摘要:

J O U R N A L A. CHASTON CHAPMAN. A.W.CROSBLEY,C.M.G.,D.SC,,F.R.S. SIR JAMES J. DOBBIE M.A. D.Sc. M. 0. FORSTEB D.Sc. Ph.D. F.R.S. T. A. HENRY D.Sc. J. T. HEWITT M.A. D.Sc. Ph.D. IT. R. S. P. R. 8. OF 0. A. KEANE D.Sc. Ph.D. T. M. LOWRY O.B.E. D.Sc.,F.R.S. G. T. MORGAN D.Sc. F.R.S. J. C. PHILIP O.B.E. D.Sc. Ph.D. A. SCOTT M.A. D.Sc. F.R.S. 5. SMILES O.B.E. D.Sc. F.R.S. J. F. THORPE C.B.E. D.Sc Ph.D. F. R. S. THE CHEMICAL SOCIETY. G. BAROER M.A. D.So. H. W. BYWATERS D.Sc. Ph.D. H. M. DAWION Ph.D. D,Sc. W. GODDLN B.Sc. W. S. MILLAR M.A. B.Sc. Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. E. H. RODD D.Sc.@ J. C. DRUMIUOND D.Sc. G. F. MORRELL Ph.D. D.Sc. T. S. PATTERSON D.Sc. Ph.D. ABSTRACTS OF PAPERS ORGANIC PHYSIOLOGICAL AND AGRICULTURAL CHEMISTRY. ON S. B. SCHRYVER D.Sc. Ph.D. W. P. SKERTCHLY. F. SODDY M.A. F.R.S. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc. Ph.D. J. F. SPENCER D.Sc. Ph.D. D. F. !hISB D.Sc. A. JAMIESON WALKER Ph.D. B.A. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1919.Abstractors of the J o u r d of the.Sooiety of Chemkat haustry who have contributed t o this volume. S. S. AUSTIN. J. F. BRIGW. T. H. BURNHAM. J. H. JOHNSTON M.Sc. J. H. LANE. C. A. MITCHELL M.A. B. NORTH. J. P. OGILVIE. W. E. F. POWNEY. A. B. SEAF~LE. R V. STORR M.Sc. J. S. G. THOMAS B.Sc. I?. 0. THOMPSON. W. J. WRIGHT. PRINTED Iw ORBAT BBITAIN BY RICHAILD CLAY & 8OkJSq LIYI1.C:P YRONYWICS OT. BTAYI'CJORD ST. 8.L 1 AXD BOXOAT IUIIPOLY.

ISSN:0368-1769    

DOI:10.1039/CA91916FP001

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年代:1919

数据来源: RSC

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J O U R N A L A. CHASTON CHAPMAN. A.W.CROSSLEY,C.M.G.,D.SC.,F.R.S. Id. 0. FORSTER D.8c. Ph.D. F.R.S. T. A. HENRY D.Sc. J. T. HEWITT M.A. D.Sc. Ph.D. SIR JAMES J. DOBBIE M.A. D.Sc. F.R.S. F.B.S. OF C. A. KEANE D.Sc. Ph.D. T. M. LOWRY O.R.E. D.Sc. F.R.S. J. C. PHILIP O.B.E. D.Sc. Ph.D. A. SCOTT M.A. D.Sc. F.R.S. S. SMILES O.B.E. D.Sc. F.R.S. J. F. THORPE C.B.E. D.Sc. Ph.D. G. T. MORGAN D.Sc. F.R.S. F.R.S. THE CHEMICAL SOCIETY. G. BARQER X.A. D.Sc. H. W. BYWATERS D.Sc. Ph.D. H. M. DAWSON Ph.D. D.Sc. J. C. DRIJMMUND D.Sc. W. GODDEN B.Sc. W. S. MILLAR M.A. B.Sc. Ph.D. G. F. MORRELL Ph.D. D.Sc. T. S. PATTERSON DSc. Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. Ph.D. E. H. RODD D.Sc. ABSTRACTS O F PAPERS PHYSICAL INORGANIC MINERALOGICAL ANALYTICAL CHEMISTRY. ON AND S. B. SCHRYVER D.Sc. Ph.D. W. P. SKERTCHLY. F. SODDY M.A. F. R.S. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. D. F. TWISS D.Sc. A. JAMIESON WALKER Ph.D. B. A. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc. P1i.D. 1919. Vol. CXVI. Part 11. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C.4 1919.Abstractors of the Jourlnal of the Society of Cheinical Industry who have contributed t o this volume. S. S. AUSTIN. J. F. BRIGGS. T. H. BURNHAM. J. H. JOHNSTON M.Sc. J. H. LANE. C. A. MITCHELL M.A. B. NORTH. J. P. OGILVIE. W. E. 3’. POWNEY. A. €3. SEARLE. B. V. STORR M.Sc. J. S. G . THOMAS B.Sc. F. C. THOMPSON. W. J. WRIGHT.

ISSN:0368-1769    

DOI:10.1039/CA91916FP003

出版商:RSC    

年代:1919

数据来源: RSC

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INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 23 The Determination of the Molecular Complexity of Liquid Sulphur. ALEX. MITCHELL KELLAS (T. 1918 113 Occurrence of Hydrogen Selenide in Rain and Snow. Y. KARRZR (Helv. C‘hirn. Acta 1918 1 499).-Repetition of Gass- mann’s experiments (A. 1918 ii 309) has led the author to the conclusion that selenium is not present in snow or rain. Starting and Stability Phenomena of the Oxidation of Ammonia and Similar Reactions. F. G. LILJENROTH (CJzewz. mill M e t . Enq. 1918 19 287-293).-Conversion curves have been plotted for the oxidation of ammonia a t various temperatures showing that whilst little oxidation takes place a t 400° it rises rapidly between 450° and 500° t o nearly loo% reaches a maximum a t about 750° and then decreases first slowly and afterwards rapidly.The temperature of the gauze or catalyst may also be plotted for various percentages of ammonia-oxidation and the curve is found to be a straight line the position of the line termed the “ heat of reaction line,” on the conversion curve diagram depending on (1) the initial temperature of the gas and (2) the initial composition of the gas. The effects of changes in the velocity and the composition of the gaseous mixture on the relative positions of these two curves are described and the conditions for (1) the cessation of the reaction (2) overcoming the prejudicial effects of catalytic poisons are indicated. The reaction does not start spontaneously but must be initiated by heating to a particular ignition temperature which is below the reaction temperature.The use of oxygen is shown to be not justified as it merely results in a higher temperature necessitating water cooling of the gauze. A cheap low-grade catalyst may be possible for the first gauze and a platinum gauze for completion of the oxidation in a manner analogous to the sulpliuric acid process. The synthetic ammonia process is also considered and it is shown that in this case a heat exchanger must always be used and additional heat must usually be supplied. With a high pressure and a good catalyst however no heat need be supplied except during the starting period. 903-922). H. JV. B. N. The Oxidation and Ignition of Coal. RICHARD VERNON WHEELER (T. 1918 113 945-955). Oxidation of Carbon Monoxide in Contact with Copper. K.A. HOFMANN (Ber. 1918 51 1334-1346).-Continuing his search for a reagent. t o oxidise carbon monoxide a t the ordinary temperature (A. 1916 ii 637) t.he author has shown that hydratedii. 24 ABSTRACTS OF CHEMICAL PAPERS. copper oxide in the presence of aqueous alkali converts carbon mon- oxide into a carbonate although a t only a slow rate. The addition of platinum metals especially iridium increases the rate five times. In contact with metalh copper moistened with aqueous alkali carbon monoxide mixed with air is oxidised two or three times more rapidly than it is when in contact with a copper oxide surface of the same area. The copper is converted into a peroxide Cu20 or CuO which is the real oxidising agent. The addition of a trace of iridium to the copper does not change the oxidising power of the peroxide but increases the adsorptive capacity of the surface for carbon monoxide and thus increases the rate of oxidation.It is very remarkable that the rate of oxidation of hydrogen in contact with an alkaline copper surface is only 1/70 (with addition of iridium 1/50) of that of carbon monoxide the copper surface having a very small capacity of adsorbing molecular hydrogen. The experiments were performed in a Hempel gas pipette filled with rolls of copper gauze moistened with 15% potassium hydroxide sdu- tion. The concentration of the alkali does not appreciably affect the results. c. s. WILLTAM NORMAN RAE (T. 1918 113 880-884). The Action of Chlorine on the Alkali Iodides. Literature on the Solubility of Systems Relating to Nitre Cake.H. W. FOOTE (J. Ind. Eizg. Ch,em. 1918 10 896-897).-A resume of the literature dealing with the solubility relationships of the systems Na,S'0,-H,S04-H,0 ; Na,SO,-RSO,- H,O; and RS04-€3,S0,-H20 (R=Fe" Cu Ra Ca G1 etc.). J. F. S. Recrystallisation of Nitre Cake. BLAIR SAXTON (J. h2d. Eng. Chem. 1918 10 897-901).-Equations based on solubility deter- minations have been developed by means of which the amount of any one solid phase that can be separated from the Bystem Na,S04-H,S04-H,0 can be calculated if the composition of the original nitre cake and the acid concentration after crystallisation are known. These equations are for the temperature 25O. Further equations are given for the same temperature by means of which the amount of water t o be added to the nitre cake may be calcu- lated in order t o leave a calculated amount of one of the solid phases. Further equations for obtaining the maximum amount of each solid phase from solution a t temperatures of Oo and 2 5 O are also given.Leaching processes are outlined by means of which sulphuric acid may be concentrated in the solution and sodium d p h a t e in the solid. It is found experimentally that this separa- tion can be carried out more efficiently a t Oo than a t 25O. J. F. S. Colloidal Silver. ALWYN PICKLES (Chem. News 1918,117 358). -When well-washed silver oxide is reduced by a rapidly stirred 50% solution of formaldehyde a solution of colloidal silver is pro- Xuced. This solution is very stable and varies in colour from paleINORGANIC CHEMISTRY.ii. 25 lilac to rich ruby-red. Acetaldehyde has not the same effect and with formaldehyde t.he coloured solutions are only produced at about 3 5 O . The colour is discharged slowly by salt solutions and by nitric acid. Hydrogen peroxide is slowly decomposed by the solution. J. F. S. Rational Preparation of Superphosphates. A. AITA ( ~ ~ d i Glhim. AppZ. 1918 10 45-103) .-On dissolving increasing quantities of monocalcium phosphate in a given weight of water a t constant temperature the proportion of free phosphoric acid con- tinually increases and tends towards a limit in accordance with the equation 2CaH4(P04)2 t CaH4(P0& + CaHP0 + HSPOk. Up to the saturation point a t 1 5 O there would thus be a liquid phase conslmug 01 water monocalcium phosphate and free phosphoric BCICL auu a Solid phase comlsting solely of dicalcium phosphate lormea by hydrolysis or the monocalciuni phosphate.Beyond the saturation point with increasing quantities ot calcium made and phosphoric oxlde the liquid phase remains unaltered whilst the solia phase is constantly enricned by monocalcium phosphate. On raising the temperature the decomposition of the monocalcium phos- pnate is accentuated w h i s t the saLuration point is retarded. hiono- calcium phosphate appears in the solid phase at the same limit of concentration i o r the calcium oxide but a t a greater concentration 01 the phosphoric omde. I n the case of. commercial superphosphates containing about li2-20% of soluble phosphoric oxide and lU-2U% 01 water there is a system with a fairly hgh proportion of phos- phoric oxide and a very low proportion of water.In estimating nee phosphoric acid in such products it is necessary to use anhy- drous ether for the extraction since water alcohol or ordinary ether cause more or less hydrolysis of the monocalcium phosphate according to the amount ot water originally present. The physico- mechanical properties of superphosphates depend on the proportion oE free phosphoric acid and water the former depending on the nature and physical conditions of the components of the reaction and the latter mainly on the concentration of the sulphuric acid used in the preparation. On these grounds commercial superphos- phates may be classified as normal or abnormal products the former containing not more than lO-li?% of water or 1-2% of phosphoric oxide as free phosphoric acid (about '5-10% of the total soluble phosphoric oxide).Dicalcium phosphate is invariably present and the fraction of phosphoric oxide in that form of combmation should be equal to that present as free phosphoric acid. The mono- and dicalcium phosphates and calcium sulphate are mainly present in the hydrated form. In the case of superphospliates of abnormal constitution the water of the liquid phase exceeds 12% and the free phosphoric acid exceeds 2% o r 10% of the soluble phmphoric oxide whilst the salts are mainIy in the crystalline condition and there is little or no dicalcium phosphate present. It is commonlyii. 26 ABSTRACTS OF CHEMICAL PAPERS. accepted in accordance with Kollb’s view that the reaction between sulphuric acid and mineral phosphates takes place in two stages 3Ca,(PO,) + GH,SO = 4H,PO + Ca3(P0,) + GCaSO but the observed facts show that the main reaction is more correctly represented by the equation 5Ca,(P04) + 11H,SO = 4CaH,(PO,) + 2H,PO + 11CaS0,.The infiuence of raising the temperature on the reaction is to increase the concentration of free phosphoric acid in the liquid phase whilst in the solid phase the dicalcium phosphate increases in equal proportion with the free phosphoric acid. !!?hem constitu- ents gradually interact to form monocalcium phosphate so that the existence of dicalcium phosphate in an industrial product will (1 epend on the proportion of free phosphoric acid originally present. Hence in products prepared with an excessive quantity of sulphuric acid and thus containing a high proportion of free phosphoric acid the dicalcium phosphate will be reduced or disappear altogether.I n fact monocalcium phosphate is not hydrolysed in presence of an excess of phosphoric acid and in such cases the solid phase of the system will consist solely of monocalcium phosphate. The applica- tion of these principles to the industrial preparation of superphos- phates yields products with the desired physico-mechanical proper- ties. Ca,(P0,),+4H,P0,=3CaH4(P0,) [See also ,7. SOC. Phem. Znd. 1919 33tl.l C . A. M. The Decomposition of Barium Peroxide and the Re- activity of the Resulting Barium Oxide. J. A 4 ~ ~ ~ HEDYALL (Zeitsch. auorg. Chem. 1.918 104 163-168).-The decomposition of barium peroxide by heat a t atmospheric pressure has been fol- lowed by means of the heating curve.The peroxide was heated in a carbon tube furnace and the temperature recorded a t 10 sec. intervals by means of a platinum-platinum-rhodium thermo- element. The reaction being endothermic its range is indicated on the heating curve by a pronounced flattening towards the time axis. The temperature a t which the vapour pressure of the evolved oxygen is equal to 760 mm. was found to be 795O. This agrees with the value 796O found by Le Chatelier. The higher temperature 825O obtained by Eildebrnnd is accounted for by the fact that this observer used very carefully dried materials,.for in the absence of moisture the reaction is verv slow and incompIete. I n presence of copper oxide barium peroxide starts to decompose a t about 200° the reaction becoming most vigorous a t 625-660°.a? shown by the heating curve. When the wroxide is heated with amorphous silica. however the rate of rise of temperature increases above 400O. The endothermic decomposition of the peroxide is evidently accompanied by a more strongly exothermic reaction probably the formation of a barium silicate; brought about by the ereat reactivity of the barium oxide a t the moment of its forma- tion. Even when powdered quartz glass or crushed quartz is usedINORGANIC CHEMISTRY. ii. 27 in place of arnorphoiis silica there is evidence in the heating curve of silicate formation. E. H. R. Solubilitv of Cupric Hydroxide to a Certain Concentra- tion in Sodium Hydroxide and Potassium Hydroxide. En.JUSTIN-MUELLER (Compt. rend. 1918 167 779-780) .-Cu~ric hydroxide dissolves in aqueous sodium hvdroxide (D 1*345-1*370) or aqueous potassium hydroxide (D 1*453-1*498) to the extent of 0.78 gram in 100 c.c. giving bright *blue solutions which do not qive any precipitate when boiled directlv or first diluted and then boiled. Solutions prepared with more dilute alkali are not stable. W. G. Scandium from a Brazilian Source. C. JAMES (J. Amer. Chem. Soc. 1918 40 1674).-Whilst working up quantities of Brazilian zirconia the author obtained a gelatinous residue which on examination was shown to consist of scandium fluoride. J. F. S. Rare Earths. VIII. Separation of Yttrium from Erbium ; The Ratio Er,O 2ErC1,. EDWARD WTCHERS R. S. HOPKINR. and C.W. BATXE ( J . Amer. Chem. Soc. 1918 40 1615-1619. Compare A . 1917 ii 34).-Using material containing only erbium and vttrium the authors have investigated the newer methods pro- posed f o r the separation of these two elements. The cobalticyanide and the nitrite precipitation methods were found to give good results the latter being the more efficient and practicable. The older nitrate fusion method was found to give results far superior to the other methods and bv this method erbium compounds of a hiph degree of purity were ohtained. The ratio of erbium oxide t o erbium chloride was determined in seven analyses. The ratio was found to vary with the temperature and length of time of ipnition of the oxide. Erbium oxide prepared bv the ipnition of the oxalate and ignited for several hours a t 800° and two hours a t 900° was found to retain considerable amounts of carbon dioxide This is contrary to Hofmann’s results (A.1910 ii 1073). and con- sequently brings into disrepute the Present accepted value of the atomic weight of erbium. Until erbium oxide of the definite com- position Er,O is prepared no ratio in which the-oxide is one term can be trustworthy for the purpose of atomic weight determivations. J. F. S. Preparation and Properties of Yttrium Mixed Metal. .T. F. G. HICKS (J. Amer. Chem. SOC. 1918 40 1619-1626).- Experiments of a preliminary nature dealing with the preDaration of vttrium mixed metal are described. It is shown that the method of preparing anhydrous chlorides of the metals of the yttrium earths by heating the hydrated chlorides with ammonium chloride t o drive off five of the six molecules of water of crystal- lisation and then in a current of hydrogen chloride to remove theii.28 ABSTRACTS OF CHEMICAL PAPERS. last molecule of water is capable of being used on the large scale. The mixed metal has been prepared in the form of powder by heating the anhydrous chlorides with sodium in a vacuum a t llOOo and also by electrolysing a mixture of the molten chlorides in a protected graphite crucible using a graphite anode. Electro- lysis of a solution of the mixed oxides in fused cryolite also yields the mixed metal in the form of powder but the method is less efficient than the foregoing methods. I n all these processes there is considerable loss of yttrium chloride owing to its volatility a t t.he temperature of the experiments.The powdered products have been obtained in a coherent form by sintering in a vacuum but the resulting mass easily disintegrates. The product obtained has a mean “atomic weight” of 120 and contains 94*05-95*70% of metal which corresponds with 37.5% of yttrium. It burns in the air a t a dull red heatl with a very bright light and yields a light brown oxide. It is slowly oxidised by moist air a t the ordinary temperature. It glows when heated in hydrogen nitrogen or carbon dioxide. It does not amalgamate with mercury and is readily attacked by water. Yttrium mixed metal is pvronhoric but not so strongly as the cerium metal iron alloys. Effects of Heat on Chemical Glassware. R. G. SHERWOOD ( J .Amer. Chem. Soc. 1918 40 1645-1653}.-When glass is heated there is shown to be evidence of two distinct kinds of gaseous evolution that resulting from adsorbed material which is readily removed at temperatures below 300° and that resulting in all probability from a decomposition of t.he glass itself. The latter effect; becomes importantl above 400° for the softer glasses and above 500* for the harder glasses. There is some evidence of a definite characteristic rate of gaseous evolution for each tempera- ture to which glass is subjected. increasiny with the temperature and extending over a considerable period. Observations on one sample a t 500° showed a small continuous evolution even after heating for twenty hours. Adsorption products are confined t o quantities which ar0 represented approximately by a layer of gas about one molecule deep and are removed with much greater rapidity a t lower temperatures than the other products obtained.which are due to the heating of the glass. The most important of the gaseoiis evolution products obtained from glass under the influence of heat-is water. which as the temperature is raised to the softening point of the glass constitutes almost the entire quantity of the evolution but its amount a t a lower temperature may be relatively unimportant,. Plasticity and ‘Strength’ of Clay. OTTO KOLTE (3ied. Zentr. 1918 47 108-109).-Extraction of a heavy Silesian clay with alcohol and ether did not cause any diminution in the plas- ticity or ‘strength’ of the clay. The presence of a certain pro- portion of organic matter therefore does not affect.these qualities of the clay. The extract was found to contain sulphur and an organic compound which was not identified. J. F. S. J. F. S. H. W. €3.INORGANIC CHEMISTRY. ii. 29 Zirconyl Basic Chromate. F. P. VENABLE and L. V. GILES (e7. ,4n~er. Ghem. Soc. 1918 40 1653-1656).-A basic zirconium chromate is prepared as a granular yellow precipitate by dissolv- ing zirconium hydroxide in a boiling solution of chromic acid diluting and again boiling the solution. The compound obtained loses a considerable quantity of its water a t l l O o but the whole of it is only lost a t 200O. The compound is shown to have the formula 2Zr0( OH)2,ZrOCr0,.8H,0 and it is suggested that its formation occurs as follows first normal zirconium chromate is formed which is immediately hydrolysed to ZrOCrO ; some of the zirconium hydroxide is partly dehydrated to give ZrO(OH),. These two substances then combine t o give the yellow insoluble compound described above.The present work is a t variance with earlier work on zirconium basic chromates by s a b e r (A. 1897 ii 295). J. F. S. Antimonic Acids and Antimonates. GEBHARDT JANDER (Ko7loid Zeitsch. 1918 23 122-144).-Analyses of the various hydrates of antimony pentoxide have been made and the dehydra- tion curves of these compounds obtained by keeping them over sulphuric acid in a desiccator. The behaviour of the anthonic acids toward hydrochloric and sulphuric acids and toward solutions of potassium and sodium hydroxides has been studied. The potassium and sodium salts of these acids have also been investi- gated. The experiments show that tlhe properties of the antimonic acids vary with the method of preparation and with previous treat- ment.Thus modifications which differ in their water content stability solubility and their behaviorir towards acids and alkalis are obtained (i) by the action of water on the pentachloride (ii) by the action of acids on antimonates and (iii) by the hydro- lysis of the trichloride in the presence of nitric acid. These varie- ties of antimonic acid differ only slightly from one another and probably as in the case of the stannic acids the difference is due to a difference in the size of tihe particles. The experiments indicate that the tri- and tetra-antimonic acids that is the soluble antimonic acids are hydrosols of small stability and that the definite hydrates of antimony pentoxide known as ortho pyro- and meta-antimonic acid can have no free existence.The hydrates of antimony pentoxide exhibitl a marked selective absorption towards dilute alkalis. Thereby are formed amorphous subthances which apparently are alkali antimonates. The composition of these substances however varies continuously with the composition of the solid hydra€e. I n concentrated alkali solutions the hydrates of antimony pentaxide dissolve and from these solutions at low temperature and by careful evaporation. various alkali antimonat.es may be crystallised hiit the nature of the salt depends on the con- centration of the mother liquor. 1-71K,0,Sb20,,8R,0 has been obtained in this way.The compound J. F. S.ii. 30 ABSTRACTS OF CHEMICAL PAPERS. Bismuth Hydride. FRITZ PmEm (Zeitsch. Elektrochem. 1915 24 298-299).-Working from the point of view that isotopes and their compounds are identical the author is of the opinion that bismuth hydride is capable of existence and that it is gaseous and only moderately stable much less so than antimony hydride. These statements are based on the fact that by the action of hydro- chloric acid on magnesium which has been covered with thorium-C (an isotope of bismuth) a radioactive hydride IS produced which has the properties enumerated above. Hydroxylamine Platinum Bases. LEO ALEXANDROWITSCIF TSCHUGAEV and ILJA ILJITSCH TSCHERNJAEV (T. 1918 113 J. F. S. 384-897). Mineralogical Chemistry. ' Hydromagnocalcite " from the Tatra Mountains Car- pathians EMANUEL GLATZEL (Centr. Mzm. 19lS 307-31 l).- The compact chalk-white material with conchoidal fracture is found as loose blocks in the Lopusna valley near the village of Liicsivna on the southern slopes of the Tatra Mountains. Analysis gave results approximating t o the formula CaCO,+ Mg(OH),. CsO. MgO. co,. HeO. Total. Sp. gr. 36-55 23.15 28.75 10.60 99.05 2-412 [This is evidently pencatite which was long ago proved to be a mechanical mixture of calcite and brucite (Mg[OH],) .] L. J. S .

ISSN:0368-1769    

DOI:10.1039/CA9191605023

出版商:RSC    

年代:1919

数据来源: RSC

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ii. 30 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Quantitative Analysis of Small Quantities of Gases. H. M. R Y D ~ ( J . Amer. Chem. Soc. 1918 40 1656-1662).-A somewhat complicated apparatus is described by means of which a quantitative analysis of 5 cu. mm.-1 C.C. of a gaseous mixture of water vapour carbon dioxide carbon monoxide oxygen hydrogen nitrogen and methane may be carried out with an accuracy of about 5% for each constituent The apparatus makes use of a McLeod gauge and an optical lever gauge but for details the original should be consulted. OLIVER D. BURKE (Chenz. News 1918 117 368-369).-The glass tube through which the J. F. S . Gas Bubbler for Gas Analysis.ANALYTICAL CHEMISTRY. ii. 32 gas enters is drawn out into a fine capillary. Another glass tube 1s fused on to the side of the first tube and bent so that the end extends just below the end of the capillary where it is flattened and the top surface ground.The capillary is made to fit tightly on the ground surface so that the gas escaping from the capillary is broken up into very fine bubbles. [See further J . SOC. Chem. I d . January 1919.1 w. P. s. Oxidising Action of Potassium Dichromate as Com- pared with that of Pure Iodine. CARL’ R. MC~ROSKY (J. Amr. Chenz. SOC. 1918 40 1662-1674).-The author has studied the trustworthiness of potassium dichromate as a standardising agent in iodometric determinations. It is shown that potassium di- chromate always liberates more than the theoretical quantity of iodine from hydriodic acid. This excess of iodine may be reduced but not wholly removed by removing dissolved air from the solu- tions by drying and fusing the dichromate in the absence of air and by recrystallising repeatedly to remove oxidising impurities.It is also shown that the excess of iodine is not due in any way to the catalytic action of chromium chloride. J. F. S. Estimation of Active Oxygen in Sodium Peroxide. JAROSLAV MXLBAUER ( J . p. C’hem. 1918 [ii] 98 l-S).-The following methods have been proposed for the estimation of active oxygen in sodium peroxide (1) liberation of hydrogen peroxide by water followed by titration with potassium permanganate (2) treatment of sodium peroxide with potassium iodide and potassium hydrogen carbonate and titration of the iodine liberated with sodium arsenite and (3) measurement of the oxygen liberated by water in the presence of cobalt nitrate.The results obtained by the first method are very low those by the second are somewhat better but still low whilst the third method gives high results. The methods have been critically examined and improved; the following processes yield accurate results (1) Water (100 c.c.) is mixed with concentrated sulphuric acid (5 c.c.) and chemically pure boric acid (5 grams); sodium peroxide (0.5 gram) is gradu- ally added to the mixture which is kept briskly shaken and the liberated hydrogen peroxide is titraked with potassium perman- ganate. The usual permanganate method gives low results since a portion of the hydrogen peroxide is catalytically decomposed by the manganese sulphate formed during the process. (2) Sodium peroxide is gradually introduced into a solution of potassium iodide (2 grams) in dilute sulphuric acid (1 in 20; 200 c.c.); the iodine is titrated with standard thiosulphate.The results agree fully with those obtained by the permanganate method. (3) Sodium peroxide (0-2-0.3 gram) is mixed with about 10 C.C. of copper sulphate solution (0.05%) in a small flask connected to a nitro- meter; the flask is shaken and decomposition is complete within a minute when the liberated oxygen is measured. The gas evolved contains about 0.32% of carbon dioxide and 0.08% of5. 32 ABSTRAWS OF CHEMICAL PAPERS. hydrogen. With cobalt nitrate as catalyst the results are in- variably high; the authors consider this may indicate the presence of an oxide higher than t,he peroxide. The action of the atmosphere on sodium peroxide has also been investigated; moisture appears to be more active than carbon dioxide in causing decomposition. H.IV. Pregl's Micro-estimation of Nitrogen. HANS FISCHER (Ber. 1918 51 1322-1325) .-The estimation of nitrogen in difficultly combustible substances by the micro-Dumas method (compare Dubsky A. 1918 ii 130) gives untrustworthy results and the author now employs only the original Pregl method. The causes of the inaccuracies in the former method are discussed. The author uses the micro-Pregl method in preference t o the Lassaigne test for tihe detection of nitrogen in rare or very valuable organic compounds. c. s. Detection and Estimation of Hydrogen Phosphide in Hydrogen. J .SOYEB (Ann. C k m . anal. 1918 23 221-225). -Hydrogen prepared by the action of sodium hydroxide on ferro- silicon always contains traces of hydrogen phosphide. The presence of the latter may be detected by burning the hydrogen from a platinum jet and directing the flame on to the edge of a porcelain basin; the flame has a green coloration. When examined with the spectroscope the flame exhibits the phosphorus spectrum. If tt drop of water suspended on a glass rod is held in the flame for fifteen seconds and then tested with molybdic acid reagent a yellow precipitate is obtained. The amount of hydrogen phosphide present is estimated by passing a definite volume (from 2 t o 30 litres) of the gas together with a large excess of air through a platinum jet arranged in a silicon tube heated to bright redness; this tube is inclined slightly and its lower end is connected with absorption vessels containing water.When the desired quantity of the gas has been burned the tube and the contents of the absorption vessels are rinsed into a basin treated with 5 grams of ammonium nitrate concentrated t o about 40 c.c. and the phos- phoric acid precipitated with molybdic acid reagent. [See further w. P. s. J . Soc. C"hem. Id. 1918 765a.I Estimation of Minute Quantities of Arsenic. 0. BILLETER (Helv. Chim. Acta 1918 1 475-498).-A more extended and somewhat modified account of the method previously published (A. 1915 ii 578). The estimation of arsenic in organic substances is effected in the following manner. The organic matter is destroyed either by treatment with a mixture of nitric and concentrated sulphuric acids or in the case of urines by rendering the latter alkaline with sodium carbonate evaporation to a syrup admixture with potassium perchlorate (2 grams) and potassium sulphate (4 grams) for each 100 C.C. of urine desiccation of the mixture at 120° andANALYTICAL CHEMISTRY.ii. 33 gradual introduction of the latter into a platinum crucible heated to dull redness followed by more intense ignition until tranquil fusion is attained The arsenic is separated from other metals by distillation with a mixture of sodium chloride (2 grams) and potassium bromide (0.2 gram) for each 20 C.C. of sulphuric acid (the addition of bydrazine sulphate previously recommended is found t-o be unnecessary) or if destruction of organi matter has been effected with potassium perchlorate by treatment with potassium bromide (0.1-0.2 gram) and sulphuric acid (go% 6 c.c.).Mercury is completely retained by one distillation but if antimony is present it is necessary to redistil after addition of 5-6 grams of sulphuric acid (90:L). Hydrochloric acid is eliminated from the distillate by breatment with hypochlorous acid and the solu- tion is evaporated t o dryness. The residue is dissolved in sulphuric acid (lZ% 1 c.c.) and evaporated on the water-bath to destroy any chloric acid that may be presentl; after addition of water (0.85 c.c.) it is transferred to a Marsh’s apparatus. By this method 0.01 mg. of arsenic may be detected The precautions necessary for ensuring the requisite purity of the reagents are fully described.The commercial pure sulphuric acid is diluted to 85(;. and heated with sodium chloride (3%) and potassium bromide (0.3:4,) in a quartz flask; the treatment is twice repeated with smaller quantities of salts and the acid is finally distilled from a quartz retort and collected in a quartz flask. The nitric acid and the salts are purified by Lockemarm’s method. Zinc is conveniently obtained by the electrolysis of an aqueous solution of zinc sulphate using a zinc anode and copper cathode; the metal is obtained in the pulverulent state and dissolves readily in dilute sulphuric acid without being activated. It is free from arsenic. Hypochlorous acid is best prepared by the solution of chlorine monoxide in water. The sensitiveness and constancy of the arsenic mirrors depend considerably on the quality of the calcium chloride used in desic- cating the gas.Commercial fused calcium chloride is unsuitable as it is always strongly alkaline; a neutral product can be obtained by dehydrating the crystalline substance a t ZOOo and subsequently gradually heating the finely divided product to its melting point in a quartz tube in a slow current of dry hydrogen chloride. The best results are obtained by starting from metallic calcium. H. W. Amount of Amorphous Silica in the Soil. BELA VON HORVATH (Bied. Zentr. 1918 47 97-98).-For the estimation of the amorphous silica 5 grams of the soil are extracted with 100 C.C. of a 1% sodium carbonate solution for fifteen minutes a t looo. Solutions of sodium carbonate of greater concentration than 1% dissolve silicates and quartz besides amorphous silica the results obtained being consequently too high.When estimated by the author’s method soil is found to contain only a few milligrams per cent. of amorphous silica. El. w. B.ii. 34 ABSTIEACTS OF CHBMICBL PAPERS. Estimation of Metals by Electrolytic Deposition without using an External Supply of Electricity. NAURXCE E’RAN~OIS (Compt. rend. 1918 167 725-727).-A strip of nickel is placed across the top of a platinum crucible and a zinc rod 5 m. in diameter is suspended from the strip; the rod is notched so as to fit on to the nickel strip and the lower end of the rod extends nearly to the bottom of the crucible. The zinc rod is amalgamated at least twenty-four hours before being used and is wrapped in filtier-paper which is tied on to the rod with ordinary cotton thread.The electrolyte used for the deposition of silver or gold consists of 9 C.C. of 10% potassium cyanide solution 5 C.C. of potassium hydroxide solution (D 1*332) and 2 C.C. of ammonia; for the depositaon of mercury the solution should consist of 20 C.C. of 10% sulphuric acid containing 0-5 gram of potassium iodide. I n all cases the deposition requires twenty-four hours for com- pletion. [See further J . SOC. Chem. Ind. 1918 784a.1 w. P. s. Quantitative Estimation of Ions by Microanalytical Methods. I. ROBERT STREBINGER (&sterr. Chem. Zeit. Lii] 21 71-73; from Chem. Zentr. 1918 ii 471).-The author has extended Pregl’s method of quantitative organic micro- analysis to inorganic substances and describes the estimation of silver nickel arsenic iron chromium and copper and the separations of silver from copper and lead from tin.Precipita- tion of nickel with a-benzildioxime is unsuitable for micro- analytical purposes the results being too high. H. W. Gravimetric Analysis. VI. Estimation of Calcium. VII. Separation of Calcium from Magnesium. L. W. WINKLER (Zeitsch. angew. Chem. 1918 31 187-188 203 214-216).-Estimation of calcium as oxalate or carbonate was submitted to critical examination. It is recommended that the precipitation as oxalate should be made from an acetic acid solu- tion in the presence of ammonium chloride; the calcium oxalate should be weighed as such since ignition to oxide is less trust- worthy especially in the presence of sulphates.If the latter are present the oxalate always contains sulphate but the weight is not affected since the two have practically identical molecular weights. For the separation of calcium from magnesium the calcium is precipitated as described from an acetic acid solution; the magnesium is subsequently precipitated as ammonium mag- nesium phosphate and weighed in this form. [See further J . SOC.. Estimation of Calcium and Magnesium in different Saline Solutions. E. CANALS (Bull. SOC. chim. 1918 [iv] 23 4 2 2 4 3 0 ) .-The simplest and most satisfactory method of estim- ating calcium is t o precipitate it as oxalate in ammoniacal solu- tion and weigh it as oxide. The method of precipitation as Chem. Ind. 1919 29A.I w.P. s.ANALYTICAL CHEMISTRY. ii. 35 sulphate and weighing as such is also very exact providing that numeroas precautions are taken. [See further J. SOC. Chem. Ind. January 19191. W. G. Sensitiveness of the most usual Tests for Copper. A. WOBEB (Osterr. Chenz. Z e i t . [ii] 21 105-107; from Ch-em. Zentr. 1918 ii 560).--The usual tests for the detection of copper have been investigated with respect t a sensitiveness with a view to their application in microanalysis; the results are given in the form of a table. H. w. Separation of Hydroxides in the Ammonium Sulphide Group. W. D. TREADWELL (Schzuezz. Chem. Zeit. 1918 2 59-61 71-74; from Chem. Zenltr. 1918 ii 663-664).-The separation of bivalent f ro,m tervalent metals of the ammonium sulphide group by simple precipitation with dilute ammonia from solutions containing ammonium salts is generally not quantitative.Transitory local excess of the reagent cannot be avoided and the precipitate then carries down varying amounts of the bivalent metal. The necessary asymptotic approach to the neutral point can be easily att'ained by leading a current of dilute ammonia (obtained by blowing air through a saturated solution of ammonium chloride in the presence of calcined magnesia) through the solution. Precipitation by the gas has the advantage that it is possible to approach the neutral point with the necessary caution without correspondingly diluting the solution. I n the presence of manganese ammonia should not be added until neutralisation is complete since the manganese ion is readily oxidised by air in neutral solution and passes into the precipitate; neutrality to litmus is the farthest possible limit.I n the separation of chromium and manganese the latter is always adsorbed by the chromium hydroxide. The hydroxides of the tervalent metals carry down nickel and cobalt more readily than manganese and zinc. The error can be somewhat diminished by precipitating and filtering the main portion of the sesquioxides in distinctly acid solut.ion and subsequently precipitating the remainder from the filtrate after fresh addition of ammonium salts. The precipitates contain much more basic sulphate than chloride. Precipitates from solutions containing sulphates are more sandy in character and do not adhere to glass; when washed they lose the sulphate ion and become slimy.Mercuric oxide is not suitable for the precipitatioii of the ter- d e n t metals of the ammonium sulphide group as hydroxides. When warmed with dilute ammonium sulphate solution it only liberates an insufficient quantity of ammonia ; addition of ammonium chloride effects an improvement due to the formation of complex mercury salts. The precipitates are very easily filtered; they are ignited wet; when the admixed mercury compounds are quantitatively volatilised. For the precipitation of aluminiumt chrominm ancl iron afi. 36 ABSTRACTS OF CHEMICAL PAPERS. freshly prepared mixture of sodium or pobassium nitrite and ammonium chloride is to be preferred to the very unstable ammonium nitrite. The precipitates obtained from solutions of ferric salts by this process are very difficult to filter and are greatly contaminated with basic salta.The difficulty may be avoided by displacing the iiitrous acid from the solution by a current of inert gas at the temperature of the water-bath. 'The utility of the method is limited oming to the oxidising action of the nitrous fumes. A portion of the aluminium remailis in solution when a dilute solution of aluminium chloride is precipitated by sodium thio- sulphatei and boiling is continued until sulphur dioxide is com- pletely expelled; precipitation is still less complete in the case of chromium. H. VV. Arsenite Titrations of Perrnangaaate Solutions. ALOKE BOSE (Chem. News 1918 117 369-370).-Results of experiments are recorded showing that free nitric acid is not the cause of the abnormally high reducing value of sodium arsenite solution when this is used for the titration of permanganate (compare Ibbotson A.1918 ii 175). The formation of manganic compounds does iiot seem to be possible. Some complicated reactions may take place during the titration but- i t is quite clear from the results of titratious with ammonium ferrous sulphate solution thatl all the manganese is present as permanganate before the titration with arsenite is commenced. [See further J . SOC. Chem Znd 1919.1 w. P. s. Separation of Germanium from Arsenic by the Dis- tillation of the Chloride in the Presence of a Chromate. PHILIP E. BROWNING and SEWELL E. SCOTT (,4nzer. J. Sci. 1918 [iv] 46 663-665).-A modification of a method described previously (A. 1917 ii 546); chromic acid is used to oxidise the arsenic and t,he germanium chloride is then distilled from the hydrochIoric acid solution. Five C.C. of 10% potassium dichromate solution are sufficient to oxidise 0.25 gram of arsenious acid. A current of carbon dioxide inay be passed thrmgh the apparatus during the distillation t o facilitate the removal of the germanium chloride. If as little as 0.0005 gram of germanium oxide is pre- sent the distillate yields a white precipitate of germanium sulphide 011 the addition of hydrogen sulphide. [See further ,7. Snc. The Estimation of Phenol and the Three Isomeric Cresols irm Mixtures of these Substances. HARRY MEDFORTH DAWSON and CHRISTOPHER ARCHIBALD MOUNTFORD (T. 1918 113 C h e s n . J u d . 1918 7 8 5 ~ 1 w. P. s. 935-944)

