precipitate which remains in suspension and prevents the exact observation of the end-point of the reaction. The simplest method of obviating this is to add a known quantity of glucose in the following manner 10 C.C. of the copper solution and 10 C.C. of the alkaline solution (corresponding to 0.05 gram of glucose) are mixed with 2 C.C.of a solution containing 0.01 gram of glucose and boiled. The copper oxide is immediately precipitated and the operation is then continued in the usual way with the urine to be examined. C. A. M. The Determination of Nitrosophenol. L. Lemaire. (Bull. SOC. Chim. Nord France 1906 64; through Arm. dc Chtim. anal. 1906 vol. ll. pp. 262 263.)-The method is based on the fact observed by Spitzer that on gently heating a solution of phenylhydrazine with a solution of a nitroso compound in glacial acetic acid nitrogen is liberated in accordance with the following equation : R.NO + C,H,N.NH = R.N + C,H + H20 + N,. Commercial nitrosophenol is a brown substance usually moist and containing variable amounts of impurities derived from the reagents used in its manufacture.In making an analysis 2.5 grams of the well-mixed sample are incorporated little by little with glacial acetic acid and the whole made up to 100 C.C. with the same acid. The apparatus used by the author is a 200 C.C. flask closed with a stopper in which are three openings. Through one of these passes a tube for the introduction of a current of carbon dioxide ; the second receives a bromine bulb the opening of which communicates by means of a T-tube with a carbon dioxide supply-tube whilst the third is connected with a condenser. A tap is placed between the T-tube and the flask so that the carbon dioxide can be passed directly into the flask or by way of the bromine bulb. The condenser is connected with a Duprk’s apparatus containing a solution of potassium hydroxide (1 2).Twenty C.C. of the solution of nitroso-phenol (= 0.5 gram) and 20 C.C. of glacial acetic acid are placed in the flask and the air expelled first from the flask and then from the bromine bulb by means of the carbon dioxide. The refrigerator is then connected with the collecting vessel and the expulsion completed by means of a slow current of the gas. A solution of 2 C.C. of phenylhydrasine in 40 C.C. of acetic acid is now introduced into the bromine bulb, the flask gently heated and the evolved nitrogen collected measured with the usual corrections for temperature etc. and calculated into NO. The percentage o THE ANALYST- 339 nitrosophenol NO.C,H,.OH in 0.5 gram of the substance can be obtained by means of the formula z = 1.449 x V" ( b - W) where V" represents the volume of nitrogen at 0" C.b represents the atmospheric pressure and w the tension of water vapour plus the tension of benzene vapour in mgms. of mercury at the temperature t. C. A. &I. Direet Estimation of Nitroglyeerine in Cordite etc. 0. Silberrad, H. A. PhiIlips and H. J. Merriman. (Journ. Xoc. Chem. Ind. 1906 XXV. 628-630.)-The method is based on the reduction of the saponification products of nitroglycerine FIG. 1. to ammonia with zinc iron and caustic soda. A weighed quantity of the ground cordite sufficient to yield about 2 grams of nitroglycerine is placed in a thimble in the Soxhlet retractor A which is fitted up as shown in Fig. 1. Eighty C.C. of absolut THE ANALYST. 340 ether is poured into the flask and extraction carried out in the usual way.When extraction is complete the thimble containing the residual nitrocellulose is washed with a little fresh ether and removed from the extractor. The absorption flasks C, containing 10 C.C. of & acid are now affixed and about 50 C.C. of a solution prepared by dissolving 5 grams of sodium in 100 0.0. of absolute alcohol run into the flask little by little through the side tube D. Reaction rapidly takes place and is com-pleted by warming on the water-bath for about six hours after which the ether is distilled up into the Soxhlet and run off by means of the tap the residue dissolved FIG. 2. in water and made up to 250 c.c. the aqueous Soxhlet and ether washings being also added to the solution. Fifty C.C. of this solution are then transferred to the flask F (Fig.2) 50 grams of a mixture of powdered zinc (2 parts) and reduced iron (1 part) added together with 50 C.C. of 40 per cent. sodium hydroxide solution and the ammonia distilled off in a slow current of air and collected in about 75 C.C. TG acid in the absorption flask H the excess of acid being titrated back. Each C.C. of & acid corresponds to 0.00757 gram of nitroglycerine. W. H. S. The Determination of Proteids by Means of Acetone. F. Bordas and Tout-plain. (Comptes Rendus 1906 cxlii. l345,1346.)