摘要:

J O U R N A L E. F. ARMSTRONG Ph.D. D.Sc. C. F. BAKER Ph.D. B.Sc. G. BARGER M.A. D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. E. GOULDING B.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. E. HORTON B.Sc. L. M. JONES B.Sc. Z. KAHAN B.Sc. L. DE KONINGH. A. HCKENFTE MA. d.Sc. OF N. H. J. MILLER Ph.D. G. T. MORGAN D.Sc. K. J. P. ORTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. W. ROBERTSON. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc 1,. J. SPENCEE M.A. J. J. SUDBOROUG'B Ph.D. D.Sc. A. JAMIESON WALKER Ph. D. B. A. E. W. WHEELWRIGHT B.A. Ph.D. M. A. WHITELEY D.Sc. G. YOUNG Ph.D. THE CHEMICAL SOCIETY. ABSTRACTS OF PAPERS. H. E. ARMSTRONG Ph.D. LL.D. E. 0. (3. BALY. HORACE T. BROWN LL.D. F.R.S. A.W. CROSSLEY D.Sc.. Ph.D.. P.R. S. F. R. 5. WYNDHAM X. DUNSTAN D.Sc.; Ph. D. F.R.S. M. 0. FORSTER D.Sc. Ph.D. F.R.S. R. MELDOLA F.R.S. G. T. MORGAN D.Sc. S~~W.RAMSAY,K.C.B. LL.D.,F.R.S. A. SCOTT M.A. D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. JOHN WADE D.Sc. bbifax SP,b-@;bitrrr J. C. GAIN D.Sc. Ph.D. A. J. GREENAWAY. ~asistant Sub-&bitor C. H. DESCH D.Sc. Ph.D. 1907. Vol. XCII. Parts I. 6 11. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1907RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNUAY SUFFOLK.J O U R N A L H. E. ARMSTRONG Ph.D. LL.D. E. C. C. BALY. HORACE T. BROWN LL.D. F.R. S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. WYNDBAM R. DUNSTAN D.Sc. Ph.D. F.R.S. F. It. S. OF M. 0. FORSTER D.Sc. Ph.D. F.R.S. R. MELDOLA F.R.S. G. T. MORGAN D.Sc. Sir W.RAMSAY K.C.B. LL.D. F.R.S. A. SCOTT M.A. D.Sc. F.R.S. W. A. TILDEN D.Sc. F. R.S. JOHN WADE D.Sc. THE CHEMICAL SOCIETY. E. F. ARMSTRONQ Ph.D. D.Sc. 0. F. BAKER Ph.D. B.Sc. G. BARGER M.A. D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. E. GOULDING B.Sc. P. HAAS B.Sc. P1i.D. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. E. HORTON B.Sc. L. M. JONES B.Sc. Z. KAHAN B.Sc. L. DE KONINCIH. A. MCKENXIE M.A. D.Sc. ABSTRACTS OF PAPERS ON ORGANIC CHEMISTRY. N. H. J. MILLER Ph.D. G. T. MORGAN D.Sc. K. J. P. ORTON M.A. Ph,D. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. W. ROBERTSON. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. L. J. SPEXCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph. D. B. A. E. W. WHEELWRIGHT B.A. Ph.D. M. A. WHITELEY D.Sc. G. YOUNG Ph.D. 1907. Vol. XCII. Part I. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1907.RICHARD CLAY &5 SONS r41MITED BREAD STREET HILL E.C. AND BITNQAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90792FP001

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

J O U R N A L H. E. ARMSTRONG Ph.D. LL.D. E. C. C. BALY. HORACE T. BROWN LL.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. WYNDHAM R. DUNSTAN D.Sc. Ph.D. F. R. S. F. R. S. OF M. 0. FORSTER D.Sc. Ph.D. F.R.S. R. MELDOLA F.R.S. G. T. MORGAN D.Sc. Sir W. RAMSAY K.C. B. LL.D. ,F.R.S. A. SCOTT M.A. D.Sc. F.R.S. W. A. TILDEN D.Sc. F.R.S. JOHN WADE D. Sc. THE CHEMICAL SOCIETY. ABSTRACTS OF PAPERS PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. ON AND E. F. ARMSTRONG Ph.D. D.Sc. 0. F. BAKER Ph.D. B.Sc. G. BARGER M.A. D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. B.Sc. T. EWAN B.Sc. Ph. D. W. H. GLOYER Ph.D. E. GOULDINO B.Sc. P. HAAS B.Sc. Ph.D. W. D. HALLIBURTOK M.D. F.R.S. T. A. HENRY DSc. E. HORTON B.Sc. L. M. JONES B.Sc. Z. KAHAN B.Sc. L. DE KONINGH. A. MCKENZIE M.A. D.Sc. N. H. J. MILLER Ph.D. G. T. MORGAN D.Sc. K. J. P. ORTON M.A. Ph.D. J. C. PHILIP M.A. Ph.D. T. H. POPE B.Sc. W. ROBERTSON. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMITH D.Sc. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph.D. B.A. E. W. WHEELWRIGHT B.A. Ph.D. M. A. WHITELEY D.Sc. G. YOUNG Ph.D. 1907. Vol. XCII. Part 11. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW. 1907.RICEARD CLAY & SONS LIMITED BREAD STREET BILL E.C. AND BUNUAY 921FPOLK.

ISSN:0368-1769    

DOI:10.1039/CA90792FP005

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

Page 1651 841 1019 373 5oa 508 508 508 145 663 964 a9 946 8 9 9 10 10 10 11 105 105 ERRATA. COLLECTIVE INDEX 1893-1902. Line 6 col. i for “iminodithio- ” read “irninothio-.” VOL. LXXXIV (ABSTR. 1903). PART I. PART II.-INDEx. VOL. LXXXVI (ABSTR. 1904). PART I. 13’ for “ *CO,Et” read “ *C02H.” 15 col. ii for ‘‘ A. ii 224” read (‘ A. i 224.” 22 23 (‘ saccharic ” read ‘ ‘ saccharinic. I’ 25 ) ‘ metasaccharate ” read ‘ ( mtmaccharinate. ” 21 * ‘ parasacchuratc ” read ‘‘ parasmharinute.” 19* (‘ saccharate” read (‘ sacchurinde.” 19” for “ parasaccharic ” read “ parasaccharinic.” ‘( isosaccharate ” read “ isosacchurinate. ” VOL. LXXXVIII (ABSTR. 1905). PART I. 23 for ‘( 1904 ii 42 ’’ read ‘I 1904 i 480.” 17* “the” read “methyl.” 17’ 16’ ‘(C(CO,Et),[CH(CN)-CO,Etl read ) ) ‘( ethyl” read ‘( ay-dintethyl Bt-diethyl.” ‘‘ C( CO,Et)dCH(.CN) *CO2MeJ,.” VOL. XC (ABSTR. 1906). PART I. 3 2 for ‘( 1905 ” read I‘ 1906.” ‘6 88” ” ‘( 70-71”.” 3* ) I ) ( ( acetophenone ” read ‘( phoroce.” PART 11. 18 for ‘‘ hydrogen ” read I‘ water vapour.” col. i for (‘A ii 974” read ;‘A. i 974.” I’NDEX. VOL. XCII (ABSTR. 1907). PART I. 26 18 19* ricin ” read “castor oil. for ‘‘(‘ ARBASOFF ” read “ AR~SOFF.” ’ “cocoa butter” read (‘cocoa nut oil.” ‘‘ BARTELL ” re”! ‘( BARTELT.” “conine” read “ conime.” 22 ’Q3 10” 16* ‘c benzoylconine re@ “ benzoylconiine.” 11* * From bottom.ERRATA (continued). ?f; 131 166 182 224 232 234 242 248 248 258 259 262 262 326 Line 5 for ‘11881 39” read “1906 89.” 17 1* “ p-hydrmyphenylazo &c. read “ p-hydroxybenzeneaxo &c.” 11* 23 21 4 “ ethyl ethyl-i-aspartate ’’;Ted “ethyl i-aspartate.” “ C,H,-CMe’CHO ” read “ C,H,-CHMe’CHO,.,’’ ) “ Acyl Derivatiuei” rend “ Aryl Defivatlver. ‘‘ MEEGEN ’’ read “ MEIGEN.” “ NHYh.CS+3CH2*C0,Et ” read “ C,,H,.NH*CS.S’CH,II]O2Et.” t l C( OE t) :CPh ” ‘ ‘ C(0H) :CPh I read c,,H,M~< 1 N=CH N=CH 10 9 9 13* after (‘ 5-GhZoro-3-phenyl-l;rltethylpyraxole ” insert ‘‘ m t J ~ h l o r i d e .” ; L C C 1 Z CH ( 6 C C 1 F CH 12’ for NMe< I read NMe< I NM e 01 * C Ph NMeC1:CPh 20 “ Sale ” read ‘‘ Salts. 11 ‘ ‘ sodium ” read ‘ ‘ silver. ” 16 “ WILHELM ” read ‘‘ WALTHER.” “ 1:2:4:5-tetrazine-3:6-carboxylic acid ” read ‘ ‘ 1 :2 4 :5 - tetrazine-3 6 -dicarbo xy lic acid. ’ iii 509 5 after “ forms ’’ insert “ the corresponding amide. The urethane pre. yred from this has b.p.,?23”/12 mm.m.p. 60-61” and on distil. ation with lime furnishes 509 6 and ?delete “ the urethane has b.p. 123”/12 mm. m.p. 60-61”.” 606 15* for “ 2:2’:5:5’-Tetramethmgbenzylideneazine ” read ‘ ‘ 2:2’:5:5’- Tetramthoxydibenzylideneazine.’ 619 13 (‘ l-Methylcyclohexyl-4-acetarnide ” read “ 1 -Methylcyclohexene-4-acetamide. ’ 726 17* ii} “ C,,H70*CO*” read ‘( Cl,H,70*CO’ ” /C6H3(:NEt2C1,\ ‘ I 0 /C ‘C6H4’C02Et.’ ‘C6H3(NE+ 729 19 ‘‘ butylene ” read “ buzylene” 952 11 “ 6-hgdroxy-4-isopr~yZ~uvone” read 355; 1; i !; 24} foT t l flavanol J’ remi ‘( flavono1.F’ ‘‘ 6-methoxy- 4-isopripyZ$ava?wm. ’ for ‘‘ cumenol ” read ‘‘ cuminaldehyde.” 953 16 957 23’ “ Dioxycodeine ” read “ Deoxycod$ne.” 1088 11* F y “ 4-Bromo-3-methyZ-l-ethyltr~a~oZe read ‘‘ 4-Bromo-3-methyl-l-ethylosotriazole.’~ PART 11.12 3” for ‘‘ euricic ’’ read erucic.” 108 5” “ lactase” read “lactose.” 117 14 ) ‘( DZIERGOWSKY ” read “ D~IERZGOWSKY.” 144 17” “Tabloid ’’t read “Pellet. :: 268 19 “Xolybdenum” read “Tungsten.” ’!:} “ tabloids ” t read ‘‘compressed pelleta.” * From bottom. t ‘( Tabloid ’’ being a registered trade-mark may not be used.ERRATA (continued). Page Line 268 292 24 “OMe~C,,H,(OAc),:NOH” read “OMef?,,H,(OAc),:NOH.” 420 4* for ‘‘ WO,CI ” read “WO,F,.” 5 et seq. should read “ Lecoq de Boisbaudran has stated (Abstr. 1887 3) that calcium sulphate phosphoresces yeen under the action of the cathode rays and similarly the author finds that the su phide phosphoresces yenuw and the phosphate red under these conditions.?’ 520 20 for “ 1,254“ red ‘‘ 1:254.” 970 8” “48” read ‘‘44.” 976 23 “ Pilicis maria’’ read “Bppidium Filix mas.” INDEX. 1024 col. i insert DeUuc G. See Tlwm.us Roman. 1097 col. ii insert Boman T?wmas and a. Dellnc presence of traces of zinc in alcohol and its detection A. ii 397. * From below.

