摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. 61 Regulator Mixtures Recent Indicators etc. GEORGE STANLEY WALPOLE (Biochem. J. 1914 8 628-639).-The diagram presented in a previous paper (A. 1910 ii 995) has been modified by the inclusion of the data for a number of indicat'ors referred t o in the recent literature. Amongst these reference may be made t o 2 5-dinitroquinol which is of especial interest in that it gives a t a glance the approximate reaction of any solution for which P lies between 3 and 9.5 (c,=lO-3 and Over this range the indicator shows a steady change' of colour. In dilute acid sollutions i t is green and assumes a yellowish tinge a t P,=3. I n neutral solution (PH=7) it is bright reddish-brown and a t P,=9.5 a purple tint is reached which undergoes no change on further addi- tion of alkali.The change from green tot brown is very sharp at P,=3'4 to 4.7 and so is that from brown to purple in the region P,=8*3 to 9.3. The results obtained in recent measurements of the hydrogen-ion concentration of regulator mixtures including acetic acid + sodium acetate hydrochloric acid + sodium acetate and cacodylic acid + Bodium cacdylate are also incorporated in the new chart.ii. 62 ABSTRACTS OF CHEMICAL PAPERS. Incidentally i t has been found that phenolphthalein reacts quite normally as an indicator of the hydrogen-ion concentration even in solutions containing ammonia. Solutions containing (1) sodium dihydrogen borate (2) ammonium chloride + sodium hydroxide which gave the same tint with phenolphthalein were found to have the same hydrogen-ion concentration as measured by the hydrogen electrode method.H. M. D. Estimation of Hydrogen in Gas Mixtures by means of Colloidal Palladium. (2. A. BURRELL and G. G . OBERFELL ( J . Ind. Eng. Chem. 1914 6 992-994).-Results are recorded of the use of Paal and Hartmann's method (A. 1910 ii 237) for estimating hydrogen; the method was found to be trustworthy. W. P. S. Method for Estimating the Critical Moisture Content of Soils. R. 0. E. DAVIS (J. Ind. Eng. Chcm. 1914 6 1008-lolo).- The critical moisture content corresponds with that physical con- dition of the soil when it is most suited for plant growth and for cultivation. The air-dried soil is ground in a mortar just suffici- ently to break up any lumps and is then filled into a brass tube about 1 foot long and 1 inch in diameter; a slit is cut in this tube about half an inch wide and extending almost the whole length of the tube and a strip of celluloid placed over the slit forms a kind of window.The lower end of the tube is covered with a piece of cloth and the tube is tapped until the soil column becomes so solid that the t'op does not break when the tube is placed in a horizontal position. The tube is then placed in water until the soil column becomes wet an inch o r more above the water-level; i t is then removed from the water the wet end is covered with a piece of sheet rubber to prevent evaporation and placed in a hori- zontal position for eighteen hours. The length of the soil column should be such that the dry soil beyond the point t o which the moisture has advanced is at least 2 inches.The tube is now opened and the moisture estimated in a sample taken from the first inch of moist soil next' t o the dry portion. This moisture content represents the critical moisture content of the soil. w. P. s. Very Sensitive Reaction for Hydrogen Peroxide. A. ROUAI (Ann. Chim. Applicata 1914 2 341 ; from Stax. sperim. agrar. itat?. 1914 67 569).-Two or three drops of freshly prepared ferrous sulphah solution a few drops of potassium thiocyanab solution and 5-6 C.C. of ether are mixed in a test-tube. A small amount of the liquid to be tested for the presence of hydrogen peroxide is then shaken with the mixture the ether assuming a colour ranging from pale red to blood-red according t o the content of the peroxide.One-tenth of a c.c. containing 0*0000144 gram of hydrogen peroxide gives a sharp reaction. The ether employed should be as pure as possible and free from oxidation products formed by the action of light. It may be pre- parefd by shaking the ether with ferrous sulphate solution and dis-ANALYTICAL CHEMISTRY. ii. 63 tilling from the latter and is best stored in a coloured bottle in contact with aqueous ferrous sulphate. Simple and Accurate Method for the Estimation of Chlorides in Albuminous Liquids. C. GAZZE~TI (Arch. di FigioZ. 1914 11 81-88 ; from J. SOC. Chem. I m d . 1914 33,1173).-8 small measured quantity of the liquid is diluted with water in a 100 C.C. flask 3 C.C. of 50% ferric alum are added the precipitated ferric albuminate is dissolved by the addition of concentrated nitric acid drop by drop and a measured excess of N/50-silver nitrate is added t o the clear solution; the colloidal matter in the solution prevents the precipitation of silver chloride.The mixture is diluted with water to aboutl 97 c.c. and is then made up to the mark by the addition of concentrated nitric acid. This causes the flocculation of the albumin and the precipitation of silver chloride. The whole is filtered and in 50 C.C. of the clear filtrate the excess of silver nitrate is estimated by titration with N / 50-potassium thiocyanate. T. H. P. c. s. New Apparatus for Use in the Winkler Method for Oxygen Dissolved in Water. HYMAN L. SHOUB (U.S. Byg. Labor. Bull. No. 96 83-85).-An apparatus consisting of a 200 C.C.pipette and a pressure regulator has been designed whereby the water which has been prepared for tilratiori in Winkler’s method can be automatically ‘drawn into the pipette and maintained there in- definitely without contact with the air. By opening a stopcock 200 C.C. of the water are rapidly discharged into any desired receptacle . c. s. Comparison of Methods for the Determination of Oxygen in Waters in the Presence of Nitrites. ELIAS ELVOVE (U.8. Hyg. Labor. BUZZ. No. 96 15-35).-Experimental data are recorded in support of the following stat’ements. Levy’s method of estimating the oxygen dissolved in water containing nitrites is untrustworthy. Hale and Melia’s potassium acetate modification of Winkler’s method gives accurate results when the following precautions are observed.I n the presence of a considerable amount of nitrite the results may be too high if there is not a sufficiently long period intervening between the addition of the potassium acetate and the titration of the iodine. At 20° with a water containing 5 parts of nitrite per million the proper interval is fifteen minutes. Hale and Melia’s explanation of the counteracting effect of the acetate on the nitrite interference is insufficient in view of the fact that an acetic acid medium does not prevent these1 interferences. The r81e of the potassium acetate is to diminish the concentration of the hydrogen ions and an excess of the salt therefore is essential. The permanganate modification of Winkler’s method since i t is aprslicable in the presence of nitrites and organic matter is prefer- able to the acetate modification which counteracts only the inter- ference from nitrites.I n carrying out the permanganate modifi- cation in bottles of about 270 C.C. capacity each bottle should con-ii. 64 ABSTRACTS OF CHEMICAL PAPERS. tain not less than 0.45 gram of potassium iodide and the amount of the excess of potassium oxalate should not be more than 1 C.C. of the 1% solution. R. GAUNT (Ana~?yst 1915 40 9-ll).-The following method is recommended for the estima- tion of sulphur in caoutchouc and vulcanised materials by direct combustion in oxygen and absorption of the resulting sulphur dioxide; the procedure described prevents the formation of any volatile produck which may escape combustion. From 0.2 t o 0.3 gram of tlie sample is placed in a small hard-glass tube closed at one end and this is inserted into the centre of a combustion tube about 35 cm. long.One end of the combustion tube is drawn out and connected with two small absorption flasks each containing 25 C.C. of 20 vol. hydrogen peroxide; a plug of platinised asbestos is placed in this end of the tube. The tube is heated by a burner while a current of dry oxygen is passed through the apparatus the residual mass being strongly heated towards the end of the com- bustion; any carbon deposited on the inner surface of the tube or on the asbestos is burnt by moving the burner along the tube. The sulphur dioxide collected in the absorption flasks may be estimated gravimetrically or by titration with standard alkali solu- tion.I n the case of caoutchouc containing much mineral matter the sulphates in the residual ash must also be estimated. The results obtained by the method agree with those yielded by the Lime-Sulphur Sprays their Composition and Analysis. A. A. RAMSAY (J. Agric. Sci. 1915 6,476-483." Compare ibid. 194). -Calcium disulphide occurs in lime-sulphur solution in addition t o the compounds previously mentioned-calcium hydroxyhydro- sulphide thiosulphate and sulphate and sulphur. The method of analysis is as follows. The concentrated solution (50 c.c.) is first diluted to 500 C.C. Of this 25 C.C. are titrated with N/lO-iodine until the yellow colour is discharged. The number of C.C. usedx 0.0016 and by 0*0028 gives the amount of sulphur and lime re- spectively. The titration is then continued until there is a tinge of yellow.The number of C.C. used ~ 0 . 0 0 6 4 and 0.0056 give re- spectively the sulphur and the calcium as thiosulpha te. The titrated solut'ion is next filtered and the sulphur as sulphate and sulphite est'imated with barium chloride. Another 10 C.C. of the diluted solution is further diluted with aboutl 25 C.C. of water and twice extracted in the usual manner with 10 C.C. of carbon disulphide. The weight of the residue obtained dried a t 70° or less is that of the free sulphur. The total sulphur is estimated in another 10 c.c. to which 6-43 grams of sodium peroxide are added. After a few minutes water (50-75 c.c.) is added and then hydrochloric acid until clear. After adding a few drops of a 15% solution of potassium iodide the solution is boiled diluted to 200 c.c.and precipit'ated with barium chloride. * and J. Eoy. Soc. New South Wales 1914 48 242. c. s. Estimation of Sulphur in Rubber. Carius process. w. P. s.ANALYTICAL CHEMISTRY. ii 6.5 The total calcium is estimated in 10 C.C. of the diluted solution iii the usual manner af ter decomposing the sulphides and thio- sulphates with N / 10-iodine solution and filtering off the sulphur. N. H. J. &I. Estimation of Nitrogen in Steel. L. E. BARTOK ( J . Ind. 8 n g . Chem. 1914 6 1012-1013).-When the nitrogen in &tee1 is converted into ammonia and this estimated coloriinetrically by Nessler’s re- agent it sometimes happens that the test solution and the com- parison solution yield different colorations with the reagent ; there is also a tendency for the solutions t o become turbid.These difi- culties may be overcome by adopting the following procedure the essential point being the preparations of the test and comparison solutions under exactly similar conditions. Forty C.C. of sodium hydroxide solution and 500 C.C. of water are placed in a flask and distilled until &he distillate no longer gives a coloration with Nessler’s reagent. Five grams of the sample of steel are then dis- solved in hydrochloric acid the solution is added t o the contents of the flask and distilled 150 C.C. of distillate being collected. Twenty- five C.C. of standard ammonium chloride solution are then added to the flask and distilled 150 C.C. of distillate also being collected in this case.These two distillates are employed in the colorimetric estimation of the ammonia. w. P. s. Kjeldahl Distillation Apparatus. ARTHUR D. HOLMES (J. Ind. Eng. Chem. 1914 6 1010-1012).-An apparatus is describod for making ten or more distillations atl one time; the bank of condensers is so arranged that each is entirely separate and may be removed without interrupting the action of the others. The water supply t o each condenser is regulated by separate taps as is the gas supply to the burners under the distillation flasks. w. P. s. Modification of Kjeldahl’s Method for the Estimation of Nitrogen in Organic Substances. MAX WUNDER and OCTAVIEN LASCAR ( A m . Chim. anacl. l914,19,329-332).-l?rorn 001 to 0.6 gram of the substance according t o its nitrogen-content is placed in a flask together with 3 grams of oxalic acid 2 grams of sodium oxalate and 0.5 gram of vanadium pentoxide; a mixture consist- ing of 5 C.C.of phosphoric acid (D 1-71) and 25 C.C. of sulphuric acid is added and the contents of the flask are heated gradually until the colour changes from black to greenish-yellow. After cool- ing 100 C.C. of water and about 0.75 gram of fine iron wire are added the solution is heated for about thirty minutes and the ammonia is then estimated by distillation. When the nitrogen in the substance is in combination with oxygen i t is necessary t o introduce iron wire before and after the digestion with the acid mixture. w. P. s. Detection of White Phosphorus i n Matches. EARLE B. PHELPS (U.5”. H-yy. Laboy. Bull. No. 96 5 1-54).-Thorpe’s method (T.1909 95 440) for the qualit,ative separation of white phos- VOL. CVLII. ii. 5ii. 66 ABSTRACTS OF CHE?IIIICAL PAPERS phorus in matches gives satisfactory results but is not sufficiently sensitive for the detection of small quantities and is not sufficiently rapid for the examination of a large number of samples. The author’s method which is based on the volatility of white phos- phorus with steam and its luminescence in contact with oxygen detects 0.1 mg. suspended in 10 C.C. of water. I n a specially designed apparatus which is figured and described a current of hydrogen is washed by alkaline pyrogallol and then is passed through a small jet into boiling water in a test-tube containing ten or twelve match-heads. The gas issues through a fine capillary a t a relatively high velocity (under these conditions the intensity of the glow is increased). The capillary is enclosed in a dark chamber and is viewed through a small microscope. The upper two inches of the capillary are heated electrically t o prevent con- densation but this and also the washing of the hydrogen are refinements which are not necessary in the case of ordinary phos- phorus matches.The method is applicable in the presence of nitrates chlorates hydrogen sulphide (from the so-called phos- phorus sesquisulphide in matches) or carbon disulphide. C. S. The Gravimetric Estimation of Minute Quantities of Phosphorus HENRY STANLEY RAPER (Biochem. J. 1914 8 649-655).-A method is described for the gravimetric estimation of quantities of phosphorus as low as 0-1 mg.It is a rnodificatioii of Ibbotson and Brearley’s method for the estimation of phosphorus in steel (A. 1900 ii 757; 1901 ii 343). After preliminary oxida- tion t o phosphoric acid the phosphorus is precipitated under special conditions as ammonium phospliomolybdate. The molyb- denum in this is then estimated as lead molybdate. The method is rapid and accurate. W. D. H. S treagth of Nitric Acid Period of Extraction and Ignition as Affecting the Gravimetric Estimation of Phosphoric Acid in Soils. 0. L. BRAUER (J. Jnd. Eng. Chem. 1914 6 1004-1005). -All the soluble phosphoric acid is extracted from a soil by nitric acid when the strength of the latter is not less than Zfl; the extrac- tion need not be continued for a longer period than two hours on a steam-bath.The quantity of phosphoric acid soluble in nitric acid decreases when the soil is ignited before being extract’ed; the decrease may amount t o 0.026% of P,O after one hour’s ignition a t a red heat. w. P. s. Blood-Charcoal as a Purifying Agent for Arsenic Solutions Previous to Titration. ROBERT M. CHAPiN (J. I d . Eng. Cltem.. 1914 6 1002-10@3).-Blood-charcoal may be used for decolorising such solutions as used sheep-dip liquids before the arsenious acid present is titrated with iodine solution. The charcoal absorbs a small quantity of the arsenious acid; this quantity is recovered when the charcoal is washed not however as arsenious acid but as arsenic acid. The absorption is proportional t o the weight of the charcoal employed and in the estimation of arsenious acid a correction isANALYTICAL CHEMISTRT.ii. 67 ampplied for this quantity as estimated under the conditioiis obtain- Estimation of Mixtures of Argon and Nitrogen by the Aid of Liquid Air. L. HAMBURGER and H. FILIPPO JUN. (Chan2. Week- blat 1915 12 2-6).-A description of a type of differential vapour-tension thermometer adapted t o the analysis of argon employed in the manufacture of half-watt lamps. The sample under investigation is cooled with liquid air and its vapour tensioii compared with that of a sample of pure argon under the same conditions. A. J. W. ing in the analysis. IV. 1'. s. Estimatian of Radium. I€. SUHLUNDT ( U e t . mtd Chm2. E n y . 1914 12 709-710; from J. Xoc. Chem. Znd. 1914 33 1173).-Iu t'he emanation method which consists in introducing the emanatioii from the ore into a standardised air-tight electroscope or an ionisa- tio'n vessel connected with an electrometer the solution method (fusion with mixed alkali carbonates followed by solution and boiling) of obtaining the ernanation from rocks etc.which do not dissolve in hot acids gives only 70-80% of the values obtained by the fusion method. The latter consists in fusing the ssmple with a suitable flux such as the mixed alkali carbonates in a closed electrically heated furnace ; the liberated emanation is freed from carbon dioxide and collected. Fusion with the mixed alkali carbonates is better than with potassium hydrogen sulphate except in the case of carnotite. Borax as flux gives low results. The emanation is separated com- pletely from uranite by solution in nitric acid and by fusion with ordinary fluxes.c. s. Titration of Silver in Argentum Colloidale and Argentum Proteinicum. A. KORKDORPER (PI~arm. J. 1914 93 809; from Apoth. Zed. 1914).-Argsrctum Colloidale 0.2 grarrr of the buhstance is dissolved in 5 C.C. of water 5 C.C. of dilute sulphuric acid are added the solution is heated slightly and then boiled with the addition of 10 C.C. of 3% hydrogen peroxide solution until colour- less. After cooling 50 C.C. of water are added and the solution is titrated with N / 10-thiocyanate solution in the usual way. Argenturn Proteim-cum 0.5 gram of the substance is heated with 5 C.C. of water and 5 C.C. of dilute sulpliuric acid; 15 C.C. of 3% hydrogen peroxide solution are then added and the mixture is boiled until the colour of the solution is yellow. The cooled solu- tion is diluted with 100 C.C.of water and titrated with N/lO-thio- cyanate solution. w. P. s. Estimation of Peroxide in Commercial Lead Oxide. L. 8. DEAN (Chem. News 1915 11 1 2).-A method described hy Andrews (A. 1903 ii 682) in which the peroxide is decomposed by hydro- chloric acid in the presence of potassium iodide and the excess of the latter tlitrated back with potassium iodate solution using chloro- form or carbon tetrachloride as thO indicator was found t o be trust- 5-2ii. 68 ABSTRACTS OF CHEMICAL PAPERS. worthy. Bunseii inetliod. w. 1’. s. The results obtained a,greed with those yielded by the Volumetric Estimation of Copper in its Salts and in many of its Alloys.G. ZUCCARI (Ann. Chim. Applicata 1914,2,287-290 ; Hall. Chim. Farm. 19 14 53 32 1-323).-0opper may be readily estimated by titration with a standard sodium nitroprusside solu- tion the reaction being expressed by the equation Na,Fe(CN),NO + CuSO yNa2S0 + CuFe(CN),NO If the sodium nitroprusside solution contains 46.866 grams of the crystallised salt (+ 2H,O) per litre each C.C. corresponds with 0.01 gram of copper. When the liquid has almost lost its blue colour a drop is filtered through a thin tight filter paper and yellow ammonium sulphide solution brought into contact with the paper immesiately surrounding the drop. If copper is still present in appreciable proportion in the iiltratle a brownish coloration is formed but witih minimal traces of copper only the yellow colour of the ammonium sulphide is seen.Excess of sodium nitroprussicie gives on the other hand a violet coloration which rapidly dis- appears when the excess is very slight. This method is applicable to commercial copper salts containing salts of iron zinc metals of the alkaline earths etc. The iron should be oxidised to the ferric state by boiling the solution with nitric acid the cold liquid being then titrated in the manner described above since frele nitric acid does not affect the reaction. Zinc salts are without influence a t low concentrations 50 grams of zinc sulphate per litre being necessary to disturb the titration. Sodium nitroprusside does not precipitabe the metals of the alkaline earths manganese aluminium tin lead etc. The method may also be used for the estimation of copper in alloys free from cadmium and nickel but the concentration of the solution of the alloy should not exceeld 2-3%.It serves likewise for the estima- tion of alkali nitroprussides. I f stored in the dark in a bottle of non-alkaline glass fitted with a ground stopper the sodium nitroprusside solution remains un- altered for months ; faint acidification for instance with sulphuri: acid increases the stability of the liquid against the effects of alkaline glass and of light. T. H. P. Volumetric Estimation of Mercury. J. E. CLENNELL (Eng. and Mining J 1914 787-789 ; from J. SOC. Chem. Ind. 1914 33 1173).-Mercury is rapidly and accurately estimated by precipita- ting the hydroxide by an excess of sodium hydroxide dissolving the precipitate in a measured quantity of standard potassium cyanide and titrating the excess of the latter with standard silver nitrate; potassium iodide serves as an indicator the end-point being denoted by the appearance of a yellow turbidity (1) HgO + 4KCN + H20 = KAg( CN) + KNO,.Samples containing mercurous salts can usually be completely dissolved by a preliminary treatment with saturated bromine water. K,Hg(CN) + 2KOH; (2) &Hg(CN) + &NO = Hg(CN)2 +ANALYTICAL CHEMISTRY. ii. 60 The excws of bromine must be completely expelled by boiling before the soldium hydroxide is added. Other metals such as copper nickel or zinc which react with potassium cyanide can be readily eliminated by utilising the insolubility of mercuric sulphide in moderately concentrated nitric acid. The presence of iron obscures the end-point.The iron is oxidised to the ferric state by boiling with nitric acid before the addition of sodium hydroxide; after the standard potassium cyanide has been added the ferric hydroxide is removed by filtration. To obtain accurate results a large excess of potassium cyanide must be avoided. A moderate excess of alkali does not affect the result. The loss of mercury salt on boiling the solution for thirty seconds is 'negligible. c. s. Rapid Estimation of Iron in Industrial Pyrophoric Alloys (Iron-Cerium Alloys). I. BELLUCCI (Ann. Chim. Applicata 1914 2 366-369).-The automatic pocket light'ers now so largely used con- tain an alloy of iron with metals of the cerium group small pro- portions of aluminium manganese zinc copper lead antimony magnesium silicon phosphorus and carbon being present as impuri- ties. The iron present may be estimated as follows 0.2-0-3 gram of t'he alloy is dissolved at the ordinary temperature in a small quantity of concentrated hydrochloric acid gaseous hydrocarbons being evolved and a little carbon and silicon deposited.Hydrogen sulphide is passed through the slightly diluted and gently hented acid solution. The filtered liquid is heated in a porcelain basin on a water-bath until frele from hydrogen xulphide 5-10 C.C. of 3% hydrogen peroxide solution being afterwards added to the liquid which is then evaporated t o dryness. The residue is extracted with water faintly acidified with hydrochloric acid and the iron in ths solution thus obtained estimated iodometrically. T.H. P. Estimation of Cobalt in High-speed Steels. LAWRENCE DUFTY (J. I r o n Steet Inst. 1914 90 52-65).-Neither the cyanide nor the nitrite method gives good results in the estimation of cobalt in high-speed steels. The best results are obtained by the following method. Three grams of steel drillings are dissolved in 50 C.C. of concen- trat'ed hydrochloric acid oxidised with a very slightl excess of nitric acid and evaporated t o a syrup with another 20 C.C. of hydro- chloric acid. After mixing with 5 volumes of 5% hydrochloric acid it is filhered through pulp the tungstic acid being washed with dilute hydrochloric acid. The filtrate is exactly neutralised with ammonia and ammonium carbonate while hot 20 C.C.of 33% acetic acid are added and the boiling solution precipitated with ammonium acetate boiled made up t o 750 c.c. and 500 C.C. filtered through a dry filter. The precipitate contains the whole of the chromium molybdenum and vanadium with the iron. All cotbalt nickel and manganese are left in the filtrate. Any small quantity of iron is removed from the fikate by add- ing 5 C.C. of hydrochloric acid evaporating t o small bulk and pre-ii. 70 ABSTRACTS OF CHEMICAL PAPERS. cipitating with ammonia. This precipitation must be repeated. The united filtrates are neutralised with acetic acid adding 4 C.C. in excess and 15 C.C. of ammonium acetate solution. Cobalt is pre- cipitated by passing a rapid stream of hydrogen sulphide for fifteen minutes The sulphide is washed with water containing ammonium acetate and manganese may be estimated in the filtrate.The cobalt sulphide is dissolved in nitric acid any residue being ignited dissolved and added. The solution is mixed with 20 C.C. of hydrochloric acid and after evaporating to 10 c.c. is diluted and precipitated by adding 1 gram of ammonium phosphate and just enough ammonia to give a slight precipitate in the hot solu- tion followed by 15 C.C. of ammonium acetate after which ammonia is added drop by drop until faintly alkaline. On stirring the flocculent blue precipitate becomes pink and crystalline and is ready for filtration after fifteen to twenty minutes on the water- bath. The ammonium cobalt phosphate is ignited to pyro- phosphate. A minut'e quantity of cobalt remains in the filtrate and may be recovered by means of hydrogen sulphide. Manganese is then estimated in the filtrate.Nickel if presentl is separabed by means of dimethylglyoxime after the acetate separation. The excess of dimethylglyoxime is removed by nitric acid before precipitating cobalt. A Sensitive Test for Chromates. P. N. VAN ECK (Chem. Weekblad 1915 12 6-8).-Addition of a trace of a-napht,hylamine to a solution of pot-assium dichromate and acidification of the mixture with tartaric acid produces an intense blue coloration. The reaction is applicable to the colorimetric estimation of chromates. A. J. W. C. TI. D. Electrolytic Method of Precipitating Tin. L. HUMPHREVILLE (Eng. and Min. J. 1914 98 964; from J SOC. Chern. Id. 19 14 33 1228).-The tin weighing from 0.2 t o 0.3 gram is separated a8 its sulphide; this is dissolved in 16 C.C.of ammonium sulphide 20 C.C. of 40% sodium sulphite solution are added the solution is diluted to 120 c.c. and electrolysed at 60° with a current of 5.5 amperes at 4 volts. Cylindrical gauze electrodeg are used and the electro- IytR is agitated by a stirrer making 600 revolutions per minute; the deposition of the metal is completed in twenty-five minutes. Before use the platinum cathode is coated with copper and tin in succession or with cadmium alone. Impurities present in ordinary ammonia solution interfere with the accuracy of the method; the ammonium sulphids should therefore be prepared by saturating with hydrogen sulphide an ammonia solution (D 0.91) obtained by dissolving ammonia gas in water.The sodium sulphite is employed to render the tin solution colourless. w. P. s. Estimation of Vanadium in Ferro-Vanadium and Steel. 0. WILMS and P. FISCHBACH (Stuhl und Eisen 191 4 34 417-418).- The method of evaporating a solution of the metal in nitric acid with hydrochloric acid and titrating the oxychloride with potassiumANALYTICAL CHEMISTRY. ii. 7 1 permanganate in presence of phosphoric acid a t 80-85*,. gives low results owing to the volatility of the oxychloride. This may be avoided by evaporating with sulphuric acid until fumes are pro- duced in order to convert the oxychloride intlo the non-volatile oxysulp hate. C. H. D. Detection of the Substitution of Denatured Alcohol for Rectified Alcohol. F. RICHARD (J. Pitarm,. Chim. 1914 [vii] 10 429-437).-The test proposed depends on the presence of acetone in denatured alcohol and the detection of this constdtuent by means of the iodoform reaction.Alcohol and acetaldehyde also give the iodoform reaction but the iodoform formation is slow whilst with acetone the reaction takes place immediately. One part of acetone in 10,000 parts may be detected by the test. Denatured alcohol also decolorises potassium permanganate solution but rectified alcohol does so only after some lapse of time. The iodoform test may be used for the detection of denatured alcohol in tinctures essences etc. after any essential oils which may be present have been removed by shaking the diluted sample with ether. w. P. s. Physical Chemistry Applied to Wine. C. MENSTO and E. GARINO- CANINA (Ann. Chim,.AppEicata 1914 2 315-340).-From the results of their experiments and the consideration of those obtained by previous investigators the authors draw the following general con- clusions. I n all wines the strong acids present must be regarded as completely combined and the weak organic acids as partly free and partly combined. Further the combined tartaric acid for example is united with various bases and not solely with potassium so that the official estimation of the hydrogen tartrate and of the free tartaric acid is valueless. The acidity of wine is characterised best by the hydrogen-ion concentration and the acidities of the wines examined are comparable with those of N / 1000-N/ 3000-hydrochloric acid. The concentration of the hydrogen ions serves in the calcuIation of the free and combined proportions of the various acids.Valuable information is furnished also by the curve representing the variation in electrical con- ductivity of a wine the acidity of which is gradually neutralised with baryta the characher of the variation depending on the phos- phates the strong and weak acids and bases etc. From a know- ledge of the constituents of the ash the proportions of each acid combined with the different bases may be deduced. T. H. P. Estimation of Sucrose in the Molames of Beetropte. Method of Inversion by Neutral Double Polarisation. EMILE SAILLARD (Compt. rend. 1915 160 31-34).-1n order to avoid the errors due to the presence of active nitrogenous substances and of salts in the molasses the author suggests the following procedure for deter- mining the percentage of sucrose in the molasses of beetroats. Four times the French normal weight of neutralised molasses are put into a 200 C.C.flask defecated with just sufficient basic leadii. 72 ABSTRACTS OF CHEMICAL PAPERS. acetate the liquid made up t o 200 c.c. and filtered (filtrate I!). To 50 C.C. of this filtrate potassium chloride just equivalent. to the hydrochloric acid to be used for inversion is added the solution made up t o 100 c.c. shaken with a little purified animal charcoal filtered and polarised a t 20° (reading A ) . A second 50 C.C. of li are inverted with 6.8 C.C. of hydrochloric acid ( 2 2 O B) neutxalised with potassium hydroxide cooled to 20° made up t o 100 c.c. clarified with animal charcoal and polarised a t 20° (reading U).Then the percentage of sucrose equals lOO(A + B ) / (coefficient of inversion - i t ) . The amount of hydrochloric acid equivalent t o the sulphuric acid in the sulphated ashes of the French normal weight of molasses is calcu- lated. A pure sucrose solution (2’) of the same polarisation as the filtrate K above is prepared. Fifty C.C. of this solution P are taken and there is added pot’assium chloride equivalent to 8.6 C.C. of hydrochloric acid (D 1-18>; this is made up t o 100 c.c. shaken and polarised at 20O (reading A / ) . To 50 C.C. of P 5 C.C. of hydrochloric acid (D 1.18) are added mixed inverted cooled 3.6 C.C. of hydrochloric acid added neutralised with potassium hydroxide made up t o 100 c.c. shaken and polarised a t 20° (reading B’).Anot’her 50 C.C. of P are taken diluted to 100 c.c. shaken and polarised a t 20° (reading A/’). Then the coefficient of polarisation equals [100(A’+B’) +gtA”]/A//. The resuI$s obtained by this method are about 1*5Yh higher thi111 those obtained by the usual Clerget method but are tlie same as those obtained by Bertrand’s method after inversion and defecx- tion. W. G. The coefficient of inversion is determined as follows. Suppose it t o be 1.8 C.C. of acid (D 1.18). Hydrolysis of Maltose by Hydrochloric Acid under the Herzfeld Conditions. WILLIAM A. DAVIS (J. Ayric. Sci. 1916 6 413-416).-A reply to Kfuyver (Biochem. Xuikerbepd 1914). When heated with hydrochloric acid under Herzfeld conditions maltose undergoes slight hydrolysis amouiitIng to about 2% in 1% solu- tions.When maltose is likely to be present it is therefore prefer- able to employ 10% citric acid. N. I€. J . M. Estimation of Carbohydrates. IV. Presence of Free Pentoses in Plant Extracts and the Influence of Other Sugars on Their Estimation. WILLIAM A. DAVIS and GEORGE CONWORTH SAWYER (J. Agric. Sci. 1915 6 407-412).-Pentoses were found and estimated in the leaves of a number of plants such as mangolds turnips carrot potato etc. The amount can be esti- mated in the usual manner or by the reducing power aft,er fer- mentation. When the amounts of pentoses are small large amounts of other sugars being present’ it is desirable t o ferment the solutions before using the distillation method. N. R. 5. M. New Reaction for Salicylic Acid.P A x t i m ‘~‘OI~TI (/loll. Chim. Farm. 1914 53 dOO).-When heated with a :drop of nitric acidANALYTICAL CHEMISTRY. ii. 73 (U 1.40) a crystal of salicylic acid dissolves giving a yellow colora- tion. Eveii without heating a vigorous reaction commences after some time with development of heat and liberation of nitrogen peroxide ; subsequently the reaction proceeds slowly with evolution of colourless gas bubbles. After the liquid has cooled minute shining lemon-yellow crystals separate which dissolve in water alcohol or ether forming yellow solutions. The latter give an intense red coloration witill aqueous 1% ferric chloride solution the sensitiveness of this reaction being similar to that between ferric chloride and salicylic acid. The yellow colour OF the above aqueous alcoholic or ethereal solution becomes intlensiiied to orange on addition of sodium hydroxide solution subsequent introduction of an acid being followed by gradual return of the original yellow colour. T.H. P. Estimation of ‘( Saccharin ” and of Sodium o-Sulphonyl- aminobenzoate. U. PAZIENTI (Ann. Chim. Applicata 19 14 2 290-294).-GlUckmann’s method of estimating “ saccharin ” (A 1901 ii 588) assumes the absence of impurities other than p-sulphonylaminobenzoic acid but gives good results with “ saccharin ” obtained by precipitating sodium o-sulphonylamino- benzoate in aqueous solution by means of 67; hydrochloric acid. saccharin ” present in commercial sodium o-sulphonylaminobenzoate may be estimated as follows. An excess of 6% hydrochloric acid is added t o a 10% aqueous solution of the salt ( + 2H,O) thel precipitated I f saccharin ” being washed on the filter with the 6% acid until free from sodium and the filtrate evaporated to dryness; the sodium chloride in the dry residue is then estimated either gravimetrically o r volumetrically 58.5 parts of sodium chloride corresponding with 153 parts of “ saccharin.” Another method consists in drying the precipitated saccharin,” collected on a weighed filter and washed as described above a t 60° until no further loss in weight occurs; in this case! however the solubility of the “ saccharin ” must be allowed f o r by increasing the weight found by 0,0403 gram per 100 C.C.of total filtrate and washing liquid. I n sodium o-sulphonylaminobenzoate shown by qualitative’ tests t o bs pure the “saccharin” may be estimated by titrating a neutral solution of the salt with standard silver nitrate solution in presence of a few drops of potassium chromate until the colour of silver chromate appears in the liquid.With a particular sample of sodium o-sulphonylaminobenzoate this volumetric method gave 81.94% of “ saccharin,” tho percentage of ‘‘ saccharin ” found by weighing being 81.78 and the calculatled proportion f o r the pure salt 82.06%. T. R. P. The proportion of Determination of Hubl Iodine Numbers in Alcoholic Solu- tions. Iodine Numbers of Essential Oils. R. MARCILLE (Cornpi. Tend. 1914 159 1004-1007).-Determinations of the Hubl iodine numbers of essential oils in alcoholic solutions gave different results when the concentration of the alcohol or the intensity of tlhe lightii.74 ABSTRACTS OF CHEMICAL PAPERS varied. I n order to obtain concordant and comparable results for this iodine number when working with alcoholic solutions it. is essential that the alcoholic concentration shall always be the same and the reaction must be allowed to take place in the dark. W. G. Rate of Inactivation by Heat of Peroxydase in Milk. SYLVESTER SOLOXON Z~LVA (Biochem. J. 1914 8 656-669).-The temperaturecoefficient for the changel is 2.23 per degree a value of the same order as that for the inactivation by heat of certain lysins and for the rate of coagulation of egg albumin. Below 70° the rate of inactivation is so small that the peroxydase reaction cannot be utilised as a test for “ pasteurisation.” It may however indicatle whether milk has been overheated.Small addi- tions of acid retard and of alkali accelerate the rate. Salls retard the sate both in milk and whey but the1 action is variable and independent of the valencies of their ions. I n both milk and whey the reaction is one of the first order. W. D. H. Determination of the Freezing Point of Fats. J. HARTING and J. VAN DONGEN (Phawn. Weekblccd 1 9 14 5 1 14 15-1 418).-For determining the freezing point of fats and especially of fatty acids the authors recommend the apparatus devised by Polenske (Zeitsch. Nahr. Genussm. 1907 13 758) but consider that his modus operandi would be impro’ved by constant stirring of the liquid and by taking the maximum reading of the thermometer as the freezing point.A. J. W. Estimation of Fat in Fzeces. FRANK C. GEPHART and FRANK A. CSONKA (J. Biol. C h w ~ 1914 19 521-531).-By the Liebermann-SzBkely method a small amount of cholesterol is deter- mined with the fatty acids. The Kumagawa-Suto method is laboriop and difficult; and does not yield good results with pure fats or cholesteryl esters. The method proposed is easy and gives good results; its steps are (1) to saponify with alcoholic potash the powdered or moist material; (2) dilute with water and acidify with hydrochloric acid; (3) extract with ether and wash the ethe’real extract; (4) distil off the ether and dry the fatty acids; (5) dissolve in light petroleum filter and titrate with N/lO-alco- holic potlash. Calculation c.c. N / 1 0 o.oa97 x 100 = tristiearin %.weightl of substance - W. D. H. Estimation of Cineole (Eucalyptol) in Eucalyptus Oil. JOSEPH L. TURNER and RALPH C. HOLMES (Phclrm. J. 1915 94 60-62).-Arsenic acid forms an additive product with cineole and the reaction affords a method of estimating the latter; the com- pound is more stable than the similar one formed with phosphoric acid. Ten C.C. of eucalyptus oil cooled t o Oo are mixed with 10 C.C. of 85% arsenic acid solution the mixtlure is stirred untilANALYTICAL CHEMISTRY. ii. 75 precipitation is complete and then kept at Oo for ten minutes. If a t this point the mixture fo'rms a hard mass indicating an oil rich in cineole 5 C.C. of light petroleum are added. The mixture is then pressed between filter paper until the cineole arsenate is dry and separates readily when touched; the pressing is not complete while the mass remains hard.The cineole arsenate is now decom- posed by heating it with water in a flask provided with a graduated neck and the volume of the cineole is read. I n the case of eucalyptus oils containing less than 25% of cineole the separation of cineole arsenate is not quantitative and it is necessary to add 5 C.C. of pure cineole to the 5 C.C. of oil taken for the estimation. The results obtained by the method are concordant within 2%. w. P. s. Estimation of Non-protein Nitrogan and Urea-nitrogen in Blood. C. G. L. WOLF (J. PhysioZ. 1914 49 89-94).-Modifica- tions of the methods a t present in use (Folin's van Slyke's etc.) are described; the apparatus used is figured. A considerable pro- portion of the residual nitrogen is not in a fo'rm which yields nitrogen with nitroas acid.W. D. H. Estimation of Allantoin in Urine in the Presence of Dextrose. ROBERT HENRY ADERS PLJMMER and RUTH FILBY SKELTON (Biochem. J 1914 8 641-648).-Tbe estimation of allantoin in urine containing dextrose can be effected by Folin's magnesium chloride method if the sugar is first removed. This can be done by precipitation with basic lead acetate and sodium hydroxide if the proportions are 2C,H,,O 5[Pb(OH),,PbAc2] 1ONaOH. W. D. H. Characteristic Reaction8 of Phenylalanise. L. CHELLE (Ann. Chirn. anal. 191 4 19 109 ; from Bull. SOC. Pharm. Bordeaux 1913). -An orange coloration is obtained when a solution of phenyl- slanine in concentrated sulphuric acid is treated with a drop of formaldehyde solution ; the colour changes rapidly to brown.When a solution of phenylalanine in sulphuric acid is mixed with a drop of a solution of paracetaldehyde in 90% alcohol a lemon- yellow coloration develops within about ten minutes ; this colora- tion increases gradually in intensity and after one hour exhibits a green fluorescence. The reaction with paracetaldehyde may be used for the colorimetric estimation of phenylalanine. W. P. 8 DeteGtion of Cocaine. G. DENIGES (BUZZ. 8 ~ . Pharwz. Bordeaux 52 385; from Zeitsch. anal. Chern. 1914 53 407).-If a 0.5% solution of a cocaine salt is treated with an equal volume of a 5% solution of sodium perchlorate a precipitate composed of long very fine needles is formed; with very small quantities the pre- cipitation is observed under the microscope.New Test for Morphine. T. H. OLIVER (Chem. and Druggist 1914 85 45; from The Xed. Chronicle).-If a morphine solutionii. 76 ABSTRACTS O F CHEMLCAT PAPERS. is treated with a few C.C. of liydrogen pcroxide mil :I srtiall quantiby of concentrated ammonia arid then stirrctl with a piece of copper wire the previously colourless solution assumes a deep port-wine tint; there is also a considerable evolution of gas. The test is stated to be capable of detecting as little as 0.02 mg. of morphine but in dealing with very small amounts a few drops of potassium cyanide solution should be added before the copper wire is introduced. Conversely the reaction is also a sensitive test for copper. Methylamine may be substituted for the ammonia in the test but not dimethylamine or sodium hydroxide.Codeine and dionine (methyl- and ethyl-morphine respectively) which cannot be distinguished from morphine by the usual tests do not give the reaction ; apomorpliine yields an orange coloration but negative results are obtained with strychnine brucine atropine narcot,ine heroine cocaine nicotine cephaeline emetine veratrine physo- Detection of Oxymorphine in the Presence of Morphina. L. GRIMBERT and A. LECLBRE (J. Pharm. Chim. 1914 Lvii] 10 425-428).-When a solutlion containing oxymorphine hydro- chloride is treated with two drops of 1% potassium ferricyanide solution and two drops of sodium acetate solution a turbidity or preeipitatle is produced; this test will detect the presence of 1 part of oxymorphine in 20,000 parts of solution and the reaction is nob given by morphine codeine thebaine apomorphine quinine strychnine brucine atropine o r caffeine. If the precipitate is collected dissolved in hydrochloric acid and the solution neutralised with sodium carbonate the precipitate is formed again but dissolves in an excess of sodium carbonate; an excess of potassium hydrogen carbonate does not however dissolve t’he pre- cipitlate. Pure oxymorphine yields a red coloration when treated with sulphuric acid and formaldehyde; the] addition of a trace of potassium ferricyanide changes the colour to bright green. The violet colorat,ion obtained when morphine is treated with sulphuric acid and formaldehyde is not affected by the presence of potassium stigmine pilocarpine and coniine. w. P. s. f erricyanide. w. P. s. Quantitative Extraction of Diastases from Plant Tissues. R. W. THATCHER and GEO. P. KOCH ( J . Amer. Chem. Soc. 1914 36 2542-2543).-A reply t o Hulton’s criticisms (AnaJyst 191 4 39 260) of the authors’ paper (A. 1914 ii 508). E. G.

