496 ABSTRACTS OF CHEMICAL PAPERS PROCEEDINGS OF THE SOCIETY OF PUBLIC ANALYSTS AND OTHER ANALYTICAL CHEMISTS. ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS. FOOD AND DRUGS ANALYSIS. Nitrogenous Substances in Barley and Malt. 111. : Transformation of the Proteins during Mashing, Boiling of Wort, and Fermentation. H. Schjerning. (Compt. re?td. des Travaux du Lab. de Carkberg, 1913, 9, 237-396.)- The analytical methods employed are similar to those described in a former paper (ANALYST, 1910, 35, 350).The acidity of wort is now determined by a titration with sodium hydroxide “ t o the tone of colour which is produced when 2 C.C. of a, solution of phenolphthaleln (1 per cent.) and 4 C.C. of a & solution of disodium hydrogen phosphate are added to 25 C.C. of distilled water which has previously received an addition of Bismarck brown and tropeolin 0 in quantity to give the solution the same colour as the wort the acidity of which is to be determined.” Ammoniacal nitrogen is estimated by distilling the wort with a convenient excesB of magnesium oxide.The amino-acid nitrogen titratable with formaldehyde and the concentration of hydrogen ions were determined in a dilute wort by Sorensen’s method (ANALYST, 1908, 33, 19; 1909, 34, 498).Peroxidase and catalase were measured by methods previously described (Conzpt. rend. des Travaux du Lab. de Carlsberg, 1909, 8, 67 ; 1910, 8, 200, 321 ; ANALYST, 1910, 35, 350). A large amount of experimental matter is included in the paper, together with over fifty tables of figures, the summary of the (‘ principal results ” alone occupying ten pages of matter.Through all the stages of mashing, boiling, cooling, fermentation (primary and secondary), the effect of different water treatment, wort concentration, mashing temperatures, boiling-time, hop variation, aeration, etc., on the wort is followed by estimating, among other variables, the amounts of total extract, ash, acidity, total nitrogen, assimilable nitrogen, peptic cleavage products, tryptic cleavage products, ammonia, ‘‘ albumin I.and II.,” proteose, peptone, denuclein, and hydrogen ion concentration. H. F. E. H. Composition of the Seeds of Cicer Arietinum, L. (Chick-pea). A. Zlataroff and S. Stoikoff. (Zeitsch. Unterszsch. Nahr. Genussm., 1913, 26, 242- 247.)-The chick-pea is a dwarf pea cultivated in Bulgaria and Southern Europe generally, and used as a food like lentils.Resdts of analyses of twenty-four samples showed it to have the following average composition : Water, 10-47 ; proteins, 22-63 ; fat, 5.08 ; starch, 49.33 ; crude fibre, 3.09 ; ash, 2.138 per cent. The total phosphoric acid amounts to 0.88 per cent (as P,O,), of which 0.125 per cent.is present asFOOD AND DRUGS ANALYSIS 497 lecithin-phosphoric acid. The peas are frequently roasted before use, and are then known under the name of (‘ leblebiji.” A product known as (( ssimitt ” is prepared by allowing the peas to germinate and ferment. The germinated peas contain oxydase, zymase, protease, diastase, and rennin ; and the products of fermentation are hydrogen, hydrogen sulphide, carbon dioxide, butyric acid, lactic acid, succinic acid, sugar, ethyl and higher alcohols, leucine, asparagine, and aromatic substances (aldehydes and esters 1).w. P. s. Examination of Chloroform. K. Enz. (Apoth. Zeit., 1913, 28, 672-674; through Chem. ZentraZbZ., 1913, II., 1172-1173.)-The impurities of commercial chloroform include chloral alcoholate and similar chloral compounds.These may be estimated by treating the chloroform with &.alkali and titrating the excess. Pure chloroform is not affected by alkali of this strength. Aldehydic and similar com- pounds are detected by means of Nessler’s reagent, which gives with impure chloroform a red-brown deposit rapidly changing to greenish black. Pure chloroform does not give any reaction.C. A. M. Detection of Formaldehyde in Foods. F. Rachel, (Pharm. Zentralhalle, 54, 759-761 ; through Chem. ZentraZbE., 1913, II., 903.)-Friese’s method for the detection of formaldehyde in milk has been modified to make it applicable to meat, caviare, and fish preparations. The sample is treated with phosphoric acid and dis- tilled with steam in the usual way. One to two c .