摘要:

J O U R N A L HORACE T. BROWN LL.D. F.R.S. A. W. CROSFILEY D.Sc. Ph.D. F.R.S. H. B. DIXON M. A. Ph.D. F.R.S. M. 0. FORSTER D.Sc Ph.D. F.R.S. C. E. GROVES F.R.S. J. T. HEWITT M.A. D.Sc. Ph.D. A. MCKENZIE M. A DSc. Ph. D. F.R.S. OF R. MELDOLA F.R.S. G. T. MORGAN D.Sc. Sir WILLIAM RAMBAY K.C. B LL.D. A. SCOTT M.A. D.Sc. F.R.S. Sir EDWARD THORPE C.B. LL.D. F.R.S. F. R. S. THE CHEMICAL SOCIETY ABSTRACTS OF PAPERS ON ORGANIC CHEMISTRY. E. F. ARMSTRONG Ph.D. D.Sc. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. C. H. DEBCH D.Sc. Ph.D. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. E. GOULDING D.Sc. W. D. HALLIBURTON M.D. F.R.S. T. A. HENRY D.Sc. E. HORTON B.Sc. 2. EAHAN B.Sc. L. DE KONIXOH. F. M. G . MICKLETHWAIT. N. H. J. MILLER Ph.D. T. H. POPE B.Sc. T. SLATER PRICE D.Sc. PI1.D. E. J. RUSSELL D.Sc. S. B. SCHRYVER D Sc. Ph.D. G. SENTER Ph.D. B.Sc. W. P. SKERTCHLY. C. SMICH D.Sc. F. SODDY M.A. F.R.S. L. J. SPENCER M.A. R. V. STAXFORD M.Sc. Ph.D. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph.D. B.A. G. S. WALPOLE B.Sc. W. 6. WOOTTOY B.Sc. __ 1010. Vol. XCVIII. Part I. LONDON 1910. GURNEY & JACKSON 10 PATERNOSTER ROW.RICHARD CLAY & Sam LIMITLD BREAD STREET HILL E.C. -ND BUNGAY 5TFBOLX

ISSN:0368-1769    

DOI:10.1039/CA91098FP001

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

J O U R N A L HORACE T. BROWN LL.D. P.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. H. B. DIXON M.A. Ph.D. F.R.S. M. 0. FORSTER D.Sc. Ph.D. F.R.S. C. E. GROVES F.R.S. J. T. HEWITT M.A. D.Sc. Ph.D. A. MCKENZIE M.A. D.Sc. Ph.D. F. R. S. OF R. MELDOLA F.R.S. G. T. MORGAN D.Sc. Sir WILLIAM RAM\AY ILC. B. I,L.D. A. SCOTT M.A. D.Sc. F.R.S. Sir EDWARD THORPE C.B. LL.D. F.R.S. F. R. S. THE CHEMICAL SOCIETY. E. F. ARMSTRONG Ph.D. D.Sc. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAW~ON Ph.D. D.Sc. C. H. DEPCH D.Sc. Ph.D T. EWAN B.Sc. Ph. D. W. H. GLOVER Ph.D. E. GOULDING D.Sc. W. D. HALLIBURTOK M.D. F.R.S. T. A. HENRY DSc. E. HORTON B.Sc. Z. KAHAN B.Sc. L. DE KONINGH. F. M. G. MICKLETHWAIT. N. H. J. MILLER Ph.D. ABSTRACTS O F PAPERS PHYSICAL INORGANIC MINERALOGICAL PHYSIOLOGICAL AGRICULTURAL ANALYTICAL CHEMISTRY. ON AND T. H. POPE E.Sc. T. SLATER PRICE D.Sc. Ph.D. E. J. RUSSELL D.Sc. S. B. SCHRYVER D.Sc. Ph.D. G. SENI'ER Yh.D. B.Sc. W. P. SKEETCHLY. C. SMITH D.Sc. F. SODDY M.A. F.R.S. L. J. SPENCER M.A. R. V. STANFORD M.Sc. Ph.D. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKEP. Ph.D. R.A. G. S. WALPOLE B.Sc. W. 0. WOOTTON B.Sc. 1910. Vol. XCVIII. Part 11. LONDON GURNEY & JACKSON 10 PATERNOSTER ROW 191 Q,RICHARD CLAY & SONS TJIMITED BREAD bTREET HILL E.C. AND BTJNQAT SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA91098FP003

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 27 Anodic Formation of Hydrogen Peroxide. FRANZ RICHARZ (Bey. 1909 42 4674-4675. Compare Riesenfeld and Reinhold Abstr. 1909 ii 879).-The secondary formation of hydrogen peroxide at the anode has been observed by the author (Abstr. 1885 624; 1888 12 769). C. H. D. Diseociation of Eydrogen Bromide and Hydrogen Iodide at High Temperatures. KURT VOCEL VON FALCKENSTEIN (Zeitsch. physikal. Chenz. 1909 68 270-280).-The measurements were made by determining the partial pressure of the hydrogen by Lowenstein's method (compare Abstr. 1906 ii 272). The dissociation of hydrogen bromide is 0.50% a t 1024O 0.73% a t llOSa and 1.08% at 1222'; that of hydrogen iodide is 32.9% at 1022' and 37.55% at 1217O. The results and also the fact that at the high temperatures used the ha1 ogen molecules are partly dissociated according to the equations Br2=2Br' and 12=21 will be discussed in a later communication G.S. Electric Conductivity and Density of Solutions of Hydrogen Fluoride. ERNEST G. HILL and ANNODA P. SIRKAB (Proc. Roy. Xoc. 1909 A 83 130-148).-Measurements have been made of the electrical conductivity and density of mixtures of water and hydrogen fluoride ranging from the one pure substance to the other. A satisfactory conductivity cell mas constructed from paraffin wax of low melting point (40.4'). The density measurements were made by weighing a lead cylinder coated with paraffin wax in the various liquids Curves are plotted which show the variation of the specific con- ductivity and of the density with the percentage composition of the solutions.These are of approximately the same type and exhibit a well-defined maximum for a solution containing 75% of hydrogen fluoride. The curve which is obtained when the molecular con- ductivity of the hydrogen fluoride is plotted as a function of the concentration shows two distinct breaks one at a b w t 91% the other between 51% and 55% of hydrogen fluoride. The former corresponds with the composition 9HF,H,0 the latter with HF,H,O and theii. 28 ABSTRACTS OF CHEMICAL PAPERS authors draw the conclusion that definite hydrates of this composition ar0 present in the solutions. From values obtained for the conductivity at 0' and lSo the tern- perature-coefficient has been calculated. This is constant and equal to 0.0125 for solutions containing less than '7-7yA of hydrogen fluoride.By applying this temperature correction molecular conductivity data €or 25' are obtained. On comparison with Ostwald's numbers for dilute solutions aqsatisfactory agreement is obtained a t the dilution v = 4 but for more dilute solutions the authors' numbers are much smaller than Ostwald's the difference increasing with the dilution. H. M. D. Production of Ozone by Ultra-violet Light. EDMOND VAN AUBEL (Compt. rend. 1909,149 IlS3-985).-Bordierand Nogier (Conzpt. rend. 1908 14'7 354) could not find that ozone was produced from the oxygen of the air-by the action of ultra-violet light although previous observers (compare Abstr. 1906 ii 224 ; 1909 ii 657) had observed its formation. Using a quartz mercury lamp as the source of ultra- violet light the author definitely proves that ozone is produced.Instead of using water to absorb the ozone olive oil and light petroleurn were employed in the first experiments being placed in porcelain dishes inside the large glass globe surrounding the quartz tube. After several hours' exposure starch iodide showed the presence of ozone in these liquids. When distilled water was submitted to the action of the ultra-violet light for fourteen hours the presence of ozone mas detected by its action on a photographic plate. Starch iodide paper was turned blue in two minutes except where i t was covered with a piece of quartz and thus prevented from coming into direct contact with the ozonised air. T. S. P. Boiling Point of Sulphur Corrected by Reference t o New Observations on the Absolute Expansion of Mercury.HUGH L. CALLENDAR and HEEBERT Moss (I'roc. Roy. Xoc. 1909 A 83 106-108).-As a result of new measurements of the expansion of mercury between 0' and 300° it has been found necessary to add a correction factor to the result obtained for the boiling point of sulphur by Eumorfopoulos (Abstr. 1908 ii 1029). This raises the tempera- ture from 443.58' to 444*55' which is in practically perfect agreement with the value previously assumed (444.53'). H. M. D. The Dynamic Allotropy of Selenium. HUGO R. ERUYT (Xeitsch. anorg. Chern. 1909 64 305-326).-The study of the electrical con- ductivity is uncertain as a means of investigating the dynamic allotropy of selenium conductivity not being an additive property.The author has therefore used the specific gravity the reciprocal of which is a strictiy additive property of solid solutions. The material was purified as described by Marc in his study of selenium (Abstr. 