ISSN:0368-1769    

DOI:10.1039/CA9191605030

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ii. 37 General and Physical Chemistry. The Optical Behaviour of Water of Crystallisation. KATHE BRIEGER (Ani~. Physik 1918 [iv] 57 2 8 7 4 2 0 ) .-Experi- ments have been made to compare the reflection intensities of crystals of a number of hydrated salts in the infra-red region h=2+5-7*.0 l ~ with that of water. The reflection curve for water shows a well-marked maximum intensity a t h=3-07 p and very similar maxima are found for hydrated crystals (compare Schaef er and Schubert) n. 1916 ii 5X). Of the nine isomorphous alums examined eight show two maxima in the intensity curves in place of the single water maximum a t 3*07p their positions being near 3 . 0 2 ~ and 3-51 p but differing slightly in the different alums. The curve for czsium alum however shows a third maximum and in this respect is abnormal.The water maximum a t A= 6.22 p also becomes doubled in the case of the alums. As examples of uniaxial crystals the hexahydrated nickel sulphate and selenate (tetragonal trapezohedral) were examined. I n the case of these salts the water maximum is shifted only slightly. The intensity of the reflectioii depends on the position of the optic axis relative t o the reflecting surface the water of cryst allisation exhibiting dichroisin. Siilzilarly in the case of mono- clinic crystals of the magnesium sulphate and zinc-ammoniuni sulphate groups the reflection properties are closely related t o the optical properties the water being trichroic. It is concluded that the symmetry properties of the water in hydrated salts correspond with the symmetry of the cryst’als.The bearing of the results on Werner’s theory of the constitution of hydrated salts is discussed. Preliminary experiments with analcime indicate a shift of the water maximum towards the shorter wave-lengths whilst in every other case the shift is in the other direction. Further experiments may be expected to throw light on the constitution of the zeolites generally especially with regard to the state of combination of the water which bhey contain. Effect of the Electric Field on Spectrum Lines. VII. The Fowler Helium Series. J. STARK 0. HARDTKE and G . LIEBERT (9 mi. Phyxik 1918 [iv,] 56 569-576. Compare Fowler A. 1913 ii 811).-The effect of an electric field on the lines A3203 and A2733 of ths Fowler helium series has been studied.The effect is compared with that on the B a h e r hydrogen series and it is shown that both effects are very similar the lines in both cases being symmetrically resolved into their components. The intensity of the two components is eqiial. Effect of an Electric Field on Spectrum. Lines. VIII. New Principal Series of Helium Lines which Appear in the Electric Field. J. STARK ( A m . Physik 1918 [ivl 56 577-588. See preceding abstract) .-During an investigation of the influence of an electric field on the helium spectrum two new E. H. R. J. F. S. VOL. CXVI. ii. 2ii. 38 A3STRACTS O F CHEMICAL PAPEES. principal series of lines were ciiscovered. The lines of the first of these the He 1 principal diffused series are given by the formula v =h'~(u) - Lz(m,d). i n the electric field the lines of this series are resolved in such a way that the components do not lie sym- metricsliy but are displaced about 1 A.unit in the direction of shorter wave-lengths. The second new series of helium lines the He Z sharp series is represented by the formula v = Ez(h) - Lz(m,s) The lines of this series in an electric field were not resolved into several conipoxents but were displaced towards the longer wave- leiigths. The He+ ion possesses twelve series which can be arranged in two systems of six series. I n each system there are three principal series with the same end-number and three sub- sidiary series also with the same end-number. Effect of an Electric Field on the Ultra-violet Lines of Helium. G. L~EBERT (B?zn. Physzk 1918 Lit.] 56 539-609.See preceding abstracts) .-The ultra-violet lines of the principal series He I are displaced towards the red end of the spectrum under the influence of an electric field. Both the components undergo the same amount of displacement-. The lines of the second subsidiary series are displaced without resolution toward the red by an electric field. In this case the displacement is rather more than the proportional amount. The lines of the principal series He I1 are displaced toward shorter wave-lengths by an electric field. I n the case of the third subsidiary series of He I a displacement of the lines toward longer wavelengths is brought about by an electric field. J. F. S. A New Helium Series under the Influence of an Electric Field. G. LIEBEHT (Bniz. Physik 1918 Liv] 56 610-616).- Corresponding with the third Me I series a subsidiary He ZZ series becomes visible in a strong electric field whereas in a weak electric field i t has no noticeable intensity.The electric effect on every member of the principal series corresponds with the effect on the similar member of the subsidiary series. The lines of the sub- sidiary series like those of the principal series are displaced toward the shorter wave-lengths. Spectrum of the Chromosphere. An Eruptive Protuber- ance of the 6th July 191'7. P. CARRASCO (Ailtal. Pis. &aim. 1918 16 700-706) .-A comparison of the author's observations of the chromosphere spectrum with the results of Rowland and of Adams. The presence of the helium series 6678.1 4922.1 etc. is noted as a characteristic of the spectrum.The helium series 7665.6 4713.2 etc. was not observed. Optical Researches on the Constitution of Sulphurous Acid its Salts and Esters. KONR. SCHAEFER [with WILLY KOHLER] (Zeitsch. anorg. Chem. 1918 104 212-250).-Aqueous solutions of sulphur dioxide show an absorption band in the ultra- violet in the same position as the band given by sulphur dioxide gas although somewhat broader. Beer's law is not followed the J. F. s. J. F. S. W. S. M.QENPRAL AND PHYSICAL CHZMISTRY. ii. 39 baiid becoming much shallower wibh increasiug dilution. The absorbing substance in aqueous solutioiis is a hydrate of sulphur dioxide SO,. ..OH which appears t.0 be aiore active than sulphur dioxide itself. Since the normal sulphites and the sulphite esters Et*SO,.OEt and f30(O&t)2 are both transparent in the ultra- violet it is coriciuded that sulphurous acid itself is non-absorbing both i n the unionised and ionised condition.The diminished absorbing power of solutions of sulphur dioxide on dilution is attributed t o a change oi equilibriuin from left to right in the equation SO,. . .O H zz H2kW3. The aqueous solution contains very little suiphurous acid and it is considered that measurements of the ion concentration in sulphur dioxide solutions have given rise to false ideas regarding the degree of dissociation of sulphurous acid and consequently of the strength of the acid. At higher temperatures solutions of sulphur dioxide absorb more strongly owing to a shift in the equilibrium of the above equation towards the left.Similarly addition of sulphuric acid to an aqueous solution of the gas increases the depth of the band in the same manner butl only t o a certain limit. When the sulphuric acid exceeds 5X the absorption again decreases prob- ably owing to dehydration in the sense SO,.. .OH2 5- SO,+ H20 the free sulphur dioxide being a less strong absorber than its hydrate. I n pentane and chloroform solutions the absorption is similar to that of the free gas aud the solutions follow Beer’s law. In solutions of methyl and ethyl alcohols and ethyl ether the absorption is much increased and in the case of ethyl ether the band passes into general absorption in the ultra-violet. These solu- tions also follow Beer’s law and it is concluded that stable com- pounds of the type 0,s ...OHEt and 0,s ... OEtS must be present in such solutions. Normal sulphites show oiily end absorption in the extreme ultra- violet and when a solution oE a riornial sulphite solution is half neutralised with sulphuric acid the resulting metal hydrogen sulphite solution atl first shows only end absorption but after a few days particularly under the influence of light the sulphur dioxide band develops. When the metal hydrogen sulphite is formed how- ever by mixing solutions of sulphur dioxide and normal sulphite the band is present immediately. A solution of potassium pyrosulphite ‘ when freshly prepared shows only end absorption in the extreme ultra-violet but the band gradually develops. Similarly sodium methyl sulphite which in methyl alcohol shows only end absorp- tion in aqueous solution gradually develops the sulphur dioxide band more quickly in stronger solutions owing to hydrolysis into sodium hydrogen sulphite and methyl alcohol.The equilibrium conditions in aqueous sulphur dioxide solutions are represented by the scheme EO f SO,. . .OH p]‘ O H [ OSOH 0 -j’ [ OS0 0 - p [ OS0 01’’ t- IT‘.G. 40 ABSTRACTS 03’ 0HEIILIICA.L PAPERS. The hydrogen sulphite ion HS03/ is probably unstable and under- goes transformation into sulphurous acid and SO,” thus ZHSO,’ = SO,’ + H,SO,. The sulphurous acid then comes into equilibrium with sulphur dioxide hydrate in the sense €12S0 SO,. . .H,O. These changes would explain the gradual develop- ment of the absorption band in hydrogen sulphite solutions. The view is expressed that the sulphite ion [SO,]” has a symmetrical constitution and hence also the normal sulphites.This view is supported by the observation that selenious acid and the dialkyl selenites have similar absorption spectra t o the normal sulphites (compare A. 1917 ii 61 186; 1915 ii 389). The Ethylene Chrornophore. H. LEY (Ber. 1918 51 1808-1819. Compare Ley A. 1917 i 261; Kauffmann ebenda. 391).-The absorption spectra of styrene stilbene and cinnamie acid and their derivatives have been studied. Bathochromic effects are produced by the introduction of a methyl methoxy- or ethoxy-group in the o-position in styrene whilst a hypsochromic effect results when the methyl or ethoxy-group is substituted in the a-position ; hypsochromic effects are also observed with 7-methylstilbene P-methylcinnamic acid P-ethoxycinnamic acid and a-methyl- cinnaxnic acid as compared with the parent substances.Attempts are also made to connect absorptiomekic anomalies with abnormal values f o r the molecular refraction. The esters of a- and P-methylcinnamic acid are less absorbent than the parent substance and have lower values €or the exaltation Za. &Methylstyrene ’has an absorption similar to that of styrene and its refraction anomaly is of the same order. With the hydroxy-derivatives a somewhat similar parallelism is observed the hypsochromic eff eet of the ethoxy-group in the a-position corresponding with a distinct diminution of the exaltation. Since in general an increase in refractive and disper- sive power corresponds with an increase in the unsaturated nature of the coImpound the explanation of the “ disturbing ” action of substitGents on the absorption spectra of substances by the assump tion of alteration in the degree of unsaturation appears t o receive f uather suppori;. The extinction-coefficients of chloroform solutions of I 3 5-tn- nitrobenzene and styrene a-ethoxystyrene B-ethoxystyrene and B-methoxystyrene respectively ’have also been measured but the ’ results scarcely lead t o a definite conclusion.Kauffrnann’s criticism of the author’s views (Zoc. c i t . ) is reviewed. E. H. R. H. W. Crystalloluminescence . 11. Triboluminescence and Crystalloluminescence. HARRY B. WEISER (J. Physical Chem. 1918 22 576-595. Compare A. 1918 ii 419).-For the further investigation of the relationship between crystalloluminescence and triboluminescence the phenomena have been studied with crystals of arsenic trioxide and the double sodiunilpotassium sulphate 2K2SO,,Na+3O,. In each case the colour of the light emitted by the crystals during rapid formation (crystalloluminescence) and t.hat>GENERAL AND PHYSICAL CHEMISTRY.5. 41 produced by rubbing or crushing the crystals (triboluminescence) have been determined by photographing through an appropriate series of light filters and it is shown that the light rays resulting from the two phenomena are identical in colour that from arsenic trioxide differing considerably however from that from the double salt. The colour of the luminescence is therefore a specific property of the compound. The phenomena are held to be chemical in origin.Crystalloluminescence which is only exhibited by a few inorganic compounds is due to the rapid re-formation of molecules broken up by the process of electrolytic dissociation. Triboluminescence is due to the re-formation of molecules broken LIP by t h s violent disruption of crystals. Whilst all crystalloluminescent substances are also tri- bolumir,escent the reverse is not true. I n certain newly-formed crystals a state of strain may exist and if outside force is applied t o such crystals before the internal forces have become adjusted violent disruption of the crystal may ensue with consequent molecular decomposition and triboluminescence. The intensity of the tri- boluminescence depends on the force needed to break u p the mole- cule and the magnitude of the coilversion factor for light in the luminescent reaction.E. H. R. Spectrum of the Ruby and Emera'd. IV. Spectrum Phenomena in the Chromium Compounds. JAMES MOIR (Trans. Roy. SOC. S. A fTz'ca 1918 7 129--130).-It has been shown previously (ibid. 2 321 ; 3,271,273 ; 4,339) that the almost unique spectra of ruby and emerald are due to chromium oxide which has been compelled to vibrate in an abnormal or constrained manner leading to the production of narrow absorption bands ; the constrain- ing substance in the case of the ruby is crystalline alumina and in the case of the emerald it is glucinnm silicate. The present com- munication describes attempts t o induce the constrained vibration of ordinary chromium oxide by artificial means.Suitable methods consist in dissolving chromic oxide in concentrated sulphuric acid and gradually addinq an organic substance such as starch until the orange colouF has changed to deep peen or more strikingly by replacing the sulp'huric acid by glacial phosphoric acid. It would appear possible to get a very close imitation of the emerald spectrum by the latter process; but the ruby spectrum on the other 'hand has not been reproduced except by means of alumina. Concentrated hydrochloric nitric perchloric. formic acet.ic and citric acids did not Geld very characteristic results although a faint hazy band a t A 6800 was seen in several of these solutions. R. W. A New Electrometer for the Measurement of Radioactivity. B. SZILARD (Anal. Fa's. Q z c ~ ~ . 1918 16 690-699).-A detailed description of a new irnmoved electrometer of the attracted alumin- ium needle type especially adapted for radioactive nleasiirements.W. S. M. Radioactivity of some Canadian Mineral Springs. J. SATTERLY and R. T. ELWORTIXY (Trans. Roy. Soc. Canada 1917-1918 [iii] 11 17-26).-The water of some sixty minerdii. 42 ABSTRACTS OF CHEMICAL PAPERS. springs has been esamiiied with respect t o its content of radium emanation and dissolved radium. Measurements of the rate of flow and temperature of the water are also given together with the nature of the strata. The emanation content varies from 11.2 x 10-12 curies per Iitre to 345 x 10-12 curies. The dissolved radium varies between the merest trace and 46 x 10-12 gram per litre although in most cases the amount is very small.A tabular comparison is given between the factors for these springs and those of American and European springs. Thermal springs are shown to be more active t.han the cold springs. J. F. S. The Radioactivity of Mud from Rockanje. E. H. BUCHNER (C’hem. 5VeekbZa$ 1918 15 243-246) .-Exniniiiations of samples of mud from the Waal lake near Rockanje (A.. 1913. ii 821) showed proportions of radium of the order of 1 x parts by weight. Subsequent; examination in t>he following year confirmed this figure. More recent work on samples of the same material by Folmer and Blaauw (A. 1918 ii 145) indicate a radium con- tent of the order generally found in common rocks and depositas namely 1 x 10-12. The author has examined some OE the samples tested by Folmer’ and Blaa17~ and confirms their results.The discov.dance between the later figures and the earlier result’s can- not be attributed t o differences in the methods of working o r to experimental error but is possibly due to deposition from the river water in isolated places of matter containing a high pi-oportion of some uranium mineral o r its degradation products. s. 1. L. The Radioactivity of the Mud from Rockanje. A. H. RLAAUW (Chem. Tl~eekblarl 1918 15. 361-364) ,-Biichner’s argu- ments (preceding abstract) t o account for the differences shown by the later analyses in the radioactivity of the Rockanje deposits are criticised and the asstumptions of patches of higher activity cruestioned. Other geological arquments suggested by Buchner are shown t o be incorrect.It is claimed that the later examination was complete. s. I. L. Ionisation and Resonance Potential €or Electrons in vapours of Magnesium and Thallium. P A m D. FOOTE miid FRED L. MOHLER (Phil. &fay. 1919 rvi1 37 33-50).-The ion- isation and resonance potentials for electrons in vapours of mag- nesinm and thallium have been measured by the Tate modification of the Pranclr and Hertz method. The experimental values for magnesium vapour were 2-65 volts and 7.75 volts €or the resonance and ionisation potentials respectively. The values calculated from the cruantum relation hv=eP are 3-70 volts and 7.61 volts respectively. I n the case of thallium va~oui- the values 1-01 volts and 7.3 volt’s were obtained for the reconance and ionisation Dotentids resnectively.The theoretical valii e f o r the former quantity is 1.07 volts whilst that of the latter is unknown. The ionisation potential for magnesium is obtained from the limit ofGENERAL AND PHYSICAL CHEMISTRY. ii. 43 the combination series 1 *5S - rnp2 and the resonance potential is determineJ by the iirst h e in this series m = 2 . I n the case of thallium the resonance potential is determined by the shorter wave-length member of the first term of the principal series of doublets. No known series in thallium has a convergence fre- quency greater than 49,263. The observed ionisation potential for thallium suggests the presence of an undiscovered series of single lines converging a t v = 1 *5S = 57,000 to 60,000. The present work offers evidence that the single line spectra of magnesium and thallium are h=4571 and 11,513 A.rekpectively. The general behaviour of the metals as regards ionisation and resonance potentials appears to be identical for metals in the same group of the periodic table. I n the case of thallium the component of the doublet having the higher frequency determines the value of the energy quantum absorbed by the atom. This fact! suggests either the possibility of separate excitation of the components of a doublet by electronic impact or a behaviour of thallium vapour thus excited analogous to the emission of characteristic X-rays for which the A? group does not appear until the energy of the impact- ing electrons is greater than that corresponding with X y . The authors have obtained a value of Planck’s constant h by the method of ionisation and resonance potentials.Using thirteen determinations on seven different metals the final mean value h=6*55 x 10-27 erg. sec. was obtained which is in excellent agree- ment with recent deterninations by other methods. The question of photoelectric sensibility of metallic vapours has been briefly discussed and recent work on ionisation and resonance potentials has been considered critically. J. F. 8. The Emission of Fositive Electricity by Salts of the Alkalies and Alkaline Earths under the Influence of Canal Rays. W. VOLKER (Ann. Physilc 1918 [iv] 57 257-277).-1t is shown that when a suitably prepared thin layer of lithiulrr chloride or of calcium sulphate connected with a conducticg hystem is subjected to bombardment by canal rays the induced currents can only be explained on the assumption that when the cathode fall of potential exceeds a certain limiting value positive charges are emitted by the salt.The limiting value of the cathode fall in the case of lithirxm chloride is about 5130 volts and with calcium sulphate about 1500 volts. These values correspond with the limit- ing values found by Stark and Wendt. (A.> 1912 ii 720) above which these salts under the influence of canal rays. emit the characteristi-c metallic series lines. It is concluded that the carriers which emit the series lines which are only observed in the space immediately adjacent Do the salt are the positive ion. of the metallic elements themselves. E. IT. R. Measurement of Concentration of Hydrogen Ions and a New Form of Calomel Electrode.W STURM (Chem. ;I/iTeekhlad 1918 15 912-916).-7’he author has designed aii. 44 ABSTRACTS OF CHEMICAL PAPERS. hydrogen electrode which reaches equilibrium in sbou t five minutes. This consists of a flask fitted with a rubber stopper pierced with three holes. The electrode which passes through one of the holes consists of a glass tube open at its lower end and is surrounded by a cylinder of platinum gauze. An inner tube carries a copper wire connected to the platinum gauze by means of mercury and a platinum wire. Rydrogen enters through a tube in the second hole passes up the electrode and escapes through a side-tube. The third opening carries a thermometer. The arrangement has the advantage that! the fluid is throughout agitated in contact wit-h the hydrogen which results in a rapid equilibrium.The disadvantage however. is that a considerable volume of fluid is required. Oxygen is removed from the hydrogen by means of heated platinised asbestos; the presence of small quantities of oxygen must be stndiously avoided. A form of calomel electrode iq described in which mercury. mercury-calomel paste potassium chloride crystals and saturated potassium chloride solution are employed ; such an apparatus has been in use for eight months satisfactorily. S. T. T,. Electrolytic Conductivity in Non-aqueous Solutions. 11. Electric a1 Conductivity of p - Tolyltrimethylammonium Iodide in Water and several Organic Solvents. HENRY JERMAIN MAUDE CREIGHTON and D. RERBERT War ( J .I”ra~2kZin Znst. 1918 186 675-698. Compare ibid. 1916 182 745).- The electrical conductivity of p-tolyltrimethylammoniv.m iodide has been determined at 25O in water methyl alcohol ethyl alcohol propaldehyde anisaldehyde. benzaldehyde acetone Iormic acid acetic acid propionitrile. benzonitrile nitromethane nitrobenzene and epichlorohydrin. I n the case of some of the solvents measure- ments have also been made a t Oo and 1 8 O and the t,eniperature coefficient calculated. ~TolyltrimethVlamn1onitirn iodide like most. strong electrolytes does not follow Ost,wald’s dilution law in aqueous solution but+ is approximately in agreement with the Storch empirical dilution equation. The ionic conductivity of the ptolyltrimethylammonium ion a t 2 5 O in aqueous solution is 40.3.The equivalent conductivitv at infinite dilntion has been extra- polated for ?~-tolyltrimethylammoniui~~ iod.ide in all the solvents used and it is shown that. the values varg from dm =13 in anis- aldehyde to A m =I88 in acetone. Further the mapnitucle of this value bears a relationship t o the chemical constitiition of the solvent. which may he qenerally stated thus the equivalent con- ductivity of an electrolyte at infinite dililtion. 2nd conseanentlv the vetocitv of the ions is greater in an a h h a t i c solvent than in an aromatic solvent of corresnonding constitutioii. Thus A m f o nitrompthane= 115. for nitrohenzene 38 for mooionitrile 143 whilst for henzoiiitrile A x 4 4 . Tn a n homolocons wrieq the value for A w is preater the nearer- the solvent stands t o the heginninF of the series.For example A* for water=llfi. methvl ~lcohol 100 ethyl n!cnhol 48 formir acid 90. acetic acid 2 5 OfGENERAL AND PHYSICAL CHEMISTRY ii. 4.5 the various substituting groups the influence of the aldehyde group on the magnitude of A- is greatest whilst that of the carboxyl group is the least as is shown by the series acetaldehyde A =188 iiitroniethane 115 methyl alcohol 100 acetic acid 25. J. F. S. Electrolytic Deposition of Iron from Organic Solvents. E. H. *%RCHIBALD and L. A. PIGUET (Trans. Roy. s o c . Canada 1917-1918 [iii] P 1 107-112).-Solutions of ferric chloride in acetone ethyl alcohol and acetone and water and acetone have been electroiysed by various currents and a t various voltages at 250. The experiments were carried out' between platinum elec trodes but in some experiirieiits a silver cathode was employed.I n all cases the iron can be completely deposited; in the case of acetone and of acetone-water mixtures the iron is deposited free from carbon. At low voltages the iron is deposited in the metallic condition; as the voltage is increased i t comes down as a red deposit which is adherent and allows the iron t o be removed from the solution. From the acetone-alcohol solutions the iron although completely deposited is contaminated with carbon. Jbom acetone-water solutions of ferrous sulphate the iron can be completely deposited but the deposit? contains a considerable amount of carbon. Aldehyde is not formed during the electrolysis of any of the solutions. Electrolytic Precipitation of Zinc.D. MCINTOSH ( TTCL~ZS. Roy. SOC. Canada 1917-18 [iii] 11 113-119).-The electrolytic depoeition of zinc from solutions of the sulphate has been studied under various conditious with the object of ascertaining the most suitable conditions for obtaining good deposits. It is shown that the best results are obtained when the solution is free from colloids and when the amount of iron present> is low. The metals arsenic antimony copper cobalt nickel and all metals more electropositive than zinc must he absent. The solution particularly in tanks con- taining large amounts of acid should be cold. The zinc deposits in a semi-passive form ; but when it begins to dissolve solution. cannot be stopped in any simple way. The zinc concentration should be as high as possible (6-7"L) and n o attempt should be made t o electro- lyse solutions containing less than 1*5--2*0% of zinc.With the ordinary cascade system the maximum current density is 25-30 amperes per sq. foot. A large number of photographs of deposits obtained under varying coiiditions are reproduced in the paper. J. F. S. J. F. S. Critical Phenomena. WILLIAM R. FIELDINU (Chem. flews 1918 117 379-383).-The' relation between the critical pressure and critical temperature of an element can be expressed by the formula (T + 2363) / JPc = 70.9. This relation holds strictly for hydrogen and the members of the halogen group and less closely for nitrogen and xenon whilst in the case of oxygen the divergence is considerable. For series of inorganic compounds such as that of the 2"ii.46 ABSTRACTS OF CHEMICAL PAPEES. halogen acids a similar iormula holds (T - z) / JT= A where x and k are constants f o r any particular series. In inorganic compounds t h e critical pressure rises with the critical temperature in any series but in organic compounds the presstare falls as the temperature rises. For a number of organic compounds the value of T x d z has been calculated. In higher members of aliphatic series this quantity tends to become constant. Ia the aromatic series of hydrocarbons with the introduction of alkyl groups into the benzene ring it first decreases and as the complexity of the alkyl groups increases it becomes practically constant. Nultiplication of benzene’ rings in t h e molecule produces a considerable increase in the value of the quantity.E. H. R. Calorimetric Lag. WALTER P. WHITE ( J . Anzer. c’henz. SOC. 1918 40 1858-1872).-Lags may pertain t o the thermometer t o various portions of the calorimeter or to outlying bodies including air. I n this paper the lag of external bodies such as a thin metal shield surrounding the calorimeter is treated in a mathematical manner. The effects prove to be three one equivalent to a change in the heat capacity of the calorimeter which can be eliminated by direct calibration of the calorimeter ; another much smaller depending on the amount of thermal leakage which can be avoided by using the adiabatic method; and a third dependent on the jacket temperature which disappears if this is constant. On account of the lag effect the effective heat capacity of a shield midway between calorimeter and jacket is only one-fourth its actual capacity and with due regard to the possibility of change such shields may often be used to reduce thermal leakage.Used as a cover such a shield has a specially small error and offers a parti- cularly easy method of dealing with evaporation. (Compare A. 1918 ii 149.) E. H. R. The Conditions of Calorimetric Precision. WALTER P. Wmm ( J . ,4mer. Chem. Soc. 1918 40 1872-1886).-1n a Cali- brated calorimeter most of the errors arise in thermometric measurEments and most of these come in the ‘‘ cooling correction,” the determination of the effect of thermal leakage. The leakage effect is equal to K+,T where T is the time # is the difference between calorimeter and environment temperature and H the leakage modulus of the calorimeter.By diminishing Ii as by rneane of a vacuum the effect of errors in # is diminished. These errors arise from the difliculty in getting the jacket and calorimeter temperatures uniform. The advantage of diminishing # t h e thermal head is largely illusory. since the main error t h a t in deter- mining X by means of the cooling rate is little affected. Lags which vary with K and are independent of T and + can be made t o cause little or no error. The rate of stirring should be as uni- form as possible since the heat produced varies as the cube of the speed. The tvpe of stirrer and design of the calorimeter with reference to stirring may be important. E. H. R.GENERAL AND PHYSICAL CHEMISTRY ii.47 Calorimetric Methods and Devices. WALTER 9. WHITE ( J . Amer. Chem. Soc. 1918 40 1887-1898).-The general rules for calorimetric precision (preceding abstract) are applied to jacket covers and stirrers and to such special devices as vacuum-jacketed vessels the adiabatic method aneroid or dry calorimeters double or differential calorimeters and measured-shield calorimeters and the advantages of the different forms of calorimeter are compared. The measured-shield calorimeter is a new device having between the calorimeter and the jacket a thin metal shield connected to the wall o f the jacket by therino-elements which are used to measure the thermal head. E. €3. R. Sensitive Bath Thermostat. A. HORMAN MHAW (Tmzs. Boy. SOC. Camda 1917-18 [iii] 11 129-135).-A thermostat on a rather large scale is described which differs but little from the well- kfiown types.A nots on the regulation of temperature is appended t o the paper. An Accurate Method for Measuring the Density of Gases. 0. MAASS and J. RUSSELL (2. Arne?.. Chem. Soc. 1918 40 1847-1852).--The method described is applicable to' tlie deter - mination of the density of those gases which can be condensed by liquid air or some other freezing agent. The purified dry gas is condensed in a suitable vessel and thence transferred to a large exhausted glass flask (abouti 22 litres capacity) the volume of which is accurately known. The flask has r2 coniiection t o a manometer and the pressure is read a t Oo the flask being immersed in ice. By a suitable arrangement of tubes the gas in the flask can be transferred to an exhausted glass bulb immersed in liquid air.When the gas has liquefied the bulb is sealed off and weighed and again weighed after it has been opened and the liquid allowed to1 evaporate. The pressure of the gas remaining in the flask a i d connecting tubes is read after the bulb1 has been detached to enable the volume of gas taken into tile bulb to be calculated. The accu- racy of the method is limited by the accuracy with which the height of the mercury in the manometer can he read. The probable error with the method used is 0*0504; with tlie aid of a cathetometer it could be reduced t o 0.01%. The following densities were determined acetylene 1.1695 ; methyl ether 2.1103 ; hydrogen bromide 3.6397. The Change of Density of Liquid Mixtures with In- creasing Temperature.mT. HERZ (Zeitsch. anorg. Chem. 1918 104 251-252).-The formula expressing the relationship between density and temperature 1 / d =a - h log (0 - t ) where dt is the density at temperature t 8 is the critical temperature and n and 71 are1 constants has been found t o hold for liquid mix- tures as well as for pure liquids. Different binary mixtures of benzene toluene aniline and nitrobenzene were used for the experiments aC temperatures between 25O and 905 and the differ- ences between observed and calculated densities were very small. J. F. S. E. H. R. 2*-2K 48 ABSTRACTS OF CHEMICAL PAPERS. The critical temperature 6 of the mixture was calculated from those of the constituents 8 and 8 by means of the formula B = no + (100 -n)O2/ 100 where and (100 - n ) are the percentages of each constituent.E. H. R. Molecular Attraction and Attraction of Mass and some New Gas Equations. JAMES KAM (PhiE. Mag. 1919 [vi] 37 65-97) .-A theoretical paper in which gas equations are deduced from considerations of the actual and theoretical co-volumes. A general equation is deduced which considers the effect of tempera- ture on the relation of the co-volumes to the volume. Further reduced isothermals and reduced border-curves are considered. It is shown that the cohesive forces causing the “ inward pressure ” appear to follow a law similar to the inverse square law of mass attraction. From the deviations from the gas laws a value for the tensile strength of iron is deduced which is of the same order as the experimental value.It is further shown that whatever the ultimate nature of the cohesive forces may be they seem to be proportional to the square of the molecular weight and to obey the inverse square law-a Iww consequently similar to Newton’s law of attraction of mass. J. F. S. Internal Molecular Forces of Solid Substances and their Relations with the Elastic Properties. STEFANO PAGLIANI (Nuovo Cim. 1918 [vi] 15 i 103-129).-The existence of three forms of internal molecular forces in solids is considered and their values calculated. The first P termed intermolecular force of coherence enters as a factor in the internal work into which thermal or mechanical energy can be transformed without change in the volume of the substance. The second T termed internal pressure is analogous in character t o external pressure and enters as a factor in the internal work in which thermal energy is used with variation of the volume of the substance.The third called intermolecular force of change of phase enters as a factor in the internal work accomplished during changes of phase-in the fusion of solids; this force which acts a t the temperature of fusion where Lindemann considers that the amplitudes of the atomic oscillations about their equilibrium position become of the same order of mag- nitude as the mean distance between the atoms appears t o be of the same nature as P which acts with definite values a t different temperatures. The magnitude of the force F exhibits relationships with the values of some of the magnitudes considered in the study and appli- cations of the elastic properties of solids.The simplest of these relations with the moduli of elasticity od tension E of rigidity n and of flow N are as follows E=1.70 F or approximately E = 5 F / 3 n=F/?r and N=2F/7r. The relatively great value of the ratio between E and F depends an the fact that the load E which should double the init.ia1 length of the solid is only an ideal load unattainable in practice. It is hence more accurate to replace E in technical forrnulz by F this being a real magnitude the valueGENERAL AND PHYSICAL- CHEMISTRY. ii. 49 of which a t different temperatures may be calculated by means of physical magnitudes exactly measurable ; a number of expressions are given in which this substitution is made.The modulus of elasticity for each species of defo’rmation is found to be directly proportional to the inolecular force of coherence. The Adsorption of Arsenious Acid by Ferric Hydroxide. MAITLAND C. BOSWELL and J. V. DICKSON ( J . Amer. Chem. Soc. 1918 40 1793-1801).-The adsorption of arsenious acid from solution by ferric hydroxide wliicli had been prepared several months previously has been studied both in presence and absence of sodium hydroxide. The adsorption of the arsenious acid by the ferric hydroxide is diminished by the preeeiice of sodium hydroxide whilst the adsorption of the sodium hydroxide is itself increased by the presence of the arsenious acid. The age oE the ferric hydr- oxide and the addition of sodium chloride appear riot to have any effect on the quantitative data recorded.The results follow only approximately the ‘ I adsorption law,” E=PA4T’ where I? is the concentration of the adsorbed substance in the adsorbing pliase ,4 its concentration in the solution at equilibrium and /3 and p are constants. The equation can be written log E = p log A -I- B . Hence if the logarithms of the con- centrations in the adsorbent and the solution be plotted a straight line should be obtained the slope of which gives the value of p whilst the intercept gives the value of B =log P. The curves thus obtained from the results of the authors’ experiments approximate to straight lines but all show a distinct concavity t o the x or logA axis. The adsorption phenomenon cannot. be exactly represented by the above equation. The adsorption of arsenious acid by ferric hydroxide was also studied by Mecklenburg (A.1913 ii 676) who concluded that the adsorption curves for any particular gel p r e pared under varying conditions are so related t o a unit curve that the ratio of any ordinate on one curve to the corresponding ordin- ate on the unit curve is a constant. The authors interpret this to mean that the exponent p in the equation E=FfA4p is constant for any particular gel -whilst /3 is a variable depending on the condi- tions of preparation of the gel. The values of p calculated from t>lie authors’ and Mecklenburg’8 results agree when arsenious acid is used alone but in presence of sodium hydroxide! its value increases. E. H. R. T. H P. Ferment Action. I1 a Adsorption of Amino-acids and Poly- peptides by Animal Charcoal.Relation of the Observed Appearances to the Cleavage of Polypeptides by Yeast Juice. EMIL ABDERHALDEN and ANDOR FODOR (Fermentfomch. 