THE ANALYST 95 ORGANIC ANALYSIS. A Volumetric and Gas-volumetric method for the Determination of Hydroxylamine and Hydrazine. I(. A. Hofmann and F. KGspert. (Berichte, 1898 xxxi. 64-67.)-This is based on the oxidation of hydroxylamine or hydrazine, with a dilute solution of a vanadium salt in sulphuric acid the nitrogen evolved being collected and measured and the partially-reduced solution titrated back with per-m anganate . I. 2NH,O + 0 = N + 3H20. 11. N2H + 2 0 = N + 2H,O. Should other reducing substances be present a deduction is made based upon the amount of nitrogen calculated to hydroxylamine or hydrazine. The vanadium solution is prepared by dissolving 5 grammes of ammonium meta-vanadate in 50 C.C. of sulphuric acid kept cool and diluting to 1 litre. The substance to be analysed is dissolved in dilute sulphuric acid and the vanadium solution added slowly until a green coloration results.The nitrogen evolved at the ordinary temperature is collected which requires about twenty minutes. The flask is then warmed at about 60" C. for a few minutes at the end of wbich the green colour should still remain and finally the solution is transferred to a porcelain dish and titrated with standard permanganate until there is a permanent rose tint. The following results were obtained with hydrazine sulphate (15 grammes in 1,000 c.c.). The permanganate solution used contained 1.794 grammes of available oxygen per litre. Hydrazine Vanadium Permanganate. Oxygen Nitrogen at 0" C. Solution. Solution. consumed. and 760 mm. c. c. c. c.C.C. C.C. 10 50 20.51 0.03680 10 50 20.23 0.03630 10 50 20.20 0-03624 10 50 19.97 0,03583 19.85 = 22-09 per cent. The calculated amount of nitrogen =21*58 per cent. and the results were therefore in accordance with the equation N,H6S04 + 2 0 = N + 2H,O + H,S04. The results obtained with hydroxylamine sulphate hydroxylamine nitrate and hydrazine mercury sulphate showed a similar agreement with those required by theory. C. A. M. The Estimation of Phenylhydrazine. H. Causse. (BzLZZ. xoc. Chiin, 1898, xix. 147-149.)-This is based on ths fact that arsenic acid oxidizes phenylhydrazine, liberating nitrogen and leaving pheno€ and that a corresponding quantity of the arsenic acid is reduced to arsenious acid. As,O + C,H,N = N + H20 + C6H,0 + AS,^,. The reaction is quantitative in an acetic acid solution and the arsenious acid produced may be estimated either by titrating the standard arsenic acid solution with uranium before and after the reaction so as to obtainithe amount not reduced or by titrating the arsenious acid produced with iodine in the presence of sodium bicar-bonate (As,O + 21 + 2H,O = 4HI + As,O,) 96 THE ANALYST.About 0.20 gramme of phenylhydrazine or preferably of its hydrochloride are heated gently under a reflux condenser with 60 C.C. of an arsenic acid solution prepared by dissolving on the water-bath 125 grammes of arsenic acid in a mixture of 450 C.C. of water and 150 grammes of concentrated hydrochloric acid filtering when cold and making up to a litre with glacial acetic acid. When the bubbles of gas have ceased the liquid is boiled for about forty minutes and allowed to cool.After the addition of 200 C.C. of water a solution of caustic soda (free from sulphides) is added until the liquid is just alkaline. Hydrochloric acid is then added to acid reaction and when cold 60 C.C. of a cold saturated solution of sodium bicarbonate are added and the liquid titrated with decinormal iodine. If V be 'the volunie of iodine solution required the quantity of phenylhydrazine is obtained from the formula V x 00495 x 0.5454. The results given by the author agree well with theory and it is stated that the method is equally applicable to the analysis of compounds of aldehydes and phenyl-hydraxine although if the aldehyde belong to the fatty series it should be eliminated on account of its action on the arsenic acid; if however it belong to the aromatic series its presence is without effect and the estimation can be made on the compound itself.C. A. M. Examination of Wax with the Refractometer. J. Werder. (Clzenz. Zeit., 1898 xxii. 38 and 59.)-The author finds that the Zeiss butter refractometer may advantageously be employed in the examination of different kinds of wax especially whea the amount of material at disposal is very limited and that the indications obtained with it are quite as valuable as in the case of oils and fats. Owing to the high melting-point of the wax it is necessary to work at a higher temperature than usual preferably 66" to 72" C. and then to reduce the results to the normal tempera-ture 40" C. As shown in the annexed table the figures given by genuine beeswax vary from 42%" to 45*4" the great majorityof specimens falling between 44" and 45"; and it seems to make little or no difference to the refractive power whether they are tested before or after bleaching.Samples 19 to 24 had previously been examined chemically and had been rejected on the ground of their abnormal acid and ester numbers which were as follows : Number of Sample. Acid Yumber. Ester Number. 19 . 18.48 . 66.64 20 . 127.1 . 13-4 21 . 59.08 . 3.36 22 . 1045' . 14.3 23 . 41.0 . 57-0 24 . 