1904 ii 105 ; 1906 ii 226 280 742 ; 1907 ii 453). Grey crystalline selenium which has not been heated above 120° has D 4-5-4.6 whilst sublimed selenium has D 4.80. The difference is not due to the presence of amorphous selenium After fusion passageINORGANIC CHEMISTRY ii. 29 of the amorphous into the crystalline form and heating to 125O the preparation has D 4.77. The denser form passes into a modification with D 4.77 when heated to 125'. There is thus an equilibrium Se Z Se high temperatures favouring the denser form. Exposure to the light of an arc lamp or even t o bright diffused light the selenium being enclosed in a dilatometer with alcohol produces an increase of volume; the quantity of Se is therefore increased by illumination.The changes in the electrical conductivity are explained on the assumption that Se and Se form solid solutions and also form a compound giving a diagram of the same form as is obtained from mixtures of bromine and iodine (Terwogt Abstr. 1906 ii 15) and alloys of magnesium and cadmium (Grube Abstr. 1906 ii 355). The conductivity has then two minima with a sharp cusp on the curve corresponding with the compound. The anomalous behaviour of specimens cooled from 200" is explained as being due to the combined action of light and heat in altering the equilibrium and also in changing the velocity with which equilibrium is attained.The conclusion is drawn that all phases of selenium contain Se and Se whilst red crystalline selenium is labile and may perhaps also occur in two modifications. C. H. D. Coefficients of Absorption of Nitrogen and Oxygen in Distilled Water and Sea-Water and of Atmospheric Carbon Dioxide in Sea-Water. CHARLES J. J. Fox (Trans. Faraday Soc. 1909 5,68-86).-The apparatus used for determining the coefficients of absorption of nitrogen and oxygen was a modified form of Estreicher's adaptation (Abstr 1900 ii 205) of Ostwald's apparatus. The pressure used could be varied at will whereas Estreicher's had to make the measurements a t exactly atmospheric pressure. Special precautions mere taken to free the water from dissolved air and it is suggested that the method used by Estreicher was not satisfactory so that his values for the absorption coefficients for argon and helium may be respectively 0.2 to 5% and 0.5 to 10% too low.Two series of measurements of the solubility of atmospheric nitrogen in distilled water between 0' and 50' mere made. A correction had to be applied due to the different solubilities of nitrogen and argon and the variation of the partial pressures with temperature. The relation between the absorption coefficient (aN) and the temperature is given by the formula 1000aN = 22.998 - 05298t + 0-0091962P - 0.00006779t3. In the case OF oxygen the formula obtained was 10OOa= 49939 - 1,3440t + 0*28752t2 - 0*0003024t3. These formuls give the following values for gas absorbed in C.C.per litre. 0" 10" 20" 30" 40" 50" Nitrogen ... 23.00 18'54 1 5 5 4 13.55 12.15 11'02 Oxygen ... 49'24 38.37 31.44 26-65 23'30 20.95 Determinations were also made on sea-waters of four different salinities. These values were then combined with those obtained for distilled water and formule obtained connecting the absorption coefficient temperature and salinity (chlorine-content) of the sea-water for nitrogen and oxygen at the partial pressures they have in air.ii. 30 ABSTRACTS OF CHEMICAL PAPERS. Tables are then given showing the amount of nitrogen (containing argon) and oxygen (in c.c.) absorbed by 1000 C.C. of sea-water from a free dry atmosphere of 760 mm. pressure at temperatures from 0’ t o 2S0 and the chlorine content 0-20 per mille.In the case of carbon dioxide the pressure in sea-water varies probably between 1 and 7 parts per 10,000; the total alkalinity also variw and for the open ocean is equivalent to about 40 mg. OH per litre. The carbon dioxide pressure was determined by a modification of Pettenkofer’s method. It was first of all established that the ratio of total CO to total OH is rectilinear and as a result of the law of mass action no C0,”-ions are formed; all the combined carbon dioxide must be in the form of HCO,‘. The effect of varying pressure on only one alkalinity that selected being 40 mg. OH per litre was then deter- mined. From these results an interpolation formula connecting the carbon dioxide per litre of sea-water the salinity the alkalinity the temperature and the pressure was obtained and tables of the calculated results are given.From these tables a calculatiop can be made of the power of the sea to conserve the constancy of carbon dioxide in the air (compare Arrhenius Pld. Mag. 1896 [v] 41 273). The conclusion IS drawn that for the open ocean (OH = 40 mg. per litre and t = 12”) it requires 17.6 times as much carbon dioxide to raise the carbon dioxide partial pressure as for the same volume of air; or if a quantity of carbon dioxide is poured into the air as for example by volcanic action two- thirds will eventually be absorbed by the sea. The final equilibrium will not be attained however until either the insoluble carbonates on the sea-bottom or the carbon dioxide in the air have completely gone into solution in the form of HC03’.The time necessary for this is not known but it must be very important geologically. The concentrations of the free ions HCO,’ and He for ocean-water are calculated to be respectively 2.24 x and 1.6 - 2.6 x 10-6 gram- equivalents per litre ; thus sea-water is just slightly more acid that distilled water. The paper also contains a description of the apparatus used for extracting and analysing gases dissolved in liquids. T. S. P. Red Phosphorus and the so-called ‘‘ Hittorf’s Phosphorus.” ALFRED STOCK and FRANZ GOMOLKA (BeT. 1909 42 4510-4527). -Hittorf’s phosphorus having the high density 2.3 is the only variety other than yellow phosphorus which is at all well defined the ordinary red variety being a mixture. Hittorf’s phosphorus is best prepared by heating 3 grams of pure phosphorus with 200 grams of lead in a sealed Jena glass tube packed in sand to 800’ for forty-eight hours.The glass is broken and removed in a freezing mixture and the lead cleaned by brushing and by washing with hydrofluoric acid. As nitric acid attacks the phosphorus the lead is best removed by electrolysis in acetic acid containing lead. The cathode is placed at the bottom of the vessel a clock-glass being fixed below the rod. The residue thus obtained contains some lead mechanicdly dislodged from the anode and is purified by boiling withINORGANIC CHEMISTRY ii. 31 hydrochloric acid in an atmoaphere of carbon dioxide followed by treatment with hydrofluoric acid. The purest product still contains 1.5% of lead. Bismuth may be used in place of lead but it dissolves only one-fifth as much phosphorus and the crystals obtained are less pure.The metals appear to be held in solid solution Only very minute quantities of Hittorf’s phosphorus are obtained by sublimation. Ordinary red phosphorus melts at 605-610° and Hittorf’s phosphorus a t 620’. The product obtained by fusion in a closed tube is heterogeneous Hittorf’s phosphorus corrected for the dissolved lead has D 2 31-2 33. It is much less chemically reactive than ordinary red phosphorus a t high temperatures but both oxidise slowly in the air to deliquescent products. The statement often made that red phosphorus is stable in air is incorrect. Oxidation of Phosphorus. WILLEM P. JORISSEN and N. H. SIEWERTSZ VAN REESEMA (Chem. Weekblud 1909 6 931-938.Compare Schmidt Abstr. 1902 ii 237 ; Schenck Mihr and Banthien Abstr. 1906 ii 326 ; de Broglie and Brizard Abstr. 