1917 2 74-102; from Chem. Zentr 1918 ii 738. Compare A 1917 i 306).-Animal charcoal adsorbs scarcely a trace of glycine but it adsorbs a little alanine and a comparatively large quantity of leucine. Similar variations are observed in the case of the poly- peptides even isomeric substances being adsorbed t o very different extents by the charcoal. T”h0 amount adsorbed a t various dilutionsii. 50 BBSTBACTS OF CIiElCIfCAL PdPERS. varies according t o the laws of adsorption just as has been observed in tlie case; of enzymes. The adsorptive power trf charcoal differs from thati of the enzymes however in being uninfluenced by changes in the concentration of the hydrogeu and hydroxyl ions in the solution.When mixtures of amino-acids or polypeptides are treated with animal charcoal the adsorption of the substances containing t110 more complex molecules is relatively increased whilstr tihati of smaller molecular substances is decreased. H. W. B. Ferment Action. III. Adsorption of Amino-acids and Polypeptides and also of various Carbohydrates by Animal Charcoal. Emd ABDERHALDEN and ANDOR FODOR (Ferwzeitt- forsch. 1911 2 151-L66; from Chern. Zenffr. 1918 ii 739. Com- pare preceding abshract) .-Z-Arabinom lamdose and inositol are less readily adsorbed by charcoal than dextrose sucrose and other disaccharides and trisaccharides Tkre presence of carbohydrates diminishes the adsorptive power of animal charcoal towards pdy- peptides and conversely the adsorption of carbohydrates is adversely influenced by polypeptides.H. W. B. Retardation by Sugars of Diffusion of Acids in Gels. EVARTS A. GRAEAX and HELEN TEEDWAY GRABAX ( J . Anzer. Chenz. Soc. 1918 40 1900--1917).--The rates of diffusion of a number of inorganic and organic acids into gelatin sottitions containing vary- ing amounts of dextrose smxose and lactose have been measured. All the sugars have a niarked retarding influence on the diffusion of any acid the disaccharides having a considerably greater eEecl than the monosaccharide. In agreement with the general diffusion law the ratio of the distance of diffusion to the square root of the time is found to ba a constant in gelatin bath with and without sugar.The retardation is not proportional tol the concentration of the sugar but is relatively greater for smaller concentrations of sugar. I f the ratio d l Jf is equal t o KO without sugar and E with sugar %he relative retardation is given by (I~o-E')/.E'~~ or A/Ko. The relation between concentration-of sugar and retardalion can be expressed approximately by the equation (A. I go)" =CW where c is the concentration and a and .n are tonst.ants. I n 10% geIatiii nitric acid behaves abiiorrnalfy in that the ratio d i i s not constant but increases rapidly a t first and after remaining constant for some time again decreasw. Hydrochloric acid shows the1 same behaviour in 3% gelatin. Sodium chloride aha reta.rds the diff mion of acids into gelatin but to a less extent than the sugars when equimofecular solutions are compared. This is the reverse of their effect in reducing the acid sqcslling of gefatin in which sodium chloride is more effective than sugar The physiologkal bearing of the results obtained is briefly discussed particular1-y with reference to the protective actiun of dextrose in cases of chloro€orm poisoning the effects ofGENERAL AND rHYSICAL CHEMISTRY.5. 51 which are ascribed to t'he presence of free hydrochloric acid in the substance. The mechanism of the retardation is also discussed. E. H. R. Chemical Affinity in Crystals and the Velocity of Crystallisation. hl. PADOA (Atti €2. Accad. Lzncez 1918 [v] 27 ii 59-64; Gazzetta 1918 48 ii 139-147).-The suggestion is made that in rnost cases crystallisation represents a transposi- tion effected by means of valencies among the more or less free molecules of the gaseous or liquid phase so t h a t velocity of crystal- lisation may be regarded as velocity of reaction.The author has measured the velocities of crystallisation of a number of super- cooled compounds with the object of ascertaining (I) if with isomorphous compounds of similar structure the velocities of crystallisation are equal or of the same order of magnitude and (2) i f in a series of coapounds of perfectly analogons chemical coiistihtions the velocities of crystallisa tion are comparable and ceteris p r i b z t s depndent on the mo!ecular weights. Similar values are obtained f o r m-bromo- (600) and w -chloro-nitrobenzene (882) and also for p-clichloro- (4800) p-dibromo- (7000) and piodo-benzene (6300) the low value f o r p-chloroiodobenzeiie (1 153) being apparently dependent 011 its markedly difierent viscosity.The introduction of methyl into the benzene ring greatly retards the cry-stallisation ; naphthalene and its anzlogues show far lower values than henzene the isomeric anthrwene and phenanthrene 'having identical velocities. Sirrilaritv also exists between the velocities f o r isomorphous inorganic compounds. Of two compounds of similar structure the one ssturatpd and the other unsaturated the latter should nresent the ?rester velocitv of crystallisatior since the latent affinities in the dolihIe linkirirrs should favour the prwecs of crv4?llisstinn.This conclticion is comp!etely confirmed by tilie result8s oFtqiver7 for a niimher of v2ir of isomorphous orcanic compounds cne member of esch psir h i n g satizrated or a t least less u n s a t ~ a t e d than the other mewber. The general conclusicns drawn are (1) the velocitv of crvst.11- lisation is a constitutive propert-v and (2) the bonds hetween the atoms in crystalline networks are of the same nature as rliemical valencies. T. H. P. Point of Transformation betweeil Reversible Modifica- tions. C. VIOLA (Atti B. ilccad. Lii.tccz 1918 [v] 27 ii 107-112).-The author applies the law of maximum work and Curie's law t o the consideration of the possible co-existence a t 9 temperature different from i l l of two reversible crystslline modifica- tions which occur in contact in stable equilibrium a t temperature 2' and a t a definite pressure.It is shown that either where a process is effected reversibly and crystallisstion takes place and should take place according to Curie's law or where between two modifications in contact a minimal surface tension is established a point ofii. 5.2 ABSTRACTS OF CHEMICAL PAPERS. transformation must always exist there ; vice versa the surface tension is a minimum a t a transformation point between two modi- fications. T. H. P. The Artificial Coloration of Liquid Crystals. PAUL GAUBERT (Compt. rend. 1918 167 1073-1075).-Indophenol may be satisfactorily used for colouring liquid crystals and also solid crystals of a large iiumbei- of organic compounds. The presence of the indophenol lowers the solidification point of the molten substances and in the case of substances giving several biref ringent liquid phases all the melting points or transformation points are lowered.There exists for the ir:dophenol a coefficient of so1ubilit”y particular to each phase this coefficient diminishing with the molecular vollume. The optically positive liquid crystals obtained by combining cholesterol with glycollic acid glycerol etc. are i i ~ t coloured by indophenol although the isotropic liqvid dissolves i t . W G. Theory of the Velocity of Coagulation. 11. FREUNDLICH (fi-olloid Zeitsch. 1918 23 163-173).-A theoretical paper in which it is shown that the velocity of slow coagulation of hydro- phobe sols increases very much with increasing concentration of the coagulating electrolyte whilst for rapidly coagulating sols the velocity of coagulation is constant and independenC of the nature and concentration of the electrolyte.Srnoluchomsk explains the rapid coagulation by assuming that the collisions between the partlicles are noa-elastic and lead to the coagulation of all the particles which cqme within the sphere of influence. The rapid increase in velocity of the slow codgulation is explained by the assumption that in the concentration present the charges on the particles produce a repulsion and only those paxticles are coagu- fated the kinetic energy of which is greater than a certain criticaf value. This critical value is greater the greater the charge on the particle. The number of these particles increases as the electrolyte concentration increases.A f orinula giving the relationship between electrolyte concentration and velocity of coagulation is given and this is in keeping with observed results. J. F. S. The Brownian Movement and the Coagulation of Colloidal Solutions. H. T.V. WOUDS’L‘RA (Chem WeekbZnd 1918 15 679-680) .-The author claims priority over Kruyt and van der Spek (A. 1917 ii 563) in directing attention to the func- tion of the Brownian niovement of the colloid particles in the coagulation of a colloidal solution. w. s. M. The Brownian Movement in Relation to the Mechanism of Flocculation. D. J. HISSINK (Chem. TVeekbZad 1919 16 20-21).-The author disputes the contention of Henri and Ostwald (see Grundriss der allgemeinen Chemie,” 1917 544) that the Brownian movements are diminished by addition of a coagu-GENERAL AND PHYSICAL CHEMISTRY. ii.53 latiing electrolyte before coagulation and conkends that by micro- scopic observation i t can easily be seen that the coagulation itself is the cause of the diminution of the movement which is therefore a consequence of the coagulation and does not precede it. s. I. L. The Lowering of the Degree of Dissociation. K. N. DE HAAS (Chem. Weefiblad 1918 15 1352-1355).-An elementary mathematical consideration of the fundamental equation of mass action with reference t o the shifting of the equilibrium consequent on the addition of oiie of the products of dissociation or ionisation t o the system. W. S. M. Heterogeneous Equilibria between Aqueous and Metallic Solutions The Interaction of Mixed Salt Solutions and Liquid Amalgams.V. A Study of the Ionisation Relations of Potassium and Strontium Chlorides in Mixtures. G. McP. SMITH and EDWIN ARTHUR REES ( J . dnzer. Chem. Soc. 1918 40 1802-1847).-To study t.he equilibrium between mixed strontium and potassium amalgams and the mixed aqueous solu- tions of the chlorides of these metals a definite quantity of either strontium amalgam or potassium amalgam of known concentration was shaken up with successive portions of a known aqueous solu- tion of the mixed chlorides until equilibrium was reached. The quantities of strontium and potassium in the amalgam were then determined by analysis. Experiments were made on the effect of varying (1) the amalgam concentration up to about 0.6 Inilli- equivalent of potassium or strontium per 10 grams of mercury (2) the total salt concentration in the aqueous phase from 0’05&\- to 3Ar ( 3 ) the ratio of the two salts in the aqueous phase a t different total salt concentrations and (4) the temperature from 1 5 O to 40°.To interpret the data obtained the value of the ex- pression (Sr,,)(K-ealt)2/ (R,,)2(Sr-salt8) = C was calculated in which (SrKg) and (KH2) are the respective atom-fractions in the mercurial phase and (K-salt) and (Sr-salt) are the mol-fractions in the aqueous phase (compare A. 1917 ii 247). The value of the ‘’ equilibrium expression ” C increases proportionately with the total conceiitration in the mercurial phase up to 0.3 milli- equivalent per 10 grams of mercury a t temperatures from 15-45O.V7hen the amalgam concentration is kept constant and the con- centration of the aqueous phase increased the proportions of the two salts being kept constant the value of C first falls rapidly as the concentration rises to about 0-4fl but with stronger so’1utions i t approaches a constant value. Assuming that in the most dilute solutions examined 0*05N an equimolecular mixture of the two salts is completely ionised it is shown that as the concentration in the aqueous phase is in- creased but the salt‘ ratio kept constant the proportion of K+ ions t o Sr++ ions increases I-apidly; also whea the ratio ofii. 54 ABSTRACTS O F CHEMICAL PAPERS. potassium chloride to strontium chloride is increased the propor- tion of K+ ions increases at’ a greater rate.The results obtained at different temperatures have been used to calculat*e the heab of reaction accompanying the changes between 1 5 O and 40°. With rising temperature the reaction is exothermic and the heat of reaction is found to decrease with increasing total salt concentration. As regards the dissociation of potassium and strontium anialgams it is shown that the ordinary mass-action expression holds good for mixtures of t,he two up to a total concentration of about 2 milli-equivalents per 100 grams of mercury. There is evidence of the formation in the aqueous salt mixture of molecular complexes and complex ions the results being in harmony with ViTerfzer’s views. E. H. R. Influence of Substitution of the Components of Binary Equilibria in Solution XIII.The Solution Equilibria of the Three Isomeric Phenylenediamines with Phenols and the Dinitro-derivatives of Benzene respectively. ROBERT KREMANN and WOLFGANG STROESCHNEIDER (Monatsh. 1918 39 505-570. Compare this vol. ii 15).-Melting-point and cooling curves have been obtained for the six binary systems made up of the three phenylenediamines with either a-naphthol or P-naphthol f o r the four binary systems composed of a- or &naphthol with a- or P-naphthylamine for the system 8-naphthol and ptduidine for the nine binary systems composed of one of the three diphenylamines with one of the three dihydroxybenzenes for the three binary systems composed of 2 4-dinitrotoluene with each of the phenylenediamines and for the nine binary systems composed of one of the three phenylenediamines wit.h one of the dinitrobenzenes.The results are given in curves and in voluminous tables. It is shown that 1,-phenylenediamine forms compounds with two molecules of a-naphthol (m. p. l l O o ) and with two mde- cules of P-naphthol (m. p. 150-5O). One molecule of m-phenylene- diamine forms compounds with two molecules of P-naphthol (m. p. 1 1 4 O ) and with one molecule of a-naphthol (m. p. 359. One mole- cule of o-phenylenediamine f o m s compounds with one molecule of a-naphthol (m. p. 60°) and with one molecule of P-naphthol (m. p. 8 6 O ) respectively. a-Naphthol forrrs two compounds with a-naphthylamine with one and four molecules of the latter to one of the former colmnound. A compound is formed contailling two molecules of P-naphthol to three molecules of a-naphthvlamine.b u t no compounds are formed between a-naphthol and 8-naphthvl- amine a simnlie eutectic is produced by these substances a t 47O and contains 56.5% of the last-named component. An equimole- cular comnonn d ir formed between B-nanhthol and ptoluidine (m. p. 87-Fi0). Equimolecular compounds are forwed with m-ohenvlenedianiine and catechol frn . p. 64*5O) m,-nhenylene- diamine and reForcinn1 (m. p. ‘?go). v-phenvlenediamine and quinol (ni. 1’. 1 2 7 O ) . with two molecules of catechol and one mofe-GENERAL AND PXYSICAL CHEMISTRY. ji. 65 cule of p-phenyleuediamine with three iiiolecules of cat echo1 and two molecules of p-phenylenediamine and with three molecules of quinol with one molecule of p-phenyfenediamine.The details of the system o-dinitrobenzene-p-phenylenediamine have not been worked out because of a secondary chemical reaction which inter- feres with the measurements. Compottnds are formed between m-dinitrobenzene and the three pheiiylenediarnines of the follow- ing composition (i) three molecules of the nitro-compound with two molecules of o-phenylenediamine (ii) two molecules of the nitrecompound with one molecule of o-phenylenediarnine and (iii) m e molecule of the nitro-compound with two molecules of tn-phenylenediamine ; no compounds are formed between pphenylenediamine and m-dinitrobenzene. I n the case of pdinitrobenzene and the three phenylenediamines compounds are not formed with 0- and m-phenylenediamine but with p-phenylene- diamine a compound of two molecules of t-he amine and one mole- cule of the nitro-compound is formed.Full details of the numerous eutectics are given in the paper. The Dilution Limits of Inflammability of Gaseous Mixtures. 111. The Lower Limits of some Mixed Inflammable Gases with Air. ITT. The Upper Limits of some Gases Singly and Mixed in Air. HUBERT FRANK COWARD CITARLES WILLIAM CARPENTER and WILLIAM PAYMAN (T. J. F. 8 . 1919 115 27-36). The Propagation of Flame through Tubes of Small Diameter. 11 WILT,IAN PAYMAN and RICHARD VERNON WHEELER (T. 1919 115 36-45). The Inflammation of Mixtures of Ethane and Air in a Closed Vessel. The Effects of Turbulence. RICHARD VERNON WHEELER (T. 1919 115 81-94). The Ignition of Explosive Gases by Electric Sparks. JOHN DAVID MORGAN (T. 1919 115 94-104).The Range of Existence of Substances Kinetic Analysis and the Estimation of Vapour Pressures from Reaction Velocities. M. TRALTTZ (Zeitach. rmory. Chem. 191 8 104 169-210) .-The author distinguishes between the range of stability and the range of existence of any substance. The stability of a substance is dependent on the chemical factors which bring about its formation and is measured by the energy of the reaction whilst its range of existence is determined only by the heat of activation needed to bring about its decomposit'ion. The upper limit of existence of a compound is determined by the heat of activation of that binary decomposition which requires the least energy. From the point of view of the author's theory of reaction velocity (A. 1917 ii 23; 1918 ii 151) a large number of reactions areii.66 ABSTRACTS OF CHEMICAL PAPERS. discussed. The formation of nitrosyl chloride or of nitrosyl bromide is apparently a reaction of the third order but in all probability is made up of superimposed reactions of lower orders and formulz are developed by means of which the higher order reaction can be expressed in terms of reactions of lower orders. On the assumption that nitrosyl chloride formation proceeds in the two stages NO +- (21% NOCI NOC1 + NO = 2NOC1 a method of kinetic analysis is developed which enables tAhe concentration and heat of formation of the intermediate product t o be calculated. The heat of fomiation of NOC1 is 2500 cal. The reaction between hydrogen and oxygen in porcelain vessels was supposed by Bodenstein to he of the t-hird order but the velocity constants do not distinguish between a third- and a second- order reaction.Moreover probable values €or the impact consta,nt. are obtained only i f it is treated as a second-order reaction. The course of the reaction is probably B + 0 = H202 (measurable) ; H,O + H = 2H,O (imiiieasurably fast). The probable value of the heat of activation for N,+0 is 46,374 cal. and the mean diameter of oxygen and hydrogen molecules 1-62 x 10-8 cni. The formation of nickel carbonyl from nickel and carbon mon- oxide which is apparently a third-order reaction probably pro- ceeds in the three stages . Ni + CO = NiCO (momenta,ry equil- ibrium) NiCO + CO = Ni(CO) (measurable) and Ni(CO),+ 2CO= Ni(CO) (immeasurably fast). It is shown how from the velocity of the reaction the vapour pressure of nickel can be calculated and also its probable boiling point 3358O A.T.The true order of a reaction for example in the case of nickel carbonyl formation can be determined by consideration of the absolute reaction velocity and its temperature coefficient when the mean molecular diameter is assumed. The velocity of surface reactions is fully discussed and in this connexion the decomposition of ammonia phosphine arsine and antimony hydride are considered. These reactions are assumed to be of the firstl order corresponding with XH -+- XH+H (measurable). The heat of activation in this series decreases with increasing molecular weight. From the heat of activation the maximum wave-length of the actinic rays which will bring about the decomposition is calculated from the formula qo= (2.843 x l V ) / h .It is concluded that ammonia phosphine and arsiii'e should show absorption in the ultra-violet antimony hydride in the visible spectrum. For ammonia the maximum wavelength is shown to be 219*6,up and in confirmation of this it is shown experiment'ally that light of 214-203 pp is photochemically active towards ammonia. Other reactions discussed are the f omation and decomposition of sulphuryl chloride the decomposition of sulphur trioxide and hydrogen selenide the formation of hydrogen sulphide and hydrogen selenide from their elements and the slow combustion of hydrogen iodide of phosphorus sulphur and carbon. From RhearlGENERAL AND PHYSICAL CHEMISTRY. ii.57 and Wheelers experiments on the combustion of carbon t o carbon monoxide (T. 1912 101 846) assuming that the vapour of carbon is monatomic the boiling point of carbon is calculated to be 8542O and its vapmr pressure in mm. of mercury a t llOcio 4-05 x the corresponding concentration being 4.74 x mols. per litre. E. H. R. Consecutive Reactions. IV Relationships of the Constants in the Acid Hydrolysis of Esters of Oxalic and Malonic Acids. ANTON SKRABAL and (Frl.) DANICA MRAZEK (Nonatsh. 1918 39 495-503. Compare A. 1917 ii 250)- The kinetics of the acid hydrolysis of methyl oxalate ethyl oxalate methyl malonate and ethyl malonate have been studied a t 25’. The hydrolysis kas effected by 0.W-hydrochloric acid and since as has been previously shown the determination of the change in acidity did not yield a satisfactory constant the amount of normal ester remaining unchanged was determined iodometrically .In this way it is shown that the hydrolysis takes place according to the equations for first-order reactions. The ratio of the reaction constants of the two consecutive reactions is 2 1. Methyl oxalate is hydrolysed approximately twice as rapidly as ethyl oxalate but in the case of the malonic esters the rate of hydrolysis is approxim- ately the same in the two cases. J. F. S. The Conception of the Chemical Element as Enlarged by the Study of Radioactive Change. FREDERICK SODDY (T. 1919 115 1-26). Atomic Weights in 1917. E. MOLES ,(Anal. Pis. Quinz. 1918 16 625-653).-A review of the work on the determination of atomic weights published during 1917.Complex Ions. 1. N. KOLTHOFF (Chenz W-eekblud 1918 15 1636-1644).-The definitions of complex ions given by de Haas (ibid. 1917 14 752; 1918 15 1352) and Abegg and Bodltinder (A. 1899 ii 542) are criticised. The latter state “One of the ion-forming components of a complex compound is built up of a single ion with an electrically neutral molecule.” de Haas in his later paper defines an inorganic complex ion as “ a metal-contain- ing ion built up of one or more molecules and one or more ions.” The author does not regard the presence of a neutral molecule as essential. Complex ions arise from the tendency of ions to can- bine with other molecules or ions which tendency is the greater the lower is the “ electro-affinity ” of the ion; the nature of the complex is dependent also on the properties of the molecules or other ions which enter into it.It follows that for any salt form- ation of complex ions becomes important only when neutral mole- cules are present to enter into combination with the ions that is when the degree of dissociation is small. Thus salts of strongly electropositive and electronegative ions or groups and salts of oneii 68 ABSTRACTS OE CHEMTCAL PAPERS. stroug and one weak radicle being highly dissociated in solution show small tendency to complex formation; salts oi one strong and one weak radicle or element may however form complex ions by combination of the ions of the weaker element or radicle with each other. The mercuric salts afford iiurrierous examples of the formation of complex ions; dissociation of mercuric chloride forms the ions l-€gCl* Eg” and Cll and combination of the C1’ with the undis- sociated molecule gives rise to the complexes HgC1,’ and Hgc1,I’.Of these the groupc €IgCl’ has the highest concentration namely about 10,000 times as great as the concentration of the Hg” ion. A consideration of the possibilities of combination or dissociation of a group AB’ where A is a bivalent positive and B a univalent negative ionogeri will show that the neutral molecule A4W can be regarded as an intermediate pro[iuct- between the complexes AB’ and RB31. In the first the electro-affinity of both ions is great and the tendency to complex f ormatioil small increasing as the electro-affinity falls. I n the case of the chlorides of the alkali metals in solution in presence of an alkaline earth chloride for example the lower dis- sociation of the alkaline earth chloride causes the presence of its neutral molecules which form complexes with the chlorine ion of the alkali metal chloride of the type RCl,’; in concentrated solu- tions the product of the concentration of this complex and that of the ion of the alkali metal may be so great as t o cause separa- tion of double salts.I n the second class the electrocaffinity of both ions is small; itq is clear that there will be a gradual transition between the two classes. Silver iodide and merctiric cyanide form examples of slightly soluble salts in this class; here the solubility is great.ly increased by presence of eithen ion owing t o the possi- bility of complex formation which this introduces.Cadmium iodide affords a good case of a soluble salt of this class. Consideration is given to complex ions containing hydrogen. Fo’r the case of a weak &basic acid H,A two dissociation con- stants corresponding with the ions HA’ and A” have to be con- sidered the second being usually very small. It is shown that the low dissociation of HA’ as compared for example with RA‘ where R is an alkali metal is in contrast with the case of the halogen acids and the alkali haloids the former having here the higher dissociation. The following definition is finally put forward “ Complex ions break up t o a certain extent into Fimple ions generally with form- ation of neutral molecules.” s. I. L. The cases of iormation of complexes fall into two classes.The Valency-hypothesis of J. Stark. W. JACOBS (Cliem. TVeekbZad 1918 15 1566-1571) .-The theory of partial valencies has been employed to explain molecular aggregation in the fluid and crystalline states and to account for the various states of aggregation in which elements and compounds exist at ordinaryGENERAL AND PHYSICAL CHEMISTRY. ii. 59 temperatures and &he changes in the states of aggregation whch they undergo with change of temperature. l'he lines of jiorce of a valency-electron can be distributed partly to atoms of the same molecule and part'ly to other molecules ; consequently intramole- cular linking and inhermolecular iinkings are essenually due to the same forces and all substances fall wiGhin a series in which the relative strength of the two classes of linhng gradually changes.If the valency-electron is adjacent to a positive surface within its own molecule intermolecular attraction will be weak and will be easily overcome by a small inflow of energy from without which will leave the intramolecular system unchanged; at the other extreme the strength uf the two kinds of linkings approaches equality the molecule behaves as it were like a single atom and intermolecular aggregation is pronounced. I n the last case any disturbance of the intermolecuiar linkings must affect strongly the internal arrangement of the single molecules and it may happen that a particular atomic system can only exist within very iiarrow limits of physical properties. Stark has directed attention to the distinction between the mean- ing of the term molecule in the chemical and in the physical sense; in the former molecules are distinguished as having identical arrangements of atoms in the latter as being particles free to move in space in a definite manner determined by thermal condi- tions.The two definitions agree f o r ni,lecules in the gaseous cow dition since here no intermolecular linkings exist. I n the crystal- line condition a chemical molecule is not free t o move independ- ently of its neighbours and the physical definition fails. I n the liquid condition molecular aggregation occurs but generally varies continually in strength and character ; physical molecules exist but are generally not identical with chemical molecules being usually built up of several chemical molecules and varying con- tinually in mass.I n the case of solution the molecules of solute by the attraction of their partial valencies form ' I solution mole- cules" with molecules of the solvent each of which is a free- moving physical molecule and changes readily with slight changes of temperature. Where intramolecular attraction is weak and the electric valency- field is diffused outside the molecule as in the case of metals and electrolytes the power of crystallisation is high and in the liquid condition the substance has low vapour pressure; where the intra- molecular linkings are very st-rong as with the inert gases the substance cannot be liquefied or solidified at ordinary temperatures. The gradation of physical properties of the hydrocarbons similarly is explained by the gradual decrease of strength of the intra- molecular bonds as the number of Fimilarly linked atoms within the molecule increases. s. I. L. A Device for Introducing a Vapour into a Gas. E. H. ZEITFUCHS (J. Amer. Chenz. Soc. 1918 40 1899).-To introduce a known quantity of vapour into a stream sf gas the followingii. 60 ABSTRACTS OF CHEMICAL PAPERS. device is used. On to the end of a burette is sealed a glass capillary. This capillary is enclosed by t*he constricted end of a wide tube closed a t the top just below the cock of the burette by a piece of rubber tubing which keeps it in position. The capillary touches in the wide tube a roll of asbestos fibres wound round with resistance wire by which it. is heated electrically. A measured quantity of liquid can be r u n from the burette on to the asbestos fibre where it is vaporised and takeri up by a stream of gas enter- ing the constricted portion of the tubs by a side-tube and passing down through the asbestos roll. Any know771 quantit,y of vapour can thus be iutxoduced into the gas. E. H. R. Stopcock for Dropping Liquids arranged €or Equalising the Pressure Above and Below the Outlet in the Stopcock. HARRY L. FISHER ( J . I d . Eng. Ghenz. 1918 10 1014-1015).- An annular groove is provided in the key of the stopcock and a central tlube is fitted in the two aims. The groove is in connexion with the outer tube so that when the tap is turned off there is still communication between the atmospheres in the vessels above and below the stopcock. The liquid flows from the upper to the lower vessel through the central tube and the bore of the stop- cock. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9191605037

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

PHYSIOLOG'ICAL CHEMISTRY. Physiological Chemistry. i. 53 The Consumption of Oxygen and Production of Carbon Dioxide in the Blood of Dogs. I. L. BERCZELLER (Biochem. Zeitsck. 1918 90 294-301).-Sterile blood was kept under mer- cury o r paraffin a t 38O and when fresh and after keeping for vaxi- ous intervals the oxygen and carbon dioxide were estimated by Bar- croft's method. The production of carbon dioxide was generally found to be greater than the oxygen consumption. Similar experi- ments were carried out in the presence of dextrose. Here again there was no direct relationship between oxygen consumption and carbon dioxide production. There was a much larger oxygen con- sumption and carbon dioxide production than in normal blood. S. B. S. Analysis of Blood Gases. 11. Haemofflobin as an Indicator.The Theory of Indicators. H. STRAUB and KLOTHILDE MEIER (Biochem. Zeitsch. 1918 90 305-336).-There is a discontinuity of the curve expressing the amount of carbon dioxide taken u p by the blood (hzemolysed by saponin freezing etc.) plotted against the carbon dioxide tension. This discontinuity does not follow the ordinary laws of mass action but begins when p,=7*0 at which point one molecule of carbon dioxide is taken up by one molecule of haoglobin. This indicates that when pH>7.0 the hzemoglobin molecules carry a negative charge which they lose as soon as p,=7. When p,= 6-39 a second point of discontinuity is reached in the curve which indicates that a t this point the hano- globin molscules acquire a positive charge. These phenomena are explained in reference to the charges carried by the colloidal par- ticles and not by the laws of mass action for the position of the bends in the curve depends also on the presence of other ions than those of hydrogen.Univalent anions and cations and bivalent cations exert no influence on the position of the bend; tervalent anions shiftl tho position of the first bend from plr=7.00 to pIi=6'80,i. 54 ABSTRACTS OF CHEMICAL PAPERS. and are without action on the position of the second bend. Ter- valent cations also exert a strong influence on the position. The application of these facts t o the use of hzemoglobin as an indicator is discussed. S. B. S. The Influence of Narcotics on the Permeability of Blood-corpuscles €or Dextrose and Carbamide. GERTRUD KATZ (Biochem. Zeitsch.1918 90 153-165).-The entrance of dextrose into human blood corpuscles is not inhibited by the nar- cotics hcptyl alcohol and thymol. The entrance of carbamide into ox-corpuscles is delayed by thymol. s. B. s. The Part Played by Acid in Carbohydrate Metabolism. 111. H. ELIAS and E. S'CHUBERT (Biockem. Zeitsch. 1918 90 229-243).-The glyco- gen content of the muscles of dogs' legs differs the right from the left by about 2-3% in the mean. Interarterial injection of lactic acid over several hours does not reducs t<o any appreciable extent the amount of glycogen; the muscle glycogen appears to be far more resistant to external stimuli than does the liver glycogen. Acid and- the Glycogen of the Muscles. S. B. S. Salivary Amylase. I. A Preliminary Experimental Study of its Stability in Saliva.RomN C. MYERS and T,EONARD C. SCOTT ( J . Amer. Chem. SOC. 1918 40 1713-1716).- Salivary amylase in sterilised saliva without preservative is found t o be relatively stable for a year. The relative stability may vary froni practically no change to that of more than 50% of its former amyloclastic activity the variation depending probably on slight differences in the composition of the saliva. The causes which lower the stability of salivary amylase in saliva are not solely the degrading action of bacteria mould spores yeast plants and special preservatives. The inherent chemical weakness of the enzyme molecule must be taken into account which weakness may be increased by the maintenance of temperatures from 1 8 O to; 30° by diffused light and by compounds in the saliva.Salivam amylase in saliva is relatively stable for a year when preserved with toluene thymol and chloroform. Toluene has the least destructive action on the enzyme and thymol and chloroform follow in order. Saliva may be kept for two ant1 a-hdf years under the ordinary 1 -t,horatorg conditions without pmservative and may still show :L form of amyloclastic activity. H. W. The Presence of Food Accessories in Urine Bile and Saliva. A. M. MUCKENFUSS (J. Amw. Chem. SOC. 1918 40 1606-1611).-As a result of a series of experiments on pigeons with acute symptoms of polyneiiritis the aut'hor is led t o the con- clusion that tho antineuritic vitamine is probably present in com- paratively small quantity in clean? fresh filtered bile from t;bcVEGETABLE PHYSIOLOGY AND AGRICULTWRE.i. 55 bladder of the ox and that traces of i t appear to be present in fresh filtered human urine. H. W. W. J. CROZIER ( J . 4mer. Chem. SOC. 1918 40 1611-1612. Compare Fischer A. 1918 i 129 130 131; Henderson and Cohn ibid. i 316).-The author has carried out a series of experiments on the intracellular acidities in the tissues of three species of sponges one echinoderm and a nudibranch mollusc. The observations made increase the difficulties in the way of accepting Fischer's conception of water metabolism since they indicate a range of intracellular acidities in animal tissues within which it is known tlrat no signi- ficant protein swelling occurs and since they show that an intra- cellular acidity even remotely approaching that a t which significant swelling might be possible is irreversibly associated with natural death. H. W. The Storage and Excretion of Arsenic after Administra- tion by Salvarsan in Serum and Water. HAXS BERGMANN (Biochem. Zeitsch,. 1918 90 348-360).-The author investigated the rate of excretion of arsenic excreted in the urins of man after administration of neosalvarsan in serum (human) and in aqueous solutions. I n the latter case the excretion is much greater. Experi- ments are quoted which tend to show that the salvarsan undergoes clremical change more rapidly in aqueous solutiaii than in serum. A series of experiments is also described. in which the accumulation of arsenic in the organs of rabbits after administration of salvarsan was investigated. They tend t o indicate a greater accumulation after administration of the drug in serum. Fischer's Theory of Water Absorption in Edema. X. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9191600053

