ORGANIC ANALYSIS 17 ORGANIC ANALYSIS. Phosphorus Content of Casein. A. W. Bosworth and L. L. van Slyke. (J. Biol. Chem., 1914,19,67-71; through J. SOC. Chem. Ind., 1914, 33, 1023.)-The phosphorus content of casein is usually given tls about 0.85 per cent., but by treating a solution of casein in ammonia with ammonium oxalate, adding an excess of ammonia and allowing the mixture to stand for twelve hours, the phosphorus is reduced to about 0.70 per cent.Some of the casein is hydrolysed by the treatment and some phosphorus is split off, but the hydrolysed portion is not precipitated by acetic acid, and does not affect the composition of the final preparation. The higher figure ordinarily given is due to the presence of inorganic phosphorus compounds (dicalcium phosphate) derived from the milk and not removed by the usual methods of preparation.As the molecular weight of casein is approximately 8888, the lower percentage corresponds very closely with the presence of two atoms of phosphorus in the casein molecule. Analyses of various caseins show that there is a general relation between the yield of ash and the phosphorus content. Essential Oil of Eetichvysum SaxatiZe.L. Franeesconi and E. Sernagiotto. (Gazz. Chim. Ital., 1914, 44, 419-421.)--Various plants of the He& chrysum species yield essential oils. A sample of the oil of H. avtgustifolium from Genoa had sp. gr. 0.9182 and +0*40. H. saxatile, which is found in various parts of Sardinia, contains a yellow essential oil with a characteristic pungent odour, but whioh, when sufiiciently diluted, resembles the odour of rose.A sample of the oil gave the following constants : : Sp. gr., 0-9020 ; [%In, 1-4769 ; [u,,] - 11.71. It did not oolour Schiffs reagent nor reduce ammoniacal silver nitrate. I t began to * No temperatures given.18 ABSTRACTS OF CHEMICAL PAPERS distil at 240" C., and the bulk of it passed over at that temperature.It contained no acids or phenols, and appeared to consist, in the main, of a compound belonging to the hydro-aromatic series (carbon = 79.50 ; hydrogen, 12.11 ; oxygen, 8.39 per cent.]. C. A. M. Leaf and Twig and Cone Oils of Western Yellow Pine and Sugar Pine. A. W. Sohorger. (J. Ind. and Eng. Chem., 1914, 6, 893-895.) -The leaves (needles) and twigs of the western yellow pine, Pinuspom-hvosa, yield from 0.04 to 0.126 per cent.of oil having sp. gr. at 15" C., 0.8718 to 0.8849; [N], ~ B O C . , 1,4789 to 14838; [U],~O~C., - 15.73"to - 19-59'; acid value, 0.67 to 2.36; ester value, 3-88 to 8.10; ester value after acetylation, 24.11 to 35.68. The cones of this tree yield 0-063 per cent. of oil having sp. gr. at 15" C., 0.8757 ; [N], 15" c., 14789 ; [aID 2 0 " ~ .- 11.48 ; acid value, 1-27; ester value, 7.20; ester value after acetylation, 22.41. The leaves and twigs of the sugar pine, Pinus Zambertiana, give from 0.045 to 0.120 per cent. of oil having - 1640'; acidvalue, 0.68 to 2.38; ester value, 2-22 to 5.91; ester value after acetylation, 23-25 to 32-04. The cones of the sugar-pine yielded 0.32 per cent. of oil having sp. gr.at 15" C., 0.8692 ; [N), 15" c., 1.4771 ; [a]= 20~~,, - 23.18' ; acidvalue, 0.63 ; ester value, 3.75 ; ester value after acetylation, 17.04. SP. g. at 15" C., 0.8676 to 0,8738 j [N]D 150 c., 1.477'7 to 1.4794 ; [.ID 20" c., - 11.07' to The percentage composition of the oils was as follows : Furfural ... ... ... I-a-Pinene ... ... ECamphene . . . ... I-P-P' inene ... ... Dipentene ...... Ester, as bornyl acetate Free alcohol (I-borneol) '' Green oil '' . . . ... Losses ... ... ... Sesquiterpene (?) ... -- Western Yellow Pine. Leaf and Twig Oil. - 2 75 6 2 7 3 5 - - Cone Oil. Trace 6 60 12 to 13 2.5 4 3 to 4 10 - - Sugar Pine. ~~ Leaf and Twig Oil. Trace 21 51 12 1.5 8 1 7 - - Cone Oil. Trace 22 21 39 to 40 4 to 5 1.5 3.5 1 7 - w. P. s. Rapid Method of Detecting and Estimating Solid Hydrocarbons in Fatty Acids.G. Verona-Rinati. (Annuli Chim. .4ppZic., 1914, 2, 201-202.)