1909 ii 535 ; Riboul ibid. ii 718; Elster and Geitel Physikal. Zeitsch. 1902 3 475 ; 1903 4 111 293 436 457 ; Ber. deut. physikccl. Ges. 1906 640).-!I!he work of Elster and Geitel and of Schmidt on the oxida- tion of phosphorus has bean repented. The results obtained support the conclusions of Elster and Geitel but indicate that Schmidt’s statements are erroneous. Preparation of Hypophosphoric Acid. JACQUES CAVALIER and E. CORNEC (Bull. SOC. chim. 1909 [iv] 5,1058-1060).-A number of glass rods are placed across the bottom of an ordinary photographic washing dish and on these are laid transversely sticks of phoephorue separated from each other by glass rods.Water is then poured into the dish until the phosphorus is half submerged. The whole is covered by a glass plate resting on a layer of cotton wadding so that air is slowly b u t continuously admitted. The acid formed can be neutral- ised by sodium carbonate to form sodium hydrogen hypophosphate or the latter salt can be obtained at once by substituting a solution of sodium acetate for water in the dish. From this sodium salt the acid is best recovered by making the lead salt by double decomposition and regenerating the acid with hydrogen sulphide. By this process and using a dish 13 x 18 cm. from 30 to 50 grams of sodium hydrogen hypophosphate may be obtained in five to six days. Decomposition of Water by Hypophosphites in Presence of Palladium aa a Catalyst.ALEXIS BACH (Ber. 1909 42 4463-4470).-The formation of copper hydride from sodium hypo- phosphite and copper sulphate takes place at the ordinary temperature and is an example of the decomposition of water by an oxidisable substance in presence of a substance capable of combining with hydrogen. The same reaction takes place in presence of a catalyst hydrogen being set free An improvement of this method is being studied. C. H. D. A. J. W. T. A. H.ii. 32 ABSTRACTS OF CHEMICAL PAPERS Solutions of sodium hypophosphite and palladium chloride are used the course of the reaction being followed by measuring the volume of hydrogen evolved. The velocity of decomposition increases much more rapidly than the quantity of palladium added the con- centration of the hypophosphite being kept constant.The velocity decreases rapidly with time and is not increased by further additions of palladium but rises to the original value on further addition of bypophosphite. With constant palladium the velocity increases less rapidly than the quantity of added hypophosphite. Hydrocyanic acid prevents the decomposition or if palladium sponge is used instead of the chloride slowly brings it to a standstill. The analogy of the behaviour of palladium in this case to that of a peroxydase is pointed out both departing from the laws of chemical kinetics. The intermediate formation of an unstable palladium perhydridc is assumed. C. H. D. Phosphorescent Oxidation of Arsenic. L ~ O N BLOCH (Compt. rend. 1909 149 775-777. Compare Abstr.1909,; ii 395).-The phosphorescence of arsenic at 200° like that of sulphur and phosphorus is accompanied by oxidation by which arsenic trioxide is produced. As in the case of sulphur no ionisation occurs and there is also no formation of ozone which is produced by both sulphur and phos- phorus. The product of oxidation of arsenic either phosphorescently or with flame always contains arsenic oxide just as some phosphoric oxide and sulphur trioxide are always produced in the parallel cases. The arsenic oxide which may amount to 1/30th of the whole seems to be formed directly from arsenic since arsenious oxide cannot be oxidised under the conditions. The author assumes conversely that arsenic oxide is the sole original product and this is mainly decomposed into arsenious oxide by a secondary change.The synthesis of sulphur chloride and arsenic chloride without incandescence is unaccompanied by ionisation. R. J. C. Formation of Silicon Sulphide in the Desulphurisation of Iron. W. FIELDING (lkans. Faraday Xoc. 1909 5 110-1 1 l).-The object was to find the conditions under which ferrosilicon can react with ferrous sulphide and liberate a sulphide of silicon. The reaction was investigated by heating mixtures of the two compounds in a vaciium at known temperatures. The heating was effected in a crucible in the form of a hollow graphite rod heated electrically. With commercial ferrous sulphide the mass fused at about 930° and a vigorous reaction set in accompanied by a rise in temperature. With pure ferrous sulphide no reaction was observed up to about 1300° so that the readion noted with the impure compound was probably due to reduction of oxide of iron present by the ferro- silicon.I n all the experiments a yellow sublimate appeared on the walls of the tube at 1500'. This was found to consist of approximately 50% of silicon sulphide (assuming the formula to be SiS,) the remainder being iron sulphide which had volatilised silica resulting from the action of moisture in the air on the silicon sulphide and a small amount ofINORGANIC CHEMISTRY. ii. 33 finely-divided ferric oxide. I n different experiments products of variable composition were obtained and it has not been possible completely to identify the silicon sulphide present in the product. T. S. P. Thermal Analysis of the System K2S0,-KF.16. KABANDEEFF (Centr. %in. 1909 728-733).-0n the basis of observations on the rate of cooling of fused mixtures of potassium sulphate and potassium fluoride a temperature concentration diagram has been constructed. The freezing-point curve consists of three branches corresponding with the two components and with a double salt KF,K,SO respectively. The eutectic temperatures 883' and 788O correspond respectively with 41 and 83 mold.% of potassium fluoride. The double salt melts a t 88'7'. It is only stable at temperatures above 5 7 8 O and on cooling below this breaks up into its components. Potassium sulphate undergoes a change in crystalline form at 599'. H. M. D. Existence of Real Percarbonates and their Differentia- tion from Carbonates with Hydrogen Peroxide of Crystal- lisation.E. H. RIESENFELD and B. REINHOLD (Ber. 1909 42 4377-4383).-According to the authors Constam and von Hansen (Abstr. 1897 ii 550) did not definitely prove that the substance which formed at the anode in the electrolysis of concentrated solutions of potassium carbonate was potassium percarbonate. The substance was never obtained pure the hydrogen carbonate and water being always present so that it was possible that it was a hydrogen peroxide additive product of potassium carbonate since the authors have recently proved the anodic formation of hydrogen peroxide in strong solutions of potassium hydroxide at low temperatures (compare Abstr. 1909 ii 879). The authors have now succeeded in preparing a pure potassium percarbonate of the formula K,U,O and containing neither water nor hydrogen carbonate so that it could not be an additive product of hydrogen peroxide.It was made by the electrolysis a t - 30' to - 40' of a very istrong solution of potassium carbonate contained in a U-tube. was a platinum wire the cathode beiag. of platinum Foil and surrounded by parchment paper. The current used was 0.5 ampere. After six hours the salt formed at the anode was collected washed with cold water alcohol and ether and dried and then proved to have the composition given above. When added to a neutral solution of potassium iodide at the ordinary temperature it immediately liberates iodine according to the equation no oxygen being evolved whereas hydrogen peroxide reacts very slowly under such conditions. This reaction is characteristic of a real percarbonate and can be used t o distinguish them from additive products of carbonates and hydrogen peroxide.It is found that the percarbonates described by Tanatar (Abstr. 