ISSN:0368-1769    

DOI:10.1039/CA907920X006

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

18 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Ignition Temperatures of Hydrogen-Oxygen Mixtures. KAUFMAN G. FALK (J. r1me.r.. Chem. Xoc. 1906 28 1517-1534)- Previous determinations of the ignition temperature of detonating gasINORQANIC CHEMISTRY. 19 have been made either by plunging a sealed bulb of the gas into a bath of known temperature or by passing the gas through a tube heated to a definite temperature. The results obtained by these methods show considerable variation which is due to the fact that the whole of the gas does not reach the ignition temperature at the same instant. The heat would reach the outer layers of the gas first and in the time necessary for the whole of the gas to attain the required temperature an indefinite amount of combination would have occurred.In order to overcome these objections a method has been devised for generating the necessary heat by the adiabatic compression of the gas itself in a steel cylinder fitted with a steel piston. The apparatus and method are fully described with the aid of diagrams. Mixtures of hydrogen and oxygen were employed in the volumetric proportions of 4 1 2 1 1 1 1 2 and 1 4. The whole of the hest involved in the experiments was produced by the adiabatic compression which mas so rapid that radiation to the walls of the vessel was impossible. Two forms of apparatus were employed one of which was larger than the other and probably gave more accurate results. The ignition temperature was calculated by a method based on the equation for adiabatic changes and the following average results were obtained which are expressed as absolute temperatures.I n the smaller apparatus 4H2+0 874O; 2H2+0 811'; H,+O 786'. Jn the larger apparatus 4H + O 893' ; 2H + o 8 19' ; €3 + O 796O ; H + 20 808' ; H + 40 849'. The results show that the ignition temperature is independent of the final pressure of the gas for pressures greater than 39 atmospheres (the lowest pressure a t which the ignition temperature was determined) and under the conditions of the experiments is also independent of the initial temperature of the gas. The ignition temperature of the mixture H,+O is lower than that of any of the other mixtures and this minimum temperature corresponds with a maximum affinity. The probable explanation is that hydrogen peroxide is formed first in the combination of hydragen and oxygen and is subsequently decomposed the degree of completeness of this decomposition depending on the conditions. According to the theory of the explosion wave the ratio of the pressure of the gas a t the ignition point to the initial pressure should be constant for any one mixture and this has been found t o be approximately the case.The ratio found in the case of detonating gas is 36.6 which agrees fairly closely with the value deduced by Jouquet (J. math. 1906 SO). VOGEL VON YALCKEN- STEIN (Zeit. Eleklrochem. 1906 12 763-764).-Asbestos soaked in copper chloride was used as the catalyst a t 450' and platinum tetra- chloride at temperatures above 500'. The equilibrium represented by the equation 2C1 + 2H,O 0 + 4HC1 was attained from both sides.The values of the equilibrium constant K = ( p ~ 2 0 ) ~ . @ ~ 1 2 ) ~ / ( 0 2 ) ( p ~ ~ 1 ) ~ are given below ; they are the mean values of fifty-eight experiments at 450° forty-eight at 650° and five at 600'. E. G. The Equilibrium of the Deacon Process. 2-2ABSTRACTS OF CHEMICAL PAPERS. From hydrogen From chlorine side chloride side Temperature. log K. log K. LogK (cal.). 450" 1 '50 1 -49 1 -52 650 - 0.407 - 0.390 - 0.43 600 - 0 '046 - 0.050 - 0.02 From Dolezalek's experiments on the chlorine-hydrogen gas cell Nernst has calculated 10g[Cl,]~~[H,]~/[HC1]4 = - SS000/4*57 1 T- 1.6. Nernst and Wartenberg calculate from their experiments on the dissociation of steam 10g[H,0]~/[H,]2[0,] = 25050/1'- 1.7510g1'- 0*00013T'+0~2.From these expressions the value of logK in the process studied is found to be 5790/1'- 1.75 log?' - 0*000132'- 1.4. The calculated values in the above table are obtained from this expres- siou . T. E. Sublimation of Sulphur at the Ordinary Temperature. RICHARD J. Moss (Sci. Proc. Roy. DubLSoc. 1906 ii 105-106).-Some fragments of ordinary roll sulphur were sealed up in an exhausted tube tweuty- four years ago. After twentyyeara during which time the tube was placed in a horizontal position in a drawer a minute crystalline sub- limate was observed. H. M. D. The Two Forms of Liquid Sulphur as Dynamic Isomer- ides. ALEXANDER SMITH and CHARLES M. CARSON (Proc. Roy. Xoc. #din. 1906 26 352-356. Compare Abstr. 1906 ii 157).-The liquid obtained by melting sulphur which after recrystallisation has not been in contact with air contains the two liquid forms SX and Sp in equilibrium proportions the equilibrium condition being attained in a few moments.Ammonia bubbled through the melted sul-phnr also facilitates the rapid establishment of equilibrium. The conversion of Sp into SX on cooling is equally rapid so that by plunging into water ordinary monoclinic sulphur is obtained. On the other hand equilibrium is only slowly reached in the fused mass obtained from sulphur which has been exposed to the air. This inert condition is also induced by passing hydrogen chloride or sulphur dioxide through the fused mass obtained from sulphur not exposed to air after recrystallisation. These gases act as simple catalytic agents and the two liquid forms SX and Sp are t o be classed as dynamic isomer- ideP.The equilibrium proportions at any temperature may be rapidly measured by passing in ammonia to accelerate the attainment of equilibrium and afterwards sulphur dioxide before cooling to prevent further change. Iodine retards the adjustment of equilibrium but dis- places the equilibrium to a considerable extent. The solidification of molten sulphur is considered with reference to a temperature concentration diagram. The freezing point of SX is 119.25' the " natural freezing point " at which the two liquid forms are in equilibrium with solid monoclinic sulphur is 114*5O and the liquid contains 96*3°/0 SX and 3.7°/0 Sp. The proportion of Sp in the liquid increases with rise of temperature and the rate of increase is much greater above 160° than it is below this temperature as the fol- lowing numbers show :21 INORGANIC CHEMISTRY.Temperature .. . . . . . . . . . . . . . . . . . . . . . . . . 121" 164" 166" 162" 166" 167" % SEr in equilibrium condition ...... 3.75 7.5 8.0 13.5 15-5 16.7 The marked absorption of heat and fall in temperature at or just above I 60° which are observed when liquid sulphur is heated continuougly at a constant rate is shown to be due to the fact that the proportion of Sp in the liquid lags behind that corresponding to the equilibrium con- dition The observed fact that the liquid becomes viscous at a lower temperature when the rate of heating is diminished is due to the same circumstance. H. M. D. Conditions under which Metallic Sulphides are Precipitated and Redissolved.HENRI BAUBIGNY (Compt. rend. 1906 143 678-679).-A claim for priority against Bruni and Padoa (Abstr. 1906 ii 157) ; compare Abst,r. 1882 805 928 1031 1032 1172; 1883 22 24 25 ; 18S8 113 423; 1889 118 346 652 653). M. A. W. Selenium. WILLXAM OECHSNER DE CONINCK (Compt. rend. 1906 143 682). -The brick-red amorphous variety of selenium obtained when selenious acid is reduced by glucose (? lzevulose) dissolves in concentrat.ed sulphuric acid to form selenium sulphoxide SeSO [com- pare Divers and Shimosk Trans. 1883 43 329 ; 1884 45 194,201 ; Divers and Shimidzu Trans. 1886 49 5831. This slowly decomposes according to the equation SeSO + H,O = Se + H,SO yielding a different variety of selenium to that originally employed. The new variety is pale or deep brown in colour does not become fluorescent when exposed to diffused light or undergo any change in contact with carbon disulphide in which it is very sparingly soluble.On pro- longed exposure to snnlight it is slowly converted into the amorphous black variety of selenium. Vapour Pressure of Carbon Dioxide at Low Temperatures. JOHN ZELENY and ROY H. SMITH (Chem. Centv 1906 1486; from PhyaikaE. Zeit. 7 667-671.)-The vapour pressure of carbon dioxide was measured a t temperatures varying from 7" to - 134'. Solid carbon dioxide was placed in a glass tube closed at the top and connected by a side tube t o a mercury gauge. The tube was immersed in a bath of pentane the temperature of which was measured by means of a nickel-iron couple the pentane bath being itself surrounded by liquid air.The following values were obtained for the vapour pressure in atmospheres 27.8 at - 7' 19.52 at - 20° 9.88 at - 40° 4.35 at - 60° 1 atmosphere at -78.2'; 28-8 mm. at -goo 11.9 a t - loo' 1.4 at - 120° and 0.1 mm. mercury at - 134'. Theaddition of alcohol or ether has very little influence on the vapour pressure. The critical point lies at - 56.4' and 5.11 atmospheres. The value of dp/dT was found t o be 6.35 cm. per degree and the latent heat of vaporisation L was found to be - 140 Gal. M. A. W. P. H. Behaviour of Carbon Disulphide towards Nascent Hydrogen. A. GAWALOWSKI (Chern. Centr. 1906 ii 1248 ; from Zeit. Oesterr. Apoth. Per. 44 460-46 l).-Carbon disulphide when treated with zinc and sulphuric acid yields a gas which produces a pure black pre-22 ABSTRACTS OF CHEMICAL PAPERS. cipitate in a solution of lead nitrate and blackens a filter paper moistened with the same solution.The gas evolved on heating carbon disulphide with zinc and strong potassium hydroxide however yields a bright orange-red precipitate with lead nitrate solution. The colour of the stain produced on filter paper moistened with lead nitrate is orange and fades rapidly. Fractionation of Rare Gases from Mineral Waters. Pro- portion of Helium. CHARLES MOUREU and ROBERT BIQUARD (Conyt. rend. 1906 143 795-797. Compare Abstr. 1905 ii 5 ; 1906 ii 442).-By submitting the rare gases obtained from certain mineral waters to the selective absorption of wood charcoal a t - 185’ (compare Dewar Abstr. 1904 ii 652 728) the authors have separated the helium and part of the neon from the other gases but further treatment with charcoal at - 100’ or at the temperature of liquid air boiling under 40-60 mm.pressure failed to effect the separation of the neon and helium. The former gas therefore is present in quan- tities too small to be estimated. The proportion of helium in the gaseous constituents of the waters of forty-three thermal springs is given in the original and varies from 0.00063 per cent. in Chatel- Guyon spring to 5.34 per cent. in that of Maizibres; the gases from the latter source also contain krypton. Gausticising of Sodium and Potaesium Carbonate8 with Lime. MAX LE BLANC and KABL NovoiwP (Zeit. anorg. Chern. 1906 51 181-201. Compare Lunge and Schmid Abstr.1886 203; Bodlander and LUCBS Abstr. 1905 ii 634).-1n the reversible re- action Na,C03 + Ca(OH) = 2NaOH + CaCO when the solution is in equilibrium with solid calcium hydroxide and carbonate the value of the equilibrium constant k = (OH’)2/C0,” can be calculated when the solubilities of the two solid substances are known. In aqueous solu- tion calcium carbonate is partially hydrolysed and to obtain the solubility of the non- hydrolysed salt necessary for the calculation of the constant determinations have been made in excess of sodium hydroxide (by which the hydrolysis is depressed compare Gardner and Gerassimoff Abstr. 1904 ii 544) directly at 18’ and 95-10C0 and by conductivity measurements a t the former temperature. By comparison of the solubility in water with that in sodium hydroxide the degree of hydrolysis has been determined ; according to the conductivity measurements 67% and by direct measurement SO0/ of the salt is hydrolysed a t 18’.From the solubility of the non-hydrolysed salt thus obtained the value k - 16040 a t 1 8 O has been calculated. The equilibrium has also been reached directly from both sides with 1 2 and 3N’sodium and potassium hydroxides and lime a t intervals of temperature from 15-150’ in iron bombs the relative proportions of hydroxide and carbonate being determined by titration. The reaction is most complete with small concentration of carbonate; not only is the yield decreased by increase of carbonate I 2 and 3N-sodium carbonate and excess of lime giving 99 97 and 93*6O/ of hydroxide respectively at loo” but the equilibrium is somewhat displaced in favour of the carbonate.The yield is not appreciably increased by rise of temperature. P. H. M. A. W.INORGANIC CHEMISl'RY. 23 The technical bearing of these results is discussed. It is pointed out that the patents for increasing the yield by working under pressure are useless ; efforts should be directed to facilitating the attainment of equilibrium which is favoured by high temperature thorough stirring and presence of excess of lime. The possible loss of part of the soda as an insoluble double salt is also discussed. The above results are in satisfactory agreement with those of Lunge and Schmid but not in all respects with those of Lucas (Zoc. cit.). G. S. Solubility of Lithium Sulphate in Mixtures of Water and Alcohol. FRANS A.H. SCIIREINEMAKERS and WTLLEN A. VAN DORP junr. (Chem. Centr. 1906 ii 1235 ; from Chem. Weekblad. 3 557-561).-The following conclusions are arrived a t (1) hydrated lithium sulphate is not altered by mixtures of water and alcohol con- taining less alcohol than a limiting value whereas the anhydrous salt under these conditions becomes hydrated ; (2) in solutions of alcohol and water containing more alcohol than the upper limiting value the anhydrous salt is not affected whilst the hydrated form loses its water; (3) in solutions intermediate between these two both salts remain unchanged. The solubility of lithium sulphate diminishes rapidly with increase in the amount of alcohol ; it is practically insoluble in SO0/ alco holm P.H. Influence of Lithium Sulphate on the Formation of Layers in the System Water-Alcohol-Ammonium Sulphate FRANS A. H. SCHREINEMAKERS and J. TH. BORNWATER (Chem. Centr. 1906 ii 1306 ; from Chem. TVeekbhd. 3 569-575. Compare preceding abstract ; Abstr. 1906 ii 855).-In continuation of their earlier work the authors have found that whereas there are two liquid phases in the system water-alcohol-ammonium sulphate there is only one phase in the system water-alcohol-lithium sulphate or water-alcohol-lithium- ammonium sulphate. The effect of lithium sulphate on the forma- tion of two layers in the system water-alcohol-ammonium sulphate has been studied and the results are recorded in tabular form. At first the addition of lithium sulphate increases the amount of alcohol in the alcoholic layer and diminishes the amount in the aqueous layer; then the reverse phenomenon takes place and the composition of the two layers becomes more and more alike.P. H. Silver Chromate. 11. BENJAMIN M. MARGOSCHES (2ei.f. anorg. Chem. 1906 51 231-235. Compare Abstr. 1904 ii 731).-The behaviour of silver chromate towards certain inorganic acids has been described in the previous paper and the investigation has now been extended t o some weak acids more particularly acetic acid with regard to which there are contradictory statements in the literature. Silver chromate is practically insoluble in water and in glacial acetic acid but dissolves to a considerable extent in dilute acetic acid. It behaves in a similar manner with propionic lactic and other organic acids Chromates can be detected most readily by conversion into the24 ABSTRACTS OF CHEMICAL PAPERS.lead stilt which is insoluble in acetic acid. When the red modification of the silver salt is dissolved in dilute acetic acid and the solution con- centrated the greenish-black modification separates. Action of Alkali Chlorides on the Double Silicates of Calcium and Aluminium. F. H. CAMPBELL (Lmadw. Versuchs.-Xtat. 1906 65 247-252).-The object of the experiments was to ascertain the amounts of calcium liberated from calcium aluminium silicate (prepared by precipitating a solution of the chlorides with sodium silicate) by shaking for some days with solutions ( N / 5 to 8N) of lithium sodium potassium and ammonium chlorides. Lemberg (Zeit. deut.geol. Ges. 28 579) and Dittrich (Abstr. 1903 ii 176) have shown that the power of parting with calcium is greatly reduced or even lost altogether after ignition. It is now shown that even drying at 100’ considerably reduces the amount of - calcium dis- placed by 3-sodium chloride. The action is very slow at 25* but the amount of calcium replaced is very little less. than a t 32.5’ the tem- perature finally adopted. The amount of calcium displaced rises in each case with the increase in concentration of the alkali salt ; but less with higher than with lower coacentratione. With sodium potassium and ammonium chlorides the maximum is reacbed with 3s-solutions whilst in the case of lithium chloride the maximum is with a 6N-solution. With low concentrations the displacing power of lithium sodium and potassium chlorides increases with the atomic weight; it is greatest in the case of ammonium chloride.A t higher concentrations sodium and potassium chlorides have nearly the same maximum; lithium chloride has a higher and ammonium chloride a much higher maximum. N. H. J. M. Molecular Weights of Inorganic Compounds in Boiling Quinoline. ERNST BECKMANN [with WERNER GABEL] (Zeit. anorg. Chern. 1906 51 236-244).-The quinoline was dried over phosphoric oxide or potassium hydroxide and fractionated from ‘ $ active ” aluminium. The mean value of the molecular elevation of the boiling point determined with benzil benzoin and other organic compounds is 56.1. The chlorides bromides and iodides of zinc and cadmium and the chlorides and bromides of cobalt and nickel have the normal molecular weights in this solvent whilst cuprous chloride gives results which indicate that the CuC1 molecules present in dilute solution associate to Cu,Cl molecules in more concentrated solution.Isomorphous Crystals of Lead and Barium Nitrates. P. GAUBERT (Compt. rend. 1906 143 776-777).-The investigation of selective absorption exhibited by the cubic and octahedral faces of lead nitrate crystals towards organic colouring matter (Abstr. 1906 ii 152 343) is extended also towards isomorphous nitrates such as barium nitrate. The so-called mixed crystals of lead and barium nitrates are not homogeneous but vary in composition with the nature of the face to which they correspond. G. s. G. S.INORGANIC CHEMISTRY. 25 The experiments were conducted as follows from the crystals deposited at 18-25' by a saturated solution of 500 grams of barium nitrate and 10 grams of lead nitrate 1 gram each of the crystals below the octahedral faces and the cubic faces respectively were separated and the amount of lead in each determined by means of a colorimetric method ; the results showed that the parts of the crystals corresponding with the octahedral faces contained more lead than those under the cube faces and similar results were obtained with crystals of lead nitrate which had been grown in a solution containing a little baryta and nitric acid. M.A. W. Influence of Small Quantities of Elements in Copper on its Reactions with Nitric Acid. JOHN H. STANSBIE (J. SOC. C h m . Ifid. 1906 25 1071-1075).-The investigation is a continua- tion of experiments described in a former paper (Abstr.1906 ii 166) the apparatus having been modified somewhat to facilitate the deter- mination of the amount of nitrous acid formed in the reactions. For this purpose the solution was not allowed to come into contact with air until the free acid had been neutralised by addition of a measured quantity of sodium carbonate in excess. The nitrous acid was then estimated by means of ferrous ammonium sulphate and potassium permanganate solutions and the unneutralised sodium carbonate gave the amount of acid used in the reaction. Experiments with pure copper a t temperatures from 15-85O indicate that the secondary change by which nitric oxide is produced is practically uninfluenced by a rise of temperature whereas the amount of nitrous acid formed decreases considerably. The nitrous acid is supposed to result from the oxidation of nitric oxide according to the equation 2N0 + H20 + HNO i= 3HN02.A t all temperatures a certain amount of nitric acid disappears in changes other than the formation of nitric oxide and nitrous acid. This may be ascribed in part to the formation of ammonia but the quantities of ammonia observed are not large enough to explain the entire loss. Pure bismuth dissolves according to the equation 2Bi + $HNO,= 2Bi(N03),+4H,0+2N0 and the whole of the nitric acid used is accounted for by the nitric oxide and nitrous acid formed Arsenic also reacts in a simple manner and the nitric acid used corresponds with the equation 6As + 1 OHNO = 3As,O + 5 H,O + 10NO.Experi- ments with copper alloys containing 0-3"/ of arsenic or antimony at 6 5 O show that the decrease and increase in the amount of nitrous acid formed as the amount of the second element increases follow pretty closely the decrease and increase in the volume of -the liberated nitric oxide (Zoc. cit.). I n the case of copper-bismuth alloys the amount of nitrous acid formed increases slightly until the percentage of bismuth reaches about 0.25 and then decreases exactly as was observed for the volume of nitric oxide liberated. The author considers that the conclusions drawn in the first paper are supported by these further experiments. H. M. D. Mercury Chromates. A. GAWALOWSKI (Chem. Centr. 1906 ii 1307 ; from Pfmwn. Post 39 602).-Nercuric perchomate is obtained26 ABSTRACTS O f CHEMICAL PAPERS.as it scarlet-red granular precipitate on adding a solution of potassium dichromate and some 25O/ sulphuric acid to a solution of a mercuric salt. The dried substance on ignition evolves water oxygen and mercury vapour and leaves a brownish-black modification of chromic oxide. If sulphuric acid is not present R brick-red earthy pre- cipitate of mercury dichromate is obtained which on ignition yields a finch-green modification of chromic oxide. When metallic mercury is left for several days covered with a cold solution of potassium dichro- mate and an excess of concentrated sulphuric acid a bright red variety of mercuric chromate is formed which is probably a poly- chromate ; this substance on ignition leaves about 4 2 O / of a leaf-green variety of chromic oxide.P. H. Chemistry of the Rare Earths. 11. GREGOIRE N. WYROUBOFF and AUGUSTE VERNEUIL (Ann. Chim. Phys. 1906 [viii] 9 289-361. Compare Abstr. 1906 ii 88).-This paper is chiefly a det.ailed account of work already published relating t o the nature of the oxides of cerium and the separation and purification of cerium compounds (compare Abstr. 1897 ii 452 ; 1898 ii 222 ; 1899 ii 224 423 598,613) ; also polemical against Brauner regarding the atomic weight of the element (compare Abstr. 1897 ii 492; 1898 ii 294; and Brauner Abstr. 1903 ii 295). The red sulphate of cerium (com- pare Rammelsberg Abstr. 1873,601 ; Muthmann and Stutzel Abstr. 1900 ii 544 ; Meyer and Aufrecht Abstr. 1904 ii 175) forms hexagonal crystals which are strongly dichroic appearing a beautiful red when viewed across the base and deep orange or yellow in a per- pendicular direction; the composition of the salt is represented by the formula Ce,0,,3Ce0,8S0,,S0,H2,28H20 and it is to be’regarded as the sulphate of the violet oxide Ce70 (Ce30,,4CeO).M. A. W. Elements of the Ytterbium Group. CARL AUER VON WELSBACII (Monatsh. 1906 2’7 935-945).-Most of the supposed elements of the ytterbium group which have been described are compounds. The present paper contains a description of a part of the author’s work on the isolation of the true elements of t h i s group. The material for the in- vestigation consisting of crude ytterbium oxdate obtained from monazite and containing cerite earths thorium and phosphoric acid was treated in the manner previously described for the working up of crude earths (Abstr.1884 717; 1885 350 1113j and the elements of the ytter- bium group separated finally as the basic nitrates. These were purified by recrystallisation as follows one-half of the substance was stirred with water and neutralised with nitric acid; the other half was then recrystallised from the neutral solution of the nitrate and a series of fractions of the basic nitrate obtained the final liquid giving only a weak erbium spectrum. This process was repeated twenty-one times when the fractions which were free from yttrium all contained erbium ytterbium holmium and dysprosium. To separate the elements of the ytterbium group advantage is taken of the differences in the solubility in a saturated solution of ammonium oxalate of the double oxalates which are formed by precipitation of the moderately concentrated solution of the nitrates with a hotINORGANIC CHEMISTRY.27 saturated solution of ammonium oxalate. The solubility of ytterbium ammonium oxalate in a saturated solution of ammonium oxalate is ten times that of holmium ammonium oxalate. The method of fractional crystallisation is described in detail. Of the seriesof about one hundred fractions obtained the first is almost colourless about the next fifteen are light yellow then orange-yellow passing through the rose-coloured erbium to the colourless ytterbium salts at the other end. Observed directly by transmitted light the first fractions show a changed dysprosium with traces of the neodymium spectrum ; the light yellow fractions give the normal dysprosium the orange-yellow the holmium and the intensely rose-coloured the characteristic erbium spectrum.As the rose-colour weakens the erbium spectrum changes into a modified spectrum which is termed Ery after which the thulium lines appear to disappear in the colourless ytterbium fractions. The spark spectra of the first fractions are complicated and contain lines which do not coincide with those of any known element. The orange-yellow fractions which give the most intense holmium absorption spectrnm give a yttrium spark spectrum in which the holmium lines are absent but in which other groups of lines appear The rose- coloured fractions give the erbium the colourless soluble fractions the ytterbium spark spectra.The mother liqnors from the crystallisation of the ammonium oxalates were further investigated and found to contain ytterbium traces of scandium thorium uranium iron and substances such as alumina and silicic acid which are derived partly from the water and partly from the ammonium oxalate. The fraction which should have contained pure ytterbium gave a spark spectrum which shows marked difierences from the ytterbium spectrum; this is considered to be the first certain indication of the degradation of ytterbium G. Y. Catalytic Action of Muminiurn Chloride. PAUL ROHLAND (Cimn. Zeit. 1906 30 1173-1174).