--Fatty acids are soluble in a-dichlorhydrin saturated with water, whereas paraffin wax, ceresin, etc., remain insoluble even at 65" to 70" C. Seven C.C. of anhydrous a-dichlorhydrin @.-pt., 174O C.) are mixed with 1.2 C.C. of water in a tube (about 15 C.C. capacity) graduated in tenths of a C.O.The fatty acids (1-43 grms.) are added, and the tube closed and immersed in water at 65" C. until its contents are homogeneous. AfterORGANIC ANALYSIS 19 ten minutes the amount of undissolved hydrocarbon is read, the tube vigorously shaken, and again allowed to stand for ten minutes at 65" C., after which a second reading is made. Each 0.1 C.C. corresponds to 5 per cent.of solid hydrocarbons. To ascertain whether paraffin wax or ceresin is present, about 2 to 3 grms. of the sample are shaken with the hot aqueous dichlorhydrin, and cooled, the solidified hydrocarbon separated and pressed between filter-paper, and 0.2 grm. thereof dissolved in 10 C.C. of hot anhydrous a-dichlorhydrin. In the case of paraffin wax, the turbidity tempera- ture of the solution will lie between ST and 92" C.; whereas with ceresin it will range from 112" to 115" C. Mixtures of the two waxes give intermediate values, but these are not sufficiently constant for quantitative purposes. C. A. M. Destruction of Organic Matter by the Fresenius-Babo Method after Previous Treatment with '' Antiformin ." A. Friedmann. (Zeitsch. Physiol.Chem., 1914, 92, 46-53.)-1n the Fresenius-Babo method, the organic matter is destroyed by the action of hydrochloric acid and potassium chlorate. The author finds that time is saved by previously treating with (( antiformin," an alkaline solution of sodium hypochlorite, prepared by treating bleaching powder with sodium carbonate solution and sodium hydroxide, and which contains 795 per cent. sodium hydroxide and 5.3 per cent.available chlorine. The dried and powdered material is mixed with a 50 per cent. antiformin solution and stirred until a uniform paste is formed. After standing for twenty-four hours this is heated on a water-bath to 80" C. and con- centrated hydrochloric acid gradually added until frothing ceases. Potassium chlorate is then added until the supernatant liquid becomes wine-yellow, and no further decolorisation occurs on continued heating.The solution is then diluted with water, heated to 60" C., filtered, and washed with water at 60" C. The filtrate, after being freed from chlorine by means of a stream of carbon dioxide, can be immediately treated with hydrogen sulphide. Should it be necessary to concentrate the filtrate, colour may develop, in which case the liquid must be again treated with hydrochloric acid and potassium chlorate.E. W. Methods of Analysis of Paint Materials (Pigments). (Report of the American Society for Testing MateriaZs, 1914, 42-61.)-Methods are described for the analysis of white pigments and of red lead. Many of the processes recommended are well known, and in other estimations the procedure is obvious, so that the following synopsis of the report will consist mainly of an outline of the various estimations which should be made in order to ascertain the quality of a pigment.Very small quantities of iron in lead pigments may be estimated by treating the substance with nitric acid, adding sulphuric acid to precipitate the bulk of the lead, filtering off the lead sulphate, and treating the filtrate with thiocyanate after it has been rendered ammoniacal and then slightly acid with nitric acid.In the case of other pigments, the treatment with sulyhuric acid may be omitted. Basic Lead Carbonate (White Lead). - Estimations should be made of the moisture, silica, barium sulphate, total lead, carbon dioxide, acetic acid (Thompson's method, ANALYST, 1905, 30, 253), sulphuric acid, sulphur dioxide, and metallic lead.20 ABSTRACTS OF CHEMICAL PAPERS Bask Lead SuZphate.