1903 ii ZOS) when added t o a neutral solution of potassium iodide cause a brisk evolution of oxygen and the solution remains colourless. All these compounds The anode c,o," + 21' = 2c0," + I VOL. XCVIII. ii. 3ii. 34 ABSTRACTS OF CHEMICAL PAPERS. must therefore be classed as additive products of hydrogen peroxide and carbonates. The percarbonates obtained by Wolff enstein and Peltner (Abstr. 1908 ii 180 183 ; 1909 ii 574) are also doubtful. It was not found possible to prepare solid percarbonates of lithium sodium rubidium and cssium although the anolyte reacted towards potassium iodide as if it contained percarbonate.T. S. P. Reduction of Sodium Sulphate by Carbon. ALBERT COLSON (Compt. rend. 1909 149 1076-1078).-When an intimate mixture of sodium sulphate and animal charcoal is heated in an iron pipe practically DO interaction takes place below 950° but at this tempera- ture the reduction is rapid and uniform especially if charcoal is used in the proportion required by the equation Na,SO + 4C = Na,S + 4CO. With increase of temperature the rate of action augments rapidly. T. A. H. Action of Safety Explosives containing Ammonium Nitrate in the Presence of Carbon Paper and Paraffin. H. DAUTRICHE (Compt. rend. 1909 149 926-928) -Safety explosives containing ammocium nitrate are used in coal mines and since oxygen is set free in the explosion it is important to investigate their action on charcoal powder which would be equivalent to coal dust in the mine and on paper and paraan the latter being used in making the cartridges.Experiments carried out under conditions very similar t o those obtaining in a mine with an explosive consisting of 90 parts of ammonium nitrate to 7 parts of trinitrotoluene show that charcoal powder surrounding the cartridges is burnt arid that all the oxygen is used up with the formation of carbon monoxide. The combustion of the paper and paraffin depends on the diameter of the cartridges. When these are 30 mm. in diameter the combustion is feeble but when 40 mm. in diameter it is very marked. T. S. P. True Atomic Weights. Stas’ Determinations.111. Lou19 DUBREUIL (Bull. SOC. chim. 1909 [iv] 5 1049-1053 1053-1055 1055-105S).-A series of three papers continuing (this 1 ol. ii S86) the critical revision of Stas’ determinations the cases now considered being (1) silver iodate (2) silver bromate (3) silver chlorate. The apparent atomic weights found for the three cases are (1) silver 107-9990 and 107-9991 iodine 126.9790 and 126-9991 oxygen 16.0149 and 16.0128 (2) silver 107-9995 bromine 79 9995 and oxygen 16.0061 (3) silver 107.9996 chlorine 35 4996 and oxygen 16-0036. T. A. H. So-called Electrolytic Peroxide of Silver. MARGRETE BOSE (Zeitsch. physikal. Chem. 1909 68 383-384).-The author’s work on the same subject (compare Abstr. 1905 ii 299) has not been mentioned by Baborovskp and Kuzma (compare Abstr.1909 ii 666). G. S. Silver and Thallium Iridichlorides and Iridochlorides. MARCEL DELEPINE (Compt. rend. 1999 149 1072-1 074. Compare Abstr. 1908 ii 702).-The fugitive blue precipitate formed when potassiumINORGANIC CHEMISTRY ii. 35 iridichloride is added to silver nitrate consists of silver iridichloride Ag21rC16. This when kept either alone or in presence of excess of silver nitrate passes into silver iridochloride Ag3T.~-Cl which is yellow and on treatment with ammonia changes into the greenish- yellow argentodiammonium iridochloride ( Ag2NH,)31rC16 which loses part of its ammonia on exposure to air and the whole of it on warming (compare Claus J. pr. Chena. 1847 i 42 348). Thallium iridichloride T121rC16 forms small opaque greenish-blue cubes and is more stable than the corresponding silver salt.Boiling hydrochloric acid decomposes it forming the iridochloride T131rC16 which crystallises out on cooling the liquid in bronze-tinted lamellae. Nitric acid re-converts it into the iridichloride. T. A. H. The Calcium Silicides and their Absorptive Power for Nitrogen. AUALBERT KOLB (Zeitsch. m o r g . Chem. 1909 64 342-367).-By heating together calcium and silicon two silicides are obtained according to the component in excess. The products contain 53.5% and 36.68% Si respectively corresponding approximately with the formulae Ca,Si and Ca,,Si (compare Hackspill Abstr. 1908 ii 589 ; Tamaru Abstr. 1909 ii 400). Both silicides are crystalline evolve hydrogen with acetic acid and evolve spontaneously inflammable hydrogen with dilute hydrochloric acid.Silicones are obtained with concentrated hydrochloric acid. The first silicide yields an orange or yellow crystalline silicone the second yields a silicone containing less silicon. Both silicides absorb nitrogen actively near 1000° the first com- pound being the mme energetic. The products have the respective compositions CaSizNs and Ca,,Sil,N,,~ Structural formulae are pro- posed for the silicides silicones and silico-nitrides. C. H. D. Calcium Ferrites. SIEGFRIED HILPERT and ERNST KOHLMEYER (Bur. 1909 42 4581-4594).-Mixtures of pure ferric oxide and lime are heated in a platinum crucible protected by an outer crucible of spinel mass in an electric furnace of which a hollowed-out carbon rod forms one pole the other being an outer iron cone the space between being filled with granulated carbon.Mixtures containing only small percentages of iron oxide are not completely fusible under these conditions being on y pasty. The last portion solidifies at 1410° when they become completely solid. The lime forms well-developed crystals. When the lime falls below 75 mol.% the primary crystallisation is that of the orthoferrite. The first complete fusion is obtained with 69 mol.% CaO freezing beginning at 1550O. Calcium orthoferrite 3Ca0,Fe203 melts at 1 410° and disintegrates like calcium orthosilicate on f u t ther cooling. The next compound 3Ca0,2Fe,03 melts a t 1450O. At 1220O a reaction occurs in the solid state the compound formed having a formula near to 5Ca0,3Fe203 (compare the aluminate 5Ca0,3A1,03 Shepherd Rankin and Wright Abstr.1909 ii 1015). There IS a eutectic point at 1200O and 50 mol.% CaO and a second maximum at 1400° corresponding with 3-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. the compound 2Ca0,3Fe20,. Calcium metafeerrite CaO,Fe,O appears to be formed below the eutectic point. The behaviour of mixtures rich in ferric oxide is complicated partly owing to the escape of oxygen and the formation of crystals of magnetite. Ferric oxide melts at 1565' and the magnetic oxide at 1527'. The colour of the mixtures becomes darker with increasing iron. The specific volume curve shows a sharp change of direction at the formula CaO,Fe,O and another less distinct near 20 mol.% CaO. The magnetic properties diminish with the proportion of iron and become insignificant at 67 mo1.s CaO.The electrical conductivity is very small throughout even that of fused ferric oxide being only that of iron. Solid solutions are not formed and the low conductivity is unexplained. The calcium ferrites are much less readily attacked by reagents than the silicates hence the advantage of their presence in cements exposed to sea-water. The mixtures containing 60-70 mol.% CaO are hydraulic. Calcium ferrites are less easily reducible than ferric oxide. C. H. D. Compounds containing Iron Peroxide FeO,. LUDWIG MOESER and H. BORCK (Ber. 1909 42 4279-4283. Compare Abstr. 1903 ii 546).