~ . of the distillate are thoroughly shaken with 4 C.C. of milk free from formaldehyde and 10 C.C. of hydrochloric acid (sp. gr. 1-19> containing 1 drop of 25 per cent. nitric acid in 300 C.C. If formaldehyde be present, a blue coloration is immediately produced. Since the reaction only takes place with traces of formaldehyde, it is advisable, in the case of a negative result, to repeat the test after diluting the distillate.In order to determine whether the formaldehyde is present in the free or combined condition, a separate portion may be distilled without the addition of phosphoric acid. J. F. B. Estimation of Total Formaldehyde in Fumigators and Commercial Solutions. J. J. Hinman jun. (J. hzd. and Eng. Chem., 1913, 6, 752-755.)-The author has tested comparatively, by nine different methods, a number of samples of formaldehyde preparations containing polymerides and foreign matters.The ammonia methods are not very rapid, and the end-point of the titration in presence of rosolic acid is not distinct. The litmus end-point is more satisfactory. The hydrogen peroxide methods are more rapid, and the results are easily checked.The end-point of the sulphite methods is sharper than in either of the other processes. The titrations are direct. For formaldehyde solutions they require the minimum of tims, but when polymers are to be titrated the Kleber method is the most rapid of all. For an occasional analysis the peroxide method of Haywood and Smith (ANALYST, 1905, 30,401), using litmus indicator, or the sodium sulphite method of Seyeweti and Gibello (ANALYST, 1904, 29, 288) seem to be preferable, whilst for regular analyses of large numbers of samples the bisulphite method of Kleber (ANALYST, 1904, 29, 161) would be most suitable.Legler’s ammonia method498 ABSTRACTS OF CHEMICAL PAPERS gives too low results, and Blank and Finkenbeiner's peroxide method gave the highest results.Haywood and Smith's method gave slightly lower percentages than Blank and Finkenbeiner's, closely followed by Kleber's and the other methods. J. F. B. Baobab Oil. V. Thomas and F. Boiry. (BzLZZ. SOC. Chim., 1918, 13, 827-832.) -The seeds from different varieties of baobab (Adansonia) contain considerable quantities of oil, but those of Adansonia grandidieri, a tree growing in Madagascar, appear to contain the largest amount.These seeds, in the undecorticated condition, yield 43 per cent. of a yellow-coloured oil, whilst the decorticabed seeds yield 65.4 per cent. of a white fat having the consistence of butter. The following figures were obtained on the examination of the oils, and the fatty acids separated from them : From Whole Seeds. Oil : Sp.gr. .. . ... ... Melting-point ... ... Solidifying-point . . . ... Refractive index at 40" C. . . . Saponification value . , . Iodine value (Wijs) ... ... Reichert-Meissl value ... Hehner value ... ... Melting-point ... ... Solidifying-point . . . ... Acid value ... ... ... Saponification value , . . Iodine value . . . ... ... ... Fatty Acids : ... 0.9190 (at 20° C.) 20°-210 c. 13" C.1-4585 192.4 65-66 0.77 95 *5 51'-52" C. 44.5" c. 179.0 202.5 66-67 From Decorticated Seeds. 0-9135 (at 40' C.) 39"-40' C. 33" c. 14521 196.0 36.9 - - 45'-46" C. 204.5 207.6 34-35 - The difference between the acid and saponification values in the case of the oil from the undecorticated seeds indicates the presence of lactones, and further ex- amination showed that the fatty acids contained 11.4 per cent.of lactones, the nature of which, owing to lack of material, could not be investigated. The mixed fatty acids consisted of myristic acid, 7 per cent.; palmitic acid, 32.5 per cent.; oleic acid, 36.5 per cent. ; and linoleic acid, 8.7 per cent. Stearic and arachidic acids were not present. w. P. s. Hickory Nuts and Hickory Nut Oil. G. 0. Peterson and E.H. S. Bailey. (J. Ind. and Eng. Chenz., 1913, 5, 739-740.)