106.9 " 48.1 No. 24 is a product called "glanzwachs," obtained by adding some of the mixture of stearic and palmitic acids as used in the manufacture of stearin eandles (No. 28) to a genuine wax this being a form of adulteration commonly employed in Switzerland THE ANALYST.97 REFRACTIVE POWER OF DIFFERENT KINDS OF WAX. Temperature of Refraction at Observation. 40" C. Sample. 1. Bleached from Egypt . . . 66.0 . 44.1 2. 1 1 , Turkey . . . 67.0 . 44-8 3. ,? , Moldavia . . 66.5 . 44.2 4. Yellow ) Egypt . . . 66.0 . 42.8 5. 3 9 , Monte Christ0 . . 71.0 . 44.8 6. 9 1 , France . . . 67.5 . 44.1 7. 1 ,) Savoy . . . 67.0 . 42.6 8. 91 ? California . L 69-5 45.2 ) ) North Bfrica . . 71.0 . 45.0 9. 9 , 10. 9 ) , Massowah . . . 71-5 . 44.3 70.0 . 44.9 70.0 . 44.0 68.5 . 44.6 69.5 , 44.2 $ 9 9 45 3 11. ) ) Y ) Italy 12. 7 , 13. 1 9 $ 9 14. , $ 9 Mexico}different samples { 67.0 . 15- 9 16. ) ? , Syria . . . 69.5 . 44-2 17. 9 7 , Casablanca _ .. 68.0 . 45.4 18. ,? , Smyrna . . . 70.0 . 44.7 19. Bleached in chips (professedly genuine) . 70.5 . 41.3 20. White Church candles . 67.5 32.0 21. . 68.0 32.5 22. 3 9 7 68.5 82-6 23. Yellow wax source unknown . . 66.0 . 38.3 24. Wax adulterated with No. 28 . . 65.5 . 38.8 25. Paraffin . . . . 65.0 22.5 26.- Ceresin . . . . . 77.0 . 41-0 27. Tallow . . I . . _ . 71.5 . 48.5 28. Stearin candle material . . . 70.0 . 30.0 29. Carnauba wax . . . . 91.0 . 66.0 30. Japan was . . . . . 71.0 . 47-0 . . ) ? 1 different samples . . 7 , 9 9 . . . . . F. H. L. On the Estimation of Unsaturated Fatty Acids. E. Twitchell. (Jour. SOC. Chena. Ind. 1897 1002-1004.)-The author bases a method for separating satura;t;ed from unsaturated fatty acids on the fact that the latter combine (in all probability quantitatively) with sulphuric acid forming addition compounds which are insoluble in petroleum spirit.As it was found that the saturated acids could not be extracted from a concentrated sulphnric acid solution by petroleum spirit and that the addition of water decomposed the sulpho-fatty acids experiments were made with sulphuric acid previously diluted and eventually 85 per cent. was fixed upon as the most satisfactory strength. The method of separation tentatively adopted is as follows From 0.5 to 1 gramme of the fatty acids are melted in a stoppered Erlenmeyer flask the flask chilled in ice-water 3 C.C. of 85 per cent. sulphuric acid added and the ternpersture allowed to rise. As soon as the action commences a clear solution is rapidly obtained, and the flask is again cooled.Fifty C.C. of petroleum spirit are then introduced th 98 THE ANALYST, flask well shaken the petroleum spirit decanted into a separator-funnel the flask rinsed out twice with 10 C.C. of petroleum spirit and the total extract washed with water the solvent evaporated and the residue consisting of saturated fatty acids, dried and weighed. Crude oleic acid solidifying at 12" C. when examined in this way gave a crystalline residue melting at 37" C. and the following results were obtained with the fatty acids from three different samples of oil : Origin of Fatty Acids, Lard . . Cotton-seed-oil . . . Ditto . . Solidifying Point, O c. 40.75 30.89 31.90 Amount used. Gramme. 0.7815 0.6150 0.5875 Petroleum Spirit Extract per cent.42-35 32-60 23.91 Melting-point of Saturated Acids "C. 53-5 53.0 . From the melting-points of the residues being somewhat low the author did not consider the saturated acids thus obtained qui,te pure although the impurity must have been slight. A second extraction of the sulphuric acid solution of the cotton-seed-oil fatty acids with 50 C.C. of ether yielded 0.019 gramme of residue which did not solidify at the ordinary temperature such residue being attributed to the dtlcomposition of a small amount of sulphostearic acid. The petroleum spirit used must first be tested to see whether any non-volatile substances are produced by treatment with sulphuric acid. If so it can be purified by being digested for an hour at 100" C.with about half its weight of concentrated sulphuric acid and then washed and distilled. C. A. M. Estimation of Phenol in Disinfectants in Presence of Soap. W. Spalteholz. (Chem. Zeit, 1898 xxii. 58.)-In the examination of neutral disinfectants such as creolin lysol and '( soluble cresol," where the phenols are not in a state of combina-tion there is no necessity to add any acid before distillation as recommended by Fresenius and Makin (ANALYST xxi. 301) since calcium phenolates are readily de-composed when heated in aqueous solutions. The sample is placed in an iron retort and distilled in a current of steam between 200" and 220" C. until the distillate no longer yields any oily matter. Bodies which contain soaps of oleic acid must not be heated above 210" lest the latter are decomposed ; but should 'this happen it will at once be rendered apparent by the presence of a layer of oil floating on the top of the water in the receiver.Alkali-rosin soaps easily resist a temperature of 220". The distillate consists of phenols alone in the case of lysol ; of phenols and tar hydro-carbons in the case of creolin mixed with the water ; and the simplest way of separating them is to extract the whole with benzene remove the aqueous portion and estimate the phenols themBelves with caustic soda. (Koppeschaar's process is not adapted for the analysis of mixed phenols of unknown composition.) Tried on a number of known products the author's method has given results usually 0.5 per cent. but occasionally 1.0 per cent.below the theoretical ; and it is therefore quite accurate enough for ordinary work THE ANALYST. 