-When a mixture of concentrated solutions of ferric and strontium nitratm (1 mol. 1-2 mols.) is evaporated to dryness and the finely-powdered residue heated a t a temperature of not more than GOO3 in a stream of oxygen until oxides of nitrogen are no longer evolved a compound is obtained which seems to have the formula SrO,FeO,.Determination of the proportion of active oxygen t o ferric oxide showed that i t could not be a compound of strontium peroxide and ferric oxide. A similar compound was indicated in the residue obtained by heat- ing a mixture of barium hydroxide and ferric hydroxide a t 400' in a current of oxygen. These compounds are black substances which are stable below 650° but decompose gradually above that temperature. They are slowly acted on by water with evolution of oxygen. Hydrogen per- oxide reacts violently with liberation of oxygen ; acids act in a similar manner. Hydrochloric acid gives both chlorine and oxygen ; oxalic acid oxygen and carbon dioxide.Mixtures of air and alcohol or other inflammable vapours when led over the heated compounds are oxidised to water and carbon dioxide and when once the combustion has started it proceeds of its own accord. It is possible that a compound of iron peroxide with lithium oxide has been obtained but it was not found possible to prepare siich compounds with other bases. In an appendix H. Borck describes a compound of strontium and ferric oxides which is obtained in a hydrated condition as a yellowish- brown precipitate by warming a suspension of freshly-precipitated ferric hydroxide in a concentrated solution of strontium hydroxide for some time on the water-bath. On heating it loses water and becomes brown and at temperatures above 300' it absorbs oxygen forming the compound SrO,FeO,. T.S. P.INORGANIC CHEMISTRY. ii. 37 Hexahydrated Glucinum Sulphate. MARIO LEVI-MALVANO (Gaxzetta 1909 39 ii 438-440. Compare Abstr. 1906 ii 165).- The author gives a new example of crystallisation of one salt under the catalytic influence of another dissolved salt. When prepared in the ordinary way hexahydrated glucinum sulphate forms a mass of crystals incapable of being measured ; but when a solution containing equimolecular proportions of gluciuum and potassium sulphates is concentrated on the water-bath and allowed to cool it deposits large crystals of hexahydrated glucinum sulphate belonging to the cubic system [ZAMBONINI] and melting partly at 78-80° and completely at 95-96'.T. H. P. Bmic Magnesium Chlorides. WILLIAM 0. ROBINSON and W. H. WAGGAMAN (J. Physical Chem. 1909 13 673-678).-Solutions con- taining from 2.36 to 34.23% of magnesium chloride were shaken with small amounts of magnesium oxide for six months at a temperature of 25O. A t the end of this time the residues had become homogeneous and the solutions constant in composition. From an examination of the diagram on which the solubility data are plotted the conclusion is drawn that the solid substance in equilibrium with solutions contain- ing less than about 10% of magnesium chloride is an indefinite solid solution whereas the solid residue in contact with more concentrated solutions is a basic salt of the composition 3MgO,MgC1,,1 OH,O. Microscopic examination showed that this consists of very small acicular crystals.H. M. D. Zinc Amalgams. ERNST COHEN and KATSUJI INOUYE (Chem. Weekblad 1909 S 921-930. Compare Roozeboom and Byl Abstr. 1901 ii 507; Kerp and Bottger Abstr. 1900 ii 656; Pushin Abstr. 1903 ii 212 ; Hulett Abstr. 1900 ii 543).-The authors have investigated the solubility of zinc in mercury at temperatures between 0" and looo and found that it increases. Kerp and Bottger's method gives erroneous results especially between 20' and 100'. Pushin's results are also incorrect. A. J. W. Double Fluorides of Univalent Thallium. FRITZ EPHRAIM and LEON~D HEYMANN (Ber. 1909 42 4456-4463).-That?lous manganosomunganic Juoride 5TlF 21SlnF3,MnF2 obtained by pre- cipitating manganous acetate with ammonia and hydrogen peroxide dissolving the well-washed precipitate in hydrofluoric acid and adding thallous fluoride forms Clare t-coloured prisms decomposed by water but soluble in cold concentrated sulphuric acid or in dilute oxalic or tartaric acids to violet soliztions decolorised on heating. Attempts to prepare the manganic compound result in the formation of this salt.The three antimony compounds TIF,SbF,; T1F,2SbF3 and T1F,3SbF3 are all crystalline. Thallous fluoride and an excess of asolution of vanadism pentoxide in hydrofluoric acid yield minute insoluble crystals of the salt 3T1F,2V02F. By previously reducing the vanadium solution with sulphur dioxide,ii. 38 ABSTRACTS OF CHEMICAL PAPERS. small green crystals of the salt 2’1’1F,VOF are obtained whilst reduction of the pentoxide with hydrogen followed by solution in bydrofluoric acid and addition of thallous fluoride leads to the formation of green crystals of T1F,VF3,2H,O or of 2T1F,VF,,H20 according t o the proportions taken.The thallous tcmatulum compound 2T1F,TaF5 forms bright glisten- ing crystals. Three tungsten CompoundF 2T1F WO,F 3TlF,2 WO,F and TlF,WO,F are obtained by adding different proportions -of thallous fluoride to a solution of tungstic acid in hydrofluoric acid. C. H. D. Conditions which Determine the Composition of Electro deposited Alloys. Part I. Copper-Zinc Alloys. SAMUEL FIELD (Trans. Paruday SOC. 1909 5 172-194).-To trace the effect of varying conditions on the composition of electro-deposited alloys the composition of electro-deposited brass obtained from a cyanide solution under different conditions of (a) cornposition of solution ( b ) strength of solution (c) temperature (d) current density and (e) presence of free cyanide was determined.The conditions for quantitative deposition from cyanide solutions of the metals separately mere first found and the solutions were then mixed. It was found that with a solutisn containing about equal quantities of the two salts in the absence of any notable amount of free cyanide ( a ) Copper is the more readily deposited. (6) The percentage of zinc increases with the current density and also as the amount of zinc compound is increased. (c) Even with a large excess ofs zinc i n the electrolyte deposits containing a fair proportion of copper are readily obtained ( d ) Dilution raises the percentage of zinc because of the higher E.M.F. necessary to maintain the same current density. (6) Rise in tempera- ture increases the proportion of copper deposited. (f) With appreciable amounts of free cyanide the percentage of copper is always high even with high current density. Free cyanide does not increase the conductivity of the solution to any great extent but it prevents the formation of insoluble single cyanides at the anode. Uniform deposition is not maintained in cold stationary solutions and the insoluble cyanides formed at the anode may completely insulate the plates. With a warm and moving solution uniform deposits may be obtained without the presence of much free cyanide the anodes dissolving freely. These cyanide solutions are subject to continual changes of composition which soon prevent the exact repetition of similar conditions.These changes are due to (2) differing proportions of copper and zinc dissolved at the anodes and precipitated at the cathodes and (2) to the different amounts OF cyanide absorbed or set free by the metals. The zinc compound used in the above experiments corresponded with the composition Zn(CN)2,KCN whilst the copper compound had the composition CuCN,KCN. This latter compound was obtained by saturating a hot solution of Kahlbaum’s potassium cuprocyanide of the composition 3CuCN,KCN + 5ECN with freshly precipitated copper carbouate and then allowing it to crystallise T. S. P,INORGANIC CHEMISTRY. ii. 39 The Corrosion of Iron. J. NEWT~N FRIEND (J.Iron and &eel Inst. 1909 Reprint 3-7. Compare Abstr. 