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTWRE. i. 55 Chemistry of Vegetable Physiology and Agriculture. A Bacterium present in Water and in Bitter Wines which is capable of Dehydrating Glycerol. A New Reaction for Glycerol. E. VOISENRT ( A ~ t n . Inst. Pastezw 1918 32 476-510. Compare A. 1914 i 462).-The new bacterium termed Bacillus uitiurcccrylus is related to B. coli and B typkosm.~ but is not pathogenic. When cultivated in dextrose solution it forms carbon dioxide and hydrogen like B . coZi but it' does not form indole from tryptophan. Inoculation of a medium containing glycerol with the new bacterium results in the production of acraldehyde which is its characteristic reaction. The Inter-relationship of certain processes in Meta- bolism of Bacillus coli communis . FRITZ VEIL~ER (Biochem X ~ i t w h .1919 91 1--45).-Tliree main series of investpigations werc H. TV. B.i. 56 ABSTRACTS OF CHEMICAL PAPERS. instituted (1) The influence of certain poisons on the different processes (2) the influence of one metabolism product on the forma- tion of others (3) the regulation of the1 formation of a product by its own accumulation. The processes investigated were (a) gas formation from dextrose ( 6 ) acid formation from dextrose and lac- tose ( c ) indole formation (d) reducing action on dyes (e) multi- plication of the bacteria. (1) Protoplasmal poisons phenol formaldehyde and mercuric chloride inhibit all the processes in about the samel concentration. Crystal-violet shows slight inhibition of gas formation but strong inhibition of reducing processes.The respiratory poison potassium cyanide inhibits strongly gas formation and still more strongly reduction processes and indole formation in concentrations in which the acid formation is not affected. The narcotic chloroform inhibits respiration but not as stronglv as potassium cyanide; in contrast to the latter it also inhibits acid formation. Alcohol acts but less strongly like chloroform. The author draws the conclusion that the only really essential vital process is the formation of acid from dex- trose. (2) From the study of the presence of acid on indols formation i t was found that the latter is inhibited entirelv by the presence of acids and is only normally produced from proteins or peptones by the bacteria in the absence of dextrose; scission of this by the bacteria produces acid to inhibit indole formation.(3) The influence of the presence of acids and alkalis on the further formation of acids by the bacte'ria was investigated. It was found that when the acid in the culture medium reached a certain concentration further formation of acid was inhibited and also further formation of carbon dioxide and multiplication of b,acteria. If supar insufficient to produce the amount of acid necessary f o r inhibitions is present alkali formation sets in until the medium attains a slightlv alkaline reaction when further formation of alkali is inhibited. The formation takes place only in presence of oxygen. From acid (except formic acid) no qas is formed either after reach- ing. its maximum concentration or during formation of alkali.Inhi- bition of oxidation causes a compensatory increased production of acid. S. B. S. Phvtochemical Reductions. XI11 . Asymmetrical Re- duction. Conversion of Racernic Valeraldehyde (.&a- Methylbutaldehvde) into I-Amvl Alcohol. C . NEURERC and M. RINGER (Biochem. Z~itsch. 1918 90. 388--394).-The amyl alcohol produced from dZ-a-methvlbutaldehyde by a suqa r-yeast ferment a tion mixture is lzevorot ator y. S'. B. S. The Method of Formation of Succinic Acid in Nature. 111. Conversion of Aldehydopropionic Acid into Succinic Acid by Yeast. C. NEUBERU and M. RINGER (Biochenz. Zeitsch. 1918 91 131-136).-By means of maceration juice and in absence of air aldehydopropionic acid can be converted into succinic acid.VlWETABLl1 PHYSIOLOGY AND AGRICULTURE.i. 57 The conversion of glutamic acid into succinic acid follows therefore the following stages CO,H*CH,*CH,*CH (NH,) C02H -+ CO,H*CH,*CH,*CO* C0,H -+ CO,H*CH,*CH,*CHO (aldehydopropionic acid) + CO,H*CH,-CH,*CO,H. All these stages except tlie first which takes place as far as investi- gations have gone only in the living cell can be accomplished by Physiological Investigation of a New Yeast which Flourishes in Tanning Liquors. T~ICHI ASAI (J. Coll. Sci. Imp. Univ. Tokpo 1918 39 (7) 142).-The new yeast desig- nated Mycoderma tannica forms dark brown or brownish-black spots on leather undergoing the tanning process. The isolated yeast can be cultivated in a solution containing dextrose or hvulose or other carbohydrate and an ammonium salt or amino-acid as a source of nitrogen. It does not readily grow in a dilute pure tannin solution but when dextrose and aspartic acid are also present rapid decomposition of the tannin occurs owing to the excretion of tannase into the surrounding medium.The growth of the yeast is attended by the production of small quantities of alcohol snd carbon dioxide indicating the presence of zymase. Addition of tannin to the medium increases slightly the alcoholic fermentation. H. W. B. purely enzymatic reactions. s. B. s. Kinetics of the Cell-free Fermentation [by Zymase]. OTTO MEYERHOF (Zeitsch. physid Cheni. 1918 102 185-225). -The addition of sugar to an extract of dried yeast containing zymase but free from cells is succeeded by a period of quiescence during which no sign of fermentation is observable.The interval which elapsm between the addition of the sugar and the first appearance of fermentation is termed the ‘‘ induction period.” The duration of the induction period is determined by various factors ; it is shorter for sucrose than for eitlher dextrose or lzvulose; it can be shortened by previously warming the sugar solution with disodium hydrogen phosphate or by grinding the dried yeast with glass powder. The presence of a small amount of hexoBe phosphate abolishes the induction period. The rate of fermentation is dependent on the amount of free phosphate present. Increasing the amount of disodium hydrogen phosphate reduces the rate a t which the velocity of fermentation increases but the maximum velocity eventually attained is higher than in the absence of free phosphate until a certain maximum amount of the phosphate is reached; further addition of the phos- phate then reduces the maximum velocity of fermentation attain- able.The addition of other salts such as sodium chloride pro- duces similar effech on the velocity of fermentation. The free phosphate functions therefore as a salt as well as exerting its specific zymase-activating action.i. 5s ABSTRACTS OF CHEMICAL PAPEBS. Hexose phosphate exerts an accelerating action on fermentation in proportion to its concentration due to the decomposition of the ester itself. Fermentation is accelerated also by the addition of co-ferment in the form of boiled yeast juice; the extent to which it is affect>ed depends on the concent?ration and not an the absolute quantity of the co-ferment presentl in relation to zymase.The inhibiting influence of narcotics on the fermentation of dextrose by zymase is somewhat intensified by the addition of salts. H. IV. B. RGle of the Phosphate in Alcoholic Fermentation. HANS EULER and S. HEINTZE (Zeitsch. physiol. Ckem. 1918 102 252-261).-The esterificaticm of phosphoric acid by dried yeast in the presence of a protoplasmic poison such as phenol is related t o the amount of water remaining in the yeast after the drying process. The maximum esterificatim is observed when dried yeasts cant,aining from 10 to. 15% of moistare are employed. Increasing the quantity of yeast used in the individual experiments appears to occasion a much greater increase in the amount of hexose phosphate produced.H. W. B. Fumaric Acid Fermentation of Sugar. C. WEHMER (Bey. 1918 5 1 1663-1 668).-A spergdlus ficmaricus smoothly ferments relatively large quantities of sugar yielding in addition to a little citric acid fumaric acid in the free state; Che solution turns Congo- paper blue atid dissolves calcium carbonate. Oxygen is necessary and for continuous fermentation calcium carbonate. Thus 20 grams of sugar (20% solution) and 2.87 grams (dry weight) of Aspergillus funzam'c~cs dissolve 15 grams of calcium carbonate and produce about 33 grams of calcium salts consisting chiefly of the sparingly soluble normal calcium furnarate but containing also varying quantities of the easily soluble hydrogen fumarate about 4% of calcium citrate and the calcium salt of another unidentified acid.The sugar is fermented completely and 60-70% of it is con- verted into acids. The optimum temperature is about 22O the maximum about 30a c. s. Behaviour of Organic Compounds in Plants. X. G. CIAMICIAN and C. RAVENNA (Gazzetta 1918 48 i 253-304. Compare A. 1918 i 473).-The first part of this paper dealing with the action of certain compounds on the germination and development of plants has been already abstracted. The second part describes further investigations on the oxida- tion of organic compounds by the agency of enzymes contained in spinach leaves. The results of experiments in an at4mosphere of carbon dioxide show that the disappearance of wrt'ain substances in an ahasphere of oxygen as a result of the action of such enzymes is due to an oxidation process.In an atmosphere of carbon dioxide saligenin is converted into the polyanhydride saliretin this change being effected moreVEG1i;TdBLE PHYSIOLOGY AND AGRICULTURE. i. 59 promptly by apple pulp than by spinach leaves. Ethyl alcohol and mannitol are not sensibly oxidised. Acetaldehyde which undergoes little auto-oxidation in an atmosphere of oxygen is not affected by the presence of the enzyme The oxidation of acetone to formic and acetic acids under the influence of light is catalysed by the presence of the enzyme. Of the three amino-acids examined glycine alanine and asparagine only the last is oxidised by t h e enzyme in an atmosphere of oxygen no change occurring in carbon dioxide. Cinnamic acid is not oxidised a t the double linking only minimal traces Leine transformed into the isomeric isocinnamic acid; this isomerisation does not occur in carbon dioxide.Of the alkaloids examined caffeine and strychnine remain unchanged whereas morphine quinine and cinchonine are largely oxidised. The enzymes of spinach leaves are also able to determine certain &her reactions. Thus in oxygen dextrose is completely oxidised probably to carbon dioxide whilst in carbon dioxide i t yields a substance giving dextrose on hydrolysis with acid. Further in either oxygen or carbon dioxide tartaric acid undergoes change partly into a compound yielding tartaric acid under the action of emulsin. The results of the experiments described in the third partl of the paper sho'w that when inoculated into t.he living plant (maize) pyridine and nicotine are partly eliminated through the leaves the transformation of further quantities by the plant being also indicated but not defiiiit.ely proved.T. H. P. The Influence of Immersion in certain Electrolytic Solutions on Permeability of Plant Cells. MAUD WILLIAMS (Ann. Bot. 1918 32 591-599).-Cells of London Pride (Sazi- fraga umbrosa) petioles after immersion in solutions of certain electrolytes were found to be permeable to a 0.2% solution of ferric chloride the entrance of the ferric chloride being indicated by formation of a blue colour wit!h the tannin contained in those cellls. The time of immersion in a given solution necessary to pro- duce this abnormal permeability varied with the electrolyte and its concentration.I n the cases of aluminium and potassium chlorides and potassium and barium nitrates the results obtained could be #expressed approximately by the equatioii where T is the time of immersion in the solution of the electro- lyte needed to produce the abnormal permeability C is the con- centration in gram-mols. per litre K is an independent constant and A a constant depending on the electrolyte used. Abnormal permeability wit.h respect t o ferric chloride was not always accom- panied by permeability to the rose-coloured pigment frequent in the sap of the cells. logT=R-A(1og c+ l) W. G . The Occurrence of Melezitose in a Manna from the Douglas Fir. C. S. HUDSON and S. F. SHERWOOD (J. Anzer. Chem. Soc. 1918 40 1456-146O).-A sample of manna fromi.fi0 ABSTRACTS OF CIIEMICAL PAPERY. the Douglas fir yielded about 50% of pure crystalline melezitose and there is evidence that it contained sucrose and some reducing sugar probably a mixture of dextrose wit<h a smaller quantity of lzevulose. The composition of the sample of dry manna was approximately melezitme 75-83% sucrose 2.9% reducing sugars 11.5%. At present the only other known natural source of melezitose in any quantity is the Tarkestan manna (Tarandjabine) which is however considerably inferior to the Douglas fir product in point of yield. H. w. Occurrence of Allantoin in the Rhizome of Sgmphytum officinale and other Borraginaceze. ALFRED VOGL (Yhcwnz. Post. 1918 51 181-184; from Chem. Zentr. 1918 ii 36).- Large quantities of allantoin crystals in the form of monoclinic prisms are found in the rhizome of Symphytum offieinale.The author has also succeeded in identifying allantoin crystals in the sections of the rhizome and has determined their distribution in the tissue. Crystallisation in the sections is best effected by pour- ing on them alcohol containing amtic acid (ZO%) covering with a cover-glass and sealing with paraffin. The allantoin content of the rhizome of S. oficinarle varies with the time of year; it is a t a maximum from autumn to early spring a t a minimum in the height of summer. The rhizomes of S. tuberosum S. cordaturn S. caucasicum and other Bormginacea appeared to be free from allantoin possibly owing to unf avourable supply of material. H. W. Action of Ammonium Salts on Plants. I. H. G. SODERBAUY (Kungl. Landtbruks-Akad. HancElingar 1917 56 537-561 ; from Physiol. Abstr. 1918 3 351).-This paper reports experiments with small grains and potatoes grown in pots using ammonium salts as fertilisers; sodium nitrate was used in part for control purposes. The favourable influence of these salts on the total yield ranks as follows diammonium hydrogen phosphate ammonium carbonate sulphate nitratme sodium nitrate ammonium chloride. The phosphate gave a crop four times as large as an equivalent amount of the sulphate; the chloride proved very dis- advantageous. Up to a certain limit the addition of ammonium sulphate gave a progressively increased yield but when the limit had been passed there was a marked decrease. The adverse action of an excess of the salt was not the same in the case of each plant. Rye and potatoes were least sensitive in this respect and wheat and barley most so whilst oats occupied an intermediate position. Where there is neither soil acidity nor a deficiency of calcium ammonium sulphate may be used to advantage in the field as the amount applied in practice does not reach the limit where toxicity manifests itself. H. W. B.

ISSN:0368-1769    

DOI:10.1039/CA9191600055

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ii. 60 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Recovery of Perchlorate Residues &om Potassium Estimations. A. V~RTHEIM 9 (Chem. Weekblad 19 18 15 581-584. Compare A. 1917 ii 568).-The usual method for the recovery of perchloric acids is to transform all the reagent into its potassium salt which is easily purified by recrystallisatic and t o distil the mixture of this' salt with an excess of sulphuric acid in a vacuum. This method allows of recovery of only 25% of the quantity of acid originally used and moreover requires a good vacuum pump. A method has now been devised which consists of the addition of unslaked lime to the collected alcoholic filtrates filtration and washing of the precipitate with alcohol and recovery of the mixed perchlorates of calcium sodium and magnesium by distilling off the alcohol.The solid residue is warmed in a basin with sufficient 50% sodium carbonate t o convert the mixed salts completely into the sodium compound the whole filtered and the filtrate concentrated t o crystallisation point. A large excess of 40% hydrochloric acid is added the clear liquid decanted from the precipitated sodium chloride the last drops being separated on a vacuum filter and the solution of sodium perchlorate concentrated to D 1-125. A series of determinations carried out with recovered material gave uniformly higher results than duplicate tests carriedINORaANIC CHEMISTRY. ii. 61 out with pure perchloric acid. Investigation showed that the presence of sodium perchlorate in the recovered material diminishes the solubility of the potassium salt and that therefore more accurate results are obtained by using the recovered material than Appearance of Fogs in Chemical Reactions.VIKTOR ROTHNUND (Monntsh. 1918 39 571--601).-The nature of the fogs produced in certain chemical reactions has been investigated. I n the case of the fogs produced when ozone enters into reaction with a large number of reagents (particularly reducing agents) I t is shown tlhat the fog consists mainly of water in which a small quantity of the products of the reaction are dissolved. These fogs only Occur when the reducing agent is of a volatile nature and when the reaction products are soluble in water. The size of the fog particles is practically the same in a number of very different reactions.The approximate diameter as calculated from the rate of subsidence is 10-4 cm. The stability of the liquid drops in saturated water vapour is explained by the increased curvature brought about by the solution of the products of the reaction which effect a reduction of the vapour pressure. In the case of ozone and hydriodic acid a larger value is calculated for the diameter and this is explained by the formation of hydrogen peroxide. The ammonium chloride fogs the fogs from fuming acids fogs pro- duced by the action of radium emanatioii on sulphur carbon disulphide camphor and iodine as well as the electrically pro- duced and atmospheric fogs are also considered. In all cases the fog produced shows an analogous behaviour t o the ozone foes and generally ha! drops of about the same size.The Waters of the Atlantic Ocean on the Argentine Coasts. HERCULES CORTI and HECTOR H. ALVLREZ (Anal. SOC. Quim. Lilrgentiim 1918 6 108--120).-A detailed study of samples of sea-water taken under varying conditions a t different places on the Aiwntine coast. Extensive tabular staternen ts are given of chemical composition and of general and phvsico-chemical properties. The methods of Synthesis of Sufphuryl Chloride in Presence of Organic Compounds. GUIDO CUSXANO (Atti R. Accad. Lincei 1918 [v]. 27 ii 201-204).-The keto-ciueole described by the author an3 Linari (A* 1912 i 272) is similar in many of its chemical proper- ties to camnhor which it may replace in the preparation of sulphuryl chloride from sulphur dioxide and chlorine by Schulze’s method.The reaction SO? + CL = SO,C;1 is also accelerated by cyclohexanone. menthone or tetrahgdrocarvone but does not occur in presence of a-bromocamphor Reychler’s camphorsulphonic acid camphorquinone or rnonobromo- or monochloro-ketocineole (to be described elsewhere) with the halogen attached t o the methvlene contiguous to the carbonyl group; khe reaction is however by working with chemically pure perchloric acid. s. 1. L. J. F. S. analysis adopted are briefly indicated. w. s. M.ii. 62 ABSTRACTS OF CHEMICAL PAPERS. activated by introducing into the compounds just named a positive radicle for instance by transiorming the sixlphonic acid into either the amide or the anilide or camphwquinone into the monoxime or isonitrosocamphor. Pernitrosocamphor also catalyses this reaction but not the anilitlle of chlorocamphorsulphonic acid.These results are not in disagreement with the view that the catalytic action of camphor is connected with the formation a t low temperatures of one or more compounds of sulphur dioxide with camphor. T. E. P. New Method for the Synthesis of Ammonia. H. HAMPEL and R. STEINAU (Chen~. Zeit. 1918 42 594).-Metallic iron ammonium chloride and nitrogen are heated together a t 300° under 50 atmospheres pressure. The reaction proceeds according to the equation 3Fe + GNN,Cl+ 2N= 3FeC1 + 8NH,. A gaseous mixture is obtained containing up t o 99% of ammonia. The por- tion of this derived from the ammonium chloride may be allowed to react with the ferrous chloride; the ferrous hydroxide formed is reduced and the animonium chloride recovered for further use.[See further J . Soc. CAem. Im?. 1929 February.] W. P. S . Mixtures of Nitrogen Peroxide and Nitric Acid. TTILLIAM ROBERT ROUSFIELD (T. 1919 115 45-55). Oxidation Pressure Limits (A Theory of the Pressure Limit in Antoxidation). W. P. JORISSEN (Chem. Weekblnd 1918 15 705-714).-A r6sum6 of the observations and measure- ments on the lower limit of pressure in the autoxidation of phcw phorns in oxvgen and of the theories which have been advanced to account for the facts observed. The author considers the phenomenon to be a particular case of the ignition of an inflammable gas mixture (phosphorus vapour and oxygen) whenever the ratio of combustible constituent t o oxygen becomes sufficiently large the temperature in this case being sufficiently high to cause spontaneous ignition.W. S. M. The Atomic Structure of Carborundum determined by X-Rays. C. L. BURDICK and E. A. OWEN (J. Amer. Chem. Soc. 1918 40 1749-1759).-The angle between the edges of the elementary rhombohedron of carborundum which crystallises in the ditriqonal pyramidal class of the hexagonal system is 89O56*6’ the departure from the simple cube being due to a shortening by only 0*150/ of one trigonal axis of the cube. The results of the X-ray rneasiarements here recorded irsing rays from a palladium tarqet. show a very close relationship between the crvstal structure of carbornndum and t h a t of diamond. The silicon and carhon atoms in the carhoriindiim crvstal are each arrsnped on face- centred rhombohedra1 (nearlv cubic) lattices.In the mism Dlanes (lOT01 and (11%). the carhon and silicon atoms lie in the same planes from which i$ follows t h a t in the direction of the principalINORGANIC CHEMISTRY. ii. 63 axis the carbon and silicon atoms alternate there being no lateral displacement between the two kinds of atom with respect to this axis. From the relative intensities of the reflections of the spectra of different orders by the different planes the displacement of the carbon planes from the silicon planes in the direction of the prin- cipal axis is calculated to be equal t o 0-36 of the distance between two consecutive carbon o r silicoii planes. The carborundum Struc- ture can then he derived from that of the diamond by replacing the carbon atoms of one of the two iiiterpenetrating face-centred cubic lattices of the diamond by a similar lattice of silicoii atoms s?iorten- ing one trigonal axis by 0*15% and displacing the atoms of one lattice from a position 0.25 to one 0-36 of the distance between successive planes of t'he other lattice in the direction of the shortened axis.From the values Q€ the distances between the atom planes derived from the inea surements t-he demity of carborundum is calculated t o be 3-11 the observed value being 3.123. F,. H. R. Electrolysis of Potassium Phosphate. A. RIUS IT M I R ~ ( A rial. Fis. Q ~ i r n . 2918 16 573-6lQ).--The electrolytic oxida- tion of potassium phosphates is assumed to1 take place in two stages the first. being the formation of perphosphate and the second that of monoperphosphate.F o r dipotassirim hydrogen phosphate the primary reaction can be represented by the equation 2K2T-TB0 + 0 = K.%P208 + E,O. The perphosphate then undergoes fhrther oxidation to monoperphosphate H,P,O -+ 0 + H20 = 2K,RPOi. A. J. W. The Fusion of Sodium Hydroxide with some Inorganic Salts. ~IAITLAXD C. HOSWELL and J. V. DICKSOY (J. Bnzer. C7mnz. SOC. 1918 40 1773--1779).-Whea certain salts which can function as osygen acceptors are fused a t high temperatures (30O-4QO0) with sodium hydroxide trhe salt is oxidised and hydrogen evolved. Quantitative experiments have been made with sodium arsenite and ferrous sulphate and it is found that the hydropa given off is equivalent t o the oxygen taken up by the salt. Stannous chloride and vanadium srilphate are also oxidised and cerotis and uranous sulphates to a small extent.It is remark- able that such readily oxidisable salts as sodium nitrite and sodium sulphite are not oxidised when fused with sodium hydroxide. It i s perhaps noteworthr thatl all the bases the salts of which were foiind t o be oxidieed belong with the exception of iron to groups 4. 5. or 6 of the periodic table The mechanism of the reaction consists ultimatelv in the decom- position of water. the oxygen carrying the oxygen acceptor to a higher staqe of oxidation whilst the hvdrocen is evolved as gas. The general oxidisiiig action of water catalvsed bv sodium hvdr- oxide is also shown by the evolution of hydrocen when such metals as zinc and aliiminium are boiled with sodium hydroxide solution.33. H. R.ii. 64 ABSTRACTS OP CHEMICAL PAPERS. Some Properties of Magnesium Ammonium Phosphate and Magnesium Pyrophosphate. %. KARAOGLANOV and P. DIMITROV (Zeitsch. anal. Chem . 1918 57 353-371).-The con- version of magnesium ammonium phosphate into magnesium pyro- phosphate by ignition somet.imes is and sometimes is not accom- panied by incandescence. The presence or absence of the pheno- menon is found to depend on the coiiditions under which the mag- nesium ammonium phosphate is precipitated. If precipitated slowly a t the boiling temperature the productl does not incandesce but if formed quickly a t lower temperatures it invariably does whether precipitated from a magnesium solution o r from a phos- phoric acid solution. The pyrophosphate formed with incandes- cence is grey t o black in colour.whilst that formed without in- candescence is quite white. The authors conclude from their experiments that only samples of magnesium ammonium phosphate which contain traces of organic matter will incandesce on ignition. since when organic matter such as filter paper is carefully ex- cluded no incandescence is observed. There are apparently two modifications of magnesium pyrophospfiate differing considerably in physical properties. The one formed without incandescence is loose i n texture and white in colour; the other the formation of which is always accompanied by incandescence is hard and lava- like grey to black in coloixr and more resistant to hydrochloric and nitric acids. Its colour is due to enclosed particles of carbon and 4s only with difficulty removed at; a very high temperature by ignition but can be destroyed hy treatment with acids or an oxidising agent such as ammonium nitrate.The incandescence of any sample of magnesium ammonium phosphate can be prevented by evaporating it before ignition with an ammonium salt or by heating very slowly t o the decomposition temperature. The opinion of Balareff (A. 1917 ii 90) that the properties of the magnesium uyrophosphate obtained depend on the vapour tension (degree of hydration) of t'he rnagiiesimm ain~oninmn phosphate before calciii- ation is shown t o he incorrect. E. H. R. Adsorption of Metals from Drinking Water by Glass. K. SCRERINGA (Ph,arrn. TVeekblad 1919 56 8-9).-The propor- tion of lead in drinking-water can considerably diminish within a few hours.T t is known that if an aqueous magenta solution be boiled in a glass vessel the latter cannot afterwards be cleaned in the ordinary way; this absorption however does not occur i f the vessel has been previously cleaned carefully with soap and water and afterwards well rinsed out. Since then organic dyes are not adsorbed bv a cleaned glass stirface it anpears very doubtful that metallic salts should be so adsorbed. This conclusion was con- firmed bv estimating colorimetrically soltitions of various salts which had been allowed to remain f o r two days in carefiilly cleaned glass vessels. I n no case was the sliqhtest diminution of &he amount of metal in solution detected. It appears therefore that the diminution in the case of lelad is due t o chemical action eitherINORGANIC CHEMISTRY.ii. 65 by disturbance of an equilibrium when the water is removed from contact with the lead or by precipitation of finely divided lead carbon ate. s. I. L. Anhydrous Mercuric Fluoride. OTTO KUFF and GUSTAV BAHLAW (Ber. 1918 51 1752-1760).-;rLrrzhyd’?.o.us mercuric fiuorzde may be prepared by heating mercurous fluoride i n a current of dry chlorine a t 275O o r of dry bromine at 400° o r by heating mercurous fluoride at 4503 under 10 mm. pressure. Mercuric fluoride forms transparent octahedral crystals m. p. 645”; its b. p. is estimated a t 65W. *4ttempts to determine the vapour tension at; various temperatures did not yield satisfactory results since the vessels are attacked by the vapours.The sub- stance is very sensitive to moisture and becomes discoloured by traces of water vapour which are not analytically demonstrable; on exposure to air hydrogen fluoride is evolved and mercuric oxyfiuoride and ultimately mercuric oxide remain. With small quantities of water a white hydrated oxyfluoride is formed whilst with larger quantities mercuric oxide is gradu- ally produced. Mercuric fluoride dissolves in hydrofluoric acid solution (40%) and on cautious evaporation the hydrated fluoride NgF,,ZH,O is obtained in small colourless crystals. The vapours of mercuric fluoride attack platinum above 500°; mixttures of the fluoride with silver copper lead aluminium magnesium zinc tin chromium iron or arsenic react vigorously when strongly heated locally yielding amalgams and metallic fluorides tThe latter being easily isolable in the pure condition i f an excess of mercuric fluoride is used.Sulphur tetrafluoride appears t o be formed when mercuric fluoride is heated with sulphur but no reaction occurs with amorphous or graphitic carbon. The fluorine does not appear to be replaced when the fluoride is heated in a stream of chlorine ar bromine. Merczric chZoro&uoride HgClF is obtained as a pale yellow substance by passing dry chlorine over mercurous fluoride at 120°; the pale yellow bronzo$uo~ide is similarly prepared a t 105O. The preparation of mercuric flnoride in quantity is best effected by the p~ocess first described. It has D1j 8.95. Hg3E’,(OH),,3H,O H. W. Double Catalytic Process in the Oxidation of Aluminium in the Presence of Mercury.Oxidation of Aluminium Powder at the Ordinary Temperature. P. RONCERAY (BULL Sci. Pharmacol. 1918 25 193-198; from Chem. Zentr. 1918 ii 699).-AIuminium in a fine state of division is oxidised by t.he air and under watei. Pieces of aluminium in contact with iron do not oxidise in water but in the prepence of a small quantity of mercury aluminium tindergoes oxidation through the operation of two catalytic processes. The mercury owing to the formation of an amalgam reduces the aluminium t o a molecular state and the mercury oxide produced acts as an agent for the transfer ofii. 66 ABSTRACTS OF CHEMICAL PAPERS. oxygen from the air to the aluminium. Pieces of aluminium after rubbing with mercury oxide are rapidly osiciised in the air and under water.H. 177. B. Solubility of Aluminium Hydroxide. E. H. ARCHIBALD and Y. EABASIAN (Tmns. R o y . Soc. Co~nuda 1917-1918 [iii] 11 l-B).-The solubility of aluniinium hydroxide in ammonia solu- tions of different concentrations and in similar solutions t o which various amounts of animoiiiurn or potassium nitrate had been added has been determined a t 20° and 3Qo. The method consisted in shaking the freshly precipitated hydroxide in sealed tubes with the solvent for twelve hours in it thermostat filtering evaporating msasured weights of the solution in a platinum crucrble igniting and weighing. The following weights of Al(O€€) dissolve in 100 C.C. of solution of ammonia a t 20° Normality of NH,OPP 0-050 0.100 0,125 0.200 0.500 1.00.Grams of id( 0*0070 0.0080 0.0250 0.0380 0.0450 0.0240. The solubility increases theref ore with the ammonia concentra- tion t o a maximum which lies atl 0*5i’\’-ammonia and then decreases. In these experiments it is shown that the amountl of aluminium hydroxide in solution after thirty minutes’ shaking is considerably more than the above quantity but decreases as the shaking pro- ceeds until equilibrium is reached which is always achieved in less than twelve hours. The presence of ammonium nitrate de- creases the solubility of aluminium hydroxide in ammonia and the decrease is greater the higher the temperature and the concentra- tion of ammonium nitrate. The addition of potassium nitrate increases the solubility sf aluminium hydroxide to a very marked extent. It is pointed o u t that in the quantitative estimation of aluminium only a small excess of ammonia should be used and a 10% solution of ammonium nitrate should be used in the washing.J. F. S. Relation between Molecular Structure and the Activity towards Hydrogen Sulphide of Oxide of Iron. G. WEYMAN ( J . Soz. Chertt. Ind. 1918 37 333-336~).-Iron oxides obtained by heating a t looo to 650” are equally active as regards absorption of hydrogen sulphide in the cold but at 750° a change occurs which may also be effected a t lower temperatlures by very pro- longed heating. It seems t.hat the activity of the oxide is dependent primarily on molecular structure and not on any par- ticular degree of hydration but the oxide is derived in almost all cases from some form of hydrate.w. P. s. Chro niatscobaltiamrnines . SANUEL HENRP CLIFFORD BRIUGS (T. 1919 1’15 67-76). The Evolution and Oxidation of Chromic Hydroxide in Alkaline Solution. F. BOURION and A. S h h r A L (Compt. rend. 1919 168 59-62) .-An alkaline solution of chromic hydroxideINORGANIC CHEMISTRY. ii. 67 undergoes a change an keeping which tends to make it lose its chemical activity particularly in respect to its powers of reducing hydrogen peroxide. This change is the more rapid as the coil- centration of the chromium is greater and of the alkali is smaller. It is however possible to oxidise 97"/; of the chromium in chrome alum to chromate by adding sodium hydroxide t o the solut.ion of the alum containing four times the calculated quantity of hydrogen peroxide and then immediately destroying the excess of peroxide by shaking the solution with manganese dioxide.W. G. The Crystalline Structure of Grey Tin. A. J. BIJL and N. H. KOLKMEIJER (Chent. Weekblad 1918 15 1264).-A pre- liminary note on the crystalline structure of grey tin. The authors have shown that the crystals belong to the regular system. w. s. M. Bismuth Hydride and Polonium Hydride. FRITZ YAXETH (Bey. 1918 51 1704-1728).-By application of the methods used in the study of radioactive substances the author has succeeded in demonstrating that bismuth forms a gaseous hydride which possesses considerable stability a t the ordinary temperature and is not decomposed with much greater readiness than antimony hydride ; with increasing temperature the substance rapidly becomes less stable and is decomposed into its elements at a red heat.The gas can be almost completely condensed by the use of liquid air and subsequently in part regasified. Bismuth hydride is obtained by the solut-ion of an alloy of magnesium with thorium-C or radium4 in O*ZA'-hydrochloric or sulphuric acid. The alloy is prepared by exposing magnesium foil to the radiations of a radiothorium preparation contained in B glass capsule covered with silk paper which is impermeable to tihorium-X; shortly after its remo'val in consequence of the rapid fiecay of thorium emanation and thorium-A the deposit! consists 3ntirely of thorium-B and thorium-I:. The alloy is placed in a weighing bottle connected with an electroscope in such a manner ,hat a regular current of nitrogen can be sent through the tpparatus.After determination of the natural leak of the electro- icope O.2N-hydrochloric acid is dropped on to thel alloy; the !lectroscope. soon indicates an activity which becomes feebler after L few minutes. The results of this and similar experiments show when magnesium superficially alloyed with bismuth and lead s dissolved in dilute hydrochloric acid a few thousandths of the tismuth are converted into such a state that. they can be carried by a gas current through a cotton wool filter and that a similar eaction does not occur with lead. A series of controi experiments hows that the observed effects are actually due to a volatile cam- ound of bismuth and not for example to the liberation of horium-17 t o the selective action of the filter .or t o the relatively reater volatility of thorium-C chloride.The alloy Polonium hydride is prepared in a similar manner.ii. 68 ABSTRACTS OF CHEMICAL PAYERS. of magnesium and polonium is prepared by the electrolysis af a feebly acid solution of polonium chloride a piece of magnesium foil being used as cathode. When the alloy is dissolved i n dilute acid and the gases evolved are led into an electroscope an activation is observed which does notl decrease-in the course of a day and therefore is caused by polonium. The gas closely resembles bismuth hydride. It is remarkable that a current of oxygen can be used instead of hydrogen or nitrogen for t-he transport of the gas with- out sensibly diminishing the yield. The latter is less than in t,he case of bismuth hydride and up t o the present it has not been found possible to convert more than a few tenths’ part per thousand of tahe polonium into the gaseous state.If the gas current is cooled to -&Lo the polonium hydride is only partly condensed. The investigation of the gas is rendered very tedious since in each experiment the electroscope becomes permanently damaged and does not recover when left to itself for a time. H. W. Bismuth Hydride 11. FRITZ PANETH aad EBICH WINTERNITZ (Bey. 1918 51 1738-1743).-The application of radioactive methods having shown that bismuth hydride is capable of exist- ence and having indicated its mode of preparation and general properties (preceding abstract) the authors now describe attempts to prepare it in weighable quantity from non-radioactive material. Yhe requisite bismuth-magnesium alloy is prepared by heating equal weights of powdered bismut.h and magnesium (as free from silicon as possible) in an iron crucible i n a rapid stream oE dry hydrogen.The alloy is dissolved in approximately 4N-hydro- chloric or sulphuric acid (or in some cases nitric acid). Bismuth hydride is thus obtained in sufficient quantity to permit its detec- tion either by the formation of a bi$mut;h mirror or by luminescence tests. The bismuth mirror is obtained in the usual Marsh’s apparatus and very closely resembles t-he antimony mirror- As generally obtained it consists of a strong brown ring in front of and a fainter ring behind the heated spot. The former deposit appears to be frequently burnt into the glass and to be unsuitable for furbher experiments.This drawback can be overcome by placing a pierced clay disk on the tube and allowing t-he flame t o play against this as also by increasing the velocity of the gas current. The antimony arsenic and bismuth mirrors are most readily dis- tinguished by a number of chemical tests involving the use of sodium hypochlorite yellow ammonium sulphide hydrogen sulphide etc. which are fully described in the original. Attempts to estimate the yield of bismuth hydride by weighing the bismuth mirrors show that about 5 x 10-5 of the bismuth used is converted into the hydride or that the yield is only about one-twentieth of that obtained from thorium*. It should be noted however in this cannexion that circumstances have prevented the aukhors from determining the optimum conditions of experimenting.The authors have also applied Donau’s luminescence method (A,,INORUA31C CHEMISTRY. ii. fir! 1913 ii 743) to the ctetectioii of traces of bjsnluth aiid find the procedure very rapid and so sensitive that i t is rapable of proving tlis preseuce of traces of bismuth which cannot lie detected by the ring test. For this purpose the gases issuing from the Marsh's apparatus are ignited and a piece of pure calciunt carlwiiate is held 011 a plat,inum loop in the flame; the bismuth hydride i h clecoiiiposed and a poi-tion of the bismuth is deposited 011 the lime. The latter is alloxed to cool and then placed at the edge of the hydrogen flame wheii the preseiice of bismut,h is betrayed by the cornflower-blue luminesceme; in similar c ~ ~ - c u ~ ~ s ~ ~ I I c ~ s mtirnony is readily detected by a sky-blue lumiiiescence.Itot,h colora t.ioii5 being readily visible in bright daylight. The absorption of bismuth hydride by various reagents has bseii euamiiiecl ; t.he most suitable solutioii for this purpose appears Lo lie 0'4T-silver nitrate solution. Water absorbs the gas to some degree and 4AT-sulphuvic acid to about the same extent. O*S.T-Soc'iuin carbonate solution aiid -7'-potassium hydroxide 501~- tioii are more active whilst the gas is also absorbed by desiccating agents such as caleirim chloride or soda-lime. It is completely decomposed by concentrated sulphuric acid. An aqueous solution of hydrogen siilphide is not niore efficient than pure water.TI. w. Gold Amalgams. 3. PARRAVASO (Atti I t . Accud. L ~ ~ L c c ~ 1918 [v] 27 ii 168- -1'70; GoTxtta 1918 48 ii 123-128).- - Objections are raised to the argumeiit of Guertler (2ifetallogrophir 524) who concludes that mercury dissolves in gold giving origin t o a solid solution containing at inost about 10% of gold and that in the amalgams containiiig 90-Oo/ of gold no other crystalline individual is formed. The author has made the following experi- ments ( I ) Definite quantities of saturated *amalgam aiid of gold are placed in a vessel and the latter exhausted; distillation of the mercury on t o the gold then proceeds until the composit.ion of the amalgam formed reaches that of the solid in equilibrium with the liquid amalgam. (2) A current of hvdrogen is passed over the amalgam the quantity of mercury thus trailsported will be a fuiictioii of the t,eiision of the mercury of the amalgam provided that in any series of experiments the form of the apparatus and f lie velocity and duration of the gaseons current are maintained constant.The resuIts show that gold amalgams contain a t least the two compoiinds An,€€g? and Aii;Flg. T. FT. P. Amalg&ns. I. Colloidal Gold Amalgam. C. PAAL :mtl HERMANN XTEI'CTL (1<07loid Zcit,~ch . 1918 23 145- -3 58).-Hydro- sole. of gold amalgam have been prepared (1) by shaking gold sols with metaIlic mercury. (2) by allowing a gold sol t o remain in con- tact wit% metalIic mercury a t rest (3) bv mixing solutions of gold hydrosol with merciiry hy-drosol and (4) by precipitating both gold and inercixv from a solrition of the mixed chlorides i n the presenct. of a protecting colloid.I n the last-named case amalgam 'hydrosols VOL. cxvr. ii 3i. 7 0 ABSTRACTS OB CHEMICAL 1'Al'EES. of the coinpositioii represented by the €orniulze A~i,€lg aiid Au,tIg were prepared by reducing a iiiixtiir-e of suit'able concentration of the two chlorides in alkaline solution by hydraziiie in the presence of the sodinin salts of protalbic aiicl lysalbic acidh. The solutions after dialysis were evaporated to dryness ill a vacuum a i d gave brittle substances which possessed a black or greenish-black colour and a. ruetallic lustre. These substances readily dissolved in water with the production of colloidal solutiotis. The stability coin- positioii and general properties of the hydrosols varied with the niethod of preparation.J. F. S. Solubilities of Ammonium Platinichloride Platini- bromide and Iridichloride and the Separation of Platinum and Iridium. E. H. ARCHIBALD a d JOHN W. KERX (Trans. K o y . iSoc. ~ ' ~ i / ~ ~ l u 1917-- 1918 [iii] 11 '7- -16).-The solubility of the aiiirrioniuni salts of chloroplatinic bronioplatinic aiicl chloro- iridie acids has beeii cletermitied a t a series of temperatures in water aiid in solutions of various strengths of amnionium chloride and aniinoiiurn bromide. It is shown that 100 grams of water dis- solve 0.2902 gram of aiiiiiioiiiurri platiiiichloride a t 0*lo 0.3653 grain at 7 . 2 O . 0.4869 grarii a t 18'0° 0-5761) gram a t 25*4O 0.6370 gram a t 2 9 * 9 O 0.7870 gram a t 3 8 * 9 O 1.0131 graiiis at 4 9 .7 O . 1.4740 grams a t GO.2O l*744ff granis a t 70*0° 2.1800 grams a t $ 0 * 2 O 2.6150 grams a t 90.0° and 3.2515 g r a m a t 99O. AinmoniLuri platiiiibroinicle is somewhat rtiore soluble in water than the fore- going salt; 100 grams of water dirsolve 0.4165 gram a t O*:'O 0.5002 graizi a t 7.3O. 0.6438 orair1 a t 19.0° 0.7384 gram a t 25*0" 0.8147 gram a t %.To 1.03& granis a t 40*0" 1.2087 grains a t ZOO 1.5780 grarits a t 60*0° 1.9'365 grams a t 70-O0 2.3002 grams a t 80.0° 2.8370 grams a t 9O0 and 3,5866 grams a t 9 9 O . Arnrrioiiittm iridiuhloride is much more solriltle than either of the platinurn coiiipounds ; 100 grariis of water dissolve 0.5661 firmi at 0*2O 0.7055 grain a t 10*Oo. 1.0910 grams a t 25.O0 1-2066 grams at 30*Oo 1.5665 grams a t 40.0° 1.9664 grain.a t 50*Oo 3.4567 qarris a t 60-Oo and 4.3815 grarris a t 80*0*. In the presence of arii~iioiiiurti chloride the solubility of the ammoiiiuin salts of chloro- platinic acid aiid chloroiridic acid is much reduced but that of the iiyidichloride is several times as large as that of the platinichloride. Ammonium bromide reduces the solubility of the platinibroinide. In all three cases the reduction in the solubility is proportioiiaI t o the concentration of the ammoilium haloid. The differeuce in the solubility of aniinoniuiti platiiiicWoride arid iridichloride furnishes a good method for the complete separation of plat inurn and iridium. Ammotiiiim platiiiichloride i? appreciably less soluble than 1 )o t a ssi u m plat i 11 ichl or i d e . J. F. 8. Dehydrogenation of Palladium Hydrogen Hydrosol by Metallic and Colloidal Mercury. C. PAAL ttntl HERMANN STEYEB (Her. 1918 51 1743--1752).-Tt has beeii previously shown (Paal and Nartmanri. A . 1918 ii 303) that palladiumMIPr’ERALOGICAL OHEMISTRY. ii. 71 hydrosol gradually loses its catalytic activity in the presence of irtetallic or colloidal mercury; in the course of experiment,s on the action of the hydrosol on mixtures of hydrogen and oxygen in the presence of mercury it was observed that the catalyst speedily hecame passive and thatq the gradual slight absorption of hydrogen was preceded by a temporary increase in the volume of the latter. ‘Phis phenomenon forms the subject of the present communication i f 1 which i t is demonstrated that the palladium hydrogen hydrosol i.; decomposed by mercury with evolution of hydrogen and that tlehydrogenation is effected more rapidly by metallic than by volloidal mercury. Analysis of the residual palladium hydrosol and of the mercury proves that a portion of the palladium has passed into the mercury and that some of the latter has passed into the hydrosol. The action of colloidal mercury on palladium hydrogen hydrosol only leads to uniform results when care is taken that only the least possible excess of hydrazino is used as reducing agent ill the formation of the mercury hydrosol. H. W.