-Two varieties of hickory nuts have been studied-Carya ovata, or shell-bark hickory, the edible variety, and C. arnara, the swamp hickory, the nuts of which are only fed to pigs. The kernels of the edible nuts have a high food value, containing 70.2 per cent. of oil and 13.2 per cent. of protein. By cold pressing, followed by hot pressing, 65 to 66 per cent.of the totalFOOD AND DRUGS ANALYSIS 499 oil present may be extracted. The oil retains the flavour of the hickory nut, and is practically equal to olive oil as a table oil. The oils obtained from the two species of nut are practically identical, and are similar to cottonseed oil in their chemical and physical characters. The resemblance is so close that a diflerentiation from cottonseed oil would be difficult. The following constants were obtained for the two varieties of oil, and are compared with those recorded for a sample prepared at the Maine Experiment Station : CONSTANTS OF HICKORY NUT OILS.(7. Amara. - Sp. gr. at 24' C. ... ... Refractive index at 20" C. ... 1-4699 Hehner value ... ... ... 95.6 Reichert-Meissl value ...0.48 Iodine value ... ... ... 105.2 Saponification value ... ... 190.0 C. Ovata. 0.9119 1.4699 95.7 0.47 106.8 189.6 Maine Experiment Station. 0.9164 1.4696 - - 102.8 - J. F. B. Analysis of Maple Products. I. : Electrical Conductivity Test for the Purity of Naple Syrup. J. F. Snell. (J. Ind. and Eng. Chem., 1913, 5, 740-747.)-When maple syrup is adulterated with commercially pure sugar, the percentage of non-sugar constituents is reduced, and, since sugar is a non-conductor, the electrical conductivity of the syrup falls.An examination of a number of samples of genuine maple syrups showed that their conductivities varied within somewhat wide limits inversely as their densities. On dilution with water the conductivities increased until a point of maximum conductivity was reached, after which the conductivities decreased owing to the dilution of the electrolytes.The point of maximum conductivity occurs at a dilution corresponding to one volume of syrup to two volumes of water. This observation is made the basis of a rapid test for the purity of maple syrups. A suitable quantity of the syrup (15 c.c.) is measured out in a graduated cylinder and drained into a small beaker ; the cylinder is then twice washed out with equal volumes of water, and the syrup is dissolved therein.The solution is poured into the conductivity cell, the temperature is adjusted to 25' C., and the measurement is made. The constant of the cell is divided by the number of ohms, and the result inultiplied by 100,000. The values for genuine syrups lie between 110 and 200, but further experience may extend these limits a little. Syrups giving conductivity values distinctly outside these limits may be condemned without further examination ; but those giving normal values are not necessarily pure, and should be examined by the usual methods.The essential features of the apparatus are : A low voltage electrical current operating an induction coil ; a con- ductivity cell of a form suitable for liquids of low conductivity and with electrodes not easily displaced; a Wheatstone bridge with telephone; a device for exact500 AESTRACTS OF CHEMICAL PAPERS regulation of temperature.An examination of the ash of pure maple syrups indicates that the organic salts of potassium and calcium are the principal electrolytes of the syrups, and the tabulated results show close relationships on the one hand between conductivity and total ash, and on the other hand between conductivity and alkalinity of the soluble ash.Estimations of conductivity values of non-maple syrups showed that syrup from granulated sugar is practically a non-conductor, but that molasses show values many times greater than the average for pure maple syrup.Syrup made from pale brown sugar showed a value of 178, thus within the limits for pure maple, and it is evident that various mixtures of partially refined products could be made to show normal values. Consequently a normal conductivity value is in no sense evidence of purity, but the method is extremely rapid and useful for sorting out obviously adulterated samples (cf.ANALYST, 1912, 37, 538, 543). J. F. B. Detection of Added Water in Milk by Means of the Refractometer Value of the Serum. G. Schutz and L. Wein. (Zcitsch. Untersuch. Nahr. Genussnz., 1913, 26, 177-184.)