99 Lysol and ‘‘ soluble cresol” contain between 50 and 60 per cent. of phenols ; creolin from 0 to 28 per cent, although samples which emulsify well with water seldom have more than 18 per cent. The relative values of the two materials how-ever cannot be judged merely by the proportion of phenols found in them for if a creolin gives an oily precipitate on dilution with water that portion of the substance is wasted ; while on the other hand the neutral hydrocarbons present also exhibit distinct germicidal properties. F. H. L. A Reaction distinguishing between Creosotes and Guaiacols. H. Fonzes-Diacon. (BUZZ. SOC. Chim. 1898 xix. 191 192.)-A small quantity of the sample is dissolved in water 2 or 3 C.C.of a solution of copper sulphate (about 4 per cent.) added and 1 or 2 C.C. of a 4 per cent. solution of potassium cyanide. An immediate striated precipitate is produced which viewed by transmitted light is emerald-green in the case of creosote grayish-red with poor guaiacol and maroon-purple with rich guaiacol. I n this way it is possible to determine whether a product is a creosote containing 12 to 25 per cent., a guaiacol containing 65 to 70 per cent, or a guaiacol with 85 to 90 per cent. of crystallizable guaiacol without having recourse to a colour scale of typical solutions The emerald-green colour changes rapidly to yellow. in Adrian’s colorimetric method (ANALYST xxii. 162). C. A. M. Detection of Halogens in Organic Compounds.P. N. Raikow. (Chem. Zeit. 1598 xxii. 20.)-Some ten years ago Giinzburg recommended the use of an alcoholic solution of phloroglucinol and vanillin to detect free hydrochloric acid in the gastric juice; for the reagent gives an intense permanent red colour on warming therewith although it is unaffected by organic acids. If the same solution is heated with an organic body containing a halogen only in a few cases is the red colour pro-duced. If the substance is liquid and combustible it may be mixed with a few drops of the phloroglucinol-vanillin solution in a flat porcelain basin and the alcohol ignited. As the spirit burns away the red colour usually develops; but to render the test uni-versally applicable it is better to operate as follows A piece of porcelain is moistened with the reagent the solvent allowed to evaporate and the dried film (which is now colorless) is held over the flame of a spirit-lamp into which the suspected substance is introduced on the end of a platinum wire The test is roughly quantitative for according to the amount of halogen present more or less of the surface is turned red.If the organic substance is an inflammable gas it may be set light to and the porcelain dish held over the flame. F. H. L. Estimation of Carbon and Oxygen in Organic Bodies by Moist Combustion. J. K Phelps. Oxidation of Carbon with Potassium Permanganate.-Many organic substances are completely oxidized on warming with sulphuric acid and permanganate so that t;he evolved carbon dioxide may be absorbed in barium hydroxide and determined with iodine and arsenious acid as previously mentioned (ANALYST xxii.55). The apparatus consists of a wide-necked 75 C.C. flask fitted with a stoppered funnel and leading-tube for the gas the latter being expanded into a bulb immediately over the (Zeds. anorg. Chem. 1898 xvi. 85. I00 THE ANALYST. cork ; and a condensing-flask of 250 C.C. capacity provided with an inlet tube reaching to the bottom and an outlet closed by a screw clamp The two corks are of rubber, and so long as they do not come in contact with the liquids they willnot be attacked. The subatance is rinsed into the small flask with 10 or 15 C.C. of water ; 3 or 5 C.C. more of standardized caustic baryta solution than is necessary to absorb all the gas is introduced into the larger vessel the pressure reduced by means of a pump to 200 or 225 mm.the organic solution warmed excess of perrnanganate run in through the tube funnel and finally 10 C.C. of 1 4 sulphuric acid. The mixture is boiled for five minutes care being taken to maintain some vacuum while the receiver is well shaken and kept cold in a basin of water; pure air is then allowed to enter through the funnel to restore the atmospheric pressure and to drive the last traces of carbon dioxide into the baryta. The cork of the large flask is removed tha tubes washed another rubber cork carrying a funnel and a set of nitrogen bulbs put in its place; the liquid is heated decinormal iodine added till it becomes permanently red then cooled again and the excess of iodine titrated with decinormal arsenious acid.The permanganate solution should be boiled with sulphuric acid until all GO, is driven off; the water and acid must also be boiled till free from the gas. 0x;altltie~ may be decoinposed very smoothly in this way ; but in the case of formates and tartrates more than sufficient pure caustic soda (not ammonia) should be added a t first to neutralize the acid in the permangqtnate and then after the whole has been raised to the boil an excess of dilute sulphuric acid run in as before. The process was checked on ammonium oxalate barium formate and tartar emetic ; the figures show an average error of about 0.2 milligramme in estimating 0.15 to 0.6 gramme of GO,. Oxidation of Carbon with Clwonzic Acid.