ISSN:0368-1769    

DOI:10.1039/CA9191605060

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

i. 61 Organic Chemistry. Methane. WILLIAM MALISOFF and GL'STAV EGLOFF (J. PhYsicaZ C'hem. 1918 22 529-575).--A summary is given of the work which has been published from all sources on the physical and chemical properties of methane and a number of important problems requiring investigation are enumerated. [See J . Soc. Chena. Id. 1919 35A.l E. H. R. Organic Chemical Reagents. 11. Amylene. tert.-Amy1 Alconol. KOCER ADAMS 0. KAUX and 0. S. MARVEL (J. Arum. Chem. Soc. 1918 40 1950-1955).-Dehydration of p h a r y alcohols by sulphuric acid generally proceeds less satisfactorily as the molecular weight of the alcohol increases. Amylene may how- ever be satisf actonly obtained from commercial amyl alcohol under the following conditions. Amy1 alcohol (1 -5 litres) and concen- trated sulphuric acid (100 c.G.) are heated to vigorous boiling under a reflux condenser in which the water is maintained a t such a tkmperature (60-90°) as t o allow a considerable amount of vapour to distil out of the apparatus; the top of the condenser is con- nected with a second eiliciently cooled condenser attached so as to permit downward distillation.The heating requires a maximum time of about eight hours. At first water and amyl alcohol pass over whilst subsequently amylene distils. The distillate is washed with sodium. hydroxide to remove sulphur dioxide and the amylene isolated by fractionation. It appears to consist of P-methyl-&- butylene and /3-methyl-Afi-butylene containing only a negligible amount of y-methyl-Aa-butylene. The residue in the original flask contains amyl alcohol and isoamyl ether which are recovered by distillation with steam and subsequent fractionation.*4bo.ut 250 C.C. of amylene 400 C.C. of istlarnyl ether and 500 C.C. of amyl alcohol are obtained from 1500 C.C. of the latter. Larger amounts of amylene are more conveniently obtained by the pyrogenic-catalytic method using aluminium oxide as catalyst a t 500-540O. A suitable electrically heated furnace is fully described. The general procedure is similar to that indicated by Ipatieff (A.y 1903 i 593). The yield of amylene is 70--80% of the theoretical and the product* is about 98-99% pentene. The catalyst retains its activity over lengt-hy periods. tert-Amy1 alcohol is prepared by the gradual addition of amylene to a mixture of concentrated sulphuric acid and ice.The product is diluted with ice-water (after removal of any unchanged amylene) rendered alkaline with sodium hydroxide and distilled. 275-300 Grams of a product b. p. 100-103° may be obtained from 325 grams of amylene. H. W Geometrical Isomerism. A. E. LACOMBL~B (Chem. ~ ~ e e ~ ~ l 1918 15 605-610) .-The inconsistencies which are introduced VOL. CXVI. i. 1i. 62 ABSTRACTS OF CIIERT1CA.L PAPEBS. by the attempts to explain the existence of the cis- and $ranis- isomerides of ethylenic compounds of the type (A,B)C = C(A,B) by the theories of Werner and Stark are pointed out. All such theories set out to explain how the existence of the double bond prevents free rotation of the two doubly-linked carbon atoms about the line joining their centres.The explanations of Werner and of Stark are shown t o be inconsistent with the hypotheses which they put forward as to the nature of the atoms and the mechanism by which the atoms are linked together. The author points out that it is hopeless to attemptl to base an hypothesis of the structure of the benzene ring for example 011 theories which are inadequate to Derivatives of Trihalogeno-tert.-butyl Alcohols. 11. The Propionic and Butyric Esters of Tribromo-teyt,-butyl Alcohol (Brometorae). T. B. ALDRICH ( J . Anze~. Clzem. SOL 1918 40 1948-1950. Compare Aldrich and Beckwith A. 1917 i 77) .-&Tribromomethylpropan-&oI is converted into the corre- sponding prop'oiznte white crystals in. p. 2 7 O by the action of propionyl chloride. The similarly prepared hiityrate is an oil b.p. 144-l45O/I 3 - 4 4 inni. Both are comparatively inactive phar~nacologically due probably to their notI being decomposed into soluble constituents having a typical physiological action and are rather slowly absorbed. Glyceryl Methyl Ether Dinitrate (a-Methylin Dinitrate). DAVID TREVOR JONES (T. 1919 115 76-81). The Action of Sodium Hydroxide on Carbon Monoxide Sodium Formate and Sodium Oxalate. MAITLAND C . BOSWELL and J. V. DICKSON (J. ilmer. CThem. Scre. 1918 40 1779-1786).-It has been shown (this vol. ii 63) that; fused sodium oxide is very active in effecting oxidations. It is now demonstrated that a t 410-430° carbon monoxide in contact with fused sodium hydroxide is oxidised t o carbon dioxide an equi- valent amount of hydrogen being produced a t the same time.Sodium forniate when fused with sodium hydroxide at 2 7 5 O a temperature much below its decomposition temperature is oxidised almost quantitatively t o carbon dioxide in a very short time an equivalent amount. of hydrogen also being formed. Sodium oxalate is similarly oxidised a t B O O . ln both these cases it is the water present in the fusion cat~alysed by the sodium hydroxide which is the effective oxidising agent. It is held that the general reaction involving the replacement of the carboxyl group by hydrogen in alkali fusions for example in the formation of benzene from sodium benzoate involves simultaneous oxidation and reduction by the oxygen and hydrogen of water. [See also J . SOC Chem. znd. 1919 February.] E.H. R. PAUL PFEIFFER and THEODOR B~TTLER (Ber. 1918 51 1819-1829. Compare Pratt and Perkins A 1918 i 167).-Maleic anhydride is related explain the mechanism of t,he double bond. s. I. L. H. W. Quinonoid Character of Maleic Anhydride.ORGaMC CHEMXSTRY. i. 63 Go furan in the same manner as quinone t o benzene; it may there- fore be regarded as a quinone of furan and in the present com- munication evidence is adduced to show that the formal analogy is reproduced in its properties. A characteristic property of quinones is their ability to yield more o r deeply coloured molecular compounds with aromatic hydro- carbons amines phenols and phenol ethers (A. 1914 i 551; 1917 i 205); this property is shared by maleic anhydride which although yielding colourless solutions in benzene toluene or m-xylene gives coloured solutions with durene hexamethylbenzene naphthalene 2 4 5 2' 4' 5/-hexamethylstilbene 0-tolyl methyl ether and quinol and dimethylaniline.The influence of sub- st'ituent~s in the molecule of the solute and solvent respectively is similar in hhe cases of p-benzoquinone and of maleic anhydride. Thus methylation in the quinone molecule exerts a hypsochromic netion on the colour of the quinhydrone; similarly solutions of citraconic anhydride are less intensely eoloured than corresponding solutions of maleic anhydride. Methylation in the benzenoid com- ponent produces a deepening of colour in the cases of p-benzo- quinone and 05 maleic anhydride. The introduction of an ortho- condensed benzene nucleus has a similar influence in each instance as is proved by the comparison of a-naphthaquinone with pbenzo- quinone on the one hand and of phthalic anhydride with maleic anhydride on the other.The deepening in colour caused by ths introduction of halogen atoms into the quinone molecule is remark- ably characteristic; the same effect is produced in the anhydrides as proved by examination of bromomaleic dibromomaleic and tetrachlorophthalic anhydrides. Attempts to isolate the additive compounds of maleic anhydride or its bromo- or methyl derivatives in the crystalline state were not successful but similar substances were readily obtained from tetrachlorophthalic anhydride and durene (long pale yellow needles) and hexamethylstilbene (orange- coloured shining feaflets m. p. 183-184") respectively.The effect of alteration in the structure of the anhydride has also been investigated. Succinic anhydride yields colourless solu- tions in all the media mentioned above whilst the solutions of itaconic anhydride are much less deeply mloured than those of citraconic anhydride. When dissohed in dimethylaniline it aconic anhydride is gradually isomerised to citraconic anhydride. On passing from the anhydride to the corresponding acid or its esters the quinonoid character is largely 1mt and the solutions are colsur- less or less intensely coloured as is shown a t the instances of maleic and dibromomaleic acids of methyl fumarate and of methyl tetra- chlorophthalate. The substance CO,H*CBr:CBr*CHO scarcely possesses any quinonoid characteristics but these are more marked with transdibenzoylethylene.y-Pyrone and the ketones of the distvryl ketone series are less nearly related to quinone than is maleic anhydride ; the former yields completely colourless solutions whilst those of the latter only show faint colorations. It was t o be expected that h i d e s of the type sf maleinhide d 2i. 64 ABSTRACTS OF CHEMICAL PAPERS. would also show quinonoid characteristics; this is actually the case but solutions of citraconanil and tetrachlorophthalimide are less deeply coioured than those of citraconic and tetrachlorophthalic anhydrides. Maleic citraconic phthalic and tetrachlorophthalic anhydrides do not exhibit halochromic phenomena when treated with concen- trated sulphuric acid trichloroacetic acid or tin tetrabromide.Further investigation of this problem has led to the conclusion that the carbonyl groups of the substances which yield quin- hydrones and of typical halochromic compounds must differ markedly in t'heir chemical nature. H. W. Oxidation of Organic Compounds by Silver Oxide. ROBERT BEIIREND and KARL DREYEH (dmnaterh 1918 416 203-225).-1t has long been known that many acids and alcohols are oxidised by silver oxide but hitherto a systematic investigation 'has not been made of the relation between the constitutions of substances and their tendency to oxidation or of the nature and quantity of the products of oxidation. The present paper deals with these points in the case of the simpler hydroxylic aliphatic compounds. In order that it substance may be oxidised by silver oxide in alkali hydroxide or ammoniacal solution it mustl contain a ;CH*OH (or CO or C[0HJ2) group combined with two *CH,*OH two :CH*OH or two *C02H groups? or with any two of these three groups.Tartronic tartaric dihydroxytartaric glyceric mucic saccharic and gluconic acids dextrose glycerol and mannitol are thus oxidised. For oxidation in neutral or acid solution it suffices that the :CH*OH group shall be combined with a carboxyl group and also with H CH or CH,. Glycollic lactic malic (and also formic) acids are thus oxidised. Propylene glycol ethyl alcohol isopropyl alcohol and oxalic acid suffer little or no oxidation. In alkali hydroxide solution substances of the group first mentioned are oxidised rapidly and completely; the rate of oxidation is accelerated but the relative quantities of the products of oxida- tion are unaffected by an increased concentration of the alkali hydroxide.In ammoniacal solution silver oxide oxidises the alkali salts of the acids completely in fifty minutes a t 90°. The acids are more easily oxidised in the form of alkali salts than in the form of ammonium salts. An excess of ammonia or of ammonium salt retards the oxidation. The products of oxidation in alkaline solution contain at most two atoms of carbon and are never obtained in simple molecular proportions. All the substances with the exception of glycerol yield carbon dioxide as one of the products of oxidation in acid or in alkaline solution. Formic acid is a product of oxidation in alkaline solution and then only if the oxidisable substance con- tains a :CH*OH group united with a :CE€-OH or *CH,*OH group as well as with a :CH*OR *CH,.OR or *CO,H group.Formic acid may be an intermediate producb of oxidation in acid solution but in such circumstances it undergoes further oxidation. Oxalicacid is almost always the chief product of oxidation in alkaline solution; in neutral or acid solution it is formed in much smaller quantity. I n neutral solution malic acid yields malonic acid and lactic acid and propylene glycol yield acetic acid. Tastronic Acid. ROBERT BEHRERD and AUUUST PRO WE (Annuten 1918 416 233-339),-Tartronic ,acid has been pre- pared by eleven investigators who record eight different m. p . ' ~ between 1 4 5 O and 1 8 5 O . The correct value appears to be 156-158O Preparation of Gulonolactone. F.B. LA FORCE ( J . Bid. Chem. 1918 36 34?-349).-To a solution of 150 grams of xylose in 300 C.C. of water 30 grams of hydrocyanic acid are added and then a few drops of ammonium hydroxide. The reaction com- mences a t once and is completed in about six hours a t 3 5 O . Slightly more than one equivalent (55 ,;rams) of sulphuric acid diluted with a small amount. of water is added t o the solution which is then concentrated a t once to a viscous syrup. Hydrolysis of the nitrile takes place and on cooling and keeping the lactone crystal'lises out. The yield after recrvstallisation from 60% alcohol amounts to 55 to 60% of the weight of xylose used. Crystallography and Optical Properties of Three Aldopentoses. EDGAR T. WHERRY (J.Amer. Chem.. Soc. 1918 40 1852-1858).-The optical properties of the crystals of the three sugars a-d-lyxose a-d-xylose and B-d-arabinose enable them to be readily distinguished and a determinative table is given for this purpose For the determination of the refractive indices by the immersion method suitable mixtares of turpentine oil (n 1-47) clove oil (n 1-53) and ~-bromonaphthalene (n 1.66) are used. ad-lgxose forms monoclinic probably sphenoidal crystals n b c= 1.608 1 1.828 ; B = 62O1Of mean refractive index n 1.541 ; D20 1.545 molecular refraction M 30.60. a-d-Xylose. rod-shaped monoclinic probablv sphenoidal crystals a h :c=l*655:1:1.776; B=62O55'; n 1.536; D20 1.525; M 30.67. P-J-Arahinuse rhombic. Drohahly Fphenoidal needles a b c= 1*497:1 :0*738; TL 1.568; Dm 1.605; M 30.61.Lvxoss and xvlose a re obviously very closely related crostallo- graphically and B-arahinnse although crystalliFing in a different svstem from the others shows dsselv similar inter-facial angles and the three stiPars form an essentially isomorphous group. The molecular refractivities Rre all slirht1-y lower than that calcnlated from the atomic refract9ivities. 31.2. The diverqence is nrobably due to some peculiarity of molecular configuration. Tetramethylammonium Azide. FRANK V. FRIEDLANDER ( J . A mer Chem. Soc. 1918 40 1945-1947).-Tetrarn(~~~~- nmmoni?tm azide NMe,N is prepared by the gradual addi- tion of a sohition of tetramethylammonium iodide to an aqueous suspension of a slight excess of silver azide The eryshls belong to the tetragmal system (ca:c=l :0*7245).It) is a fairly 6. S. (d ecomp.). c. s. F€. W. B. E. R. R.i. 66 ABSTRACTS OF CHEMICAL PAPERS stable substance which does not explode when struck with a hammer when ground in a mortar or when dropped on a hot plate; the dry salt begins to decompose a t about 1 2 5 O . Attempts t o transform it into the isomeric tetrarnethyltetrazons NM+*N:N*NM% have been unsuccessful up to the present. H. W. Glycosine. ROBERT BEHREND and HERMANN KOLLN (A?z?znle?t 1918 496 230-233).--ln addition to glyoxaline very small quantities of glycosina are obtained by the action of ammonia on glyoxal. The yield of glycosine is considerably increased by the following procedure. In a tall cylinder are placed 20 C.C. of nitric acid D 2.4 containing ten to fifteen drops of fuming nitric acid 25 C.C.of water and 25 C.C. of paraldehyde the three liquids being introduced with as lit,kle intermixture as possible. The cylinder is immersed in water the level of which is higher thau that of the liquids in the cylinder. When the liquids have iuter- mixed after some days and the evolution of gas has ceased the mixture is repeatedly evaporated with wat'er to remove volatile acids as completely as possible and the residual syrup is diluted to 50 C.C. with water producing an approximately 20% solution of glyoxal. One-half of this solution is evaporated until the tempera- ture is 120° 25-30 grams of ammonium acetatle which has been heated a t this temperature are gradually added the resulting brownish-black liquid is dried a t 100-llOo and treated with water.The black residue of crude glycosine is dried in air and then at 70° dissolved in warm 35% hvdrochloric acid (which is added drop by drop) the solution is diluted with water boiled with animal charcoal (free from iron) filtered after keeping for twenty-four hours in the warm the brown filtrate is boiled again with animal charcoal? and the colourless filtrate is neutralised by ammonia whereby &cosine is obtained in 42.576 yisld. A modification of Pinner's method of preparing trichlorolactic acid from chloral is described. @. s. P-Aminoethyl Alcohol and its Derivatives. SIGMUND FRXNKEL and MARTEA CORNELIUS (Ber. 1918 51 1654-1662).- The following derivatives have been prepared to facilitate the identifi- cation of the amino-alcohol.NHBz*CH,*CH,-OH prepared by boiling an alcoholic solution of the dibenzoyl deriv- ative with t*he quantity of solid potassium hydroxide calculated t o eliminate one benzoyl group forms colourless leaflets m. 13. 66-67O. j3-A cetylaminoet hyt acetate NHAc*CH,*CH,-OAc b. p. 103O /0.049 mm. is obtained by boiling j3-arninoethyl alcohol with acetic anhydride. &A cetylaminoethyl alcohol prepared from the amino-alcohol and acetvl chloride at< Oo f o m s co'Iourless needles m. p. 63-65O. 13-Nn7?htt7talenes?rl.13hon?~lami?toethyl crlcoho! C,,R[,*SO,*NH*CHT,*CH~*OH asbestos-like crystals m. p. 86-87O is obtained by adding A7-sodium hydroxide to an ethereal solution B-Benxo?/lamiizoet~~~~ alcohol,ORGANIC CHEMISTRY. i. 07 of P-naphthalenesulphonyl chloride (2 mols.) and p-arninoethyl alcohol (1 mol.) and subsequently acidifying the aqueous solution.P-m-Nitro b enzoylamimoet hyl m-nitro b enzoate NO2*C,H4=CO *NH*CH,.CH,*O*CO*C,€I-I4.NO colourless needles m. p 152-153O obtained by heating &amino- ethyl alcohol (1 mol.) and m-nitrobenzoyl chloride on the water- bath is reduced by the calculated quantity of tin and hydrochlorio acid to @-m-aminobenzoyZarninoethyl m-aminobenzoate hydro- chloride C,,H,,0,N3,2HC1 crystals m. p. 232O. P-p-NitrobenzoyZ- anzinoethyl p-nitrobenxoate yellow needles m. p. 188-189O) and fl-p-amin obenzoylaminoethyl p-aminob enzoate crystals m. p. 206O are obtained by similar methods. P-Phenylcarbamidoethyl phenyl- carbamate NHPh*COgNH*CM,*CH,*O*CO*NNPh colourless crystals m. p. 19O-19lo is obtained by adding phenylcarbimide drop by drop to cold P-aminoethyl alcohol and then heating the mixture in a sealed tube a t looo.fLBmirzoethyl hydrogem stdphate NH,*CH,*CH,*O*SO,H colourless crystals m. p. 230° is obtained from the amino-alcohol and fuming sulphuric acid in a freezing mixture. /3-Glycylaminoet hyl glycine NH,*CH,*CO*NH*CH,*CH,.O.CO.CH,.NFI obtained by adding chloroacetyl chloride (2 mols.) t o a chloroform solution of 6-aminoethyl alcohol (1 mol.) a t Oo in the presence of lead carbonate warming the mixture for a nionient on the water- bath and after the cessation of the reaction and evaporation of the chloroform treating the residual yellow syrup with ccmcen- trated aqueous ammonia is a yellow syrup which is converted by the Schotten-Baumann method into P-hipprvlaminoethyt hippurat e NHBz*@H,=CO*NR* CH,*CH,*O*CO * CH,*NHBz colour- less leaflets.m. x). 144O. 7 m. p 88-90° is obtained by the prolonged action of carbony1 chloride on P-aminoet'hyl alcohol in chloroform solution in the presence of lead carbonate FAminoethyl alcohol in very dilute solution responds t o the iodoform test. By treating an aqueous solution of the aminor alcohol with sodium nitrite and Ehrlich's reagent (2% alcoholic p-dimethylaminobenzaldehyde and dilute hydrochloric acid) an intense canary-yellow coloration is produced which is notl destroyed by warming or by the addition of aqueous ammonia or potassium hydroxide. @-Benzoylaminoethyl alcohol ~-n2-aminobenzoylaminoetihyl ?it-aminobeuzoate hydrochloride and P-p-aniiiiobenzoylaminoethyl 12-aminobenzoate are not anzesthetics.P-Hydroxytrimethylenediglycine . HUGO KRAUSE (Ber. 1918 51 1556-1571. Compare A. 1918 i 156 337).-&Hydr- oxytrimethylenediglycine has D :j 1-348 by the swimming method. I t s solution in formalin or water produces on a pine shaving a greenish-yellow but not very intense coloratioii ; the reaction may c. s.i. 68 ABSTRACTS OF CHEMICAL PAPERS. be used as a sensitive method of detecting glycine. The colora- tion is destroyed by alkali hydroxide or carbonate and by ammonia. Esters of P-hydroxytrimethylenediglycine are obtained by the action of aqueous sodium hydroxide on a solution of the glycine ester hydrochloride in formalin. OH*CH(CH,*NH*CH,*CO,Me) a viscous colourless liquid still containing 10% of formaldehyde DI5 1-18 is obtained in only 19% yield but the ethyl ester is more readily obtained. When pure it has b.p. 140-150°/16 mm. (partial decomp.) D15 1.150 and a molecular weight in benzene or naphthalene corresponding with its formula. It is comparatively stable towards sodium hydroxide but is decomposed quantitatively by cold dilute hydrochloric acid yielding methyl alcohol form- aldehyde and ethyl glycine hydrochloride. When the ethyl ester (84% purity) is heated a t 16-18 mm. the distillate apart from formaldehyde and unchanged ester consists of a pale yellow oil b. p. 200°/16 mm. which appears to be ethyl ?nethylenaegZycine CH,:N*CH,*CO,Et or ethyl ethyleriedigly&ne C,H,(NH*CH,*C0,Et)2 more probably the former. I n the expectation of preparing the amide ethyl B-hydroxytri- rnethylenediglycine was heated with alcoholic ammonia a t 68-70° for twenty-four hours but the chief product was a substaace C,,H2,0,N3 which may have the formula NH:C( CH,*NH-CH,*CO,Et) The silver salt C3H60,NAg previously described (loc.cit .) can also be prepared by dissolving glycine in 30% formaldehyde solution in the cold neutralising this solution immediately with 4X-potassium hydroxide (phenolphthalein as indicator) and add- ing 20% silver nitrate solution. It is decomposed in aqueous suspension by hydrogen sulphide yielding formaldehyde and glycine. The acid corresponding with the silver salt is therefore probably AT-hydroxymethylgl ycine OH*CH,*NR CB,* C0,E. The methyl ester c. s. Comparisons and SimiIarities Water and Ammonia.G. CIAMICXAN (Atti R . Accad. Lincei 1918 [v] 27 ii 141-146). -Attention is directed to the chemical analogy between OH and NH3 between =OH and *NH and between :O and :NH (compare Angeli A. 1910 ii 844 948; 1915 i 847). Such analogy is clearly shown in the relation between C:O and C:NH the ready oxidation of cyanides to cyanates corresponding with that of carbon monoxide t o carbon dioxide and the reduction by zinc of cyanic acid with that of carbon dioxide. These relations are further rendered evident by the following. series of equations CO + H,O = CO(OR),; CO,+NH,=OH*CO*NH,; 0:C:NR +NR,=CO(NH,),; C(:NH) + H,O = CO(NH,) ; C(:NH) + ROH= OR*C(:NH)*NH ; C(:NH) + NH,= NH:C(NH,),. The polymerisation of cvanamide t o dicyanodiamide corresponds with the synthesis of guanidine and its derivatives the two tautomeric forms of cyanamide being reparded as reacting C(:NH) + C3T.NET = N€€,*C(:NH)-NH*CN.Other similar analogies are recorded. T. 3. P.ORGANIC CHEMISTRY. i. 69 Formation of Carbamide from Ammonium Carbonate and Related Substances. FR. FICHTER H EINRICH STEIGER and THEOPHIL STANISCH (Verb. S c h e r a . Nat. Ges. 1916 28 ii 66-103; from Ghem. Zemtr. 191t3 ii 444-446).-1n a previous communication (Fichter Stutz and Grieshaber A. 1913 i 713) the formation of carbamide by the electrolysis of ammonium carbamate was attributed to the intermediate production of formamide by the action of hydroxylamine on ammonium carbamate; this view can no longer be maintained since direct experiment shows that ammonium carbarnate is not reduced by hydroxylamine.On the other hand carbon dioxide reacts with hydroxylamine in the same mmner as with ammonia giving according to conditions hydroxylamine carbonate or the dihydr- oxylamine salt of hydroxycarbamic acid OH*NH CO,H 2NH2*OH. The expmiments on the electrolysis of ammonium carbamate solu- tion (Zoc. cit.) have therefore been repeated the same solution being used as in previous experiments but every care being taken to keep the anode and cathode solutions separate by enclosing the elect’rodes in porous pots immersed in it trough all vessels contain- ing the same solution. The results show that carbamide is pro- duced exclusively a t the anode but no trace of a corresponding reduction product such as formic acid or formamide could be detected a t the cathode.Under the experimental conditions Liebig’s method of detecting carbamide is unsuitable but Fmse’s method (A. 1914 ii 756) gives trustworthy results is not affected by the presence of ammonium salts and allows the isolation of carbamide by the action of alcoholic hydrogen chloride on the dixanthylcarbamide. Attempts have also been made t o effect the oxidation of ammonium carbarnate t o carbamide by purely chemical means ; hydrogen peroxide or calcium permanganate gives small but dis- tinctly recognisable quantities of carbamide. Oxidation may also be effected by ozone either by leading ozonised oxygen into ammonium carbamate solution or over powdered ammonium carbonate or by mixing ozonised oxygen ammonia and carbon dioxide. The yield depends on the concentration of ammonia and the temperature.The chemical and slectrochemical oxidations have the transformation of ammonia into ammonium nitrate as a common feature; also the local increase in temperature caused by the reaction is sufficient to cause a purely thermal transformation of ammonium carbamate into carbamide. The general explanation of the equilibrium between ammonium carbamate and carbamide is that the former passes into the latter by loss of a molecule of water. This however. is opposed to the law af mass action; the change is more probably represented by the scheme NH2*C0,NH + H20 (NTf,),CO CO(NH,) + 2H,O. Direct experiment shows that the rate of formation of carbamide is increased by water in the early stages of the reaction as is required by_the above hypothesis.The authors are therefore led t o the conclusion that normal ammonium carbonate is the d*i. $0 ABSTRACTS OF CHEMICAL PAPERS. actual source of carbainide ; since however the presence of water has an effect disadvantageous to the carbamide in the final eyuil- ibriurn (NH4)&03 := CO(NH,),+ f3H,O it is advisable to operate with substances containing the components of ammonium carbonate but having less water such as amnionium carbamate. At the temperature of the reaction the small quantity of hygroscopic moisture is sufficient+ to start the conversion of the carbamate into carbonate and as soon as the latter commences t o be transformed into carbamide water is liberated in amount sufficient to complete the hydration of the carbamate. I n the anhydrous condition ammonium carbamate is more stable than the carbonate; in the presence of water however it becomes unstable and above a certain temperature is incapable of existence.I n the region above 135O there is only the equilibrium between ammonium carbonate and carbamide in which the latter is favoured by further rise of temperature; below 135O on the other hand the complex equil- ibrium of the first scheme exists. The maximum yield obtained at 135O thus finds a simple explanation. The equilibrium (NH,),CO CO(NH,),+ 2H,O has been investigated a t 1 2 5 O looo 78O and 37*3S0 and the combined effects of temperature and dilution are explicable from t'he point of view of the complex equilibrium scheme. Lowering of temperature renders the carbamate and the carbamide more stable; increase in the quantity of water acts in the opposite direction in each case.According to the preponderance of one or the other factors the following effects may be observed at. temperatures below 1 3 5 O with a constant mole- cular ratio of carbamate to water (1) the second portion of the scheme may be so far favoured that the yield of carbamide is in- creased since the amount of water suffices to convert a larger pro- portion of carbamate into carbonate in spite of the actual increased stability of the former; (2) the yield may remain constant since the increase in stability of the carbamate balances the increased tendency to formation of carbamide; ( 3 ) the increased stability of the carbamate is not counterbalanced by the amount of water and the yield of carbamide sinks.All three possibilities have been experiment alIy realised. Free ammonia favours the carbamide in the equilibrium (NH,),C03 CO(NH,) + 2H,O in the absence of water but is without influence in presence of the latter. H. W. Acetylmethylcarbamide . ROBERT BEHREND and HANS ODENWALD (Annalem 1918 416 228-229).-Fifty-nine grams of acetamide (1 mol.) are dissolved in 88 grams of bromine (0.55 mol.) a 20% solution of potassium hydroxide (56 grams; 1 mol.) is added the solution is heated on the water-bath until it becomes yellow and is no longer alkaline and is then cooled when acetylmethyl- carbamide crystallises. Further quantities can be obtained from the mother liquor the total yield being 75% of the theoretical. With even a slight excess of alkali the yield falls t o zero.C. S.ORGANIC CHEMISTRY. i. '71 Substitution in Aromatic Compounds. 13. J. PRINS (Clzem. tf'cekbEad 1918 15 571-58O).-It has been shown in an earlier paper (&id. 98) that substitution in aromatic compounds begins by addition to a carbon atom of the ring followed by reaction with the hydrogen atom attached to that carbon atom; the reactivity of the hydrogen atom depends therefore in the first place on the degree of unsaturation of the atom to which it is attached as is true also in the case of alcohols and ainines. Since unsaturation is distributed aver t"he whole nucleus addition can obviously occur a t more than one carbon atom. The analogy with alcohols and amines is shown not only in tha carbon atoms of the nucleus but in oxygen or nitrogen atoms in side-chains attached t o the nucleus and substitution can be brought about in all these cases by the same catalysts.Substitution may be no& w l y direct but indirect also as in the. case of chloroacetanilide ; the reaction here is uiiimolecular and may be ascribed to a disturbance of t.he equilibrium between the energy of the atoms (atom-energy) and the energy of combination between the atoms (link-energy). Substitution occurs then in the first place a t the least saturated carbon atom but this may not yield the most stable system and the substituting group may finally take up a different position. The entry of any substituent X into the benzene ring must cause a change in the relation between atomenergy and link- energy both in the substituent.and in the nucleus. Two cases may arise. I n the first in which the link-energy between X and C; the carbon atom tno which X becomes attached is greater than that between C and the hydrogen atom displaced; the atom-energy of C is therefore reduced and to restore this as far as possible the link-energy between C and its neighbours C2 and C3 is reduced with the consequence that the link-energy between C and C and between C3 and C5 is increased (C and C being the neighbours of C2 and C remote from (2,). and that between C and CB and c5 and C is diminished; C therefore by the diminution of it,s link-energy receives an increase of atom-energy and is therefore rendered more reactive. The effect of introducing X therefore is t o make the para-carbon atom more reactive. I n the second case in which the link-energy between C and the substituent is less than between Cl and hydrogen the redistribution of energy causes an increase in the atom energy of C4 and C5 that is of the carbon atnoms in the meta-position.The fact that a suhstituent which directs a second substituting ~ ~ O U ' P to the meta-position also causes a reduction in the velocity of substitlltion is taken to indicate that the atom-energy of the atoms of the snhstihted nucleus is less than t,hat of the atoms of the unsiibstituted benzene ring itself and hence it follows that the introduction into the rinq of a group which directs to the meta- position causes the transformation of atomenergy into link-energy throughout the ring as a whole.*i. 73 ABSTRAOTS OF CHEMIUBL PAPERS. It is shown that substitution iu the benzene ring cannot be ex- plained by the assumption of a conjugated system as attempted by Boeseken (A. 1912 i 430) and by Holleman (Chem. FVeekbZad 1913 10 615 61S) without postulating many other conditions. s. I. r,. Pyrogenic Acetylene Condensations. V. RICHARD &!EYER and WILHELM MEYER (BeT. 1918 51 1571-1587. Compare A. 1917 i 313).-In addition t a the substances previously identified in the product of the pyrogenic condensat.ion of acetylene o-xylem (identified as o-phthalic acid} and indene have been detected and the presence of mesitylene and q-cumene confirmed. Durene and isodurene could not be detected. The methylthiophen obtained by the condensation of acetylene methane! and hydrogen sulphide (Zoc.c i t . ) is proved to be a-thiotolen and thionaphthen has been found in the product of the condensation of acetylene and hydrogen sulphide. A complete list is given of all the products obtained by pyrogenic acetylene condensations. Hvdrindene brorninated in the cold in the presence of a little iodide yields 4 5 6 7-tetrabro.mor7lydr~~ene C,Br <gz>CX2 needles m. p 200° (which is converted into tetrabromo6hthalic acid by oxidation) but brominated in boiling chloroform yields 1 2 S-t~ibromoh~d;rindeme feathery crystals m. p. 134O which yields phthalic acid by oxidation and is also obtained by the further bromination of indene dibromide. About 0.5 C.C. of aniline was obtained when the vapour of 3 litxes of benzene mixed with ammonia was passed during twenty- four hours through a tube heated a t 550° initially and a t 700° finally; aniline could not be detected if the temperature was maintained a t 550° throughout.[See also J . Sac. Chem. Ind. The Optically Active moMethylhydrindamines . J OSEPH WALTER HARILIS (T. 1919 115 61-67). The Fusion of Sodium Hydroxide with Several Phenols and Sulphonic Acids. MAITLAND C. BOSWELL and J. V. DICKSON ( J . A m e r . Chem. Soc. 1918 40 1786-1793).-A number of experiments were carried out in which sodium benzene- sulphonate was fused wit'h sodium hydroxide a t temperatures of 30O-35Oo in a closed vessel in presence! or absence of air the gaseous contents of the tube being analysed before and after the experiments. It was found that when the fusion was carried out in presence of air a considerable quantity of hydrogen was formed and a much smaller quantity of methane or other gaseous hydro- carbon.At the same time some of the oxygen originally present disappeared the volume ratio of hydrogen formed to oxygen used up being approximately 1 2. When air is excluded from the fusion however no hydrogen or methane appears. It was found working on comparatively large quantities of material that by 1919 3 5 ~ . ] c. s.ORGANIC CHEMISTRY. i. 73 carrying out the fusion in an atmosphere of nitrogen instead of air the yield of phenol could be increased from 90% to 98% of the theoretical. In the presence of free oxygen secondary reactions evidently occur involving the absorption of oxygen followed by an oxida- tdon involving the elements of water.To determine whether any of the dihydroxy- or trihydroxy-benzenes are formed as secondary products the fusion of all six of these with sodium hydroxide in presence or absence of air was studied. I n the case of five of them hydrogen was formed in presence not in absence of air. In the case of hydroxyquinol much hydrogen is evolved even in absence of air and also considerable quantities of methane. It is not considered that any of these can be the direct cause of hydrogen formation in the benzenesulphonate fusion. Sodium hydroxide does not bring about catalytic oxidation of the dihydroxybenzenes of pyrogallol of P-naphthalenesulphonic acid or phenylglycine-o-carboxylic acid. With sodium anthra- quinone-6-sulphonate however oxidation occurs in absence of oxygen with format'ion of free hydrogen. REX& DUBRTSAY TRIPIER and TOQUET ( Compt.rend. 1918 167 1036-1038) .-The coefficient of reciprocal miscibility of phenol and water st"eadi1y increases with the addition of alkali hydroxides t o the water. Curves are given for sodinm hydroxide a t concen- trations varying from A7/Z0 to J77/3. The action of the alkaline earth hydroxides is similar but less marked On the other hand acids and salts of the strong acids cause a diminution in the coeffcient and the same holds good €or the alkali carbonates. E. R. R. The Miscibility of Phenol and Alkaline Solutions. W. G. Aromatic Derivatives of Orthosulphurous Acid. X. M. RICHTER (AnmaZen 1918 416 291-304. Compare A. 1917 i 34).-The attempt to prepare aryl sulphates in the same way as aryl sulphites (Zoc.cit.) by mean9 of sulphuryl chloride and nvridine failed chlorinated liquid products being obtained. Phenyl sulphate is obtained indirectly by dissolving phenyl sulphite in concentrated snlshuric acid with cooling and ponrinq the solit- tion into water. The amorphous precipitate obtained separates from formic acid solrxtion in plates with blunted angles n. p. 388O (decomp. ; rapidly heated) or 280-282° (decomp. ; slomlv heated). The srtbstance is regarded as it double salt of ctinhenyl su1phat.e (1 mol.) and diphenyl sidphite (3 mols.) havinq the formula SO,rO*S(OPh),l %,hat ic; i t is a wlphnte of tri~henv7- o7.Aho.~iclph?crozcs m2. It iR essilv solitble in formic sulphuric and phosphoric acids in methyl sitl~hate and in alkali hvdroxides and carbonates ammonia and alkali sulnhides dissolves slightly in warm methyl or ethyl alcohol and in boiling water and is insoliihle ilt all other Common solvents.It is converted by alcoholic hydro- chloric acid a t 70° into the rhloride of tri~honvbortho v ~ t p f i w o ~ ~ ~ nrk'. 8((3Ph),CT long. prismatic needles m. p. 356O (decamp.) snrl in clilntfi potassiirm hydroxide mltition by a soltition of Fyrirlinei. 74 ABSTRACTS OF CHEMICAL PAPERS. hydrochloride containing a11 excess of pyridine into trip7,eibylortito- sulphurous acid OH*S(OPh) an amorphous powder i n p. 233O. The last substaiice is amplioteric. Its acidic character is weaker than that of carbonic acid whilst it6 basic properties are such that a hot 50% alcoholic solution has an alkaline reaction towards litnius.The three phenyl groups are not eliminated by hydro- lysing agents. By treating an alcoholic suspension of the acid with the requisite acid the bromide S(OPh),Br needles m. p. 241-242O (decomp.) iodide short needles m. p. 194-195O (reddening) nitrate hair-like needles m. p. 160-161O (decomp.) acetate waxy mass and picmte yellow mass are obtained. Ethyl ti.iphcnylorthosulphite OEtt-S(OPh) amorphous powder m p. 244O (decornp.) is obt"ained from the chloride and alcoholic sodium ethoxide. The szclphate 80,[0*S(O*C,I-I,~~e),l crystals In. p. 296O (decomp.) prepared from di-o-tolyl sulphite and the correspond- ing sulplzate m. p. 3 1 5 O (decornp.) prepared from di-m-tolyl sulphite are obtained in the same way as the phenyl analogue; the latter yields tl.i-m-toZ?/lorthos~~l~~h~~.ous acid amorphaus powder m.p. 2 6 7 O (decornp.) by treatment with pyridine hydro- chloride as above. The colourless amorphous szrlphate m. p. 232O (decornp.) obtained by pouring a solution of dithymyl sulphite in concen- trated sulphuric acid into water is regarded as a mixed anhydride of sulphuric dithymvlortliosulphurous and trithpylortho- sulphurous acids (C,,l"i,,*O),S.0*S02*0.S(O*C,,R,3),.0H. It is soluble in alcohol but by treating its solution in aqueous-alcoholic potassium hydroxide with alcoholic sulphuric acid a szdphate SO,[O*S(O*C',,H,,),f amorphous powder m. p. 280-281* (decomp.) is precipitated which is insoluble in alcohol. The in- soluble sulphate yields trcth?