-The serums obtained, respectively, by the use of calcium chloride (ANALYST, 1907, 32, 117) and by means of carbon tetrachloride and acetic acid (ibid., 1912, 37, 450) are equally suitable for refractometric purposes.The calcium chloride method of preparing the serum is simple and rapid, whilst the carbon tetrachloride method yields a serum which may be used for determining constants other than the refractometer value. I n the case of the calcium chloride serum, the increase in the refractometer value, due to the formation of acidity in the milk, may be prevented by the addition of a few drops of formaldehyde to the milk.Another source of error consists in the solubility of precipitated lime coin- pounds when the serum is allowed to remain too long a time in contact with the coagulum ; the serum should be separated within thirty minutes. w. P. s. Black Mustard Powder. H. Imbert and A.Juillet. (Bull. h'ciences Pharrnacol., 1913, 20, 385-388 ; through Chem. Zentralbl., 1913, II., 1170-1171.)- Ally1 mustard oil is estimated by the Codex method of hydrolysing the potassium myronate by means of myrosin in the presence of water. For the detection of white mustard, 5 grms. of the powder are boiled for two minutes with 100 C.C. of water containing 20 drops of alkali hydroxide solution, and the boiling mixture diluted with 200 to 300 C.C.of cold water. The deposit is separated, washed two or three times, and examined under the microscope for uncrushed particles of white mustard seed. Black mustard powder of different origin was found to contain from 0-493 to 0.899 per cent. of mustard oil, whilst a sample of white mustard powder contained 0.068 per cent.Many samples of the black powder contain turmeric and linseed- meal as impurities. C. A. M. Composition of Rums. J. Sanarens. ( A m . Falsv., 1913, 6, 488-495.)- Analyses of numerous authenticated samples of rum are recorded, and the minimum and maximum results obtained are given in the following table ; hhe results obtainedFOOD AND DRUGS ANALYSIS 501 on the examination of six samples of artificial rum are also given.The figures express grms. per 100 litres of absolute alcohol. Total acids : Minimum ... Maximum ... Minimum ... Maximum ... Minimum ... Maximum ... Higher alcohols : Minimum ... Maximum ... Furfural : Minimum ... Maximum ... Aldehydes : Esters : Msrtin- ique . 65 394 3 90 37 797 19 395 1 9 Guadc- loupe. 82 138 5 36 31 72 80 194 1 3 Rum imported from- Rdunion.128 245 4 41 56 101 73 93 1 4 Cochin- China. 20 50 6 17 12 29 153 319 trace 1 British Guiana. 80 87 10 41 24 46 139 164 1 2 Jamaica. 123 176 13 16 632 938 22 39 1 2 Artificial Ruin. 82 159 4 14 127 2,240 14 70 1 5 w. P. s. Examination of Turpentine Oil by the Methods of the German Pharma- copoeia. (Pharm. Zeit., 1913, 58, 470-471 ; through Chem.Zentmlbl., 1913, II., 1085-1086.)-For the estimation of the bromine value, 2 C.C. or 2 grms. of the sample are made up to 100 C.C. with petroleum spirit, and 4 C.C. of the solution added to a mixture of 50 C.C. each of the potassium bromate and potassium bromide solutions of the German Pharmacopoeia. Five C.C. of sulphuric acid are then added and the flask immediately stoppered, and shaken for about a minute, after which the turpentine solution is added drop by drop with continual shaking, until the petroleum spirit layer is decolorised.The bromine value is calculated from the total number of C.C. of the turpentine solution consumed. If 2 grms. of the sample were taken the value is 1,200; and if 2 C.C. were takenit is , where s represents the sp. gr.of the turpentine oil. Pure oil of turpenbine has a bromine value of 215 to 230, rarely as low as 210. Testfor Pine Oil.-Five C.C. of the sample are boiled with 5 drops of nitro- benzene, 2 C.C. of 25 per cent. hydrochloric acid then added, and the liquid again boiled for ten seconds. All pine oils give a deep brown coloration of the oily layer, whilst the acid layer becomes brown or black.In the case of turpentine oil there is either no coloration, or the oily layer shows a greenish tint, whilst the acid layer is coloured light brown. By means of this test an addition of 5 per cent. of pine oil to oil of turpentine may be detected. H. Wolff. 