--Moisture, matter insoluble in boiling hydrochloric acid oontaining ammonium chloride, total soluble sulphates, soluble zinc sulphate, total lead and zinc, iron, aluminium, manganese, calcium, magnesium, sulphur dioxide, and carbon dioxide.The soluble sulphuric acid is calculated into zinc sulphate, and any remaining zinc is returned as zinc oxide, The total sulphuric acid, less soluble sulphuric acid, and the equivalent of the sulphur dioxide, are calculated into lead sulphate, and any excess of lead is returned as lead oxide. Zinc-Lead, Leaded-Zincs, and Zinc- White.-The estimations necessary are those mentioned under basic lead sulphate.Lithopone.-This should contain from 69 to 70 per cent. of barium sulphate, the remainder being zinc sulphide with small amounts of zinc oxide and carbonate. Coppalle's method of analysis (ANALYST, 1907, 32, 233) is used for the estimation of these constituents and any impurities which may be present. Calcium Pigments (Whiting, Gi~psum, Plaster of Paris, etc.).-A fairly complete analysis may be necessary. Whiting should also be tested for alkalinity due to the presence of free calcium hydroxide, or possibly to sodium or potassium compounds. Bariwn Pigments (Bar@).-This pigment is seldom adulterated. I t should be white, well ground, and contain at least 93 per cent. of barium sulphate. Miscibility, opacity, specific gravity, whiteness of colour, together with a microscopic examina- tion, will probably give more useful information than chemical analysis.Estimations may, however, be made of moisture, iron oxide, alumina, soluble sulphate, carbon dioxide, barium carbonate, and water-soluble substances. Silica Pigments (Silica or Silez).-At least 95 per cent. of the material should be insoluble in boiling hydrochloric acid, and this portion should be tested for barium sulphate. Iron, aluminium, calcium, and magnesium are estimated in the soluble portion. Moisture and loss on ignition are also estimated.China Clay and Asbestine.-In addition to estimations of moisture and loss on ignition, qualitative tests to prove that the substances are as represented will gene- rally suffice, but a complete analysis may be made if desired.Red Lead.-The moisture is considered to be the loss in weight when 2 grms. of the sample are dried at 105" C. for two hours. The presence of organic colouring matters is detected by boiling a portion of the sample successively with alcohol, water, and ammonia. These solvents should not become coloured. Estimations .should be made of the total lead, silica, zinc, carbon dioxide, soluble sulphate, and water-soluble matter. Iron oxide is estimated by Schaeffer's method (ANALYST, 1912, 37, 520). For the estimation of lead peroxide and actual red lead, 1 grm.of the sample is mixed into a paste with a small quantity of water and treated with a solution prepared by heating together 30 grms. of sodium acetate, 2.4 grms.of potassium iodide, 10 C.C. of 50 per cent. acetic acid, and 10 to 12 C.C. of water. This solution muet be cooled before being added to the red lead. When nearly all the latter has dissolved, 30 C.C. of water containing 5 grms. of sodium acetate are added, and the mixture is titrated at once with thiosulphate solution. Towards the end of the titration, any undissolved particles are rubbed with a glass rod until free iodine no longer forms, starch solution is added, and the titration continued.A slight excess of thiosulphate solution may be added and titrated back with Fv iodine solution.ORGANIC ANALYSIS 21 Oil No. 1. The thiosulphate solution is standardised against pure iodine. The iodine value of the solution multiplied by 0.94193 gives the quantity of PbO,, or by 2.69973, the quantity of Pb,O,.w. P. s. American-Grow n oils. Oil No. 2. Tests on Chinese Wood Oils. (Report of the American Society for Testing Naterials, 1914, 17-38.)