/rn?/lort?~os?Ilplt.2lrolra acid amorphous powder m.p. 274-275O (decornp.). by ths pvridine hydrochloride method whilst t-he soluble sulphate by treatment with alcohol and the requisite acid yields the chloride SCl(O*@,,R,,) amorphous powder darkening at 295-300O without. melting bromide small crystals decornp. 330-340° iodide crvsta'ls. and nitrafe small rectangular plates blackening a t 285-290° without melting. c. s. Thiophenol in Synthetic Phenol. G. CAPPELLI (Gaxzetta 1918 48 ii 107-113).-The repulsive odour exhibited by some samdes of synthetic phenol is sometimes attributed to the presence of thioplien in the benzene used in the manufacture. The author shows that such odour is due to a small pronortion of thiophenol formed from particles of sodium benzenemlphanate which during the fusion with alkali. escape contact with t*he latter and underqo deoxidation a t the surface of the iron in the manner observed bv Stenhouse (,4n?zden.1866 148. 284 1869. 149 42). The phenol may be freed frcin this impuritv by fusing it adding a 'little alcohol to keep it liquid and then addinp per kilo. of Phenol about 50 C.C. (more if continued formation of !xscipitate shows it to he netes-ORGANIC CHEMISTRY. i. 75 sary) of 1076 alcoholic mercuric chloride solution. The excess of mercuric chloride is eliminated by leaving the clear liquid for a couple of days in contact with copper turnings o r foil; the mercury deposited on the latter may be recovered by distillation. Frac- tional distillatioii of the decanted solution gives (I) below 179* water and alcohol aiid (2) a t 179-183° pure phenol with its characteristic odour.T. H. P. Organic Salts of Bivalent Chromium. G. SCAGLIARINI (Atti R. ilccad. Liizcei 1918 [v] 27 ii 87-89; Gmzetta 1918 48 ii 148-150) .-The greyish-green salt obtained by Calcagni (A. 1913 i 1154) either from chrome alum and sodium salicylate or from chromic hydroxide and salicylic acid and regarded by him as a chromous compound is probably a salt of tervalent chromium in which also the phenolic hydroxyl groups take part in the salt- formation. All other chrornous salts of organic acids including those now described by the author are red. Cfhroinozcs salicylate C,,H.t<-O->Cr,3H20 coo0 prepared by re- ducing chrome alum solution with zinc and hydrochloric acid and adding sodiuni salicylate solution free from air.forms mall red crystals but rapidly oxidises and becomes greenish-grey in the air. Clzrornous propionate 2( C,H,O,),Cr,H,O was also prepared and analysed and the butyrate and valerate prepared. Nitro-2 4-phenylenedithioglycollic Acid and Some of its Colouring Derivatives. C. FINZI and N. BOTTIGLIERI (Gazztta 1918 48 ii 113-122).-The authors have prepared the nitro-derivative of ?r~-pheiiylenedithioglycollic [m-phenylene- dithiolacetic] acid and as this yields on reduction not an amino- acid but a ketothiazine derivative the conclusion is drawn that the nitro-group enters the benzene nucleus in the ortho-position to one of the substituents. The sulphone corresponding with the nitro-compound undergoes ring-closure on reduction still more easily the resultant compound being quite analogous to Clausz's sulphazone (A.1912 i 389) aiid being hence termed sulphazon- sulphonacetic acid. This acid has been coupled with various diazo- compounds the derivatives thus obtained CO,H*CH,*S being of different colours and serving as sub- (an- nexed formula) obtained from m-phenylene- dithiolacetic acid and gitric acid forms 2-Keto-2 3-cFihydrothiasine-6-thi~~~cetic acid (annexed formula) obtained by reducing the previous com- 8 pound forms tufts of silky white needles. m. p. 2 1 0 O ; its sodifcm salt (+ 3RaO) was prepared and analysed. 4-xitro - ni - nhPn?,tened~.~idnhonacetic NH acid NO,.C,H,( S0,*CH2*C0,H) pre- pared by the action of hydrogen per- T. H. P. /T stantive dyestuffs for silk.\ - / 4 -Nit yo- m-ph en y lenedit hiolac e ti c n cid CO,H*CH,*S NO slender yellow needles m. p. 174O. CO,H*CH,*S y \ y E 2 \/\ P oi. 76 ABSTRACTS OF CHEMICAL PAPERS. oxide on the nitro-acid forms long white needles m. p. 199O (decornp.). On reduction with tin and hydrochloric acid it yields S~clpl~azc~n-6-suI~horwtcetic acid so2 C0,HCHI*S02f\)/\FH \ / \ P O NH which forms white mammillary masses of slender needles m. p. 219O (decomp.). p-Sulp7~ o b en z e n ea z osutphaz on- 6-sul p It ona ce tic acid so " NH obtained by condensing the preceding acid with diazobenzene- sulphonic acid forms small needles of the colour of chromic anhydride. A t 40-50° in aqueous solution it is fixed directly on silk giving a brilliant orange-yellow colour stable against soap and light; wool fixes it with more difficulty but assumes a stable yellow coloration.4-Szclp~Lona~I~thnlenenzosulphazonace tic acid SO .. NH \-/ dyes silk an old-gold ysllow stable against soap and light. SaJicytic- acid- p -G odiphe I? y 1 - p -as osdphaa onszc1ph on nce tic a cid so* forms a brownish-black colouring matter almost insoluble in water and directly colours silk yelIow k i t h an olive-green tinge. T. H. P. 4-Aminoisophthalic Acid and its Derivatives. RUDOLF WEGSCHEIDER HANS MALLE ALFRED EHRLICH and ROBERT SKUTEZKY ( M o w tsk-. 19 18 39 3 15-41 7).-4-Acetylaminoiso- phthalic acid is conveniently prepared by oxidising 4-acetu-m- xylidide with a boiling aqueous solution of calcium pennanganate ; when rapidly heated it becomes yellow a t about 270° melts a t 295-296O (corr.; decomp.) immediately resolidifies and then remains unchanged up to 350° ; when slowly heated decomposit,ion frequently occurs without visible liquefaction. (The cdciam saltORGA.NIC CHEMISTRY. i. 77 [+3H,OJ is described.) During the heating one molecule of acid loses its acetyl group and the residue reacts as an amine with a second molecule of acid yielding thereby ri-keto-3-phe~~l-2-methyl- 3 4dihydropzcinazoline-6 2' ; 4t-tricarboxylic a*cicE (annexed formula) m. p. 416O CO,H (corr.). [Ethyl ester m. p. 332O (corr.) after 'co2K sintering a t 33OO.l The esters of 4-acetyl- aminoisophthalic acid were prepared by acetylation of the corresponding esters of the aminotacid methyl 4acetyl- c7*mimisophthdlate has m. p. 125-126"; 1-methyl 3-hydrogen 4-acetylaminoisophthalate melts a t 218-219O ; the corresponding normal and acid ethyl esters have m.p.'s 109-llOo and 193-5-194'5O respectively. Attempts to esterify the acetylamino- acid by methyl alcohol and mineral acids led as in the case of acetylaminoterephthalic acid (Wegscheider and Faltis A. 1912 i 463) to the deacetylation of the acid. 4-Aminoz'sophthalic acid is most conveniently prepared from its acetyl derivative by esterifying the latter with methyl alcohol and mineral acid and subsequent hydrolysis of the puri6ed amino- ester so formed; it has m. p. 336-337O (corr.; decomp.). The dimethyl and dietlzyl esters have m. p.'s 131*5O and 79-80° re- spectively whilst I-methyl 3-hydmgen $-aminuisophthalate and the corresponding ethyl ester melt a t 224-225O (decomp.) and 216-5-218O.The acid behaves contrary t o the usual rule since it yields the same ester by treatment with mineral acid and methyl alcohol and by half-hydrolysis of the normal ester. The methylation of the amino- and acetylaminoacids and their esters has been studied under varying conditions. 4-Dimethyl- aminoisapht hnilic acid is most conveniently prepared by treatment of the corresponding dimethyl ester with methyl sulphate a t looo and hydrolysis of the ester (m. p. 70°) with alcoholic potassium hydroxide; its m. p. depends greatly on the mode of heating. The silver s d t is described. Methylation of the free acid is very in- complete either by the action of methyl sulphate on the dry potassium salt in the presence of potassium hydroxide solut>ion or in the presence of water and barium carbonate.The use of methyl iodide and potassium hydroxide dues not lead t o better results. 4-Acetylaminoisophthalic acid is methylated with still greater difficulty yielding small amounts of dimethylaminoi.s~phtha1ic acid. Methyl sulphate does not act on dimethyl 4-acetylaminoi~o- phthalate below 1 1 5 O ; a t 120-124°. however trimethyl 4-heto-3- p?w?~yl-2-m e t 11&3 4-&78~1~?9-0q 7 1 in a OJ~TLC-6 3 f 4 !- tm-carh o my la8 4 m. p. 305'5O is produced. 4-A cetylmet 7~~ylnn-tinoisop~~tTtalic acid is prepared by the action of methyl iodide on the sodium or preferably the potassium salt of dimethyl 4-ncetylaminoiso~~t~a~a~e and subsequent hydrolysis with alcoholic potaPsiiim hydroxide solution ; it frsrms colourlew __- CO co,&/ AN-/ 1 \1 AM*\--/ \/\/ Ni.78 ABSTRACTS OF CHEMICAL PAPERS. needles the m. p. of which depends on the mode of heating. 4-Methy2aminoiso~~~thalic acid has m. p. 297.5-298'5O (carr.) after decomposition a t 29Go when placed in a bath preheated to 293O; the corresponding dintethyl ester melts a t 115O. l-Met?qZ 3 -It ydrog e n 4- nt e t h y laminoisop?s t hnla t e m. p . 2 38-2 3 (decom p. ) is obtained by the partial esterification of 4-methylaminoisophthalic H. w. Colour and Chemical Constitution. 111. Derivatives of the Unknown op-Phenolphthalein.. JAMES A1 OIR (I'ralzs. Roy. Soc. S. Africa 1918 7 123-127. Compare A. 1917 ii 349 557). -The preparation and absorption spectra of a number of phthalein derivatives containing one hydroxyl group in the o?*tho- and a second in the para-position to the central carbon atom are described. Thus phe~~ol-p-cresolpF,IhuEein is obtained by heating a mixture of p-cresol and phydroxybenzoylbenzoic acid in the presence of zinc chloride.The following substances are prepared in a similar manner op-phenolpWthalei~m-carboxylic acid and its methyl ether hydroxydipkeny1p~Lth~li~e carb oxylic acid m-amin 0- op-phenolph t ?salein* the corresponding m-me t h ylamin o - derivatives and its o-carboxylic acid m-phe~~l-op-phenolpTLth.aleil7 and m-nitro-op-phenol~hthalei~. Attempts to prepare op-phenol- phthalein by reduction of rn-iodo-op-27henolphth~lein did not yield the desired result and further work in this direction was aban- doned since it was discovered t-hat p-hydroxybenzoylbenzoic acid yields a phthalein-like substance when heated a t above ZOOo or a t a lower temperature in the presence of concentrated sulphuric acid; this substance which resembles phenolphthalein very closely can also be obtained by heating phenolphthaleinoxime with a mall quantity of sulphuric acid a t above ZOOo and it therefore appears probable that the so-called oxime is in reality the p-hydroxyanilide of p-hydroxybenzoylbenzoic acid.It is possible to find a particular strength of alkali in which any phthalein gives a colourless solution in the cold but which becomes coloured on heating to near the boiling point and again fades on cooling and keeping. For ordinary phenolphthalein the concentration of alkali is slightly above normal ; tetraiodo- phenolphthalein requires a much weaker alkali whilst a-naphthol- phthalein requires about 2N-alkali.Phenolphthalein-o-carboxylic acid is coloured faintly pink by ammonia and deep violet-pink by alkali hydroxide; as an indi- cator it resembles thymolphthalein but has a more favourable colour. The comesponding dicarboxvlic acid is useful in proving the presence of definite caustic alkalinity a t about N/100. acid with methyl alcohol and hydrogen chloride. H. W. Constitution of the Hydrazone of Benzaldehyde . J. SUREDA BLANES (Amal. Fis. Quim. 1918 16 707-718).-The author summarises the evidence for and against the cyclical formula of Curtins for the aliphatic diazo-comporrnds RR-C!<+ 8s corn- NORGANIC CHEMISTRY. i. 79 pared with the lineal formula RRCNiN suggested by Angeli and later by Thiele.The easy oxidation of hydrazones to diazecompounds suggests the investigation of the constitution of the former substances. The hydrazone chosen for preliminary examination is that of benz- aldehyde which on oxidation gives phenyldiazomethane. The alternative structures which may be assigned to benzaldehyde- hydrazone are CHPh<hH and CHPh:N*NH,. NH The following reactions establish the fatter formula (1) Benzaldehydehydrazoii e aEd phenylcarbimide CHPh:N*N€€ +- CONPh = NHPh*CO*NH*N:CHPh. (2) Benzaldehydehydrazone and phenylthiocarbimide CHPh:N*NH + SCNPh = NHPh*CS*NR*N:CHPh. (3) Benzaldehydehydrazone and diphenylketen CHPh:N*NH + CPh,:CO = CHPh,-CO*NH*N:CHPh. The product of the last reaction forms white crystals insoluble in alcohol ether o r benzene slightly soluble in light petroleum and glacial acetic acid m.p. 196O. These reactions are incom- patible with the cyclical formula for benzaldehydehydrazone and therefore the lineal formula must be assumed. W. S. M. Anilinoquinones . HERMANN SUIDA and WILHELM SUIDA (8nnden 1918 416 113-163).-The generally accepted view thatl anilinoquinones are always formed by trhe transformation of an additive compound of the type N HAr*CH<C('~~)'cH>CK.~HAr CH . C (OH) into NHAr*C<~~.~>C."HAr with the removal of four atoms of hydrogen which reduce two further molecules of the quinone is found not to hold. I n so'me cases the reaction recognisably passes through the monoanilide. I n the case of the simplest and most reactive components monoanilides are smoothly formed in accord- ance with the equation 2C,H,02 + NH,Ar = C,H30,-NHAr + C6H!(OH)%.The capacity of the group *CO-CH:CH-CO* to form anilincr-compounds must be connected in some way with the struc- ture of the benzene nucleus because maleic and fumaric esters and the cis- and trans-modifications of dibenzoylethylene in which this group occurs do not react in this way with aromatic amines. Under the conditions of the authors' experiments the following generalisations have been made. p-Benzoquinone in aqueous faintly acetic acid solution yields with all pronouncedly basic primary and secondary aromatic arnines anilinoquinones pre- dominantly and even sometimes exclusively monoanilinoquinones. The intensity of the reaction diminishes as the basic character of the amine is weakened by the entrance of acidic substituent,s.Thus the strongest bases (aniline and its homologues diamines etc.) yield mono- and di-anilides simultaneously the weaker bases (secondary amines iiitroanilines etc .) yield only monoanilides,i. 80 ABSTRACTS OB OHEMIUAL PAPERS. whilst the weakest bases do not react in aqueous solution. Tolu- quinone yields only monoanilides and s-xyloquinone does not react. I n alcoholio solution p-benzoquinone forms only dianilides ; monoanilides are present in the mother liquor only when the basic component contains acidic substituents. Tolu- and naphtha- quinones yield only monoanilides and s-xylquinone none. The reactions also proceed in glacial acetic acid solution. There- fore by a suitable selection of the solvent and of the temperature it is possible to make a quinone react once or twice with an amine or a monoanilinoquinone to react with a different base producing a mixed dianilinoquinone. The following new derivatives of p-benzoquinone have been pre- pared 5-anili.r~o-2-a-naphthylamin 0- CBH,,O,N yellowish-brown powder m.p. 278-280° ; 2-p-chlocr.oanilino- sepia crystals decomp. about 1 1 5 O ; 2 5-di-p-chioroaizilino- pale brown crystals ; 2-0-tolu- idino- dark violet-brown crystals m. p. 100-104° ; 2 5-di-o-tolu- idino- rust-red needles m. p. 250-252O ; 2-m-toZuidino- dark violet- brown crystals m. p. 90-100° (decomp.) ; 2 5-di-m-toZuidino- crimson-red needles m. p. 256-257O ; 2-p-toZuidino- aggregates of violebblack needles m.p. 134-137O (bath a t 134O) ; 2 5-di-p- toluidilzo- crystals m. p. 31W; 2-p-acetylaminmnili/no- dark crystals ; 2-as-m-xyZidino- reddish-brown crystals m. p. 1 0 2 O ; 2 5-di-as-m-zylidino- pale brown crystals M. p- 297-300° ; 2-$-cumidino- brick-red crystals m. p. 90-106' ; 2 5-di-$- cumidino- pale red crystals xn. p. 301-303" ; Z-o-anisidino- brownish-violet leaflets with metallic lustre m. p. 1 1 4 O (not sharp). With the object of preparing monoanilides soluble in water the aminobenzenesulphonic acids have been utilised. These do not react satisfactorily with p-benzoquinone but give good results with the less reactive 2 6-dichloro-~benzoquinone. By adding t o a hotl alcoholic solution of this a hot aqueous solution of sulphanilic acid (1 mol.) and subsequently an aqueous solution of sodium acetate (1 mol.) and then barium chloride barium 2 6-dichZoro- 5 -n n irin o -p-5 enz o pzt in one-p f -su2 phona t e ( C,HCI,O,oNR* c6134* SO,),Ba copper-red leaflets is obtained the mother liquor containing 2:6-dichloroquinol.If the temperature is about 60° at the beginning and about 30° a t the end of the experiment the pro- duct is mainly the barium hydrogen. salt. An aqueous solution of the barium salt a t looo rapidly acquires chlorine ions and deposits a blackish-brawn powder which appears to be the barium salt of ~-chlorcu-5-p-sulphoa7til~.no-6-hy~oxy-~-be~zoqu~none. By adding sulphanilic acid to a hot aqueous solution of the first-mentioned barium saltl the barium hydrogen salt of 6-chZoro-2 5-dianilino-p- b enzoqzcinone-p'pN-d~sul~~onic acid is obtained 8s a brovnish-black powder.2 -&Wet hyladino-p- h enz oqzcimmze c?6H,0,*NMePh prepared by adding a cold 50% acetic acid solution of methylaniline (1 mol.) to an aqueous solution of p-benzquiqane (2 mols.) foms dark redOR(XANI0 (;1HEMISTRY i. s1 ueedles LII. p. 125-130O. 2 5-L)imethyZan/ilino-p-ben~~p.u.iraone leaflets m. p. 205O is obtained from itx components in alcoholic solution. * 2-~lethylanilin~pbenzquinone like all other monoanilino- quinones of the same type yields mixed dianilinoquinones by tri- turation with an aromatic base or by warming with it in alcoholic solution. The following 2-methylanilino-p-benzoquinones of this kind have been prepared 5-am-Zino- NhlePh*C6H,020NHPh orange-red crystals ; 5-p-carboxyar~ilino- dark red leaflets ; 5-m-carb oxyanilino- brownish-red crystals ; 5-m-chloroaniZino- garnet-red needles ; 5-o-~~ydroxya?ailino- brown leaflets ; 5-m-hydr- oxyandino- brownish-yellow metallic crystals; 5-p-bromoandino- red crystals ; 5-p-suZphoanilino- prepared in the presence of sodium carbonate and 3% hydrogen peroxide and isolated as the sodium salt ; 5-a-naphthylamino- dark brown crystals ; 5-j3-naphthylamino- dark violet-brown crystals; 5-p-Benaeneazounilina- violet-brown crystals.2-Methylanilinepbenzoquinone (2 mols.) and p-phenylenedi- amine (1 mol.) react in boiling alcohol t o form a substance C&&aO4N4 brownish-green crystals probably (NMePh~C,H20,*NH),C,H4 whilst in the ratio of 4:1 in alcohol glacial acetic acid or nitro- benzene or by moistening the mixture of the two compmenb with a little solvent and warning on the water-bath a dark green crystalline substance [(NMePh*C6HzOz)zN],C,H4 is obtained 2-Methylanilino-p-benzoquinone and benzidine react in warm m.p. 250-260°. alcohol t o form the compound NMePh*CsH,O,*NH*C,H,*C,H,*NH brown needles m. p. 215-218° which is converted by chloranil in glacial acetic acid solution into the substance C1,Cl,O,( NH*C~H,°C,H,*NHo~6H,0,.NMePh)z crystals. 2-Methyl-ptoluidino-pbenzoquinone and pphenylene- diamine in hot alcoholic solution yield a dark green substance probably (C,R,*NMe* C,H,Os*NH),C,H,. 2-Ethzylanilino~p-benzoqui72.one forms dark needles m. p. 85' with previous sintering. 2-Renz?/ltznilino-p- b enzoquimone f o m s almost black needles m.p. 60-70° whilst 2 5dibenz?ylaniZino- p-bermspinme C,R,O,(NPh*CH,Ph) crystallises in blood-red needles m. p. 155-1560. 2 - M e t h y Z - p - t o Z ~ i ~ ~ o - p - b e n z o ~ ~ ~ ~ n o ~ a forms reddish-yellow needle9 m. p. 1 2 7 O and 2 5-dimethyl-p- fo.hidino-p-h enzoquinon e yellowish-brown rhombic plates m . p. 20 6O. OH*C,H,*NMe*C,H,O and 2 5-di-o-Ttpdroxymet hplanil~~o-p-benzol).?l.in~nc are described. 2-0 -Hydro xyme r5 hqlrnJin o-n-b en a nqilinone A table j s given of the colorations of the anilinoquinoneq in Polymerisation PhenomenR in the Simple 'Monoanilinn- benzouuinoaes . HERMANN SUIDA (AnmZen 191 8 4 16 I 164-181. Compare preceding abstract) .-The monmnilinoquin- concent'rated sulphuric acid. c. s.i. 82 ABSTRACTS OF CHEMICAL PAPERS.oues derived from priniary bases are only stable in the pure dry state ; they polymerise in solution. Dianilinoquinones and also monoanilinoquinones derived from secondary bases show no tendency to polymerise. The polymerisation is probably repre- sented thus 2C,H,0z*NHhr + C,H,O,*NAr-C,H,(OH),*NHAr ; the b e r i c meriquinoiioid form produced can undergo further polymerisation. The polymerisation is brought about by heating the monoanilinoquinone at its m. p. by heating with water or dilute acetic acid by prolonged boiling with alcohol o r by exposing its cold alcoholic solution to intense light. Thus 2-ptoluidino-p- benzoquinone yields the dimeride (C,3H,,0,N) m. p. 265-267O (in carbon dioxide) from which by reduction with alcoholic stannous chloride is produced the quinoL7 C,H,(OH),*N( C7H7) *CcH,(OH).7*NIIP.C,T~~ pale yellow crystals m.p. 236-237O (in carbon dioxide). Dimeric 11- tolziidino-p-71 enzoqzci?zone C,H,O,*N( C,H,)-~~H,O,*NH*C,H; produced by auto-oxidation by boiling the dimeric meriquiizone in glacial acetic acid or nitrobenzene forms violet-black crystals with green lustre which remain unchanged a t 400° ; the oxidation is also effected by ferric chloride in dilute alcoholic solution. c. s. Anilinoquinones from Benzoquinone and the Nitro- anilines . GUIDO MEYER and HERBIANN SUIDA (Annalm 1918 416 18l-l88~.-The nitroanilines do not react as easily as aniline with benzoquinone. I n cold aqueous solution a reaction between the nitroanilines and p-benzoquinone is only observed when the nitroaniline is used in the form of its hydro- chloride in the presence of an excess of hydrochloric acid; in all three cases reddish-brown crystalline additive compounds separate after some hours but if kept in contact with the mother Liquor for several weeks change into the mononitroanilino-p-benzoquinones. The latter are obtained immediately from the nitroanilines and p-b enzoquinone in boiling aqueous solution.2 -m-.lVi troanilin o - p - bemoquinorze and the p-nitro-compound are daik brown and do not crystallise well. The o-dro-compound is less readily obtained. All three compouiids have indefinite m. p.'s between 290' and 300° and develop with sulphuric acid a reddish-violet coloration which turns blue on warming. I n cold alcoholic solution a reaction occurs only between m-nitroanihe and p-benzoquinone whereby the additive com- pound is formed.I n hot alcoholic or better hot glacial acetic acid solution the 2 5-~~nitroanzililto-p-be?zzoqzti?zortes decomp. 310-360° are obtained. The nitroanilino- and dinitroanilino-p-benzoquinones are not attacked by mild reducing agents. Tin and hydrochloric acid con- vert the latter into phenylenediamines and aminoanilinoquinols which could not be isolated. p-Nitroianilinobenzoquinone was reduced by tin and hydrochloric acid to a base which was isolated as the sulpha te C,H,( OH),*NH* C6H,*NH,,2H,S0 prismatic needles; the base itself could not be isolated. @. s.ORGANIC CHEMTSTRY. i. 83 Action of the Isomeric Chloromethylanilifles on Benzo- and Tolu-quinones. HEINRICH TEUTSCHER (Aiznalen 1918 41 6 139-202.Compare Suida and Suida this vol. i 79).-The chloromethylanilines in aqueous faintly acetic acid solution yield exclusively monoanilinoquinones with p-benzo- and tolu-quinones ; as usual a second molecule of the quinoiie is reduced to the quinol. Additive products could not be isolated although they are un- doubtedly formed. I n alcoholic solution p-benzoquinone yields dianiliiioquirioiies whilst toluquiiroiie yields only the monoanilino- quinone; here again evidence (colour change) has been obtained of tahe intermediate formation of additive compounds. Toluquinone being a weaker oxidisiag agent than p-benzoquinone reacts more slowly with the aromatic bases. Of these o-chloroinethylaniline reacts most slowly and the p-ccmpouizd most rapidly.2-p-C Jdorome t h ylalzilino-p-b en z oquiizone C,H,O,*NniZe*C,H,Cl is a dark red crystalline powder in. p. 145O the m-chloro-compound a reddish-brown powder m. p. 1W0 sintering a t 120° and the o-chZw-0-compound crystallises in pale red needles m. p. 133O (decornp.) sintering a t 60°. 4-p-Chloro.meth?~Z~7iilz;rzotolzcquiiq~e forms a dark red crystalline powder with metallic lustre m. p. 156O (from aqueous solution) and dark red needles M. p. 184O (decornp.) (from alcoholic solution) and the o-chloro-compound red leaflets with metallic lustre m. p. 146O (decomp.). 2 5-Di-p-chlororrzet~~Za~z'l~no-p-beszeogzcinone forms deep bronze leaflets with metallic lustre m. p. 2 2 3 O the m-chloro-compound deep pellow leaflets m. p. 1 9 8 O and the o-ch7uro-compound reddish-bronze leaflets with metallic lustre m.p. 2 5 8 O . 2 5-Di-2' 4'-dz'chlorornerh?/1nrzilino-p-bensoguinone which re- quires the presence of hydrogen peroxide for its quick preparation forms brick-red leaflets m. p. 2400. c. s. Citronellol. H. J. PRIM (Chenz. Weekblad 1918 15 1378-1 380) .-Distillation of citronellol yields two fractions one with b. p. 217-219O and the other with b. p. 219-221O. The liquids probably contain isomerides but these cannot be separated by fractionation. When free from geraniol and other substances but containing these isomerides citronellol of maximum purity should have DIO 0-867-0.869 and its index of refraction should be 1-4586-1.4589. A. J. W. Constituents of Oil of Cassia. 11. FRANCIS D. DODGE (J Ind. Eng. Chern. 1918 10 1005-1006 Compare A.1916 i 155).- Oil of cassia was found to contain cinnamaldehyde (75 to go%) cinnamyl acetate phenylpropyl acetate ( a ) o-methoxycinnam- aldehyde salicylaldehyde (0.1 to 0*2:6) coumarin benzoic acid salicylic acid an unidentified liquid acid benzaldehyde and o-methoxybenzaldehyde. [See further J . Soc Chem. I d . 1919.1 w. P. s.i. 84 ABSTRACTS OF CHEltII(3AL PAPERS. Constitution of Substances from Guaiacum Resin. G. SCHROETER L. LICHTENSTADT and D. IRINEU (Ber. 1918 51 1587-1613).-!L'he milk test with extract of guaiacum resin is not entirely satisfactory since it depends on the quality of the extract. Before examining the chemistry of the blue compound it is neces- sary to determine the structure of the substance (or substances) in the resin which produces it.The two substances of unknown constitution obtained by the dry distillation of guaiacum resin are guaiene and pyroguaiacin. The latter is known to he a hydroxymethoxy-derivative of the former (Herzig and Schiff A 1897 i 254; 1898 i 327 530). Guaiene is now proved to be 2 3-dimethylnaphthalene by synthesis. P-Phenylisopropyl bromide CH,Ph*CHMeBr b. p. 107-109°/ 16 mm. D16a4 1.2908 obtained from the alcohol and hydrobromic acid (saturated a t 0.) a t looo reacts with ethyl malonate and alcoholic sodium ethoxide on the water-bath to form ethyl P-phercyl- iso~opyZmaZomnat e CH,Ph*CHMe*CH (CO,Et) b. p. 182-1 83O / 14 mm. D16.4 1.0673. This is converted in the usual manner into ethyl ~-pheizy~iso~opylmeth.ylmalonate b. p. 188O f 16 mm. Dl8.4 1.0505 which yields the acid CI3Hl6O4 colourless crystals m.p. 158-160O (decoxnp.) by hydrolysis. The acid heated a t 170-1 90° yields y-phenyl-aP-dimet hgylbutcyric acid CH,Ph* CHMe*C'HMe*CO,H b. p. 179-180-5°/13 mm. the acid chloride of which b. p. 136-143°/13 mm. is converted in light petroleum (b. p. 60-70°) by aluminium chloride into 1-&lo-2 3-dimethyZLl 2 3 4-tetra- h,ydrmaphthdene b. p. 148--150°/17 mm. m. p. -lo D21 1.019. This is reduced by sodium and alcohol t o 2 3-dirnethyltetrahydro- naphthol m. p. 110-114° h. p. 148-152O/18 m. which loses water a t above 200° and yields 2 3dimetkyl-~~-di~~yd.ronaphthalene b. p. 120-140°/16 mm. the dibronzid'e of which is converted by boiling methyl-alcoholic potassium hydroxide into 2 3-dimethyl- naphthalene m.p. 104-104.5° (picrate m. p. 123-124O) which is identical with guaiene. Pyroguaiacin is converted by boiling alcoholic potassium hydr- oxide and methyl sulphate into pyroguaict.cin methyl ether C,IH,,(OMe) leaflets m. p. 149-150° the oxidation of which by sodium dichromate and glacial acetic acid a t 95-115O yields pyro- guaiacinguinme methgl ether C,,H,,04 yellow needles m. p. 241-242O. For reasons given below pyroguaiacin is almost certainly 6-hydroxy-7-methoxy-2 3-dimethylnaphthalene. Guaiaretic acid the extraction of which from guaiacum resin by ether is described in detail has the formula C,,H,,O (Henig and Schiff koe. cif. give C,,H,,04) and is now found to be optic- ally active [alp - 9 4 O in alcohol and unsaturated. It is converted by methyl sulphate and hot aqu ems-alcoholic potassium hydroxide into R methy2 ether C,,R,,(OMy) cdourless needles m.p. 94-950 fa$ -92O in alcohol which is reduced by sodium and boiling alcohol or in solution in tetrahydronaphthalene at 180° by hydrogen and a nickel catalyst under a pressure of 40-50 Slog.ORGANIC CHEMISTRY. i. 85 to hychoyiiaiaretic acid metkyl ether C,8H,8(OMe) ; in both cases a mixture of the i-acid crystals m. p. 100-lO1° and the l-acid fiat prisms m. p. 86-87O [alp - 2 7 O in alcohol is obtained. Herzig and Schiff’s norguaiaretic acid (loc. cit.) obtained in poor yield from guaiaretic acid and boiling hydriodic acid is obtained in much better yield from hydroguaiaretic acid methyl ether and is reconverted ivtto this by methylation; it is therefore norhydroyuaiaretic acid.i-Dib7.ornoliydroguaiaretzc acid methyl ether C18H,,Br2(0Me) colourless needles m. p. 130-5-131.5° is obtained by the bromin- ation of i-hydroguaiaretic acid methyl ether or guaiaretic acid methyl ether in glacial acetic acid dehydroguaiaretic acid methyl ether (below) being also formed in the latter case. 1-Dibromo- hydroyuaiaretic acid methyl ether colourless crystals m. p. 121-122° [a] -420 in alcohol is obtained by brominating I-hydroguaiaretic acid methyl ether. i-Dinitro hydrogztaiare t i c acid methyl ether C,&f,,( NO,),( OMe) yellow crystals m. p. 150-151° obtained by adding nitric acid D 1.4 t o i-hydroguaiaretic acid methyl ether or guaiaretic acid methyl ether in glacial acetic acid solution is smoothly reduced in tetrahydronaphthalene solution by hydrogen and nickel t o i-diamiizohydroguaiaretic ucid methyl ether faintly violet needles m.p. 124-125O; attempts to resolve this base by means of d-t,artaric acid were unsuccessful. l-Dinitrohydroguaiaretic acid methyl et7zer yellow crystals m. p. 122-123O [a] - 4 9 ~ 5 ~ in glacial acetic acid is obtained by the nitration of I-hydroguainretic acid methyl ether. The reduction of I-guaiaretic acid and of its methyl ether yields a mixture of optically active and inactive hydro-derivatives and therefore possibly racemisation has occurred. Since it is shown however that the hydro-derivative. racemise with great &fficulty an alternative explanation of the formation of the inactive modif- cation is that a second carbon atom is rendered asymmetric by the reduction the inactive hydro-derivative being internally compen- sated.In favour of the symmetric structure thus postulated is the formation of the probably symmetrically substituted dibrorno- and dinitro-derivatives and the failure to resolve the diamina- derivative. Hydroguaiaretic acid methyl ether would therefore be a~-diveratrvl-fly-dimethylbut~ane C,R,(OMe),*CR,*CRMe*C~~~e*@n,*C,PI,(OMe) and guaiaretic acid methyl ether mould have the formula C,H,(OMe),=CB~CMe*CHMe~CH,*C,H,(U~le) the positions of the two methyl groups being determined by the fact that paiaretic acid can be converted through pyroguaiacin into guaiene (2 3-dimethylnaphthalene). An extraordinary transformation of guaiaretic acid methyl ether is its rechcction to hydroguaiaretic acid methyl ether by potassium pemanganate in acetone-glacial acetic acid solution veratric acid also being formed.The explanation is found in the action of Hubl’s iodine solution on guaiaretic acid methyl ether (1 mol.),i. 86 ABSTRACTS OF CHEMICAL PAPERS. whereby a mixture of i-hydroguaiaretic acid methyl ether and dehydroguaiaretic acid methyl ether C,,H2,O colourless crystals m. p. 178*5-179O optically inactive is obtained in the proportion of 1 2 by the consumption of 1 mol. of iodine. This change is represented by the equation 3 C H ( O M e ) * ~ H @ M e * ~ ~ M e * ~ ~ 2 * ~ ~ ~ ~ ( ~ M e ) 2 = C,H3(OMe),*CH,*C13N6e.CHMe.CH,.C,H,(OMe)~ + It is probable therefore that in the preceding reaction with potassium permanganate a portion of the guaiaretic acid methyl ether undergoes ring closure to a naphthalene derivative (which is then oxidised yielding veratric acid and other products) the hydrogen produced reducing another portion to hydroguaiaretic acid methyl ether which is stable towards pemanganate.By treatment with 2N-sodium hydroxide and methyl sulphate guaiaconic acid yields a methyl ether an amorphous yellow powder m. p. 94-10Z0 softening a t 82O which unlike guaiaconic acid does not develop a blue colour with lead peroxide. By oxida- tion with potassium permanganate in acetone-glacial acetic acid. solution the ether yields a comparatively large amount of veratric acid and other products which were not identified. Believing at first that guaiene was 1 2-dimethylnaphthalene the authors synthesised this substance as follows.By treatment of their sodio-derivatives with methyl iodide in warm benzene the P-phenylethylmalonic esters yield respectively methyl 8-phenyl- ethylmethylmlmate b. p. 178-180°/18 mm. and the-ethyl ester b. p. 182-184O/ 12 mm. from which B-gF~ienylethylmethylmalo~ic acid colourless crystals m. p. 150° (decomp.) is obtained. At 150-180° the acid is converted into y-~henyl-a-methylbutyric acid b. p. 167O/11 nun. the acid chloride of which b. p. 125*/12 mm. is converted in light petroleum solution by aluminium chloride into 1-keto-2-methyl-l 2 3 4-tetrahydro- naphthalene b. p. 127-131°/12 mm. This is converted by ethereal magnesium methyl iodide into I-hyd~oxy-1 2-dimethyl- 3 2 3 4 - t e t m h ? / ~ r o n c T ~ t T ~ ~ e n e b. p.135-140°/15 mm. m. p. 64-66O. which at 160-180° yields 1 Z-dimetTt?/l-Al-dihyd.ro- ?mnTztknlene b. p. 250-251°/atm. or 114-116°/15 xnm. D17 0.9885 q$n 1.5763. The dibromde of the latter a pale yellow oil is converted by boiling met.hyl-alcoholic potassium hydroxide into 2-met 7w2-l-nt e t T~?/lene-~"-dih,~4dro72arrTtffi.c~len c b. p. 157'1 15 mm. which yields 1 2-~~methvliiapktfi.nteite b. p. 139-140°/ 15 mm. (il)ic/xte oranpe-red crvstals m. p. 129*5-130'5°) by boiling with glacial acetic acid containing hydrogen chloride. c. s. Classification of Organic Colouring Matters. M. DOMINIKIEWICZ (Cheni. Z e i t . 1918 42 549-550 562-564) .- In the method of classification proposed the substances are arranged under chief types depending on the constitution of theORGANIC CHEMISTRY.i. 87 nucleus these types being subdivided into classes. The types include the quinone type the diphenylmethane type the safranine type t.he indigo t.ype etc. Sulphur derivatives and substances of Tannin and the Synthesis of Similar Substances. V. EMIL FISCHER and MAX BERGMANN (Ber. 1918 51 1760-1804. Compare A. 1912 i 471 887; 1913 i 479; 1915 i 437).- Previous attempts to prepare pentadigalloylglucose did not lead to the desired result owing to the unfavourable properties of tho methylcarbonat,o-compounds. Recently however it has been found possible to prepare the penta-acetyl derivatives of ?n- and p-digallic acids and the corresponding chlorides in the crystalline state (A. 1918 i 172) ; from these the pe~ta-(pent~-acetyldi~alloyl)-glucoses have now been prepared as well as the corresponding penta- (digalloy1)-glucoses.Penta-(m-digalloyl)-P-glltcose is shown to be remarkably similar to Chinese tannin the only point of difference noted being in the specific rotation in aqueous solution. Since however tlie solutions are colloidal in character and their optical activity is greatly influenced by sinall factors the authors do not consider the discrepancy is necessarily fundamental. The chemistry of the pentagalloylglucoses has been further studied (compare A. 1915 i 437) and through the triacetyl- galloyl derivatives i t has now been found possible to isolate pro- ducts which consist almost entirely of the pentagalloy1 derivatives of a- and &glucose respectively. unknown constitution form two separate classes.w. P. s. The preparation o€ 1-galloylglucose C,H,(OH),*CO*O*CH*(IH (OH)*CH(OR)*C H*CH(OH)*CH,*OH I 0 I is also described this being the first acyl derivative of glucose to which a definite structure can Is0 with certainty assigned. It is in all respects identical wit.h the gfucogallin isolated by Gilson from Chinese rhubarb (A. 1903 i 355). [pen ta-ace t my-m- b e n zo yloxy b e ncoyl] chloride @,I~,(OBC)~=CO~O~C,~~(OA~)~*COCI six-sided plates m. p. 18Q0 (corr.) after slight previous softening is obtained by the action of phosphorus pentachloride on m-digallic acid in the presence of chloroform and is converted by methyl alcohol in the presence of quinoline into met.hyl penta-acetyl-nz-digallate 1x1. p. 167-168O (corr.) (compare A 1918 i 174). It.reacts with P-glucose to yield i ~ e n t c c ( i M e i a t c c - n c e t y l - ~ ~ ~ a l ~ o ~ l ~ - P - ~ ~ u c ~ ~ ~ [C,I~,(OAc),-CO~O*C,H,(OAc)2*CO],C,13[,06~ two specirneiis of which had [a] -I-3.79O and [a] +2-60° i i i s-tetrachloroethane. [Pc rbta- (pert tn-ace tyl-p-digalZoyl)-~-glucose is obtained in a similar manner; it has [a]? + 1 . 5 4 O (in s-tetrachloro- ethane) and resexnbles the nz-derivative so closely that an analytic a1 distinction is alnios tr impossible.] Pen t a-( rn -digaZlqZ)- &glucose is prepared by deacetylation of the acetyl derivative with cold aqueous sodium hydroxide a t Oo and is purified by meam of the potmsizcnz salt; according t o the method of separatiion it forms I'enta-ace tyl-m-digalloyli. 88 ABSTRACTS OF CHEMICAL PAPERS.a pale brown light amorphous powder or a compact honey-yellow brittle mass. When hydrolysed by dilute sulphuric acid it gives approximately the same amount of dextrose and gallic acid as does Chinese tannin When treated with diazomethane i t yields penta-(penta~~thyldigalloyl)-glucose which like the earlier pre- parations is not perfectly uniform but which shows a very close analogy with the methyl derivative of the natural Chinese tannin. Reacetylation of penta-(m-digalloyl)-&glucose shows that a certain amount of change (possibly isomerisation of the &glucose to a-glucose derivative) occurs either during hydrolysis or on treat- ment with acetic anhydride. Penta-(pentu-ucetyl-m-digalloyZ)-a-glucose is prepared in the same mmner as the &derivative ; individual preparations had [a]= + 30*8O + 2 7 * 7 O and + 25’5O (in s-tetrachloroethane) point- ing to admixture with varying amounts of the @-isclmeride.[The corresponding penta-(pelcta-ucetyZ-p-G?~g~lloyl)-a-g~uc~se shows the closest analogy with the ,&compound 3 Penta-(m-~,~gaZZoyZ)-a- gZucose is a pale brown amorphous powder which can only be dis- tinguished from the &glucose derivative by its specific rotation ; it has [a] +43*8O (in water) [a] +35*8O (in alcohol) and [a] +40.1* (in acetone). Acetylation of Chinese tannin yields a penta-(penta-acetyldi- gallo y1)-glucose closely similar to penta-( pen t a-acetyl-m -digalloyl)- P-glucose; the regenerated tannin however is found t o differ some- what from the original specimen. Pen~ta-(tr~ucetylgulZoyl)-a-glucose ~C,B,(OAc),~CO~,C,”,OF is prepared in the usual manner from a-glucose and triacetylgalloyl- chloride; it forms an amorphous mass having [a] +42-7O to -t 46.95O in s-tetrachloroethane.Deacetylation is accomplished by means of sodium acetate in aqueous acetone solution; the penta- galloyl-a-glucme thus obtained is distinguished from the previous preparation (by hydrolysis of penta-[t rimethylcarbona t ogallo yl] -a- glucose by alkali) by a considerably higher specific rotation in aqueous and alcoholic solution but otherwise the resemblance is very close. On treatment with acetic anhydride the original acetyl derivative is regenerated. Diazomethane converts it into penta-(trimethylgalloy1)-a-glucose identical with that previously described (Zoc. cgt.).Pentn-( trincet?