摘要:

J O U R N A L E. C. C. BALY C.B.E. F.R.S. 0. L. BRADY D.Sc. A. W. CEOSSLEY C.M.G. C.B.E. D.Sc. F. R. S. C. H. DESCH D.Sc. Ph.D. F.R.S. C. S. GIBSON O.B.E. M.A. B.Sc. M.Sc. I. M. HEILBRON,D.S.O.,D.SC. Ph.D. J. C. IRVINE C.B.E. D.Sc. F.R.S. T. M. LOWRY C.B.E. D.Sc. F.R.8. OF 3. W. MCBAIN M.A. Ph.D. F.R.S. J. I. 0. MASSON M.B.E. D.Sc. W. H. MILLS M.A. Sc.D. F.R.S. J. C. PHILIP O.B.E. D.Sc. Ph.D. R.H. PICKARD D.Sc. Ph.D.,F.R.S. T. S. PKICE O.B.E. D.Sc. Ph.D. N. V. SIDGWICK M.A. Sc.D. F.R.S. J. F. THORPE C.B.E. D.Sc. F.R.S. W P. WYNNE D.Sc. F.R.S. F. R.S. THE CHEMICAL SOCIETY. G. BAROER M.A. D.Sc. F.R.S. H. J. EVANS B.Sc. W. E. GARNER M.A. W. GODDEN B.Sc. c. R. HARINGTON B.A. H. HUNTER M.Sc. C. K. INGOLD D.Sc. K. KASHIMA I3g.S. W. 0. KERMACK M. A. BSc. H. KING D.Sc. G. A. R. KON M.A.D.Sc. S. I. LEVY B.A. B.Sc. F. A. MASON M.A. Ph.D. S. S. MIHoLfC Ph.D. U. F. MORRELL D.Sc. Ph.D. W. S. NORRIS Ph.D. ABSTRACTS OF PAPERS ON ORGANIC PHYSIOLOGICAL AND AGRICULTURAL CHEMISTRY. T. H. POPE B.Sc. G. W. ROBINSON bf.8. E. H. RODD D.Sc. W. P. SKERTCIILY. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. Sc.D. E. STEDYAN B.Sc. J. S. G. THOMAS D.Sc. W. THOMAS B.A. M.Sc. R. TRUSZKOWSKI B. Sc. E. E. TURNER M.A. D.Sc. D. F. TWISS D.Sc. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc.,Ph.D. S. 5. ZILVA D.Sc. Ph.D. 1923. Vol. CXXIV. Part 1. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1923.Abstractors of the Journal of the Society of Chemical Industry who have contributed to this volume. .J. F. BRIOGA. T. H. BURNHAM. W. 'l'. K. BRAUNHOLT~ P1i.D. L. A. COLES. J. B. FIRTH D.Sc. A. J. HALL. H. HOLLIKGF M.Sc. C. IRWIN. H. MOOKE M.Sc.Tech. J. P. OGILVIE. A. G. POLLAKD. A. R. POWELL. H. C. REYNARD. E. M. VELLAN. T. S. WHEELER B.Sc. PIUNTLD IN GRFAT BAITAIY HI l t i c H A U C I A I & bcn5. LIMITED. HINGAl. %LtkOlK

ISSN:0368-1769    

DOI:10.1039/CA92324FP001

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

J O U R N A L E C. C. BALY C.B.E. F.R.S. 0. L. BRADY D.Sc. A. W. CROYSLEY C.M.G. C.B.E. C. H. DESCH D.Sc. Ph.D. F.R.S. C. S. GIBSON O.B.E. M.A. B.@c. I.M.HRILBRON D.S.O. D.Sc. Ph.D. J. C. IRVINE C.B.E. DSc. F.R.S. T. M. LOWRY C.EE. D.Sc. F.R.S. D.Sc. F.R.S. 11. sc. OF J. W. MCBAIN M.A. Ph.D. F.R.S. J. I. 0. MARSON M.B.E. D.Sc. W. H. MILLS M.A.,Sc.D. F.R.S. J. C. PHILIP 0. B.E. D.Sc. Ph.D.; R.H. PICKARD D.Sc. Ph.D.,F.R.S. T. S. PKICE O.B.E. D.Sc. Ph.D. N. V.SIDGWICK M.A. Sc.D. F.R.S. J. F. TIIORPE C.B.E. D.Sc. F.R.S. W. P. WYNNE D.Sc. F.R.S. F.R.S. THE CHEMICAL SOCIETY. 0. BARGER M.A. D.Sc. F.R.S. H. J. EVANS 13.S~. W. E. GARNER M.A. W. GODDEN R.Sc. C. R. HARINGTON B.A. H. HUNTER MSc. C. K. IXGOLD D.Sc. K. EABHIMA l3g.S. W. 0. KEELMACK M.A. B.Sc. H. KING D.Sc. G. A. R. KON M.A.DSc. F. A. MASON M.A. Ph.D. S. 5. MIHOLfC Ph.D. G. F. MORRELL D.Sc. Ph.D. W. S. NORRIS Ph.D. 5. I. LEVY B.A. B.Sc. T. H. POPE B.Sc. G. W. ROBINRON M.A. E. H. RODD D.Sc. W. P. SKERTCHLY. J. F. SPENCER D.Sc. P1i.D. L. J. SPENCER M.A. Sc.D. E. STEDMAN B.Sc. J. S. G. THOMAS D.Sc. W. THOMAS R.A. M.Sc. R. TRURZKOWBIII B.Sc. E. E. TURNER M.A. D.Sc. J. C. WITHERS Ph.D. H. WREN M.A. D.Sc. Pl1.D. S. S. ZILVA D.Sc. Ph.D D. F. ‘rWI88 D.s~. 1923. Vol. CXXIV. Part 11. LONDON GURNEY & JACKSON 33 PATERNOSTER ROW E.C. 4. 1923Abstractors of the Journal of the Society of Chemical Industry who have contributed to this volume. J. F. BRIGGS. T. H. BURNIIAY. W. T. K. RRAUKHOLTZ P1i.D. L. A. COLES. J. €3. FIRTH D.Sc. A. J. HALL. H. HOLLINGS M.Sc. C. IRWIN. H. blooRE M.Sc.Tech. J. P. OGILVIE. A. G. YOLLARD. A. R. POWELL. H. C. REYNARD. E If. VELLAN. T. S. WHEELER B.Sc. PRINTED IN GREAT BRITAIN BY R I ~ A R D CLAY & SONS LIMITED BUNQAY bUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA92324FP003

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ii. 20 ATJSTrLACTS OF CIIEMICAL PAPERS. Inorganie Chemistry. The [Suggested] Formation of Helium and Neon in Geissler Tubes containing Hydrogen. ARNALDO PIUTTI (2. Elelitro- chem. 1922 28 452-453).-The author has varied the experi- inental conditions operating in Geissler tubes with a view to the production of helium and neon from hydrogen. In all 70 different experiments were carried out and variations were made in the size of the electrodes their difference apart the nature of the current etc. In no case was found any trace of the D line of helium or of the D line of ncon or any evidence of the conversion of hydrogen into neon or helium (cf. A. 1920 ii 311). Hydrogen as a Halogen in Metallic Hydrides. DWIGHT C. BARDWELL ( J . Amer. Chem. Xoc. 1932 44 2499-2504).-A new method is described for the preparation of pure sodium and potassium hydrides. Pure sodium or potassium was placed in a steel test-tube and heated to 400" by immersing in a eutectic bath of sodium and potassium nitrates.Pure hyclrogen made by passing electrolytic hydrogen through a tube containing platinised asbestos at 400" two tubes containing phosphoric oxide and finally bubbling through sodium potassium eutectic alloy was passed into the molten metal by a steel tube when the hydride formed in fine white crystals higher up the test tube where i t was scraped into glass side tubes and sealed up. Calcium hydride free from metallic calcium was similarly prepared in the form of white crystals. The absence of free metal in the above-named compounds was demon- strated by leaching with liquid ammonia which remained quite colourless.Solutions of the hydrides in a molten eutectic mixture of potassium and lithium chloride were electrolysed when it was found chiefly in the case of calcium hydride that hydrogen was liberated a t the anode in quantities strictly in keeping with Faraday's law whilst no gas was liberated at the cathode. J. F. S. CHARLES A. KRAUS and WILBUR B. DEXTER ( J . Amer. Chem. Xoc. 1922 44 2468-2 i?l).-Water having a specific conductivity of 0.12 x 10-6 W. E. G. Improved Still €or Producing Pure Water.ENORGANIC CHEMISTRY. ii. 21 0hl;zs-l may be obfainsd in large quantities by the use of a still constructed as follows. A copper boiler of 90 litres capacity is connected a t the top with a block tin tube which leads to a tinned copper chamber containing a filter of asbestos fibre or glass wool between two pieces of nickel gauze.The steam passes through the filter and a portion condenses and runs off through a drip tube. The residue of the steam passes into a settling chamber also of tinned copper and thence to a block tin worm in which the water is condensed. ohms1 a t 18" may aklo be prepared in quantity. The principle on which the preparation depends consists in allowing about 20% of the steam to pass away uncondensed. This carries with i t practically all the carbon dioxide and other volatile impurities present in the water. The still used in this case is a copper boiler as before connected directly by a block tin pipe to the settling chamber. From this the steam passes through a block tin pipe which at its lower end is surrounded by a condenser jacket to a separating chamber wiiere a large fraction about 70-80~o of the water condenses and xns away; the residual 20% of the steam carrying all the volatile impurities escapes from the top of the separating chamber.In both the above cases ordinary distilled water is placed in the boiler and this is made alkaline with sodium hydroxide and a little potassium permanganate is added. When not in use the water i n the boiler is kept near to the boiling point so that air is not dissolved in it to any large extent. Structure of Mcdecules of Water. IRVING LANGMUIR (Science 1921 53 580).-1n view of Dennison's demonstration (Physical Rev. 1921 !17 20) that ice consists of molecules of the formula H,O a strUci,ure is proposed in which the four hydrogen nuclei bind the two oxygen atoms. The duplet held by each hydrogen nucleus has one of its electrons in each of the oxygen octets instead of the more usual arrangement in which both electrons of a duplet form part of the same octet.Properties of Pure Hydrogen Peroxide. 111. 0. MAASS and W. H. HATCHER I J . Amer. Chem. Soc. 1922 44 2472-2480; cf. A. 1921 ii 106).-A continuation of previous work in which the properties of pure hydrogen peroxide have been investigated. It is shown that hydrDgen peroxide is diamagnetic and has a sus- ceptibility of 8-8 x 10-7 a value which is larger than that of water. This may be taken as evidence in favour of a structure for hydrogen peroside in which the oxygen atoms are not connected in the same way as in the oxygm molecule.The solubility of anhydrous hydrogen peroxide has been measured in a number of organic solvents with the following results a t 0". Benzene is quite im- miscible alcohol completely miscible and ether partly miscible. The solubility curves of sodium chloride sodium nitrate sodium sulphate and sucrose in anhydrous hydrogen peroxide have been determined and it is shown that the degrec of dissociation is of the same order as in water. The tendency toward the formation of molecular compounds is less than in the case of water there Water having a specific conductivity 0.05 x J. F. S. A. A. E.ii. 22 ABSTRACTS OF CHEMICAL PAPERS. being evidence of only one compound namely Na,S04,2H202. The action of the halogen hydrides on pure hydrogen peroxide and its aqueous solutions has been examined and the conditions have been determined under which the oxidation of the haloid occurs.These are to form the subject of a future paper. The halogen8 are found to be less soluble in hydrogen peroxide than in water. Am- monia dissolves in pure hydrogen peroxide with the formation of a crystalline compound which melts at 24.5" and is stable in the absence of water. This compound is slightly soluble in ether and may be formed by passing ammonia into an anhydrous solution of the peroxide in ether. A compound of the formula 2NH3,H20 was not obtained. The stability of the compound NH3,H20 shows that i t is the hydroxyl-ion which causes the decomposition of hydrogen peroxide.Water dissociates or possibly hydrolyses it and with the consequent formation of hydroxyl-ions the decom- position is cumulative. Whether or no this compound is an ammonium salt NH,O,H is not certain. The vapour pressure dielectric constant and conductivity of salts in hydrogen peroxide are under investigation and the results will be published shortly. J. F. S. Activation of Chlorine. GERSLD 1,. WENDT ROBERT 8. LANDAUER and W. W. EWING ( J . Amer. Chem. Xoc. 1922 44 2377-2382).-A number of methods have been used in an attempt to activate chlorine but neither the light from a 3000-watt Bovie mercury lamp nor a high potential electric discharge was found capable of converting clilorinc into an active form such that it would react with hydrogen in the dark. The experiments described by Draper (PhiE.Mag. 1843 [iii] 23 431; 1848 25 9 1845; 26 473; 27 327) have been repeated and confirmed. It is shown that the fact that the latent period in the hydrogen-chlorine reaction can be destroyed by previous insolation of the chlorine must be attributed to the destruction of substances which inhibit the reaction rather than to any activation of the chlorine itself. Preparation of Pare Ozone and Determination of its Mole- cular Weight. SEBASTIAN KARRER and OLIVER R. WULF ( J . Amer. Chem. SOC. 1922 44 2391-2397).-Pure ozone may be prepared by leading the gas issuing from an ozoniser into a bulb condenser cooled with liquid air until the bulb in which the liquid mixture is collected is about one-half to three parts filled with the deep blue liquid mixture of ozone and oxygen.I n this process a considerable concentration may be obtained by periodically lifting the condenser from the liquid air and so effecting a partial con- densation only. The mixture is then distilled a t -182" when for a long period oxygen containing only 0.8% of ozone passes off that is the distillation proceeds as though liquid oxygen and liquid Ozone were immiscible. At the temperature stated liquid ozone has a vapour pressure of G mm. After distillation has been carried on for some while and most of the liquid has passed off and the residue is very small in vol~imc the temperature rises slowly to -11go and then a blue gas practically pure ozone commences J. F. S.INORGANIC CEEMSTRY. ii. 23 to distil over. At this st,age of the operations extreme care is necessary if explosions are to be avoided.After the blue gas has distilled over for some time it becomes much darker in colour and this gas which is pure ozone was collected in a globe of known volume. The pressure of the gas in the bulb the weight and the pressure after decomposing the ozone by heating to ordinary temperature were determined and the molecular weight was cal- culated. As a mean of many experiments the value 47.3 was obtained. It is shown that there is no evidence to confirm the existence of tetratomic and hexatomic allotropes of oxy en. f. F. S. The Polythionic Acids. F. FOERSTER and A. HORNIG (2. nnorg. Chem. 1922 1.25 86-146).-The reaction between sul- phurous acid and hydrogen sulphide can be represented by the equilibrium H2S+H2S03 =s= H,S,O,+H,O.Further reaction with hydrogen sulphide produces sulphur whereas excess of sulphurous acid leads to the formation of pentathionic acid. Of the poly- thionic acids and their alkali salts the tetrathionates are the moat stable and the trithioriates the most unstable ; the pentathionates occupy a mean position. None of these compounds is completely stable in aqueous solution the following decompositions taking place S,O,” =+= S406:’+S. S,O,” e. S3?61’+S. S,O,”+HzO= SO;’+S2O,”+2H’. 5,0 +He + HSO +S. Themsolubihty of sulphur removes it from the equilibrium and a t boiling temperature the sulphur dioxide is removed and SO,” is alone left in solution; side reactions were also found to take place. The more sulphur dioxide and sulphur there remains in the solution the greater is the tendency of thiosulphuric acid to polymerise e.g. S,O,”+ A high concentration of hydrogen-ion retards the decomposition of tetra- and penta-thionic acids but not of trithionic acid. S,O(’H’ S40,”+ Hi30,’. S40 g’+ S20,”+ H’ += S50 6/’+ HSO,’ . W. T. Specific Volume of Liquid Ammonia. C. S. CRAGOE and D. XI. HARPER (U.S. Bur. Standards Sci. Papers 1921,420 287- 315) .-The apparatus used in the determination of the specific volume of saturated liquid ammonia is described and the results obtained for every degIee from -70“ to 100” are tabulated. These may be expressed by the equation p=[4-2830+0.s130552/133-8 where p is expressed in C.C. pey g. and 8 in “C. A. R. P. OLIVER R. WULF FARRINGTON DANIELS and SEBASTIAN KARRER (J.Amcr. Chem. Soc. 1922 4.4 239&2401).-The oxidation of nitrogen tetroxide to nitrogen pentoxide by ozone has been investigated a t 25”. The oxidation occurs almost instantaneously and in consequence a piece 0-i apparatus has been constructed whereby the oxidation can be followed titrimetricadly using the disappear- ance of brown fumes as an indication of the end-point thus carrying out a true titration in tlic gaseous phase. The results show that - 0.0082861(133 - e)]/[i + 0.424805dECCie + o.oit~38(133 - e)] Oxidation of Nitmogen Tetroxide by Ozone.ii. 24 ABSTRAC!CS OF CHEMICAL PAPERS. one molecule of ozone is required to oxidise one molecule of nitrogen tetroxide at 25" thus only one atom of the ozone molecule is avail- able in the oxidation at this temperature. This result is in striking contrast to the oxidation of sulphur dioxide to the trioxide by ozone a t temperatures below 40" in which one molecule of ozone oxidises three molecules of sulphur dioxide all three atoms of the ozone molecule being available for oxidation.J. F. S. Decomposition of Nitrogen Pentoxide in the Presence of KARRER ( J . Amer. Chem. SOC. l922,44,2402-2404).-According to the experiments of Daniels and Johnston (A. 1921 ii 249) nitrogen pentoxide decomposes rapidly a t the ordinary temperature. It is shown that in the experiments on the oxidation of nitrogen tetroxide by ozone (preceding abstract) in which a trace of ozone in excess was present a very long period of time elapsed before any visible decomposition of the pentoxide was observed. Calculations from Daniels and Johnston's results show that the brown colour ought to have returned to the gas in 15.3 minutes but actually it was found that this did not happen until the gas had been kept at 80" for 195 minutes.It follows thc?refore that a trace of ozone retards the decomposition of nitrogen pentoxide. If traces of the decom- position products are added to the system the decomposition takes place with its normal velocity. Cryoscopy of Boron Trifluoride Solutions. V. Systems with Methyl Ether and with Methyl Chloride. A. F. 0. GERMANN and MARION CLEAVELAND (Science 1921 53 582).- The melting-point curve of boron trifluoride and methyl ether shows a eutectic a t 3 mol. yo of boron trifluoride and a maximum at 50 mol. yo corresponding with the formation of the compound BF ( CH,),O previously prepared by Gasselin.The melting-point curve of boron trifluoride and methyl chloride shows two maxima at 15 mol. yo and 33 mol. % respectively of boron trifluoride and an angular point in the curve at 50%. The form of the maximum a t 150/ is identical with that a t 50% for methyl ether and the mixture yields a compound having the same f. p. and b. p. as the compound BF3,(CH3),0. It appears that methyl et,her may be present as an impurity in methyl chloride as a constant boiling mixture. The use of boron trifluoride for its detection is suggested. Ozone. FARRINGTON DANIELS OLIVER R. WULF and SEBASTIAN J. F. S. A. A. E. Catalysis in the Interaction of Carbon with Steam and Carbon Dioxide. H. A.NEVILLE and H. S. TAYLOR (Science 1921 53 677).-Potassium carbonate and other salts accelerate the interaction of carbon and steam and carbon and carbon dioxide. Reduced nickel also markedly promotes interaction of carbon and carbon dioxide. It has been shown that adsorption of carbon dioxide by carbon at 445" is increased by addition to the carbon of such accelcrating agents although the latter themselves show no adsorptive property for the gas. A. A. E.Ib'ORGANIC CIIEJIISTRT. ii. 25 Vapour Density of Technical Phosgene. A. F. 0. GERMANN and VERNON JERSEY (Science 1921 53 581).-Pure carbonyl chloride has a vapour 1;ension of about 562 mm. a t 0"; technical phosgene which contains impurities probably consisting of carbon dioxide and hydrogen chloride gives after repeated fractionation a value for the vapour density of 4-5263 g.per litre (uncorr.). A. A. E. Cryoscopy of Carl~onyl Chloride Solutions. I. System with Chlorine. A. F. 0. GERMANN and VERNON JERSEY (Science 1921 53 582).-The melting-point curve of solutions of carbonyl chloride and chlorine exhibits a eutectic point at 25 mol. yo of chlorine and angular points at Go/ 11% SO% 63% 76% and 91 yo indicating the existence of the following compounds which dissociate at the melting point 16COC1,,C12 ; 8COc1,,C1 ; COCl,,C1 ; 3COC1,,5Cl2 ; C0Cl2,3C'l ; and C0C1,,1OCl2. The mechanism of the catalytic preparation of carbonyl chloride from carbon monoxide and chlorine is briefly discussed. The Identity of Amorphous and Crystalline Silicon. WILHELM MAWCHOT (2. anorg.Chem. 1922 124 333-334).-The identity of amorphous and crystalline silicon has been proved by an X-ray examination carried out by Debye and Frauenfelder. The preparation and properties of the two forms have been given in previous papers (cf. A. 1922 ii 144 286 764). They can also be distinguished by rubbing them with lead peroxide; nothing happens in the case of the crystalline variety but the pseudo- amorphous forms ignite the brown form exploding. The greater reactivity of the latter is due to its'very fine state of division. Magnetic Analysis of Silicate$ and Silicic Acids. PAUL PASCAL (C'ompt. rend 1922 175 814--816).-Three typss of hydrated silicon dioxide were investigated magnetically all of which behaved as a mixture of anhydrous oxide and water. The conclusion is drawn that definite silicic acids do not exist (cf.van Bemmelen A. 1908 ii 838; 1909 ii 234; and Le Chatelier A. 1903 ii 1033). The Reduction of Potassium Chlorate by Ferrous Sulphate. &I. HERSCHKOWITSCH (2. anorg. Chem. 1922 125 147-154).-A dry mixture of potassium chlorate and ferrous sulphate remains unchanged up to 100"; a trace of water causes the evolution of chlorine dioxide and chlorine. In very dilute solutions the chlorate is completely reduced to the chloride. Crystd Structures of Potassium Chloroplatinite and of Potassium and Ammonium Chloropalladite. ROSCOE G . DICKINSON ( J . Amer. Chem. SOC. 1922 44 2404-2411).-Tetra- gonal crystals of po1;assium chloroplatinite and potassium and ammonium chloropalladite have been examined by X-ray methods using photographs of spectre and symmetrical and unsymmetrical Lznc photographs The simplest structure which will account for A.A. E. W. T. H. J. E. W. T.ii. 26 ABSTRACTS OF CHEMICAL PAPERS. the X-ray data has been described. In this structure each platinum or palladium atom is surrounded by four equidistant and equivalent chlorine atoms lying in one plane. The distance between the platinum atom and a chlorine atom in potassium chloroplatinitc is 2*33&0-05 A.U. It is further shown that the structure of the chloroplatinites is very closely connected with that of the cubic crystals of the chloroplatinates. The tetragonal structure is only slightly larger than the cubic one in its horizontal dimensions but considerably shorter vertically. A table is given in which the dimensions of the salts under examination are compared with those of the chloroplatinates and chloropalladates.The Hydrates of Sodium Sulphide. A. SANFOURCHE and (MLLE) A. M. LIERAUT (Bull. SOC. chim. 1922 [vl 31 966-972; cf. Sabatier A. 1879,865 and 866 ; Gottig A. 1886,980 ; Parravano and Fornaini A. 1907 ii 951).-8 thermal study of the system sodium sulphide-water reveals or confirms the existence of three hydrates Na2S,9H,O Na,S,5-5H20 Na2S,H20. The evidence for the existence of the last is less trustworthy than for the former two hydrates the reason being that experimental difficulties hinder the investigation of the system under those conditions which render the hydrate stable. The monohydrate and nonahydrate both decompose at temperatures below their respective melting points.The hydrates Na,S,H,O and Na,8,5*5Hz0 appear to undergo trans- formation into each other in the solid state. Other hydrates which have been described are not detected in this method of investigation. H. J. E. Sodium Silicate Crystals ALFEED HEINRICH ERDEN- BRECHER (2. anorg. Chem. 1922,124,339-354).-This investigation of the hydrates of sodium silicate was carried out by plotting the cooling curve of the fused salt. This on melting gives a viscous paste; it was therefore mixed with a little paraffin oil the latter having no effect on the cooling curves of sodium carbonate and sodium sulphate. The following hydrates were obtained. Na,Si03,9H,0 rhombic m. p. 47.0" ; Na,SiO3,6H,O monoclinic m. p. 62.5"; and Na2Si03,4H20 hexagonal m.p. about 85.0". The hydrate Na2Si0,,14H,0 probably exists also. The concsentration of the alkali determines which hydrate crystallises from an alkaline solution. Crystal Structure [of Csesiwn Chloride and Thallous Chloride]. WHEELER P. DAVEY and FRANCES G. WICK (Physical Rew. 1921 17 403404).-C~sium chloride is considered to be a simple cube of czsium-ions with a chlorine-ion at the centre of each cube of side 4.12 A. Thallous chloride is similarly constituted the side of the cube being 3*S5 A. These results are inconsistent with those of Bragg. The Crystal Structure of Ammonium Chloride. RALPH W. G. WYCKOPF (Amer. J . Sci. 1922 [v] 4 469475; cf. A. 1922 ii 290).-The structure of the low temperature form of ammonium chloride as determined from X-ray powder measure- J.F. S. W. T. A. A. E.INORGANIC CIIEMISTRP. ii. 27 ments is at variance with that deduccd from it study of the face development and etch figure formation of this substance. Lauc photographic data liavc been obtained by the author which are in agreement with the powder data in assigning one chemical molecule within the unit cubc. The symmetry of the crystal as a whole must be hemimorphic hemihedral (tetrahedral) or possibly holohedral but in no case can the arrangement of the atoms of the crystal agree with the enantiomorphic hemihedry which studies of face development and etch figures assign to it. The latter " chemical " means of deducing crystal structure supplies information with regard to surface of the crystal and the internal structure of the crystal is only one of a nunber of factors which Spontaneous Decomposition of Ammonium Chlorate. FRED FAIRBROTHER ( J .Arner. Chem. SOC. 1922 44 2419-2422).- About 30 g . of ammonium chlorate were kept in contact with 100 C.C. of its saturated solution a t ordinary temperature; for about three weeka the salt remained white whilst a small quantity of a colour- less gas was evolved. Later the gas became tinged with greenish- yellow and a slow but continuous evolution of gas occurred. By the beginning of the fifth week the solution had become quite yellow and the amount of solid had decreased and the rate of decomposition appeared to be increasing. The liquid gradually became darker and considerable quantities of " euchlorine " wcre evolved. The temperature rose to 3 0 4 0 " and within a few hours the system exploded.Solut'ions of ammonium chlorate in the absence of the solid may be kept indefinitely without any decom- position. The solid residue obtained from the decomposition is ammonium nitrate. It is shown that the rate of decomposition of ammonium chlorate is autocatalytically accelerated when the products of decomposition are not quickly removed. The reaction is regarded as taking place as follows. In the initial stage a very slow autoxidation of the molecule is taking place with the pro- duction of nitric acid nitrogen chlorine and water. The nitric acid reacts with more chlorate producing chloric acid and chlorine &aside. These then oxidise more of the ammonium radicle with the formation of more nitric acid and the liberation of chlorine. This takes place more rapidly than the initial stage and conse- quently the decomposition tends to increase in speed unless the acid gases are removed quickly The more stable perchlorate does not appear to be formed.WHEELER P. DAVEY and E. 0. HOFFMAN (Physical Be.. 1920 15 333).-Calcium magnesium cadmium and nickelous oxides form a face-centred cube of the metal interpenetrating a similar face-centred cube of oxygen so that the combined lattices form a simple cube of which the side is half that of the face-centred cube; the lengths of t h e side of this simple cube are 2.37 8. 2.09 h. 2.36 A. and 2.10 pi. respectively. Alumina forms a rhombohedron of which the bear on the nature of these surface phenomena. w. E. G. J. F. S. Crystal Analysis of Metallic Oxides.ii. 26 ABSTRACTS OF CHEMICAL PAPERS.hexagonal axes each have a length of 4.86 8. and the vertical axis 6-62 8. The Ammines of the Strontium Haloids. GUSTAV F. HUTTIG (2. aizo~g. Chem. 1922 124 322-332).-Uetammine strontium chloride was degraded isothermally constancy of pres- sure indicating the existence of compounds. The formation of the following ammines were thus proved [Sr(NH,),]CI (3.5") [Sr(NH3),]12 (134") [Sr(NH,)]I (204"). I n brackets are given for each complex the temperature a t which its dissociation pressure is ALFRED C . EGERTON (Nature 1922 110 773).-It has been found possible to separate zinc by fractional distillation into a distillate and a residue the densities of which bear to that of the initial metal the ratios 0.99971 1 and 1.00026 1 respectively the differences being greater than the probable experimental error.The change in the atomic weight implied by this separation is about 0.035 which is considerably less than might be expected if the metal mas com- posed of equal quantities of an isotope of atomic weight 64 on the one hand and of isotopes of atomic weight 66 68 and 70 on the other. A. A. E. W. J. BENTLY and PAUL L. STERN (Science 1921 53 143).-Ammonia free from oxygen and moisture is passed over zinc dust (previously washed with a solu- tion of ammonia and ammonium chloride alcohol and ether and dried in a vacuum) for thirts minutes a t 650" and the product cooled to at least 200" before exposure to the air. The highest yield obtained was 36.8% of nitride.A. A. E. HUBERT THONAS STANLEY BRITTON ( J . SOC. Chem. Ind. 1922 41 349- 352T) .-Various methods for the separation of glucina and alumina have been reinvestigated with the object of developing if possible a method which could be worked for the isolation of glucina from beryl. Although this object has not been completely attained it was found that more than 90% of the alumina can be easily separated from the glucina by crystallising out the former in the form of potassium alum under suitable conditions. The ore is ground to a flour and fused with potassium hydroxide. The ground product is treated with sulphuric acid and the precipitated silica separated. The filtrate containing the sulphates of glucinum aluminium and potassium with excess of sulphuric acid is adjusted to about SN-acidity by addition of potassium hydroxide as it was found that whereas the solubility of glucinum and aluminium sulphates and of alum are somewhat reduced in 5N-sulphuric acid that of potassium sulphate is considerably increased and an increase in the liquid phase of the proportion of potassium to the other sulphates caiises an increased separation of alum.The A. A. E. [Sr(NH,)]C& (45'5") [Sr(NH3) ~]Br2 (30") [Sr(NH3)2]Br2 (6s0) [Sr(NH3)]Br2 (146") [Sr(NHJ,II (31") [Sr(NH3),]& (74*5") equal to 100 rnm. w. T. Separation of tho Isotopes of Zinc. Preparation of Zinc Nitride. The Extraction of Glucina (Beryllia) from Beryl.IN ORcfUIC CHEMISTRY. ii. 29 acid liquid is therefore saturated with potassium sulphate a t the boiling temperature and set aside to crystallise at 0".The solid phase obtained under these conditions always consisted entirely of alum and represented 92.9% of the alumina present in one of the experiments quoted where the molecular proportions of glucina to alumina were 3 1 as in beryl and where 4 mols. of potassium sulphate were present in the solution for crystallisation. At 25" 87.6% of the alumina was separated. The glucina was separated from the mother-liquor by adding sodium hydroxide sufficient to redissolve the prccipitate diluting and boiling when glucinum hydroxide was precipitated. The paper contains full data and curves representing the solubility of potassium sulphate in sulphuric acid of various strengths. Constitution of Aqueous Solutions of Thallium Salts.C. DRUCKER (2. Elektrochem. 1922 28,463467).-From measure- ments of the depression of freezing point and concentration potentials of solutions of thallous nitrate it is shown that this salt gives rise on ionisation to appreciable quantities of T1,"-ions. Below C=0*06 molar the solutions follow the simple Ostwald dilution law and the association of T1' to Tl," may be neglected. At higher concen- trations all the ionic equilibria obey the law of mass action and for 2T1' e Tl," K=2-1. For TINO e Tl'+NO,' K=0*27 for all of the concentrations investigated. The mobility of the complex thallium-ion is 110. These data for the bivalent thallium-ion are in accord with the previous work on thallium sulphate solutions (cf. A. 1921 ii 161). The interpretation of the conductivities of thallous salts is satis- f actorily explained on the classical dissociation theory.The Ghosh theory of complete ionisation of electrolytes leads to erroneous results when applied to solutions of thallous nitrate. G. F. M. W. E. G. The S-re and Chemical Activity of Copper Films and the &lour Changes accompanying their Oxidation. C. N. HINSHELWOOD (Proc. Roy. SOC. 1922 [ A ] 102 318-328).- The diffraction colours produced on it copper surface by oxidation become more intense as the surface increascs in chemical activity. ,4fter repeated oxidation and reduction the permanent colour sequence is purple blue green light green (almost yellow) puryle blue black and this order of colours may be traversed time after time. The film of copper which is formed in this manner is com- posed according to Beilby of small discrete units giving an " oFen formation " or granular structure.These granules are shown by the author to possess an order of magnitude less than 1 p. The extent to which these granules are converted into oxide determines the colour of the diffracted light the colour phenomenon being independent of the thickness of the film. Thus when the granulcs are one-third copper oxide and two-thirds copper the colour of the scattered light is bright blue. No diffraction effects occur during the reduction of the oxide. The reduction phenomena arc in agreement with the view that fresh nuclei of copper grow a t theexpense of the oxide nuclei. After repeated treatment the copper film becomes incapable of further sub-division and a limiting velocity of oxidation is attained.W. E. G. Phenomena of Diflhsion in Metals in the Solid State and Cementation of Non-ferrous Metals. 111. Influence of the Vapour Pressure of the Migratory Elements in the Form- ation of the Superficial Cementated Layer. G. SIROVICH and A. CARTOCETI (Gnxzetta 1 932 52 ii 233-245).-The cementation of copper by inems of ferro-manganese or chromo-manganese (cf. A. 1922 ii 68 671) consists first of the formation at the surface of the bar of a layer of alloy containing the migratory element in definite concentration mid secondly of the flow of this element into the interior of the bar. The authors explain the first stage of the process on the assumption that a t the experimental tem- perature employed the cementated material exhibits a certain vapour or dissociation pressure in the various elements constituting it so that the medium in which the material to be cementated may after some time be regarded as saturated as regards the vapours of these elements. This idea is develoDed and the results of further experiments are brought into conformity with it.T. H. P. Phenomena of Diffusion in Metals in the Solid State and Cementation of Non-ferrous Metals. IV. Cementation of Copper by means of Ferro-aluminium. G. SIROVICH and A. CARTOCETI (Gazzetta 1922 52 g 245-249; cf. preceding abstract) .-Cementation of copper by means of aluminium like that by means of manganese may result in the penetration of the metal to considerable depths and by relatively high proportions of the migrating metal.T. H. P. Relation between Colour and Texture of Alloys. MASUMI CHIKASHIGE (2. anorg. Chem. 1922 124 335-338).-Copper reflects red to orange-yellow light the addition of tin gives a white alloy and the whiteness reaches a maximum when the composition corresponds with Cu,Sn. The colour then gradually assumes the uolour of tin which only reflects light from red to the beginning of blue. W. T. Catalysis in the Reduction of Oxides and the Catalytic Combination of Hydrogen and Oxygen. R. N. PEASE and H. S. TAYLOR (Science 1921 53 677).-Oxygen and water vapour when present in hydrogen used for the reduction of copper oxide markedly inhibit Che reaction whilst the addition of reduced copper to the oxide appears to accelerate the reaction. The induction period in the reaction is attributed (a) to initial drying of the oxide ( b ) to slow initial formation of copper which then acts as a catalyst.The mechanism of the catalytic combustion of hydrogen and oxygen in presence of copper is briefly discussed. A. A. E.MOROANIC CHEMISTRY. ii. 31 Separation of Isotopes by Distillation and Analogous Processes. ROBERT S. MULLIKEN ( J . Amer. Chem. Xoc. 1922 44 2387-2390).-A continuation of previous work on the separ- ation of the isotopes of mercury. It is shown that the separation coefficient of mercur is 0.0063 and not 0-0057 as previously stated (A. 1922 ii 295). $he progress of the separation has been followed by means of density determinations. The effect of various factors such as pressure rate of distillation and form of the apparatus on the efficiency of separation of isotopes by the method of non- equilibrium distillation has been studied and it is shown that an efficiency of 50% is readily attained. A film of dirt on the mercury increases the efficiency a t the higher rates of distillation.It is pointed out that irreversible distillation may be applied it6 a new factor in the separation of non-isotopic liquid mixtures. The failure of attempts to secure a separation of the isotopes of mercury by electrolytic solution or by reaction with sulphur is ascribcd t o the great difficulty of obtaining non-equilibrium conditioiis a t the boundary between two condensed phases. Potassium Ammonioaluminate and Ammonionianganite. FRANCIS W. BERGSTROM (Science 1921 53 $78).-Po&ssiUrrz ammonioaluminate Al(NH,),*NHK has been prepared by the action of potassamide in liquid ammonia solution on amalgamated aluminium and potassium ammoniomunganite Mn(NHK),,2NH3 by the action of an excess of potassamide on manganese thiocyanate.The Growth of the Grains in Unworked Iron and the Appearance of a Striated Structure after Heating it at more than l l O O o KARL DAEVES (2. anorg. Chem. 1922 125 167- 172).-1ron which contains but a small amount of carbon m~umes a new structure on being heated at 1125" ; this is due to the separ- ation of ferrite and pearlite in certain directions which are orientated crystallographically. Rapid cooling results in the incomplete separation of pearlite. This structure is closely associated with the development of coarse grains and the iron is deteriorated; it can be overcome by heating a t 900".W. T. L. DEDE (Z. anorg. Chem. 1922 125 2846).-The addition of phosphoric acid solution to a ferric chloride solution results in a considerable imrease in the specific conductivity of the solution; the latter also increases rapidly with the further addition of the acid solution and reaches a constant value when equivalent amounts of salt and acid are mixed. This is assunled to be due t o the formation of the complex t I ichlorophosphatoferric acid [CI,Fe(PO,)]H,. This complex acid could not be isolated; the same applies to its salts. Further addition of phosphoric acid solution whilst having no appreciable effect on the conductivity resulted in the replace- ment of the three chlorine atoms of the complex by another phos- phato-group i.e. cliphosphutoferric acid; this wm isolated and analysed ; it corresponds with [Fe(P04),]H,+S$H,0.The com- plex is very stable and the author pomts out its application to J. F. S. A. A. E. Complex Phosphato- and Arsenato-metal Acids.ii. 32 ABSTRAC!L'S OR' CHEIIIICAL PAPERS. analysis. Arsenic acid gave analogous compounds. Aluminium and glucinum salts also show a considerable increase in specific conductivity on being mixed with a solution of phosphoric acid. These are being further investigated. Behaviour of the Stannic Acids towards Solutions of Alkaline Hydroxides. GEORGE ERNEST COLLINS and JOHN I~EEFOOT WOOD (T. 1922 121 2760-2765). Crystal Structure of Titanium Zirconium Cerium Thorium and Osmium.ALBERT W. HULL (Physical Rev. 1921 18 88-89).-Tifanium crystallises in the hexagonal system holohedra.1 class with axi@ ratio 1.59&0'01. The side of the unit triangular prism is 2.97 A. and its height 4-72 8. The lattice is made up of two sets of these prisms the atoms of one set being in the centre of the prisms of the other set. Zirconium has a similar structure,owith axial rat'io also 1.!S. The side of the unit triangle is 3.23 A. and its height 5.14 A. Cerium has a similar structure with axial ratio 1-62. T,he side of the elementary tri- angle is 3.65 A. and height 5.96 A. A face-centred cubic form with sido of cube 5-12 A. is also present but may possibly be due to the presence of impurity. Thorium has a face-centred cubic lattice with side of cube 5.04 a. Osmium crystallises in a face- centred cubic lattice with axia'l ratio 1.59. The side of the unit triangle is 2.714 A. and its height 4.32 8. The Isotopes of Antimony. F. W. ASTON (Nature 1922 110 732).-The mass-spectrum of antimony obtained by the use of antimony trimethyl gives two lines at 121 and 123 respectively the former being the more intense by 10-20~o. The masses of these isotopes of antimony are most probably less than whole numbers by one to two parts per thousand. The results are in excellent agreement with the atomic weight (121 *77) obtained by Willard and McAlpine (A 1921 ii 405) but not with the accepted figure (120.2). A. A. E. The Alleged Variable Composition of Triple Chlorides containing Silver and Gold. HORACE L. WELLS (Amer. J . Sci. 1922 [v] 4 476-482; cf. A. 1922 ii 449 514).-From Bayer's analyses of cssium silver gold chloride (A. 1920 ii 688) the conclusion is drawn that the triple salt Cs2AgAuC1 is a definite invariable compound and that Bayer analysed mixtures of this salt with Cs,Au,Cl, and CsAuC1,. The rubidium salt Rb,Ag,Au,CI,,~ is also invariable. It is probable also that Suschnig (A. 1922 11 014) analysed mixtures in his investigation of the triple bromides of rubidium silver and gold. Hydrolysis of Platinum Salts. 11. Potassium Platini- bromide. EBEN HENRY ARCHIBALD and WILLIAM A. GALE (T. W. T. A. A. E. W. E. G. 1922 121 2849-2857).

ISSN:0368-1769    

DOI:10.1039/CA9232405020

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ANALYTICAL CHENISTRY. ii. 33 An a1 y ti eal Chemi s t r y. Bimetallic I. Systems WILLARD and Electrode Systems in Electrometric Analysis. comprising Two Dissimilar Metals. H. H. FLORENCE FENWICK ( J . Amer. Chem. SOC.. 1922. 44 250&2515).-The constant half -;ell of the usual electrometrid titration apparatus may be replaced by a metal or certain alloys of metals of the platinum group other than pure platinum or pure palladium and by tungsten. The end-point obtained with such a bimetallic system differs in character from &hat given by an uni- metallic electrode but is situated in exactly the same position. Such a bimetallic electrode system has the advantage of being essentially simpler than the usual system and the end-point is much more distinct than with the ordinary electrode.J. F. S. Bimetallic Electrode Systems in Electrometric Analysis. 11. Theory of Bimetallic Systems Systems comprising Two Similar Metals. H. H. WILLARD and FLORENCE FEN- WICK ( J . Amer. Chem. SOC. 1922 44 251&2529).-1n aqueous solutions of multivalent elements in which the concentration of either state of oxidation approaches the limiting value the potential unattackable electrodelsolution is determined by the magnitude of the solution pressure of gas absorbed by the electrode and the end-point obtained in oxidimetric titrations with systems com- prising two unattackable electrodes is given only by virtue of a difference in the solvent power of the two metals for gas. When t'he concentration of oxygen-ion or hydrogen-ion becomes vanish- ingly small the osmotic pressure is too low for a saturation of the electrodes with the corresponding gas.The two elements receive the charge in accordance with the distribution law and a difference in potential develops which is at its maximum with minimum concentration of the corresponding ion and falls rapidly as this ion-concentration rises to a value in excess of that required ,for thp saturation of both electrodes. The bimetallic systems described (cf. preceding abstract) provide a type of electrode system essentially different from those previously used. A com- parison of the relative values of the usual unimetallic and bi- metallic systems may be based on the difference in the mechanism of the end-point in the two cases. The change in voleage with the former which is a true oxidation-potential is continuous khroughout and rises to a maximum at the end-point.With the latter practically all change is confined to within less than 0.5 C.C. of the completion of the titration. Although the actual mag- nitude of the break is normally less than with unimetallic com- binations it is relative to the preceding rise much greater hence the sharpness of the end-point is correspondingly increased insuring greater speed and accuracy. With the use of polarised bimetallic systems the break may be increased so much as to leave no possible 9 VOL. cxxrv. ii. Yii. 34 ABSTRACTS OF CHEMICAL PAPERS. comparison favourable to the unimetallic system. It thus becomes possible t o titrate solutions which offer too small potential differences between two possible states of oxidation for a good end-point with the usual apparatus.The polarising circuit may be made an integral part of the usual apparatus which requires rro attention and presents no difficulties. The disadvantages of the new system lie in the greater localisation of the total potential change which makes it more difficult to anticipate the end-point. Enough warning is given however to make the danger of over- titration negligible after very little practice. Estimation of Chlorine in Benzaldehyde. J. VOIGT (2 angew. Chem. 1922 35 654-655).-An apparatus is described by means of which traces of chlorine in volatile organic com- pounds particularly in synthetic benzaldehyde can be accurately estimated. From 10-20 g. of benzaldehyde are weighed into a wickless lamp arranged in an air-bath which can be heated by bunsen burners.The exit of the lamp is connected with a pipette- shaped combustion tube through which oxygen is passed. Hydro- gen is passed over the warmed benzaldehyde and mixing with the vapours it carries them forward through a jet situated in the wide part of the combustion tube. The issuing gas is ignited in the oxygen by heating the tube externally and it continues to burn quietly until all the benzaldehyde has been volatilised. The products of combustion pass over 2-3 g. of granulated anhydrous sodium carbonate packed in the narrow stem of the combustion tube and heated by a row of burners. The water is collected in a calcium chloride tower. About 7 g. of benzaldehyde can be burnt in an hour and a t the end of the combustion the soda is washed out of the tube by means o€ dilute nitric acid and titrated with standard silver nitrate.As little as O . O O l ~ o of chlorine can be estimated accurately by this method and it is therefore necessary to apply a correction for the chlorine content of the hydrogen employed as although undetectable by ordinary methods the amount which is always present may make an appreciable difference in the present case. Hydrogen in cylinders contains on the average 0.003 g. of chlorine per ni3. Detection of Chlorides and Bromides in the Presence of Thiocyanates. G. SPACU (BuZ. SOC. hytiinje CZuj 1922 i 302- 305 ; from Chem. Zentr. 1922 iv 733).-Neutral solutions con- taining chlorides and bromides in the presence of thiocyanates are treated with a little pyridine and excess of 10% copper sulphate solution.The thiocyanate ion is quantitatively precipitated as copper pyridine thiocyanmte [CuPy,](CNS) and the filtrate may be tested in the ordinary way for chlorides and bromides. J. F. s. G. I?. M. G. W. R. A Gasometric Method of Estimating the Halogen in Organic Compounds. ALEXANDER KILLEN MACBETH (Chem. News 1922 125 305-306).-Some organic halogen compounds in which the halogen possesses an induced electropositive natureANALYTICAL CHEMISTRY. ii. 35 (cf. Henderson and Macbeth T. 1922 121 892) are reduced quantitat,ively by hydrazine the volume of nitrogen evolved depending on the amount of halogen or halogen compound dealt with. A list of substances to which the method has been success- fully applied is given.With some halogen-substituted malonic esters the reaction is not quantitative and in the case of certain di-subst,ituted compounds only one halogen atom reacts the other being unattacked in the cold. Estimation of Fluorides. N. K. SMIT (Chem. Trade J. 1922 71 325).-A simplification of Greeff's method (A. 1913 ii 975). To 5 or 10 C.C. of the neutral fluoride solution are added 5 C.C. of 10% ammonium thiocyanate solution and 25 C.C. of alcohol and the mixture titrated directly with alcoholic ferric chloride stand- ardised against potassium fluoride. The reaction between ferric chloride and fluorides can also be applied to the detection of the latter. A. A. E. GEORGES CHAUDRON and LOUIS BLANC (Compt. rend. 1922 175 885-887).-In estim- ating oxygen in steel by heating the metal in a current of hydrogen and measuring the quantity of water formed the addition of other metals to enable the estimation to be carried out at a lower tem- perature was not found to affect the result obtained.When dealing with molten mixtures of iron and oxide of manganese or of iron and silicon dioxide the method is inaccurate owing to incomplete reduction of the oxides and to the relatively small amount of water obtained which is of the same order as the correc- tions necessitated by the method. Estimation of Sulphur in Iron and Steel. FERDINAND NIKOLAI (Chem. Ztg. 1922,4.6,1025-1026).-The iron or steel turn- ings or powder are treated with hydrobromic acid (d 1*48=47.4y0) in an apparatus consisting of a small flask ground on to a tube the first 12 cm.of which act as a reflux air condenser and is then bent round and carried vertically downwards into a cylinder containing 2.5% sodium hydroxide solution. The mixture of iron and hydro- bromic acid is gradually raised to its boiling point and the hydrogen sulphide liberated is absorbed in the sodium hydroxide solution which after adding 10 C.C. of potassium iodide solution and some starch is titrated with ,V/150-iodine solution. The whole estim- ation requires twenty to twenty-five minutes and very concordant results are obtainedl which agree well with those obtained using Fresenius's method. The results obtained by the above method are higher than those obtained using either dilute or concentrated hydrochloric acid because the aqueous solution of hydrobrolnic acid which distils unchanged contains 47.4% HBr whereas the corresponding hydrochloric acid solution only contains 20 yo HC1.H. J. E. The Estimation of Oxygen in Steel. H. J. E. H. C. R. The Rapid Estimation of Sulphur Dioxide. R. MARCXLLE (Ann. Fdsif. 1922,15 395401).-For the rapid and approximate 2-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. estimation of sulphur dioxide in wines 10 C.C. of the wine are heated with LO C.C. of a solution of 60 g. of sodium hydroxide per litre in a wide-necked conical flask until the volume of the contents is reduced to one-half. The solution is cooled diluted with 100-150 C.C. of water and enough dilute sulphuric acid added to neutralise the sodium hydroxide. Starch solution is added and the solution is titrated with iodine solution containing 4 g.or 8 g. per litre (1 c.c.=l mg. or 2 mg. of sulphur dioxide). If the alcohol and aldehydes are not driven off by heating the results may be 200 mg. per litre too low. The presence of more than 5 g. of dextrose per litre in the wine affects the results obtained and the sulphur dioxide must then be separated by distilling 10 C.C. of the wine acidified with 5 or 6 drops of syrupy phosphoric acid the distillate being led into 10 C.C. of the sodium hydroxide solution which is afterwards treated as in the direct method described above. The results obtained by this method agree well with those given by Haas's method and the degree of accuracy is sufficient for all practical purposes. H. C. R. New Process for the Volumetric Estimation of Ammonia and Carbamide Nitrogen by the Mypobromite Method.J. TTUMANS and A. KRUGER (Z. angew. Chem. 1922 35 686- 687).-A simple glass apparatus is described for the estimation of ammonia or carbamide by the hypobromite method. It consists essentially of an upper cylindrical portion provided with a ground- glass stopper and a draw-off cock drawn out to a h e opening. The upper vessel fits with a ground-gla,ss joint into a lower vessel and communication between them is established through a vertical tube extending nearly to the top of the upper chamber which is charged with brine to a level of 3 4 cm. below the top of the vertical communication tube. When the draw-off cock is opened and the apparatus is otherwise closed brine runs out until equilib- rium is attained between the inside and outside pressures.The lower vessel being previously charged with hypobromite solution the reaction is then started by rotating a boat containing the carbamide or ammonium salt on its axis so that its contents fall into the solution and the nitrogen evolved causes the displace- ment of an equal volume of brine from the upper vessel through the draw-off cock. The boat is fixed to a horizontal axis which is ground to pass through and fit into a tubulure in the side of the lower vessel and the boat can be reversed by turning the pro- jecting portion of the axis through 180". The apparatus can be utilised for urine investigations by placing the urine in the lower vessel and running in the hypobromite by means of a tap funnel through the vertical communication tube.The Estimation of Aliphatic Nitrates in the Presence of certain Nitro-aromatic Compounds. WILBERT J. HUFF and RICHARD D. LEITCH (J. -4mer. Chem. SOC. 1922,4-4,2643-2645).- Aliphatic nitrates may be estimated in the presence of certain aromatic nitro-compounds by reduction with ferrous sulphate in G. El. M.ANALYTICAL CHEMISTRY. ii. 37 excess the unoxidised ferrous salt being titrated with standard permanganate solution. A Kjeldahl flask is fitted with a two- holed rubber cork carrying a pear-shaped dropping funnel and a tube bent twice a t right angles and having its external orifice closed by a mercury seal. The air is expelled from the flask by boiling in it 25 C.C. of distilled water and when the flame is removed the nitrate ester mixed with the aromatic compound and dis- solved in glacial acetic acid is slowly run into the flask.Then a known volume of a standard solution of ferrous sulphate in dilute sulphuric acid is slowly added and this is followed by concentrated hydrochloric acid in volume equal to that of the liquid already in the flask. The reaction mixture is then evaporated to 10-15 C.C. and nearly neutralised with sodium carbonate and when cool is diluted to 600 C.C. and after the addition of 2-3 g. of manganous sulphate is titrated with permanganate solution. Satisfactory results were obtained for mannitol hexanitrate but those for glyceryl trinitrate were slightly low probably owing to the partial vaporisation of the nitrate before it was completely hydrolysed.W. G. New Reagent for the Detection of Nitrites in Water. GEORGES RODILLON ( J . Phurm. Chim. 1922 [vii] 26 376-379).- To the water to be examined contained in a test-tube 3 4 C.C. of a reagent composed of a 6% solution of resorcinol in pure sulphuric acid are added so as to form two layers. In presence of nitrites a rose-coloured ring is formed a t the junction of the two layers. An approximate estimation of nitrous acid can also be arrived a t if desired by comparing the density of colour and the appearances of the ring and the aqueous and sulphuric acid layers with those obtained with standard sodium nitrite solutions. Thus the coloration of the ring with solutions containing in 1 litre I g. of sodium nitrate is brownish-black fading away above and below to red ; 0.1 g.brownish-red similarly fading to red at the edges ; 0.01 g. carmine and 0.001 g. a very pale rose. The sulphuric acid layer ranges in colour with these concentrations from an intense amethyst- violet to the unchanged yellow of the original reagent. G. F. M. Volumetric Estimation of Phosphate in Solution. FRANK W. BURY ( J . Xoc. Chem. Ind. 1922 41 352~).-In the volumetric estimation of phosphate in solution by Rosin’s method (A.? 1911 ii 768) the solution is kept neutral by means of zinc oxide. The neutralisation is very tedious and copper carbonate was tried but showed no advantage. The best results were obtained by neutralising with borax the procedure being as follows. A measured quantity of phosphate solution is added to a measured excess of N/lO-silver nitrate and N/lO-borax solution is run in until the liquid is neutral to litmus.The solution is then filtered and the excess of silver nitrate estimated either by Volhard’s method or by adding a measured excess of N/10-potassium chloride and titrating back the excess with N/lO-silver nitrate using potass- ium chromate as indicator. G. F. M.ii. 35 ABSTRACTS OF CHEMICAL PAPERS. The Titration of Boric Acid in Presence of Phosphoric Acid. I. M. KOLTHOFF (Chem. Weekblad 1922 19 545-546; cf. A. 1922 ii 867).-An answer t o the criticisms of Deerns (A. 1922 ii 867) on the citrate method put forward by the author. s. I. L. Estimation of the Radium Content of Low-grade Radium- Barium Salts. VICTOR F. HESS and ELIZABETH E. DAMON (Physical Rev.1922 20 59-64 ; cf. Trans. Amer. Electrochem. SOC. 1922 41).-The y-ray method for the estimation of radium is inapplicable to salts containing much less than lo4 g. of radium per g. if the customary apparatus is used and the eman- ation method involves errors due to dilution and other causes if the sample contains more than lo-' g. of radium per g. For the examination of salts of intermediate radium content the y-ray method has been modified by the adoption of a shallow container with two curved sides each concentric with the cylindrical string electrometer and only a small fraction of the radius of curvature apart. Readings are taken with the container in position full of the salt t o be measured first alone and then with a small radium tube of known strength placed first immediately in front and then immediately behind the container.The ratio of the first reading to the mean of the other two gives that of the radium content of the salt under examination to the sum of the same and the standard to within 1%. Bismuth Sodium Thiosulphate ; its Preparation and Use in the Estimation of Potassium. V. CUISINIER (Bull. SOC. chim. 1922 [iv] 31 1064-1088).-0bservations on the thio- sulphates of bismuth and alkali metals have been made by Carnot (A. 1876 ii 426) Hauser (A. 1003 ii 487) Sanchez (A. 1912 ii 562) and by Vanino and Mussgnug (A. 1920 ii 44) but the substances have not been fully described and their use in the estimation of potassium salts has given inconsistent results. A salt of the approximate composition Na,Bi( S203) can be prepared crystallising in yellow prismatic plates rapidly turning brown on exposure to air.On attempting to carry out estimations of potass- ium by precipitation as potassium bismuth thiosulphate and sub- sequent treatment of the precipitate with iodine it was found that the results obtained were too high. Further the amount of precipitate obtained appears to be influenced by the concentration of the reacting solutions; the iodine value is not proportional t o the potassium content of the solution investigated and the volume of the alcohol used as precipitant also affects the result obtained. [Cf. J.S.C.I. 1922 981A.l A Photochemical Test for Silver in Thin Sections of Ores. G. SILBERSTEM and E. WIESS (2. anorg. Chem. 1922 124 355- 356).-On placing the section in a saturated solution of an iodide for five minutes the silver is covered with a thin film of silver iodide which under the microscope showed the characteristic reaction to light.The authors propose investigating the practical A. A. E. H. J. E.ANALYTICAL CHEMISrnS. ii. 39 liinits of this test and also the light reaction of silver sulphide with the object of applying it to test for sulphur in metals by shaking them with a solution of a silver salt. W. T. Contradictions and Errors in Analytical Chemistry. 111. The Separation of Zinc from Magnesium Calcium and Aluminium by Precipitation of the Phosphates. IV. The Conversion of Alkali Sulphates into Chlorides. FRIEDRICH L. HAHN [with (111) J. DORNAUF and (IV) R. OTTO] (Ber. 1922 55 [R] 3434-3436; cf.A. 1922 ii 873).-111. The separation of magnesium calcium and aluminium from zinc can be effected according to Voigt (A. 1910 ii 74) by precipitation with phosphate in ammonical solution containing ammonium salts whereby only the zinc remains dissolved. This method of separation has great advantages when only small quantities of foreign metals are present but the subsequent operation of precipitating the zinc as the zinc ammonium phosphate cannot be effected quantitatively by simply boiling the solution until the excess of ammonia is expelled. Accurate results are obtained if the filtrate containing the zinc is treated with hydrochloric acid until just acid to methyl-red and subsequently with an excess of phosphate. If the solution is rich in ammonium salts it is preferable to expel the bulk of the ammonia before addition of the acid.IV. Potassium cannot be separated from sodium as the per- chlorate or chloroplatinate if the metals are present as sulphatles. The usual procedure of precipitating the latter with barium chloride removal of excess of barium with ammonium carbonate and sub- sequent volatilisation of the excess of ammonium salts is inaccurate since barium sulphate always carries down alkali sulphate. This difficulty can be overcome by precipitating the barium sulphate in extreme dilution. For this purpose moderately dilute solutions of sulphate and barium chloride are added simultaneously and a t approximately equivalent rates to a small quantity of boiling hydrochloric acid. Pure barium sulphate is thereby precipitated in well-formed coarse crystals which are readily filtered and washed.The presence of varying amounts of alkali chloride and even of nitrate in the sulphate solution is without influence. If ferric iron is present ammoniacal barium chloride solution must be used and the solution be acidified after the precipitation. H. W. I. M. KOLTHOFI and J. C. VAN DIJK (Pharm. ‘CVeelcbZud 1922,59 1351- 1360).-The fact that zinc sulphide is almost always precipitated to some extent with copper sulphide from solutions of the two metals is not due to adsorption since zinc sulphide is only with difficulty soluble in acids of low concentration. The precipitation of zinc from acid solutions by hydrogen sulphide depends on time and temperature as well as on the concentration of zinc- hydrogen- and sulphide-ions and is accelerated by presence of copper In the quantitative separation of copper and zinc by hydrogen The Carrying-down of Zinc by Copper Sulphide.‘ sulphide .ii. 40 ABSTRACTS OF CHEMICAL PAPERS. sulphide the time must be as short as possible. If sulphuric or hydrochloric acid is used the acidity must be at least 0.5N; with the former room temperature is best; with the latter the gas should be led in a t the boiling point. s. I. L. Some Applications of Sodium Peroxide in Analytical Chemistry. W. M. STERNBERG (Xcience 1920 52 162) .-The decomposition of lead and zinc ores by fusion in an iron crucible with a t least six to eight parts of sodium peroxide is rapid and complete. I n the case of lead ores the aqueous solution of the fused mass after treatment with 1.4 parts of oxalic acid to reduce the lead dioxide is acidified with sulphuric acid boiled cooled and the lead sulphate collected and washed with 5% sulphuric acid.It is then dissolved in a solution of ammonium chloride or of ammonium chloride and sodium acetate and titrated with ammonium molybdate. I n the case of zinc ores the fused mass is dissolved in ammoniacal ammonium chloride solution the solution boiled filtered and washed with hot ammonium chloride solution acidified with hydrochloric acid boiled and titrated with potassium ferrocyanide after the addition of hydrogen sulphide. It is necessary that the solutions should be standardised against a standard ore treated by the same method. A. A. E. Gravimetric Analysis.XXVI. Estimation of Lead. L. W. WINKLER (2. angezu. Chem. 1922 35 662-663).-For the gravimetric estimation of lead in neutral solution 100 C.C. of lead nitrate or lead chloride solution containing from 0.60 t o 0.01 g. of lead is acidified with 1 C.C. of normal nitric acid solution and boiled. Ten C.C. of 10% ammonium sulphate solution are slowly run in and the whole is allowed to remain then filtered. The precipitate is washed with 50 C.C. of a cold saturated solution of lead sulphate and the edge of the filter washed with 1-2 C.C. of dilute alcohol. The precipitate is dried for two hours a t 130". Modifications of the procedure necessitated by the presence of nitric or hydrochloric acid and salts of potassium or other metals are discussed and details are given of the method of estimation of lead in crude lead minium lead chromate and lead salts of organic acids.J. S. G. T. A New Sensitive Reaction for Copper Thiocyanate and Pyridine. G. SPACU (Bull. Xoc. Lytiinfe Cluj 1922 1 2 8 6 2 9 1 ; from Chem. Zentr. 1922 iv 737).-The reaction consists in the formation of a light green precipitate when a neutral solution of a copper salt is treated with a neutral thiocyanate and a few drops of pyridine. The precipitate has the composition [CuPy,]( CNS) and is almost completely insoluble in water. The reagent must be neutral and excess of pyridine must be avoided. The pyridine should be added before the thiocyanate. One part in 300,000- 800,000 of copper can be detected according to the conditions of experiment. For pyridine the sensitiveness is one part in 2000 and for thiocyanate one in 50,000.G. W. R.ANALYTICAL CHEMISTRY. ii. 41 The Hindering of the Precipitation of Copper Sulphide by the Presence of Sodium Chloride. WILHELM BILTZ (Ber. 1922 55 [B] 3393).-In a recent communication Dede and Bonin (A. 1922 ii 766) have shown that lead and cadmium sulphides are only incompletely precipitated in hydrochloric acid solution in the presence of relatively large quantities of the chlorides of the alkali or alkaline-earth metals. Similar observations have been recorded in the case of copper (cf. Biltz and Marcus A. 1909 ii 101 1). Precipitation of copper sulphide is however quantitative in a 5% solution of sodium chloride. Magnesium chloride or carnallite does not appear to have an inhibiting action.H. W. A New Microchemical Reaction for the Estimation of Copper. G. SPACU (Bull. Xoc. Stiinfe Cluj 1922 1 296-301; from Chem. Zentr. 1922 ivy 737-73S).-After precipitation of copper as copper pyridine thiocyanate CuPy,(CNS) (see this vol. ii 40) the precipitate is separated in an appropriate apparatus (Rothe’s shaking funnel) by successive extraction with chloroform. The precipitate is then weighed after removal of the chloroform in a vacuum desiccator. Alternatively the precipitate may be ignited and the copper estimated as cupric sulphide or cupric oxide. G. W. R. Volumetric Estimation of Copper and its application to the Estimation of Reducing Sugars. ED. LASAUSSE ( J . Pharm. Chim. 1922 [vii] 26 401406).-The precipitated cuprous oxide formed by the reducing action of the sugar on a cupro-tartrate solution is collected on a Gooch crucible and dissolved by means of 2-3 C.C. of nitric acid.The filter is finally washed with water the total volume of filtrate and washings being kept below 25- 30 C.C. The nitrous acid present is then eliminated by adding 2% permanganate solution drop by drop to the boiling liquid until the pink coloration just persists and the latter is reduced by the addition of a few drops of alcohol. After boiling for a minute longer the precipitated oxides of manganese are filtered off the filtrate is made up to 100 c.c. and the copper is estimated iodo- metrically in the usual way after the addition of an excess of sodium acetate to displace free mineral acid. In order to obtain the best results in the estimation of reducing sugars the procedure of Quisumbing and Thomas should be followed (A.1922 ii 92) as a granular cuprous oxide is thereby obtained which can readily be collected and washed. The amount of dextrose is given by the formula 0~474x+O~Oool 15x2 and of invert-sugar by 0504x+ 0~000087x2 where x is the weight of copper reduced. Iodometric Estimation of Copper in Bronze and Brass. G. BATTA and G. LATHIERS (Bull. SOC. chim. Belg. 1922 31 297- 302).-The application of the iodometric method of copper estim- ation to bronze and brass gives results which are of sufficient accuracy for many purposes. It is rapid and useful when electro- lytic methods cannot be employed. G. P. M. H. J. E.f i b 42 ABSTRACTS OF CHEMICAL PAPERS. Rapid Electrolytic Estimation of Mercury.A. DE M E E ~ S (Bull. Soc. Aim. Belg. 1922 31 302-323; cf. Bottger A. 1921 ii 351).-A study of the factors which are said to cause inaccuracies in the electrolytic estimation of mercury. Good results were ob%&twd,wi$4 a platinum cathode but gold was found to be more suitable forbthe purpose as the mercury deposit is more adherent a& so pepnits of the use of alcohol and ether for washing ; in the ease of other metals this should be done with water only as the more rapid method occasions loss. Experiments carried out with .mercuric salts in presence of substances which form complexes 'give similar results with gold and platinum cathodes but the method is more satisfactory when simple acid electrolytes are used as solvents. The method is applicable to mercurous salts which are oxidhed before electrolysis. Constancy of the Titer of Permanganate Solutions and Different Methods of Standardisation.0. HACKL (Chem. Ztg. 1922 46 1065).-N/lO-solutions of potassium permanganate made from the freshly prepared pure salt remained permanent if stored in a dark place for one year whereas solutions made from a ten-year old preparation altered considerably in the course of a few months. Tests showed that the most satisfactory com- pound for use in standardisation of permanganate solutions is sodium oxalate. The composition of oxalic acid crystals and ferrous ammonium sulphate was found to vary within narrow limits but these are sufficient to lead to discordant results in the titration.H. J. E. A. R. P. The Electrometric Estimabion of Iron and Vanadium when present together. ERICH MULLER and HANS JUST (2. anorg. Chem. 1922 125 155-166) -Ferrous salts and vanadium salts can be accurately estimated electrometrically with perman- ganate. Ferrous salts are more vigorous reducing agents than the salts of quadrivalent vanadium and the authors find that they can be estimated \+hen together in the same way. To the mixture a decinormal solution of potassium permanganate is gradually added until there is a sudden change in the E.M.F. This indicates the end-point for the ferrous salt; the titration is then continued until a second sudden change occurs which repre- sents the end-point for the vanadium salt. The latter titration is best carried out a t about 70" as the reaction is very slow a t the ordinary temperature.W. T. W. S. HENDRIXSON and L. M. VERBECK ( J . Amer. Chem. Xoc. 1922 44 2382-2386).-A slightly acid solution of titanous sulphate may be used to standardise solutions of potassium permanganate or potassium dichromate. The method consists in adding the titanous ;solution to the permanganate or dichromate solution and measuring the E.M.F. of the solution toward a platinum electrode against a calomel electrode. The E.M.F. changes very rapidly at the end-point which is thelhefore made very precise; in the case of Electrometric Standardising of Titanous Solutions.ANALYTfCAL CHEMISTRY. ii. 43 dichromate the change in E.M.P. on adding a slight excess of titanous ion to a slight excess of dichromate is about 0.6 volt whilst in the case of permanganate the change in E.M.F.is about 0.9 volt. This difference makes it possible to estimate two sub- stances of quite different oxidising power in the same solution. The authors have investigated the estimation of titanous and ferrous ions by means of permanganate or dichromate of f e h - i r o n and dichromate or permanganate by means of a titanous solution and have found that the method is trustworthy. New Method €or the Gravimetric Estimation of German- ium. JOHN HUGHES M~~I;LER (J. Amer. Chem. Xoc. 1922 44 2493-2498).-A new method of estimating germanium is described which is based on the precipitation of this metal as magnesium orthogermanate and weighing the dried and ignited precipitate. Magnesium orthogermanate is a snow-white infusible substance which is prepared by the action of magnesium sulphate ammonium sulphate and ammonium hydroxide on a solution of germanic acid.No precipitate is formed until the ammonium hydroxide has been added and the reagents are added in the order named. Magnesium orthogermanate is amorphous and is very soluble in dilute solutions of acids but after ignition it is only slowly dissolved by concentrated acids. It dissolves in water to the extent of 0.000016 g. per C.C. at 26". In a mixture of two volumes of ammonia (0.880) and three volumes of water the solubility is 0.00002 g. per c.c. whilst in an ammoniacal solution of 10% ammonium sulphate the solubility is 0-00013 g. per C.C. a t 26". The estimation of germanium is effected by adding an excess of 2N-magnesium sulphate to the cold solution of germanic acid ; this is followed by at least an equal volume of 2N-ammonium sulphate and then ammonium hydroxide (0.880) is added in amounts varying from 15 C.C.to 20 C.C. for each 100 C.C. of solution and the mixture stirred vigorously raised to the boiling point for a few minutes and kept for ten to twelve hours before filtering. The precipitate is filtered washed with a mixture of 90 C.C. of water and 10 C.C. of ammonia dried and ignited with free access of air. Analysis of Mixtures of Hydrogen with Paraffin Hydro- carbons. J. G. KING (Fuel 1922 1 103-106).-The estimation of hydrogen in admixture with paraffin hydrocarbons is effected by fractional combustion over copper oxide a t 280" in an apparatus which is a modification of that of Jager ( J .Gasbeleuchtung 1898 41 764). Carbon monoxide and hydrogen are thereby consumed whereas the paraffins remain unchanged. Identification of Methyl Alcohol in Liquids containing Ethyl Alcohol. I. M. KOLTHOFF (Pharm. Weekblad 1922 59 1268-1274).-The method of Denig&s (A. 1910 ii 461) namely oxidation with permanganate in presence of acid removal of excess with oxalic acid and testing for formaldehyde with Schiff's reagent will detect 0.05% of methyl alcohol in ethyl alcohol. The reagent J. F. S. The results of the analyses are excellent. J. F. S. CHEMICAL ABSTRACTS.ii. 44 ABSTR.ACTS OF CHEMICAL PAPERS. is best prepared as suggested by Elvove (A 1917 ii 341) and if kept in stoppered bottles is stable for long periods.The usc of qhosphoric acid in place of sulphuric acid as recoiiiiiiended by Chapin (A 1921 ii 50&) is found advantageous. The method can be applied to the examination of tinctures and inedicinal preparations containing alcohol without preliminary distillation. The reagent will also detect fornialdehyde in milk. 8 I. L. Colour Reaction for Phenols based on the Use of Selenious Acid. VICTOR E. LEVINE (Bcience 1920 52 207).-A reaction of great sensitivity and wide applicability consists in the faci; that phenols in contact with a solution of selenium dioxide (O*5(y0) or sodiuin selenite (0-75 yo) in concentratfed sulphuric acid give rise to characteristic green or blue colorations. On heating or on the addition of water the colour changes to brown or xed.It is considered that the phenol causcs the liberation of seleiziuiii which then dissolvcs with a green colour in concentrated sulphuric acid t o forin selenosulphur trioxide. A list is given of phenolic substances to which the test liar; been applied. The Action of Proteins on the Phenol Reagent of Folin and Denis. VICTOR E. LEVIKE (Science 1920 52 612-G13).- The phosphotungstic-phosphoinolybdic reagent of Polin and Denis (*4. 1913 ii 1011) is not specific for the phenolic group. The colour reaction is given by proteins and in faet by a large number of iiiorgahic and organic substances. The reagent appears t o be uflccted by substances possessing iiiore or less reducing properties. VICTOR E. LEVINE (Science 1920 52 301).-0ne to 2 C.C. of urinc m e heated for several minutes .with 5 C.C. of i5 2yo solutioh cf sodiuiii teilurito in 10% sodiulil carbonatc. Itcduction to telluriuitl takes piace in the presence of carbohydmtes possessing a frce carbonyl group. With small aiiiounts of sugar the telluriuni foriiis a colloidal solution; which has a characteristic browii colour i:i transmitted light and is reyish- blnclr in reflected light ; largcr amounts yield a greyis%-bhcic precipitate. A. A. E. The Partition Coefficiebts and the. Estimation by Extrac- tion of Organic Acids. JOX. PINKOW (2. Unters. iVnJu. Genussvz. 1932 44 204-209).-Bcetic and formic acids forin cloublc inoleculcs in ethereal solution and the irrcgularities observcd in the partition cocfficicnt of the latter acid- may be ascribed t o this cause. Assuming that no doublc molecules occur in the aqueous solutions tlie dissociation coefficients of the doublc mole- culcs 1iavc the following vafues a t L 5 O acetic acid 1.776; formic acid 4-77 The partition cocfkieiits (watcr/ether) of tlic siiiiple molccules at 15' are acetic acid 2 21; formic acid 2.38. At 26.3" formic acid 2.79. Saga hais no cffect oil the cxtractiozi of succiiiic acid frroni its aqueous solution. A. A. E. A. A. E. Test for Sugar in Urine. H. C. R.