ISSN:0368-1769    

DOI:10.1039/CA9150805061

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 67 The Respiratory Exchange in Fresh-water Fish. 11. Brown Trout. JOHN ADDYMAN GARDNER and CONSTANCE LEETHAM (Biochem. J. 1914 8 591-597. Compare A. 1914 i 1149).- Brown trout are asphyxiated by water the oxygen content of which is sufficient t o keep roach alive. I f the water is saturated with oxygen the consumption of oxygen by trout is doubled by a rise of loo. Hence they pump more water through their gills a t the higher temperature. The extra work done in respiration is a factor which has to be also taken into account. W. D. H. The Solubility of Oxygen in the Serum of Limulus poly- phemus L. and in Solutions of Pure Limulus Hernocyanin. CARL L. ALSBERG and WILLIAM MANSFELD CLARK (J. Biol. Chem. 1914 19 503-510).-The serum of Limulus under diminished pressure sets free about as much oxygen as distilled water or sea water under similar conditions.A 10% solution of hzemocyanin which cont'ains about three times as much hxmocyanin as the serum liberates about 20% more. This increase is too slight t o warrant the assumption that hzmocyanin is an oxygen carrier. This contrasts with the results of Henze on Octopus blood. The Limulus hEmocyanin may however be more efficient in this direc- tion than the gas analyses reveal since its combination with oxygen doe@ not dissociate appreciably a t low pressures. With the aid ofi. 68 ABSTRACTS OF CHEMICAL PAPERS. the copper of the pigment oxygen may perhaps be catalytically transferred t o the tissues within the body. W. D. H. The Water Content of the Blood.E. I?. TERROINE (Bull. Xoc. chim. 1914 [iv] 15 152; from Compt. rend. SOC. Biol. 1914 76 523).-The normal organism in the case of the dog maintains its water content of the blood constant variatioiis of 5% being excep- tional. The digestive processes have but very slight influence on the hydremic constant. On the other hand during inanition the water content of the blood varies the direction of these variatioiis being different in different animals. Inactivation of Complement by Shaking HANS SCHMIDT ( J . Hygiene 1914 14 417-436).-Shaking produces alterations of the physical conditions in the serum which account for the loss of complementing power it undergoes. The conception that the complement is a ferment is unnecessary although it is admitted that this is not yet fully proved.W. G. TV. D. H. Berkefeld Filtration of Complement. HANS SCHMIDT (J. Hygiene 1914 14 437-452).-In the Berkefeld filtration of fresh guinea-pig serum adsorption on the filter surface takes place and the serum passes unaltered if the saturation of the adsorbing surface has become complete. The adsorption involves most probably the albumins first ; this secondarily influences the filtrability of the globulins. The physical conditions of the serum as regards salt concentration and dilution as well as hydrogen-ion concentration modify the effect of filtration t o a great extent. Mf. D. H. Influence of Polyhydric Phenols and Phenolcarboxylic Acids on the Diastatic Hydrolysis of Albuminoids by Pepsin in Presence of Acid LUIS QUGLIALMELLI (Anal. SOC.Quim. Argentina 1914 2 186-195).-A study of the inhibitory action exerted by phenol dihydric and trihydric phenols and salicylic gallic and tannic acids on the process of digestion. The exbent of the influence is conditioned not only by the nature of the substituents attached to the nucleus but also by their relative position. A. J. W. The Metabolism of the Salivary Gland. I. The Nitrogen Metabolism of t h e Resting Gland. C. G. L. WOLF and J. BARCROFT (J. Piwsiol. 1914 49 95-108).-1n five out of eight experiments on the dog’s submasillary gland the gland took more non-protein nitrogen from the blood than it contributed t o it; in one there was equilibrium and in the remaining two1 there was a balance towards the blood. The maximal amount taken up was 0.18 mg. of nitrogen per gram of gland per minute.I n three of six experiments no urea-exchange occurred; in one the blood and in two the gland acquired urea; the maximum urea- exchange was 0.014 mg. per gram of gland per minute’; the main exchange is therefore in ‘‘ residual nitrogen.” The maximal differ-PHYSIOLOGICAL CHEMISTRY. i. 69 ence in composition between the arterial and venous bloods in non- protein nitrogen was 5.5 k0.8 mg. per 100 C.C. of blood. W. D. H. Fatty Acid Metabolism in the Liver. 111. Fatty Acid Infiltration of the Liver During Pregnancy and Lactation. R. COOPE and V. H. MOTTRAM (J. PhysioE. 1914 49 23-33. Com- pare A. 1910 ii 525).-In cats without' previous dieting fatty infiltration of the liver was found in both pregnant and non- pregnant animals. I n rabbits kept on an ample diet a decided increase in the fat' of the liver occurred at or about the time of parturition.This confirms the view that the change is physio- logical rather than pathological. TV. D. 13. Endogenous Uric Acid Metabolism. G. W. EAims 11 DUBIN and A. 1. RINGER (J. Biol. Chem. 1914 19 473-485).-0n a meat- free diet the outputl of uric acid in ten people was found t o be much lower than previously accepted ; during rest this remained nearly constant par diem. It is raised by work or protein food I n changing diets a t least a week must elapse before the true value of the output becomes constant. I f the diet is also nuclein-free the output drops to half of what$ occurs on a vegetable diet (0.04 gram per day).The small values render the investigation of endogenous uric acid metabolism very difficult. The Influence of the Vagus on Pancreatic Secretion. G. VON AUREP (J. PhysioE. 1914 49 1-9).-Evidence is adduced thst apart from the action of the chemical stimulus the vagus nerve contains secretory fibres (paralysed by atropine) which affect the pancreas. I n these experiments any entrance of acid chyme into the duodenum was prevented by ligaturing the pylorus. There are also secreto-inhibitory fibres. The secretion of the juice provoked by secretin is stopped by stimulation of the vagus. Both sorts of fibres are equally distributed in all branches of the nerve. The latent period is always a long one and sometimes no secretion appears until after several stimulations have been applied and even then the effect is a small one compared with that produced by secretion; and the experiment of stimulating the vagus always fails to produce any secretion a t all unless the spinal cord has been divided without injury t o the bulb.The Existence of Philothion in the Lens of the Eyes of Animals. J. DE REY-PATLHADE (Compt. rend. 1915 160 37-38).- The author has shown philothion t o be present in the lens of the eyes of cows calves sheep horses pigs rabbits of a cephalopod Octopus vulgaris and in the lens of his own left eye operated on eight months previously for cataract. This fact places the tissue of the lens in the same category with striated muscle. The Action of Poisons on Reductase and Attempts to Isolate the Enzyme. DAVID FRASER HARRIS and HENRY JERMATN W.D. H. W. D. H. W. G. MAUDE CREIaHTON (Biochem. J. 1914 8 585-590).-The reductasei. 70 ABSTRACTS OF CHEMICAL PAPERS. of pigeon’s liver and muscle is soluble t o some extent in normal saline solution and in a mixture of normal saline and glycerol but not in pure glycerol. All attempts to isolate the enzyme failed. The poisonous action on the enzyme of ten substances chosen a t randosm was investigated. W. D. H. The Distribution of Arsenic in a Human Body. FRANK P. UNDERHILL (J. Biol. Chem. 1914 19 513).-The body was exhumed three months after death in a medico-legal case. A table is given of the amount of arsenic in the various organs. A new feature brought out is that significant quantities were obtained from the brain and spinal cord.The case was one of chronic poisoning. W. D. H. The Presence of So-called c complement'' in Milk. R. TANNER HEWLETT and CECIL REVIS (J. Hygiene 1914 14 481-497). -Milk always contains a ‘‘ complementary substance.” This is specially abundant in colostral and mastitis milks; in the latter ambocepto,r may be present as well. No relation between the amount of complementary substance and cellular elements in the milk could be traced. This hzemolytic system is of great delicacy. The true nature of milk “complement” is doubtful. W. D. H. The Excretion of Creatinine in Man on a Prolonged Creatine- free Diet. A. I. RINGER and G. W. RAIZISS (J. B i d . Chem. 1914 19 487-492).-1n four people Kept on prolonged creatine- and creatinine-free diet the excretion of creatinine dropped 10 or 22%.Tables of the daily output are appended. W. D. H. The Isolation of p-Hydroxyphenylacetic Acid from the Urine in Disease. N. MUTCH (Proc. physiol. Soc. 1914 ; J Physiol. 49 ii-iii).-In diseases of the alimentary tract where there is delay in the passage of food hydrophenolic substances were deteckd in the urine (seventy cases) by applying Millon’a test to an ethereal extract of acidified urine. Normal urine gives no such reaction. I n one case p-hydroxyphenylacetic acid was separated from the urine. Six litres were acidified with sulphuric acid and extracted with ether. The extract was evaporated a t room temperature and the residue’ extracted with chloroform which was also slowly evaporated. The residue was dissolved in 5% sodium carbonate filtered acidified refiltered and extracted with ether.The ether was evaporated as before and hippuric acid removed by cold benzene to which a little chloroform had been added. The final residue was repeatedly recrystallised from boiling benzene and found to consist of flat needles melting a t 148O and when mixed with synthetic p-hydroxyphenylacetic acid at 148.5O. The excreted acid doubtless arises from tyrosine in the intestine an intermediate stage produced by bacteria being p-hydroxyphenyl- ethylamine. W. D. H.PHYSIOLOGICAL CII EMISTRY. i. ?1 The Respiratory Exchanges of the Heart in the Diabetic Animal. E. H. STARLING and C. L. EVANS (J. Ph~piO?. 1914 49 67-88).-Experiments with the heart-lung preparation show that the normal dog's heart uses 3-52 C.C. of oxygen per gram when doing moderate work and the respiratory quotient is 0.85.It is calcu- lated that on a mixed diet the heart uses about 1.6 mg. of carbo- hydrate per gram per hour; the lung uses not more than 0.5 mg. of sugar per hour. The respiratory quotient of the heart in pan- creatic diabetes is 0.71 and this is not raised by the addition of dextrose o r in the acceleration produced by adrenaline. This indicates a depression of the utilisation of carbohydrate by diabetic tissue but there are also other modifications of tissue metabolism which might mask moderate carbohydrate consumption. The oxygen usage by the diabetic heart is the same as in the normal state. The normal heart does not alter its metabolism when fed with diabetic blood; the diabetic heart is also unchanged when fed on normal blood.Acid extracts of pancreas act on the normal heart like adrenaline. The effects on the diabetic heart are similar but prolonged rises of the respiratory quotient have been obtained. W. D. I€. Liver Nitrogen in Anaphylaxis. GEORGE BARGER and HENRY HALLETT DALE (Biochem. J. 1914 8 670-679).-The Htatement of Hashimoto and Pick (A. 1914 i 769) that the liver and spleen in anaphylaxis contain exceBs of non-coagulable nitrogen appeared to be rich in promise for further work. The authors' desire to work along these lines has however been frustrated by a complete failure to corroborate the findings of Hashimoto and Pick. W. D. H. The Destiny of Chloralose in the Organism and its Relation- ships with the Glycuronic Conjugation.Rf. TIFFENEAU (Compt. rend. 19 15 160 38-4 1 ).-The administrat ion of chloralose t o a dog either by way of the mophagus or by injection into the peritoneum results in an elimination of a portion of this substance unchanged in the urine. A t the same time there is excreted in the urine another organic chloro-derivative which has been shown to be a chZoraJose-glycuronic acid having the constitution Neither the acid nor its salts could be obtained in a crystalline state but on hydrolysis chloralose and glycuronic acid were isolated as the only products. From urine this compound is not precipitated by normal lead acetate but almost entirely by ammoniacal lead acetate. The formation of this compound does not support the hypothesis of Sundwick and Fischer on the mechanism of the glycuronic conjugation since according to their views chloral and trjchloroethanol should have been amoagst the products of hydrolysis.Chlo'ralow does not decompose in thei. 72 ABSTRACTS OF CREMICAL PAPERS. animal organism into chloral and dextrose but' the physiological effects produced by its administration are due t o the chloralose as such and not to any liberated chloral. w. G . Behaviour of Ethylurethane Piperonaldehyde and Piper- onylidenebisurethane in the Organism. G. BIANCHI (BoEI. Chini. Farm. 1914 53 324-335).-0ne thousand grams of water dissolve 0.0649 gram of piperonylidenebisurethane (compare A 1913 i 482) a t 11*5* and 0.762 gram a t looo. Owing perhaps t o its slight solubility this comp oun d ex hi b i t s 1 it t 1 e physiological activity a n d functions as a mild hypnotic capable of producing sound although not too deep sleep but not of depressing the cardiac or respiratory functions. This act'ion is partly due t o the slow absorption of small proportions of nascent ethylurethane gradually liberated together with piperonaldehyde in the organism ; the aldehyde may possibly intensify the hypnosis but has no further appreciable effect. Administration of piperonylidenebisuretliane occasions also the formation of an excessive proportion of carbamide and the biochemical synthesis of two conjugated glycuronic acids one from the ethylurethane and the other from the piperonaldehyde. T. ir. P.

ISSN:0368-1769    

DOI:10.1039/CA9150800067

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i. 72 ABSTRACTS OF CREMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Protective Action against Magnesium Carbonate of Calcium Carbonate for Azotobacter chroococcum. CHAS. 13. LIPMAN and PAUL S . BURGESS (J. Agric. Sci. 1915 6 484-498).-In man- nitol solution cultures of A . chroococcum calcium carbonate acts only as a stimulant and is not toxic in concentrations of 2%. Mag- nesium carbonate under similar conditions is toxic in concentra- tions in excess of 0*1-0*2%. I n soil cultures calcium carbonate up t o 1.4% of the dry weight of the soil has no effect; higher amounts have a slightly toxic effect; in a sandy soil. I n this soil nitrogen fixation is almost ~omplet~ely inhibited by 0.1% of magnesium carbonate; this is due t o the magnesium and not to its alkalinity which is beneficial. I n solution and in soil cultures calcium carbonate has a pro- tective action against the toxic effect of magnesium carbonate. I n solutions the besb ratio is CaCO,/MgCO,= 6 1 when the absolute values are 0.2% and 1.25% respectively of magnesium and calcium carbonates. I n soil cultures the best ratio seems to be 15 1 when 0.1% of magnesium carbonate is present. N. H. J. &f.