/l~aZlo?ll)-8-g~ucose is a pale yellow amorphous mass which has [a]; + 5*61° o r -I- 4.lo in s-tetrachloroet,hane; when deacetylated it yields pentagallo~l-~g.Iucose having ra]; + 23-3O (in alcohol) [a]; +13*6* and +13.lo in 10% and 1% aqueous solution. When treated with diazornethane it givee a penta-(tri- methvf~alIoyl)-~-~lucose which in its properties and optical activity closely resembles the preparation previously described (A. 1915 i 438\ but which unlike the latter could not be caused t o crystalhe. ReacetyIafion yields a produet closely resembling the original substance. Rydi-olysis of the two penta-(triacetyl- galloy1)-glucoses by alkali at Oo yields a- and /3-derivatives re- wectively which are quite distinct although less so than whenORGANIC CHEMISTRY.i. 89 sodium acetate is used. (In the case of the corresponding methyl- carbonatcmompounds practically identical products were obtained when the hydrolysis was effected by alkali a t the ordinary tempera- t u e . ) Yentu-(pace toxy b enzoy1)-a-glucose [CGH4(0Ac)*CO],C”,H706 forms fine needles m. p. 158-169O (corr.) [u] +124*7O in s-tetra- chloroethane ; during the preparation considerable quantities of the P-isomeride are formed which are removed during purification. The corresponding penta-(p-hydroxybenzoy1)-a-glucose could not be caused t o crystallise but the specific rotation of the product (+ 163-4O in alcohol) was considerably greater than that previously found ; on reacetylation it yielded the crystalline acetyl derivative in excellent yield. The preparation of penta-(p-acetozybenzoy1)- @-glucose and of penta-(p-hydrozyb enaoyl)-fl-glucose is also described but the substances could not be caused to crystallise and are probably admixed with the corresponding a-derivatives. 1-Triacetyigalloyl-2 3 5 6-tetra-acetylgiucose is prepared from acetobromoglucose and silver triacetylgallate ; it f oms microscopic needles or four-sided leaflets m.p. 125-126c (corr.) after slight softening [u]g -24.4O in s-tetrachloroethane. It may also be obtained from tetra-acetylglucwe and triacetylgalloyl chloride. When dissolved in alcohol and treated with ammonia a t 20° it yields 1 -monogalloyl-fl-glucose microscopic oblique prisms or plate- lets m. p. 214-215O (corr.; decomp.) when rapidly heated 202-203c (corr.; decomp.) when slowly heated; it has {a]:- 25’6’ in aqueous solution. The product is quite distinct from the gluco- gallic acid described by Feist (A 1912 i 566 888; 1913 i 70). When reacetylated it yields triacetylgalloyltetra-acetylglucose. Its action towards enzymes has been investigated. I t s identity with glucogallin is established both by chemical tests and by measurement of the crystals. l-Gall~yl-~-glucosemtrnoacetate forms colourless nwdles [u] +10-5O (in alcohol); it has no dis- tinct m. p. but when rapidly heated is converted into a viscous turbid liquid a t about 15OC after marked softening. 1-Gdloyl-@- gZulucosetetra-acetate ( 1 ) crystallises i n needles rn. p. about 136-137O [u]= +38-7O (in alcohol) but its isolation in the pure condition is not claimed.1-Benzoyltetra-acetylglucose is prepared from benzoyl chloride and 2 3 5 6-tetra-acetylglucose and agrees in its properties with the product described by Zernplh and Lfiszl6 (A. 1915 i 651) except in specific rotation ([aE - 26.6O in chloroform). 1-o-A cet- oxyb enzoyl-2 3 5 6-tetra-ncetyzg~ucose crystallises in microscopic flat prisms. It has m. p. 116-117O (corr.) [u] -41*Oo in s-tetra- chloroethane. H. W. Structure of P-Glucosidogallic Acid. EMIL FISCHER and MAX BERGMANN (Ber. 1918 51 1804-1808).-The work of Fischer and Strauss (A. 1913 i 180) has led to the supposition that P-glucosidogallic acid contains the sugar residue attached to the p-hydroxyl group of gallic acid; this hypothesis is confirmed by its conversion into glucosyringic acid (Mauthner A.1910 i 667).i. 90 ABSTBACTS OF CHEMICAL PAPEBS. Ethyl tetra-acetylglucosidogallate is converted by diazomethane into ethyl tetra-acetylglucosyringate from which glucosyringic acid is obtained by hydrolysis with barium hydroxide; the free acid has m. p. about 225O (decomp.) when moderately rapidly heated and [a]~-18*1S0 (as sodium salt) in water. Ethyl triacetylgallata has m. p. 138-139O (corr.) instead of 132-134* (A. 1915 i 683). Ethyl hexa-acetylglucosidoganate bas m. p. 176-177O (corr.) [u]’ - 19*Oo in tetrachloroethane solution. H. W. Digitalis Substances. XXXVIII. H. KILIANI (Bey. 1918 51 1613-1639. Compare A. 1916 i 493).-The pre- liminary cryst.allisation f rom 85% alcohol is nnnecessary in order to separate the digitonin from $he gitonin in “crude digibnin srnylate” (Bey. 1916 49 701).It suffices to dissolve the crude ainylate in ten parts of boiling 50% alcohol; o n cooling gitonin material separates first and pure digitonin subsequently. A sample of “ soluble digitonin ” supplied by Merck proved .Lo be identical with a new glucoside obtained from the final mot-her liquor of the crude digitonin (loc. cit.). The sugar syrup previously obtained (Zoc. c i t . ) could iiot be made t o crystallise because the sugars in the syrup which had beeu produced in an alcoholic medium are present chiefly in the form of ethyl glucosides. After a second hydrolysis with hydrochloric acid a partial crystallisation can be effected and d-galactose obtained by inoculation ; dextrose identified as d-gluconic acid is present and apparently also a third sugarJ 3 ketose since the syrup is shown to contain oxalic and glycollic acids. (The hydro- chloric acid was removed by silver oxide and it is known thatq silver oxide acts on hexoses particularly keto-hexoses t o produce these two acids.) During the conversion of digitogenin C31H5006 into digitogenic acid CBH4*08 three atoms of carbon are removed.Their fate has not been ascertained; it is shown that they do not appear as acetone acetaldehyde malonic propionic or carbonic acid. Digitogeiiic acid has [a] - 67-1O in aqueous potassium hydr- oxide and forms a magnesium salt C28H4,0,Mg,7H,0 small hard nodules of minute needles. P-Digitogenic acid has [afD - 6 0 ~ 2 ~ in aqueous potassium hydroxide and forms a magnesium salt micro- scopic prisms and needles with 7H20.The m. p. of digitogenic acid is altered by crystallisation and is therefore no safe criterion for identification. The acid is not reduced by hydrogen and colloidal palladium amalgamated zinc and hydrochloric acid or zinc dust and acetic acid. The acid CI6H2*O7 obtained by the oxidation of digitogenic acid in about 15% yield (loc. c i t . ) is obtained in about 27% yield by oxidising the amorphous precipitate thrown down by adding water t o the mother liquor of the crude digitogenic acid. It is oxidised by potassium permanganate in strongly alkaline solutionORGANIC CHEMISTRY. i. 91 yielding an amorphous acid C15H220,,Hz0 decomp. 120-130° softening a t about 70° which forms an amorphous maynesium salt (%.E3[1@7)&gdjH2O.The mother liquor of the crude acid CI6H,O (Zoc. cit.) con- tains in addition to other substances a t least two very easily soluble acids one of which has been identified as ethylsuccinic acid. The oxidation of gitogenic acid by hot chromic acetic and sulphuric acids yields an acid C18H2806 tufts of needles m. p. 210° sintering at about 206O (calciuni salt C18Hz606Ca,2H@) an acid C19H3000 m. p. 201-202° (calciunz salt; ClsHzsO6Ca amorphous) and ethylsuccinic acid. Digitoxigenin is not reduced by hydrogen and colloidal palladium and is oxidised by chromic and acetic acids yielding a neutral substance C1,H2,0 crystals m. p. 1 8 5 O . Digitaligenin forms an cccetyl derivative c2,H,80,Ac colourless prisms or needles m. p. 201-202O (digitaligenin also has m.p. 201-202° not 210-212O as stated previously) and is reduced in aqueous methyl-alcoliolic solution by hydrogen and colloidal palladium yielding a szcb.sta?z ce C1SH2ir(or3(1,03,H2Q crystals m. p. 182-184O sintering a t 1 7 5 O which is oxidisecl by chromic and acetic acids yielding a neutral szcbstmzce C1SH2ciurs)08 stout crystals m. p. 190-192O and an acid C,,H,,O (by analysis) or CllH1603 (by titration and by analysis of the calcizcm salt) colour- The Isomeric Lactones Caryophyllin and Urson. FRANCIS D. DODGE (J. Amer. Ckem. SOC. 1918 40 1917-1939).- Comparison of caryophyllin and urson shows a very close similarity of these compounds ; in strictly chemical properties no differences have been observed but the variations in the physical properties appear to warrant the conclusion that they are isomerides of very similar structure. The balance of evidence is in favour of a lactonic constitution but in certain respects (practically instantaneous neutralisation of alkali in alcoholic solution opening of lactone ring on acetylation) an unusual behaviour is exhibited. Caryophyllin is most readily obtained in the pure state through the potassium salt and crystallises in white needles (+ 2H20) ; the anhydrous substance has ni.p. about 310° (corr.) [a]= +54-5* in alcoholic solution; in a vacuuin t u b a t 280-300° it sublimes in characteristic rosettes. The potcrssiic m salt forms well-defined prisms (+ 1.5H20) ; the anhydrous salt has [a];k” + 63.4O in ethyl alcohol + 67.7O in methyl alcohol. Analyses lead to the formula C,,E,,O,K f o r the salt and hence to (C10H16.0)3 for caryo- phyllin.The calcizcm lead magnesium zinc and szlver salts are described. Acetylation of caryophyllin under various conditions leads t o the formation of diacetylcaryophylllinic acid and acetylcaryophyllin ; the former substance is somewhat unstable but can be obtained in the pure state by evaporation of an ethereal Eolution of the crude acetylation product a t the ordinary temperature. It slowly loses acetic acid a t the ordinary temperature; and is converted into less prisms sintering a t 240-245O without melting. c. s.i. 82 ABSTRACTS OF CHEMICAL PAPERS. acetylcaryophyllin by boiling ethyl alcohol or glacial acetic acid. The potassium salt is described. Acetylcaryophyllin forms white efflorescent needles m.p. 260-265° and yields a potassium salt which is readily soluble in alcohol. A very sparingly soluble sub- stance possibly a polymeric acetate is also obtained during the acetylation of caryophyllin. Qxida tion of caryophyllin with fuming nitric acid yields caryo- phyllic acid which is shown to be a somewhat unstable tribasic acid C27H,,03(C0,H)3 giving a characteristic sparingly soluble mono-potassizim salt. When heated with acetic anhydride it yields a compound m. p. 210-213O (slight decomp.) which appears to be an acetyl dilactone C31H4606 a molecule of carbon dioxide being eliminated during the process. Urson in its general properties is very similar to caryophyllin. The most striking difference is shown by t'he potassium salts that derived from urson being freely soluble in ethyl alcohol in which the caryophyllin salt is sparingly soluble; a method of separation is based on this dissimilarity The lead zinc magnesium and am- monium ( ?) salts of urson are described.Urson diacetata (diacetyl- ursonic acid) closely resembles the corresponding derivative of caryophyllin but is in general more soluble and less stable. Ds composition to the mono-acetate occurs so readily that it was found impossible to prepare a pure compound. Acetylurson separates from alcohol in plates or prisms (I- 5H20) quite different in appear- ance from the caryophyllin compound. It was not found possible to purify the product formed by the oxidation od umon with fuming nitric acid. H. W. 4-Phenylcounarins. 11. ADOLF SONN (Ber. 1918 5 1 1829-1832.Compare A. 1918 i 4Ol).-Further examples of the formation of 4-phenylcouznarins are given. Chloroacetylresorcinol dimethyl ether m. p. 114-115O after softening a t 112O [Tambor and du Bois (A. 1918 i 395) give 119O1 is obtained by the action of hydrogen chloride on an ethereal sotu- tion of resorcinol dimethyl ether and chloroacetonitrile in the pres- ence of zinc chloride and is converted by potassium cyanide into cy~noacetytresorcinoz dimethyZ ether prisms or plates m. p. P52-153O. The latter condenses with phloroglucinol in glacial acetic acid solution under the influence of zinc chloride and hydro- gen chloride yielding 5 7-dihydroxy-2/ 4 ' ~ ~ r n e t h o x ? i - 4 - ~ h e ~ ~ ~ c o z l - marin hexagonal prisms m. p. 2 3 2 O (decomp.). Similarly c~~arcoacety2catechol m.p. 222O (decomp.) after previous softening condenses with phloroglucinol to 3' 4' 5 7-tetrahydraxy- 4-phenylcozcmarin which after being purified through the acetyl derivative forms platelets (-t 2H,O) m. p. about 270° (decomp.). H. W. Improvements in and Relating to Synthetic Drugs [Mydriatic Alkaloids]. NAGAYOSHI NAGAI (Brit. Pat. 120936). -Synthetic racemic N-methylmydriatine OH*CHPh*CHMe*NHMe,ORQAMC CHEMISTRY. i. 93 or its salts is prepared by the condensation of benzaldeliyde with nitroethane by agitation for several hours a t the ordinary tempera- ture in the presence of a small quantity of a solution of a weak alkali such as an alkali carbonate or hydrogen carbonate or phos- phate or pyridine etc. The condensation product phenylnitro- propanol OH*CHPh*CHMe*NO is separated by extraction with sther and freed from benzaldehyde by shaking the ethereal solution with aqueous sodium hydrogen sulphite.The oily residue is dis- solved in dilute alcohol the calculated quantity of formaldehyde is added and the mixture is reduced a t a low temperature by adding dilute acetic acid and zinc dust The liquid is filtered and the zinc precipitated by hydrogen sulphide; the solution is evaporated in a vacuum and the resinous residue is shaken with dilute hydrochloric. acid and ether. The hydrochloride of tlie base is obtained by eva- porating the aqueous layer and is recrystallised from absolute alcohol. This synthetic ephedrine differs in constitution from Fourneau’s ephedrine (A.? 1907 i 762) and is the racemic form of natural ephedrine. J.F. B. Alkaloids of the Betel Nut. KARL FREUDENBERG (Bey. 1918,5 1 1668-1682).-Guvacine is 1 2 5 6-tetralnydropyridine-3-carboxylic acid according to the author (A 1918 i 403) and 1 2 5 6-tetra- liydropyridine-4-carboxylic acid according to Hess and Liebbrandt (A*? 1918 i 401). The author now shows that his view is the correct one by (i) tlie direct comparison (mixed m. p.’s etc.) of corresponding derivatives of guvacine and Wohl and Johnson’s 1 2 5 6-tetrahydropyridine-3-carboxylic acid (2) by the identity of N-methylguvacine with natural arecaidine and (3) by a compari- son of dihydroguvacine with nipecotinic acid and isonipecotinic acid. Contrary to the statement of Hess and Leibbrandt dihydroguvacine differs in every way from isonipecotinic acid and is completely identical with nipecotinic acid (piperidine-3-carboxylic acid).Di- hydroguvacine has m. p. 261O (decomp.; corr.) not above 320° as stated by Hess and Leibbrandt (Zoc. cit.). The nipecotinic acid used by Hess and Leibbrandt was in reality almost pure isonipeco- tinic acid. Several other errors in their paper are corrected; for example N-methylguvacine (arecaidine arecaine) when esterified by alcoholic hydrogen chloride is not demethylated a t the nitrogen atom. c. s. The Physical Constants of Nicotine. I. Specific Rotatory HARRY JEPHCOTT Power of Nicotine in Aqueous Solution. (T. 1919 115 104-108). Some Derivatives of Pyrrole. IV. G. KARL ALMSTROM (AnnuEen 1918 416 279-290. Compare A. 1913 i 1240; 1915 1 989 ; 1916 i 568).-In some reactions 5-hydroxy-4-acetyl-1 3-di- phenylpyrrole (A.? 1916 i 568) behaves as though it were the s-keto- compound. It is not attacked by boiling alkali hydroxide and benz- aldehyde but by heating with methyl iodide and alcoholic sodium methoxide a t 100° yields a mixture of 4-acetyt-1 3-diphenyl-4- VOL.CXVI. i. ei. 94 ABSTRACTS OF CIIERIfCAL PAPERS. ~ i e t J ~ y 1 - 5 - 1 ~ ~ r ? ' o ~ o t ~ ~ colourless crystals ni. p. 115-116O (semicc11.7~ cmme m. p. 2 1 7 O [decomp.]) and 1 S-cCiphetiyl-4-meI?~yl-5-ir?/l.roEo~~ e colourless needles m. p. 113-114O. The latter of these is also obtained by heating the former with moderately concentrated sul- phuric acid and is oxidised by chromic and acetic acids t o yrhenj/l- >NPh pale yellow quadratic 11 r t Jt,yIttialeit~pJ~ ejiy1 imide l'lates m. p.106-10'i0 from which aniline and plAe/iyZnLetlbyl- rrinleic cmhyd~ide m. p. 94-9rio are obtained by boiling with alcoholic sodium ethoxide. By heating on the water-bath with 2N-sodium hydroxide and a large excess of methyl sulphate 5-lnydroxy-4-acetyl-l 3-diphenyl- pyrrole yields 1 3-diphenyl-4-methyl-5-pyrrolone and 4-uce tyl-5- rihethozy-1 3-diphenyZpyrrole7 colourless crystals m. p. lolo which forms a semicarbnzone pale yellow crystals m. p. 215O (decomp.) yields 1 3-diphenyl-5-pyrrolone by heating with moderately concen . trated sulphuric acid and is converted into 4-cinnamoyZ-5-metJioxy- 1 3-dip?heiLylpjrrole7 yellow crystals m. p. 111-112° by heating with aqueous-alcoholic sodium hydroxide and benzaldehyde.1 3-L)iphenyl- 4 - etlzyl - 5 - pyrrolone colourless plates m. p. 118-119° yields pJ~e.nylethyZmaleii~phenyl~m~~e yellow rhombic plates in. p. 79-80° by oxidatlion from which aniline and phenyrll- etliylmaleic uithydride m. p. 46O are obtained by the action of sodium ethoxide. 5-€Iydroxy4-acetyI-l 3-diphenylpyrrole does not yield crystalline products by treatment with acetic anhydride diazometliane or acetyl chloride but it reacts wit,h magnesium methyl iodide and tlien with acetyl chloride t o form a szLbstnncu CI8HlGO3N colourless EMe-CO CPh*CO Iieedles m. p. 119-120°. c. s. General Reaction of Ketones. I GUARESCHI (Gazxetta 1918 48 ii 83-98).-The author has extended his work on the condensation of ketones with ethyl cyanoacetate in presence of ammonia o r an amine (A.1902 i 819) to benzyl methyl ketone and its homologues in order to ascertain which ketones react incom- pletely or not a t all with the cyanoacetate and to study the manner in which the new compounds decompose with formation of hydro- carbons. 3 5 -Dicyan o - 2 6-dik et o -4-7 P 11 zyl-4 - m e t Ji y l i i pe r'idin e tlie 1-ammonium derivative of which is formed from benzyl methyl ketone ethyl cyanoacetate and ammonia crystallises in shining needles or prisms m. p. 255-257* and has an acid reaction in aqueous solution; its ammonium salt is crystalline and in aqueous solution decomposes with difficulty into toluene and the ammonium derivative of 3 :A5-dicyano-2 6-dik&o-4-methyl-A3-tstrahydropyridine7 ~ ~ O g C ( ~ ~ ) ' - ' c * > " ~ * .CH(CN)*COORGANIC CHEMISTRY. i. 05 With bromine water 3 5-dicyano-2 6-dil;et0-4-benzyll-iriethyl- piperidine gives a dibromo-derivative which when boiled with alco- hol best with addition of a little formic acid rapidly loses bromine yielding 3 5-dicyano-4-t~,zz;?/l-4-~tiethyltrimet7~~7e1eec~icarborfLz’.nzi~r v >NH IY~. p. 266-268’. C( CN)*CO C( CN)*CO CH,Pli*CMe < I p-P henylet’hyl ‘methyl ketone yields 3 5-dicyano-3 6-diketo-4-6- 3 5-Dicyuti 0-2 6di/kto-4- betiz;?/l-4-etZi?lll”’periclin e phenylethyl-4-methylpiperidine which has been already described. obtained from benzyl ethyl ketone forms crystals in. p. 222-226O wliich absorb bromine giving the dibromo-derivative. The latter loses its bromine when boiled with alcohol and formic acid yielding 3 5-clicyuno-4-bett syl-4-met h yltrimethylen eclicnrboni~ri ide >NH C(CN)*CO C(CN)* co CH,Ph*CEt< I m.~ 4 . 226-228O. 3 & 5 -1) icycr n o - 2 6 -cli?c e t 0-4-/3-ph e IZ yle t lql-4-e t hylpz*pe ridin e prepared from /3-phenylethyl ethyl ketone forms crystals ni. p. 181-183O. forms colourless needles m. p. 248.5-249.5O. When treated with alcohol and formic acid its dibromo-derivative decomposes yielding a colourless crystalline compound m. p. 255-257O which is prob- ably 3 5-dicyan~-4-benzyl-4-isopropyltrimethylenedicarbonimide. Benzyl isobutyl ketone condenses with ethyl cyanoacetate and ammonia giving a small quantity of a compound which crystallises in needles m. p. 223-225O but was not analysed. With d i u r n hydrogen sulplGte benzyl methyl ketone B-phenyl- ethyl methyl ketone and benzyl ethyl ketone form crystalline coin- pounds but this is apparently not the case with @-phenylethyl ethyt ketone or benzyl isobutyl ketone.T. H. P. The Three Phenacylaminobenzoic Acids. M. SCHOLTZ (Ber. 1918 51 1645-1653).-The t‘hree aminobenzoic acids reack with w-bromoacetophenone in boiling alcohol to f o m o-phenacyl- aminobenzoic acid COPh*CH2*NH*C,H,*C0,H yellow leaflets m. p. f90° (phenylhydrazone yellow needles m. p. ISSO) the m-isomeride e 2 :i. 96 ABSTRACTS Oh’ (THJ3MICAI; PAPERS. colourless crystals in. p. 20Z0 and the pisomeride colourless needles m. p. 2 1 1 O respectively. If alkali hydroxide or carbonate also is present in the reaction in the case of the ortho- and para- compounds a by-product is the phenucyl ester COPh*CH2-NH*CGH4*CO*O*CH2*COPh (0-ester hair-like crystals m.p. 180O; p-ester colourless needles m. p. 186O). By treatment with boiling acetic anhydride wt- and p-phenacylaminobenzoic acids are converted into the corresponding N-acetyl derivatives pointed prisms m. p. 2 1 7 O and leaflets m. p. 1 76* i*espectively but the ortho-conipound is converted into a sub- stance C17€€!,02N colourless needles m. p. OH Ph 288O which is regarded as 8-liydroxy-3-keto- b i y I - phenylpropenylene - 2 1 - i d o l e (annexed formula). It develops a blood-red coloration /‘”’’‘~’’\~~~ with alcoholic ferric chloride forms a di- rn. p. 265O and is converted by hot aqueous alcoholic potassium hydroxide into the potassium salt of an acid C(17H@3N colourless needles m.p. 300O (decomp.) which does not give a coloration with ferric chloride forms a dibromide pale yellow needles and yields a phenylhydrazone yellow needles m. p. 221° anti is therefore regarded as indo~~l-2-P-cznnamic acid a l ’ \</-- 3- ”0 hromide C17Hl102NBr2 pale yellow needles I t is acetylated by warming with acetic anhydride but the product C‘17H1203NAc rhombie crystals m. p. 1 6 7 O no longer exhibits the properties of an acid ; it regenerates indoxylcinnainic acid after pro- longed boiling with aqueous sodium hydroxide. By boiling with phenylhydrazine in glacial acetic acid all three phenacylaminobenzoic acids yield the phenylhydrazmze of s-phen- acylphenylhydrazine NHPh*N:CPh*CH,*NH*NHPh yellow needles m. p. 1 4 7 O (acetyl derivative C2,Hl,N4Ac yellow crystals m.p. o-Bromoacetoplienone and phenylhydrazine react in boiling alco- 1.10~1 to form not the preceding compound but a substance CZ8Hz4N4 colourless needles m. p. 174O which is regarded as tetw- and is isomeric with fi Ph*CH2*NPh*n N-NPh-CH2-C Ph’ 1’7Le~~E-P-tetracarbazo~~ the substance m. p. 137O obtained by Hess in 1886 from the same Aldehyde Derivatives of Rhodaniaes and their Fission Products. I. RUDOLF ANDREASCH (Nonatsh. 1918,39 419-440). -A stildy of the oxidation reduction and fission of various con- densation products of aldehydes and r’hsdanines. A solution of phenylbenzylidenerhodanine in boiling glacial acetic acid is oxidised by bromine t o phenylbenzylidenethiocarbimideglycol- lide m. p. 209O (compare A. 1917 i 663 in which the m.p. is given as 239O in error) ; similarly phenyl-o-nitrobenzylidenerhodanine yields phenyl - o - nitrobelz~!ylidertethiocarbimideglycoE~de woolly needles m. p. 204O. 2010). two reagents in alcoholic solution a t Oo. c. s.ORGANIC CHEMISTRY. i. 97 The followilrg substances have been prepared with a view to the study of their reduction 5-ethylrhodanine (from ethyl a-bromo- butyrate and ammonium dit'hiocarbamate) yellowish-white crystal- line powder m. p. 1 0 5 O ; 3-phenyl-5-ethylidenerh&anime thin pale yellow plates m. p. 123O ; 3-~henyl-5-ethylrhodanine pale yellow needles m. p. 83O ; o-nitrobenzyl p~~enyldit?Liocarhamate NHPhm CS*S CH,. CGH4*N0 sulphur-yellow needles m. p. 120-121O. Attempts to reduce ethyl- idenerhodanine and phenyletjhylidenerhodanine have not yielded satisfactory results u p t o the present.The various aldehyde condensation products of the shodanines are found to be decompossd with widely differing velocities by alkali ; those containing a hydroxy-group in the phenyl residue are particu- larly resistant so that in general they are only decomposed under conditions which lead to the further degradation of their fission products. The most suitable reagent is a solution of sodium amyl- oxide in amyl alcohol probably by reason of the higher temperature which can be attained. Under these conditions phenplpiperonyl- idenerhodanine yields phenylthiocarbimide and rnethylenedioxy-a- thiolcinndmic acid CH,O,:CGH,*CH:C(SH)*CO,H yellow micro- scopic needles which begin to decompose a t ca.170° and are com- pletely molten a t 208-210°. The latter acid is transformed bv iodine into ~iSUlZJhidObiSnzethylene~~ox~ci?7ltctmic acid m. p. 228O. Sirnil arl y p-hyderow/-m -m e t hozy-a- thiol cinnamic acid OH*C,H,(OMe)*CH:C( SH) *C09H palo rlirome-yellow rlioinbic plates m. I). 183O after softening at! 1 70° is obtained from the condensation product of vanillin and pheuylrhodanine whilst the anhydride of o-hydroxy-a-thiolcinnamic acid (m. p- of benzyl derivative 164-165O) is prepared from phenyl-o-hydroxybenzylideiiethiocarbimide~lycollide. Phenylfuryl- id enerhodanine yields f u r y It hio la crqlic acid C,H,O*CH :C(SH)*CO,H fine needles m. p. 102-103° which is transformed by iodine into the corresponding disdphido-acid lemon-yellow needles or hexagonal plates m.p. 190-1 91 O. Fission of p-hydroxybenzylidenerhodanine m. p. 2 7 4 O after softening a t 260° did not lead t o the isolation of p-hydroxy-a-thiolcinnarnic acid but its formation was proved by the separation of its h ei?uyZ derivative colourless microscopic needles m. p 1 8 3 O . The free acid chrome-yellow needles m. p. 1860 was prepared by the action of a solution of sodium amyl oxide in hot amyl alcohol on ph en?/l-p-hy~ro~ybenzylide~erh.oda~i?~~ cadmiuni-yeIIow needles m. p. 285O. The corresponding disulpltido- c~cid is a yellow crystalline powder m. p. 197O. pDimethyZamino- a-thiolcinnarnic acid has rn. p. 160° ; the corresponding disutphido- acid is a scarlet powder m. p. 198O. PCAminobenzylidenerhodaniize forms fine woolly needles rescm- bling chromium trioxide which soften a t about ZOOo and are not completely melted a t 290° ; 2 4-diEeto-5-p-aminobenzylidenethiazol- iditbe 7 o-s>C:~H-C,H,*NH is a dark reddish-brown powder NH*COi .98 ABSTRACTS OF CHEMICAL PAPEltS. which further darkens from about 200° and has 110 definite H I . p. Attempts to decompose these sdbstances as also phenyl-o-nitrobeiizyl- idenerliodanine by alkali led to negative results. H. W. Parabanic Acid. BQBERT BEHREND and ADOLF ASCHE (Amalen 1918 416 226-228).-Parabanic acid can be obtained in about 33% yield by rapidly adding 8.4 g a i m of uric acid to 39 C.C. of nitric acid D 1.3 heated at 70° evaporating the solution ti0 dry- ness and evaporating the residue two or three times with nitric acid D 1.4 until the evolution of gas ceases. The product is New Compounds to be employed as Colouring Matters or in the Production of Colouring Matters.ANJX~EA ANGEL (Eiig. Pat,. 121347 1917).-R new type of compoiiiids for which 1 he iianie of “ parazones ” is suggested coiitains two benzene iiiiclei (or nuclei of benzene derivatives or other cyclic groups) linked togekher through four para-carbon atoms of the nuclei by two nitrogen atoms. Of the three phases of the foimula which may be assigned to parazene two (I and TIT) become identic&l in the absence of uiisyminetrical substitution crystallised from boiling water. c. s. -+ (111.) Parazelies are prepared by heating a parahalogen substituted aniline or a-naphthylamine or derivatives of either containing indifferent groups in the nuclei with a condensing agent such as zinc chloride ferric chloride aluminium chloride or phosphoric oxide.The product oi the reaction is a hydroxyparazene which is converted by reduction into para- zene. The parazene thus obtained from 2,-chloroaniline is a dark blue powder -which when dissolved in dilute acetic acid may be used for dyeing wool or silk. Special colouring matters may be produced by introducing auxochromic groups by t,he ordinary methods. Parazelies mill form salts with acids by addition to one 0% both of the nitrogen atoms. [See further ,7. SOC. Cham Ind. 1919 February.] C. A. M. Interaction of Aliphatic Diazo-compounds and Diphenyl- keten. J. SUREDA Y BLANES ( A m l . Fis. (Jziiin. 1918 16 611-624). -With phenyldiazomethane diphenylketen produces a substance C,,H,,ON white crystals m.p. 1 9 6 O . Diphenyldiazomethane and diphenylketen yield yeIlow crystals m. p. 133-135O (decomp.). The product from diphenylenediazomethane arid diphenylketen is a dark yellow powder m. p. 1 5 7 O (decomp.). The constitution of these sribstances is being farther investigated. A. J. W,ORGANIC CHEMISTRY. i. 99 Preparation of True Vat Dyes from Di- and Tri-aryl- methane Dyes. HEINRICH WIELAND (D.R.-P. 308298 fro111 Clwni. Zentr. 1918 ii 782-783).-33y treatment of the dyes with alkali hyposulphite solution colourless alkali salts are obtained which are soluble in water and are reoxidised to the original dyes with extraordinary rapidity by atmospheric oxygen. For example crystal violet yields sodiu-m hexamethyltriamiiiotriphenyl- niethanesulphonate C(C,II,*NMe,)3*S0,Na crystallising in glisten ing needles.H TV. B. Some Derivatives of Isatin. ANDRB MEYER (Conzpt. ?-e?zd. 1918 167 1070-1073) .-When the amino-oxindole obtained by the reduction of isatoxims with tin and hydrochloric acid ii oxidised by potassium f erricyanide in dilute solution in additioii to isatin a small amount of a red compound is obtained. If the isatosime is reduced by zinc and acetic acid the z i n c salt C,,H,O,N,Zn of this red compound is obtained. From its behariour on reduction with sodium hyposulphite or when dis- solved in sulphuric acid the author considers that the red com- pound is probably identical with Me F -C-N=C' " Wahl and Bagard's isoindigotin. 3XeN 60 1 Mixed rubazonic acids of the isatiii %<\/ series may be prepared by condensing in alcoholic solution amino-anti- pyrine with isatiii 5-bromoisatii7 5 7-dibromoisalin and naplithisatin.They have the general COII- stitulion (annexed formula). where X represents the substituted \/ NPh benzene 01- naphthalene nucleus. 117. G. Derivatives of the Iadole and Indigotin Groups Sub- stituted at the Nitrogen Atom. AUGUST ALBERT (Aitsznlciz 1918 416 240-278. Compare A. 191G i 821).-l-IIydroxy-2- t~hio-3-benzoyloxyoxindole (A.? 1915 i 595) only reacts in the thioii form in forming the acetyl derivative. In all other cases it reacts in the thiol-form C,H,<CH'*~~>C*SH. For example it reacts with phenylhydrazine in cold alcoholic or glacial acetic acid solution to form 2-thiol-3-b e?izrr?/lox?/ocinclolepir cnylii ydrnsoir I - I - .. C H - J/,yclrnte NHPh*NH*N(OH) <c~s&>CI?l*OB~ pale yellow plates 111. p. 123-126° (decoinp.). whi'ch is also formed from the acetyl derivative acetic acid being eliminated. The phenylhydrazone hydrate is interesting in that the sulphur can be extraordinarily easily eliminated. LY/ 2-Sodium hydroxide converts it into 1 I' - bisphei2?/2hydrazi.II oindigo t in,i. 100 ABSTRACTS OF CHEMICAL PAPERS. which the presence of the tlwo carbonyl groups is shown (1) by heating on the water-bath with aniline or ptoluidine and its hydrochloride whereby the hydrochloiide of the and steel-blue needles decomp. 240° or of the p-tolil greenish-blue crystals decomp. 218-223* is obtained and (2) by heating with phenylhydrazine and its hydrochloride whereby the bisphenyl- hydrazone C40H34N10 yellow plates decomp.200-206° is obtained. Certain reactions indicate that 1 1'-bisphenylhydrazinoindigotin is able to react in the tautomeric enolic form Ck,H,,N,,2HC4 C (OH)-- c (OH)-- C6H4<h(:N.NHPh) )c:Q<g( :* .N Hph)>CBH 3 Thus the substance is insoluble in dilute aqueous sodium hydr- oxide and is only sparingly soluble in alcohol but dissolves extremely easily in alcoholic sodium hydroxide the colour of the solution changing from yellow t o blood-red; the yellow colour is regenerated by the addition of water. These colour changes are still more pronounced in the case of the 1 1'-bisphenylmethyl- hydrazinoindigotin mentioned below ; the yellow colour of its alcoholic solution is changed t o dark green by alcoholic potassium hydroxide and is regenerated by the addition of water.The presence of two hydroxyl groups is proved by means of benzoyl chloride. I 1'-Bisph enylhydrazinoindigotin is boiled with 10N- sodium hydroxide unt"i1 t,he dark red sodium derivative is formed the mixture is then cooled and treated with benzoyl chloride whereby according to the conditions the dib enzod derivative. plates containing 2Hi0 m. p. 140-145O [hydrated] or 186-189O [decomp. ; anhydrous]) or the tetrnbenzoyl derivative yellow or yellowish-brown rhombic plates m. p. 158-159* i s obtained. The tetrabenzoyl derivative is converted into the dibenzoyl derivative by careful treatment with sodium ethoxide and into the bisphenylhydrazone of the latter by warming with phenylhydrazine and its hydrochloride a t 50°.By treatment with as-phenylmethylhy drazine I-hydroxy-3 - benzoyloxy-2-thio-oxindole is converted into a phenylmethylhydr- azone which could not be obtained crystalline and is readily changed by N/2-sodium hydroxide into 1 1 -6isphenylmethtyZ- hydrazinoindzgotin C3,H,602N6 yellow or yellowish-red needles m. p. 2 0 2 O (bisphenylhyd'razo~ne C42H38N10 yellowish-brown plates,ORGANIC CHEMISTRY. i. 101 decomp. 1 6 5 O ) . and methyl sulphate to form the dimethyl ether This reacts with cold alcoholic potassium ethoxide dark bluish-red plates m. p. 105O and its sodium derivative reacts with benzoyl chloride to form only a dihenzoyl derivative yellow quadratic plates M. p. 150-151°. The dibenzoyl deriv- ative is converted into the preceding bisphenylhydrazone decomp.165O by warming with phenylhydrazine the two benzoyl groups being eliminated 1 1 f-Bis-p - 71 rom oph e ti yl hydra einoindig ot in C,,R2,,0,N,Br2 f o m s orange-yellow rectangular plates m. p. 2 4 7 O (decomp.) and is converted by warm aniline and aniline hydrochloride into the Jtydrochloride of the anil C,,,H,N8Br2,2HCl blackish-blue micro- scopic plates m. p. 227-231O (decmp.). The preceding bisphenylhydrazino- and substituted bisphenyl- hydrazino-indigotins do not yield vat dyes on reduction but undergo profound decomposition the products depending on the nature of the reducing agent. The course of the reduction in acid media will be described in a later paper. The reduction of I 1 '-bisphenylhvdrazinoindiqotin suspended in benzene by alcoholic ammonium sulphide yields dihydroindigotin aniline and ammonia.Its reduction by N-sodium hydroxide and zinc dust in an atmo- sphere of coal gas for six days yields a pale yellow solution from which is precipitated by means of atmospheric oxyqen a dark blue zinc salt- probably of 1 1'-diaminoindigotin from which is liberat,etl by dilute hydrochloric acid the Jw/drochZoride of indigotin-1 1'- CQ--Q==zC ,or) imide I I I violet rectangular plates decornp. C,H,*N*NH*N-C,H ' 1 8 5 O . This' base forms an acetyZ derivat'ive a very sparingly soluble s u l p h t e 2C,GJ390?N3,H,S0 needles and other crystalline salts and is a true vat dye yielding with alkaline sodium hypo- sulphite a yellow vat from which the imide is regenerated by means of oxygen. The preceding zinc salt yields dihydroindigotin by reduction.c. s. Compounds Derived from Proteins by Energetic Treat- ment with Nitric Acid. VII. CARL TH. M~RNER (Zeitsch. physiol. Chem. 1918 103 80-83. Compare A. 1918 i 198).- The occurrence of 5-nitroglyoxaline-kcarboxylic and glyoxaline-4- glyoxylic acids both oxidation products of histidine among the products of the oxidation of protein is confirmed (see Knoop A. 1918 i 412). D. BREESE JONES and CARL 0. JOHNS ( J . Biol. Chem. 1918 36 323-334).-Kafirin the alcohol- soliible protein of kafir ( A ndropogon ~or~yhzcm) contains 21 -a?/ H. W. B. Hydrolysis of Kafirin.i. 102 ABSTEACTS OF CHEMICAL PAPERS. gliitairric acid 15.4% leucine 8.1 y6 alanine 7.8% proline 5*5() tyrosine 4.3% valine 3.5% ammonia 2-37; phenylalanine 2*3”/ aspartic acid 1 *S% arginine 1.1% histidine 0.9576 lysine and 0*84’j cystine.Tryptophan is also present but glycine is absent. liafirin theref ore closely resembles zein the alcohol-soluble protein of maize except in regard t o its content of tryptophan. H. W. B. Froteins of the Peanut Arachis hypogzea. 111. The Hydrolysis of Arachin. CARL 0. J o m s and D. BREESC JONES ( J . Bio?. Ciiem. 191 8 36 491-500. Compare preceding abstract). -Arachin contains 16.7% glutamic acid 13.5% arginine 5.5% Lyrosine 5.3% aspartic acid 5.076 lysine 4*1°4 alanine 3.9% leucine ?6(jL pIienylalanine 3.0°! aiiimonia 1*97& liisthicline 1 ‘4% proliiie absent. H. W. B. 1 .] n/ ,* valine and 0.9:; cystine. Tryptophan is present glyciue Chemical Study of Enzyme Action.I!. G . FALK (Scieizcc 1918 47 423-429; from Ph,?,ts~oI. A hsfr. 1918 3 407).-The chemical nature of enzymes is discussed in the light of the results od experiments previously published (compare A. 191’7 i 598). H. W. B. Studies in Fermentation. 111. Pepsin and Peptic Digestion. W. BIEDERMARN (_Zicn7~ciztforsc7. 1917 2 1-57 ; from Cfrem. %;elit?*. 1918 ii 741-742. Compare A 1917 i 62).-A suspension of coagulated egg white in water can be employed €or detecting a small amount of pepsin. The former is prepared from dried commercial egg albumin by dissolving in water acidifying with acetic acid adding sodium chloride and then heating to the Foiling point with continua1 stirring. The protein separates in very finely divided flocks which after washing and pressing can be rubbed u p with a little glycerol t o form a paste in which form it can be preserved indefinitely. A small fragment about the size of a pea in 10 C.C. of water forms a milky fluid which does not yield a perceptible sediment for several hours. On digestion with a trace of pepsin and hydro’chloric acid the turbidity quickly disappears. Fibrin is dissolved by dilute hydrochloric acid even in the absence of pepsin. Repeated addition of fibrin results in an increased rate of solution which appears t o indicate that an autolytic or peptic e:izyme is closely associated wit,li fibrin o r is formed from the fibrin by liydrolysis. If the fibrin is boiled prior to tlie experiment it doe. not dissolve so readily in the dilute acid. R. W. B. Trypsin and a New Method of Purifying Enzymes. JOSEPH T. WOOD ( J . SOC. t l h e m . Ind. 1918 37 313-315~).-1t has been stated by Holzberg (A. 1913 i 662) that when a saturated solution of safranine is added t o a neutral or very faintly alkaline sol11 tion of trypsin a precipitate is form etl which possesses proteo- lyiic. properties. This diitellleiit is coiifinirctl by tlie autlior. and it,PI~YSIOLOGICAL CHEMISTRY. i. 103 is shown that the precipitated inaterial consists of protein matter with the safraniiie and the enzyme in an adsorbed condition. Trypsin or other enzyme can be purified by dissolving in a small quantity of water and allowing the solution t o soak into filter or blotting paper. After rapid drying a t a low temperature the pro- teins are retained more tenaciously by the paper than the enzyme and on placing in water for a few minutes and then filtering a soln- tioii of the enzyme is obtained practically free from protein. Such a protein-free trypsin solution does not give any precipitate with safraniiie. H. W. B. Action of Mercuric Acetate on p-Toluidine. I. L. VECCHIOTTI (Gazzetttr. 1938 48 ii; 78-83. Compare A. 1914 i lT)G3).-The interaction of mercuric acetate (I mol.) aiirl gi4olu- i tl i t t e (I ni of. ) y i el cl s 11- f o 7u idi n c nz e rc I I ria cc f u f c NH2*C,H,Me*Hg*ORc which foims shining white crystals rn. p. 184O ; the mercuriacetato group probably occupies tlie ortho-position to tlie amino-group. Tlie corresponding hydroxide NH,*C,H,Me*Hg*OH crystallises in pale yellow plates m. I). 212-213O which begin t o turn brown a t about 1 20° ; it renders water strongly alkaline. The chZor2'cZ~ C,H,NClHg forms prismatic need!es m. I). 170°. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9191600061