ISSN:0368-1769    

DOI:10.1039/CA9232405033

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ii. 45 General and Physical Chemistry. The Secondary Spectrum of Hydrogen. A. C. MENZJES (Nature 1922 110 876).-Silberstein’s solution of the three-substance problem applied by him to the case of neutral helium has been modified so as to apply to hydrogen and the value of N has been corrected so as to take account of the fact that with two electrons instead of one the correction to the mass of the electron for the finite mass of the nucleus is no longer the same. Frequencies have been calculated from the formula v = N ~ (1 /n12-f 1 /n22- l/m12- 1 /m22) where N =N,( 1 +m/M). Forty-seven lines in the secondary spectrum of hydrogen were found to agree with the calculated values within an absolute error of one unit of frequency. The frequencies are regarded as a kind of “summation tone,” being the sums of a Balmer or a Paschen frequency and a frequency in the ultra-red.In several cases a physical similarity of behaviour was cummon to “ series ” of the lines grouped according to values of m and n. Spectrum of Active Nitrogen as Affected by Admixture of the Inert Gases with a Note on the Origin of the Cyanogen Spectrum. LORD BAYLEIGH (Proc. Roy. Soc. 1923 [A] 102 453459).-The afterglow accompanying the reversion of active nitrogen to ordinary nitrogen was shown by E’owler and Strutt (A. 1911 ii 678) to be composed of a selection of the first positive bands of nitrogen. The addition of inert gases to the nitrogen produces considerable changes in the intensities of these bands. The maxima of the three groups of bands green yellow and red are shifted towards the red.The addition of helium neon or argon makes the red group as a whole; more intense at the expense of the others. The movement of the bands is proportional to the concentration of the inert gases present. Evidence is adduced for the belief that the red aurora line X 6320 is due to the presence of nitrogen and helium in the upper atmosphere. It is not yet determined whether the effects on the after-glow spectrum are produced in the electric discharge or in the process of the after-glow. The influence of carbon in developing the cyanogen bands is discussed. W. E. G. The Carbon Arc Spectrum in the Extreme Ultra-violet. I?. SmmoN (Proc. Roy. SOL 1923 [A] 102 484496).-Measure- ments are made of the ultra-violet lines of the carbon arc spectrum by means of a vacuum grating spectrograph.Colour sensitised Schumann plates were used both for the extreme ultra-violet as well as for the ordinary violet region. A table is given of the wave- lengths and intensities of the lines observed and comparison made with the values of other workers. Some of the lines photographed in the Lyman region have not been mentioned by any previous A. A. E. VOL. CXXIV. ii. 3ii. 46 ABSTRACTS OF CHEMICAL PAPERS. worker and some of the lines in the higher orders of spectrum have been shown to consist of close groups of lines. The line 599.0 attributed by Lyman to helium is due to carbon present as an impurity in the helium. The lines in the Lyman region a t 1194,945 858 687 651 640 599 and 595 have not been previously observed in the arc spectrum of carbon but these lines correspond with prominent lines in the " hot spark " spectra of Millikan.Groups a t 1657 1329 1260 1194 1036 and 651 have been resolved into a number of lines. W. E. G. The Spectrum of Neutral Helium. LUDWIK SILBERSTEIN (Nature 1923 111 46-47).-1n reply to Raman's criticisms (A. 1922 ii 803) it is shown mathematically that the probability that the forty-five coincidences previously described are fortuitous is less than 1.7~10-13; it is further claimed that the use of the value 109723 for the Rydberg constant in the formula applied to the case of the neutral helium atom (with two electrons) is justifiable. It is now found that the whole diffuse series of singlets 1P-mD is represented by the formula v=4N(18 .2n/20.4)E-N(9.n/lO .2) two final and one initial quantum numbers being fixed. The possibility of reducing 4N to N based on the fact that all numbers are even is mentioned but not discussed ; physically interpreted it would mean that the helium nucleus attracts each of its electrons with only one-half of its total charge as if its lines of force formed two bundles each entirely engaged with one of the two trabanh. A. A. E. Relative Visibility of Spectra when an Electric Discharge is Passed Through the Vapours of Alkali Amalgams. F. H. NEWMAN (Phil. Mag. 1923 [vi] 45 181-189).-The relative intensities of the spectra of the alkali metals and mercury have been examined by placing alkali amalgams in an electric discharge tube. ' For sodium and mercury the spectrum of the former was prominent a t all temperatures but below 100" the mercury spectrum was the brighter.At 200° the mercury lines are almost entirely masked. At this temperature a very brilliant yellow radiation is emitted which forms a very convenient source of the sodium D-lines. The ionising potentials of sodium (5.13 volts) and mercury (10.2 volts) and the partial pressures of their vapours are the two main factors operative in determining the intensity of the spectra. At low vapour pressures the atoms of both sodium and mercury will be so far apart that the electrons attain the necessary energy to ionise the mercury atoms before inelastic collision occurs. Under these conditions approximately equal numbers of mercury and sodium atoms will be ionised. As the temperature rises the density of the vapour increases and the electrons attain less frequently the speeds corresponding with 10.2 volts so that although the number of mercury atoms will be far more numerous that those of sodium the actual number of the former ionised will be very small.Thus a t 200" the mercury lines are suppressed. Except in the case of potassium where theGICNBRAL AND PHYSICAL CHEMISTRY. ii. 47 lines are faint a t all temperatures the other alkali amalgams show similar phenomena. W. E. G. The Excitation of the Mercury Spectrum. The Influence of Helium. GEORGES D~JARDIN (Compt. rend. 1922 175 952-955).-An examination of the radiations emitted by mercury vapour traversed by electrons of different velocities showed that when the speed of the electrons is slightly greater than the critical ionisation velocity a large number of the arc spectrum lines are obtained these being due to collisions between electrons and mercury atoms.When the conditions are such that the electron charge is neutralised a luminous region appears near the electrodes the spectrum of which also exhibits the characteristics of that of the mercury arc. The author concludes that the emission spectrum appears to depend on the ionisation of the atom and notes the conditions under which certain of the lines become visible. In the presence of helium and with a potential greater than 20.4 volta considerable modifications of the mercury spectra take place. Details of the variations in intensity and the appearance of new lines are given the action of helium being apparently selective on certain lines as in the case of cadmium (cf.Collie and Watson A. 1918 ii 383). H. J. E. Spectroanalytical Investigation of a New Element in the Terbium Group and the Arc Spectrum of Terbium. JOSEF MARIA EDER (Sitzungsber. Akad. Wiss. Wien Math.-naturwiss. KZccss. 1922 [iia] 131 199-298; cf. ibid. 1920 129 422).- The determination of the spectra of a number of terbium dysprosium and gadolinium fractions has led to the discovery of a new element giving a well-defined and characteristic line spectrum. This element which was present in a fraction between terbium and dysprosium is named Welsium. The lines of the new element are weakened in the spectra of the fractions rich in terbium and are practically absent in the spectra of the dysprosium fractions.In agreement with the observations of Eberhard no evidence has been found for a new element in the fractions between terbium and gadolinium. Many thousands of lines of the terbium spectrum have been measured between A7257 and 2400 8. and compared with the measurements of Urbain Eberhard and Auer. W. E. G. The Line Spectrum of Vanadium in Fused Salts. A. DE GRAMONT (Compt. rend. 1922 175 1129-1133; cf. A. 1921 ii 73).-A solution of vanadium pentoxide in fused sodium carbon- ate was used in order to ascertain the limiting quantity of vanadium capable of spectroscopic detection. The results are shown in two tables which give for visual and photographic observation re- spectively the smallest quantity corresponding with each line in the spectrum.Non-conducting materials which contain vanad- ium give good spark spectra which are in accordance with the author's observations. H. J. E. 3-2ii. 48 ABSTRACTS OF CHEMICAL PAPERS. Absorption of Light by Chlorine. H. VON HALBAN and K. SIEDENTOPF (2. physikal. Chem. 1922 103 71-90).-The absorption of light by chlorine between 254pp and 643pp has been determined for nineteen wave-lengths using lines of mercury zinc and cadmium and between 383 pp and 451 p using a Nitra- lamp for twelve wave-lengths. The method of observation was the previously described photoelectric two-cell arrangement (A. 1922 ii 332). The results show that within the pressure range investigated (760 mm. and downwards) Beer's law is true. The absorption curve shows a maximum in the ultra-violet at about 334pp and a minimum in the yellow.From yellow to red the absorption again increases and reaches a maximum which probably lies between 614 pp and 643 pp. No difference could be observed between the absorption of dry and moist chlorine. The Ultra-violet Absorption Spectra of Toluene and the Xylenes. F. W. KLINGSTEDT (Compt. rend. 1922 175 1065- 1067).-The ultra-violet absorption of hexane solutions of toluene and of the xylenes was measured and details of the position and form of the bands are given together with a diagrammatic repre- sentation. Toluene exhibits sixteen bands as compared with eight for benzene in the same region; the intensity of absorption is a little greater than that of benzene. The bands are divided into four groups in each of which intensity decreases with wave- length.Three large bands are observed with o-xylene and five with m-xylene whilst in the case of p-xylene the absorption coefficient is about four times as great and the spectrum contains twelve bands arranged in three groups. Colour and Chemical Constitution. XV. A Systematic Study of Fluorescein and Resorcin-benzein. JAMES Mom (Trans. Roy. Xoc. S. Africa 1922 10 159-164; cf. A. 1922 ii 333).-The quantitative study of the colour of compounds of the phenolphthalein type has been continued. The results pre- viously recorded for the bromophenolphthaleins (A. 1921 ii 365) are restated in another form. The different positions open to substitution in the phenolphthalein molecule are lettered as shown. The colour modification due to the introduction of bromine into any particular position can be expressed by a factor the '' dicyclic colour factor,'' by which the characteristic H 0 / Y l ./\OH wave-length of phenolphthalein must be 31 I oHI I multiplied to give that of the derivative.These factors for the respective positions are a and d 1.018; b 1-002; c f and g 1.0145; e and h 1-0270; i and I 1.0235; j andk 1.0125. If two or more positions are substituted all the corresponding factom must be used in calculating the colour of the derivative. The colour factors for chlorine and iodine are respectively about 1/1500 smaller and greater than those for bromine. Similar factors have been worked out for various substituenb J. F. S. H. J. E. f \/\ 6 /\h/g d()co2H $ 1 "\/" bGENERAL AND PHYSICAL CHEMISTRY. ii.49 in fluorescein X=493.5. For bromine the factors for the different positions are a and d 1.0162; b 1.0000; c 1.0091 ; f and k 1.0122; g and j 1.0157. The factors for nitro-derivatives are very similar to those for bromo-derivatives the methyl factors are smaller and the methoxy-factors smaller still the largest being 1.006. The hydroxy-factors are smallest of all and in sodium hydroxide solution the hydroxy-derivatives have their absorption bands in the same position as fluorescein itself. Gallein and hydrQxyquinolphthalein are exceptions to this rule. Resorcin-benzein which is fluorescein without the carboxyl group is practically identical with fluorescein in alkaline solution ; the absorption band is at h492. A few derivatives which have been examined show that the colour factors for the f g j and k positions are the same as those of phenolphthalein.In the phenyl ring the effect diminishes in the order d c b but is still positive for b although in fluorescein it appears to be nil for this position. E. H. R. Ultra-violet Absorption Spectra of Alkaloids of the iso- Quinoline Group. Papaverine and its Hydrochloride. PIERRE STEINER (Compt. rend. 1922 175 1146-1149).-A com- parison of the absorption spectra of papaverine with those of iso- quinoline and veratrole the substances of which the alkaloid is constituted shows that it is similar to that of isoquinoline but simpler. The simplification appears to be due to the veratrole group which also determines a displacement towards the red and an increase in absorption.The spectrum of the alkaloid is similar in ethereal and in alcoholic solutions; in the latter a shifting of four bands towards the red is observed. The combination with hydrochloric acid causes a fusion of three absorption bands exhibited by the alkaloid together with a general displacement towards red and increase in absorption. The spectrographic method applied to the detection of papaverine permits of the recognition of 0.03 mg. in 2 C.C. of solution. Kinetics of Photochemical Reactions. RUDOLF WEG- SCHEIDER (2. physikal. Chem. 1922 103 273-307).-A theoretical paper in which the laws of photochemical kinetics are developed on the basis of the assumptions made for ordinary chemical reactions. Van’t Hoff’s law of the proportionality between the amount of chemical change and the amount of light absorbed holds when the conversion of only one molecular species into the reactive condition by the light determines the velocity of the reaction; that is the spontaneous return of the active molecules into the inactive form may be neglected and all other partial reactions of the total change take place instantaneously.It is to be expected that the law will not hold for the total reaction if‘the photosensitive molecular species is in excess of the other molecular species participating in the reaction; t’his is particularly the case in changes which have proceeded nearly to completion. Einstein’s equivalent law determines for energy storing reactions the velocity constant of van’t Hoff’s formula or gives a t least the upper limit H.J. E.ii. 50 ABSTRACTS OF CHEMICAL PAPERS. for the total reaction. An upper limit of the velocity only can be obtained by thermodynamical methods for energy storing reactions. Velocity equations have been integrated on the assumption of van’t Hoff’s law and a homogeneous parallel beam of light for a system which is continuously agitated and in which the light is absorbed either by a molecular species which is being destroyed by the reaction or by a sensitiser which may have a constant concentration or may be produced by the reaction. A number of other possibilities and conditions in the reactions are also theoretically considered. It is also shown that when in a given reaction two photosensitive molecular species are present it is not likely that the velocity of reaction will be proportional to the product of the two quantities of absorbed light but rather is a proportionality between the velocity and the second or higher power of the light intensity to be expected if a slower subsequent reaction requires the participation of several activated molecules.J. F. S . Photochemical Decomposition of Hydrogen Peroxide. CHR. WINTHER (Canske Vid. Selsk. illat.-phys. Medd. 1920 2 3-18 ; from Chem. Zentr. 1922 iii 981).-Hydrogen peroxide in the presence of potassium ferrocyanide in dilute solution is decomposed on illumination with ultra-violet light. The reaction proceeds a t first slowly then more rapidly and finally slows down. This decomposition of hydrogen peroxide is attributed to the formation of a catalyst by the influence of light on potassium ferrocyanide solution.The production of the catalyst increases with the time of illumination and reaches a maximum which depends on the amount of energy of the ultra-violet radiation and also to some extent on the concentration of hydrogen peroxide. G. W. R. Spacial Progression of Photochemical Reactions in Jellies. A. BENRATH and K. SCHAFFGANZ (2. physikal. Chem. 1922 103 139-154).-The photochemical actions between ferric chloride and tartaric acid silver bromide and chlorine water have been examined when the reacting substances were uniformly distributed through various jellies such as silicic acid starch egg-albumin gelatin and various animal membranes. It is shown that the progression of photochemical reactions in jellies proceeds according to Lambert’s law if the jelly absorbs the active rays but if the jelly does not absorb these rays then the progression of the reaction is proportional to the time.From the experiments on the decom- position of chlorine water i t is shown that the photosensitive com- ponent is the hypochlorite-ion. Organic jellies are shown to possess a considerable transparency for ultra-violet light whilst animal membranes allow only a very little of the ultra-violet light to pass through them. J. F. S. Photocatalysis. 111. The Photosynthesis of Naturally Occurring Nitrogen Compounds from Carbon Dioxide and Ammonia. EDWARD CHARLES CYRIL BALY ISIDOR MORRIS HEILBRON and HAROLD JACOB STERN (T. 1923 123 185-197).GENERAL AND PHYSICAL CHEMISTRY.ii. 51 Spectrophotoelectrical Sensitivity of Argentite (Ags). W. W. COBLENTZ (Bull. Bur. Standards 1922 18 265-280; Xci. Paper No. 446).-A study of the effect of crystal structure on the photoelectrical sensitivity of silver sulphide. A comparison is made between the results for acanthite (A. 1920 ii 212) and those now obtained for argentite. Appreciable changes in the electrical resistance of argentite and acanthite occur when these substances are exposed to wave-lengths of light extending from 0.3-2 p maxima being obtained at 1-35 p and 0-41 p. Argentite reacts slightly to radiation of wave-lengths 0-5 to 1.1 p whereas acanthite shows a strong photoelectrical sensitivity in this region. The maximum at 1-35 p is symmetrical in the former and unsym- metrical in the latter case.The maximum shifts to short wave- lengths a t low temperatures. The photoelectrical reaction of argentite differs from that of acanthite in being free from an induced photonegative polarisation. On increasing the intensity of the radiation in both cases a more rapid change is produced in the long wave-lengths than in the short wave-lengths and the maximum photoelectrical sensitivity is shifted toward the long wave-lengths. Mechanical working of the crystals of acanthite and argentite lowers the photoelectrical sensitivity. The worked specimens of these minerals give practically identical infra-red maxima a t low temperatures the effect of temperature being less than in the naturally occurring crystals. Thus apart from the effect of crystal structure silver sulphide has a characteristic photoelectrical response spectrum.Crystal structure has however a marked effect upon photoelectrical sensitivity. W. E. G. The Excitation of Characteristic X-Rays from Light Ele- ments. J. C. MCLENNAN and (Miss) M. L. CLARK (Proc. Roy. Xoc. 1923 [ A ] 102 389-410).-Following the method of Hughes (A. 1922 ii 184) the critical absorption wave-lengths of the K- and L-series were determined for the elements boron glucinum and lithium and the critical absorption wave-lengths of the L-series for carbon. The following values were obtained carbon L-series X=166-7 A. ; boron K-series X=83.6 8. L-series A= 292.2 8. ; glucinum K-series X=llS.2 8. L-series X=428.1 8. ; lithium K-series X=290-8 pi. L-series X=1019.0 8. The result for the K-series for boron is in good agreement with that obtained by Hughes but considerable difference occurs between the re- spective values for the L-series.The critical absorption K-wave- lengths for lithium represent the first two members of a series with a frequency formula given by v=N( 1 - 1 /m2) beginning approx- imately a t 387.7 8. and extending to 290.8 8. The model of the atom put forward by Bohr makes no provision for this series. The wave-lengths for the K-series for glucinum would extend from about X=157.6 8. to X=118.2 A. and the configurations 4(3)4(21. would appear to provide a spectral series with limits approximating to the above wave-lengths. For the elements from potassium to glucinum the square rootsii. 52 ABSTRACTS OF CHEMICAL PAPERS.of the critical potentials for the K-series are very closely propor- tional to the respective atomic numbers but lithium helium and hydrogen show a departure from the linear relation. The results however support the view that the Lyman ultra-violet series for hydrogen is the K X-ray series of this element and also that the convergence wave-length of the K-series for helium is approximately X=485.5 A. The Moseley law which is known to apply for the L-series of the heavier elements ceases to apply for elements lighter than argon but a linear relationship obtained between the atomic numbers of the lighter elements and the exciting voltages of their L-series merges into the ordinary Moseley law when the element argon is reached. W. E. G. Corpuscular Spectra and the Photoelectric Effect.MAURICE DE BROGLIE and LOUIS DE BROGLIE (Compt. rend. 1922 175 1139-1141).-Whiddington has stated (Phil. Mag. 1922 [vi] 43 1126) that corpuscular rays were not observed when h(v-v,) is less than hv v being the frequency of the exciting radiation and V that of the critical discontinuity c. The authors point out that under these conditions the rays are much less easy to obtain. Further Whiddington’s generalisation that the K-rays of tungsten do not excite corpuscular rays in the case of elements of atomic number greater than 50 does not appear to hold in the case of barium (Atomic No. =56) where very feeble rays were observed. This was also the case with iodine (Atomic No.=53) but no visible rays were obtained with samarium (Atomic No.=62).The vari- ation in intensity of the corpuscular rays excited by a radiation of frequency v is calculated; the total energy of the corpuscles composing the ray is AvCa”-Kc and if v is replaced by its value as a function of the atomic number the expression may be regarded as such a function. Brillouin’s theory (Compt. rend. 1920 170 274) introducing the idea of thermal agitation on electronic impact is briefly discussed and it is stated that its developments are not inconsistent with the experimental results obtained with respect to the photoelectric effect of X-rays. Dielectric Constants at the Critical Temperature. W. HERZ (2. physikal. Chem. 1922 103 269-272).-The author has calculated the dielectric constant of thirty-three liquids at the critical temperature.These substances a t ordinary temperature have dielectric constants varying between 81.1 and 1.491. The dielectric constant a t the critical temperature ought theoretically to be constant for all substances. The author finds that although the value is not constant it shows a decided tendency toward a constant value; the calculated values vary between 2-40 and 1-17. v4 H. J. E. J. F. S. The E and I Potential at the Interface Barium Sulphate- Water. A. GYEMANT (2 physikal. Chem. 1922 103 260- 268).-The dependence of the potential of barium sulphate onGENERAL AND PHYSICAL CHEMISTRY. ii. 53 the concentration of the barium-ions has been determined by means of E.M.P. measurements. The experiments lead to the conclusion that in order to explain the y potential the barium-ions and all other ions present must be taken into account.The observed dependence of the potential on the concentration of barium-ions cannot be deduced from the dependence of the E potential on the barium-ion concentration when the changes of E are evaluated by the method of Chapman (Phil. $lug. 1913 [vil 25 475) and of Herzfeld (Physikal. Z . 1920 21 28) in which the adsorption is neglected. J. F. S. Curves of Electrocapillarity in Non-aqueous Solutions. H. WILD (2. physikul. Chem. 1922,103 1-38).-Electrocapillarity curves have been constructed for saturated solutions of potassium chloride potassium nitrate mercurous nitrate and also for nitric acid in each of the two liquid layers of the liquid pairs water and amyl alcohol phenol furfuraldehyde ethyl acetate ethyl ether aniline chloroform propyl alcohol and isobutyl alcohol re- spectively the whole system in each case being in partition equilib- rium.The results show that two such solutions in equilibrium have the same Nernst potential rI=rr2 towards a given metal. This equality is true within the limits with which the absolute potential can be deduced from the electrocapillarity curves that is 5-10 m.-volts. With the same accuracy it is deduced that the tension at the interface between the two phases a t equilibrium r3 is zero or smaller than 5-10 m.-volts. This behaviour is true for all the cases examined and can be held to be a general rule for all solvents but the generalisation of the rule to all ions would be unsafe for it is quite possible that the capillary active ions may behave differently in different cases particularly in those cases where well-marked ion adsorption potentials are shown.I n these cases an additional potential difference must be noticed namely that due to the partition of the ions. J. F. S. Forces at the Boundary between Phases. EMIL BAUER (2. physikul. Chem. 1922 103 39-42).-A theoretical paper in which on the basis of the experiments of Wild (cf. preceding abstract) the author discusses the origin of the potential difference at the boundary between two liquid phases. In an earlier paper (A. 1916 ii 231) the author expressed the view that the potential difference was due to ion adsorption whilst Beutner (A. 1918 ii 214; 1919 ii 263) maintains that a partition of the ions between the phases is the cause.The author now shows that his view is suppbrted by the electrocapillarity measurements of Wild. J. F. S. Theory of Electrocapillarity. I. Electrocapillary Pheno- mena in Non-aqueous Solvents. A. FRUMKIN (2. physikul. Chem. 1922 103 43-54) .-Curves of electrocapillarity have been determined for 0.1N- and ,!-ammonium nitrate AT-sodium bromide and N-sodium iodide in methyl alcohol 0-2N-ammonium 3*ii. 54 ABSTRACTS OF CHEMICAL PAPERS. nitrate N-lithium chloride and N-sodium iodide in ethyl alcohol N-lithium chloride in mixtures of ethyl alcohol and water 0-9N- lithium nitrate 0-5N-lithium chloride and N-ammonium thio- cyanate in acetone N-ammonium thiocyanate and 1.6N-sodium iodide in pyridine. The results show that the activity of the anion in these solutions manifests itself in exactly the same way as in aqueous solutions. The maximum in these solutions when compared with aqueous solutions of corresponding composition is found to be displaced to the left that is it corresponds with a smaller cathodic polarisation.Theory of Electrocapillarity. 11. A. FRUMKIN (2. physikal. Chem. 1922 103 55-70; cf. preceding abstract).-It is shown that the whole of the electrocapillary phenomena are governed by the equation dy=cd+-Srldp where y is the thermodynamic potential in the solution containing pi ions (b is the potential difference of solution/metal and ri the number of ions which must be added to the solution so that pa remains constant when the surface of the metal is increased by a unit. The values of dy/dq and E the quantity of electricity combined with Fr ions have been determined experimentally for 2N-sulphuric acid saturated with mercurous sulphate E (calc.) 39 X coul./cm.2 E (obs.) 39 x 10-6 coul./cm2. ; N-sodium chloride saturated with mercurous chloride E (calc.) 50 x 10-6 coul./cm2. E (obs.) 47 x coul. /cm2. ; N-potassium hydroxide saturated with mercuric oxide E (calc.) 21 x 10-6 coul./cm2. E (obs.) 17 x coul./cm2. ; N-potass- ium nitrate and 0-OW-potassium iodide saturated with mercurous iodide E (calc.) 86 x 10-6 coul./cm.2 E (obs.) 90 x coul. /cm.2 with the results stated. It is shown that the Lippmann-Helm- holtz differential equation for solutions is true both for those with normal electrocapillarity curves and for those with abnormal curves. The potential of a dropping electrode always coiiicides with the value given by the corresponding electrocapillarity curve.A potential difference exists between mercury on the one hand and water methyl alcohol ethyl alcohol and acetone on the other when the surface layer contains either ions or adsorbed molecules of a dissolved substance. I n investigations of the present type it is necessary to differentiate between thermodynamic and electro- capillary solution tensions. J. F. S. Decomposition Tensions of Fused Mixtures of Sodium Hydroxide with Zinc Oxide or Cadmium Oxide. L. ROLLA and R. SALANI (Gaxxetta 1922 52 286-313).-Experiments similar to those of Sacher (A. 1902 ii 120) have been made on mixtures of molten sodium hydroxide with zinc oxide or cadmium oxide. Fused sodium hydroxide shows two points of cathodic decomposition the lower one 1-20 volts corresponding with the discharge potential of the hydrogen-ions ; the higher point corre- sponding with the discharge potential of the sodium-ions has the value 2-08 volts a t 460° 2.13 volts a t 412" and 2-24 volts at 364".With the mixtures containing zinc or cadmium oxide the decom- J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 55 position occurring is that of zinc or cadmium hydroxide the decom- position tensions for the zinc- and cadmium-ions being respectively 1.80 and 0-89 volts. T. H. P. The Electrolytic Dissociation of Dibasic Acids. Deter- mination of the Second Dissociation Constant of Acids from Electrometric Measurements. ERIK LARSSON (2. anorg. Chem. 1922 125 281-294).-The author applies the theory of Bjerrum (A.1919 ii 9) to the ionic equilibria in a solution which contains the neutral salt and the free dibasic acid. He shows how the second dissociation constant can be calculated from the hydrogen- ion activity measured electrometrically. The results obtained agree well with some earlier results obtained by the conductivity met hod. W. T. Formic Acid. 11. Electrolytic Dissociation of Formic Acid. FR. AUERBACH and H. ZEGLIN (2. physihZ. Chern. 1922 103 178-199).-The electrical conductivity of formic acid and of sodium formate has been determined over a wide range of con- centration at 18". It is shown in agreement with earlier investig- ators that small quantities of formic acid and sodium formate are decomposed a t the platinised electrodes.The decomposition has been investigated and in the case of the formate shown to consist in an oxidation to sodium hydrogen carbonate and to be due to the oxygen occluded in the platinised electrodes. This disturbing factor may be removed by suitable treatment of the electrodes with hydrogen before the measurements. The limiting value of the molecular conductivity of sodium formate at 18" is extrapolated to 91 and from this value the limiting value for formic acid is calculated to be 362.5. The dissociation constant for formic acid is shown to be inconstant and to vary with increasing dilution from 2-05 x lob4 to 1.91 x and this difference is shown not to be due to experimental error. Formic acid belongs there- fore to the acids of medium strength which do not follow the law of mass action closely.Values have been calculated for the electrical conductivity of formic acid which agree with the experi- mental values exactly over the whole range of concentration on the basis of Ghosh's hypothesis. The Anomaly of Strong Electrolytes. HENRY J. S. SAND (Phil. Mag. 1923 [vi] 44 129-144).-A critical examination of the theories of Ghosh (A. 1918 ii 215 348 392 790) and of Milner (A. 1918 ii 148). Employing the Boltzmann theorem and the Born theory of the potential energy of a pair of attracting ions estimations are made of the degree of association of a com- pletely ionised electrolyte immersed in a medium of uniform dielectric constant. It is shown that the probability of the two ions of a binary electrolyte (N/10-solutions) being in contact in a given small volume is only 8.1 times as great as the probability of their occurrence in any two volumes of the same size so situated that the attraction between the ions is negligible.The hypothesis of complete ionisation in the case of salts like sodium chloride is J. F. S. 3*-2ii. 56 ABSTRACTS OF CHEMICAL PAPERS. thus completely established. It is shown that a preponderating proportion of the ions will be subject to the inverse square law of electrical action. The relation P V = 2RT - +RThf( h) obtained by Milner from the Clausius' virial theorem can have only approximate validity. The Ghosh theory of the "crystalline" arrangement of the ions in aqueous solutions is criticised and i t is concluded that the space lattices in this theory are merely theoretical " distributions of reference." The deductions from Ghosh's and Milner's osmotic pressure formulae are compared with the experimental results.The agreement between the mean experimental values of (2-4) for univalent binary chlorides in aqueous solutions and the same value derived from Ghosh's formula is good ; the agreement a t the higher concentrations is better than that attained by Milner's theory. Relationship between the Specific Heat of Liquids. W. E. G. W. HERZ (2. anorg. Chem. 1922 125 295-300).-A theoretical paper. It is shown that the specific heats of liquids a t two-thirds their critical temperature divided by the values at one-half the critical temperature gives a fairly constant value. This constant for the twenty organic liquids quoted is about 0.8.Liquids in a homo- logous series show an increase of about 9 for the introduction of a CH group but with aniline-dimethylaniline there is an exception the difference being very small ; in this series the specific heat decreases with increasing molecular weight. In homologous series the molecular heat of evaporation increases about 10 for each CH group but there are many exceptions. The introduction of a chlonne atom in place of a hydrogen atom increases the molecular heat of evaporation by about 9.5 units the introduction of a second chlorine atom has a less effect. A double bond lowers it by about two units. W. T. [Determination of Boiling Points.] Boiling Points of Ammonia Sulphur Dioxide and Nitrous Oxide.F. W. BERGSTROM ( J . Physical Chem. 192Z726,876-894).-A comparison has been made of the efficiency of single-walled and vacuum- jacketed boiling vessels. It is found that the boiling point of ammonia determined in a single-walled vessel is about 0-2" high even with internal electrical heating. Determination in a Cottrell tube reduces this error. Boiling points may be determined accur- ately in a vacuum-jacketed vessel a t temperatures as low as - 90° but in such cases a correction should be applied for the depth of immersion of the bulb and there should be no uncooled stem. The Cottrell apparatus can be used successfully a t temperatures at least as low as - 33.4". Better equilibrium between vapour and liquid is obtained and uncertain temperature corrections are eliminated by using this apparatus and a smaller quantity of liquid is generally required.The following boiling points have been determined a t 760 mm. ammonia - 33-41"&0~1" sulphur dioxide - 10~02"&-0~1" and nitrous oxide - 89.5"&0*2". J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 57 Application of the Method of Continuous Variations to Ebullioscopic Phenomena for the Determination of Double Salts in Solution. F. BOURION and E. ROUYER (Compt. rend. 1922 175 1406-1408).-The method of continuous variations as applied to ebullioscopic measurements was tested in the case of solutions of cadmium chloride with potassium chloride and ammonium chloride respectively and solutions of cadmium iodide with potassium iodide and found to give quite as satisfactory results as when applied to cryoscopic measurements.W. G. A Micro-method for the Determination of Molecular Weight in a Melting-point Apparatus. 11. Determinations with Extremely Minute Quantities. KARL RAST (Ber. 1922 55 [B] 3727-372S).-The author has succeeded in further refining his micro-method for the determination of molecular weight in freezing camphor to such an extent that it is possible t o obtain accurate results with scarcely visible amounts of substance. The capillary tube is slightly conical in shape and rather wider (2-3 mm.) than those recommended previously; it is essential that i t should be very thin in the wall and that the bottom should be hemispherical. The solutions are prepared in the capillary itself the substance under investigation being first introduced and sub- sequently the camphor.The materials are pressed together by a small glass rod. The capillary is sealed and subsequently drawn out to a long thread by means of which i t is attached to the thermometer. Mixing of the components is effected by melting and re-solidification. The column in the capillary must not be more than 2 mm. in height so that in general 0.2-0.3 mg. of substance and 2-3 mg. of camphor are required. It is essential to guard against undue concentration of the solutions which however may sometimes be greater than normal. H. W. The Influence of the Velocity of Cooling on the Hardness and Microstructure of Eutectic Mixtures. N. S. KURNAKOV and A. N. ACHNASAROV (Z. unorg. Chem. 1922 125 185-206).- The hardness of eutectic mixtures increases with the rate of cooling and with the degree of fineness of the grains. This tendency to increase in hardness decreases with increasing brittleness e.g.zinc-antimony. Increasing fineness of grains also results in increasing passivity of the alloy. Homogeneous phases of pure metal and solid solutions show no change in hardness on rapid cooling. The above conclusions were obtained from a study of the systems cadmium-silver silver-copper gold-nickel zinc- antimony. W. T. General Theory of the Adsorption of Solutions. BROR. GUSTAVER (Kolloid Z. 1922 31 358-362).-A theoretical paper in which the author criticises the views put forward on the adsorp- tion of solutions by Ostwald and Izaguirre (A. 1922 ii 480). It is shown that the theory is not in keeping with the author's results on the sorption of vapours by charcoal (A.1922 ii 479) neither isii. 58 ABSTRACTS OF CHEMICAL PAPERS. it in keeping with respect to the thickness of the adsorbed layer as determined by the author and others. J. F. S. Adsorption of Ions by Freshly Precipitated Manganese Dioxide. P. B. GANGULI and N. R. DHAR ( J . Physical Chem. 1922 26 836-844) .-The authors have investigated the adsorp- tion of kations by manganese dioxide and also the effect of various anions on the adsorption. Manganese dioxide was prepared in the solution of ions under investigation by the addition of equiva- lent quantities of potassium permanganate and manganous sulphate and the amount of adsorption determined by analysing the filtered solution after equilibrium had been reached. Some thirty-five salts have been used in the investigation and the results show that the coagulating powers of the different electrolytes as calculated from the percentage of kation adsorbed from approximately normal solutions of the electrolytes follow the Schulze-Hardy law very imperfectly.The effect of the anions on the adsorption of kations by manganese dioxide is found to be very marked. There is however no regularity in the variations shown by the adsorption values of the kations with variation of the anion. In the case of ferric salts the adsorption of ferric-ions by manganese dioxide is abnormally large; a result which is probably to be attributed to a partial hydrolysis of the ferric salt with the separation of ferric hydroxide.Among the electrolytes of metals occurring in the same group of the periodic system the values of the percentage adsorption are generally found to be in the order of the atomic weights of the kations. Physical Chemistry of Dyeing. Acid and Basic Dyes. T. R . BRIGGS and ARTHUR W. BULL ( J . Physical Chem. 1922 26 845-875).-The process of dyeing wool with acidic and basic dyes has been investigated from the point of view of the adsorp- tion hypothesis as formulated by Pelet- Jolivet and Bancroft (Applied Colloid Chemistry 1921 115). The effect of dyes on the adsorption of acids by wool and of acids on the adsorption of dyes has been determined quantitatively for typical acid dyes. It is shown that the taking up of dyes is a case of adsorption and that the amount of dye adsorbed varies continuously with a change in the hydrogen-ion concentration of the dye-bath.No evidence of chemical action between dyes and wool has been obtained. J. F. S. J. F. S. The Determination of the Dissociation Pressures of Hydr- ated Salts by a Dynamical Method. 11. JAMES RIDDICK PARTINGTON and DONALD BENNETT HUNTINGFORD (T. 1923 123 160-170). A New Explanation of Diffusion. ALEXANDR BAT~K (Chem. Listy 16 [9] 295-299).-Pick’s theory for the diffusion of liquids (Ann. Phys. Chem. 1855 [ii] 94 59) is discussed and its experimental basis questioned. Certain discrepancies betweenGENERAL AND PHYSICAL CHEMISTRY. ii. 59 the results calculated on this theory and those obtained experi- mentally by Voit (Ann. Phys. Chem. 1867 [ii] 130) are pointed out.The technique of optical methods for the determination of rates of diffusion is examined and possible sources of error are suggested. Weber's confirmation (Awn. Phys. Chem. 1870 [iii] 7 469 536) of the applicability of Fourier's law to the diffusion of liquids is shown to be doubtful and the necessity for a recon- sideration of the whole question emphasised. The mechanism of the diffusion of liquids is then discussed from first principles and the use of the conception of limiting states of solutions in helping to elucidate the problems of diffusion of liquids is substantiated. R. T. Diffusion in Solid Solutions. H. Wmss and P. WERRY (Compt. rend. 1922 175 1402-1405).-A study of the inter- penetration by diffusion of gold and silver at the temperatures 935" 885" and 835" shows that the form of the law of diffusion in fluids is valid.The values of the constant K a t the temperatures used when interpolated to 870° give a value 0.0000375 which is in very close agreement with the value obtained by Fraenkel and Houben (A. 1921 ii 491). Process of Diffusion in Gelatin. Liesegang's Ph&omenon. CARL ADOLF SCHLEUSSNER (Kolloid Z. 1922 31 347-352).- With the object of employing the diffusion into gelatin as a means of testing the suitability of various specimens of this substance for use in the manufacture of photographic plates the author has examined the conditions under which the Liesegang rings are produced. It is shown that for a regular and uniform diffusion the gelatin must be in a uniform condition. The necessary condition can only be obtained after the gelatin has been held in solution for at least twenty-four hours.It is shown that from the character of the ring formation conclusions may be drawn as to the purity of the gelatin. The intermediate rings which may be observed with a lens between the main rings are shown to be silver salts of phosphoric and halogen acids and are due to impurities in the gelatin. A bibliography of the work on the formation of Liesegang rings and allied phenomena is included in the paper. The Relation between the Crystal Structure and the Con- stitution of Carbon Compounds. I. Compounds of the Type CX,. Racemates and Pseudo-racemates. PHILIPPE LANDRIEU (Bull. Xoc. chim. W. G. J. F. S. ISABEL ELLIE KNAGGS (T. 1923 123 71-79). Double Compounds and Mixed Crystals.1922 [iv] 31 1217-1241).-Lectures delivered a t the College de France. G. F. M. Hydrogen-ion Concentration and the Properties of Emulsoid Colloids. ROBERT HERMAN BOGUE ( J . Physical Chem. 1922 26 801-811).-A theoretical paper in which it is shown that the various physical properties of the emulsoid colloids includingii. 60 ABSTRACTS OF CHEMICAL PAPERS. the viscosity jelly strength melting point and joining strength are a t a minimum a t a hydrogen-ion concentration corresponding with the isoelectric point. As the acidity or alkalinity of the solution is increased from this point the whole of these properties increase in value. It is shown that salt precipitations for gelatin contents should be made a t the isoelectric point if the maximum precipitation is to be obtained.The necessity for a careful control! of the hydrogen-ion concentration in investigations on the proteins is emphasised and the desirability of a similar control in the gelatin and glue plant during manufacture is also pointed out. The limitation of the benefit obtainable from such conDro1 however makes the practicability of such methods when applied to the improvement of the quality of the material very questionable. The estimation of the hydrogen-ion concentration is urged as a test in the evaluation of gelatin and glue but it is not recommended that all tests of viscosity jelly strength and joining strength be made a t a specified hydrogen-ion concentration. J. F S. Present Position of the Theory of Peptisation. W. MOELLER (2. Leder Gerb.Chem. 1922 1 360-376; cf. A. 1915 i 439).- A theoretical paper in which the author discusses the theory of peptisatiod particularly in connexion with its application to tanning and the leather industry. It is shown that the mechanism of tanning consists in the destruction of the sol-condition of the peptised solution by the substance of the hide. The hide substance removes the sol by adsorbing the peptising agent and the separ- ated coagulated oil surrounds the micells of hide to form micro- crystals. The author defines tan as a system which of itself is quite insoluble but by peptisation may be converted into a colloidal solution. Leather is defined as an animal hide the elementary particles of which are crystalline micells protected by a sheath of tan particles from hydrolytic influences.J. F. S. Protective Colloids. XII. Gelatin as a Protective Colloid. 111. Colloidal Platinum. A. GUTBIER and A. ZWEIGLE (Kolloid Z. 1922 31 346-347; cf. A. 1922 ii 485).-Solid platinum colloids may be prepared by reducing chloroplatinic acid in aqueous chloroform solution by means of hydrazine hydrate in the presence of solutions of gelatin. When five parts of a 1 yo solution of chloro- platinic acid in water saturated with chloroform is mixed with five parts of o*14y0 gelatin solution and slowly reduced by the addition of 0.1 yo solution of hydrazine hydrate a colloidal solution which is black by transmitted light and dark brown by reflected light is produced. This sol on keeping deposits a small quantity of a black powder and on dialysis yields a very stable sol.The black precipitate is reversible t o the extent of about 70%. The sol is stable towards heat and quite insensitive to electrolytes which are capable of producing an hydroxyl-ion. Solutions of neutral salts coagulate the sol only after keeping for several days whilst acids even in dilute solution produce a rapid coagulation. On evaporation a t 27" in a vacuum over sulphuric acid a solidGENERAL -4ND PHYSICAL CHEMISTRY. ii. 61 colloid is obtained which is completely reversible in cold water and contains 18*76y0 of platinum. When the quantities of the reagents employed are one part of 0.14% gelatin five parts of 0.1 yo solution of chloroplatinic acid and four parts of chloroform water the solid sol obtained by the same process is also com- pletely reversible to form stable secondary sols in dilute solution and the solid itself contains 55-67y0 of platinum.J. E. S. Validity of the Law of Mass Action for Ionic Equilibria. J. N. BRONSTED and KAI PEDERSEN (2. physikal. Chem. 1922 103,307-31 5) .-The reaction between ferric chloride and potassium iodide has been investigated in aqueous solution a t 25" and from the results it is shown that the law of mass action is valid for ionic equilibria when these are set up in concentrated salt solutions as solvents. A convenient method for determining solubility in the absence of air is described and used to determine the dissociation constant of the tri-iodide-ion. The value for the equilibrium constant of the dissociation IiZZI,+I' a t 25" is 0*00611 a t 15*0" 0.00502 and a t 18.5" OaO0540.J. P. S. Formic Acid. 111. Partition of Formic Acid between Ether and Water and its Application to Analytical Purposes. FR. AuERBacH and H. ZEGLIN (2. physikaE. Chem. 1922 103 200-237).-The partition coefficient of formic acid has been determined a t 18" for ether and water O*SN-sulphuric acid and 0*5N-sulphuric acid containing 100 g. of sodium chloride per litre respectively. In the case of ether and water the coefficient was determined for concentrations up to 1 mol. per litre and in spite of corrections for the electrolytic dissociation of the formic acid in water the partition coefficient of the undissociated acid was found to be inconstant but to vary in a linear manner with the con- centration in the aqueous phase ; the value f =C,/Cw varies from 0.395 for Cw=0*0446 to 0.454 for C,=1*343.In the case of ether and 0-SN-sulphuric acid in which the electrolytic dissociation in the aqueous phase is practically zero the partition is displaced in favour of the ether layer but here also the coefficient is dependent on the concentration of the aqueous layer. Sulphuric acid con- taining sodium chloride gave similar results to the acid and ether alone. The progression of the partition coefficient is explained by the polymerisation of the formic acid in ethereal solution From the law of mass action the extent of the polymerisation is calculated on the assumption of double molecules by means of the formula x=[(HCO,H),]/[HCO,H]~ ; the following values of x are obtained for ether saturated with water x=0.139; for ether saturated with 0.5N-sulphuric acid x=0-147 and for ether satur- ated with 0-SN-sulphuric acid containing 100 g.of sodium chloride per litre x=0*158. The small differences in the polymerisation constant are due to the varying water content of the aqueous phase. The true partition coefficients have been calculated from the above-mentioned quantities and the experimental results. The partition coefficient of undissociated unimolecular formic acidii. 62 ABSTRACTS OF CHEMICAL PAPERS. a t 18" has the following values between ether and water,fo=0*393 ; between ether and 0.5N-sulphuric acid f0=0*398 and between ether and O.5N-sulphuric acid containing 100 g . of sodium chloride per litre f0=0*400. For the purpose of applying the partition coefficient to analytical purposes the volume changes of the phases when ether is shaken with water or N/S-sulphuric acid solution were either determined or taken from the unpublished work of Mylius.By means of the volume correction factor and the par- tition coefficient the concentration of formic acid in a 0.5N-aqueous sulphuric acid solution may be calculated from the concentration in the ethereal layer after shaking the sulphuric acid solution with ether. Equations for this calculation have been derived and tables of numerical factors are given in the paper. Formic acid in 0*5N-sulphuric acid solutions may be estimated by this method for amounts of formic acid between 2.4 g. and 0.011 g. with an average error of 0*38%. If the sulphuric acid also contains 100 g.of sodium chloride per litre the average error of the estimations is 0.26%. J. P. S. J. A. CHRISTIAN- SEN (8. physikal. Chem. 1922 103 91-98).-A theoretical paper in which on the assumption that only molecules in a definite quantic condition react the author has developed a velocity formula for reactions of the type AB + A +B. The equation deduced has the form E= (pm/pn)e-(em-+JIRF . v'/( 1 -e-hv'/R*) where E is the velocity constant pm and pn are the a prior! probabilities respectively that the molecules are in the m-quantlc or normal condition when the m-quantic condition is that necessary for reaction ; the other symbols have their usual significance; those with the dash such as v' refer to the products of the reaction. The author shows that when hv'/RT is small the equation reduces to the form k=(pm/pn) x e-(em-cn)lRF - RT/h which is practically the same as the expression deduced by Herzfeld (A.1922 ii 136) from Stern's expression for unimolecular reactions. When hv' /RT has a comparatively large value the expression reduces to k= (pm/pn) . e-('m-en)/RT x v' which is the same as the expression obtained by Dushman (A. 1921 ii 315). J. F. S. Thermal Decomposition of Carbonyl Chloride. J. A. CHRISTIANSEN (8. physikal. Chem. 1922 103 99-138).-The thermal decomposition of carbonyl chloride both alone and mixed with chlorine has been investigated' at a number of temperatures between 655" and 782" absolute. The results indicate that over the range of temperature 705-745" Abs. the reaction takes place according to the equation h=k~Cc,,(Ccoaz-f) where his the velocity k a constant and f=Cco .C,,/K K is the equilibrium constant of the reaction COC1,t CO+Cl,. The equation only holds when the concentration of the carbonyl chloride carbon monoxide and chlorine are of the same order (10-3-10-4 mol./litre). At the commencement of the reaction that is until the above condition obtains the divergences from the equation are always positive Velocity Law of Unimolecular Reactions.GENERAL AND PHYSICAL CHEMISTRY. ii. 63 in the sense that the observed velocity is always greater than the value calculated according to the above equation. The velocity is not markedly affected by a change in the relative glass surface in the ratio 50138. The velocity is unaffected by the presence of air when the concentrations of carbon monoxide and chlorine are considerable from the commencement of the reaction.When it is assumed that the expression for the velocity does not change with temperature the value of the constant k can be found by means of the expression log k= -11420/T+15.154 for the temperature range 685-782". An experiment a t 655" was found to be less exact but it agreed with the above expression within the limita of the experimental error. The Velocity of Reaction in Mixed Solvents. IV. The Influence of the Base on the Velocity of Saponification of Esters. ALBERT ERIC CASHMORE HAMILTON MCCOMBIE and HAROLD ARCHIBALD SCARBOROUGH (T. 1923 123 197-207). Chemical Kinetics of Heterogeneous Systems. IV. The Mechanism of Chemical Reaction when Noble Metals Dis- solve in Potassium Cyanide Solution.EIICHI YAMAZAKI ( J . Chem. SOC. Japan 1922 43 686-690).-According to Bodlander (2. anorg. Chern. 1896 19 583) gold and other noble metals dissolve in potassium cyanide solution owing to the catalytic action of hydrogen peroxide produced as an intermediate; but this explanation and Bodlander's formulz cannot explain the author's experiences. The reaction velocity is approximately pro- portional to the square root of the concentration of oxygen but not to the concentration itself. The production of hydrogen peroxide is a secondary reaction which may of course accelerate the dissolution of the metals and produce the peroxides when Ba" or Ca" are present in the solution. When the dissolution of the metal is normal the reaction proceeds as follows Ag=Ag'+O ; 0+2@-+0" ; H20+0"+20H' ; or 2Ag+H,O+30,=2Ago+ 20H' etc.K. K. $ome Properties of the Active Nickel used as Catalyst in Organic Chemistry. ANDRB BROCHET (Compt. rend. 1922 175 1073-1075 ; cf. this vol. ii 181.-The pyrophoric property of nickel prepared for use as a catalyst is entirely due to occluded hydrogen and if the metal is freed from that gas under conditions which maintain in the nickel the property of being readily trans- formed into oxide its catalytic activity remains unimpaired. There is no relation between the pyrophoric condition and the catalytic efficiency although the extent of the former is a convenient indi- cation of the progress of the preparation of the catalyst. Catalytic nickel if washed and dried loses its pyrophoric property; in cases in which the catalytic activity is affected by this operation it may be restored by heating for a short time in hydrogen. The author appends a brief discussion from the point of view of employment as a catalyst of the extent and condition of the metallic surface and the property of occluding hydrogen.J. F. S. H. J. E.ii. 64 ABSTRAOTS OF CHEMICAL PAPERS. Catalytic Hydrogenation with Nickel. Factors Determin- ing Catalytic Activity. R. THOMAS ( J . SOC. Chem. In&. 1923 42 21-26~).-A description is given of some of the methods which may be employed for the preparation of catalytically active nickel and the relative activities of variously prepared nickel catalysts in the hydrogenation of oils have been determined.The most active catalyst was that obtained by the reduction by means of hydrogen a t 350-500" of nickel hydroxide precipitated on kieselguhr. A nickel catalyst prepared by reduction with charcoal a t 600° or by electrical disintegration or by the decomposition of nickel carbonyl was less than one-fourth as active whilst nickel precipitated from its salts by means of aluminium showed only about one-sixth of the activity. The author concludes with a theoretical discussion as to what are ultimate factors which influence catalytic activity and what form of energy transference occurs between the catalyst and reacting substances. It is suggested that the catalyst activates a certain number of molecules of the reactants by thermionic emission and that the bulk of the mole- cules are then successively activated by electron emission from molecules already in an activated condition through the instru- mentality of the catalyst.G. F. M. Heterogeneous Catalysis and the Orientation of Adsorbed Molecules. H. R. KRUYT and C. F. VAN DUIN (Proc. K . Alcad. Wetensch. Amsterdam 1923 25 324-326) .-In continuation of previous work (A. 1921 ii 392) the authors find that the reaction between aqueous solutions of dibromosuccinic acid (meso- or racemic form) and potassium iodide is considerably accelerated in the presence of charcoal. The greater acceleration occurred in the case of the meso-form a result in accord with stereochemical considerations. The result confirms the conclusion that positive contact catalysis is to be anticipated only when the reacting group of molecules is directed away from the adsorbent and towards the surrounding medium.J. S. G. T. A Type of Ideal Electric Atoms. J. L. (Nature 1922 110 873).-The mathematical solutions arrived at by Hargreaves (this vol. ii 19) give a possible structure for an ideal atomic nucleus of the Rutherford type. Speculation Concerning the Positive Electron. HORACE H. POOLE (Nature 1923 111 15-16).-Lodgeys speculation (A. 1922 ii 836) is examined from the point of view of the relative abundance of the lighter and heavier elements the case of hydrogen being considered in particular. An immense discrepancy is appar- ent. Doubtless some negative protons would combine with previously formed positive complexes but since about half the complex nuclei first formed would be negative so that some of the positive protons would be lost by combination with them these effects would be expected to balance approximately.If however it is assumed that when two unequal nuclei combine the A. A. E.INORGANIC CHEMISTRY. ii. 65 sign of the combination is determined by that of the larger cornti- tuent it is conceivable that if the first set of nuclei formed happened to be positive they might so direct the course of subsequent events as to lead to the existing distribution of the elements. A Laboratory Apparatus for Rapidly Drying Sensitive Organic Substances. J. BOUILLOT ( J . Phclrm. Chim. 1923 [vii] 27 23-28).-A tube of glass 15 cm. long and 30 mm. wide sealed at one end and fitted with a heat-resistant cork at the other carries the siibstance to be dried in a boat The tube has two slightly narrower tubes attached vertically t,o its upper surface by narrow necks contlaining plugs of cotton wool and in the openings of these tubes are fitted corks carrying narrow glass tubing termin- ated inside by being drawn out in narrow hooks so as to avoid violent currents of air impinging on the boat below. The whole apparatus can be immersed in an air-bath at the required tem- perature and currents of dried air can be aspirated over the contents of the boat a t any required pressure. J. F. BREWSTER ( J . Ind. Eng. Chem. 1923 15 32).-A solid rubber stopper is cut about three-quarters through a t the small end so that a thin flap of rubber is left to serve as the valve leaf. The stopper is then bored leaving the flap intact to receive a short length of glass tubing which is pushed through to within a few mm. of the valve seating. A piece of glass tubing of such diameter as to allow free play of the valve flap but at the same time to fit the stoppers tightly is closed a t one end by the valve stopper and a t the other by a one-hole stopper. The contrivance will allow the passage of air or liquid from the direction of the valve stopper to the one-hole stopper but not in the reverse direction and is useful for preventing amongst other things a " suck back " of wafer from a water vacuum pump into the apparatus during a vacuum distillation etc. A. A. E. H. K. A Simple Check Valve. G. F. M.