ISSN:0368-1769    

DOI:10.1039/CA9150800072

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i. 73 Organic Chemistry. A Method of Determining the Constitution of the Mono- glycerophosphoric Esters and the Constitution of Crystalline Sodium Glycerophosphate. L. GRIMBERT and 0. BAILLY (Compt. rend. 1915 160 207-210 ; compare Carre A. 1912 i 155 ; Paolini A. 1912 i 826).-The authors hrve devised a chemical method of determining whether sodium glycerophosphate and monoglycero- phosphoric esters in general are a-esters (formula I.) or p-esters (formula II.) PO(ONa),*O*CH,*CH(OH)*CH2*OH PO(ONa),*O*CH(CH2*OH)2 I. 11. An a-ester on oxidation in the absence of all hydrolysis should give a compound of the type R*CO*CH,*OH which can be character- ised by Denigh’s reactions (compare A 1909 ii 272 273 353). This test has been applied to the crystalline sodium glycerophosphate obtained by Pouleoc’s method and to the uncrystallisable salt ob- tained a t the same time.The oxidising agent used was bromine water containing 0.25% bromine the oxidation being eeected in the cold to avoid any hydrolysis by the nascent hydrogen bromide. The oxidation product from ‘the crystalline salt gave neither of the Denigba’s reactions whilst that from the uncrystallisable salt gave both the reactions. PO,Na C,H (0 H ) ,5 H,O is therefore a salt of the P-acid and its constitution is represented by formula 11. W. G. Crystalline sodium glycerophosphate The Preparation of Some Esters. F. BODROUX (Compt. rend. 1915 160 204-207).-0n slowly distilling a mixture of formic acid ethyl alcohols and water ethyl formate was obtained the yield-of t h e ester diminishing as the amount of water present was increased.Attempts were made t o use formic acid as catalyst in the esterification of acetic acid but its influence was found to be far less than that of oxalic acid or of picric acid. The author has prepared the corresponding alkyl bromides from ethyl propyl isobutyl and allyl alcohols by distilling them with the hydrate of hydrogen bromide HBr,5H20. I n these reactions the yield was greatly increased except in the case of allyl alcohol by replacing the hydrogen bromide hydrate by a mixture of this hydrate with sulphuric acid obtained by passing sulphur dioxide iuto a mixture of bromine and water in suitable proportions until it was just decolorised. The yields obtained by this method varied from 75-90% of the theoretical amount.isoButyl alcohol gave a mixture of primary and tertiary isobutyl bromides. W. G. Preparation of E thy1 Acetate from Acetaldehyde. CON- SORTIUM FUR ELEKTROCHEMISCHE INDUSTRIE (D.R.-P. 277 188. Add. to D.R.-P. 277187; from J. SOC. Chem. Ind. 1915 34 152).-1n the VOL. CVIII. i. hi. 74 ABSTRACTS OF CHEMICAL PAPERS. preparation of ethyl acetate from acetaldehyde by the process described in the chief patent (this vol. i 3) the aluminium alkyl- oxide catalyst is used in solution preferably in ethyl acetate. The aldehyde may be added to the solvent used for dissolving the catalyst. c. s. The System Lead Oxide-Acetic Acid-Water. SHIGEHISA SAKABI (Mem. CoZl. Xci. Kyoto 1914 1 57-61).-A systematic examination of the equilibrium relations a t 25' has shown tbat the only solid compounds which cam exist in contact with solutions a t this temperature are the normal salt Pn(C,B,0,),,3H20 and the basic salts Pb(C,H,O,),,Pb(OH) and Pb(C,H,0,),,2Pb(OH)2. The solution in equilibrium with the first two compounds has the composition-water 86.90% acetic acid 7*92% lead oxide 5*lS% whilst that of the solution in equilibrium with the two basic salts is water 85*59% acetic acid 7*26% lead oxide 7*15%.The complete data are utilised in the con- struction of a triangular graph which shows clearly the general nature of the solubility relations. H. 15. D. Oxidation of Oils and Fatty Acids. J. HYLAND and L. L. LLOYD ( J . Xoc. CAem. I 7 d 1915 34 62-65).-The object of the investiga- tion is the valuation of the partially hydrogenated oils which are being placed on the market as substitutes for olive oil for use in the worsted trade etc. The production of sulphuric acid by the action of sulphur dioxide and oxygen on oils for a definite time a t a constant temperature is constant for some oils but f w many others particularly those which char i n contact with sulphuric acid concordant results cannot be obtained.The yield of sulphuric acid is greatly increased in the presence of a drier the increase varying with the amount and the nature of the drier The order of activity calculated from the produc- tion of sulphuric acid of the metals which have been tested when dissolved as reainates in the oils is as follows-copper cobalt man- ganese nickel chromium and iron It has also been observed that the addition of small amounts of oxidisable oils to " non-drying oils " greatly increases the rate at which these oils absorb oxygen and affects the amount of sulphuric acid formed by the action of sulphur dioxide and oxygen.The authors have made a series of experiments in which oleic acid ethyl oleate and olive oil each alone and also in the presence of 5% of manganese resinate have been oxidised in a current of air (usually moist air at SO') until the maximum increase in weight has been attained ; the iodine values have been determined before and after the oxidation. The results show that the ratio between the increase in weight and the diminution in the iodine value corresponds with 0 = I and also that the oxidation products of ethyl olehte and of olive oil are more stable than those of oleic acid.I n connexion with the preceding a comparison has been instituted between the iodine value of an oil and its liability to firing. It appears t h a t the iodine value is of little use as a guide to liability to firing. Although firing is due primarily to oxidation it is affectedORGANIC CHEMISTRY i. 75 by other factors such as acidity the constitution of the fatty acids and the decomposition of the oxidation products. Ethyl oleate is far safer than the free acid probably on account of the greater stability of i t s oxidation products. The most dangerous oils are those the oxidation products of which are most easily decomposed or polymerised. c. s. Polyrnerised Drying Oils. R. S. NORRELL (J. SOC. Chem. Znd. 1915 34 105 -109).-Variou~ drying oils have been thickened by heating usually in an atmosphere of carbon dioxide to avoid oxida- tion ; for example linseed oil has been heated at 260-280" for tmenty- eight to sixty hours and tung oil (Chinese wood oil) at 240' for twenty minutes.The density refractive index molecular weight (in benzene) acidity saponification value iodine number and percentage of glgceryl in t h e thickened and unthickened oils have been deter- mined. Also the methyl esters prepared from thickened linseed oil by Ball's method have been examined. The followiog conclusions have been drawn from the data thus acquired. (1) Linseed and poppy-seed oils contain mixed glycerides of variable amounts of unsaturated acids in addition to small quantities of saturated glycerides the acids being interchangeable and their amounts are dependent on the sources and probably on the ripeness of the seeds.(2) Thickening by polymerisation without change in chemical composition OCCUI*S when there are at least two pairs of doubly linked carbon atoms in the molecuies of the acids OF the glycerides. (3) Before polymerisation occurs there is a shifting of the linkings in the molecule and in the case of tung oil there is some slight evidence of ring formation (4) Thickening is due to polymerisation of the mixed glycerides and the first stage is the formation of a product insoluble in acetone which may be a double molecule of linked glycerides in the case of linseed oil or a quadruple molecule in poppy-seed oil. (5) The change depends on the temperature and equilibrium is established when 50% of the modification has been formed.( 6 ) A t higher temperatures the final stage is the formation of a polymeride insoluble in light petroleum which seems. to be determined in linseed oil by the linolenic acid glyceride. A comparison of the properties of olive oil and heated olive oil shows that the evidence of isomeric change in a non-drying oil is very slight c. s. Ammonium Citrate. ROBERT A. HALL (J. Ainer. Chem. sbc. 1915 37 208-216).-A quantitative yield of normal ammonium citrate (NH,),C,H507 can be readily obtained by passing dry ammonia into a boiling solution of anhydrous citric acid in absolute alcohol. The salt thus prepared is crystalline and stable; it is very soluble in water but catinot be recrystallised from aqueous solutions.When a saturated solution cooled by means of a mixture of ice and Falt is poured into absolute alcohol similarly cooled a mass of long slender crystals is obtained which probably consists of ammonium citrate with one or more molecules of water of crystallisation. Aqueous solutions of normal ammonium citrate give an alkaline reaction with rosolic h 2i. 76 ABSTRACTS OF CHEMICAL PAPERS. acid. A solution D20 1.09 can be substituted for the so-called neutral " ammonium citrate solutions employed in estimating the insoluble phosphabs in commercial fertilisers. E. G . Esters and Unimolecular p- a n d y-Lactones of d-Mannonic and d-Gluconic Acids ; o-Bis-d-galactonic Acid d-Galactono-7- lactone and its Monohydrate. OSCAR F. HEDENBURG (J.Amer. Chem. SOC. 1915 37 345-372).-A detailed account is given of certain experiments the chief results of which have already been recorded by Nef ( A . 1914 i 491 492 497). Ethyl d-mannonate has m. p. 160-1 61'. d-Glucono-P-lactone has m. p. 153" and [u] + 63.4" after it has been in solution for five minutes. Ethyl d-gluconate has m. p. 62-63". d-Glucono-y-lactone has m. p. 134-136' and [u] +67*52' after it has been in solution for nine minutes. d-Galactono-y-lactone has rn. p. 108-1 11" and [aE - 76.97' ; the monohydrate has m. p. 66' and [a] - 70.1'. E. G. Biochemical Synthesis by Means of Emulsin of the P- Monoglucoside of Ordinary Propylene Glycol. EM. BOURQUELOT M. BRIDEL and A. AUBRY (CompC. rend. 1915 160 214-216).- Propane-ap-diol has been converted into its monoglucoside by dissolv- ing in i t one quarter OF its weight of dextrose adding a little water and some ewulsin and allowing the mixture to remain for six mooths at 33'.A t the end of this time it was heated on a water-bath for twenty minutes and then the water and unchanged glycol distilled off under reduced pressure. The unchauged dextrose was removed from the residue by solution in water and fermenting with top yeast. The residue finally obtained after this treatment still contained some unchanged glycol which was removed by five successive extractions with ethyl acetate. Attempts to obtain the colonrless transparent residue in a crystalline form by precipitation with ether from alcoholic solution were unsuccessful. So purified however i t had [a] - 30-32" and analysis showed it t o be a monoglucoside.I t was readily hydro- lysed either by dilute sulphuric acid or by emulsin in aqueous solution the product being in each case i-propane-up-diol. W. G. Diverse Colloidal States of Starch. MAX SAYEC (Intern. Zeitsch. phys.-chem. Biol. 1914 1 173-188. Compare A. 1912 ii 144; 1913 i 17 1155; 1914 i 930).-A summary of work previously published. H. W. B. Oxycellulose. WILDER D. BANCROFT (J. Physical Chem. 19 15 19 159-168).-Experiments have been made t o ascertain to what extent the properties of oxycellulose or the oxycelluloses differ when prepared by the action of nitric acid permanganate chloric acid and bleaching powder on cellulose. The results obtained afford no evidence for the existance of three different oxycelluloses.The substance described as a-oxycellulose is appareu tly unchanged cellulose more or less contami- nated with certain products oE decomposition. Except in regard toORQAXIC CHEMISTRY i. 77 the degree of agglomeration p- and y-oxycellulose appear t o be identical. None of the above oxidising agents gives a completely oxidised product and it ia doubtful whether a pure oxycellulose has as yet been obtained. The reducing action on Fehling's solution is not a characteristic of oxycellulose but is probably due to other products of the oxidation reaction. Experiments with a number of metallic mordants indicate that these are not absorbed to any large extent. H. M. D. Introduction of the Guanidine Nucleus into the Molecule of Polypeptides. I. AKTONINO CLEMENTI (Gazzetta 1915 45 i 56-59).- Glycocyamylglycine NH C( NH,)-NH*CH,* CO*NH* CH a* CO,H pre- pared by the action of cyanamide on glycylglycine in presence of ammonia forms microscopic white needles which turn brown a t 218-220' and decompose at about 235'. It yields negative results with the biuret reagent and with sodium nitroprusside. T. H. P. Complex Ions of Nickel a n d Cobalt with Cyanogen. G. ROSSI (Gazxetta 1915 45 i 6-lO).-The maximal electrical conductivities attained on gradual addition of potassium cyanide solution t o solutions of nickel and cobalt chlorides correspond with the formation of the complex ions Ni(CN) and Co(CN) the salts formed having the formulae K,Ni(CN) and K,Co(CN) respectively. T. H. P. Melting Point of 2 4 6-Trinitrotoluene.WILLIAM RINTOUL (J Soc. Chem. Ind. 1915 34 60-61).-Values between 78.85' and 82' have been recorded by various observers as the m. p. of 2 4 6- trinitrotoluene. The author has obtained the following values using carefully purified materials and recrystallising each nitro-compound until the m. p. of the last crop of cryc-tals is the same as that of the solid obtained by evaporating the mother liquor p-nitrotoluene m. p. 51*6-51*9'; 2 4-dinitrotoluene m. p. 69-9-70.2O ; 2 4 6-trinitro- toluene m. p. 80°80-80*850. The most efficient method of purifying commercial trinitrotoluene is crystallisation from alcohol or benzene. c. s. Action of Chloral Bromal and Benzaldehyde on the Poly- cyclic Hydrocarbons in the Presence of Aluminium Chloride. 11. G B. FRANKFORTER and W.KRITCHEVSKY (J. Amer. Chem. h'oc. 1915 37 385-392),-1n an e ~ r l i e r paper (A. 1914 i 1059) it has been shown that in presence of aluminium chloride chloral reacts violently with benzene and its derivatives at the ordinary temperature whilst at low temperatures a condensation takes place. The study of this reaction has now been extended to the polycyclic hydrocarbons. Chloral reacts very energetically with naphthalene but if the temperature is not allowed to rise above 0' a nearly quantitative condensation is effected with formation of a mixture of dichloro-aa- dinaphthylethylene C(CI0H7) CCI m. p. 147-148" and dichloro- p/l-dinaphthplethylene m. F. 219'. By the action of bromal on naphthalene at 0" in presence of alu-i. 78 ABSTRACTS OF CHEMICAL PAPERS.minium chloride dibromo-PP-dinaphthylethylsne C(Cl,H7),:CRr m. p. 223-225' is produced which forms colourless crystals. By the action of chloral on anthracene in presence of aluminium chloride and light petroleum PP-dichZorodiccnt?wpZeth$ene C(C,,H9)2 CCI 2 is obtained as a brownish-yellow powder. When heated it darkens and begins to decompose at 340'. If benzene is employed instead of light petroleum a different reaction occurs and PP-dichZom-9 10- anthrenylethylerw C,,H,:U:CCI is produced as a yellow amorphous powder. When carbon disulphide is used as the solvent a third reaction takes place with production of PPP-trichloro-9 lO-anth?*enyZ- etharie C,,H,:CH*CCI which forms a ye\lowish-brown powder. When anthracene is treated with brornal in presence of aluminium chloride and carbon disulphide PPP-tribron7o-9 1 0-anthyen ylsthane C,,H8:CH*CBr is obtained as a chocolate-brown powder which does not melt at 360'.By the action of chloral on phenanthrene in presence of alurniniiim chloride and carbon disul phide PPP-trichloro-9 1 O-pkena?zthrenylethane C,,H,:CH*CCI is produced as a yellow powder without a definite rn. p. PPP-Tribrorno-9 1 0-phenanthrenylethane C,,H,:CH-C Br3. formed by the action of bromal under sitnilat. conditions IS a yellow powder which can be heated at 300' without change. By the action of benzaldehyde on phenanthrene in presence of alu- micium chloride and carbon disulphide there are produced phenyl- diphe9i~nt?~ryZnaethccne CRPh(C,,H,) m. p. 165' (decornp.) which form8 a dark yellow powder and dibenzpZidenemesotrip?maanihresze C,,H,(CHPh*C,,H,) m.p. 195-197' (decomp.) obtained as a brown powder. E. G . Molecular Weights of the Hydroxybenzoic Acids. W. ~ C H S N E R DE CONINCK (Compt. rend. 1915 160 67-65. Compare A. 1914 i 95).-The author has determined the molecular weights of salicylic acid by a n a l p i s of its pure calcium and ammonium salts and of m- and p-hydroxybenzoic acids by analysis of their pure ammonium salts. The mean value for all the determinations is 137,986. W. G. Tautomerism of Phenylpgruvic Acid. J. BOUGAULT and (MLLE.) R. HEMMERLE (Comnpt. rend. 1915 160 100-102. C'ompAre Bull. Xoc. Chim. 1914 [iv] 15 529j.-'I'he authors b r i ~ ~ g forward further experimental results in support of the view that phenyl- ppruvic acid exists in two tautomeric forms tho free acid being in the enolic form and the normal saltsin the ketonic form.A 10% solution of sodium phenylpyruvate does not give a precipitate immediately on the addition of hydrochloric acid although the free acid is insoluble in water. A precipitation slowly occurs as the unstable ketonic form passes into the stable enolic form. On dissolving phenylpyruvic acid in a n aqueous solution of potassium hydrogen carbonate and then acidifying with acetic acid a partial precipitation of the enolic form of the free acid occurs but on leaving the mixture this precipitate slowly dissolves the enolic form of the acid passing to the soluble ketonic form.ORGANIC CHEMISTRY. i. 79 A freshly prepared solution of phenylpyruvic acid (0.04 gram) in 1 C.C.of 4% aqueous potassium hydrogen carbonate required 2 . 2 C.C. of a solution of potassium permanganate to colour i t permanently whereas 1 C.C. of the same solution after remaining twenty-four hours only required a few drops of the permanganate. A solution of sodium phenylpyruvate (0.34 gram) in 5 C.C. of water to which were added in turn 5 C.C. of ether 0.5 C.C. of con- centrated hydrochloric acid and 0.2 gram of semicarbazide hydro- chloride gave an abundant precipitate of a semicar bazone insoluble in water and very soluble in ether whereas free phenylpyruvic acid under the same conditions gave no trace of semicarbazone. The authors show that small quantities of alkali can like the acid& and more rapidly than them convert the ketonic form into the enolic form.Finally as a proof of the existence of the enolic form they have obtained an acetlJte having the constitution C HPh:Cl(OAc).CO,H b. p. 1 6 8 O by boiling either the free acid or i t s sodium salt with acetic anhydride. W. G. 3-Nitro-4-hydroxycinnamic Acid and its Methyl Ether. TREAT B. JOHNSON and EDWARD F. KOHMANN (J. Anzer. Che?n. Soc 1915 37 162-167).-During the course of an investigation of nitrated protein specimens of 3-nitro-4-hydroxycinnamic acid and its methyl ether were required for purposes of identification and the compounds were therefore prepared by Einhorn and Grabfield's method (A. 1888 477). Nitroanisaldehyde (3-nitro-4-methoxybenzaldehyde) m. p. 83" can be readily obtained by Einhorn and Grabfield's method (Zoc. cit.) if the temperature is kept below 0' ; a t higher temperatures however a pro- duct results which has m.p. about 73" and seems t o be a mixture of mono- and di-nitroanisaldehyde. 3-Nitro-4-hydroxycinnamic acid has m. p. 233' and its methyl ether m. p. 247-248'; Einhorn and Grabfield have given the m. p.'s of these compounds as 198' and 140' respectively. Ethyl 3-nitro-4-hydroxycinnamate has m. p. 110 -1 11' ; the methyl ester m. p. 142-144* crystallises in rosettes of slender yellow needles. When 3-nitro-4-hydroxycinnamic acid methyl ether is treated with a solution of bromine in ether no reaction takes place (compare Einhorn and Grabfield Zoc. cit.) but on treatment with bromine dis- solved in glacial acetic acid it reddily yields 3-nitro-4-methoxyphenyl- up-dibromopropionic acid. E.G. Valency of Nitrogen in Ammonium Salts. WILLIAM A. NOYES and KALPH S. POTTER (J. Amer. Chem. Soc. 1915 37 189-203).-An account is given of the preparation of certain amino- derivatives of camphoric acid. A study of the specific rotation of these substances has indicated that amino-acids whlch can form cyclic sitlts containing quinquevalent nitrogen and a ring of six atoms form salts of the general formula R<"->O in aqueous solutions. NH3i. 80 ABSTRACTS OF CHEMICAL PAPERS. Amino-acids which would give a ring of seven atoms in formiog a cyclic salt seem t o exist in solution as compounds of the form NH2*R*C02H. These relations afford evidence that nitrogen is quinquevalent in ammonium salts and t h a t the hydrogen of the acid combines with the nitrogen instead of remaining united t o the acid radicle as has been supposed by Werner. Amino-camphonanic acid has [aJ$ - 29.2' and its anbydride [a] - 60.5".On hydrolysing the anhydride with 20% hydrochloric acid aminocamphonanic acid hydrochloride is produced which has [a]g + 24.9'. The acetyl derivative of the anhydride C H <yo has b. p. 260-262' and [a]= + 72.7' ; the nitroso-derivative has [a] + 153'. a-Amino-campholic acid decomposes at 300-320' without melting and bas [a]? + 67%'; its hydrochloride has m. p. 248-250' and [ag + 44.7". a-Camphidone has m. p. 230-231' and [a] - 33.9'; its nitroso-derivative C,H,,<Co->N*NO has m. p. 125 -126' and [a]? -59.0'. Aminodihydrocampholytic acid has [a% + 54*7' and its hydrochloride [a] + 41 *3'.The nitroso-derivative of amino-campholytic anhydride has [uE - 83.3'. @.Aminocampholic acid has [a] +16.4' and its hydrochloride m. p. 218-220O and [a] +41*3'. @-Camphidone has m. p. 234-235' and [a]? +63*2'; its nitroso-derivative U s H l < ~ ~ ~ > N * N O bas m. p. 164 -165' and [a12 + 103'. E. G. Bismuth Salts of Halogenated Derivatives of Gallic Acid. P. LAMI (Boll. Chirn. Farm. 1914 54 2-5).-Basic bismuth dicl7dol.o- gdute C,CI 2(0H),*C02 *Bi (OH) prepared from dichlorogallic acid m. p. 155* is almost lemon-yellow and of no therapeutic value. Basic bimuth dibi-ornogallate C,H,O,Br,Bi prepared from dibromo- gallic acid m. p. about 150° is olive-green and basic bismuth di-iodo- gallate C,H,071,Ri dark yellow. Tbem two salts are lyoluble in concentrated sulphuric acid with formation of a red and then a black coloration and evolution of vapours of the halogen.Both are useful in dermatology and act as local astringents. Additive Compounds of Aldehydes and K e t o n e s with Organic Acids. JAMES EENDALL and WILLJS A. GIBBONS (J. Amer. Chem. Xoc. 1915 37 149-162).-Jn earlier papers (A. 1914 i 858 1069) i t has been shown t h a t dimethylpyrone yields additive compounds with organic acids which vary in stability according to the strength of the acid used. A study bas row been made of the f. p. curves of trichloroacetic acid with various aldehydes and ketones. Of the aldehydes salicyl- aldehyde m-hydroxybenzuldehyde 0- m- andp-nitrobenzaldehydes and nitropiperonaldehyde did not yield additive compounds. Benzaldehyde furnished the compound C,H,*CHO,CCI,*CO,H m.p. 8.4' ; p-hydroxy- benzaldehgde the compound OH*C,H,*CHO,CCI,*COzI-I m. p. 67.8' ; l4 NAc' ( 3 3 2 Cyanodihydrocampholytic acid has [a] + 25.3'. T. H. P.ORGANIC CHEMISTRY. i. 81 anisaldehyde the compound OMe*C6H4*CH0,CC13*C!02H m. p. 30.9' ; vanillin the compounds OMe.C,H3(OH)*CH0,2CCI,*C0,H m. p. 14*3O OMe*C,H,(OH)*CHO,CCI,*CO,H m. p. 23O and 20Me* C,Ef,(OH) CHO,CCI,*CO,H m. p. 45' ; and piperonaldehyde the compou12d~ C,H60,,2CC1,*CO,H m. p. 37*4' and CsH60,,CCI,*C0,H m. p. 35". Of the ketones additive compounds could not be isolated in the case of benzophenone phenyl anisyl ketone benzil and benzoquinone but acetophenone yielded the cornpound C6HB*CO*Me,CCI;CO,H m. p. 26O and distyryl ketone the compounds C17H,,0,2CC13*C0,H m.p. 8 6 * 5 O and m. p. 1 1 7 O . A few of these aldehydes and ketones mere also investi- gated with chloroacetic and benzoic acids but in no case was there any indication of the formation of additive compounds. The results of this work confirm the view expressed in the earlier papers that the reaction is ionic and that the compounds formed are oxonium salts. K. G. C,pHl4O,CC13*CO,H Anhydrohydroxylamines of Unsaturated Ketones. L. FRANCESCONI and G. SANNA (Gazzetta 1915 45 i 35-41).-The authors find that the tendency to form auhydro-bases similar to that ob- tained by Semmler (A. 1904 i 437 602) from pulegonehydroxylamine is exhibited generally by unsaturatrd cyclic a/?-ketones having the double linking outside the nucleus and by unLaturated a/?-ketones of the aliphatic series.These anhydro-bases may be obtained by Harries and Jablonski's method (A. 3898 i 400) but the compound described by these authors as a n isooxazole derivative is more probably an imino-base. The action of dry hydrogen chloride on pulegonehydroxylamine in ethereal solution gives a small yield of the base prepared by Semrriler (Zoc. eit.) but prolongation of the action results in the formation of an oxime which separates in tufts of prismatic crystals m. p. 141' and appears to be the normal oxime of pulegone /-\ CMe,. \J NOH yH,-CH >C<$Ee2 prepared CHMe*CO A nh y drocamp~oronehydroxylamine by passing dry hydrogen chloride into an ethereal solution of camphor- onehydroxylamine (compare Harries and Maftus A 1899 i 629) is obtained as an optically active slightly basic oil n 1.468; it forms a picrate which crystallises with difficulty and exhibits many of the reactions of alkaloids.T. H. P. Derivatives of 1 2 3 5-Tetrahydroxybenzene. G. BARGEL- LINI (Gaaxetta 1915 45 i 85-93).-The action of propionyl chloride in presence of sublimed aluminium chloride on 1 2 3 5-tetra- methoxybenzene (compare Bargellini and Binj A. 191 1 i 211) dissolved in carbon disulphide yields (1) 2 3 4 6-Tetruhydroxy- propiophenone trimethyl ether OH*C,H (OMe),*COEt which forms straw-yellow prismatic crystals m. p. 124-126" and with ferrici. 82 ABSTRACTS OF CHEMICAL PAPERS. chloride in alcoholic solution gives a yellowish-brown coloration and with concentrated sulphuric acid a yellow solution becoming deep violet when heated.I t s acetyE derivative Cl4HISO6 forms white needles m. p. 73-74'. (2) 2 3 4 6-Tetramethoxypropiophenone C,H(OMe),*COEt which may also be obtained by the action of methyl sulphate on the preceding compound ; it forms white c'rystals m. p. 55-56' and dissolves in concentrated sulphuric acid giving a yellow coloration which turns deep violet on heating. Under similar conditions t h e action of benzoyl chloride on 1 2 3 5 - tetramethoxybenzene yields (1) 2 3 4 6-Tet~~ahydroxybsnxophenolze trimethyl ether OH*C6H(OMe),*COPh which forms white crystals m. p. 87-89' and gives an intense reddish-brown coloration with ferric chloride in alcoholic solution ; with concentrated sulphuric acid it gives first a bright red coloration and then a yellow solution which changes t o green and afterwards t o deep violet when heated.Its acetyE derivative C18H1806 forms white needles m. p. 130-132'. (2) 2 3 4 6-Tetramethoxybenxophenone CGH(OMe),*COPh which forms white crystals m. p- 125-126' ; with concentrated sulphuric acid it behaves similarly to the preceding compound. T. H. P. Blue Hydrocarbon Occurring in Some Essential Oils. ALFRED E. SHERNDAL (J. Amer. Chem. ~S'oc. 1915 37 167-171).- Several essential oils yield blue fractions boiling between 275' and 300' and it has usually been supposed that their colour is due to the presence of a blue compoutid consisting of a n oxygenated substance related to the sesquiterpene alcohols. The compound has now been isolated by shaking a very blue fraction with 63% sulphuric acid in which it is soluble.The acid liquid was diluted and extracted with light petroleum. The blue solution in light petroleum was then shaken with S5% phosphoric acid and the dark red acid solution t'hus obtained was diluted and extracted with ether. On evaporating the ethereal solution a residue was obtained consisting of a n intensely blue slightly viscid liquid with a faint thymol-like odour. This substance is a hydrocavbon C15H18 which has D 0.9738 and boils at 185-195O/25 mm. or at 295-300° under ordinary pressure leaviug a brown tarry residue ; when exposed to light and air i t is gradually converted into a brown resin The author proposes t o term the substsince azulene a name originally assigned by Piesse to a blue fraction obtained froin oil of wormwood.Solutions of the compound in mineral acids are strongly fluorescent. By the action of acetic anhydride and sulphuric acid the hydrocarbon is converted into a sulphonic acid which yields a crystal- line sodium salt. The aqueous solution of the sodium salt is violet but becomes pale green when acidified; i t yields precipitates with solutions of calcium or barium salts and is decolorised by bromine water. E. G. Turpentine and Turpentine Oil of Aleppo Pine. D. E. TSAEALOTOS (J. Pharm. China. 1915 [vii] 11 70-72).-A sample of turpentine (resinous exudation) collected from Aleppo pines (Pinus halepensis) growing i n Attica Greece yielded the following percentageORGANIC CHEMISTRY. i. 83 results on analysis turpentine oil 21.4 dry residue 70.8 solid impurities 4.5 water and loss 3.3 (compare A.1909 i 818). The turpentine oil consisted almost entirely of d-pinene. w. P. s. Oils of the Conifere. IV. The Leaf and Twig Oils of Digger Pine Lodgepole Pine and Red Fir. A. W. SCHORGER (J. Ind. Eng. Chem. 1915 7 26-26. Compare A. 1914 i 1203).