-Although a concentrated mixture of chromic and sulphuric acids is a much more powerful oxidizing agent than potassium permanganate there are many organic substances as Cross Higgin and Bevan have pointed out which yield some carbon monoxide on treatment therewith.The following arrangement ensures complete oxidation with-out the necessity for passing the gases over red-hot copper oxide The construction of the apparatus is explained by the annexed cut. The large flask is made of thick glass and holds 1 litre; the cone in the neck is of platinum and serves to protect the rubber cork from splashes when the vessel is shaken. The separating funnel holds 100 c.c.; the stopcock is well ground in, and moistened with strong metaphosphoric acid. The condensing flask holds 500 C.C. The substance to be analysed is weighed into a thin glass bulb the aperture thereof sealed the bulb dropped into the large flask and an excess of pure potassium bichromate added.A suitable amount of caustic baryta solution is poured into the condenser the apparatus put together 10 C.C. of pure sulphuric acid introduced into the generator and both flasks are boiled till about 2 or 3 C.C. of water have been evaporated from each and a vacuum is produced. The flames are removed the two clamps shut the little bulb is broken by a jerk and 20 C.C. of stron THE ANALYST. I01 sulphuric acid (previously freed from organic matter by heating with a few crystals of bichromate) run in through the funnel; The flask is well shaken heated to about 105” C. (the maximum temperature permissible if loss of oxygen is to be avoided), water added to dissolve the chromic acid crystals and the whole is again boiled (without allowing the pressure to exceed that of the atmosphere) for five minutes with constant agitation.By this time any CO will be oxidized; 60 or 70 C.C. of water are introduced the clamp between the two flasks is opened and the carbon dioxide is permitted to pass into the condenser which is kept cold and shaken as before. The contents of the generator are once more heated to the boil and a steady current of pure air is passed through the apparatus for fifteen minutes. Finally the CO is estimated in the manner already given. Estimation of Oxygen. -In the above process if a known amount of pure bichromate is employed and the excess of chromic acid remaining unreduced after the operation is determined it is evident that the quantity of oxygen required to burn the carbon may be calculated ; and from the total GO recovered by a simple sub-traction the oxygen in the original body may be deduced.The only special precaution necessary is that the sulphuric acid shall not become too strong lest it begin to act on the bichromate causing the evolution of oxygen instead of chlorine in the second distillation. Twenty C.C. of sulphuric acid are used in the C estimation, and the boiling is allowed to proceed-quietly. The volume of water added in the final dilution should be adjusted so as to leave 60 or 80 C.C. in the flask when the CO, has been driven off. This liquid is brought into a Voit flask connected wikh a Drexel washing apparatus containing an excess of sodium arsenite of known strength and a, set of nitrogen bulbs filled with dilute caustic soda.I t is treated with 35 C.C. of HCI (specific gravity 1*2) boiled in a gentle current of CO, which has been washed in a solution of iodine in potassium iodide and then in HI alone until some 30 or 40 C.C. have distilled off. Sometimes red vapours of chromyl chloride are produced during the boiling; but as this substance is reduced by the arsenious acid it is a matter of no consequence to the analysis. The latter liquid is acidified with sulphuric acid, made alkaline with potassium carbonate and titrated with decinormal iodine. The double method (for C and 0) was tested on ammonium oxalate phthalic acid pure sugar paper tartar emetic and barium formate.The results are exemplified in a table they are especially for the carbon eminently satisfactory ; the error in the oxygen determinations varies from 0-0 to 2.1 milligramines in 0.1 to 0.5 gramme. Organic substances which are volatile and yet difficult to oxidize cannot be subjected to this moist combustion ether is easily oxidized to acetic acid but it cannot be completely burnt up ; for although liquid acetic acid is very rapidly attacked by nascent chromic acid yet in the gaseous state (as it exists owing to the conditions of the reaction) it resists oxidation. Similarly naphthalene is not amenable to the author’s process. F. H. L. Separation of Ethylene from Benzene in Gas. E. Harbeck and G. Lunge (Zeits. anorg. Chem. 1898 xvi.26-50.)