1200 X XS C. A. M.502 ABSTRACTS OF CHEiMICAL PAPERS Estimation of Chlorides in Wine. C. von der Heide and M.Kartschmar. (Zeitsch. anal. Chem., 1913, 52, 645-651.) -In wines containing less chloride than corresponds to 5 mgrms. chlorine per 100 c.c., it is unnecessary to add alkali before igniting the residue ; but with wines containing 10 mgrms. or more chlorine per 100 C.C. there is considerable loss if the addition of alkali be omitted. Incinerating wine residues to which alkali has been added is troublesome, often attended with loss, and the authors have tried several alternative methods for the estimation of chlorine in wine, and recommend the following, which gives exact results with natural wines : A measured and more than sufficient amount of TG silver nitrate solution is added to 100 C.C.of wine, together with 2 to 3 grms. of animal charcoal in the case of white wines, or 5 to 8 grms.in the case of red wines. The mixture is boiled for fifteen minutes, 20 C.C. of dilute nitric acid is then added, boiling continued for a further ten minutes, and the solution filtered. The charcoal and filter are washed with 200 to 300 C.C. of hot very dilute nitric acid, and the filtrate and washings are allowed to cool. Carbamide is added if necessary to destroy nitric oxide, and the excess of silver titrated with thiocyanate. Direct volumetric determination of chlorine in the original wine is impossible on account of the colour, and the results of gravimetric determinations on the original wine are always too high, Musts and very sweet wines are best treated as follows : The sugar is fermented away as far as possible, and the fermented liquid is evaporated to a syrup, mixed with 10 grms.of slaked lime, dried, and burnt. The ash is extracted with water, and the aqueom extracts are filtered into a vessel containing 25 or 50 C.C. & silver nitrate solution. Finally the lime is dissolved in dilute nitric acid, and this solution also filtered (from particles of carbon, etc.) into the vessel containing the silver nitrate.The excess of silver is then determined by titration with thiocyanate. G. C. J. Estimation of Tartaric, Succinic, and Malic Acids in Wine. P. Dutoit and M. Duboux. (BUZZ. SOC. Chim., 1913, 13, 832-862.)-A detailed description is given of the combined volumetric and conductivity method (cf. ANALYST, 1909, 34, 56 ; 1912, 37, 600) for the estimation of organic acids in wine.The procedure is as follows : The total acidity and sulphates are first estimated, and let a denote the number of C.C. of f alkali solution required to neutralise 1 litre of the wine. One hundred C.C. of the wine are then heated in a flask to boiling, and a quantity of barium chloride solution just sufficient to precipitate the sulphates is added, followed by the addition of 2 C.C.of a 25.2 per cent. uranium nitrate solution. The mixture is shaken for a few minutes, neutralised with sodium hydroxide, 0-18 C.C. x a of f silver nitrate solution and 250 C.C. of 95 per cent. alcohol are added, and the mixture is filtered. The filter and precipitate are transferred to the flask, and mixed thoroughly with 0.12 C.C. x a of sodium bromide solution (prepared with 50 per cent.alcohol) and 100 c.0. of 47.5 per cent. alcohol. After the lapse of about ten minutes the mixture is diluted to 202 C.C. with 47.5 per cent. alcohol, and filtered. The filtrate now contains the organic acids, and is used for the estimation. Estimation of Tartaric, Malic, and Succiizic Acids.-A definite volume of the solu tion of the acids (according to the acidity of the wine; see below) is placed in theFOOD AND DRUGS ANALYSIS 503 conductivity vessel, an equal volume of 47.5 per cent.alcohol is added, then 0.5 C.C. of Tc acetic acid, and the conductivity of the solution is determined while the latter is titrated with lanthanum nitrate solution which has been standardised in a similar way against f sodium tartrate solution..Acidity of the Wine in C.C. per Litre. Below 90 90-115 115-140 Above 140 Volume of the Acid Solution to bc taken. Volume of 47.5 per Cent. Alcohol to be added. Estimation of Tartaric, and Malic Acids.