ISSN:0368-1769    

DOI:10.1039/CA9232405045

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. ii. 65 In or gani e Chemistry. A Convenient Method €or the Preparation of Aqueous Hydrobromic Acid of Constant Boiling Point. J. G. F. DRUCE (Chem. News 1923 126 l).-The method described by Pickles (A. 1919 ii 411) gives rather a dilute acid and the dis- tillation is difficult to carry out without " bumping " taking place. The following modification obviates the latter difficulty and gives a distillate containing more than 48% of hydrogen bromide 10 C.C. of strong sulphuric acid are added to a solution of 15 g. of potassium bromide and 0.2 g. of stannous chloride in 25 C.C. of water. After remaining over-night the clear liquid is decanted from the crystals of potassium hydrogen sulphate which haveii. 66 ABSTRACTS OF CHEMICAL PAPERS. sepm&& and distilled the fraction coming over between 120" and 125" being collected. The yield is more than 90% of the theoretical and the product contains only a trace of chlorine.The Structure of the Sulphur Dioxide Molecule. A. 0. RANKINE and C. J. SMITH (Proc. Physical Xoc. 1922,35 33-38).- The authors' method of determination of the molecular dimensions of gaseous molecules from viscosity measurements (A. 1921 ii 192) has been employed to decide between the relative merits of two formulze for sulphur dioxide. That proposed by Langmuir O=S-0 should possess the dimensions of a neon-argon-neon complex with the components arranged in a line or arranged so that the lines joining the neon to the argon atoms make an angle of 135". The calculated mean collision area of this model is con- siderably in excess of that deduced from viscosity measurements 0*94xlO-15 cm.2.On the other hand the calculated value for S<? is 0.99 x 10-15 cm.2 which is in much closer agreement with experiment. W. E. G. Formation of Sulphur Dioxide from the Sulphates of the Alkaline Earths and Iron or Iron Sulphide. F. MARTIN and 0. FUCHS (2. anorg. Chem. 1922,125,307-348).-The authors found that the alkaline sulphates on being heated with metallic iron are completely reduced to the sulphides; this reduction begins at temperatures lower than that required in the case of coal. The reduction is complete in half an hour at 750" for calcium sulphate at 850" for strontium sulphate and at about 950" for barium sulphafe. In the presence of insufficient iron and at about 150" higher a rapid evolution of sulphur dioxide takes place.The best conditions for this are for calcium sulphate the mixture 16CaSO4+15Pe giving 80% of the theoretical yield of sulphur dioxide ; for strontium sulphate the mixture 9SrSOp+SPe giving an SS.9y0 yield. These reactions lead to the formation of well defined ferrites 3CaO,2Fe,O3=Ca3Fe,O ; 2Sr0,Fe20,=Sr2Fe,05 and Ba0,Fe,0,=BaFe20p. Too little iron leads to the formation of alkaline-earth sulphide too much iron gives also iron sulphide. Sulphur dioxide is also evolved by heating the alkaline-earth sulphates with iron sulphide; this can be carried out commercially by using pyrites to which has been added a little iron oxide. Catalytic Hydrogenation of Sulphurous Anhydride. A. R. P. 0 W. T.( MLLE) MARGARET G. TOMKINSON (Compt. rend. 1923 176 35-36).- When a mixture of dry sulphur dioxide and dry hydrogen is passed over finely divided nickel or over nickel sulphide a t 400-450" a mixture of water vapour hydrogen sulphide and sulphur is obtained and if the gases are passed sufficiently slowly the whole of the sulphur dioxide is decomposed. Cobalt sulphide and to a lesser degree ferrous sulphide may also be used as catalysts for the hydrogenation. W. G.INORGANIC CHEMISTRY. ii. 67 Preparation of Sulphuryl Chloride. L~ONCE BERT (BUZZ. Soc. chim. 1922 [iv] 31 1264-1270).-Ruff's method (A. 1902 ii 13) consisting in boiling chlorosulphonic acid with about 1% of mercury or mercuric sulphate is the most practical process for the laboratory preparation of sulphuryl chloride the operation being conducted under a reflux condenser kept at about 70° in order to return unchanged chlorosulphonic acid to the flask.For the successful conduct of the process attention must be directed to the following important but hitherto unpublished points. To prevent risk of fracture the tube of the reflux condenser should be of iron connected with the neck of the flask with a stopper of asbestos paper and silicate cement which resists the action of chlorosulphonic acid admirably. The top of the iron tube is con- nected by means of asbestos thread and silicate to a short glass tube leading to a condenser and receiver for the sulphuryl chloride. The reaction does not proceed so rapidly as Ruff asserted (bc. cit.) and slows down considerably in the latter stages.In one hour a 40%. yield in three hours 60% and six hours 75.8% yield was obtained and for this reason when considerable quantities of sulphuryl chloride are required it is preferable to collect for one hour only and then change the flask for another containing a fresh charge of chlorosulphonic acid. The latter is conveniently obtained by saturating 70% fuming sulphuric acid with hydrogen chloride and distilling. G. I?. M. Phosphorus. ALFRED STOCK (2. anorg. Chem. 1922 125 228-234).-A theoretical paper in which the paper of Marckwald and Helmholtz (A 1922 ii 845) is criticised. The author points out that the melting point of phosphorus depcnds to a very large extent on the rate of heating. MAURICE L. HUGGINS ( J . Physical Chem. 1922 26 833-835).-The author criticises the view held by Stock that boron in the boron hydrides is quadrivalent and puts forward structures for the hydrides B,H B4HI0 B6H12 Bl0HI4 in which boron is regarded as tervalent.These structures are strikingly like those adopted for ethylene butadiene benzene and naph- thalene respectively. The hydrogen atoms are held by means of four-electron bonds such as often exist a t least temporarily in unsaturated organic compounds. Each such four-electron bond is surrounded by four atoms. C. MAZZETTI and F. DE CARLI (Atti R. Accad. Lincei 1922 [v] 31 ii 119-120).-Almost quantitative yields of boron chloride were obtained by passing dry chlorine through a porcelain tube containing ferro-boron heated at about 500". Silicon Hydrides.XI. The Action of Oxygen on S s 4 and SiH,. ALFRED STOCK and CARL SOMIESKI (Ber. 1922 55 [B] 3961-3969).-The oxidation of the simplest hydrides of silicon has been studied in the hope that the reaction would provide W. T. Boron Hydrides. J. F. 8. Preparation of Boron Chloride. T. H. P.ii. 68 ABSTRACTS OF CHEMICAL PAPERS. a more convenient method of obtaining compounds of the types SiH,*OH SiH,O than is afforded by the hydrolysis of the halides. As oxidising agents oxygen air and mixtures of nitrogen and oxygen containing less of the latter than air have been used. The violence of the reaction is moderated by very slowly adding the oxidising agent to an excess of the gaseous liydride under greatly diminished pressure and at a temperature varying between -70" and -1140".Measured volumes of the reagents are employed and the nature of the volatile products is elucidated by the authors' vacuum process. The necessary apparatus is fully figured and described in the original text. Reaction invariably occurs immedi- ately and in spite of the precautions described above is frequently explosive. The products consist of unchanged hydride (including SiH during the oxidation of Si,H,) nitrogen (and argon) when air or artificial mixtures of nitrogen and oxygen are used (the oxygen is invariably consumed completely) a Considerable quantity of free hydrogen water and in certain cases small quantities of volatile silicon compounds formed during the oxidation. In addition a colourless non-volatile residue which generally con- tains brown particles is produced.This consists partly of compact crusts formed near the point of entry of the oxidising agent partly of a fog in the interior of the reaction vesspl and partly of a uniform vitreous deposit on the whole wall of the vessel. The colourless components are fairly readily dissolved by very dilute alkali and appear to consist of substances such as polymeric prosiloxan (SiH,O) silicoformic anhydride [( SiHO),O] etc. ; the brown components contain silicon and possibly highly condensed silicon hydrides poor in hydrogen; they appear to be iormed chiefly when the action is accompanied by considerable local heating and a deficiency of oxygen. I n spite of variation in the temperature and in the degree of dilution of the oxygen the reaction occurs fairly uniformly.The oxidation proceeds beyond the stage SiH,*OH since the presence of (SiH,),O in more than traces could not be established and the stability of the gas is such that it could not have escaped detection. The main derivatives of silicon produced during the oxidation are the polymeric forms of SiH,O OH*SiHO SiO(OH) etc. The water is regarded as produced from hydroxylated silicon compounds which become decomposed as the temperature is allowed to become atmospheric thus SiH,(OH) -+ SiH,O+H,O. The liberation of free hydrogen is surprising. I n those cases in which elementary silicon is deposited a part of it is doubtless due to the thermal decomposition of monosilane. Its production is not due to a secondary hydrolysis of silane or its primary oxidation products by water formed during the reaction.It appears to be a primary product of the oxidation SiH,+O=SiH,O+H,; a reaction of this type is unusual and apparently due to the preponderating affinity of silicon for oxygen. The production of hydrogen accounts for the peculiarities observed during the combustion of silicon hydrides which differs markedly in its violence from similar cases of spontaneous ignition such asii. 69 INORB-4NIC CHEMISTRY. the quiet inflammation of phosphorus hydride. The process con- sists of the following successive steps inception of oxidation liberation of hydrogen formation of a mixture of oxygen and hydrogen and ignition of the latter when the temperature has been raised sufficiently by the heat of the reaction. H. W. Theory of the Structure and Polyrnorphism of Silica.ROBERT B. SOSMAN ( J . Pranklin Inst. 1922 194 741-764).-A theory of the molecular structure of the various forms of silica is advanced. It is suggested that the silica atom-triplet maintains a certain degree of individuality in its amorphous and crystalline states as well as in its compounds and the freedom of the oxygen atoms to change their positions with respect to the silicon is re- stricted. The triplets are assumed to assemble into chains or threads in the liquid and glassy states and a thread structure persists in the crystalline states. The three principal crystalline modifications (cristobalite tridymite quartz) are built up by com- bining the threaded triplets in three different ways the connexion between the threads being through the oxygen atoms and it is maintained by the sharing of electrons. The high-low (a-p) inversions in all the forms are thought to be due to the same under- lying mechanism namely a change in the state of motion of certain electron orbits resulting from increased thermal vibration of the atoms whereby the shape of the silica triplet and the relative positions of the two oxygen atoms are suddenly altered.The theory gives a satisfactory explanation for many silica phenomena such as the minimum in the temperature-volume curve of silica glass the relation between the specific heats of the crystalline forms the fact that natural quartz formed at a high temperature is always homogeneous whilst low-temperature vein quartz is right- and left-twinned etc.G . F. M. The Constitution of the Silicates. G. TAMMANN (2. anorg. Chern. 1922 125 301-306).-The author finds that the mole- cular specific heats of the silicates are additive and concludes that the molecules are independent and at temperatures far re- moved from their melting point do not vibrate appreciably. This conclusion is supported by the fact that only in the neighbourhood of the melting point do isomorphous complex substances diffuse into one another visibly. In solution silicates undergo hydrolysis and this therefore gives no definite information as to the molecules which exist in the solid The structure of molten silicates cannot be investigated. The complex silicates differ from the carbon compounds in that they are decomposed in solution and in the fused state and the molecular theory of organic chemistry finds no application in the chemistry of silicates.The [Suggested] Formation of Helium and Neon in Dis- charge Tubes containing Hydrogen. A. PIUTTI and E. Boaa~o- LERA ( B e r n . Accud. Lincei 1921 [v] 13 657-701).-Full details of work a summary of which has already appeared (cf. Piutti this W. T.ii. 70 ABSTRACTS OF CHEMICAL PAPERS. vol. ii 20 and also Piutti and Cardoso A. 1920 ii 311; Baly Annual Report 1914 45; 1920 29 30). T. H. P. The Rectilinear Diameter of Neon. E. IMATHIAS C. A. CROMMELIN and H. KAMERLINGH ONNES (Compt. rend. 1922 175 933-935).-The density of neon was studied between its critical temperature (-228.71') and its normal boiling point (-245.92"). Prom the experimental values obtained the angular coefficient of the diameter was found to be a=-0.00716146 a notably high figure At the critical temperature the critical density is calculated to be d,=0*4835 whilst the critical coefficient is (RTcd,)/p,=3.249 the smallest value yet obtained experimentally with the exception of that for helium.The general conclusion is drawn that neon follows the law of rectilinear diameter. H. J. E. Electrical Preparation of Solid Alkali Amalgams in Quantity. PAUL M. GIESY and JAMES R. WITHROW (J. Ind. Eng. Chem. 1923 15 57-60).-Kerp's method (A. 1898 ii 516; 1900 ii 656) for the electrical preparation of amalgams can be much simplified and improved by allowing the mercury at the bottom of the cell as well as that from the flowing jet to receive current.I n this way the current can be increased to a very great extent with a corresponding reduction in manipulation and in the time of the run. If the current be led out at the tip of the jet tube a single jet tube with a stop-cock can be used instead of the changeable jets used by Kerp. It was also found that it is not necessary to work in an atmosphere of hydrogen in order to produce a pure product. Smith and Bennett's method (A. 1909 ii 663; 1910 ii 500) can be improved by strongly cooling the electrolyte when used for the preparation of sodium amalgam and also by forcing the current. If a suitable diaphragm could be found which was unacted on by solutions of alkali hydroxides or by the amalgams themselves and whilst offering a low electrical resistance was a non-conductor Shepherd's method (A.1903 ii 210) would undoubtedly be the best but no suitable material could be found. It is pointed out in conclusion that all solid alkali metal amalgams are lighter than mercury and not heavier as recorded by Kerp. Isomorphism of Potassium Fluoborate and Permanganate. FERRUCCIO ZAMBONINI (Atti R. Accad. Lincei 1922 [v] 31 ii 67- 73).-The author claims priority over Barker (T. 1912 101 2484) for his discovery of the isomorphism between potassium fluoborate and perchlorate (2. Kryst. Min. 1905 41 60). In order to ascer- tain whether alkali fluoborates are isomorphous with or merely exhibit crystallographic relations towards alkali perchlorates and permanganates the author has examined the crystals deposited from a solution containing equal weights of potassium fluoborate and permanganate. Mixed crystals of the fluoborate type con- taining at most 0.4% of the permanganate are formed but on the permanganate side the miscibility is practically zero.G. F. M. T. H. P.INORGANIC CHEMISTRY. ii. 71 Crystalline Form of Trihydrated Sodium Chlorite. ETTORE ARTMI (Atti R. Accad. Lincei 1922 [v] 31 ii 65-67).-This salt NaC10,,3H20 (cf. Levi A. 1922 ii 567) crystallises in the triclinic system a b c=0.4041 1 0.6353 a=103' 43~5'~ p=119" 3' and y=81" 46.5'. Purification of Sodium Hyposulphite A Modification of Jellinek's Method. WALTER G. CHRISTIANSEN and ARTHUR J. NORTON ( J . Ind. Eng. Chem. 1922 14 1126-1128).-An apparatus is described by means of which sodium hyposulphite of 98.3% purity can be rapidly obtained in 42% yield from the commercial article by a modification of Jellinek,s procedure.It consists essentially of a source of carbon dioxide connected on the one hand with a bottle cemented with litharge and glycerol into a Biichner filter the bottom of the bottle being removed and replaced with canvas and hardened filter-paper and on the other with a litre bottle standing in a 2-litre beaker which serves as a water-bath and provided with a combined stirring and filtering device. The latter consists of an inverted glass funnel sealed on to a glass tube which acts also as the shaft of the stirrer. The whole apparatus is exhausted and filled with carbon dioxide the solution of commercial hyposulphite in freshly distilled water is introduced into the Buchner filter and the clear yellow filtrate is passed by the gas pressure into an intermediate receiver and thence into the litre bottle previously charged with the requisite quantity of sodium chloride.The stirrer is set in motion for about thirty minutes to ensure complete solution of the salt and pre- cipitation of the hydrated hyposulphite. The washing dehydration and drying of the precipitate is carried out as in Jellinek's method (A. 1911 ii 278). The ferricyanide method was found superior to either the copper or silver methods for the estimation of the purity of the product. Sodium Chromite. ERICH MUUER (2. angew. Chem. 1922 35 557-558).-Chromium hydroxide was precipitated from a solution of a chromic salt by ammonia dried over sulphuric acid shaken with sodium hydroxide of different concentrations and the concentration of chromium determined from time to time.The presence of hydroxide in solution begins to be noticeable with SN-sodium hydroxide solution. The hydroxide used contained about 6 mol. of water to 1 mol. of chromium trioxide. The amount of hydroxide dissolved was found to be dependent on the time the mixture was agitated rising to a maximum and after this decreasing to an almost constant value. The minimum solubility set in after from ten to fourteen days. The chromium seems to exist in solution as a complex ion and not as a colloid. It is con- sidered that a tervalent chromium salt of sodium is formed. H. M. T. H. P. G. F. M. Ammoniacal Silver Fluoride. DERVIN and OLMER (Compt. rend. 1922 175 1058-1061; cf.Gore Chem. News 1870 21 28; Bruni and Levi A. 1916 ii 482 617).-Anhydrousii. 72 ABSTRACTS OF CHEMICAL PAPERS. silver fluoride dissolved in cold concentrated ammonia solution and the solution evaporated first in a vacuum then at normal pressure over concentrated sulphuric acid yielded colourless ortho- rhombic prisms having the composition AgF,2NH3,2H,0. Light slowly decomposes this substance but it may be preserved un- changed in the dark. It is very soluble in water the solubility increasing on addition of ammonia and although the solubility in alcohol is increased by the presence of water addition of alcohol to the aqueous solution does not result in precipitation. Dry ammonia gas is without action on the crystals; if placed in a vacuum over sulphuric acid they lose water and when the an- hydrous state is reached loss of ammonia takes place.On being heated ammoniacal silver fluoride detonates the products including nitrogen finely divided silver and ammonium fluoride. The authors suggest that the decomposition may be represented by the equation 3(AgF,2NH,,2H20) -+ Ag3N+3NH4F+2NH3+6H,0 with subsequent breaking up of the silver nitride into its elements. H. J. E. The Dissociation of Calcium Sulphate at High Temper- atures. P. P. BUDNIKOV and J. K. SYRKIN (Chem. Ztg. 1923 47 22).-Samples of calcium sulphate were heated t o constant weight at temperatures of from 800" t o 1375" and the proportion of calcium oxide in the product was determined in each case. After heating a t lOOO" only 0.21% of calcium oxide was present a t 1300° 3.00% and a t 1375" 98.67%.Above 1300" the salt melts and a vigorous evolution of fumes takes place corresponding with almost complete decomposition. A. R. P. Valency. XIX. The Ammonia Compounds of Barium Halides. GUSTAV P. HUTTIG and WILHELM MARTIN (2. anorg. Chem. 1922 125 269-ZSO) .-The following ammonia compounds were found to exist BaC1,,8NH3 ; BaBr,,8NH3 ; BaBr,,4NH3 ; BaBr2,2NH3 ; BaBr,,NH ; Ba12,10NH3 ; BaI,,9NH3 ; Ba12,8NH3 ; Ba12,6NH3 ; Ba12,4NH3 and Bal,,2NH3. The method of investig- ation was the same as before (cf. A. 1920 ii 293 and 318). The dissociation temperature a t which the pressure equals 100 mm. is given in each case and also the heat of formation as calculated by Nernst's formula. W. T. Complex Magnesium Salts.111. G. SPACU and R. RIPAN (Bulet. Xociet. qtiinje Clwj 1922 1 267-283; from Chern. Zentr. 1922 iii 1046-1047 ; cf. this vol. i 96).-Monoaquopentammine- magnesium chloride [&Ig(NH3),,H,0,]C12 prepared by passing ammonia into a solution of magnesium chloride in absolute alcohol at the ordinary temperature is a colourless crystalline powder. The following are also menticned hexamminemagnesium bromide a white crystalline powder ; tetra-aquodiamminemagnesium sulphate [Mg(NH,),(H,O),]SO a crystalline powder ; triaquotriammine- magnesaum sulphate [Mg(NH,),(H,O),]SO colourless crystals ; diaquodiamminemagnesium sulphccte [Mg(NH3),(H,0),]S04 whiteINORGANIC CHEMISTRY. ii. 73 powder ; triaquopiperidinemagnesium sulphute a slightly green substance ; penta-aquobenxylamin emccgnesium sulph- a-te a white crystalline powder.[Mg (w-%) (H,O),IS04 G. W. R. The Solidification of the System MgCl,-KCl-BaCl,. J. VALENTIN (Compt. rend. 1922 175 1061-1063).-A thermal study of the three salts was made and the results are shown in a series of diagrams. Two compounds MgCl,,KCl and BaC12,2KC1 are formed so that the complete triangular diagram is divided into five regions each corresponding with the deposition of a pure substance and contains three triple points. H. J. E. A Simple Method for the Preparation of Highly Phos- phorescent Zinc Sulphide. JULIUS SCHMIDT (Ber. 1922 55 [B] 3988-3989).-Equal weights of pure zinc sulphate and sodium acetate are dissolved in water and the hot solution is treated with hydrogen sulphide until the precipitation of the zinc is complete. The zinc sulphide is washed by decantation and finally completely on the filter after which it is dried on the water-bath.The product (200 g.) is moistened uniformly with a solution of mag- nesium chloride (20 g.) calcium chloride (10 g.) strontium chloride (10 g.) and crystalline barium chloride (10 g.) in water (200 c.c.) to which 0.04 g. of ammonium tungstate dissolved in 10 C.C. of water has been added. The mixture with the zinc sulphide is evaporated to dryness with occasional stirring on the water-bath. The product is slowly heated to redness in a crucible (the operation should require about an hour) and maintained at this temperature during thirty to forty minutes after which it is allowed to cool in the furnace. The soluble salts are removed by water and the residual zinc sulphide is dried on the water-bath.It exhibits a strong green fluorescence. Mixtures of salts other than those described have little influence on the strength but considerable effect on the colour of the phos- phorescent light and the readiness with which the phosphorescent effect is excited by illumination Rijntgen rays or radioactive materials. Most metallic salts induce a green phosphorescence but that caused by manganese is yellow (cf. Hofmann and Dacca A. 1904 ii 690). Phosphorescence appears to be weakened or completely inhibited by metallic salts which give dark coloured or black sulphides (cf. MacDougall Stewart and Wright T. 1917 111 663). H. W. Action of Natural Waters on Lead. JOHN C. THRESH (Analyst 1922 47 4 5 9 4 6 8 500-505) .-The presence of varying quantities of silicates carbonates sulphates and salts of organic acids together with the organic acid and free carbon dioxide causes the differences observed in the action of natural waters on lead.Silicates prevent the oxidation of lead iron and aluminium and moorland water after t'reatment with sodium silicate ceases to act on lead w. P. s.ii. 74 ABSTRACTS OF CHEMICAL PAPERS. Complex Salts of Copper and Thallium. G. CANNERI (Gaxzettu 1922 52 ii 266-270).-The following complex com- pounds analogous to the simplest types of those of the alkali elements (cf. Rosenheim and Steinhauser A. 1900 ii 653) are described T12Cu(S0,),,6H20 blue crystals ; Tl,Cu(SO,) yellow powder ; CuS03,3Cu2S03,T12S03 cinnabar-red crystals &ssolvmg in aqueous ammonia to a blue solution; T1,Cu(S20,) a straw- yellow microcrystalline powder.No more than one compound corresponding with one and the same series was obtained in spite of variation of the conditions of formation. T. H. P. The Vapowr Tension of some Copper-Zinc Alloys in the Solid State. L-EoN GUILLET and MARCEL BALLAY (Compt. rend. 1922 175 1057-1058).-The rate of volatilisation of zinc from copper-zinc alloys depends on the temperature and on the nature of the surrounding atmosphere. When the latter can exhibit oxidising properties the surf ace film of oxide mechanically retards loss of zinc from the alloy whilst in an atmosphere of carbon monoxide nitrogen or hydrogen no film is formed and the tem- perature alone is the controlling factor.In such cases the vapour pressures observed cannot be represented as a linear function of the atomic percentage of dissolved copper as the alloys used ( C ~ = 5 5 - 2 0 ~ ~ Zn=44-75%) were not dilute solutions of copper in zinc. Raoult's law therefore does not hold. H. J. E. Solubility of Halides of Univalent Copper in Sodium Thio- sulphate. G. CANNERI and R. LUCHIXI (Guzzettu 1922 52 ii 261-266).-1n the compounds originating when cuprous halides are dissolved in ammonium thiosulphate solution the univalent copper apparently exerts its co-ordinating power not merely towards the thiosulphuric radicle but also towards the halogen. To the compounds formed which have the general formula CUX,NH,X,~(NH~)~S~O~ where X represents a halogen atom or the thiocyanogen radicle (cf.Rosenheim and Steinhauser A. 1900 ii 653) Werner (" Neuere Anschauungen," 1913 168) ascribed the formula [ R (c&3)J(NH4)s R in this case representing Cu. On the basis of this formula the integrity of the nucleus within the brackets should not be diminished by replacement of the ammonium residue by an atom of an alkali element of similar chemical character such as sodium. There seems therefore to be no reason sufficient to explain the difference in behaviour between the ammonium salts and those of other alkali metals other than the varying solvent power on the cuprous halides. The authors find that sodium thiosulphate fused in its own water of crystallisation dissolves considerable proportions of freshly prepared cuprous halides and cuprous thiocyanate the following salts being formed CuCl,5Na2S,0 ; CuBr,5Na2S,03 ; CuBr,Cu2S2O3,9Na2S2O3 ; CuBr SNazS,03.,NaI ; 2CuCNS ,5Na2S,0,. To these compounds which form white crystals unaffected by the action of light and give clear colourless aqueous solutions,INORGANIC CHEMISTPY.ii. 75 the following formulz analogous to those attributed by Werner to the complexes formed by ammonium thiosulphate might be Such hypothetical structural formule cannot however be supported by experimental data other than the colour of the salts this indicating that the cuprous ion forms part of a complex radicle constituted of groupings in such condition that they exhibit increased resistance to react with their specific reagents. The dissociating action exerted by water on these complex compounds prevents physical measurements of any value in this connexion being made.T. H. P. The Preparation of Metallic Phosphides by the Action of Hydrogen Phosphide on Solutions of Metallic Salts. A. BRUKL (2. anorg. Chem. 1922 125 252-256; cf. Moser and Brukl A. 1922 ii 393).-~ercurous phosphide PHg is obtained when hydrogen phosphide is allowed to react on a solution of mercurous sulphate in dilute sulphuric acid as a black amorphous precipitate; it is rapidly oxidised by the oxygen of the air and gradually by dilute nitric acid. Phosphine is gradually evolved by the action of cold concentrated hydrochloric acid but much more rapidly by the action of the hot acid; with concentrated sulphuric acid sulphur dioxide is evolved. The compound is not explosive.Pure mercuric phosphide P2Hg can be obtained by the action of a solution of mercuric chloride in ether on hydrogen phosphide; it is a dark brown solid becoming grey on exposure to air. I n the cold water alkalis and dilute acids are without action but on warming phosphine is evolved; it is oxidised in the cold by dilute nitric acid. A solution of lead acetate in alcohol reacts with phosphine to form a black flocculent precipitate of lead phosphide P2Pb an unstable compound decomposed in the cold by water and alkalis. Cadmium phosphide P,Cd3 obtained as a black flocculent precipitate by the action of phosphine on an ammoniacal solution of cadmium sulphate is unstable and yields hydrogen phosphide when treated with dilute hydrochloric acid. It is very vigorously oxidised by concentrated nitric acid.Its reactions are similar to those of lead phosphide. Alloys of Iron and Aluminium. N. KURNAKOV G. URASOV and A. GRIGORIEV (2. anorg. Chem. 1922 125 207-227 and J . Rziss. Phys. Chem. Xoc. 1918 50 270).-The system iron- aluminium was studied by (1) thermal analysis ( 2 ) the micro- structure of the alloys and ( 3 ) the clectrical conductivity and hardness. In the interval 32-1-39.5 atom. yo iron the endothermic compound Al,Fe crystallises from the fused mass ; below 1100" this decomposes into the a- and p-solutions of aluminium in iron. Between 24.2 and 34 atom. yo iron there exists a stable W. T.ii. 76 ABSTRAC,TS OF CHEMICAL PAPERS. phase which the authors call the 6 phase having properties very different from those of the adjoining phases.This crystalline phase corresponds with the maximum change in properties of the system iron-aluminium ; i t possesses the minimum electrical conductivity acd temperature coefficient the maximum hardness and i t is extremely brittle. The authors regard i t as a chemical individual of variable composition (cf. Kurnakov and Shemt- SUSUMU M~YAMOTO (Japan J. Chein. 1922 1 57-80 and Sci. Papers Inst. Phys. Chem. Research 1922 1 31-65).-An English translation of the papcr previously published in Japanese (cf. A. 1922 ii 647). The expression K=ed-B/p( 1 +O.7BCK,,) in the earlier paper should be replaced by K=ed-B/T(l +0.70C‘,,H). The Higher Oxide of Cobalt. OWEN RHYS HOWELL (T. Triple Nitrites of Bivalent Cobalt. V. CUTTICA and M.PAOLETTI (Gazxetta 1922 52 ii 279-286 ; cf. following abstract). -The analytical data given by Erdmann ( J . pr. Chem. 1866 97 385) for the three triple nitrites Co(N0,),,Ba[Ca,Sr](N02),,2KN0 being incomplete the authors have prepared and analysed these compounds as well as various other triple nitrites of cobalt. The above three complex nitrites form dirty yellow powders stable in the air and may be regarded as salts of one and the same complex quadrivalent ion Co(NO,),. The latter is however not stable in presence of water in contact with which the salts yield an insoluble golden-yellow compound K,Co(NO,) the stable cobaltonitrous ion being hence [Co(NO,),]””. The high value of the active mass of the ion [NO,]’ present in the conditions of the reaction in which the triple salt originates tends to displace the equilibrium [Co(N0,),]”+2N02’ Z [Co(NO,),]”” towards the right a dis- placement in the same sense that is towards the formation of undissociated molecules of the triple nitrite being determined also in the equilibrium [Co(N02),]””+2K”+Ca”(or Ba,Ca) Z These cobalt compounds are analogous in corn- position to the corresponding nickel compounds but exhibit greater stability towards the dissociating action of water the co-ordin- ation valency representing a far stronger linking in this case.If the potassium is displaced by thallium a salt of analogous com- position is obtained but when sodium is introduced the composi- tion is changed. Triple cobalt zinc (cadmium mercury) potassium nitrites have also been obtained these being stable in dry air and of the formula Co(NO2)G .The salts described and analysed are cobalt calcium potassium nitrite ; cobalt barium thallioLm nitrite ; cobalt barium sodium nitrite Co(N0,),,2Ba(NO2),,NaNO a dirty green powder ; cobalt zinc potassium nitrite 2Co(NO2),,Zn(NO,),,6KNO dirty yellow ; cobalt schuschny A. 1913 ii 190). w. T. Reducing Action of Ferrous Hydroxide. K. K. 1923 123 65-71). Co(N02)G Ca. [ ]Iz2 [ I,”:INORGANIC CHEMISTRY. ii. 17 cadmium potassium nitrite pale chestnut and cobalt mercuric potassium nitrite rather deeper chestnut precipitate. Triple Nitrites of Nickel. V CUTTICA and G. CAROBBI (Gazzetta 1922 52 ii 270-279; cf. A. 1922 ii 448).-Both the double and triple nitrites of nickel undergo profound ionic scission immediately on contact with water the supposed ion [Ni(NO,)J” being hence classified with the “ imperfect ” complex ions.Hence in the passage of these salts into solution the mobility of the con- stituent simple ions predominates over the co-ordinating action exerted in such conditions by the nickel. In general accumulation of electronegative radicles in a complex ion is accompanied by increase in the extent of the ionic dissociation of its salts. With the complex nitrites the large number of NO radicles displaces the electrolytic equilibrium pi(N02)6]K4 t 4K’+ [Ni(NO,),r”’ almost completely towards the right and the equilibrium [Ni(NO,),]”” Ni(N0,)2+4N0,’ must also undergo displace- ment in the same sense. The results of cryoscopic measurements in water of some of the double and triple nitrites of nickel show indeed the almost exclusive presence of simple ions the nickel nitrite molecules alone remaining undissociated.The following triple nitrites have been prepared. Nickel mercuric potassium nitrite Pi(NO,),]% forms dark green almost black crystals and gives a green aqueous solution. Cryoscopic measurements indicate decomposition into seven ions. Two nickel mercuric thallium nitrites of the respective composi- tions 3Ni(N02)2,Hg(N0,)2,6TlN0 orange-yellow crystals and 2Ni(N02),,Hg(N0,),,8TlN02 are obtained according to the experi- mental conditions employed. Nickel zinc potassium nitrite 2[Ni(N0,),]K,,Zn(N02)2 forms a flesh-red microcrystalline mass. A chestnut-brown nickel uranyl thallium nitrite was prepared but no simple formula could be derived from the results of its analysis.Nickel cobalt potassium nitrite is a greenish-yellow salt of the formula T. H. P. Nickel cobalt thallium nitrile is a dark red salt which when treated with water leaves undissolved the orange-red complex Tl,Co(NO,),. Unsuccessful attempts were made to prepare a nickel magnesium potassium nitrite. Some New Series of Phosphotungstates. F. KEHRMANN and R. MELLET (Helv. Chim. Acta 5 942-944).-When a very concentrated solution of a mixture of sodium tungstate and phos- phate is acidified faintly with acetic acid a t the end of a few days a mass of crystals separates containing two. salts. One of these Its formula is probably Co(NO,) Nf 4T1PU’o2. T. H. P. I lT1 VOL. CXXIV. ii. 4ii. 78 ABSTRACTS OF CHEMICAL PAPERS.can be freed from the other by washing with cold water in which the first i s sparingly soluble. This salt which cannot be recrystal- bed has the composition corresponding with the formula 14Na20,5P205,19W03,aq or 29Na,0,10P20,,39W03,aq. The second salt is readdy soluble in cold water and forms supersaturated solutions which may not crystallise for months. The salt corre- sponds with the formula 3Na,O,P2O5,6WO3,aq. representing the simplest series of phosphotungstates. A sodium salt described by Scheibler (Ber. 1872 5 801) was thought to belong to a P,0,,6W03 series but is now shown to belong to the series 3M,0,P20,,7W0,,aq. It is proposed to continue the study of these three new series of phosphotungstates. E. H. R. Properties of Tin Especially the Density. R.HOFFMANN and W. STAHL (Metall. u. Erx. 1923 20 5-8).-Tin of 99.8% purity produced from Bolivian ore at the Wilhelmsburg Works was found to have d! 7.312 in a vacuum and go 7.311. [Cf. J.S.C.I. 1923 Feb.] A. R. I?. The Equilibrium in the Reduction of Tin Dioxide by Carbon Monoxide. W. FRAENKEL and K. SN~PISCHSHI (2. anorg. Chem. 1922 125 235-252).-The equilibrium Sn02+2C0 =+ Sn+2CO was studied. It was found that the same equilibrium was reached from both sides and it was independent of the amount and composition of the solid phases. The equilibrium concentration of carbon monoxide increases gradually with in- creasing temperature up to 900" and then suddenly increases very rapidly. The temperature coefficient was studied; at 500" equilibrium sets in after some weeks whereas at 600" equilibrium is reached in a few days.An improved method for the preparation of stannous oxide consists in dissolving stannous chloride in the least amount of hot concentrated hydrochloric acid and gradually adding sodium hydroxide solution until the solution reacts alkaline towards phenolphthalein ; the resulting milky liquid is then kept boiling . in a bath of saturated sodium chloride solution. In a few hours a blue lustrous powder is obtained; this is then washed and dried. Composition of Micella?. I. Stannic Acid Peptised by Alkali. ROBERT WINTGREN (2. physilcal. Chem. 1922 103 238-259) .-Electrical conductivity and transport measurements have been carried out with stannic acid sols which have been peptised by alkali and also with the filtrates from these obtained by ultrafiltration.From these measurements by Ducleaux's method (A. 1905 ii 432) the portion of the conductivity and of the transport which is due to the micellar portion of the sol has been calculated and from Zsigmondy's conception of the qualitative composition of the micellae an attempt has been made t o apply Kohlrausch's law of the independent migration of ions to inorganic colloid ions by regarding the micellar ions as ordinary multivalent ions. From the conductivity values the niean quantitative com- W. T.INORGANIC CHEMISTRY. ii. 79 position of the micella equivalent has been approximately deter- mined that is the number of molecules of stannic oxide contained in one equivalent of colloidal stannic acid. This quantity has been termed the equivalent aggregation.Further from the conductivity determinations it is shown in agreement with Varga's calculations from transport measurements (Kolloid Chem. Beihefte 1919,11,25) that a measurable large quantity of the alkali used for peptisation is enclosed in the micellze. The amount of enclosed alkali and the equivalent aggregation may be obtained indirectly from the trans- port measurements and the quantifies so obtained agree within a very little with those obtained from conductivity measurements and with those obtained by Varga. That considerable quantities of alkali are enclosed is shown by the fact that a t the cathode instead of an increase in alkali concentration occurring a decrease is actually found. From the decrease in alkali concentration the amount enclosed can also be calculated and the quantity so obtained agrees well with the quantity obtained by the other methods.With increasing alkali content the equivalent aggregation decreases as also does the percentage of enclosed alkali. On account of the small vaIue of the conductivity of the sols with small alkali content the composition can only be regarded as correct in respect of its order and not as to its actual value. An example of the composi- tion of a stannic acid sol examined is expressed as follows zH,O:SnO,H'). _ - +n;K'. J. F. S. Magnetic Analysis of the Stannic Acids. PAUL PASCAL (Compt. rend. 1922 175 1063-1065; cf. this vol. ii 25).- The theoretical values of the molecular magnetic susceptibilities of the acids Sn(OH) and SnO(OH) calculated from those of stannates methylstannonic acid and metallic tin were compared with those obtained experimentally from stannic acids prepared by various methods.The results indicate that the acids are not definite compounds but mixtures of anhydrous stannic oxide with water. H. J. E. Zirkite Ore. J. G. THOMPSON ( J . Physical Chem. 1922 26 812-832) .-The mineral zirkite an impure zirconium dioxide containing silica iron and titanium has been investigated with the object of making it suitable for use as a refractory. It is shown that 90-95% of the silicon may be removed from the mineral by heating a mixture of the ore and carbon to a tem- perature above 2220" in an electric furnace. The best results are obtained by heating a mixture of the ore and coke in an arc furnace the amount of carbon being approximately that required to transform only the silicon into carbide.If carbon in excess of this amount is used the separation of silicon is less complete due to the formation of stable double carbides of silicon and zirconium. It is suggested that if the above treatment is followed by the removal of iron by treatment with chlorine a product impure 4-2ii. 80 ABSTRACTS OF CHEMICAL PAPERS. zirconia is obtained which is sufficiently refractory for most purposes. Zirconium carbide is shown to be exceedingly refractory and infusible in a 40-50 kw. arc but its use as a refractory is restricted because it is necessary to protect it from oxidation. The various methods of analysis of zirconium compounds are discussed and a method for the estimation of zirconium silicon titanium and iron in zirkite is outlined.J. F. S. The Missing Element of Atomic Number 72. D. COSTER and G. HEVESY (Nature 1923 111 79) .-From theoretical con- siderations it is probable that the element of atomic number 72 is not a rare-earth metal but a homologue of zirconium. Further the conclusions of Dauvillier (A. 1922 ii 463) and of Urbain (A. 1911 ii 115) are considered not to be justified since it appears that the quantity of the element in the sample examined by the former by an X-ray spectroscopic method must have been so small that its identity with the element claimed to have been detected by the latter in the same sample by optical and magnetic examination is improbable. The only lines La and L& detected by Dauvillier were extremely faint and the wave-lengths given are about 4X.u.(lX.u.=lO-ll crn.) smaller than those obtained by a rational interpolation in the wave-length tables of Hjalmar and Coster for the elements in the neighbourhood of atomic number 72. The authors have however by investigation of the X-ray spectrum of extractions of zirconium minerals detected the lines La,=1565*5 a2=1576 p,=1371*4 p,=1323.7 pa= 1350.2 y,=1177 X.U. which must be ascribed to the element of atomic number 72. The L a and Lp lines exactly agree with the anticipated mutual distance and relative intensity and the wave- lengths all agree within one X.U. with those obtained by inter- polation. A sample of a Norwegian zirconium mineral was estim- ated to contain a t least 1% of the new element whilst ordinary zirconium probably contains 0*01-0.1 yo.Experiments are in progress to isolate the new element for which the name " hafnium " is proposed and to determine its chemical properties. [Cf. Scott T. 1923 123 311.1 The Anode Oxidation of Gold. FR. JIRSA and OT. BURYBNEK (Chem. Listy 16 299-305; cf. A. 1922 ii 713).-A strong current was passed through a cell having a gold anode and dilute sulphuric acid as electrolyte. After twenty-four hours the current was stowed and the back E.M.F. of the anode measured. For A. A. E. the cell* AAu~Au,0,,NH2S04~NH2S04,H,~Pt this was + 1-24 volt's a t 18". The same voltage was obtained whether the anode was prepared in the dark or-in the light of a mercury-vapour lamp and reduction of the strength of acid from normal to N/1000 made no difference to this result.The rates of polarisation of gold anodes using currents of 0-02 and of 0.5 milliampere/cm.2 were next measured and the results shown on a graph. It was noticed that below 0.02 milliampere the results obtained were untrust- worthy owing to the slow rate of oxidation producing passivity in the gold. The rate of discharge of polarised gold anodes wasANALYTICAL CHEMISTRY. ii. 81 measured under various conditions and with the introduction of different resistances in order to retard the rapidity of discharge. Gold anodes were next depolarised by passing currenta of increasing magnitude through the cathode until the polarisation E.M.P. disappears. The magnitudes of the polarisation currents produced by stationary and rotating oxidised gold anodes using acids of different concentrations were measured and curves drawn showing the relation between the galvanometer readings and the voltage.R. T. The Occlusion of Hydrogen by Palladium. MITUO YAMADA (Phil. Mag. 1923 [vi] 45 241-243).-The crystalline structure of palladium containing large quantities of absorbed hydrogen has been determined by X-ray analysis. Except for slight con- tractions of the intervals between the lines on the rontgenogram there is practically no difference between the figures for pure palladium and for this metal containing occluded hydrogen. The slight contraction corresponds with a uniform expansion of the space lattice. No new lines were observed and hence a compound is not formed between the hydrogen and the palladium. The results are in accord with the view that the hydrogen is adsorbed in the state of solid solution. The expansion of the lattice deter- mined from the displacement of the lines was 2*8% which is in good agreement with the expansion 29% obtained by direct measurement. W. E. G. Mi n e r a1 o g ie a I C h e mist r y. Riebeckite from Vallone delle M i d r e (Valle della German- asca). E. GRILL (Atti R. Accud. Lincei 1922 [vJ 31 ii 137- 142).-Black crystals of riebeckite up to 7 mm. in length and with submetallic lustre and pronounced prismatic habit were found on the eastern slope of Vallone delle Mini&re (Piedmont). They exhibit pleochroism and have d 3.44 ; the angle (100) (110 is 55" 5'455" 20'. SiO TiO Al,O Fe,O FeO MnO CaO MgO Na,O K,O H,O- H,O+ Total 51.53 trace 2.71 16-22 17.11 0.22 0.79 1-01 7-81 1.13 0.31 1.20 100.04. These results are in accord with the empirical formula Analysis gives :

ISSN:0368-1769    

DOI:10.1039/CA9232405065

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

PIEYSIOLOGICAL CHEMISTRY. i. 71 Physiologieal Chemistry. The Comparative Concentrations of Alcohol in Human Blood and Urine at Intervals after Digestion. WALTER R. MILES (J. Pharm. Expt. Ther. 1922 20 265-319).-Estimations of the alcohol in the whole blood plasma and urine of men who had consumed a known quantity of alcohol show a greater con- centration in the plasma than in the whole blood. At first the concentrations in the blood and in the urine are approximately the same but soon that of the urine becomes appreciably greater and exceeds that of the plasma. Factors which Determine the Concentration of Calcium and of Inorganic Phosphorus in the Blood-serum of Rats. BENJ. KRAMER and JOEIN HOWLAND (Bull. Johns Hopln'ns Hosp. 1922 33 313-317).-The normal concentration of calcium in the serum of rats is from 9.5 to 10.5 mg.per 100 C.C. and that of phosphorus from 7 to 8.5 mg. per 100 C.C. These values were not increased by changes in the diet or by treatment with ultra-violet W. 0. K.i. 72 ABSTRACTS OF CHEMICAL PAPERS. light. By lowering the amount of calcium or phosphorus in the food sufficiently the concentration of the same in the serum could be diminished by as much as 50%. Subsequent addition of fish- liver oils to the food brought the values back t o normal. The same result could be obtained with phosphorus by illumination with light of wave-length less than 3000 A. A similar effect could be obtained by starvation for a few days. CHEMICAL ABSTRACTS. Sodium Chloride and Selective Diffusion in Living Organ- isms. JACQUES LOEB ( J .Cen. Physiol. 1922 5 231-254).- Sodium chloride calcium chloride and cerium chloride inhibit the diffusion of strong acids into the egg of Fundulus as shown by the decrease in the mortality among the eggs immersed in the acid on the addition of the chloride and also by the decrease in the rate of fall of the hydrogen-ion concentration. M / 8 sodium chloride corresponds with M/l,OOO calcium chloride or M/30,000 cerium chloride in producing this inhibition. Weak undissociated acids are buf feebly inhibited by these chlorides if a t all. The diffusion of strong alkalis is accelerated by sodium chloride and more so by calcium chloride. Sodium chloride in moderate con- centration accelerates also the diffusion of potassium chloride into the egg of Fundulus whilst calcium chloride does not.W. 0. K. Dextrose in Eggs of Vertebrates. G . GORI (Atti R. accad. fisiocrit. Siena 1920 21 711-716; from Chem. Zentr. 1922 iii 927).-Dextrose is absent from the yolks of eggs of Torpedo and of fishes the amount of urea present is insufficient to obscure the reaction. Using material dried first at 45" and then in a vacuum dextrose was found to be absent from mammalian ova present combined and free in birds' eggs and present in the free state in amphibian eggs. G. W. R. The Synthetic Formation of Kynurenic Acid in the Surviv- ing Liver. Z. MATSUORA and S. TAKEMURA ( J . Biochem. [Japan] 1922,1,175-180).-Kynurenic acid is produced by the perfused liver of dogs when either tryptophan or indolepyruvic acid is added to the blood.It is suggested that indolepyruvic acid is probably an intermediate step in the transformation of tryptophan into kynur- enic acid. This hypothesis is based on the fact that the same amount was produced (0.1285 and 0.1202 g.) with 1 g. of either the tryptophan or indolepyruvic acid in the perfusing mixture. CHEMICAL A~STRACTS. Some Compounds Extracted from Human Skeletal Muscles. R. ENGELAND and W. BIEHLER (2. physiol. Chem. 1922 123 29O-294) .-The following compounds have been isolated from human skeletal muscles ; carnitine C,H,,O,N ; neosine C,H1,O,N ; myokynine C,1H2,0,N ; and mirgeline isolated as the chloro- aurate CllH2203N2,HAuC14 light yellow nodular crystals. W. 0. K.PHYSIOLOGICAL CHEMISTBY. i. 73 The Pharmacology of Cell Breathing. 11. The €"unction of Iron in Cell Breathing. 111.The Dependence of Cell Respiration on the Hydrogen-ion Concentration. PH. EILIN- GER and N. LANDSBERGER (2. physiol. Chem. 1922 123 246- 263 2 6 4 4 7 9 ) .-Amino-acids are oxidised by oxygen in presence of an emulsion of zinc sulphide-copper phosphor in a gelatin solution as they are in presence of charcoal (Warburg A. 1921 i 230; 1922 i 190) or by an emulsion of broken-up goose erythrocytes. Potassium cyanide decreases the velocity of oxidation in the case of the goose cells but at the same time i t is itself oxidised. The rate of absorption of oxygen shows a minimum a t a low concen- tration of potassium cyanide and the same phenomenon is observed in the case of isolated frog's muscle if potassium cyanide is applied. The oxidation is parallel to the fluorescence and phosphorescence of the cells under ultra-violet illumination.This is taken to indicate that the efficiency of the cells in catalysing oxidation is connected with the ability of the iron to lose an electron and so activate the oxidisable material. The rate of consumption of oxygen with charcoal or with cells depends on the hydrogen-ion concentration and this effect seems to be exerted primarily on the amino-acid which is being oxidised. W. 0. K. ROBERT FRICKE (2. physiol. Chem. 1922 124 1-7).-fUdol in the urine of diabetics is only partly detected by the " dimedon" method previously employed (A. 1922 i 300; ii 326). Improvements are described which render the method more sensitive and accurate. W. 0. K. The Presence of Aldol in the Urine of Diabetics.The Sugar Content of Cerebrospinal Fluids. K. MIFUJI ( J . Tokyo Med. SOC. 1921 35 No. 10; Japan Med. World 2 78).-The normal sugar content of the spinal fluid of the Japanese averages O*052yo. The factor obtained by dividing the blood- sugar content by the spinal fluid sugar content is largest in children and least in the senile cases. In the atrophic form of beri beri the sugar content of both liquids is practically the same as normal but in the oedematous form they are both increased. In epidemic cerebrospinal meningitis the blood-sugar content is as high as the maximum normal (0-114y0) but that of the spinal fluid is remark- ably decreased. In epilepsy the spinal fluid sugar content in the intermissions of an attack was low 0.021 yo but returned to normal eighteen hours zfter the attack.E. D. OSBORNE ( J . Amer. Med. Assoc. 1922 79 615-617; from Physiol. Abstr. 1922 7 453).-After the administration of sodium iodide by the mouth there is an increase in the concentration of sodium in the blood whilst only a trace of iodine was found in the serum proteins when these were precipitated by tungstic acid or alcohol. On the other hand after oral administration of potassium iodide there is no increase of potassium in the blood but an increase of sodium CHEMICAL ABSTRACTS. Pharmacolo,gy and Therapeutics of Iodides. whilst 7 to 26% 6f the iodine given was found in the serum proteins W. 0. K;i. 74 ABSTRACTS OF CHfEMZCAL PAPERS. Urea. A. MARIE (Compt. rend. Xoc. Bid. 1922 86 998; cf. ibid.1922 86 72).-Intravenous injections of adrenaline hydrochloride produce a considerable increase in the urea content both of the blood and of the parenchyma of the liver freed com- pletely from blood. Adrenaline has also been found to suppress the decomposition of urea in vitro when added t o a soja bean extract. Although the vegetable urease may be entirely unlike the hepatic urease the test-tube experiments lead to the con- clusion that the increase in urea content observed after an injection of adrenaline is likewise due to a suppression of the hydrolysis of urea. CHEMICAL ABSTRACTS. The Separation of Ethereal Sulphates in Rabbits after Administration of Phenol p-Bromophenol and Bromo- benzene. H. RHODE (2. physiol. Chem. 1922 124 15-36).- If phenol is administered to rabbits (0.2 g . per kg.) 12% is elimin- ated in the urine as the ethereal sulphate whereas if cystine taurine or sodium sulphite is administered at the same time 33% 17% and 27% respectively of the phenol is eliminated. Thiosulphate and sulphate are without influence on the elirnin- ation of the phenol. In the cases of p-bromophenol and of bromo- benzene the effect of the simultaneous administration of cystine is to decrease the output of ethereal sulphates the ex lanation cases. This indicates that the bromobenzene in the animal organism is first of all oxidised to p-bromophenol. Pharmacology of Benzyl Compounds. 11. CARL NIELSEN and JOHN A. HIGGINS ( J . Lab. Clin. Med. 1922 7 579-588; cf. ibid. 1921 6 388).-The observations suggest that the relaxing power of benzyl esters on the smooth muscle fibres of the intestine as a rule is dependent on the benzyl content and on the rate of hydrolysis of the benzyl compound. apparently being that phenylmercapturic acid is forme f in both W. 0. K. CHEMICAL ABSTRACTS.

ISSN:0368-1769    

DOI:10.1039/CA9232400071

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

i. 74 ABSTRACTS OF CHfEMZCU PAPERS. Chemistry of Vegetable Physiology and Agriculture. The Relation of the Reaction and of Salt Content of the Medium to Nitrifying Bacteria. CAROLYN S. MEEK and CHARLES B. LIPMAN ( J . Qen. Physiol. 1922,5,195-204).-Nitrifying bacteria are particularly resistant to hydroxyl-ions surviving in a medium of PET 13 and yielding their characteristic products in a medium of PH 11. Sodium sulphatc is not nearly so toxic to these products as sodium chloride or sodium carbonate. Nitrification. IV. The Carbon and Nitrogen kelations of the Nitrite Ferment. AUGUSTO BONAZZI ( J . Bact. 1921,6,479- 499.-A study of the functions of autotrophic carbon assimilation and nitrogen nutrition of the nitroso-ferment. These functions are W. 0. K.VEGETABLE PHYSIOLOOY AND AGRICULTURE.i. 75 intimately connected and mutually interdependent the bacterial cell being able to assimilate the abundant stores of nitrogen in a nutritive solution in the absence of free carbon dioxide even although a carbonate as such be present in the medium. Conse- quently the process of nitrogen oxidation which follows the absorp- tion and leads to the formation of nitrous acid and its salts is dependent on the presence of this free carbon dioxide. CHEMICAL ABSTRACTS. Ergosterol in Yeast. A. WINDAUS and W. GRossKoPF (2. physiol. Chem. 1922 124 8-14).-Ergosterol is extracted from yeast in a yield of about 0.15y0 and purified as ergosteryl acetate m. p. 180-181". On reduction with palladium black and hydrogen this acetate unites with six hydrogen atoms to form ergostunyl acetate C29H5002 small white needles m.p. 103" which on hydrolysis yields ergostanol C,,H4,0 fine leaflets m. p. 129". By treatment of ergostanol with phosphorus pentachloride and subsequent reduction with sodium in amyl alcohol the hydrocarbon ergostane c,-$3489* white leaflets m. p. 72-73" [a] +24-5" is obtained w ich IS not identical with sitosane $-cholestane (coprostane) or cholestane. Ergostmol on oxidation with chromic anhydride yields ergostanone fine white needles m. p. 5&57". Comparison of a- and p-Glucose in Fermentation. RICHARD WILLSTATTER and HARRY SOBOTKA (2. physiol. Chem. 1922,123 1&169).-No difference can be detected in the rate of fermentation of a- and @-glucose. This cannot be due to an equilibrium between the two forms being set up quickly as the rate of this change under the conditions of the experiment is much slower than the rate of fermentation.The Selective Fermentation of Mixtures of &gars. RICHARD WILLSTATTER and HARRY SOBOTKA (2. physiol. Chem. 1922 123 170-175).-Although glucose fructose and a mixture of these are all fermented by yeast with approximately the same velocity yet on fermenting a mixture the glucose ferments more quickly than the fructose. This is apparently because the glucose is more active in the initial stages of fermentation whilst the final stages of the reaction are the same for both sugars. These final stages however are the slowest and so they decide the rate of the reaction as a whole. The same holds for the fermentation of a W.0. K. W. 0. K. mixture of the a- and p-forms of glucose (see preceding abstract). w. 0. K. Selective Fermentation with Yeast Trained to Ferment Galactose. RICHARD WILLSTATTER and HARRY SOBOTKA (2. physiol. Chem. 1922 123 176-180).-Yeast may be trained so that it will ferment galactose more rapidly than glucose but it is found that such a yeast will still preferentially ferment glucose out of a mixture of glucose and galactose. An explanation of this phenomenon is indicated on the lines suggested in the precedmg abstract. W. 0. K.i. 76 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Copper Salts 011 the Yield of Sterigmato- cystis nZgra [Aspergillus rriger]. MARIK MOLLIARD (Compt. rend. 1922 175 838-841) .-The retarding action of solutions containing copper on the growth of A .niger renders direct comparison with the control solution of no value as the two may be a t different stages of development. The author has compared the yield-Le. the ratio of the weight of mycelium obtained to that of sugar con- sumed-in a control solution and one containing copper sulphate of a concentration of 1/3750 making allowance for the slower growth in the latter. The general result of the presence of copper is diminution of yield but during a considerable portion of the time the reverse effect mas observed. H. J. E. Some Aspects of Selective Absorption. W. J. V. OSTER- HOUT ( J . Gen. Physiol. 1922 5 225-230).-Analysis of the cell sap of the marine alga Vulonia shows much more potassium and less sodium magnesium calcium and sulphate-ion than exists in the surrounding sea-water whilst the chloride is approximately con- stant.The organic material in the cell sap is small and this seems to exclude the possibility of accounting for the high concentration of potassium by the assumption that it combines with some organic compound. w. 0. I<. Fixation and Polyrnerisation of Formaldehyde in the Dark by Green Plants. Carbon Dioxide Assimilation by Plants. TH. SABALITSCHKA (2. ungew. Chem. 1922 35,684-685).-Experi- ments with the nasturtium and the water-weed Elodea canadensis showed that these plants are capable of fixing formaldehyde and polymerising it to carbohydrates even in the absence of light. The plants were placed in an enclosed space and deprived of carbon dioxide. The sugar and starch content of the leaves was deter- mined after some decrease had occurred below the normal by reason of the exclusion of carbon dioxide and some of the plants were then exposed to formaldehyde either in the form of vapour or in solution in the case of the water weed whilst others were kept for comparison.After some days the carbohydrates in the leaf were again estimated; as an example of the results in one case 462 mg. of sugar and 1048 mg. of starch per 100 g. of leaf were found after treatment with formaldehyde compared with 144 mg. of sugar and 495 mg. of starch in the blank experiment. The quantity of these substances in the formaldehyde experiment was actually higher than a t the commencement whereas in the control experi- ment the carbohydrates had continued to decrease.This shows that the plants were able to replenish their stock of carbohydrate depleted by the absence of carbon dioxide by making use of the formaldehyde and that the polymerisation takes place in the absence of sunlight. Further it provides additional evidence for the hypothesis that formaldehyde is an intermediate product of the photosynthesis of carbohydrates from carbon dioxide and water. G. F. M.VEGETABLE PIIYSIOLOQY AND AGRICULTURE. i. 77 Anthocyanin Pigments and Phlobatannins in Plants. ST. JONESCO (Compt. rend. 1922 175 904-907; cf. Combes A. 1922 i 206).-The red leaves of Pruitus Pissardii dried and powdered were extracted with ethyl ether. The solution on evaporation yielded two separate substances one soluble in water and crystallising in tablets and needles the other soluble in ethyl alcohol but not in water and obtained as a yellow amorphous substance on evaporation. Various reactions given by the former indicate that it is a tannin ; the latter being precipitated by addition of water gives somewhat ambiguous results with aqueous reagents.It is however not converted into a red pigment when heated with dilute acids. Further extraction of the dried leaves with ethyl acetate and amyl alcohol yielded t'he anthocyanidins and pseudo-bases. The latter are readily transformed into anthocy- anidins under the influence of dilute hydrochloric acid their colour changing from yellow to red. The anthocyan constituents -i.e. the total of the pigments present in the various organs- are divided into anthocyanins red violet or blue substances not extracted by amyl alcohol anthocyanidins red substances existing uncombined and readily soluble in amyl alcohol and a third group of substances the pseudo-bases yellow in colour which the author proposes to designate leuco-anthocyanidins.H. J. E. The Action of Hexamethylenetetramie on Higher Vege- tation. E. NICOLAS and G. NICOLAS (Compt. rend. 1922 175 836-838).-Solutions of hexamethylenetetramine the concen- tration of which lies between 0-1 and 0.3 g. per litre are utilised as food by beans but on increasing the concentration a toxic effect is produced. In the former case the action is shown by increase in weight of the plant and by the enhanced leaf develop- ment. H. J. E. The Chemical Constituents of Green Plants.XXII. The Presence of Succinic Acid and of Oxalic Acid in the Currant (Ribes rtsbmm). HARTWIG FRANZEN and FRITZ HELWERT (2. physiol. Chem. 1922 124 65-74; cf. A. 1922 i 310).-By converting the acids in the filtrate from the lead acetate precipitate from the currant into their esters and subsequently into the hydr- azide or the benzylidene compounds the presence of succinic acid malic acid and citric acid has been demonstrated. Other acids some unsaturated are present in traces including probably oxalic acid and possibly lactic acid. W. 0. K. Colouring Matter of the Fruit of Gurdeniu fiorida L. TETSUJIMUNESADA ( J . Phurm. Soc. Japan 1922 No. 486,666-671). -The colouring matter of the fruit of Gardenia florida L. from China when extracted with water (cf. Kasyer A.1885 59) and decomposed with dilute hydrochloric acid in a current of carbon dioxide yielded an amorphous powder which is identical with crocetin from saffron (cf. Decker A. 1914 i 979). It gave a potassium salt C,,-,H,,O,K orange-yellow crystals sodium salt,i 78 ABSTRACTS OF CHEMICAL PAPERS. short yellowish-red needles and ammonium salt reddish-yellow needles. K. K. Preservative Principles of Hops. I. FRANK LEE PYM~N HAROLD ROGERSON and THOMAS KENNEDY WALKER (J. Inst. Brewing 1922 28 929-934).-Attempts were made to isolate crystalline hop- bitter acids by fractional extraction with alkalis of increasing strength of an ethereal solution of the soft resins obtained by extraction of ground hops with light petroleum. Lupulon was isolated in small yield in colourless prisms m.p. 94.5-95.5". No humulon was obtained by this method and the only other crystalline compounds isolated were lactaric acid C15Hso02 a saturated fatty acid previously found only in the fungus Agaricus integer and small quantities of thc constituents of the wax hentriacontane ceryl alcohol and cerotic acid. G. F. M. Nitrogenous Constituents of the Fruit of Chayote (Sechiuni edule). KIYOHISA YOSHIMURA ( J . Biochem. [Japan] 1922,1,347- 351).-The fruit of Sechium edule (a member of the Cucurbitacece) was examined with the following results Water 95.973% and dry substance 4.027y0. The dry substance contained crudc protein 16.264% fat 1.16!3% crude fibrc 7.311y0 nitrogen-free extract 68.392y0 ash 6.864% total nitrogen 2.602% protein nitrogen 1.66% and non-protein nitrogen 1.041y0; that is of the total nitrogen 59.99y0 was protein and 40.009y0 non-protein.20 Kg. of the fresh fruit were pressed and then extracted twice with hot water ; from the extract were isolated a small quantity of adenine and choline 0.7 g. of arginine (as nitrate) and about 1.5 g. of guanidine (as chloroaurate). The Mannan of Vegetable Ivory. 11. Hemicelluloses. HANS PRIKQSHEIM and KARL SEIFERT (2. physiol. Chem. 1922 123 205-212; cf. A. 1912 i 833).-Mannan prepared from vegetable ivory shavings by the action of 5% sodium hydroxide solution is treated wth acetic anhydride containing hydrogen bromide when it yields munnan triacetate C,H,O,( OAc) a white amorphous non-hygroscopic substance [a]? -27.4" in acetylene tetraahloride. Mannan on treatment with acetic anhydride con- taining a small amount of concentrated sulphuric acid yields a white amorphous Substance from which on hydrolysis and treat- ment with phenylhydrazine mannosephenylhydrazone can be obtained besides a quantity of glucosazone and also apparently the osazone of a disaccharide.Relation of certain Nutritive Elements to the Composition of the Oat Plant. J G . DICKSON (Amer. J. Botany 1921 8 256-274).-A study of the growth and compoeition of Avena sativa ariSta& in relation to climate and nutrition. The oontent of calcium oxide is reduced proportionally to its reduotion in the culture salution; it is also greatly reduced by deficiency of phos- pharus or nitrogen. The extent to which the content of phos- K. K. W. 0. K.VEGETABLE PHYSIOLOGY AND AGBIOULTURE.i. 79 phorus of the grain and straw is reduced by reduction in the pro- portion of phosphate or potassium in the culture solution and increased by similar reduction of calcium or nitrogen has been determined. The content of phosphorus of both grain and straw is modified by seasonal differences except for plants grown in solutions deficient in phosphorus. The content of calcium of the grain is modified even when solutions deficient in calcium are employed whilst that of the straw shows no consistent respoiise to climate. CHEMICAL ABSTRACTS. The Comparative Assirnilability of Tricalcium Phosphate and the Phosphates of Aluminium and Iron. CH. BRIOUX (Cmpt. rend. 1922 175 1096--1099).-1n soils containing little or no calcium carbonate a considerable proportion of the phosphoric acid exists as ferric or aluminium phosphate.Experiments with six different species of plants showed that measured by the pro- duction of dried organic matter the use of equivalent quantities of tricalcium ferric and aluminium phosphates results in the highest yields being obtained in the case of aluminium and the lowest with iron although the last-named gives results considerably above the control yield. The author points out that the usual solvents for “ available phosphate ” give results which are incon- sistent with those of his experiments although 1% citric acid is more trustworthy than others which have been recommended. H J. E T h e Availability of Mineral Plant Food (A Morncation of the Present Hypothesis).NOIGMAN M. COMBER ( J . Agfic. Xci. 1922 12 363-369).-The conception that plants can take up from the soil only mineral matter whch is in solution is criticbed. Three main objections are advanced namely the difficulty of cor- relating the composition of the soil solution with the amount of misera1 matter taken up by the plant; the absence of any explan- ation of the intake of iron by plants and the difKculty of explaining the availability of phosphates. A modified hypothesis is presented in which the absorption of colloids by plant roots is assumed. The possibility of a definite union of root hairs with solid miners€ particles i s discussed and the subsequent dissolution of the mineral particle by the organic matter of the root hair is suggested. A. G. P. Theory of Soil Acidity.J. N. MUHHERJEE (Nadure 1922 110 732).-Experimental evidence is adduced in support of the author’s view (A. 1922 ii 689) concerning the origin of soil acidity. Silioa has been found to adsorb appreciable quantities of acetic citric hydrochloric and nitric acids so strongly that on repeated washing the adsorbed substance cannot be removed and the aqueous extract soon becomes neutral. Treatment with aqueous potassium chloride then results homvef in %hedevelopment of acidity. Simultaneous experiments on electro-osmosis indicate that the anions of the acids and not their entire molecules are adsorbed on the surface by chemical forces and it is suggested that an equivalenti. 80 ABSTRACTS OF CHEMICAL PAPERS. number of kations form a mobile second sheet of the double lager - - the forces acting on these being mainly electrical in nature.A. A. E. Sulphur Changes in Soil. KURT LANTZSCH (Intern. Mitt. Bodenk. 1922 12 22-35).-Nutrient solutions containing calcium sulphate and inoculated with soil extract showed no formation of sulphide after forty-seven days. The ratio CaO SO was how- ever changed slightly in some cases Nutrient solutions to which 20 g. of soil were added to 200 C.C. and allowed to remain under anaerobic conditions for sixty days showed no appreciable formation of sulphides when titrated with iodine solution. A solution con- taining 0.09% of potassium sulphide together with asparagine and other nutrients developed an odour of butyric acid and lost small amount of sulphur. A somewhat similar solution containing no organic carbon showed a production of nitrogen dioxide and ammonia when ammonium chloride was the only source of nitrogen ; when sodium nitrate was used instead nitrogen dioxide and ammonia were not produced.In each case however some of the sulphur was oxidised to sulphate in the inoculated solutions whilst the control gave negative results. The control tubes were treated with 0.2 C.C. of 40% formaldehyde solution per 100 C.C. of solution. CHEMICAL ABSTRACTS. The Depletion of Soils by Chemical Denudation. MILTON WHITNEY (Scie-me 1922 56 21&218).-The information hitherto collected concerning the rate of chemical denudation of soil and rock material has been based mainly on the translocation of material in true solution disregarding all matter in colloidal solution. The results have shown that the loss of silica alumina and iron is surprisingly small in comparison with that of potassium. It is indicated however that in the breaking down of silicates to a point at which potassium goes into solution silica alumina and iron also go into colloidal solution in the same proportion as they bear to the potassium content in the original material. This view is supported by the fact that when finely ground silicates are brought into contact with water soluble salts go into solution (as determined by conductivity or chemical test) and at the same time there is released a relatively large amount of colloidal material. Further investigation on t,hese lines is necessary before it will be possible to state whether chemical erosion is a selective process which might change the chemical composition of the soil or whether by the materials leaving the soil in about their original ratiw there is no material change in the composition of the soil on which water has acted. A. A. E.