- The physical and chemical constants of the leaf and twig oils of the digger pine (Pinus sabiniana) the lodgepole pine (Pinus contorta) and the red fir (Abies magnijca) were found to be as follows Digger pine yield 0.078 to 0.102%; D15 0.8517 to 0.8566 ; ng 1.4670 to 1.4708 ; a2,0 - 20.93' to - 38-36'; acid number 1-41 to 2.05 ; ester number 6:77 t o 11.98. Lodgepole pine yield 0.234%; D15 0.8690; n 1.4381 ; Red fir yield 0.154%; D15 0.8665 ; m$ 1.4861 ; a - 16-70' ; acid number 0.75 ; ester number 9-93.- 17.84" ; acid number 0.90 ; ester number 6.02. The percentage composition of the oils was Fnrfuraldehyde ..................... n-Heptane ........................... Z .a-Pinene ........................... I-Cnmphene ........................... I-P-Pinene ........................... Z-Phellandrene. ...................... Dipenteiie ........................... I-Limonene ........................... Bornyl ester (as acetate) ............ Free alcohol (I-borneol) ............ Methylchavicol ..................... ' ' Green oil " ........................ Cadinene ........................... Loss etc. .............................. Digger pine. 3 58-59 - - - 18 3.5 6 ? 2-3 9.5 - Lod,aepole pine. trace 3 5-6 49-50 - - 2 7-5 ? - I 6 Red fir.trace 2 - - 16-18 52 0 3.5 7 *5 13 6 - - - w. P. s. Tormentole the Extractive Principle of Potentilla Tormentilla. A. GORIS and CH. VISCHNIAC (Compt. rend. 1915 160 77-80).-To~,.nzentoZe can be extracted from the fresh or dried roots of Potentilla Tormentilla by powdering the roots moisten- ing them with basic lead acetate solution and extracting the maFs three times with boiling acetone and filtering. The extract is cooled and the lead compounds and a yellow oil allowed to separate. The clear acetone solution is decanted and excess of water added. The precipitate is collected dissolved i n cold alcohol and the solution purified with basic lead acetate the excess of lead being removed by sulphuric acid (10%). The liquid is finally distilled under reduced pressure until crystallisation occurs the crystalline product being recrystallised from dilute alcohol.Tormentole so obtained crystailises in slender needles m. p. 227-228' to which proviyioually the formula C33H50010,5H20 is assigned. It is a neutral saturated subst tnce containing an hydroxyl group and being also an ester. It loses its 5H,O at 100" or on drying over suiphuric acid in a vacuum the anhydrous product obtained in the first cclse being yellow in colour andi. 84 ABSTRACTS OF CHEMICAL PAPERS. non-crystallisable. The rotatory power of the h j drated substance varies with the solvent being in alcohol [.ID + 10.78' and in acetic acid [a]D + 20*77O these being calculated for the anhydrous product. The anhydrous product obtained a t 100' has [.ID + 32-13' in alcohol and + 33.03' in acetic acid On saponification with alcoholic potassium hydroxide tormentole yielded an alcohol m.p. 310' and an acid m. p. 280° neither of which has as yet been characterised. Tormentole is esterified on heating with acid anhydrides but in every case a mixture of products which could not be sepa~ated was obtained. W. G. Chlorophyll. RICHARD WILLSTATTER (J. Amer. Chem. Xoc. 1915 37 323-545).-A review of the work hitherto carried out on chlorophyll. The methods employed in the investigations are described an account is given of the isolation of chlorophyll and its separation into its components and the constitution of tho substance is discussed. E. G. Coumarins. a. BARaELLINI and LYDIA MONTI (&xxatta 191 5 45 j 90-98. Compare A.1911 i 855).-Various coumarin derivatives have been subjected to the action of potassium persulphate in alkaline solution with a view to determining their constitutions. With coumarin itself this treatment yields only 5-hydroxy- coumarin. With 4-methoxycoumarin (umbelliferone methyl ether) 5-hydroxy-hetboxycoumarin identical with the monomethyl et.her m. p. 184O formed on partial methylation of aesculetin is obtained. Scopoletin m. p. 204' which is also an axxuletin monomethyl ether must consequently be 4-hydroxy-5-methoxycoumarin as indeed was demonstrated by Moore (T. 1911 99 1043). T. €3. P. Constitution and Synthesis of Scutellarein. G. BARGELLINI (Gazxotda 19 15 45 i 69-79).-2 3 4 6-Telrasnethoxybenzoyl-4- methoxywcetopheno~e C6H(o~~e),*co~cHz~CO~C6H;OMe prepared by the condensation of 2 3 4 6-tetramethoxyacetophenone (compare Bargellini and Bini A.2911 i 211) with methyl anisate in presence of sodium forms yellowish crystals m. p. 104-106" and in alcoholic solution .gives a garnet-red coloration with ferric chloride. When heated with hydriodic acid this compound undergoes dernethglation and then loses the elements of water with formation as sole product of a compound which must be either 5 7 8 4'- or 5 6 7 4'-tetra- hydroxyflavone. As this compound is identical with natural scutellarein these results confirm the constitution of the latter deduced by Goldschmiedt and Zerner (A. 1910 i 576). An attempt is now being made to decide between the two alternative structures. T. H. P. Pentahydroxyflavone. G.BARGELLINI and LYDIA MONTI (Gazxetta 1915 45 i 64-69).-With the object of devisiug a general method for the conversion of flnvones into flavonones and thence into flavanols the authors have attempted to apply the results of their investigations on the tranhfor mation of phengl styrpl ketones into phenyl phenylethyl ketones (compare this vol. i 19).ORGANIC CHEMISTRY i. 85 3 4 5-Trimet~oxybernxoyl-2 4 6-t.rimetlioxyacetoplienone CGH2(0Me),*CO~CH2*CO*C6H2(OMe) prepared by the condensation of 2 4 6-trimethoxyacetophenone with the trimethyl ether of methyl gallate in presence of sodium forms white crystals m. p. 136-1 38' and gives a red coloration with ferric chloride in alcoholic solution whilst with concentrated sulphuric acid i t gives first a red coloration and then a yellow solution.When the methyl groups of this compound are removed by treatment with boiling hydriodic acid the enolic modification of the revul ting hexshydroxy- OH benzoylacetophenone loses the elements of water yielding 5 7 3' 4' 5'-penta- OH/\-O-C- / \OH hydroxpflavons (annexed formula) which blackening and gradually decomposing a t above 270'; with ferric chloride i t forms a greenish brown-yellow coloration and it dissolves in sodium hydroxide solution giving an orange-red and in concentrated sulphuric acid giving a yellow coloration. The corresponding penta-acetyl- derivative C,,H,,O, forms white needles m. p. 216-2 18". Attempts to prepare a methyl ether of the pentahydroxyflavone resulted in the formation of a small proportion of a product m.p. 112-118° which is probably the 5 3' 4' 5'-tetramethyl derivative. Hydrogenation of the double linking of 5 7 3' 4' 5'-penta- hydroxyflavone or its penta-acetyl derivative could not be effected in the conditions successfully employed with the phenyl styryl ketones namely under slight pressure and in presence of palladium black. Attempts to hydrogenate 6 7-dimethoxyflavone its didcetyl derivative and its dimethyl ether (compare Reigrodski and Tambor A 1910 i 578) were also unsuccessful. - \,-CO.CH I I " \-/ forms a yellow crystalline powder OH T. H. P. Sempervirine a T h i r d Alkaloid from Gelsemium. A. E. STEVENSON and L. E. SAYRE (Phccrm. J. 1915 94 159; from J. Amer. Pharm. ASSOC. 1915 60).-A substance described as a third alkaloid has been isolated from gelsemium by extracting a large quantity of the latter with alcohol evaporating the alcoholic solution to a syrup and shaking this with chloroform ; the chloroform solution was then evaporated to a small volume which was shaken with dilute hydrochloric acid and the acid solution then shaken with benzene to remove gelsemic acid.The acid solution was next shaken with chloroform the chloroform solution evaporated the residue extracted with water the aqueous solution evaporated to dryness the residue dissolved in alcohol mixed with sand again evaporated to dryness and the powder extracted first with acetone and then with alcohol. On evaporating t h i s alcoholic solution the hydrochloride of the alkaloid separated in the form of crystals. The salts of the alkaloid are very insoluble in dilute acids; the addition of nitric acid to an aqueous solution of the hydrochloride precipitates the salt so completely that the supernatant liquid yields only a faint opalescence with Mayer's reagent.The nitrate is sparingly soluble in alcohol and crystallises from it in the form of yellow needles m. p. about 280' (decomp.) ; the alkaloid itself prepared from the recrystallised nitratei. 86 ABSTRACTS OF CHEMICAL PAPERS. occurs as pale yellow crystals. The hydrochloride is readily soluble in alcohol. Gelsemium coutains only very small quantities of this alkaloid for which the name sempervirene is suggested. Struxine a New Alkaloid in N u x Vomica. H. H. SCHAEFER (Pharm. J. 1915 94 241; from J. Arner. Phcwm. ASSOC. 1914 1 677).-Stmxine C,,H,,O,N colourless crystals decomposing about 2E0° has been obtained in about 0.1% yield from a few samples of beans from Cochin-China which were insect-eat en and partly decomposed by prolonged exposure on wet fields.It is pre- cipitated when the acid solution of the crude alkaloidal sulyhates of nux vomica is just neutralised or is still faintly acid whilst strychnine and brucine &till remain in the solution as sulphates. The new alkaloid is regarded as a product of the decomposition hy fermentation or oxidation of strychnine or brucine. It responds to the usual alkaloidal tests is only very slightly bitter and forms normal and acid salts ; the sulphate hydrogen sulphate hydrochloride hydrobromide and Action of Pyridine on Certain Organic S u l p h u r and Selenium Compounds.M. RAFFO and G. ROSSI (Gaxxetta 1915 45 i 28-34. Compare A 1914 i 572).-'l'he action of pyridine on further sulphur compoiinds and on various selenium compounds has been investigated. When a pyridine solution of thiophenol is boiled the principal reaction consists in the formation of phenyl disulphide evolution of hydrogen sulphide indicating that secondary reactions also occur. When a pyridine solution of thiobenzanilide is bGiled until libera- tion of hydrogen sulphide ceases the compound m. p. 202O to which Jamieson ascribed the structure NPh:CPh-NPh*CSPh (A 1904 i 396) is obtained. The authors consider i t more probable that this compound has the constitution NPh:CPh*S*CPh:NPh. Similarly phenylallylthiocarbamide yields hydrogen sulphide allyl- tbiocarbimide and 3-pheny lpropg lene-+-thiocarbamide W.P. S. hydrogen tavtrate have been prepared. c. s. 11. ? H M e * S p . N H -ph CH,-N (compare Prager A. 1890 159). Under similar conditions diphenylseleniocarbrmide decomposes principally into hydrogen selenide and carbodiphenylimide the latter being converted by the water of the moist pyridine into carbanilide ; the other products formed are aniline and ti-iphenylguanidine this probably resulting from the interaction of aniline and carbodiphenyl- imide. T. H. P. LAMBERT THORP and E. A. WILDMAN (J. Amtr. Chem. Soc. 1915 37 372-377).- This investigation was undertaken in the hope of effecting the synthesis of fluorene by the action of metals on 2 2'-dibromodiphonyI- me thane. 3 3'-Diacetylaminodi?~~~yZ~et?~ane m.p. 193" forms colourless leaflets. When a solution of this substance in glacial acetic acid is treated with bromine 6 6'-dibronzo-3 ; 3'-diacetylaminoLCi~~~enylm~t~~an~ Syntheses in the Diphenylmethane Series.ORGANIC CHEMISTRY. i. 87 m. p. 284O is produced which crystallises in small colourless plates and on hydrolysis with hydrochloric acid is converted into 6 6'-dibromo- 3 3'-diaminodiphenylmethane m. p. 1 1 4 O . The latter compound is somewhat unstable and becomes brown on exposure to the a i r ; its hydyochloride and sulphate were prepared. 2 2'- L)ibromodz~he?zylmetharne was obtained by the diazotisation of 6 6'-dibromo-3 3'-diaminodiphenylmethane as a colourless liquid with b. p. 234-235'/40 mm. ng 1.6300 and DSo 1.619'7.Attempts to induce this substance to undergo condensation with ring formation mere not successful. Although it was treated with sodium in ether and in boiling xylene and subjected to the action of copper .bronze a t 260' and of magnesium a t the same temperature i t was in all cases recovered unchanged. On heating a solution of 2 2'-dibromodiphenylmethane in glacial acetic acid with chromic acid 2 2'-dibromobenxoplienone m. p. 86O is produced which forms hexagonal plates; attempts were made to prepare its oxime and semicarbazone but without success. E. G. Antipyrine Methylarsinate. L. BARTHE (Pharm. J. 191 5 95 99 ; from Bull. Xoc. Phccrm. Bordeaux 19 14 348).-Antipyrine mebhylarsinnte ASOM~(OH),,~C~~H~~~ON~,~H~O is obtained by boiling together 1 mol.of methylarsinic acid and 2 mols. of antipyrine in alcoholic solution filtering and leaving the solution to crystallise over sulphuric acid. The substance is soluble in alcohol and in water ; at 30° 100 parts of water dissolve 28.5 grams It is not optically active. I t s aqueous solution yields a white precipitate with sodium or potassium hydroxide but not with ammonia a red coloration with nitric acid a fluorescence with copper sulphate a greenish-blue coloration with nitrous acid and a blood-red coloration with ferric chloride ; alkaloidal reagents yield precipitates and an odour like that of bitter almonds is produced when the substance is treated with sodium hypochlorite. Mercurous nitrate added to the aqueous solution gives a blackish precipitate and not yellow as with antipyrine.w. P. s. Antipyrine Cacodylate L. BARTHE (Yharm. J. 1915 94 99; from Bull. SOC. Pharm. Bordeaux 191 4 353).-Antipyrine cncodylate AsO;Me,-OH,C,,HlzON,,2H,0 m. p. below loo' is prepared by adding 1 mol. of antipyrine dimdved in dilute alcohol to a concen- trated alcoholic solution of 1 mol. of cacodylic acid boiling the mixture and leaving i t to crystallise over sulphuric acid. The substance is soluble (24.5%) in water and in alcohol. I t s aqueous solution yields a white precipitate when treated with potassium or sodium hydroxide but not with ammonia ; copper sulphate solution produces a slight fluoreecence but no precipitate. Nitrous acid (sodium nitrite and acetic acid) gives a blue coloration ferric chloride a blood-red colour whilst the usual alkaloidal reagents all give precipitates.An odour like that of bitter almonds is produced when an aqueous solution of antipyrine cacodylate is treated with sodium h ypochlorite. w. P. s.i. 88 ABSTRACTS OF CHEMICAL PAPERS. Hydantoins. XXIX. Geometrical Isomerism in the Hydantoin Series. TREtli7 €3. JOHNSON and SIDNEY E. HADLEY (J. Amer. Chsm. SOC. 1915 37 171-177).-An account is given of the first case of geometrical isomerism obsenved in the hydantoin series. When 2-thio-1 3-diphenylhydantoin is prepared by heating ethyl phenylaminoacetate with phenylthiocarbimide (Wheeler and Braut- lecht A. 1911 i 501) a secondary product is obtaiued m. p. 212O. Byithe condensation of benzvldehyde with 2-thio-1 3-diphenylhydantoin the 4-benzylidene derivative LLI.p. 197* is produced together with two other compounds one of which appears to be a stereoisomeric modification of the hydantoin (m. p. 197O) whilst the other seems to be identical with the secondary product of the reaction between ethyl phenylaminoacetate and phenylthiocarbimide. On reducing Z-thio- 1 3-diphenyl-4-benzylidenehydantoin with hydriodic acid 2-thio-1 3- diphenyl-4-benzylhydantoin (Johnson and Shepard A. 1914 i 1091) is produced. When 2-thio-1 3-diphenyl-4- benzylidenehydantoin is digested with chloroacetic acid it yields two stereoisomeric forms of 1 3-diphenyZ-4- The tmns-modi hation 6enxy2idenehydantoin N Ph< m. p. 192O crystallises in pale yellow tetrahedral prism+ an 1 the ci8- form m. p. 152O forms rosettes of prisms. These two compounds can also be obtained by the condensation of 1 3-diphenylhydsntoin with benzaldehyde. On reduction with hydriodic acid both forms are cm- verted into 1 3-diphenyl-4- benzylhydantoin (Johnson and Shepard Zoc.cit.). E. G. Hydantoins. XXX. Stereoisomeric Modifications of Benzylidenehydantoin. TREAT B. JOHNSON and JOSEPH S. BATES (J. Amer. Chern. SOC. 1915 37 383-385).-Johuson and Hadley (preceding abstract) have shown that the condensation products of disubstituted hydantoins with aldehydes are capable of existing in isomeric modifications. It has now been found that benzyliciene- h y dan toio NH<Co. :CHPh also occurs in two modifications. The ordinary form of benxylidenehydantoin m. p. 220’ (Ruhemann and Stapleton T. 1900 77 246) is the cis-modification.From the alcoholic mother liquor from which the substance had separated a small quantity of the ti*ans-modification m. p. 246O has been isolated which crystallises in aggregates of distorted prisms ; the yield is less than 1% of the theoretical. Pyrimidines. LXXIII. Alkylation of 2-Thiolpyrimidines. TREAT B. JOHNSON and HOWARD W. HAGGARD (J. Amer. Chcm. Soc. 1915 37 177-183).-The earlier papers on the alkylation of 2-ttiiol- 6-pyrimidones have dealt with the results obtained with compounds in which the thiol group contained a saturated alkyl radicle and with one exception all such thiol groups have been found to favour substitution in the 1- and 3-positions of the pyrimidine ring. A study has now been made of the alkylation -of 2-allylthiol-4-methyl- COYPh CO.C :CHPh. CO*YH E. G.ORGANIC CHEMISTRY. i. 89 dihydro-6-pyrimidone and in this case 110 substitution in the 3- position bas been observed. 2- Allylthiol-4-methyZdihydro-6-pyrimidone C(S*CH,* CH CH,) N NH<CO CH>CMe m. p. 131° prepared by the action of allyl bromide on the sodium salt of 2-thio-4-methyluraci1 forms colourless needles. When treated with methyl iodide and sodium ethoxide it yields 2-ally& thiol-l ; 4-dimeth yldihydro-6-p yrimidone C( S*CH,*CH CH,) N NMe<Cio (&CMe %( 0. CH,.CH:CH,) CH. m. p. 43O which crystallises in hexagonal tables and is hydrolysed by hydrochloric acid with formation of 1 4-climethyluracil. 6- A El y lox y-2 -ally lthiol- 4 - meth y lp y pimidine C( S*CH,*CH :CH,)=N>CICle was obtained as an oil by the action of allyl bromide on the sodium salt of 2-allylthiol-4-methyldihydro-6-pyrimidone ; on hydrolysis it furnished 4-methyluracil.When a solution of 2-allylthiol-4-methyldihydro-6-pyrimidone in glacial acetic acid is treated with bromine it is converted into 5-bromo- 2-/3y-dibromopropylthiol-4-methyldihydro- 6-pyrimidone C(S*CH,*CHBr*CH,Br) N NH<CO CBr m. p. 160-165' (decomp.) which crystallises in rosettes of needles. By the action of ethyl bromide on the sodium salt of 2-allylthiol- 4-methyldihydro-6-pyrimidone a mixture of 2-allylthiol-4-methyl- 1-ethyldihydro-6-pyrimidone and 6-ethoxy-2-allylthiol-4-methyl- pyrimidine was obtained which could not be separated ; on hydrolysis the product yielded a mixture of 4methyluracil and 4-methyl-1- ethyluracil. Benzyl chloride reacted with the sodium salt of 2-allylthiol-4- rnetbyldihydro-6-pyrimidone with formation of a mixture of 6-benzyl- ox y- 2 -ally lthiol- 4-me t h y lpyrimidine and 2 -ally1 t hiol- 1 - benzyl- 4 -me thy 1- dihydro-6-pyrimidone which on hydrolysis furnished 4-methyluracil and 1-benzyl-4-methyluracil.When the sodium salt of 2-methylthiol-4-methyldihydro-6-pyrimid- one is treated with allyl bromide 6-~6lEyloxy-2-rnethylthiol-4-me~~yl- N>CMe b. p. 160-164'/17 mm. is obtained as a yellow oil; on hydrolysis it is converted into 4-methyluracil. E. G. Pyrimidines. LXXI V. Synthesis of 4-Phenylcytosine. TREAT €3. JOHNSON and E. HEATON HEMINGWAY (J. Ainer. Chem. Soc. 1915 37 378-383).-Johnson and Hill (A. 1914 i 879) have shown that 4-phenylisocytosine exists in four isomeris modifications.With a view to elucidating the nature of this isomerism a study has now been made of 4-phenylcytosine and i t has been found that this compound exists in two distinct forms. 2-Thio-4-phenyluracil can be readily obtained in a yield of about VOL. CVIII. 1. a C( S Me) pyrimidine N<qO.CH,.C":Cq. CHi. 90 ARSTRACTS OF CHEMICAL PAPERS. 73.3% of the theoretical by heating a n alcoholic solution of thio- carbamide with ethyl benzoylacetate in presence of sodium ethoxide ; when digested with chloroacetic acid i t is converted quantitatively into 4-phenyluracil (Wheeler and RTerriam A. 1903 i 525). 2-Ethylthiol- 4-phen yldih ydro-6 -p yrinhidone NH<CO-(JH/ c ( s E t ) h'>cph 3 m. p. 226' obtained in 78% yield by the action of ethyl bromide on the sodium salt of 2-thio-4-phenyluraci1 crystallises in needles ; i t is converted by phosphoryl chloride into 6-chloro-2-ethyZtl~ioZ-4-phenyl- pyyirnidine N<CCl-cH>CPh C(SEt):N b.p. 232'/26.5 mm. which gives LL quantitative yield of 4-phenyluracil on hydrolysis with hydrochloric acid. When this chloropyrimidine is heated with alcoholic ammonia at 130 -1 35O 6-amino-2-ethylthioZ-4-phen~l~~~i~~idine m. *p. 120° is produced which Skjmtallises in thin plates. On hydro- lysing this compound with hydrobromic acid i t is converted into hydrochloride both crydtalliie in long needles with 1H,O ; the former does not melt below 300" and the latter has m. F. 274' (decomp.) ; the nitrate crystallises in either needles or prisms and decomposes above 245'.4-Phenylcytosine when first prepared crystallises in rosettes of needles but when recrystallised from boiling absolute alcohol it is obtained in the form of rhombohedra1 prisms. On crystallisation from 95% alcohol a mixture of both needles and prisms is obtained. Neither modification gives a definite melting or decomposition point. E. G. 5-Keto- 1 -phen yl-4 5 -dihydrotriazole-3-sulphinic Acid and 5. Keto-1 -phenyl-4 5~dihydrotriazole-3-rnethylsulphone. E W. ESSLINGER and S. P. ACREE (J. Amer. Chein. Soc 1915 37 183-189). -Earlier work has shown that 1 -phenyl-3-thiourazole yields only one mono-alkyl derivative on alkylation by various methods (A 1903 i 867) whereas 1-phenylurazole yields a mixture of the 2-N- and 3-0- derivatives. These facts can be explained on the assumption that urazole salts exist in two tautorneric forms (A.1908 i 919; 1910 i 520). When the alkyl derivatives of 3-thio-1 -phenylnrazole are heated with acids at 125' under pressure an alkylmercaptan is produced indicating t h a t the alkyl group is attached to the sulphur atom. Experiments have now been carried out which show that on oxida- tion 1-phenyl-3-thiourazole yields very soluble sulphinic and sulphonic acids whilst its alkyl derivatives furnish insoluble sulphone-like sub- stances. The conclusion is therefore drawn that these alkyl derivatives have an alkyl group attached t o the sulphur atom and not to the nitrogen atom and that 3-thio- 1-phenylurazole is alkylated in the >C*SH. NPh-N TPh-N>C*SH and C(0H):N I CO*NH tautomeric thio-enol forms,ORGANIC CHEMISTRY.i. 91 5- Keto-1 -phenyZ-4 ; 5 -dihydrotriazoZe- 3-sulphinic acid >G*SO,H YPh-N CO*NH m. p. 174-178O obtained by oxidising the sodium salt of l-phenyl-3- thiourazole with alkaline solution of potassium permangmate or with 30% hydrogen peroxide yields a disiZvei* salt rPh-N C (0 Ag) K 5- Keto- 1 -pheny 2 - 4 5-dih ydrotriazole- 3 -met h y lsulpho rae >C.SO A g E,O. rPh-N CO*NH >C*SO,Me m. p. 206-207' formed by the oxidation of 3-thio-1-phenylmethyl- rPh--N >C-SO,Me. On treating urazole furnishes a silver salt C (OAg) N the sodium salt of the sulphone with methyl iodide i t yields about 40% of 5-keto- 1 -phenyl-4-methy2-4 5-dihy~~otriaxole-3-metf~y?suZ~hone YPh--N>C*SO,Me m. p. 94-95' together with 60% of 5-methoxy- C 0.NMe 1-pheny l-4 5-dihydrotriazole-3-methylsulphone. 5- Keto-1 - phenyl - 4 5 - dihgdrotriuxole - S-ethyZsuZplt,orze bas 113. p. 199*5-20@* and yields a stable silver salt. By the action of ethyl iodide 011 the sodium salt of this sul phone 5-keto-l-~he.lzyl-4-ethyZ-4 5- di?~ydrotriaxole-3-ethyZsuZphone m. p. 74-75' is obtained ; the ratio of this ketonic substance to the eoolic compound formed siniultaneously was 40 60. E. G. Precipitation of Serum-Albumin and Gelatin by Alkaloidal Reagents. PAUL J. HANZL~K ( J . Biol. Chem. 1915 20 13-24).- For the alkaloidal reagents a certain amount of free acid is necessary for the formation of complex insoluble compounds. For dialysed horse-serum and gelatin the mectianism of precipitation by tannin is different. It behaves like certain alcohols (phenol resorcinol etc.) since the maximum of precipitation occurs a t the iso-electric point.The precipitation in the case of serum is not iufluenced by wide differences of concentration nor by the addition of such neutral s d t s as chloride and thiocyanate. Simpler Nucleotides from Yeast-Nucleic Acid. WALTER JONES and A. E. RICHAHDS (J. Biol. Chem. 1915 20 25-35).- Levene and Jacobs showed that yeast-nucleic acid a tetranucleotide can be split into its four component mononucleotides by boiling with mineral acids; the two which contain pyrimidine bases are not further broken up. In a mixed nucleotide the separation of purine and pyrimidine bases is no longer necessary but an estimation of the liberated phosphoric acid gives a measure of the amount of both present.I n enzymatic hydrolysis the first cleavage is into two di- nucleotides one containing guanine and cytosine the other adenine and aracil. Thannhauser has also described a tri-nucleotide obtained by the digestive action of duodenal juice; in this uracil is lacking. I n the present paper the two dinucleotides and guanylic acid ate discussed. W. D.H. i 2i. 92 ABSTRACTS OF CKEMICAL PAPERS. As the tissue enzymes are so numerous which act on nucleic acid and the factors complex which influence the reaction full details are given of the precautions to be adopted in the method of preparing the dinucleotides by the action of pancreas on yeast-nucleic acid. Analyses and some constants are also given. A method is also described for preparing guanylic acid from guanosine obtained by the action of fresh pancreas extract on yeast-nucleic acid.The interesting suggestion is made that when guanylic acid is found in animal tissues it comes from vegetable food. W. D. H. Fibrin. A. W. BOSWORTH ( J . BioE. Chem. 1915 20 91-94).- Fibrin combines with four equivalents of base to form a compound neutral to phenolphthalein. It also forms acid salts with one two and three equivalents of base ; all the combinations with sodium potassium and ammonium are soluble. The calcium fibrinates containing one and two equivalents are insoluble ; those with three and four equivalents are soluble. Fibrin combined with one equivalent of acid is insoluble and with more than one soluble. Fibrin unljke caseinogen is not strong enough as an acid to decompose calcium carbonate.The mole- cular weight of fibrin is given as 6666. Carbon dioxide precipitates fibrin from a solution of calcium fibrinate but not from solutions of sodium potassium or ammonium fibrinate. W. D. H. Influence of Certain Capillary-activa Substances on Enzyme Activity GEORGE H. CHAPNAN (Intern. .&itsch. phys. -chem. Biol. 1914 1 293-337).-The author has investigated the action of alcohols esters ketones and other substances which readily alter the surface tension of solutions on invertase pepsin trypsin catalase and lipase. A general relation between concentration of the capillary- active substance the surface tension and the rate of enzyme action could not be discovered in the case of any of these enzymes.I n the presence of sucrose the inhibitory action of the capillary- active substances on invertase was very much reduced. Neither sucrose nor Witte’s peptone had a similar protective influence on pepsin except against the lower alcohols H. W. B. Studies on Enzyme Action. XII. Esterase and Lipase of Castor Beans. K. GEORGE FALK and K. SUGIURA (J. Amer. Chem. Xoc. 1915 37 217-230).-In an earlier paper (A 1914 i 98) i t was shown that castor beans appear to contain two enzymes one of which is soluble in water and is more active towards ethyl butyrate than towards glyceryl triacetate whilst the other is insoluble and is more active towards glyceryl triacetate than towards ethyl butyrate. For convenience the former is referred to as esterase and the latter as lipase. The effect of sodium chloride and sodium sulphate solutions on the activity of these enzymes has been studied. It has been found that the action of the esterase is inhibited by sodium chloride at all con- centrations whilst that of the lipase is accelerated at some concentra- tiow and inhibited at certain higher concentrations Sodium sulphate does not affect the activity of the castor bean preparation towardsPHYSIOLOGICAL CHEMISTRY. i. 93 ethyl butyrate but causes a marked acceleration of its action on glyceryl triacetate. The activity of the castor bean preparation is not affected by desiccation in a vacuum in presence of calcium chloride or phosphoric oxide but it is greatly decreased when the material is heated a t 100-1 1 oo. An esterase preparation was separated by extraction with water and its propertieswere studied both in solution and in the solid state; it is suggested t h a t this enzyme is probably identical with gljcerophos- phatase. A lipase preparation extracted with 1.5 N-sodium chloride was also investigated. It is shown tbat both the esterase and lipase are essentially of a protein character. E. G.