1908 ii 698; Proc. 1909 25 90).-A criticism of recent experiments on the rusting of iron. The presence of an acid is necessary to the initiation of rusting. C. H. D. The Action of Air and Steam on Pure Iron. J. NEWTON FRIEND (J. Iron and Steel Inst. 1909 Reprint 2-11. Compare preceding abstract).-At temperatures above 200' pure iron oxidises in air dried by means of phosphoric oxide. Steam carefully freed from carbon dioxide is without action on iron a t 100-250'. Slight action begins at 330° and is rapid at 445'. Traces of air may have been present. ExperimeEts in silica tubes indicate that the tem- perature at which action begins is near 350'. The action of steam probably takes place in two stages the steam being first dissociated and the oxygen thus set free acting on the iron.An estimate is made of the dissociation pressure of iron oxide. 0. H. D. Reduction of Iron Oxide by Hydrogen and Carbon Monoxide. SIEGFRIED HILPERT (Bey. 1909 42 4575-4581).- The temperature at which the reduction of ferric oxide by hydrogen begins depends on the temperature t o which the'oxide has been previously heated. A sudden fall in the reducibility of oxide pre- pared From the hydroxide occurs at 900° at which point there are indications of a polymorphic change. Oxide prepared from the oxalate only shows this change at 1000'. In both cases the final product behaves like natural hEmatite and is only reduced from 330' onwards. It is impossible to obtain a product containing a deter- mined quantity of oxygen by these means as the reaction takes place unequally in different parts of the mass.Carbon monoxide is active even at 240° but the resulting oxide is impure containing carbon. C. H. D. Chromi-aquo-triammines. E. H. RIESENFELD and F. SEEMANN (Ber. 1909 42 4222-4232. Compare Abstr. 1906 ii 760)-If chromtetroxide-triarnmine is added in small quantities at a time to a cooled dilute solution of hydrochloric acid a violent reaction takes place with evolution of oxygen and chlorine and formation of a red solution. Addition of concentrated hydrochloric acid to this solution produces after a long time a precipitate of dichloroaquotriammine- chromichloride [Cl,Cr OH C1 in the form of reddish-violet di- chroitic crystals which are soluble in water to a blue solution. If concentrated hydrochloric acid is used instead of the dilute acid a light green solution is obtained from which grey needle-shaped crystals of a second modification of the above chloride separate which is scarcely soluble in cold water but dissolves in hot water to a red solution.A third modification is obtained by heating a hydrochloric acid solution of the first chloride for some time at 60'. The solution gradually becomes green in colour and on evaporation in a desiccator dark green crystals are obtained which dissolve in water to a green (NH3)3 Iii. 40 ABSTRACTS OF CHEMICAL PAPERS. solution. is therefore probably contained in the complex in all three salts. all probability they are stereoisomerides Neither of these three chlorides readily loses water which I u N H NH3 C1 I NH C1 ~ I NH C1 I NH NH3 1- / Cr / C1 I H,O I / I br 1 Crr 1 R,O 1 NH H,O I C1 C1 NH NH3 A t present it is impossible to say which formula corresponds with which isomeride.If the aqueous solution of either of the three isomeric chlorides is heated to the boiling point the colour changes to a violet-red and on careful evaporation violet -red crystals of the chlorodiaquot riammine- chromichloride [ (NH,),Cr(OC~2)2]C12 are obtained. These crystals are readily soluble in water to a red solution from which by the addition of concentrated sulphuric acid and precipitation with alcohol pale violet hygroscopic crystals of the chlorodiaquotriamminechromi- sulphate (NHJ3Cr(OCE2)2 SO are obtained. Chromtetroxide-triammine dissolves in concentrated nitric acid to a red solution from which rose-red crystals of nitro-diaquotriammine- chrominitrate [(N H3)3Cr(*H,),] (NO,) separate.Triaquotriamminechromichloride [(NH,),Cr(H,O),]CI is obtained by dissolving chromtetroxy triammine in dilute hydrochloric acid and passing hydrogen chloride into the resulting solution. After a time bright red needle-shaped crystals of the triaquochloride separate. I f the hydrogen chloride is passed in for too long a time the solution becomes green in colour and crystals either of the dichroitic or of the grey monoaquochloride are obtained. If the aqueous solution of the triaquochloride is treated with concentrated nitric acid deep red crystals of the triaquotriammine-chromichloride nitrate - I / I / 1 --_I- [ 1 NO3 [ (NH,)@(OH,),] :& are obtained. Each member of the series of the chromi-aquo-triammines with the exception of the first [Cl,Cr(NH,),] has thus been obtained.The separate membecs are characterised by their different colours not only as solids but also in aqueous solution and it is noteworthy that the colours are exactly analogous to those of the corresponding cobalt compounds as shown by the following table M = CO. [(NH,\,M,H,O] ...... Bluish-green solution ,..... Bluish-green solution. [( NH3),M,2H,0] . . . . . . Reddish-blue . . . . . Violet-red [(NH,),M,3H20] . . . . . . Purple . . . . . . Piirple $ 2 This similarity ‘in colour is all the more remarkable since the ordinary cobalt and chromium salts are so different in colour. The conclusion is therefore drawn that the colour of a salt depends more M = Cr.INORGANIC CHEMISTRY.ii. 41 on its constitution than on the metal which forms part of the cation. Assuming that the atoms in the molecule are bound together by electrical forces the constitution of the molecule will depend on its electron-content and on the distribution of the electrons. It follows that absorption (of light) electron-content and the distribution of electrons are all closely connected a conclusion which has been arrived at in quite another way from optical considerations. T. S. P. The Isomerism of the Stannic Acids. WERNER MECKLEXBURGH (Zeitsch. anorg. Chem 1909 64 368-374).-The two modifications of stannic acid are best regarded as colloidal substances differing in the size of their particles as suggested by van Bemmelen (Abstr.1888 1160; 1905 ii 461). The greater adsorptive power and reactivity of the a-acid indicates that it has the finer structure. The absence of any direct relation of the /3-acid to the crystalloid compounds of tin is evidence of its coarser structure. C. H. D. Double Halogenides of Ter- Quadri- and Quinque-valent Antimony. FRITZ EPHRAIM and S. WEINBERG (Ber. 1909 42 4447-4456).-Derivatives of quadrivalent antimony have n great tendency to decompose into mixtures of compounds of ter- and quin- que-valent antimony with the exception of the thallium salt T1C1,,TlC1,2SbC14 which is stable (Ephraim and Barteczko Abstr. 