-The addition of 0.2 molecule of alumi,nium chloride per litre to a mixture of quicklime and water con- siderably accelerates the setting of the lime.The rate of hydration of the two sulphates of calcium containing respectively l&H,O and 2H,O is also increased whereas that of the anhydrous sulphate is decreased. The setting of Portland cement is accelerated by small quantities of aluminium chloride but is retarded by quantities above 7"/,. The accelerating effect of aluminium chloride is increased by the presence of sodium carbonate or of aluminium sulphate. A summary is given of the other reactions in which aluminium chloride acts as a catalytic agent. P. H. Crystallised Aluminium Sulphate. A. GAWALOWSKI(C~~. Centr. 1906 ii 1236 ; from Zed. Oesterr. Apoth. Verein. 44 460).-Crystal- 1 ised aluminium sulpliate A12(S0,)3,1 8H20 is obtained by dissolving " aluminium carbonate " in sulphuric acid adding nitric acid and evaporating until no more nitric oxide is evolved; it crystallises in smooth tetrahedra with truncated edges.The salt obtained by heating the carbonate with sulphuric acid alone differs from aluminium sul-28 ABSTRACTS OF CHEMICAL PAPERS. phate in evolving nitric oxide when treated with nitric acid; the author considers that the aluminium in the " carbonate " is combined in the form AlO*OH. P. H. Revision of the Atomic Weight of Manganese. GREGORY P. BAXTER and MURRAY A. HIKES (J. Amer. Chem. Xoc. 1906 28 1560-t580).-From a computation of the values of the atomic weight of manganese obtained by previous workers Clarke has found the most probable value to be 54.987. The present investigation was carried out with manganous chloride and bromide.These salts have been analysed previously by Dewar and Scott (Abstr. 1883 S56) who obtained for the atomic weight the values 54-91 from the chloride and 54.97 from the bromide. Four specimens of manganese bromide were employed. Two of these ( A and B) were prepared from pure potassium permanganate in the following manner. The solution mas treated with sulphur dioxide ammonium carbonate was added to the resulting solution of manganous sulphate and the precipitate was well washed and then dissolved in nitric acid. The manganous nitrate thus obtained was crystallised repeatedly from a solution acidified with nitric acid was afterwards treated with ammonium carbonate and the precipitate was thoroughly washed and dissolved in hydrobromic acid in a quartz dish.The solution of the bromide was heated to expel bromine and the salt was repeatedly crystallised and finally dried in a vacuum over potassium hydroxide. The third sample (6') was prepared from pyrolusite by dissolving it in hydrochloric acid boiling the solution to expel chlorine passing hydrogen sulphide into the solution and fractionally precipitating with sodium hydroxide until the precipitate was obtained free from iron. The manganese was then precipitated with ammonium carbonate and the manganous carboncte was treated as in the preparation of the previous samples. The fourth sample (D) was prepared from manganous sulphate by treating the solution with hydrogen sulphide converting the sulphide into carbonate and heating the latter as in the former cases.Two samples of manganous chloride were prepared one from the carbonate obtained in the preparation of sample B and the other from the mother liquors of the manganous nitrate resulting from the preparation of samples 12 and D. The hydrobromic hydrochloric and nitric acids and the silver employed were carefully purified by methods which are described. The analysis of the bromide and chloride was effected by titrating weighed portions of the salts after fusion in hydrogen bromide or chloride against weighed portions of pure silver ; the precipitated silver salts were collected and weighed. I n some experiments the silver nitrate was added to the manganous salt whilst in other cases the operation was carried out in the reverse manner. Various precautions were taken t o ensure accuracy and vacuum corrections were applied.Manganous bromide bas Dj6 4.385 and manganous chloride Di5 2.977.INORGANIC CHEMISTRY. 29 Thirty-one analyses were made of the bromide and fourteen of the chloridg and the results are tabulated. The average of the results obtained with the bromide gives Mn=54*957 and the average of those obtained with the chloride gives Mn = 54.958LAg = 107.930 ; Br = 79.953 j C1= 35.4731. E. (3 Corrosion of Iron by Acids. C. F. BURGESS and S. G. ENGLE (Trans. Amer. Electrochem. Soc. 1906 9 199-206).-The rate of solution of different kinds of iron in normal solutions of sulphuric and hydrochloric acid has been measured. Electrolytic iron deposited from a solution containing sulphate and chloride the same iron which had been heated to about 1000° and allowed to ccjol slowly soft sheet-iron containing little carbon tempered steel and ordinary cast-iron were used in the experiments.The electrolytic iron before heating dissolved about four times as rapidly as the steel six times as rapidly as the cast-iron and about forty times as rapidly as the soft sheet-iron. After heating the rate of solution of the electrolytic iron diminished to about one-fortieth of its original valua. The authors suppose that this is indirectly due to the removal of hydrogen by the thermal treatment but suggest that change of the crystalline structure is the primary cause. A coarsely crystal- line sample of electrolytic iron was found to dissolve more rapidly than a more dense deposit.Electrolytic iron is suggested as a means of obtaining pure hydrogen by the action of acids. Traces of arsenic exhibit a very marked influence in protecting iron from the corroding action of acids. No definite relationship between the difference of potential ekhibited by the various samples of iron in acid solution and the rate of corrosion could be detected. H. M. D. Roussin’s Salts. ITALO BELLUCCI and C. CECCHETTI (Atti R. Accud. Lincei 1906 [v] 15 ii 467-4’74. Compare Abstr. 1905 ii 253).-Roussin’s salts or nitrosulphides of the first series when treated with alkali hydroxide pass into nitrosulphides of the second series Fe(NO),SR‘. When the sodium salt Fe4(NO),S,Na,2H20 is treated with hydrazine o r hydroxylamine in either acid or alkaline solution i t yields the corresponding hydrazine or hydroxylamine compound whilst with phenylhydrazine hydrochloride it gives the phenylhydrazine derivative (compare Hofmann and Wiede Abstr.1896 i 391). The hyldrazine salt Fe,(N0)7S,H,N,H4 dissolves slightly in water and readily in alcohol or ether. The hydroxylamine derivative is readily soluble in water alcohol or ether. The phenylhydraxine compound Fe4(N0)7S,H,N,H,Ph melts under hot water ia which and in benzene it is sparingly soluble and dissolves in alcohol or ether. The semicarbaxide salt Fe,(N0)7S,H,N,H3*CO*NH2 dissolves in water alcohol or ether. All these new compounds form shining black crystals and are Fe*( N 0)7S,R’ Fe,(NO)$3 H,N H30,30 ABSTRACTS OF CHEMICAL PAPERS. markedly stable. unaltered for a long time in the absence of light.They can be crystallised from water and remain T. H. P. Behaviour of Chromium towards Sulphuric Acid. ALFRED BURGER (Ber. 1906 39 4068-4072. Compare Doring Abstr. 1902 ii 660; 1906 ii 451 ; Mazzucchelli Abstr. 1905 ii 57Oj.-The author has attempted without success to estimate chromium by measurement of the hydrogen evolved on solution of the metal in an acid. When dissolved in boiling sulphuric acid a sample of chromium prepared by Goldschmidt's process and containing 99"/ of chromium forms a blue or a t lower temperatures a greenish-blue solution. I n both experiments more hydrogen is evolved than corresponds with the formation of the chromous salt a pure solution of which cannot be obtained. On concentration of the solution a further evolution of hydrogen takes place but is not complete on addition of dilute sulphuric acid and re-evaporation until fumes of sulphuric acid are given off.The rate of oxidation of the cbromous to the chromic sulphate is found to be greatest in a 48°/0 solution. The oxidation takes place more rapidly in hydrochloric acid solution. The chromous salt present in the solution is estimated best by addition of an excess of ferric sulphate and titration of the resulting ferrous sulpbate with potassium permanganate and the total chromic salt by oxidation to chromic acid by means of persulphate and titration with ferrous ammonium sulphate and potassium permanganate. A sketch is given of the apparatus employed. G. Y. Reduction of Chromium Oxide by Boron. ARMAND BINET D; JASSONEIX (Compt.rend. 1906 143 897-899).-Moissan (Abstr. 1894 ii 454) first prepared a crystalline chromium boride by heating the two elements in a carbon crucible in an electric furnace; Tucker and Moody (Trans. 1902 81 14) showed that the compound has the composition represented by the formula CrB; and Wedekind and Fetzer (Chem. Zeit. 1905 29 No. 98) obtained the same compound by the alumino-thermic process ; the author however finds that when chromium oxide is reduced by boron in magnesia crucibles heated in an electrical furnace the fused masses thus obtained contain 5 to 17'1" of combined boron the boride CrB (B= 17*4"/,) representing the limit of saturation of chromium by boron. These borides are very hard and scratch glass or quartz; those containing about 7°/0 of boron have a well-marked crystalline structure which disappears as the proportion of boron increases and the boride CrB is not crystalline.The densities vary from 6.8 (7'1 boron) to 6.1 (26O/ boron) and all the compounds are attacked by hydrofluoric hydrochloric or sulphuric acid even in the cold with the formation of boric acid. Nitric acid or alkaline solutions have no action on them; chlorine attacks them with in- candescence but incompletely below a red heat forming a mixture of chromous and chromic chlorides ; hydrogen chloride attacks th-em under similar conditions liberating hydrogen and forming chromousINORGANIC CHEMISTRY. 32 chloride and they are oxidised with incandescence by the action of fused alkali carbonates or hydroxides. When the reduction of chromium oxide by boron is carried out in carbon crucibles the fused products have a crystalline structure but always contain carbon.M A. W. Derivatives of Quinquevalent Chromium. 11. RUDOLF F. WEINLAND and M. FIEDERER (Bey. 1906 39 4042-4047. Compare Weinland and Fridrich Abstr. 1906 i 37)-Chromium oxychloride forms double salts with chlorides of the alkali metals. The yotnssium salt CrOCI8,2KC1 forms rhombic prisms of a dark garnet-red colour. Its oxidising power gradually diminishes when it is kept in a desiccator. Corresponding rubidium ccesium and ammonium salts have been prepared and analysed. Their crystalline forins are similar to those of the corresponding double salts derived from molybdenum oxychloride (Klason Abstr. 1901 ii 162; Nordenskjold ibid.454) and from columbium oxychloride (Weinland and Storz Abatr. 1906 ii 764). The cssium compound has been shown to be isomorphous with the compound CbOC12,2CsC1. J. J. S. Reduction of Metallic Sulphides. OLIVER W. BROWN (Trans. Amer. Electrochelm. h'oc. 1906 9 109-1 15).-The product obtained by heating molybdenite in graphite crucibles at a high temperature contains considerable quantities of sulphur. Complete reduction can however be effected by heating the sulphide with a mixture of lime and coke. An excess of lime is advantageous but an excess of carbon leads to the formation of carbide which retains a considerable quantity of molybdenum. This method of reduction is superior to the ordinary method of roasting and subsequent reduction with carbon in that it prevents loss of metal by volatilisation of the oxide.When galena is similarly heated in the electric furnace with lime and coke very little lead is obtained and this is probably due to the formation of a stable double sulphide of lead and calcium. The reduction of st,ibnite is also very incomplete. H. M. D. New Molybdenum Silicide. OLIVER P. WATTS (Trans. Amer. Electrochem. Xoc. 1906 9 105-1 07. Compare Vigouroux Abstr. 1900 ii 144).-A molybdenum silicide of the probable formula MoSi has been obtained by heating a mixture of the oxides of molybdenum silicon and boron with metallic copper and aluminium in an arc furnace with the addition of cryolite as a flux and lime as a retarder to prevent the reaction from becoming too violent By successive treat- ment of the product with nitric acid and dilute hydrofluoric acid dark coloured crystals with a metallic lustre were obtained.These corre- spond closely with the formula RloSi but contain small quantities of boron and iron. The silicide is not acted on by boiling nitric acid boiling aqua regia or boiling hydrofluoric acid but reacts with incandescence with fused sodium carbonate and slowly with fused sodium nitrate D2"' 6.31. H. M. D.32 ABSTRACTS OF CHEMICAL PAPERS. Reduction of Molybdic Acid in Solution by Molybdenum and the Titration of the Reduced Solution by Permanganate. MARCEL GUICHARD (Compt. rend. 1906 143 744-746. Compare Abstr. 1901 ii 659).-When a solution of the compound Mo0,S08 containing not less than 560 grams H,SO per litre is placed in contact with a large excess of powdered molybdenum in a closed vessel for a period of several months a brown solution is obtained which contains a salt of the oxide &Io,O and not of the oxide MOO as stated by Rammelsberg (Avzn.Phys. Chem. 1864 127 281). This fact taken in conjunction with the results obtained by Bailhache (Abstr. 1902 ii 243) and Klason (Abstr. 1901 ii 162) render it probable that the oxide MOO does not form salts. The titration of the reduced solution was conducted in an atmosphere of hydrogen by means of a perman- ganate solution which had been standardised against iron reduced in hydrogen. M. A. W. Preparation of Hydrated Hypovanadic Acid. GUSTAVE GAIN (Cornpt. rend. 1906,143 823-825).-The sulphite 2V20,,3S0,,10H,? prepared by dissolving in a saturated solution of sulphur dioxide in air- free water the mixture of oxides V,O and V,O obtained by calcining ammonium metavanadate at a dull red heat forms fine silky clear blue needles and when an aqueous solution of the salt is boiled sulphur dioxide i d evolved and crystals are deposited which after drying on porous tile form a pale red crystalline powder of hydrated hypovanadic acid V,O 2H,O.M. A. W. Alloys of Palladium and Copper. RUDOLF RUER (Zed. anorg. Chem. 1906 51 223-230).-The freezing-point curve of the palladium-copper alloys falls regularly from the melting point of palladium (which in accordance with the most recent determinations is taken as 1541O) to the melting point of copper 1084O the part representing alloys rich in copper being nearly horizontal.Although the course of certain parts of the curve is somewhat uncertain owing to a tendency to super-cooling there is no evidence of chemical com- bination the metals forming a complete series of mixed crystals. On etching alloys containing 30-70°/0 of palladium with dilute aqua regia slender needle-shaped crystals were observed. The pro- portion of these crystals was not appreciably altered by heating for two hours a t 1500O or for the same period at 1180° just above the melting point of the mixture and did not attain a maximum with a definite composition of the alloy so that they do not indicate the formation of a chemical compound. of palladium the alloys retain the structure of copper. Those containing 10°,lo of palladium are red in colour; when more than 2O0l0 of the same element is present they are white.The alloys are rather harder than the metals themselves and this property attains its maximum when the components are present in equal parts by weight. Even up to G. S.MINERALOGICAL CHEMISTRY. 33 Solid Solutions in the Dissociation of Palladous Oxide and Gupric Oxide. LOTHAR WOHLER (Zed. Elektrochem. 1906 la 781-786).-Further experiments have been made on the dissociation of palladous oxide (compare Abstr. 1906 ii 94). The principal results are that the pressure observed depends on the relative quantities of oxide and metal present and also on the time of heating. The greater the relative amount of metal the lower is the pressure. The results are best explained by supposing that palladium slowly dissolves in the oxide forming a solid solution the dissociation pressure of which is lower than that of the pure oxide. The dissolution takes place very slowly so that the pressure observed depends on the time of heating. The dissociation pressures of cupric oxide were measured at tempera- tures between 9603 and 1084'; its m. p. was found to be 1064'. That solid ,solutions are formed in this case was shown by heating 2 grams of the oxide in a vacuous quartz tube (volume 20 c.c.) at lOOO' equilibrium is reached in a few minutes at 111 mm. The tube was again evacuated and equilibrium re-established ; the repetition of these operations gave pressures of 106 104 101 95 and 91 mm. Similar results were obtained at other temperatures. An experiment with 7.3 grams of the oxide gave a dissociation pressure of 50 mm. at 960'; taking this as the dissociation pressure of the pure oxide and using the beat of dissociation of copper oxide 2CuO = Cu,O + 0 - 33.6 Calu. the dissociation curve of the pure oxide is calculated from van't Hoff's equation. The curve so obtained gives higher pressures than any of those measured with mixtures of copper and copper oxide but the experimental curves approach it more nearly the purer the copper oxide used. T. E.

ISSN:0368-1769    

DOI:10.1039/CA9079205018

出版商:RSC    

年代:1907

数据来源: RSC

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MINERALOGICAL CHEMISTRY. Mineralogical Chemistry 33 Researches on Vulcanism. ALBERT BRUN (Arch. Xci. phys. mat. 1906 [iv] 22 425-448).-1t is suggested that the gases produced by the dissociation of ammonium chloride and ammonium nitrate which salts are of deep-seated origin are the main causes of volcanic explosions and that aqueous vapour is of little importance in this connexion. L. J. 8. Lead and Arsenic Minerals as Fumaroleproducts in the Recent Eruption of Veauvius. ALFRED LACROIX (Compt. rend. 1906 143 727-730).-During the recent oruption of Vesuvius numerous fumaroles were opened along fissures near the crater. On May 3 these were in an acid stage evolving water vapour charged with hydrochloric and sulphuric acids ; the temperature was 350O. Specimens of the solid material deposited by the fumaroles were collected on this date and alao subsequently in July and September The VOL.XCII. ii. 334 ABSTRACTS OF CHEMICAL PAPERS. most abundant consists like that of earlier eruptions of chlorides of iron potassium sodium calcium magnesium &c. but with the exception of erythrosiderite the mineral species are not well indi- vidualised. The chlorides are coated in places with realgar either as fused glassy isotropic crusts or as minute crystals. Galena was also noticed as small cubes (compare Abstr. 1906 ii 766) in association with crystals of magnetite (.or magnesioferrite) haematite pyrrhotite and pyrites. The galena would have been formed by the action of hydrogen sulphide on vapours of lead chloride. In some cases it has been altered t o lead chloride by the action of hydrochloric acid as shown by the existence of pseudomorphs of cotunnite after galena.Lead chloride is also present in the scoria and may be extracted by boiling water. This occurrence of lead is commented on in connexion with the formation of mineral-veins. L. J. S. Formation of Quartz in Silicate Fusions. P. D. QUENSEL (Cenntr. Min. 1906 657-664).-A mixture of oligoclase (74 parts) and silica (26 parts) was heated with 1-6'1 tungstic oxide for several houra at temperatures of 800- 1000' while superheated steam was forced through the mass. The microscopical examination of the glassy products proved the presence of minute crystals of quartz. The tungstic oxide acts as a '' mineraliser " by reducing the viscosity of the mass and lowering its temperature of fusion.Tridymite was formed when silica was fused with a large excess of sodium tungstate at 950-1000°. L. J. S. Dioxides of Elements of the Fourth Group of the Periodic System. JACOB BECKENKAMP (Zeit. Kryst. Min. 1906,42,448-474). -Constants are deduced for a theoretical tetragonal modification of silica and are compared with those of the known crystallised modifica- tions of silica; and the latter are compared with the pseudo-rhombo- hedral forms produced by the twinning of rutile. The relations between atomic weights and crystallographic constants in the several oxides are discussed. L. J. 8. [Cassiterite Jamesonite Tapiolite &c. from South Dakota.] WILLIAM P. HEADDEN (Proc. Colorado Sci. Soc. 1906 8 167-182).- Cccssiterite.-Analyses I-1V are of material from various mines in the Black Hills district of South Dakota; also anal.V of cassiterite from Mecklenberg North Carolina. Tantalite is associated with some of the specimens but appears to have no connexion with the presence or absence of tantalic acid in the cassiterite SnO,. Ta,O,. Pe,O,. SO,. Insol. Ign. Total. Sp. gr. I. 94-36 2.42 1-80 1.00 - - 99'58 6'622 11. 96'08 - 1.90 0.88 - 0.12 99-68 6.680 - - 100*11 6.767 111. 98.22 - 0 . i 2 - 0*64 0.34 99*92 IV. 98.13 - 0.43 - 1-40 - 99.96") 7.OI9 V. 95.18 3'82 '.I1 - \(FeO) * Also trace of CaO. Jccmesonite.-Columnar masses occur in qunrtz-veins at Sheridan,MINERALOGICAL CHEMISTRY. 85 Pennington Co. S.D. ; analysis V I agrees fairly closely with the formula 2 P bS ,S b,S,.Meneghinite. - Analysis VII of fibrous material from Rochford Pennington Co. S.D. agrees with 4PbS,Sb2S S. Sb. Pb. Fe. Cu. Zn. Co. Insol. Total. Sp. gr. VI. 18.90 26.99 51.15 1-30 0'24 0.05 trace 1.13 99-70 5.81 VII. 17.51 18.20 fi285 trace 0'86 - - 0'49 99'91 * 6'21 * Also traces of As Bi Cd. Hiibnerite.-Crystallised material from Cornstock mine Lawrence Go. S.D. gave anal. VIII; massive material from Sunday Gulch Pennington Co. S.D. anal. IX W03. SnO,. Cb,O,. Ta,O,. MnO. FeO. CaO. TotaI. VIII. 75'12 - - - 20.54 3-01 1.04 9 9 7 1 IX. 74.46 - - - 19.90 3.29 1.05 99.87" X. 0'11 0.07 4.29 78.61 - 16.85 - 100.24 t XI. 0 '59 3.90 78-58 - 15.60 - 99.96 $ - * Including Insol. 0.42 ; Ignition 0.75. t Including Cassiterite 0.31 ; TiO trace. $ Including Insol.1 '29. TapioZite.-Indistinct crystals from granite a t Cluster City S.D. were determined by Penfield to be tetragonal D. 7.218; analyses X and XI on the same sample of material. The method employed for the determination of tantalic and niobic acids is discussed. Analyses are also given of some zinc-blendes which phosphoresce when scratched ; the material is mixed with other minerals and the analyses suggest no cause for the phosphorescence. L. J. S. The Gas Observed when Tantalite is Attacked by Potass- ium Hydroxide. CAMILLE CHABRI~ and F. LEVALLOIS (Compt. rend. 1906 143 680-681).-When tantalite is heated t o redness in a vacuum there is a slight evolution of gas containing 84O/ carbon dioxide 1 2 * 4 O / nitrogen and 3*1"/ oxygen. If the mineral is subsequently fused in a vacuum in a Jena glass tube lined with silver with potassium hydroxide dried by prolonged fusion in a current of hydrogen water vapour is formed and a gas is evolved a t the rate of 11.5 to 14.5 C.C.per gram of tantalite which consists of 93*2O/ hydrogen 4.6'/ nitrogen and 1-2*/ oxygen. The nitrogen and oxygen are due t o air occluded in themineral the water and hydrogen are formed by the replacement of the ferrous oxide of the mineral by potassium oxide and its subsequent oxidation at the expense of the potassium hydroxide with the formatiou of hydrogen water and iron sesquioxide according to the equation 2TaO,,FeO + 4KOH = 4KTa0 + Fe203 + H,O + H (compare Moissan Abstr. 1881 74). Ilmenite (titaniferous iron) is similarly decomposed when fused with potassium hydroxide hydrogen and water being evolved ZTiO,,FeO + 4KOH = 2K2Ti0 + Fe,O + H,O + H,.M. A. W. 3-236 ABSTRACTS OF CHEMICAL PAPERS. Hellandite from Kragero Norway. WALDEMAR C. BROGGER (Zeit. Kryst. Min. 1906 42 417-439).-In the granitic pegmatite- veins which are quarried for felspar in the neighbourhood of Kragero the following minerals are found microcline-perthite quartz tourma- line orthite titanit e (yttrotitanite) thorite euxenite apatite pbenacite and hellandite ; brief descriptions are given of each of these and a detailed description of hellandite (Abstr. 1903 ii 657). Hellandite when fresh is nut-brown with a resinous lustre on the conchoidal fracture ; some of the optical characters are now given ; usually however the mineral is much altered and is then optically isotropic.The following are new analyses by L. Andersen-Aars both made on altered material; the more altered material of analysis I1 was white and earthy. I n analysis I 6°/0 of the water is lost gradually up to 500° and the remaining 5O/ is expelled only at a red heat. The latter appears therefore to enter into the con- stitution of the mineral and a new formula is given as Ca2R'3[ Err'( OH)J3[ SiO,],. SiO,. A1,0,. Fe,O,. Mn,O,. Ce,O,. Y203. Er,O,. Thop I. 23.66 10'12 2.56 5-91 1'01 19-29 15'43 0.62 11. 27'88 9.67 2-01 3-13 0.37 19'71 13-26 0.30 CaO. MgO. Na,O. K20. H,O. Total. I. 9-81 0.10 0.23 0.06 11-75 100.55 - 11. 9.97 0.13 0'41 13-09 99.93 A relation is traced between the crystallographic and chemical characters of hellandite guarinite danburite and topaz.Hellandite is near to but distinct from gadolinite kainosite rowlandite thalen- ite and yttrialite. L. J. S. Manganese-Garnet containing Yttrium. CARL BENEDICKS (Bull. Geol. Inst. Upsala 1906 7 27 1 -277).-Speseartite occurs at Klrarfvet near Falun in Sweden as rounded masse.' rarely as distinct crystals embedded in quartz and albite. Analyses Ly 0. Tenow of pale red material (I and 11) and of dark brown (111) gave SiO,. A1,0,. Y,O,. FeO. MnO. CaO. Total. Sp. gr. 11. 36'23 19.15 1'18 18.76 23.44 0.56 99.38) 4'197 I l l . 35'36 22.34 1'23 22-01 18-80 trace 99'74 4.068 IV. 5.5 n. d. 0.7 3 '1 1.4 11. d. I. 35.67 22 50 1-19 19'17 21.91 trace 100.44 - - Under 1V is given the compositiou of the portion which went into solution when the pale red material was digested with dilute hydro- chloric acid. The few previous analyses of garnets containing yttrium and those of Swedish spessartite are quoted. Alkali Quartz-Porphyries in Corsica. Remarkable Occur- rence of Orthoclase. J. DEPRAT (Compt. rend. 1906,143 753-756). -.Dykes of quartz-porphyry containing phenocrysts of quartz and anorthoclase and microliths of aegirite and riebeckite occur in con- nexion with the soda-granites of Corsica. A description is also given of simple and twinned crystals of orthoclase from a weathered mlcro- granulite frcim Corsica. L. J. S. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9079205033