ISSN:0368-1769    

DOI:10.1039/CA9150800073

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

ii. 77 General and Physical Chemistry. The Spectra of Helium and Hydrogen. E. J. EVANS (Phil. Mag. 1915 [vi] 29 284-297).-1n view of the difficulty which attaches to the differentiation of the series lines of hydrogen and helium experiments have been made to obtain the helium spectrum free from hydrogen lines and also to obtain more accurate values for the wave-lengths of the lines of the Pickering series. The results show that with a helium discharge tube which shows no trace of the hydrogen lines of the Balmer series i t is possible t o observe the first member (~4686) of the series v=109750 [1/(1&)2- 1/(73/2)2] and also a line (A 6560.4) which agrees in wave-length with the first member of the series v=109750 [l / P - 1 / (n/.2)2] which includes the Pickering lines and the helium lines predict'ed by Bohr on the basis of his theory of the constitu- tion of the helium atom.The wave-lengths of the Pickering lines agree with the values calculated by Bohr within the limits of experimental error. The results point t o the conclusion t'hat the series spectrum of hydrogen consists only of lines which are represented by the formula v = 109704 (I /n12- 1 / T Z ~ ~ ) and that the series spect'rum of helium consists in addition t o the ordinary helium lines of all the lines which are represented by the formula v=109750 [1/(%/2)2- 1/(n2/2I2* H. M. D. Light Absorption and Fluorescence. 11. E. C. C. BALY (Phil. Mag. 1915 [vi] 29 223-240. Compare A 1914 ii 318).- As a consequence of the application of the quantum theory t o the phenomena of light absorption and fluorescence the author has been led t o the conclusion that if v is the frequency of the char- acteristic infra-red vibration energy can only be absorbed a t the frequencies vl v2 v3 etc.where vl v2 v3 are successive multiples of vZ. It follows that the absorption bands must show a constant frequency difference. Assuming that the bands in the short-wave infra-red region are due to atomic vibrations and those in the ultra-violet are due t o electronic vibrations i t should be possible t o combine these two vibrations in the manner indicated by Bjerrum (A. 1912 ii 1114). I f t'hen v is the characteristic vibration frequency in the ultra- violet we should expect t o find pairs of absorption lines with frequencies equal to v +v where v represents the frequencies of the short-wave infra-red bands.The same relationship is of course t o be expected in the case of the fluorescence bands. ThO structure of the ultra-violet absorption spectrum of benzene is cibed as evidence in support of the correctness of the above views. It is found that the lines form a series of pairs which are symmetrically distributed about a central line and that every VOL. CVIII. ii. 6ii. 78 ABSTRACTS OF CHEMICAL PAPERS. infra-red band in the short-wave region has a corresponding line or pair of lines in the ultra-violet absorption spectrum. The spectra of toluene 0- m- and p-xylenes and naphthalene have aiso been examined from this point of view. On account of the lack of symmetry of the molecule it cannot be expected that the absorption of these substances should exhibit the same degree of symmetry as is found with benzene.Of the disubstituted deriv- atives the para-isomeride is the most symmetrical and this is also found t o be expressed in the structure of the ultra-violet absorption spectrum. I n toluene o-xylene and m-xylene the want of mole- cular symmetry finds expression in the existence of fewer absorp- tion lines on the ultra-violet' side of the central line. The Phototropy of Inorganic Systems. System of Strontium Sulphide. JOSE RODRIGUEZ MOURELO (Compt. rend 19 15 160 174-176. Compare A. 1914 ii 159).-A study of the photo- tropy and phosphorescence of strontium sulphide when mixed with one or two phosphorogens. Thel experimental results are given for mixtures of strontium sulphide with varying proportions of manganese alone or manganese and bismuth the mixtures being prepared by adding t o strontium carbonate 0.15% of anhydrous sodium carbonate 0.05% of sodium chloride the given amount of the phosphorogen and lastly flowelrs of sulphur and maintaining the whole mass a t a red heat for four hours. The theoretical discussion of the results is reserved for a later paper.Optical Superposition. IV. Z-Menthylamine Tartrates and I-Amy1 Dimethoxysuccinates. THOMAS STEWART PATTERSON and DOROTHY CHRISTINA PATTERSON (T. 1915 107 142-155. Compare T. 1907 91 705).-CTnsound methods of testing the validity of van't Hoff 's principle of optkal superposition have been adopted by Walden and Guye. Tschugaev and Glebko employing a more trustworthy method draw the conclusion that their results agree with the demands of the principle at least as a first approxima- tion (A.1913 ii 897); they have howeve'r overlooked the really important question which is whether the difference between the mean of the rotations of the d-A d-B and d-A I - R compounds and that' of the d - A i-B compound is greater or less than the experi- mental error. If i t is greater van't Hoff's principle is disproved but the converse is not necessarily true. The authors have examined the three di-I-menthylamine tartrates and the three di-l-amyl dimethoxysuccinates. I n the case of the former in methyl-alcoholic solution ( c = 1.311) [MI has the value - 193.2O for I-menthylamine I-tartrate - 57*9O for I-menthylamine d-tartrate (mean - 125*5O) and - 147.5O for I-menthylamine i-tartrate.Similar results are obtained for the three di-Z-amyl dimethoxysuccinates at' 20° 60° looo and 140° but the results contain an element of uncertainty since the I-amyl alcohol used in the investigation was not quite pure. The rotation of dimethyl d-dimethoxysizccinate has been examined from about - 20° t o 180° in the homogeneous condition and also in solution in ethylene dibromide and in nitrotbenzene. H. M. D. W. G.GENERAL AND PHYSICAL CHEMISTRY. ii. 79 Alkyloxy-esters are readily obtained ; for example dimethyl dimethoxysuccinate is prepared almost quantitatively by the gradual addition of silver tartrate t o silver oxide and boiling methyl iodide. c. s. Special Case of Racemism. M. PADOA and G. KOTONDI (Gazzctta 1915 45 i 51-56).-1n his theoretical considerations dealing with the means of distinguishing racemic compounds mixed crystals and inactive conglomerates Roozeboom (A.1899 ii 401) did not t,ake into account cases of polymorphism with labile modifications which Tammann’s investigations have shown to be very common. I n order to ascertain what influence such complications exert on the characterisation of inactive mixtures the authors have investigated the case of bromocamphor each enantiomorph of which crystallises in two forms one1 labile with m. p. 45O difficult t o observe and the other stable m. p. 75O. Determination of the labile and stable solidifying points of various mixtures of d- and I-bromocamphor shows that a t a definite concentration the stable form becomes labile and vice versa.The form of the solidification curves and the composition of the different solid phases which separate indicate that the racemic compound exists between 44O and 50’5O but that it is resolved at lower temperatures into inactive agglomer ates T. H. P. Temperature Coefficients of Phototropic Transformations. M. PADOA and G. TABELLINI (Gazxetta. 1915 45 10-15).-Pre- liminary experiments with piperil-o-blylosazone and benzaldehyde- phenylhydrazone show that the thermal coefficients of the decolor- isation of thesel compounds in the dark are comparable in mapi- tude with those of ordinary reactions occurring without the aid of light whilst the influence of the temperature on the darkening of the same compounds in the light is very slight.The conclusion is drawn that phototropic transformations exhibit the characters of true chemical reactions. T. H. P. The Magnetic Deflexion of the Recoil Stream from Radium-A. H. P. WALMSLEY and W. BfAKowm (Phil. Mag. 1915 [vi] 29 253-258. Compare Abstr. 1910 ii 1022 and 1023).- If the velocity of the recoil particle is in agreement with the simple application of the law of momentum the radius of curvature of the particle in a magnetic field should be twice that of thel a-particle simultaneously expelled since the recoil particles carry one atomic charge and the a-particle carries two. Measurement of these radii of curvature in the same magnetic field f o r the a-particles of radium-A and the recoil particles of radium-B were made in a vacuum by means of a photographic plate.It was found that if the plate were left for three hours after receiving the recoil particles the a-rays from the radium-C formed in the interval produced a measurable image. As a mean of five experiments the 2 l ratio in the radii of curvature was found t o hold with considerable accuracy. F. 8. 6-2ii. 80 ABSTRACTS OF CHEMICAL PAPERS. The Velocity of the a-Particles from Radium-A. N. TUNSTALL and W. MAKOWER (Phil. Mag. 1915 [vi] 29 259-260. Compare preceding abstract).-With the apparabus used t o measure the magnetic deflexion of the recoil particle from radium-A lines on the plate due to the a-particles of radium-C formed during the exposure from radium-A were observed in addition to those from the' a-particles of radium-A. A direct comparison of their radii of curvature gave t'he ratio 0.8792.Taking the velocity of the a-particles of radium4 as 1.922 x l o 9 cm. per sec. that of the a-particles of radium-A is 1.690 x 109 in good agreement with the value 1.693 x lo9 calculated indirectly from the ranges of the two a-particles by Geiger's fornzula. Interaction of Hydrogen and Chlorine under the Influence of a-Particles. HUGH STOTT TAYLOR (J Amer. Chem. SOC. 1915 37 24-38).-Lind (A. 1912 ii 513 1027) studied the ozonisation of oxygen under the influence of a-particles and formulated an ionic theory of ozonisation which was shown to be applicable t o all the reactions caused by radioactive energy with the exception or" the combination of hydrogen and chlorine. An investigation of the combination of hydrogen and chlorine under the influence of the a-particles from radium emanation has therefore been carried out by the method used by Lind in his work on ozonisation.The results show that the union of hydrogen and chlorine under the influence. of a-particles is a reaction of the first order. The hydrogen chloride formed does not affect the velocity. Oxygen retards t'he reaction the velocity at all stages of the decomposition being inversely proportional to the oxygen concentration. The experimental facts may be interpreted by the reaction velocity equation d[ZHCl]/dt =k . J[Cl,]/[O,] where ,7 is the radiant energy employed. It is evident therefore that the reaction is strictly analogous to the photochemical reaction. The bearing of the results on the problem of the photochemical and Rontgen-ray reactions is discussed.E. G. F. S. Electric Conductivity of Mixtures of Oxygen and Autoxi- disiag Vapours of Benzaldehyde and Pinene. W. P. JORISSEN and J. A. VOLLGRAFF (Chem. IVeokbZad 1915 12 93-97).-Under the ivfluence of the ravs of a uviol lamx the autoxidation of benz- .I I aldehyde or pinene increases the electric conductivity of oxygen. A. J. 17. Electrical Conductivity of Solutions of Certain Electrolytes in Organic Solvents. J. N. PEARCE (J. Physical Chem. 1915 19 14-49).-Measurements have been made of the electrical conduc- tivity of various electrolytes dissolved in aniline quinoline and pyridine a t Oo 25O and 3 5 O or 50°. The salts examined in aniline solution were' silver nitrate aniline hydrochloride and hydro- bromide ethylaniline hydrochloride mercuric iodide ammonium thiocyanate and tetraethylammonium iodide ; in quinoline solution aniline hydrobromide silver nitrate and cobalt chloride ; in pyri-GENERAL AND PHYSICAL CHEMISTRY.ii. 81 dine solution silver nitrate lithium chloride bromide and iodide sodium iodide,. potassium and ammonium thiocyanates mercuric chloride bromide and iodide cupric chloride and nitrate cobalt chloride iind cadmium nitrate. Tables are given showing the variation of tho molecular conductivity with the dilution at different temperatures and also1 the magnitude of the temperature- coefficient. The data afford examples of solutions in which the molecular conductivity increases with the concentration and also of solutions for which the molecular conductivity attains a mini- mum a t a particular concentration.An attempt is made to explain the behaviour of such solutions by the formation of polymerised molecules which readily undergo' ionisation. The ions in the more concentrated solutions differ therefore from those which are formed in more dilute solutions. H. M. D. Inclusion of Electrolyte by the Deposit in the Silver Voltameter. T. W. RICHARDS and F. 0. ANDEREGG (J. Amel*. Chem. Soc. 1915 37 7-23).-An account is given of an investigation of the presence of included electrolyte in the crystalline silver deposited in a silver voltameter (or coulometer). The porous cup coulometer (Richards and Heimrod A. 1902 ii 592) was employed. The presence of included electrolyte was proved (1) by the quantitative analysis of the crystals dried at 160° (2) by igniting the crystals on the cathode a t a dull red heat (3) by igniting the crystals removed from the cathode in a quartz tube so arranged as to preventl evaporation of silver and (4) by showing that simul- taneous deposits which were of unequal weight before ignition had become' equal after ignition.The included mother liquor has been shown t o be partly within the crystals and partly between the crystals and the wall of the cathode. The amount of the included impurity is approximately proportional t o the area of the surface on which the! silver is deposited and increases with the roughness of the cathode; it was found to vary from 0.004 to 0.035% of the weight of the silvsi.. The silver left after ignition at a dull red heat contains less than 0.001% of impurity.Bates and Vinal (A. 1914 ii 520) in comparing the iodine coulometer with the1 silver coulometer obtained a value 126.898 for the atomic weight of iodine when that of silver was taken as 107.88 ; when corrected for inclusions in the silver this becomes 126.917 which agre'es much more closely with the best result 126.932 obtained by Baxter (A. 1911 ii 112). It is pointled out that the correction f o r included electrolyte is of great importance since i t affects the value of the electrochemical equivalent the Faraday the value assigned t o the Weston cell and all ratios of atomic weights determined electrically. Behaviour of Half- Watt Lamps Filled with Nitrogen Containing a Small Proportion of Methane or Carbon Monoxide.L. HAMBURGER (Chem. Vpekblad. 1915 12. 62-73).- The presence of more than 0-050/0 of methane or 2% of carbon E. G.ii. 82 ABSTRACTS OF CHEMICAL PAPERS. monoxide in the nitrogen employed for filling +-watt lamps renders the filament brittle and shortens the life of the lamp. A. J. W. New Thermochemical Method for Sub-dividing Accurately a Given Interval on the Thermometer Scale. THEODORE W. RICXARDS and THORBERGUR TEORVALDSON (J. Amer. Chem. Soc. 1915 37 81-86).-A method is described for accurately divid- ing any given interval on the' thermometer scale by thermochemical experiments. As an example of the method the heat of dilution of hydrochloric acid has been studied. It has been found that by choosing varying initial concentrations and varying final concen- trations temperature changes can be obtained of any magnitude from a few thousandths to several tenths of a degree.Acid of the strength HC1,20H20 was diluted with exactly 80H,O ; this reaction gives sufficient heat to raise the temperature of the total amount of liquid abouti 0*25O and by this means the interval between 16O and 20° was divided into sixteen parts. Allowaneel has t o be made of course for the1 temperature-coefficient of the reaction and other d.etails depending on changing heat capacity. The method is vary suitable for standardising short ranges such as are used in thermo- chemistry. E. G. Thermal Dilatation of Sodium Potassium and Lithium. ARCIERO BHRNINI and CARLO CANTONI (Nuovo Cim. 1914 [vi] 8 ii 241-26O).-By means of a dilatometer of special construction containing vaseline oil the authors have measured the thermal expansions of these metals at a number of temperatures ranging from Oo to 2 3 5 O .I n all cases the expansions are expressible by equations of the second degree with reference t o the temperature the values of the coefficients a and P of t and t 2 respectively,being as follows Temperature Increase of volume Melting in torval. a. B. on fusion. point. 97 -6" 62.04" 0-78' 0.031816 0.06280 Na{ ~~~~~'~~~ 100-235" 0'0,2599 0.0,286} 031% '{Liquid .. 78-235" 0'0,2681 ::$;!:} 2'44% L i { ~ ~ ~ ~ d . ~ ~ ~ 182-235" 0'0,1743 0*0,106) Solid ...... 0-56" 0'0,2112 180'1" 0-178" 0.031535 0.0792 The low values obtained by Hackspill (A. 1913 ii 503) for the increase in volume of sodium on fusion and for the melting point of this metal Ere attributed t o the use of impure material T.H. P. The Coefficient of Expansion. L. GAY (Compt. vend. 1915 160 64-67).-A mathemat'ical paper in which the author shows that in the case of a substance giving more than one hydrate it is possible starting with the coefficients of expansion of these hydrates t o calculate the expansion pressures corresponding withGENERAL AND PHYSICAL CHEMISTRY. ii. 83 equilibria between these hydrates taken two a t a time. The limits of perfect stability with respect to all these hydrates of any one of them will be on the one hand the highest pressure amongst those corresponding with equilibrium mixtures with the lower hydrates and on tlie other tlie lowest pressure amongst those corresponding with equilibrium mixtures with the higher hydrates. I f this first limit pressure is greater than the second then the hydrate will always be in a metastable state.W. G. The $olubility of Hydrates. L. GAY (Compt. rend. 1915 160 171-173).-A mathematical paper in which the1 author shows that it is possible to calculate the limits of stability of a hydrate with respect t o its solution from the coefficient of expansion of the hydrate with respect to the anhydrous compound (preceding abstract). W. G. Specific Heat at Low Temperatures. I. Measurements of the Specific Heat of Lead between 14" and 80" and of Copper between 15" and 22' (absolute). W. H. KEESOM and H. KAMERLTNOR ONNES (Pvoc. K. Akad. Tveetensch. Amsterdam 1915 17 894-914).-The method employed was t h a t developed by Nernst in which a block of the metal provided with wires for heating and temperature measurement is suspended in a vacuum in a liquid hydrogen thermostat.A measured quantity of heat is developed within the block by an electric current and the increase of temperature produced is determined. A gold wire resistance thermometer was used for this purpose this being calibrated with the aid of a hydrogen vapour-pressure apparatus and by this means the scale of the gold resistance thermometer could be reduced to1 that of platinum. A constantin wire was employed for the heating current and this was calibrated in the same manner as the resistance thermometer. The results obtained with lead show t h a t the atomic heat C has thq yalue 1.56 a t 14*19O 2.98 a t 22.31° 5-04 a t 46*253 and 5.67 a t 80.86O.Over this range the variation of the lieat capacity agrees fairly well with Debye's formula although the deviations exceed tlie uncertainty of tlie experimental results in the region of liquid hydrogen temperatures. For copper the atomic heat C increases from 0.0500 a t 15'24O to 0.1414 a t 21.505O. Over this range of temperature the atomic heat agrees with t h a t calculated from Debye's formula within 2%. H. 31. D. Metastability of the Metals in Consequence of Allotropy and its Significance for Chemistry Physics and Technics. 111. ERNST COHEN and G. DE BRUIN (Proc. K. Akad. Wetensch. Amsterdam 1915 17 926-934. Compare A 1914 ii 799).- Reference is made t o the different values wliicli have been obtained for the specific heat of certain metals a t one and the same tempera- ture by different observers.These differences are supposed t o beii. 84 ABSTRACTS OF CHEMICAL PAPERS. partly the result of differences in the previous thermal history of the metals. The recent measurements of Griffiths (A 1914 ii 245; compare also A. 1914 ii 798) of the specific heat of sodium in the solid and liquid states show clearly that the true specific heat of solid sodium is dependent on its previous thermal history. The slowly cooleld and the! quencheld metals yield definite and reproducible values of the specific heat a t a definite temperat'ure. An inter- mediate previous thermal treatment gives values f o r the specific heat which fall between the values obtained f o r the annealed and the chilled metal respectively.These1 observations lead the authors t o the conclusion that sodium is enantiotropic and that a transition temperature will be found between Oo and 90°. As usually obt'ained sodium repre- sents a metastable system consisting of a mixture of two allotropic modifications the proportions of which depend on the previous thermal treatment. H. M. D. Measurement of Vapour Pressure Lowering by the Air Saturation Method. EDWARD W. WASHBURN and EDWARD 0. HEUSE (J. Amer. Chem. Xoc. 1915 37 309-321).-This work was under- taken with a view t o obtaining an accurate method for investi- gating the molecular constitution of aqueous solutions over a large range of concentrations and a t a constant temperature. A modification of the air saturator method is described which combines the differential process first used by Ostwald and Walker with the absorption of the moisture in absorbers of such size and form as t o be capable of being accurately weighed.The type of absorber and the comparatively high rate of aspiration used necessitatled the employment of small differential manometers t o measure the fall in pressure through the apparatus. I n order to test the trustworthiness of the method measurements have been made with weight molar solutions of sucrose a t 25". The average deviation of the individual results from the mean was 0.476 whence it is evident that fairly concordant results can be obtained a t this concentration. The accuracy of the results was tested by calcula- ting the corresponding values of the osmotic pressure and com- paring them with the values obtained by Morse by direct measure- ment; the agreement between these values shows that the air- saturation method gives correct results.The work has shown that by means of the authors' apparatus values of ( p o - p ) / p o of the order of magnitude of 0.02 can be measured with an accuracy of 0.5% in an experiment of twenty- fow hours' duration. The method is now being extended t o the measurementl of the lowering of vapour-pressure of solutions of mannitol a t 2 5 O and 35O. E. G. Fractional Distillation with Regulated Still-beads. I. Gases in which the Boiling Point Passels through a Maximum or a Minimum. M. A . ROSANOFF and C. W BACON (J. A m e r . Chem. Xoc. 1915 37 301-309).-The first systemat'ic investigation of aGENERAL AND PHYSICAL CHEMISTRY.ii. 85 regulated still-head was carried out by Brown (T. 1880 37 49; 1881 39 517) who made extensive observations on the effect of cooling a saturated binary vapour to a given constant tempera- ture and enunciated the following law “ I n distillation with a still-head maintained a t a constant temperature the composition of the distillate is constant and is identical with that of the vapour evolved by a mixtarel whose boiling point equals the temperature of the still-head.” Further investigation of the regulated still-head has shown that this law requires serious modification before it can serve as the basis of a rational process of fractional distillation. I n the present paper the authors show how the regulated still-head should be expected t o function in cases in which the boiling-point curve passes through a maximum or minimum and in which therefore there may be two mixtures boiling at one and the same tempera- ture or in the words of Brown’s law two mixtures who^^ b.p. equals the temperature of the still-head.” Experiments have been made with mixtures of carbon disulphide and acetone and of ethyl iodide and ethyl acetate in which the boilinq-point curve passes throwh a minimum and with mixtures of chloroform and acetone in which the boilinppoint curve passes through a maximum. I n the case of the experiments with carbon disulphide and acetone the temperature of the still-head was maintained a t 40°; a mixture containinp only a small percentage of acetone yielded seven consecutive fractions containing 75-1-75.2 molar % of carbon disulnhide whilst a mixture con- taininp only 29% of carbon disulphide gave fifteen consecutive fractions containinq 55-2-55.4 molar ”/o of carbon disulphide.The temperature of the still-head was kept a t 71’22O during the experiments with ethyl iodide and ethvl acetate; a mixture1 con- taininp only a small percentaye of ethvl acetate gave four con- secutive fractions containing 89.9 89.3 89.2 and 89.1 molar % of ethyl iodide respectively whilst a mixture of the two com- ponents in about equal parts cave four consecutive fractions containinp 49.4 49.3. 48.9 and 48.9 molar % of ethyl iodide. I n the case of the experiments with chloroform and acetone the still- head was maintained at 6 2 O a mixture containing about 6% of acetone mve six consecutive fractions containing 92.3-92-5 molar % of chloroform whilst a mixture1 containinq rather more than 40% of chloroform vielded six consecutive fractions containing 30.8-30.9 molar % of chloroform E.G. Improved Beating Apparatus for Maintaining Constant Temperatures in Work with Polarimeters and Refractornetem. J. N. PEARCE (J. Amer. Chem. Xoc. 1915 37 147-149).-The apparatus consists of a cylindrical vessel surrounded by a layer of felt o r asbestos paper. On the bottom of this vessel is fixed a small cylinder within which rotates a motor-driven stirrer. At a point a little below the water-level is an iron tube and a similar tube opens directly into the small cylinder a t the bottom of the bath.The open ends of these tubes are attached directly t o aii. 86 ABSTRACTS OF CHEMICAL PAPERS. jacketed observation tube by pieces of rubber tubing. The water is heated by one or t,wo immersed incandescent lamps and the temperature is electrically controlled by a contact toluene1 regu- lator in series with a telegraph relay and battery. By heating the bath with a Bunsen burner the water can be rapidly heated and adjusted t o any higher temperature than that obtainable from the lamps. The bath is equally adapted f o r use with ice; for temperatures between Oo and t h a t of the room a cooling coil connected with the water supply may be introduced. The temperature of the bath can be maintained constant within 0*01-0*02° f o r any desired length of time.E. G. Densities and Degrees of Dissociation of the Saturated Vapoure of the Ammonium Haloids and the Related Thermal Data. ALEXANDER SMITH and ROBERT 33. LOMBARD ( J . Amer. Chem. Soe. 1915 37 38-70).-Previous determinations of the vapour densities of the ammonium haloids have been made on the assump- tion t h a t the dissociation is complete. This aasumption however is far from correct and only the densities of the unsaturated vapours have been measured. An investigation has now bmeeii made of the saturated vapours by the method employed by Smith and Meiizies (A. 1912 ii 114) for determining the density of saturated mercurous chloride vapour. The results together with the corresponding dissociation pressures (Smith and Calvert A 1914 ii 628) have rendered possible the calculation of the values of the degrees of dissociation the dissociation constants the1 partial pressures of the dissociation products the heats of dissociation and the latent heats of vaporisation.Ammonium chloride vapour is dissociated between 280° and 330° to the extent of 67-63% the degree of dissociation decreasing slightly between these temperatures. Ammonium bromide vapour is dissociated t o about 39% a t 320° and a t higher temperatures the percentage dissociation decreases linearly reaching about 10% a t 388O. Ammonium iodide vapour is associated especially at lower temperatures but as the temperature rises the amount of association decreases. The assumption that ammonium haloid vapours are completely dissociated is tlieref ore no longer tenable.The dissociation constant of ammonium chloride vapour increases steadily with the temperature whilst that of ammonium bromide vapour reaches a maximum a t about 320° and then decreases. The heat of dissociation of ammonium chloride vapour com- puted by the van't Hoff equation is represented by the relation [,(the heat evolved) = - 12800 - 0.009677'2 cal. The dissociation of ammonium bromide vapour above 320° is accompanied by the development of heat but the actual value of the heat of dissocia- tion cannot be computed. The latent- heats of vaporisation were calculated by the Clausius- Clapeyron equation. That of ammonium chloride is 32.9 Cal. between 280° and 330° and is const8ant within 1%; that of ammonium bromide is 28.7 Cal. a t 320° and decreases t o 24.1 a tGENERAL AND PHYSICAL CHEMISTRY.ii. 87 388O; that of ammonium iodide increases from 18.0 Cal. a t 300° bo 24.2 a t 3 8 0 O . E. G. Molecular Aasociafion of Liquids. DANIEL TYRER ( J . Physicul Chew. 1915 19 81-112. Compsre A. 1912 ii 739).-6 further examination of the methods which have been suggested as suit- able for the determination of the degree of association of a liquid. I n addition to the conditions laid down in the previous paper (Zoc. c i t . ) it is now shown that any equation which can be used for the accurate determination of association factors must be valid for mixtures as well as for pure liquids. This is necessitated by the fact that an associated liquid is in general a mixture of different kinds of molecules. Approximate minimum values of the association f act'ors a t the boiling points may be obtained by means of the empirical equa- tion Ts=KVTslogM in which T is the boiling pointl ITs the molecular volume a t the boiling point &I the molecular weight and K a constant equal t o about 37.The minimum values thus obtained are water 6.3 ; methyl alcohol 2.55 ; ethyl alcohol 1.89; formic acid 2.71 ; acetic acid 2-05. The re'lation of Kistiakowski a2J1/T8=K where a2 is the capillary rise in a tube of 1 mm. radius and K is a general con- stant may also be considered a good test f o r association. Molecular weights od liquid substances may also be calculated from the equation M ( C P - - C ~ ~ ) / I 7 ~ = = K in which Cp and C are the specific heats a t constant pressure and constant volume and V is the molecular volume.This equation is approximately satisfied by the data f o r a considerable1 number of normal liquids but others usually regarded as normal would appear t o be associated on the basis of this equation. This is the case f o r example with carbon disulphide and it is shown that this substance behaves frequently as if it were an associated liquid although several of the recognised methods of molecular-weight measurement indicate that it consists essentially of simple molecules. It has been shown previously (A. 1914 ii 431) that the equa- tion P y4j3/ T1/3 = A' in which P is the isothermal compressibility y the surface tension and T the absolute temperature holds for a large number of liquids. This relation does not involve the molecular weight but wate'r ethyl alcohol and carbotn disulphide yield values fof K which are too high.To explain these and other anomaJies it is sugge'sted that the mean kinetic energy of the molecules of such liquids is less than the kinetic energy of free gas molecules at the same temperature. I n the case of carbon disulphide this is the1 only factor which produces anomalies in certain of the physical properties whilst' with water and the alcohols moleculaz association also comes into play. H. M. D. Capillarimeter Viscostagonometer and Stalagmometer T. TRAUBE and R. XOMOGYI (Intem. Zeitsch. phys.-chem. Biol. 1914 1 485-490) .-These three apparatuses give practically identical results for the surface1 tension of non-colloidal liquids. Withii. 88 ABSTRACTS OF CHEMICAL PAPERS.colloidal liquids the results obtained with the viscostagonometer am lolwer than those given by t'he stalagmometer b'ecause the colloidal material slowly moves towards the surface. The viscostagonometer measures the surface tension of the older (Iongelr existing) surfaces whereas the stalagmometer measures those newly formed. The capillasimeter cannot be used with colloidal liquids. H. W. B. Stalagmometric Studies of Solutions of Colloids and Crys- talloids. IV. Diffusion in the Surface Layer. L. BERCELLER (Intern. Zeitsch. phys.-chem. Biol. 1914 1 124-132. Compare A. 1913 ii 760).-In the measurement of the surface tension of solutions by means of Traube's stalagmometer varying results are obtained with varying rates of formation of the drops. The quicker the drops form and fall the greater the value obtained for the surface tension.The int'erpretation given to this pheno- menon is that the surface layer forms so rapidly in the drop that the dissolved substance has not sufficient time to accumulate in it and attain to the concentration it reaches when tho surface of the liquid is a t rest. It follows that the slower the rate of diffusion of a substance the more marked should be the alteration of the surface tension of its solution with change in the rate of drop formation and in accord with this i t is found that solutions of colloids such as the proteins and soaps produce much greater variations than solutions of the crystalloids such as acetone and the alcohols. H. TV. B. DifFusion of Hydrogen through Palladium.ALFRED HOLT (Proc. Roy. Soc. 1915 [ A ] 91 148-155).-The diffucion of hydrogen through a palladium septum a t temperatures ranging from 70° to 300° has been investigated by (I) measurements of the rate of diffusion of hydrogen a t constantl pressure into a vacuum ; (2) measurements of the rate of diminution of pressure when diffusion takes place into a vacuum; (3) measurements of the rate of diminution of pressure on one side and increase of pressure on the opposite side of the septum during the diffusion of a definite quantdty of hydrogen. If the logarithm of the pressure (decreasing) is plotted against time the experimental data f o r each experiment in which the pressure decreases yield two intersecting straight lines. I n the case of increasing pressures the graph of log (760 - p) against time affords similarly two straight lines.The conclusion drawn from the results is that a t pressures between 700 and 100 mm. the rate of diffusion is proportional t o the pressure of the hydrogen. As in the case of the rate of dissolution of hydrogen in palladium where discontinuity has also been observed the two straight lines of different slope are accounted for by metallic allotropes. A t pressures below 100 mm. the diffusion becomes much slower and the rate of diffusion does not seem to be related to the pressure in any simple manner. H. hl. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 89 Effect on their Solution Tensions of Dissolving the Alkali and Alkali Earth Metals in Mercury a n d the Constitution of Such Solutions. GEOBGE MCPHAIL SMITH (J.Arner. Chem. Soc. 1915 37 76-80).--In an earlier paper (A. 1908 ii 159) it was suggested that in some cases when metals aro dissolved in mercury compounds of mercury and the dissolved metal are formed containing a single atom of the latter in the molecule. More recently (A 1914 ii 543) the author has shown by means of the diffusion method that in mercury solution compounds prob- ably exist such as LiHgs NaHg KHg CaIIg and BaHgG. Confirmatory evidence has now been obtained by a study of the solution tensions of the alkali and alkali earth metals in mercury. I f small equimolar quantities of these metals in equal large quantities of mercury exist in solution in the form of free monatomic molecules their solution tensions should be lowered but in a more or less uniform manner; the relative magnitude of the solution tensions should not be greatly altered.If however the metals combine with mercury t o form compounds containing only one atom of the amalgamated metal to the molecule the solution tensions should be lowered t o a much greater degree and not uniformly but in accordance with the relative affinities of the metals f o r mercury. The results of the present work show con- clusively that the latter actually occurs; the solution tensions of the metals when dissolved in excess of mercury decrease in the order K Rb Cs Na and Ca Sr Ba. E. G. Electric Synthesis of Colloids. JNANENDBANATH MUKHOPADHYAYA (J. Amer. Chem. h'oc. 1915 37 292-297).-This investigation was undertaken in order t o elucidate the process of the formation of colloid solutions by Bredig's electric method (A.1899 ii 78). Benedicks (A. 1913 ii 99 307) has expressed the opinion that the process is mainly of a thermal character the metal melting into fine drops which remain suspended. Experiments have now been made in which various substances were placed between the carbon electrodes of an electric arc immersed in water and it has been found that at the intense heat of the arc discharge the substance is volatilised and the fine particles on condensation form sols. The method gave good results with sulphur selenium and phosphorus; the sols were fairly stable and showed the Tyndall phenomenon. I n the case of cadmium and copper the hot metal reacts with the water with formation of some hydroxide'; the colloidal solution obtained is unstable and soon coagulates the precipitate consisting of a mix- ture of the metal and its hydrotxide.The method is very rapid in the case of mercury and yields a stable grey sol. The results of these experiments support the view that the formation of the sols is a thermal process due to' the high temperature of the electric arc. E. G. Value of Viscosity Measurements for the Gharacterisation J. SCHIBIG (Intern. Zeitsch. plays.-chem. Biol. of Organic Colloids.ii. 90 ABSTRACTS OF CHEMICAL PAPERS. 1914 1 260-.268).-A summary of the theoretical considerations already expressed in a published dissertation. €1. w. B. Study of the System Water Potassium Iodide and Iodine at 0'. GRINNELL JONES and MINER LOUIS HARTMANN (J.Amer. Chem. Xoc. 1915 37 241-258).-Bray and MacKay (A. 1910 ii 820) have determined the conductivities a t 25O of potassium iodide solu- tions saturated with iodine. A similar investigation has now been made a t Oo by the same methods. The conductivities of potassium iodide solutions and of the same solutions saturated with iodine have been measured a t concentra- tions between 0.lN and O*OOlX. The solubility of iodine in these potassium iodide &solutions and in water has also been determined at Oo; the solubility in water is 0*0006383 mol. per litre. The viscosities of the solutions a t Oo and 25O have been detlermined and the results applied t o the correction of the degree of dissociation of potassium iodide a t these temperatures. The mobilities of the iodide and tri-iodide ions a t Oo are 43.4 and 22.8 respectively.The hydrolysis constant of iodine in water a t Oo is 9 x 10-15. Bray and MacK.ay found that a t 25O the ratio of the iodide and tri-iodide ions I- 1 decreased from 1.14 to 0.99 with increasing concentrations of 0-001N t o 0-IN and became 0.35 at N . A t Oo however no such marked deviation occurs although a slight tendency in that direction appears in the 0-05N- and O'lN-solu- tions. Assuming that this apparent deviation from the mass law a t 25O is due to the formation of higher complexes than KI it is evident that the' formation of these higher complexes is much less at Oo than a t 25O. E. G. Equilibrium in the System Water Phenol and Benzene. SHINKICHI HORIBA (illem. CoZZ. Xci. Kpoto 19 14 1 49-55).-The equilibrium relations in the above ternary system have been examined a t 25".The phenol in the solutions was estimated by means of bromine and the benzene and water by measuring the quantities of each which were necessary for the production of permanent turbidity. The results are recorded in a series of tables and also in the form of a triangular graph. H. M. D. Theory of Dyeing. IV. WILDER D. BANCROFT (J. Physical Chem. 1915 19 50-64. Compare A. 1914 ii 436).-A further discussion of observations recorded in the literature relating to the distribution of substances between solid and liquid phases. I n general these observations afford no evidence of the formation of definite compounds and thus furnish support for the author's view that the formation of definite compounds plays no important part in the practice of dyeing.H. M. D. Theory of Dyeing. V. WILDER D. BANCROFT (J. PhysicaZ Chew. 1915 19 145-158).-The question of the fastness of dyes is dis- cussed by the methods followed in the previous papers belonging to this series (compare preceding abstract). It would appear thatGENERAL AND PHYSICAL CHEMISTRY. ii. 91 the many contradictory statements rellative t o the fastness of dyes on different fibres are mainly due t o unspecified differences in the conditions of the experiments. The fact that many dyes are faster to light in iron chromium and copper mordants as conipared with aluminium and tin mordants is said t o be probably due t o differences in the absorption of light. H. &I. IL). Rate of Reduction of Mercuric Chloride by Sodium Formate.G. A. LINHAHT (J. Amer. Chern. Soc. 1915 37 70-'76).-In an earlier paper (A. 1913 ii 490) an acconnt was given of an investigation of the rate of reduction of mercuric chloride by phosphorous acid. A similar study has now been made of the reduction of mercuric chloride by sodium f ormate with special reference to the influence of sodium chloride on it. This reaction has already been investi- gated by Findlay and Daviw (T. 1913 103 1550) who consider that it is of the second order Bince when their results are substi- tuted in an equation representing a reaction of the third order the reaction velocity-coefficient gradually increases to about 40% whilst if substituted in one of the second order t'he velocity-coeffi- cient decreases by only about 17%.The present work shows that the mechanism of the reaction between mercuric chloride' and sodium formate may be interpreted in a similar manner to that of mercuric chloride and phosphorous acid and that concordant velocity constants may be obtained if the experiments are carried out under suitable conditions. It has been proved both experimentally and theoretically that the reaction is one of the second order. The sodium chloride formed during the reaction exerts a remarkable retarding effect. This effect however was reduced to a minimum by using dilute solutions of mercuric chloride and by adding initially a large excess of sodium chloride t o the reaction mixture so that the amount of sodium chloride formed in the reaction was rendered negligible.Under these conditions concordant velocity constants were obtained. E. G. Oxidation of Sucrose by Potassium Permanganate. C. W. R. POWELL (J. Roy. SOC. New South Wales 1914 48 223-241).- Measurements have been made of the rate a t which potassium permanganatle reacts with sucrose in acid neutral and alkaline solution. The rate of the reaction is least in neutral solution and higher oxides of manganese are precipitated during the course of the reaction unless a oertain quantity of acid is present a t the beginning. For this reamson the majolrity of the observations were made in acid solution. The author considers that the results point to a bimolecular reaction although the velocity-coefficient increases during the course of the change. The increase in velocity is attributed to the accelerating influence of the manganese sulphabe which is formed during the reaction.Within certain limits the nature of the reaction does not seem to be affected by the concentration of the acid but the initial velocity is approximately proportional to theii. 92 ABSTRACTS OF CHEMICAL PAPERS. hydrogen-ion concentration. The velocity is increased in the ratio 3.0 1 for a rise of temperature of loo. Although dextrose reacts with permanganate more rapidly than sucrose this does not seriously affect the results obtained for the quantity of dextrose formed during the time required by the experiments is comparatively small. H. M. D. Gatalytic Action of Alkaloids on Various Physical and Ghemical Processes (Precipitation Oxidation and Saponifica- tion).1. THAUBE and N. ONODEHA (Intern. Xeitsch. phys.-cliem Bzol. 1914 1 148-157. Compare Traube A 1912 ii 740).-An intro- ductory paper giving results of experiments in which alkaloids have exerted an inhibitory or accelerating influence on the velocity of various reactions. Alkaloids although univalent greatly acce- lerate the precipitation of arsenious sulphide from its colloidal solution and hasten the oxidation of oxalic acid by permanganate. A few alkaloids inhibit the Saponification of ethyl acetate by potassium hydroxide whilst the majority aid it. Pilocarpine and atropine have a similar action on the first two processes but on the saponification process pilocarpine has a very strong accelerating and atropine an inhibitory action so that in this case a striking example is afforded of the antagonistic action of these two alkaloids.The antagonistic action observed betweed these two drugs in the body in relation to gland secretion dilation of pupil etc. is possibly to be correlated with their action on hydrolytic processes. H. W. B. The Series Spectrum of Hydrogen and the Structure of the Atom. N. BOHR (Phil. Mag. 1915 [vi] 29 332-335).-The author criticises certain deductions made by Allen (this vol. ii 33) in which it was assumed that the nucleus of the Rutherford atom has the properties of a small magnet in addition to its electric charge. The argument put forward shows that the sugges- tion of the nuclear magnet can scarcely be considered as supported by the accurate measurements made by Curtis (A.1914 ii 761) of the wave-lengths of the series lines in the hydrogen spectrum. In view of the doubling of the hydrogen lines it seems unjustifi- able to compare the results of these measurements with any theo- retical formula. Since the distance between the components is much greater than the deviations from the Balmer formula and since also the componenta are of unequal intensity i t is not possible to place any satisfactory interpretation on measurements of the “centre of gravity” of the lines. As a possible explanation of the doubling of the lines i t is suggested that this may be due to the orbits of the electron not being circular. H. M. D. The Gyroscopic Theory of Atoms and Molecules. ALBERT C. CREHORE (PhiZ. Mag. 1915 [vil 29 310-332. Compare A. 1913 ii 689).-A theoretical paper in which the author develops a theory of atomic structure which differs considerably from that of Ruther-GENERAL AND PHYSICAL CHEMISTRY.ii. 93 ford according to which the electrons circulate in orbits which are very large compared with the radius of the central positive nucleus. I n the author's theory the densiby of the positive and negative electricity is the same and has a constant value which is approxi- mately equal to 10l2 grams per C.C. The mass of the atom is accounted for by the larger volume of the positive electricity the ratio of the volumes of the positive and negative electricity being the ratio of the masses of the hydrogen atom and the electron. It is assumed that there is no radiation of energy from the atom so.long as the electrons describe circular orbits in the stleady state but a disturbance of this state iiiay give rise t o rapid nutations of the ellect.rons both natural and forced which will account for the emission of X-rays. I f there E's more than one electron in the same orbit the natural nutation frequencies are not easily obtained from analogy with gyroscopic equations and it is assumed that these frequencies are prolportional t o the number of electrons per ring. This assumption in combination with the grouping of the electrons which has been described previously (LOC. cit.) leads to a tentative dist'ribution of electrons which will account for the K and L series of X-ray spectra. Light vibrations are attributed to the precessional frequencies of the electrons in their orbits and it is shown that the principal constant in Balmer's formula f o r the hydrogen series can be expresseld in terms of constants characteristic of the hydrogen molecule. The atomic model described by the author is capable of response to any frequency of light because there are precessional frequencies produced in the atom which are proportional to those of the impressed force.I n this connexion i t is pointed out that no form of atom which is capable of resonance1 a t fixed frequencies only can accoant for the experimental facts relating to the photo-electric effect. The theory shows further that there is a limiting value of th0 atomic weight in t'he neighbourhood of uranium. I n this region the outside ring of eledrons is unshable and comparatively small forces suffice t o drive an electron outside the region of positive electricity leading to1 an internal readjust'ment and the display of radioactive properties.H. M. D. Calculation of the Molecular Dimensions from the Sup- position of the Electric Nature of the Quasi-Elastic Atomic Forces. J. J. VAN LAAR (Proc. K. Akad. Ivetensch. Amsterdam 1915 17 877-884. Compare A. 1914 ii 801).-A theoretical paper in which the author makes use of a formula given by van der Waals in ordelr t o obtain values for the' size of molecules. For argon hydrogen and helium the values obtained for the molecular diameter are 3.5 3.2 and 3 . 2 ~ 10-8 em. respectively. I n spite of the difference in molecular weight there is therefore very little difference in the molecular diameter.For other not too complex substances the value obtained rarely exceeds 4 x 10-8 cm. VOL. CVIIT. ii. 7 H. M. D.ii. 94 ABSTRACTS OF CHEMICAL PAPERS. Classification of the Elements. J. R. RYDBERG (J. Chim. Phys. 1914 12 585-639).-A grouping of the elements is described which differs in many respectis from the MendelBev system. The arrangement involvw the view that the atomic weight is not a fundamental property of the elements and hence i t is not t o be expected that the properties will be dependent on the atomic weight,. The quantities which are substituted for the atomic weights as being of fundamental character are the successive intlegral numbers commencing with unity. The change of the independent variable is based on the idea that the “ordinal numbers ” correspond with certain states which we designate as atoms and which possess the property of mass.This property increases continuously as the corresponding ordinal N increases although other properties show a more or less pronounced periodicity. Arranged in the above manner the1 elements fall into a series of groups containing 4 9 elements where p is equal to 1 2 3 4 . . . Thus the first group contains four elements whilst the second third and fourth groups contain sixteen thirty-six and sixty-four respectively. Since the known elements terminate with uranium (LV=94) the first four groups are more than sufficient t o accommodat’e all the elements and actually i t is found that the elements belonging to the fourth group are confined t o the first half of this group with the exception of radium (go) thorium (92) uranium (94) and three unknown elements (89) (91) and (93).The first group GI begins with hydrogen (1) and ends with helium (4) and between these are two more or less hypothetical elements supposed t o be identical with coronium (2) and nebulium (3). The second group G begins with lithium (5) and ends with argon (20); the third G begins with potassium (21) and ends with xenon (56); whilst the incomplete fourth group G begins with cxsium (57) and includes all the remaining elements. The first half of the fourth group terminates a t niton (88) and from msium to niton there are 32 elements whereas MendelBev’s system requires 36 elements in this interval. Plausible arguments are advanced in support of the smaller number which is required by the autlhor’s system of classification. Although mechanical mass is an attribute which appears to be confined to the elements for which N = or >I i t would seem that A7=0 should correspond with a state of matter and N=O is supposed to represent the electron which thus forms the first member of the entire series and the only member of the group Go.The author describes his methods by means of which i t is possible to represent diagrammatically the relations between the groups and the periodic recurrence of atomic properties. In one of these the members of the four groups are placed in order along succes- sive turns of a spiral. Periodicity in properties is not only deter- mined by a complete turn of the spiral but recurrence of simi- larity in properties is also found in elements which occupy corresponding positions in the four quadrants of the successive turns of the spiral.GENERAL AND PHYSlCAL CHEMISTRY.ii. 95 This periodicity is very clearly shown in respect of the valency and the valency relations exhibited by the author's system are discusse'd ilr detail. The analysis of the valency relations leads the author to the' conclusion that the valency of an element is deter- mined by the operation of two entirely different factors one of which is independent of the ordinal number N whilst the other is determined by the magnitude of N . When the first factor only operates the probable valency is three although the neighbouring valencies two and four may also be impressed upon the atom in certain cases.The relations exhibited by the' valencies are con- sidered to add considerable weight to the classification which the author describes. H. M. D. Electron Conception of Valence. VI. Inorganic Com- pounds. J. M. NELSON and K. GEORGE FALK (J. Amer. Chem. Soc. 1915 37 274-286).-1n this paper the electron conception of valence (A. 1911 ii 104 171; 1913 ii 768; 1914 ii 44 193) is applied to the constitution and reactions of inorganic compounds and particularly to the views of chemical structure based on the classificatio,ns developed by Werner. E. G. Modified Kipp Generator. TEEODORE COHEN (J. Arner. Chem. Xoc. 1915 37 145-146).-A simple form of gas generator is described which can be used as a substlitute for Kipp's apparatus and is particularly suitable for the use of individual students for ensuring a ready supply of hydrogen sulphide. It consists of three gas bottles an inverted reservoir bottle f o r the acid which is connected by rubber tubing t o an upright bottle which is in turn connected by a glass tube to' another inverted bottle containing the ferrous sulphide or other material. The reservoir bottle is fitted with a thistle-funnel with bent-up tube for admitting the acid and the generating bottle bears a glass tube which passes from the bottom of the bottle downwards through the stopper is then bent outwards a t right angles and has a piece of rubber tubing and a pinch-cock at the end. On opening the pinch-cock the pressure within the apparatus is released and acid flows down into the upright bottle whence it is forced up into the generating bottle. On closing the pinch-cock the acid is auto- matically driven back into the reservoir bottle. E. G. Vacuum and Pressure Stopcocks. MERLE RANDALL and F. RUSSELL VON BICHOWSKY (J. Amer. C h m . Soc. 1916 37 137-144).- A description is given of the form and dimensions of the various stopcocks used in the chemical laboratory of the University of California. These include diff ererit types of vacuum stopcocks pressure stopcocks and multiple stopcocks. E. G.