-Proteids such as albumin casein, fibrin and gelatin are insoluble in acetone whether pure or diluted with a suitable quantity of water. Diastases and peptones are also precipitated by acetone which is thus a good reagent for the separation of fats from proteids.When the precipitation is made in the cold from proteid solution which should be neutral or nearly so th THE ANALYST. 341 liquid separated from the precipitate by means of centrifugal force will contain only a trace of nitrogen. I n the case of cheese 2 grams are ground up with 5 to 10 C.C. of water and 30 to 35 C.C. of acetone added little by little withcontinual stirring. The insoluble proteids are collected washed with dilute and finally with pure acetone, dried weighed ignited and the amount of ash deducted. Milk is analysed by treating 10 C.C. with 20 C.C. of acetone shaking the mixture to effect complete precipitation, separating the precipitate in a centrifugal machine and treating it as above described. For butter 10 grams are extracted with pure acetone and the residue treated with aqueous acetone which leaves the pure casein.On the Execution of the Comparative Analyses with '' gewachsene " (porous) Alu-mina. Wislicenus. (Ledermarkt Collegium 1906, 77 8 7 ; through Chem. Ztg. 1906 xxx. Rep., 167.)-The comparative analysis with '' porous alumina " (v. ANALYST 1904 xxix. 377) had to be delayed until a uniform material could be made on the large scale which has now been done by E. Merck. In the meanwhile it has been shown that the absorption of the tannin by the alumina, increases with increasing dilution of the solution, reaching a maximum at a concentration of 0.1 per cent. of tannin and decreasing again below this limit. The analysis is carried out in the apparatus shown in the figure.The Allihn tube F shortened to 7 ems. is charged with 2 grams of freshly ignited alumina and placed in the beaker B which contains the tanning solution diluted to twice its original volume. The vessel G serves to receive the first 10 C.C. of the filtrate which are not always quite clear; the tube S automatically interrupts the filtration when 110 C.C. have passed over which should require from one to three hours ; 100 C.C. of the filtrate are then evaporated and C. A. M. I dried for the determination of the '* non-tanning " materials. A. G. L. The Detection and Determination of Syringin. J. Vintilesco. (Journ. Pharm. Chim. 1906 xxiv. 145-154.)-Both the gIucoside prepared by the author from the plant and the commercial product after recrystallization from water had the characteristics given by Koerner.They contained 4-16 per cent. of water of crystallization melted at 190' to 192" C. and gave an intense violet-red coloration with concentrated sulphuric acid. The anhydrous syringin was found to have an optical rotation of aD = - 17O and on hydrolysis to yield d-glucose and an insoluble substance syringinin-Cl7H2.40 + = 2 0 = %Hl*O* + CBH1206 342 THE ANALYST. The author’s method of determining it in extracts of the leaves etc. of the lilac or privet is based upon its hydrolysis by means of emulsin the insoluble syringinin sub-sequently carrying down the small quantities of the enzyme left in the solution. Experiments with the pure anhydrous glucoside showed that 48,387 per cent. of glucose were formed by the action of the emulsin.Hence the quantity of the glucoside in a liquid not containing any other glucoside (which was the case with lilac and privet) could be calculated by means of Bourquelot’s formula, 1oog = 2Bm + 1059’ where q represents the amount of glucose set free in 100 C.C. of liquid and cor-responding to a return of 1” to the right in the optical rotation (L = 200 mm.) ; g the amount of glucose furnished by 1 molecule of the glucoside ; R the rotatory power of the glucoside ; and m its molecular weight (= 372). Thus a return of lo to the right in a solution of syringin acted upon by emulsin corresponds to the formation of 0-570 gram of glucose in 100 C.C. of the liquid-ie. to 1.178 gram of the glucoside. For the extraction of the syringin in quantity the author made use of the fact that hot ethyl acetate saturated with water will remove all glucosidal substances without extracting any appreciable quantity of sugars.One kilogm. of the finely-divided leaves etc. was thrown into 3 litres of boiling water containing calcium carbonate in suspension and the boiling continued for a few minutes to destroy any enzymes. The mass was then crushed in a machine and once more boiled in the hot water for a, few moments. The liquid was then cooled filtered and distilled under reduced pressure until a soft paste remained. This was extracted with the hot ethyl acetate and water and the extract on cooling left a deposit of syringin which could be obtained pure by a single recrystallization from water. Extracts of the fresh plant behaved differently to solutions of pure syringin on treatment with emulsin.I n the latter case it was necessary to add from time to time fresh quantities