ISSN:0368-1769    

DOI:10.1039/CA9232400074

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

i. 81 Organic Chemistry. The Influence of the Structure of Organic Compounds on their Sulpho-chromic Oxidation. L. J. SIMON (Corn@. rend. 1922 175 1070-1072; cf. A. 1922 ii 867 868).-Among the substances which are completely oxidised by the sulpho-chromic mixture are certain straight-chain compounds phenolic derivatives and ring-substituted aromatic acids. I n other cases molecular structure influences the extent of oxidation e.g. methyl benzoate is completely whilst toluic or phenylacetic acid is only partly oxidised. From a study of a considerable number of such examples it is seen that this method of oxidation indicates structural differ- ences and may be used to investigate such problems as tautomerism or intramolecular change. The author has devised a formula based on the number of carbon atoms present in the molecule and the number which escape oxidation and regards the '' oxid- ation deficit" which i t furnishes as a first step towards a new method of structural investigation.P. A. LEVENE and F. A. TAYLOR ( J . Biol. Chem. 1922 54 351-362).-Further examples are given of the preparation of tertiary hydrocarbons by the malonic ester synthesis (cf. Levene and Cretcher A. 1918 i 250). The various stages of the syntheses are represented by the following series of compounds. Revised constants are given for certain compounds which have previously been described. Ethyl ethylbutylmalonate [previously prepared but not char- acterised by Raper (T. 1907 91 1837)] b. p. 128-129"/7 mm. df 0.9646 n$ 1.4284. Ethylbutylmalonic acid C,H,,O m. p.115". a-Ethylhexoic acid b. p. 228-229" (Raper gave 225"); ethyl- a-ethylhemute C,oH,oO b. p. 189-191" di0 0.8628 ng 1.4128. p-Ethylhexyl alcohol C,H,,O b. p. 181-183" df 0.8328 nZ1.4328 ; p-ethylhexyl iodide CsH1,I b. p. 89-90"/11 mm. d? 1.3365. y-Methylheptane b. p. 120-122" (cf. Clarke A. 1909 i 349) dp 0-7069 ?a 1.3980. Ethyl cc-methylheptylmalonate Cl5H2,O4 b. p. 157-158"/10 mm. 0-9496 ng 1.4324. p-Methylnonoic acid CloHzoOz b. p. 147- l48"/12 mm. & 0.9012 niy 1-4342 ; ethyl P-methylnonoate Cl2HZ4O2 b. p. 115"/13 mm. di0 0.8653 nz 1.4240. y-Wethylnonyl alcohol C10H220 b. p. 103-103*5"/9 mm. di0 0.8342 nz 1.4361 ; y-methyl- nonyl iodide Cl0H2,I b. p. 115"/10 mm. djo 1-2515. y-Methyl- nonane C10H22 b. p. 165*5-166.5" d;O 0.7354 nz 1.4126. c-Methylnonane (p-butylhexane of Levene and Cretcher loc.cit.) c-Propylnonane C,,H2 b. p. 804-305" dy 0.7559 nz 1.4228 was obtained by reduction of 6-butyloctyl iodide (cf. Levene and Cretcher). Ethyl butylmalonate b. p. 122"/12 mm. (cf. Adams and Marvel VOL. CXXIV. i. e H. J. E. Oxidation of Tertiary Hydrocarbons. b. p. 164-166" d;' 0.7319 ?i$ 1.4116.i. 82 ABSTRACTS OF CHEMICAL PAPERS. A. 1920 i 283) dy 0-9745 .ze 14222. Ethyl butylheptylmlonate Cl8H,O4 b. p. 177-178"/12 mm. d;O 0.9318 nz 1.4366; but$ heptylmlonic acid C14H26O4 needles m. p. 117". cc-Butylnonoic acid C,,H,,O b. p. 179"/13 mm. di0 0.8860 n; 1.4403; ethyl a-butylnonoate C15H3002 b. p. 115"/1 mm. d? 0.8560 ng 1.4290. p-Butylnonyl alcohol C,,H,,O b. p. 112-114"/0*5 mm. dy 0.8359 nz 1.4430 ; p-butylnonyl iodide C,H,,I b. p.121-123"/0.5 mm. 6-Methyldodecane C13H28 b. p. 22r6-227" djo 0.7576 nz 1-4244. When r-methylnonane was oxidised with alkaline permanganate acetic and butyric acids were identified amongst the products of the reaction; the presence of some formic acid was also detected. Apparently the oxidation proceeds mainly according to the following scheme CH2Me*[CH2]2*CHMe*[CH2]2*C€€2Me -+ CH,Me*[CH,],*C O*CH,+ CH,Me*CH,*CO,H. CH,Me*[CH,],*CO*CH -+ CH,Me*CH,*CO,H+ CH,*CO,H. E. S. The Formation of Hydrocarbons during the Action of Potassium on Ethyl Acetate. HELMUTH SCHEIBLER HEIN- RICH ZIEGNER and EMIL PEFFER (Ber. 1922 55 [B] 3921- 3931) .-The action of potassium on an ethereal solution of ethyl acetate has been shown to lead to the formation of ethyl potassio- acetate CH,:C(OK)*OEt (cf.Scheibler and Voss A. 1920 i 366; Scheibler and Ziegner A. 1922 i 426). In addition acidic sub- stances are produced which will be described subsequently and neutral compounds which are the subject of the present com- munication. Potassium and ethyl acetate in varied proportions are allowed to react in the presence of ether and the products are decomposed either by sulphuric acid (30%) or carbon dioxide. The neutral portions are freed from admixed ester and ketones by successive treatment with concentrated potassium hydroxide solution a t 80" and sodium hydrogen sulphite and are subsequently distilled whereby a series of fractions boiling over the range 120-260" are isolated. The carbon and hydrogen content of these increases with increasing boiling point at the expense of the oxygen content.The analytical composition of the fraction b. p. 210-240"/atmospheric pressure agrees with that required by the formula C12H2 whereas that of the fraction b. p. above 250" harmonises with the formula Cl2HZ4. The constitution of the substances has not been elucidated. The insolubility of the bulk of the product in concentrated sulphuric acid indicates the absence of olefines and the low hydrogen content makes it unlikely that paraffins are present. It is most probable that the hydrocarbons are homologues of benzene or mono- or poly-cycloparaffins . Only traces of hydrogen are evolved in the gaseous state during the action of potassium on ethyl acetate. It appears that the liberated hydrogen reduces a portion of the ethyl potassioacetate extensively and that in the course of the change intermediateORGANIC CHEMISTRY. i.83 substances are produced which are more readily hydrogenated than ethyl potassioacetate a considerable proportion of which remains after complete solution of the potassium. The fractions boiling below 200" consist mainly of hydrocarbons but appear to contain a certain proportion of ethers; their instability towards alkaline permanganate indicates the unsaturated nature of one or both components. The formation of hydrocarbons is not observed when potassium is replaced by sodium"under otherwise identical conditions. H. W. The Chlorination of Methane. ARTHUR SCHLEEDE and CURT LUCKOW (Ber. 1922 55 [B] 3710-3726).-The chlorination of methane has been studied by passing mixtures of the gases through electrically heated quartz or glass tubes.Inflammation occurs when the gases are used in molar proportions but the flame gradually dies out; it is permanent when an excess of chlorine is employed. If on the other hand an excess of methane is used ignition is not observed ; under these conditions chlorine is only quantitatively utilised if the temperature is not below a certain minimum depend- ing on the precise composition and rate of flow of the mixture. The phenomena are not greatly affected by the presence of catalysts or by an increase of temperature of 100" above the minimum. The products of the reaction are freed from hydrogen chloride by passage through warm concentrated potassium hydroxide solution (water is unsuitable since it dissolves appreciable amounts of methyl chloride) and are subsequently condensed at a temperature not exceeding -110".(The vapour tensions of methyl chloride below -30" of methylene chloride and chloroform below 0" and of carbon tetrachloride below -20" have been measued.) Methyl chloride can be conveniently separated from the condensate by Stock's method of fractional distillation in a high vacuum but the process is inapplicable to the separation of methylene chloride chloroform and carbon tetrachloride which are therefore estimated approximately by the technical distillation method. When the velocity of passage of the gaseous mixture per unit of surface exceeds a certain value and a large increase of the heating (catalysing- surface is not also provided the reaction tends more and more towards a steady ignition and increased formation of higher pro- ducts is observed which takes place particularly at the expense of the chloroform.The greater the velocity of the gas the greater must be the catalysing surface. If the rate of flow is below the ignition value (or a suitable increase of the heating surface is pro- vided) higher products are not formed in appreciable amount but the relative proportions of the chlorinated methanes are not those which would be expected from a step-wise reaction. When the rate of flow is below the ignition value marked changes resulting in the production of carbon tetrachloride and higher products are only observed when the catalysing surface is enormously increased (for example by the use of activated charcoal).This result is The results may be summarised as follows. e 2f . 84 ABSTRACTS OF CHEMICAL PAPERS not appreciably modified when the minimum temperature is ex- ceeded by as much as loo" when the heating zone is increased or diminished or when catalysts such as ferric chloride molybdenum pentachloride or antimony pentachloride are present. On the other hand the results obtained are not in harmony with the values calculated from Martin's formula (2. Elektrochem. 1921 27 150). If the rate of flow is considerably below the ignition value an increased production of chloroform and carbon tetrachloride or substances of similar boiling point at the expense of methyl and methylene chlorides is observed. The causes which are operative in producing results differing so greatly from those of a step-wise reaction are discussed in detail.The most probable are the dissociation of methane and subsequent changes such as those represented by the equations CH3C1+ CH4= C2H6 + HCl CH,CI +CH4= CH2C1*CH3+ HC1 CH3C1 + CH,C1=CH,C1*CH3+HC1 and CH,C1,+CH3C1=CH,Cl*CH,C1 (or CH,*CHCl,) +HC1. The preparation of methyl chloride from methane and carbonyl chloride (cf. Hochstetter A 1916 i 625) has been re-examined. The action appears to be due to greatly diluted chlorine. R. DE FORCRAND (Compt. rend. 1923 176 20-23).-Thallous ethoxide was prepared by the method of Lamy (Ann. Chim. Phys. 1863 67 395; 1864 3 373) and was isolated as an oily liquid d 3-55. It reacts with other alcohols to give the corresponding alkyloxides.I n this way the author has prepared the monothallium derivatives of ethylene glycol OH*C,H,*OTl and of glycerol C,H,( OH),*OTl both of which separate as yellow solids and thallous phenoxide which is white and micro- crystalline. Thallous hydroxide may be similarly prepared. For the preparation of thallous acetate the ethoxide is the best starting point and for the neutral sulphate the hydroxide is best used. H. W. The Thallous APkyloxides. W. G . The Alkylglycerols. Preparation of Alkylvinylcarbinols [Alkylallyl Alcohols]. RAYMOND DELABY (Compt. rend. 1922 175 967-970; cf. Lespieau A. 1911 i 347).-Homologues of glycerol were obtained by the action of magnesium alkyl compounds on acraldehyde yielding unsaturated secondary alcohols.These were brominated and the resulting bromohydrins converted into diacetins by means of potassium acetate ; hydrolysis under pressure or alcoholysis by methyl alcohol of the diacetins then yielded the alkylglycerols. The alkylallyl alcohols obtained in the first stage have the following properties. Aa-Buten-y-ol (methylvinylcar- binol) b. p. 94-96' ; d 0.854 ; d:* 0.835 ; r2$ 1.4087 (cf. Wohl and Losanitsch A. 1908 i 934). Aa-Pentene-y-ol (ethylvinylcarbinol) b. p. 37'/20 mm. ; d f 0-839 ; ng 1.4182 (cf. Wagner A. 1885,370). ha-Hexeue-y-ol (propylvinylcarbinol) b. p. 133.5-134" ; d! 0.851 ; df2 0.834 ; n'," 1.4215. A-Heptene-7-01 (butylvinylcarbinol) b. p. 153.5-154"; d 0.852; diz 0.835; n$ 1.4275. These alcohols yielded crystalline allophanates m. p. 151-152" 152-153" 139.5-140" and 156.5-157" respectively.ha-Heptene-y-ol wasORGANIC CHEMISTRY. i. 85 resolved into its optical isomerides by Pickard and Kenyon's method (T. 1911,99 45). Alkylglycerols Transformation of Alkylvinylcarbinols into Alkylglycerols. RAYMOND DELABY (Compt. rend. 1022 175 1152-1 154 ; cf. preceding abstract).-Experimental details of the transformation of brominated alkylvinylcarbinols into diacetins and of the hydrolysis of the latter into homologues of glycerol are described. Propylglycerol m. p. 60-62" b. p. 167-6- 16S0/14 mm. and butylglycerol m. p. 52-54' b. p. 175-175.5"/17 mm. are hygroscopic crystalline substances ; their triacetutes have b. p. 157-159"/15 mm. and b. p. 174'121 mm. respectively. Methylglycerol has b. p. 162-5-163*5"/15 mm.(cf. Lieben and Zeisel A. 1881 710); ethylglycerol has b. p. 165-166"/15 mm. (cf. Wagner A. 1889,231). The method gives yields corresponding with 60% of the secondary alcohol used. SVIGEL POSTERNAK (Swiss Pat. 91727; from Chem. Zentr. 1922 iv 837-838; cf. A 1921 i 225).-A solution of inositol is heated with excess of orthophosphoric acid in the presence of sufficient excess of phos- phoric oxide to combine with the water produced in esterification. The resulting products are dissolved in dilute sodium hydroxide solution and the sodium metaphosphate is changed into sodium pyrophosphate by heating at 100". The latter salt is fractionally crystallised out from the viscid solution of the sodium salt of inositol polyphosphate. Other metallic inositol polyphosphates may be obtained from the sodium salt by double decomposition.Calcium magnesium and ferric salts are mentioned and a crystalline calcium sodium salt having the comnosition H. J. E. H. J. E. Preparation of Inositol Polyphosphate. c 6H602~P6N~8Ca,,3H@ is also obtained ; it probably occurs in seeds. G. W. R. Cyclic Derivatives of Mannitol. P. VAN ROMBURGH and J . H. N. VAN DER BURG (Proc. K . Akad. Wetensch. Amsterdam 1923 25 335-340).-The unsaturated oxide C6H,01 produced by heating the hexaformate of mannitol is shown to he identical with 2-vinyrdihydrofuran and its structural formula ~~$~>CH*CH:CH confirmed. The reduced oxide C6H,,0 prepared by reduction of C,H80 with hydrogen under a pressure of two atmospheres in the presence of palladium sol is shown to be identical with %ethyl- tetrahydrofuran. The structural formula 1-0-1 ?H CH,*~H*~H*CH*CH*CH,*OH OH OH proposed by van Romburgh and van Maanen (Diss.Utrecht 1909) for mannitan is confirmed and that similarly proposed for isomannide YH,*CH*CH*YH*YH*CH2 shown probably to be p T O P l 0- OHi. 86 ABSTRACTS OF CHEMICAL PAPERS. correct. isoMannide increases the electrical conductivity of an aqueous solution of boric acid only very slightly. The increase in the case of mannitol and mannitan respectively is considerable (cf. Boeseken A. 1921 i 843). J. S. G. T. Investigations on the Dependence of Rotatory Power on Chemical Constitution. XIV. The Normal Aliphatic Ethers of d-p-Octanol. JOSEPH KENYON and REGINALD ARTHUR MCNICOL (T. 1923 123 14-22). The Ability of ay-Glycols to Form Acetone [isoPropylidene] Compounds.J. BOESEKEN and P. H. HERMANS (Ber. 1922 55 [B] 3758-3760).-Trimethylene glycol unites with acetone to form an isopropylidene ether a mobile liquid with a camphoraceous odour b. p. 123-125" difi5 0.9587 nz5 1.4252 the isolation of which is rendered difficult by the unfavourable position of the equilibrium of the reaction glycol+acetone isopropylidene + water and by the considerable volatility of the compound with the vapours of acetone. The relatively difficult formation of an isopropylidene compound from trimethylene glycol is due not only to the presence of the hydroxyl groups in the ay-position and the consequent necessity of forming a six- instead of a five-mem- bered ring but also and chiefly to the unfavourable steric position of these groups.Instances in which the hydroxyl groups are more f avourably placed are found in anhydroenneaheptitol (Mannich and Brose A. 1922 i 1118) and pentaerythritol which yields mono- and di-isopropylidene compounds m. p. 116' and 135' respectively. The place of hydrogen chloride in the condensations may be taken by other acids which are soluble in acetone. Good results are obtained with $-&% of concentrated sulphuric acid which is subsequently neutralised with a considerable excess of recently- ignited finely-divided lime. H. W. FAR- BENFABRIKEN VORM. FRIEDR. BAYER & CO. ( D . R . - P . 358125 ; from Chem. Zentr. 1922 iv 888).-The alcohol is converted by the usual methods into the corresponding carbamate. For example tri- chloroethyl alcohol dissolved in anhydrous ether is treated with carbamide hydrochloride or the alcohol dissolved in benzene in the presence of quinoline is treated with carbonyl chloride and the trichloroethyl chloroformate thus formed treated with ammonia.Trichloroethyl carbarnate forms white needles m. p. 64-65'. It is a soporific. G. W. R. A New Phosphoric Ester Produced by the Action of Yeast Juice onHexoses. ROBERT ROBISON (Biochem. J. 1922,16,809- 823).-The new ester is prepared in the following way. Lawdose or dextrose is fermented with yeast-juice and constant additions of disodium hydrogen phosphate. When the inorganic phosphate is no more utilised barium acetate is added to the fermentation mixture which is then neutralised and precipitated with an equal volume Preparation of an Ester of Trichloroethyl Alcohol.ORGANIC CHEMISTRY.i. 87 of alcohol. The precipitate is then extracted with 10 parts of cold water reprecipitated several times with basic lead acetate purified by treatment with mercuric acetate and finally precipitated with alcohol as the barium salt. Hexosemonophosphoric acid has [a]? +25.0" in water. The metallic salts with the exception of the basic salts of the heavy metals are all readily soluble in water and are amorphous. A crystalline brucine salt was obtained. The phenylhydrazine salt of the osazone of hexosemonophosphoric acid is not identical with the isomeric compound obtained from the hexosediphosphoric acid. On hydrolysis by acids or by emulsin the hexosemonophosphoric acid yields free phosphoric acid and a dextrorotatory substance from which glucosazone is obtained.The rotatory power of this product of degradation is however less than that of dextrose. Preparation of Thiohydrins. FARBWERKE VORM. MEISTER LUCIUS & BRUNMG (Brit. Pat. 185403) .-Propylene thiohydrin or mixtures of this with ethylene thiohydrin are obtained by heating propylene chlorohydrin or mixtures of this with ethylene chloro- hydrin such as are obtained by the action of hypochlorous acid on olefine gas mixtures with aqueous sodium sulphide solutions the product being isolated by evaporating the water in a vacuum separating the sodium chloride by pressing and distilling the crude thiohydrin under reduced pressure. Propylene thiohydrin boils a t 120°/4 mm. and probably has the constitution S(CH,-CHMe-OH),.The thiohydrins are useful as solvents in dye printing. Varying Valency of Platinum with Respect to Mercaptanic Radicles. SIR PRAFULLA CHANDRA RAY (T. 1923 123 133- 141). Stability of Sodium Formate Acetate and Oxalate towards Oxidation under Pressure. HANS SCHRADER (Ges. Abh. Kenntnis Kohle 1920 5 193-199; from Chem. Zentr. 1922 iii 1154).-At 160" no oxidation of these salts takes place in three hours. Oxidation takes place freely at 210" and rapidly a t 260". Sodium formate and sodium oxalate are oxidised equally quickly whilst sodium acetate is more slowly attacked. The presence of sodium carbonate or sodium hydroxide has no marked effect. Intermediate stages between the three organic acids and carbon dioxide were not observed. No oxalate was formed from formate neither was oxalate or formate formed from acetate.s. s. z. G. F. M. G. W. R. Investigations on the Dependence of Rotatory Power on Chemical Constitution. XIII. The Spatial Configuration of the Unbranched Aliphatic Chain. ROBERT HOWSON PICKARD JOSEPH KENYON and HAROLD HUNTER (T. 1923,123 1-14). The Anodic Preparation of Pure Lead Tetra-acetate Tetra- propionate and Silver Diacetate. C. SCHALL and W. MELZER (2. Elektrochem. 1922 28 47-77) .-The specific conductivities and the corresponding temperature coefficients of solutions ofi. 8s ABSTRACTS OF CHEMICAL PAPERS. anhydrous and crystalline lead diacetate in acetic acid have been measured and the products obtained on electrolysis of these solu- tions examined. When the water content of the mixture is less than 0.6y0 very little change is observable at the anode and when greater than 2y0 the anodic product is mainly lead dioxide.At intermediate concentrations of water pure lead tetra-acetate may be obtained in good yield if the apparatus is surrounded by ice. The pure salt may be prepared also from a solution of the diacetate in 99.4% acetic acid in the presence of dry sodium acetate. Small amounts of lead tetrapropionate and silver diacetate may be similarly obtained. W. E. G. Relationship between the Iodine Values and Refractive Indices of some Hardened Vegetable Oils. J. J. SUDBOROUGH H. E. WATSON and I). Y . ATHAWALE ( J . Ind. Inst. Xci. 1922 5 v 47-69).-Samples of cotton-seed linseed a,rachis mohua (Bassia latifolia) sesamk sardine castor hongay (Pongamia glabra) and coconut oils were refined and hydrogenated a t 180" using nickel catalysts and the relationship between iodine value and refractive index was determined.Except in the case of castor and hongay oils the relationship between the two constants is independent of the time and of the type of catalyst used. In the case of the f i s t six oils mentioned the curves representing the relationship between iodine value and refractive index lie very close together and may be represented by the equation nr= 1 -4468 + 1 -03 x lo4+ ( I . v.) + 7.3 X 1W8(I. v.)2 to an accuracy of about 0-0005. The refractive indices a t 60" of the above six oils when completely hardened are practically identical a t the value 1.4468. The refractive indices of hardened coconut oil are much lower than those of other oils with the same iodine value.I n the case of castor oil the relationship between the iodine value and the refractive index is not independent of the type of catalyst or of the time of hardening owing to the varying extent to which the hydroxyl groups are reduced. It is possible that the case of hongay oil is similar although its acetyl value is only 24. H. C. R. The Catalytic Decomposition of Castor Oil. A. MAILHE (Compt. rend. 1923 176 37-39).-VYhen passed over aluminium and copper turnings castor oil undergoes decomposition the products varying with the temperature. The products are hydro- carbons and heptaldehyde. Below 600" the hydrocarbons formed are almost entirely homologues of methane but above 600" aromatic hydrocarbons such as benzene toluene and m-xylene are also formed.W. G. The Transition from the Colloidal to the Crystalloidal State. Solutions of Potassium Oleate. LOUIS LEIGHTON BIRCUMSHAW (T. 1923 123 91-97). Dissociation Constants of Sulphoacetic and a-Sulphopro- pionic Acids. H. J. BACKER (ROC. K . A k d . Wetemch. Amster- dam 1923 25 359-363).-Values of the respective molecular conductivities at 25" of aqueous solutions of sulphoacetic acid,ORGANIC CHEMISTRY. i. 89 mono- and di-sodium sulphoacetates sulphopropionic acid mono- and di-sodium sulphopropionates propionanilide-a-sulphonic acid and sodium propionanilide- a-sulphonate in dilutions corresponding with 1 g. mol. per 16 32 64 128 256 512 and 1024 litres have been determined.The mean values of the respective dissociation constants of. sulphoacetic and a-sulphopropionic acids calculated therefrom are 8-9 x J. S. G. T. Optical Resolu- tion of the cis-Potassium Salt. M~RCEL DEL~PINE (Cmpt. rend. 1922 175 1408-141 1 ).-Potassium iridodichloro-oxalate K,[IrC12(C20,)2] as prepared by Vdzes and Duffour (cf. A. 1909 i 762) was found to occur in the cis- and trans-forms and the cis- form was resolved into its two optical isomerides by means of its strychnine salt. The I-salt is the less soluble and has [a],-23*8". The active salts are more soluble than the racemic mixture. The trans-salt is not resolved by means of its strychnine salt. The cis- and trans-isomerides are capable of being transformed into one another under suitable temperature conditions.Investigations on the Dependence of Rotatory Power on Chemical Constitution. XVI. The Di-d-P-octyl Esters of the Saturated Dicarboxylic Acids. LESLIE HALL (T. 1923 123 3 2 4 ) . The Syntheses of y-Hydroxy- and a-Amino-y-hydroxg- pimelic Acids. HERMANN LEUCHS and WERNER NAGEL (Ber. 1922 55 [B] 3950-3960).-The compounds are prepared from the lactone ester ?0-o>CH*CH2*CH(C02Et)2 described by Leuchs and Mobis (A. 1909 i 361). Attempts to halogenate the lactone ester or the corresponding acid in the malonic residue and subsequently to eliminate the carbethoxy- or carboxy-group did not lead t o satisfactory results since only impure non-crystalline products could be obtained which even after re-esterification could not be distilled without decomposition.The lactone ester is transformed by aniline a t 160-170" into the mono-anilide C1,H,,O,N lustrous leaflets m. p. 79-80". Hydrolysis of the lactone ester and subsequent removal of carbon dioxide from the product leads to the formation of the lactone of 7-hydroxypimelic acid ?o-o>CHfCH2],*C02H four- or six-sided plates m. p. 80-82-5". It is converted by methyl alcohol and hydrogen chloride into methyl y-chloropimelate which could not be isolated in a homogeneous condition but is characterised bv its conversion by and 6.0 x lO.-5 The cis- and trans-Iridodichloro-oxalates. W. G. CH,*CH2 CH,*CH2 ammda into P-pyrrolidoneprop~o~~~de (?~~~~!>CW*[CH2-J2*CO*NH2 -~ colourless needles m. p. 144-145" (decoinp.) when slowly heated. Hydroxypimelolactone is brominated by Volhard's method and the product is converted by methyl alcohol into the methyl ester e*i.90 ABSTRACTS OF CHEMICAL PAPERS. of or- bl.omo-y-iiydroxypimelokr;ctone which could not be distilled without decomposition ; the brominated ester is hydrolysed with boiling hydrobromic acid and the resulting mid which could not be caused to crystallise is aminated with aqueous ammonia. The expected products could only be isolatcd in the form of the copper salts one of which (+H,O) sky-blue crystals is the normal salt CH,*CH2-C0 /"' of y-hydroxy- a-aminopimelic acid OH*CH< whereas the remaining two greyish-blue crystals (+iH,O) and paler greyish-blue needles (+ $H,O) are considered to be derived from the two racemic forms of a-aminopimclolactone CH,*CH(NH2)*C02 \ ?H2*CH2> CH*CH,*CH (kH,)*CO,H.CO-0 The lactone ester is converted by ethyl bromide in the presence of alcoholic sodium ethoxide into the corresponding a-ethyl deriv- ative (?o-o>CH*CH2*CEt(C0,Et) an odourless liquid b. p. CH9*CH9 206-208"jl4 &m. which is hydrolysed to a non-crystalline acid and is converted by methyl alcoholic ammonia into the di-amide C,,Hl,04N2 colourless prisms or oblique plates m. p. 170-171". The acid is transformed by loss of carbon dioxide into or-ethyl- y-hydroxypimeloluactone ni. Q. 89-91' to which the constitution _ - o>CH*[CH2]2*C0,H is assigned. The latter substance is c 0.- bHEt*CH treated wkh bromine and a trace of phosphorus at 100" and the product after being purified through the methyl ester is treated successively with hydrobromic acid and ammonia.The product is isolated as a homogeneous copper salt (CpH140,N),Cu,~H20 although the constitution of the parent acid indicates the existence of four racemic isomerides; the corresponding free acid could only be obtained as a non-crystalline very hygroscopic mass. H. W. Keto-enolic Tautomerism. I. Desmotropy-isomerism of Ethyl Diacetylsuccinate. H. P. KAUFMANN (Annalen 1922 429 247-283) .-A general account of this work has already appeared (A. 1922 i 985). The investigation shows that in 0-1N-alcoholic solution a t 30" ethyl diacetylsuccinate becomes equilibrated to an approximation of 1 or 2% in twenty-four hours and that the mixture then contains 10% of the y-ester (diketo) 30% of the p-ester (diketo) 16% of the cc,p-ester (mono-enol) and 44% of the or#-ester (mono-enol).ERICH MULLER (2. angew. Chem. 1922 35 689-692 69&700).-In a lecture delivered before the Dresden Chemical Society the author gives an extended general account of his work on the electrolysis and catalytic decomposition of solutions of formaldehyde and related compounds and outlines his views on the hydration of formaldehyde to CH,(OH) and the amphoteric nature of the hydrate. The observations are extended to other substances C. K. I. The Amphoteric Nature of the Carbonyl Group.ORGANIC CHEWISTRY. i. 91 containing the carbonyl group such as ketones carboxylic acids and carbon monoxide. The assumption of the formation of ions the existence of which cannot be demonstrated or the quantity measured is justified by analogy with inorganic compounds such as the complex cyanides and by the fact that the very involved behaviour of formaldehyde cannot be so clearly and uniformly EMU; BAUR and A.REB- MANN (Helv. Chim. Acta 1922 5 828-832).-Moore and Webster are stated to have obtained formaldehyde from carbon dioxide solutions by the action of sunlight in presence of colloidal oxides of uranium or ferric iron (A. 1913 i 1303). The present authors have repeated these experiments and have not succeeded in de- tecting the formation of oxalic acid glyoxylic acid formic acid or formaldehyde. Failure to confirm the results obtained by the above investigators may be due to their having omitted to describe with sufficient exactitude their experimental conditions. explained by any other hypothesis.H. w. The Photolysis of Carbonic Acid. E. H. R. Acraldehyde Transformations and Antioxygenisers. CHARLES MOUREU and CHARLES DUFRAISSE (Bull. Soc. chim. 1922 [iv] 31 1152-1176; cf. Moureu and Dufraisse A. 1919 i 574; Moureu and Lepape A. 1919 i 574 ; 1920 i 10 ; Moureu Dufraisse and Robin A. 1920 i 143 ; Moureu Dufraisse Robin and Pougnet A. 1920 i 144; Moureu Dufraisse Lepape Robin Pougnet Boutaric and Boismenu A. 1921 i 395; Moureu and Dufraisse A. 1922 i 250 824).-&4 review of previous publications showing the trend of the work leading to the stabilisation of acraldehyde by addition of pyrocatechol and also by other phenols is followed by development of the subject in the direction of reviewing the chief substances capable of undergoing autoxidation and also of de- tecting the antioxygenising function in substances other than phenols.The oxidation of the acraldehyde appears to be a neces- sary preliminary to the formation of disacryl and the addition of a phenol inhibits the change. But on submitting pure acraldehyde to the action of oxygen some disacryl is always formed the quantity appearing to vary for no definite reason although the transform- ation into disacryl was not observed to take place to any considerable extent in the presence of excess of oxygen. These facts appearing to be somewhat contradictory the action of light on acraldehyde was investigated. The results showed that light effects the con- densation into disacryl in absence of oxygen and conversely that acraldehyde undergoes no condensation when prepared and kept in the dark and free from contact with oxygen.In absence of light extremely small quantities of oxygen bring about the con- densation and the authors regard the phenomenon as one of catalysis suggesting that a peroxide oi acraldehyde is the catalyst. The theory put forward to account for the lack of condensation by excess of oxygen is based on the supposed existence of two types of acraldehyde molecule one of which is activated. These molecules combine with oxygen but when oxygen is absent they e* 2i. 92 ABSTRACTS OF CHEMICAL PAPERS. combine with each other. This is shown by the fact that acraldehyde in contact with oxygen over mercury remains clear the mercury meanwhile rising in the tube but when the mercury ceases to rise oxidation is no longer occurring and the acraldehyde becomes opaque.The time at which the latter change takes place may be predicted by extrapolating the curve obtained by plotting rise of mercury against time. Reasons are given for continued use of the term " antioxygeniser )' (cf. Seyewetz and Sisley A. 1922 ii 628). H. J. E. The Hydrogenation of Aldehydes and Ketones in Presence of Pure and Impure Platinum Black. FAILLEBIN (Cmpt. rend. 1922 175 1077-1079).-1n the reduction of aldehydes and ketones to alcohols in presence of platinum black considerable experimental difficulties are experienced. The action is slow the activity of the catalyst is in many cases extremely limited and the yields obtained are poor owing to the formation of hydro- carbons. I f however the catalyst is prepared by the reduction of chloroplatinic acid containing 5% of its weight of ferric chloride good yields are obtained especially in the case of aromatic aldehydes and the speed of the reaction is increased.I f the ferric chloride is replaced by iridium chloride similar advantages are obtained but to a lesser extent. In hydrogenating an ethyl acetate solution of 4-piperonyl-2-butanone in presence of '' ferric platinum " to the corresponding secondary alcohol hitherto unknown a quantitative yield was obtained. The alcohol i s not described. H. J. E. Syntheses by means of Sodamide. A. HALLER (Bull. Xoc. chim. 1922 [iv] 31 1073-1 144).-A lecture delivered before the Soci6t6 Chimique de France in which the use of sodamide as a reagent is discussed mainly with regard to the work of the author and his collaborators.The work surveyed comprises substitution reactions of ketones and nitriles the action of the alkyl derivatives so obtained on various cyclic compounds and also the decomposition and condensation reactions which may be effected by the use of sodamide. The chief papers to which reference is made are those of von Auwers and Krollpfeiffer A. 1915 i 818; Bodroux and Taboury A. 1910 i 257; Cornubert A. 1921 i 730; Haller A. 1904 i 600; 1905 i 214 602; 1913 i 629 984 1357; 1914 i 418 ; Haller and Bauer A. 1908 i 987 ; 1909 i 108 654; 1910 i 219 300; 1911 i 299 726; 1913 i 488 829; 1914 i 418 549 724; 1915 i 411; 1918 i 24 428; 1922 i 258; Haller and Benoist A. 1912 i 570; 1922 i 350; Haller and Cornubert A.1914 i 291 842 968; 1920 i 390 441 ; Haller and Louvrier A. 1918 i 397; Haller and Rarnart-Lucas A. 1914 i 1072; 1917 i 665. Diacetone-glucose [Diisopropylidene-glucose]. P. A. LEVENE and G. M. MEYER ( J . Biol. Chem. 1922 54 805-807).- When oxidised with nitric acid the monomethyl glucose obtained from diisopropylidene-glucose yields a methyl sacchccrohctone H. J. E.ORGANIC CHEMISTRY. i. 93 C,HlOO m. p. 206-207" (after sintering and darkening at 190") [a] +15" (cf. Irvine and Hogg T. 1914 103 1386). The pro- duction of this compound indicates that the isopropylidene radicles in diisopropylidene-glucose are attached to the aP and c[ carbon atoms. If diisopropylidene-glucose has the structure of a y-glucose (Irvine and Patterson T. 1922,121 2146) the methyl group in the saccharolactone will be attached to the y-carbon atom ; otherwise it will be in the p-position.E. S. Glucosides. XI. The Glucosides of Glycerol. P. KARRER and 0. HURWITZ (Helv. Chim. Actu 1022 5 86+869).-With the object of synthesising a glucoside of glycerol of which the constitution could not be open to doubt the action of acetobromo- glucose on isopropylidene-glycerol in presence of silver carbonate was studied. The reaction proceeded smoothly giving a good yield of a-tetra-acetyl-d-gluwsidoglycerol iso-propylidene ether (annexed formula) white crystals m. p. 132" [a] -20.77". By careful hydrolysis of $JH-O yH2'o> CMe cH,*O*~,H,O,A~ this compound with dilute sulphuric acid the acetone residue was removed leaving a-tetra-ucetyl-d-glucosi~o-glycerol an amorphous substance which can be readily reconverted into the isopropylidene derivative.By the action of acetic anhydride on the amorphous substance the glycerol residue is acetylated with formation of a- (tetra-acetyl-d-glucosido)- glycerol py-diacetute a well-crystallised compound m. p. 98" [a]:' -30.96". Alkaline hydrolysis of the last gave 1-p-d-glucosidoglycerol OH*CH,*CH( OH)~CH,*O*C,HI105 [ a]g - 27.72". The p-configura- tion of the glucoside is proved by its ready hydrolysis by emulsin. It appears to be identical with the glyceryl glucoside synthesised by Bourquelot Bridel and Aubry by means of emulsin from glycerol and dextrose (A. 1917 i 379). P. KARRER and J. TERKUILE (Helv. Chim. Acta 1922 5 870-876).-1t was shown by Karrer and Smirnov (A.1921 i 766) that when tetra-acetyl- glucosidotrimethylammonium bromide is submitted to alkaline hydrolysis l-glucosan is formed. It is now found that by acid hydrolysis only the acetyl groups are removed and d-glucosido-a- trimethylammonium bromide is formed (using hydrobromic acid for the hydrolysis) as hygroscopic crystals m. p. 161-162" ; [a]? +5*0". The hydroxide C6HIl0,*NMe,*O~ was prepared in solution by the action of silver hydroxide on the bromide or chloride; it is a strong base but decomposes with evolution of trimethylamine when its aqueous solution is warmed. The chloride forms very hygroscopic crystals ; the iodide transparent slightly hygroscopic crystals m. p. 162-163" ; the chlorophtinate orange-brown crystals ; chloro- aurate; picrate beautiful yellow needles m.p. 141". Tetra- acet yl-d -glucosido -a- trimethylammonium bromide f oms rhombic crystals (a b c=0.4520 1 0.3443) ; the hydroxide resembles the parent compound in preparation and properties ; the chloride forms colourless hygroscopic crystals m. p. 173" ; [a]r +6.26" ; the perchbrute forms microscopic needles m. p. 190"; the picrate E. H. R. Glucosido-trimethylammonium Salts.i. 94 ABSTRACTS OF CHEMICAL PAPERS. crystallises in fine yellow needles m. p. 133"; the chloroplatinate in h e orange needles m. p. 209-210" (decomp.) and the chloro- aurate yellow needles which decompose when heated. MARC CRAMER and EDWARD H. Cox (Helv. Chim. Actu 1922 5 88&887).-The structure proposed by Pietet and Castan (A. 1920 i 594) for glucosan has been confirmed; the objections to this formula raised by Bergmann (A.1921 i 645) and Irvine and Oldham (T. 1921,119,1744) are therefore invalid. The attempt was first made to obtain an osazone from tribenzoylglucosan but this was unsuccessful owing to the daculty of hydrating the substance without hydrolysing the benzoyl groups at the same time. By the action of methyl sulphate on glucosan in presence of sodium hydroxide a t 35-40' a trimethylglucosan was obtained b. p. 210-212"/9 mm. This gives a reducing sugar when boiled with water and forms a yellow crystalline osazone m. p. 163-164" (decomp.). This can only be derived from a trimethylglucose of the formula E. H. R. The Constitution of Glucosan. OH*yH-yH*OMe OH*CH* O *CH*CH( OMe) *CH,*OMe ' which coiifirms the glucosan structure under discussion.A further proof depends on the observation that when glucosan is heated in a sealed tube with methyl iodide at 125-130" an additive compound is formed which when reduced with sodium amalgam gives the p-deoxymethylglucoside described by Pischer Bergmann and Schotte (A. 1920 i 422). This reaction is readily explained by the proposed formula for glucosan thus o<CH*O*CH*CH (OH) *CH,*OH'OMe.CH*O*CH*CH (OH) *CH,*OH FH-YH*OH I*yH-$!H*OH FH,-YH*OH OMe*CH*O*CH*CH( OH)*CH,*OH' -+ E. H. R. Cellulose Nitrate. EUGENE C. BINCHAM and WILLuML. HYDEN ( J . Franklin Inst. 1922,194 731-740).-The mobility of solutions of cellulose nitrate (12*11y0 nitrogen) in acetone was determined by the viscometer method at various temperatures and concentrations and with varying shearing stresses in order to investigate whether the fluidity is a linear function of the concentration only or whether as seemed probable it is influenced by the shearing stress.It was found that there was a steady increase in the mobility with the pressure and as already known to be the case with many plastic materials the efflux in ml. per second was a linear function of the shearing stress. When the shearing stress is extrapolated to its value when the efflux is zero the friction or " yield value " is obtained which may be defined as the shearing stress a t the wall of the tube necessary t o start the flow. The "yield value '' increased with increasing concentration and with decreasing tem- perature. On plotting the " yield value '' against temperature for a 7-708 :& nitrocellulose mixture a sharp transition temperatureORGANIC CHEMISTRY. i.95 was indicated at 43" where the " yield value " became zero and the material loses its plastic character and becomes a viscous liquid. It seems probable that this transition temperature is independent of the concentration. The mobility of cellulose nitrate dispersions is characterised by the great depression produced by very small percentages of the solid a 1% solution having a mobility only 20% of that of the pure acetone whilst that of an 8% solution is 0.1% of that of the solvent. This is one of the most noteworthy distinctions between the polar and the nonpolar type of colloid. The mobility increases with the temperature in a nearly linear manner.G. F. M. Cellulose Acetate. EMII; KNOEVENAGEL and KARL KONIG (Cellulosechemie 1922 3 113-122).-Gelatinisation of solutions of cellulose acetate takes place when kept in the presence of small quantities of suitable catalysts such as sulphuric acid or sulpho- acetic acid the gelatinised product becoming insoluble in the usual solvents. If the system is not completely anhydrous as for instance solutions of cellulose acetate in acetone or in glacial acetic acid this gelatinisation may be accounted for by a large decrease in the acetyl value owing to acid hydrolysis of the ester and it takes place more rapidly as the concentration of the catalyst is increased. If fhe system (solution of cellulose acetate in glacial acetic acid) be rendered anhydrous by the addition of acetic anhydride another set of conditions arises and gelatinisation may be delayed for three months when an increase of acetyl value and a large increase in copper value indicative of acetolysis are recorded.When however moisture is totally excluded from the first a different type of gelatinisation is characterised which may be described as the result of condensation or polymerisation of the cellulose ester. The purified gelatinised product is then insoluble in the usual media with the exception of tetrachloroethane the acetyl value is only slightly changed either slightly increased or lowered and the copper value is slightly decreased. This type of gelatinisation may be produced by completely drying 3 g. of the cellulose acetate a t 105" in a glass tube dissolving this in lOOyo acetic acid sufficient to give a 15% solution and keeping this solution in a desiccator over sulphuric acid.Next day a small quantity of catalyst e.g. 47 mg. of sulphuric acid or 96 mg. of sulphoacetic acid is stirred into the viscous solution 0.476 g. of acetic anhydride is added to react with any moisture which may have been absorbed during the operations and the tube is sealed up. Gelatinisation takes place after two to three days but if the quantity of catalysk is increased it is further delayed. With 115 mg. or more of sulphuric acid the solution does not gelatinise but considerable acetolysis takes place. J. F. B. Hydrocellulose [Preparation of Dimethylhydrocellulose 1. E m HEUSER and WALTER VON NEUENSTEIN (Cellulosechemie 1922 3 101-107).-Chopped viscose fibre partly dried and con- taining &lo% of moisture was placed in a bottle with a paraffinedi.96 ABSTRACTS OF CHEMICAL PAPERS. cork and the air was displaced by passing dry carbon dioxide through for two hours. A current of dry hydrogen chloride was passed very slowly so that fumes appeared a t the outlet after two to three hours. The bottle was then tightly closed and allowed to remain for several hours until a test showed that the hydrocellulose was completely soluble in 10% sodium hydroxide. The fibre was neutralised and washed. For methylation 5 g. of the hydro- cellulose (1 mol.) was dissolved in 50 C.C. of 10% sodium hydroxide solution (4 mols.) and after some hours 10 g. of methyl sulphate (3 mols.) were added in small quantities at a time with continuous agitation.The temperature rose to 60" after ten minutes. Subse- quent operations were performed without separating the methylated product using the same proportions of the reagents but taking the sodium hydroxide in the form of a 25% solution instead of 10%. After the fifth operation the greater portion of the methylated cellulose remained insoluble in the saline liquid. An excess of alkali was added and while hot the cellulose ether was collected. The precipitate was dissolved in cold water the solution filtered to remove traces of under-methylated residue and the ether which was precipitated on heating collected while hot and washed with boiling water. When completely methylated this ether retained its solubility in cold water even after drying.Theoretical yields were obtained when the operations were performed with mechanical stirring and the maximum degree of methylation corresponded with a methoxyl content of 33.76. (See also this vol. i 17.) J. F. B. Complex Magmesim Salts. 11. G. SPACU (BuZ. Foc. Ytiinfe Cluj 1922 1 247-266; from Chem. Zentr. 1922 iii 1045-1046 ; cf. A. 1922 i 859).-Magnesium tetrapyridine chZoride Mg(C,NH5)4Cl prepared from magnesium chloride and anhydrous pyridine a t the ordinary temperature is a white crystal- line powder; it is very hygroscopic with separation of pyridine. This salt differs from the corresponding bromide and iodide in that it is not co-ordinately saturated. Magnesium triethylenediamine chloride Mg en3 CI forms colourless crystals which cannot be resolved into their optically active components.It is highly hygroscopic. The chloride reaction is given with silver nitrate. Magnesium diaquodiethylenedinmine iodide Mg en,(H20),12 forms crystals ; it is unstable in air. Magnesium triethylenediamine sulphate Mg en3 SO,,aq is a hygroscopic white powder. Mag- nesium tetrapyridine thiocyanate Mg(C5N€€5),(CNS)2 from magnesium thiocyanate and anhydrous pyridine forms small colourless highly refractive crystals ; it is very hygroscopic. Magnesium hexa- pyridine thiocyanate forms large colourless highly refractive crystals. Magnesium hexammine thiocyanate Mg(NH3),( CNS),,. pre- pared by the action of ammonia on solid magnesium tetrappdme thiocyanate is a colourless powder. Magnesium tetra-aquodipyridine chloride dipotassium chloride Mg(C5NH,),(H,0),C1,,2KC1 is obtained by prolonged shaking of powdered carnallite with anhydrous pyridine.It is a white crystalline powder. G. W. R.ORGANIC CIIEMISTRY. i. 87 Preparation of Chloro-substitution Products of Hexa- methylenetetramine. ROMOLO BURATTI (Swiss Pat. 90703 ; from Chem. Zentr. 1922 iv S9l).-An aqueous solution of hexa- methylenetetramine is mixed with a solution of a hypochlorite previously neutralised with an organic or weak mineral acid and the mixture concentrated to the point of crystallisation. Using neutral sodium hypochlorite containing 10 yo of active chlorine the reaction is as follows C,~~12N4+4HC10=C,H,~4cl~+4H20. The tetrachlorohexamethylenetetramine thereby formed separates on con- centration of the solution as a colourless mass; it forms salts with acids.G. W. R. A Hydrolysis of Glycine. EMIL BAUR (Nelv. Chim. Acta 1922 5 825-828).-When a freshly prepared solution of glycine in air-free water is shaken for a long time in absence of air with animal charcoal gradual decomposition takes place. After 240 hours a t 40° using 10 g. of charcoal to 1 g. of glycine 17.6% of the nitrogen present is found in solution as ammonia. Since the final solution is always neutral the reaction is probably a simple hydrolysis according to the equation NH2*CH2*C02H+H20= OH*CH2*C02*NH4. Attempts to separate calcium glycollate from the solution were unsuccessful but the salt was recognised micro- scopic ally. E. I€. R. LESLIE JULIUS HARRIS (Biochem. J. 1922,16 739-746).-Cysteine forms metallic derivatives much more readily than cystine.The former compound was found to give coloured metallic derivatives with the following ions Fe'" Mn"' MnVI0 CU" Co Ni Cr Bi. Cuprous salts give a characteristic white derivative insoluble in neutral solutions. Tin also gives a compound with it. No oxidation takes place on addition of stannic chloride and it is suggested that owing to the strong affinity of tin for sulphur it protects that atom in cysteine from oxidation. The mercuric ion but not the mercurous acts as precipitant of cysteine. The colorimetric ammonia test for cysteine is only effective in the presence of traces of a metallic compound. I n alkaline solution and in the presence of oxygen the reduced metal formed an oxygen acceptor whilst in the absence of oxygen the oxidised metal can act as an oxygen-donator the cysteine acting as the oxidisable substance.The system is there- fore reversible so long as unoxidised cysteine is present. A. LANGHANS (2. ges. Schiess- u. Sprengstoflw. 1922,17 122-126 131-133 141- 143 150-153 159-162).-The properties of the brown product produced by drying mercury fulminate for prolonged periods (A. 1922 i 328) and the action of dilute and concentrated nitric acid aqua regia sulphuric acid chlorosulphonic acid and hydro- fluoric acid on mercury fulminate are described. Mercury fulminate dissolves readily in boiling sodium sulphite solution. Two forms of crystals are obtained from the solution both having the formula HgSO,,Na,SO,,€I,O. If enough fulminate is added to produce a marked foaming the salt Na2S0,,2HgS03,H20 A Series of Metallo-cysteine Derivatives.S. S. Z. The Decompositions of Mercury Fulminate.i. 98 ABSTRACTS OF CHEMICAL PAPERS. is obtained. When treated with concentrated sodium sulphide solution mercury fulminate gives off a little carbon dioxide and is coloured black owing to formation of mercuric sulphide which dissolves in excess of the sodium sulphide. With yellow ammonium sulphide the black precipitate a t first produced turns red and cinnabak is produced. Wet mercury fulminate is converted into mercuric sulphide ammonium thiocyanate and carbon dioxide by treatment with hydrogen sulphide. Grey mercury fulminate dissolves in sodium thiosulphate giving an almost clear solution but the solution of white fulminate is always opalescent and a greyish- black mass is gradually deposited which however shows no trace of inercury globules under the microscope.The decrease of alkalinity on keeping of a thiosulphate solution in which mercury fulminate has been dissolved is ascribed to the liberation of acid owing to the oxidising action of fulminat'e on the thiosulphate the reaction being analogous to that with mercuric chloride (Na2S,03~2HgC1,+H20=Na2S0,-tHg,Cl,fS+ 2HC1). The change of thiosulphate into sulphate was followed quantitatively by precipitating the latter with barium chloride after various intervals of time had elapsed and the amount of sulphate formed mas found to be directly proportional t o the amount of fulminate added and inversely proportional to the concentration of the thiosulphate.I n using Brownsdon's titration method for estimating mercury fulminate 23 % of the thiosulphate was found to be converted into sulphate ten minutes after the addition of the fulminate. A thiosulphate solution stronger than N/10 is recommended in this determination. The electrolytic determination of mercury in mercury fulminate was successfully carried out using the following solutions potassium cyanide ammonia pyridine warm 10 yo sodium chloride potassium bromide yellow sodium sulphide (10 yo) 2 yo hydrogen peroxide 5% potassium chlorate sodium hypochlorite hypobromite and hypoiodite and ammonium oxalate. The electrolytic deposition of mercury was not quantitative using sodium thiosulphate potass- ium iodide ammonium thiocyanate or sodium picrate.H. C. R. The Salt-like Nature of Sodium Ethyl. Indirect Electro- lysis of Zinc Ethyl. FRANZ HEIN (2. Electrochem. 1922 28 469471).-A solution of sodium ethyl in zinc ethyl is a good conductor of electricity and can be readily electrolysed giving metallic zinc a t the cathode and a niisture of hydrocarbons a t the anode. The gaseous products consist of 82:/ of ethane and ethylene in equal proportions and the remainder contains hydrogen and butane. Their production can be represented by the equation 2C2H5+2 @ - 2C,H - C,H,+C,H,. These experiments prove the salt-llke nature of sodium ethyl and support the view that the solution contains Na' and either C,H,' or Zn(C,H,),' ions. The specific conductivity of a solution of 2 rnols. NaC,H in 3 mols.Zn(C,H,) is 0.01082 mho at 25". Zinc ethyl on the other hand does not conduct the electric current appreciably . W. E. G.ORGANIC CHEMISTRY. i . 99 Is Kekul6’s Benzene Theory Tenable? C. W. A. LELY (Chern. WeekbM 1922 19 593-598).-A triangular formula is put forward for benzene in which the six carbon atoms lying all in one plane are differentiated into three primary and three secondary. The three primary form a chain of three each having two valencies saturated by the other two primaries and two saturated by neighbouring secondaries. The three secondaries have each two valencies saturated by primaries and two by hydrogen atoms the latter lying in planes perpendicular to the plane of the six carbon atoms ; an additional hypothesis of synchronous rotation of the hydrogen atoms or their substituents accounts for the occur- rence of only three isomeric disubstituted benzenes and the absence of optical isomerism.Numerous reactions are cited to support the new formula and the idea is extended to put forward formulze for naphthalene Willstiitter’s cydooctatetraene anthracene etc. s. I. 1,. Specimens of Cymene and Ethylbenzene of Different Origin. K. VON ATJWERS and H. KOLLIGS (Ber. 1922 55 [B] 3872-3879).-1n a previous communication (A. 1922 ii 174) it has been pointed out that the physical constants of hydrocarbons of the benzene series and in particular the refractive indices are frequently dependent on their mode of production. Since par- ticularly marked differences in the various specimens are noticeable in the case of cymene the hydrocarbon has been re-examined and the observations have been extended to ethylbenzene as a simple representative of the series.It is found that the “ cymene ” prepared from toluene isopropyl bromide and aluminium chloride is contrary to the general rule a meta-derivative since it gives isophthalic acid when oxidised. Specimens of p-cymene obtained from p - p-iodoisopropyltoluene cuminol terpinene a-terpineol and p-aa-dichloroisopropyltoluene and oil of Ajowan have closely similar physical constants if the preparation first mentioned (the uniformity of which is somewhat doubtful) is not taken into account. It is remarkable however that p-cymene derived from camphor has a particularly low refrac- tive index; even lower values have been observed by Wheeler (Schimmel and Co.Rep. 1921 105) for a preparation from spruce oil of turpentine. Specimens of ethylbenzene have been examined which are obtained by reduction of freshly prepared styrene by sodium and alcohol of acetophenone by amalgamated zinc and hydrochloric acid by Fittig’s method from bromobenzene and ethyl bromide by Friedel and Crafts’ process from thiophen-free benzene and ethyl bromide and by the action of concentrated hydrochloric acid at 130” on p-ethylbenzenesulphonamide m. p. Pogo repectively. Although all the preparations are to be regarded as “ pure ” in the generally accepted sense of the term they exhibit differences in their physical constants similar to those observed with cymene. The products obtained from styrene or by Clemmemen’s method have higher densities and refractive indices whereas the constantsi.100 ABSTRACTS OF CHEMICAL PAPERS. of all the other specimens agree well among themselves and with the values recorded previously. Since there can be no question of steric influences in the case of ethylbenzene it appears to be established that the differences are due to traces of impurity which cling obstinately to the various specimens. These cannot be detected by elementary analysis. Attempts to use the determination of the heat of combustion as a criterion of purity do not appear to be successful. H. W. Investigations on the Dependence of Rotatory Power on Chemical Constitution. XVII. A New Type of Walden Inversion. HENRY PHILLIPS (T. 1923 123 44-59). Nitration of 3-Chloroacenaphthene.GLADYS FARNELL (T 1923 123 60-61). Studies in the n-Butyl Series. 11. The Four Stereo- isomeric Py-Di-p-tolylamino-n-butanes. GILBERT T. MORGAN and WILFRED JOHN HICKINBOTTOM (T. 1923 123 97-105). The Reduction of Nitriles with Hydrogen in Presence of Nickel. HANS RUPE and KARL GLENZ (Helv. Chim. Acta 1922 5 937-942) .-When optically active valeronitrile was reduced with hydrogen in presence of nickel instead of the expected hexyl- amine the secondary amine dihexylamine was obtained. Reduc- tion of the nitrile with sodium and alcohol readily gave optically active hexylamine. The reaction appears to be general since phenylacetonitrile and P-phenylpropionitrile likewise gave almost entirely secondary amine when reduced with hydrogen and nickel. a-Cyanocamphor did not give the corresponding secondary amine but a base which has not been identified.When o-tolylcarbylamine was used it acted as a poison towards the nickel catalyst and a poor yield of a base was obtained probably methyl-o-toluidine. The dihexylamine obtained from ordinary amyl alcohol through the cyanide had b. p. 109-115"/12 mm.; its hydrochloride C,,H,,NCl forms lustrous leaves; the nitrosoamine is an oil with an aromatic odour giving Liebermann's nitroso-reaction. Di- p- phenylethylamine (C,H,*CH,-CH,),NH from phenylacetonitrile is a viscous oil ; its hydrochloride C,,H,,NCl forms white lustrous leaflets; the nitrosoamine forms white leaflets m. p. 53-54'. Di-7-phenyZprop ylumine NH( CH,*CH,*CH,Ph) gives a hydro- chloride C1,H,NC1 white silky leaflets ; the nitrosoamine crystallises in white felted needles m.p. 55-56'. E. H. R. Phenyltrimethylammonium Perhalides . HAMILTON Mc- COMBIE and THOMAS HAROLD READE (T. 1923 123 141-153). The Thiocarbimide Reaction. SHINTARO KODAMA (Japan. J . Chem. 1922,1,83-93).-An English version of the paper previously published in Japanese (cf. A 1921 i 237). K. K.ORGANIC CHEMISTRY. i. 101 Preparation of Complex Silver Compounds of Aromatic Thiocarbamides. 3'. HOFFMANN-LA ROCHE & Co. (Swiss Pats. 90808 91780 and 91781 ; from Chem. Zentr. 1922 iv 944-945).- Aryl thiocarbamides of the composition Aryl*NH*CS*NE€ the aryl group being substituted or unsubstituted in excess are treated with silver salts such as silver chloride or silver nitrate. The complex silver compounds of the p-hydroxyphenylthiocarbamide of p-thiocarbamidosalicylic acid OH*C,H,*( CO,H)*NH*CS*NH m.p . 221" are thus prepared. The latter compound is prepared from 4-aminosalicylic acid hydrochloride and ammoniuin thiocyanate. The complex silver compound of 6-amino-3-thiocarbumido-10- methylacridine (from 3 6-diamino- 10-methylacridinium chloride) is also mentioned. L. MASCARELLI (Atti R. Accud. Lincei 1922 [v] 31 ii 116--118).-Since the molecule of o-methylcyclohexanol contains two asymmetric carbon atoms having unequal rotatory values four optically active and two racemic forms of this compound should exist. The compounds obtained by Godchot and Bddos (A. 1922 i 334) and by Sabatier and Mailhe (A. 1905 i 275) probably represent the two racemides. The cycloheptylcycloheptanol prepared by Godchot and Brun (A. 1922 i 350) should exhibit similar optical isomerism to o-methyl- cyclohexanol. An analogous case is presented by the two modi- fications of decahydro-p-naphthol (cf.Mascarelli A. 1911 i 964 ; Mascarelli and Recusani A. 1912 i 761). The Oxide of Methyl-A3-cycZohexene and the Dimethyl- cyclohexanols. MARCEL GODCHOT and PIERRE BBDOS (Compt. rend. 1922 175 1411-1414).-1t has previously been shown (A. 1922 i 334) that the action of organomagnesium complexes on the oxide of cyclohevene gives ortho-substituted homologues of cyclo- hexanol and that the latter compounds are stereoisomerides of the secondary alcohols obtained by the catalytic hydrogenation of the corresponding phenols. It is now shown that in a similar manner methyl-A3-cyclohexene gives a dimethylcyclohexanol different from those obtained by the catalytic hydrogenation of the xylenols. Methyl-A3-cyclohexene oxide b.p 141-142' (corr.) d14 0.949 ng 1.4518 is obtained from methyl-A3-cyclohexene either by the action of iodine and yellow mercuric oxide followed by the action of solid potassium hydroxide on the product in ethereal solution or by oxidation with perbenzoic acid. When heated with water at 130" for six hours it is hydrated giving 1-methykyclohexan-3 4-dio1 in. p. 60° b. p. 112-115" which gives a diphenylurethane m. p. 176-177". The oxide described above reacts with magnesium methyl iodide to yield an alcohol b. p. 173-174" (corr.) which is probably a 1 4-dimethylcyclohexan-2-01. It has dls 0.9106 ng 1.452.It does not give a phenylurethane and on oxidation yields a dimethyl- cyclohexanone b. p. 171" (corr.) &lo 0.9044 ni; 1.4427 which gives a semicarbaxone m. p. 122". These physical constants are different from those of similar compounds obtained from 1 3 4- and G. W. R. The T w o Forms of o-Methylcyczohexanol. T. H. P.i. 102 ABSTRACTS OF CHEMICAL PAPERS. 1 4 2-xylenol by catalytic hydrogenation and subsequent oxid- ation. W. G. Catdytie Hydrogenation of Liquids by means of the Com- mon Metds. VII. Phenols. A N D R ~ BROCHET (Bull. SOC. chim. 1922 [iv] 31 1270-1280).-The effect of temperature and pressure on the catalytic hydrogenation of phenols in presence of a reduced nickel catalyst was studied. With pheno1 itself the absorption of hydrogen commences a t about 50" a t atmospheric pressure and the velocity of the reaction increases rapidly as the temperature is raised to 150".To obtain complete hydrogenation to cyclohexanol within a reasonable time it is necessary to use pressure however and a t 20 atmospheres and temperatures of 200-230" the absorption of 6 atoms of hydrogen per mol. was complete within an hour. For the preparation of pure cyclo- hexanol pressures of 10-20 atmospheres and a temperature of about 150" constitute good practical working conditions and if an apparatus is employed in which the catalyst can be filtered from the hydrogenised product and used again with fresh phenol it is possible completely to reduce 150 g. of the latter per 1 g. of catalyst without any appreciable loss in activity.The cyclo- hexanol obtained boiled a t 160*5"/760 mm. d:5=0.950. The cresols are not hydrogenated appreciably below loo" but a t 150" absorption proceeds with the same facility as with phenol and by using pressures of 10-20 atmospheres reduction to the correspond- ing methyl cyclohexanols was readily achieved. o-Methylcyclo- hexanol boils a t 163-164" m-inethylcyclohexanol a t 170-171" and p-methylcyclohexanol a t 170-171". G. 3'. M. Catalytic Hydrogenation under Pressure in the Presence of Nickel Salts. 111. Phenetidine. JULIUS VON BRATJN and ERICH HAEX (Ber. 1922 55 [B] 3770-3779).-Under the con- ditions adopted by the authors phenetidine can be hydrogenated without loss of the ethoxyl groups; the main product appears to be a mixture of stereoisomeric 4 4'-diethoxydicyclohexylamines OEt.C,H,*NH*C sH,o* OEt . The hydrogenation of phenetidine is effected a t 210-230" in the presence of tetrahydronaphthalene ; the absorption of the gas occurs somewhat slowly and the relative amounts of the various products appear to be considerably affected by unknown catalytic influences. About a quarter of the phenetidine used is converted into a product b. p. 208-216"/16 mni. which can be separated by means of light petroleum into two isomeric 4-ethoxyphenyl-4'- ethoxycyclohexylamines m. p. 78-79" and 37-38" respectively. The isomeride of higher melting point is produced in relatively very small amount so that it has not been possible to make a complete investigation of it. It yields a non-crystalline hydro- chloride picra,te and picrolonate a crystalline quaternary rnethiodide m.p. 156" and an acetyl derivative colourless crystals m. p. 84". The variety of lower melting point yields a non-crystalline hydro- chloride picrate and picrolonate an acetgl compound m. p. 4 2 4 3 " ,ORGANIC CHEMISTRY. i. 103 b. p. %35-240"/18 mm. a nitroso-derivative in. p. 'is" and a very hygroscopic quaternary methiodide (the corresponding methochloride is hygroscopic but yields a well-defined chloroplatinate a rnicro- crystalline orange-red powder). Fission of the quaternary am- monium hydroxide is effected very readily and gives 4-ethoxy-Al- cyclohexene a mobile liquid b. p. 158-160" (which is converted by fuming hydrobromic acid into truns-1 4-dibromocyclohexane m. p. 113") dimethylphenetidine m.p. 35-36" (picrate m. p. l42') and the tertiary base C1,H,,O,N ni. p. 40" which gives a non- crystalline hydrochloride picrate and picrolonatc. 4- Ethoxyphenyl-4'-ethoxycyclohexyZamine is readily hydrolysed by concentrated hydrochloric acid a t the temperature of boiling water the ethoxyl group attached to the cyclohexyl nucleus being first affected . 0H.C ,HIo*NH*C,H4*OEt crystallises in colourless leaflets m. p. 84-85' (di-p-nitrobemoyl derivative m. p. 192"); it loses water when distilled under diminished pressure giving p-ethoxyphenylcyclohexenyhmine OEtbC6H4*NH-C6H? a viscous pale yellow liquid which could not be caused to solidify and has not been investigated further. 4-Hydroxyphen yl-4'- h ydroxycyclohexylamine has m. p 136-1 3'7 O. 4 - E t hox yphen y 1 - 4'-hgd rox y c y clo hex y lme thy lamin e 0Et.C ,H,*NMe*C ,H OH 112.p. 72" yields a p-nitrobenxoyl compound a pale yellow crystal- line powder m. p. 189". The residues left after the distillation of 4 4'-diethox-yphenyl- 4- Ethoxyphenyl-4'-hydroxycyclo hexy Zarnine cyclohexylamine yield a substance C20H2802N2 colourless "&ystds m. p. 169-170"; it yields a di- OEt OEt OEt OEt hgdrochloride decomp. 290" a di- /\ /\ ' \ nitroso-derivative C,,H2,0,N pale [I )-I 11 I 1' ( 11 yellow crystals m. p. 190° and \N/HE>iEt'\<i>dHEt a di-acetyl compound m. p. 240". ,... . .- . One of the annexed formula is (1.1 (11.) suggested. H. W. Investigations on the Dependence of Rotatory Power on Chemical Constitution. XVIII. The Di-Z-menthyl Esters of the Saturated Dicarboxylic Acids.LESLIE HALL (T. 1923 123 105-113). Catalytic Hydrogenation under Pressure in the Presence of Nickel Salts. 11. Hexahydrodiphenylene Oxide from 2 2'-Dihydroxydiphenyl. JULIUS VON BRAUN (Ber. 1922 55 [B] 3761-3770).-The catalytic reduction of 2 2'-dihydroxy- diphenyl follows a somewhat unexpected course which leads to the complete hydrogenation of one nucleus and the formation of the oxide ring. The latter is extraordinarily stable towards further reduction but readily undergoes fission when treated with oxidising agents. Hexuhydrodiphenylene oxide ?GH4->0 a colourless liquid b. p. C6HlOi. 104 ABSTRACTS OF CHEMICAL PAPEFUS. 138-141"/100 mm. is conveniently prepared by treating 2 2'- dihydroxydiphenyl at 230" with four atomic proportions of hydrogen and subsequent fractional distillation of the product.It is in- merent towards sodium and alcohol zinc and acetic acid or magnesium phenyl bromide. It reacts slowly with bromine but does not yield a crystalline product. Warm concentrated sulphuric acid converts it into a monosulphonic acid the sodium salt of which is described. It is converted by cautious nitration with nitric acid (d 1.4) and glacial acetic acid a t -15" 'N into nitrohexahydrodiphenylene oxide (annexed formula) ) m. p. 126" which is reduced by stannous chloride \/\ and concentrated hydrochloric acid to aminohexa- I hydrodiphenylene oxide pale yellow leaflets m. p. 56" /\/ (hydrochloride colourless needles decomp. 250" after m. p. 186"; acetyl derivative m. p. 123"). , I I darkening at 225" and softening a t 235"; picrate Hexah ydrodiphenylene oxide readily becomes resirdied under the conditions of the griedel-Crafts' synthesis but under definite conditions it can be converted into the corresponding methyl ketone (annexed formula) colourless crystals,m. p.67-68". The oxime of the latter m. p. 167' is reduced by sodium and alcohol to aminoethylhexahydro- \ /\ diphenylene oxide a colourless liquid which rapidly I (I absorbs atmospheric carbon dioxide b. p. 210- /'/ 213"/16 mm. (hydrochloride m. p. 267-268" after I 1 darkening a t 264"; chloroplatinate decomp. 200" \/ after gradual darkening ; picrate decomp. 250" after darkening at 240"). It is remarkable that the oxide ring is not ruptured during the reduction. With oxalyl chloride hexahydrodiphenylene oxide gives the acid C02H*%H3->~ colour- less crystals m.p. 250" after softening a t 240" in very poor yield. Hexahydrodiphenylene oxide is readily oxidised by chromic acid in glacial acetic acid to 6-o-hydroxybenzoylvaleric acid OH*C6H,*CO* [ CH2],*C02H long colourless needles m. p. 94" b. p. 240-242"/12 mm. (oxime m. p. 128"; semimrbaxone m. p. 186"; phenylhydrazone yellow leaflets m. p. 173'; benzoyl derivative m. p. 82"). The acid is slowly converted by methyl iodide and alkali in methyl-alcoholic solution into the methoxy-acid OMe*C6H,*CO*[CH,],*C02H m. p. 82" (semicurbaxme m. p. 175-176" ; methyl ester prismatic needles m. p. 28'). 6-o-Hydroxybenzoylvaleric acid is smoothly converted by isatin into 2-o-hydroxyphenyl-3-propylpuinoline-y 4-dimrboxylic acid C,H4< c ~ c 0 ~ H ) ~ ~ * ~ c H ~ ~ 3 ' c 0 ~ H m.p. 295" (decomp.). Molten N=C *C sH,* OH sodium hydroxide rapidly transforms 6-o-hydroxybenzoylvaleric acid into phenol and adipic acid. Nitrohexahydrodiphenylene oxide is oxidised by chromic acid to 8-m-nitro-o-hydroxybenxoylvaleric acid small yellow needles m. p. 116" which does not appear to be readily obtainable by mtration of the parent acid. coYe~>' C6H10 H. W.ORGANIC CHEMISTRY. i. 105 Elimination of the Amino-group of Tertiary Amino- alcohols. I. ALEX. MCKENZIE and ANGUS CAMPBELL RICHARD- SON (T. 1923 123 79-91). Catalytic Hydrogenation of Liquids by means of the Com- mon Metals. VIII. Naphthols. A. BROCHET and R. CORNU- BERT (Bull. Xoc. chim. 1922 [iv] 31 1280-1285).-By the hydro- genation of a- and p-naphthols under pressure using a reduced nickel catalyst both the ac- and ar-tetrahydronaphthols are obtained in each case.The hydrogenation of a-naphthol a t 130" gives a mixture of 85% of ac-tetrahydro-a-naphthol and 15% ar-tetra- hydro-a-nuphthol the former boiling at 139-140"/17 mm. (corr.) and having d;' 1.0896 ng 1.5671 R 44.37 showing an exaltation+0*27. It is a thick liquid becoming brown on prolonged contact with air. The phenylurethane melts a t 121". ar-Tetrahydro-a-naphthol is a solid m. p. 68" (corr.). Hydrogenation of fi-naphthol a t 150" gives 75% of the alicylic tetrahydro-derivative and 25% of the phenolic derivative. ac-Tetrahydro- p-naphthol is a viscous liquid which darkens on contact with air and on keeping. It boils a t 1445- 145*6"/20 mm.(corr.) G7 1.0715 mg 1.5523 R 44-16 showing exaltation+0.06. The phenylurethune melts at 99". ar-Tetrahydro- /%naphthol is a solid m. p. 57.5". Benzo-polymethylene Compounds. 11. Hydroxy-bases and P-Ketones of the Tetrahydronaphthalene and Hydrindene Series. JULIUS VON BRAUN OTTO BRAUKSDORF and GEORG KIRSCHBAUM (Bey. 1922 55 [B] 36484663) .-The bromine atom of ac-2-bromo - 1 -hydroxy (alkyloxy) tetrahydronaphthalenes (A 1921 i 407) can be replaced readily by basic residues. The hydroxy-bases formed in this manner differ greatly from ac-p-amino- tetrahydronaphthalene and its alkyl derivatives since they are relatively non-toxic and have a more or less marked antipyretic character whereas the corresponding alkyloxy-compounds are strongly poisonous. The constitution of the latter substances is established by the mode of production but in the case of the hydroxy-compounds the possibility that the hydroxyl group may occupy position 2 is not defiiritely excluded (cf.Straus and Rohr- backer A. 1921 i 171); comparative experiments on the fission of piperidino-derivatives by cyanogen bromide indicate that this is not the case and that the striking difference in physiological properties is therefore attributable solely to the replacement of the hydroxyl by the alkyloxyl group. The following alkyloxy-bases are described 2-Dimethyhmino- CH(OEt)*yH*NMe b. p. 1 - et hox yt etrahydromp hthalene C 6H4<CH CH 152"/13 mm. and its oily hydrochloride picrate m. p. 199" and methiodide m. p. 166" ; p-piperidino- 1 -ethxytetrahydronuphthalene an almost colourless liquid b.p. 170-172"/10 mm. ; 2-diethylamino- 1 -all yloxyt etrah ydronuphthulene b . p . 1 65 " / 10 mm . ac- 1 -Aminotetrahydronaphthalene is readily prepared by the reduction of 1 -oximinotetrahydronaphthalene with sodium and G. F. M.i. 106 ABSTRACTS OF CHEMICAL PAPERS. alcohol and is converted by ac-dibromopentane in boiling alcoholic solution into ac-1-piperidinotetrahydronaphthlene a colourless liquid b. p. 1'74-176"/17 mm. The hydrochloride hydrobromide and methiodide could not be caused to crystallise; the chloro- platinate is amorphous whereas the picrate crystallises in dark yellow needles m. p. 145-146" after softening a t 140". ac-2- Piperidinotetrahydronaphthlene is a colourless odourless liquid b.p. 186-187"/16 mm. (hydrochloride m. p. 230-231"; hydro- Iwonzide m. p. 233-234"; methiodide m. p. 209"; picrate m. p. 203-204"). Both piperidino-compounds suffer fission under the influence of cyanogen bromide but the production of bromotetra- hydronaphthalene is much more marked with the 1- than with the 2-derivative. 2-Piperidino- 1 -hydroxytetrahydronaphthalene (cf. Straus and Rohrbacker loc. cit.) has b. p. 192-194"/14 mm. m. p. 75-76' (hydrochloride m. p. 185-186"; picrate m. p. i 52" ; chloroplatinate m. p. 192"). 2-Piperidino-1-benzoyloxy- tetrahydronaphthalene is acted on by cyanogen bromide giving cyanopiperidine in a yield which points to the presence of the basic group in the 2- rather than in the 1-position. ac-2 - Amino- 1 -hydroxytetrahydrompht~lene m .p . 109 " b . p . l6Oo/ll mm. is prepared by the action of concentrated ammonia solution on the corresponding bromo-compound. The hydro- chloride m. p. 227"; chloropkltinute m. p. 215"; picrate yellow leaflets m. p. 192" ; phenylthiocarbamide m. p. 134" ; benxylidene derivative m. p. 115"; salicylidene derivative m. p. 108"; acetyl derivative m. p. 203" ; p-nitrobenxoyl deriva'tive m. .p. 228" ; p-aminobenxoyl derivative m. p. 208" and the hydrochlorzde of the latter m. p. 239" are described. When the base is warmed with an equivalent quantity of ethylene oxide in chloroform solution it is converted into 2 - p - hydroxyethylamino- 1 - hydroxytetrahydronuph- thlene C6H4<CH,-CH a very viscous liquid b. p. 190-196"/vacuum ; the corresponding hydrochlcy-ide has m.p. 155". 2-Benxylamino-1-hydroxytetrahydronaphthalene is a colourless viscous liquid b. p. 243-246"/13 mm. (picrate m. p. 192" ; hydrochloride m. p. 237"). 2-Nortropyl-1-hydroxytetrahydro- naphthulene b. p. 210-212"/14 mm. yields a picrate m. p. 174" and an extremely hygroscopic hydrochloride. 2-Dimethylamino- 1-hydroxytetrahydronaphthalene m. p. 40" (cf. Straus and Rohr- backer loc. cit.) yields a picrate m. p. 138" and a methiodide m. p. 138-139"; the benzoate and acetate and its salts show little tendency towards crystallisation. The p-nitrobenxoate and p-arnino- benzoate have m. p. 112" and 137" respectively. 2-Methylamino- 1-hydroxytetrahydronaphthalene picrate has m. p. 1'72". 2-Diethyl- amino-1 -1iydroxytetrahydronaphthalene gives a crystalline chZoro- platinate m.p. 192" and a liquid acetate. If the methiodide of 2 - dimethylamino- 1 - hydroxytetrahydro - naphthalene is treated with silver oxide and the solution thus obtained is heated tetrahydronaphthalene oxide is produced. When the iodide is heated alone at a temperature very slightly above its melting point i t is decomposed into trimethylarnine CH( OH)*yH*NH*CH,*CH,*OHORGANIC CHEMISTRY. i. 107 hydrochloride and 2-ketotetrahydronaphthalene b. p. 140"/20 mm. 130"/10 mm. di6'9 1-1055 (semicurbaxone m.. p. 190-191") the yield being 80-85% of that theoretically possible. The behaviour of the ketone does not appear to be well expressed in the formula C6H4<CH,.CH,. which does not explain the formation of an intense blue colour under the influence of air and alkali the difficulty with which it forms additive compounds and the apparent absence of an activated methylene group.The application of hard's reaction to tetrahydronaphthalene gives a mixture of the 1- and 2 -ketones. CH2-70 ac-2 - Dimet hyhmino- 1 - hydroxyhydrinden e C H < ~ ~ ~ ~ 1 > O H * N M e 2 a colourless crystalline subsiance which rapidly darkens when exposed to air b. p. 153-156"/9 mm. m. p. 62" gives a hydro- chbride m. p. 183-184" a picrate m. p. 145" and a methiodide m. p. 161-162". The latter substance is decomposed when dis- tilled under diminished pressure into trimethylamine hydriodide and P-ketohydrindene; the conditions of the change are more drastic and the yield of ketone is smaller than with the corresponding tetrahydronaphthalene derivative.H. W. Benzo-polyrnethylene Compounds. VII. Pharmaco- logical Analogues of ac-2-Aminotetrahydronaphthalene. JULIUS VON BRAUN HEINRICH GRUBER and GEORG KIRSCHBAUM (Ber. 1922 55 [B] 36364-3674).