ISSN:0368-1769    

DOI:10.1039/CA9150805077

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 93 History and Development of Physico-chemical Research in Biology. H. J. HAMBURGER (hter?&. zeitsch. phys.-chem. Biol. 191 4 1 6-27) .-Histo8rical. H. W. B. Internal Friction and Surface Tension in Biological Pro- cesses. 1. TRAUBE (Intern. Zeitech. yh/s.-cherrL. Bid. 191 4 1 275-291. Compare Schryver A. 1911 i 245).-The author points out thai; Schryver's assumption of a limiting layer between the two phases of a heterogeneous system is of great significance in the interpretation of the most varied biological velocity-processes (hzmolysis ferment destruction narcosis osmosis etc.). The viscosity and surface tension of such a limiting layer will modify the hzmolytic power of lipoid-soluble substances (Traube A 1908 ii 708) for the greater the viscosity the greater the resistance t o the entrance of the hzmolytic fluid and the greater the difference in surface tension required t o bring about hzemolysis.The viscosities of various se'ra have been measured by the author and itl is louiiil that the serum of the guinea-pig which has the lowest' viscosity has the greatest contlent of (' complement." The alteration in surface tension and the content of complement of sera appear t o run parallel. The relation between the inhibitory influence of certain narcotics on clot fo'rmation and their surface tension (Schryver A. 1914 i 616) probably becomes an absolute one when the effect of the viscosity of the limiting layer is taken into account. An osmotic law of the nature of Ohm's law is formulated in the terms that the osmotic velocity of a substance (the quantity of material osmotically moved in a unit of time) is proportional to the cohesion o r surface pressure and inversely proportional to the viscosity constant. II.W. B.i. 94 ABSTRACTS OF CHEMICAL PAPERS. Changes in the Blood After Muscular Activity and During Training. EDWARD C. SCHNEIDER and LEON C. HAVENS (Arner. J. YAysioZ. 1915 36 239-259).-During rest a guantit'y of blood i.; stagnant in the splanchnic area. On exertion carbon dioxide is produced which stimulates the adrenal gland ; the increased output of adrenaline forces the stagnant blood into the general circula- tion ; this increases the specific gravity hzmoglobin and corpus- cular content of the blood. Muscular contraction accelerates also the flow of lymph and lymph rich in leucocytes is thrown into the blood.Figures are given to support these general conclusions. Abdominal massage corrects stagnation of blood there. At a great altitude exercise does not have these effects except in so far as a rise in white corpuscles and plat'elets is seen. During athletic training the red corpusclea and hzmoglobin increase ; leucocytes and platelets do not alter. Mononuclear cells increase 4%. No change in total oxygen capacity or total blood volume occurs. W. D. €I. The Effects of Thyroid Extracts on Blood Pressure. G. C. FAWCETT JOHN ROGEHS JESSE M. RABE and S. P. BEEBE (Amer. J. Physiol. 1915,36 113-125).-1odine was present io all the fractions used but those richest in iodine (coagulable fractions) produce little or no fall of blood pressure; the residue after the removal of the1 coagulable fractions has a depressor effect after intravenous but not after subcutaneous injection ; rapidity of the heart is sometimes also produced. The active substance is not precipitated by basic lead acetate is unaffected by boiling or by passage through a Berkefeld filter and is soluble in alcohol. No immunity was observed during the limit of the experiments (four t o six hours). W.D. H. I. A. RABENS (Amer. J. PApioZ. 1915 3 6 294-398).-The transfusion of blood has no effect on the kidneys (as Hedon considers) nor on the body metabolism generally. Factors Affecting the Coagulation Time of Blood. VI. The Effect of Rapid Progressive Hemorrhage. KATHERINE R.DRINKER and CECIL K. DRINKER (Anzey. J. Physiol. 1915 36 305-324).-Rapid progressive hzmorrhage produces progressive lessening in the coagulation-time of blood. An occasional animal shows no change. Antithrombin is lessened when the coagulation- time decreases and remains constant when it does not. Prothrom- bin tends to increase slightly a t first and then decreases slightly. Fibrinogen estimated as a heat-coagulum decreases as hzmorrhage progresses. The blood-platelets show no alteration. W. D. H. The Blood Relationship of Animals as Displayed in the Composition of the Serum-Proteins. 111. A Compftrison of the Sera of the Hen Turkey Duck and Goose with respect to their Content of Various Proteins. W. R. THOMPSON ( J . BioE. Chem. 1915 20 l-6).-Brailsford Robertson's reFractometric The Influence of Blood Transfusion on the Kidneys.W. D. H.PHYSIOLOGICAL CHEMISTRY. i. 95 method was employed for the estimations; the birds were kept fasting between leighteen and twenty hours before they were bled. The following table summarisee the average results obtained Tot a1 proteins per cent. of serum. Hen ................................. 5.0 Rooster ............................. 6.0 Turkey .............................. 6-2 DU& .............................. 6.7 Goose .............................. 4.1 InsolukJt? Total Total globulin gIobulins albumins per cent. of the total proteins. 14-9 23 77 11.4 19 81 7'4 16 84 21% 29 72 17-2 26 74 W. D. H. The Blood Relationship of Animals as Displayed in the Composition of the Serum-Proteins.IV. A Comparison of the Sera of the PigeoD Rooster and Guinea Fowl with respect t o their Content of Various Proteins in the Normal and in the Fasting Condition. R. S. BRIGGS (J. Biol. Chem. 1915,20,7-11). -This investigation was carried out by the same method as in the preceding paper and the following table gives the results Total proteins pw cent. of serum. Pigeon normal .................. 4-4 fasting ................... 4.8 Rooster normal ..................... 3 '3 . fasting ..................... 4 *1 Goinea-fowl normal ............... 3'7 fasting ............... 4 '1 Insoluble Total Total gl obnlin globulins albumins per cent of the total protoins. 7.3 28 72 2.7 14 86 16.4 38 62 12-1 33 68 6.2 30 T O 4'7 5 95 A r- \ W. D. H. Physico-chemical Researches on Blood Sera.I. TRAUBE (Intern. Zeitsch. phys.-chem. Biol. 1914 1 389-41 l).-The auhhor has determined the following constants for a large number of human and animal sera (a) viscosity ( b ) surface tension (c) alka- linity and (d) quantity of capillary-active acids. The first two constants have been measured by the viscost'agonometer (A* 1912 ii 832) and the last two by the stalagmometer. The new method of est,imating the alkalinity is based on the observation that the surface tension of solutions of many alkaloids is lowered by the addition of a trace of alkali. Applying this method to the blood it is found that human blood serum has an alkalinity corresponding with a 0~05-0~06N-po~tassium hydroxide solution. The methad for the estimation of the capillary-active acids in serum depends on the fact that strong mineral acids liberate them from the serum.Of all the animal sera examined that of the guinea-pig (which contains the largest quantity of "complement ") possesses the smallest viscosity the least alkalinity and the smallest amount ofi 96 ABSTRACTS OF CHEMICAL PAPERS. capillary-active acids. The alkalinity of the sera of birds is greater than that of mammals whilst the serum of the frog has the least alkalinity of all. The1 results of the examination of human sera were most dis- tinctive in the cases of the viscosity constant and the surface tension. The viscosity constant is considerably increased in jaun- dice heart disease etc. and lowered in anzemia etc. The alkalinity of human serum is lowered in all cachectic diseases-carcinoma pernicious anzemia pneumonia etc.H. W. B. Capillarimetric Researches on the Serum and Cerebrospinal Fluid of Man. BRUNO KISCH and OTTO REMERTZ (Intern. Zeitsch. phys.-chern. Biol. 1914 1 354-388).-The surface tension of human blood serum in health and in many diseased conditions is exceed- ingly constant provided the specimen is clear and not discoloured with hzmoglobin. Chylous sera and those tinged red with hzmo- globin have a distinct'ly lower surface tension. The chief instances in which the surface tension was constantly lower than normal were obtained in cases of epilepsy eclampsia urzmia and jaundice. InactJvation of sera by warming a t 56-60° f o r half-an-hour lowers the surface tension due apparently to an alteration in the condition of the serum colloids.After having once been inacti- vated repeated warming and cooling of the serum does not change the surface tension. Serum from fetal blood has a distinctly lower surface tension than thai; from tho mother and it becomes still lower when inactivated a t 56". This is possibly due t o the presence of capil- lary-active substances in the fetal blood or to a difference in the composition of its colloid constituents. Throughout pregnancy the blood serum remains normal with respect to its surface tension and behaviour on inactivation. The cerebrospinal fluid also has. a remarkably constant surface tension which is always considerably higher than that of the blood serum. Any alteration in the1 latter is usually accompanied by a corresponding alteration in the former.Age and sex have no influence on the surface tension of either the blood serum or the cerebrospinal fluid. H. W. B. Hmmolysis. I. Hemolysis by Capillary-active Substances in Cold-blooded Animals. BRUNO KISCFI (Intwn. Zeitsch. phps. - chem. Biol. 1914 1 60-8l).-The author has ascertained t h e concentration and surface tension of the solutione of a series of capillary-active substances (methyl ethyl propyl isobutyl and isoamyl alcohols acetone and ethyl ether) which Just hzmolyse the erythrocyt>es of certain cold-blooded animals (Sipzcncuhs n.udus Scyllium catulus Torpedo marmorata Scorpena scrophn. Lophius piscatorius Labrus tardus and L. festiuus). It is found that hzmo- lysis is not accomplished by iso-capillary solutions and consequently some other factor besides surface tension and lipoid-solubility is concerned in the hzemolytic process.The subjects of experimentPHYSIOLOGICAL CHEMISTRY. i. 97 are enumerated above in the order corresponding usually with the relative ease with which their erythrocytles are hEmolysed by the alcohols employed Sipunculus requiring the lowest concentration of the alcohol and Labrus the highest. H. W. B. Lipoids in Immunity. 11. I?. H. THIELE and DENNIS HMBLETON (J. Path. Bact. 1915 19 349-371).-The hzmolytic power of serum is not related t’o i€s lipolytic activity. Hzemolysin is not lipase. Anti-substances cannot be1 pro’voked against tissue fats lipoids or phosphatides. The phosphatides of the tubercle bacillus however provoke the formatlion of anti-substances which are not wholly specific.Anaphylaxis was also noted. W. D. H. The Mechanism of Anti-substance Action. F. H. THIELE and DENNIS EMBLETON (J. Path. Bact. 1915 19 372-391 ).-The act,ivity of complerment depends on its concentration not on its amount. Amboceptor combines quantitatively with its antigen and its adivity does not depend on its concentration. The curves of complement action resembles those of enzyme action. W. D. H. Physico-chemical Behaviour of Ferments in the Stomach After Administration by the Mouth. Nature of Proferrnents. ERNST P~IBRAM and A. PERUTZ ( T n t e r n . Zeitsch. phys.-chem. BioZ. 19 14 1 269-274).-When rennet o r pepsin is introduced into the rabbit’s stomach i t is quickly adsorbed and if the animal is killed from thirty minutes to1 an hour after feeding the adsorbed ferment can be extracted from the mucous membrane by means of sodium carbonate solution.On acidifying the extract the active enzymes are set free. The mucous membrane of the normal rabbit’s stomach when similarly treated yields neither pepsin nor rennet. Trypsin in alkaline solution is also rapidly adsorbed by the living mucous membrane of the stomach and can be subsequently extracted by dilute acid and shown to’ be active by its behaviour towards protein in the presence of alkali. These adsorbed fer- ments stand in the same position as the so-called ‘(proferments” or “ zymogens,” and yield the active enzymes by exactly similar treatment. The authors also found that when the enzymes were adminis- tered in a 10% sucrose solution the adsorption phenomena did not occur the enzymes (pepsin and rennet) meanwhile retaining their activity unchanged.H. W. B. Quantitative Relation between Temperature and Standard Metabolism in Animals. AUGUST KROGH ( I n t e r n . Zeitsch. p h p - chem. Bid. 1914 1 491-508).-The effect of varying the tempera- ture of animals on the metabolism (as measured by the oxygen output) has been determined under conditions involving the mini- mum functional activity that is the nearest attainable approxi- mation t o the basal metabolism which would obtain when all organs were absolutely at rest. Under these standard conditionsi. 98 ABSTRACTS OF CHEMICAL PAPERS. (all nervous influences being abolished by curare and methyl carbamatle) the influenoe of temperature on the metabolism of an animal is regular and constant and can be expressed in a definite curve which is not a straight line and cannot be expressed by Arrhenius’ formula or van’t Hoff’s rule indicating the temperature relations of chemical reactions. The curves obtained for frogs and goldfish and in a single experiment for a young dog are identical while that for chrysa- lides of Tenebrio is distinctly different although of the same general type.H. W. B. Nature and Formation of the Fertilisation Membrane of the Echinoderm Egg. J. F. MCCLENDON (lnlerm. Zeitsch. phys.-chern. Biol. 1914 1 163-168).-1f the mucus layer (jelly choreion zona pellucida) is removed from t’he sea-urchin’s egg before fertilisation a fertilisation membrane is not formed although the egg segments.The author was also unable t o detect the presence of any mem- brane of the toughness t-hat characterises the fully-developed ferti- lisation membrane on the surface of the unfertilised egg. These observations confirm the author’s view that the fertilisation mem- brane is formed by the mutual precipitation a t their surface of contad’ of two oppositely charged colloids-the mucus and the perivitelline jelly. H. W. B. Parallelism between Increase in Permeability and Abnormal Development of Fish Egge. J. F. MCCLENDON (Intwn. Zeitseh. phys.-chem. Biol. 1914 1 28-34. Compare A. 1912 ii 1196)- Distilled or sea-water solutions of nicotine o r the salts of lithium sodium potassium calcium or magnesium all produce abnormali- ties in the development of the eggs of the smelt o r of Fundulus heteroclitus placed in them in early segmentation strages.These substances are found to increase the permeability of the eggs t o salts or their ions the eggs being normally impermeable to salts in pure water o r “balanced” salt solutions. Since the increase in permeability occurs before the abnormalitiea appear i t is prob- able that the abnormal permeability is the cause of the structural abnormality. H. W. B. Antagonistic Action of Carbon Dioxide and Adrenaline on the Heart. S. W. PATTERSON (Proc. IZoy. Soc. 1915 [R) 88 371-396).-The author has investigated the action of carbon dioxide and adrenaline on the heart isolated from the nervous system by Starling and Knowlton’s method (A. 1912 ii 571) the animals employed being dogs and cats.It is found that carbon dioxide in all doses appears to have a depressant action on all the functions of the heart; the contractile stress is developed more slowly and the output of blood is dimin- ished. The coronary circulation is unaltered. Adrenaline increases the rate of contraction of the heart and the rate of development of the contractile stress. It seems t o have a specific actior in mobilising the “ contractile substance ” andPHYSIOLOGICAL CHEMISTRY. i. 99 increasing the energy changes taking place a t the surface of the muscle fibres during contraction. The result is that the ventricle contracts violently and the blood is expelled under great pressure into the aorta. The coronary circulation is greatly increased and the nutrition of the heart improved.Relaxation takes place rapidly but the onset of the next systole comes so early that the filling of the’ heart and consequently the output of blood per beat are less than normal although the total output of the ventride per minute may be equal to o r greater than normal. By combining carbon dioxide with adrenaline in proper ascer- tained doses greater rate of contraction and relaxation may be obt’ained together with a lengthening of the whole diastolic period. There is thus time for greater filling and therefore increased output of blood per beat and per minute. The coronary output is also increased and the slower contraction of the heart is more effective in driving the blood into the aorta. The combined action of carbon dioxide and adrenaline in conditions such as accompany short but severe muscular exercise enables the heart t o respond quickly and furnish the maximum output of blood.The Influence of Oxalates Citrates and Tartrates on the Isolated Heart. WILLIAM SALANT and SELIG HECHT (Arnev. J. Physiol. 1915 36 126-144).-The order of toxicity is citrate oxalate tartrate. The effect does not support the view that the salts precipitate calcium o r lead to the formation of non-ionised calcium salts since calcium citrate and tartrate can be utilised by the heart. The action is rapid and the theory that the changes are due to penetration into t’he cells is rejected. The effects are due t o ext ra-cellular changes. E. H. BRUNEMEIER and A. J. CARLSON (Amer. J. Physiol. 1915 36 191-195).-Gastric juiee chyme acids alkalis water milk and oil introduced into the small intesttlne in dogs inhibit gastric t40nus and gastric hunger contractions. This is due partly t o mechanical but mainly to chemical stimulation ; the reflex path may be long (central) and short (by Auerbach’s plexus).H. W. B. W. D. H. Reflexes from the Intestinal Mucosa to the Stomsch. W. D. H. Presence of Histidine-like Substances in tho Pituitary Gland (Posterior Lobe). T. €3. ALDRICH (J. Amer. Chem. Soc. 1915 37 203-208).-An examination of the desiccated defatted pos- terior lobe of the pituitary gland has been tested for histidine by Jnouye’s modification of Pauly’s reaction (A. 1913 ii 164). Although a positive reaction was obtained i t is probable that; it was not due t o histidine since Fischer’s modification of Weidel’s reaction and Knoop’s reaction with bromine both gave negative results It therefore seems likely that the substance in the pitui- tary gland material was not histidine but some compound or compounds related to histamine (P-aminoethylglyoxaline) These substances are probably present either in the free state or combined with something other than protein.i. 100 ABSTRACTS OF CHEMICAL PAPERS.The results of this work indicate that Pauly's reaction is not specific for histidine unless other compounds such as tyrosine p-hydroxyphenylethylamine; fl-amino-4-ethylglyoxaline and adrena-' line have been removed but is rather a general reaction for a class of compounds. E. G. Degree of Acidity of Muecle under Various Mechanical Conditions of Contraction.F. PORCELLI-TITONE (Intern. Xeitsch. phys.-chem. Biol. 1914 1 338-353).-The concerttrntion of hydrogen ions in the muscle (frog's gastrocnemius) expressed in grams per litre increases from 16 x 10-8 in the restdng condition t o 61 x 10-8 after t.etanisation until it just ceases to contract. When the muscle does work the acidity rises still higher t o 98 x 10-8 after two hundred con tractions. Muscles contracting two hundred times under isometric conditions reached the corresponding figures 89 x 10-8 and under a constant lolad t o 44 x 10-8. These results are regarded as confirming the hypothesis that the metabolism of the muscle varies according to the conditions under which it contracts. H. W. B. Local Deposits of Cholesterol in the Tissues.MATTHEW J. SmwART (J. rath. Ract. 1915 19 305-31 4).-Crystalline cholesterol is deposited in the tissues in various pathological conditions; this induces a cellular reaction in which numerous I' foamy " endo- thelial cells and giant cells probably of endothelial origin made their appearance. W. D. H. Action of Hydrogen Ions on the Phagocytosis of Carchesium lachmani. N. K. KOLTZOV (Irktern. Zeitsch. php-chem. Biol. 1914 1 82-107. Compare A 1913 i 224).-The author has studied the influence of acids and acid-salts on the power of the infusoria Carchesium Zachrnani to1 ingest particles of Chinese ink. The phagocytic power is greatest when the infusoria are in neutral solutions a slight excess of hydrogen o r hydroxyl ions exerting a distinct inhibitory action.The reduction of the acidity of a medium by the addition of sodium citrate or phosphate enables phagocytosis t o occur to a correspondingly greater extent. The reactivity of the infusoria to the slightest alteration in the acidity of the1 medium is so sharp as to' lead the author t o suggest that' i t mag form the basis ol a new method f o r the estimation of the concentration of hydrogen ions in a solution. H. W. B. Experiments on the Nature of the Photogenic Substance in the Firefly. E. NEWTON HARVEY (J. dmer. Chern. Soc. 1915 37 396-401).-Experiments on the firefly are described which show that the dried material can be extracted with ether chloroform cold ethyl alcohol carbon tetrachloride acetone o r toluene without impairing its phosphorescent power. Boiling ethyl alcohol cold amyl alcohol and ethyl butyrate destroy the light-producing material.The photogen is also destroyed when the tissue is extracted for an hour with oxygen-free water. The same resultPHYSIOLOGICAL CHEMISTRY. i. 101 was obtained on extraction with Ringer's solution sea-water 0*125ill-sodium chloride 0-05M- and O*OlH-sodium hydroxide and 0*02M-hydrochloric acid. These results indicate that water oxygen and a photogenic substance are not the only factors involved in the production o€ light and show that the photogen is very unstable. E. G. Experiments on the Nature of the Photogenic Processes in the Lampyridze. F. ALEX. MCDERMOTT ( J . Amer. Chem. Xoc. 1915 37 401-404).-Experiments have been made on the same lines as those described by Harvey (preceding abstract) with material prepared from Ykotinus pyralis and Y.castus and attempts have been made to obtain evidence of the breaking down of nucleic acid during the photogenic process as suggested by Lund ( J . Exper. Zool. 1911 11 415). The results confirm those obtained by Harvey showing that a phospho,rescent substance cannot be extracted from the dry tissue by dilute acid or alkaline solutions even in the absence of oxygen and also indicate that the deposits of purine substances which form the so-called reflecting layer of the phot'ogenic organs of the L a m p y r i h cannot be traced satisfactorily to the breaking down of nucleic acids. E. G. The Body Surface of Flounders and its Relation to Gaseous Metabolism. SEEGIUS MORGULIS (Amer. J. Physiol.1915 36 207-216).-The surface of flounders is computed by the ordinary formula S=Xvw2 K being 13-44. The metabolic processes bear no direct relation either t o the weight or surface of the flounder; the oxygen consumption diminishes per gram-hour but increases per square centimetre-hour as the animals become larger. Removal of the fins reduces the surface by more than 30% without materi- ally influencing the weight of the fish; this does not affect the oxygen consumption. Under these conditions the oxygen consump- tion is proportional t o the mass. During fasting K is higher than normal. W. D. H. Fasting Flounders. SERGIUS MORQULIS ( J . Bid. Chew/. 19 15 20 37-46).-Aquatic animals depend on particulate food and live on their own tissues during fasting. Organic mattler dissolved in sea-water plays no r6le in their nutrition.The absolute loss of protein is much greater than that of fat. I n fish nitrogenous metabolism is stated t o be the principal source of energy. The average respiratory quotient during fasting in flounders is 0.76. W. D. H. Absorption of Water through the Skin of a Frog. J. F. MCCLENIION (Intern. Zeitsch. phys.-chem. 'Biol. 1914 1 169-172).- The absorption of water through the skin of a live frog is found by the author t o be greater in relation to' the surface area than that' through the skin of a pair of amputated legs. I f the skin of one amputated leg is removed and filled with 0.7% sodiumi. 102 ABSTRACTS OF CHEMICAL PAPERS. chloride solution and then immersed together with the other unskinned leg in water the amount of water absorbed in the first hour is the! same in each case.The conclusion drawn by the author is that the absorption of water by a frog's leg is the result of the osmotic pressure of the fluids in and between the cells of the tissues. Experiments also showed that the rate of osmosis through frog's skin is constant whether the water is passing inwards or outwards. H. W. B. Permeability of Cells for Acids. E. NEWTON HARVEY (1ntes.n. Zeitsch phys.-chem. BioZ. 1914 1 463-478).-A pigment ante- donin occurring in the epithelium of the viscera of the Prickly Fish a holothurian S t i c h o p s a.?aalms has been used as an indi- cator for the penetration of acids. Living tissues are resistant to the penetration of all acids except salicylic benzoic and possibly valeric acids.The degree of resistance varies with the acid and is not nearly so marked as in the case of alkalis. The rate of penetration of hydrochloric acid is roughly proportional to the concent>ra tion. There is no relation between the degree of dissociation of an acid and its rate of penetration or between degree of dissociation and to'xicity. It is found that acids which penetrate most readily are most toxic irrespective of their strength. A general relation exists between penetrability lipoid solubility and capillary activity; but i t is not exact and not quantitative. The order of the acids arranged in accordance with penetrability is not in exact agreement with that f o r the lipoid solubility or for lowering of surface1 tension acetic propionic and butyric acids being most out of place.Cells behave towards acids and alkalis as if they were droplets of fat or fat solvent. If an acid is soluble enough in fatty sub- st'ances it encounters no resistance a t the cell surface; if it is insoluble in lipoids or only slightly soluble it appears as if the cell surface must be destroyed before it can enter. The strength of the acid and possibly also a specific action of the anion on the surface proteins then determine its rate of entrance or better its rate of alteration of cell surface. Dead cells are readily permeable to all acids. H. W. B. The Effect of Pituitary Extract o n the Secretion of Cerebro- spinal Fluid (Choroidorrhcea). LEWIS H. WEED and HARVEY CUSHING (Anier. J. Physiol. 1915 36 77-1 03).-Dixon and Halliburton (A.1913 i 1413) found no effect on the secretion of cerebrospinal fluid. The present authors obtained negative results with several preparations. These vary a good deal in the relative amounts of various active principles; but there was always a suffi- ciency of positive results Lo indicate that extracts of the posterior lobe increase the rate of secretion of the fluid. It is a true secre- tion of the choroid plexuses and not a mere gush produced mechanically. The experiments were performed on dogs thePHYSIOLOGICAL CHEMISTRY. i. 103 cannula being inserted through the corpus callosum into the third ventricle. Volatile anaesthetics were used. W. D. H. The Effect of Repeated Injections of Pituitrin on Milk Secretion. SUTHXRLAND SIMPSON and R.L. HILL (Amer. J Physiol. 1915 36 347-351).-The intravenous intramuscular or sub- cutaneous administration of pituitary extract to a lactating animal causes a marked increase in the amount and fat-content of the milk formed. Butl if the injection is continued for months in a goat immunity is established. W. D. H. Nature of the Deposit Obtained from Milk by Spinning in a Centrifuge. H. S. HALCRO WAHDLAW (J. Boy. J'oc. New South IC'ulas 1914 48 152-17 I).-The d e p 4 t which is obtained when milk is subjected t o centrifugal actmion has t'he following average composition Caseinogen 57yA ; other proteins 16% ; lactose 16% ; other non-nitrogenous organic substances 3% ; ash 8%. The rate of deposition of the substance is not constant a t first decreasing and then increasing; the amount of ash shows a variation in the opposite direct'ion to that of the rate of deposition.The ash contains 43.10/; of CaO and 43-9:L of P,O,. From 25% t o 70% of the deposit is soluble in water and about 90% of the ash is found in the soluble portion. The removal of the deposit does not lower the freezing point of the milk. w. P. 8. The Diffusible Phosphorus of COW'S Milk. H. S. HALCHO WAEDLAW (J. Zioy. ~ O C . New Soiith Wctks 1914 48 253-266).- When a large volume of milk is dialysed against a small volume of water the freezing point of the dialysate after twenty-four hours approximates t o that of the milk and does not change as the dialysis is continued; a definite state of equilibrium is reached. The diffusible phosphorus of cow's milk amounts to 35-55?; of the total quantity present whilst the diffusible calcium amounts t o 3 0 4 0 % of the total present.Milk freed from fat by centrifugal action contains 3%] more ash-forming substances than does whole milk. w. P. s. The Retention of Iron in the Organs in Hzemolytic Anmmia. ROBERT MUIH arid JOHN SHAW DUNN ( J . Path. Brcct. 1915 19 417428).-1n acute hzemolytic anzmia nearly all the iron of the destroyed haemoglobin is deposited in the liver spleen and kidneys ; more than half the body hxmoglobin may be destroyed within three days. If hzmoglobinuria occurs some iron escapes with the urine and the amount' of iron deposited in the kidneys is roughly proportional t o this. A third of the iron of the blood may be deposited in the organs named within twenty-four hours. With regard to deposits of hzmosiderin a broad distinction can be made between that resulting from lysis and that resulting from phago- cytosis of red corpuscles.W. D. H.i 104 ABSTRACTS OF CHEMICAL PAPERS. The Neutralising Power of Saliva in its Relation t o Dental Caries. JOHN A L B E ~ ~ T MARSHALL ( A m e r . J. Ptiysiol. 1915 36 260-279).-A large number of human salivas were investigated with various indicabors ; the reaction found was very variable whether caries was present or not or whether the people took care to cleanse their teeth or not. As compared with resting saliva ‘‘ activated saliva ” (that is saliva collected after chewing) shows a smaller acidity and a rise in alkalinity. The magnitude of this factor is less in people free from caries than in those whose teeth are carious.W. D. H. The Influence of Blood Transfusion on the Hyperglycaemia and Glycosuria of Pancreatic Diabetes in the Dog. A. J . CARLSON and H. GINSBURG (Amer. S. Phyeid. 1915 36 280-293).- Transfusion of normal blood into dogs with pancreatic diabetes causes a lotwering of the sugar in blood and urine which lasts four to eight hours. I f diabetic blood is transfused no effect follows. The effect is not due t o kidney injury; there is indication that the telmporary reduction of sugar excretion is followed later by an increase. W. D. H. Fat in the Blood in a Case of Lipmmia. C. G . Iniar~ (J. Bid. Chem. 1915 20 87-90).-1m a fatal case of pancreatic disease. the blood-serum looked like cream ; glycosuria was present.The serum contained neutral fat and cholesterol 14.06 ; cholesterol (un- saponifiablel matter) 1.5; and fatty acids originally present in the form of soaps 0.38%. Phosphatides were absent. The condition is explained on the supposition that mobilisation of connective tissue fat had occurred. W. D. H. The Synthesis of Hippuric Acid in Experimental Tartrate Nephritis in the Rabbit. F. B. KINGSBURY and E. T. BELL (J. Biol. Chem. 1915 20 73-82).-Severe injury of the convoluted tubules does not affect the1 synthesis of hippuric acid. The glomeruli of collecting tubules are not seriously injured in tartrate nephritis. I f the kidney really synthesises hippuric acid which is doubtful in the rabbit the synthesis must occur in glomeruli the collecting tubes or the degenerating cells of the convoluted tubules. W.D. H. Affinity and Biological Activity of Acids. W. KOPACZEWSKI (Intern. Zeitsch. phys.-chem. Biol. 1914 1 420-432).-Acids act on various biological processes in different ways and the order in which a series of acids can be arranged corresponding with the magnitade of the! action which they exert on one biological process differs from the order f o r any other process. These statements are illustrated by various examples and thel conclusion reached is that the degree of dissociation and the hydrogen-ion concentration are not the only factors in determining the extent of action of the acids. H. W. B.PHYSIOLOQICAL CHEMISTRY. i. 105 Colloidal State of Alkaloids. Relations between Surface Tension Size of Particle and Toxicity.T. TRAUBE and N. ONODERA (Infern. Zeitsch. phys.-chem. UioZ. 1914 1 35-59).- Alkaloids such as atropine and quinine the molecular weight of which exceeds a definite limit are found by means of the ultra- microscope t'o be present in solution in a colloidal state whilst the corresponding salts form true solutions. The surf ace tension of water is scarcely affected when salts of the alkaloids are dissolved in it but when a small quantity of alkali is also added the surface tension is diminished owing to the liberation of free alkaloid which forthwith assumes the colloidal condition. Corresponding with the diminished surface tension tlicre is increased toxicity of the solu- tion as has been ascertained experimentally with tadpoles small fishes etlc.I n a few hours the small particles are seen under the ultramicroscope to become aggregated into large masses. I n a corresponding degree the surface tension increases and the toxicity diminishes. On adding a little alkali to such an attenuated alkaloid solution the aggregates disperse the surface! tension falls and the toxicity reaches or surpasses its former intensity. It is suggested that the localisation of action of the various alkaloids may be partly due t o the variation in the alkalinity of the different organs of the body. Where only a low degree of alkalinity exists quinine for example might be potent and atsopine inert because quinine is found to be activated much more than atropine by alkali. The toxicity of solutions of some of the alkaloids as f o r example quinine is increased by boiling and subsequently cooling them and the authors have found that corresponding alterations occur in the size of the particle surface tension and toxicity.The antagon- istic action of pilocarpine on atropine is accompanied by similar changes. I n a series of related alkaloids the toxicity and surface tension increase as the molecular weight Falls; and even when alkaloids of different classes are compared it is found that the alteration in surface tension is the chief factor in determining the degree of toxicity. The hypothesis put forward t o account for this relation between toxicity and surface tension is that any alteration in the surface tension disturbs the equilibrium or affects the normal velocity of the reactions taking place in the organism and this becomes apparent as a toxic effect. The toxicity of alkaloids is due.apparently chiefly to tlhe physical instead of to the chemical changes produced. The passage of an electric current through a solution of an alkaloid causes the smaller particles t o wander towards the cathode whilst the larger aggregates accumulate a t the anode H. W. B. Many of the free alkaloids are unstlable in solution. Synergism and Antagonism of Drugs and Poisons. I. TRAUBE and N. ONODERA (Intern. Zeitsch. phy(ls.-chsm. Biol. 1914 1 133-147. Compare preceding abstract).-The authors have studied the effect of the addition of one alkaloid to the solution of another on the VOL. CVIII. 1. 7ci. 106 ABSTRACTS OF CHEMICAL PAPERS. surface tlension measured by the stalagmometer.The surface tension of quinine solutions is increased by atropine aconitine veratrine and nicotine and in relation to the latter drug it is suggested that smokers are probably more susceptible to quinine than non-smokers. I f an alkaloid is added t o the solution of the salt of another alkaloid the extent of alteration of the surface tension depends o n the relative basicity of the two alkaloids. The relative toxicity of the alkaloids is given by the following series of basicities nico- tine>pilocarpine>atropine physostigmine>quinine>aconitine> ver a trine. The effect on surface tension of combinations of solutions of various narcotics has been studied with results very similar to those recorded by Fuhner (A. 1914 i 235).The action of nicotine is increased by ethyl carbamate thymol and chloral hydrate and diminished by ebher and chloroform. Alcohol and ether are anta- gonistic whilst both ethyl carbamate and chloral hydrate are synergetic tuwards alcohol. The authors suggest that the latter substances may be more efficient narcotics than ether o r chloro- form f o r anzesthetising drunkards. The effect of narcotics on drugs affecting the heart's action was also investigated. The authors point out that in the body the synergetic or anta- gonistic influence of two substances (drugs narcotics etc.) on each other may be due t o an indirect actdon on the velocity of the proto- plasmic reactions instead of to the direct action on the surface tension such as is considered in this communication.13. W. B. Residual Valency of Anaesthetics and its Importance in Anaesthesia. Chemical Theory of Anaesthesia. A. P. MATHEWS (Intern. Zeitsch. phys.-chern. Biol. 1914 1 433-449).-The author points out that a direct relation is not apparent between the cohesional attractions of certain anzesthetics and their anzesthetis- ing powers (compare A. 1914 ii 643). The anzesthetic does not therefore become attached to protoplasm through the agency of this attraction. The author considers that the union between protoplasm and anzesthetic is due t o the residual valency of the anzesthetic and is of the nature of a molecular union. The average amount of residual valeney per molecule possessed by various anzesthetics has been computed from the cohesion and it is found that a general but not complete parallelism exists between anzes- thetic power and amount of residual valency.Lack of complete parallelism may be due t o the f a c t that the spatial relation of the valencies must also be important in determining anzesthetic power. The theory of anzesthesia put forward is that the irritable substance in protoplasm is a molecular oxygen-protoplasmic union or a peroxide union unstable and similar to oxyhzemoglobin. On stimulation this unstable molecular union passes by molecular rearrangement into a stable form oxidation taking place and carbon dioxide being produced. The anzesthetic produces anzes- thesia by occupying the oxygen receptors of the cell thus forming a non-irritable dissociable anaesthetic-protoplasm compound. TheVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 107 author explains the various phenomena of anaesthesia on this the or y . H. W. B. Narcosis. I. Effect of Ethyl Carbamate and Chloral Hydrate on the Carbon Dioxide Production of the Nerve Fibre. SHIRO TASHIRO and H. S. ADAMS (Intern. Zeitsch. phys.-chsm. Biol. 1914 1 450-462).-The production of carbon dioxide by the claw nerve of the spider crab is greatly diminished after the nerve has been narcotised by placing in solutions of either ethyl carbamate or chloral hydrate of such concentrations as to produce a reversible loss of excitability. With a weak concentration of these narcotics the carbon dioxide output is increased. This is in accord with the fact that tlhese concentrations primarily stimulate or increase the irritability of the nerve. Certain nerves were found to be unexcitable without apparent cause and the metabolism of such nerves as measured by the carbon dioxide output was invariably abnormally low. The conclusion drawn by the authors is that metabolism in the nerve is interfered with by narcotics and the results stand in agreement with Mathews’ theory (preceding abstract) according t o which-the primary action of the narcotic on the protoplasm is t o replace the oxygen and thus interfere with the normal metabolism. H. W. B.