of the enzyme in order to effect the complete hydrolysis of 1.22 gram of syringin in 100 C.C. of water ; but this was not necessary in most instances with the extracts even when they contained a much larger amount of the glucoside (e.g., 3 grams in 100 C.C. in the liquid from lilac leaves and 3.6 grams from Japanese privet). The solubility of pure syringin is about 1.4 grams in 100 C.C. of water and as the above-named 3 and 3-6 grams were soluble in the extracts from the plants it shows that the solubility was increased by the presence of other extractives. The emulsin can only be added to the extracts from the plants after inversion of the cane sugar by the action of invertin and a determination of the cane sugar can thus be made simultaneously.C. A. M, The Amount of Sulphur in Commercial Petroleum Oils. R. Kissling. (Chem. Rev. Fett- u. Harz-Id 1906 xiii. 157 158.)-It was asserted by Grafe that commercial petroleum oils were approximately free from sulphur and in any case hardly ever contained more than 0.02 per cent. This is not confirmed however by the independent analyses of Engler and the author who have found that a proportion of 0.05 per cent. of sulphur is by no means exceptional in commercial petroleum lamp oils and that samples containing less than Griife’s maximum of 0.02 per cent THE ANALYST. 343 are of rare occurrence. The following are typical results Kaiser oil 0.01 ; astral oil, 0.02 ; ordinary Pennsylvanian petroleum 0.027 to 0.029 ; Russian (Baku) 0.027 to 0.029 ; Galician 0.039 to 0-061 ; American (Ohio) 0.039 to 0.05 ; and German (Alsace) 0-05 to 0.068 per cent.of sulphur. C. A. &I. The Examination of Turpentine Oils Utz. (Chenz. Rev. Fett- ZL. HaTx-Ind., 1906 xiii. 161-163.)-A determination of the bromine value was advocated by Vaubel (ANALYST xxxi. 200) as a means of judging of the purity of turpentine oil. From 1 to 2 grams of the sample were dissolved in chloroform the solution mixed with 100 C.C. of water 5 grams of potassium bromide and 10 C.C. of hydrochloric acid, and titrated with a standard solution of potassium bromate. The absorption of bromine was regarded as complete after thirty minutes and the absorbed bromine was calculated a8 having combined with the pinene to form a tetrabromide any further decomposition of this being neglected : C,,H,,+4Br= C,,H,,Br,, according to which 100 grams of pinene absorb 254 grams of bromine.In general, commercial turpentine oils were found to have a bromine value of 220 to 230 corresponding to 86.6 to 90.5 per cent. of pinene whilst the limits were 204 and 240. I n the author's experiments with this method the following values were obtained : Turpentine oils 222.2 to 241.2 ; pine oils 196.8 to 1974 ; double rectified pine oil, 197.4 ; pinoline (3) 3'7.68 to 90.48 ; rosin oils 65.22 to 78.24 ; dark rosin oil 113.70. Turpentine substitutes Ultra-turpentine oil 11.22 ; terpentane 9.6 ; hallol 107-0. From these results the author concludes that the variation in genuine oils is so great that the method cannot be relied upon as a test for the purity of turpentine oil, although it may be found of value in determining whether or no a given substitute contains pinene.Indian Turpentine Oil.-A sample obtained from Pinus long~olia (Roxb.) gave the following results Specific gravity 0,8734 ; optical rotation + 3' 13' ; solubility in 90 per cent. alcohol 1 in 7 or 8 ; and refraction at 15' C. 1.4788. C. A. M. The Characteristics of Owala Oil. K. Wedemeyer. (Chem. Rev. Fett- U , €€am-Ind. 1906 xiii. 210 211.)-The seeds known as '' Owala," are obtained from Peiztaclethra macrophylla a tree belonging to the Nimoseq and growing on the West Coast of Africa. The brilliant chestnut brown shells are flat and oval in shape.One kgm. of the fruit yielded on the average from 8 to 20 grams of seeds 20.6 per cent. of which was shells and 79.4 per cent. kernels. The entire fruit yielded 30.4 per cent. of oil on extraction with ether and contained 29.39 per cent. of proteids whilst from the kernel alone 41.6 per cent. of oil mas extracted and the residual pulp contained 48.25 per cent. of proteids. The extracted oil had a slight yellow colour and was fluid at the ordinary temperature though giving a slight deposit. I t had a pleasant taste with an after bitterness and an aromatic odour. When refined it gave a fine oil which would be suitable for food purposes. The following analytical results were obtained Specific gravity at 25" C. = 0.9119 ; refractometerireading (Zeiss) at 40" C.= 59.2" ; Hehner value 95.6 ; Reichert-Meissl value 0.6 ; saponification value 186.0 ; iodine value 9993 ; acid value 9.0 ; acety 344 THE ANALYST. value 37.1 ; unsaponifiable matter 0.54 per cent. ; melting-point of fatty acids, 53.9" C.; and solidification-point of fatty acids 52.1. The oil itself gave a white flocculent deposit when cooled to 18" to 19" C. and at 4O C. became a butter-like mass. C. A. M. The Occurrenee of Clupanodonic Acid in Herring and Whale Oils. M. Tsujimoto. (Journ. CoZZ. Engineering University of Tokio 1906 iv. ll-l4.)