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

MIPr'ERALOGICAL OHEMISTRY. Mineralogical Chemistry. ii. 71 Mineralogy of the H.B. Mine Salmo British Columbia. 7'. L. WALKER (Toronto Cniu. Studies G'eol. Ser. No. 10 1918 reprint 25 pp.).-The oxidised zinc-lead ores of this *ne consist of' a mixtnre of hemirnorphite cerussite and limonite and occur as bedded I ' veins " in metamorphosed limestone with associated quartzite and schists and penetrated by dykes of minette. A cave iu the mine contains also a iiuinber of zinc phosphate minerals I'orming large stalactitic pillars which yielded about a hundred toris of ore. These stalactites consist mainly of a core of spencerite with a thin crust of hemimorphite and between the two solutioii cavities containing crystals of hemimorphite (anal. I deducting G-667L calcite) spencerite hopeite parahopeite (anal.11 D 3*236) and hibbenite. Crystallo'graphic descriptions are given of each of Lhese minerals except the hibbenite the existence of which is not confirmed. On the floor of the cave and partly coating the stalactites is a deposit of a grey or cream-coloured non-plastic zincif erous clay (anal. III) resembling the so-called moresnetite and vanuxemite in composition but doubtless a mixture of some zinc mineral with clay. The phosphoric acid of these minerals was perhaps derived from the solution of apatite in .the surrounding rocks. ZnO. MgO. A120,. Fe,08. SiO,. P,Os. H20. Total. I. ...... 67.35 - - - 25.32 - 7-33 100~00 11. ...... 54.69 - - - - 30.46 15-31 100.46 111. ...... 19-99 3.97 16.07 8.01 39.49 0.26 11.12 98.91 The zinc phosphate minerals now known are the following; they 3"ii.72 ABSTRACTS OF CHEMICAL PAPERS. are all reniarkable for their chemical puriby) there being a com- plete absence OF elements n o t shown in the formulz (A. 1908 ii 397). Hopeite.. . . . . . . . . . . Zn,(P0,),,4H20 orthorhombic Parahopeite . . . . . . Zn,(P0,),,4H20 triclinie Tarbuttito Spencerite Hibbenite ......... 2Zn,(l’0,),,Zn(OH),,6$H2O orthorhombic (A 1916 ii 669). 1 . . . . . . Zns(PO4)Jh(OH) triclinic .. . . . . Zns(Y0,),,Zn(OH),,3H207 monoelinic (A 1916 ii 629). L. J. S. Examination of the Hot Springs at Banff Alberta. R. T. ELWORTHY (Trans. Roy. SOC. Cmmda 1917-1918 [iii] 11 27-33).-An analysis of the water of and the gases evolved from the six hot springs a t Banff Alberta has been carried out.The upper hot spring contaiiis the following amounts of dimolved solids in parts per million of water 634 SO,; 10 (3; 133 HCO,; 239 Ca; 39.7 Mg; 9.1 alkalis; 31 SiO,. The total solids amount to 1100 parts per million. Among other metals present are iron aluminium manganese strontium magnesium lithium pot assiurn and sodium. The gases evolved by the springs contained methane hydrogen oxygen carbon dioxide nitrogen helium aiid argon. Full analyses are recorded in the paper. These springs are the most radioactive of any yet examined in Canada the emana- tion content of the gas being (1910-2370) x 1 0 - 1 2 curies per litre whilst that of the water is (221-640) x 10-l2 curies per fitre. The dissolved radium is (8-5-23.5) x grams per litre. J. F. S. The Thermal Mineral Springs of Rio Hondo. HPRCULES CORTI ( A nd. SOC. Qicim. Aryentinct 1918 6 215-229).-A detailed accoiint of the medicinal properties and chemical com- position of the thermal springs of Rio Hontlo in the province of w. s. M. Santiago tlel Ester0 in the Argentine.

ISSN:0368-1769    

DOI:10.1039/CA9191605071

出版商:RSC    

年代:1919

数据来源: RSC