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. 37 Physiological Chemistry. Reaction of the Blood in Rarefied Air as Determined by Titration and by t h e Electrometric Method. ALBERTO AGGAZZOTTI (Atti R. Accccd. Lincei 1906 [v] 15 ii 474-483).- The author has measured (1) the concentration of the hydrogen ions and (2) the acidity towards sodium hydroxide of the blood of small dogs after these have been subjected to a moderately rapid diminution of pressure under the bell jar of an air-pump. It is found that the alkalinity of the blood undergoes diminution under these conditions but not to SO great an extent as when the dimiuution in pressure is attained by ascent of a mountain in which case the action is of longer duration (cornpare Galeotti ibid. 1903 [v] 12 ii 646). M. PIETTRIC and ANTONY VILA (Compt.rend. 1906 143 737-790. Compare Abstr. 1905 i 399 500; 1906 ii 373).-The stroma obtained from the red corpuscles by hzmolysis and extraction with ether forms a soft viscous substance greyish-red or yellowish-white in colour soluble in water and readily fermented. The amount obtained from a litre of defibrinated blood varies with the nature of the blood; the blood of the horse yields 2.65-2.54 ; the pig 2.90 ; the dog 3.65 ; the guinea- pig 3.74 and the pigeon 21.55. The percentage numbers obtained by analysing the dried product were C 53-32 ; 33 7.47 ; N 11.70 in the strorrrs from horse’s blood and C 54-22 ; H 8.30 ; N 13.21 in the stroma from dog’s blood. The amount of anh in stroma isolated as above is much higher than that obtained by previous workers (compare Pascucci Abstr.1905 ii 729) the percentage amount being as follows horse 2.32-3-0 ; dog 2.9 ; duck S.25 ; pigeon 8-96. The ash contains manganese is free from chlorine and contains 0*31-0*33 ; 2.6 or 2.3 per cent. of phosphorus according as it is derived from the blood of horse fowl or duck respectively. T. H. P. The Stroma of t h e Red Corpuscles. M. A. W. Action of Photodynamic Substances on Golourless Cor- puscles. HUGO SALVENDI (Chem. Centr. 1906 ii 1511 ; from Arch. klin. Med. 87 356-364).-In diffuse daylight eosin shows a harmful action on frog’s leucocytes in six hours in sunlight in two to three hours. The action on lymphocytes is more rapid. Other substances fluorescein Bengal red &c. act in the same way but not so rapidly. The action of these material on Pccrama?cizcm is similar.W. D. H Photodynamic Action in Alkaline Neutral and Acid Media. R. DAX (Chem. Centy. 1906 ii 1511-1512; from Avch. k&. Med. 87 365-372).-1f the photodynamic action of eosin and similar substances is due to the amount of acid liberated the action should be greater in an alkaline than in a neutral or acid medium. But the action on Paramcecium is not greater in an alkaline than in a38 ABSTRACTS OF CHEMICAL PAPERS. neutral or acid medium. at which they destroy invertase. The reaction also does not influence the rate W. D. H. The Chemical Nature of Fertilisation. JACQUES LOEB (Bioclhem Zeit. 1906 1 183 -206).-A somewhat condensed account of the author’s work and theories ; artificial parthenogenesis is regarded as an acceleration of oxidation processes directed into certain channels.The influence of agents and reagents on these is discussed. W. D. H. The Physiologico-pathological Meaning of Hyperacidity of the Gastric Juice. A-DOLF BICKEL (Biochem. Zed. 1906 1 153-160).-A discussion from the medical point of view of hyper- chlorhydria. The symptom is probably an indication of a complex condition in which nerves are concerned and opinions regarding its meaning require revision. W. D. H. Action of Trypsin. I1 and 111. KARL MAYS (Zeit. physiol. Chem. 1906 49 124-187 ; 188-301).-Pancrentic juice has an ereptic action. This may be due to the continued action of trypsin or to the presence of a second enzyme (pancreatic erepsin). Vernon’s positive statement that the second enzyme exists is criticised but with the present methods for the separation of ferments the question must still be an open one.Bayliss and Starling state that the fresh pancreatic juice of the dog contains no trypsin until i t is activated by the succus entericus. They attribute the feeble proteoclastic power of the fresh juice to the action of pancreatic erepsin. The view taken by the present author is that it is due to the presence of a small amount of trypsin for ereptic action in Cohnheim’s sense is absent. Extracts of pancreas have only a feeble ereptic action. Mr. D. H. Digestion and Rennet-action. MARTIN JACOBY (Biochem. &it. 1906 1 53-74).-This research arose out of Pawloff’s theory that peptic and rennetic actions are both due to one enzyme. Although i t is admitted that preparations can be obtained which in certain con- centrations exhibit one action only Pawloff’s view is favoured on the whole on account of the resemblances in the action of certain factors which influence the two activities.No specificity was found in the be haviour of an ti-su bs tances. ‘317. D. H. Metabolism Experiments in a Woman with a Permanent Biliary Fistula. PHILIP SHAFFER (Amer. J. Physiol. 1906 17 362-391).-The patient’s metabolism was normal except for poor absorption of fats high excretion of indican (due to increase of intestinal putrefaction) a lorn excretion of creatinine (to be discussed in a future paper) and a high excretion of ammonia the cause of which is not under- B ood. The taurine of the bile is not to any extent the source of the neutral sulphur of the urine. The latter was not lower t,han normal an8 was not increased when bile was given by the mouth or through the fistula.In jaundice it is suggerjted that the increase in neutralPHYSIOLOGICAL CHEMISTRY. 39 sulphur may be derived from taurine absorbed from the bile passages into the circulating blood and thus diverted from the normal bile cir- culation. Absorption of fat was not increased by bile medication or bile injection ; absorption of proteids was good. No relation between the composition of the bile and t,he amount of proteid in the food was found. Excretion of bile is increased by bile medication or bile injection ; the bile given is probably not a hepatic stimulant but merely furnishes the liver with ready-made bile constituents which it excretes by the usual channel.W. D. H. Nutritive Value of Glycerol. BERNHARD KNAPP (Chem Cent?. 1906 ii 1510; from Arch. kZin. Med. 87 34O).-Glycerol has “proteid-sparing” action and is thus of nutritive value. A t the commencement of the glycerol periods sugar appears in the urine and a portion of the glycerol given leaves the body as such. W. D. H. The Behaviour of Moss Carbohydrates in the Human Body and their use in Diabetes Mellitue. E. POULSSON (Chem. Cent?. 1906 ii 1511 ; from Hammarsten’s Feutschyijt xiv).-The carbo- hydrates of two mosses Cetraria islcmdiccl and C. nivnlis were investi- gated. I n the former plant about half of the water-soluble carbo- hydrate consists of lichenin which on acid hydrolysis yields amorphous products and dextrose.The insoluble carbohydrates are hemicelluloses of which dextran mannan and galactan were identified ; about 3”/* of pentosans and a small amounb of true cellulose are present. Given in bread about half the carbohydrates present are absorbed and burnt in the body. C. nivnZis.has a similar composition except that lichenin is less and hemicelluloses more abundant. A bread prepared from it muses disturbances of health due to the presence of usnic acid. W.D. H. Proteid Synthesis in Animals. VALDEMAR HENRTQUES and C. HANSEN (Zeit. Physiol. Chem. 1906,49,113-123. Compare Abstr. 1905 ii 1 SO).-The experiments were made on white rats to determine whether the hydrolytic products of casein obtained by the action of acids act as “proteid-sparers ’’ and whether protarnines given in addition assist in lessening the loss of nitrogen.The answer to both questions is in tbe affirmative ; the loss of nitrogen in the body was diminished especially when protamines were given also as compared with periods during which the animals received no nitrogenous food. W. D. H. Behaviour of Ovo-mucoid in the Organism. K. WILLANEN (Biochem. Zeit. 1906 1 108-128).-This gluco-proteid occurs in con- siderable amount preformed in eggs (1Oolo in hen’s egg-white) ; it is not altered by boiling. If given by the stomach to men and animals it is destroyed and behaves like other proteids. If injected intra- venously from 14 to 28O/ of it reappears in the urine. This does not occur if it is injected subcutaneously. I n gastric digestion and during putrefaction its carbohydrate group (glucosamine) is split off. This does not occur during tryptic digestion or in autolysis produced by40 ABSTRACTS OF CHEMICAL PAPERS.splenic tissue. broken up. I n the later stages of putrefaction the glucosamine is Ovo-mucoid gives a feeble Adamkiewicz reaction. W. D. H. Effect of Alcohol on Secretion of Bile. WILLIAM SALANT (Amer. ,? Phyeiol. 1906 17 408-428).-Physiological doses of alcohol how- ever introduced into the body exert little or no direct secretory action on the digestive glands. This conclusion was confirmed by the present experiments which were conducted on dogs the alcohol being given intravenously. An increased flow of bile sometimes noticed may as in the case of other digestive glands be nervous in origin or due to the formation of secretin which stimulates the liver as well as the pancreas.W. D. H. Maintenance of Cerebral Activity in Mammals by Arti- flcial Circulation. CHARLES C. GUTI’IRIE F. H. PIKE and GEORGE N. STEWART (Amer. J. Physiol. 1906 17 344-349).-Saline solutions are quite inadequate to sustain the reflex or voluntary functions of the brain in a freshly decapitated auimal. Defibrinated blood is effective for eight or nine minutes only ; oxygenated active blood from the cir- culation of another animal of the same species prolongs the period to nineteen minutes. W. D. H. Influence of Temperature on Rate of Heart in the Light of the Law for Chemical Reaction Velocity. CHARLES D. SNYDER (Amer. J. Physiol. 1906,17 350-361).-Experiments on the hearts of various animals invertebrate and vertebrate (including mammalian) show that the velocity is the same as that for known chemical reactions as influenced by temperature.This is expressed by the formula (Arrhenius) logk = - A/T+ constant in which A is a constant and k is the heart rate at any temperature T which falls within certain limits. W. D. H. The Action of Carbon Dioxide and Alcohol on Muscle. FR. W. FR~HLICH ,,(Chem. Centr. 1906 ii 1443-1444; from Verh. Ges. Dezct. Nutui$ Brzlc 1905 ii 405-406).-Before paralysis sets in as an action of the two agents investigated the contractions of muscle and the action currents of nerve increase. This is not regarded as clue to an increase in vital processes but as an accompaniment of the destruc- tion of life especially oh the anabolic side.W. D. H. The Influence of Muscular Work on the Weight and Composition of the Organs. FELIX ROUOZINSKI (Biochem. Zeit. 1906 1 207-228).-1n dogs muscular work causes no change in the physical or chemical characters of the blood. The muscle substance becomes poorer in water which will account for the loss of weight. W. D. H. The Contents of a Chylous Cy&. OTTO Sc~uam (Zed. physiol. Chem. 1906 49 266).-The cyst mas situated in the mesentery and its contents measured about 1500 C.C. It contained total solids,PHYSlOLOGICAL CHEMISTRY. 41 39.76 ; fat {ether extract) 35.76 ; fatty acids (from soaps) 0.43 ; proteids 1.97 ; ash O-9’/o. On microscopic examination it was found to contain fat globules and crystals of a mixture of calcium palmitate and stearate. The proteids were globulin albumin and a small amount of proteoses.The ash was specially rich in calcium and sodium chloride ; i t also contained phosphoric acid and potassium. Leucine tyrosine and sugar were absent. The fluid contained a peroxydase and probably a fat-decomposing ferment but no proteo- elastic enzyme. The fat present had the same characters as in human adipose tissue. W. D. H. A Heptose in Human Urine. F. ROSENBERGER (Zeit. physiol. Chem. 1906 49 202-209).-1n a case of diabetes in addition to the ordinary fermentable sugar a second lzevorotatory carbohydrate was found which was identified as a heptose. Crystals of Z-mannoheptos- azone (m. p. 203’) were prepared from it. W. D. H. Methylguanidine in Normal Human Urine. W.ACHELIS (Chem. Centr. 1906 ii 1445 ; from Cerbtr. Physiol. 20 455).-The statement of Kutscher and Lohmann on this subject is confirmed. Thirty litres of urine yielded about 0.7 gram of the picrolonate. W. D. H. Ehrlich’s Diazo-reaction and RUSSO’S Methylene-blue Reaction in Urine. REINHOLD DUNGER (Chom. Centr. 1906 ii 1518 ; from Deut. med. Woch. 32 1582-1583).-Russo’s reaction (Riforma rned. 1905 507) consists in shaking 4 or 5 C.C. of urine with four drops of a lolo solution of methylene-blue. A positive reaction is the appearance of an emerald-green colour ; a bluish-green or blue colour is negative. Positive results were obtained by him in typhoid measles small-pox and other diseases. I n the present research 1100 urines were examined b u t the reaction is of no value.It is given by many urines which do not give Ehrlich’s diazo-reaction and vice versa. It is not a chemical reaction a t all but is simply due to a mixture of colours and if the urine contains more than 0*6’/0 of urochrome the result is the green which Russo describes as his positive reaction. W. D. H. Acetonuria in Dogs. A. BAUUQARTEN and H. POPPER (Chem. Centr. 1906 ii 1452; from Centr. Physiol 20 377-381).-1n extra-uterine pregnancy hzemorrhage into the peritoneum leads to intense and lasting acetonuria which disappears when the blood is removed. I n the present research isovaleric and butyric acids after neutrslisation by ammonia were injected (1) into the peritoneal cavity of dogs or (2) under the skin in amounts of 1 to 2 grams per kilo. of body weight.I n the first case ncetonuria ensued ; in the second it did not. W. D. H. Phloridzin Diabetes. KARL GLAESSNER (and ERKST P. PICK) (Chem. Centc. 1906 ii 1451 ; from Yerh. Ges. Deut. Natuq$ Arzte 1905 ii 41 1-41 2)-The influence of various amino-acids on the ex-42 ABSTRACTS OF CHEMICAL PAPERS. cretion of sugar in diabetes caused by phloridzin in rabbits was inves- tigated. In well-fed animals alanine and glutamic acid produced the strongest effect leucine and glycine less and asparagine none at all. Acetamide sodium lactate caffeine and chloral hydrate also gave negative results. If the animals were fasting no amino-acid gave a positive result. If however the liver of phloridzinised rabbits was administered subcutaneously glycosuria ensued. If the rabbits’ kidneys were removed phloridzin given and the animals killed twenty-four hours later their blood or liver substance given sub- cutaneously to dogs produced no glycosuria.Phloridzin appears to be destroyed in the blood or rendered inactive. The Cause of Death in Acute Diseases of the Pancreas. N. GULEKE (Chem. Centr. 1906 ii 1451 ; from Verh. Ges. Beut. Natur- Arrxte 1905 ii 116-1 19).-‘l‘he pancreatic secretion causes in many cases fatal poisoning and in destruction of the pancreatic tissue passes into the blood or lymph stream by which means it is distributed to the tissues which it destroys. W. D. H. The poisonous substance is trypsin. W. D. H. Action of Magnesium Salts. IV. SAMUEL J. MELTZER and JOHN AUER (Amer. J. Plqsiol. 1906 1’7 313-320 ; compare Abstr.1906 ii 473). -Subcutaneous and intravenous injections of magnesium salts produce neither purgation nor intestinal peristalsis. Peristalsis produced in other ways can be completely inhibited by an intravenous injection of magnesium sulphate or chloride in doses insufficient to embarrass the respiration. Intravenous injection of these salts also inhibits the muscular tremor produced by intravenous injection of physostigmine. W. I). H. Behaviour of Nutrose given Subcutaneously and ita Relation to the Excretion of Rynurenic Acid and Allantoin. A. BAUMGARTEN and ERNST P. PICE (Chern. Centr. 1906 ii 1449 ; from Verh. Ges. Deut. Natug. Ayxte 1905 ii 413-414).-In dogs the hypodermic administration of 7- 8 grams of nutrose increased the excretion of kynurenic acid whereas the excretion after adminis- tration by the mouth is very small.The proteid given is considered to be the source of the acid. No definite conclusion is drawn regard- ing allsntoin. I n rabbits Ellioger’s statement is confirmed that hypodermic injection of tryptophan leads to the occurrence of kyn- urenic acid in their urine but the similar injection of nutrose OT proteoses led to a negative result. W. D. H. The Action of Morphine. I. KUDOLF MAGNUS (P’iiyer’s Archiw 1906 115 316-330).-1n cats a prolonged milk diet causes chronic diarrhea which is stopped by the subcutaneous injection of 4 or 5 centigrams of morphine hydrochloride. Morphine has the same action after the whole of the sympathetic nerve supply from stomach to anus has been cut through and undergone degeneration.The pre- sence of inhibitory nerve fibres is therefore not necessary for morphine action in this direction. After small doses of morphine the peris-VEGETABLE PHYSIOLOGY AND AGRlCULTURE. 43 taltic sodium chloride reflexes of the small intestine cannot be observed with cert,ainty. W. D. H. The Liver in Phosphorus Poisoning. JULIUS WOHL~EMUTH (Biochem. Zeit. 1906 1 161-165).-The main outcome of the examination of the livers in cases of phosphorus poisoning in rabbits is that the nuclear material is much less and much more slowly broken down than the cell-protoplasm. W. D. H. Toxity of some Rare Earths. Their Action on Certain Ferments. ALEXANDRE HEBERT (Compt. Fend. 1906 143 690-693). -The sulphates of thorium cerium lanthanum and zirconium have no toxic action on guinea-pigs or frogs when injected subcutaneously in quantities of 160 lug. per kilo. of body weight. Fishes (minnows) die in solutions of the sulphates containing 0.5 gram per litre the zirconium and thorium salts are the most poisonous then follow those of cerium and lanthanum. Geriiiinating seeds of the pea wheat or rape are killed when transplanted t o a solution containing 5 grams of the rare earth sulphates per litre whilst experiments conducted on Aspergillus niger beer yeast diastase and emulsin show that thorium and zirconium sulphates are poisonom towards the lower organisms and ferments solutions containing 0.5 or 1 gram of salt per litre being in this respect comparable with solutions of mercuric chloride. Cerium and lanthanum sulphates have no toxic action on the cultures even in such quantities as 5 or 10 grams per litre. M. A. W.

ISSN:0368-1769    

DOI:10.1039/CA9079205037

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRlCULTURE. 43 Chemistry of Vegetable Physiology and Agriculture. Oxidation of Hydrogen by Bacteria. A. J. NABOKICH and A. F. LEBEDEFF (Centr. Bakt. YCCT. 1906 ii 17 350-355).-The results of several experiments with Russian black soils (Odessa) and Polish soil showed that hydrogen is oxidised by autotrophic rod bacteria (compare Kaserer Abstr. 1906 ii 113 ; and Immendorff ibid. 1892 3i4). N. H. J M. Formation of Arabin by Bacteria and their Relation to the Gum of the Amygdaleae. W. RUELAND (Chern. Centr. 1906 ii 1345 ; from Ber. deut. bot. Ges. 24 393-401).-Cultivations of Bacillus spongiosus on sucrose give rise to production of mucus; a similar result was obtained with raffinose but the time required was longer. With mannitol the production of mucus was very slight whilst with dextrose and lsevulose there was none at all.The gum of the mucus was pure arabin without galactin hemicellulose or nitro- genous matter. It was shown previously that the bacillus (obtained from diseased44 ABSTRACTS OF CHEMICAL PAPERS. cherry shoots) causes a flow of gum when cherry trees are inoculated with i t and that.the gum is a mixture of arabin and galactin. N. H. J. M. Formation of Free Oxalic Acid by Aspergillus Niger. CARL WEHMER (Chem. Cent?*. 1906 ii 1348; from Ber. deut. 60t. Ges. 24 381-384).-1n former experiments an abundant production of oxalic acid by AspergiZZus niger was always observed whilst subsequent experiments gave negative results. New experiments have confirmed the results first obtained ; the later negative results were perhaps due t o impurities in the calcium carbonate.N. H. J. M. Causes of the Formation of Aldehyde in Wines and the Amounts in some Tuscan W-ines. NAPOLEONE PASSERINI (Chem. Ceqhtr. 1906 ii 1280-1281 ; from Stax. sper. ugrur. ital. 39 221-240).-Tuscan wines (62) were found to contain from 1 to 60 mg. of aldehyde per litre. The amount is generally higher in wines containing much alcohol than in those with low amounts of alcohol and white wines generally contain more than red wines. The amount seems to increase with the age of the wine. Aldehyde is produced by aerobic ferments (Mycoderma vini and Permenturn aceticum) but not by anaerobic microbes. N. H. J. M. Formation of Fuse1 Oil by Yeast. FELIX EHRLICH (Ber. 1906 39 4072-4075. Compare Pringsbeim Abstr.1906 ii 880).-Fuse1 oil is not formed by the action of acetone-yeast (Albert Buchner and Rnpp Abstr. 1902 ii 521) on sugar alone or in presence of d-leucine which remains unchanged. G. Y. Influence of the Chemical Constitution of the Nitrogenous Food Material on the Fermenting Power of Yeast. HANS PRINGSHEIM (Bey. 1906 39 4048-4055).-Yeast which has been grown in a medium free from sugar but containing other carbon compounds and suitable nitrogenous food will induce alcoholic fermentation when brought into a solution containing sugar. Suitable nitrogenous compounds are those containing the grouping *NH* CH CO* such as glycine alanine leucine tyrosine and aspartic acid also phenylglycine allantoin phenylalanine and hippuric acid. The compounds with the longer side chains for example propionic acid derivatives react more readily than acetic acid derivatives.Guanine and uric acid which contain the grouping *NH*C*CO* may be used and also ammonia. Yeast will grow in a lo"/ sucrose solution containing small amounts of potassium hydrogen phosphate magnesium sulphate traces of common salt and ferrous sulphate and certain nitrogenous sub- stances without inducing alcoholic fermentation. Such nitrogen compounds are sulphnnilic acid metanilic acid naphthionic acid aniline and its salts benzamide benzy lamine acetamide acetanilide met hylaniline diphenylamine dimethylaniline hydrochloride andVEGETABLE PHYSIOLOGY AND AGRICULTURE. 45 pyridine. The addition of a compound containing the group *NH*CH*CO* t o such an inactive solution readily starts alcoholic fermentation.J. J. S. Mutual Effect of Nicotiana Tabacum and N. afflnis in Graft- ing. VIKTOR GRAFE and K. LINSBAUER (Chem. Centr. 1906 ii 1276; from Ber. deut. bot. Ges. 24 366-371).-When a variety of tobacco containing nicot-ine is grafted on to one containing little or no nicotine (Nicotiana aflnis) or vice z;ersd the leaves of the vaiiety wbich in ordinary circumstances contains very little nicotine mill be found to contain relatively large amounts. N. H. J. M. [Cyanogenesis] in Plants Growing in Belgium. P. FITSCHY (Bull. Acad. roy. BeZg. 1906 613-617).-Smsll quantities of hydro- cyanic acid have been obtained by macerating the following plants previously ground in water Ranunculus repens R. arvensis Gyneriuna ccrgeqzteum Melica altissinaa M.nutans M. unajfora M. ciliata. I n R. repens G. argenteum M. altissima a cyanogenetic glucoside appears to be present which is decomposed by sweet almond emulsion. T. A. H. Occurrence of Vanillin. EDMUND 0. YON LIPPMANN (Ber. 1906 39 4147).-Vanillin may be obtained from dahlia bulbs. A. McK. Chemistry of the Scleroderms. 11. Scleroderma auran- tium (S. vulgare). MAX BAMBERGER and ANTON LANDSIEDL (Monutsh. 1906 27 963-967. Compare Abstr. 1905 ii 852).- Ripe specimens of Xcberodernaa uurnntium from the neighbourhood of Graz were dried and the peridium and hymenium investigated separately. The light petroleum extract of the peridium yields two crystalline substances. The substunce C,,H,,O crystallises from chloroform on cooling or from a mixture of chloroform and acetone in transparent rectangular plates m.p. 183.5’ in an open or 188’ in a closed capillary tube ; with Liebermann-Burchard’s reaction the aqueous emulsion is orange-yellow and becomes green red and finally yellow whilst the chloroform solution is orange-yellow and changes through rose and lilac to blue; Liebermann’s reaction gives similar colour changes. The substance C H3402 obtained from the chloroform filtrate from the preceding substance crystallises from a mixture of acetone and alcohol in stout hexagonal plates or from ether in thin needles m. p. 196-197O in a closed capillary tube; this gives with Lieber- mann’s and Liebermann-Burchard’s reactions colour changes similar to those described above. The peridium contains also large amounts of mannitol which is found only in small quantities in the hymenium.The hymenium yields small amounts of substances which give colour changes resembling those of ergosterol. G. Y.46 ABSTRACTS OF CHEMICAL PAPERS. Investigations on the Properties of Wheat Proteids. JOSEPH S. CHAMBERLAIN (J. Amer. Chena. Soc. 1906 28 1657-1667)- Osborne and Voorhees (Abstr. 1893 i 741) have stated that wheat contains five proteids namely gliadin glutenin an albumin a globulin and a proteose. The gliadin and glutenin together con- stitute about SO-SS0/ of the total proteids ; the former is soluble in 70% alcohol whilst the latter is insoluble. The three other proteids are soluble in dilute salt solutions. It is now found that on extracting air-dry wheat or flour with cold 70°/0 alcohol the gliadin is removed together with a large part of the proteids which are soluble in saIt solutions and i t is therefore necessary that a correction should be made for the latter when quantitative separations are attempted.Potassium sulphate solution (5%) eEects the same extraction as sodium chloride solution and has the advantage that the evolution of hydrogen chloride in the Kjeldahl operation is obviated. Dry gluten from wheat flour consists of about 75°/0 of proteids and 25°/0 of non-proteids. Of the total proteids present in the wheat itself about 60-65°/0 are retained in the gluten whilst 35-40°/0 are lost in the washings this loss being at the expense of gliadin or glutenin. For these reasons it is considered that the estimation of gluten is incapable of yielding any information which cannot be obtained by the estimation either of the total proteids or of those which are soluble in alcohol and those which are insoluble.E. G. Nature of the Phosphoric Acid Compounds in Barley and their Changes during Brewing Processes. WILHELM WINDISCH and W. VOGELSANG (Ckem. Cerhtv. 1906 ii 1573 ; from Toch. Brau. 23 5 16-5 19).-Barley does not contain any inorganic phosphate. During germination the organic phosphoric acid compounds are decomposed. The breaking up of the phosphoric acid compounds in malt is attributed to enzyme action. N. H. J. M. Proteids of Barley in the Grain and During the Brewing Process. HENRIK SCHJERNING (Chem. Centr 1906 ii 1209-1 210 ; from Compt. rend. Lab. CccrZsberg 6 229-307).-The amount of proteids in barley grain does not always indicate the quality.The size of the grain seems to some extent to depend on the duration of the growing and ripening period. The transformation of soluble nitrogenous compounds into insoluble substances is more rapid when the period of development is short than the assimilation of nitrogen and the prodtiction of soluble proteids from amides is intensified. Proteoses are exclusively products of the hydrolytic breaking down of higher proteids and any marked amount of proteoses in barley grain is evidence of a very unfavourable crop. Loss of dry matter during storage is unlikely when the conditiors of storage are suitable and when the grain has reached the right degree of ripeness before cropping. The composition of the dry matter of the grain as regards the various groups of nitrogenous substances mineral matter and acid compounds soluble in water is independent of the variety and type ofVEGETABLE PHYSIOLOGY AND AGRICULTURE. 47 barley.Climatic conditions affect the amounts of ash constituents total nitrogen and amides but have less influence on the other nitrogenous constituents the amounts of which depend rather on the degree of ripeness and time of storage. Influence of the Ash Constituents of the Lower Portions of Oat Stems on the Falling of the Stems. D. LIENAU and ALBERT STUTZER (Landui. Vemuchs-#tat. 1506,65 253-263. Compare Lienau Inaug. Diss. Konigsberg 1903).-According to Wieler (Bot. Zeit. 1889 32) and Wolff (Prakt. Diingerlehre? 1886,158) phosphoric acid has the effect of strengthening straw whilst much nitrogen and potassium cause softening ; Guffroy (J.d’dgric. prat. 1901 i 65) found that the cell-walls become thin under the influence of nitrogen whilst phosphoric acid has the opposite effect. The results of anatomical and chemical investigations with oat straw grown on variously manured plots showed that phosphoric acid is the manure which most promotes the thickening of the cell-wall and that its effect is greatly lessened when much potassium or calcium is applied along with it. Large amounts of potassium or nitrogen reduce the thickness of the cell-walls nitrates having more effect than ammonium salts. The amounts of total ash and potassium are increased by manuring with large amounts of potassium nitrogen and calcium whilst phos- phoric acid in many cases reduced the total ash and potassium The amount of phosphoric acid in the straw does not depend on the amount applied as manure but is increased by large applications of potassium calcium and nitrogen.The calcium in the straw is increased by ammonium salts and diminished by phosphoric acid. The amounts of sodium iron and silicon seem to have no relation to the manuring. The thickening of cell-walls is greatest the less the amounts of total ash and potassium. The relations as regards calcium and phosphoric acid remain to be ascertained. Amounts of Potassium and other Important Constituents in Various Grasses. ALBERT STUTZER (Landw. Versuchs-Stat. 1906 65 264-274).-Determinations of dry matter nitrogen potassium calcium .phosphoric acid and silica in a number of grasses grown i n soil in pots without manure with phosphoric acid both alone and in conjunction with potassium and with potassium and nitrogen.The effect of phosphoric acid on the yield was very slight except in the case of Alopecurws pratensis Avena javescens and Aiathoxantum odoraturn. The grasses were able to assimilate considerable amounts of potass- ium although the soil contained very little soluble in cold hydro- chloric acid. The greatest amount was taken up by Dactylis glomerata which with Phalai-is umndinacea also acquired the greatest amount -of nitrogen (from the unmanured plot). The amounts of calcium are small as compared with potassium and Pot Experiments with Soils Containing Copper.ALBERT STUTZER (Landw. Versuchs-Stat. 1906 65 285-288).-TrifoZizcm N. H. J. M. N. H. J. M. nitrogen. N. H. J. M;48 ABSTRACTS OF CHEMICAL PAPERS pannorticum was grown in pots containing 10 kilos. of a mixture of sand and garden soil with addition of calcium carbonate (100 grams) and mineral manures. Two pots received finely-powdered copper (10 grams and 1 gram) two the same amounts of powdered copper oxide and two no copper. No injury was observed except in the case of the pot which had 10 grams of copper oxide; the plants of this pot failed in part and those which grew at all remained small. No copper could be detected in any of the plants or roots. It is therefore doubtful whether TgifoZiurn pannonicum is a plant which takes up relatively large amounts of copper as has been stated.Soil which contains much copper is to be regarded as permanently sterile. N. H . J. Iul. Nitrogenous Nutrition of Agricultural Plants. E. WEIN (Chem. Centr. 1906 ii 1454; from Verh. Ges. Deut. Naturf. k’rxte 1905 ii 11 9-123).-The results of field experiments showed that calcium cyanamide is a t least equal in value to ammonium sulphate. On peat soil containing much calcium carbonate both calcium cyanamide and sodium nitrate gave good results whilst ammonium sulphate caused a diminished yield. N. H. J. M. Pot Experiments on the Action of Calcium Cyanamide. ALBERT STUTZER (Landw. VersuclwStut. 1906 65 275-282).-Pot experiments are described in which rye was manured with calcium cyanamide ammonium sulphate and sodium nitrate respectively.Subsequently mustard was grown three times in the same pots without further manuring. When the amount of nitrogen applied was 0.5 gram per pot (16 kilos. of soil) 68*4°/0 of the ammonia nitrogen was recovered in the plants 65*9’/ of the calcium cyanamide and 55-2’/ of the nitrate. The last result is attributed to loss of nitrogen in the winter the sodium nitrate having been applied in the autumn. N. H. J. M. Employment of Thiocg anates as Manure. RENATO PEROTTI (Chem. Centr. 1906 ii 1282 ; from- Stux. sper. ugrar. itaZ. 39 193-21 2).-The manure ‘‘ sulphocyanide ” contains total N 5.06 ; N as ammonia 1.66; K 2.28; Ca 1-73 ; P,O 0.8 ; SO 2.01 ; total S 23*89’/,. It contains about 4.5’1 of ammonium thiocyanate but no potassium thiocyanate. It is nearly completely and fairly quickly decomposed in the soil without loss. N. H. J. M. Action of Wolter’s Phosphate. ALBERT STUTZER (Lundw. Versuchs-Stat. 1906 65 283 -284).-Pot experiments with hemp manured with equal amounts of phosphoric acid in the forms of superphosphate and Wolter’s phosphate showed that the two manures are about equal. N. H. J. M. Amount of Chlorine in Rain Water. WILLEM P. JORISSEN (Chern. Cmtr. 1906 ii 1579; from Chem. WeekbZud 3 647-649. Compare Abstr. 1906 ii 486).-As the result of 154 more analysesANALYTLCAL CHEMISTRY. 49 of rain water if is found that the average amount of chlorine is 32.5 mg. per litre. The author also quotes analyses of 121 samples of rain water collected in casks. P. H.