-Two samples of herring oil from CZupeapdasi and one of whale oil from Rhachianectes gluuca have been examined by the author. The fatty acids from the herring oils yielded 21-7 and 12.68 per cent.and those from the whale oil 27.8 per cent. of white bromides insoluble in ether and turning black before melting. All three contained from 69.23 to 70.12 per cent. of bromine (C,,H,,Br,O requires 69.84 per cent. of bromine) and the amount of carbon and hydrogen also agreed with the composition of clupanodonic octobromide. Hence the author concludes that clupanodonic acid is an important constituent of these oils though the amount (3.82 to 8.39 per cent. of the mixed fatty acids) is much less then in the case of Japanese sardine oil. No evidence could be obtained from an examination of the bromine cornpounds of the two highly unsaturated fatty acids C,,H,,O and C,,H,,02 found by Bull (Chem. Zeit. 1899 996) to be present in herring oil. C. A. M.The Detection of InOSite in Urine and other Fluids. G. Meilliere. (Tribune Mkdicale; through Ann. de Chim AnaZ. 1906 vol. 11 pp. 294 295.)-The following method is recommended as giving better results than any of those ordinarily used 25 C.C. of the urine are acidified with 2.5 C.C. of glacial acetic acid and treated with about 2.5 C.C. of a saturated solution of barium nitrate and the same quantity of a solution of lead nitrate (1 5) fol~owed by 3 to 8 C.C. of a 10 per cent. solution of silver nitrate. The precipitated silver chloride is separated with the aid of centrifugal force and the clarified liquid treated with ammonium hydroxide until a persistent turbidity appears then rendered distinctly alkaline with 12 drops of ammonium hydroxide and heated gently with 3 C.C.of lead subacetate solution (strength not given). The resulting precipitate which will contain the whole of the inosite is separated by centrifugal force triturated in 25 C.C. of water containing 5 drops of ammonium carbonate solution and again separated in the centrifugal machine. It is next suspended in 25 C.C. of water and treated with hydrogen sulphide the liquid evaporated to about 2 c.c. and after the addition of 20 C.C. of alcohol and 15 C.C. of ether allowed to stand for some time after which it is whirled. Subsequently the deposit is washed with 2 or 3 C.C. of water which is separated in the same way to remove the uric acid and the inosite can thus be obtained in a crystalline state. Obviously if the urine contained albumin the latter must be removed before testing for inosite whilst any sugar must be separated by means of fermentation.Inosite can be identified by treating it with nitric acid which converts it into an acid the cadmium and strontium salts of which have characteristic colours. Another test is to evaporate the inosite with a small quantity (10 drops) of acid mercuric nitrate a red d o u r being obtained as soon as the residue is dry. The reagent is prepared by mixing 10 grams of yellow mercuric oxide and 20 C.C. of nitri THE ANALYST. 345 acid with sufficient water to make up 200 C.C. The red coloration should not disappear on the addition of glacial acetic acid and on then adding 3 C.C. of water and 5 drops of a 20 per cent. solution of strontium acetate and warming the liquid should change to a dichroic rose tint recalling that of eosin solutions.According to the author inosite is a frequent constituent of urines especially of those that give an abnormal reduction when heated with Fehling’s solution with a green precipitate and apparently no deposit of cuprous oxide. C. A. M. Extraction of Fat from Fzeces and the Occurrence of Lecithin. J. H. Long. (Journ. Anzer. Chem. SOC. 1906 xxviii. pp. 704-706.)-The fat in faeces is found to be more completely extracted by spreading 10 to 15 grams of the sample (after moistening with very dilute HCl to decompose any soaps) over a strip of paper, rolling up the paper drying and extracting in a Soxhlet apparatus for two days with anhydrous ether than by drying grinding with sand and extracting from a paper shell in a Soxhlet for the same period. The amount of phosphates determined in the extract after evaporation of the ether amounted in three samples to 1.35 0.84 and 1.26 per cent. P,O respectively on the dry faeces which calculated as lecithin would correspond to a daily excretion of lecithin of 3 to 5-5 grams. No evidence could be obtained of any pathological condition in the man furnishing the material examined, and two further samples of faeces of the same individual tested some weeks later yielded 0.294 and 0.298 per cent. P,O respectively corresponding to an excretion of about 1 gram of lecithin daily. W. H. S