-Substances which contain an aliphatic amino-group in the P-position with respect to an aromatic nucleus have the property of causing an increase in the blood pressure. In addition to this property ac-2-aminotetrahydro- naphthalene has also a mydriatic action and causes a marked increase in the body temperature. The effects obviously depend on the simultaneous presence of an aromatic and a hydroaromatic ring. The examination of a number of analogous compounds has shown that similar physiological properties are exhibited by sub- stances which contain an aliphatic amino-group in the P-position to the aromatic portion of the tetrahydronaphthalene complex ; if this condition is fulfilled the further mode of attachment is immaterial.The catalytic reduction of o-hydroxydiphenyl with hydrogen under pressure a t 210-220" in the presence of nickel salts to 2-phenylcycZohexano1 is attended with considerable experimental difficulties since the completion of the reaction is not marked by any abrupt change in the rate of absorption of the gas. The products obtained when the action is continued to the almost complete cessation of absorption are dicyclohexyZ b. p. 103- 105'/12 mm. and 2-cycZohexylcycZohexano1 b. p. 134-135"/12 mm. which is probably a mixture of cis- and trans-isomerides (cf. Wallach A. 1911 i 473). The latter substance is oxidised by chromic acid to 2-cyclohexyZcyclohexano~ze b.p. 128-130"/10. mm. (benzylidene compound m. p. 100"; semicarbazone rn. p.i. 108 ABSTRACTS OF CHEMICAL PAPERS. above 200"). Less complete reduction of o-hydroxydiphenyl gives a mixture of phenylcyclohexane dicyclohexyl 2-phenylcycZohexano1 and 2-cyclohexylcycbhexanol. The alcohols are nearly exclusively produced when only six atomic proportions of hydrogen are used but they cannot be separated conveniently from one another. Oxidation of the mixture with chromic acid gives the corresponding ketones from which 2-phenylcycZohexanone is isolated partly in substance and partly as the oxime slender needles m. p. 1 7 6 1 7 5 " ; 2-phenylcyclohexanonesemicarbaxone has m. p. 193". 2-Phenyl- cyclohexanol prepared by the reduction of the pure ketone with sodium and alcohol has b.p. 143-144"/11 mm. m. p. 5 6 - 5 5 " and yields a phenylzrrethane m. p. 138-139'. 2-PhenylcycZo- hexanoiieoxime is reduced smoothly by sodium and alcohol to 2-phenylcyclohexyZamine b. p. 133-134"/12 mm. m p. 59-60'. The hydrochloride m. p. 253" chloroplatinate reddish-yellow needles decornp. 222" ncetyl derivative m. p. 130" phenylthiocarbamide m. p. 185" and methiodide m. p. 235" are described. The base causes an increase in the blood pressure; but is not otherwise similar to ac-2-aminotetrahydronaphthaleneY probably for the reason that the association of the aromatic and hydroaromatic nucleus is not sufficiently close. ac- l-Aminomethyltetrahydronaphthalene is obtained in 20% yield by -the reduction- of a-naphthonitrile ; the hydrochloride m.p. 230" picrate m. p. 170" and benzoyl deriv- ative m. p. 125-126" are described. The following process does not give the base in better yield. a-Ketotetrahydronaphthalene is condensed with zinc and ethyl bromoacetate to form the unsatur- ated ester b. p. 183-184"/16 mm. which appears to have the double bond in the nucleus as shown bv the formula It is readily hydrolysed t o the ckesponding a&d colourless needles rn. p. lOO" which is slowly hydrogenated in the presence of palladium chloride to 1-tetrahydronaphthylacetic acid m. p. 35-36'. The latter is convertible through the amide but in small yield into ac- 1 -aminomethyltetrahydronaphthaIene. The physiological properties of the base are similar to but weakerthan those of ac-2-aminotetrahydronaphthalene.ar- 1 -BenzoylaminomethyltetrahydronaphthaIene is converted by phosphorus pentachloride into ar- 1 -chZoromethyltetrahgdronaphthal- ene b. p. 144-145"/13 mm. m. p. 50-51". (ar-2-ChZoromethyZ- tetrahydronaphthalene has b. p. 141-142"/12 mm. but does not solidify when cooled.) It is converted smoothly by potassium cyanide in aqueous alcoholic solution into ar- 1 -cyanomethyltetra- hydronaphthlene colourless needles m. p. '\/\ 69-70' b. p. 168-169"/10 mm. The latter 1 is reduced by sodium and alcohol to ar- >'\/ l- P-aminoethyZtetrahydronaphthulene (annexed NH,*CH,*CH formula) a colourless somewhat viscous ItORGANTC CHEMISTRY. i. 109 liquid b. p. 146-149"/16 mm. The corresponding hydrochloride m.p. 245" (decomp.) picrate small leaflets m. p. 231" and benxoyl derivative m. p. 123" are described. Physiologically the base closely resembles ac-2-aminotetrahydronaphthalene. H. W. P. FRIED- UNDER and A. SIMON (Ber. 1922 55 [B] 3969-39SO).-An- thracene is readily converted by sulphur chloride into 9-anthryl dithiochloride C,,H,*S,*Cl yellowish-red lustrous crystals m. p. 117-118" (decomp.) when rapidly heated; it reacts readily with ammonia and aromatic bases but only gives resinous products. With dimethylamine it gives the compound C,4H,=S,-NMe yellow prisms m. p. 70-71" ; the corresponding piperidide is described. A solution of anthryl dithiochloride in benzene is converted by a concentrated solution of sodium sulphite a t the atmospheric tem- perature into sodium 9-anthryl thiosulphate C,,H,*S*SO,Na pale yellow leaflets ; the corresponding barium salt is intensely yellow but appears to yield a colourless hydrate.9-Anthryl hydrogen thiosulphute C,,H,*S*SO,H crystallises in slender colourless needles; it decomposes slowly in warm aqueous solution rapidly in the presence of hydrochloric acid into sulphuric acid and 9-anthryl disulphide lustrous orange-yellow octahedra m. p. 223" (see later) ; this compound (in addition to thiosulphate) is also produced when a solution of the sodium salt is warmed with sodium hydr- oxide. 9-ThioZanthrucene orange-yellow octahedra m. p. 90-91" is most conveniently prepared by the action of anthryl dithiochloride on a solution of hydrated sodium sulphide in methyl alcohol; the corresponding sodium salt forms orange-yellow leaflets and the methyl ether needles m.p. 153". The thiol is the sulphur analogue of anthranol (Meyer A 1911 i 193) but unlike this compound it exhibits little tendency to pass into a substance of the anthrone type. 9-Anthryl disulphide (see above) is obtained quantitatively by the oxidation of an alkaline solution of the thiol with potassium ferricyanide. 9-Anthrylthiohcetic acid Ci,HS*S*CH,*CO,H slender very pale yellow needles m. p. 164" is prepared by the addition of the sodium compound of 9-thiolanthracene to an alkaline solution of sodium chloroacetate ; the sodium salt lustrous leaflets am- monium salt and the methyl ester small yellow needles m. p. 67" are described. The acid is converted by phos- CH phorus pentachloride in the presence of light petrol- /\ eum (but less conveniently by thionyl chloride 7 90 which also causes chlorination) into 9-anthrylthiol- ,/\ ,/\/\ acetyl chloride compact yellow needles from which I I I I the corresponding amide colourless needles which \/\/\/ soften but do not melt a t 197" is prepared.The chloride is converted by aluminium chloride in the presence of light petroleum at 30-40" into 3-keto-peri-anthra- cenopenthiophen (annexed formula) sma11 tile-red crystals m. p. 150-152". The substance is transformed by hot nitrobenzene into The Action of Sulphur Chloride on Anthracene. bis-peri-anthracenope?zth~op~e?z C,,H8<&>C:C<&>C,,H darki . 110 ABSTRACTS OF CHEMICAL PAPERS. green needles and condenses with a-isatinanilide in the presence of yyridine to give 3'-indoxyl-(2 2')-peri-anthracenopenthiophen C,,R,<~,>C:C<~~>C,H dark coloured needles.Investigations on the Dependence of Rotatory Power on Chemical Constitution. XV. Some n-Alkyl Ethers of d- Benzylmethylcarbinol. HENRY PHILLIPS (T. 1923 123 22- 31). X. spim-Compounds Derived from cycloHeptane. JOHN WILLIAM BAKER and CHRISTOPHER KELK INGOLD (T. 1923 123 Preparation of Esters. LABORATOIRE-USIRE (F.P. 531960 ; from Chern. Zentr. 1922 ivy 943).-Alkyl carboxylates are heated with aluminium derivatives of alcohols. The reaction takes place according to the equabion 3R*CO2R'+A1( OR"),=3R*C0,Rf'+ &(OR') where R" has a higher molecular weight than R'. The aluminium alkyloxides are prepared by heating the corresponding alcohols with aluminium amalgam or other easily decomposed aluminium alloys.For example aluminium amyl oxide and ethyl acetate give amyl acetate. Amy1 phenylacetate a-phenylethyl acetate p-phenylethyl phen ylacetute and linalyl acetate are similarly prepared. G. W. R. L. G. RADCLIFFE and W. H. BRINDLEY (Perf. Essent. Oil Rec. 1922 13 414415).-Anisic acid was obtained in almost theoretical yield by the oxidation of anis- aldehyde with alkaline permanganate. Cannizzaro's method- treatment of the aldehyde with potassium hydroxide-proved unsatisfactory large amounts of unchanged material being recovered. The following esters were prepared by saturating solutions in the respective alcohols with dry hydrogen chloride. Methyl ester m. p. 48" b. p. 256".Ethyl ester m. p. 7-So b. p. 263" d:66 1.106 n1u9'5 1.5245. n-Propyl ester b. p. 176"/15 mm. d:6'.i 1.09 nl,s'5 1-5149. n-Butyl ester b. p. 183"/40 mm. di6'5 1.054 ~2;'~ 1.5141. isoButyl ester b. p. 170"/46 mm. di6'5 1,052 1.5072. isoAmyl ester b. p. 188"/30 mm. CZ:'~ 1.040. Phenylpropylester b. p. 256"/35 mm. d:";" 1.111 nK5 1.5623. Only the lower members of the aliphatic series have pronounced odours the higher members are practically odourless. G. F. M. Preparation of Alkyl Dihydroxynaphthoylbenzoates. 91106 and 91107; from Chem. Zentr. 1922 iv 890).-1 5- or 1 6-Dihydroxynaphthoyl-o-benzoic acid is esterified in the usual way with aliphatic alcohols. Ally1 1 6-dihydroxynaphthoyl-o- benzoate forms white prismatic needles ni. p. 128". Ethyl 1 ti- dihydroxymphthoyl-o- benzoate forms slightly yellow crystals in.p. 156". Ethyl 1 5-dihydroxynaphthoyl-o-benzoate forms white needles m. p. 146". G . W. R. H. W. The Formation and Stability of spiw-Compounds. 122-133). Some Esters of Anisic Acid. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (swiss Pats. 90806,ORGANIC CHEMISTRY. i. 111 The Degradation of Hydroaromatic Acids of the Glutaric Acid Series. A. WINDAUS F. KLANHARDT and G. REVEREY (Ber. 1922 55 [B] 3981-3987).-1n a previous communication (Windaus and Klanhardt A. 1921 i 392) it has been shown that the silver salts of the aliphatic glutaric acids react with iodine in accordance with the schemes C0,Ag*[CH,]3*C0,Ag+12=2AgI+ -OGO*[CH,],*CO*O- and -O*CO-[CH,],-CO=O- -+ (a) ~O*[CH,],-CO+O or ( b ) ~O*LCH,],-CH,+CO or (c) CH,:CHMe+ BCO,.The observations have now been extended to acids which may bo regarded as glutaric acids of which one or more carbon atoms are members of a hydroaromatic ring. The action is found to occur normally in the case of the cis-acids unless the glutaric acid substitutes a five-membered ring in the 1 3-position. Silver cyclohexanediacetate is converted by iodine into the _- - 0- -1 - o--' Zuctone CH,< CH2*CH2>~<CH2Y it colourless viscous liquid CH,*CH CH,*COy b. p. 273"/759 Gm. (slight de:omp.) 154"/16 mm. di!:! 1.0755 nz 1.48386 n 1.48668 n; 1.48631. The barium and silver salts of the corresponding hydroxy-acid have been prepared. The lactone is oxidised by alkaline permanganate or by potassium dichromate and sulphuric acid to cyclohexane-1 -acetic-1 -carboxylic v acid CH,<CH,.CH CH2'CH2>C(C02H)*CH2*C02€€ colourless prisms m.p. 131" (uncorr.) [Gf. NOOrris and Thorpe T. 1921,119 12061. Silver cis-hexahydrohomophthalate is readily converted by iodine into hexahydrophthulide FH2*CH2*YH*CH~ 0 a colourless liquid b. p. 134-138"/25 mm. the constitution of which is estab- lished by its oxidation with potassium dichromate and sulphuric acid to cis-hexahydrophthalic acid; the same lactone is obtained in smaller yield and with greater difficulty from silver truns- hexahydrohomophthalate. isoPhthalic acid is hydrogenated in glacial acetic acid solution to a mixture of cis- and truns-hexahydroisophthalic acids in which the former preponderates the more considerably when the reduction proceeds rapidly; the cis-acid however is not converted into the trans-variety if subsequently agitated with glacial acetic acid and platinum black.Silver cis-hexahydroisophthalate and iodine give the lactone of cis-cyclohexanol-3-carboxylic acid b. p. 127- 135O/2l mm. (cf. Perkin and Tattersall T. 1907 91 488) the identity of which is established by converting it into cis-cyclo- hexanol-3-carboxylic acid m. p. 132-133" and cis-3-bromocycb- hexanecarboxylic acid m. p. 61-63". Silver camphorate is transformed by iodine into camphorio anhydride; a neutral lactone does not appear to be produced. CH,*CH,*CH*CO H. w. The- Chemistry - of the Glutaconic Acids. XIII. The JOCELYN FIELD THORPE Isomerism due to Retarded Mobility. and ARTHUR SAMUEL WOOD (T. 1923 123 62-64).i. 112 ABSTRACTS OF CHEMICAL PAPERS.a-Benzyl-P-methylglutaconic Acids. PRANZ PEIST and ED. RATJTERBERG (Ber. 1922 55 [B] 3697-3705).-In extension of previous investigations (A. 1922 i 521 522 553) the authors have examined the ozonisation of a substituted glutaconic acid which might be expected to yield stable fission products and for this purpose have selected a-benzyl- @-methylglutaconic acid (cf. Bland and Thorpe T. 1912 101 1740). It is shown that the (normal) acid of higher melting point and its esters and also the esters of the labile acid are constituted in accordance with the annexed formula (I) whereas the labile acid appears to be a mixture of the two trans-forms (I1 and 111). The complex nature of the CH2Ph*R* C0,H CH,Ph*E*CO,H CH,Ph*CH (CO,H)*$Me Me*C* CH *CO ,H CO,H* CH,*C*Me H*C*CO,H (1.1 (11.1 (I11 .) latter product explains its low melting point as compared with that of the homogeneous cis-acid.cis- a-Benzyl- P-methylglutaconic acid gives an oxonide which is hydrolysed to phenylpyruvic acid m. p. 153-154" [oxime m. p. 159" phenylhydraxone m. p. 187-188" (decomp.)] acetone and carbon dioxide. The ozonide of its ethyl ester similarly yields ethyl benzylglyoxylate and ethyl acetoacetate. trans-a-Benzyl- @-methyl- glutaconic acid is converted successively into its ozonide and acetic acid phenylethyl methyl ketone and benzoic acid ; the formation of oxalic and glyoxylic acids could not be established. The oxonide of ethyl trans-a-benzyl- @-methylglutaconate is hydrolysed to acetic acid ethyl acetoacetate ( ?) ethyl phenylpyruvate and benzoic acid.Ethyl phenylpyruvate is converted into a diphenylhydraxone CH,Ph*C( :N*NPh,)*CO,Et small yellow crystals m. p. 105" and a p-nitrophenylhydrazone pale yellow crystals m. p. 181". Ring-chain Tautomerism. IV. The Effect of the Methyl Ethyl Grouping on the Carbon Tetrahedral Angle. BALBIR SINGH and JOCELYN FIELD THORPE (T. 1923 123 113-122). M. GOMBERG and D. L. TABERN ( J . Id. Eng. Chem. 1922 14 1115-1117).-Pure tetraiodo- fluorescein was prepared by direct halogenation of fluorescein in hot dilute acetic acid with excess of iodine and subsequent puri- fication by washing with dilute sulphuric acid and alcohol and precipitation from solution in dilute sodium hydroxide. This product did not contain free iodine but was amorphous and the iodine content was low owing to the presence of about 6% of di- iodofluorescein from which it was purified by conversion by boiling with acetic anhydride into the diacetate which after three recrystallisations from bromobenzene alternated with acetone was obtained analytically pure and melting a t 293-294".Hydrolysis of the acetate gave pure crystalline tetraiodofluorescein. This was converted into erythrosin by neutralisation with sodium carbonate in suspension in absolute alcohol. The salt was deposited in red H. W. Composition of E+ythrosin.ORGANIC CHEMISTRY. i. 113 crystals after concentration of the solution and addition of ether. It contained both water and alcohol of crystallisation and the former was not completely expelled even by long d r p g at 160- 170".The fully hydrated salt contains 4H20 and the conclusion seems justified that the true composition of erythrosin is C&,O5I4Na2,H20 and that it is almost impossible to dehydrate it beyond this point without risk of decomposition. G. F. M. The Semi-pinacolinic Transformation of Alkylhydro- benzoins Influence of the Alkyl Groups. MARC TIFFENEAU and ALEX. OR~KHOFF (Compt. rend. 1922 175 964-967; cf. Meerwein A 1920 i 2 ; Orekhoff and Tiffeneau A 1922 i 458).- The transformation of alkylhydrobenzoins under the influence of concentrated sulphuric acid may take place in two different ways yielding either a phenyl a-alkylbenzyl ketone or a benzhydryl alkyl ketone and the authors have investigated the influence of the nature of the alkyl group on the relative proportions of the resulting products.The conclusion is drawn that alkyl groups such as methyl isobutyl and phenyl which have a strong " satur- ation capacity" (Meerwein loc. cit.) yield the former type of product and conversely. The groups of intermediate " satur- ation capacity "-ethyl butyl propyl isoamyl-form hydro- benzoins which yield on dehydration mixtures of the two possible products. The results show that the influence of the alkyl group may render the secondary less stable than the tertiary hydroxyl group. This property is evident only in presence of concentrated sulphuric acid and may result from a temporary linking of the acid with the secondary group. H. J. E. The Action of Alcohols on Phenyl a-Bromostyryl Ketone. Formation of Various Saturated and Ethylenic Compounds.CH. DUFRAISSE and P. G~RALD (Bull. Xoc. chim. 1922 [iv] 31 1285-1304) .-Phenyl a- bromostyryl ketone readily unites with alcohols in presence of small quantities of the corresponding sodium alkoxide giving a- bromo- P-alkoxybenzylacetophenones of the general formula COPh*CHBr*CHPh*OR which can be isolated if the reaction is conducted within suitable narrow limits of tem- Derature. but which when warmed with the reaction mixture. lose hydrogen bromide giving phenyl p-alkoxystyryl ketones COPh*CH:CPh*OR. The course of the reaction and the nature of the product initially obtained by Wislicenus (A. 1900 i 37) by the action of alcoholic potassium hydroxide on phenyl p-bromostyryl ketone is thus elucidated. The phenyl P-alkoxystyryl ketones are obtained with even greater facility and in purer condition by the addition of alcohol to benzoylphenylacetylene in presence of sodium alkoxide. All attempts to prepare the two stereoisomerides which are theor- etically possible in the case of both the saturated and unsaturated compounds or to prepare derivatives from secondary alcohols or phenols failed.The preparation and properties of the following compounds are described. Phenyl a-bromo- p-ethoxystyryl ketone VOL. CXXTV. i. fi. 114 ABSTRACTS OF CHEnlICAL PAPERS. m. p. 60-61' b. p. 182-183'/3-4 mm. white crystals readily decomposed by alkalis and hydrolysed to dibromobenzylaceto- phenone by hydrobromic acid. a-Bromo- p-methoxybenzylacetvphen- one white crystals m. p. 76-77". a-Bromo-p-propoxybenzylaceto- phenone m.p. 95-96". u-Brmo-p-butoxybenxylacetophenone m. p. 81-82'. a-Bromo-p-isobutoxybenxylacetophenone m. p. 110-111". Phmyl p-ethoxystyryl ketone yellowish-white crystals m. p. 77- 78" b. p. 209'15 mm. readily hydrolysed to dibenzoylmethane by boiling with 15% alcoholic hydrogen chloride. Phenyl p-methoxy- styrp? ketone whitish-yellow crystals m. p. 65-66". Phenyl P-propoxystyryl ketone m. p. 59-60". Phenyl p-butoxystyryl ketone a yellow oil b. p. 204-206"/2 mm. Phenyl p-isobutoxystyryl ketone yellowish crystals m. p. 55-56'. Phenyl p-isopropoxystyryl ketone crystals m. p. 49-50" b. p. 180-183'/2-3 mm. G. F. M. Preparation of Condensation Products of ap-Unsaturated Ketones and Phenols. CHEMISCHE FABRIKEN VORM. WEILER- TER MEER (D.R.-P. 357755; from Chem. Zentr. 1922 ivy 890- 891) .-up-Unsaturated ketones in the presence of acids or their acid additive products are condensed with phenols.The reaction in the case of the unsaturated ketones is as follows CR With reactive phenols such as resorcinol or N-substituted m-amino- phenols the reaction is almost quantitative. The compound from the condensation of phenol and styryl methyl ketone is a grey powder. The compound from resorcinol and styryl methyl ketone is a yellow powder. The compound from the hydrogen chloride additive product of phenyl styryl ketone (3-chloro-1-keto-1 3- diphenylpropane) and resorcinol has a red colour ; it forms an acetyl derivative (annexed formula). Other con- densation products are formed from phenyl /\/\CH m-hydroxystyryl ketone and pyrogallol OAc I I ICHPh (brown) ; from phenyl styryl ketone and pyro- \/\/ gallol (bluish-grey) ; from phenyl p-dimethyl- aminostyryl ketone and m-dimethylamino- phenol (greyish-blue) ; from resorcinol and thiodiketobenzylidenethi- azolidine (reddish-brown) ; from styryl methyl ketone and p-cresol (light brown) ; from p-acetamidophenyl o-chlorostyryl ketone and quinol (reddish-violet).G. W. R. CPh 0 Crystallographic Study of uy-Diketohydrindene. ANGELO PICHSTW (Atti R. A c d . Lincei 1922 [v] 31 ii 143-146).- ay-Diketohydrindene d21 1.37 forms crystals belonging t o the hipyramidal tetragonal clags of the tetragonal system a c= 1 0.9414. T. H. P.OWAXIC CHEMISTRY. i. 115 o-Quinones and 1 2-Diketones. VI. JI-Benzils. II. Benzils of the Peroxide Type 2 2'-Diethoxybenzil a De- rivative of Benzil which is Colourless in Solution.A. SCH~N- BERG and W. M A L ~ O W (Ber. 1922 55 [B] 3746-3752).-1n a previous communication (Schonberg and Kraemer A. 1922 i 663) the isolation of a number of colourless solid benzils has been described which give more or less intensely coloured solutions. The superoxide structure TogR has been assigned to the colour- less and the diketonic structure to the coloured benzils. This con- ception is strengthened by the observation that the faintly coloured solutions react less readily than those which are intensely coloured with the usual reagents for 1 2-diketones. In 2 2'-diethoxybenzil colourless quadratic leaflets m. p. 157" the authors have now found a substance which not only is colourless when solid but also yields colourless solutions in cold alcohol acetic acid benzene and light petroleum (b.p. 100-llO") which become pale yellow when heated. It melts to a dark yellow liquid which re-solidifies to colourless crystals. It is unimolecular in its colourless solutions so that the absence of colour cannot be attributed to polymerisation. It is an unusually stable compound which is indifferent to con- centrated aqueous ammonia under pressure and is not affected by hydrogen peroxide in acid or alkaline solution. It does not react with naphthylenediamine hydrochloride in boiling glacial acetic acid but in the presence of boiling dimethylaniline it is slowly converted into 2 3-di-o-phenetyEu~-naphthaquinoxaline O*CR OEt*C6H4*$!:N OEt*C,H4*C:N>C1*6' colourless pointed prisms m.p. 180". Similarly 2 2'-dimethoxy- benzil is transformed by o-phenylenediamine hydrochloride in the presence of boiling dimethylaniline into 2 3-di-o-unisylpuino~line colourless quadratic prisms m. p. 183" by 3 4-diaminofoluene hydrochloride into 2 3-di-o-anisyZ-6-methyZquinomline colourless prisms m. p. 135" and by naphthalene-1 2-diamine hydrochloride into 2 3-di-o-anisyl-up-~pht~qui~~line colourless prisms m. p. 180". The method of condensation appears to be of general applicability . 2 2'-Dimethoxybenzil is reduced by amalgamated zinc and concentrated hydrochloric acid to up-di-o-anisylethane m. p. 86" (cf. Spath A 1914 i 1). 4 ; 4'-Diethoxy-~-phenylbenzoin E t O*C,H4*C( OH)Ph*CO *C6H,*OE t colourless needles m. p. l l l " is prepared by the addition of an ethereal suspension of 4 4'-diethoxybenzoin to an ethereal solution of magnesium phenyl bromide.3 3'-Dimethoxybenzoin colourless prisms m. p. 55" obtained by the action of potassium cyanide on m-methoxybenzddehyde is oxidised by Fehling's solution in boiling aqueous alcohol to 3 3'-dimethoxybenzil yellow prisms m. p. 83". The latter sub- stance is converted by o-phenylenediamine hydrochloridc in the f si. 116 ABSTRACTS OF CHEMICAL PAPERS. usual manner into 2 3-di-m-anisylquino~aZine~ colourless leaflets m. p. 110". H. W. o-Quinones and 1 2-Diketones. VII. +b-Benzils. 111. Separation of a 1 2-Diketone into its Coloured Crystalline Ketonic and its Colourless Crystalline Peroxide Form. A. SCHONBERG and W. BLEYBERG (Ber. 1922,55 [B] 3753-3758; cf.A. 1922 i 163 and preceding abstract).-4 4'-Dibenzyloxy- benzil has been prepared in coloured and colourless forms. A solution of 4 4'-dihydroxybenzil in absolute alcohol is treated with the calculated quantity of potassium ethoxide and a slight excess of benzyl bromide whereby the diketonic form of 4 4'-di- benzyloxybenzil is obtained as dark yellow prisms m. p. 126". If the hot concentrated solution of the dibenzyl ether in alcohol glacial acetic acid or light petroleum (b. p. 100-110") is suddenly cooled by immersion in ice-water the colourless peroxide variety ?*f?c6H4*0*CH2Ph m. p. about 124" after becoming distinctly O*C~C6H4*O*CH2Ph' yellow a t 121" separates. The success of the isolation depends greatly on the rapidity with which the cooling is effected so that it is only possible to work with small quantities a t a time.A further essential condition is that the mother-liquor should be removed as rapidly as possible since although the colourless form is stable when dry it rapidly passes into the yellow variety when in contact with solvents; this change occurs with such rapidity that the colourless compound appears to yield immediately coloured solutions. 4 4'-Dibenzyloxydibenzyl is rapidly converted by hydrogen peroxide in boiling alcoholic solution in the presence of sodium hydroxide into p-benzyloxybenzoic acid m. p. 189" (cf. Cohen and Dudley T. 1910 97 1732). It is converted by naphthalene- 1 2-diamine hydrochloride in the presence of boiling dimethyl- aniline into the corresponding wphthaquinoxaline C38H2802N2 prisms m.p. 156". H. W. E. GRAND- MOUGIN (Compt. rend. 1922 175 970-973).-The introduction of acyl groups into aminoanthraquinones results in the formation of a series of substances the tinctorial characters of which depend on the nature of the substituent entering the amino-group. If a hydroxyl group which acts as an auxochrome is present in addition acetylation or benzoylation of this group brightens the colour but usually diminishes the value of the substance as a dye. In the case of a-benzamidoanthraquinone the colour is changed from bright yellow to deep rose by the introduction of a hydroxyl group in the para position and to scarlet by a methoxyl group. Further addition of benzamido-groups results in a deepening of the colour.Isomerism influences the colour and in addition the tinctorial properties ; the author states that no adequate explanation of these facts has yet been put forward. The following substances all crystalline and of high m. p. were prepared; their colours and the tints they impart to vegetable fibres are noted 4-Benxamido- The Acylamidoanthraquinones as Vat Dyes.ORGANIC CHEMISTRY. i. 117 I-hydroxyanthraquinone red deep red. 4-Benxamido-l-acetoxy- anthrapuinone yellow rose 4-Acetumido-I -acetoxyanthraquin brownish-red light brown. 4-Benxamido-l-benxoyIccnthraquinone orange- yellow pale rose. 4-Benzumido-l-methxyanthraquinone orange -yellow scarlet. 4- A cetamido- 1 -methoxyanthraquin orange-yellow light salmon. 1 4-Diacetamidacnthraquinone orange-yellow light brown.1 4-Dibenzumidixznthraqukne reddish -yellow 1 5 - Di benzuvnido - 8 - h ydroxy - anthraquinone red red. 1 5-Dibenzamido-4 8-dihydroxyanthra- quinone violet-blue violet-blue. 1 5-Dianisarnido-4 8-dihydr- oxyanthraquinone violet-blue violet-blue. 4 5-Dibenmrnido- 1 8-dihydroxyanthraquinone violet-blue light violet. 1 5-Di- acetamido-4 8-dihydroxyanthraquinone orange-brown. 1 5-Di- acetumido-4 8-diacetoxyanthraquinone brownish-yellow. 4 5-Di- acetamido-1 8-diacetoxyanthraquinone reddish-brown. 4 5-Di- benmmido-4 8-diacetoxyanthrapuinoneY yellowish- brown. The tinctorial colours of the four last-named are not stated. red& h -yellow. H. J. E. The Investigation of meso-Thioanthracene Derivatives. I. Observations on the Production of Dithioanthraquinone Dithiodianthrone and Other Closely Related Derivatives. ISIDOR MORRIS HEILBRON and JOHN STANLEY HEATON (T.1923 Condensation Products of Phenylhydroxylamine With Hydroxymethylene Compounds and Carbinols. IV Methyl- enecamphorphenylhydroxylamine. H. RUPE and W. DIEHL (Helv. Chim. Acta l922,5,906-922).-The reduction of methylene- camphorphenylhydroxylamine to anilinomethylene-camphor (cf. A. 1921 i 426) can be accomplished by means of sodium hydrogen sulphite in aqueous alcoholic solution. When methylenecamphor- phenylhydroxylamine is treated with thionyl chloride in ethereal solution methylenemmphorphenylchloroamine is formed ; it crystal- lises in short yellowish-white prisms m. p. 102-103". The chlorine appears to be firmly attached to the nitrogen atom; that it has not wandered into the phenyl group was shown by con- densing hydroxymethylenecamphor with p-chloroaniline when p-chloroanilinomethylenecamphor was obtained which crystallises in small white prisms m.p. 167-169". Methylenecamphorphenyl- hydroxylamine combines with 1 mol. of hydrobromic acid to form a hydrobromide C8H14<~~*cHBr*mh*0H yellow needles m. p. 121" (decomp.). Similarly it readily combines with bromine in glacial acetic acid solution to form a dibrmide yellow needles m. p. 117" (decomp.). When the hydroxylamine compound is heated with phenylhydrazine in glacial acetic acid phenylhydroxyl- amine is removed and a derivative formed which was found to be identical with the phenylcamphopyrazole described by Bishop Claisen and Sinclair (A.1895 i 63). C8HI4<(?:">NPh C=N 123 173-185). The formulai. 118 ABSTRACTS OF CREMICAL PAPERS. is to be preferred to that given by those authors in which the phenyl group is attached to the 1-nitrogen atom. By the action of semicarbazide on methylenecamphorphenylhydroxylamine the simple semicarbazone of hydroxymethylenecamphor is fornied. Its m. p. is 205-206" not 217-218" as given by Wallach (A 1904 i 106). The oxidation product of methylenecamphorphenylhydroxyl- amine obtained by boiling it with cupric acetate (A. 1921 i 425) can be obtained in much better yield by oxidising in cold alcohol with potassium ferricyanide It crystallises in monoclinic needles or prisms a b c=0*9971 1 1.065; p=103" 50'. Its properties agree with the double formula [c,H14<c0 ?:CH'y<gh]2. Its form- &ion requires one atom of oxygen to two molecules of the hydroxgl- amine.The double molecule takes up four atoms of bromine to form a tetrabromide C34H4004N2Rr4 which decomposes when heated. When a solution of the tetrabromide in chloroform is warmed hydrogen bromide is evolved and a compound crystallises ; white lustrous aggregates of needles m. p. 205-208" (decomp.). From the chloroform solution of the tetrabromide a dibromide was also obtained C3,H3804N,Br m. p. 123-126" (decomp.). All these bromo-derivatives are very unstable. When the above oxidation product of methylenecamphorphenyl- hydroxylamine is dissolved in 75% sulphuric acid and then pre- cipitated by dilution a new cumpound C34H4406N2 is obtained. It appears to be a hydration product and the formula [c8H14<~~H)*CH:NPh(oH).1 2 cf 1 ,H,oO,NBr is suggested for it. It has no sharp melting point but sinters from 170" decomposing a t 190-195". Molecular-weight determinations in different solvents gave very discordant results. It forms a methyl derivative C,,H,,O,N m. p. 226-228". The above formula expresses the fact that the compound is a stronger acid than the parent substance dissolving readily in barium hydroxide solution. There is a possibility that in the condensation of hydroxymethyl- enecamphor with phenylhydroxylamine intramolecular change occurs to give a p-aminophenol derivative. This has been disproved by condensing p-aminophenol with hydroxymethylenecamphor. The product could not be crystallised but when methylated with methyl sulphate gave p-anisidinomethylenecamphor white leaflets m.p. 169-172". It also gave an acetyl derivative white leaflets m. p. 221-223". E. H. R. Action of Sulphur and certain Compounds of Sulphur on Terpenes. P. P. BUDNIKOV and E. A. SCHILOV (Ber. 1922 55 [B] 3848-3853; cf. A. 1922 i 944).-Pinene or mixtures of limonene and silvestrene are converted by prolonged boiling with sulphur into a viscous reddish-brown liquid from which a homo-ORGANIC CHEMISTRY. i . 119 geneous substance could not be isolated by fractional distillation ; the pwcentage of sulphur in the various fractions increases with increasing boiling point The products yield unstable precipitates when mixed with the chlorides of mercury gold or platinum lead acetate or arsenic iodide in the presence of acetone or alcohol but these are not suitable for analysis.The action of methyl iodide on the fractions gives methyl terpenesulphinium iodide CloH16S,CH31 a microcrystalhe precipitate m. p . about 121" after previous darkening (the constant is given with reserve by reason of the lack of uniformity of the original material). The substance behaves as a typical sulphinium iodide and is converted by moist silver oxide into the corresponding base. When treated with the theoretically necessary quantity of mercuric iodide in accordance with Smiles's procedure (T. 1900 77 163; 1907 91 1394) the iodide gives the compounds C,oH,6S,CH31,HgI pale yellow microscopic prisms and Cl~oH16S,CH31,2HgI lemon-yellow prisms decomp. about 100". With arsenic tri-iohde the com- pound ClOHl6S,CH3I,AsI3 dark orange-coloured crystals is pro- duced.The yields of the methiodide are not satisfactory but it was not found possible to effect any improvement in the initial action by the use of aluminium chloride mercuric chloride or mercuric iodide as catalysts. Better results are obtained when sulphur is replaced by sulphur chloride but the course of the change has not yet been elucidated. The primary action of sulphur on terpenes appears to consist in the formation of a monosulphide which probably combines with a further quantity of sulphur to give polysulphides. Evidence of the formation of thio-ozonides as suggested by Erdmann has not been obtained. H. W. Higher Terpene Compounds. VII. The Constitution of Eudalene Selinene and a-Santalene.The Carbon Frame- work of the Sesquiterpenes. L. RUZICKA and M. STOLL (Helv. Chim. Actu 1922,5 923-936; cf. A. 1922 i 560).-On theoretical grounds it seemed probable that eudalene is formed from sesqui- terpene compounds of the type (I) by dehydro- /\/\ genation and loss of a carbon atom. If this were \-I 1 I the case eudalene should be isomeric with the / \/ \ / 2 -methyl- 8-isopropylnapht haIene obtained from cadalene (A. 1922 i 1001) and should give the (1.1 same naphthalene-1 7-dicarboxylic acid as this when oxidised with dilute nitric acid. This was found to be the case. Naphthalene-1 7-dicarboxylic acid forms a nearly white amorphous precipitate sinters from 200° and melts at 265" to a dark brown liquid. There were also obtained in small quantity a nitro-2-methyl-8-isopropylnaphthulene yellow needles m.p. 112-113" and a rtitrmphthoic acid m. p. 225-227". The identity of eudalene with 1 -methyl-7-isopropylnaphthalene was confirmed by synthesis of the hydrocarbon as follows. Cuminol was condensed with ethyl bromoacetate by Reformatzky's method and from the product ethyl p-isopropylcinnamate was oht,nined. 1i. 120 ABSTRACTS OF CHEMICAL PAPERS. This was reduced by Bouveault's method giving p-isopropylphenyl- propyl alcohol C,H,*C,H,.[CH,],*CH,*oH b. p. 149'112 mm. This was converted through the bromide and cyanide into 7-p-cumyl- butyric acid C,H,°C,H,o[CH,],~~O,H b. p. 186'112 mm. crystal- lising in leaflets m. p. 31-32". The acid chloride is a mobile oil,- b. p. 156"/12 mm. When this chloride was treated with aluminium chloride 8-keto-2-isopropyl-5 6 7 8-tetrahydronaphthalene was obtained b.p. 156"/12 mm. It forms a aemicarbazone m. p. 195". This was boiled with magnesium methyl iodide and 1-methyl-7- isopropyl-3 4-dihydronaphthalene was obtained b. p. 137"/12 mm. This was dehydrogenated by heating with the theoretical proportion of sulphur and gave 1 -methyl-7-isopropyl naphthalene identical with eudalene The constitution of eudalene having been established it is shown that the two forms of the sesquiterpene selinene which readily gives eudalene when treated with sulphur probably have the following constitutions H Me H H Me B-Selinene. a-Selinene. It has now been shown that there are two types of carbon skeleton in the sesquiterpene series derived from three isoprene units.These may be called the cadinene type (11) and the eudesmol type (I). The structure of a-santalene was /\/\ determined by Semmler (A. 1910 i 574) who how- I l- ever considered two formula possible belonging to h/ what he called the camphor-type and the camphene- type. It is shown that these two "types" are but /\ (II.) different plane projections of the same three- dimensional structure. The structure is definitely related to the eudesmol type (I). It can now be concluded that all known sesquiterpenes are closely related and are derivable from a regular tri-isoprene chain of the kind present in farnesol. I I E. H. R. The Nature of Shellac. Shellolic Acid. C. HARRIES and W. NAGEL (Ber. 1922 55 [B] 3833-3848).-A preliminary account of partly completed work on shellac and sticklac.The lac is freed from wax and colouring matter by successive treatment with light petroleum and water and the residue is repeatedly agitated with ether thereby leaving an insoluble '' pure resin " which is the subject of investigation and is the vehicle of the characteristic properties of shellac. The " pure resin " is attacked by N-potassium hydroxide solution at the atmospheric temperature which causes the deposition of potassium aleuritate the amount being 22-24% of the resin taken. The filtrate from the salt is acidified with sulphuric acid and extracted with ether thus yielding a mixture of shellac resin acids; these are purifiedi. 121 ORGANIC CHEMISTRY. by agitating their ethereal solution with aqueous barium hydroxide and treating the latter with carbon dioxide when the precipitated barium carbonate adsorbs a portion of the coloured resinous matter.The filtrate contains small amounts of sparingly soluble barium aleuritate and the freely soluble barium salts of the shellac resin acids. Attempts to isolate a homogeneous material from the latter by dialysis were not completely successful but it is shown thereby that the salts are devoid of colour. More rapid but less complete purification can be effected through the zinc salts. The free acids do not crystallise readily. The most satisfactory results are obtained by taking advantage of the observation that the shellac resin acids unlike other resin acids are at any rate in part esterifiable by methyl-alcoholic hydrogen chloride (3%) a t the atmospheric temperature where by methyl shellohte C,,H,O 6 long prismatic rods m.p. 149" b. p. 284-288"/0-1 mm. (slight decomp.) [a]$ +32-61" in methyl-alcoholic solution is obtained the amount being S-lO% of the weight of the "pure resin" taken. The ester is hydrolysed by boiling aqueous N-sodium hydroxide solution to shellolic acid (shellenedioldimrbox ylic acid) colourless leaflets m. p. 199.5-201" decomp. 202-203" which gives the Liebermann cholesterol and the Salkowski-Hesse reactions. It does not reduce Fehling's solution or decolorise a solution of bromine in chloroform ; its unsaturated nature is demonstrated by its instability towards alkaline permanganate and the apparent formation of an ozonide. The sodium and barium salts are colourless amorphous and freely soluble in water; the silver copper and lead salts dissolve more sparingly.The hydrazide Cl5H,O4N crystallises in well-defined prisms m. p. 243-244" (decomp.) the non-crystalline acetyl derivative and the diphenyldiurethane C3,Ha08N2 m. p. 92-94" (decomp.) according to the rate of heating are described. The CH.C02H annexed formula for shellolic acid is suggested tentatively ; the positions of the hydroxyl and carboxyl groups can- HO*HC!,~,CH*OH not yet be definitely assigned. The position of the double bond accounts for the inactivity of the acid towards The non-crystalline residue of esters from which methyl shellolate has been separated (21.5.) has b. p. 180-210"/0*1 mm. and appears to consist of compounds of hydroxy-acids.The latter are themselves amorphous but give solid phenylurethanes. The investigation has rendered it very improbable that shellac resin is the aleuritic ester of a higher alcohol since no trace of the latter could be detected and i t must be present in considerable quantity if it were an actual constituent Since it is established that the resin does not contain a free acid it appears probable that the shellac molecule is composed of hydroxy-acids which are united in the form of lactides. For one of the simpler components the constitution Xo>C,,H,,( OH)CO*O*CIGH,,(OH)<?o 0 is sug- C02H.CH H2C'\8/)CH HC CH 1 1 bromine. H2C CH2 \/ CH2i. 122 ABSTRACTS OF CHEMICAL PAPERS. gested the composition of which is very similar to that of the pure resin." H.W. Centaureidin a Decomposition Product of Centaurein the Glucoside of Roots of Centaureu Jucea. M. BRIDEL and G. CHARAUX (Compt. rend. 1922,175 1168-1170).-Centaureidin C,,H,,O (this vol. i 50) crystallises from 50% alcohol in micro- scopic yellow needles containing water of crystallisation which is lost a t 50". The crystals melt a t 197" the anhydrous substance at 203". It is insoluble in water but dissolves in many organic solvents. With aqueous alkalis or sulphuric acid it gives a golden- yellow solution. As the result of a general study of its properties the authors suggest that it may be a flavone derivative although the evidence on behalf of such a conclusion is mainly negative. < ( H. J. E. Polysaccharides. XVII. Chitin. P. KARRER and ALEX. P. SMIRNOV (Helv.Chim. Acta 1922 5 832-852).-To determine how the glucosamine residues are combined in chitin a study was made of the decomposition products obtained when chitin was distilled with zinc dust. From 300 g. of chitin from lobster shells 37 g. of a brown oil were obtained which consisted chiefly of pyrrole compounds with a small quantity of pyridine bases among which a-picoline was identified. From the mixture of pyrrole compounds a fraction was isolated which was identified as 2-methyl-1-n-hexyl- pyrrole. This compound and 2 5-dimethyl-1-n-amylpyrrole were synthesised for comparison with the compound from chitin to which the name chitopyrrole is applied. 2 5-Dimethyl- 1-n-arnylpyrrole was prepared by heating acetonyl- acetone with n-amylamine. It is a colourless oil b.p. 225-227" with an orange-like odour and gives a cherry-red pine-shaving reaction. 2-Methyl- 1 -n-hexylpyrrole was prepared from potassium 2-methylpyrrole and n-hexyl iodide. It is a colourless oil rapidly .turning brown b. p. 200-210" smelling like old fungus and gives an intense red pine-shaving reaction. Chitopyrrole boils over a somewhat wider range than 2-methyl-1 -n-hexylpyrrole 190-220" but essentially the two appear to be identical. Both are oxidised by chromic or nitrous acid to a substituted maleinimide which when hydrolysed gives maleic acid and n-hexylamine. The last was identified by preparation of the picrolonate m. p. 188-189" which was also prepared from synthetic n-hexylamine. The formation of 2-methyl-1-n-hexylpyrrole from chitin indicates the presence in the latter of two glucosamine residues combined through a nitrogen atom as in the following formula Neither the position of the acetyl groups nor the number of glncos- amine residues present in the molecule can yet be stated.Chitosan which is formed from chitin by hydrolytic removal of the acetyl groups is converfed by nitrous acid into a reducing sugar witlhORUAHIC CHEMISTRY. i. 123 total loss of its nitrogen in the elementary form. This behaviour is quite in accordance with the above representation of chitin as an aldehyde-ammonia derivative. E. H. R. Betulin. OTTO DISCHENDORFER (Ber. 1922 55 [B] 3692- 3693) .-A preliminary account of the author's observations induced by the recent publication of Schulze and Pieroh (A. 1922 i 1045).Monobromobetulin m. p. 215" and the corresponding diacetute m. p. 193" have been prepared. Analyses 6f the latter indicate the possibility of the formulae C3,H,,O2 or C,,H,O for betulin whereas Schulze and Pieroh (Zoc. czt.) regard C32H5202 or C,H,O as probable. H. W. Strophanthin. I. Strophanthidin. WALTER A. JACOBS and M~CHAEL HEIDELBERGER ( J . Biol. Chem. 1922 54 253-261).- When dried in a vacuum a t 110" over phosphoric oxide stroph- anthidin decreases in weight by an amount corresponding with the loss of +H,O. The anhydrous substance therefore has the formula C23cH32O6. The loss of l&H,O noted by Windaus and Hermanns (A. 1915 i 704 705) was evidently due to partial decomposition. A final decision between the C formula and the C27 formula of Feist is rendered possible by the preparation of the p-bromo- benzoate C30H3507Br,H20. In the anhydrous condition this compound has m.p. 222-224' (decomp.) [a]? +42" in acetone. isostrophanthidin (strophanthidinic acid lactone of Feist iso- cyxnarigenin of Windaus and Hermans) has the same formula as strophanthidin crystallises with +H20 and forms a benzmte C30H3607 rosettes of microscopic leaflets m. p. about 270" after sintering [a]E + 38.0" in chloroform. When reduced with hydrogen in the presence of colloidal palladium strophanthidin slowly absorbs two atoms of hydrogen with the formation of dihydrostrophanthidin C23H3P06 which melts a t 190-195" when anhydrous and crystallises with one or two molecules of water according to the method of crystallisation. The dihydrate has [a]2+34*85' in methyl alcohol.Dihydrostrophanthidin forms a benzoate CNH3,O7 minute glistening prisms m. p. 225-227" (decomp.). The presence of a carbonyl group in strophanthidin is shown by the pre- paration of the oxime C,,H,O,N glistening prisms m. p. 270-275' (decomp.) [a]2,7+71.3" in pyridine the phnyZhydraxone glistening prisms m. p. 230-232" after sintering a t 175" [ar]5-5-0" in chloroform and the p-bromophenylhydraxone stout pointed prisms which soften a t 180-185" and become com- pletely molten at ZOO" and have [a15 6+ 105%" in chloroform. C2,H3805N2,2H20 9 C,,H3 70 5N,Br 1 +MeOH E. S. [Catechin.] M. NIERENSTEIN (Ber. 1922 55 [B] 3831- 3833).-A reply to Freudenberg (A. 1922 i 756). The author maintains that catechincarboxylic acid can be pre- pared according to his method and promises further details with regard to Kostanecki's catechone.With respect to the production f* 2i. 124 ABSTRACTS OF CHEMICAL PAPERS. of optically active catechin from inactive catechincarboxylic acid the inactivity of the latter is maintained but the optical activity of Gambier catechin is not considered to be established. Pure Gambier- and aca-catechins are not precipitated by solutions of elatin. Freudenberg's observation that tetramethylcatechin cannot t e demethylated by the author's method is correct so far as the derivative of Gambier catechin is concerned but is not true for that of aca-catechin. The identity of the methylated product of the reduction of catechin with pent amet hoxy - a'y -dip henylpro pane is not regarded as established.The homogeneity and optical inactivity of aca-catechin m. p. 204-205° is maintained. H. W. Tannins and Similar Compounds XII. The Tannin of the Native [German] Oak. KARL FREUDENBERG and ERICH VOLLBRECHT (Annalen 1922 429 284-317).-A more expanded account of work already published (cf. A. 1922 i 1046). C. K. I. Constitution of Thiophen. WILHELM STEINKOPF [with HAL- VARD AUQESTAD-JENSEN and HANS DONAT] (Annalen 1922 430 78-112).-The lability of the hydrogen atoms in the thiophen nucleus is well illustrated by its behaviour towards cyanogen bromide with which it reacts analogously to compounds of the type of ethyl acetoacetate and ethyl malonate which are known to contain labile hydrogen. Thus ethyl acetoacetate and cyanogen bromide react giving ethyl y-bromoacetoacetate. Ethyl malonate yields ethyl bromo- malonate.Acetophenone yields O- bromoacetophenone and in a similar way 2 - acet o t hienone yields O- bromo - 2 - acet o t hienone. Phenol and cyanogen bromide yield p-bromophenol whilst indene and cyanogen bromide give 1 - bromo-2-hydroxyhydrindene. Thiophen reacts with cyanogen bromide giving bromothiophen b. p. 151-151.5" and dibromothiophen b. p. 195-206" and with cyanogen iodide giving 2-iodothiophen (identified as the 5-iodo-2-mercurichloride). Bromothiophen is converted by cyano- gen bromide into dibromothiophen and 2-thiotolen into bromo- thiotolen b. p. 173-177". Alkylthiophens in which both a-positions are substituted are also brominated by cyanogen bromide. 2 5-Dipropylthiophen yields 3-bromo-2 5-dipropyZthiophen b.p. 130-132~5"/10 mm. and 2-ethyl-5-isoamylthiophen yields 3-(or 4-)bromo-2-ethyl-5-isoamylthio- phen b. p. 122-127"/14 mm. The above 2 5-dialkylthiophens mere synthesised by way of the corresponding ketones. 5-Ethyl-%popiothienone b. p. 137- 138"/19 mm. prepared from 2-ethylthiophen propionyl chloride and phosphoric oxide gives a semicarbazone m. p. 195-196" and on reduction with zinc and hydrochloric acid gives 2-ethyl- 5-propylthiophenY b. p. 196-197". 5-Propyl-2-propiothienone b. p. 137-138-5"/13 mm. prepared from 2-propylthiophen propionyl chloride and either phosphorus pentoxide or aluminium chloride yields a semicurbaxone prisms m. p. 174-175" and on reductionORGANIC CHEMISTRY. i. 135 gives 2 6-dipropylthiophen b. p.213-214". 6-isoAmy1-2-aceto- thienone b. p. 149-151"/13 mm. prepared from 2-isoamylthio- phen acetyl chloride and phosphorus pentoxide gives a semi- carbaxone leaflets m. p. 212" and on reduction yields 2-ethyZ- 5-isoamylthiophen b. p. 103~5-106~5"/12 mm. None of these 2 5-dialkylthiophens gives well characterised mercury compounds on treatment with mercuric chloride. The Thiophen Series. XV. Cyclic Mercury Compounds and Experiments on the Formation of Mixed Thiophen- Mercury Compounds. WILHELM STEINKOPF WILHELM BIELEN- BERG and HALVARD AUGESTAD- JENSEN (Annalen 1922 430 40-78).-The experiments carried out with the object of pre- paring the mixed mercury compound C4H,S*HgPh were based on the reaction between magnesium phenyl bromide and phenyl mercurichloride the products of which are mercury diphenyl and magnesium chloride and bromide.Pure mercury phenyl thienyl could not be isolated from the product of the action of magnesium phenyl bromide in 2-thienylmercurichloride although evidence of its formation was obtained. Mercury diphenyl is also formed by the action of mercurous chloride on magnesium phenyl bromide and by the action of stannous chloride on magnesium phenyl chloride. Similarly mercury 2 2'-dithienyl is the product of the reduction of thienyl-2-mercurichloride by stannous chloride. A series of cyclic mercury-thiophen compounds is described of which dimercury 2 2' 5 5'-dithienyEene I >S S< is typical. This substance is obtained from 2 5-thienylenedimercuri- chloride and either sodium iodide or sodium thiocyanate in the presence of pyridine. Pyridine and mercuric chloride convert it into mercury 5 5'-dithienylene-2 2'-dimercurichloride which may also be obtained by the action of pyridine on thienylene-2 5- dimercurichloride.Dimercury 3 3'-(or 4'-)diethyl-2 2' 5 5'-di- thienylene mercury diethyl-5 5'-dithienylene-2 2'-dimercurichloride and dimercury 3 4 3' 4'-tetramethyl-2 2' 5 5I-dithienylene are also described; like the unakylated parent substances they are all exceedingly insoluble compounds which do not melt at 320". Dimercury diethyldithienylene on treatment with mercuric chloride under regulated conditions yields mercury diethyldithienylene- dimercurichloride but excess of the reagent effects complete dis- ruption of the molecule the product being 3-ethylthienylene- 2 5-dimercurichloride. A colorimetric method of estimating the rate of separation of mercuric sulphide when an organic mercury compound is treated with sodium sulphide is described in the original.Synthesis of Substituted Thianthrens. I. Thianthren and Nitrothianthren. SRI KRISHNA (T. 1923 123 156-160). Production and Reactions of 2-Dithiobenzoyl. nhRy MCKIBBEN and ERNEST WILSON MCCLELLAXD (T. 1923 123 C. K. I. CH:C-Hg-C:CH CHX-Hg-C H C. K. I. 170-173).i. 126 ABSTRACTS OF CHEMTCAL PAPERS. The Alkaloids of the Northern Aconite (Acon2tum septen- trtonak Koelle). GUNNAR WEIDEMANN (Arch. ex@. Path. Phurm. 1922 95 166-180).-Two alkaloids isolated from the northern aconite have been investigated. forms hard glass clear six-sided prisms m.p. 223" [a] +27.0' in chloroform. It is a monoacid base and contains three methoxyl p u p s . It forms a chloroplatinate C,H4,0,N,,HPtC1 and a chlorouurate C,,H,20,N,,HAuC14. On hydrolysis with alcoholic potash it yields lappaconitic acid C,H,O,N shown to be acetyl anthranilic acid and a base lappaconine C,H,50,N,2H20 m. p. 93O [a]2"+2%41°. It forms a hydrochloride C,,H,507N,HCl large colourless crystals. Septentrionaline C,,H,O,N,( OMe)4 the other alkaloid investigated is an amorphous white powder m. p. 131" [a32 '+32.71" forming a chloroplatimte C,H4,0gN,,HPtC1,. On hydrolysis with alcoholic potash there is obtained (1) an acid C,H,O,N m. p. 125-126" which when boiled with sodium hydr- oxide solution yields anthranilic acid losing CH,O and (2) a base C2,H,O7N m.p. SO" [a] 6+29.55" forming a hydrochloride CZ5H3,O ,N,HCl. W. 0. K. Lappaconitine C32H420$N2 Paniculatine the Alkaloid from Acodtum punicuZutzcm Larn. G . E. BRUNNER (Schweiz. Apoth. Ztg. 1922 60 357- 358 ; from Chem. Zentr. 1922 iii 1007).-Paniculatine C,,H,,O,N the alkaloid from Aconitum panniculatum Lam. is not identical with aconitine. It forms small rhombic prisms with m. p. 263". G. W. R. Melanins Arising from Adrenaline. PIETRO SACCARDI (Biochem. Z. 1922 132 439-442).-Melanin-like pigments ob- tained by the oxidation of adrenaline with chlorine water are described. W. 0. K. Pre aration of a Quinine Derivative. AKTIEN-GESELLSCHAFT BACHSTEZ (D.R.-P. 357753; from Chem. Zentr. 1922 iv 951).- Equimolecular amounts of quinine and 4-ethoxyphenylmalonamic acid are fused together and crystallised from hydrolysing solvents or allowed to react as such or in form of their salts in the presence of hydrolysing solvents.Quinine 4-ethoxyphenylmalonamate forms long colourless needles m. p. 72-73'. FGR L ILIN-FABRIKATION JULIUS ALTSCHUL and M~RCELL G. W. R. Quiteninone. SIGMUND FRANKEL CHARLOTTE TRITT-ZIRMING and Lrzly GOTTESMANN-GRAUER (Ber. 1922,55 [B] 3931-3935).- The action of hydrogen peroxide (30%) on a solution of quinine sulphate in dilute sulphuric acid in the presence of copper or ferrous sulphate as catalyst and a t the atmospheric temperature leads to the production of quiteninone C,gH2,,04N2~ needles m. p. 156". The reaction appears to be considerably mfluenced by external factors and to take place through a number of intermediate pro- ducts of which quinine oxide (cf.Speyer and Becker A. 1922,ORGANIC CHEMISTRY. i. 127 i 674) is one. Quiteninone is also produced by the oxidation of quitenine (cf. Nierenstein A. 1920 i 875). It gives a p'crate m. p. 140". The constitution of quiteninone is partly elucidated by the preparation of the methyl ester picrate C2,,H220,N2,2C6H30,N decomp. 270° and the methyl ester dihydrocMde m. p. 181". Quiteninone could not be caused to react with phenylhydrazine p-nitrophenylhydrazine or semicarbazide hydrochloride ; with hydroxylamine in alkaline solution it gives an oxime which is identified as the corresponding $cr& C,,H210,N3,C3H30,N m. p. 126". H. W. Esterifmation of Creatine. ARTHUR W. Dox and LESTER YODER ( J . Biol. Chem. 1922 54 671-673).-Saturation of a suspension of creatine in an alcohol with hydrogen chloride results in the formation not of creatinine but of an ester of creatine the hydrochloride of which separates on the addition of ether.By this means the author has prepared creutine methyl ester hydrochloride slender needles m. p. 139-140" ; crmtine ethyl ester hydrochloride needles m. p. 163" ; creatine n-butyt ester hydrochloride flat needles m. p. 138". Each salt melts with the evolution of gas and leaves a solid residue of creatinine hydrochloride. Ergot. A. STOLL (Schweix. Apoth. Ztg. 1922 60 341-346; from Chem. Zentr. 1922 iii 1007; cf. Spiro and Stoll A. 1922 i 47).-The specific effect of ergot is not considered to be due to the presence of simple amines such as tyramine. After addition of acid reagents such as aluminium sulphate to ergot extraction of one kg.of the material with ether and benzene removes 350- 400 g. of alkaloid-free ergot oil together with soluble acid and neutral substances such as organic acids phytosterol and colouring matters. From the acidified cell material a crystalline alkaloid was separated. Ergotarnine CsH3503N5,2COMe2,2H,0 (from acetone) forms highly refractive rhombic pmms ; it has [a]$ -155" in 0.6% chloroform solution ; the monoacid base and its compounds de- compose on heating a t 140"; a t 180" a brown mass is formed with evolution of gas. On keeping an ethyl-alcoholic solution or warm- ing a methyl-alcoholic solution of ergotamine an isomeride ergot- aminine of weaker basic character is formed.It crystallises in triangular leaflets and has [a] +381" in 0.6% chloroform solution. Ergotaminine may be reconverted into ergotamine. Both isomer- ides give a blue coloration with strong sulphuric acid. Ergotarnine is unstable in air. G. W. R. E. S. The Hydroxycodeinone Series. EDMUND SPEYER [with 8. SEUG and MARTIN HE=] (Annulen 1922,430,1-40).-A further account (see A. 1915 i 580; 1916 i 157 758; 1921 i 685) of derivatives of codeine and thebaine including the reduction of hydroxycodeinone to hydroxythebainol and the conversion of the latter into a nitrogen-free substance by exhaustive methylation All results are interpreted on the basis of Knorr's farmula for morphine.i. 128 ABSTRACTS OF CHEMICAL PAPERS. Hydroxycodeinone is converted either by electrolytic reduction or by zinc and formic acid into hydroxythebainol m.p. 234" CH,- NMe f CH NRft the formate of hydroxythebainol m. p. 227" and 7-hydroxy- codeine being obtained as by-products in the latter case. Hydroxy- thebainol yields a crystalline hydrochloride hydrobromide m. p. 252-253" [ ~ ] g -157*7" hydriodide m. p. 247" and picrate m. p. 204-5206". On treatment with benzoyl chloride it gives a benxoyl derivative needles m. p. 257"; with bromine and acetic acid a perbromide which on reduction by sulphur dioxide gives a mono- homo-derivative m. p. 230-231" reducible to hydroxythebainol and with hydrogen peroxide an N-oxide which crystallises in prisms m. p. 237". On methylation with methyl sulphate and alkali hydroxythebainol yields the methyl ether methiodide rhombs decomp. 233" which with hot alkali hydroxide gives deR-N-methyl- hydroxythebainol methyl ether OMeH\ OMe/\ OMell I OMel \//\CH \/\ 1~ ~ E k m e or IIcH CH,:CH-CH/\/ NMe,*CH,*CH,CH/\d HO-CH~ llCCH H O ~ H ! ,,!ICE CH-OH \/ CH-OH small needles m.p. 195-197". The hydriodide forms needles m. p. 255O and the methiodide obtained with the aid of methyl iodide microscopic prisms decomp. 239-240". On treating this substance successively with silver oxide and concentrated alkalis trimethyl- amine is eliminated and the nitrogen-free substance 2 3-dihydroxy- 5 6-dimethoxy-4-vinyl-2 3 4 4a-tetrahydro~henanthrene~ is ob- tained. This forms stout prisms m. p. 188-189" and is insoluble in alkali which shows that the two hydroxyl groups are in the aliphatic part of the molecule.An improved method of preparation of hydroxythebainone is described. Its dibromide obtained by the use of bromine and chloroform decomposes at 258" and on reduction by hydrogen and palladium black gives hydroxydihydrothebainone which may be obtained directly from hydroxythebainone by means of the same reducing agent. The methiodide of hydroxythebainone forms prisms m. p. 245" the acetyl derivative needles m. p. 197" andORGANIC CHERIISTRY. i. 139 the oxime of the acetyl derivative prisms m. p. 216-218". The methiodide of the acetyl derivative decomposes a t 212-213" and gives a non-crystalline deoxy-base on decomposition by alkalis. The methiodide of the acetyl derivative of 7-hydroxycodeine sinters a t 230" and decomposes a t 256".Reduction of hydroxycodeinone oxime by hydrogen and palladium under various conditions yielded hydroxydihydrocodeinone and it was not found possible to prevent the elimination of the oximino- group. Parallel experiments with styrylmethylketoxime and di- styrylketoxime yielded analogous results the products being benzylacetone and dibenzylacetone respectively. The Pilocarpine Series. 11. Pilocarpic Esters and their Derivatives. MAX POLONOVSKI AND MICHEL POLONOVSKI (Bull. SOC. chim. 1922 [iv] 31 1185-1201; cf. this vol. i 52).- Although it is generally accepted that a y-lactone group is present in pilocarpine and its isomeride few of the properties of a y-lactone have been actually shown to be characteristic of these substances. The authors find that the esterification of pilocarpine by means of methyl or ethyl alcohol and hydrogen chloride does not yield the ethyl ester of pilocarpic acid but the ethyl y-chloro-ester thus confirming the y-lactone grouping by the characteristic reaction of simultaneous esterification of acidic and alcoholic groups by alcohol and halogen respectively.Methyl y-chloropilocarpte forms small transparent prisms m. p. 4 2 4 4 " [.ID +32*6" and is a strong base; the nitrate forms lustrous plates m. p. 157" [alD 3-20". Ethyl 7-chloropilocaryate was obtained as an oil [a]D +29.2"; the nitrate forms lustrous plates m. p. 136" [.ID + 23.4". On treat- ment of the nitrate with concentrated sulphuric acid it is converted into ethyl 7-chloronitropilocarpate. The y-chloro-esters of pilo- carpine are readily relactonised with loss of the halogen atom and the alkyl group; this is accompanied by the transformation of cz portion of the alkaloid into its isomeride.isoPilocarpine behaves in a similar manner to pilocarpine on esterification. Methyl 7-chloroisopilocarpate is an oil of very alkaline reaction [.ID -7.5" (nitrate hygroscopic crystals m. p. about loo" [aJD -5.6") ; the ethyl ester is also an oil aD -5" (nitrate crystalline m. p. 95" [.ID 0). All these chloro-esters are unstable even in the solid state a t the ordinary temperature a portion of the substance being transformed into the hydrochloride of a quaternary base. The chloro- esters react readily with sodium ethoxide or methoxide yielding an oily mixture of the ethyl esters of a- and p-anhydropilocarpic acids separable by the Werence in solubility of their nitrates in water.a-Anhydropilocurpic acid C,,H,,O,N forms lustrous plates m. p. 243" [a]= -19"; the hydrochlorzde has m. p. 18'7"; the ethyl ester is an oil and yields a nitrate colourless needles m. p. 165" [.ID -19" in alcohol and +3-4" in water. @-Anhydropilocarpic acid forms prismatic crystals m. p. 186" [.ID +42" ; the hydrochloride has m. p. 142" ; the ethyl ester forms large transparent tablets m. p. 48" and gives a nitrate m. p. 95" [.ID -28" in water. C. K. I.i. 130 ABSTRACTS OF CHEMICAL PAPERS. On bromination ethyl a-anhydropilocarpate gives a bromo-deriv- ative C13H1902N2Br from which on hydrolysis the bromo-acid m. p. 138-139". is obtained. are suggested as possible for the isomeric acids.The Pilocarpine Series 111. isoPilocarpinani1 or Phenyl- isopilopyrrolidone. MAX POLONOVSKI and MICHEL POLONOVSHI (Bull. SOC. chim. 1922 [iv] 31 1201-1204; cf. preceding abstract).-Pilocarpine combines with aromatic amines yielding very stable pyrrolidone compounds. This reaction points to the existence of a lactone group in pilocarpine (cf. Emmert and Meyer A. 1921 i 268). The same substances may be obtained from the y-halogen acids derived from the alkaloid. Prolonged heating being necessary the products are derivatives of isopilocarpine. isoPiZocurpinuniZ is a hard substance slightly alkaline in reaction which gives with mineral acids crystalline salts of acid reaction. The nitrate colourless plates m. p. 162" [a]D+21*20 and the hydro- chloride white hygroscopic prisms m.p. 135" were prepared. The base yields on nitration a substance containing a nitro-group in the benzene ring which was not further investigated. The Pilocarpine Series. IV. Metapilocarpine. MAX POLONOVSK~ and MICHEL POLONOVSI~ (Bull. Soc. chim. 1922 [iv] 31 12061208 ; cf. preceding abstracts).-As substances obtained by the authors from the decomposition of 7-chloro-esters of pilo- carpine seemed to be identical with the metapilocarpine described by Pinner (A. 1905 i 658) it appeared that the latter could not be a simple stereoisomeride. An examination of its properties resulted in confirmation of Pinner's observations. The substance is inactive towards polarised light and although neutral to litmus and giving with acids salts of acid reaction does not combine with alkalis.Its reactions lead to the conclusion that in metapilocarpine the lactone grouping is absent and the acid group which replaces it is neutralised either by the basic glyoxaline ring or by a betaine linking CO-0-N-. The authors prefer the second explanation and therefore represent the transformation of pilocarpine into metapilocarpine by Et-$!H-YH-CH2-F :CH>NMe + Et-yH-yH-CH2-y :CH>NMe H. J. E. H. J. E. \I/ COO CH2-N:CH + - COO CH N:CH + - H. J. E. The Pilocarpine Series. V. Isomerism of Pilocarpine and isoPilocarpine. lMAx POLONOVSKI and MICHEL POLONOVSKI (Bull. Xoc. chim. 1922 [iv] 31 131&1330).-The authors discuss the evidence for and against the various hypotheses advancedORGANIC CHEMISTRY. i. 131 to account for the isomerism of pilocarpine and isopilocarpine and reject as untenable theories based on position isomerism in favour of stereoisomerism arising in or near the lactonic group. Their conclusions are largely based on the isomerisation of pilocarpine and its derivatives to isopilocarpine and its corresponding deriv- atives by action of small quantities of sodium ethoxide on alcoholic solutions of the alkaloid in the cold.It was found that pilo- carpine and nitropilocarpine were completely isomerised under these conditions by traces of sodium ethoxide that molecular quantities of sodium ethoxide gave an isomerised and delactonised product the de-lactonisation proceeding much more slowly than the isomerisation and requiring twenty-four to forty-eight hours for completion and that sodium pilocarpate sodium nitropilo- carpate and ethyl chloropilocarpate were not isomerised to the iso-derivatives ; in other words esterification or salt formation causes a stabilisation of the pilocarpine molecule whence it is con- cluded that for isomerisation by sodium ethoxide the presence of the unchanged lactone grouping is essential and this group is probably the seat of the isomerism.Whilst the nature pf the stereoisomerism must for the present be left an open question the authors incline to the view that it may be a case of partial racemisation of one of the two asymmetric C atoms of the lactonic group in view of the similarity between the isomerism of pilocarpine and that of hyoscyamine. G. F. M. Strychnos Alkaloids. XXXV. Ethers of Hydroxydihydro- brucinolone and the Violet Colour Reaction of the Nitro- pinones obtained therefrom.HERMANN LEUCHS JOHANNES GR~~ss and HARRY HEERING (Bey. 1922 54 [B] 3729-3738; cf. A. 1921 i 883).-The mtion of boiling methyl-alcoholic potassium hydroxide solution on brucinolone or its acetyl derivative leads to the formation of small amounts of methoxy- dihydrobrucinolone c22H2,@6~2,3H2qy coarse prisms or plates m. p. 82" [a]" -50.3" m glacial acetic acid solution and (mainly) a product m. p. 200-202" after softening at 190" which is con- verted by acetic anhydride into acetylmethoxydihydrobrucinolone C,-H,,0,N2 m. p. 258-270° [a] -92*5" in glacial acetic acid solution and acetylcryptobrucinolone. Attempts to separate the mixture m. p. 200-202" into its components by methyl-alcoholic ammonia at 100" were unsuccessful.Under these conditions cryptobrucinolone is converted into a base C2,H2,05N3 (isolated as the hydrochloride) identical with that isolated previously but in much poorer yield from crude acetylbrucinolone and ammonia (Leuchs A. 1914 i 317); its formation in the latter instance appears to depend on the presence of cryptobrucinolone or its ester in the acetylbrucinolone. It unites with phenylcarbimide to give the compound C,,H,O,N small prisms m. p. 200". Ethoxydihydrobrucinolone is converted by 6N-nif1-k acid at 0" into the corresponding quinone a yellowish-red resin which yields a semicurbame slender orange-coloured needles m. p. 240" after change at 211". The free quinone is reduced by sulphur dioxidei. 132 ABSTRACTS OF CHEMICAL P,QPERS.to a colourless amorphous product ; the corresponding acetate could not be caused to crystallise. The action of 5N-nitric acid on ethoxydihydrobrucinolone a t 50-60" leads to the formation of the nitroquinone hydrate C21H,0a3 golden-yellow leaflets which is further transformed into the semicurbaxone C22H260~ slender pale yellow needles and the crude monoethyl ester. The nitroquinone hydrate is reduced by sulphurous acid to the nitro- quinol hydrute C2,H2,0,N3 an amorphous dark violet powder m. p. (variable) about 185" (decomp.). The latter is converted by hydrogen chloride in methyl and ethyl alcohols into the methyl and ethyl esters amorphous violet substances. The triacetyl derivative of the nitroquinol has m. p. 175-180" (decomp.).The relationships of the quinonc and quinol compounds are illustrated by the scheme 0 0 .. .. /\-R NO,J'\-?*CO,H + y - N \/-NH No2011 II 1 >co -f II 11 0 G 0 OH OH NO/\-E~CO,H -+ HO*N:/\-~CO,H I I \/-N I I \/-'YH OH OH H. W. Strychnos Alkaloids. XXXVI. The Preparation of Meth- oxy- and Ethoxy-dihydrostrychninolones and of Strychninol- one-c; Oxidation of the Latter. HERMANN LEUCHS and RUDOLF NITSCHKE (Ber. 1922 55 [BJ 3738-3745; cf. A. 1921 i 883 ; Leuchs Griiss and Heering preceding abstract).-Strych- ninolone-a is converted by methyl-alcoholic potassium hydroxide solution initially into the b-form and finally into an inseparable mixture of methoxydihydrostrychninohe and strychninolone-c. The former has been isolated only as a resin which is converted by sodium acetate and acetic anhydride into a crystalline acetate C,,H,P5N2 colourless quadratic crystals m.p. 237-239" after softemng a t 230" [a] -109" when dissolved in glacial acetic acid. The course of the change is followed more readily when the methyl- is replaced by ethyl-alcoholic potassium hydroxide solu- tion since in this instance ethoxydihydrostrychninolone needles m. p. about lOO" [a] -51*9" in glacial acetic acid solution m. p. (+MeOH) 65-70' can be isolated directly. Strychninolone-c is transformed by acetic anhydride and sodium acetate into acetylstrychninolone-c C21H2004N2 domatic prisms m. p. 256-257" [a]. -229.6" in glacial acetic acid solution. The latter substance is oxidised in acetone solution by powdered potassium permanganate to an acid C2,H,0,N2,H20 colourless prisms m.p. 280-282' (decomp.) after softening a t 260" in which however the water of crystallisation appeam to be retained withORGANIC CHEMISTRY. i. 133 unusual tenacity. The acid is converted by hydrochloric-wid into acetic and oxalic acids and a non-crystalline unstable kych- chloride. The behaviour of acetylstrychninone-c is closely- ana- logous to that of cryptobrucinoIone; each probably contains the oxidisable group CHGRzr which is transformed by oxygen into CO,H*R:N*CO*CO,H. H. W. Strychnos Alkaloids. XXXVII. The Degradation of Methylcacotheline and its Violet Colour-reaction with Sodium Sulphite. HERMANN LEUCHS BERNHARD WINKLER and W. ROBERT LEUCHS (Ber. 1922 55 [B] 3936-3950).- Among the violet products which are formed from cacotheline and analogous substances of the brucine series methylcacotheline methosulphite (A.1919 i 35) occupies a peculiar position since it becomes isomerised when heated with the production of a violet isomeride which is therefore not formed in the usual maimer by the addition of two atoms of hydrogen. The isomerism cannot be regarded as definitely proved by analytical methods since the presence of two additional atoms of hydrogen in the molecule does not greatly affect the composition but it is now placed beyond doubt by the observations that the substance is produced in 50% yield by the action of one molecular proportion of sodium sulphite on two molecular proportions of methylcacotheline that sulphuric acid is not produced thereby and that the remainder of the methyl- cacotheline passes into the yellow methylbetaine (cf.A. 1920 i 179) which is convertible by further treatment with sodium hydrogen sulphite into the violet methosulphite. The reactions which take place in the production of the violet methosulphite are indicated by the scheme CH-CO’ .. 0 H 9 Hb’ P O$Il /\*$*CO,H I1 + ?yIe 02NI/J8.C02H + i NOS 0,H iN*O*SO,- \/*m 0 (1.) (11.1 OH 0 OH Me 02N-/f)i~-C0,H + Me HO*N/\*?*CO,H 1 iN-O-SO,*\/.N I 1. IN* o*s o,*\/ *NH OH OH (111.) (IV.1 The ammonium sulphite becomes added to the quinone nucleus with the formation of a phenylsulphite ester group or a sulphonic acid whereupon the quinone becomes isomerised to quinol without addition of extraneous hydrogen ; the nitro-group subsequently passes into the isonitro-form with production of a new quinonoid arrangement and development of the dark colour. The so-called violet ‘‘ methosulphite ” (formula IV) is convertedi. 134 ABSTRACTS OF GHEMICAL PAPERS.by drastic tmatment with hydrogen chloride and ethyl dcohol into a rnolzoe6hyZ ester (&~Ol&El dazk violet p h w and by acetic anhydride and anhydrom sodium acetate at 100" into an anhydride C,,H,O&S (the ammonium salt orange-coloured needles and the diacetyl derivative C,,H2,OllN3S pale yellow leaflets are described). The sulphite C,,H,,010N3S is trans- formed by methyl sulphate and alkali hydroxide mto a monomethyl derivative C23H2,0,0N3S a blackish-violet crystalline powder. Reduction of the violet sulphite or of the corresponding quinone with tin and hydrochloric acid has been shown previously (A.1919 i 36) to yield a colourless compound C,,H2,0,N3S the formation of which is now interpreted as due to the reaction of the :NH and *C02H groups to form :N*CO*. The main product formed by the action of sodium sulphite and sulphurous acid on the quinol from methylcacotheline (A. 1920 i 178) is the compound C2,H2,011N3S2 almost colourless four-sided plates or prisms in which the :N*CO* group of the substance described above has become transformed into :NH*CO,H and the NH group into *NH*S03H. A second product C,,H,08N,S needles appears to be derived from C22H2507N3S by the conversion of the amino- into the hydroxy-group. The violet methosulphite is converted by passing oxygen through its ammoniacal solution into a substance (cf.A. 1919 i 35) to which the composition C,,HBO1+S (instead of Cz1HSOl,N3S) is now assigned and for which the annexed 0 structure is suggested. The substance is i;\.a,co2H re-transformed into the violet metho- sulphite by drastic reduction with sulphur- i N*O*S02*\/*NH ous acid whereas when treated with tin and hydrochloric acid it gives the amine hydrochloride C,,H,,0,N3S,HCl,4H20 (the corresponding sulphate nitrate and hydrobromide are described) and small quantities of a cornpound C22H290&3S,HC1,2H20 thin prisms. Esterification of the compound C,,HSO1,N3S by methyl or ethyl alcohol in the presence of hydrogen chloride yields pro- ducts which contain halogen whereas when su€phuric acid is used the corresponding dimethyl compound C,H,,Ol2N3S pale green prisms and diethyl derivative C2,H,01,N,S rectangular pmms which is hydrolysed by potassium carbonate solution to the monoethyl compound C,H2,0,,N3S almost colourless short prisms are obtained.The dialkyl derivatives are produced by the esterifica- tion of the carboxy-group and the addition of alcohol consequent on the rupture of the ethylene oxide bridge with production of the group :C( OH) *C( OAlk) . The oxidation of the violet nitroquinol by air does not therefore lead to any consLderable degradation of the molecule. A more drastic change is effected when the original material methyl- cacothehe is treated with a solution of bromine in hydrobromic acid. Two products are thereby obtained the first of which produced in 30% yield has the formula CzoHz50sNzBr and crystal- lises in colourless rect'angular prisms or leaflets [aJ$ -6.75" in No2'l)0 11 I 5ORGANIC CHEMISTRY. i.135 aqueous solution (corresponding nitrate colourless needles or prisms [a]': -7.4" when dissolved in water); it appears to be analogous to the salt Cl&C,0,N2*HBr prepared by Hanssen (A. 1887 505; cf. Leuchs Millbrand and Leuchs A. 1922 i 1052) by the action of bromine water on cacotheline. The second cmpound is obtained initially in unstable union with sulphurous acid after the removal of which it has the composition Cl8H2,O,N2Br3 [a]:" -4.3" in aqueous solution; it appears to be a N-methyl derivative of a dibrominated bromide. The methyl ester of the oxime of cacotheline methochloride is converted by methyl alcoholic ammonia a t 100" into the methyl ester of the nitrosophenolmethylbetaine C,H2,07N4 apple-green prisms.H. W. Nitropyrroles. ANGELO ANGELI (Atti R. A c d . Lincei 1922 [v] 31 ii 3-5).