1909 ii 236). The equilibrium SbCl,+SbCl =1 2SbC1 is greatly dependent on the temperature and on the possibility of ionisation the addition of sulphuric acid or of salts favouring the tetrachloride.On adding solid ammonium chloride to a fused mixture of antimony tri- and penta-chlorides the liquid becomes black and solidifies on cooling to a violet mass which slowly loses its colour at the ordinary temperature ultimately becoming white. The dark metastable salt is best obtained by pouring the hot mixture into chloroform; it then remains for some hours without change. The ammonium compound of antimony tetrahromide (NH,),SbBr prepared by adding the requisite quantity of bromine followed by ammonium bromide to a solution of antimony tribromide in [con- centrated hydrobromic acid forms black octahedra stable in air. The free acid was obtained in a state of doubtful purity.A ferric ammonium andimony chloride 9NH,C1,2FeC1,,3SbC14 is obtained by mixing the chlorides in concentrated hydrochloric acid and forms black octahedra. It may be regarded as 3(NH,),SbCl,+ 3NH,Cl 2FeC1,. Compounds of antimony tri- and penta-halogenides with salts of alkylamines are also described. SbCl,,NH,MeCl and SbCI,,NH,MeCl form very large colourless prisms and micro- scopic crystals respectively. The bromide 2Sbsr,,3NH3MeBr,3H20 forms lemon-yellow six-sided leaflets and the iodidey 2Sb13,3 N H,MeI 5H,O forms yellowish-red leaflets with golden reflex. The methylamine compounds,ii. 42 ABSTRACTS OF CHEMICAL PAPERS The ethylanaine compounds 2SbBr3,3NH3EtBr a yellow salt containing water ; SbBr,,NH,EtBr dark red leaflets and are described. 25 bI 3NH,EtI The following diethylamine compounds are described SbCl,,NHEt HCI long transparent neodles ; S bCl,,NHEt HC1; SbBr,,NHEt,,HBr ; SbEr5,2NHEt,,HBr black crystals violet in thin fragments ; and SbBr,,NHEt,,HBr garnet-red rectangular crystals.C. H. D. Effect of Ferric and Cupric Salt Solutions on Gold. W. J. BICCAUGHEY (J. Amer. Chem. Soc. 1909 31 1261-1270).-In the analysis of gold bullion containing a large proportion of tin it was found that the gold could be most conveniently separated by pre- cipitation with ferrous sulphate. The precipitate however still contained tin and if sufficient hydrochloric acid was present to keep all the tin in solution the gold was not completely precipitated. Preliminary experiments having shown that gold is soluble in solutions of both ferric and stannic salts in presence of hydrochloric acid an investigation was carried out to ascertain the effect of the concentration of the salt and acid and the presence of ferrous sulpbate on the solubility.The solvent action of cupric chloride was also studied. The experiments were conducted a t 38-43' and at 98-100'. The results are tabulated and plotted as curves. It has been found that gold is soluble in solutions of iron alum and cupric chloride containing hydrochloric acid the solubility increasing with the concentration of the acid or salt. An increase in the con- centration of the acid has a greater effect on the solubility than an increase in the concentration of the salt and particularly in the case of the copper salt. The rate of solubility in the presence of iron alum is eleven times greater at 98-100' than a t 38-43' and in the presence of cupric chloride is 32 times greater at the higher tern- perature.By doubling the concentration of the acid the solvent action of cupric chlofide solution is increased seven times at 38-43' and five times at 98-looo. Iron alum is capable of dissolving gold even in presence of a ferrous salt but the solvent action decreases as the concentration of the ferrous salt increases. In the precipitation of gold by ferrous sulphate it is therefore advisable to use considerable excess of the reagent and to allow the solution to cool before filtering it since the solvent action of ferric salts is much greater at the higher temperatures. The solubility of gold in solutions of ferric salts gradually decreases with time and approaches a limit but in the case of cupric chloride the amount of gold dissolved is directly proportional to the time.E. G. Gold Hydrosols. CARL THOMAE (J. pr. Chim. 1909 [ii] 80 518-520).-Zsigmondy's red-gold hydrosol which can be kept for a year is prepared with water distilled repeatedly through a silver condenser. However a hydrosol which is tenable for four months can be obtained with ordinary distilled water as follows. The water 120 c.c. is brought to the boil in a Jena qask and 2.5 C.C. of goldINORGANIC CLZEMISTRY. ii. 43 chloride solution (1 gram of crystallised salt 167) and 3.2 C.C. of potassium carbonate (2.5 100) are added successively. Whilst the water is boiling vigorously and the flask is being violently shaken 5.0 C.C.of formaldehyde solution (3 grams of commercial approxi- mately 36% formalin 100) are added drop by drop. If the first drop causes a separation of gold the addition is stopped and the boiling is continued until the gold has disappeared. Gold should not separate until many drops of the formaldehyde have been added; then the formation of a slight gold mirror is immaterial. The liquid is blue at first and finally dark red. It is decanted into another flask. The formation of a filminess or turbidity indicates that the reducing agent has been added too quickly or in too large quantities. c. s. Magnesium Aurides. G. G. URAZOFF (Zeitsch. anorg. Chem. 1909 64 375-396. Compare Vogel Abstr. 1909 ii 896).-Alloys of gold and magnesium are best prepared by heating the components in the proportions required to form the compound Aulslg in a graphite crucible enclosed in an iron cylinder with screw cap.Combination takes place readily at 700° and the compound may be fused quietly with further quantities of gold or magnesium under a layer of alkali chloride. Four compounds are indicated on the freezing-point curve AuMg with a maximum at 1150'; AuMgP with a maximum at 788'; Au,Mg at a break in the curve at 798O and AuMg with a third maximum at 818'. Gold foras solid solutions with nearly 30 atomic % Mg and the compound AuMg forms solid solutions ranging from 43 to 66 atomic % Au. The compound Au2Mg undergoes a transformation at 721'. Alloys rich in gold may be etched with hydrochloric acid and bromine ; those containing little gold are etched sufficiently by polishing while wet.The microscopical examination confirms the indications of the cooling curves. C. H. D. Atomic Weight of Platinum. EBENEZER H. ARCHIBALD (Proc. Boy. SOC. Edin. 1909,29 721-747).-From a consideration of earlier determinations the author draws the conclusion that the platinum salts analysed must have contained appreciable amounts of impurities for very divergent results are obtained when the weight of original salt is used in the calculation of the atomic weight. To obtain pure platinum the metal was precipitated in the form of ammonium platinichloride the precipitate being thoroughly washed and dried and then reduced in a current of pure hydrogen. After removal of ammonium chloride the platinum-black was boiled with successive portions of concentrated hydrochloric acid t o dissolve out traces of iron. The platinum was then redissolved and the above processes repeated several times. After three operations all indications of iridium bad disappeared.To avoid the difiiculty of removing the last traces of nitric acid from a solution prepared by dissolving platinum in aqua regia the metal was brought into solution by making it tbe anode in an electrolytic cell containing hydrochloric or hydrobromic acid. From such solutions $he potassium and affimonium salts of chloro- and bromo-platinic acidii. 44 ABSTRACTS OF CHEMICAL PAPERS. were prepared With these four salts four series of determinations were made by reduction in a current of pure dry hydrogen.Before reduction the potassium salts were heated at 400° and the ammonium salts at 175O for the purpose of expelling absorbed and occluded moisture. After reduction the platinum metal the halogen salt and the halogen acid given off were estimated. These measurements give several ratios from which the atomic weight of platinum can be deduced. Rejecting those in which the weight of original salt is concerned twelve values are obtained for the atomic weight the lowest of which is 195.21 and the highest 195.24. The mean value adopted is 195.23. Incidentally it is shown that the same results are obtained for the weight of reduced platinum whether this is heated and cooled in hydrogen and weighed at atmospheric pressure or heated cooled and weighed in a vacuum.