-1n the ordinary analysis of coal or coke-oven gas it is usual to estimate the “heavy hydrocarbons” by absorption with fuming sulphuric acid or bromine making no distinction between the benzene an 102 THE ANALYST. the ethylene in spite of the fact that these substances are of very different value either for illuminating or heating purposes. The authors have investigated two methods of separating these hydrocarbons the first depending upon the conversion of ethylene into ethane in presence of hydrogen and platinum black the second on the nitration of the benzene. A full description of the preliminary experiments the apparatus necessary and the final calculations is given in the original article ; but it is too lengthy and replete with detail to be properly abstracted; the following cursory account however explains the principles underlying the two processes, Conversion of EthyZene into Et7zaizeL-A U-shaped tube about 10 cm.long and 3 mm. in internal diameter with capillary ends is filled with 0.5 gramme of platinized asbestos ( = 0.11 gramme of Pt) through an aperture in the base which is afterwards sealed up. I t is hung within a glass or metal beaker full of water or copper turnings, according to the temperature at which it is to be employed. A current of pure hydrogen is next passed through it for two hours at 100" C. and two hours in the cold to saturate the platinum black; and the apparatus is then ready for use. I n one sample of the gas to be analysed which must obviously contain an excess of hydrogen the total amount of ethylene and benzene is determined by absorption in fuming sulphuric acid the other constituents being estimated in the usual way.A second sample is freed from oxygen with alkaline pyrogallol and led two or three times over the platinized asbestos at 100" C. The residue is treated with funling sulphuric acid as before which now absorbs the benzene only the difference between the volume taken up before and after condensation thus giving the percentage of ethylene. As I volume of ethylene unites with 1 volume of hydrogen to form 1 volume of ethane the proportion of the former ingredient may be more simply deduced from the contraction; but by operating in this manner it is impossible to determine also the hydrogen and the methane. Unfortunately the process is not available for those many cases in which carbon monoxide is present in the original gas.Diyect Estimation of the Benzene by Nitration.-The sample of gas is passed through a 10-bulbed tube containing a mixture of equal parts by weight of pure strong sulphuric acid and fuming nitric acid (specific gravity 1-52) which converts the benzene into metadinitrobenzene and removes the whole of the ethylene The acid liquor is diluted with ice-cold water neutralized with caustic soda (also in presence of ice) the bulk of the dinitrobenzene collected on a filter-paper (if there be sufficient of it precipitated to be worth filtering) and washed till free from acid. The filtrate and washings are made up to some convenient volume and an aliquot portion is extracted twice with ether.The solvent is distilled off the residue dried in a current of air dissolved in fresh anhydrous ether mixed with the rest of the product the solution filtered again evaporated and the solid matter dried at 70" or 80" C. (or over sulphuric acid in vacuo) and weighed. The precipitate thrown down on neutralization is quite pure and without odour ; that extracted by means of the ether is apt to be contaminated with inononitrobenzene ; but the melting-point of the whole is generally about 86.5" C. (instead of 90" C.). The reaction is perfectly quantitative ; the products formed by the action of the acids on ethylene remain in the aqueous liquid and do not affect the purity of the dinitrobenzene. Nevertheless as the process is somewhat tedious and requires THE ANALYST.103 complicated apparatus it should only be resorted to for specially important analyses as a check on the former method. To convert the weight (N) of dry dinitrobenzene in grammes into the percentage by volume (V) of moist benzene vapour in moist gas at the temperature to and pressure b mm. the following formula may be used s is the proportion of benzene plus ethylene W that of the hydrogen in the original gas and e the tension of aqueous vapour at to C. N(1+ 0*00367t)(100- S) V = 98.50564 x - W(b - 2; e) F. H. L. Use of Lead Carbonate in Analysis. G. Morpurgo. (Giorn. di Farm. di Trieste 1897 ii. 355; through Chem. Zeit. Rep. 1898 19.)-The author recom-mends the use of freshly-precipitated lead carbonate in all cases where the acetate is usually employed e.g.for the removal of coloring-matter acids tannins etc., from complex solutions. The moist carbonate only requires shaking with the liquid, does not dilute it while the minute trace of lead which passes into solution can be easily removed by a small crystal of sodium sulphate. F. H. L. Oil of Basil. J. Dupont and Guerlain. (Bull. Soc. Chim. 1898 xix. 151-154.) -Two essences are known by the name of basil-one collected in the South of France and in Germany having 8 sweet characteristic odour; the other imported from Reunion being marked by a strong smell of camphor which partly masks the characteristic odour. Moreover the former is lmo-rotatory the latter dextro-rotatory. Dumas and Peligot (Ann. Chim. Phys. lvii. 334) extracted from oil of basil a crystalline inodorous product which they considered to be a hydrate of terebenthine CloH,,+3H,0.The authors however have not been able to find any trace of this substance in two samples of the French essence. The French oil examined by them was an oily yellow liquid