ISSN:0368-1769    

DOI:10.1039/CA9079205043

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

ANALYTtCAL CHEMISTRY. 49 Analytical Chemistry. Improved Eudiometar ; its Application to Measuring I Fire- damp. Detection and Estimation of Methane and Carbon Monoxide. NESTOR GRBHANT (Compt. rend. 1906 143 813-815). -A modification of the eudiometer consists in the employment of a fine platinum wire heated by an electric current to fire the gases ; the wire is supported on two copper terminals which pass through a rubber stopper closing the eudiometer tube. The presence of lolo of methane in air can be measured with an accuracy of 92°/0 in an eudiometer of this form by passing the current 400 t o 600 times. Comparative experiments conducted on rabbits on the poisonous action of small quantities (1 5000 or 1 10,000) of carbon monoxide in air show that the amount of carbon monoxide absorbed by the blood becomes constant after five hours (compare Abstr.1900 ii 95). M. A. W. Standardisation of Normal Solutions [Acids and Alkalis] ; Note on the Zeiss Immersion Refractometer. B. WAGNER A. RIKCK and F. SCHULTZE (Ch,em. Zeit. 1906 30 1181-1183).-The acid hydrochloric acid for instance is first tested by Lunge's sp. gr. process. It is then titrated by means of standard potassium hydr- oxide free from impurities and the liquid is evaporated to dryness with the usual precautions. The residual potassium chloride is weighed and the result represents the amount of hydrogen chloride. The sp. gr. and the titration results serve a s a useful check. A further check may be made by testing the acid or alkali or the resulting potassium salt in the Zeiss immersion refractorneter.The authors have const,ructed a new table for nitric acid at 17.5" and other tables are in course of construction. When using this instru- ment it is of fundamental importance that the temperature should be 17.5" exactly and a new warming arrangement and special thermo- meters should therefore be used for a description of which the original paper and drawings must be consulted. L. DE K. Use of Alkaline Mercuric Iodide Solution as an Oxidising GYSBERT ROMIJN (Ber. 1906 39 Agent in Volumetric Analysis. 4133).-A claim for priority (compare Rupp Abstr. 1906 ii 902). A. McK. VOL. XCII ii 450 ABSTRACTS OF CHEMICAL PAPERS. Detection of Traces of Water. F. SCRIBA (Chem. Centr. 1906 ii 1458; from Zeit. phys. chem. Unterr. 19 298).-A test paper is made by soaking strips of filter paper in a 5"10 solution of ferrous ammonium sulphate; the dried paper is then sprinkled over with finely-powdered potassium ferricyanide.The most minute drop of water produces a blue spot. L. DE K. Estimation of Halogens in Carbon Compounds by Means A. STEPANOFF (Bey. 1906 39 of Sodium and Ethyl Alcohol. 4056-4057).-See Abstr. 1905 i 335 Estimation of Sulphur in Pyrites. Chern. 1906 19 1854-1855).-Polemical GEORCI LUNGE (Zeit. anyew. A reply to Drepnstedt and Hassler (Abstr. 1906 ii 896). L. DE K. Estimation of Sulphur Existing as Zinc Sulphate in Roasted Blendes. V. HASSREIDTER (BUZZ. Xoc. chim. BeZg. 1906 20 163-164).-Zinc sulphate contained in roasted zinc ores may be extracted with water and the zinc titrated as usual 1 part of zinc= 0.492 part of sulphur Insoluble basic zinc sulphate is also present in the roasted ore but in negligible quantity.L. DE K. [Kjeldahl] Ammonia Distillations with or without Cooling Arrangement. ERNST PESCHECK (J. Land. 54 [ iv] 367-384)- Equally satisfactory results may be obtained in the Kjeldahl process either with or without the use of a cooling arrangement if only care be taken to have the condenser made of glass poor in alkali (Jena glass). Loss of ammonia may be prevented as follows the liquid in the distilling flask should occupy about 300 c.c. the amount of sodium hydroxide added should not be excessive the acid in the receiver should be diluted to 100-150 c.c. and the delivery tube which a t the lower end should have a diameter of 0.5 cm.should reach almost to the bottom of the acid. If no cooling arrangement is used the acid in the receiver is considerably heated and must be allowed to cool before it can be titrated; this however depends on the nature of the indicator used 1,. DE K. Estimation of Nitric Acid in Soils. ERNST GUTZEIT (Lalndw. Yersuchs-Stat. 1906 65 2 17-2 19). -Precipitation of the humus present in soil extracts before estimating nitrates by reduction does not cause high results as stated by Buhlert and Fickendey (Abstr. 1906 ii 125). It was found that results obtained with solutions from which the humus had been precipitated were considerably lower (37O/,) than those obtained with the original solutions containing humus. N. H. J. M. Eatimation of Phosphoric Acid by Woy's Method.(x. B. VAN KAMPEN (Chrn. Centr. 1906 ii 1357 ; from Chern. Weekbkctd 3,376-379),-The author confirms the accuracy of Woy's gravimetrioANALYTICAL CHEMISTRY. 51 process (weighing as 24M00,,P,05) but equally good results are obtained by the volumetric molybdate method. L. DE K. Moisture in Goal. E. E. SOMERMEIER (J. Amer. Chem. Xoc. 1906 28 1630-1 638).-This apparently simple determination only gives trustworthy and concordant results when careful attention is paid to the following points. It is absolutely necessary that care be taken t o prevent changes in moisture in the coarse sample during transit. The fine sample for chemical analysis should be in nearly an air-dry con- dition. The air of the drying-oven should be of a uniform dry con- dition and the dried sample should be cooled in a desiccator over sul- phuric acid.L. DE K. Estimation of Moisture and Volatile Matters in Goals. HENRI PELLET and ALBERT ARNAUD (Ann. Chim. anal 1906 11 428-431).-Moisture.-Having made a series of experiments the authors conclude that the moisture in coals may be determined equally well by heating 2 grams of the powder for fifteen minutes a t 100-105° and drying for an hour at go’ or by placing the sample in a desiccator over sulphuric acid for forty-eight hours a t 25-28’. Volatile Matters,-l’mo grams oE the sample are heated rapidly in a small platinum crucible provided with a suitable lid; when the flame ceases the heating is continued for another three minutes. A correction should be applied for carbon oxidised by the air inside the crucible generally 2 or 3 mg. This may be determined readily once for all by reweighing the coke several times after a six minutes’ re-ignition thus obtaining the average loss due to oxidation. L.DE K. Estimation of Carbon Dioxide alone or in Admixture with Hydrogen Sulphide or Chlorine. GEORG LUNGE and AUUUST RITTENER (Zeit. angew. Chern. 1906 19 1849-1852),- Combined carbon dioxide is liberated as usual with hydrochloric acid over brine in presence of a little aluminium the gas is collected in a gas burette and the volume of carbon dioxide estimated as usual by means of aqueous sodium hydroxide. Waste gases are passed through the burette and treated similarly. If hydrogen sulphide should be pre- sent the gas is distributed in two burettes ; in one of these the joint volume of carbon dioxide and hydrogen sulphide is found by absorp- tion and in the second one a known volume of standard iodine is introduced which is then titrated with sodium thiosulphate as usual ; the weight of the hydrogen sulphide thus found is then reduced to volume.In presence of chlorine the last traces of carbon dioxide are ex- pelled from the liquid by boiling with a little hydrogen peroxide. The joint carbon dioxide and chlorine are then found by absorption and the chlorine in the alkaline liquid is estimated by the arsenic titration process. L. 1)E K. 4-252 ABSTRACTS OF CHEMICAL PAPERS. Detection of Barium Strontium and Calcium. STANLEY R. BENEDICT (J. Amer. Chem. Xoc. 1906? 28 1596-1598).-The method is based on the fact that barium and strontium solutions are pre- cipitated completely. by excess of potassium iodate; the latter pre- cipitate however is soluble in dilute hydrochloric acid.A few C.C. of the neutral solution are mixed with half the volume of 5N-hydrochloric acid and to the mixture is added an equal volume of saturated solution of potassium iodate. An immediate precipitate indicates barium; a precipitate forming but very slowly may be due to strontium and in such a case the presence or absence of barium should be confirmed in a portion of the original solution with potassium dichromate. The filtrate is then tested for strontium by boiling the last portion of it with an equal volume of saturated ammonium sul- phate solution. Another portion of the original neutral solution is then mixed with twice its volume of potassium iodate and after a minute or so the filtrate is tested for calcium with ammonium oxalate and a drop of ammonia.L. DE K. Separation of Barium Strontium and Calcium. CARON and RAQUET (Bull. Xoc. citim. 1906 [iii] 35 1061-1069).-The mixed carbonates separated in the usual way by the group reagent are dissolved in excess of acetic acid the solution boiled and from this the barium is precipitated by the addition of a solution containing To the filtrate ammonia solution is added until the liquid assumes a pale yellow colour and has a distinctly ammoniacal odour ; strontium chromate is then pre- cipitated unless only small quantities are present when it is necessary to add alcohol (60-70°). To the filtrate from this potassium ferro- cyanide is added when potassium calcium ferrocyanide is precipitated ; a t once if a considerable quantity of calcium is present but only on warming if the amount present is small.By this method 0.001 gram of barium chloride can be detected in pre- sence of 0.5 gram of strontium chloride or calcium chloride the two metals being precipitated in the first instance as carbonates. If the reagerhs are applied directly to a solution containing both chlorides one part of barium chloride can be detected in presence of 8000 parts of strontium chloride. A critical &sum8 of other methods in use for the separation of these three elements is given. of ammonium chromate and 5O/ of acetic acid. T. A. H. Separation and Estimation of Glucinum. CHARLES L.PARSONS and S. K. BARNES (J. Amer. Chem. Soc. 1906 28 1589-1595).-The authors have found that glucinum may be separated quantitatively from iron and aluminium by heating the neutrdised solution to boiling with excess of sodium hydrogen carbonate; lo"l0 of the solid salt should be added which causes the precipitation of the iron and aluminium and leaves the glucinum in solution. The precipitateANALYTICAL CHEMISTRY. 53 must be freed from any glucinum hydroxide by redissolving in hydro- chloric acid neutralising with ammonia and reprecipitating with sodium hydrogen carbonate. From the mixed filtrate the glucinum is recovered by adding excess of hydrochloric acid boiling and precipitating with ammonia. The precipitate is washed with a solution of ammonium acetate ignited and weighed L.DE K. Quantitative Separation of Glucinum and Aluminium. CARL FRIEDHEIM (Bey. 1906 39 3868-3869).-The method described by Glassmann (Abstr. 1906 ii 902) Bas been used previously by Joy (J. p ~ . Clwm. 1864 [i] 92 235) and also by Zimmermann (Abstr. 1888 323). J. J. 5. A Highly Sensitive Method of Precipitating Zinc. GABRIEL BERTRAND and MAURICE JAVILLIER (Compt. rend. 1906 143 900-902).-Zinc is precipitated in the form of sparingly soluble highly refractive crystalline hydrated calcium zinc oxide Ca(O*Zn*OH)2,4H,0 (Bertrand Abstr. 1893 ii l l S j when a very dilute solution of a zinc salt containing 'calcium hydroxide is boiled with excess of ammonia. and this reaction can be employed for the estimation of one part of zinc in 500,000 parts of water.For this purpose 500 C.C. of the solution is mixed with a few C.C. of dilute milk of lime or 50 C.C. of lime water and 10 to 15'10 of concentrated ammonia solution filtered and then boiled until alkaline vapours are no longer evolved; the precipitate of calcium zinc oxide and calcium carbonate is collected on a small filter dissolved in hydrochloric acid the solution evaporated to dryness the residue taken up with a little water and the calcium precipitated as the oxalate in the presence of excess of ammonia. By evaporating and igniting the filtrate in the presence of sulphuric acid the zinc is obtained and can be weighed in the form of the sulphate or in cases where the amount of zinc 'is too small to admit of estimation its presence can be detected by dissolving the residual sulphate in water and adding hydrogen sulphide or potassium ferrocyanide solution.It is essential that all the reagents employed shall be free from zinc and the result of each experiment must be corrected for errors introduced by the slight solubility of calcium oxalate and of glass in water by subtracting from the weight of the zinc sulphate the weight of the residue obtained in a control experiment. M. A. W. Influence of Ammonia and Ammonium Salts in the Schaffner Zinc Titration. ALPHONSE DECKERS (BUZZ. Xoc. chim. BeZg. 1906 20 164-166).-Experiments showing that the accuracy of the Schaff ner process (titration with sodium sulphide) is seriously affected by the amount of free ammonia and ammoniacal salts present in the liquid. I n order to obtain trustworthy results the comparison liquid should therefore contain the same amount of ammonium54 ABSTRACTS OF CHEMICAL PAPERS.compoundp. Owing to the action of these salts on the zinc sulphide they should not be introduced too liberally. L. DE K. Quantitative Estimations of Metals by Electrolysis. FRITZ FOERSTER (Zeit. arzgew. Chern. 1906 19 1842-1849 1889-1895).- A lengthy review of the subject dealing principally with the electrolytic estimation of nickel zinc cadmium and copper. A large number of tables and formula are given. The use of wire gauze electrodes is strongly recommended. L. DE K. Volumetric Estimation of Copper by means of Potassium Iodide. H. CANTONI and M. ROSENSTEIN (BUZZ. Soc. chim. 1906 [iii] 35,1069-1073).-1t is shown that the results obtained by this method are not influenced by the quantity of potassium iodide added and are but little affected by the presence of potassium sodium ammonium zinc or magnesium sulphate whilst the results are considerably modified by the presence of varying amounts of water or acetic acid.The method gives excellent results when carried out under certain well-defined conditions and it is indispensable that the solution of sodium thiosulphate employed should be standardised under conditions similar to those which will hold when the actual determination is being made and that the solution of iodine should be standardised with reference to the particular type of copper salt which i t is proposed to estimate with it. T. A. H. Solubility of Iron in Vinegar.W. HOFFMANN (Chem. Cent?'. 1906 11 1368-1369; from Deut. Essigind. 10 306).-Iron is decidedly soluble in vinegar communicating a green colour to maIt vinegar and a yellow or red colour to distilled vinegar. This iron interferes with the ordinary titration of samples which should there- fore be submitted to distillation L. DE K. [Estimation of] Chrome and Acid in Chrome-tanning Liquors. F. W. ALDEN (Chern. Centy. 1906 11 1460; from J. Amel.. Leather Chem. ASSOC. 1 174).-A quantity of the liquor sup- posed to contain 2-3 grams of chromic oxide is diluted with water to 500 C.C. Ten C.C. are then diluted with 15 C.C. of water and 2 grams of sodium peroxide are added. After boiling for a very-short time excess of hydrochloric acid is added and the chromate formed is then titrated as nsua.1 with potassium iodide and sodium thiosulphate.The combined acid is estimated by adding 50 C.C. of the liquor to a boiling solution of 50 C.C. of N/2 sodium carbonate diluted with 150 C.C. of water and diluting when cold to 500 C.C. Two hundred C.C. of the fil- trate are then titrated back with N/2 hydrochloric acid. L. DE K. Conditions of Quantitative Precipitation of Uranium Per- oxide. ARRIGO MAZZUCCHELLI ( A t t i R. Accad. Limei 1906 [v] 15 ii 429-438 and 494-500 Compare Fairley Trans. 1877 127; Melikoff and Pissrtrjewsky Abstr. 1898 ii 165).-The author hasANALYTICAL CHEMISTRY. 55 studied the conditions under which uranium peroxide UO is pre- cipitated quantitatively from solutions of uranpl salts by means of hydrogen peroxide.The solubility of uranium peroxide expressed in grams of UO per litre of solution is (1) in water 0*0061 at 20' and 0.0084 at 90° and (2) -in N/10 ammonium chloride 0.0053 at 20° and 0*0088 a t 90'. I n presence of free acetic hydrochloric or nitric acid the precipita- tion of uranium peroxide from solutions of uranyl salts by hydrogen peroxide is incomplete the amount remaining in solution depending on the extent of dissociation of the acid. When free sulphuric acid is present the precipitation is slight in amount and slow probably owing to abnormal ionisation of the uranyl sulphate. Hence the acidity of the solution should only be slight and sulphuric acid should be absent. I f the solution contains ammonium chloride (best in about N-concentra- tion) the precipitated uranium peroxide is easily filtered and washed ; the washing liquid should be N/10 ammonium chloride.A tempera- ture of not above 70" and an excess of the hydrogen peroxide accelerate the precipitation. Moderate amounts of the chlorides sulphates and nitrates of the alkali metals or ammonium do not interfere appreciably with the pre- cipitation of uranium peroxide but acetates fluorides oxalates or tartrates hinder it to a greater or less extent. Large proportions of the chlorides of the alkaline earth metals prevent the precipitation in some degree which is however diminished by the addition of ammonium chloride. The anion present in uranyl salts may be estimated by adding a slight excess of hydrogen peroxide and titrating in presence of the precipitate with sodium hydroxide or ammonia solution using phenol- phthalein as indicator; the liquid assumes an orange colour when alkaline T.H. P. Nitrogenous Compounds and Silica in Sea-water. WILHELM E. RINGER (Chem. Centr. 1906 ii 1459; from Chem. Teekbkad 3 585-608).-Raben's process is recommended. The sample must be examined without delay; otherwise it should be preserved by addition of 0*1"/ of mercuric chloride. One hundred C.C. are distilled with a few drops of acetic acid and the distillate is examined colorimetrically for nitrous acid (phenylenediamine test). One gram of magnesium oxide is then added and the free ammonia collected and determined by the Nessler test. The residue may then be tested for nitrate by reducing it with aluminium foil and sodium amalgam and Nesslerising the ammonia formed.Silica is estimated in the usual manner by evaporating 3 litres of the sample with hydrochloric acid in a platinum dish and taking up the residue with dilute acid. L. DE K. Estimation of Manganese in Drinking Waters. JOHANNES PBESCHER (Chem. Centr. 1906 ii 1458 ; from Pitarm. Centr.-Ha& 799-802).-The residue obtained from 1 litre of water is treated56 ABSTRACTS OF CHEMICAL PAPERS. with nitric acid and potassium chlorate (Hampe’s process for estimat- ing manganese in iron) and the resulting manganese dioxide is titrated as usual with standard oxalic acid and potassium permanganate. L. DE I(. Detection of Small Quantities of Dextrose in Urine. CE. PORCHER (Chem. Centr. 1906 ii 1362; from Bull. Assoc. Chim. Sucr. Dist.24 155-159).-The sample is precipitated with mercuric nitrate then neutralised and diluted to ten times its volume. The excess of mercury is removed by zinc dust or hydrogen sulphide the filtrate is evaporated in a vacuum to a small bulk the residue is mixed with excess of alcohol and the filtrate evaporated in a vacuum. The residue is then tested for dextrose by the usual phenylhydrazine method (osazone reaction). An excess of this reagent should be avoided. L. DE K. Laevulosuria. Detection of Lmvulose in Urine. ADOLF JOLLES (Arch Pharm. 1906 244 542-549).-L;levulose may occur in urine alone as well as in conjunction with dextrose. Lmdose is detected by adding to 10 C.C. of the urine a little resorcinol and about 3 C.C. of lOo,l0 hydrochloric acid and heating to boiling ; an immediate red coloration indicates kevulose (Seliwanoff’s reaction).For the estimation of lzevulose Ost’s method (Abstr. 1891 125) is the best. The urine is boiled with a solution of copper sulphate in aqueous potassium carbonate and potassium hydrogen carbonate and the precipitate is reduced to metallic copper and weighed. If dextrose is present a polarimetric determination is made also the urine being first clarified with normal lead acetate; from the results of the two experiments the amounts of dextrose and lzevulose can be calculated. The method of calculation is exemplified in the paper and some test analyses are given. C. F. B. Separation of Starch and Glycogen. EMIL BAUR and EDUARD POLENSKE (Chem. Centr. 1906 ii 1360-1361 ; from Arbb. Kais.Ges. A. 24 576-580).-Estimution of the Slarch.-A few decigrams of the mixture of starch and glycogen obtained from sausages are dissolved in 30 C.C. of water and 11 grams of powdered ammonium sulphate are added. This precipitates the starch which is washed first with a solution of ammonium sulphate of the same strength and then with proof spirit. The aqueous filtrate (60 c.c.) contains the glycogen which may be recovered by adding 300 C.C. of water and 500 C.C. of alcohol. Estimation of Glycogen in Meat.-A modification of Mayrhofer’s process. Sixty grams of meat are treated with alcoholic potassium hydroxide the hot liquid is mixed with 100 C.C. of prJof spirit and the crude glycogen is collected. It is washed first with alcoholic potassium hydroxide (80 grams in 1 litre 90% alcohol) and then with 90% alcohol until the filtrate is no longer rendered turbid by hydro-ANALYTlCAL CHEMISTRY I 57 chloric acid.The precipitate is then dissolved in 50 C.C. of N-aqueous potassium hydroxide and when cold acidified with acetic acid and diluted to 110 C.C. From the filtrate the glycogen is precipitated by addition of alcohol collected in a Gooch crucible and washed first with 70°/0 alcohol then with absolute alcohol and finally with ether. After weighing any mineral impurity is found by incineration. L. DE K. Methods of Determining Esters Aldehydes and Furfur- aldehyde in Whisky. LUCIUS M. TOLMAN and T. C. TRESCOT (J. Amer. Chem. Xoc. 1906,28,1619-1630)-A lengthy investigation as to the merits of the various procasses recommended for the estima- tion of esters aldehydes and furfuraldehyde in whisky.All these processes give unsatisfactory results unless applied t o the distillates when the whisky is coloured with caramel. For further particulars the original paper and tables should be consulted. L. DE K. Estimation of Soluble and Insoluble Volatile Fatty Aoids [in Butter]. J. DELAITE and J. LEGRAND (Bull. Soc. chim. Belg. 1906 20 230-233).-The glycerol-soda saponification process is not safe in practice as the soluble volatile fatty acids decrease on slightly prolonged heating whilst the insoluble volatile acids increase. When saponifying with alcoholic potassium hydroxide the boiling should not be prolonged to more than half an hour as shown by the following experiment. After boiling for fifteen minutes the Reichert-Meissl figure of a butter was found to be 30.03; after thirty minutes 30.14; after forty-five minutes 30.58 ; after an hour 31.98 ; after two hours 34.89 and after five hours 46-53.L. DE K. Rapid Method for Estimating Citric Acid in Lemon Juice. CELSO ULPIANI and A. PARROZZANI (Atti R. Accad. Zinc& 1906 [v] 15 ii 517-518).-This method is based on the fact that in a cold solution of citric acid containing calcium chloride sodium hydroxide produces a precipitate when the total acidity is neutralised whilst if the liquid is hot precipitation takes place when only one-third of the acidity is neutralised. After the total acidity of the juice has been estimated approxi- mately by titration with N-sodium hydroxide 50 C.C. of the juice are placed in a 200 C.C.flask together with sufficient N-sodium hydroxide solution to neutralise about one-tenth of the acidity ; the latter value represents the maximum proportion of tartaric and oxalic acids which are hence precipitated after the liquid is boiled (wide irLfra). About 17 grams of calcium chloride and 5 grams of animal charcoal are added to the solution which is then boiled cooled made up to volume and filtered. The following estimations are made in the filtrate (1) to 60 c.c. N-sodium hydroxide solution is added in the cold until a faint permanent turbidity appears; (2) another 50 C.C. is boiled and58 ABSTRACTS OF CHEMICAL PAPERS. N-sodium hydroxide solution is run in until a permanent turbidity appears. The difference between the volumes of sodium hydroxide solution used in (1) and (2) represents two-thirds of the citric acid free and combined present in the juice. T.H. P. Estimation of Salicylic Acid in Canned Tom&oes Cat- sups &c. WILBUR L. DUBOIS (J. Arner. Chem. SOC. 1906 28 1616-1619).-The following method has been adopted finally by the author fifty grams of the pulped tomatoes are transferred t o a 200 C.C. flask containing 50 C.C. of water the mixture is neutralised with ammonia and 15 C.C. of milk of lime (1 lOj are added. The whole is diluted to the mark well shaken and filtered. 150-160 C.C. of the filtrate are acidified with hydrochloric acid and extracted four times in succession with 75-100 C.C. of ether. After washing the mixed ethereal extracts twice with 25 C.C.of water the ether is recovered by distilling slowly until about 20-25 C.C. are left which are then left to evaporate spontaneously. The residue is dissolved in hot water and when cold diluted to a definite bulk. The salicylic acid is then estimated colorimetrically in the usual manner with ferric alum solution. L. DE I(. [Assay of] Sodium Salicylate. FRANK H. ALCOCK (Pharrn. J. 190G 597).-0.5 gram of the sample and 0.5 gram of ammonium chloride are dissolved in 10 C.C. of water and evaporated to dryness in a platinum dish. During this operation ammonia is evolved and also salicylic acid together with any phenol if present. The residue is now gently ignited and the mass which consists of sodium chloride is then dissolved in water and titrated with N/10 silver nitrate of which 31.2 C.C.should be required. An allowance should of courge be made for any chloride pre-existing in the sample L. DE K. Estimation of Humus Acids in Soils by Tacke’s Method. C. I(. VAN DAALEN (Chem. Centr. 1906 ii 1468. Compare Tacke Abstr. 1898 ii lO3).-The difficulty of the method is attributed t o the slow evolution of carbon dioxide and to the complexity of the reactions which cannot be represented as the result of a single reaction. N. H. J. M. Estimation of Fatty M a t t e r in Butter. A. FROEHNER (Chem,. Zeit. 1906 30 1250-1251).-0*63 gram of the sample is melted preferably in a graduated tube with 10 C.C. of water t o remove the salt 10 C.C. of alcohol are added then 25 C.C. of ether and the whole is well shaken. The shaking is now repeated after addition of 26 C.C.of benzene. When the aqueous layer has separated 25 C.C. of the ethereal layer are withdrawn and evaporated in a weighed dish. I n calculating the amount of fat the total volume of the ethereal solution may be taken as 52.8 C.C. (52.3 C.C. + a correction of 0.5). The salt may be titrated in the aqueous solution in the usual manner. L. DE K.ANALYTICAL CHEMISTRY. 59 The Examination of Wool-fat. W. HERBIG (Chem. Rev. Feett. Ham. Ind. 1906,13,303-304).-Concordsnt results may be obtained in the estimation of the saponification number of wool-fat by dis- solving the latter in light petroleum before boiling with the alkali. The figures obtained tend to be higher than those yielded by the ordinary process but are constant between themselves for each parti- cular sample.The increase in the saponification number observed on boiling the fat and alkali mixture for a long time is not due to the action of the alkali on the higher alcohols present. w. P. 8. Constants of' Carnauba Wax. LIONEL G. RADCLIFFE (Phurm J. 1906 596-597).-A sample of the pure unbleached wax gave the following result m. p. 84' ; acid number 2.9 ; saponification number 88.3 ; ether number 85.4; iodine number 13.17. The free acidity was found as usual by boiling with absolute alcohol and titrating with Nj20 aqueous potassium hydroxide. The saponifica- tion number was found by boiling with a mixture of redistilled amyl alcohol and alcoholic potassium hydroxide for several hours and titrating the excess of the latter. The iodine number was obtained by dissolving the sample in chloroform and treating with Wijs's reagent (iodine monochloride in glacial acetic acid) ; the original Hub1 solution was almost inactive.L. DE K. Estimation of Camphor [in Celluloid]. ALOIS ARNOST (Zeit. Nahr. Genussm. 1906 12 538-539).-In the method described the camphor is obtained in alcoholic solution which is shaken with light petroleum and acidified water; the increase of the volume of the light petroleum is equivalent with certain corrections to the quantity of camphor present. Ten grams of the finely-rasped celluloid are agitated for one hour in a flask with 100 grams of 25O/ sodium hydroxide solution. The flask is then connected with a condenser and its contents heated to a temperature of about 80' until homogeneous By increasing the heat the camphor is volatilised into the condenser and is carried over into the receiver (a 100 C.C.flask) by adding Eeveral successive small quantities of alcohol to the distillation flask. The distillate is diluted to 100 C.C. with alcohol and the camphor estimated as follows 90 C.C. of water acidified with sulphuric acid are placed in a bulb-shaped vessel the neck of which is graduated showing each 0.05 C.C. from 98 C.C. to 100 C.C. ; the bulb holds exactly 90 c.c. and the part of the neck between the 90 C.C. and 98 C.C. marks is widened out into a small bulb. Above the graduated neck is an upper pear- shaped bulb provided with a short neck which may be closed with a stopper. Ten C.C. of the alcoholic camphor solution are next intro- duced into the apparatus and then 50 C.C.of light petroleum D 0.64-0.67. After closing the apparatus with an indiarubber stopper the contents are shaken for two minutes allowed to separate for half an hour and the increase of the volume of the petroleum read off all the readings being taken a t 15'. This increase is due to the extracted camphor and to the contraction caused by the mixing of the alcohol and aqueous layers. The quantity of alcohol actually present60 ABSTRACTS OF CHEMICAL PAPERS. is ascertained by transferring 50 C.C. of the aqueous portion to a flask adding an excess of sodium hydroxide and distilling the alcohol. The sp. gr. of the distillate when the latter has been diluted to 50 C.C. indicates the percentage of alcohol and the contraction due t o its presence is then found by reference t o tables The corrected increase of the volume of the light petroleam gives the voZume of the camphor in the 10 C.C.of solution taken for the estimation. Camphor has D:; 0.993 Contraction Tuble. Alc o h 01. c. c. 3 s o 0 4-00 5 -00 6 .OO 7.00 8.00 9 *oo 10.00 Water C.C. K 90. 91. 92. 93. 95. 96. 97. 98. 2 176 176 175 175 175 175 174 174 174 174 173 242 242 242 241 241 241 241 240 240 240 240 311 311 311 310 310 310 310 309 309 308 308 384 384 383 382 381 381 380 379 879 378 378 469 459 458 468 457 456 455 454 453 451 450 540 539 538 537 536 534 533 532 531 530 529 628 626. 624 621 618 616 614 613 612 611 610 717 715 713 711 709 706 704 702 700 698 696 The contractions are expressed in cubic millimetres. W.P. 5. Direct Estimation of [Quebracho] Tannin. H. FRANKE (Chem. Centr. 1906 ii 916-917 ; from Phurm. Centy.-Halle 47 599-604). -One hundred C.C. of an aqueous decoction of Quebracho wood or a solution of 0.2 gram of the tannin obtained from it by Korner's process (Ledermurkt 1897 No. 37) in 100 C.C. of water are heated to boiling with 50 C.C. of formalin; 25 C.C. of 25 per cent. hydro- chloric acid are added and the whole is heated for ten minutes longer. After half an hour the precipitate is collected washed with water alcohol and ether and dried a t 110'. Its weight x 0.9834 = que- brachotnnnic acid. L. DE K. Separation of Proteoses and Peptones from the Simpler Amino-compounds. WILLARD D. BIUELOW and F. C. COOK (J. Amer. Chem. Xoc. 1906 28 1485-1499).-Acomparison has been made of the action of the proteid precipitants tannin-salt solution and phospho- tungstic acid on amino-compounds such as glycine alanine crentine phenylenediamine and sarcosine both singly and in mixtures. It has been found that a satisfactory separation of proteosee and peptones from the simpler amino-compounds can be effected by means of a solu- tion containing 4 to 5 grams of sodium chloride and 15 grams of tannin in 100 C.C. The re- agent should be kept in a cool place and should not be left more than a few days before being used. An error is occasioned by the precipi- tation of a portion of the creatine by the reagent but this may be corrected by estimating the creatine in a portion of the solution before applying the reagent and in the filtrate from the precipitate given by that reagent. E. G. The precipitation is best carried out at 12".