-Fischer and Zerweck (A. 1922 i 758) state inaccurately that the nitration of alkylpyrroles may be effected smoothly by means of nitric acid (cf. Angeli A. 1911 i 397). The compounds investigated by these authors are not alkylpyrroles but esters of carboxylic acids derived from keto- formyl- etc. derivatives of pyrrole and the action on them of nitric acid con- sists not in true nitration but in replacement of acetyl aldehydo- methyl etc. groups by nitro-groups. Melanins from Pyrrole Derivatives. PIETRO SACCARDI (Biockm. Z. 1922 132 443-456).-A general review of the relations of melanin pigment to the pyrrole group.The Tetrachlorodipyridioiridiates. UCEL DELBPINE (Compt. rend. 1922 175 1075-1077; cf. A. 1922 i 859).- Details of the preparation of the red and orange isomerides of potassium tetrachlorodipyridinoiridiate by the action of pyridine on potassium iridichloride or potassium aquapentachloroiridiate are given together with an account of certain of their properties. The introduction of pyridine into the complex diminishes the number of acid functions and a t the same time renders the substance more stable. H. J. E. The Reaction between Acetylene and Aniline at High Temperatures. RIKO MAJIMA TADASHI UNNO and KASHICHI ONO (Ber. 1922 55 [B] 3854-3859).-The production of small quantities of indole by subjecting a mixture of acetylene and aniline to a red heat has been observed previously in the presence of aluminium oxide as catalyst.Experiments in which the latter was replaced by the oxides of silicon iron chromium thorium nickel cobalt manganese molybdenum tungsten vanadium or titanium or by metallic nickel iron cobalt platinum palladium osmium or copper did not lead to satisfactory results; nickel is the most powerful catalyst but speedily loses its activity. Better results are obtained by leading a mixture of aniline vapour acetyl- ene and carbon dioxide through a tube heated at 600-700" whereby under the most favourable conditions t'he yield of indole T. H. P. W. 0. K.i. 136 ABSTRACTS OF CHEMICAL PAPERS. amounts to 34% of the changed aniline. Benzene carbazole and p-naphthylamine are produced in considerably smaller quantity and still smaller amounts of pyrrole naphthalene and quinoline are formed.Glass and porcelain tubes are unsatisfactory on account of frequent breakage but excellent service is rendered by wide iron tubes which have been subjected to previous protracted heating a t 600-650" in a current of acetylene whereby the inner surface becomes coated with a thin black compact layer possibly composed of carbon. The formation of indole and @-naphthylamine is probably due to the intermediate production of vinylaniline thus NH,Ph+ CHiCH . . -+ NHPh*CH:CH 1% C6H4<gg>cH and NHPhGHzCH -+ CH,:CH*C,H4*NH2 +'aH# C,,H,*NH,. Carbazole is probably attributable to intermediate diphenylamine. It is uncertain whether carbon dioxide acts merely as a diluent or takes part in the change in accordance with the equation NH,Ph + C,H,+ CO,= C6H4<g>CH+ CO +H,O ; other gases such as ammonia hydrogen nitrogen or water vapour give less satisfactory results.Catalytic Hydrogenation under Pressure in the Presence of Nickel Salts. IV. Qwinoline Bases. JULIUS VON BRAUN ADOLF PETZOLD and JON SEEMANN (Ber. 1922 55 [B] 3779- 3792).-Under the conditions used by the authors quinoline is readily and quantitatively hydrogenated a t 210-215" into 1 2 3 4-tetrahydroq~inoline~ which can thus be prepared more readily than by the older methods. At 250" a portion of the tetrahydro-base is reduced further to decahydroquinoline and another portion is reduced to tertiary bases of pyridine character which have not been fully examined. Quinoline derivatives which contain a substituent in the benzenoid nucleus or in position 1 behave in the same manner as the parent bases whereas those which have a substituent in position 3 are also hydrogenated in the benzenoid nucleus to an extent which depends on the particular substituent present.The reductions are effected with the pure bases or with solutions of them in tetra- or deca-hydronaphthalene. The results are similar in every case and the rate of absorption of the gas is not appreciably influenced by the diluent. 6-Methylquinoline is converted at 120" into 6-methyl-1 2 3 4- tetrahydroquinoline b. p. 131-133"/9 mm. m. p. 37-38" the yield being 90% of that theoretically possible. 6-Chloro-1 2 3 4- tetrahydropinoline long colourless needles m. p. 43" b. p.155"/18 mm. is prepared a t 160"; the corresponding hydrochloride m. p. 190" picrate yellow needles m. p. 150" and nitroso-derivative yellow lustrous prisms m. p. 67" are described. [With A. SCHULTHEISS.]-~ 7-Ethylenedioxyquinoline (Sonn and Benirschke A. 1921 i 805) is very readily hydrogenated at 180-190" to 6 7-ethylenedioxy-1 2 3 4-tetrahydroquinoline H. W.ORGANIC CHEMISTRY. i. 137 b. p. 193"/11 mm. m; p. 101" (picrate m. p. 168"; hydrochloride m. p. 199" (Sonn and Benirschke give m. p. 201") ; nitroso-derivative m. p. 110"). 2-Phenyl-1 .2 3 4-tetrahydroquinoline b. p. 196-197"/12 mm. is obtained from 2-phenylquinoline a t 150". 3-Ethylpinoline an almost colourless liquid with an odour of quinoline is prepared in 80% yield by the action of n-butyraldehyde on o-aminobenzaldehyde a t 120-130" (cf.Wislicenus and Elvert A. 1909 i 420); it has b. p. 135-138"/12 mm. d? 1*0508 ng 1.6030 (hydrochloride m. p. 173" ; picrate m. p. 197" ; methiodide m. p. 191"). The base is readily hydrogenated a t 180-lW" yielding thereby a mixture of 3-ethyl-5 6 7 8-tetrahydroquimline and 3-ethyl-1 2 3 4-tetrahydroquinoline which are separated from one another with the aid of benzoyl chloride. The former is a colourless liquid b. p. 125-128"/12 mm. di0 0.99218 n1,8 1.5311 (it gives a methiodide m. p. 120" and a picrate yellow crystals m. p. 158"). The latter has b. p. 140"/12 mm. d 19041 ng 1.5625 (hydrochloride m. p. 210" ; picrate m. p. 142" ; methiodide C,,H,,,NI m. p. 205"; the benxoyl and nitroso-derivathes are non- crystalline). 3-n-AmyZquinoline prepared in almost quantitative yield from o-aminobenzaldehyde and heptaldehyde at 180" is a colourless liquid b.p. 179'116 mm. di7 1.0048 n$ 1.5715 (hydrochloride m. p. 174"; picrate m. p. 153"; methiodide m. p. 69"). It is hydrogenated at 180-190" with the formation of approximately equal amounts of 3-n-amyl-1 2 3 4-tetrahydroquimZine a colour- less liquid b. p. 159-164"/12 mm. di7 0.96625 ng 1.5339 (hydro- chloride needles m. p. 124" methiodide C,,H,,NI m. p. 145"; the picrate benzoyl compound acetyl derivative and nitroso-com- pound are non-crystalline) and 3-n-amyl-5 6 7 8-tetrahydro- quimline a colourless nearly odourless liquid b. p. 167"/12 mm. di7 0.96028 ng 1*5188. The latter substance gives a picrate long needles m.p. 135" and a methiodide m. p. 105" whereas the chloride and chloroplatinute are non-crystalline; it does not react with acetic anhydride or nitrous acid. The base is oxidised by potassium permanganate to oxalic and pyridine-2 3 5-tricarb- oxylic acids. 3-Phenylquinoline is hydrogenated with remarkable ease a t 160" to a mixture of 3-phenyl-1 2 3 4-tetrahydroquinoline and 3-phenyl- 5 6 7 8-tetrahydroquinoline from which the former is very readily separated by taking advantage of its sparing solubility in alcohol with which the latter is readily miscible. 3-Phenyl- 1 2 3 4-tetrahydroquinoline i s a colourless crystalline sub- stance m. p. 83" (hydrochloride matted needles m. p. 229" ; picrate m. p. 181"; picrolonute a yellow powder m. p. 205"; acetyl deriv- ative feathery crystals m.p. 78"; nitroso-compound m. p. 147"). 3-Phenyl-5 6 7 8-tetrahydroquinoline is a colourless liquid b. p. 211-212"/18 mm. (hydrochloride m. p. 235" after darkening at 225-230"; picrolonute a yellow powder m. p. 201"; methiodide C,,H,,NI m. p. 240-243"; the base does not react with nitrous acid or acetic anhydride). 3-Phenyl-5 6 7 8-tetrahydro-i. 138 ABSTRACTS OF CHEMICAL PAPERS. quinoline is reduced by sodium and ethyl alcohol to 3-phenyl- deuzhydroquinoline colourless crystals m. p. 98" after softening at 95" (nitroso-derivative m. p. 110" ; picrate m. p. 210-212" ; the acetyl compound could not be caused to crystallise). The Relative Stability of Cyclic Bases. VII. Substituted Tetrahydroquinoline Rings. JULIUS VON BRAUN JON SEE- MANN and ADAM SCHULTHEISS (Ber.1922 55 [B] 3803-3817).- In previous communications (von Braun and Neumann A. 1917 i 282; von Braun Heider and Neumann A. 1917 i 167) it has been pointed out that whereas the stability of the tetrahydro- quinoline ring towards scission during reduction by sodium amalgam is little affected by the introduction of the methyl group in position 2 that of the dihydroindole ring is modified profoundly by 2 or 3 methylation. The presence of a methyl group in position 3 or 4 in the tetrahydroquinoline ring is now shown not to exert a marked effect on the course of the change. On the other hand the presence of a phenyl group in position 2 causes the almost quantitative) rupture of the non-aromatic ring linking whereas when the group is in position 3 the three possible types of change are realised.H. W. CH2-FHMe 1 ; 3-Dimethyl-1 2 3 4-tetrahydroq~inoline~ "H4<Nlyre.CH. ' an almost colourless liquid b. p. 130-132"/17 mm. is obtaiGed by the reduction of 3-methylquinoline methiodide by tin and hydrochloric acid ; the very hygroscopic hydrochloride m. p. about 110" picrate m. p. 131" and methiodide m. p. 204" are described. The corresponding quaternary chloride is converted by sodium amalgam into a mixture of 1 3-dimethyl-1 2 3 4-tetrahydro- quinoline and y-phen yl- p-methylpropyldimethylamine CH,Ph*CHMe*CH,*NMe from which the former is removed by treatment with formaldehyde in hydrochloric acid solution. The latter base is a colourless liquid b. p. 100-105"/7 mm. 22l"/atmospheric pressure (hydro- chloride m.p. 90"; picrate m. p. 87"; methiodide m. p. 140"). 1 4-Dimethyl-1 2 3 4tetrahydroquinoline methiodide is con- verted into the corresponding chloride which is transformed by sodium amalgam into 1 4-dimethyl-1 2 3 4-tetrahydroquinoline and y-phenylbutyldimethyiylamine CHMePh*CH,CH,*NMe a liquid b. p. 112-115"/7 mm. (hydrochloride m. p. 100"; picrate rn. p. 98"; methiodide m. p. 125") which constitutes 60% of the mixture of bases. 2-Phenyl-1 2 3 4-tetrahydroquinoline is converted by methyl iodide and aqueous alkali mainly into 2-phenyl-1-methy,?-1 2 3 4- tetrahydroquinoline colourless crystals m. .p. 101" b. p. 188- 192"/14 mm. ; the corresponding hydrochlorzde m. p. 157" chloro- platinate m. p. 172" nitroso-compound a microscopic green powder m.p. 75" and diphenylmethane derivative C33H34N2 m. p. 60" after slight previous softening are described. The base unites with difficulty with methyl iodide to give the quaternary iodide C17H20NI rn. p. 185". The quaternary chloride (chloro-ORGANIC CHEMISTRY. i. 139 pkrtinute orange-coloured crystals m. p. 203") is almost quantit- atively converted by sodium amalgam into o-y-phenylpropjldi- methylaniline NMe,C6H4*CH,*CH2*CH2Ph b. p. 175-178"/10 mm. The picrate golden-yellow needles m. p. 110" the non-crystalline hydrochZoride and the chloroplatinate a yellowish-brown powder m. p. 170° are described. The base does not unite reaGly with methyl iodide thus proving that the dimethylamino-group is attached to the benzenoid nucleus and is sterically hindered and that the compound is not the isomeric substance CH,Ph*CH,*CHPh*NMe,.2-Phenyl-l-methyl-l 2 3 4-tetrahydroquinoline suffers fksion in accordance with the scheme C,H,< CH2-(?H2 +BrCN -+ CN*N~e-.C6H,.CH2*CH,*CHPhBr to the extent of a t least 50% when treated with cyanogen bromide in a gently boiling water- bath. Since cyanoamides cannot be distilled without decom- position and seldom crystallise the product of the action is treated directly with an excess of piperidine whereby i t is converted into a portion insoluble in acid b. p. 218°/vacuum and a bromine-free amorphous base which readily unites with methyl iodide giving the substance C2,H3&1 a pale-brown microcrystalline powder which loses methyl iodide without definitely melting above 60".The hydroxide C 6 H 4 (CH2-cH,>CHPh "Me2(OH) is mainly decomposed with loss of methyl alcohol when distilled under diminished pressure giving 2-phcnyl-1-methyl-1 2 3 4-tetrahydroquinoline. In striking contrast to the 2-phenyl derivative 3-phenyl- 1 2 3 4-tetrahydroquinoline is readily converted by methyl iodide into the quaternary iodide C,,H$I m. p. 172" which loses methyl iodide when distilled under diminished pressure and gives 3-phenyl-1-methyl-1 2 3 4-tetrahydroquinoline m. p. 42" b. p. 195-202"112 mm. The corresponding picrate m. p. 17S0 the non-crystalline hydrochloride and chloroplatinate m. p. 192" the nitroso-compound m. p. about 105" and the diphenylmethane derivative C,,H,,N m. p. 92" are described. The quaternary chloride (chloroplatinate m.p. 204O) is converted by sodium amalgam into a mixture of 3-phenyl-1-methyl-1 2 3 4-tetra- hydroquinoline (47 % ) P y -diphen ylpropyldimethylarnin e CH,Ph-CHPh*CH,*NMe (45%) and 0- p - phen yl pro pyldimeth ylaniliiz e NMe,*CGH4*CH2-CHPhMe (8%). The two bases last mentioned are separated by taking advantage of the inability of the o-dimethylaniline derivative to unite with methyl iodide in ethereal solution. The quantity of 0- p -phenylpropyldimethylanihe available was insufficient to permit its isolation in a homogeneous condition and it is characterised by its picrate m. p. 166-167" non-crystalline hydrochloride and chloroplatinate m. p. 181 '. py-Diphenylpropyldimethylamine meth- iodide is exceedingly hygroscopic; it is conrerted into the corre- sponding chloride (chhoaurute yellow needles m.p. 164" ; chloro- platinate a microcrystalline powder m. p. 236"). The constitution NMe-CHPhi. 140 ABSTRACTS OF CHEMICAL PAPERS. of the iodide is established by the observation that the corre- sponding hydroxide is decomposed when distilled under diminished pressure into u-benzylstgrene CH,Ph*CPh:CH a liquid b. p. 140-143"/vacuum @ 1.0143 nz 1.5903 (corresponding dibromide colourless crystals m. p. 98"). 3-Phenyl-1-methyl-1 2 3 4- tetrahydroquinoline is converted to a slight extent by cyanogen bromide into the corresponding methobromide (identified by its conversion into the chloroplatinate m. p. 203") but mainly into 1-cyano-3-phenyl-1 2 3 4-tetrahydroquinoline m. p. 78" ; fission of the ring as in the case of the 2-phenyl compound is not observed.6 7-Ethylenedioxyquinoline methiodide m. p. 270" is reduced by tin and hydrochloric acid to 6 7-ethylenedioxy-1-methyl- 1 2 3 4-tetrahydroquinoline colourless leaflets m. p. 53" b. p. 165-170"/8 mm.; the hydrochloride m. p. 203" picrate m. p. 170" and the methiodide m. p. 220° are described. The latter compound is prepared more advantageously by exhaustive methyl- ation of 6 7-ethylenedioxy-1 2 3 4-tetrahydroquinoline. It is converted into the corresponding chloride which is transformed by sodium amalgam into a mixture of 6 7-ethylenedioxy- 1-methyl- 1 2 3 4-tetrahydroquinoline (40%) and y-3 4-ethylenedioxy- phenylpropyldimethylamine C2H4O2:C6H,*[CH2J,~NMe2 b. p. 162- 164"/7 mm. which are separated from one another by careful fractional distillation ; the methiodide m.p. 165" picrate m. p. 167" and hydrochloride m. p. 169" of the latter base are described. H. W. The Mechanism of Syntheses of isoQuinoline from Benzyl- amine Derivatives. PAUL STAUB (Helv. Chim. Acta 1922 5 888-894).-Many attempts to synthesise isoquinoline derivatives by ring closure in appropriate benzylamine derivatives are recorded in the literature but few were successful. In an attempt to deter- mine the conditions requisite for success the following new com- pounds were prepared for ring closure experiments. u-Benzylidineaminoiso~o~l alcohol CHPh:N*CH,-CHMe*OH was obtained by reducing nitroisopropyl alcohol NO,CH,*CHMe *OH and condensing the product with benzaldehyde; it crystallises in needles m.p. 76-76.5". Benzylaminoisopropyl alcohol CH,Ph*NHCH,*CHMe*OH was obtained by the action of benzyl chloride on aminoisopropyl alcohol; b. p. l42"/11 mm. Benxenesulphonbenxyl- p-hydroxyethylamide CH,Ph*N(SO,Ph)*CH,*CH,*OH was prepared by heating benzenesulphonbenzylamide with ethylene oxide a t 170"; it formed a viscous liquid crystallising slowly and was not purified. CH,Ph*N( S02Ph)-CH2*CH2Br was formed by the dction of ethylene bromide on sodium benzene- sulphonbenzylamide in ether ; m. p. 82-5-83" Benzenesulphonbenz yl- p-bromoethylamide,ORGANIC CHEMISTRY. i. 141 Benzenesulphonbenzyl phenacylamide CH,Ph*N( S0,Ph) *CH,*COPh was prepared by the action of bromoacetophenone on sodium benzenesulphonbenzylamide in ether. The product was not crystallised.Acetobenzylphenmylarnide CH2Ph*NAc*CH,*COPh was obtained as a syrup from the action of bromoacetophenone on sodium benzyl- acetamide. In no case could any i.soquinoline derivative be obtained by the action of any of the usual ring-closing agents on any of the above six compounds. It is concluded that a benzene derivative containing the chain Ph*C*N*C*C- must if it is to be convertible into an isoquinoline base conform to two rules. In the lateral chain it must have (1) a system of conjugated double bonds actual or potential; (2) a hydroxyl or alkoxyl group in P-position to the nitrogen atom. The compound CHPh:N*CH,*CH( OEt) conforms to condition (1) by loss of alcohol and readily forms isoquinoline. Benzyl- aminoacetaldehyde CH,PhmNH*CH,*CHO which is converted by fuming sulphuric acid into isoquinoline may be supposed to undergo oxidation and by passing into the tautomeric form CHPh:N*CH:CH*OH satisfies the conditions.E. H. R. Catalytic Hydrogenation under Pressure in the Presence of Nickel Salts. V. The Carbazole Complex. JULIUS VON BRAWN and HEINRICH RITTER (Bet-. 1922 55 [B] 3792-3803; cf. Padoa and Chiaves A. 1908 i 772).-The process used by the authors does not cause the hydrogenation of pyrazole even a t 260" and under a pressure of 30 atmospheres in spite of the use of a material which has been exhaustively purified in several different manners. Nevertheless the authors are inclined to the view that pure pyrazole is not unusually resistant to hydrogenation and that the failure of their experiments is due to some unknown catalytic impurity.The N-alkylcarbazoles are readily hydro- genated with initial addition of four hydrogen atoms to one benzene nucleus. Subsequently the second benzene nucleus is attacked with addition of a further four atoms of hydrogen. 9-Methylcarbazole readily absorbs about seven atomic pro- portions of hydrogen a t 210-215" and 25 atmospheres pressure. About 40% of the initial material remains unchanged whilst a portion is perhydrogenated with production of ammonia. The liquid pro- duct of the reaction is a mixture of the octahydro- and tetrahydro- derivatives with 9-methylcarbazole from which the first-named is readily separated by treatment with hydrochloric acid (20y0) in which it alone dissolves. The remaining bases cannot be separated from one another by distillation or crystallisation ; the presence of the tetrahydro-compound is established by the formation of the strongly basic hexahydro-derivative when the mixture of bases is treated with tin and hydrochloric acid.i.142 ABSTRACTS OF CREMICBL PAPERS. c I3 C3-:l'lethyEocta~~yd~ocu~~~zoZe MeN< I 6 8 lustrous leaflets m. p. 94" b. p. 176-178"/16 mm. is somewhat unstable towards air and does not give the pine-shaving or the dimethylaminobenzalde- hyde reaction. It does not give a well-defined picrate or meth- iodide; it is readily oxidised by chromic acid potassium perman- ganate or ferric chloride but it has not yet been found possible to isolate uniform products of the action. It is conveniently reduced by tin and boiling hydrochloric acid (20%) to 9-methyZ- decahydrocarbaxole MeN< I 6 8 a colourless mobile liquid b.p. 138-139"/12 mm. which is stable towards air ; the non-crystalline hydrochloride hydrobromide m. p. 202-204" picrate m. p. 162" and methiodide m. p. 189" are described. The presence of the double bond in the base is betrayed only by its instability towards permanganate ; it yields only the hydrobromide when treated with fuming hydrobromic acid and does not unite with bromine or hydrogen even under widely varied conditions. The methiodide is transformed by successive treatment with silver oxide and dis- tillation into 2 -dimeth ybamino- A1 1'- dic yclohexen yl "-'\ (annexed formula) an almost colourless liquid b. p. ()We2 'I I 148"/15 mm. which is conveniently characterised \' as the picrate m.p. 157". The new base is some- what unstable and is readily converted by sulphuric acid (10%) into 2-A1-cyclohexenyZcyclohe~anone (annexed formula) b. p. 137- CH CH 139"/14 mm. diB 1.015 n 1.515 (semicurbaxone /\ /\ m. p. 191"). The ketone is certainly not p - 9 ~ (p2 identical with the compound obtained by Wallach (A. 1911 i 473) by the auto- %' '' CH CH2 condensation of cyclohexanone and it would \' \A2 therefore appear that the latter has the CH2 alternative constitution C,H,O:C,H,o sug- gested by Wallach. 2-Al-cycZoHexenylcyclohexanone is readily reduced by hydrogen in the presence of palladous chloride to 2-cycZohexylcycZohexanone b. p. 135"/11 mm. d:6 0.987 ny 1.4915 (cf. Wallach Zoc. cit.). The reduction of 9-ethylcarbazole is very similar to that of the methyl compound.9-EthyZoctahydrocarbuzoZe lustrous leaflets m. p. 43" b. p. 162-163"/9 mm. is unstable towards air; it does not give a methiodide or a picrate. It is readily reduced to 9-ethyldecahydrocarbuzoZe a colourless liquid which is stable towards air b. p. 140-141"/12 mm. ; the non-crystalline hydrochloride the picrate m. p. 133" and the methiodide m. p. 176-177" are described. 2 - M ethylet h ylarnino-A1 1'- d icyclohexen yl is a colourless liquid b. p. 148-150"/12 mm. which gives a non-crystalline picrate and methiodide. It is readily transformed by dilute sulphuric acid into 2-A1-cycZohexenylcycZohexanone and methyl- ethylamine. 9-EthyZhexahydrocarbuzoZe is a colourless odourless liquid b. p. 155-167"/8 mm. 292-293"/749 mm.; it gives a well-defined methiodide m.p. 174". The base is transformed by a mixture of nitric and sulphuric acids at 0" into the nitro-com- C6H8 C HORGANIC CHEMISTRY. i. 143 /\ pound (annexed formula) golden-yellow needles f) I I m. p. 142" which is reduced by stannous chloride \/\/\/ to 7-amino-Q-ethylhexahydmcarbazole an almost colourless very viscous liquid b. p. 224-226"/24 mm. which shows all the cdour reactions characteristic of the simpler meta-diamines of the aromatic series. It has not been found possible to effect the smooth dehydro- genation of 9-methyl- or 9-ethyl-hexahydrocarbazole ; if the substances are passed over lead oxide and pumice the alkyl residues are lost and carbazole is produced. Benzo-polymethylene Compounds. VIII. Cyclic Analogues of Atophan. JULIUS VON BRAUN and PAUL WOLFF (Ber.1922 55 [B] 36763688) .-1 -Ketotetrahydronaphthalene condenses readily with isatin to give 5 6-dihydro-a-naphthacridine-7-carb- oxylic acid (annexed formula) which readily undergoes further change. Constitutionally the new compound (for f2\ which the name tetrophan is proposed) is allied I somewhat closely to 2-phenyl-4-cinchoninic acid &hAh/\/ 120 (atophan) from which however it differs entirely 'I 16a 61 in its physiological action having a characteristic p/x($/ effect on the spinal marrow somewhat resembling that of strychnine. The physiological properties of a number of its derivatives have been examined. Substitution in the benzenoid nuclei of the isatin and tetrahydronaphthalene complexes does not affect the qualitative nature of the action.The presence of the basic nitrogen atom and of the carboxyl group appears essential. A new ring produced by the insertion of more than one carbon atom into the atophan complex must be present which must not be eccentrically united. The group -CH,*CH,- need not be so fully hydrogenated. Since tetrahydroatophan shows close physiological resemblance to tetrophan it is to be expected that the action of the latter would be considerably enhanced by transforming it into its tetrahydro- derivative; the reverse is however found to be the case. 5 6-Dihydro-a-naphthacridine-7-carboxylic acid slender pale yellow needles m. p. 252" (decomp.) is prepared smoothly by heating a mixture of isatin and 1-ketotetrahydronaphthalene with aqueous- alcoholic potassium hydroxide solution.It reacts incompletely with mineral acids yielding salts which are hydrolysed by water. The sodium lead basic copper and silver salts are described; the ethyl ester long coarse needles m. p. 80" is prepared from the latter. The acid is decomposed when heated somewhat above its melting point into 5 6-dihydro-u-naphthucridine b. p. 237- 238"/10 mm. m. p. 60"; the corresponding hydrochloride long needles m. p. 226" picrate m. p. 206" and methiodide a reddish- yellow crystalline powder decomp. 191" are described. The base is readily dehydrogenated by lead oxide at 300-320" with production of a-naphthacridine m. p. 108". It is oxidised by chromic acid in glacial acetic acid solution to 5 6-diketo-u-nuphth- acridine an orange-coloured powder m.p. 242" (a salt with chromic acid is described). NEt H. W.i. 144 ABSTRACTS OF CHEMICAL PAPERS. 5 6-Dihydro-ct-naphthacridine-7-carboxylic acid is converted by bromine and glacial acetic acid a t 120-130" into u-naphth- acrid~ne-7-mrboxylic acid a yellow powder m. p. 261" ; the cobalt copper mercuric and silver salts are described. The methyl ester has m. p. 83". When heated above its melting point the acid is converted into a-naphthacridine m. p 108". 5 6-Dihydro-a-naphthacridine-7-carboxylic acid /\ is reduced by sodium and ethyl or amyl alcohol to 5 6 6a 7 12 12a-hexahydro-a-naphthmridine- /\/\/\/ 7 -carboxylic acid (t etrahydrot etrophun) (annexed I I I formula) m. p. 190" (decomp.) after softening \/\/\/ at 180" ; the corresponding nitroso-compound after softening a t 244" are described.6 6-Dihydro-ll-methyl-a-naphthucridine-7-carboxylic acid colour- less crystals m. p. 188" (decomp.) is prepared from l-ketotetra- hydronaphthalene and o-methylisatin ; its metallic salts closely resemble those of the parent acid. 5 6-Dihydro-11-methyl- u-naphthacridine has m. p. 93-94" b. p. 248-253"/16 mm.; it yields a picrate m. p. 141" and a hydrochloride long pale yellow needles m. p. 173" but could not be caused to react with methyl iodide. 11-Methyl-a-naphthucridine m. p. 107" gives a picrate m. p. 155" and a hydrochloride m. p. 136" but does not react with methyl iodide. 5 6- Dihydro-9-methyl- a-naphthctcridine-7-carboxylic acid has m. p. 293" (decomp.); the sodium salt dissolves very sparingly in water.9-Clhloro-5 6-dihydro-a-naphthacridine-7-carboxylic acid m. p. 283" (decomp.) is converted when heated above its melting point into 9-chloro-5 6-dihydro-a-naphtFridine m. p. 102" b. p. 257- 26Zo/14 mm. The hydrochloride of the latter has H2 m. p. 240". The base loses the chlorine atom H2/\H2 when it is treated with lead oxide. I 9-Bromo-5 6 - dihydro-u-napht7Lcccridine- 7 -curb - H k / N oxylic acid has m. p. 265"; the silver salt and the It ,) methyl ester yellow leaflets m. p. 128" are de- /\/\/\ /' scribed. 9-Bromo-5 6-dihydro-a-naphthacridine 1 (I I IH crystallises in pale yellow needles m. p. 168" \/\/\/ (hydrochloride m. p. 211-212"). 5 6-Dihydro-1 2 - tetramethylene - a - naphthacr - idine-7-carboxylic acid (annexed formula) is pre- pared from isatin and a-keto-octahydrophenanthrene ; it has m.p. 210" (decomp.) after darkening at 180". 'OZH 2-Acenaphthylquinoline-4-carboxylic acid pre- pared from 4-acetylacenaphthene and isatin has pared from ar-u-aminotetrahydronaphthylamine pyruvic acid and benzaldehyde forms yellow crystals m. p. 260" after softening at 255"; its NH I eo,H I m. p. 149" and acetyl derivative m. p. 247" I" H2 '\/\ 'I 1 IPh m. p. 234" after previous softening. T'etramethyleneafophan (annexed formula) pre- H2 physiological action resembles that of atophan. H. W.ORGANIC CHEMISTRY. i. 145 The Relationship between Fluorescence and Chemical Constitution in the Case of Derivatives of Benzoxazole. 11. F. HENRICH [with H. SUNTHEIMER and c. STEINMANN] (Ber. 1922 55 [B] 391 1-3921).-1n a previous communication (A.1921 i 886) it has been shown that the development of fluor- escence in alkaline solutions of hydroxybenzoxazole derivatives an aromatic nucleus directly attached by one of its carbon atoms to the p carbon atom and when the hydroxyl group is in the para- position to the nitrogen atom. This regularity is now shown to be true of certain derivatives of 2 4-dihydroxytoluene. 2 4-Dihydroxytoluene m. p. 106-107" is prepared from 2 4-diaminotoluene through the compounds 2-amino-4-acetamido- toluene 4-acetamido-2 - hydroxytoluene and 4- amino-2 - hydroxy- toluene ; the necessary conditions for each change are described fully in the original. It is converted by amyl nitrite and potassium hydroxide in absolute alcoholic solution into 5-nitroso-2 4-di- hydroxytoluene decomp.175-180" according to the rate of heating after darkening and softening at 146"; the potassium salt and the dibenzoyl derivative m. p. 146-153" are described. 2 4-Dihydroxytoluene is converted by fuming nitric acid in the presence of ether into a mixture of 3-nitro-2 4-dihydroxy- toluene bright red needles m. p. l l l " and 5-nitro-2 4-dihydroxy- toluene orange-yellow needles m. p. 118-119" which can be separated from one another by takiag advantage of the volatility of the former with steam with which the latter does not volatilise. 5-Amino-2 4-dihydroxgtoluene hydrochloride long colourless needles is prepared by the reduction of the corresponding nitroso- or nitro-compound with stannous chloride and concentrated hydro- chloric acid.The free amine is obtained by the addition of sodium hydroxide to an aqueous solution of the hydrochloride; it dis- solves to a dark blue solution in an excess of the reagent and readily absorbs oxygen without however becoming converted into dyes of the type of litmus. The hydrochloride is transformed by acetic anhydride into 6-acetoxy-2-methyl-5-methylbenzomzole (an- nexed formula) colourless needles m. p. 94" which is converted by alcoholic potassium hydroxide solution into Me/\/N\ 6-hydroxy-2 5-dimethylbenxoxaxole colourless crystals m. p. 221"; the latter substance does ~ c ~ ( / j ~ / not fluoresce in aqueous alkaline solution. 6-Benzoxy-2 -phenyl- 5-methylbenxoxaxole colour - less crystals m. p. 164-165" after softening a t 163" is prepared from 5-amino-2 4-dihydroxytoluene hydrochloride and benzoyl chloride and is hydrolysed by alcoholic potassium hydroxide solu- tion to 6-hydroxy-2-phenyl-5-methylbenzoxazole colourless crystals m.p. 242" after softening a t 236" which has a green fluorescence in aqueous sodium hydroxide solution. 3-Nitro-2 4-dihydroxytoluene is reduced by stannous chloride and concentrated hydrochloric acid to 3-amino-2 4-dihydroxy- toluene hydrochloride colourless needles which is converted by HO*C,H,<O>C*R(p) N is observed only when R in position p is CMe VOL. CXXIV. i. Bi. 146 ABSTRACTS OF CHEMICAL PAPERS. successive treatment with benzoyl chloride and alcoholic potassium hydroxide solution into 4-hydroxy- 2 -phen yl-5-meth ylbenxoxazole colourless crystals which do not exhibit fluorescence in alkaline solution.H. W. The Relative Stability of Cyclic Bases. VIII. The Phen- morpholine and Homotetrahydroquinoline Rings. JULIUS VON BRAUN and JON SEEMANN (Ber. 1922 55 [B] 3818-3825).- It is shown that the stability of the morpholine ring is increased to an unexpected extent by its association with an aromatic ring so that it is at least as stable towards cyanogen bromide as 1 2 3 4- tetrahydroquinoline and even more stable towards sodium amalgam. Homo-1 2 3 4-tetrahydroquinoline does not suffer fission under the action of cyanogen bromide. The nine rings (pyrrolidine piperidine morpholine dihydro- indole dihydroisoindole 1 2 3 4-tetrahydroquinolineY 1 2 3 4- tetrahydroisoquinoline phenmorpholine and homo- 1 2 3 4-tetra- hydroquinoline) exhibit uniformity in their behaviour towards cyanogen bromide sodium amalgam and the Hof mann degradation if the dihydroindole and the phenmorpholine systems are not considered.The peculiarity of the latter rings appears to be caused by the presence in them of the group -Ar-T-CH,-CH,-. N - p-Hydroxyethyl-o-anisidine is conveniently prepared in 75- 80% yield by heating o-anisidine with a considerable excess of ethylene chlorohydrin on a water-bath; the picrate m. p. 140" and the hydrochloride m. p. 134" are described. The base is con- verted by successive treatment with concentrated hydrochloric acid at 160-180" and with dilute aqueous alkali into Dhenmor- I I pholine C&,< '-YH2 b. p. 127-128"/12 mm. The latter is NH*CH transformed quantitatiGly by methyl iodide and sodium hydroxide into l-methylphenmorpholinium methiodide which is decomposed when distilled under diminished pressure into 1 -methylphenmorph- oline b.p. 124"/12-5 mm. (picrate m. p. 144"). 1 -Methylphenmorpholine reacts slowly with cyanogen bromide at the temperature of boiling water giving unchanged material 4-methylphenmrpholine methobromide in. p. 213" and 4-cyano- phenmrpholine C,H,< '-YH2 aliquid b. p. 115-118"/1 mm. ; the'latter could not be obtained in a perfectly homogeneous con- dition and is characterised by converting it into the guanidine derivative C6H4< YH2 small colourless needles m. p. 152" the non-crystalline hydrochloride and chloroplatinate m. p. 144" of which are described. 4-Methylphenmorpholine methochloride is converted by sodium amalgam almost entirely into 4-methylphenmorpholine which is characterised by its con- version into the diphenylmethane derivative C,,H,20,N2 a very viscous liquid b.p. about 260"/2 mm. (decomposition occurs before completion of the distillation) (dimethiodide m. p. 157"). N( CN) *CH O-- N[C(:NH)*NHPh]*CH,'ORGANIC CHEMISTRY. i. 147 The difficulty of methylating homo-1 2 3 4-tetrahydroquinol- h e c6H4<NH2%H2>CH2 CH *CH has been indicated previously (von Braun and Bartsch A 1913 i 197) ; it has now been found possible to isolate the products of the action in a homogeneous form. The quaternary iodide C,,H,,NI has m. p. 155". 1-Methylhomo- 1 2 3 4-tetrahydroquinoline has b. p. 108-110"/10 mm. and gives a picrate m.p. 139" a non-crystalline hydrochloride and a chbroplatinate m p. 186"; it combines very slowly with methyl iodide. It is obtained as the sole basic product when the correspond- ing quaternary hydroxide is distilled in a vacuum It is converted by cyanogen bromide into 1-methylhomo-1 2 3 4-tetrahydro- quinoline methobromide (identified as the corresponding chloro- platinate m. p. 197") and 1-cyanohomo-1 2 3 4-tetrahydro- quinoline C,H,<F$*> b. p. 178-182"/13 mrn. which could not be obtained completely free from bromine and is identified bv transformation into the guanidine derivative 2 Condensation of Benzidine with Formaldehyde. HEISA- BURO KONDO and SUEZO ISHIDA ( J . Pharm. SOC. Japan 1922 979-985; cf. H. Schiff A. 1892 1223).-By adding 30 C.C.of 35% formaldehyde solution to benzidine (10 g . ) dissolved in abso- lute alcohol (200 c.c.) a greyish-white light amorphous condens- ation product dimethanolbenxidine C1,H,(NH*CH2*OH) is pre- cipitated; it has m. p. 271-272" after sintering a t 260" and is sparingly soluble in alcohol or water but readily soluljle in hydro- chloric acid. It is not identical with dimethylenebenzidine m. p. 140-141" obtained by Schiff by the same method. When dissolved in dilute hydrochloric acid the odour of formaldehyde is perceptible and from the solution methanolbenxidine hydrochloride NH,*C,H4*C6H4*NH*CH2*OH,2HC1 colourless needles of high melting point was isolated by adding concentrated hydrochloric acid. When kept for a long time the solution in hydrochloric acid gave a reddish-violet product identical with the compound C,,H,,N obtained by Schiff.K. K. The Behaviour of certain Dibenzamidoethylene Derivatives Prepared from Iminazoles towards Acid Anhydrides. A. WINDATJS and W. LANGENBECK (Ber. 1922 55 [B] 3706-3709; cf. Windaus Doxies and Jensen A. 1922 i 61).-Dibenzamido- ethylene derivatives are converted by the anhydrides of fatty acids into glyoxalines which contain the alkyl group of the fatty acid in position 2. ap-Dibenzamido-Aa-propylene is converted by acetic anhydride a t 180" into 2 4(2 5)-dimethylglyoxaline identified as the picrate m. p. 142". The action of propionic anhydride under similar con- ditions leads to the formation of 4( 5 ) -methyl-2-ethyZglyoxaZine hygroscopic crystals m. p. 45" (oxalate colourless leaflets m.p. Y 2i. 148 ABSTRACTS OF CHEMICAL PAPERS. 145" ; picrate yellow prisms m. p. 131" ; hydrochloride hygroscopic leaflets m. p. 132"; nitrate m. p. 129"). 4(5)-Ethylglyoxaline (cf. Kolshorn A. 1904 i 675) is converted by benzoyl chloride and sodium hydroxide into ccp-dibenxamido- A"-butylene NHBz*CH:CEt*NHBz needles m. p. 146" which is transformed by acetic anhydride a t 140" into 2-methyl-4(5)-ethyl- glyoxaline (picrate yellow needles m. p. 90-91" ; oxahte m. p. 141"). The glyoxaline obtained by Windaus and Ullrich (A. 1914 i 662) by the action of ammonia on rhamnose is identified as 4( 5) -methyl- 5( 4) -ethylglyoxaline. BRITISH DYE- STUFFS CORPORATION LTD. JAMES BADDILEY and ERNEST HARRY RODD (Brit. Pat. 189295).-New dyes of the triarylmethane series are obtained by condensing a 4 4'-dialkyldiamino-3 3'-dimethyl- benzophenone with a suitable secondary or tertiary amine by warming with phosphoryl chloride with the addition of a neutral diluent if desired.These new basic products dye cotton mordanted with tannin-antimony valuable shades of bright reddish- to bluish- violet. Those containing phenyl benzyl or naphthyl residues substituted in the amino-groups can be sulphonated by warming with 20% fuming sulphuric acid giving new acid dyes which dye wool level shades of violet. The ketones required for the synthesis may be obtained by boiling the corresponding thio-ketones with concentrated hydrochloric acid and the latter are produced by the condensation of monoalkyl-o- toluidines with formaldehyde and converting the resulting diphenylmethane derivatives into thio- ketones by the process of Brit.Pat. 20615/14. 4 4'-DiethyZdi- amino-3 3'-dimethylbenxophenone m. p. 165" when condensed with ethyl-o-toluidine gives the triphenylmethane dye in the form of a bronze-coloured paste which dyes mordanted cotton a reddish- violet. Bluer shades are obtained by condensing the ketone with benzylethylaniline or dibenzylaniline. CHEMISCHE FABRIK AUF ACTIEN (VORM. E. SCHERING) (D.R.-P. 358397 ; from Chem. Zentr. 1922 iv 950).-Ammonia is allowed to act on pyridine or its homologues in the presence of alkali metals. For example anhydrous pyridine a t 80" is added to a suspension of finely divided sodium in toluene and anhydrous ammonia is passed in. After the sodium is used up the temperature is raised to 130" and so maintained until no more ammonia is absorbed.From the pro- ducts of the reaction by extracting with ether distilling off the ether and fractionation of the residue 2-aminopyridine b. p. 103- 1lOo/20 mm. 4 4'-dipyridyl b. p. 173-180"/20 mm. and 4-amino- pyridine are obtained. 6-Amino-2-methylpyridine a yellow oil b. p. 120-130"/20 mm. is similarly prepared from 2-methylpyridine (ac-picoline). GI. W. R. Preparation of Amino-alcohols of the Quinoline Series. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pats. 92001 92607 92608 and 92609; from Chem. Zentr. 1922 iv 950- 951) .-2-Pheny1-4-quinolyl methyl ketone is halogenated on the H. W. Preparation of Triarylmethane Dyestuffs. G. F. M. Preparation of Aminopyridines.ORGANIC CHEMISTRY.i. 149 methyl group and the halogen derivative allowed to react with primary or secondary amines. The N-alkyl-2-phenylquinolyl 4- aminomethyl ketone thus formed is reduced to the amino-alcohol. 2-Phenyl-4-quinolyl methyl ketone yellow crystals m. p. 75" is prepared by condensation of ethyl 2-phenylquinoline-4-carboxylate with ethyl acetate and elimination of carbon dioxide from the intermediate ethyl 2-phenylquinoline-4-acetute m. p. 52-54" or from 4-cyano-2-phenylquinoline by Grignard's reaction. By the action of bromine on the ketone 2-phenyl-4-quinolyl b r m e t h y l ketone hydrobromide is obtained; it forms yellow crystals m. p. about 225" (decomp.). The free bromomethyl ketone forms light yellow crystals m p. 91". With dimethylamine it gives 2-phenyl-4- quinolyl4-damethylaminomethyl ketone which forms a hydrochloride light yellow crystals m.p. 208" (decomp.) and a hydrobromide m. p. about 206". Reduction of this compound gives p-dimethyl- amino- a-2-phenylquinolylethanol (annexed CH(oH)*CH2'NMe2 formula) a white plastic mass. The /\/\ dihydrochloride forms crystals m. p. 175" I I IPh (decomp .) . 2- Phen yl-4-quinolyl diethyl- \/\/ aminomethyl ketone is similarly prepared ; the hydrobromide forms yellow felted needles m. p. about 188" (decomp.). 2-Phenyl-4-quinolyl piper- idinomethyl ketone gives a hydrochloride m. p. 235" and a hydrobromide m. p. about 241" (decomp.). 2-Phenyl-4-quinolyl anilinomethyl ketone forms yellow crystals m. p. 123-125". These ketones may be reduced to the corresponding amino-alcohols.~-Diethylamino-cc-2-phenyl-4-quinolylethanol gives a dihydrochloride which forms crystals m. p. about 185" with darkening. p-Piperidino- ~-2-phenyl-4-quinolylethanol gives a dihydrochloride m. p. about 199" (decomp. ) . (3-Anilino- a-2-phen ylqzcinolylethnnol C,NH,Ph*CH (OH)*CH,*NHPh has m. p. 146". N G . W. R. Preparation of a Primary Amino-alcohol of the Quinoline Series. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pat. 92301 ; from Chem. Zentr. 1922 iv 951 ; cf. preceding abstract).- 2-Phenyl-4-quinolyl methyl ketone is changed into its oximino- derivative and this is submitted to reduction. 2-Phenyl-4-quinolyl oximinomethyl ketone forms yellow crystals m. p. 182" (decomp.). By reduction p -amino- a -2 - phen yl- 4- quinol yl ethan 01 CgNH ,Ph*CH (OH) *CH,*NH is obtained. It forms a dihydrochloride colourless crystals m.p. about 190" after softening a t about 145". OTTO DIMROTH and FRITZ FRISTER (Bey. 1922 55 [B] 3693-3697).-The formation of 1 1'-diacetyldihydro-4 4'-dipyridyl by the action of acetic anhydride on the dark violet solution obtained by the reduction of 4 4'-dipyridyl with nascent hydrogen has been described previously (Dimroth and Frister A. 1922 i 678). It is now shown that the violet solution contains a semiquinonoid compound G. W. R. Reduction of 4 4'-Dipyridyl.i. 150 ABSTRACTS OF CHEMICAL PAPERS. of molar proportions of 4 4'-dipyridyl and 1 l'-dihydro-4 4'- dipyridyl which has been isolated as the dihydrochloride for which the name dipyridyl-violet chloride is proposed. The dye differs from other semiquinonoid substances in that the reduced half is quinonoid and the oxidised half has the aromatic constitution.4 4'-Dipyridyl is obtained conveniently and in 90-95% yield by the action of oxygen on a suspension of 1 1'-diacetyltetra- hydro-4 4'-dipyridyl in glacial acetic acid and subsequent addition of sodium hydroxide to the solution. Titration of an aqueous solution of the substance with chromous chloride solution in the absence of air shows that the dye is produced by the action of one equivalent of hydrogen on a molecule of dipyridyl and that further reduction is not caused by chromous chloride. The dye is isolated as a dark green crystalline powder C,,H,,N,Cl? by the action of chromous chloride on a solution of dipyndyl in the presence of calcium chloride ; the precipitated product is washed successively with water and alcohol in the absence of air towards which it is unusually sensitive.H. W. Syntheses in the Indole Group. 11. The Influence of the Solvent on the Grignard Reaction. RIKO MAJIMA and MUNIO KOTAKE (Ber. 1922 55 [B] 3865-3872).-The unexpected differences observed in the production of indole-3-aldehyde from magnesium indolyl iodide and formic ester according as the reaction is effected in the presence of aliphatic or arylaliphatic ethers (Majima and Kotake this vol. i 156) has led the authors to examine possible further cases of this kind. Better yields of the products of the action of magnesium indolyl iodide on carbon dioxide acetone or benzaldehyde are obtained in the presence of anisole than in that of ethyl ether whereas the reverse is the case when ethyl chloroformate acetyl chloride or chloroacetyl chloride is used.Indole-3-carboxylic acid m. p. 218-ZZO" is obtained by the action of carbon dioxide on magnesium indolyl iodide in anisole or ethyl ether. The reaction has been examined previously by Qddo (A. 1911 i 486) who has thus isolated indole-1-carboxylic acid m. p. 108"; the cause of the discrepancy has not been elucid- ated. Magnesium indolyl iodide and acetone give di-3-indolyl- dimethylmethane m. p. 163-165" (cf. Scholtz A. 1913 i 520). Di-3-indoZyZphenyZnaethune CHPh CH<g&>NH) m. p. 149- 152" (+0*5C&6) rn. p. 120-121" is prepared from magnesium indolyl iodide and benzaldehyde; i t is oxidised by ferric chloride in alcoholic solution to the red dye NH<!$%>CH CPh :C<(&>N<g m.p. about 245-248". Ethyl chloroformate and magnesium indolyl iodide give ethyl indole-3-carboxylate colourless crystals m. p. 118-119"; Oddo's observation (Zoc. cit.) that ethyl indole- 2-carboxylate m. p. 107" is produced could not be confirmed. Acetyl chloride and magnesium indolyl iodide yield 3-indolyl ( 2ORGANIC CHEMISTRY. i. 151 methyl ketone NH<z&>C*COMe m. p. 188-189" (oxime m. p. 143-146") identical with the products described by Odd0 (loc. cit.). 3-lndolyl chlorornethyl ketone forms small rhombic crystals m. p. 212-214". H. W. K. VON AUWERS and H. BROCHE (Ber. 1922 55 [B] 3880-3911).-An examination has been made of the Dossibilitv of the existence of IsoYmeric Relationships in the Pyrazole Series.isomerides of the types RN HcH'(?H and iN<x?l$ in the 'N=CH pyrazole series analogous to those observed with the closely related indazoles C,H4<NR>N and C,H4<h->NR. The alkyl and phenyl derivatives of 3-methyl- and 3 5-dimethyl-pyrazole have been investigated but evidence of existence of isomerides of the expected type has not been obtained. The observations which have been made throw doubt on the identity of 3- and 5- derivatives of pyrazole as assumed by Knorr and other investigators. 3-Methylpyrazole is converted by an equivalent amount of methyl iodide in ethereal solution at 120" into 1 3-dimethyl- pyrazole (picrate m. p. 1726'; cf. Jowett and Potter T. 1903 83 467) a portion of the base remaining however unchanged.The same substances are obtained by boiling 3-methylpyrazole with methyl iodide and sodium methoxide in methyl alcoholic solution. 1 3-Dimethylpyrazole b. p. 141-142' is readily isolated in the homogeneous condition by the dry distillation of its meth- iodide m. p. 255-256". In a similar manner the ethylation of 3-methylpyrazole with ethyl bromide at 100" or in the presence of alkali gives 3-methyl- 1 -ethyZpyraxole a colourless liquid b. p. 152"/atmospheric pressure (picrate slender yellow needles m. p. 141"); the formation of quaternary salts in this case is much less pronounced than when methyl iodide is used. The products of the benzylation of 3-methylpyrazole are readily separated by taking advantage of the insolubility of the benzylated compounds in water in which the original material and the pyrazolium salt are soluble; experiments in the presence or absence of alkali yielded l-benzyl-3-rnethylpyrazole a colourless liquid with an odour of hyacinths b.p. 140-141"/14 mm. (picrate slender yellow needles m. p. 112.5-113.5"). In contrast to the indazoles 3-methylpyrazole when alkylated by different methods gives only one definite substitution product. The proof that this is a 1 3-(and not a 1 &)derivative is deduced in the following manner. The benzoic ester of hydroxymethyleneacetone CH,*CO*CH:CH*OBz (colourless crystals m p. 91-92' prepared by the action of benzoyl chloride on a suspension of the sodium compound of hydroxy- methyleneacetone in pyridine and anhydrous ether) is condensed with methylhydrazine and benzylhydrazine whereby dimethyl- and benzylmethyl-pyrazoles are obtained identical with the products described above ; unfortunately it was not found possible to isolate the intermediately formed benzoates but the mode of formation CH CH 9*i.152 ABSTRACTS OF CHEMICAL PAPERS. leaves practically no doubt that 1 3-derivatives are formed. Under similar conditions phenylhydrazine gives 1 -phenyl-3-methyl- pyrazole m. p. 37". The condensation of hydroxymethyleneacetone with methylhydrazine leads to the production of 1 3-dimethyl- pyrazole without any isomeric substance and differs therefore from the action with phenylhydrazine which yields a mixture of 1 3- and 1 5-compounds. The observations have been extended to 3 5-dimethylpyrazole I A " CMe'CH NH<N-:bMe the symmetrical structure of which excludes - the formation of structurally isomeric 3- and 5-derivatives ; any case of isomerism must therefore be due to difference in a ring structure since the production of 4-derivatives is excluded.It is converted by methyl iodide in the presence of alkali into 1 3 5- trimethylpyrazole the picrate of which has m. p. 144-145" whereas Knorr gives 131-133". Similarly 3 5-dimethylpyrazole and benzyl chloride a t 170" give exclusively l-benxyl-3 5-dimethyl- pyrazole a colourless liquid b. p. 144-146/10 mm. (picrate lustrous greenish-yellow needles m. p. 126.5-127-5"). The latter compound is also produced by the action of acetylacetone on benzylhydrazine although in this case the primary production of a three-membered ring might be expected.Finally l-phenyl- 3 5-dimethylpyrazole bas been prepared by the action of phenyl- hydrazine on acetylacetone and methyl a-bromopropenyl ketone CHMeXBrCOMe respectively ; the compound obtained in either case gives a picrate m. p. lolo and there is no evidence of the production of an isomeric compound. fiom the foregoing it appears therefore that cases of isomerism due to the different structure of the ring are not found in the cases of alkylated and arylated pyrazoles. It is however still more remarkable that the number of position isomeric alkylpyrazoles is smaller than would be expected from theoretical considerations since 1 3-derivatives are frequently formed exclusively when mixtures of them with 1 5-compounds or when the latter alone would be normally expected.In the hope that the reactions in the pyrazole series would resemble those in the indazole group an examination of the effect of heat on pyrazolium salts has been made. 1-Phenyl-3-methylpyrazole methiodide m. p. 144" and l-phenyl-5-methylpyrazole methiodide m. p. 282" lose methyl iodide when subjected to dry distillation and re-form 1 -phenyl- 3-methylpyrazole and l-phenyl-5-methylpyrazole respectively. Contrary to expectation however pure 1 3-dimethylpyrazole and 3-methyl-l-ethylpyrazole are obtained from l-benxyl-3-methyl- pyrazole methiodide m. p. 153-154" and l-benxyl-3-methylpyraxole ethiodide colourless prisms m. p. 149.5-150*5". The formation of 1 3- instead of 1 5-compounds discloses a surprising atomic .A v CH-CMe migration in accordance with the scheme zHeN(C,H,) CH-CMe >N.The irn-ORGANIC CHEMISTRY. i. 153 portance of the observation has caused special attention to be directed to the constitution of the pyrazolium salts. The possibility that contrary to rule the addition of alkyl iodide occurs a t the nitrogen atom which is already attached to an allryl group is excluded by the observation that 1-benzyl-3-methylpyrazole methiodide differs from 1 3-dimethylpyraxole benzyliodide colourless leaflets m. p. 167' (corresponding picrate flat yellow needles m. p. 126"). The further possibility that the difference in the two iodides is due to the different spatial arrangement of the sub- stituents around the same nitrogen atom and not to structural differences is improbable and is more defmitely excluded by the apparent impossibility of effecting their mutual interconversion.The wandering of alkyl groups during the fission of certain pyrazol- ium salts must therefore be regarded as cstablished. Nevertheless. it does not follow that 1 5-dialkylpyrazoles are incapable of existence since the high temperature involved in the fission can greatly facilitate the transformation of the primary products of the change into the 1 3-isomerides. The synthesis of 1 5-dialkylpyrazoles has therefore been attempted under conditions which are less likely to involve trans- formation. The action of phenylhydrazine on a-bromocroton- aldehyde leads to the formation of 1 -phenyl-5-methylpyrazone (cf. Vignier A. 1913 i 444) but under precisely similar conditions methylhydrazine gives 1 5-dimethylpyrazole in good yield.A possible explanation of the difference in the reaction lies in the assumption that the alkylhydrazine unlike the aryl compound becomes primarily added a t the double bond thus (?Br:CHMe + NH,-NHMe-+ CHBr-CHMe>NH I + CHO CHO NHMe yHBr*CMe>N -f CH-CMe>N 1 1 CH,-NMe CHeNMe * This hypothesis is shown to be improbable in the following manner. P-Keto-n-butyl alcohol condenses with methylhydrazine sulphate in aqueous solution in the presence of acetic acid and sodium - ... acetate to yield 1 3-climethylpyrazoline (?H2'rH2>NMe a colour- CMe-N less liquid b. p. 127-129" (picrate yellow needles m. p. 131-5- 132.5") ( I-phenyl-3-methylpyrazoline m. p. 71-72' is prepared similarly from phenylhydrazine) .If crotonaldehyde which may be assumed to react in the same manner as its bromo-derivative is similarly condensed with methylhydrazine it must yield 1 3- dimethylpyrazoline if the hydrazine is added initially a t the double bond and 1 5-dimethylpyrazoline if the initial reaction occurs a t the aldehyde group. It is found that the compound which is produced is not identical with that derived from p-keto-n-butyl alcohol and hence must be regarded as 1 5-dimethyZpyraxoliney it is a colourless very hygroscopic liquid ?H,*CHMe CH-N > m e ; b. p. 124-125" which gives a picrate thin golden-yellow leaflets ff 2i. 154 ABSTRACTS OF CHEMICAL PAPERS. m. p. 113-114”. It must therefore be considered that the production of 1 3-dimethylpyrazole from methylhydrazine and bromocrotonaldyde instead of the expected 1 5-derivative is actually due to atomic wandering. Attempts to convert 1 3- and 1 5-dimethylpyrazolines into the corresponding pyrazoles by cautious oxidation with bromine led to remarkable results. The 1 3-compound is transformed smoothly into 1 3-dimethylpyrazole ; the 1 5-derivative is largely resinified but is partly converted into 1 3-dimethylpyrazole. It therefore appears that under usual conditions 1 5-dimethyl- pyrazole (and presumably other 1 5-dialkylpyrazoles) are incapable of existence whereas 1 -phenyl-3-methylpyrazole and 1 -phenyl- 5-methylpyrazole are stable substances. Knorr’s conception that the pyrazole molecule is symmetrically constituted owing to the oscillation of the double bonds and of ” the hydrogen atom united to the nitrogen RHoNH>N e CH-CH YH’”>NH can scarcely be extended to the alliyl derivatives CH.CH of pyrazole since a continuous oscillation of an alkyl group between two nitrogen atoms is contrary to all experience of tautomerism and the firmness of attachment of akyl groups.The authors do not regard the production of 1 3-dialkylpyrazoles in place of the expected 1 5-derivatives as due to the identity of the two series of compounds in consequence of ‘‘ mobile ” double bonds and oscillatory atomic displacements; i t is caused by the great instability of the 1 5-derivatives which immediately after formation become isomerised in accordance with the scheme H. W. The Polymorphism of Antipyrine Vanillin and the Ery- thritols.PAUL GAUBERT (Compt. rend. 1922 175 1414- 1417).-In general a substance which can be superfused or better can pass into the amorphous state will occur in several crystalline forms depending on the temperature. This appearance may be favoured by the presence of some impurity or sometimes by the more or less prolonged heating of the substance a t a temperature above its melting point. I n this manner it is shown that antipyrine melted on a glass plate may occur in three crystalline modifications vanillin may give four crystalline modifications and the erythritols two crystalline forms. The conditions for obtaining these modifi- cations and the forms obtained are detailed. W. G. Preparation of a Derivative of Barbituric Acid Soluble in Water.HERMANN STAUDINGER (Swiss Pat. 91561; from Chem. Zentr. 1922 ivy 840) .-Diallylbarbituric acid or ethylallylbarbituric acid is treated with ozone and the ozonide is changed into the corre- sponding carboxylic acid. Diallylbarbituric acid gives a crystalline ozonide which is decomposed by heating over a water-bath withORGANIC CHEMISTRY. i. 156 formation of a dicurboxylic acid (I) colourless crystals m. p. 280" (decomp.) . Ethylallylbarbituric acid gives similarly a monocurb- oxylic mid (11) which forms colourless crystals m. p. 280-281" (I.) 7 O-NH-$!O The compounds have therapeutic uses and serve as intermediates (11.) F O-NH-YO NH-CO-C( CH,*CO,H) NH-CO-CEt*CH,*C02H' for the preparation of other barbituric acid derivatives. G. W. R. Preparation of a Compound of 5-isoPropy1-5-allylbarbi- turic Acid.F. HOFFMANN LA ROCHE & Co. (Brit. Pat. 188251). - 5-isoPropyl-5-allylbarbituric acid when fused in ap- proximately molecular proportions with 4-dimethylamino- 1-phenyl-2 3-dimethyl-5-pyrazolone form as double compound which is appa,rently homogeneous and melts sharply a t 92-93'. It is yellow in colour and dissolves in hydrocarbons to a deep yellow solution. Water and other solvents containing hydroxyl give only slightly yellow solutions indicating that in these solvents the compound is resolved into its colourless components to a con- siderable extent. The compound is valuable therapeutically as it combines the soporific action of the barbituric acid with the analgesic action of the pyrazolone and can therefore partly replace the opiates.G. F. M. Complex Metallic Compounds of Indigotin. I. K. KUNZ (Ber. 1922 55 [B] 3688-3691).-During the course of experi- ments on the production of 1 1-diphenylindigotin (Friedlander and Kunz A. 1922 i 765) it was observed that boiling solutions of indigotin in o-nitrochlorobenzene are rapidly decolorised by cuprous chloride and sodium acetate or copper powder. A similar change is now shown t o occur in other solvents of high boiling point. It leads to the formation of the compound C3,H1804N,~ which is rapidly decomposed by mineral acids and gives a normal indigo vat with hyposulphite. In analogy with Willstatter's formulation of chlorophyll the C,H~<-N>C:C<NH> C ,H annexed constitution is suggested. The action of zinc foil on a solution C6H4<&>C:c<co->C,H4 of indigotin in tar oil (b.p. 240- 250") methylnaphthalene or o- nitrochlorobenzene leads t o the formation of a zinc compound C3,Hl8O4N4zn black lustrous prisms which unlike the copper compound is rapidly hydrolysed by warm water with production of indigotin. A crystalline nickel derivative has also been prepared by the use of nickel sulphate and sodium acetate but it has not yet been found possible to prepare a magnesium compound. co CO- N> c u ':::.NH H. W. Benzbisthiazoles. 11. STEPHEN RATHBONE HOLDEN EDGE (T. 1923 123 153-156).i. 156 ABSTRACTS OF CHEMICAL PAPERS. Syntheses in the Indole Group. I. A New Synthesis of r-Tryptophan. RIKO MAJIMA and M ~ I O KOTAKE (Ber. 1922 55 [B] 3859-3865) .-Indole- 3 -aldehyde C,H,<$gz!>CH m.p. 193-195" is conveniently prepared in 40% yield by the successive action of indole and formic ester on a solution of mag- nesium ethyl iodide in anisole which is cooled in a mixture of ice and salt; in ethereal solution only traces of the aldehyde are formed (cf. Alessandri and Florence A. 1915 i 452). Phenetole may replace anisole and ethoxymethyleneaniline may take the place of formic ester but the yields are thereby somewhat reduced; amyl ether is as unsuitable as ethyl ether. The aldehyde is heated with hydantoin anhydrous sodium acetate and acetic anhydride a t 106-108" and the product is treated with aqueous sodium hydroxide solution where by 3 - indol yl id eneh ydantoin; /C H CO-YH NH*CO' NH\-&$>C*CH :C< m.p. about 320" decomp. 325" is formed the yield being 46.6% of that theoretically possible. 1 -Acetylindole-3-aldehyde is obtained as a by-product of the action; it therefore appears probable that it is this derivative which actually undergoes con- densation and that acetyl-3-indolylidenehydantoin is hydrolysed by the treatment with sodium hydroxide; the inefficiency of acetic acid and sodium acetate as condensing agents thus receives an explanation. 3-Indolylidenehydantoin is reduced by sodium amalgam in alkaline solution to o-hydantylscutole NH<-@wcH,*cH<~.~ C H CO-NH * colourless needles m. p. 220-221". The latter is hydrolysed by aqueous barium hydroxide solution a t 108" to r-tryptophan NH<~&>C*CHz*CH(NHz)*COz€€ hexagonal leaflets m.p. 283- 285' after becoming discoloured at 250". As by-product a sub- stance Cl,H130,N3 leaflets in. p. 207" (decomp.) is isolated. H. W. Preparation of a Condensation Product from p-Iminazolyl- ethylamine [4-~-Aminoethylglyoxaline]. SOCIETY FOR CHEMI- CAL INDUSTRY IN BASLE (Swiss Pat. 92297; from Chem. Zentr. 1922 iv 890).-When formaldehyde or prefer- ably inethylal is added slowly to a suspension of 4- p-aminoethylglyoxaline in fuming hydrochloric EH acid at 100" and the mixture heated for several HzC C-N hours in a reflux apparatus p-imidaxolylisopiper- \/ idine [tetrahydro-l 3 6-benxtriazolel (annexed CH2 formula) is formed. The hydrochloride is crystal- line and has m. p. 249". Determination of the Constitution of Colouring Matters from their Absorption Spectra.IV. F. KEHRMANN and M SANDOZ (Helv. Chim. Acta 1922 5 895-905; cf. A. 1921 i 276). -In continuation of previous v70rk the absorption spectra of CH NH '"' Hr G. W. R.ORGANIC CHEMISTRY. i. 157 salts of &amino-derivatives of methyl- and phenyl-phenazine have been examined. The introduction of a second symmetrical amino-group into the monoaminomethylphenazine previously described (Zoc. cit.) lightens the colour of the mono-acid salt from cherry-red to orange-red. The absorption maxima are at X 530 and X 483. Introduction of a phenyl group into each amino-group deepens the shade to bluish-violet and there is now only one absorption maximum at X 572. The corresponding ditolyl deriv- ative has an absorption maximum a t X 580. The monoacid salts of the diaminophenylphenazies chosen for examination were the perchlorates on account of their great stability.The mono-acid salt of 2 7-diaminophenylphenazine (annexed formula) is blue and to it may be ascribed the same para-quinonoid structure as to aposafran- ine which is violet-red. The di-acid salt /\N\/\NH2 is red corresponding very closely with I I 1 I aposafranine from which it is inferred NHzxk\/\'\/ that the second amino-group has been neutralised but that no change in the disposition of the double bonds has occurred. When the dizimino- phenylphenazonium perchlorate is dissolved in concentrated sul- phuric acid the colour of the solution is green. The colour is due to the tri-acid salt (annexed formula) and is similar to that of the di-acid salt of aposafranine.Again there is no change of structure and it is in- "/\'\NHsX teresting to note the colour-deepening effect of the fixation of an equivalent of acid by a doubly-linked atom form- ing part of the chromogen. Finally in fuming sulphuric acid the colour is reddish-brown resembling the di-acid salt of phenylphenazine. This salt must have an ortho- quinonoid structure. The perchlorate of 1 3-diaminophenylphenazine is green in water yellowish-green in alcohol approaching a yellow of the second order. Although the amino-group in position 1 has a considerable colour-deepening effect the structure is still probably paraquinonoid. The di-acid salt of this compound resembles aposafranine as in the case of the 2 7- isomeride but the tri-acid salt obtained by direct solution in concentrated sulphuric /\@\/\ acid is not green but yellow resembling the 1 I I 1 mono-acid salt of phenylphenazine.The NH3X'\/&$>/ structure of this salt must therefore be orthoquinonoid (annexed formula). When the perchlorate is dissolved in fuming sulphuric acid the reddish- brown colour of the tetra-acid salt is obtained. The perchlorate of the third isomeride phenosafranine is red with an ofange fluorescence in solution. Here again as with methylphenazine the second symmetrical amino-group brightens the shade whilst the colour intensity is increased. The di-acid N NPh H X \/ N I I I I NH,XH\/\ /\/ NPh m3x I Ni. 158 ABSTRACTS OF CHEMICdL PAPERS. salt is blue indicating that the second acid equivalent is combined with chromogenic nitrogen (annexed formula).The tri-acid salt is green resembling as expected t,he di-acid salt of uposafranine. The tetra- XNH /\@\/\ acid salt is the normal reddish-brown. I I I INH It is concluded that all the observed m2xH\/\/\/ facts can be explained if it is granted that two states ortho- and para- quinonoid are possible in this series. It is further shown briefly that acetylation of an amino-group in this series has a similar effect on its auxochromic properties to neutralisation of the group with acid. GEORG BARKAN (2. BioZ. 1922 76 267-266).-The solubility of freshly pre- cipitated amorphous sodium urate (C,H,O,N,Na,H,O) a t 18" is 2.03 g. or 9.8 x On keeping or more particularly on stirring in contact with its solution the solubility decreases and approaches that of the crystalline form.NPh E. H. R. The Solubility of the Salts of Uric Acid. grain-molecules per litre. W. 0. K. Oxidation of Benzeneazoresorcinol. DINO BIGIAVI and GIULIO GIANNMI (Atti R. Accad. Lincei 1922 [v] 31 ii 109- 116).-Of the two possible diacetyl derivatives (a) C6H,'NO:N*C6H3( OAC) and (p) C,H,*N:NO*CGH3(OAc) obtainable by the oxidation of the diacetyl compound of benzeneazoresorcinol by means of hydrogen peroxide only the latter is actually obtained the a-form probably undergoing further oxidation. OH - p-4-Benxeneaxoxyresorcinol C,H,*N:NO-( >OH crystallkes \-/ in red granules m. p. 144" giving a chestnut-yellow powder. The dibenzoyl derivative forms pale yellow needles m. p. 113" and the diacetyl derivative long pale yellow silky needles in.p. 102". 4-Benzeneuxoxy-2 6-dibrornoresorcinoZ C,H5*N:NO*C6HBr,( OH) crystallises in transparent greenish-yellow cubes m. p. 153" and yields aniline when reduced by means of zinc and acetic acid. 4-op- Di bromo benzeneaxox y-2 6-di brornoresorcinol forms long red needles m. p. 229" (decornp.) and gives 2 4-di- bromoaniline when reduced by means of tin and hydrochloric acid. 2 6-Dibenxeneuxo-4- benxeneaxoxyresorcci?zol C ,H 5*N20*C ,H ( OH) 2( *N,Ph ) is a red compound m. p. 220". When treated with alcoholic potassium hydroxide the diacetyl derivatixe of p- benzeneazoxyresorcinol yields a dark red compound m. p. about 190" which has not yet been characterised. C12HG03N2Br4 T H. P.ORGANIC CHEMISTRY. i. 159 Oxidation of Benzeneazonaphthols. I. DINO BIGIAVI and RENATO CERCHIAI (Atti R.A&. Lincei 1922 [v] 31 ii 27- 30).-Owing to the divergent behaviour towards alkali shown by the three isomeric benzeneazonaphthols a phenylhydrazonic constitution is attributed to 1 - benzeneazo-2-naphthol whilst 4-benzeneazo-1-naphthol and 2-benzeneazo-1-naphthol are con- sidered 'to possess the ordinary hydroxylic formuls (Goldschmidt and Brubacher A. 1891 1209; Willstatter and Parnas A. 1907 i 425 1056). Marked differences are found also in the behaviour of these compounds towards 30 yo hydrogen peroxide solution and acetic acid. Thus under these conditions 1 -benzeneazo-2-naphthol and also its acetyl-derivative undergo slow oxidation in the cold to carboxy- cinnamic acid CO,H*C,H,*CH:CH*CO,H m. p. 200" whilst in the hot they yield the isomeric dihydroisocoumarincarbosylic acid C,J34<CH,.CH,Co2H m.p. 153" which is also obtained when carboxycinnamic acid is fused for a few moments. Similar oxidation of P-naphthol yields the products obtained by Ehrlich by the action of permanganate (A. 1889 1001) namely (1) Carboxycinnainic acid for which however this author gave m. p. 183" instead of 200"; (2) an acid C,H,,O m. p. 281" which although regarded by Ehrlich as dibasic gives only mono- silver and monoethyl derivatives and has probably the structure f)co2H ?o'o-I ) 1 This acid reduces permanganate but \/-CHIC--\/\/ not so rapidly as does carboxycinnamic acid. Reduction of Ethyl Diazobenzylidenegluconate. P. A. LEVENE ( J . Biol. Chern. 1922 54 809-813).-When reduced with aluminium amalgam in isopropyl-alcoholic solution ethyl diazo- benzylidenegluconate yields a mixture of ethyl benzylidenedeoxy- gluconate and ethyl benzylidene chitosamate.The former product is identical with that previously obtained (A. 1922 i 1028) by reduction of ethyl benzylidene-ccp-anhydromannonate ; the latter was not isolated but was identified by hydrolysis into chitosamic acid. The reduction apparently takes place asymmetrically for no trace of an epimeride of chitosamic acid can be detected. That the deoxy-compound is not produced through the intermediate formation of an unsaturated compound is shown by the fact that the amide of benzylidene- ap-anhydromannonic acid is unchanged when submitted to similar treatment. co-p / /\ T. H. P. E. S. The Formation of Aromatic Thiocyanates by the Diazo- reaction. A.KOECZYNSKI [with J. KNIATOWNA and F. KANIN- SKI] (Bull. Xoc. chim. 1922 [iv] 31 1179-1185).-1n the trans- formation of o-nitrodiazobenzene thiocyanate into o-nitrophenyl thiocyanate under the catalytic influence of a metallic thiocyanate the yield obtained depends on the metal of which a salt is used and on the temperature being greater in the majority of casesi. 160 ABSTRACTS OF CHEMICAL PAPERS. studied at 15-20" than a t 60-70". The most effective catalysts of the substances used are the thiocyanates of iron and tungsten. The Tryptophan Content of some Proteins. CLARENCE E. MAY and EMBREE R. ROSE ( J . Biol. Chem. 1922 54. 313- 216) .-The colour which tryptophan yields with Ehrlich's reagent has been utilised for the estimation.The protein (0.05 to 1 g.) is added to a mixture of concentrated hydrochloric acid (50 c.c.) water (50 c.c.) and a 5% solution of p-dimethylaminobenzaldehyde in 10% sulphuric acid (1 c.c.). It is then incubated a t 35" for twenty-four hours left a t the ordinary temperature for at least twenty-four hours and the colour then compared with a casein standard. It is assumed that casein yields 1.5% of tryptophan. Application of the method to a number of proteins yielded the following values lactalbumin 2.4 gliadin 1.05 glutenin 1.80 edestin 1.5 glycinin 1.65 ovovitellin 1.74 egg-albumin 1.11 phaseolin 0.80 maize gluten 1.08 legumin (vetch) 1*05y0. No colour developed in the case of zein and gelatin. The Isoelectric Point of Globin. SEIUNGO OSATO (Biochem. Z. 1922 132 485-487).-The isoelectric point of globin from blood-corpuscles is found by the precipitation method to be at P H 8.1.W. 0. K. I. The Preparation of Nucleic Acid from the Nucleoprotein of Tubercle Bacilli (Tuberculinic Acid). 11. The Pyrim- idines contained in Tuberculinic Acid the Nucleic Acid of Tubercle Bacilli. TREAT B. J o i m s o ~ and ELMER B. BROWN ( J . Bio2. Chem. 1922 54 721-730 731-737).-I. A method is described for the preparation of tuberculinic acid from tubercle bacilli (cf. also Ruppel A. 1899 ii 237; Levene A. 1901 i 299). The protein which remains after removal of this nucleic acid has been analysed for nitrogen distribution with the following results amide-N 11.83 humin-N 4.1 1 cystine-N 1-26 arginine-N 10.63 histidine-N 11.48 lysine-N 3.69 monoamino-N 47.39 non-amino-N 9.34%. Tryptophan was also present. 11. Cytosine and thymine have been isolated from the products of hydrolysis of tuberculinic acid; the presence of uracil could not be detected. E. S. The Results and Aims of General Enzyme Chemistry. H. VON EULER (Ber. 1922 55 [B] 3583-3600).-A lecture delivered at the centenary of the Versammlung Deutscher Natur- forscher und Aerzte. K. w. The Isolation of Enzymes. RICI~ARD WILLST~TTER (Bey. 1922 55 [B] 3601-3623).-A lecture delivered a t the centenary of the Versammlung Deutscher Naturforscher und Aerzte. H. J. E. E. S. H. W. Saccharase. E. CANALS (BUZZ. SOC. chim. 1922 [iv] 31 1333-1341; cf. A. 1922 i 1075).-The author traces a relation- ship between the magnesium and phosphate content of saccharases of various origins and their respective diastatic powers whichORGANIC CHEMISTRY. i. 161 seems to some extent to support the opinion of Salkowski that invertase is the magnesium salt of a nitrogenous phosphated acid. A direct relationship cannot be traced however between the total magnesium and phosphoric acid content and the diastatic power since if the preparation is purified by dialysis the diastatic power is enhanced whilst there is a loss of about 40% of Mg and 58% of P,O and all the magnesium and phosphoric acid of the saccharase is therefore not essential for the hydrolysing activity Purification by precipitation with alcohol results in a similar loss in magnesium and an even greater loss in phosphoric acid and in this case the diastatic power is greatly diminished owing probably to a profound modification of the colloidal system of the enzyme by this treatment. Alcoholic precipitation is therefore not suitable for the purification of saccharase. It is observed that the magnes- ium of the saccharase dialyses less easily and is less readily separated by alcoholic precipitation than the phosphate and it would there- fore seem to enter to a greater extent into the constitution of the inicelle. G. F. M. The Wuence of Neutral Alkali-metal Salts on Diastatic Ferment. V. AMANDUS HAHN and HUGO MEYER (2. BioZ. 1922 76 227-246) .-Purified diastase from commercial pan- creatin ‘‘ Rhenania ” is influenced as regards its activity by the presence of neutral salts of the alkali metals similarly to saliva diastase and to unpurified pancreatin. The optimum PH depends on the buffer solution used being 7.2 with a phosphate mixture and 5-6 with an acetate mixture resembling saliva which has corresponding optimum at PH 6.6 and PH 5.6. The influence of neutral salts is much more marked with acetate buffer mixtures than with phosphate buffer mixtures. In both cases the effect is to increase the optimum Pll. Arseno-metallic Compounds. 11. Isomeric Silver Sal- varsans. A. BINZ and W. H. LUDWIG (Ber. 1922 55 [B] 3826--3831).-The silver complex of silver salvarsan has been considered by Ehrlich and Karrer (A. 1916 i 95) to be co-ordin- atively attached to the arsenic atom and by Binz Bauer and Hallstein (A. 1920 i 401) as united by the residual affinity of the nitrogen atom. The isolation of two isomeric silver salvarsans apparently justifies both formula At present the allotment of the structure to the isomeride is somewhat arbitrary and is due to the fact that one form is lighter in colour than the other and resembles t o this extent the complex compounds containing silver and nitrogen but not arsenic. Silver salvarsan I NH,*C,H3( OH)*&:As*C,H,( OH)*NH,. . . AgOH is obtained by adding sodium carbonate solution to salvarsan and silver nitrate dissolved in water ; it is insoluble in sodium carbonate and stable towards reduction with hypophosphorous acid. It dissolves in sodium hydroxide solution with the dark brown colour of technical silver salvarsan and from the solution carbon dioxide precipitates the isomeride NH,*C,H,(OH)*As:As( ... AgOH)*CGH3(OH)*NH W. 0. K.i. 162 ABSTRACTS OF CHEIIICAL PAPERS. a dark brown substance which dissolves in sodium carbonate solution and is reduced by hypophosphorous acid. Silver salvarsan I is rapidly converted by hydrochloric acid into the cmpound NH,*C,H,( OH)*As:As*C,H,( QH)*NH,. . . AgC1 a pale yellow powder. The dark brown isomende II appears to be unaffected by similar treatment after several hours but gradually becomes converted into the chloride just described the formation of which from the chloride NH,*C,H,( QH)*As:As(. . .AgC1)*C,HB(OK)*NH takes place very slowly in comparison with the change in the reverse direction in alkaline solution. The same change occurs when solutions of technical silver salvarsan are treated with hydrochloric acid the brown colour in this case persisting for a considerable time and gradually giving place to a pale yellow precipitate. H. W.