ISSN:0368-1769    

DOI:10.1039/CA9150800093

出版商:RSC    

年代:1915

数据来源: RSC

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ii. 96 ABSTRACTS OF CHEMICAL PAPERS. In organic Chemistry. Molecular Weight of Sodium Garbonate and the Atomic Weight of Carbon Referred to Silver and Bromine. THEODORE W. RICHARDS and CHARLES R. HOOVER (J. Amer. Chem. Xoc. 1915 37 95-107).-The molecular weight of sodium carbonate has been determined by the following method. A weighed amount of pure fused sodium carbonate was dissolved in water and neutralised exactly with hydrobromic acid. The quantity of silver required to precipitate this hydrobromic acid was then determined by tlie usual process. The chemical equivalence between tlie weights of sodium carbonate and silver coluld thus be simply deter- mined and the silver haloid standard referred directly t o sodium carbonate. A full account is given of the various precautions taken to ensure the purity of the materials and t o eliminate all sources of error.It has been found that 29.43501 grams of sodium carbonate are equivalent to 59.91676 grams of silver and also to a weight of dilute hydrobromic acid capable of precipitating 104.3023 grams of silver bromidel. From the results the molecular weight of sodium carbonate and the atomic weight of carbon have been calculated and found t o be 105.9'95 and 12.005 respectively (Ag = 107.880 ; Br = 79.916 ; Na = 22.995). If the atomic weight of silver is taken as 107.871 and thatl of sodium 22.993 the atomic weight of carbon becomes 12.000. E. G. Molecular Weight of Sodium Sulphate and the Atomic Weight of Sulphur THEODORE WILLIAM RTCIIARDS and CHARLES R HOOVER ( J . Amer. Chem. Xoc.1915 37 108-113).-The molecular weight of sodium sulphate has been determined by the following method. A weighed amount of pure fused sodium carbonate was treated in a platinum retort with a very slight excess of pure sulphuric acid; the solution was freed from carbon dioxide and evaporated in a quartz flask with the aid of a current of air but without boiling and the residual salt was fused and weighed. 'The ratio of the equivalent weights of sodium carbonate and sodium sulphate was found to be 1*00000 1.340155. From the value of the molecular weight of sodium carbonate 105.995 when Ag = 107.880 (preceding abstract) the molecular weight of sodium sulphatei was found to be 142.050. Calculating from this result the atomic weight of sulphur becomes 32.060 (Na = 22.995 ; C=12.005) which agrees well with the value 32.069 obtained by Richards and Jones (A 1907 ii 685) by the conversion of silver sulphate into the chloride.The mean of these two values 32'065 is regarded as the mosb trustworthy value hitherto recorded. I n order t o correct the weight of the sodium sulphate obtainedINORGBNIC CHEMISTRY. ii. 97 in the experiments t o the vacuum standard the density of the fused salt was determined and found to be 2,698. E. G. Method of Determining the Hydrates Formed by a Salt. H. W. FOOTE (J. Amer. Chem. Soc. 1915 37 288-292).-The method described in this paper depends on the fact that the addition of a sufficient quantity of sulphusic acid to a saturated solution of a hydrated salt with which the acid does not react causes t,he salt; to crystallise either as a lower hydrate o r in the anhydrous form.It is shown that in a series of solubility deter- minations of a salt with gradually increasing amounts of sulphuric acid the presence of a pure salt is indicated by varying solubility and constant composition of the residue whilst the presence of two salts as a mechanical mixture is indicated by const'ant solu- bility and a residue of variable composition. I n this way the detection of all the stable hydrates of a normal sulphate which form at a given temperature can be effected except when an acid sulphate is formed before the anhydrous sulphate. The method has been applied t o the detelrmination of the hydrates of copper sulpliate a t 25O and the results are plotted as a curve showing the range of conditions under which each of the three hydrates CuS04,5H,0 CuS04,3H,0 and CuSO,,H,O is formed.The conditions for the trihydrate are very narrow; the pentahydrate has the widest range being st,able in contact with solutions containing as much as 49% of sulphuric acid. E. G. Search for an Alkali Element of Higher Atomic Weight tban Casium. GREGORY PAUL BAXTER (J. Amer. Chena. Soc. 1915 37 286-288).-A large quantity of msium nitrate prepared from pollucite has been submitted to a prolonged fractional crystallisatJon and the at'omic weight of the metal in the least soluble fraction has been determined by the analysis 08 the chloride. The average result of the determinations gavel the value 132.82 which agrees closely with that adopted by the International Committee on Atomic Weights namely 132.81.The experiments did not give any indication of the existence of an unknown alkali element and thus confirmed the conclusion arrived ak by Richards and Archibald (A. 1903 ii 367) who worked with a much smaller quantity of material. E. G. Solubility of Strontium Sulphste in Solutions of Calcium Salts. M. RAFFO and G. ROSSI (Gazxetta 1915 45 i 45-50).- The authors have determined the solubility in calcium nitrate solutions of various concentrations of strontium sulphatel pre- cipitlated in the solution. The amount of strontium sulphate dis- solved per 1 C.C. increases from 0.0483 gram for a 0.5% calcium nitratle solution to 0.1955 gram f o r a 676 solution. The solubility of barium sulphate in water is not affected by the presence of calcium chloride or nitrate.These results obtained gravimetric- ally were confirmed by measurements of the electrical con- ductivity. T. H. P.ii. 98 ABSTRACTS OF CHEMICAL PAPERS. Alloys of Zinc and Manganese. N. PABRAVANO [witb in part u. PERRET] (Gaxaetta 1915 45 i 1-6).-The author has made a thermal study of zinc-manganese alloys containing less than about 30% of manganese. The fusion diagram is similar tlo that of the zinc-iron alloys (compare von Vegesack A. 1907 ii 170) the two compounds MnZn and MnZns being formed. The alloys are hard and brittle; those containing 5-20? of manganese are porolus but those with a great(e1r proportion of manganese are more compact . T. H. P. Lithopone. W. J. O'BRIEN (J. Physicul CImn. 1915 19 113-144).-Lithopone is an intimate mixture of barium sulphate and zinc sulphide precipitated by mixing solutions of barium sulphide and zinc sulphat'e.By special treatment its physical properties are modified so t h a t i t becomes suitable for use as a pigment. Experiments have been made t o ascertain the nature of the change which is involved in the darkening of lithopone and also the conditions under which this colour change is retarded or inhibited. It is found that zinc sulphide is reduced in a moist atmosphere under the influence of light with the formation of metallic zinc and hydrogen sulphide. To prevent the darkening of the litho- pone i t is necessary that the zinc sulphide should be covered by a protecting film. A lithopone of this character was obtained by producing a film of zinc oxide on the sulphide the percentage of oxide varying from 3 t o 5%.Aluminium oxide can be substituted for zinc oxide and a film of sulphur retards the colour change. I€. 31. I). Revision of the Atomic Weight of Cadmium. 111. Electro- lytic Determination of Cadmium in Cadmium Chloride. GREaoRY PAUL BAXTER and MINER LOUIS HARTMANN (J. Amer. Chenz. Soc. 1915 37 113-131).-Perdne and Eulett (A 1911 ii 397) Laird and Hulett (Tram. Rmer. Kle'lectrochem. SOC. 1912 22 385) and Quinn and Hulett (A. 1914 ii 127) determined the atomic weight of cadmium by methods of electrolytic deposition and obtained the values 112.30 112.31 and 112.29 respectively. Baxter and Hines (A. 1905 ii 321) and Baxter Hines and Frevert (A. 1906 ii 541) found the atomic weight of cadmium to be 112.417 and 112.418.I n view of this discrepancy deter- minations have now been made of the cadmium in the anhydrous chloride by direct electrolysis. It has been found that cadmium material can be rapidly and efficiently purified by crystallisation of the bromide. A modified form of electrolytic cell with a mercury cathode is described which was found to be very satisfactory for the direct electrolysis of cadmium chloride solutions. The amount of cadmium in cadmium chloride was found to be 61*319% as compared with 61.298% recorded by Quinn and Hulett (Zoc. c i t . ) . The atomic weight of cadmium calculated from this result is 112.417 (C1= 35.457) which agrees closely with the value found by Baxter Hines and Frevert from the analysis ofINORGANIC CHEMISTRY.ii. 99 cadmium chloride by titration against pure silver. If the atomic weight of chlorine is taken as 35.458 t h a t of cadmium becomes 112.421. Cadmium bromide is being investigated by a similar electrolytic method and these results also confirm the higher value for the atomic weight of cadmium. G. A. LINHART (J. Amw. Chem. Soc. 1915 37 258-274).-Tt i R shown in this paper that the discordant results obtained in determina- tions of the molecular weight of mercuric chlozide in aqueous solu- tion and the unusual behaviour of mercuric chloride in distribu- tion ratio measurements are due to the presence in the aqueous solution of double molecules of the salt. It has been found that when a solution of mercuric chloride in benzene is shaken repeatedly with a saturated solution of sodium chloride the mercuric chloride is completely removed owing t o the formation of complexes such as NaHgC1 and Na,HgCl which are practically insoluble in benzene.The mercuric chloride in such sodium chloride solutions can be readily estimated by pre- cipitation with hydrogen sulphide. This method of analysis has rendered i t possible to prove the existence of double molecules of mercuric chloride in aqueous solution by measuring the distribution ratio of mercuric chloride between benzene and water a t 25O and 40°. The equilibrium constants were found to be fairly concordant from extreme dilu- tion to saturation for a given temperature and i t may therefore be assumed that Hg,Cl is the only complex in aqueous solutions a t any concentration and a t any temperature between Oo and looo It is shown that the association of mercuric chloride in aqueous solutions can also be established from the results of Morse and of Hantzsch and Vagt on the distribution ratio of mercuric chloride between water and toluene from those of Biltz obtained by cryo- scopic measurements and from those of Kahlenberg Landsberger and Beckmann obtained by ebullioscopic determinations.Electrolysis of Solutions of the Rare Earths. L. M. DENNIS and B. J. LEMON (1. Amer. Chem. SOG. 1915 37 131-137).-0n the fractional elect'rolysis of a neutral solution of the nitrates of neodymium praseodymium lanthanum and samarium the lanthanum collects in the last fractions and can thus be separated from the other earths of the didymium group.Lanthanum can be satisfactorily separated from praseodymium by this method. On the fractional electrolysis of the earths from xenotime erbium collects in the early fractions and yttrium in the later fractions. The results of this work indicate that separations of some of the rare earths can be effected more rapidly and conveniently by this method than by the usual methods of fractional crystallisation and precipitation. E. G. HERBERT T. KALMUS and C. HARPER (J. h d . Eng. Chem. 1915 7 6-17).-Pure cobalt prepared by reduction of cobalt oxide (A. 1914 ii 275) was E. G. Association of Mercuric Chloride in Water Solution. E. G. Physical Properties of the Metal Cobalt.ii. 100 ABSTRACTS OF CHEMICAL PAPERS. found to have Dt7 8.7918 (unannealed) D:"'" 8.8105 (annelaled) Di6'5 8.9253 (swaged) ; m.p. 1478O k 1.lo ; tensile strength cast and unannealed 34,400 lb. per sq. in. annealed 36,980 lb. per sq. in. and rollled more than 100,000 lb. per sq. in.; compressive stlrrength cast and unannealed 122,000 lb. per sq. in. annealed 117,200 lb. per sq. in. ; electrical resist'ance 89.64 10 ohms per cm.3; specific heat from Oo to 890° 0*1058+ 0.0000457t + 0~000000066t2. The hardness of cast cobalt is con- siderably greater than that of either iron or nickel being approxi- mately 124.0 (load 3500 lb.). The presence of from 0.06 t o 0.3% of carbon in the metal increases the tensile and compressive strength and t'he electrical resistance but has little effect on the hardness. Pure cobalt may be machined in a lathe as readily as pure iron or nicked but it is somewhat brittle; cobalt contlaining a small quantity of carbon machines like mild st'eel and whilst putre cast cobalt cannot be rolled or swaged without developing cracks cobalt containing carbon may be rolled o r swaged down from cast bars to any extent' provided that the metal is worked at a red heat. w. P. s. The Double Salts of Stannous and Potassium Chlorides. TOSHITSUNE FUJIMURA (Mem. Colt. Xci. Kyoto 191 4 1 63-67).-A systematic investigation of the system KCl-SnC1,-H,O a t 25O has shown that the only double salts formed are those represented by KCl SnCl,,H,O and 2KC1,SnC1,,2H20. The solubility data are employed in the construction of a graph in which the ratios SnCl,/R,O and KC1/H20 are plotted on rectangular axes. This graph shows clearly the limits of existence of the two double salts in contact with aqueous solutions. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9150805096

出版商:RSC    

年代:1915

数据来源: RSC

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ii. 100 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Separation of the Constitiients in a Natural Gas from which Gasolene is Condensed. GEORGE A. BURRELL and FRANK M. SIEBERT (J. Amer. Chern. Xoc. 1915 37 392-396).-The authors' method for separating a natural gas into its constituent hydrocarbons by fractional distillation in a vacuum (A. 1914 ii 741) has now been applied to the analysis of a natural gas obtained atl a plant where it is treated for the commercial condensation of gasolene. The results showed that the gas consist,ed of methane 36.8%; ethane 32.6 ; propane 21.1 ; butanes (chiefly) 5.8 ; pentanes and hexanes 3.7%. I n addition about 1.0% of nitrogen and 0.03% of carbon dioxide were present but were left out of calculation in the andysis. E. G. Lawsonite from the Central Coast Ranges of California.AUSTIN F. ROGERS (Amer J. Sci. 1915 [iv] 39 lfl5-112).-A brief summary is given of the literature of lawsonite. Two distinctMINERALOGICAL CHEMISTRY. ii. 101 modes of occurrence are recognised (1) as a secondary mineral in slightly altered or saussuritised diorites and gabbros (California Corsica Piedmont Gorgona New Caledonia) ; (2) as an accessory or essential constituent of schists and gneisses which usually con- tain glaucophane (California Corsica Piedmont Sautes-Alpes). Several new occurrences are described from Santa Clara and Alameda Counties in California. Crystals from Arroya Mocho in Alameda County analysed by H. L. SMALL gave the following results agreeing with the usual formula H,CaAl,Si,O SiO,.A1,0,. CaO. CO,. H,O. Total. 38'10 32.21 17.74 1.12 10'85 100'02 L. J. S. Meteoric Iron from Sarns Valley Oregon. W. M. FOOTE (Amer. J. Sci. [iv] 1915 39 80-86).-This mass of iron weighing nearly 7 kilos. was found in 1894 in the Sams Valley Jackson County Oregon. The crystalline structarel is that of a medium octahedrite. D 7.794. Analysis by J. E. WHITFIELD of the nickel-iron (93.781% of tihe mass) gave I and of the schreibersite (6.194%) the results under 11 Fr. Ni. 00. Cu. C. P. S. Si. Total. 11. 65'13 20.93 - - - 13.94 - - 100*00 I. 89.357 9.762 0'682 0.017 0'016 nil 0.059 0'009 99.992 This composition is very simihr t o that of the Mount Edith meteoric iron from Western Australia (A. 1914 ii 481). L. J. S. Physical and Chemical Constants of Mineral Waters. F. BORDAS (Alnn. Falsq. 1914 7 387-407).-Resolts of examinations of French mineral waters are given the following constants being recorded refractive index capillary pressure freezing point electrical resistance and coaductivity ionisatlion and estimation of the total solids alkalinity chlorine nitric nitrogen and various elements characteristic of the waters. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9150805100

出版商:RSC    

年代:1915

数据来源: RSC

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MINERALOGICAL CHEMISTRY. Analytic a1 Chemistry. ii. 101 New Method for Estimation of Acidity. I. TRAUBE and R. SOMOQYI (Intern. Zeitsch. phys.-chem. Biol. 1914 1 479-484).-The method is based on the observation t'hat the addition of a stirong capillary-inact'ive acid (a strong acid which on dissolving in water does not lower the surface tension of the solvent) t o the capillary- inactive salt of a weaker capillary-active acid sets the weak capillary-active acid free and causes a lowering of surface' tension from which the quantity of strong acid added can be calculated.ii. 102 ABSTRACTS OF CHEMICAL PAPERS. The capillary-inactive salt chosen for employment was the sodium salt of isovaleric acid and tjhe mode of operation for the estirna- tion of the acidity of various human and animal blood-sera and other tissue fluids was to mix 5 C.C.of a 2./ solution olf sodium isovalerat'e with 0.2 C.C. of serum or othes fluid and measure the lowering of surface tension by the viscostagonometer a t 2 3 O . The result,s are tabulated and compared with the corresponding alkalinities obtained by Traube's method (this vol. i 95). H. W. B. Determination of Very Weak Acids and Bases by Means of Electrolytic Conductivity Measurements. SHINKICHI HORIBA (Mem. Coll. Sci. Kyoto 1914 1 35-47).-Theelectrical conductivities of mixtures of aniline and hydrochloric acid and of phenol and sodium hydroxide have been determined in dilute aqueous solution a t 25O. Empirical foraulze have been deduced which represent the change in conductivity with change in the relative proportions of acid and base.It is sho'wn that the change in the conductivity may be applied to the estimation of weak acids and bases which cannot be estimated by the ordinary methods of alkalimetry or acidimetry. In the case of aniline and hydrochloric acid the conoentration of aniline in a solution containing 0.02 t o 0.04 mol. of acid per litre is given by the equation C= - (Rm-K,)/0.2895 in which K is the conductivity of the pure acid solution and Rm that of the solution which contains in addition C mols. of aniline per litre. The concentration of the phenol in a sodium hydroxide solution is related to the change in the conductivity in a similar way but the denominator varies with the concentration of sodium hydroxide solution in accordance with the equation in which Kb and C(b represent the conductivity and concentration of the pure sodium hydroxide solution Ti that of the solution which contains in addition C mols.of phenol per litre. The formula may only be applied to solutions for which Ch lies between 0.02 and 0.04 mol. per litre and the concentration of phenol must be less than $cb. The conductivity data give the mean value of 2.50 x 10-5 for the hydrolysis constant of aniline hydrochloride and 0.95 x 10-4 for sodium phenoxide. H. M. I). C= -(K,,-Il'b),'(0~154+0.0433Cb~) Standardisation of Alkalimetric Solutions. FRANCIS D. DODGE ( J . Id. Eng. Ch~m. 1915 7 29-30).-Potnssium hydrogen phthalate is recommended for use in standardising alkali solutions. The salt has the formula KRC,H,04 is stable non-hygroscopic soluble i n water has a high molecular weight and may be prepared readily from phthalic anhydride and potassium hydroxide.W. P. S. New Chemical Hygrometer. ERIC K. RTDEAL and A. HANNAH (Analyst 1915,40,48-54) -The principle of the apparatus described depends on the fact that sulphuric acid will completely remove the moisture from air a t one contact which is not the case withANALYTICAL CHEMISTRY. ii. 103 solid dehydrating substances. The apparatus consists essentially of two bulbs of equal capacity (about 20 c.c.) provided a t their lower ends with mercury reservoirs; above the surface of the mercury in one of the1 bulbs is placed a small quantity of sulphuric acid and the acid ocupies a bulb above the main bulb when this is filled with mercury.The upper stem of the other bulb is graduated and the upper stems of both bulbs are connected through a tube carrying a threeway tap this tube also carrying an aniline U-gauge provided with a bulb. The sample of air is drawn into the bulb provided with the graduated stem then passed into the sulphuric acid bulb and the diminution in volume ascertained from the volume of mercury in the other bulb w. P. s. Detection of Bromides in Presence of Thiocyanates Cyanides and Ferrocyanides. Lours J. CUBTIAN and ALAN G. WIKOFF (.I Amw. Chenz. Soc. 1915 37 298-3Cll).-Experirnents have been nade to determine the extent to' which thiocyanates cyanides and ferrocyanides interfere with the detection of bromides by means of chlorine water. The following method has been devised which is capable of detecting 2 mg.of bromine in presence of 500 mg. of any of these int,erfering substances. The solution to be t'eeted which should be either neutral or slightly acidified with sulphuric acid is treated with 15 C.C. of a saturated solution of sulphur dioxide. The solution is heated until it boils and whilst still hot an excess of 2N-copper sulphate solution is slowly added with constant stirring. The hot solution is filtered the precipitate washed twice with water and the wash- ings are added t o the filtrate which is then concentrated to about 5-10 C.C. The liquid is cooled and transferred t.0 a test-tube treated with 1 C.C. of 3N-sulphuric acid and 1 C.C. of 1% potassium permanganate and shaken. About 0.5 C.C. of carbon disulphide is now added and the mixture again shaken.If the carbon disulphide becomes yellow the presence of bromine is indicated. The test can be carried out completely in about fifteen minutes. Numerous tests have been made which prove that the method is trustworthy. E. G. Estimation of Iodine in Pharmaceutical Preparations. CH. LORMAND (Ann. Falsif. 1914 7 432-441).-The author discusses the methods given in the French codex for the estimation of iodine in pharmaceutical preparations; in a few cases the method to be used is not prescribed. I n the case of tincture of iodine,the official method simply estimates the free iodine and does not take into account the hydriodic acid which is always formed although direc- tions are given to test for the presence of this acid. The total quan- tity of iodine in this tincture may be estimated by treating 5 grams of the sample with sodium hydrogen sulphide neutralising the excess of the latter with sodium hydroxide acidifying the solution with nitric acid .tnd precipitating the iodide with silver nitrate.It is pointed out that a portion of the iodine in iodine-iodide ointment enters into combination with the fatty constituents andii. 104 ARSTRACTS OF CHEMlCAL PAPERS. that the iodine content diminishes gradually with time for this reason. Iodine in iodo-tannin-phosphated wines may be estimated by treating the wine with an excess of milk of lime filtering acidi- fying the filtrate with nitric acid and precipitating the iodide with silver nitrate. w. P. s. Use of Mercuric Salts for the Detection of Sulphur Dioxide in the Atmosphere.G. DENIG~S (Ann. Chim mu!. 1915,2O,10-11; from Butt. SOC. pharm Bordeccux 19 14J- The reapen ts yielding the best results are (I) 5 grams of mercuric oxide dissolved in 20 C.C. of sulphuric acid (D 1-84) and 100 C.C. of water; (2) 5 grams of mercuric acetate dissolved in 100 C.C. of water containing 1 C.C. of glacial acetic acid; (3) 5 grams of mercuric nitrate dissolved in 5 C.C. of nitric acid (D 1-39} and 50 C.C. of water. A glass rod is dipped in any one of the reagents then exposed in the atmo- sphere to' be testled and its surface' after the exposure examined under the microscope. Characteristic crystals will be observed if the atmosphere contains even minut'e quantities of sulphur dioxide. w. P. s. Gaseous Impurities in the Air of Railway Tunnels.ATHERTON SEIDELL and PHILIP W. MESERVE (U.S. Public IIeaZth Service Hygienic Lab. Bull. No. 02 1914 pp. 1-47) -Eighty-eight samples of air from railway tunnels in the city of Baltimore were examined ; those from tnnnels through which steam locomotives passed contained on an average 15.1 parts of sulphur dioxide and 267 parts of carbon monoxide per million parts of air whilst the corresponding figures for a tunnel on an electrified railway were 2.9 and 25 parts respectively. A review of the available literature on the physiological effects of small amounts of these two gases showed that the concentrations of the gases which produce an unmistakable harmful effect are somewhat greater than the maxi- mum amounts which were found in the samples of tannel air examined.On account of the particular conditions under which the investigation was made methods based on the aspiration of the sample of air through a small volume of liquid followed by a gravimetric or volumetric estimation of the ret'ained sulphur dioxide could not be used but trustworthy results were obtained by direct titratlion with N / 1000-iodine solution after applying a correction (compare A. 1914 ii 484). When the samples of air were kept in moist bottles practically the whole of the sulphur dioxide disappeared within one hour; in dry bottles the loss during the1 first two hours was usually very small although in the case of very small quantities of the gas an appreciable loss was noticed within thirty minutes. Of small amounts of sulphur dioxide liberated in a closed room only about 30-60% could be recovered.The iodine pentoxide method (A. 1908 ii 66) was used f o r the estimation of the carbon monoxide special bulbs having narrow connecting tubes being employed for the absorption of the resulting carbon dioxide and liberated iodine and the closed aspiration system was adopted in passing the sample of air throughANALYTICAL CHEMISTRY. ii. 105 the apparatus. Analyses of test mixtures of very small quantities of carbon monoxide with air showed that from 88% t o 98% of the former could be recovered. w. P. s. The Folin-Farmer Method for the Colorimetric Estimation of Nitrogen JOSEPH C. BOCK and STANLEY R. BENEDICT ( J . Biol. Chew. 1915 20 47-59).-The Folin-Farmer method contains certain sources of error.The results usually agree with the Kjeldahl method witthin 2 or 37L; the latter method generally gives the higher reisult but variations betweea + 4 and -11.8 occur. Some modifications are suggestled. W. D. H. Comparison of the Gunning Copper Method and the Kj eldahl-Gunning-Arnold Method for the Estimation of Nitro- gen OVE F. JENSEN (J. I n d . Eng. Chem. 1915 7 38-39).-With dried blood the period of digestion in the Gunning copper method should be continued for two hours in order to convert the whole of the) nitrogen into ammonia whilst one hour’s digestioa is sufficient in the Kjeldahl-Gunning-Arnold method. I n the case of numerous other substances examined a digestion of one and a-half hours was sufficient for either method. The Gunning copper method (use of copper sulphate and potassium sulphate) has the advantage over the1 Kjeldahl-Gunning-Arnold mlethod (mercury and potassium sulphate) in that the addition of potassium sulphide is unnecessary in the distillation of the ammonia; further in adding the sodium hydroxide solution before distilling the copper sulphate acts as an indicator and a large excess of alkali may be avoided. W.P. S. Rapid Method of Estimating Nitrates. EDMUND KNECHT (J. Xoc. Chem. Ind. 1915 34 126-127).-The process is based on the discovery that nitrates are reduced t o ammonia quantitatively and almost instantaneously by titanous hydroxide. A solution of the nitrate (in amount about equivalent to 0.1 gram of pot’assium nitrate) is treated in a copper flask with an excess of sodium hydroxide and about 20 C.C.of commercial titanous sulphate or chloride. The ammonia produced is removed by distillation. The process is a130 tlrustlworthy for the estimation of nitrites. C. S. Comparison of a Few Methods for the Estimation of Total Phosphoric Acid in Superphosphate. C. A. PETERS (J. Ind. Eng. Chern. 1915 7 39-40).-The official (American) method for estimating total phosphoric acid in superphosphate gives too high results unless silica is removed previously by evaporating the solution to dryness treating the residue with dilute nitric acid and filtering the solution. Other methods such as that described by Baxter (A.7 1903 ii ISO) Pemberton’s volumetric method and direct precipit’ation as ammonium magnesium phosphate in the presence of ammonium citrate yield trustworthy results.w. P. s.ii. 106 ABSTRACTS OF CHEMICAL PAPERS. Destruction of Organic Substances in Urine by Hydrogen Peroxide. C. E. CARLSON (Ann. Chinz. anaZ. 1915 20 16-17; from Svensk. farm.. Tidscvgt 1914 65).-In testing urine €or arsenic mercury etc. the preliminary operation for the destruction of the organic substances may be carried out by treating 500 grams of the sample with an equal weight of 1576 hydrogen peroxide solution and evaporating the mixture tol dryness; the residue is then trans- ferred to a flask boiled with several successive quantities of 25 C.C. of hydrogen peroxide and again evaporated t o dryness. The residue is hesated slightly and if any appearance of charring is noticed the treatment with hydrogen peroxide is repeated.The final residue is then heated a t 300° to1 elxpel ammonium salts. w. P. s. Volumetric Estimation of Silver. C. DEBRUN ( A m . FaZsif. 1914 7 407409).-The strength of the sodium chloride solution used in tlhe Gay-Lussac method foir the titration of silver is so adjusted that a t 15O 100 C.C. of the solution are equivalent to 1 gram of silver; if used al; other temperatures the silver-value of the solution is altered; thus a t Oo 100 C.C. of the solution (measured a t 15.) will memure 99.953 c.c.; a t 5O 99.938 c.c.; a t loo 99.956 c:c. ; a t 20° 100.092 C.C. ; a t 25O 100.205 c.c.; at 30° 100.328 c.c.; and at' 35O 100.484 C.C. w. 9. s. Electrolytic Separation of Zinc Copper and Iron from Arsenic. A. K. BALLS and C. C. MCDONNELL ( J . 17zLcJ.Eng. Chern. 1915 7 26-29).-Zinc7 iron and copper may be separated electro- lytically from arsenic by using an electrolyte containing a large excess of potassium hydroxide. The arsenic must always be present in the higher state of oxidation. The mixture of the metal and arsenic is dissolve'd in 5076 potassium hydroxide solution (tartaric acid is added in the case of iron and copper) an excess of about 20 grams of the alkali is added the mixture is diluted t o 95 C.C. and submitted to elect8rolysis a nickel basin being used €or the cathode and a rotating platinum paddle f o r the anode. The addition t o the electrolyte of 0.2 gram of potassium nitrate renders the deposit of zinc more smooth and adherent whilst 2 grams of the nitrate may be added in thel case of copper without appreciably interfering with the accuracy of the separation.The arsenic may be estimated in the solution from the electrolysis. w. P. 8. Estimation of Copper and Lead in Babbitt Metal. E. 'CV. HAUMAIEE (Met. and Chem. Eng. 1914 12,753 ; from J. SOC. Chern. Id. 1915 34 87).-TO 1 gram of the alloy 15 C.C. of hot water and sufficient tartaric acid are added t o keep the tin and t,he antimony in solution; 5 C.C. of nitric acid are added and the liquid is boiled until solution is complete. The solution is heated with 5 C.C. of sulphuric acid until nitrous fumes cease to be evolved charring being avoided. The mixtnre is cooled 50 C.C. of water are added and the lead sulphates is filtered off. The filtrate is diluted to 400-500 c.c. and after the addition of 1-2 C.C.of hydrochloricANALYTICAL CHEMISTRY. ii. 10'1 acid the copper is precipitated on a &rip of pure aluminium and is estimahed in the usual manner. c. s. Separation and Estimation of Aluminium Associated with Iron by the Action of Acetyl Chloride in Acetone. H. D. MINNICI (Amer. J. Xci. 19 15 [iv] 39 197-200).-Alun~i1~i11m chloride is precipitated complet'ely as the hydrated compound AlCl,,GH,O when its concentrated solution is mixed with a solu- tion of 1 part of acetyl chloride in 4 parts of acetone; ferric chloride remains soluble under these conditions. The solution containing aluminium chloride and ferric chloride is evaporated to the smallestl possible volume then cooled to 1 5 O 20 C.C. or more of the acetyl chloride-acetone mixture are added drop by drop the precipitate is cofllected dried and converted into oxide by igni- tion.The iron may be estimated in the filtrate by precipitation as hydroxide. The acetyl chloride smployed should be free from phosphorus compounds ; these are frequently present in ordinary acetyl chloride and cause the iron results t o be too high owing t o the formation of ferric phosphate. w. P. s. Reduction of Ferric Sulphate in Acid Solution by Means of Cadmium Amalgam for Titration of Iron and Free Sulphuric Acid. J. €3. CAPPS and O..eW. BOIES (J ._ Physical. Chem. 1915 19 65-75).-In addition to the substances which are usually found in naturally occurring waters mine waters frequently contain free sulphuric acid and ferrous and ferric iron. On account of the hydrolysis of the ferric salt the free sulphuric acid cannot be estimated by titration with alkali and the application of the hydrogen electrode method yields unsatisfactory results by reason of the influence of the platinised platinum electrode on the ferrous- ferric equilibrium.A satisfactory method for the estimation of the iron and the free sulphuric acid in waters of this type has been worked out. This involves the reduction of the ferric iron t o ferrous by the action of cadmium amalgam. The water is placed in a small flask provided with a two-holed rubber stopper through which passes a separating funnel for the admission of the amalgam and a tube for connecting the flask with a vacuum pump. The air in the flask as well as that in solution is removed by exhaustion. Hydrogen is then admit'ted and the amalgam run into the water.After shaking for thirty to sixty seconds the ferric iron is reduced and the free acid can he titrated with sodium carbonate solution with methyl-orange as indicator. Titration of the reduced solution with standard permanganate gives the total iron whilst ferrous iron is obtained by titration of the original water. Separation of Tungsten from Molybdenum. EDWARD ELLSWORTH MARBAKER (J. Amer. Chem. Soc. 1915 37 86-95).- The following method for the quantitative separation of tungsten and molybdenum is based on Mdivani's method of estimating tungsten (A 1911 ii 230). B. M. D.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. The solution containing sodium tungstate and rnolybdate is heated t o boiling and treated with a solutlion containing 50 grams of stannous chloride (SnC12,2H,0) in 200 C.C.of concentrated hydro- chloric acid. The amount of the reagent must be carefully regu- lated and should be used in the proportion of 20 C.C. for each 0.15 gram of tungsten t'rioxide. The volume of the solution for analysis should be kept between 60 C.C. and 300 C.C. according to the quantity of tungsten present. After the mixture has been boiled f o r a few minutes the blue precipitate (W,O,) is allowed to subside and the supernatant liquid is filtered. The precipitate is washed wihh hot 5% hydrochloric acid until the washings are free from molybdenum. The precipitate is collected on the filter and allowed to drain and the filter is then ignited gently in a porcelain crucible.The resulting tungsten trioxide is cooled in a desiccator and weighed. The filtrate and washings are united and evaporated t o a small volume. If a large amount of molybdenum is present the solution is diluted to 250 C.C. To 50 C.C. of this solution 5-10 grams o€ 20-mesh zinc are added. The tin separates as metal and when the precipitation is complete the solution is filtered and the tin is washed several times with hot water. The washings are added t o the filtrate and heated to 60°. The reductor flask is charged with 20 c.c. of 10% ferric ammoaium sulphate and 20 C.C. of the " titrating solution " (consisting of 90 grams of manganous sulphate 650 C.C. of water 175 C.C. of syrupy phosphoric acid and 175 C.C. of concentratred sulphuric acid). Fifty C.C. of dilute hydro- chloric acid (containing 2.5% of the concentrated acid) are passed through the reductor followed by the solution containing the molybdenum and then by 150 C.C. of the dilute hydrochloric acid and finally by 150 C.C.of hot water. The solution in the flask is now titrated with O*lll'-potassium permanganate and from the result obtained the amount of molybdenum present is calculated (compare Randall A. 1907 ii 912). The quantity of tungsten in a sodium tungstate solution can be estimated by Mdivani's method if sodium chloride is previously added. E. G. Use of Bettendorf's Reagent in Testing the Purity of Drugs Containing Antimony. ALFREDO PAQNIELLO (Boll. Chim. Fawn. 1914 53 689-691).--The fact that certain antimony drugs give precipitates with Bettendorf 's reagent which consists of stannous chloride and hydrochloric acid is shown t o be due to reduction of the antimony compounds t o metallic antimony and not t o the presence of arsenic derivatives as impurities.Pharmaceutical products containing antimony may however be examined for the presence of arsenic by means of the official test given in the '' Deutsches Arzneibuch " for antimony pent(asu1phide 0.5 gram of the latter is heated for two minutes a t 50-60° and stirred with 5 C.C. of aqueous ammonium carbonate solution satur- ated in the cold; acidification of the filtered liquid with hydro- chloric acid should not be followed by formation of yellow arsenicalANALYTICAL CHEMlSTHY ii. 109 flakes within six hours. I n the case of any other antimony compound the latter is converted into the pentasulphide which is separated by filtration and then purified by dissolution in ammonium sulphids solution and precipitation by means of hydro- chloric acid.The purified pentasulphide is then digested with ammonium carbonate solution as described above. T. H. P. A. MONNIER (Ann. Chim. anal. 1915 20 1-4).-Titanium trichlorido may be used as a reagent for the identification of certain metals and organic acids the reactions depending on the reducing property of the reagent. Platinum iridium and palladium chlorides are reduced whea heated with titanium trichlorids solution a black precipitate of the metal being formed; gold chloride is reduced in the1 cold with the formation of a blue coloration. Tungstates give a blue coloration and molybdates a brown colour which changes t o greeln or blue when the mixture is heated.Vanadates are decolorised by titlanium trichloride but a blue coloration develops on heating. Chromates and dichromates are reduced to green chromium compounds selenious acid gives a red precipitate of selenium and talluric acid is reduced when heated with the reagent. All these reactions take place most readily in dilute hydrochloric acid solution. Sulphur is deposited when sulphurous acid sulphites or thiosulphates are treated with titanium tri- chloride. The following reactions occur when salts of various organic acids are heated with titanium trichloride solution Formates and acetates violet-black precipitates ; oxalates yellowish- brown prelcipitate ; succinates violet precipitate; tartirates grey precipitate; lactates blue coloration no precipitate; benzoates brownish-green precipitlate 3 salicylates yellow precipitate ; tannin reddish-orange precipitate.A characteristic violet coloratioii is obtained when a citrate solution is boiled with titanium trichloride ; this coloration is not affected by the presence of formic acetic succinic lactic and benzoic acids citric acid inhibiting the reactions given by these acids. Oxalic and salicylic acids however interfere Estimation of Organic Matter in Potable Water. J. D. FILIPPO and H. J. BACKER (Chenz. Weekblnd 1915 12 73-78).- Carbohydrates and other organic matter present in wat8er are oxidised to oxalic acid by permanganate in alkaline solution. To avoid the error thus intlroduced the solution should be acidified before determining the excess of permanganate by titration by the iodometric mebhod.A. J. W. Separation of the Illuminants in Mixed Coal and Water Gas. G. A. BURRELL and I. W. ROBERTSON (J. I d . Eng. Chem. 1915 7 17-21).-The following results were obtained on the analysis of a gas consisting of 1 part of carburetted water-gas and 3 parts of coal-gas the method used being t'hat dwcribed by Burrell and Seibert (A. 1914 ii 741) in which the various gases are separated from each other by fractional distillation a t low Titanium Trichloride in Qualitative Analysis. with the reaction yielded by citric acid. W. P. 5. VOL. CVIII. ii. 8ii. I10 ABSTRACTS OF CHEMICAL PAPERS. temperatures; the figures in parentheses show the figures found by ordinary methods of analysis Carbon dioxide 2.63 (2.64) ; oxygen 0.81 (0.81) ; carbon monoxide 13-25 (13.34) ; hydrogen 37.33 (37.04) ; methane 31.13 (30-96) ; ethane 2-10 (1.82) ; nitrogen 4-23 (4.72) ; propane 0.43 ; ethylene 6.05 ; propylene 0.60 ; butylene 0.11 ; benzenel 1.33 ; (illuminants 8.67).A method is described for the estimation of benzene in coal gas; after water- vapour has been removed from the gas the latter is cooled t o -7S0 and as much gas is removed as possible by means of a pump the cooling medium being then removed and the condensed liquid vaporised. The pressure obtained compared with the original pressure of tlhhe gas gives the quantity of benzene in the gas. w. P. s. Method for the Estimation of Glycerol in Pharmaceutical Preparations C.H. BRIGCS (Pimrm. J. 1915 94 157; J. Amer. Pharm. ASSOC. 1915).-A quantity of the preparation containing about 2 grams of glycerol is mixed with 0.5 gram of magnesium oxide and 75 C.C. of santal oil and distilled under reduced pressure until about two-thirds of the oil has been distilled. The con- denser is then rinsed with 100 C.C. of light petrolenm next with 5 C.C. of water both of these are added t o the distillate and the aqueous portion is separated. The oil solution is now shaken three times in succession with 5 C.C. of water the united aqueous extracts are shaken with 30 C.C. of light petroleum t o remove any traces of oil the aqueous solution being then evaporated below 50° and the residue of glycerol dried for twenty-four hours under reduced pressure over sulphuric acid.w. P. s. Detection and Estimation of Free or Combined Glycerol. Application to Glycerophosphates. Estimation of Phosphorus in Glycerophosphates. M. FRAN~OIS and E. BOISMENU (J. Pharm. chin^. 19 15 [vii] 1 1 49-68) .-Glycerol may be identified by heating it with potassium hydrogen sulpliate acraldehyde being formed ; if the acsaldehyde vapours are passed into magenta-sulphurous acid reagent a red coloration is obtained which changes to blue when the solution is heat'ed. Combined glycerol in glycero- phosphates may be identified by the1 same means. The dichromate method is recommended for the estimation of glycerol; a large excess of dichromate should be employed the mixture of glycerol and dichromate solution must be acidified with concentrated sulphuric acid and the oxidation continued for two hours a t a boiling temperature.The same method may be used directly for the estimation of glycerol in glycerophosphates. Phosphorus is estimated in the latter by heating the substance f o r two hours with potassium dichromat$el and sulphuric acid reducing the excess of dichromate with sodium sulphite then adding sodium acetate and precipitating the phosphoric acid with molybdic acid reagent. The ammonium phosphornolybdate is next converted into ammonium magnesium phosphate and weighed as magnesium pyrophosphate. w. P. 8.ANALYTICAL CHEMISTRY. ii. 111 Reaction of P-Naphthol. J. KATAYAMA and B. IKEDA (J. Phavrn. Chim. 1915 [vii] 11 73-74 ; from Yakugakuzashi 1914).-A violet coloratio,n is obtained on adding 0.05 C.C.of a 0.01% sodium nitrit'e solution tlo 1 C.C. of a P-naphthol solution mixed with a few drorss of concentrated sulBhuric acid. The reaction mav be obt'iined with 0*0002 gram i f P-naphthol per C.C. of solut'ion' w-. P. s. Volumetric Fehling Method using a New Indicator. A. M. BRECKLER (J. Ind. Eng. Chem. 1915 7 37-38).-The method described depends on a constant volume of solution a t the end of the titration a constlant time of boiling and the use of sodium sulphide solution as an external indicator. A preliminary titra- tdon gives approximately the quantity of the sugar solution re- quired to reduce 10 C.C. of Feliling's solution; towards the end of the titration a drop of the solution is added t o a drop of 4% sodium sulphide solution the end of the titration being denoted by the drop remaining colousless after the suspended cuprous oxide has turned black and settled as a precipitate.Ten C.C. of Fehling's solution are then mixed with about 97% of the quantdty of sugar solution used in the preliminary experiment and sufficient water to make the final volume up t'ot 30 c.c. the mixture is boiled for one and a-half minutes and the titration completed which can usually be done by two additions of the sagar solution. w. P. s. Estimation of Sugar in Small Quantities of Blood. ROBERT C. LEWIS and STANLEY R. BENEDICT (J. Biol. Chem. 1915 20 61-72).-The estimation of sugar in human blood in cases of diabetles is most necessary; a review of previous methods is given. The new method proposed is performed with 2 C.C.of blood and is colorimetric the reagents added being picric acid and sodium carbonate; the picric acid is added first t o the blood previously laked with w a h ; this precipitates all the protein and no sugar; the sodium carbonate is then added to the filtrate which is evaporabed until precipitation occurs wates is added and the liquid again heatted t o boiling made up to volume and filtered into the colorimeter chamber. The figures given show that the method is trustworthy. Any traces of creatinine in the blood are insufficient t o affect the colour values. The normal percentage of dextrose in human blood is 0.09 t o 0.11 average 0.1%. W. D. H. Estimation of Formic Acid in Ketchup. C. A. PETERS and L. P. HOWARD (J. Ind. Eng. Chem. 1915 7 35-37).-From 91 to 92% of the formic acid added to ketchup can be obtained by Fincke's prooess (A.1911 ii 282; 1913 ii 442); 1000 C.C. of distillate should be collected and the formic acid retained in an intermediate flask containing calcium carbonate and water. 8-2 w. P. s.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. Influence of Hydroxy-acids and Lactones on Determina- tions of the Chemical Constants of Fatty Acids. C. A. BROWNE ( J . Ind. Eng. Chem. 1915 7 30-34).-The author discusses the influence of hydroxy-f atty acids particularly those having a pro- nounced tendency to form lactones on the estimation of the acid saponification ester and acetyl nunibers of fatty acid mixtures. w. P. s. Estimation of Potassium Hydrogen Tartrate and Tartaric Acid. H. ASTRUC (Ann. FaZsiJ 1914 7 416-417).-The racemate melthod (A.1910 i 651; ii 359; 1911 ii 666) is recommended as being trustworthy. w. P. s. Estimation of Total Tartaric Acid and Potassium in Wines. A. KLINC and A. LASSKEUR (Ann. Pal$. 1914 7 410-416).-The t,otal quantity of tartaric acid in wine may be estimated rapidly by the following modification of the racemate method (A. 1911 ii 666). Twenty-five C.C. of the wine 10 C.C. of a 27; ammonium Z-tartrab solutdon and 20 C.C. of a solution containing 16 grams of calcium carbonate and 120 C.C. of glacial acetic acid per litre are mixed and after thirty minutes the precipitate of calcium racemate is colleckd washed dissolved in dilute sulphuric acid and the sdution titrated with potassium permanganate solution. Potassium is estimated by the perchloratel method.The ash of tlie wine is treated with a few drops of water and a small quantity of perchloric acid solution the mixture’ is evaporated t o refmove the greater parti but not all of the excess of perchloric acid the residue is mixed with alcohol collected on a filter and washed with alcohol. This residue containing thel potassium perchlorate is then heated with sodium carbonate and the resulting chloride is titrated by Volhard’s process. The method estimates the potassium present in the wine in the form of salts of organic acids and as sulphate. w. P. s. Determination of the Freezing Point of Milk. J. J. VAN ECK J. D. FILTPPO F. H. VAN DER LAAN A. LAM A. VAN RAALTE and L. TH. REICHER (Chem. Weekbkad. 1915 12 1OS-l16).-Determina- tions of the freezing point of a number of samples of milk have proved that the method of Dekliuyzen and that of the Dutch ‘‘ Codex alimentarius ” yield equally trustworthy results.A. J. W. Analysis of Butter (Estimation of Water). ISNARD (Ann. Fahi$ 1914 7 442-443).-The amount of water in butter may be estimated by separating the aqueous portion (containing the casein etc. in suspension) from the fat evaporating it and weighing the dry residue. The sum of the weights of this residue and of tlie fat subtracted from the weight of the butter taken for the) estima- tion gives the quantity of water present. w. P. s.ANALYTICAL CREMISTRY. ii. 113 Spermaceti Its Solidifying and Melting Point. ROBERT MELDRUM (Chem. News 1915 11 1 37-39).-The following results were obtained in the determination of the! solidifying point of spermacelti by various methods Dalican's method 45'75O; in small-bore tubel 45*75O; by slow cooling 45-75" to 45'95O; by con- tinuous stirring 45'75O; by opacity method 45*8O to 4G.Oo; by capillary 44.7O to 45'0O.Determinations of the m. p. were also made by diffelrent methods namely thermometer-bulb method 45'3O to 45'5O; open capillary 45*1° t o 45'4O; closed capillary 4 5 - 9 O to 46.0°; opacity method 4G.Oo t o 46.4O. Previous re- peatied heating of the spermaceti a t looo and cooling does not affect the solidifying point; further this constant is not affected by the presence in the spermaceti of 0.1% of water glycerol or oleic acid. The pre'sence of 5% of sperm oil lowers the solidifying point by about 0'2O.m7. P. s. Method for the Estimation of Unsaponifiable Matter Applicable to Ether Extracts Fats Oils and Waxes. J. B. KATHER (J. Ind. Eng. Chem. 1915 7 34-35).-1n the method described the fatty acids are removed from the unsaponifiable substances by precipitation from ethereal solution. A quantity of about 0.4 gram of the fat is boiled in a flask for one hour with 20 C.C. of 2N-alcoholic sodium hydroxide solution the mixtare is evaporated nearly to dryness and the residue is treated with 3.5 C.C. of glacial acetic acid 50 C.C. of ether and 25 C.C. of water. When the residue has dissolved the solution is transferred to a separating funnel and the flask is rinsed with five successive quantities of 20 C.C. of ether. The aqueous layer is then drawn off the ethereal solution is shaken twice with 10 C.C.of 33% sodium hydroxide solution and 25 C.C. of warm water and next with five successive quantities of 30 C.C. of cold water. The ethereal solution is then evaporated in a weighed flask the residue dried a t loo" and weighed. To correct for a small quantity of fatty acids retained by the unsaponifiable substances the reeidue is dissolved in ether the solution shaken with hydrochloric acid the ethereal solution is again evaporated t o dryness the residue dissolved in alcohol and titrated with N / 10-sodium hydroxide solution ; the number of C.C. of the latter required is multiplied by 0.028 and the result deducted from the weight found previously. w. P. s. Substances which Mask the C'olour Reactions of Strych- nine. EFISIO MAMELI (Boll.Chirn. Purrn. 1914 53 366-369).- Otto's reaction for strychnine consists in the formation of violet streaks in sulphuric acid solution in contact with crystals of potassium dichromate and Mandelin's reaction in the formation of a bluish-violet coloration changing to violet-red and later or on addition of water to red with a sulphuric acid solution of ammonium vanadate. The following compounds if present in large proportion entirely prevent the appearance of these reactions or if present in quantities small in comparison with that of the alkaloid weaken the reactions considerably phenacetin migraninii. 114 ABSTRACTS OF ChIEMICAL PAPERS. (mixture of antipyrine caffeine and citric acid) 0- or p-phenebidine paminophenol “ phenocoll,” salacetol protocatechuic acid amino- methylenecatechol dormiol (amylenechloral) guaiacol acetyl- guaiacol piodoguaiacol heroine (diacetoxymorphine) helmitol (hexamethylenetetramine anhydromethylenecitrate) pyramidone zinc phsnolsulphonats glycerol and hydrochloric acid.Both re- actions are inhibited by even small proportions of phenol anisole phenetole &naphthol P-naphthyl salicylate j3-naphthyl benzoate’ and pphenetylcarbamide. Otto’s reaction is prevented by a small amount of acetylacetone or phenyl salicylate but larger quantities of the.se are necessary to intlerfere with the action of Mandelin’s reagent which then gives a green coloration. Aniline acetic acid tart’aric acid methyletlhyldimethylarninomethylcarbinyl benzoate hydrochloride and hexamethylenetetramine d o not disturb Man- delin’s react’ion but diminish the intensity of or completely pre- vent Otto’s reaction.o-Toluidine and zinc lactate inhibit Otto’s reaction and render Mandelin’s reaction less marked; the same is the case with quinoline and terpenes with which Mandelin’s reaction rapidly disappears so that the usual changes of colour cannot be observed. Piperonaldehyde lecithin and papain do not interfere with Otto’s reaction appreciably but modify Mandelin’s reaction. I n large1 proportions antipyrine o-acetoxybenzoic acid menthol analgen,” apo’lysin (phenetidine citrate) and salicylic acid mask Otto’s reaction and with Mandelin’s reagent give a transitory bluish-green or a stable dirty green coloration (salicylic acid). Both reactions are modified or retarded by preponderating propor- tions of citric o r pjperonylic acid quinine euquinine dextroee or mannitol.On the other hand the red streaks given by anilides with potassium dichromate are readily distinguished from those obtained with strychnine and neither of the above reactions is disturbed by a large number of compounds in therapeutic use these including caffeine ‘‘ salophene,” amygdophenine (phenylglycolyl-p-pheneti- dine) theobromine o-benzoicsulphinide saligenin sulphonal trional tetronal veronal and antithermine (lzvulic acid phenyl- hydrazone). I n the toxicological investigation of strychnine thel latter may be separated from extraneous substances by taking advantage of its almost complete insolubility in cold water absolute alcohol and anhydrous ether it5 very slight solubility in boiling water its slight solubility in cold 90% alcohol benzene carbon tetrachloride amyl alcohol glycerol light petroleum and carbon disulphide and its ready solubility in chloroform.T. H. P. Analysis of Tanning Materials. I. An Improved Basic Chloride Shake Method. HUGH GARNER BENNETT (J. Xoc. Chern. Znd. 1914 33 1182-1184).-The basic chloride shake method ’.’ now in use as the official method f o r the analysis of tanning matelrials does not sharply distinguish betwemen the tannin and noln-tannin coatlent of the material a considerable proportion of non-tannin substances being absorbed by the hide powder andANALYTICAL CHEMISTRY. ii. 115 reported as tannin. The author suggests that more trustworthy results would be obtained that is the tannin content would be lower and the non-tannin content higher if the method were modified as follows (1) The hide powder to be exactly neutlralisecl before chroming.(2) Only 5 grams of hide powder to be used for each analysis. (3) To 100 C.C. of infusion of ordinary strength 100 C.C. of water to be added before the! prepared hide powder and the total volume to be made up t o 220 c.c.; any convenient aliquot portion of the solution may be evaporated and the residue weighed. (4) The chroming liquor to be a solution of the salt Cr,(OH),Cl2 instead of Cr,(OH)3Cl,. w. P. s. Analysis of Tanning Materials. 11. Tannery Liquors. HUQH GARNER BENNETT (J. SOC. Chem. Ind. 1914 33 1184-1186).-The modified basic chloride method (see preceding abstract) is more trustworthy than the usual method when applied to the analysis of used tan liquors.The liquor is filtered and diluted so as to contain from 0.17 to 0.23% of tannin; 50 C.C. or less of this solu- tion are evaporated with the addition of 5 C.C. of 0.5% tartaric acid solution and the residue is dried for one hour a t looo. The weight of the residue less that of the added tartaric acid gives the total solids prwent!. One hundred C.C. of the solution are then mixed with 2.5 grams of neutralised and chromed hide powder 12.5 C.C. of water less the amount contained in the hide powder are added the mixture is shaken f o r fifteen minutes filtered and tlhe solids estimated by evaporating 55 C.C. or less of the filtrate with the addition of tartaric acid. The result gives the quantity of non-tannins in the liquor.The hide powder is prepared for use by estimating the moisture in it theln neutralising a portion equivalent t o 2.5 grams of the dry powder after the addition of ten times its weight of water and treating it with 0.5 C.C. of a solution obt'ained by dissolving 100 grams of crystallised chromic chloride and 40 grams of anhydrous sodium carbonate in 1 litre of water. The hide po'wder and chrome solution are shaken f o r one hour the powder is_then washed until free from chlorides squeezed to contain about 70% of water and weighed; the quantity of water remaining in the 2.5 grams of hide powder is thus ascertained. w. P. s. Tannins of Valonia Oakwood and Chestnutwood. HUGH GARNER BENNETT (J. SOC. Chem. Ind. 1914 33 1186-1 187).-These three tannins may be distinguished from each other by the action of bromine water on a solution of the products obtained when the solid extracts are submitted to dry distillahion.The extract is heated in a test-tube provided with a delivery tube and the dis- tillate is received in another tube. The distillate is then shaken with 15 C.C. of water the mixture is filtered and the filtrate treated with an excess of bromine water. Under this treatment valonia yields a dense yellow crystalline precipitate of tribromophenol bromide m. p. 139-141O (decomp.); the precipitate should be washed with cold alcohol before the melting point is determined.ii. 116 ABSTRACTS OF CHEMTCAL PAPEKS. The distillate from chestnut tannin does not give a precipitate with bromine whil& that from oakwood tannin yields a turbidity only.w. P. s. The Catalytic Reactions of Blood. I. The Factors Involved in the Benzidine Test for Occult Blood. W. G. LYLE L. J. CURT- MAN and J. '1'. W. MARSHALL (J. BioE. Chern. 1914 19 445-457).- The sensitiveness of the test is influenced by the relative concen- t'rations of the reagents used-benzidine acetic acid and hydrogen peroxide. Under favourable colnditions occult blood can be detected when diluted one to five million times. But if inhibiting substances are present the reagent can be made more resistant to them by increasing the strength of the benzidine but then it fails to respond to very dilute blood. The acetic acid merely holds the benzidine in solution; excess lessens the delicacy of the test and increases the speed of fading.The peroxide supplies the necessary oxygen and bleaches the blue colour; excess must therefore be avoided ; excess further destroys the catalytic power of the blood and by reacting with benzidine produces inhibitory substances. The water used should have been distilled in glass vessels. The peroxide should be added last. Identification of Traces of Bilirubin in Albuminous Fluids A. A. HYMANS VAN DEN BERQII and J. pJ. DE LA FONTAINE SCHLUITER (Proc. K . h a d . Wetensch. Amsterdam 1914 17 807-81O).-To detect with certainty the presence of small quantities of bilirubin in blood serum or other albuminous fluid 20 C.C. of pure acetone are added to 10 C.C. of the serum and the more o r less intensely yellow solution after removal of the albumin precipitate is evaporatled in a vacuum a t the ordinary temperature until the acetone has been removed. The residual aqueous solution is treated with ether to remove the fatty substances 2 C.C. of chloroform are added and the mixture is faintly acidified with hydrochloric acid and well shaken. The chloroform solution containing tile bili- rubin is tlhoroughly washed with water to remove all the hydro- chloric acid and is dried if necessary with anhydrous sodium sulphate. Bilirubin can be detected in the yellow chloroform solu- tion by the usual tests by the reactions of Gmeliii and of Elirlicli and by the isolation of yellow microscopic crystals. The following remarkable observation has been made during the examination of the serum of tlwo patients suffering from obstructive jaundicel and only in these two1 cases. After the blood serum had been treated by the preceding method the final chloroform so'lution was allowed to evaporate slofwly a t Oo; when the concentration had reached a certain value the yellow colour of the solution changed suddenly to green evidently owing to a change of bilirubin to W. D. H. biliverdin. c. s. 3