ISSN:0368-1769    

DOI:10.1039/CA9079205049

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

61 General and Physical Chemistry. Spectroscopic Observations at Very High Temperatures. RAFFAELO NASINI and FRANCESCO ANDERLINI (Gazzetta 1906 36 ii 561-570).-With the help of Helbig’s carbon tube heated in an electric furnace the authors have examined the spectra of iodine and nitrogen at high temperatures. The former shows bands of a luminous spectrum distinctly at a temperature somewhat higher than 1000° and with nitrogen a luminous line and band spectrum is obtained at about 3000O. T. H. P. The Ultra-violet Phosphorescence Spectrum of Fluorspar. Variations in the Phosphorescence Spectrum of the same Element in the same Diluent. GEORGES URBAIN and C. SCAL (Compt. rend. 1907 144 30-32. Compare this vol. ii 3).-In fifteen specimens of fluorspar the presence of rare earths has been recognised by the appearance in their cathodic phosphorescence spectra of ultra-violet bands characteristic of gadolinium.On comparison of the gadolinium spectra of natural and synthetical fluorspar striking differences were observed in the intensity of bands of the same wave- length. These are due to the greater diminution in intensity of one group of bands as compared with that of the other group when the proportion of gadolinium is decreased. This was shown by preparing the fluoride from pure chalk and less than one-thousandth part of gadolinite; its spectrum is identical with that of natural fluorspar. This phenomenon is observed with other phosphorescent systems (compare Abstr. 1906 ii 138) and is termed the phenonaenon of dilution. E. H. Photochemistry and the Phase Rule.WILDER D. BANCROFT (J. Physical Chem. 1906 10 721-728).-The displacement of the equilibrium. in systems under the influence of light is considered from the standpoint of the phase rule. The variability of the intensity of the light introduces another degree of freedom. Strictly speaking there are as many degrees of freedom as there are kinds of active light but for most purposes a beam of light may be treated as though it were homogeneous. If the independent variables of a system are the n components the pressure the temperature and one kind of active light the coexistence of n + 3 phases will constitute an invariant system. Reference is made to the equilibrium between oxygen and ozone. For a given initial quantity of oxygen a t agiven pressure and temperature the equilibrium percentage of ozone is fixed if these are the only variables; it is not fixed however if ultra-violet light ia introduced as an independent variable.The case of the displacement of the equilibrium between two modifications of a light-sensitive substance in solution is also discussed. H. M. D. VOL. XCII ii. 562 ABSTRACTS OF CHEMICAL PAPERS. Radium. ALBERTO MAYORAL OLIVER (Anal. li”is. Quim. 1906 4 132-1 35).-Actinographs obtained by means of the rays from an incandescent lamp of 5-candle power were found to have blurred outlines whilst those produced by the agency of 5 mg. of radium bromide had sharply-defined contours. The blurring is regarded as an effect due to the secondary rays. BERTRAM B. BOLTWOOD (Amer. J.Sci. 1906 [ivj 22 537-538).-The fact that the experi- mentally determined rate of production of radium from uranium is very much smaller than that indicated by theory is supposed to be duo to the existence of a relatively slow-changing intermediate product and the author suggests that this is actinium. Measurement of the rate of production of radium emanation in the actinium separated from a kilogram of carnotite has furnished numbers from which the time required for the decay of the activity of radium to one-half its initial value is about 3300 years This is of the same order of magnitude as the most recent estimate made by Rutherford and this result is supposed to afford evidence in favour of the view that actinium is the intermediate disintegration product between uranium and radium.G . T. M. Production of Radium by Actinium. H. M. D. Radioactinium. OSKAR HAHN (Phil. Mctg. 1907 [ vi] 13 165-180. Compare Abstr. 1906 ii 323).-Radioactinium is a direct disintegration product of actinium and is the direct parent of actinium X . The transformation of actinium into radioactinium is rayless. The latter product emits only a-rays and is half transformed in about 19.5 days. The methods of separation employed for the isolation of radioactinium throw no definite light on its properties. J. C. P. The Supposed Derivation of Radium from Uranium. JOSE MuRoz DEL CASTILLO (Anal. Pis Quirn. 1906 3 60-64).-The experimental results obtained in the examination of the radioactive pyromorphite of Issy l’Ev&que the radioactive barytes of Carlsbad and the radioactive deposits of the thermal springs of Battaglia Baden- Baden and Nauheim (all of which materials are quite free from uranium) favour the view that radium thorium and uranium are three independent radioactive chemical elements.G. T. M. Relative Activity of Radium and Thorium Measured by the 7-Radiation. A. 5. EVE (Amer. J. Sci. 1906 [iv] 22 477-480. Compare Abstr. 1906 ii 593).-1t is found that radium is 6.9 x lo6 times as active as thorium when both are in radioactive equilibrium when the activity is measured by the y-rays. I n the preparation of the commercial salts of thorium about one-half of the radiothorium in the radioactive minerals is abstracted. By measurement of the y-activity it is found that the thorium and its products in thorianite is about 2.5 times as active as the thorium and its products in thorium nitrate.This result is in good agreement with those obtained by the a-ray method and by the emanation method.GENERAL AND PHYSICAL CHEMISTRY. 63 In consequence of the continued increase in the proportion of radiothorium commercial thorium nitrate cannot be used as a standard for 7-ray 4easureruent a8 was suggestod previously. H. 31. D. Velocity and Energy of the a-Particles from Radioactive Substances ERNEST RUTIIERFORD (PhiZ Mug. 1907 [ vi] 13 110-117. Compare Abstr. 1906 ii 719; Rutherford and Hahn ibid ).-The initial velocities of expulsion of the a-particles from the products of the radio-elements all lie between 1.56 x lo9 and 2.25 x 109 cm. per second. The a-particles emitted from thorium C have the greatest velocity and those from uranium and radium have the least velocity.The average velocity and average energy of the a-particles from the thorium and actinium families are nearly eqnal and are greater than the corresponding values for the radium family. The total energy liberated in consequence of the successive disin tegrations of a radium atom is less than the corresponding value for the thorium atom but is greater than that for actinium. It is noteworthy that for n large number of the radioactive products the velocity of expulsion of the a-particle for each of the radioactive families increases progressively as the period of transformation decreases. Hence it is probable that tho velocity of expulsion of the particle is least for the most stable atoms J.C. P The Radioactivity of Spanish Medicinal Springs JosB Mufioz DEL CASTILLO (Anal. Pis. Quim. 1006,4 119-120,147-149). -The waters from four teen medicinal springs obtained from nine hydropathic establishments have been examined with the result that several samples formerly supposed to possess no radioactive properties have now been found to exhibit a slight degree of radioactivity. Another series of investigations carried out with Engler and Sieve- king’s apparatus showed that specimens from fourteen different springs were all with one exception more or less radioactive. As these samples lose their radioactivity very appreciably on keeping the tests were made as soon as possible after collection. I n the case of the water from Burgas de Orense the dissolved gases were also very radio- active. G.T. M. The Radioactivity of Medicinal Springs containing Nitrogen. J o d M U ~ O Z DEL CASTILLO (Anal. Fie. Quinz. 1906 4 189-192).- Those Spanish mineral waters containing nitrogen which are reputed to have a valuable therapeutic action owe this property to the presence of a radioactive emanation. Samples from ten different sources all exhibited radioactivity; these specimens contained some carbon dioxide but oxygen was mor0 or less displaced by nitrogen. G. T. AT Probable Relationship Subsisting between the Radio- activity of Minerals and Cold Springgl in the Sierra de Guadarrama. JOSE Musoz DEL CA~TILLO (And. Pis. Quim. 1906 4 263-269).-A study of the radioactive minerals and springs found in the vicinity of Guadarrama leads to the view that the water owes its 5-264 ABSTRACTS OF CHEMICAL PAPERS activity to the fact that it has percolated throughlayers of radioactive minerals.These minerals belong to many different species all of which are rare ; titanium and iron are the predominant elements accompanied in certain instances by manganese bismuth copper and other common elements. The most radioactive specimens show traces of uranium. These very active substances were found on the highest points of the Sierra so that the melted snow at once comes into contact with them. G. T. M. Radioactivity of Thermal Mud deposited from the Bagni di Lucca (Tuscany). GIUSEPPE MAGRI ( A t t i R. Accad. Lincei 1906 [v] 15 ii 699-704j.-The author has separated the constituents of the mud deposited by the thermal springs of Bagni di Lucca by means of the ordinary group precipitants and has tested the radioactivities of equal weights of the various precipitates by means of the electro- scopic method. In this way he has demonstrated the presence of several radioactive substances and the physical examination of the emanations are in accord with the chemical properties of the groups in indicating the presence of radium and thorium. The sulphide pre- cipitate of Group I1 exhibits strong dispersion which is possibly due t o polonium or one of the radium products.No conclusion can be drawn as regards the presence of actinium. T. H. P. The Radioactivity of Ashes from the Last Eruption of Vesuvius [April 19061. JosE Mu3oz DEL CASTILLO ( A n d Pis.Quirn. 1906 4 l24),.-A specimen of Vesuvian ash collected from the deck of a steamer stationed a t Naples a t the time of the eruption was found to be a light grey powder which when sifted had D 1.20 and when examined by Elster and Goitel’s method indicated less than 18-57 volts per 100 grams of material per hour G. T. M. Radioactive Minerals from Motril (Granada). JosE Mu3oz DEL CASTILLO (And. Pis. Quim. 1906 4 46-48).-Samples of minerslo containing iron and copper from Motril (Granada) were generally found to be more or less radioactive as was also in a slight degree a sample of spring water from the same locality. G. T. M. Radioactive Cinnabar from Granada [Spain]. Josh MuRoz DEL CASTILLO ( A n d . Pis. Quim. 1906,4 58-59).-1n examining the radioactivity of the non-uraniferous Spanish minerals a small specimen of cinnabar from Albufiiol Granada was studied and found t o produce an appreciablo effect on a pliot,ographic plate after twenty to thirty- two days.G. T. M. Radioactivity from the Human Body. Josh Mv5oz DEL CASTILLO ( A n d Pis. Quim lt)06,4,202-205).-The rate of decay of the radioactivity exhibited by the medicinal water of Caldas de Oviedo was determined at frequent intervals (four to seven days) and i t was found that it had practically disappeared iii one-and-a-half months. Fresh samples of this water were administered to a human subjectGENERAL AND PHYSICAL CHEMISTRY. 65 with the result that a slight amount of radioactivity could be detected by Engler and Sieveking's apparatus in the urine and also in the expired air.G. T M Electrical Conductivity of Alloys. I. Relation between Conductivity and Constitution. W. GUERTLER (Zeit. unorg. Chem. 1906 51 397-433).-From a comparison of the curves representing the relation between the electrical conductivity and composition of numerous binary alloys with the constitution of tlhe latter as deter- mined more particularly by thermal and microscopic methods a number of rules showing how the constitution of alloys can be deduced from their electrical conductivity have been established. The available data on conductivity and on constitution are discussed in detail and it is shown that the rules in question give results which are trustworthy and in good agreement with those obtained by other methods when account is taken of the very different temperatures at which the conductivity and thermal observations have been carried out.The conductivity data are taken from papers by Matthiessen Le Chatelier and others and are compared with the results of thermal and microscopic observations by Tammann and his pupils by Heycock and Neville and others. The more important rules connecting conductivity and constitution of binary alloys are as follows (1) Alloys the electrical conductivity of which is a linear function of the volume concentration of the components are not mutually miscible to any appreciable extent in the solid state and conversely ; (2) the conductivity curve (the values of the conductivity being plotted as ordinates against the volume con- centration) of alloys which form a complete series of mixed crystals is continuous but falls rapidly on both sides from the points representing the conductivity of the pure metals and shows a flat minimum; (3) if the components show only limited miscibility the first law holds for the parts of the curve between the concentrations of the saturated mixed crystals the second law for the parts between the pure metals and the saturated mixed crystals ; (4) if two metals form m compounds the complete diagram can be divided up into m + 1 single binary diagrams and conversely from the shape of the curve information as to the existence of compounds can be obtained It is pointed out that a sharp point on the conductivity curve always indicates the presence of a chemical compound but contrary to the view of Liebenoff the converse does not always hold.I n the course of the paper the effect of small quantities of other metals on the properties of iron are discussed and it is shown in accordance with the above laws that the conductivity of the iron is only seriously affected when the admixture is present in solution. From an investigation of the system copper-zinc Shepherd (Abstr. 1904 ii 662) had drawn the conclusion that the elements do not enter into chemical combination whilst the conductivity curve as determined by Matthiessen indicates formation of a compound The author points out that Shepherd's observations may be interpreted as indicating the existence of a compound of the formula Cu,Zn3. A bibliography of the subject is appended. G. S.68 ABSTRACTS OF CHEMICAL PAPERS.Variation of Electrical Condtlctittity with Change of Temperaturd id Solutions of Sodium and Potassium Chlorides. AURELIO SUAREZ INCL~N (Anal. Pis. Quim. 1906 4 94-98).-The electrical condiictivities of solutions of 1 mol. of sodium chloride in 17.73 26.52 and 35.36 mols. of water were determined over a range of temperatures from 2-96' ; the results when plotted Rhowed points of inflexion for the first solution a t 20° and for the other two at 35'. Solutions containing 1 mol. of potassium chloride in 11.85 23.70 35.55 and 47.40 mols. of water were similarly examined at 3-94'; the first solution seemed to have a point of inflexion below Oo whilst with the other three the inflexion occurred at 50° SO0 and 7 5 O respectively G. T. M.Relation of Solution Pressure to Surface Condition In Metals. CHARLES E. FAWSITT ( J . SOC. Chenz. Ind. 1906 25 1133-1134).-The surface condition of rods of iron silver and gold has been examined by measuring the difference of potential between these and solutions of the corresponding salts. By rotating the rods a t about six revolutions per second constant results were readily obtained. With a series of steels containing different amounts of carbon i t was found that the potential difference in 0.5 molar ferrous sulphate solution is practically constant and equal to that of ferrite. The solution pressure of brightly polished silver is diminished by annealing a t a red heat but attains its initial value after the silver has been hammered until hard. I n the case of gold after annealing and hardening the solution pressure is greater than that of the polished metal.A roughening of the surface of iron or steel by etching or blasting also produces an increase of the solution pressure. This is attributed to the greater surface of contact of the metal with the solution. H. M. D. The Hydrogen-Oxygen Cell. 11. FRITZ HABER and GLYN W. A. FOSTER (Zeit. anorg. Client. 1906 51 259-314. Compare this vol. ii 6)-In a former paper it was showh that whilst the -&'.M.F.'s of hydrogen and oxygen concentration cells and of hydrogen- oxygen cells at high temperatures gold and platinum being used as electrodes and glass and porcelain as electrolytes are in satisfactory quantitative agreement with the thermodynamical theory the influence of varying pressures of water vapour on the E.M.F.of hydrogen concentration cells is in qualitative but not in quantitative agreement with the theory. It is now shown that this divergence is to some extent at least due to the absorption and retention of water vapour by the material of the electrolytes even a t 1000'. I n the experiments with porcelain the middle part of a tube of this material was coated outside and inside with platinum or gold; the outer electrode was in contact with a slow stream of air and served as normal electrode whilst the inner electrode was in contact with the gases under investigation. The experiments at 860" and 1000° con- firmed the results of Haber and Fleischmann (Em. cit.). As regards the influence of water vapour the thermodynamic theory requires that if the material of the electrolyte is not indifferent to it,GENERAL AND PHYSICAL CHEMISTRY.67 the effect of increased vapour pressure of water on the E.M.F. of the OXygeh concentration cell must be in the opposite direction to that in the hydrogen concentration cell and for the same change of vapour pressure the magnitude of the effect should be equal in the two cases. Experiments with porcelain show that the changes of E.M.F. are ih opposite directions as is to be expected but a slight divergence is found from the values required by theory probably due to experi- mental error. Measurements with glass were made at 450" and it is shown that the deviations from the simple formula for the E.M.F. are due to the action of water vapour on the electrolyte.G. S. The Hydrogen-Oxygen Cell. 111. FRITZ HABER (Zeit. anorg. CItem. 1906 51 356-368. Compare preceding abstract).-The paper deals with the development of a suggestion which is now finding fairly general acceptance (compare Nernst and von Wartenberg Abstr. 1906 ii 729 ; Lorenz and Hauser Abstr. 1906 ii S25) that a platioum electrode saturated with oxygen is not completely reversible an oxide of platinum being formed which is electrically active but has a smaller oxygen pressure than the gas itself. From I3ose's value for tho E.M.F. of the hydrogen-oxygen cell (1.14 volts) as compared with the thermodynamical value at the ordinary temperature 1.23 volts it is calculated that the oxygen pressure of the compound in question is I n a previous paper the reduction potential of hydrogen peroxide was estimated a t 0.8 volt and from this employing the former value for the E.M.F.of the hydrogen-oxygen cell 1.4 volts was obtained as the oxidation potential of the peroxide. With the new value 1.23 volts the oxidation potential of hydrogen peroxide is 1-66 volts and is therefore identical with the potential at which water is decomposed between platinum electrodes. On this basis it is suggested that in the latter process two O H ions unite to form hydrogen peroxide which is immediately decomposed in contact with the oxidised platinum surface. If a platinum electrode is dipped into hydrochloric acid containing chlorine and then washed thoroughly with miter and hot alkali it gives a blue coloration with potassium iodide and starch much more intense than that produced by the catalytic action of the metal on the oxygetl of the air.Since this effect is retained when the potential falls to that of platinum in contact with a solution containing Pt"" ions it is considered that the metal has been attacked with formation of a solid platinum compohnd. An electrode which has undergone anodic polarisation in sulphuric acid shows similar behaviour. These o bserva- tions also support the view that passivity is connected with the forma- tion of a superficial layer of oxide. In addition to the investigations at high temperatures with glass and porcelain as electrolytes (preceding abstract) similar measurements have now beeli carried out with potassium and sodium hydroxides as electro- lytes and it is shown that in this case also the results are in excellent accord with the thermodynamical theory.atmospheres. G. 8.68 ABSTRACTS OF CHEMICAL PAPERS. Electrolysis of Dilute Solutione of Acids and AJkaIiE) at Low Potentials Dissolving of Platinum at the Anode by a Direct Gurrent. GEORGE SENTER (Trams. Faraduy Soc. 1906 2 142-149).-Dilute solutions of sulphuric acid and sodium hydroxide have been submitted to the action of a current between platinum electrodes at a potential below that at which gaseous oxygen is evolved. The current density a t the anode was 1-2 x 10-7 amperes per square centimetre and the anode potential -1-4 to -1.55 volts the electrolysis being continued for three or four days. I n these circumstances an oxidising substance is formed in very small quantity at the anode.T t is very stable especially in alkaline solutions and is not destroyed by boiling. It liberates iodine from hydriodic acid but does not react with titanic acid like hydrogen peroxide. Under the same conditioxis small quantities of platinum are dissolved from the anode in acid solu- tions this action taking place to a greater extent with electrodes which have been used for some time then with fresh electrodes. The solvent action is not observed in the electrolysis of alkalis and the author supposes that the platinum is superficially oxidised the oxide dissolving in acid but not in alkaline solutions. H. M. D. Electrolysis of the Alkali Chlorides. Conductivity Density and Speciflc Heat of Simple and Mixed Solutions of Sodium Chloride and Sodium Hydroxide.LOUIS DEMOLIS (J. Chim. Phys. 1906 4 528-546).-Numerous data have been obtained for the electrical conductivity density and specific heat of solutions containing sodium chloride and hydroxide at a series of different concentrations and temperatures. The density of pure sodium chloride solutions and of mixed solutions can be expressed by the equation Dt = [0.999871+ 0*037298N- 0.O62455N2 + 0.00103R - 0*06688122]/1 + 0.000398 in which N and R are the numbers of grams of sodium chloride and sodium hydroxide per litre respectively and t is the temperature. The specific heat values for sodium chloride solutions are found to satisfy the formula proposed by Mathias. H. AT. D. Electrolysis of the Alkali Chlorides. Refractive Index Viscosity and Ionic Transport Ratio of Simple and Mixed Solutions of Sodium Chloride and Hydroxide.E. BRINER (J. Chim. Phys. 1906 4 547-564).-From the experimental data for the refractive index at 18' and for the sodium line the following equations are deduced. For solutions of sodium chloride n = 1.3334 + O.O31683C - O-O669C2; for sodium hydroxide n = 1.3334 + 0.032694C - 0*0628YC2 ; for potassinm hydroxide n = 1.3342 + O*O31866C- O.OGl12C2 in which C denotes the concentration in grams per litre. The refractive index of a solution containing sodium chloride and hydroxide cannot be represented accurately by an equation of this The data for the coefficient of viscosity a t 20°.can be represented by similar equations. Sodium chloride q = 0.010015 + 0-O41O04C + 0.0764C2 ; sodium hydroxide q = 0.010015 + O,O4457C + O*OG3321C2 ; potassium hydroxide y = 0*010015 + O.O418C + O*O74C2.The viscosity type.GENERAL AND PHYSICAL CHEMISTRY. GD coefficients for solutions of sodium chloride and of potassium hydroxido art! also calculated by means of the formula suggested by Euler. The transport number of the anion in sodium hydroxide a t a concen- tration of 84.2 grams per litre was found to be 0-85 a t 20-25' and 0.858 at 15O; in potassium hydroxide a t a concentration of 152 grams per litre 0.75". H. 31. D. Electrolytic Oxidation in presence of Fluorine Ions MARIO G. LEVI and F. AGENO (Atti R Accad. Lincei 1906 15 ii 549-555 615-620. Compare Skirrow Abstr. 1903 ii 69 and Miiller Abstr. 1904 ii S l l and Sl2).-Using solutions of chromium sulphate normal as regards the salt and sulphuric acid the authors find that the yield of chromic acid obtained on electrolysis is increased by the presence of hydrofluoric acid and by the use of platinised platinum electrodes.The highest yield obtained was 78% of chromic acid a value comparable with that obtained industrially by means of peroxidised lead electrodes (compare Ahrens Ekktrochemie 1903 539 and Muller and Soller Abstr. 1906 ii 66) ; the amount of hydrofluoric acid present 0*498N mas only about one-fifth of that used by Skirrow (Zoc. cit.). The diminution of the current density due to the platinising of the electrodes probably everts a favourable influence on the yield of chromic acid. The addition of sodium fluoride favours the electrolytic oxidation of sodium sulphite to dithionate with which corresponds a higher anodic potential than with the sulphate the other oxidation product of the sulphite.With smooth platinum electrodes the yield of dithionate is raised from 18.6 to 21.3% by the presence in the solution of 1.25% of sodium fluoride and from 21 to 26.1% by 3% of the fluoride. When platinised platinum electrodes are used the presence of fluorine ions is insufficient to raise the anodic potential to the value necessary for dithionate to be formed so that the sulphite undergoes complete oxidation to sulphate. The authors have also electrolysed either solutions of ammonium sulphate rendered alkaline by sodium or potassium hydroxide or solutions of free ammonia in presence of sodium or potassium fluoride the electrodes being of smooth platinum and the cathode being Eeparated by a diaphragm containing 20% sodium or potassium hydroxide solution according to the fluoride used.The oxygen and nitrogen (by difference) in the anodic gases were determined and also the nitrite and nitrate formed in the solution. I n this oxidation also the fluorine ions produce a slight but appreciable increase in the yield of the compound with which corresponds the higher potential that is the nitrate. Electrolysis of manganese salts in presence of hydrofluoric acid gave results agreeing with those of Skirrom (Abstr. 1903 ii 69). For the estimation of the permanganate the authors used a method similar to Ballmann's spectroscopic method for estimating lithium in mineral waters (compare Ranzoli Abstr.1901 ii 423) the appearance or disappearance of the characteristic striae in the absorption spectrum of the permanganate being observed Using an h u e r light and a layer of solution 10 cm. in thickness the minimum concentration of70 ABSTRACTS C1F CHkMICAL PAPERS. permanganhte for which these s t r i a are visible is 0.000002 gram per C.C. The use of fluorine ions was also applied i n the electrolysis of a number of organic compounds but no useful results were obtained. T. H. P. Specific Heat and Speciflc Gravity of Allotropic Modi- fications of Solid I Elements. ALBERT WIGAND (Ann. Physik 1907 [iv] 22,64-98).-From Kicharz’s theory (Abstr. 1893 ii 404 ; Ann. Pliysik 1899 67 704) it is possible to deduce the conclusion that the greater the specific gravity of any modification of an element the smaller is its specific heat. It is now shown partly with data obtained by the author that the rule is valid for the various modifications of carbon boron silicon phosphorus sulphur arsenic selenium tellurium and tin.J. C. P. Variation with Temperature of the Specific Heat of Solid Elements. ALBERT WIGAND (Ann. Phgsik 1907 [iv] 22 99-106). -Available data bearing on the relation of the specific heats of the elements to temperature are brought together and represented on a large diagram. The extent to which elements of low atomic weight and small atomic volume deviate from Dulong and Petit’s law is discussed and it is shown that the validity of the law is much more extensive at high temperatures than at low temperatures. J.C. P. Phenomena accompanying Fusion and Crystallisation. DANIEL VORLANDER (Zeit. phpikal. Chem. 1906 57 357-366).- - Under normal conditions p-anisylideneanisidine p-anisylidenephenet- idine and anisylidene-p-aminoacetophenone melt to isotropic liquids but if drops of the liquid substances are supercooled a fluid aniso- tropic phase appears exhibiting double refraction. The supercooling of the isotropic liquid is in fact of great importance in the search for fluid crystalline substances The following substances are capable of existence in two fluid crystal- line phases (compare Lehmann Abstr. 1906 ii 836) anisylidene- aminoacetophenone ethyl p-azoxybromocinnamate ethyl anisylidcne- p-aminocinnamate and ethyl p-acetoxyazobenzeneacrylate. There are therefore for each of these substances three temperatures which correspond with a freezing point or a transition temperature thus solid crystalline bright fluid crystalline dark fluid crystalline isotropic liquid Another interesting substance is anisylidene- p-aminobenzoic acid which exists in two solid modifications and also inelts to a crystalline fluid.The author has succeeded in observing fluid crystals with straight edges and regular angles and the photographic reproductions accom- panying the paper show that there is but little difference in the mode of growth of fluid and solid crystals. It is noteworthy that the form of fluid crystals is affected to a relatively slight extent by alterations in chemical composition 1 2 3 J C. P,GENERAL AND PHYSICAL CHEMISTRY.71 Apparatus for Sublimation in a Vacuum. R. KEMPF (CAem Zeit. 1906 30 1250. Compare Krafft and Weilandt Abstr. 1896 ii 635 ; Kiiber Abstr. 1900 ii 468).-The apparatus described and figured consists of three glass parts a long bulb which is inclined downwards and in which the substance is heated is ground into the end of a wide horizontal tube which receives the sublimate; the other end of the tube is ground into a cap fitted with a tap. The nozzle of the cap is attached to a pump and the bulb and a portion of the tube are inserted into an air-oven which is heated after the apparatus has been evacuated. The advantages claimed for the apparatus are that the sublimate cannot drop back on t o the heated surface that the sublimation may be carried out under any desired pressure or in the cat.hode-light vacuum and that the sublimate can be removed quantita- tively and the apparatus readily cleaned.G. Y. Distillation and Desiccation in Vacuum by Means of Low Temperatures. A R S ~ N E D’ARSOKVAL and FRED. BORDAS (Ann. C’him. anal. 1907 12 4-7).-The distilling flask or desiccator is connected with a water air-pump the vapours are condensed on a surface cooled by liquid air or solid carbon dioxide and acetone and the last traces are absorbed by especially prepared charcoal. A Crookes’s vacuum bulb serves as manometer. For details the original article and illustration should be consulted. L. DE K. Ebullioscopic Behaviour of Aliphatic Acids with Abnormal Vapour Densities. ERNST BECKMANN [with E. BERNHARD EREMIE- POPA and WERNER GABEL] (Zeit.physikal. Chern. 1906 57,129-146). -The boiling point elevation constant Ii can be calculated by the formula R= 0*025!2/w even for those solvents (formic acetic propionic and butyric acids &c.) the vapour densities of which are abnormally large a t their boiling points. The following table gives the mean values of Ji for the four fatty acids mentioned obtained experimentally by using such solutes as bend benzanilide and diphenylamine and also the values of K calculated from the latent heat of vaporisation I{. From b. p. K. From heat Solvent. experiments. of vaporisation. Formic acid ............. 24.0 23.2 Acetic acid ............... 29.9 30.7 Propionic acid ............ 35.1 37.5 Butyric acid ............... 39.4 33-4 The available data for the heat of vaporisation in manycases exhibit marked discrepancies and in these cases at least the experimentally deduced values of K are to be preferred.Sodium and potassium formates and potassium sulphate appear to be dissociated to a large extent in formic acid solution. Acetates pro- pionatea butyrates and stearates have in general the normal moleculsr weight when dissolved i D the corresponding acid but it is noteworthy that strontium and calcium acetates exhibit a tendency to association in acetic acid solution. J. c. P.72 ABSTRACTS OF CHEMICAL PAPERS. Thermostat for Low Temperatures. W. KUNTZE (Centr. Bakt. Par. 1906 ii 17 684-688).-A thermostat for low temperatures (about 20') is described with sketches. It consists of a double-walled wooden box containing a lower zinc water chamber which may be heated when necessary and an upper one for cooling.When desired the water in the lower chamber can be quickly cooled by means of a cooling tube connected with the upper cold water chamber. Behaviour of Certain Substances at Low Temperatures. A. HEIDUSCHKA ( A ~ c h . Phnwn. 1906 244 569-571).-The following miscellaneous observations at the temperature of liquid air - 186" are selected from those enumerated. Alcoholic solutions of indigotinsulphonic acid and of certain sulphur dyes fluoresce. The fluorescence of an alcoholic solution of methyl-violet BB was not diminished by admixture with an equal amount of aniline although a solution of the dye in this solvent exhibited no fluorescence. An alcoholic solution of methylene-violet RRA from which the fluorescence had been removed at the ordinary temperature by the addition of alcoholic chrysoidine recovered its fluorescence to some extent.Solutions of ferric and aluminium hydroxides of protargol and of egg-albumin were not coagulated ; on thawing clear solut.ions were obtained. C. F. B. N. H. J. M. Course of Chemical Reactions at High Temperatures. FRANZ FISCHER (Chem. &it. 1906 30 1291-1295).-The influence of temperature on chemical equilibrium and on reaction velocity is discussed. As an instance of the formation of a substance more stable a t high temperatures than a t low the fact that nitric oxide is obtained by the rapid cooling of a strongly heated mixture of nitrogen and oxygen is quoted The application of similar reasoning to the reaction between oxygen and hydrogen explains why hydrogen peroxide is formed on allowing a hydrogen flame to impinge on a block of ice.Several experiments which have already been published elsewhere are described in illustration of the preparation and properties of ozone and hydrogen peroxide. P. H. Heat Developed on the Addition of Bromine to Certain Unsaturated Substances. WALDIMIR F. LUGININ and IWAN A. KABLUKOFF (.L Chim. Phys. 1906 4 489-506).-The heat developed by the addit.ion of bromine by unsaturated acids of the oleic series and by certain terpenes has been measured the reacting substances being dissolved in carbon tetrachloride. For the addition of 1 molecule of bromine to 1 molecule of the unsaturated compound the followiog amounts of heat were found to be developed undecenoic acid 28,609 cal.; oleic acid 28,757 cal. ; elaidic acid 27,131 cal. ; euricic acid 29,166 cal. ; limonene 28,548 cal. ; carvene 27,545 cal. ; d-pinene (from Russian terebenthene) 35,784 cal. ; I-pinene (from French terebenthene) 35,509 cal. ; pinene 36,237 cal. The differencesGENERAL AND PHYSICAL CHEMISTRY. 73 between the last three numbers are attributed to differences in the purity of the products. By the addition of 2 molecules of bromine to one molecule of limonene 50,420 cal. are developed but this result is somewhat indefinite because about 5% of the bromine used is liberated as hydrogen bromide. In the case of carvene the proportion of hydrogen bromide liberated is smaller (2*9%) and 48,936 cal.were obtained for the heat of addition of 2 molecules of bromine to 1 molecule of the hydrocarbon. The results indicate that the addition of the second molecule of bromine is accompanied by a much smaller development of heat than that of the first. Relation between Viscosity and Absorption Coefflcient for Liquids. MAX TRAUTZ and H. HENNING (Zeit. plqsikal. Chem. 1206 57 25 1-%4).-A summary of the authors' experimental data bearing on Winkler's formula (Abstr. 1892 556) and a discussion of that worker's recent paper (Abstr. 1906 ii 342). Some objection is taken to Winkler's method of calculation and the experimental results do not conform so closely t o the formula as has been represented. A t the same time it is noteworthy that for variations in the absorption coefficient from 0.01 to 1300 and variations in the molecular weight of the absorbed gas from 2 to 160 the value of k remains of the same order of magnitude Direct Measurements of the Osmotic Pressure of Solutions of certain Colloids.BENJAMIN MOORE and HERBERT E. ROAF (Biochem. J. 1906 2 34-73).-The osmometer employed consisted of a metal chamber between the two halves of which a membrane of parchment paper could be fixed and supported by a platinum grid. The one half of the metal chamber was filled with the colloid solution and connected with a mercury manometer the other half contained water occasionally a salt solution. A 10% gelatin solution was found to give a steady osmotic pressure of about 70 mm. of mercury at 30". This pressure persists for a long period and is therefore not an effect due to the initial presence of crystalloids f o r these would gradually diffuse out and the osmotic pressure would fall to zero.The observed osmotic pressure increases with rise of temperature ; the increase however is greater than if the osmotic pressure were proportional to the absolute temperature and is probably connected with the partial dissociation of the solution aggregates in the gelatin solution. When the gelatin solution is kept for a short time a t 70" or SOo and is then brought back to 30° the value of the osmotic pressure is considerably higher than that obtained before the heating; there is however a gradual recurrence to the previous value. If heating a t 80" or 90" is continued for some time a permanent change is effected and the solution has a higher osmotic pressure.A t the same time the physical properties of the gelatin solution are altered and proteid derivatives are formed which pass through the membrane. Other colloids besides gelatin which give a distinct osmotic pressure are the serum proteids and gum acacia. Potato starch and gum tragacanth on the other hand appear to have such a high state of aggregation that they give no indication of osmotic pressure H. M. D. J C. P.74 ABSTRACTS OF CHEMICAL PAPERS. At the stage of hydrolysis of starch at which the blue colour with iodine has just disappeared the dextrine present give a permanent osmotic pressure. Sugars and uric acid behave as true crystalloids and pass through the membrane. Addition of a considerable quantity of magnesium sulphate to serum causes after an initial rise a fall of osmotic prwsure to a value which is less than that given by the original serum.A lecithin or lanolin membrane is permeable to crystalloids and hence the supposed presence of such a membrane will not explain the peculiar content of the cell in crystalloids. It is more probable that the cell protoplasm has selective absorptive powers for different ions and that such ions exist in the cell in combination or adsorption with the cell substance. J. C. P. Velocities of Diffusion of Electrolytes. GIUSEPPE BRUNI and B. L. VANZETTI ( A t t i 3. Accad. Lincei 1906 [v] 15 ii 705-715).- Tha authors have repeated some of the experiments made by Bhscaglioni and Purgotti ( A t t i If. 1 s t . Bot. I’avicc 1905 New Series ll) on the dihfiion of electrolytes and have verified their results.When the two ends of a column of 5% gelatin are placed in contact with solutions of two salts such as silver sulphute and barium chloride capable of forming two different precipitates two distinct septa form in the gelatin one of each precipitate. That this result is t o be explained by the independent migration of the ions as stated by Buscaglioni and Purgotti (Zoc. cit.) is improbable and the authors regard it as highly probable that the formation of the two septa depends on supersat,uration phenomena (compare Morse and Pierce Abstr. 1904 ii 14). The hydrolysis of coloured salts such as copper sulphate may be readily demonstrated by diffusion into gelatin. The velocity of migration of a substance into gelatin is nearly independent of the concentration of the solution.Several cases have been met with which are in disaccord with Buscaglioni and Purgotti’s hypothesis (Zoc. cit.) that the separate ions diffuse with velocities inversely proportional to the square roots of their weights. T. H. P. Modifled van der Waals’ Equation. ALEXIUS BATSCHINSKI (Arm. Physik 1906 [iv] 21 1001-1012).-The author’s form of the equation is p v = K T - A ( l / k - l/v)/(v-h) in which A k and X are constants. The applicability of this equation is tested in the case of ethyl ether with satisfactory results and the conclusion is drawn that for ethyl ether and all other substances which obey the foregoing formula the molecular mass is the same in the liquid as in the gaseous state.J. C. P. Kinetics of Successive Reactions of the First Order. ADAM RAKOWSKI (Zeit. physikaE. Chem. 1906 57 321-340).-A general mathematical study of successive reactions of the first order. “he reactions for which detailed formul~ are deduced are those of the following types (1) ill -+ AL.. -+ ; (2) JIl -3 Mz ;2 J3 ; (3)GENERAL AND PHYSICAL CHEMISTRY. 75 XI -+ M2 -+ M3 -+ M,. Even for these comparatively simple cases and especially in the last case very complicated formulp are obtained and the testing of the equations by experimental data becomes exceedingly difficult if not impossible. J. 0. P. Ionic Velocity and Ionic Hydration I. CHARLES G. CARROLL (Amer. Chem. J. 1906 36 694-509. Compare Jones and Carroll Abstr. 1905 ii 73).-The author shows that the following general law holds for solutions in water or methyl alcohol.The velocity of a given ion under a constant fall of potential is directly proportional to the valency of the ion the cube root of the ionic (atomic) volume and the specific inductive capacity or dielectric constant of the solvent and is inversely proportional to the viscosity coefficient of the solvent. The validity of the law is tested by means both of relative ionic velocities and of conductivity data and it is shown that the law admits of a simple physical interpretation. T. H. P. Ionic Reactions in Acetone. P A u r DUTOIT and HENRI DEMIERRE ( J . Chirn. Phys. 1906 4 565-575).-The velocity of the reaction CH,Cl*CO,H + MI = CH,I*CO,H + MCl where M represents sodium potassium or ammonium has been investigated in acetone solution. The progress of the reaction was followed by measurement of the electrical conductivity which is almost entirely due to the alkali iodide for the chloride is almost insolublo in acetone and the two acids are only very slightly dissociated. The experimental data obtained a t temperatures between 36' and 41' indicate that the reaction is bimolecular.The value of the constant calculated from the equation k = l/t*x/a(a - x) decreases as the reaction progresses and this is found t o be due to the fact that the change is reversible equilibrium being reached when about 94°/0 of the iodide has been converted into chloride. I n order to eliminate the influence of the reverse change in de- ducing the dependence of the velocity on the concentration the initial velocities only have been compared.The value of k thus obtained in a series of experiments increases as the concentration diminishes but kip where p is the molecular conductivity of the solution remains constant. From this the authors conclude that the iodion is the active agent in the substitution process. H. M. D. Relationehip of the Dissociation of Dissolved Substances to their Reactivity. J. TlMMERMANs (Bull. soc. chi??&. Belg. 1906 20 305-31 3).-A critical review is given of recent results experimental apd speculative bearing on Ostwald's generalisation regarding the intimate relation between chemical activity and state of ionisation in the course of which the work recorded in the following abstracts is referred t o Rohland 1899 ii 144 ; 1900 ii 468.Naumann 1899 ii 423; 1904 ii 819 ; 1905 ii 29 30. Briihl 1899 ii 10. Kahlenberg 1899 ii 397; 1902 ii 301. Walden 1901 ii 11; 1904 ii 227; 1906 ii 149. Moisean and Dewnr 1903 ii 419. Plotnikoff 1904 ii 156. Beckmann 1904 ii 235. Franklin and76 ABSTRACTS OF CHEMICAL PAPERS. Eraus 1905 ii 298. Patten 1905 ii 36. Wallace Walker Trans. 1904 85 1082. Mercuric aluminium and ferric chlorides furnish solutions in methyl chloride which exhibit marked electrical conductivities and the solution of the last-named may even be electrolysed yielding iron and chlorine. Solutions of ferric chloride mercuric chloride and cadmium nitrate in methylal do not conduct electricity and similarly mercuric and ferric chlorides dissolved in dimethylamine scarcely conduct whereas aluminium iodide i n dimethylamine shows marked conductivity.Solutions of potassium iodide in melted iodine and of potassium chloride in liquid chlorine do not conduct. Molecular weight determinations by the cryoscopic method of solutions of potassium iodide or mercuric iodide in melted iodine gave high results probably due to the formation of additive compounds in these two cases. These results the author concludes lend no support to the views put forward by Briihl and by Wallace Walker (Zoc. cit.). Shroeder 1905 ii 306. T. A. H. Reactions between Acids and Methyl-Orange. VICTOR H. VELEY (Zeit. physikccl. Chew. 1906 57 147-167).-The action of acids (almost all organic) on a dilute solution of methyl-orange has been studied by a colorimetric method.Each tube of the colorirneter was charged with 20 C.C. of the methyl-orange solution. To the one tube were then added successive portions of 0.1 C.C. of acid (generally N/200) and fresh methyl-orange solution was added to the other until the colours in the two tubes mere equally intense. If II is the number of added portions of acid and y is the increase of depth in cm. in the second tube then for all added acids which obey Ostwald's dilution law the relation between x and y is a linear one and the order of value of the coefficients in the equations y = hlx y = kax &c. is the same as the order of the affinity constants of the acids. If the added acid does not obey Ostwald's dilution law; then the x-y curve represents a para- bola or a straight line not passing through the origin.The co- efficients in the linear equations for some dibasic acids exhibit a slight variation with concentration analogous to the variation with concen- tration i n the case of the afinity constants of these acids. J. C. P. Velocity of Formation of Hydrogen Bromide from its Component Elements. MAX BODENSTEIN and S. C. LIND (Zeit. physikal. Chem. 1906 57 168-192).-At the temperatures at which the authors' experiments were carried out namely 224.7' 251 *4O 277-5" and 301*3O the reaction H + Er2 = 2HBr proceeds completely from left to right. The results for the velocity are readily reproduced and are independent of the glass surface of the containing vessel and of traces of foreign gases. The rate of change is very satisfactorily expressed byithe empirica.1 formula dx/dt = k(cc - x ) ( b - x)*/lm + z/(6 - :)I in which a and 6 are the initial concentrations of hydrogen and bromine respectively x is the hydrogen bromide concentration at time 8 and rn is a constant for which the value 5.0 is chosen.The introduction of a denominator on the right hand side of the foregoing formula is dueGENERAL AND PHYSICAL CHEMISTRY. 77 t o the fact that the combination of hydrogen and bromine is retarded by hydrogen bromide so that the reaction is an example of negative autocatalysis in a homogeneous system. This retardation is a specific property of hydrogen bromide and it is shown not to be due to any chemical combination of that compound with the bromine. The presence of other gaseous substances such as carbon tetrachloride air or water vapour does not cause -any retardation of the reaction although iodine has a very marked effect in that way.It will be noticed from the fore- going formula that the velocity of the change is proportional to the square root of the bromine concentration and hence it is suggested that the bromine reacts in the atomic condition. The temperature coefficient of the reaction has a value which is if anything slightly greater than usual. J. C. P. Rates of the Reaction6 in Solutions containing Potassium Bromate Potaasium Iodide and Hydrochloric Acid. ROBERT H. CLARK (J. Physical Chem. 1906 10 679-700).-The iuiluence of the concentration of each of the reagents on the velocity of the change has been determined by the measurement of the initial velocities.The fractional alteration in the concentration of the reagents was so small in the experiments that the velocity could be treated as practically constant during the interval of change and only in certain cases was it necessary to apply a small correction factor. The reaction was stopped at a particular point by the addition of an excess of an ammonium hydrogen carbonate solution. The data obtained indicate that the rate of liberation of iodine is proportional to the concentrations of the bromate and the iodide and to the square of the concentration of the acid The addition of chlorion in the form of sodium chloride does not alter the velocity which remains the same whether the reaction takes place in air or in an atmosphere of carbon dioxide If iodide and bromide are both present in solution these are oxidised independently the bromide much more slowly than the iodide.In the presence of iodine which forms the ion 18' the velocity of the change is slightly increased in consequence of the oxidation of the triiodion by the bromic acid. This influence is however too small to cause any disturbance in the general character of the change. The value of the temperature coefficient of the velocity between 0' and 30° is 1.85 per rise of 10'. H. M. D. Influence Exerted by a Salt in Various Concentrations on the Velocity of Decolorisation of Aqueoue Solutions of Organic Dyes under the Influence of Light. GUIDO BARGELLINI and ALDO MIELI ( A t f i R. Accad. Lincei 1906 [v] 15 ii 773-778).- From the preliminary experiments here de*cribed it appears that the addition of gradually increasing amounts of a salt to a solution of a dye such as methylene-blue causes firstly a diminution and after- wards an increase in the rate at which the solution is decolorised by the action ( I f light. There is hence a minimum rate of decolorisation corresponding with a detinite concentration of salt.With safranine and potassiuiu chloride decoloration is slowest in a solution containing about 5% of the ,salt and with methyl-violet and magnesium sulphate VOL. XCII. ii. 678 ABSTRACTS OF CHEMICAL PAPERS. the minimum is attained when about 2.5% of the sulphate is present. With solutions of magenta the phenomenon is complicated by the formation of a considerable amount of precipitate.T. H. P. A Substance which Possesses Numerous Liquid Phases of which Three at least are Stable in Regard to the Isotropic Liquid. FRANS M. JAEGER (Proc. K. Akad. Wetensch. Amsterdam 1906 9 359-362. Compare Abstr. 1906 i 742).- Cholesteryl cinnamate the substance in question softens at 151' and thereafter exhibits a brilliant display of colour until a t 157' it is a thick orange-red doubly refracting fluid. If this i s stirred the fluid crystals ar0 seen to form links of lustrous bright green and violet lamina. As the temperature is raised the liquid becomes thinner and at 199.5' it is nearly colourless. At that temperature the mass suddenly assumes a white enamel-like appearance thickens and separates into two anisotropic liquid layers. The interference colours have now entirely disappeared.On further heating the substance changes at 201 03' into a clear colourless isotropic liquid. The author thinks that this is a case where the transitions involved in the change solid -+ liquid occur continuously instead of suddenly. This makes it possible to realise a whole series of labile intermediate conditions. J. C. P. Formation of Hydrosols by the Interaction of Ions. ALWRED LOTTERMOSER (Chem. Centr. 1906 ii 1597 ; from Verh. Ges. deut. Nuturf. Aerxte 1905 ii 87-89. Compare Abstr. 1906 ii 429).-A11 amorphous silver salts may be obtained in the form of hydrosols by the interaction of ions pFovided that an upper limit of concentration is not exceeded. For this purpose it is necessary how- ever that an excess of one of the reacting ions should be present.If the latter have combined completely with the salts which practically are un- dissociated precipitation of the hydrogel takes place. The existence of the hydrosol in the case of a given ion reaction depends therefore on the presence of a definite quantity of anions or silver ions whilst on the other hand no excess of either ion can be detected in the hydrogel. The hydrosols which owe their formation to silver ions and are therefore positively charged are readily gelatinised by OH ions ; bi- and multivalent ions have also a strong action. The hydrosols prepared by means of anions are practically insensitive however to the action of H ions. E. W. W. Hydrate Theory. HARRY C. JONES (Zeit. pl'yeikul. Chem. 1906 57 244-250).-In replying to Biltz's criticism (Abstr.1906 ii 737) the author defends his claim to be the originator of the hydrate theory as applied to abnormal freezing point depression phenomena. J. C. Y. Theory of Colloidal Envelopes ('' Umhiillung "). Ultramicro- scopic Observations. LEONOK MICHAELIS and LUDWIG PINCUSSOHN (Uiochsm. Zeit.,lSCrG 2,251-263. Compare Quincke Abstr. 1902 ii 200 ; Bechhold 1904 ii 650 ; Biltz 1904 ii 392)-In continuationGENERAL AND PEYSICAL CBEMISTRY. 79 of Raehlmann’s work (Phys. Zeit. 1904,4 884 ; PfEuger’s Archiu 1906 112 128)’ experiments have been conducted with suspensions of mastic and indophenol obtained by dissolving the two substances in alcohol pouring into water and mixing the suspensions using the same volume of indophenol but varying amounts of mastic sus- pension.The indophenol suspension itself exhibits a red pseudo- fluorescence (Siedentopf Physill;. Zed. 1905’6 855) but after twenty- four hours the solution has become colourless and a crystalline precipitate of indophenol is obtained. When a small amount of mastic suspension is present a diminution of the pseudofluorescence is observed and in the ultramicroscope numerous white mastic particles are observed with only a few coloured indophenol particles When the amount of mastic has reached a certain valne the solution has a pure blue colour when observed in transmitted light the red pseudo-fluorescence has completely disappeared and also the coloured indophenol particles and the suspension may be kept for seventy-two hours without undergoing alteration. Such a mixture contains the minimum amount of mastic required to ‘‘ protect ” the indophenol present Experiments made on counting the number of particles present in a given volume and also in their electrolytic properties lead t o the view that the two types of particles unite together to form larger particles and that probably the union occurs between a particle of each component. The union produces a change in the physical properties of the particles and this is closely related to the “pro- tective action.” The disappearance of the pseudofluorescence indicates that the union produces an alteration in the inner structure of the indophenol particles.J. J. 8. A Natural System of arranging the Chemical Elements in which they fall into the Periodic Groups based solely on the Atomic Volumes and the Combining Weights. JAMES MONCKMAN (Chem. News 1907 85 6-9).-As an extension of Lothar-Meyer’s observations on the relation existing between the combining weights and the atomic volumes of the elements the author has constructed a series of new curves by plotting combining weights against the tangents of the angles that Meyer’s curves form with the horizontal. The ten curves so obtained arrange themselves naturally into three sets which are termed exionic endionic and central; they comprise respectively the lightest the heavier and the heaviest elements. The central set consists of three lines and contains the triplets iron cobalt and nickel ruthenium rhodium and palladium osmium iridium and platinum. It is claimed for this system of classification that it satisfies a number of qualities that must be found in any perfect system of classification For details of the system as well as a tabular re- presentation the original should be consulted. New Absorption Apparatus for Gases. C. JOSEPH G~LICH (Chem. Zeit. 1906 30 1302).-The liquid absorbent is introduced into the top of a narrow vertical tube resting on a pivot and escapes from it by side-tubes attached at right angles. By the flow of the liquid the tube is sot into ritpid rotation and a fine spray of liquid is P. H. 6-280 ABSTkACTS OF CHEMICAL PAPERS. projected into the surrounding gas thus ensuring efficient absorption. For details of the apparatus the diagram in the original paper should be consulted. P. H.