with a specific gravity of 0.9154 at 15" C. and a rotation in a 100 mm. tube of -7.40". Four-fifths of the oil distilled over between 190" C. and 220" C. and the distillate was further fractionated into two main portions boiling at 195" C. to 200" C. and 205" C. to 215" C. respectively. The former constituting nearly 60 per cent. of the essence was an oily liquid which was identified as linalol (C,,R,,O) by its composition and chemical and physical properties. The fraction boiling at 205" to 215" had the odour chemical and physical characteristics of p-methoxy-allyl-benzene the chief constituent of oil of tarragon.A sample of Reunion oil examined by the authors was also found to contain p-methoxy-allyl-benzene but no linalol a fact confirnied by Bertram and Walbaum (Arch. der Pharnz. February 1897) who found their sample to contain 60 per cent. of that compound and a small quantity of a dextro-rotatory camphor. The results of their analysis of a specimen of German oil showed a close agreement with those obtained by the authors in the case of French oils and confirmed their conclusions as to the presence of linalol in the European essences and of camphor in the Reunion oil. C. A. M 104 THE ANALYST. Solidi-fying point. 22.5 20.5 22.5 18-5 22.5 14-5 27.2 24.3 ~-Examination of Rose-Oil.P. N. Raikow. (Chew,. Zeit. 1898 xxii. 149,)-The present author is unable to corroborate the figures previously quoted (ANALYST, xxiii. 12) as characteristic of true rose-oil and he does not consider Dietze's specifi-cation of much value. The samples are undoubtedly genuine many of them having been extracted by himself from different varieties of the plants cultivated in different parts of the rose-growing districts. Nos. 1 2 and. 3 are mixed oils made from red and white roses (as it is the custom to do with marketable specimens); 4 is from red roses alone (22. centi-folin) ; 5 from inferior. kinds of red flowers ; 6 and 7 are the favourite and expensive '' green rose-oils 77; 8 is from Seraphimoff and Go.of Kazanlik said to be the same as that examined by Dietze who gave it an acid number of 1-2 and a saponification number of 9.2. The two samples of geranium-oil are from Konig and Co. of Leipzig-Plagwitz ; the first is called '( 01. Geranii Turkicum rect. alb.," the second " 01. Geranii Gallic. lA." The specific gravities of the rose oils were determined at 15.00- except No 8 which was at "5" '* ; those of the geranium-oils were observed both at 27.5" and at 15" C. The optical examination of the rose-oils was carried out in a 100 mm. tube at 25" C. ; that of the geranium-oils at 19" C. The solidifying-point is the tempcra-ture at which the first crystals of stearoptene were deposited. The acid and saponi-fication numbers are nearly all the mean of two or more tests; the ratio in the last column is that between the acid and the ester number.ROSE-OILS. His own results are shown in the subjoined table. 27.5" C. 17.5" No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 Specific Gravity. 0.8531 0.8583 0.8659 ----0.845 Rotatory Power. Acid Number. -2" 12' 15" - 2" 6' 50" -2" 38' 40" -2" 35' - 2" 45' -1" 43' 40" -3" 28' 30'' -3" 3' 50" Saponifi-cation Number. 17.7 16.5 16.9 13.1 (16-8) 17.8 21.1 10.8 GERANIUN-OILS. Ester Number. 16.1 14.2 15.4 12.3 14.3 18.4 9 5 -Ester Specific Rotatory Acid Saponification Gravity. Power. Number. Number. Number. 1.0 39.6 38.6 7.7 62-8 55.1 Turkish 0-8867 (27.5") 41' 20,t French 0.8869 (27-5") -70 52' 9 1 0.8960 (15") ) 9 9 0.8971 (15") } -Ratio.1 10.1 1 6.1 1 10.2 1 15.4 1 5.7 1 6.8 1 7-3 -Ratio. 1 38.6 1 7.2 h'. H. L. The author concludes that the " constants " relied on by Dietze are not sufficiently precise to allow of the certain detection of adulteration. On the Precipitation of Proteids. H. Schjerning. (Zed. aizal. Chem. 1897, xxxvi. 643-6G3.)-The fact that ash-free proteids behave in a different manner fro THE ANALYST. 105 those containing ash led the author to make experiments on the effect of adding salts to different precipitating reagents. It was found that the addition of various quantities of a 10 per cent. solution of calcium chloride did not interfere with the precipitation of proteid matter by stannous chloride.On the other hand the precipitates obtained with lead iron or aluminium acetates gradually decreased as more of a 10 per cent. solution of calcium acetate was added. From this the conclusion was arrived at that in the case of the tin precipitate a sort of double salt with two basic radicles but only one acid was probably produced, To determine the influence of salts containing a different acid radicle to that of the precipitating salts a similar series of experiments was made with a 0.4 per cent. solution of disodium phosphate. Up to a certain point the addition favoured the precipitation but when added in excess had a disturbing effect. The reactions taking place were probably as in the equations : 291b.Pb.CH3CO0 + Na,HPO = (Alb.Pb),HPO + 2CH,COONa or 2Alb.Pb.CH,C00 + Na,HPO = (Alb),Pb + PbHPO + 2CH,COONa.In applying this to the method of separating proteids the solutions of the pre-cipitants were of the same strength as given in the Zed. anal. Clzem. xxxv. 286, and whenever the proteid solution contained little or no phosphate the phosphate solution was added in the proportion of 20 C.C. to 6 C.C. of the lead acetate solution or to 0.8 gramme of ferric acetate and 40 C.C. of dilute acetic acid (15 C.C. of 40 per cent. in 1 litre). Care was taken that the proteid solution did not contain in 10 C.C. more nitrogen than corresponded to about 5 C.C. of decinormal acid. The following table gives the results obtained with various proteid solutions. A cross indicahs that the determination could not be made on account of the liquid not filtering clear or in the case of the ferric acetate owing to the iron not completdy precipitating on boiling : Malt I.. . . . . . ) ) 11. . . . . . . Egg-albumen I. . I1 .