-Two samples of Chinese wood oil, one commercial as obtained from the exporter by a large varnish manufacturer (sample No. l), and the other (No. 2) pressed in the laboratory from Chinese wood oil nuts, were examined by members of a committee of the Society.The average results obtained by the eleven investigators are summarised in the following table, which also shows the result8 of the analyses of three samples of tung oil pressed from American grown nuts : 0-9406 1,5143 3.4; 192.27 0.012 per cent. 0*0068 0.73 per cent. 169.3 3 mins. 37 secs. 9 mins.54 secs. Sp. gr. 15.5"/15*5" C. ... Refractive index at 25" C. Moisture and volatile matter Ash ... ... ... ... Acid value ... ... ... Saponification value . . . Unsaponifiable matter . . . Iodine value (Hiibl, eighteen hours) ... ... ... Iodine-jelly test ... ... Heating test ... ... 0.9396 0.9276 to 0.9416 1.5186 1.4790 to 15200 0.02 per cent. - 0.0026 per cent. - 0.47 per cent.I 090 0.2 to 0.8 193.02 188.2 to 1924 169.6 151.6 to 171.7 4 mins. 43 secs. 3 mins. to 8 mins. 9 mins. 23 secs. 10 ,, to 11.5 ,, I-- - - -- .--I - The iodine-jelly test consisted in mixing 1 grm. of the oil with 5 C.C. of chloro- form at 25" C., adding 5 C.C. of a saturated solution of iodine in chloroform, and stirring the mixture until a jelly is formed. The time required for the formation of the jelly, after the addition of the iodine, is noted. In carrying out the heating test, 5 C.C.of the oil are placed in a test-tube containing a glass rod, and then heated in an oil-bath at 282' C. After nine minutes' heating, the rod is raised at intervals of fifty seconds, and the time noted when the oil has set to a firm jelly. The test should be repeated with another portion of the sample.Although the results given above indicate certain limits for the constants of pure Chinese wood oil, the committee is of opinion that specifications should not be drawn up at present, as confirmatory tests of an important nature are expected to be developed during the coming year. w. P. s. Analysis of Shellac. Estimation of Rosin and Alcohol-Insoluble Sub- stances.(Report of the American Society f o r Testing Materials, 1914, 117-125.)- Langmuir's method (ANALYST, 1905, 30, 164) is recommended for the estimation of rosin in shellac. This Kethod depends on the different iodine values of shellac and rosin, the former having an iodine value of 18, and the latter 228.22 ABSTRACTS OF CHEMICAL PAPERS Shellac may contain insect cells, sand, fragments of wood, etc., amounting to 3 per cent. or more of substance insoluble in alcohol. Some difficulty is met with in estimating the quantity of these substances, since shellac contains about 5 per cent. of wax which is soluble in boiling alcohol, but insoluble in cold alcohol. It is recom- mended that a weighed portion of about 5 grms. of the powdered shellac be placed in a cartridge (previously extracted with methyl alcohol, dried, and weighed), which is held in a tube provided with a siphon, (as in a Knoeffler extraction apparatus. During the extraction the cartridge is heated by the vapours of the alcohol which pass round the tube, and are then condensed by a reflux apparatus to fall as liquid on to the cartridge. Methyl alcohol of 99-5 per cent. 'strength is employed as the solvent, and the extraction is continued for exactly two hours, the solvent being boiled sufliciently vigorously to cause the siphon to operate about thirty-three times per hour. The cartridge and its contents are then dried at 100" C., and weighed. w. P. s.