ISSN:0368-1769    

DOI:10.1039/CA9079205061

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

80 ABSTkACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Behaviour of the Halogens towards each other. H. W. BAKHUIS ROOZEBOOM (Proc. K. Akad. Wetensch Amsterdam 1906 9 363-364).-1n reviewing the studies that have been made from the pointl of view of the phase rule of the binary systems I + C1 1-1- Br Br+CI the author points out that IC1 is a very stable com- pound ICI and IBr are feeble compounds whilst no compound of bromine and chlorine exists. The combining power is therefore greatest in the most distant elements and greater for the pair Br + I than for the pair Br + C1. J. C. P. Density of Gaseous Hydrogen Chloride Atomic Weight of Chlorine. PHILIPPFI A. GUYX and G. TER-GAZARIAN (Compt. rend. 1906 143 1233-1235).-The recent values obtained for the atomic weight of chlorine are (for Ag = 107.93) 35.473 from the ratio Ag C1 (Richard and Wells Abstr. 1905 ii 450) ; 35.476 from the density of hydrogen chloride (Leduc corrected by Guye Abstr.1905 ii 442) ; 35.460 (Ag = 107-89) from the ratio Ag C1 (Guye and Ter-Gazarian Abstr. 1906 ii 760); and 35.463 from the synthesis of hydrogen chloride (Dixon and Edgar Abstr. 1905 ii 696). I n view of these discrepancies the authors have redetermined the density of hydrogen chloride using the method employed in the determination of the density of nikric oxide (Abstr. 1906 ii ZO) the gas being prepared by the action of sulphuric acid on sodium chloride dried over sulphuric acid and phosphoric oxide liquefied at the temperature of liquid air and submitted t o a series of fractional distillations. The mean of four determinations of the weight of a litre of hydrogen chloride at N.P.T.is 1.6398 grams (Leduc obtained 1*6407) and the corresponding atomic weight of chlorine is 35.461 which is in close agreement with the last two values quoted above but the authors regard i t as provisional only. M. A. W. New Hydrogen Sulphide Apparatus. FERNAND RANWEZ (Ann. Chim. anal. 1907 12 7-9).-The apparatus consists essentially of a broad U-shaped tube constricted at the bend and also a t a little above the bend as regards the limb which contains the iron sulphide. The top of this limb is closed with aperforsted cork through which passes a rectangularly bent tube connected with the delivery tube by means of a small rubber tube which can be closed with a pinchcock.Acid is poured into the other limb and when the rubber tube is not closed the acid comes in contact with the iron sulphide and hydrogen sulphide isINORGANIC CHEMISTRY. 81 evolved. On closing the rubber tube the acid is at once driven back Decomposition of Persulphates. MARIO G. LEVI and E. MIGLIORINI (Gazxelta 1906 36 ii 599-619. Compare Abstr. 1903 ii 474).-The reaction of decomposition of persulphates obeys the LAW of unimolecular reactions in the cases of the sodium and potassium salts but not in the case of the ammonium salt. U p t o a temperature of 30-35’ solutions of persulphates can be kept un- changed for some days the solution of the ammonium salt being most liable to change. Acids and t o a less degree alkalies exert a marked accelerating action on the decomposition of persulphates.Platinum black causes slow catalysis of persulphates in solution the greatest action taking place with ammonium persulphate ; the amount of cata- lysis is a maximum in alkaline and a minimum in acid solution. Lead and certain other metals also decompose persulphates in solution. into the other limb. L. DE I(. T. H. P. Selenates. ENRICO RIMINI and GIOVANNI MALAGNINI (Atti R. Accad. Lincei 1906 [v] 15 ii 561-563j.-The acid selenate of hydr- axine N2H4,H2Se04 is only slightly stable asare also its solutions ir water in which i t dissolves moderately readily. The double hydraxine copper selenate [(N2K,)2,H2Se04,CuSe0,]2 + H,O is isomorphous with the corresponding double sulphate and decomposes gradually when kept. T. H. P. Experiments with the Hot-cold Tube in the Electric Furnace.RAFFAELO NASINI and FRANCESCO ANDERLINI (Gazxetta 1906 36 ii 570-575).-No combination takes place between nitrogen and oxygen when heated in the hot-cold tube in the electric furnace at 2000°. nor does magnesium absorb argon appreciably a t this temperature. T. H. P. Copper Cathodes in Nitric Acid. J. W. ‘CURREXTINE (J. Physical Chem. 1906 10 715-720).-The object of the author’s experiments was to ascertain why nitric acid is reduced t o ammonia when dilute solutions of the acid are electrolysed whereas nitric oxide is the chief product in the ordinary contact action of copper on nitric acid. On electrolysing a 5% nitric acid solution between copper electrodes at a current density of S amperes per square decimetre it was observed t h a t evolution of gas (nitric oxide) did not commence until the more dense copper nitrate solution which collected in the lower part of the apparatus came into contact with the cathode.This result appears to show that the copper ions are the cause of the incomplete reduction of the nitric acid and in a further experiment in which copper was allowed t o act on 10% nitric acid solution means were devised for the removal of the copper ions as fast as these were formed. This removal of copper ions was effected electrolytically and under such conditions it was found that the reduction product of the chemical action between copper and nitric acid is ammonia. The more rapid rate of solution when nitric oxide is the reduction product is attributable t o the accelerating action of nitrous acid.H. M. D,82 ABSTRACTS OB CHEMICAL PAPERS. Preparation of Boron Sulphide from Manganese Boride. JOSEF HOFFMANN (Zeit. angew. Chem. 1906 19 2133-2134. Corn- pare Abstr. 1906 ii 745).-Manganese boride is recommended instead of ferroboron for the preparation of boron sulphide. The substance is heated in a current of hydrogen sulphide a t the melting point of antimony when the boron sulphide deposits in the cold part of the tube as a crystalline mass. It is rapidly decomposed by exposure to moist air. L. DE K. Production of Carbon from Carbides. C. HAHN and ANTON STRUTZ (Metallurgie 1906 3 727-732).-1n connexion with the question as to the possible formation of petroleum by the action of water vapour on mineral carbides the authors have investigated the action of various dry gases on carbides.Heated calcium carbide is decomposed by dry steam hydrogen chloride or hydrogen sulphide yielding amorphous carbon and the corresponding metallic compound. Acetylene is not formed unless moist steam is present. The same result is obtained with aluminium carbide. Manganese carbide on the other hand yields a glistening form of carbon resembling graphite when heated in dry hydrogen chloride. Carborundum reacts with steam at 1 300-1400° yielding silica and carbon in such an intimate state of mixture that it is not possible to determine whether the carbon is amorphous or crystalline. C. H. D. Purification of Crystalline Silicon and some Results of the Presence of Impurities in the Preparation of Copper Silicide.EMILE VICIOUROUX (Bull. soc. chim. 1907 [ivl 1 16-19 Compare this vol. ii 89).-Crgstalline silicon prepared by heating potassium silicofiuoride with aluminium in a clay crucible and purifying in the usual way by treatment first with dilute hydrochloric acid and then with dilute hydrofluoric acid contains iron which reveals itself by the formation of iron silicide FeSi when such silicon is used in making copper silicide (Abstr. 1906 ii 168 and this vol. ii 89). The author suggests that crystalline silicon prepared as above should be purified by digesting i t in ft finely-powdered state for some hours with hydrofluoric acid diluted with its own volume of water the operation being conducted in a platinum retort provided with a reflux condenser the residue resulting from this treatment is then washed and heated during one o r two hours in a platinum crucible with sulphuric acid. This treatment should be repeated until a sample of the material is entirely dissipated by treatment with a mixture of nitric and hydrofluoric acids the acids leaving no residue on evapora- tion.When crude crystalline silicon is heated in R leaden dish with hydrofluoric,acid the products evolved include a gas burning with a bluo flame which deposits on a cold surface a yellow substance. The same gas when passed through a heated glass tube furnishes a t the heated portion a similar yellow deposit. T. A. H.INORGANIC CHEMISTRY. 83 Action of Hydrogen on Silicon and Silica. A. DUFOUR (Ann. Chim. Phys. 1906 [viii] 9 433-474).-A detailed account of work already published (Abstr.1904 ii 398 482). The Anhydrous Oxides of the Alkali Metals. ~ T I E N N E RENGADE (Compt. rend. 1906 143 1152-1 153)-The oxides of rubidium potassium and sodium can be obtained in a state of purity by means of the method employed in the preparation of czesium oxide namely partially oxidising the metal and separating the unchanged metal by prolonged distillation in R vacuum (AbEtr. 1906 ii 850) ; rubidium oxide Rb,O forms small crystals which are golden yellow when hot and become pale yellow on cooling ; potassium oxide K,O is a greyish- white confusedly crystalline mass whilst sodium oxide Na,O is white and amorphous. It is probable t h a t in this method of prepara- tion a lower oxide of the metal is first formed which on heating decomposes into the oxide and metal (compare Forcrand Abstr.1899 ii 95). M. A. W. M. A. W. Optical Characters of Isomorphous Crystals. GEORG W ULFF (Zeit. Kryst. Mim 1907 42 558-686).-Determinations of the optical constants of mixed crystals of potassium and caesium sul- phatus of potassium and ammonium sulphates and of rubidium and ammonium sulphates prove that there is no linear relation between the refractive indices of the mixed crystals and those of the end members of the series. L. J. S. Conductivities of Mixtures of Sulphuric Acid with Sul- phates. Formation of Complex Salts of Hydrogen. AUGUSTE HOLLARD (Bull. Xoc. chim. 1906 [iii] 35 1240-1255).-When a 2% solution of sodium sulphate is added to a 6% solution of sulphuric acid in water there is a diminution in electrical conductivity.When the addition is mado to a 2% solution of sulphuric acid in water the con- ductivity no longer diminishes but increases slightly although it is still inferior to the sum of the conductivities of the components of the solution. On the other hand if the addition is made to a 3% solution of sulphuric acid the conductivity remains constant whatever may be the quantity of sodium sulphate added. The conductivity also remains constant when a solution of magnesium zinc or cupric eulphate is added to a 3% solution of sulphuric acid but with ammonium sulphate constancy is only exhibited by an 8% solution of sulphuric acid. These phenomena are due to the disappearance from the sulphuric acid solu- tion on the addition of solutions of the salts named of hydrogen ions which combine to form the complex ions HSO,.The measurements on which these results are based and curves illus- trating them are given in detail in the original. Action of Alkali Silicates on Soluble Metallic Salts. ROBERT DOLLFUS (Compt. rend. 1906 143 1148-1149).-When small crystals of metallic salts such as ferrous copper' or nickel sulphate manganese chloride uranium or cobalt nitrate are thrown into a solu- tion of sodium or potassium silicate a semipermeable membrane of the T. A. H.84 ABSTRACTS OF CHEMICAL PAPERS. metallic silicate is formed round the crystal and owing to h e internal osmotic pressure t h e low density of the metallic salt solution and the air bubbles mechanically adhering to the crystal the '' artificial cell " increases in size and presents the appearance of a vegetable growth. M.A. W. Allotropic Silver and its Colours. F. E. GALLAGHER (J. Physicul Chem. 1906 10 701-714).-The different colorirs of solu- tions of colloidal silver cannot be explained as an effect dire to the diffetence i n the refractive index of the colloidal particles and t h a t of the surrounding medium. The author's experiments on the other hand indicate that thephenomenon is probably due to selective light absorption depending on the thickness of the layer of solution the degree of coagulation and the concentration of the particles in the solution. Light is essential to the changes of colour the rate of change de- pending on the intensity of the light. It is supposed to act by coagu- lating the colloidal suspension or by altering the concentration of the particles by increasing the reduction of the silver in solution.With increasing thickness of the absorbing layer or with increasing size of the particles the amount of blue light transmitted decreases relatively much more rapidly than the amount of transmitbed red light. Ethyl alcohol acetone benzene and other organic liquids prevent the colour changes from taking place in the light. The action appears t o consist in the prevention of coagulation. H. M. D. Distillation of the Alloys of Silver with Copper with Tin and with Lead. HENRI MOISSAN and TOSIO WATANABE (Compt. rend. 1907 144 16-19. Compare Abstr. 1904 ii 617).-About 40 grams of each alloy of silver with copper tin and lead was distilled in the tube form of electric furnace and the residual alloy examined at short intervals. After a fifteen minutes' distillation of an alloy of equal weights of silver and copper the residue contained 95.22% of copper and 3.62% of silver.Distillation of an alloy of the composition 36.98% of silver and 64.04% of tin left an alloy containing 2.83% of silver and 93.65% of tin after ten minutes. Similarly with an alloy of 46*24%of silver and 52.95% of lead an alloy containing 96.81% of silver remained after two and a half minutes. The conclusion is drawn that lead is morevolatile than silver and silver more volatile than copper or tin. The results agree with those obtained by Kraflt ( Abstr. 1896 ii 464 635) who used very small quantities of alloy and dis- tilled in the cathodic vacuum. E.H. Reversible' Action of Oxygen on Magnesium Chloride. FPITZ HABER and F. FLEISCHMANN (Zeit. anorg. Chem. 1906 51 336-347).-The equilibrium constant of the reaction in question has been determined at different temperatures and a formula representing the dispIacement of the equilibrium with ternparatime is suggested. I n carrying out the experiments dry chlorine and oxygen i n varying proportions mixed with nitrogen were led slowly over a mixture of magnesium olride and chloride contained is a porcelain tube heated inINORGANIC CHEMISTRY. 85 an electric furnace the gaseous mixture being analysed on entering and on leaving the tube. The temperatures were such that oxy- chloride was not formed the reaction investigated being represented by the equation MgCl + $02 The equilibrium constant correqponding with this equation is Jcp = p ~ 1 ~ / p o ~ * ; it is the ratio of the partial pressures of the two gases.The most satisfactory results were obtained at 675' and 586O the mean value of kp at the former temperature being 0.25 and at the latter temperature 0.18. From these results by means of van't Hoff's equation connecting the displacement of equilibrium with temperature with & the heat developed in the reaction the value of Q a t the mean temperature of the experiments 630° is calculated as -5736 cal. whilst Berthelot gives Q = - 7800 cal. a t the ordinary temperature. It is known that Q in this case decreases with rise of temperature and on approximate assumptions as to the variation of the specific heatsof the gases with temperature it is calculated t h a t at 630' the value of Q would be - 5540 cal. in satisfactory agreement with the value given above.I n conclusion a formula is given which represents approximately the displacement of the equilibrium with temperature but this problem cannot be solved satisfactorily until the variation of the specific heats of the reacting substances with temperature is known more aecurately. G. S. MgO + Cl,. Action of Oxygen and Water Vapour on Magnesium Chloride. WILHELM MOLDENHAUER (Zeit. anorg. Chem. 1906 57 369-390).-l!he experiments described in the first part of this paper were made quite independently of those of Haber (compare preceding abstract) and have led to practically the same conclusions.MgO + C1 were carried out in a large porcelain tube into which the magnesium chloride was introduced in concentrated solution and then rendered anhydrous by heating in a current of hydrogen chloride. The magnesium oxide for the reverse reaction was introduced in a similar way. The tube was then filled with oxygen or chlorine as the case might be kept for some hours at a high temperature and the resulting mixture of gases analysed. The equilibrium was reached from both sides at 550° 650' and 700' the values of k=Cc,,/ ,/C< where CclZ and CO represent the respective concentrations of chlorine and oxygen being 17.4 25.3 and 29.5 respectively. Prom these results Q the heat evolved in the reaction at 600° is calculated as -5600 cals. i n good agreement with the calorimetric value when the variation of Q with temperature is taken into account.The action of water vapour on magnesium chloride was investigated by a somewhat similar method. In the first place by heating the chloride with aqueous vapour and hydrogen chloride until equilibrium was established and subsequently analysing the residue it was shown that from 350-505' there is an equilibrium represented by the equation MgCI + HzO MgCl-OH + HCl. At 505-510' the oxychloride is decomposed and above this point equilibrium is established according to the equation MgCI + HzO MgO + 2HC1. The experiments on the equilibrium MgCI + 40,86 ABSTRACTS OF CHEMICAL PAPERS. When equilibrium is attained at 350° 400° 500° 600° and 700° the gaseous phase contains 69.4 62.1 50.2 75.1 and 90.2 volumes of hydrogen chloride respectively.As the proportion of hydrogen chloride thus decreases with the temperature up to the point at which the oxychloride decomposes and beyond that point increases it follows that in the first reaction heat is developed-in other words half the hydrochloric acid is split off from magnesium chloride exothermically whereas the reaction MgC1 + H,O = MgO + ZHC1 is endothermic. The heat developed in the latter reaction calculated from the displace- ment of the equilibrium with temperature is in moderate agreement with the value obtained directly. I n addition to the hydrates of magnesium chloride described by van 't Hoff and Meyerhoffer a seventh hydrate MgCI,,H,O has been obtained by dehydrating the tetrahydrate in a current of hydrogen chloride above 11 1'.The technical bearing of these results is also considered. G. S. Condition8 of Precipitation of Metallic Sulphides. MAURICE PADOA and L. CAMBI (Atti R. Accad. Lincei 1906 [ v] 15 ii 787-7'96. Compare Bruni and Padoa Abstr. 1906 ii 157 ; MacLauclan Abstr. 1903 ii 716).-The authors have determined for solutions of different salts of various concentrations and containing varying proportions of acid the minimum and maximum pressures of hydrogen sulphide between which precipitation of the sulphide of the metal of the salt takes place. The salts examined were (1) cadmium chloride in presence of hydrochloric acid ; (2) zinc sulphate with sulphuric acid ; (3) zinc chloride with hydrochloric acid ; and (4) ferrous sulphate with sulphuric acid.I n the first three cases the pressures employed varied from 15 to 760 mm. and in the last from 200 mm. to 9.2 atmo- spheres. The pressures increase with the acidity of the solution. The two forms of apparatus used one for pressures up to that of the atmosphere and the other for higher pressure are described. T. H. P. Colloidal Plumbic Acid. ITALO BELLUCCI and NICOLA PARRAVANO (Aai R. Accnd. Lincei 1906 [v] 15 ii 542-549).-When potassium plumbate as free as possible from adherent alkali is treated at the ordinary temperature with water it undergoes complete hydrolysis into PbO,,Aq + ZKHO. The plumbic acid remains in solution in the colloidal state since cryoscopic measurements of the liquid indicate for the disaolved substances a molecular weight corresponding with KH0/2.The plumbic acid does not pass through a parchment membrane and the solution which appears turbid in reflected light can be filtered diluted with water heated to boiling and allowed to solidify without in any way changing the plumbic acid. The solution can be evaporated on the water-bath to a syrupy consistency without coagulating and the residual gelatinous mass provided it is not dried is soluble in water,. giving the hydrosol. I n this case the impurity which is essential for the maintenance of the plumbic acid in the condition of hydrosol the so-called " Solbildner," is potassium hydrozide the proportion of which is gradually diminishedINORGANIC CHEMISTRY. 87 by continued dialysis until after 104 hours the percentage of K,O is 1.87 and that of PbO 98.13.This proportion of K,O is of the same order as the amounts of hydrochloric acid essential for the existence of hydrosols of aluminium chromium and ferric hydroxides. T. H. P. Properties of the Plumbic Hydrosol. ITALO BELLUCCI and NICOLA PARRAVANO (Atti R. Accad. Lincei 1906 [v] 15 ii 631-635. Compare preceding abstract).-Two neutral colloidal solutions of plumbic acid containing (1) 0.3174 gram PbO and 0*0081 gram K20 and (2) 0,1288 gram PbO and 0.0330 gram K,O per 100 C.C. were found to cause no depression of the freezing point of water although other solutions containing varying proportions of alkali gave small depressions. The coagulating actions of the anions (potassium salts) decrease according to the series (I) iodide ferrocyanide tartrate fluoride ; (2) acetate chromate iodate nitrate sulphate thiocyanate chloride bromide dichromate pernianganate chlorate perchlorate ferricyanide ; (3) periodate oxalate carbonate arsenate and those of the cations {chlorides) according to the Eeries (1) aluminium ferric calcium strontium barium magnesium cadmium mercury manganese nickel cobalt copper ; (2) ammonium caesium lithium potassium rubidium sodium The anions and cations of series (1) produce total coagulation and those of series (2) partial coagulation whilst the anions of class (3) are without coagulating action.On increasing the volume of the coagulating solution used it was found that the coagulating action was almays increased but not to the same extent for all electrolytes. Solubility and Oxidation Potential of Lead Disulphate and Dioxide.FRIEDRICH DOLEZALEK and KARL FINCKH (Zeit. anorg. Chem. 1906 51 320-327. Compare Abstr. 1906 ii 597).-The solubility of plumbic sulphate in solutions of sulphuric acid of different strengths has been determined directly at 22". The concentration of the acid is conveniently expressed as the number of mols. of acid present per mol. of water. The curve representing the solubility rises rapidly from zero a t 0.3 mol. t o a maximum a t 0.6 mol. of acid slowly falls to a minimum value at 1 mol. of acid and beyond that point gradually rises. These results are in complete accord with the observations in a previous paper that below a concentration of 0.3 mol. of acid a higher sulphate cannot exist being hydrolysed to the dioxide that between 0.3 and 0.6 mol.of acid the solution is in equilibrium with the basic sulphate PbOSO,,H,O and beyond the latter point with the normal sulphate Pb(SO,),. The solubility of the former is increased that of the latter at first diminished by increasing acid concentration so that the maximum solubility coincides with the transition point. The gradual increase of solubility beyond a concentration of 1 mol. of acid is due in all probability to formation of complexes. Lead dioxide prepared by hydrolysis of the salts of quadrivaleat lead has approximately the salqe solubility in concentrated sulphuric T. H. P.88 ABSTRACTS OF CHEMICAL PAPERS. acid as the disulphate and has therefore been changed to the latter. The dioxide prepared by electrolysis or by chemical oxidation of lead salts is much less soluble.Contrary to the observations of Elbs and Rixon (Abstr. 1903 ii 427) and in agreement with these results lead dioxide is very slightly soluble in an acid solution containing less than 0-3 mol. of the latter per mol. of water. By means of a formula connecting the change of solubility with the acid concentration the solubility of the peroxide a t lower acid concentrations hss been calculated; it falls off very rapidly with dilution of the acid. The oxidation potential of the disulphate with different concentra- tions of sulphuric acid has been measured at 11.5' against a hydrogen electrode; the E.M.F. attains a maximum value of 1.9 volts at a concentration of acid corresponding with the maximum solubility of the disulphate.A formula has also been deduced showing the strength of acid which produces the most powerful oxidising effect at different temperatures. G. 8. Bismuth-thallium Alloys. MASUMI CHIKASHIG~ (Zeit. anorg. Chem. 1906 51 328-335. Compare Heycock and Neville Trans. 1892 61 S88 ; 1894 65 31).-As a result of his investigation of this system by Tammann's method of thermal analysis the author draws the conclusion that the two metals form a compound Biil?13 whilst there are indications of the formation of a second compound BiTl under certain conditions. The freezing point curve of the system shows three maxima at 212' and 37% 303.5' and 88-7% and 302' and 99.2% by weight of thallium respectively the former of which corresponds with a compound Bi,Tl,; and there are three eutectic points at 197' and 20% 186" and 53% and 297' and 93% by weight of thallium respectively.The first maximum and the second eutectic point were not observed by Heycock and Neville. T 10 compound Bi,TI forms a series of mixed crystals from 35-5-35 5% of thallium; another serics extends from 66*3-88*75% of thallium. The cooling curve of alloys from 60-76% of thallium bhows a transition point at 90° which may indicate that at that temperature the mixed crystals last mentioned react to fozm a compound BiTl,. As regards the maxima at 88.7' and 99.2% of thallium the alloys in this region behave as mixed crystals and not as chemical compounds ; and it is therefore considered that no chemical combination has taken place Heycock and Neville who obtained similar results regarded them as being due to the presence of impurities in their thallium but i t is pointed out that this cannot be the case as the thallium used in the present experiments was quite pure.The compound Bi,Tl is soft and difficult to polish the fresh surface is light grey in colour but r<ipidly becomes yellow and the compound is oxidised by long contact with air. EMILE VIGOUROUX (BUR SOC. chim. 1907 [iv] 1 7-lO).-Copper turnings freed from any visible solid impurity are heated with hydrochloric acid a few drops of nitric acid being added to the mixture from time to time to facilitate G. S. Preparation of Pure Copper.INORCtANIC CHEMISTRY. 89 solution. The black liquid so produced is filtered in the absence of air into a large excess of recently-boiled cold distilled water.The mother liquor is decanted from the precipitated cuprous chloride and a fresh supply of distilled water added to the latter. Excess of aluminium in large fragments is added to this mixture which is then set aside until the cuprous chloride is completely reduced. The excess of aluminium is then picked out with wooden tongs and the precipitated copper washed by decantation with water digested with hydrochloric acid again washed with distilled water and finally reduced by heating in a current of hydrogen. Copper may also be prepared by reducing cuprous chloride with soft iron but the latter unlike aluminium does not attack cupric chloride. Cupric sulphate is reduced by aluminium but the action proceeds slowly especiitlly in concentrated solutions of the sulphate even when these are warmed.T. A. H. Commercial Copper Silicides. ~ I L E VIGOUROUX (Bull. Xoc. chirn. 1906 [iii] 35 1233-1237. Compare Abstr. 1906 ii 168 and Lebeau ibid. ii 29).-1t is pointed out that Lebeau's statement (Zoc. cit.) that chemists who have worked on copper silicides have assumed that a silicide represented by the formula c'u,Si exists is inaccurate since the author had shown (Proces-verb SOC. Xci. yhys. nat. Bordeaux July 18th 1901) that the maximum quantity of silicon which could be combined with copper was about 1 O% corresponding with the formation of a compound Cu,Si. Three specimens of commercial copper silicides reputed t o contain 20% 15% and 10% of silicon respectively have been analysed and found to contain as impurities free silicon iron silicide FeSi man- ganese silicide MnSi in addition t o iron calcium and aluminium present in the form of silicides or aluminosilicides.The method of analysis adopted depends essentially on treating the raw material with nitric acid and is described in detail in the original. T. A. H. FRITZ FOERSTER and F. BLANKENBERG (Bey. 1906,3@ 4428-4436).-Acid cupric sulphate solutions dissolve copper forming a cuprous salt until an equilibrium is established as expressed by the equation 2 C u ' z - C ~ " + Cu. At the ordinary temperature the con- centration of cuprous sulphate is small but increases on heating. A similar equilibrium is established in amrnoniacal cupric sulphate solu- tion which in presence of copper is decolorised if the copper concentra- tion is below &/lo or when heated in stronger solution ; this becomes coloured again on cooling.From a solution containing 0-5 mol. cupric sulphate and 8.7 mol. ammonia a colourless crystalline compound Cu,S0,,4NH3,H2O is obtained which in presence of moisture decom- poses into copper and a cupric compound. Cuprous chloride forms a similar crystalline compound with ammonia. Cuprous Sulphate. E. F. A. Some Reactions of Mercuric Iodide. N. A. ORLOFF (Chem. Zeit. 1906 30 1301).-A methyl alcohol solution of palladous chloride converts mercuric iodide into the chloride with formation of palladous iodide. Freshly precipitated silver chloride turns yellow with a methyl90 ABSTRACTS OF CHEMICAL PAPERS. alcohol solution of mercuric iodide but in this casea double compound of the two salts is formed.An aqueous solution of thallium chloride gives with a methyl alcohol solution of mercuric iodide a red pre- cipitate of the latter but an aqueous solution of bismuth chloride remains quite clear and colourless on adding an alcoholic solution of mercuric iodide. L DE K. Adsorption Compound formed by Iodine with Basic Praseo- dymium Acetate. N. A. ORLOFF (Chem. Zeit. 1907 31 45).