*. Milk . 'I. . . ) ) 11. . . . . . . Witte's peptone . Liebig's flesh pep-tone . . . . . . Liebig's meat ex-tract . . . . . . . . . . . . Diastase (Merckj . Urine . . . . . . Solution. 100 graiiiiiies } in a litre 2 gamines in I 400 C.C. 75 c.cdiluted J } to 500c.c. I 2.5 gramrnes in 500 C.C. . 5 grainmes i n 800 C.C. . 5 graiiiiiies i n 800 C.C. 0 . . 12 grammes in 500 C.C. 50 C.C. diluted;; 500 C.C. . Stannous Chloiide. Vithout ! With CaCI2. 8.6 8.7 5.8 + + + 1.2 + 8.4 15.8 0-6 8.9 9.9 89.2 91.5 82.6 80-1 2.7 13'9 10.7 36.9 1.4 Lead Acetate.Vithout 1 With Na2HPOd. 18.0 18.5 90.3 88.8 S8-2 + + + + 2.0 -20.6 20.1 92.3 92.2 91.9 -+ + 19.2 + 2.4 Ferric Acetate. Yithout I With N%HPO+ -1- + + .+ + + + + + + + 31.9 33.0 97.2 94.2 93'8 93.0 59.2 56.4 25.3 80.4 3.1 Vormal Ura-nium Solu-tiun. 41.8 44.8 99.9 94.2 92-9 92.2 59.2 53.4 36.7 85.9 1'9 'recipi-tation with I- Acetic Acid. ?ulgso.$ 19.9 21.3 96.0 93.0 92.1 92.2 51.2 47'2 15.1 59.7 1.4 A very old sample 106 THE ANALYST. 1.7 7’9 1.6 0-0 From comparison with the results obtained with the malt-extract the author considers that them are two kinds of “ albumin ” present in milk.He divides the pre-cipitated proteids in the following way and adds in a subsequent note that the names 4 ‘ albumin,’’ etc. are only to be regarded as a provisional nomenclature, indicating to some extent the characteristics of hhe substances. a = Albumin I. = the tin precipitate. b = , + albumin 11. + denuclein = the lead precipitate. c = 2 + 7 + , + propeptone =the iron precipitate a= , + , + , + , +peptone=theuranium pre-e = , + , +propeptone = the magnesium sulphate precipitate. Calculating the results from this the substances were found to have the following cipitate. composition : 0-8 11-0 1-1 0.0 Witte’s Pep-tone. Liebig’s Pep-tone. Liebig’e Meat Extract. 10.7 10.2 0.0 6.1 11.4 38.4 Dia-stase.Malt Extract. Egg-Albumin. Milk. Urine. I. 8 -9 11.7 11.3 9 9 -11. 9.9 10.2 12.9 11.1 -I. 89-2 1.2 1.9 3.9 2.7 11.” 91.5 1.2 1-5 0.0 Albumin I. . Denuclein . . . Albumin 11. . Propeptone . . . Peptone . 2.7 8.0 148.5 0.0 13.9 9.2 33.2 0.0 36.9 20-7 5 22.8 5.5 1.4 1:7 0.0 0.7 0.0 Total . 41-8 44.1 98.8 94.2 93.8 I 93.0 59.2 56.3 85.9 3.8 The author remarks i iat the fact that he finds no true peptone but only’ propeptones in either Witte’s or Liebig’s peptones is in accordance with the results of Konig and Bomer ; but on the other hand he differs from them in finding a large quantity of peptone in Liebig’s meat extract ( c j . ANALYST xxi. 17). C. A. M. The Classification of Proteids.A. Wroblewski. (Berichte 1898 xix., 3045-3052.)-The author defines proteids as bodies which on complete decomposition with acids yield as final products ammonia nitrogenous organic bases (such as lysine arginine etc.) and amido acids (such as leucine tyrosine etc.). Hence pro-tamines which yield no amido acids on decomposition cannot be classed with the proteids although closely allied to them. Probably peptones also do not comply with the definition though for want of more definite knowledge they may be grouped with their mother-substances the albumoses. I n the subjoined scheme of classification the proteids are divided into three main groups I. Albuminous bodies (Eiweissstoffe) ; 11. Compound albuminous bodies (Zusammengesetzte Eiweissstoffe) ; and 111.Albuminoid bodies (Eiweiss-a hnlic he Subs t anzen). To the first group belong proteids which a?e closely related to fresh or coagulated white of egg ; they contain sulphur in their molecule. Albumi7zs are .soluble in water. Globulins are insoluble in water but soluble in dilute saline solutions, AEbumiizs soZubZe in alcohol all dissolve in dilute spirit of wine and many of theni in strong spirit. Albz~rniizatcs are formed by the action of alkalies on. albumins. They are insoluble in water but readily soluble in alkalies. Acid albumins are produced by the action of acids on albumins and are soluble in very dilute acids o THE ANALYST. 