ISSN:0368-1769    

DOI:10.1039/CA9232400081

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ii. 101 General and Physical Chemistry. Spectr ochemical Investigations on P olynuclear Aromatic Compounds in Solution. F. KROLLZFEIFFER (Annulen 1923 430 161-229).-Largely a statement in tabular form of the numerical results of the author’s measurements of the refractive indices in various solvents of a large number of derivatives of benzene naphthalene anthracene and other polynuclertr systems (cf. following abstract). Spectrochemical Peculiarities and Constitution of Naph- thalene Anthracene Phenanthrene and Fluorene. K. VON AUWERS and F. KROLLPFEIFFER (Anizulen 1923,430 230-268).- In this paper the spectrochemical measurements referred to in the preceding abstract along with similar numerical data obtained a t earlier dates and some new measurements are collected together and discussed from the point of view of their bearing on the con- stitution of the various basic ring systems.The authors favour structures for naphthalene and anthracene in which only one ring has full aromatic character and the usually accepted structures for phenanthrene and fluorene. As regards the effect of sub- stitution in naphthalene on spectrochemical properties the con- clusions are drawn (1) that large increases in the specific refraction run parallel with large dispersion; (2) that the introduction of alkyl alkoxyl carbalkoxyl groups and halogens has but little effect either on the exaltation of the refraction or dispersion; (3) that the effect of halogens is greater than in derivatives of benzene and (4) P-derivatives have as a rule a stronger exaltation in specific refraction than the corresponding a-derivatives.C. K. I. C. K. I. “Aromatic” Carbon. K. VON AUWERS (Ber. 1923 56 [B] 69-76; cf. von Steiger A. 1921 ii 473; 1922 ii 616; von Auwers A. 1922 ii 98).-A further criticism of von Steiger’s hypothesis that an essential difference exists between aliphatic and aromatic carbon atoms. The regularities observed in the thermochemistry of aromatic hydrocarbons do not necessitate the supposition of the tervalency of carbon but are equally reconcilable with the quadrivalency of the element (cf. Wibaut A. 1922 ii 239). They do not necessitate the hypothesis that the C-C and C-H linkings in aromatic hydro- carbons are equivalent from the point of view of energy which moreover is not in harmony with the principle of the distribution of energy of combination adopted by von Steiger (loc.cit.). It is only proved that the mean energy of formation of the individual linkings can be regarded as equal for purposes of calculation; this is in harmony with the similarity in the constitution of the mole- cules but does not necessitate any particular assumption with regard to the nature of carbon in these compounds. VOL. CXXTV. ii. 5ii. 102 ABSTRACTS OF CEEMICAL PAPERS. From the spectrochemical point of view it is shown in detail that the molecular refractions of anthracene and phenanthrene differ from one another to a degree which is completely outside the limits of experimental error whereas they should be identical if von Steiger’s hypothesis is correct. In general von Steiger regards discrepancies between the observed values and those calculated with the aid of the “ normal ” equivalents as defects whereas the whole history of spectrochemistry shows that such discrepancies are of the maximum value in throwing light on the constitution of the compounds under examination.Von Steiger’s method of calculating the molecular refractions is quite unsuitable for the homologues of benzene since the difference increases with increasing number of side chains. Von Steiger’s conception of the peculiar nature of ‘‘ aromatic ” carbon rests on the work of Debye and Schemer on the crystalline structure of graphite the additivity of the heats of combustion of certain purely aromatic hydrocarbons and the supposed additivity of their molecular refractions.Arguments based on the two latter points have been shown to be invalid whilst Debye and Scherrer’s observations do not depend on the existence of two differing types of carbon atom but on the formation of different types of molecule owing to the differing mode of union of identical carbon atoms. Further exception is taken to the sharp difEerenti- ation of aliphatic and aromatic carbon since this is not justifiable on purely chemical grounds and can only be applied to two extreme types of compounds which are not chemically distinctly separated. H. W. The Molecular Refraction of Anthracene. F. &ow;- PFEJFFER (Ber. 1922 55 [B] 77-83).-The molecular refraction of anthracene dissolved in quinoline has been determined the calculations being made in accordance with the formula MrL=M[rLS x 100 / p - rLB( 100 -p) lp] in which M is the molecular weight of the dissolved substance rL its specific refraction accord- ing to Lorenz and Lorentz rL8 the specific refraction of $he solu- tion rLx that of the solvent and p the percentage of solute.The mean value Mg5=65-3; this is considerably higher than that’ observed by von Steiger (A. 1922 ii 616) for anthracene dissolved in naphthalene which is in agreement with the previous observ- ations of Chilesotti. The discrepancy does not appear to be attributable to the particular solvent used since the molecular refractions of the closely allied 1 -methyl- and 9-ethyl-anthracenes are almost identical when the determinations are made with the molten materials or with their solutions in quinoline or naphthalene.Re-determimtion of the molecular refraction of anthrscene dis- solved in naphthalene has given values which agree excellently with those observed when quinoline is used as solvent and are much higher than those found by von Steiger and Chilesotti; the error in the observations of the former appears to lie in the observation of the refractive indices t,he latter in that of the density.GENERAL AND PHYSICAL CHEMISTRY. ii. 103 The values obtained for the molecuIar refraction of phenanthrene dissolved in benzene or naphthalene agree with those observed by von Steiger and Chilesotti. Calculation of the Hydrogen Dissimilar Spectra from the Inner Movements of the Electrons. 11. E. FUES (2. Physik 1923 12 1-12).-A continuation of a theoretical discussion (this vol.ii l) in which it is shown that it is possible to calculate the terms of the Rontgen and optical spectra from the movements of the electrons in a central field of force and to derive the potential curve of the atomic field. The sodium spectrum is considered in detail and the terms in its spectrum are deduced from the potential curve. The agreement for the quantum numbers of the 3 4 5 61 3 4 5 62 33 P3 5 63 and 44 members which is within 3% is a demonstration of the correctness of the recent views on the origination of series spectra. W. E. G. FREDERICK SUMNER BRACKETT (Astrophys. J . 1922 56 154-161).-The radi- ation from the central section of a long discharge tube has been analysed by means of a rock-salt prism spectrometer and a sensitive vacuum thermo-junction.Three (probably four) additional mem- bers of the Paschen series have been observed as well as the first two members of a new series corresponding with ~ = N ( 1 / 4 ~ - l / m ~ ) where m=5 6. These two lines at A 4.05&0-03p and 2-63&0-02p are due according to Bohr's theory to an electron falling into the fourth from the fifth and sixth rings of the hydrogen atom. Certain unidentified lines are recorded and it was observed that with increase of current the first Paschen line increased in intensity more rapidly than Ha. New Bands in the Spectrum of Silicon. ANGEL DEL CAMPO and Josk ESTALELLA (Anal. Ph. Quim. 1922 20 586-588; cf. del Campo ibid. 1915 13 98).-Seven new bands are described in the spectrum of silicon. They occur between h 2255.85 8.and X 2146.0 8. and appear to be composed of lines of variable intensity. A complete list of the components of the silicon spectrum is given. H. W. Visible and Ultra-red Radiation of Hydrogen. A A. E. G. W. R. The Spectrum of Neutral Helium. W. M. HICKS (Nature 1923 111 146).-A criticism of the formula employed by Silber- stein (this vol. ii 46) to express the diffuse series HeD'. A. A. E. The Visibility of Individual Spectra. F. H. NEWMAN (Phil. Mug. 1923 [vi] 45 293-299; cf. this vol. ii 46).-The relative visibility of the spectra of the vapour from alkali amalgams a t 200" is affected by the nature of the electrical discharge through the vacuum tube. The spectrum of the alkali metal is always well developed with the ordinary uncondensed discharge but is completely masked by the mercury s ctrum when the condensed discharge is sufficient to impart higher velocities to the colliding electrons is used.With the latter b r e resulttlnt increase in electrical energy 5-3ii. 104 ABSTRAUTS OF CHEMICAL PAPERS. during their mean free path and to ionise the mercury atoms although these have higher ionisation potentials than the atoms of the alkali metals. The energy attained is sufficient to remove two or more electrons as is shown by the production of enhanced lines. W. E. G. Revision of the Series in the Spectrum of Strontium. F. A. SAUNDERS (Astrophys. J. 1922 56 73-83).-Measurements have been made of the spectrograms of light from a great variety of sources and revised wave-lengths are given for most of the 180 lines from 0.22 to 3.06 p including about 70 new lines. Accurate determinations have been made of the limits of all the series and the various terms have been calculated.About half of the twenty series mentioned are believed to be new and there is evidence of the existence of new types of singlet series corresponding with the formula? (1P)-(mX) (1p)-(mX) (1P)-(my) etc. The terms are all large so that the series cannot be of the kind suggested by Sommerfeld. In the case of calcium three singlet lines are found to correspond accurately with (12’)- (mX) ( lpl) - ( m X ) and (1p2)-(mX) where (mX) is 8584.8 thus indicating a series similar to that of strontium. A. A. E. Structure of the Spectrum of Scandium. MIGUEL A. CATALAN (AnaE. Pis. Quim. 1922 20 606-623).-The lines in the spectrum of scandium fall into two classes namely those forming doublets and those forming triplets.Sommerfeld’s displacement rule holds for scandium since its enhanced spectrum is analogous to the arc spectrum of calcium. The multiplets (cf. A. 1922 ii 726) are divided into ‘‘ multidoublets ” and “ multitriplets.” Com- plete lists are given of the lines in the spectra of the neutral and ionised atom respectively. The Structure of the Arc Spectra of the Elements of Columns VI and VII in the Periodic Table. &I. A. CATALAN (Compt. rend. 1923 176 84-85).-1t has previously been shown (A. 1922 ii 726) that the manganese spectrum shows three diffuse triplets consisting of nine rays instead of six due to the fact that the diffuse term d is quintuple instead of triple.It is now shown that this is not a property peculiar to manganese but is common to other elements. The arc spectrum of chromium is very complex and presents several systems of series. Two of these determined for the first time are tabulated. They are almost identical the one being displaced with respect to the other by a constant quantity C=4436.4. The diffuse terms are quintuple and give nine rays as for manganese. W. G. The Structure of the Spectrum of Chromium. A. DE GRAMONT (Compt. rend. 1923,176 216-217).-The author directs attention to the fact that he predicted that in the spectrum of chromium there would be two triplets one corresponding with the neutral atom and the other with the ionised atom and that this prediction has now found confirmation by the measurements made by Catalh (preceding abstract).G. W. R. W. G.GENERAL AND PHYSICAL CHEMISTRY. ii. 105 The Structure of the Arc Spectra of Molybdenum Selen- ium and Chlorine. M. A. CATAL~N (Compt. rend. 1923 176 247-248).-The arc spectrum of molybdenum is extremely com- plex. The diffuse term is quintuple and the number of rays is nine. The rays of the triplet of the principal series are the ultimate rays of Gramont. The diffuse triplets of selenium are regarded as exceptional by the number the intensity and the position of their satellites. The spark spectrum of chlorine shows triplets. The photograph of the spectrum shows the presence of a t least three components in the first ray although the tables give a number of components equal to 1+3+2.Thus the diffuse term of the elements of columns VII and VI of the periodic table is quintuple and the number of rays which form the diffuse triplets is nine. W. G. Coincidence Method €or the Wave-length Measurement of Absorption Bands. H. HARTRIDGE (Proc. Roy. Soc. 1923 [ A ] 102 575-587).-A spectroscope suitable for the measurement of wave-lengths of absorption bands is described. It is designed so that two similar spectra are produced lying side by side and reversed in direction to one another. For the measurement of the mean wave-length of a band the long wave-length edge of the band in one spectrum is brought into coincidence with the corre- sponding short wave-length edge in the other. The mode of calibration of the instrument to read directly in wave-lengths is described and the application of the instrument to the quantitative estimation of pigments by wave-length measurements of their absorption bands detailed.The method depends on the principle that if two pigments are present together in solution and their respective absorption bands have different mean wave-lengths then the mean wave-lengths of the resultant absorption bands will vary with the relative concentrations of the pigments pro- vided the band of one pigment is approximately similar to a band of the other and if a t no concentration do the bands appear separate. An illustration of the application of the method is given in the case of the estimation of the percentage saturation of blood with carbon monoxide. The accuracy of measurement attainable was found to be about 0-6 8.Various sources of error are discussed. J. S. G. T. Absorption of Light by Chlorine. H. VON H-AN and K. SIEDENTOPF (2. Elektrochem. 1922,28,496-499).-A preliminary account is given of measurements of the absorption spectrum of chlorine for a large number of wave-lengths between 254 pp and 643 pp making use of the very sensitive method of measurement recently described by the authors (A. 1922 ii 332). The results show that nowhere is chlorine entirely transparent but that in all regions absorption occurs which is generally very difficult to measure. The measurements are reproducible although the absorption in some cases does not amount to more than 0.2-0-3%. J. F. S.ii. 106 ABSTRACTS OF CHEMICAL PAPERS. The Quantitative Absorption of Light by Simple Inorganic Substances.11. The Chlorides of Arsenic Antimony and Bismuth. ALEXANDER KILLEN MACBETH and NORAH IRENE MAXWELL (T. 1923 123 370-375). The Absorption Spectra of Thallim and Indium Vapours. WALTER GROTRUN (Z. Physik 1923 12 218-231).-According to the Bohr atomic theory emission lines can occur only as absorp- tion lines a t any temperature when the initial stage in the absorp- tion corresponds with a molecular or atomic state which is of frequent occurrence in the molecules of the gas. Absorption spectra are thus useful in throwing light on the variation in the quantum condition of gas molecules with temperature. Series schemes of the emission spectra given for aluminium gallium indium and thallium show that for these metals not the s but the p-terms are the greatest of all the known terms.For thallium a t a temperature of 400° two absorption lines of the 2p2 subordinate series X=3775-72 and h=2767.87 first make their appearance and a t 500-608" other lines in this series appear. With increasing temperature these lines broaden probably owing to molecular (Tl,) adsorption. At 800° the 2p subordinate series is first observed the order of appearance being X=5350-46 and then the doublet X=3529 and X=3519-24. The indium absorption spectrum behaves similarly with rise in temperature. The differ- ences between the temperatures a t which the respective lines of the 2p and the 2p1 series are first observed increase as the series aluminium to thallium is ascended for indium the temperature difference is 100-150" and for thallium about 400". An indium adsorption line is observed a t X=2836.90 which is not included in the series schemes.From these absorption experiments it is clear that the outermost electron in the aluminium series of elements follows an azimuthal two quantum orbit. The Ultra-violet Absorption Spectra of Aniline and the Toluidines. F. W. KLINGSTEDT (Compt. rend 1923 176 248-250).-Aniline in solution in hexane shows nine narrow bands between X=2991 and 2704 and a broad band at X=2340. The narrow bands are almost equidistant from one another. With respect to benzene the absorption bands of aniline are displaced towards the red and the intensity of absorption is about eight times greater. The absorption spectrum of aniline in solution in water alcohol or carbon tetrachloride is very different from the normal spectrum.In these solvents the narrow bands are fused into one broad band. The absorption spectra of 0- and p-toluidines are very different. The ortho has two broad bands whilst the para has seven narrow bands and a broad band in the extreme ultra-violet. W. E. G. W. G. The Absorption in the Ultra-violet of a Series of Deriv- atives of Camphor. A. HALLER and R. LUCAS (Cornpi. rend. 1923 176 45-49).-A study of the absorption spectra in the ultra-viole t of the benz ylidene - anisylidene- piperonylidene -,GEXERAL AND PHYSICAL CHEMLSTRY. ii. 107 m-hydroxybenzylidene- m-methoxybenzylidene- p-tolylidene and m-tolylidene-derivatives of camphor shows that all these com- pounds present a strong absorption band the maxima of which vary with each compound. On the other hand benzylcamphor and anisylcamphor do not give this absorption band.The curves for m-hydroxylbenzylidenecamphor and for m-methoxybenzylidene camphor are practically identical. The maximum of absorption in the compounds named above is displaced further towards the red as the substituent group is of greater weight. W. G. The Ultra-violet Absorption Spectra of some Alkaloids of the isoQuinoline Group. Narcotine Hydrastine and Hydrocotarnine. PIERRE STEINER (Cornpi. rend. 1923 176 244-246).-The results obtained indicate that the ultra-violet absorption spectrum of narcotine is determined by the benzene nucleus of its molecule ; the isoquinoline nucleus only displaces the absorption towards the red.For papaverine (cf. this vol. ii 2) on the other hand it is the isoquinoline nucleus and not the benzene nucleus which is the determining factor. The spectrum of hydrastine only differs from that of narcotine by a displacement of its maxima and minima towards the shorter wave-lengths and by small differences in the intensity of absorption. Hydro- cotarnine which contains a partly saturated isoquinoline nucleus has a spectrum formed of a single band in the ultra-violet. Accord- ing to the results tabulated it should be possible to estimate sp&trographically 0.07 mg. of narcotine or hjkirastine in 2 C.C. of solvent. W. G Absorption Spectra of Pyrrole and its Derivatives. 11. The Influence of Methyl Groups on the Absorption Spectra of Pyrrole and its Derivatives.G. KORSCHTJN and (Mim) C. ROLL (Bull. SOC. chim. 1923 [iv] 33 55-67).-The absorption spectra of the ethyl esters of the following pyrrolecarboxylic acids were examined 2 5-dimethyl- 2 3 5-trimethyl- 1 2 5-tri- methyl- and 1 2 3 5-tetramethyl-pyrrole-4-carboxylic acids 2 &dimethyl- and 2 3 5-trimethyl-l-aminopyrrole-4-carboxylic acids 2 Ei-dimethyl- and 1 2 5-trimethyl-pyrrole-3 4-dicarb- oxylic acids and 2 5-dimethyl- and 2 3 5-trimethyl-l-carb- amidopyrrole-4-monocarboxylic acids and also that of 1 2 5- trimethyl-pyrrole. The general conclusions drawn are that the introduction of a methyl group into position 1 (attached to nitrogen) causes a +placement of the absorption curve towards the ultra- violet. At the same time if the derivative has two absorption bands they are united into one band.On the contrary the intro- duction of methyl into position 3 causes a displacement of the curve towards the red and at the same time the first band is lowered and the second raised. The methyl groups in position8 2 and 5 in 1 2 5-trimethylpyrrole displace the curve towards the red. Three methyl groups introduced into pyrrole in positions 1 2 5 only increase very slightly the intensity of the absorption bands. G. F. M.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. Colour and Chemical Constitution. XVI. Further Miscellaneous Observations. JAMES Mom (Trans. Roy. Soc. 8. Africa 1922,1OY233-237).-1n this paper are given the absorp- tion wave-lengths of all the “ monocyclic ” and ‘‘ dicyclic ” dyes which were used in establishing the author’s theory of the colour of “ cyclic ” coloured substances (cf.A. 1921 ii 6 ; 1922 ii 333). 2 4’-Dihydroxybenzhydrol has X 543 in alkali X 486 in hydro- chloric acid and A 495 in water suspension. The 4 4’-isomeride has A 539 in dilute alkali but in acid is the same as the 2 4/-COm- pound. 2-Hydroxy-4’-dimethylaminobenzhydrol has h 561 (broad) in alkali h 500 in acid; the 4 4’-compound has X 572 in alkali and X 504 in acid. 2 4 4’-Trihydroxybenzhydrol has A 494 instead of the expected X 550. 2 4-Dihydroxy-4‘-methoxybenz- hydrol has X 380 in alkali and appears to be monocyclic; 2 4- dihydroxy-3’ 4’-dimethoxybenzhydrol-2’-carboxylic acid is also monocyclic with X 390 in alkali and so is mono-a-naphtholphthalein from phthalaldehydic acid and a-naphthol with X 370.The C- phenyl derivative of the last-named has X 401 in alkali but X 543 in strong sulphuric acid. The hydrol from p-hydroxybenzaldehyde and a-naphthol is violet with A 590 whilst that from p-naphthol is pink h 556 in alkali. Phenol-(3-naphtholphthalein has A 570. The following show differences in sodium hydroxide (1) and sodium hydrogen carbonate (2) respectively 3- hydroxyphenolphthalein X 556 (1) and X 562 (2) ; 3 6-dihydroxyphenolphthalein X 549 (1) and X 563 (2) ; 4 5-dihydroxyphenolphthalein X 558 (1) and X 568 (2). 5-Methoxyphenolphthalein has A 565 whilst the 3 6- 4 5- and 5 6-dimethoxyphenolphthaleins have X 568 h 556 and A 571 respectively. Other phenolphthalein derivatives ex- amined were 3-nitro- X 570 ; a-nitro-fgjE-tetrabromo- h 597 {cf.this vol. ii 48 for nomenclature) ; Ei-nitro- X 572 ; ahcd-tetra- chloro- X 581. Phenoldimethyl- a-naphthylaminephthalein is green X 625. The following derivatives of Ghosh’s quinolinic acid were examined phenolquinolinein X 533 ; o-cresolquinolinein X 544 ; thymolquinolinein X 593 ; resorcinquinolinein X 490 ; orcin- quinolinein X 496. In the triphenylcarbinol series the following are given o-hydroxy- malachite-green X 627 neutral X 572 in alkali X 505 in acid ; 2’-hydr- oxy-4-dimethylaminofuchsone h 490 neutral X 533 in alkali X 479 in acid ; p-methoxymalachite-green X 605 ; p-methoxybenzaurine X 551 ; p-nitromalachite-green X 642 ; p-aminomalachite-green X 581 in acetic acid. Values are also given for a considerable number of unclassified coloured substances.E. H. R. Cells with a Fluorescent Liquid. A. GRUMBACH (Compt. rend. 1923 176 88-90).-Goldmann (Ann. Physik 1908 27 449) has shown that when one of two electrodes plunged into a fluorescent liquid is illuminated an E.M.F. is set up and the illuminated electrode is positive. This was shown for saturated alcoholic solutions. It is now shown working with dilute aqueous golutions that the same effect may be obtained by keeping theGENERAL AND PHYSICAL CHEMISTRY. ii. 109 cell in the dark throughout and introducing into it near to one of the electrodes 1 C.C. of the same solution which has been intensely illuminated by a mercury arc for two hours. In this case the electrode near to which the liquid is introduced is a t h t negative.The E.M.P. a t first increases to a maximum and then decreases and finally changes its sign. With direct illumination of the electrode it is found that the E.M.P. continues to increase for some time after the source of light has been removed. Observations on the Phototropy of Inorganic Systems. J O S ~ RODR~GUEZ MOURELO (Anal. Pis. Quim. 1922 20 601- 605; cf. A. 1922 ii 604).-Further observations on the photo- tropy of sulphides of barium strontium and calcium. W. G. G. W. R. The Influence of Light on Zinc Sulphide. P. LENARD (Ann. Phyaik 1923 [iv] 68 553-573).-The cause of the darken- ing of zinc sulphide phosphors has beer traced to the polymerised sulphide molecules which are effective in phosphorescence. The darkening occurs however in zinc sulphide which is not phos- phorescent and it appears that the phenomenon has no direct relationship to the phosphorescence.The wave-lengths of the light producing darkening do not correspond with those effective in exciting phosphorescence. Water is necessary and ozone hydrogen peroxide chlorine etc. destroy the effect. On the other hand ammonia or reducing agents like formaldehyde reactivate a phosphor which has lost its sensitivity to light. The alkaline earth and magnesium phosphors do not bladcen. W. E. G. Influence of Adsorption of Ions 03 the Photochemical Sensitiveness of Silver Bromide. K. FAJANS and W. &ANKEN- BURGER (2. Elektrochem. 1922 28 499-505).-The authors have investigated the dependence of the sensitiveness of silver bromide on the method of precipitation.It is a known fact that silver bromide precipitated in the presence of an excess of silver nitrate is much more sensitive than that precipitated in the presence of an alkali halide. It is shown that under the influence of light the primary process taking place in silver bromide consists in the transference of an electron from a bromine-ion to a silver-ion with the formation of neutral atoms of bromine and silver. The work necessary to effect this change is dependent on the forces exerted on this electron in its initial and final states. In the presence of silver-ions from silver nitrate these forces are smaller and conse- quently the work required to effect the change is smaller and the sensitiveness of the silver bromide is increased. The Gamma Rays of the Family of Radium and of Thorium Studied by their Photoelectric Effect.M. DE BROGLIE and J. CABRERA (Compt. rend. 1923,176 295-296; Anal. Pis. Quim. 1922 20 467472).-By means of the apparatus previously described (A. 1922 ii 330) results have been obtained which are in accord with those of Ellis (A. 1921 ii 422; 1922 ii 466) and Meitner (A 1922 ii 416). 6" J. F. S. W. G.ii. 110 ABSTRACTS OF CHEWCAL PAPEBS. Rontgen Spectra and the Periodic System of the Elements. N. BOHR and D. COSTER (2. Physik 1923 12 342-374).-Th paper which forms a continuation of the Bohr theory of atomic structure (A. 1922 ii 363) and papers by Coster (A. 1922 ii 491 677) examines the relationship between the Rontgen spectra and the periodicity of the chemical properties and the optical spectra of the elements.It is shown that the movements of the inner electrons are subject to the same laws which operate in the case of the valency electrons. A table of the number of electrons in the various sub-groups of orbits is given for a large number of elements. This table which is based on spectroscopic data illustrates the building up of the electronic orbits with rising atomic number. The appear- ance of a new type of orbit is accompanied by a marked change in the chemical properties and the optical spectra of the elements. A new classification is proposed for the Rontgen spectra in which the principal groups are divided into sub-groups which are desig- nated by Roman numerals and to each level is given a value for n and k of the form n(kl,k2) [for example 2(2,2)L III].As in the work of Coster (Zoc. cit.) an arrangement of the Rontgen spectra is put forward which is based on a relationship between the fre- quency Y of each line and the difference between two spectral terms T' and T". In agreement with the principles of the quantum theory of line spectra these spectral terms multiplied by h give the energy required to transfer the electron from its normal orbit. The values T/B and d T 3 (where €2 is the Rydberg constant) are derived and tabulated for the K L N N 0 and P spectra and where the experimental data are missing the Rontgen spectra are interpolated from known values. Since the spectra are slightly affected by the form in which the element is excited a little uncer- tainty is introduced into the values of some of the elements with low atomic numbers; also the fine structure of some of the lines is a source of error.dFp is plotted against the atomic number for all the Rontgen spectra available and characteristic breaks are seen to occur in the curves for the L &I N and 0 spectra. The principal changes of slope occur in the neighbourhood of the platinum the rare earth and the iron groups. These irregularities are found a t those atomic numbers where it is predicted that a new sub-group of electrons makes its appearance. The appearance of electrons in the 4 orbit a t the element cerium the commence- ment of the rare earth group produces a sudden alteration in the slope of the dqB curve. At this point two of the lines in the M and N series separate into doublets. The binding energy of the 4 orbit a t atomic number 58 (cerium) is about &he same as that of the 6-quantum orbit and much less than that of the 5 and the 5* orbits.The energy of the 44 orbit increases as the atomic number rises until after the rare earth family of elements it exceeds the energy of the 5-quantum orbits. 'I'his behaviour is of undoubted importance for the study of the chemical properties of the rare earth group. The changes in energy of the electronic orbifs is more gradual at the end than a t the beginning of thisGENERAL IWD PHYSICAL CHEMISTRY. ii. 111 group. The value of dm for the 0 levels (5 quantum) changes very slightly between atomic numbers 58 and 72. This point is of greaf theoretical interest. The effective values of N and n for the 0 levels probably remain constant throughout the rare earth group.The constancy of N and n may also explain the similarity of the chemical properties and optical spectra of homologous elements in spite of considerable changes in the principal quantum number of the outer electronic orbit. The lack of periodicity in the K and L series is accounted for by the suggestion that the effective values of N and n for these orbits differ only slightly from the atomic number and the principal quantum number. Two types of doublets occur in the Rontgen spectra. The curves for one type run parallel throughout the whole of their course whereas for the other type they rapidly approach one another with decreasing atomic number. Although there is no evidence of periodicity in the Rontgen spectra in the same sense as it occurs in the optical properties it is expected that relationships will be obtained which will give a measure of the periodic behaviour of the elements.Uranium-2 and its Parent Substance. OTTO HAHN (2. physikal. Chem. 1923 103 461480).-A method is described for the determination of the relation of the activity of uranium-2 to that of uranium-X; the method has been applied to a large number of uranium-X preparations of different ages and a satis- factory constant value for the relationship obtained. The con- stancy of the value allows the conclusion to be drawn that uranium-Xl is the parent substance of uranium-2. Uranium-X1 therefore undergoes a dual P-ray disintegration of a kind which has hitherto not been observed with radioactive elements.A new method for detecting uranium-2 is de- scribed. From the activity ratio uranium-2 99.65%/\o-35% uranium-X it is shown that the branching P\\uz relationship is about 0.35%. In the calculation of this figure the absorption of the [3-radiation of uranium-2 with reference to that of uranium-X and uranium-X is taken into account. The disintegration scheme of the earlier members of the uranium series is therefore most probably represented by the annexed scheme. J. F. S. Ionisation by Collision of Hydrogen Nitrogen and Argon. T. L. R. AYRES (Phil. Mug. 1923 [vi] 45 353-368).-The ionis- ation of hydrogen nitrogen and argon molecules on collision with electrons has been measured for comparatively small values of the ratio of electric force X to the gas pressure p .The range examined is from X/p=l to X/p=600 and over part of this range Townsend and Bailey (cf. A. 1922 ii 836) have recently measured the velocity in the direction of the electric force and the mean velocity of agitation of the electrons in these gases. Ionisation by the electrons occurred for values of X / p as low as 2 in argon 5 in hydrogen and 10 in nitrogen. The effect of positive 5*-2 W. E. G. UI bX uxz<i B / \/ 711ii. 112 ABSTRACTS OF CHEMICAL PAPERS. ions was observed down to X/p=lO for argon 30 for hydrogen and 100 for nitrogen. No evidence was obtained for any appreciable variation in the ionisation due to slight contamination of the hydrogen and nitrogen but small amounts of impurities in the argon caused a marked diminution of the ionisation and increased the sparking potential.The ionisation with both positive and negative ions is in general agreement with that found by Townsend and Hurst for hydrogen and nitrogen (cf. A. 1906 ii 262). For argon however a t low values of X/p the ionisation is greater than found by earlier investigators. The nature of the metal used as electrodes is without appreciable effect on the ionisation. W. E. G. Thermal Ionisation of Gaseous Elements at High Tem- peratures. ARTHUR A. NOYES and H. A. WILSON ( J . Arner. Chem. Soc. 1922 44 280&2815).-A theoretical paper in which the thermodynamic equation used by Saha (A. 1920 ii 659) for calculating the thermal ionisation of the neutral atoms of gaseous elements into positive ions and electrons from their ionisation potentials is discussed with reference to the assumptions involved in the calculation.It is shown that the recent measurements of H. A. Wilson (A. 1916 ii 72) as well as the earlier experiments of Arrhenius (A. 1891 5 575) on the electrical conductivity of flames into which salt solutions are sprayed clearly indicate that the conduction arises from an ionisation process of the type under consideration and that they make possible a computation of the relative magnitudes of the ionisation constants. It is also shown that the relative ionisation constants of the five alkali elements calculated on the one hand from the conductivity of flames and on the other from the ionisation potentials by the thermo- dynamic equation form two series of values which run closely parallel to each other. Thus although in passing from lithium to cssium the ionisation constant increases 5700 times the ratio of the constants derived by the two methods for any one element does not differ from the mean value of that ratio for all five elements by more than 40%.The absolute values of the ionisation constants are derived from the flame conductivities with the aid of previous rough determinations of the mobility of the electrons and of the number of them per C.C. in similar flames. Although this could only furnish an estimate of the order of magnitude of the constants yet they were found to correspond well with the values calculated by the thermodynamic equation the latter being only 1.1 to 2.3 times as large.The Ionisation of Mercury Vapour in Presence of Argon. GEOROES D~JARDIN (Compt. rend. 1922 175 1203-1206 ; cf. this vol. ii 47).-Experiments were made with mercury vapour in presence of argon in order to ascertain whether the effect of the gas is similar to that of helium. The results show that ionisation resulting from impacts on mercury atoms of electrons the speed of which is greater than the critical ionisation speed (corresponding with 10.4 volts) is inappreciable and only becomes evident a t a J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 113 speed corresponding with 11-3 volts. On increasing the potential a sudden increase in the current is observed when the spatial charge of the electrons is completely neutralised and simultaneously a glow appears in the neighbourhood of the electrodes.The corre- sponding potential (the " illumination potential ") depends on the shape of the electrodes and on the pressure. Ionisation of the argon by direct impact begins a t a potential of about 15 volts. Between 11-3 volts and the illumination potential the intense lines of the mercury arc spectrum are obtained; above this limit the whole mercury arc spectrum and the red spectrum of argon are visible the latter increasing in intensity above 15 volts. Above 35 volts lines in the blue spectrum of argon are observed. The author infers from his results that for electrons traversing an atmosphere of argon there exists a first critical velocity of about 11.3 volts and that a resonance radiation emitted by the gas under these conditions ionises mercury vapour.This ionisation is not accompanied by any notable modification of the mercury spectrum analogous to that produced in presence of helium. Argon appears to exert only a feeble selective action on the second spectrum of hydrogen (Merton and Barratt A. 1922 ii 461) and on the cadmium spectrum (Collie and Watson A. 1918 ii 383). It is possible that the special influence of helium is due to the greater quantum of the radiations which it emits. H. J. E. Ionisation Produced by the Hydration of Quinine Sulphate. (M~LE) CHAMI~ (Cornpt. rend. 1923 176 251-253).-When the hydration is carried out in an ionisation chamber and the curve of increase in weight is compared with the curve of the diminution in current it is found that the duration of the phenomenon is the same for the two curves and depends on the density of the layer of the salt.Any effect which modifies the one curve modifies the other in the same manner. The weight of water of hydration as well as the maximum intensity of the current of ionisation and the quantity of electricity liberated during the hydration appear to be proportional to the weight of quinine sulphate used. W. G. Conduction Process in Ordinary Soda-Lime Glass. CHARLES A. KRAUS and EDWARD H. DARBY ( J . Amer. Chem. SOC. 1922 44 2783-2797) .-The replacement of sodium-ions in soda- lime glasses by ions of other metals has been investigated. It is shown that although the sodium-ions may be replaced by the ions of many other metals from their amalgams as well as from their fused salts under a potential gradient replacement occurs more readily from the fused salts than from the amalgams.In most instances the glass formed on replacement is not stable. In some cases the glass is completely disintegrated and in others it cracks on cooling. Sodium may be replaced by silver to a depth of about 0.1 mm. without cracking the glass. On replacing sodium by silver under the action of a potential a sharp boundary is formed between the sodium and the silver ions. From the rate of motion of the boundary the speed of the ions under a unit potential gradientii. 114 ABSTRACTS OF CHEMICAL PAPERS. has been determined; the following vahes are recorded 278" 4.52 x 10-8 ; 295* 1.46 X lo-' ; 323" 3.26 x lo-' and 343" 5.9 x cm./sec. The increased velocity of the ions with increased tem- perature corresponds with the increased conductivity of the glass with increased temperature.The fraction of the total sodium present in the glass which takes part in the electrical conduction has been calculated from the depth of penetration of the boundary and from the amount of electricity passing as well as from the change in weight of the tube. It is found that 74-82% of the total sodium present in an ordinary soda-lime glass takes part in the conduction. The remaining sodium is either not in a charged state or otherwise the ions are held in fixed positions. The fraction ionised as defined in this way increases slightly between 278" and 343". The following values of the percentage ionisation and the resistance in ohms are recorded 278" 74.4% 72800 ohms; 295" 76.8% 35000 ohms; 323" 79.4% 14200 and 343" Sl.O% 6600 ohms.5. F. S. Potential Difference between Glass and Electrolytes in Contact with Glass. WALTER S. HUGHES (J. Arner. Chem. Soc. 1922 44 2860-2867) .-The potential difference between glass and solutions of electrolytes has been investigated a t 25". It is shown that glass surface potentials are established and maintained by the passage of electricity through glass. The glass surface potential is a linear function of the hydrogen electrode only over a limited range of values. Variations in the glass surface potential may be used as the basis of an electrometric titration method in the presence of oxidising agents which render the hydrogen elec- trode useless for such purposes.In such cases the method might yield data which could not be obtained in any other way. The presence of certain substances other than hydrogen-ions such as concentrated solutions of salts or gelatin affects glass surface potentials . J. I?. S. Significance of the Electrode Potential. JAROSLAV HEY- ROVSKI? (Proc. Roy. Soc. 1923 [ A ] 102 628-640).-Evidence is adduced that the process by which a metallic electrode immersed in an aqueous solution becomes charged is represented by M+OH' + MOH+ 0. By the application of the electronic con- ception of chemical combination to a reversible thermodynamic cycle a formula is obtained for the electrode potential in terms of the ionisation potential and basigenity of the metal. The basicity of metallic oxides is discussed by means of Beketoff s principle (A.1889 332) and it is concluded that a metallic hydroxide .is the more basic the more negative the electrode potential and the greater the equivalent weight of the metal The mechanisms of galvanic and concentration celh the phenomena of electrodeposition and overvoltage and electrode processes in non-aqueous solvents are discussed in the light of the theory developed. " Absolute zero potential " values of contact E.M.F. derived from electrocapillary phenomena are shown to be illusory,GEN-ERAL AND PHYSICAL CHEMISTRY. ii. 115 and the probable potential a t which reversal of the sign of the charges in the double layer occurs is indicated. Determination of Absolute Single Electrode Potentials. ALLEN GARRISON ( J . Amer.Chern. Soc. 1923 45 374).-The methods hitherto employed for determining absolute single electrode potential differences have been enumerated and briefly discussed and a new method of effecting this determination is described. The method is based on the assumptions (1) that the mechanical force on a substance suspended in an electrolyte through which an electric force acts is due t o the charge on the suspended system (2) that the direction of the force is determined by the sign of the charge and (3) that there is no charge or potential difference relative to the electrolyte when in an electric field there is no mechanical force relative to the electrolyte. The method used consists in suspending a light metal needle shaped like the needle of a quadrant electrometer by a phosphor-bronze ribbon in an electrolyte con- taining such a concentration of the metal-ion that there is no electric double layer at their interface.This isoelectric condition is indicated by the absence of any mechanical forces when an electric field is applied through the electrolyte. The potential of the needle is at the same time compared with the potential of a standard half cell. On eliminating the liquid junction potential the measured E.M.F. is the absolute potential of the constant eleotrode. A full description of the apparatus and its method of use is given in the paper. Using a silver needle a t itas isoelectric point as the zero electrode the absolute potential of a 0-1N-calomel electrode is found to be between -0.20 volt and -0010 volt a t 25’.This result is a confirmation of Billitzer’s value of -0.13 volt and it removes the objections which have been made to the method employed by Billitzer (2. Elektrochem. 1902 8 635). J. E. VERSCHAFFELT (Rec. traa. chim. 1922 41 7-777; cf. Aten A. 1916 ii 370).-A mathematical argument in which the aixthor develops views previously put forward (Bull. Acad. roy. Belg. 1919 441). The conclusion is drawn that the variation of potential due to the application of E.M.F. is mainly effective at the cathode in the case of two electrodes of a metal in contact with a solution of one of its own salts whilst with the same salt but with electrodes of a more electropositive metal the anode potential undergoes the greater variation and thus only the anode is polarised. Activity Coefficient of Hydrochloric Acid in Aqueous Salt Solutions.HERBERT S. HARNED and NORMAN J. BRUMBAUQH ( J . Amer. Chem. Soc. 1922 44 2729-2748).-E.M.F. measuret ments of cells of the followin types have been carried out a t the kmperatures indicated HfMCl (c) in 0*1N HClIEgCl/Hg at ISo 25” and 30° where M denotes barium strontium or calcium; H,1MC12 in 0*1N HCIIKCl (sat.)lHgCIIHg a t 25O where M signifia the same metal as before; H2JKC1 (c) in HCl (c’)lAgCl(Ag and HJKC1 (c) in HC1 (c’)]HgClJHg where c’ is 0-01N and 0.001N at J. S. G. T. J. F. S. The Polarisation of Electrodes. H. J. E.ii. 116 ABSTRACTS OF CHEMICAL PAPERS. 18” 25” and 30”. From the data obtained the decrease of free energy and the decrease of the heat content of the cell reaction have been calculated as well as the changes in partial molecular free energy and heat content of hydrochloric acid in the mixtures.The mean activity coefficients of hydrochloric acid in solutions of potassium sodium lithium barium calcium and strontium chlorides have also been calculated. By means of the formula log Fa’= a’cl-P’pm’+d’ (p-cJ the values of the mean activity coefficients (Fa’) of hydrochloric acid in the acid salt mixtures containing acid a t concentrations from 0.001N to N may be calculated with considerable accuracy. In solutions of greater dilution of acid it is necessary to add a term to the above equation which is a function of the salt to acid concentration ratio thus log Fa’= a ’ ~ ~ - ~ ~ p ~ ’ + c c ’ ’ ( u - - ~ ~ ) + y ’ [ ( p - ~ ~ ) / c ~ ] is approximately valid for solutions containing acid of concentration as low as 0-001N.Thus when (p-c1)/cl is very high a considerable increase in the value of Fa‘ is observed. In the above equations c1 is the concentration of acid a’ P’ a” m’ are constants and p is the ionic strength and for uni-univalent electrolytes equals the sum of the concentrations of the salt and acid or (c+cl). It is pointed out that the effect mentioned above is probably due to an increase in activity of the hydrogen-ion. If as is to be expected the same phenomenon is observed in mixtures containing other ions it will be of considerable importance especially in dealing with the problem of the solubility of sparingly soluble salts in solutions of other salts. Evidence has been obtained which leads to the conclusion that in solutions of strong bivalent chlorides a t the same temperature and con- centration the chloride-ion will have the same activity and also that the activity of the chloride-ion in uni-univalent chloride solu- tions is greater than in bivalent chloride solutions of the same ionic strength.J. F. S. Activities of the Ions of Potassium Hydroxide in Aqueous Solution. M. KNOBEL ( J . Arner. Chem. Xoc. 1923 45 70- 76).-The author has determined the E.M.F. of cells of the type H,IKOH (c,)lKHg,lKHg,]KOH (c,)]H at 25” for concentrations of potassium hydroxide ranging from 3N to 0-0001N. The activity coefficients of the ions of the solution at various concentrations and the free energy of dilution between various concentrations have been calculated and tabulated. The data given by Chow (A.1920 ii 281) are found to be incorrect; differences of 2-8y0 are found between Chow’s values and the present values. The relationship between the activity and concentration for potassium hydroxide has been found to be similar to that for other uni- univalent electrolytes. J. F. S. Degree of Ionisation of Ethyl Alcohol. I. From Measure- ments of Conductivity. PHILIP s. DANNER and JOEL H. HILDE- *BRAND (J. Amer. Chem. Soc. 1922 44 2824-2831).-The methods available for the purification of ethyl alcohol are discussed as to their efficiency and the following method has been adopted for the preparation of absolutely pure material. Commercial 95% alcoholGENERAL AND PHYSICAL CHEMISTRY. ii. 117 was distilled with 5 C.C.of concentrated sulphuric acid and 20 C.C. of water per litre and the distillate boiled for several hours with 10 g. of silver nitrate and 1 g. of potassium hydroxide per litre. This product was distilled on to commercial quicklime 600-700 g. per litre and boiled for eight hours. The mixture was then shaken vigorously for twenty-four to thirty-six hours at the ordinary temperature and distilled on to specially prepared quicklime made by burning the mixture of calcium hydroxide and carbonate such as is obtained by drying slaked lime in the air. This product was present in the quantity 100-150 g. per litre of alcohol and the mixture was boiled for four to six hours. The alcohol was then distilled into the vessel from which the final purification was to be made and at this stage had a specific conductivity 1.0 x 10-7 ohms-1.Subsequent distillation in evacuated sealed apparatus gave a value 2.2 x 10-8 ohms-1 but here the most volatile portion was not removed. Repeated vacuum distillation with removal of the most volatile portion gave a steadily decreasing value with each repetition until the tenth distillation gave the value 1.35 x 10-9 ohms+ and this is regarded as the value for the purest ethyl alcohol. The dissociation constant calculated from this figure is 2.89 x 10-l6 for the ionisation C,H,*OH iZ C,H,O’+H’ ; the mole- cular fraction ionised is 1.0 x which i s comparable with the similar value for water 1.8 x Degree of Ionisation of Ethyl Alcohol. 11. From Measure- ments of Electromotive Force. PHILIP s. DANNER ( J .Amer. Chem. Soc. 1922 44 2832-2841 ; cf. preceding abstract).-The E.M.F. of a series of cells of the types H2PtIHC1,HgC11Hg HglHgC1,NaCllNa (2-phase amalgam) and Na (2-phase amalgam)] C2H,*ONaIPtH2 all in pure ethyl alcohol (Zoc. cit.) have been measured a t 25”. The cells were very slow in reaching an equi- librium value but were reproducible to 0-0001 volt and calculations based on the values obtained involve no assumptions as to the value of the potential a t the boundary water/alcohol since this is not present. The dissociation constant for the ionisation C,H,*OH C,H,O’+H’ is calculated to 7.28 x and the molecular fraction dissociated to 1.6 x This indicates that ethyl alcohol is dissociated only to 1/100 of the amount to which water is dissociated.The discrepancy between the present results and those given in the previous paper (Zoc. cit.) is attributed to the assumptions involved in the interpretation of the conductivity measurements since the maximum possible error of the E.M.F. measurements 0.002 volt would not produce a greater error than 10% in the value of the dissociation constant. The Ionisation of Water in Solutions of Electrolytes. E. DOUMER (BUZZ. Soc. chim. 1923 [iv] 33 49-55).-Hittorf’s assumption that water is only ionised in negligible proportions in solutions of electrolytes does not seem to be justified especially in the case of acid electrolytes and particularly of hydrochloric acid solutions. Evidence for the fact that the liberation of oxygen at the anode in the electrolysis of hydrochloric acid is a primary J.F. S. J. F. S.ii. 118 ABSTRACTS OF CHEMICAL PAPERS. effect and not a secondary reaction due to the action of nascent chlorine on water is furnished by electrolysis with a silver or mercury anode when the amount of oxygen liberated is actually greater than with platinum anodes whilst all the chlorine combines with the anode forming the metallic chloride. Initially the silver anode becomes covered with a brown film which eventually becomes white so that both chlorine and oxygen are apparently discharged simultaneously the former then displacing oxygen from the oxide when free metal is no longer available on the surface of the anode. Experiments on the electrolysis of dilute hydro- chloric acid showed that for 50 C.C. of hydrogen liberated at the cathode 16.55 C.C.of oxygen were formed at the anode and it is therefore concluded that of the total hydrogen-ions discharged 2 x 16-55/50 were derived from ionised water that is about 66%. This surprisingly high proportion finds confirmation in a deter- mination of the total loss of hydrochloric acid in the electrolyte compared with the theoretical loss had all the liberated hydrogen been derived from hydrogen chloride. Further the molecular conductivity of hydrochloric acid solutions is about three times as great as that of alkali chloride solutions and the explanation provided by the above hypothesis is that in such acid solutions there are in addition to hydrogen- and chlorine-ions about twice as many hydrogen- and hydroxyl-ions. G. F. M. Theory of the Polarisation of the Electrolytic Generation of Oxygen.11. Anodic Behaviour of Manganese in Solu- tions of Alkali Hydroxides. G. GRWE and H. METZGER (2. EZe&rochem. 1923 29 17-30; cf. ibid. 1922 28 568).-The anodic behaviour of pure manganese in solutions of sodium hydroxide has been investigated. It is shown that in hot concentrated solu- tions with small current densities manganese passes into solution in the bivalent condition with medium current densities (0.3- 0.1 amp. /dcm.2) in the tervalent condition and with higher current densities in the sexavalent condition. The solution of manganous oxide thus produced is yellowish-red in colour and that of the manganic oxide brownish-red. The sexavalent manganese forms manganate the production of which is always accompanied by the liberation of oxygen.At ordinary temperatures and also in dilute hydroxide solution manganese passes into solution in the septa- valent condition with liberation of oxygen. The potentials corre- sponding with the individual anode changes have been measured at various temperatures and concentrations of alkali. The polaris- ation of the electrolytic evolution of oxygen occurs because the manganese becomes covered with a thin film of dioxide which then forms permanganic acid according to the equation Mn0,+2H2O + 3 0 -+ MnO,/+H'. This substance then decomposes completely at lower current densities in N-sodium bydroxide with the evolution of oxygen according to the equation 2HMn0 + 2Mn0,+H20+ 3/20,; a t higher current densities only a portion decomposes in this way whilst the other portion diffuses into the solution and forms sodium permanganate.The competition of the velocityQENERAL AmD PRYSICAL CHEMISTRY. ii. 119 .of the two reactions the oxidation of manganese dioxide to per- matnganate and the spontaneous decomposition of the perman- ganic acid with liberation of oxygen determines the extent .to which the current is used for the liberation of oxygen and the formation of permanganafe and also the potential of the process. J. F. S. Effect of Fluorine on Electrolytic Oxidations. A. Rfos Y M I R ~ (Anal. Fb. Quim. 1922 20 644-661).-The electrolytic oxidation of chrome alum and potassium hydrogen phosphate is increased with increasing amounts of potassium fluoride. It is supposed that the fluoride-ions a t the moment of their discharge a t the anode react directly or indirectly by means of a peroxide of platinum with the electrolyte present.With water ozone is formed whilst in other cases per-compounds may be formed for example in the case of phosphates perphosphoric acid. The theoretical objections to this theory are discussed. Electrolysis with a Dropping Mercury Cathode. I. Deposition of Alkali and Alkaline-earth Metals. JAROSLAV HEYROVS~ (Phil. JIaq. 1923 [vi] 45 303-315).-The decom- position potentials of the alkali and alkaline-earth metals have been determined by means of a dropping mercury cathode. When the dropping electrode is made the cathode it is found that in neutral or alkaline solution hydrogen is not evolved even with high polaris- ations and hence this arrangement is convenient for the study of the cathodic deposition of the most positive metals which are otherwise attacked by water.The decomposition potentials found by this method were lithium -2.023 potassium -1.883 sodium -1.860 cEsium -1.837 rubidium -1.796 ammonium -1.787 calcium -2.023 magnesium -1.903 strontium -14362 and barium -1.814 volts. Assuming that the alkali metals form compounds with the mercury it is possible to calculate the a f i i t y of the metal for mercury this being given by the equation A= r,,-E.P. where T is the observed decomposition potential with the drop electrode and E.P. is the decomposition potential obtained by G. N. Lewis. The afhity for mercury increases with increasing atomic weight but sodium occupies an anomalous position behaving like a more noble metal.It is deduced that the E.P. of caesium is -3.3 volt. Transport Numbers of Potassium Hydroxide in Aqueous Solution. M. KNOBEL D. K. WORCESTER and I?. B. BRIGGS (J. Amer. Chem. Soc. 1923 45 77-79).-The E.M.F. of concen- tration cells of potassium hydroxide of the type H,IBOH(c,)l KOH(c,)]H have been measured a t 25" for concentrations between 3~0N and 0.01N. These values combined with those obtained for cells without transport (see this vol. ii 116) have been used to calculate the transport number of the potassium-ion in solutions of potassium hydroxide of various concentrations. The transport number of the potassium-ion is found to be constant and equal to 0-2633 over the whole range of concentration 3*0N to O-OlN and to increase with decrease in concentration below this value to G.W. R. W. E. G.ii. 120 ABSTRACTS OF CHENICAL PAPERS. 0.274 at infinite dilution. The following values of the B.3i.F. are recorded for the cells measured c1=3.0N c2=O.3N ~=0.03683&- 0.08003 ; cl= l-ON c,=O*lN ~=0*03104&0~00003 ; C1=0.3N C =O* lN E= 0.01424 &0.00003 ; c1 = 0.3N c2 = O.O3N 6 =0.029 16 & 0.00003 ; c,=O*lN ~,=0*01N ~=0~03465-+0~00015. J. F. S. Possibility of Varying Intermediate Stages in the Kobe Reaction and a Case of Anodic Ester Formation with Aromatic Acids. C. SCHALL (2. Elehrochem. 1922 28 506- 51 1) .-The electrolysis of molten lead acetate manganous acetate in benzoic acid and alkali benzoates in benzoic acetate has been investigated; it is shown that in the case of metals of constant valency the change takes place according to the equation xRCO,'+ xF=x/2R.R+xCO but when the metal has a variable valency the primary change is represented by the equation M(RCO,),+ xRC0,'f-xF=M(RCO,), and if the temperature is sufficiently high this reaction is followed by a secondary thermal action M(RC02),,=M(RC0,),+x/2R . R+xCO,. These equations indicate that intermediate compounds may be formed in the Kolbe reaction. When potassium benzoate containing benzoic acid is electrolysed using a silver anode phenyl benzoate is produced. This formation is due a t least in part to the oxidation of the acid to phenol by the silver oxide produced on the anode. The Anomalies of Strong Electrolytes with Special Refer- ence to the Theories of J.C. Ghosh. 11. HENRY J. s. SAND (Phil. Mag. 1923 Evil 45 281-292; cf. this vol. ii 55).-Alter- ations have been made in the subsidiary hypotheses of Ghosh to bring them into line with the equation p/poo=e-cflNRT where p / p M is the ratio of the molecular conductivities and G' the work required to separate one gram-mol. of ions. Although the theory is strengthened by these changes the number of subsidiary hypotheses is so great that the above equation must be regarded as an empirical formula. The hindrances to conduction in sl medium of uniform dielectric constant by the electric fields of the ions is of the nature of polarisation and the conductivity should be greater with rapidly alternating currents and high potential gradients than with small constant potential gradients.Since this conclusion is contrary to experiment the idea of a solvent with uniform dielectric constant has been abandoned. An explanation of ionisation is put forward based on the assump- tion that solvent molecules possess polar properties the ionising media consisting of a number of bipoles similar to those postulated by Debye in his explanation of the dielectric properties of the media. These bipoles which are capable of rotation are held when in the powerful electric field of the ion and their rotation stopped and converted into vibrational motion. Each ion will thus consist of the simple charged atom or group in the centre of a number of polar water molecules which is capable as a whole of rotatory or vibratory motion. The ions become bound when they meet other ions of different polarity and are then only capable of vibration around a position of equilibrium and become incapable of J.F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 121 transmitting a current. These views lead to a formula similar to that of Ghosh. The Ghosh equation whilst yielding satisfactory values for binary electrolytes breaks down for salts like barium chloride. The introduction of the Milner virial into Ghosh’s formulz! does not lead to any improvement. Faraday’s Law and the Action of the Electrical Discharge on Gases. A. DE HEMPTINNE (Bull. Amd. TOY. Belg. 1919 [v] 5 521-527).-Faraday’s law has been shown to hold with fair approximation for chemical effects produced by an electrical discharge on gases a t low pressures.Faraday’s Law and the Chemical Action of the Electrical Discharge. A. DE HEMPTINNE (Bull. Acad. roy. Belg. 1919 [v] 5 161-177).-An investigation of the reduction of unsaturated oils by hydrogen under the influence of an electrical discharge the amount of reduction being followed by the change in iodine number of the oil. A large number of experiments involving variations in thickness of dielectric density of current potential difference etc. are described and do not lend themselves to abbreviated description. The author concludes that Faraday ‘s Laws of Electrolysis are obeyed at any rate roughly. Faraday’s Law and the Action of the Electrical Discharge onMetallic Oxides. 11. 111. Tv. V. A. DE HEMPTINNE (Bull. A d . roy. BeZg. 1919 [v] 5 249-260; 1921 [v] 7 146-155 458468,590-595).-II.A study of the reduction of metallic oxides by hydrogen in presence of an electrical discharge. The results fall in Line with those previously obtained with unsaturated oils (cf. preceding abstract). Lead peroxide is taken as a standard substance for reduction and a large number of other metallic oxides and also chlorides and miscellaneous substances are compared with it. Carbon monoxide was found to be roughly as effective in reduction as hydrogen the experiments being carried out at low pressures to avoid polymerisation etc. of the monoxide. 111. The reduction of various substances by this method shows that as a rule it is unimportant whether the substance in question is in contact with the positive or with the negative electrode. Values are found for the ratio N/N’ where N is the number of hydrogen mole- cules disappearing during a reduction and N’ the number of ions and electrons (calculated from the measured current).This ratio has a value ranging from zero in the case of difficultly reduced oxides such as zinc or magnesium to above unity in the case of lead peroxide and manganese dioxide etc. the reducibility of an oxide being con- nected with the electrolytic potential of the corresponding metal. Potassium chlorate is almost unaffected under conditions sufficing for the reduction of most oxides a fact which is attributed to the purely electrical nature of the process no thermal effect being produced by the incidence of positive ions or electrons. Thus in the case of oxides the amount of reduction is approximately proportional to the amount of current passing.IV. The reduction of lead peroxide cupric oxide and ferroso- ferric oxide is effected in a dried atmosphere of hydrogen by W. E. G. E. E. T. E. E. T.ii. 122 ABSTRACTS OF CHEMICAL PAPERS. means of an electrical discharge the oxide in question being placed in contact with one of the electrodes. By measuring the variation of pressure of potential difference between the elec- trodes and the current flowing a relation is found between the number ( N ) of hydrogen molecules used in the reduction and the number of positive ions (Ni) and electrons (Nd). The point is raised as to whether in ionisation the hydrogen molecule loses one or two electrons. Activated hydrogen (H,) offers another explanation but the mechanism of the reduction remains in doubt.With lead peroxide in contact with the positive electrode N / N has values from 0 to 1.1 and when in contact with the negative electrode values of 2.7 to 1.4 for N/Ni are obtained. Similar results are obtained for other oxides. If the positive ions are formed by the loss of one electron from each hydrogen molecule and if each electron liberates one atom of oxygen which then combines with one molecule of hydrogen N/Ni and NIN should be equal to unity. Values (for these ratios) of 0.5 will correspond with the loss of two electrons when hydrogen is ionised and so on. V. In the earlier sections the loss of weight of oxides when sub- mitted to the action of an electrical discharge in presence of hydrogen was not determined.It is now found that in the reduction of lead peroxide the weight of hydrogen absorbed (as measured by the diminution in pressure) is equivalent to the loss in weight of oxide whether the latter is in contact with the positive or with the negative electrode. The oxide formed as a result of the reduction is probably lead suboxide. When nitrogen is substituted for hydrogen in these experiments no change is observed in either gas or solid except such as could be accounted for owing to defects in the apparatus. Carbon monoxide under similar conditions causes the lead peroxide to gain in weight probably owing to the formation of a deposit of a lower oxide of carbon. E. E. T. LOUIS BELL and P. R. BASSETT (Science 1922,56 512).-In the spectrum of the " negative tongue " which appears in the carbon arc at currents of at least 100 amperes there were found iifteen lines of which seven were coincident with the most conspicuous helium lines and two others with Ha and Hp.Some carbon nuclei are considered to dissociate into helium and possibly further although the hydrogen lines may be due to water vapour absorbed by the carbon. Dissociation of Carbon in the Intensive Arc. CHEMICAL ABSTRACTS. The Evolution of the Molecule of Ferric Hydroxide in Contact with Water. (MLLE) S. VEIL ( C m p t . rend. 1923 176 101-103) .-The molecular coefficient of magnetisation with reference t o iron content of the hydroxide and the oxide of iron depend to a large extent on the previous states through which the material has passed and the temperatures to which it has been heated.W. G. The Calculation of the Magneton Number of an Atom in Solution. J. H. SMITH (Phil. Mag. 1923 [vi] 45 375-3781.- The magnetic susceptibility of cobalt chloride in water is greaterr IGENERAL AND PHYSIC& CHEMISTRY. ii 123 than in alcoholic solutions and this change is associated with LI shift in the maximum of the light adsorption from O f i l O ~ to 0 . 6 5 ~ ~ Making the assumption that Wiedemann's law of the additivity of magnetic susceptibility holds for solutions the magneton number of the cobalt-ion in aqueous solution is found to be 24.6. The difference between the magnetic susceptibility in water and in alcoholic solutions may be ascribed either to a change in the diamagnetic or the paramagnetic part of the atom.A reason- able conclusion is that the frequency of the paramagnetic part of the atom is diminished. and this view is sumorted bv the decrease in the frequency oi the light absorbers in*the atom.". W. E. G. Paramagnetism and the Structure of the Atom. B. CUR- ( J . Phys. Rccdium 1922 3 443460).-The property of paramagnetism is confined very largely to the elements in column VIII of the Mendelkev classification and to the rare earths. The magnetic susceptibilities of the elements from chromium to copper following the order of the atomic numbers have been seriously studied and data are available to fix the magneton number (Weiss) of the metallic ions for many of the elements in their various stages of oxidation. For these elements the Weiss magneton number is seen to be given by a series of whole numbers which are inde- pendent of the degree of ionisation of the salt.A theoretical mterpretation of this regularity in the Weiss magneton number is sought in the structure of the atom and in particular in the N-level of electrons. This level is subdivided into N and N levels the latter first making its appearance with titanium. The number of electrons in the N level augments from Ti"" to Cu' for which element it attains a maximum value. It is assumed that the number of electrons in the M level remains constant a t 8 throughout. On plotting the magneton number of the ion against the number of electrons in the N level a symmetrical curve is obtained giving a maximum at Fe*** when the magneton number is 29 and N1 = 5.Ions containing an identical number of electrons in the N level give the same magneton numbers; thus Fe"' Mn" Mn"' and Cr" give the same values. The points corresponding with Co" and Ue" are somewhat displaced but these elements give a variable magneton number. At Ti"" and Cu' the magneton number is zero. The magnetic susceptibilities of the oxides of manganese and the oxides and sulphides of titanium and vanadium are in general agreement with the above curve. The metals offer con- siderable difficulties for the number of electrons which bind together the atoms is unknown. The work of Urbain and Janesch (cf. A. 1909 ii 116) has demonstrated the existence of two groups within the rare earths in each of which the magneton moment attains a maximum and then decreases.Qualitatively the changes in magneton number will be analogous to that of the group studied above. These results do not appear to be in accord with the modification of the M levels assumed by Bohr for this structure should lead to discontinuities in the curve of the magnetic moment.G. 124 ABSTRACTS OF CHEMICAL PAPERS. The results of Stern and Gerlach (2. Physilc 1922 9 353) are not in opposition t o the Weiss magneton. Influence of the Pitch of Sound on the Measurement of the Relationship k=cp/cv for Carbon Dioxide. BRUNO TORNAU (2. PhysiE 1923 12 48-57).-The ratio of the specific heats1 for carbon dioxide was found to be K,=1~3165&0*00032. Variation in the pitch of the sound produced no change in the value of KO. EDM. VAN AUBEL (BUZZ. Acad. roy.BeZg. 1921 [v] 7 155-159).-The validity of certain conclusions drawn by Michaud (A. 1920 ii 532) is discussed making use of existing data for the specific heats etc. of silicon boron rhombic sulphur thallium magnesium and chromium. Michaud's conclusions are shown to be untenable. Third Law of Thermodynamics. Evidence from the Specific Heats of Glycerol that the Entropy of a Glass exceeds that of a Crystal at the Absolute Zero. G. E. GIBSOX and W. I?. GIAUQUE (J. Amer. Chem. Xoc. 1923 45 93-103).- An improved calorimetric apparatus is described for determin- ations a t low temperatures. The specific heat of supercooled glycerol and the specific heat and heat of fusion of crystalline glycerol have been determined a t temperatures down to 6909°K. The specific heats of the glass and the crystals approach one another as the temperature is lowered and are almost identical below 140°K.The heat of fusion of glycerol a t the melting point 291.00"K is 47-50 cal./gram or 4370 cal./mol. and the entropy of fusion is 15.02 cal./degree per mol. or 1.073 cal./degree per gram. The entropy of supercooled liquid glycerol exceeds that of crystalline glycerol by 5-6-J=0.1 cal./degree per mol. a t 7OoK and it is concluded that this value will not be appreciably different at the absolute zero. J. F. S. E. D. EASTMAN (J. Amer. Chem. Soc. 1923 45 80-83).-The hypothesis that the expression for the mass effect in the entropy of all substances in which equipartition holds takes the same form as for monatomic gases is tested for all cases for which data are available.The results show that there is much evidence in support of the hypo- thesis and none definitely contradicting it. Several approximate equations are given for the calculation of the entropy of diatomic gases and metals. Physical and Chemical Transformations of Gibbs 's Systems. TH. DE DONDER (BUZZ. Acad. roy. BeZg. 1920 [v] 6,315- 328) .-A thermodynamical treatment of systems consisting of phases as defined by Gibbs. The author adopts a point of view very slightly different from the usual one. The Chemical Constants of the Halogens in the Monatomic and Diatomic Condition. 3'. A. HENGLEIN (2. Physilc 1923 12 245-252).