-The precipitate obtained by the addition of ammonia t o a solution of praseodymium acetate gives with iodine a violet-blue adsorption com- pound similar in properties to the corresponding lanthanum compound (Biltz Abstr. 1904 ii 339). W. H. G. Preparation of Pure Neodymium Oxide and Two New Methods of Separation of Rare Earths.OTTO HOLMBERCI (Chem. Centr. 1906 ii 1595-1597 ; from Chem. Lab. Univ. UjxaIu. Pamphlet 114 pages).-The following organic salts of rare metals have been prepared. The figures in brackets give the solubility of the anhydrous salt in 100 parts of water at 15'. Yt(C,H40,),,5H20. Malonates Ce2(C,H204),,6H20 ; Yt2(C,H,0,),,SH,0. Citrates 2cec6H50,,H,o ; 2LoC6H5O7,7H,O ; 2YtC6H,0,,5H,0. All three salts are amorphous but become crystal- line gradually. Di(C6H,S0,),,9H,0 ; Yt(C H so,)3,9H,o. m-Nitro benzenesul-phonat e: $h[ C6H4( N02)S03] 7 H20 (6 1 -0) ; (25.5) ; Ls[C6H,(N02)R0,],,6L120 (16.0) ; Pr[C6H,(N02)S0,],,6H20 (33.9) ; Nd[C,H4(N02)S03],,6H20 (46.1) ; Di C,H,(N02)S03 ,,6H,O (47.8) ; Yt[C,H4(N02)S0,]3,7H20 (48.3) ; Sa~~6H4(N02)80,33,7H2~ (5 0.9) ; Gd [ C6H,( NO,)SO,] 7 H,O (4 3 .S).m- Chlorobenzenesul- phonates La(C6H,C1S03) 9H20 ; Pr(C,H4C180,),,9H,O ; all crystallise in needles (1 3.0). La(C6H,BrSO3),,9H,O ; Di(C,H,BrS0,),,9H20 ; crystallises i n needles (13.0). Chloronitro- benzenesulphonates [Cl NO SO,H = 6 3 13 La[C6H3C1(N0,)S0,],,8H20 ; Pr[C6H3Cl(N0,)t%)3]3 1 4H,O ; Di[C6H3Cl(N02)S0,18,1 6H,o crystal- lise in flat plates (25). Pr(CloH7S0,),,6H20 ; Di( C,,H7S03),,6H20 crystallise in slender needles (5-6). 1 5-Nitronaphthalenesulphonates ; Pr[ c~oH6(No2)~03]3 6H20 ; Di[ C,,H,(N 0 2 ) S 0 ] 6 H20 ; crys t allise in prismatic needles (0.5). Tartrates Ce2(C,H,06),,6H,0 ; La,(C4H,0,),,gH20 ; Lq(C3H204) 395 2 0 ; Benzenesulphonates La(C6H,S0,)3,9H,0 ; Pr(C6H,S0,)3?gH,0 ; All crystalline (53-63). Ce[ c6H4( N02)S03]3,6H20 ui( c 6 ~ 4 c 1 s 0 3 ) 3 ~ ~ 2 0 m-Bromobenzenesulphonates a-Naphthalenesulphonates La(C,0H7S0,)3> ,O ; LaCC,,H6(N0,)S0,1a,6H,0 ; 1 6 -Nitronapht halenesulphonates La[ H 6 (NO,) s 0 3 1 3 9 H ~ o ;INORGANIC CHEMISTRY.92 Pr[C,oH,( N02)S0,],,9H20 ; Di[C,,H,(N0,)S03],,9H20 crystallise in needles (0.2). 1 7-Nitronaphthalenesulphonates Pr[C,oH,(NO,)SO,],,l 1H,O ; Di[C,oH,(N02)S03]3,9H20 crystallise in slender needles (about (1 -2). The salts of m-nitrobenzenesulphonate show the greatest differences of solubility and are also best adapted for separation on account of their slight isomorphism. Whilst the ratio of the solubilities of didymium and lanthanum ammonium nitrates is 1.6 1 that of the m-nitrobenzenesulphonates is 3 1. When 200 grams of didymium oxide which contained some praseodymium and samarium (at wt.142.4) mere dissolved in nz-nitrobenzenesulphonic acid and fractionated into twelve portions samarium gadolinium and yttrium accumulated in the mother liquors; on further separation the twelve original fractions yielded fifty-two. The differences in the atomic weights determined by the oxide-sulphate method gave an indication of successful separa- tion. The fractions containing the most neodymium were again treated and the middle portions still further fractionated; fractions 7-13 then gave a constant atomic weight = 144*0-144*1. The absorption bands of a solution of neodymium chloride were measured for eight different concentrations varying from 2 N to N/64 (Forsling) and the maxima between 689.5 and 342 pp are tabulated in the original paper.The spectra showed no trace of absorption bands of samarium lanthanum yttrium or praseodymium but the first and last fractions of the last series contained a small quantity of samarium or praseodymium. Four series of atomic weight determinations gave values varying from 144.01 to 144.13 or a mean value= 144.08. A mixture of samarium and gadolinium has also been submitted to the m-nitrobenzenesulphonic acid and to the picric acid methods of separation. Gadolinium separated first and then samarium and yttrium whilst cerium accumulated in the mother liquors. After continued fractionation the potassium sulphate method eventually yielded almost pure samarium oxide which gave an atomic weight = 150. Pure gadolinium compounds were prepared from other fractions.Gadolinium could not be readily separated from terbium by the m-nitrobenzeuesulphonic acid method but by means of picric acid and partial precipitation with ammonia gadolinium of atomic weight = 156 was finally obtained. Samarium may be separated from gadolinium by Urbain-Lacombe's bismuth magnesium nitrate method. Experiments have also been made on a terbium material which contained yttrium gadolinium samarium and neodymium by means of m-nitrobenaenesulphonic acid and picric acid. Paucity of material however prevented the complete isolation of terbium. Absolute Atomic Weight of Dysprosium. GUSTAVE D. HINRICHS (Compt. rend. 1906 143 1143-1145).-The author has applied his method of calculating atomic weights (Abstr.1893 ii 163 277 316 317 ; 1894 ii 39 87 276 ; 1900 ii 534 539; 1905 ii 517; 1906 ii 450) to Urbain's analytical data for the atomic weight of dysprosium (Abstr. 1906 ii 855)) and finds the value Dy=162*5 (S=32 H = l ) . La[CloH,(N0,)S0,13,9H,0 ; E. W. W. M. A. W.92 ABSTRACTS OF CHEMICAL PAPERS. Solubility of Carbon in Manganese Sulphide. M. HOUDABD (Compt. rend. 1906 143 1230-1233).-When manganous sulphate is reduced by means of excess of sugar carbon at the temperature of the electric furnace the product has a black metallic appearance and consists of manganese sulphide containing dissolved graphite (compare Mourlot Abstr. 1896 ii 25) the quantity varying from 0.002% to 3.20% according as the heating was prolonged during 2 or 25 minutes respectively and similar results are obtained when pure manganese sulphide is fused in the electric furnace with 10% of sugar carbon.The graphite obtained from the fusions is non-intumescent ; yields with Brodie's mixture the pale yellow crystalline oxide (Abstr. 1873 348) which on burning gives black pyrographitic acid; its ignition temperature is 640° (Moissan Abstr. 1896 ii 165 ; 1903 ii 141) and it contains 98.01-98*92% of carbon and 0.209-0*218% of ash. Manganese sulphide a t the temperature of the electric arc converts a particle of diamond almost completely into that form of graphite which is insoluble in fuming nitric acid. GUSTAV GIN (Compt. rend. 1906 143 1229-1230).-When rhodonite is reduced in the electric furnace a crystalline silicomanganese is obtained having the per- centage composition Mn = 68.64-69.26 ; Fe = 4.40-3.18 ; Al- 0*74-0.60 ; Si = 25A02-25*51 ; C = 0*16-0*18 ; S = 0.01 ; P= 0.01 ; and containing 95% of a crystalline manganese silicide Mn,Si (compare Lebeau Abstr.1904 ii 343 ; and Vigouroux Abstr. 1905 ii 822) which forms brilliant prismatic crystals sometimes 5 cm. long DI5 6.05 m. p. 125O0-13OO0; is attacked by chlorine with in- candescence at a red heat is not changed by oxygen a t the ordinary temperature but superficially oxidised a t 500' ; is readily attacked by the gaseous halogen acids by nitric or hydrochloric acid or aqua regia or by fused alkali carbonates or mixtures of carbonates and nitrates whilst sulphuric acid has no action on the compound. M. A. W. A New Manganese Silioide. &I.A. W. Influence of Chromium on the Solubility of Carbon in Iron and on the Formation of Graphite. PAUL GOERENS and A. STADELER (MetaEZurgie 1907 4 18-24).-1t is known that a part of the chromium in iron-chromium-carbon alloys is present as the carbide Cr,C,; it is not known however whether definite double carbides of iron and chromium are formed or whether the two carbides Cr,C and Fe,C merely form solid solutions with one another. The authors have melted iron with ferro-chromium in presence of an excess of carbon and have determined the freezing point and composition of the resulting alloys. It is necessary to heat t o about 1600' to insure saturation with carbon. The presence of chromium increases the solubility of carbon in iron so that when 62% of chromium is reached 9.2% of carbon is dissolved.The freezing point of these alloys increases with increasing chromium content; the results are recorded in a diagram with triangular co- ordinates. The position of the martensite-cementite eutectic point is displaced in the direction of higher carbon by addition of chromium 60INORGANIC CHEMISTRY. 93 that an alloy containing 5% of chromium and 4.7% of carbon is entirely composed of eutectic. Microscopic examination confirms the abave results. When the eutectic point is passed crystals appear which a t first have the appearance of cementite but with increase of chromium resemble more and more closely the crystals of chromium carbide. The formation of graphite is hindered by the addition of chromium even when silicon is present.C. H. D. Copper and Iron [Alloys]. HERNANN WEDDING and WiLHELnz MULLER (Stcdd. u. Eisen 1906 26 1444-1447).-Copper alloys with iron in all proportions. The alloys are conveniently prepared by Goldschmidt’s aluminothermic method. The malleability of iron is reduced by addition of copper but the hardness and strength are increased. A n alloy containing 7.77% of copper and 0.14% of carbon does not shorn any separate micrographic constituent but the crystal grains are more curved and interlocked than in pure iron. I n alloys containing more carbon the presence of copper hinders the formation of pearlite causing segregated cementite to appear. The transformation tem- perature is lowered to 620-640” by the addition of copper. C. H. D. Soluble Iron Sulphide. A.KONSCHEGCJ and HANS MALFATTI (Zeit. ccncd. Chenz. 1906 45 747-751).-A preliminary paper on the behaviour of iron sulphides towards alkali sulphides. Ferrous sulphide does not dissolve in aqueous potassium or sodium hydroxide but the mixture of ferrous sulphide and sulphur formed on adding ammonium sulphide to ferric chloride yields a dark green solution. The authors assume the presence of a polysulphide of iron with acidic properties which in presence of alkali hydroxides forms a true solution and not one cobtaining colloidal iron. I n the absence of ammonium chloride ferric hydroxide or basic phosphate dissolves i n ammonium sulphide to a dark green liquid which is precipitated by ammonium chloride and also by a large excess of ammonium polysulphide (compare also de Koninck Abstr.1906 ii 397). L. DE K. Ferrous Compounds of Nitric Oxide. WILIIELM MANCHOT and K. ZECHENTMATER (An?wZen 1906 350 368-339. Compare Gay Abstr. 1885 1109 ; Thomas Abstr. 1899 ii 368 426).-The authors have investigated quantitatively t h e absorption of nitric oxide by aqueous and alcoholic solutions of ferrous salts under varying condi- tions. The results are tabulated and expressed in curves and the following conclusions are drawn. The absorption of nitric oxide by a ferrous salt results from the formation of a chemical compound contain- ing Fe and NO in the proportion 1 1. Under all conditions therefore the limit of absorption is reached when 1 mol. of nitric oxide has been absorbed for each ferrous atom present and corresponds with the con- version of Fe” into Fe”’.The formation of the compound is a reversible reaction; the degree of dissociation varies with the ferrous salt but is dependent also on the pressure temperature concentration of the ferrous VOL. XCII. ii 794 ABSTRACTS OF CHEMICAL PAPERS. salt presence of indifferent solutes and nature of the solvent t o an extent which is in agreement with the laws of chemical dissociation. G. Y. Cryoscopy of Colloidal Solutions of Ferric Hydroxy- chloride. G. MALFITANO and LEOPOLD MICAEL (Compt. rend. 1906 143 1141-1143. Compare Abstr. 1906 ii 450 526 647).- Attempts to determine the molecular mass of the granules of colloidal ferric hydroxychloride from the difference between the freezing point of a colloidal solution and the filtrate obtained by filtering the solution though a collodion membrane (Abstr. 1906 ii 526) were unsuccessful as the differences were sometimes negative and sometimes positive.M. A. W. Acid Functions of Nickel Dioxide. ITALO BELLUCCI and S. RUBEGNI (Atti A?. ACCCC~. Lincei 1906 [v] 15 ii 778-787. Compare Bellucci and Clavari Abstr. 1905 ii 823).-The authors have confirmed the existence of the compound Ni,0,,2H20 prepared by Dudley (Abstr. 1897 ii 171). The alkali which is only removed by very thorough washing with water exists in combination with the nickel oxides in the form of the nickelite Na,Ni,O or 2Ni0 NiO Na,O which the authors have prepared and analyeed. This compound when washed with boiling water is hydrolysed t o the compound NiO 2Ni0,2H20 whilst the potassium compound NiO,,NiO,K,O (compare Hoff mann and Hiendlmaier Abstr.1906 ii 747) on hydrolysis with iced water yields the compound NiO2,Ni0,2H,O. I n both cases the product of hydrolysis retains unchanged the crystalline appearance of the original alkali nickelite. T. €€* P. t Nickel Chromates. MAX GIU~GER (Zeit. anorg. Chem. 1906 51 348-355. Compare Abstr. 190G ii 45 l).-Normal aqueous solutions of nickelous chloride were mixed with normal solutions of sodium pot'assium and ammonium chromates left for some days and the resulting precipitates washed and dried. All the products were reddish-brown in colour and proved t o be basic chromates of nickel containing varying proportions of alkali chromatee. They are hydrolysed by water alkali chromate and acid chromates of nickel going into solution and highly basic chromates of nickel remaining behind. Unlike the behaviour of the corresponding manganese and cobalt compounds no higher oxide of nickel was found in the residue.By interaction of stronger. solutions three crystalline double chromates were obtained. The compourd N iCr04,K2Cr04,2H20 occurs in yellow needles which are stable in the air but undergo hydrolysis with water. Tho compound NiCr04,(NH,),Cr04,6H20 was obtained in green crystals (compare Briggs Trans. 1903 83 391). By a slightly different method a second nickel ammonium chromate of the probable formula (NHJ2Cr04 NiCr0,,NH3,HS0 was isolated in well-formed orange-brown prisms. This compound isINORGANIC CHEMISTRY. 95 stable in the air but is hydrolysed by water with formation of basic nickel chro m ates.0. s. The Reduction of Oxides by Aluminium. Preparation of Chromium. EMILE VIGOUROUX (Bull. SOC. chim. 1907 [iv] 1 10-1 3. Compare Abstr. 1905 ii 823).-Commercial chromium prepared by the " thermit " process has the advantage of being free from carbon but frequently contains silicon aluminium iron and portions of slag. A much purer material can be prepared on a small scale by a modification of this process which consists in mixing from 10% to 20% of dried chromium trioxide with the dried chromium sesquioxide and then incorporating the necessary quantity of aluminium powder. The mixture is heated in a crucible lined with magnesia. Under these conditions a vigorous reaction ensues which when 20% of chromium triovide has been added lasts about a minute the contents of the crucible becoming thoroughly melted and the slag separating readily f r o 9 the metal.The chromium produced contains as impurities 0.36-0.4% of silicon and 0*74-0*85% of aluminium and iron. T. A. H. Definite Compounds formed by Chromium and Boron. ARNAND BINET DU JASSONEIX (Compt. rend. 1906 143 1149-1151). -Chromium-boron alloys (this vol. ii 30) contain the two definite compounds Cr,B and CrB dissolved respectively in a medium less rich in boron which can only be isolated in a state of purity from the nearly homogeneous alloys the composition of which is close to that of their own. The tioride Cr3B2 isolated from an alloy containing 11.6% of boron by the action of hydrogen chloride below a red heat has D'j 6.7 burns in fluorine when gently heated and is attacked with incandescence by chlorine below a red heat; the action of bromine is less vigorous whilst iodine vapour has only a superficial action a t a red heat.When Eeated in air or oxygen it becomes covered with a vitreous layer of the borate; it is converted into a mixture of boron and chromium sulphides together with unchanged boron by the action of boiling sulphur; it is completely soluble in concentrated or dilute hydrofluoric hydrochloric or sulphuric acid and is oxidised with incandescence by fused alkali hydroxides or carbonates ; it is not acted on by nitric acid or alkali solution or by nitrogen a t a white heat. The boride CrB isolated by the action of hydrogen chloride or chlorine below a red heat on the alloy containing 16% of boron has DI5 6.1 and whilst its chemical properties closely resemble those of the lower boride Cr3BrZ i t is in general more readily attacked; it takes fire in cold in contact with fluorine and when heated in nitrogen at a white heat forms a greyish-black substance which liberates ammonia on treatment with fused potassium hydroxide.M. A. W. The Violet and Green Varieties of Chromium Chloride. F. JOST (Ber. 1906 39 4327-4330. Compare Recoura Abstr. 1886 508 ; Piccini Abstr. 1895 ii 229 ; Werner and Gubser Abstr. 1901 ii 453).-The author shows by determinations of the molecular 7-296 ABSTRACTS OF CHEMICAL PAPERS. weight by the ebullioscopic method of the violet and green varieties of chromium chloride respectively in methyl alcoholic solution that the water plays a different r6Ze in the green chloride and violet chlorides.The violet salt gives values for its molecular weight varying from 54.7 to 60.3 whereas the green salt gives values varying from 33.1 to 33.4. The molecular conductivity of a solution of the violet salt in methyl alcohol varies from 67.7 to 97.7 whereas the green modification gives values varying from 43.6 to 64 2. The experiments quoted are in accordance with Werner’s theory in so far that in the green hydrate the water is more loosely bound than in the violet. A. McK. Cobaltimolybdates. CARL FRIEDHEIM and F. KELLER (Ber. 1906 39 4301-4310).-The cobaltimolybdates described by the authors are distinguished from cobaltomolybdates in that chlorine is evolved when they are boiled with hydrochloric acid.They are characterised by possessing a colour varying from brilliant green t o dark green. The compound 3(NH4),0,Co0,Co0,,1 2Mo03,20H,0 is obtained by adding a 30% aqueous solution of ammonium persulphate t o a mixture of cobaltous acetate and ammonium paramolybdate acidifying with dilute acetic acid and then slowly heating. It may alho be prepared by the action of cobaltous acetate on the ammonium permolybdate 3(NH4),0~5M00,,2M00,,6H,0 It forms green rhombic plates and dissolves in water to a green solution. With concentrated sulphuric acid oxygen is evolved ; ammonia is evolved by the action of potassium or sodium hydroxide. It is reduced by sulphurous acid. Hydrogen peroxide causes the evolution of oxygen whilst permolybdatss are formed. The compound 2(NH4),0,Co0,Co0,,10M00~~,1 2H,O best obtained from cobaltous acetate ammonium paramoly bdate and hydrogen peroxide forms dark green rhombic crystals.The compound 3K20,Co0,Co0,,10M00,,1 1H2O7 obtained either from cobaltous acetate potassium persulphate and potassium paramoly b- date or from cobaltous acetate and ammonium permolybdate and potassium chloride or by the addition of potassium chloride to a cold saturated aqueous solution of the compound 3(NH,),O,CoO,CoO 1 2M00,,20H20 forms greenish-white rhombic crystals. The compound 3K20,Co0,Co0,,1 2M00,,15H20 prepared. by the addition of potassium chloride to an aqueous solution of the compound 2(NH4)20,Co0,Co0,,10Mo0 12H,O forms olive-green crystals. The compouud 3 Ba0,Co0,Co0,,9M003,25H20 prepared by the addition of barium chloride to an aqueous solution of the compound 2(NH,)20,Co0,Co0,,1 OMoO 22H,O is bright green.The compound A( NH4),0 1 ~Ba0,Co0,Co0,,10M00,,18~H20 pre- pared from barium chloride and the compound is bright green. A. McK. 3(NH4)207 Co0,Co02 1 2Mo03,20H20,INORGANIC CHEMISTRY. 97 Preparation of Titanium Tetrachloride. MILE VIGOUROUX and G. ARRIVAUT (BUZZ. SOC. chim. 1907 [iv] 1 19-21).-Com- mercial ferrotitanium containing about 55% of titanium is employed RS a raw material. This i n a coarsely powdered condition is placed in a wide porcelain tube heated in a Mermet furnace. A current of dry chlorine is passed 'over the heated alloy and the reaction commences when the latter is a t a dull red heat. This method has the disadvantage that considerable quantities of ferric chloride are formed which are liable to block the tube unless they are periodically removed.This difficulty may be overcome by digesting the finely powdered ferro- titanium with dilute hydrochloric acid which leaves a product contain- ing S0-90% of titanium with small quantities of titanium dioxide. The latter may be removed by levigation and the residue is treated as before when it furnishes crude titanium tetrachloride and leaves in the porcelain tube a small residue of titanium dioxide. The titanium dioxide obtained as a by-prodnct mny also be converted into the tetra- chloride by mixing it with carbon and heating in a current of chlorine. The crude titanium tetrachloride is filtered to remove suspended ferric chloride and the filtrate on fractional distillation yields the pure tetra- chloride b.p. 136". T. A. H. Colloidal Compound of Thorium with Uranium. B ~ L A SzILARD(Compt. rend. 1906,143,1145-1 147).-Thoriumhydroxide,pro- cipitated by meansof ammoniaand well washed partially dissolves in a hot solution of uranium nitrate forming a deep red colloidal mixture which on separation in a centrifugal apparatus and drying in a vacuum over sulphuric acid forms small brilliant carmine red transparent plates which are amorphous and have the following percentage composition Th = 72-74 U = 4-5.5 H,O = 1%- 13,O = 10-1 1. The dry compound is stable towards heat and light dissolves without decomposition in hot water and yields the corresponding salts when dissolved in dilute acids; it has D18'3 4482-5*45 and when thrown into water produces a sharp hissing with evolution of a gas the nature of which is at pre- sent not determined.The compound is more readily prepared by heating the mixture of thorium hydroxide and uranium nitrate in an autoclave at 200' under 15 atmos. pressure. When uranyl chloride replaces uranium nitrate in the above reaction the colour of the colloidal compound is reddish-yellow ; the reaction proceeds very slowly when uranium acetate or sulphate is employed in place of the nitrate whilst thorium nitrate has no action on thorium hydroxide. M. A. W. Some Sulphates of Quadrivalent Vanadium. GUSTAVE GAIN (Compt. rend. 1906 143 1154-1156. Compare this vol. ii 32).- By the action of dill'erent quantities of sulphuric acid on the deep blue liquid obtained when a mixture of the oxides V,O and V,O is treated with a saturated solution of sulphur dioxide the author has prepared three acid uccnccdyl su@hates belonging to the same group as those prepared by Koppel and Behrendt (Abstr.1903 ii 551) whilst two other members of the same series have been prepared by the action98 ABSTRACTS OF CHEMICAL PAPERS. of sulphuric acid on red hydrated hypovanadic acid V20,,2H20. These new acid vanadyl sulphates are crystalline and possess blue colours 2VOS0,,3H2S0 1 5H,O is azure blue 2VOS0,,4H2S0 16H,O is tur- quoise blue 2VOSO4,5H,80,,1 5H,O is greenish-blue 2VOSO4,7H,S0 1 5H20 is bright blue and 2VOS0,,8H,S0,,16H20 is very bright blue. M. A W. Preparation and Chemical Properties of Antimony Penta- fluoride. OTTO RUFF [and in part with GRAF HELLER and KNoCH] (Bey.1906 39 4310-4327. Compare Ruff and Plato Abstr. 1904 ii 265)-Additional details for the preparation of antimony penta- fluoride by the action of hydrogen fluoride on antimony pentachloride are given. I n the course of the preparation it is probable that a compound SbF&HF is formed from which the hydrogen fluoride must be completely eliminated before the antimony pentachloride is distilled. Antimony pentafluoride has h. p. 149-150' instead of 155' as formerly stated by Ruff and Plato (Zoc. cit.). Chlorine apparently has no action on antimooy pentafluoride ; bromine forms a viscid dark-brown mass possibly containing the com- pound SbF,Br. Iodine reacts with antimony pentafluoride with development of heat and the formation either of a bluish-green liquid or of a dark brown or bluish-green solid according to the amount of pentafluoride used.When an excess OF pentafluoride is used and the mixture is hea.ted at 160-220° the compound (SbF,),I is formed as a dark bluish-green crystalline mass m.p. 110-115" which does not lose iodine at 240'; by prolonged heating in a current of carbon dioxide practically no iodide is given off but the excess of antimony pentafluoride distils over. Water decomposes i t with hissing and separation of iodine. If an excess of iodine is used and the temperature is raised above the b. p. of iodine the compound SbF,I is formed by the action of iodine on antimony pentafluoride after the excess of iodine is evaporated off. When heated above 260' iodine is evolved.The compound SbF,I m. p. slightly below SO" is dark brown and differs from the compound (SbF,),I in undergoing slow decomposition with water. The solution of sulphur in antimony pentafluoride is dark blue and yields the compound SbF,Sr m. p. about 230'. I t is very hygroscopic and when acted on by moist air yields sulphur ; antimony trichloride and thionyl fluoride are also formed. The action of water probably proceeds according to the equations 2SbF,S + H,O = 2SbF + S + SOF + 2HF and SOF + H,O =SO + 2HF. Antimony pentafluoride is acted on by phosphorus with production of flame and the formation of yellow vapour which sublimes. The majority of metals when dry do not act on antimony penta- fluoride. When heated with sodium rapid combustion occurs with the formation of white vapour.Antimony dust reduces it to the trifluoride. With little water i t forms the solid hydrate SbF,,2H20 (loc cit.). I t s aqueous solution i> nnt decomposed in hhe cold byINORGANIC CHEMISTRY. 99 hydrogen sulphide or by potassium iodide ; action does not occur until the temperature is raised. On the addition of sodium hydroxide or of sodium carbonate it forms sodium bydrogen pyronntimonate in quantitative yield. When its aqueous solution is evaporated the syrupy residue con- tains a hydrate of antimony pentafluoride which when heated is decomposed with formation of water hydrofluoric acid and antimonic acid; the syrup however does not form anhydrous antimony penta- fluoride when heated with sulphuric acid or phosphoric oxide.When a current of hydrogen sulphide is passed over it snlphur hydrogen fluoride and an antimony thiofluoride are formed. When a current of dry ammonia is passed over it a vigoroiis action . occurs and the pentafluoride becomes coated with a yellowish-red crust which prevents further action. When heated however with liquid ammonia a t 100" in a platinum tube it forms diccmino-dic~ntintony-tri- Ruo~oimide dihycZroJuoride NH(SbF,-N H,-HF) a white powder which is very readily decomposed by atmospheric moisture ; it4 is slowly acted on by water with formation of antimonic acid ; its aqueous solution is acid towards litmus. Antimony pentafluoride is acted on by nitrogen sulphide sulphur dichloride and chromyl chloride respectively. When heated to above 100' with molybdenum pentachloride it forms R molybdenum fluoride and antimony pentachloride the latter parting with some of its chlorine to form don ble compounds with the excess of antimony pentafluoride. With tungsten hexachloride it forms tungsten hexafluoride.It reacts vigorously with phosphorus trichloride with the formation of phosphorus trifluoride. With phosphoric oxide it forms phosphorus oxyfluoride. It forms a series of crystalline compounds with arsenic trifluoride. With antimony trifluoride i t forms compounds varying in composition from SbF5,2SbF to SbF5,5SbF,. Hydrogen chloride is evolved when it is mixed with tin tetrachloride titanium tetrachloride or silicon tetrachloride. Colloidal silicic acid when warmed with antimony penta fluoride forms antimonic acid and silicon tetrafluoride.The behaviour OF antimony pentafluoride towards various carbon compounds was also investigated Filter paper cork mood and india- rubber are attacked a t once. The action with benzene is vigorous hydro- gen fluoride being evolved. Ether alcohol acetone glacial acetic acid ethyl acetate carbon disulphide light petroleum toluene arid chloro- form all react with antimony pentaflnoride. With carbon tetrachloride at about 45" a gas is evolved which readily liquefied and is probably The compound SbF3,2NH is obtained by the action of liquid ammonia on antimony trifluoride as tt yellow powder which loses ammonia in contact with moist air. It is less stable than the compound obtnined from antimony pentafluoride. CC1,F. A . McK. Alloys of Palladium and Silver. RUDOLF RUEE (Zeit. anorg. Ghern. 1906 51 315-319. Compare this vol. ii 32).-The freezing- point curve falls regulaxly from the melting point of palladium 1541" to that of silver 961.5' ; unlike the system palladium-copper the curve is slightly concave to the axis of concentration. I t follows that the100 ABSTRACTS OF CHEMWAL PAPERS. metals form a complete series of mixed crystals with no indication of chemical combination and this conclusion is confirmed by microscopic observations. The hardness of the alloys lies between that of the components and increases with the proportion of palladium. The micro-structure of the alloys is described and illustrated by six microphotographs. G. S. Alloys of Palladium and Gold. RUDOLF RUER (Zeit. anorg. Chenz ,1906 51,39 1-396. Compare preceding abstract)-The freezing- point curve of the system Falls continuously from the melting point of palladium to that of gold ; like the corresponding curve for palladium- silver alloys it is concave to the axis of concentration. The metals form a continuous series of mixed crystals and there is no indicatlion of chemical combination. Alloys containing more than 10% of palladium are white. The hardness increases with increase in the amount of palladium until 700/ of the latter element is present but beyond this point decreases. The fact that none of the three elements copper silver gold enter into chemical combination with palladium is in accordance with Tammann’s rille ( Abstr. 1906 ii 346) according to which either all or none of the elements of x natural group in the narrower sense enter into chemical combination with another element. G. S.

ISSN:0368-1769    

DOI:10.1039/CA9079205080

出版商:RSC    

年代:1907

数据来源: RSC