107 alkalies. Coagulated albumiizs are the products of the coagulation of albumins by heat or by enzymes and are marked by their great insolubility.The second group comprises proteids whose molecule consists of an albumin group and another group often of a non-proteid nature. Thus in hanzoglobins there is a coloring-matter group ; in glyco-proteids a carbohydrate group ; in n z d e o -albumim a nuclein group; and in nucleins a nucleic acid group. The third group is subdivided into three classes (1) Structural substances (Gerustsubstanzen) ; (2) Alburnoses and peptones ; ( 3 ) Enzymes. In the first class are keratins constituents of horn. They contain much sulphur, are only with difficulty attacked by pepsin and trypsin and on decomposition yield much tyrosin. They are hardly soluble in reagents contain little sulphur and on deoomposition yield but little tyrosin. Collagenes contain very little sulphur and do not give aromatic amido-acids as decomposition products.Alburnoses and peptoizes constituting the second class have much smaller mole-cules than the albuminous bodies. By virtue of their toxic properties some of the albumoses are closely related to the enzymes. The enzymes grouped in the third class might be further divided in accordance with the conditions of their greatest activity. Thus some work best in acid solution others in alkaline solution. Among the former are pepsin ptyalin, diastase invertin myrosin and emulsin ; whilst representatives of the latter are trypsin steapsin and urase. PROTEIDS. EZnstim are contained in the cartilaginous tissues. GROUP I. Albuminous Sub-stances. 1. Albumins: Egg albumin Serum albumin Lact-a1 bumin iMuscle albumin Plant albumin Etc.2. Globulins : Egg globulin Seruni globulin Lacto-globulin Fibrinogen Myosin Plant globulins Vitellin (?) Etc. 3. Albuminous sub-stances soluble in alcohol chiefly of vegetable origin. 4. Albuminates. 5. Acid albumins : like. Syntonia and the 6 Coagulated albumin-ous substances : Fibrin Paracasein Coagulated white of egg. GROUP 11. Compound Albuminou: Substances. 1. Glyco-proteids : Mucins Mucoids. 2. Haenloglobin. 3. Nucleo-albumins. 4. Caseins: Of CO~VS’ milk Of human milk. 5. NuclBios. 6. Amyloids. 7. Histones ( 1 ) GROUP 111. Albuminoid Substances. Class 1. Structural substances. (Geriistsubstanzen). Keratins. !. Ela-tins.i. Collagenes : Collsgene, Glue and the like. Class 2. 91 bumoses and Peptones. Class 3. Enzymes. 1. Proteolytic : Pepsin Trypsin Papayotin and the like. 2. Amylolytic : Diastase Invertin and the like. 3. F a t - decomposing enzymes : like. Steapsin and the 4. Glucosidedecompos-ing enzymes. 5 . Amide decomposing Urase and the 6. Coagulating enzymes and the like : Rennet and the like. enzymes : like. C. A. M 108 THE ANALYST. Taka Diastase. J. Takamine. (Amel JOZWIZ. Phnim. 1898 lxx. 137-141.)-I n Japan and other Asiatic countries certain fungi are used for the production of diastase. That used in Japan belongs to the genus Aspergillus and is termeif Noyashi. This is specially cultivated on sterilized wheat bran or other suitable material and when mature is dtied and the spores separated by shaking or sifting ; the product thus obtained is called Taka-moyashi and can be preserved indefinitely.For the manufacture of diastase for commercial purposes wheat bran is moistened with water steamed and after cooling to below 40" C. is mixed with a little Taka-moyashi and spread in a layer in a room similar to a malt-floor where the tem-perature is maintained at about 25" C. and the humidity at about 80 per cent. Within forty to fifty hours the diastatic power of the mass reaches its maximum, and further growth is checked. The mass is known as Tuka-Koji and can be used in the green or dried state. The diastase it contains is soluble in water and an aqueous extract of the Taka-Koji concentrated in vacuo to a syrup has from eight to ten times the diastatic power of malt extract of similar consistency.The diastase can be precipitated from this aqueous extract by the addition of alcohol and when separated by means of centrifugal force and air dried is a non-hygroscopic j ellowish-white powder readily soluble in water and capable of converting over one hundred times its weight oE starch in ten minutes. By further purification by re-precipitation or otherwise its diastatic power which is exceedingly stable can be st ill further increased. C. A. M. A Simplo and Accurate Method of Testing Diastatic Substances. J. Taka-mine. (Amer. JozL'I'~. Pham. 1898 lxx. 141-143.)-This is based on the great stability of Taka-diastase (see preceding abstract) which does not lose its diastatic power with keeping as the author finds to be the case in the diastase isolated from malt. The exact diastatic capacity of a quantity of Taka-diastase is determined once for all by Lintner's or Junk's method (ANALYST xxi. 122) and that of any substance under examination compared with the standardized sample and expressed in any terms desired. Eight glass cylinders holding about 150 c.c. are placed in water warmed to about 40" C. and into each is poured 100 C.C. of 5 per cent. starch paste. I n the first glass is placed 1 C.C. of the saliva or other liquid to be tested whilst the other seven cylinders receive successively increasing quantities of a freshly-prepared 1 per cent. solution of the standard Taka-diastase commencing with I C.C. in the second cylinder and ending with 7 C.C. in the eighth. The contents are stirred until the starch becomes liquid and a drop from each is then removed to a white tile where it; is mixed with 1 drop of a solution of iodine prepared by dissolving 1 gramme of iodine and 2 grainmes of potassium iodide in a little water and making up to 120 C.C. The drops when spread out on the tile with the finger form a colorimetric scale, ranging from blue to purple and reddish-brown and the colour given by the substance in the first tube is readily matched. C. A. M