-Another quantity of the solution (see below) is treated with 1 C.C. of glacial acetic acid and alcohol, and titrated with lanthanum nitrate solution while the conductivity is determined.In this and in the previous titration the lanthanum nitrate solution is added in quantities of about 0.1 C.C. at a time : Acidity of the Wine in C.C. 2 per Litre. Volume of the Acid Solution to be taken. Below 90 90-115 115-140 Above 140 15 ,, 10 9 , Volume of 4 i - 5 per Cent. Alcohol to be added. Volume of 76 per Cent. Alcohol to be added. Estimation of the Tartaric Acid.-Two titrations may be necessary, according to the amount of mslic acid also present.A portion of the solution containing the acids is mixed with 5 C.O. of glacial acetic acid and 75 C.C. of 95 per cent. alcohol, and the conductivity is determined while the mixture is titrated with barium acetate solution, the barium equivalent of which has been ascertained by the conductivity method.If from the results obtained the ratio of malic acid to tartaric acid is less than 1 : 3.7, a second titration must be made, as the presence of much malic acid renders the first titration untrustworthy. Another portion of the solution is treated with C.C. per C.C. of the acid 1,000 eolution taken, rn expressing the amount of malic acid per litre in C.C. of solution, and t the amount of tartaric acid in C.C.of Five C.C. of glacial acetic acid and 75 C.C. of 95 per cent. alcohol are then added, and the mixture is titrated with the barium acetate solution. 3.7 m - t sodium tartrate solution, the quantity added being solution.504 ABSTRACTS OF CHEMICAL PAPERS Sum of Tartaric + Malic + Succinid Acids in C.C. per Litre. Below 70 70-90 90-110 110-130 First Titration.Volume of Acid Solution to be taken. Volume of 4 7 5 per Cent. Alcohol t o be added. Second Titration. Volume of Acid Sohition to Le taken. Volume of 4 7 5 per Cent. Alcohol to be added. When excessively large quantities of malic acid are present in wines, it is advisable to estimate the tartaric acid separately by the ordinary potassium hydrogen tartrate method.This also applies to wines containing citric acid, as this acid is estimated~ together with the tartaric acid in the conductivity-titration method. W. P. S. Estimation of Tartaric, Citric, Lactic, and Malic Acids in Musts, Wines, etc. L. Mathieu and L. Ferre. (BulZ. Assoc. Chim. Sucr. et Dist., 1913, 30, 842- 844; through Chem. Zentralbl., 1913, II., 709.)-In the case of wines the acids are first separated by Mestrezat’s method (ANALYST, 1907, 32, 266, 388), and the lactic acid in the filtrate estimated by Moslinger’s method. The tartaric acid is estimated in a portion of the precipitate, dissolved in sulphuric acid, by the method of Kling (,~NALYST, 1912, 37, 516), whilst another portion of the precipitate is oxidised by Mestrezat’s method in acid and in alkaline solution. One grm. of tartaric acid is oxidised by 1.447 grms. of potassium permanganate in acid solution, and by 0.620 grm. in alkaline solution ; 1 grm. of malic acid by 2.078 grms. in acid solution, and 0.615 grm. in alkaline solution; and 1 grm. of citric acid by 1.820 grms. in acid solution and 0.480 grm. in alkaline solution. If x grms. of tartaric acid, y grms. of malic acid, and z grms. of citric acid are present, the proportion of y and x may be calculated by means of the following equation, in which Vrepresents the volume of’ acid permanganate solution, and 71 the volume of alkaline permanganate solution,” and a the strength of the solution, The value of x has been found by direct- estimation : y x 2.078 + x 1.820 = Va - x 1.447 y x 0.615 + x 0.480 = Vla - x 0-620 The method is applicable even in the presence of succinic acid, since the latter, althou,gh precipitated by Mestrexat’s method, is not attacked by the permanganate solution, and may be separated by the usual methods (cf. ANALYST, 1913, 381). C. A. M.