ISSN:0368-1769    

DOI:10.1039/CA9150805101

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 107 Chemistry of Vegetable Physiology and Agriculture. Influence of Glycerol on Alcoholic Fermentation and on the Inversion of Sucrose. G. ROSSI (Boll. Chim. Parm. 1914 53 657-659).-The fermentation of dextrose is not affected by the presence of 10.6 grams of glycerol per 100 c.c. but is retarded by 21.2 and inhibited by 42.3 grams per 100 c.c.; in the last case the fermenting. power of the yeast is permanently destroyed sub- sequent dilution of the liquid not1 being followed by fermentation. The inversion of sucrose by yeast proceeds readily in presence of 50 grams of glycerol per 100 C.C. T. H. P. The Enzymes of Aspergillus Terricola. F. M. SCALES (J. Biol. Chem. 1914 19 459-472).-This mould produces inulase diastase invertase maltase alcohol-oxydase emulsin lipase protease tannase and amidase; the! fungus may therefore be concerned in the production of various organic clecomposi tion products found in the soil.Many of these products are excellent sources of carbon and nitrogen for bacteria and the ammonia produced may be directly assimilated as a salt by plants. The living organism hydrolyses a small amount of cellulose but cellulase could not be isolated from the powdered material Lad'ase and zymase are k 2i. 108 ABSTRACTS OF CHEMICAL PAPERS. absent. tions containing either carbohydrate or protein or both. The fungus has no nitrogen-fixing power in nutrient solu- W. D. H. The Soluble Polysaccharides of Lower Fungi. 111. The Influence of Autolysis on the Mycodextran Content of Aspergillus niger.ARTHUR W. Dox (J. Uiol. Chem. 1915 20 83-85).-In various cultures of age varying from threle t o one hundred and forty-two days the yield % of mycodextran in the dried fungus increased from 0.9 to 9 2 . This substance forms an integral part of the mature fungus and does not undergo hydro- lysis. The appearance of spores largely determines the larger yields. W. D. H. Physiology of the Intake of Material by the Living Plant Cell. I. Lipo-colloids in the Plasma-membrane. FRIEDRICH CZAPEH (Intern. ZeitscTL. phys.-chem. Biol. 1914 1 108-lZ3).-A theoretical communication partly polemical against Vernon (A. 1913 i 802) and maintaining that the plasma membrane of animal cells differs from that of vegetable cells in containing lipo-colloids as well as hydro-colloids the lipoids of the cell accumulating in the surface layers in accordance with the Gibbs-Thomson hypo- thesis.The capillarity law enunciated by the author as a result of his researches on vegetable cells cannot therefore be expected to' hold strictly in the case o€ animal cells. Physiology of the Intake of Material by the Living Plant Cell. 11. Changes Produced by Potassium Cyanide in the Permeability of the Vegetable Plasma-membrane. MAX KREHAN (Intern. Zeitsch. phys.-chem. Biol. 1914 1 189-259).-After exposure of vegetable cells to diIute potassium cyanide solutions it is found that as compared with similar cells preserved in water considerably higher concentrations of certain substances in solution are required to bring about their plasmolysis. Of the substances tested glycerol lactose dextrose sucrose and most salts gave positive results ; towards carbamide sodium and potassium chlorides and sodium nitrate the cells which had been treated with potassium cyanide behaved exactly like normal cells. The effect of the potassium cyallide on the cells reaches a maxi- mum when the cells have remained in the solution for a certain period of time which is the shorter the more concentrated the pot'assium cyanide solution.By longer contact the effect dimin- ishes until after several hours the cells are found t o be now more easily plasmolysed than normal cells. With low concentrations of potassium cyanide the effect is a reversible one; and after subsequent washing with water the cells become plasmolysed by the same concentration of the substance employed as before the treatment with the cyanide.With increasing concentration of potassium cyanide however the effect becomes irreversible. The increased resistance to plasmolysis is shown by the author t o be due to a specific actiosn of the cyanogen ions. The same H. W. B.VEGETABLE PHYSIOLOGY AND AGRKXJLTURE i. 109 effect on the cells is prolduced if the excess of hydroxyl ions in the cyanide solution is neutralised by the addition of an acid and moreover dilute potassium hydroxide solution has only the slightest action on the cells. Ammonium hydroaide on the con- trary behaves in a somewhat similar manner to potassium cyanide. The condition of the vegetable cell is an important factor in determining the effect produced by potassium cyanide.During the winter the results obtained were only about a half of those obtained in summer and neither differences of light intensity nor of temperature were found to be adequate to account for the variations observed. Chloroform and the lower alcohols in low concentration increase the cyanide action but in higher concentration the action is neutralised o r evm reversed. The author regards the observed effects as being due to the direct action of potassium cyanide on the plasma colloids and not t o an inhibitory action of the cyanide on the respiratory activity of the cell. H. W. B. Electric Charge of the Protoplasm and Other Substances in Living Cells. J. F. MCCLENDON (Intern. Zeitsch. phys.-chem. Biol. 1914 1 159-162).-The anthocyan in the vacuoles of living cells of red cabbage is red and on the passage of an electric current it moves towards the cathode (electrically positive).I f alkali is added t o the medium the anthocyan becomes blue and may now be observed to' move towards the anode (electrically negative) before the death of the cell occurs. The anthocyan therefore seems to be an amphoteric substance like egg-albumin. It is suggested that protoplasm moves towards the anode because it is alkaline but all attempts t o acidify the protoplasm and obtain a movement towards the cathode were unsuccessful owing to the death of the cell. H. W. B. Effect of Acid on Permeability. W. J. V. OSTERHOUT (J. B i d . Chem. 1914 19 493-501). -The method adopted was to determine the electrical resistance of the living tissues of Laminaria saccharina ; this measures the permeability of the protoplasm ; alkali increases.permeability acid decreases it rapidly ; this is followed a t once by a rapid increase until the delath-point is reached. W. D. H. Antagonism Between Acids and Salts. W. J V. OSTERHOUT (J. Bid. Chem. 1914 19 517-520).-Further experiments on Laminaria snceharina. Acid antagonism the action of sodium chloride but the degree of antagonism is not so great as between sodium chloride and calcium chloride. The favourable mixtures of these two salts maintain life1 longer than the most favourable mixtures of hydrochloric acid and sodium chloride. These results afford evidence that the plasma membrane in plants is protein in character. W. D H.i. 110 ABSTRACTS OF CHEMICAL PAPERS.Influence of the Chlorides and Nitrates of Potassium and Sodium on Germination. HENRI MICHEELS (Intern. Zeitsch. phys.- chern. Biol. 191 4 1 412-41 9).-Wheat grains previously soaked in water have been germinated in dilute solutions (M/100 and ill/ 1000) of potassium chloride and nitrat'e sodium chloride and nitrate and from the results the effects of the various ions have been deduced. The1 C1-ion has a more injurious action than the NO3-ion and the Na-ion than the K-ion. The NO3-ion exerts a beneficial action especially in relation to the length of the leaves and the weight of the plantlet4. and it also evokes a lengthening of the root-hairs. The Na-ion appears to lead t o the formation of a longer r o o t than is produced in the presence of K-ions.The same results have been obtained by passing an electric current through the solutions and observing the germination of the grains in the neighbourhood of the cathode and anode respec- tively. H. W. B. Influence of Fluorine on Vegetation. ARMAND GAUTIER (Compt. rend. 1915 160 194-195).-The author has compared the behaviour of various species of plants when grown in an artificial soil almost completely deprived of fluorine in the same soil supplied with fluorine and in ordinary arable soil. I n a few cases fluorine appears to have an inhibitory effect but in most cases i t increases the grotwth the flowering and the production of seed. W. G. Fruit of Clintonia .Borealis. HORACE A. SLIPPY (Chem. News 1915 111 2-3).-The ripe berries gathered a t Sylvan Beach New York were indigo-blue in colour had a very bitter taste and each weighed about 0.34 gram; they lost about 7576 of hheir weight when dried. The dry berries contained 4.870, of ash 13'20% of total sugars 8.75% of a gum-like substance and small quantities of citric and tartaric acids.Prolonged extraction with ether yielded 4.22% of oil but the extraction was not complete; this oil was of a deep green colour owing t o the presence of chlorophyll but after treatment with bonecharcoal became light yellow. The oil was saponified with difficulty and had D15.5 0.897. W. P. S. Rate of Liberation of Hydrogen Cyanide from Commercial Varieties of Linseed. S. H. COLLINS and H. BLAIR (Chem. News 1915 11 1 19-20).-The authors have made observations with commercial varieties of linseed from different sources in order t o ascertain the influence of the place of origin on the quantity of hydrogen cyanide and the rate a t which this is liberated.The results show that the seeds of Oriental origin are all rich in total hydrogen cyanide and are also characterised by high enzymic activity. The seed from Morocco is low in respect of both these qualities. The general effect of growing linseed in this country is t o reduce the total amount of hydrogen cyanide and to increase the activity of the enzyme.VEGETABLE PP~[PSIOLOOY AND AGRICULTURE. i. 111 From a comparison of the results obtained with linseeds grown under conditions of drought and high t’emperature with thoso grown under damp and low temperature conditions it is found that the change from the former to the latter coiiditions is on the average accompanied by a fall 01 20% in total amount of hydrogen cyanide and by a reductioii of 2476 in the time required for the liberation of half the acid present.The Red Thorn. EUCLID C. MARSTON (Chern. News 1914 110 310).-This shrub belongs t o the genus C’wduegics and is coninion from the North-Eastern United States t o the Dakotas and as i’ar south as Missouri; i t yields a dark red woody fruit about 1 cm. in diameter. The dried fruit contains 35.37% of sugars 0.760/ of oil (probably laurin) 3’18% of ash and 0.55% o€ nitrogen. Tartaric citric and acetic acids are present in the fruil the last 11. &I. D. acid probably resulting from fermentation of the sugar. . w. I?. x. Iron in Tomatoes.C. A. BRAUTLECHT and G. CRAWFORD (J. Irt,d Eng. Chem. 1914 6 1001-1002).-Tornatoes from ten counties in Florida were found to contain from 89.3 t o 95.3% of water 0.38 to 0.64% of ash and 0.034 t o 0.123% of ferric oxide. There was no fixed ratio between the water and ash or ferric oxide and ash; the ash contained from 4.38 t o 22.257; of its weight of ferric oxide. The soils on which the tomatoes were grown contained from 3-03 to 3.72% of ferric oxide. w. P. s. Toxicity of ‘‘ Saccharin.” E. VERSCHAFFELT (Pharm. Weekblad 1915 52 3746).-A comparison of the toxic action of “saccharin ” on plants with that of other related substances. Both “ saccharin ” and its sodium derivative are less poisonous than sodium benzoate but have more powerful toxic effects than related sulpho-compounds such as sodium sulphobenzoate.It is suggested that “saccharin ” may be a poison to all forms of protoplasm and hence injurious t o the human organism. A. J. W. Determination of Certain Mineral Elements Necessary for the Development of Maize. P. MAZB (Compt. rend. 1915 160 211-214).-Thel author finds that maim plants will develop com- pletely in an aseptic mineral solution prepared with spring water to which the eleven elements nitrogen phosphorus potassium calcium magnesium sulphur iron manganese zinc silicon and cerium have been added but that if distilled water is used instead of the spring water the gro’wth. stops suddenly. The sudden stoppage of growth he considers is due to the absence of one or more elements from the culture medium.To the solution there- fore one 0.1“ more of the five elements boron aluminium arsenic iodine and fluorine were added and cultures made. The results show that boron aluminiGm iodine and fluorine are necessary for the development of maize but that arsenic is injurious t o this plant. These four elements probably complete the list of mineral elements necessary for the development of maize. W. G.i. 112 ABSTRACTS OF CHEMICAL PAPEHS. Chemical Investigation of the Phosphotuagstate Precipitate from Rice Polishings. JACK CECIL DRUMMOND and CASIMIR FUNK (Biochem. J. 1914 8 598-615).-Choline and nicotinic acid are present in considerable amount ; bet'aine adenine guanine and possibly guanidine are also present Small quantities of other substances not identified also occur.The work of cerhin Japanese authors who claim to have separated the curative material as a picrate was not confirmed. It is apparently decom- posed during fractionation and all trace of it is lost. W. D. H. Increased Nitrate Content of a Soil Subjected to Temporary Drying i n the Laboratory. WALTER BUDDIN (J. Agric. Xci. 1915 6 452-455).-1n soils which were spread out t o dry it was found that practically no change occurred either in bacterial numbers or in the amounts of nitrates present. When however the soils were kept for a month there was a considerably greater increase in nitrates than in similar soils which had not been dried. N. €1. J. &I. Partial Sterilisation of Soils by Volatile and Non-volatile Antiseptics. WALTER BUDDIN (J. Agric. Sci. 1915 6 417-451.Compare Russell and Buddin A. 1914 i 242).-Wlien antiseptics are applied to soils in amounts sufficient t o bring about the usual partial sterilisation effe'cts no increase causes any further change. The paraffin hydrocarbons have so little effect that they can hardly be considered as antiseptics. Their employrnent results however in a depression in bacterial numbers arid in a decided increase in the amount of ammonia ; the nitrifying organisms and the Protozoa are not suppressed. Results similar t o these although less marked are obtained by merely air-drying the soils in thin layers for twenty-four hours. Non-volatile antiseptics give rise t o a permanent depression in bacterial numbers with the liigliest amounts. The stronger ones such as quiiione and quinol show ail initial depression in bacterial numbers when only about 0.05% is used whilst weaker antiseptics applied at the same rate merely liberate small amounts of ammonia. The traces of substances left i n tlie soil when non-volatile a&- septics are used generally produce at varying periods a great rise in the number of some special organisms. The iiew bacterial flora does not produce ammonia ; and none of the non-volatile antiseptics give rise to so great a production of ammonia and nitrates as results from the application of volatile antiseptics. N. 13. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9150800107

出版商:RSC    

年代:1915

数据来源: RSC