-The chemical constants of chlorine bromine and W. E. G. W. E. G. Atomic Heat of Simple Substances. E. E. T. Mass Effect in the Entropy of Substances. J.F. S. E. E. T.GENERAL AND PHYSICAL CHEMISTRY. ii. 125 iodine have been calculated from the dissociation and vaporisation equilibria of these gases and the values are in good agreement with those derived by Stern and Tetrode. For the monatomic gases the following results were obtained for the chemical constants chlorine +0.72 bromine +1.26 iodine +1.56 and for the diatomic gases chlorine +O.OZ bromine +1-50 and for iodine f-2.55. Bromine and iodine have the highest chemical constant of any element. The heat capacity of solid bromine has been determined and a Debye function given for the calculation of its specific heat. The chemical constants of the halogens in the diatomic condition increase slightly as the temperature rises. W. E.G. Relation' between the Absolute Melting Boiling and Critical Temperatures of Substances. EDM. VAN AUBEL (Bull. A d . roy. BeZg. 1921 [v] ?,469-472).-The value of r a constant (according to Prudhomme A. 1920 ii 83 84 376; see also A. 1921 ii 622) deduced from the absolute melting and boiling points and critical temperatures of various substances has been calculated for a number of compounds using existing data and the following values of r have been obtained Mercury 0612 mercuric chloride 1-01 mercuric bromide 1.03 mercuric iodide 1.03 antimony tri- chloride 1.04 antimony tribromide 1.01 aluminium bromide 1-16 and aluminium iodide 1.10. All these substances. therefore. with the exception of mercury give a normal value (i:e. about hits) for r. E. E. T. Method for the Determination of the Melting Point of Difficultly Fusible Metals.MARCELLO PIRANI and HANS ALTERTHUM (2. Elektrochem. l923,2Sy5-8).-The melting point of metals with high melting point may be determined by using a hole (6 mm. deep and 1 mm. diam.) bored a t an angle to the axis of a 7 mm. square rod of the metal as a black body for temperature determination. That the metal had melted was indicated by drops of it falling from the hole. The heating was effected by passing a 50-period alternating current which could be varied by steps of 10 amp. to 1500 amp. through the bar. Using this method the melting point of tungsten and molybdenum has been determined and the values 3660"&60" and 2840"&40" respectively have been obtained. These values are in agreement with other recent deter- minations. J.3'. s. Separation of Lipid Mixtures by Combined Distillation and Atmolysis. Preparation of Practically Pure Ethyl Alcohol and Nitric Acid. ~ D O U A R D URBAIN and R$MY URBAIN (Compt. rend. 1923 176 166-168).-The apparatus consists of a distillation flask surmounted by a porous porcelain tube which is jacketed with a glass tube in which the pressure can be reduced. The porous tube is fitted with a condenser on top and is so arranged that the condensed vapours can be returned to the distillation flask or run into another vessel. With this apparatus it is possible to obtain 9943% alcohol by direct distillation. The water vapour passes through the wall of the porous tube and the condensedii. 126 ABSTRACTS OF CHEMICaL PAPERS.alcohol is returned to the distillation flask. In a similar manner it is possible by means of this apparatus to prepare 9906% nitric acid. The Heat of Oxidation of the Alkaline-earth Metals. A. GUNTZ and BENOIT (Compt. rend. 1923 176 219-220).-The authors have made measurements of the heats of solution of calcium strontium and barium respectively in dilute hydrochloric acid andfrom the results and the known heats of solution of their oxides in this acid have calculated the heats of oxidation of these metals to be 152.7 141.8 and 134.04 cal. respectively. I?. BOURION (Cmnpt. rend. 1923 176 95-98).-A theoretical dis- cussion in which it is shown that in order to observe in the pro- gressive neutralisation of an acid by a base differences between the values found and those calculated by proportionality by the current thermochemical methods the afkity constant of the acid must not be greater than 10-10 with the usual order of magnitude of the heats of ionisation. W.G. The Phenomenon of Molecular Association. ETTORE CARDOSO and GABRIELE BATTISTA (Anal. Pis. Quim. 1922 20 420432).-From a combination of van der Waals’s equation and the rule of Cailletet and Mathias the densities of a liquid and its vapour respectively dl and d3 are connected with the critical constants by the relation dld3/dC2= K(pT,/p,T) or more generally dld3/dc2 =f(pT,/p,T). Deviations of this function from a linear relationship are attributable to molecular association and are the more pronounced the greater is the difference between the degree of association of the coexisting phases.The liquid phase is in- variably more complex than the coexistent vapour phase. W. G. W. G. Berthelot’s Normal Acids and the Theory of Ions. G. W. R. Cohesion Pressure Surface Activity and the Tendency to the Formation of Submicrons. I. TRAUBE (Kolloid Z. 1923 32 22-24; cf. A. 1912 ii 858; 1915 i 105).-It has been shown previously that salts of alkaloids are molecular dispersed in aqueous solution (Zoc. cit.) and because of their ionic charge have a large cohesion pressure; they are therefore unable to form sub- microns and have no surface activity. In every respect the reverse is the case for free non-ionised alkaloids. It is now shown that the salts of fatty acids are similar to the salts of alkaloids in the above respects.With the exception of formic acid the free fatty acids have a small cohesion pressure and have a surface activity and from butyric acid upwards form submicrons. Here as in the case of the alkaloids the cohesion pressure decreases with increasing molecular weight whilst the surface activity and the ability to form submicrons increases. The lower fatty acids including propionic acid do not form submicrons whilst butyric acid forms many submicrons and the higher fatty acids such as nonoic decoic and undecoic acids exist in both a surface active and an inactive form. Substances such as amyl alcohol octyl alcohol phenol creaol,GENERAL AND PHYSICAL CHEMISTRY. ii. 127 aniline and xylidine have a considerable cohesion pressure and their concentrated solutions contain submicrons and molecular dispersed particles whilst hydrocarbons and alkyl halides have small cohesion pressures and in aqueous solutions exist mainly as submicrons.From the above facts the author claims general validity for the rule previously put forward. The smaller the cohesion pressure the greater is the surface activity and tendency to form submicrons. J. F. S. Films. Spreading of Liquids and the Spreading Co- efficient. WLLLIAM D. HAREINS and AARON FELDMAN ( J . Amer. Chem. Soc. 1922 44 2665-2685).-1t is found that the spreading of films is in general related to what is defined thermodynamically as the spreading coefficient. Liquids for which the value of this coefficient 8 is positive will spread whilst those for which it is negative will not spread. Actually the value of the coefficient refers to the system spreading liquid-substance on which the spreading occurs and may be quite different when A spreads on B from what it is when B spreads on A .For example most organic liquids have positive coefficients with reference to spreading on water and therefore will spread into a film ; but water has a negative coefficient with reference to most organic liquids and will not spread over them. The value of the coefficient X is defined by the equation AS'= Wa- W in which Wa is the work of adhesion for the interface of the two liquids and W the work of cohesion of the liquid which is applied to the surface of the other liquid or solid on which the spreading might occur. Thus a liquid will not spread if its work of cohesion which indicates its attraction fqr itself is greater than the work of adhesion which indicates its attraction for the substance on which the spreading will not occur.The values of Wa and W are given by the equations W ~ = Y ~ + Y ~ - Y ~ ~ ; Wc=2yb so that the value of the spreading coefficient may be entirely defined in experimental terms by the equation #=yU- (yb+yab) where a indicates the liquid which is spreading on the hquid or solid represented by b. A large number of experiments have been made on the spreading of organic liquids on the surface of 'water on the spreading of water on the surface of organic liquids and on the spreading of water and organic liquids on the surface of mercury. The results show the importance of the spreading coefficient as a criterion of spreading.Unimolecular films are produced on water only when the spreading coefficient has a relatively high value. Since these high values seem to occur only when the spreading substance contains a polar group in its molecules it is concluded that the presence of such groups is essential for spreading on water to a unimolecular film but not at all essential for the production of a film which is thicker than this. Contrary t o the generally held opinion benzene is found to spread on a clean water surface. The non-spreading of organic liquids on water is brought about by the presence in the organic molecule of chlorine bromine iodine doubly-linked sulphur phenyl and the group =CS. Liquids which do not spread on water are insoluble in it but insolubleii.128 ABSTRACTS OF CHEMICAL PAPERS. liquids may spread on water. The addition of camphor to water appears to reduce the value of the spreading coefficient; so that many liquids which have small positive coefficients on water will not spread on water containing camphor but those which have coefficients sufficiently high are found to spread. The values of the spreading coefficients of water and organic liquids on mercury are in every case investigated found to be positive. Water and twenty- two of the other liquids were tested with reference to their spreading on pure mercury and in agreement with their positive coefficients were found to spread. The coefficients for the spreading of mercury on water and organic liquids are all negative. This corresponds with the fact that mercury will not spread on their surface.Since the free surface energy of almost all inorganic solids is high their work of cohesion is high and the work of adhesion is also high with reference to practically all liquid substances. Since the work of cohesion in water and organic liquids is in general low the values of the coeficients of spreading of these liquids on such solids should be positive and in general the value should be high. Thus the spreading of these liquids should occur on such solids when the surfaces are pure. The frequently occurring phenomenon of non- spreading is thus indicated to be due to the presence of an already existent film on the solid substance. The removal of such films may be brought about by vaporisation or by the more common process of substituting one film for another.This is the ordinary function of soap soap solutions and other cleansing agents. It is difficult for petroleum to penetrate sands which have been wetted by water and for water to penetrate sands which have been wetted by petroleum although either substitution may be effected in time. Many oil wells cease to produce petroleum because the sand becomes wet with water. Lubrication and many other phenomena depend on the wetting of solids by films. Measurement of Adsorption Processes by Means of an Interferometer. OTTOMAR WOLFF (KoZloid Z. 1923 32 17- 19).-Experiments are described to show that for industrial purposes an interferometer may be used to ascertain the amount of colloid adsorbed from solutions by any given adsorbent.J. P. S. WOLFGANG OSTWALD and RAMON DE IZAGUIRRE (Kolloid Z . 1923,32,57-64).- In answer to the criticisms of Gustaver (this vol. ii 57) the authors admit that in their recent paper they have interchanged the values u and u as used by Williams (Medd. Nobel-Inst. 1919,2 No. 27 1) owing to want of clearness in that paper. The authors deny that the equation which is put forward in their paper is the same as that due to Williams. The equation put forward by Williams is special and relates to a single case only whilst that due to the authors applies to three cases. In the best investigated case the adsorption of acetic acid solutions by charcoal the deduction made by Williams that u0=-a when c = l does not hold. The new equation furnishes more and other results than that of Williams.The necessity of differentiating between relative and absolute J. F. S. General Theory of the Adsorption of Solutions.GENERAL AND PHYSICAL CHEMISTRY. ii. 129 thicknesses of layers in the investigation of adsorpticm layers is emphasised. In the adsorption of colloid particles the adsorption layer cannot be unimolecular in thickness; it must be at least uni- micellar. The adsorption layer may have very different thicknesses depending on the size of the absorbed particles and on the amount of water which is adsorbed a t the same time. The assumption of Gustaver that the adsorption layer has a maximum thickness of one molecule is further refuted by the ultramicroscopic observations of Traube and Klein (A. 1921 ii 683) on adsorption layers of surface active emulsoids which vary up to 0.01 mm.thick. J. F. S. The Sorption of Iodine by Carbons Prepared from Carbo- hydrates. JAMES BRIERLEY FIRTH (T. 1923 123 323-327). The Absorption of Moisture by Coal (and other Fuels). I. A Relation between Degree of Humidity in the Air and Moisture Content of Coal. BURROWS MOORE and FRANK STURDY SINNATT (T. 1923 123 275-279). Adsorption of Toluene Vapour on Plane Glass Surfaces. EMMETT K. CARVER ( J . Amer. Chem. Soc. 1923 45 63-67).- Isotherms for the adsorption of toluene vapour on plane glass surfaces a t 0" have been obtained. The glass used wits after thorough cleaning kept a t 200" in a vacuum for twelve hours and any gas set free removed by a mercury vapour pump. Pressure measurements were made with the author's modified Shrader and Ryder optical lever manometer (this vol.ii 148). The results are generally in agreement with Langmuir's adsorption formula (A. 1918 ii 430) and indicate that the adsorbed layer is not more than one molecule thick. J. F. S. Fixing of Organic Dyes by Inorganic Substrates. H. RHEINBOLDT and E. WEDEKIND (KoZZ. Chem. Beihefte 1923 17 115-188).-The literature dealing with the fixing of organic dyes by insoluble inorganic substances has been collected and discussed. It is shown that acidic and basic dyes exhibit a different behaviour toward similar substrates. In particular substrates of acidic character are only fast dyed by basic dyes whilst acidic dyes only fast dye basic substrates. The results of various authors which appear to be a t variance with the above rule are in reality not so since they do not refer exactly to the same thing.A large number of experiments with many dyes and inorganic gels have been carried out and give results entirely in agreement with the above rule. This rule is not only true for acidic and basic oxides of which the fol- lowing were examined silica and tin titanium zirconium thorium and cerium dioxides ; aluminium chromium and iron sesquioxides ; and glucinum zinc magnesium and lead monoxides; but also for sulphides (arsenic antimony and cadmium) and silver chloride. In no case was a dye from both classes fixed with the single excep- tion of amorphous carbon. The electro-endosmotic migration of the dyes and inorganic substrates was investigated and it is found that fast dyeing only takes place between substrata and dye whenii. 130 ABS!E'RACTS OF CHEMICAL PL%PEWJ.they are oppositely charged. The authors are of the opinion that the unsaturated valency forces of the crystal lattice of the absorbent are responsible for the fixing of the dye. Since these valencies are identical with the normal chemical valency the behaviour of the substrate is explained. And since the valencies are of an electro- static character the parallelism of the electro-endosmosis and the adsorption is understandable. The fixing therefore consists in the binding of the dye to the substrate to form a unimolecular layer of a molecular additive compound. This process the authors term adsorption by dectro-affinity. It is held that the adsorption by electro-aeity is not restricted to substances which have ordered crystal lattices and the charge of sols gels and other colloidal material is attributed to the action of the same surface valencies.J. F. S. Exact Process for the Determination of the Coefficient of Diffusion in any Solvent. ERNST COHEN and H. R. BRUINS (2. physikal. Chem. 1923 103 349403).-The authors have summarised and criticised the method available for the determination of the coefficient of diffusion. A process for the exact determination of the diffusion coefficient has been devised. The apparatus consists of six thick glass plates of the same diameter which fit exactly on a fkm central axis. The four middle plates are firmly fixed and three holes bored through them so that in each plate there are three holes relatively in the same position.These plates are placed between the other two which constitute a base and a cover plate. The hole in the lowest bored plate is filled with the liquid of which the diffusion is to be measured by means of a small hole which can be brought above it by rotating the necessary plates. The other three plates with holes are brought into such a position that the holes in them are above one another but not above the hole in the lowest plate and filled with the solvent. The arrangement now is that of two tubes filled with liquids which by rotation of the bottom bored plate may be brought into contact. When the whole apparatus has reached the required temperature the liquids are brought into contact and the diffusion commences. After a sufficiently long period the plates are twisted so as to cut the column of liquid into four isolated parts and the composition of each is estimated by the Rayleigh Lowe interferometer.It is claimed for the apparatus that it may be used for all types of liquids of which only small quantities are necessary. It may be used a t any temperature over a wide range and there is no error due to vibration or shaking when the liquids are brought into contact. By the use of an air thermo- stat the temperature is known and may be kept constant to 0.03". The error of the method is not greater than 0.3% and individual measurements are reproducible to O.l-O.3%. Validity of the Stokes-Einstein Law for Diffusing Mole- cules. ERNST COHEN and H. R. BRUINS (2.phy8ikc-d. Chern. 1923,103,404--450) .-The validity of the Stokes-Einstein equation for the diffusion in solutions at various temperatures has been investigated by means of the diffusion apparatus previously J. F. S.GENERAL AND PHYSICAL CHEMISTRY. 5. 131 described (preceding abstract). The pair of liquids tetrabromo- ethane and tetrachloroethane has been used and the diffusion velocity measured st temperatures from 0" to 50". The viscosity of tetrachloroethane has been determined over the same temperature range with a maximum error of 0.05%. Divergences from the Stokes-Einstein law have been observed which are a t least three times as great as the experimental error. The divergences are in the sense that the temperature coefficient of the velocity of diffusion is smaller than would be expected.The following values of the relative viscosity of tetrachloroethane are recorded 0" 1.6219 10*Oo 1.3113 15" 1.1924 25" 1.0000 35" 0.8541 and 50" 0.6917. The absolute fluidity of tetrachloroethane is given by the formula +/T=O- 13796 ( 1 + 0.0 191 71 8+0~OoOo092582). The Capabilities of the Rapid Dialyser. A. GUTBIER J. HUBER and W. SCHIEBER (Chem. Ztg. 1923 47 109-llO).- Further investigation of the rapid dialyser described previously (A. 1922 ii 551). The effect of using tap water instead of distilled water for the outer liquid was studied and it was found that 80- 90% of the electrolytes can advantageously be removed from colloidal solutions by dialysing against tap water after which point distilled water must be used.Experiments indicated that dialysis was more efficient the greater the speed of rotation of the membrane and stirrer ; 100 revolutions per minute was satisfactory with slightly greater efficiency a t 150 per minute. Generally ill flow of 5 litres of water per hour in the outer vessel is sufficient. The use of more than 10 litres per hour produced no corresponding increase in the rate of dialysis. G. F. M. The Law of Solution. PAUL MONDAIN-MONVAL (Compt. rend. 1923 176 301-304).-Measurements made with a very soluble salt sodium nitrate show that it obeys very exactly the equation established by Le Chatelier for the solubility of salts in water (A 1885 340; 1894 ii 272). Solubility and Chemical Constitution. H. J. PRINS (Rec. trau. china. 1923,42,25-28).-1t has been concluded by Harkins (A.1921 ii 242) and by Langmuir (A. 1917 ii 19) that adsorption and solubility are closely related. Both authors attribute orienta- tion phenomena exhibited by organic substances with water to the tendency of the polar group to dissolve in water. It is pointed out that the arbitrary circumstance that these researches were carried out with water and an organic substance containing a group more or less similar to water may lead to erroneous conclusions. With organic acids and water solubility and adsorption are both caused by the same group but this is not generally the case. A number of examples are given showing that solubility in hydrocarbons such as light petroleum depends not on polar groups but on saturated hydrocarbon groups. Solubility depends in general on similnrity in kind and number of atoms present in the molecules of the substances in question.Adsorption represents a case of hetero-complex formation whilst in solution the complexes have the character of homo-compounds. E. H. R. J. F. S. W. G.ii. 132 ABSTRACTS OF CHEMICAL PAPERS. Contraction on Solution of Various Substances in Water. JITENDRA NATH RAKSHIT (Reprint Indian Assoc. Cultivation Sci. 1917,3 pp. 1-21),-Makinguse of data from Landolt and Bornstein’s tables the author has calculated the contraction which takes place when 100 g. of various substances are dissolved in various quantities of water. The values have been calculated for sulphuric acid nitric acid formic acid stannic chloride acetic acid methyl ethyl propyl isobutyl and isoamyl alcohols glycerol acetonitrile acetone nicotine ammonia hydrogen chloride sodium and potassium hydroxides sodium chloride tartaric acid chloral hydrate phenol sucrose Izvulose dextrose maltose and invert-sugar.In some cases the contraction increases with increasing dilution whilst in others the contraction increases passes through a maximum and then decreases with increasing dilution. Effect of Scratching the Wall of a Vessel with a Glass Rod. L. DEDE (2. Elektrochem. 1922 28 543); ROBERT FRLCKE (ibid. 1923 29 44-46).-A continuation of the controversy on the cause of crystallisation when the walls of a tube containing a solution are rubbed with a glass rod (cf. A. 1922 ii 692 744). J. F. S. J. F. S. Viscosimetric Researches on Lyophilic Sols.H. G. BUNGENBERG DE JONG (Rec. trav. chim. 1923 42 1-24).-The greater proportion of viscosity measurements recorded in the literature cannot claim an accuracy of more than a few per cent. The conditions necessary to attain an accuracy of 0.1 to 002% are discussed and in particular the two most important sources of error the systematic error of the viscosimeter and the method of setting the instrument. For a given capillary there is a maximum average rate of flow for a given liquid so that the deviation from Poiseuille’s law shall not be greater than 0.1%. A formula for calculating this rate was given by Griineisen (Wiss. Abh. Phys. Tech. Reichanstalt 1905,4,151). By means of this formula the systematic error of the viscosimeter and the necessary length and fineness of capillary can be calculated.The error of setting can be minimised by fixing the instrument so that the line joining the centres of the upper and lower reservoirs in the Ostwald viscosimeter is vertical instead of one of the limbs. Measurements of viscosity recorded in the literature are subjected to a general criticism and in particular the work of Hatschek on the viscosity of gelatin sols (A 1911 ii 98; 1913 ii 835) and that of Rothlin (A. 1920 ii 18) is discussed. Hatschek observed with a number of lyophilic sols that the viscosity depends on the rate of flow or shear and he supposes that this phenomenon supports the theory of a dodecahedra1 structure of concentrated lyophilic sols. Rothlin divides lyophilic sols into two groups one of which follows Poiseuille’s law whilst the other does not.These deviations are to be ascribed to the formation of larger aggregates in the sol through gelation; these aggregates according to the conditions of flow can be broken down to different ,extents and so give rise to the observed irregularities. This explains the fact in the case of both Hatschek’s and Rothlin’s abnormal sols that theGENERAL AND PIEYS1CA.L CHEBZISTRY. ii. 133 viscosity increased with time due to progressive gelation. At higher pressures such systems would approximate more,md* more closely to Poiseuille's law as Rothlin found. It is,concluded that for viscosimetric measurements to have any value the,system under examination must not only follow Poiseuille's law but the disperse phase must retain its stability. Experiments with agar sols show that at 50° that is above the gelation temperature agar sols follow Poiseuille's law within 0.2% although a t 27" deviations of more than 100% are shown.Moreover above the gelation temperature all hysteresis phenomena are absent and mechanical treatment has no influence on the viscosity. The only alteration in viscosity with time shown by these sols is a slight decrease due to hydrolysis of the disperse phase. When such an agar sol is diluted with electrolytes a final equilibrium is reached immediately. It is suggested that the term sol should exclude all liquid systems (1) which show deviations from Poiseuille's law; (2) where the viscosity is influenced by mechanical treatment (3) where gelation coagulation and ageing phenomena generally are present.E. H. R. Topo-chemical Reactions. Crystal Formation in Colloidal Metals. V. KOHLSCHUTTEB and K. STECK (2. Elektrochem. 1922 28 554-568).-The frequent formation of silver crystals in solutions of colloidal silver has been explained partly on thermo- dynamic grounds as the result of solubility differences between silver particles of different sizes and partly as a result of the formation of crystal aggregates of the ultramicroscopic crystalline particles due to action of a molecular field. Both views are open to criticism; on the one hand on account of the excessively small solubility of metallic silver and on the other because of the constitution of the surface of colloidal particles. The author is of the opinion that chemical reactions aze responsible for the crystallisation.It is shown that in eighteen months definite silver crystals form in Lea's sol but in pure sols prepared by the reduction of silver oxide with hydrogen no silver crystals were visible until the sol had been kept for twelve years; the same applies to gels which are free from electrolytes and protective colloids and are preserved under water. Well-formed polyhedra are produced by the action of ferric-ions or silver-ions on coagulated gels and other forms of colloidal silver. Also the reduction of a silver-ibn solution with ferrous-ions within a definite range of concentration produces a transient colloidally- dispersed metal which speedily forms crystals. The localisation of the reaction by adding a solid ferrous salt to a solution of silver-ions or by adding a solid silver salt to a solution of ferrous-ions accelerates the crystal formation.In keeping with the experimental resulfs the formation of crystals from colloidal solutions is to be regarded as due to a maturing process in consequence of the silver of the micella entering into the reversible reactions Ag+Fe'" ;t Ag' + Be'' and Ag+Ag' Z Ag,' whereby the pressing together of the reaction products in and on the colloidal particles is probably determinative af the commencement of the reaction and also of the specific form- VOL. CXXIV. ii. 6ii. 134 ABSTRACTS OF CHEMICAL PAPERS. ation of the crystalline silver. Observations on various oxides and sulphides lead to the view that in the formation of crystals in colloidal systems electromotive actions play a part.These are due to the formation of concentration cells in the colloidal systems. J. F. S. The Constitution of Colloidal Gels. J. DUCLAUX (BUZZ. SOC. chim. 1923 [iv] 33 36-43).-A theory of the constitution of reversible gels is developed in which it is suggested that they are composed of three elements the fluid which may be water or some other solvent an insoluble solid forming with the fluid an irre- versible gel or sponge-like structure of ultra-microscopic cells and a soluble solid dissolved in the solvent of the gel. The mole- cules or micellae of this substance which may be either crystalloid or colloid are too large to be able to escape from the cellules of the sponge but they are small enough for their solution to have a certain osmotic pressure in relation to the pure solvent.This solution is the " plasm " of the gel and its swelling and expansion in a solvent are due to the osmotic pressure of the plasm. The limit of expansion is reached when equilibrium is attained between this osmotic pressure and the cohesion of the cellular structure of the gel. If the osmotic forces are strong enough continued inflation of the cellules may result in the dissolution of the gel and the separation of the soluble and insoluble constituents. The mechanical properties of the gel will evidently depend on the relative proportion of the two solid constituents in gum arabic or nitro-cellulose solutions prepared in the warm ; the insoluble constituent is almost absent and the tendency to gel formation is minimum but in gum-tragacanth or cellulose-nitrate solutions prepared in the cold the insoluble constituent dominates and manifests itself by gel formation or high viscosity.The Influence of a Dissolved Crystalloid on the Rigidity of Gels. F. MICHAUD (Cmpt. rend. 1922 175 1196-1198).- By means of a method recently described (ibid. 1922 174 1282) the author has measured the rigidity of gels the moduli of which were less than any previously measured. The dissolved substances were added in solution to the liquid gel the whole being allowed to set. The rigidity of gelose or gelatin gels is considerably decreased by the presence of acids or bases. In the case of gelatin a strong acid exerts a more marked effect than a strong base whilst the converse is the case if the gel is dilute.The curves obtained show that the action of the acid is a linear function of the concentration of the gel; that of the base is parabolic so that addition to a gel of increasing quantities of base or acid eventually causes the base to exhibit a greater influence than the acid for equimolecular quantities. The disposition of the curves obtained for gelose is in the inverse sense. The author suggests that these results are consistent with the amphoteric properties of gelatin and that by analogy gelose should be regarded as amphoteric its basic being stronger than its acid function. The action of salts on the gel depends primarily on the amount hydrolysed for those which G. F. M.GENERAL AND PEXSICAL CHEMISTRY. ii. 135 are not hydrolysed the molecular lowering of rigidity is about one-tenth that of an acid or base.The action of organic sub- stances is variable ; sugars and glycerol have practically no effect urea urethane and acetamide act similarly to mineral salts whilst resorcinol quinol and above all tannin bring about a very much greater decrease than an acid or base. H. J. E. Colloid Chemistry of Urate Jellies. E. KEESER and H. ZOCHER (Ko17. Chem. Beihefte 1923 17 189-217).-An investig- ation of urate jellies particularly those of lithium and sodium. It is shown that the jelly-forming urates belong to the class of electrolyte colloids and have properties which are parallel with those of soaps and similar substances. Microscopic examination of lithium urate jellies shows the presence of long optically aniso- tropic negative doubly refracting jelly particles and also of radial structures which extend into the rest of the jelly mass. The addition of methylene-blue to the long jelly particles produces a dichroic coloration and the structure becomes fibrous.The dis- persion of the double refraction is abnormal. The long structure of the particles cannot be confirmed by ultramicroscopic examin- ation because of their size. Solutions of urates cannot be obtained in a viscous state like the anisotropic sols of vanadium pentoxide and benzopurpurin neither do the urate solutions show streaming double refraction nor magnetic double refraction. Before lithium urate solutions pass into jellies they become turbid and after the jelly has formed the turbidity for the most part disappears.It is suggested that the turbidity is due to droplets formed by an unmixing of the solution. Mechanically effected changes in the jellies are irreversible that is after displacement the jelly does not resume its original form when the displacing force is removed. The residue obtained by subjecting the jellies to pressure shows but slight swelling power. The rigidity of the jellies increases with increasing concentration of the solution of lithium urate from which they are formed. The rigidity of jellies of constant composition increases with increasing addition of a lithium salt and the transformation into the crystalline condition takes place more slowly the more rigid the jelly. In all cases crystallisation commences a t a number of isolated but equally distributed points throughout the jelly mass.The addition of non-electrolytes such as carbamide sugar glycerol or alcohols reduces the rigidity of the gels increasingly with increasing concentration and retards the crystallisation generally. Carbamide is exceptional inasmuch as it accelerates the crystallisation. Protective colloids are without effect on the jellies. Examination of the jellies by X-rays shows that particles of sufficient size to produce Rontgen interference figures are absent whereaa a similar examination of crystalline lithium urate gives very broad interference bands which shows that the true size of the particles is considerably less than that of the needles visible in the microscope. Lithium urate is a negatively charged colloid. .The residues obtained by drying the jellies are colloidal in character and have the power of adsorbing 6-2ii.136 ABSTRhCTS OF CHEMICAL PAPERS. gases. Thus 1 g . of lithium urate will adsorb 0.5 C.C. of nitrogen at atmospheric pressure. Interfacial Tension between Gelatin Solutions and Toluene. S. E. SHEPPARD and G. S. SWEET ( J . Amer. Chern. Soc. 1922 44 2797-2805) .-The general relationship of the orientation of specific atom groups in the molecule to the emulsoid colloid state is discussed. A number of experiments on the separation of gelatin at a benzene-water interface have been carried out ; these consisted in shaking l.Oyo 0.1% and O * O l ~ o aqueous solutions of gelatin with an equal volume of benzene a t 30" 40" and 50" and measuring the volumes of the resulting benzene water and foam phases.The foam or interfacial layer consists of benzene dispersed in and protected by hydrated and aerated gelatin and is partly stabilised. In further experiments air was excluded and toluene substituted for benzene and here it was found possible to shake the liquid without much separation of the gelatin in the toluene although a considerable amount of toluene was emulsified in the gelatin solution. The stability of the gelatin foam a t various hydrogen-ion concentrations was found to increase from both sides of the isoelectric point and to be most stable at this point. The interfacial tension of gelatin solutions of varying hydrogen- ion concentrations has been determined a t 30" 35" and 40" by measuring the drop number of the solution. The drop number- hydrogen-ion concentration curves all lie above the corresponding curves for water and all the gelatin solution curves show a char- acteristic break near the isoelectric point the maximum reduction of interfacial tension being at pH=4.8.Classification of Disperse Systems in Connexion with the Mechanism of True and Colloidal Solution and Precipitation. P. P. VON WEIMARN (KoZZ. Chem. Beihefte 1923 32 72-114).- A survey of dispersoid chemistry in which classifications of disperse systems according t o the state of aggregation of the particles and according to the " external " degree of dispersion are put forward. The imperfect nature of the static classification is pointed out and a large number of tables are given of the appearance of pre- cipitates of sparingly soluble substances at various times after their formation.J. F. S. Velocity of Flocculation of Selenium Sols. H. R. KRUYT and A. E. VAN ARKEL (Kolloid Z. 1923 32,29-36).-The velocity of flocculation of selenium sols of various concentrations by solutions of potassium chloride and barium chloride of various concentrations has been determined at a series of temperatures from 15" to 20". It is shown that the region of rapid flocculation for potassium and barium chloride lies a t very high concentrations of these electrolytes. This result has been confirmed by measure- ments of the boundary charge of the sols. The results show that Smoluchowski's theory is valid in the region where the velocity of flocculation is not far removed from that obtaining when the colloidal particles are totally discharged.The results deviate J. F. S. J. F. S.QFJ?ERAL AND PHYSICAL CHEMISTRY. ii. 137 strongly from this theory when smaller concentrations of elecfrolytes are used; the divergence consists in a continuously decreasing velocity of flocculation. The boundary charge of the sols has been determined in the presence of a solution of various concen- trations of potassium chloride barium ohloride potassium hydr- oxide and hexamminecobaltic chloride. It is shown that the addition of hydrazine increases the boundary potential and that after the addition of ten m.mols. of barium chloride the particles still possess a charge. The addition of potassium hydroxide increases the boundary potential and it is therefore suggested that the like action with hydrazine is due to hydroxyl-ions.CH. COFFIQNIER (Bull. Xoc. chim. 1923 [iv] 33 128-132).-The thickening or swelling of the paint in oil paintings is a colloidal phenomenon and is attributable to the action of the resin acids in the varnish on the lead or other heavy metal compounds used in the paint whereby a colloidal metallic complex is formed which behaves as a reversibre gel. The phenomenon is particularly noticeable and rapid with colophony varnishes but it also occurs with other materials possess- ing free acidity. Congo and kauri gums for example whilst not behaving in this way with white lead show the reaction with litharge or zinc white but if can be prevented in all cases by eliminating the free acidity of the resin or gum.For this purpose neutralisation with calcium carbonate or hydroxide is not so satisfactory as esterification as the “ neutralised ” material has still a certain acid value which is not reduced to zero even by calcium hydroxide. Esterification of the gum or colophony with glycerol furnishes a material from which a neutral varnish can be prepared and the troublesome phenomena above referred to then no longer occur even with litharge or zinc white. General Nephelometry. M. U. C. Al. LEDNICK$ (KoZloid Z. 1923,32,12-17).-A general discussion of the application of nephel- ometry to colloidal solutions. It is shown that in comparisons it is essential that the illumination should be uniform and symmetrical ; the beam of light should be horizontal and parallel.The surfaces of the solutions should be the same height and the concentration such that Beer’s law holds and so low that the boundaries of the Tyndall cone are sharp. The light should be monochromatic and in the case where the two solutions have not the same colour a filter must be used before the light reaches the eye. Non- Uni- and Bi-variant Equilibria. XXII. I?. A. H. SCEREINEMAKERS (Proc. K . A M . Wetensch. Amsterdam 1923 25 341-353).-1n continuation of previous work (A. 1922 ii 430) the author has investigated mathematically the condition deter- mining the equilibrium of n components in a system comprising n+l phases when the quantity of one of the components is infinitesimally small and has examined more especially the effect of a small quantity of added substance on a non-variant equilibrium.Expressions are derived for the partition of the added substance J. F. S. Colloidal Phenomena in Paintings. G. 3’. M. J. F. S.ii. 138 ABSTRACTS OF CHEMIOAIi PAPERS. between the various phases and for the temperature and pressure changes respectively occurring on such addition. F L and C representing the respective phases it is shown that when a sub- stance x is added to a system in non-variant unary equilibrium E(x=O)=P+L+Q an equilibrium arises which is represented on the P-T diagram by a curve commencing a t the non-variant point of the equilibrium E(s=O). When the added substance occurs in the liquid phase only this curve corresponds with the curve L=P+C of the system E(x=O). If the added substance occurs both as liquid and vapour then the equilibrium curve is situated in region P and its direction is determined by the partition of x between the vapour and liquid phases.When the added substance occurs both in the liquid and solid phases the curve is situated in the region G and its initial direction is determined by its partition between mixed crystals and liquid. In the case when the added substance occurs in the three phases the curve may be situated in any of the three regions L F or G . Its direction is then defined by the partition of the added substance between the three phases. J. S. G. T. Determination of the Chemical Equilibria between Various Stages of Oxidation by Means of Electrometric Measure- ments. I. The Equilibrium between the Sulphates of Bi- Ter- and Quadri-valent Manganese in Sulphuric Acid Solution.G. GRUBE and K. HUBERICH (2. Elektrochem. 1923 29 8-17) .-Oxidation potential measurements of mixtures of the sulphates of manganese in sulphuric acid of various concen- trations have been made for a large number of solutions at 12". It is found that in a solution which contains 0.05 g. atom of man- ganese in a litre of 15N-sulphuric acid when at 12" the ratio of the stages of oxidation is 1 1 the following oxidation potentials exist r o M p + Mn~~=1-511 volts C O ~ ~ I I I -+.-Iv= 1.642 volts and ~~~~n -+ M n ~ ~ = 1.577 volts. These potentials are slightly dependent on the total concentration of manganese but strongly dependent on the concentration of the acid. Increasing concentration of acid displaces the values to less positive potentials.Using the measured potentials the equilibrium constant of the reaction Mn,(SO,) .Z MnS04j-Mn(S0,) was calculated. This value also changes wth the acihty and the total concentration of manganese and has been determined for a total manganese concentration of 0.05 g. atom per litre in concentrations of sulphuric acid varying between 9.1N and 24.2N. From the determinations it is shown that a O*O5M-solution of manganic sulphate in 9.1N-sulphuric acid decomposes according to the above equation to the extent of 36% but in 24.2N-sulphuric acid to the extent of 6*7% that is the equilibrium is displaced toward the left of the equation with increasing concentration of acid. The existence of this equilibrium is the cause of the abnormal behaviour of manganic sulphate on hydrolysis.With this substance hydrolysis produces manganous sulphate and a hydroxide of quadrivalent manganese. This is due to the fact that of the components of the equilibrium quadri-GENERAL AND PHYSICAL CHEMISTRY. ii. 139 valent manganese sulphate is most easily hydrolysed whereby the equilibrium is disturbed and still more sulphata is produced so that the reaction takes place completely from left to right. J. F. S. Equilibrium Gelatin-Hydrochloric Acid. R. DE IUGUIRRE (Kolloid Z. 1923 32 47-51).-1t is shown that the view put forward by Lloyd and Mayes (A. 1922 i 280) on the basis of measurements of the hydrogen-ion concentration in solutions of gelatin containing hydrochloric acid that a t concentrations below 0.04N the hydrochloric acid is attached to the amino-group and at higher concentrations to the nitrogen atom of the poly- peptide group cannot be substantiated from the measurements. So far as the accuracy of the measurements permits it must be held that they point rather to a continuous curve for the hydrogen- ion combination curve.But from this it does not follow that a chemical combination has taken place between the hydrochloric acid and the gelatin for a logarithmic equation similar to the adsorption equation leads to a similar curve. It is also shown that the change of the electric charge of an adsorbent during an adsorption process can lead to curves of the most divergent type. Since such changes do take place during the adsorption of ions the point has to be settled whether the combination with ions is to be regarded as a chemical process or merely as an adsorptive process.J. F. S. (WE) G . MARCHAL (Cmpt. rend. 1923 176 299-301).-The decomposition of silver sulphate under the influence of heat gives rise to an equilibrium reaction forming a bivariant system which becomes univariant if care is taken to have in the gaseous phase only the gases coming from the decomposition. The author has made a study of this equilibrium under these conditions. Above 660° silver sulphate decomposes according to the equation and there exists in the gaseous phase a small amount of sulphur trioxide to satisfv the equilibrium The Dissociation of Silver Sulphate. Ag,SO,, = ~Ag*o,+S0,,+O,,aa .L 2SO e= 2~O,,&B+O,,fI Using the equation Q= [4*57(log K2-!0g K1)T1T2]/(T2-T,) the heat absorbed in the decomDosition is calculated as 82.4 cal. between 820" and 1000".Uiing Nernst's equation the values obtained are 103.9 cal. a t 820" and 103.2 cal. at 10oO". By means of the experimental results it is possible to calculate the state of equilibrium of the bivariant system for each temperature if it is arranged for the pressure of the oxygen at equilibrium to be equal to 1/5 atmos. pressure of the oxygen in the air. Equilibrium of the Reaction between Metallic Silver Cupric Chloride in Aqueous Solution and Solid Cuprous and Silver Chlorides. GRAHAM EDGAR and LAWRENCE S. CANNON ( J . Arner. Chem. Xoc. 1922 44 2842-2849).-The reaction CuCl+AgCl+H,O=CuCl,+H,O+Ag has been inves- tigated in the presence of hydrochloric acid of various coxwentrafion$ W.G.ii. 14-0 ABSTRACTS OF CHEMICAL PAPERS. at 25' and 40". The equilibrium constant ha,s been obtained from both sides. The method is t o shake the reagents together in coloured bottles and analyse the solution after equilibrium has been attained. The equilibrium constants have been calculated making use of the principle of "ionic strength" and the values 1 . 8 6 ~ 10-6 for 25" and 1-61 x for 40" obtained. From these values the increase in the heat content of the system is calculated by means of the expression AH= RT2d . log ,K/dT and the value -1755 cal. obtained. The increase of free energy of the system is calculated for 25" and the value AF=7820 cal. obtained. These values have been compared with the values obtained by Noyes and Ellis (A 1918 ii 27) Lewis and Lacey (A 1914 ii 521) and Noyes and Chow (A.1918 ii 214) and a moderate agreement has been found between the two sets of values. The present data afford a measure of support for the methods employed by Lewis and Randall (A. 1913 ii 29) in calculating the activities of mixed electrolytes. J. F. S. Liesegang Rings. I. Silver Chromate in Gelatin and Colloidal Gold in Silicic Acid Gel. EARL C. H. DAVIES ( J . Arner. Chem. Soc. 1922 44 2698-2704).-The author has in- vestigated the influence of gravity and light on the formation of silver chromate rings in gelatin and gold rings in silicic acid gel A jelly composed of 0.14 g. of potassium dichromate 4 g. of gelatin and 120 g. of water was brought into contact with a solution of 8.5 g.of silver nitrate in 100 C.C. of water the jelly being held in various positions so that diffusion could occur vertically down- ward and upward and also horizontally. It is found that diffusion is slowest when it operates against gravity but the effect of gravity may be counterbalanced by hydrostatic pressure. The mechanism of the ring formation is as follows. The silver nitrate diffuses into the gelatin and gives what appears to be an opaque region which in reality consists of opaque bands; these preliminary bands are further apart as the distance from the surface increases. These preliminary bands are due to the unequal rate of diffusion of the nitric acid and potassium nitrate produced in the reaction. The groups of silver chromate-potassium nitrate crystals which are seen microscopically to form are gradually broken up as the potassium nitrate diffuses away and the silver chromate particles become larger because of the oncoming silver nitrate.Hence the small bands lose their identity and the large bands are formed. Colloidal gold in silicic acid gel produced no rings when kept a t 0" in the dark for nine days but only isolated gold crystals. On placing these tubes in a powerful beam of light for an hour a band 1.5 cm. thick was formed. The band did not commence as a thin line and grow but the whole area developed a faint yellow colour at once and this grew in intensity as the exposure proceeded. A further tube of colloidal gold in silicic acid gel was covered with black paper and at distances of 9 cm.2 cm. bands were cut away. The tube was placed in a dark room and the light from an 80 watt lamp fell on it for nine days when slightly green colloidal bandsGENERAL AND PHYSICAL CHEMISTRY. ii. 141 developed at the openings. A similar tube showed no bands after keeping for six days in the dark but on exposure for a few minutes to an arc light bands developed a t the openings in the paper but no bands appeared between the openings. The tube was kept for for a further seven days in the dark a t 0". The paper was then entirely removed and the tube exposed to an arc light for three hours when a slight blue colour developed between the original bands. J. F. S. Liesegang Rings. 11. Rhythmic Bands of Dyes on Filter-paper and Cloth by Evaporation. Refractivity Sur- face Tension Conductivity Viscosity and Brownian Move- ment of Dye Solutions.EARL C. H. DAVIES ( J . Amer. Chem. SOC. 1922 44 2705-2709 ; cf. preceding abstract).-Rhythmic bands of dyes have been produced on filter-paper cotton cloth and unglazed porcelain by regulated evaporation. Solutions of some sixty-two dyes were used in o*04y0 and o.oo5~0 concentrations with several varieties of filter-paper. A table is given in which t'he following physical properties of the 0.04% solutions are recorded refractive index surface tension electrical conductivity viscosity and Brownian movement. The Tyndall cone and band formation are also investigated and the data recorded. It is shown that a uniform temperature and a gradual decrease in the rate of flow are the important factors in the formation of bands.It is probable that just before the band forms a film of oriented mole- cules is present. Calculation of Velocity Constants. A. L. TH. MOESVELD (2. physikul. Chem. 1923 103 481486).-The author describes a method of calculating the velocity constant of a reaction which is more accurate and less arbitrary than the generally adopted method. The velocity equation for a reaction of the nth order can be written in the form 1/(A -~)~=k't+l/A" where x is the concentration at time t and A a t t=O. The method consists in inserting the values of A-x and t in the equation for each measurement and so obtaining a series of equations with two unknowns k' and l/An. When these equations are solved by the method of least squares the value of k' is obtained which corresponds most nearly with the whole of the experimental results. Further from the divergence of the experimental value of l/(A-x)" and the value calculated from k' it is a t once shown whether the equation chosen is the correct one for the case under examination.A simplified method of working out the rather complicated calculations is given. J. F. S. The Speed of the Uniform Movement of Flame in Mixtures of the Paraffins with Air. WALTER MASON (T. 1923 123 K ~ R L GLASER (2. ungew. Chem. 1923 36 38).-The phenomenon of the roaring of the flame of the Bunsen burner is not a peculiarity of any particular gas but can be caused with any gas by sufficiently J. F. s. 200-214). The Roaring of the Bunsen Burner Flame. 6'ii. 142 ABSTRACTS OF CHEMICAL PAPERS. increasing the pressure above the normal whereby a corresponding increase occurs in the velocity of flow other things remaining equal.The conditions governing the phenomena may be expressed ai3 follows where v is the velocity of flow c the velocity of the pro- pagation of flame for the gas in question v' a factor depending on the buoyancy of the gas and c' on the preliminary heating to which the gas is subjected in the burner when v+v'< -(c+c') the flame strikes back; when v+v'=-(c+c') the burner burns normally and when v+v'> - (c+c') the flame roars. Piezo-chemical Studies. XVII. Influence of Pressure on the Velocity of Reaction in Homogeneous Liquid Systems. A. L. TH. MOESVELD (2. physikal. Chem. 1923 103 486-504).- The pressure coefficient of the velocity of reaction of the change 5HBr+HBr03=3Br,+2H,0 between the temperatures 1" and 39" has been determined.It is shown that for the temperature range examined it is independent of the temperature. The velocity of reaction a t a pressure of 1500 atm. is 15.4% less than that at 1 atm. pressure. The pressure influence is therefore negative and very much smaller than that observed in cases of hydrolysis carried out under approximately similar conditions. From this it is to be concluded that pressure exerts a specific influence on the velocity of reaction and this is not changed by changing the external conditions under which the reaction is taking place. G. F. M. J. F. S. Regularities in the Velocity of Vaporisation. W. HERZ (2. Elektrochem.1922 28 526-527).-1t has been shown recently by Volmer and Estermann that the velocity of vaporisation G is given by the equation G= 1 /d2;3 x p l / M / T where p is a constant M the molecular weight and T the boiling point in absolute degrees (A 1922 ii 193). This indicates that 1/m is proportional to G. The author has calculated the values of d M / T for a large number of substances and finds that the value increases steadily with the molecular weight in homologous series; it also increases with the replacement of hydrogen by chlorine. The removal of two hydro- gen atoms and consequent formation of a double Linking reduces the value whilst the formation of a treble linking causes a still further and much larger decrease. Ethers generally have much larger values than the corresponding saturated hydrocarbons. Solubility and Specific Rates of Hydrolysis of p p'-Dichloro- diethyl Sulphide in Water.ROBERT E. WILSON E. W. FULLER and M. 0. SCHUR (J. Amer. Chem. Soc. 1922 44 2867-2878).- The hydrolysis of p p'-dichlorodiethyl sulphide in water has been investigated. It is shown that the hydrolysis in contact with water is a two-phase reaction which affects only the molecules dissolved in the aqueous phase. The rate of the first stage of the reaction determines that of the second stage. Once steady con- ditions are established the concentration of the intermediate camyound automatically increases or decreases keeping the rate of the second stage just equal to that of the first stage. The J. F. S.GENERAL AND PHYSICAL OHEMISTRY.ii. I43 amount of intermediate compound present a t any time is extremely small and the time required to build up the equilibrium concen- tration is generally negligible. The simplest expression for the rate of hydrolysis at 25" in alkaline solutions where there is no tendency toward reversal is dc/dt=2KI(M)=0.304(M) where &/dt is the rate of hydrolysis in millimols. of hydrogen chloride produced per litre per minute and ( M ) is the concentration of gas in millimols. per litre. The second stage of the hydrolysis is sub- stantially non-reversible except in very concentrated hydrochloric acid solutions. The first stage is however reversible to a con- siderable extent even in the presence of dilute acids. This reversi- bility of one stage serves to retard but not to stop the reaction because the intermediate compound of the hydrolysis is being continually destroyed by the irreversible second stage.Indirect evidence indicates that the second stage of the reaction is catalysed in direct proportion to the hydrogen-ion concentration in acid solutions. Since the rate is also very rapid in alkaline solutions it is very likely catalysed also by hydroxyl-ions. The mathe- matical expression for the rate of hydrolysis in acid solutions is &/dt=K,(M) Tkl(I)(H*)(Cl')+k2'(I)(H*). A simpler but less obviously rational form of this equation is dc/dt=2k,(M)/( 1+ k3(C1')=0.304(1M)/( 1 +6*14(Cl'). This equation has been found satisfactory for a wide range of acid concentrations. The solu- bility of pp'-dichlorodiethyl sulphide in water a t 25" is 0.0043 mol./litre and on substituting this value in the equations above the rate of hydrolysis in saturated solutions is obtained.J. F. S. Velocity of Hydrolysis of Methoxymethyl Acetate. ANTON SKRABAL and MARIA BELAVI~ (2. physikal. Chem. 1923 103 451460) .-The velocity of hydrolysis of methoxymethyl acetate in O.1M-solution by 0.1 0.05 0.02 and 0-O1N-hydrochloric acid 0-1N-sodium carbonate and 0-1N-sodium metaborate has been determined a t 25" and the values obtained have been compared with the values previously obtained (A. 1921 ii 134) for the simple acetals methylal and methylene diacetate. The mixed acetal is hydrolysed much more rapidly in acid solution than the two simple acetals whilst the velocity in alkaline solution lies between that of the two simple acetals.Energetics of Sucrose Inversion. THOMAS MORAN and HENRY AUSTIN TAYLOR ( J . Arner. Chem. Xoc. 1922 44 2886- 2892) .-The effect of temperature on the potential difference of the normal hydrogen electrode is discussed and it is shown from E.M.F. measurements with acetic acid that it is approximately proportional to the absolute temperature. Measurements have been made on the very short ulfra-red absorption of aqueous solu- tions of sucrose dextrose and laevulose in the region 0*75-1.0 p. Sucrose and laevulose show a band a t 0-875 p which is not present with dextrose. The bearing of these results on the critical increment of sucrose dihydrate and on the mechanism of the inversion of sucrose has been discussed. J. F. S. J. F. S. 6'-2ii.144 ABSTRACTS OF (3HEMfCAL PAPERS. Process for Studying the Velocity of Formation of Pre- cipitates. ROGER G. Boosso (Cmpt. rend. 1923 176 93- 95).-A modified form of Jolibois’s apparatus for studying the mixture of liquids (A. 1920 ii 107) is used. The bottom limb of the Y-tube is cut off and the two side limbs are so adjusted that their orifices are 1 cm. apart. The liquids necessary to form the precipitate are run at the same rate down the side tubes and mix almost immediately. The resulting mixture is allowed to flow into a large volume of water saturated with respect to the precipitate the formation of which it is desired to study. This volume of liquid is held a t different distances below the point of mixing and thus the time for the formation of the precipitate is varied.The diluted mixture is filtered at once and the precipitate collected and weighed. The errors do not exceed 5%. W. G. Catalysts and Chemical Equilibrium. J. CLARENS (Bull. Soc. chim. 1923 [iv] 33,43-48).-Polemical. A reply to Durand’s criticism (A. 1922 ii ‘301) of the author’s original paper (A. 1922 ii 436). G. F. M. The Catalytic Action of Hydrogen-ions in the Hydrolysis of Esters. S. C. J. OLIVIER and G. BERGER (Rec. trav. chim. 1922,41 [ii] 637-645).-An examination of the rate of hydrolysis under various conditions of benzyl chloride a-chlorohydrin ethyl nitrate and methyl trichloroacetate showed that the presence of hydrogen-ions has practically no effect on the speed of the reaction in the case of the two first-named substances a very small effect with ethyl nitrate and a small but quite definite catalytic action with methyl trichloroacetate.The facts observed together with those described by Cavalier (A. 1899 ii 13) Wegscheider (A 1902 ii 493) and KIemenc (A. 1918 i 220) lead to the conclusion that hydrogen-ions have little or no effect on the hydrolysis of esters of strong acids. I n a brief discussion of the mechanism of the reaction the authors state that theories based on the supposed activation of the water by the acid (Rohland A. 1901 ii 152; Noyes and Sammet A. 1902 ii 498) are not satisfactory as water should also be activated in the case of esters derived from strong acids. The theory of formation of oxonium salts put forward by Stieglitz (A. 1908 ii 167) is preferred because an increase in the negative character of the group R in R-C0.O.R’ decreases the basic character of the oxygen and consequently diminishes the tendency to form such salts (cf. Kendall and Booge A.1916 i 707). It is uncertain whether the hydrolysis is effected by the ion RC0,R’-H or by activation of the ester at the moment of conversion into oxonium salt. €1. J. E. Catalase Action of Peroxydase. E. ABEL (2. Elektrochem. 1922 28 489496).-It is shown that peroxydase catalyses the reaction between potassium iodide and hydrogen peroxide only in the presence of hydrogen-ions; in faintly alkaline solution there is no acceleration of the velocity of reaction. The peroxydaseQ E N E U AND PHYSICAL CHEMISTRY. ii. 145 was obtained from horse-radish and is seen in the above-mentioned reaction to exercise the action of a catalase (cf.A 1920 ii 35 180). J. F. S. The Fine Structure of Atomic Nuclei and the Deviation from Coulomb’s Law in the Interior of the Nucleus. I. The Atomic Nuclei of Lithium and iss33eliwm. MAXIMILIAN CAMILLO NEXJBERGER (Ann. Physik 1923 [iv] 68 574-582).- A theoretical paper in which it is shown that the deviations from Coulomb’s law become smaUer as the atomic number increases (cf. Smekal Xitxungsber. Akad. Wiss. Wien 1920 130 149-157). In this paper the atoms of lithium (atomic weight=6) and isohelium are examined. The lithium atom is assumed to consist of two ai- particles (isohelium) rotating in a ring around a p-particle. This arrangement is stable and making allowance for the deviation from Coulomb’s law i t is shown that the heat of formation of one gram-atom of Lis=4.72~107 Cal.The heat of formation of isohelium from three hydrogen atoms is &=4-72 x 10s Cal. The deviation from Coulomb’s law is considerably greater for isohelium than for the Li6 nucleus. It is shown that B9 is unstable which is in agreement with Aston’s work on the isotopes of boron. The upper radius for the Li6 nucleus is 2.53 x 10-13 cm. and for isohelium 1-45 x cm. W. E. G. The Stability of Atomic Nuclei the Separation of Isotopes and the Whole Number Rule. WILLIAM D. HARKINS ( J . Franklin Inst. 1922 194 329-356 521-535 645-681 783- 814 ; 195 67-106 ; cf. A. 1922 ii 702).-A summary of previous work on the stability and methods of eeparation of isotopes and a review of the theory of Harkins and Wilson (A 1915 ii 543 544) of the evolution of atomic species from hydrogen atoms and a-particles and the experimental evidence in its favour.From the relative abundance of the different atomic species in meteorites and in the earth’s crust deductions are made as to the relative atomic stabilities and the part played by the ratio of the number of protons to electrons in the nucleus in determining the order of stability (cf. A. 1922 ii 490). Five stability principles are enunciated (1) no nucleus is stable unless the number of electrons it contains is equal to or greater than one-half the number of protons (N/P>0-5) (2) as the nucleus becomes more positive with reference to its net content of protons i t is essential for stability that it shall become more negative with respect to its relative content of electrons (3) the number of electrons in most nuclei is even (4) atomic nuclei and groups of protons and electrons in atomic nuclei are in general more stable when they contain an even rather than an odd number of protons and (5) elements of an even atomic number are much more abundant than those of odd atomic number.The determining factor for stability is the ratio NIP. The principles for the prediction of isotopes from the chemical or mean atomic weights are illustrated by means of the element lithium for which isotopes with atomic weights 6 and 7 should exist. E’or the hypothetical atom with atomicii. 146 ABSTRACTS OF CHEMICAL PAPERS. weight 5 N/P=0.4 and for that with atomic weight 8 N/P=0*625 which is higher than the ratio for any known atomic species.Hence it is concluded that these forms of lithium are incapable of existence The principle that the most abundant isotopes of elements with even atomic weights will also possess even atomic weights has received support from the work of Dempster on the isotopes of zinc and of Aston on the isotopes of tin. In general the most abundant isotope of an element has a charge and a mass equal to a whole number times the charge and mass of an a-particle. The original theory of Rutherford that the light atoms are built up mostly of particles of mass 3 was not justified. The mode of disintegration of the light atoms by the Rutherford method and the disintegration of the radioactive elements are discussed. Calcu- lations are made of the energy of disintegration of the radioactive elements.In conjunction with Lunn the loss of electromagnetic mass due to the approach of protons to electrons has been derived (cf. A. 1922 ii 703). The possibility of distinguishing between isotopes by spectroscopic measurements is considered and it is concluded that isotopes should differ chemically. A summary is given of the methods previously employed in the separation of the isotopes of neon chlorine and mercury and of the efficiencies of the processes of distillation diffusion and liquid centrifuging. Evidence is submitted of the separation of cadmium and zinc by a distillation method to the extent of 0.04 to 0.05 of it unit of the atomic weight. W. E. G. A Relation between the Atomic Numbers and the Atomic Weights of the Chemical Elements.F. LOEWINSON-LESSINB (Compt. rend. l923,176,307-309).-The sum of the atomic numbers of two adjacent elements starting from helium give the following relationships for the first twenty elements the atomic weight is equal to + or -1 to the sum of the atomic numbers of the element and of that which immediately follows it. Starting from scandium this atomic difference between the atomic weight in round numbers and the sum of the atomic numbers increases and reaches a value of 51 a t the finish but in certain groups of elements its value remains almost constant. There is in the horizontal rows of the periodic system a certain regularity in its increase. This correlation allows the atomic weights of the five elements not yet discovered to be foretold and atomic weights of certain elements to be corrected.W. G. Radicles and the Periodic Classification of the Elements. A. RIUS Y M I R ~ (Anal. Fis. Quim. 1922 20 496-500).-The atomic number of a radicle may be obtained by subtracting from the sum of the atomic numbers of its constituent elements twice the number of valencies concerned in its formation. For example in the case of ammonium the atomic number is 7+(4 x 1)-(2 x4)=3 equal to the atomic number of lithium. Atomic numbers for other radicles calculated in the same way enable them to be assigned to appropriate positions in the periodic classification. G. W. R.GENERAL AXD PIIYSICAL CREMISTRY. ii. 147 T. M. LOWRY (Rec. trav. chim. 1923,42,29).-The proposal of Centnerszwer for the intro- duction of a unit of atomic mass (ibid.1922 41 580) haa been anticipated by Sir W. H. Bragg (Proc. Php. Xoc. 1921 34 35) who proposed that the hgstrom unit of length 10-8 cm. should be made the basis of a unit of area of volume cm.3 and of mass lO-Z4g. The mass of an atom in Angstrom units is then 1-65 times its atomic weight. Molecular Dimensions Molecular Structure and the Viscosity of the Halogens and their Hydrides. HARRY SCHMIDT (2. Physik 1923 12 24-27).-An extension of the equations of Chapman (A. 1916 ii 416). The mean molecular collision area of chlorine bromine and iodine have been derived by Rankine (A. 1921 ii 192) from viscosity determinations and from these values on the assumption that the halogen molecule consists of two atoms in contact the atomic radii have been calcu- lated.From these figures and the radius of the hydrogen atom given by the Bohr theory the mean collision area of the hydrogen halides is derived and compared with data based on viscosity measurements. The agreement is satisfactory. On the other hand measurements of the viscosity of hydrogen give values for the mean collision area which are not in accord with the assumption that the hydrogen molecule consists of two hydrogen atoms in contact. W. E. G. The hgstrom System of Units. E. H. R. Magnetic Valency and the Radiation Hypothesis. F. T. PEIRCE (Phil. Mag. 1923 [vi] 45 317-323).-An inquiry into a possible mechanism of chemical change which would amign an effective r6le to radiation of a definite frequency. A theory of the valency bond is put forward which is based on the work of Oxley (cf. A. 1921 ii 82). The valency bond is due to the magnetic attraction between two ring or vortical electrons and can only be destroyed by the influence of radiation of the right frequency. The effects of temperature radiation and external illumination are discussed and compared and the conclusion is drawn that photo- catalysis should be observable only where the rate of reaction is determined by a dissociation. W. E. G. Transformations in Unsaturated Compounds. Negative Migration. A New Theory of the Conjugated System C:C.C:C. ALFRED GILLET (Bull. Soc. chim. Belg. 1922 31 365-375; cf. A. 1921 i 490 533 761).-A theoretical discussion in which the author maintains that by generalising two or three types of transformation of which several cases are known the properties of conjugated double bonds may be explained without assuming the existence of partial valencies. H. J. E. The Metallurgical Applications of Physical Chemistry. CECIL HENRY DESCH (T. 1923 123 280-294).-A lecture de- livered before the Chemical Society on December 14th 1922.ii. 148 ABSTRBCTS OF CHEMICAL PAPERS. The Identity of Geber. E. J. HOIXYA-RD (Nature 1923,111 191-193).-A criticism of Berthelot’s view now commonly held that Geber’s works are European forgeries of the thirteenth century ; the author considers the identity of Geber with Jiibir ibn Haiyiin (eighth century A.D.) to be extremely probable. The Identity of Geber. J. R. PARTINGTON (Nuture 1923 111 219-220 ; cf. preceding abstract).-An historical discussion in support of the probable authenticity of the Latin works ascribed to Geber. A. A. E. A. A. E. Improved Optical Lever Manometer. EMNETT K. CARVER (J. Amer. Chem. Soc. 1923 45 59-63).-The optical lever mano- meter described by Shrader and Ryder (Phy&d Rev. 1919 13 321) has been slightly modified whereby the sensitivity has been increased to 0.0001 mm. with an accuracy of about 0-0002 mm. of mercury. The modifications introduced are a tube of 44 mm. diam. instead of narrow as in the original apparatus ; this eliminates the error due to clinging of the mercury to the walls; a steel float instead of glass which eliminates irregular wetting of the float; the knife edges are replaced by steel points which prevent the changes which occur in the seating of the mirror support and so prevent a shift of zero; temperature changes were eliminated by placing the manometer in a thermostat with an optical glass window. J. F. S. The Production of Coloured Flames for Use with Spectro- photometers and Polarimeters. J. J. MANLEY (Phil. Mug. 1923 [vi] 45 336-337).-An apparatus is described for the intro- duction of aqueous solutions of salts acidified with hydrochloric acid into the Bunsen flame. This consists of a glass bulb of 20-30 C.C. capacity blown in the middle of a glass tube 1 cm. in diameter. The tube below the bulb is drawn out bent a t right angles and cemented on to a vitrosil tube 5 mm. in diameter with a bore of 1 mm. Three or four platinum wires 0.3 mm. diameter are placed within the pipe of vitrosil and constitute a wick extending out in a horizontal direction. The salt solutions when placed in the bulb are fed into the flame by capillary action along the platinum wires and the rate of introduction can be adequately controlled by varying the inclination of the tube. A Simple Automatic Apparatus €or Delivering Drops and Keeping a Constant Level in Washing with Acids. FRITZ REIMANN (Biochem. Z. 1922 133 112-113).-An apparatus is described on the syphon principle which delivers a slow current of liquid drop by drop a t a constant rate. W. E. G. W 0. K.

ISSN:0368-1769    

DOI:10.1039/CA9232405101

出版商:RSC    

年代:1923

数据来源: RSC