(0 = 16.) H. M. D. Metallic Iridium Disulphates. - MARCEL DEL$PINE (Compt. rend. 1909 149 785-788; Bull. SOC. chim. 1909 [iv] 5 1084-1088 1126-1 133. Compare Abstr. 1909 ii 408).-The action of sulphuric acid on potassium iridochloride gives a blue solution which does not contain a salt of the same type as the ammonium iridium disulphates already described. The ammonium in the latter can however be wholly or partly replaced by potassium sodium thallium and barium. The iridium disulphates fall into‘ two series namely the green salts which are generally acidic derived from the acid HJJd SO4),(OH)H,O] designated H,A” and the reddish- brown salts which are basic derived from the acid H,[Ir(SO,),(OH),] designated H,A’“. These tautomeric acids are easily converted into one another by addition of excess of base and acid respectively. The following basic salts are described K7H2(AN),,6H20 crystsl- lising in needles varying in colour from old rose to blackish-brown according to thickness. This sait is prepared by pouring a cold solution of NH,*H,(A”) into excess of potassium carbonate solution.Na,H2(A’”),,6H2O and 9H,O reddish-brown clusters of needles or rectangular plates is obtained by precipitation with alcohol. TI,1(KH,)7H,(A’) and T17H,(A”’),,4$H,0 dark brown crystals are very slightly soluble. Ba7H4( A’”)s,Aq is a greenish-brown amorphous precipitate turning pure green on exposure to air and slowly depositing barium sulphate. The salts of the acid H,A” are all soluble in water but less soluble in presenceof alcohol ether or another salt of the same metal The following were prepared by a variety of methods from the corre- sponding ammonium.salts K,NH4H,(A”),,3H20 green to black needles according to size. K,H,(A) 1 &H,O needles. I.,H ( A”’),,3H20 hexagonal or octahedral crystals. K,(A”),H,O opaque square crystals very dark green ; their solution is alkaline and of an impure green colour. K2H,(A”),,6H20 tetrahedra stable only in strong acids. Na8*NH,*H,(A”) 1 8H,O very soluble black crystals almostMlNERALOGICAL CHEMISTRY ii. 46 rectangular. sisting of small green needles only slightly soluble in water. crystallising in long green needles or black rectangular crystals small opaque black tetrahedra. T17(NH,),H,(A”) to T17H,(A”),,6H20 a mixture cone Ba2H2(A”)3,1 2H,O Ba(~H4)2(A”)p q o R. J. C. Oamium. ALEXANDER GUTBLER and IE(. MAISCH (Bey. 1809,424 4339-4243).-In preparation for a revision of the atomic weight of osmium,,the authors have submitted the osmichlorides to a systematic investigation. Sodium osmichloride mas first prepared by heating a mixture of sodium chloride and osmium in a current of chlorine. If the osmium is in the form of granules the reaction takes place extremely slowly b u t when the metal is in a finely divided condition the reaction is complete in about half-an-hour a t a red heat. The sintered mass which is thus obtained was dissolved in cold dilute hydrochloric acid the solution filtered and the filtrate saturated with hydrogen chloride to precipitate any sodium chloride present. After further filtration the sodium osmichloride was obtained by careful evaporation of the filtrate; this salt could not however be prepared in a quite pure condition. It was therefore used to prepare the oamichlorides of ammonium potassium rubidium and caesium by double decomposition with the chlorides of these metals. All these compounds are much less soluble than sodium osmichloride and after recry stallisation from dilute hydrochloric acid they are obtained as dark-coloured well-defined octahedral crystals which are stable in dry a i r ; on being powdered they each give a bright red powder. They are soluble in cold water but the solutions decompose on exposure to the air after a time depositing a black powder. They are easily soluble in dilute hydrochloric acid giving stablo solutions. With the exception of the sodium salt all these compounds are anhydrous. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805027

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

MlNERALOGICAL CHEMISTRY Miner a 1 o gi c a1 C h emi stry. ii. 46 The Need for a Systematic Study of Optically Active Petroleums. MICHAEL RAKUSIN (Ber. 1909 42 4675-4678. Compare Abstr. 1909 ii 246 490 586).-Mainly polemical. A reply to Ubbelohde (Abstr. 1909 ii 899). J. J. S. Selenium in Altai Minerals. P. P. PILIPENKO (BUZZ. Acad. Sci. Sit. P6terabourg 1909 1113-1 ll5).-Two samples of galena from the hltai mountains were found to have the following compositions Se. S. Pb. cu. Fe. SiO,. Total. I. 1.17 12'60 82.28 1-28 0-48 2-02 99-83 11. 1'23 13'40 83.72 0.54 0 '47 0.48 99'64ii. 46 ABSTRACTS OF CHEMICAL PAPERS The mean composition given by two analyses of a sample of grey Se. S. Sb. As. Cu. Ag. Fe. Co. ZE. SiO,. Total. 0.13 24-48 25*71 1-68 39-16 trace 2-00 0.23 4-81 0.35 99-21 A number of other Altai minerals and also the sulphide compounds of the Mineralogical Museum of Tomsk University mere examined but the above specimens were the only ones containing selenium.copper from a mine in the Altai district is as follows T. H. P. A Pitchblende probably occurring in New South Wales. T. H. LABY (J. Boy. SOC. flew South JPuZes 1909 43 28-33).-The author has examined a pitchblende which was probably obtained from the New England district of New South Wales although the exact locality is unknown. Insol- H,O UO,. UO,. PbO. Mn304. Fe,O,. CaO. Bi203. CuO. As20,. MgO. SiO,. uble. (130"). 69.0 8.8 6'0 4 2 2-7 3.7 0'4 0'1 trace trace 0.1 2.4 0.69 Its radioactivity is 4.4 times that which would result from the amount of uranium present.The absence of rare earths the presence of CuO Br2O3 and As203 the large proportion of UO and the massive and non-crystalline form of the mineral indicate that it is probably a secondary pitchblende. Analysis of the mineral gave The powdered mineral has DZ3 7.65. H. M. D. Rhodizite in the Pegmatite8 of Madagascar. ALFRED LACROIX (Conzpt. rend. 1909 149 896-899).-The author has recently noted the presence of the two borates danburite (Abstr. 1909 ii 812) and hambergite (BO,GI,*OH) in the pegmatites of Madagascar. Tetrahedral crystals 14 cm. across of rhodizite have now been found embedded in the gem spodumene of a pegmatite-vein a t Antandrokomby ; the pegmatite is composed also of quartz microcline albite red and yellow tourmaline and a tantalocolumbate probably identical with microlite.Tho rhodizite crystals are whitish-yellow with a tinge of green ; they are pseudo-cubic with optical anomalies similar to those of boracite. Mean refractive index (Na) 1.69 H 8 D 3.305. Analysis by F. Pisani gave K20 Loss on Bz03. Al,03. G10. Li,O. (+Cs,O). Na,O. SiO,. ignition. Total. 40'60 30.50 10.10 7-30 5.90 3'30 1-36 0.45 99.51 Deducting silica and the corresponding amount of alumina and lithia present as admixed spodumene this analysis gives the formula 6B,03 SA1203,4G10 4(Li K,Na,H),O. Damour's analysis (1882) made on only a small quantity of the rare and minute crystals of the Uralian rhodizite &owed no glucinum or lithium ; it is remarked however that his percentage of alumina (41.40) is equal to the sum of the alumina and glucina in the above analysis and a qualitative test now made on a Uralian crystal ehowed the presence of litbia.L. J. 5.MINERALOGICAL CHEMISTRY. ii. 47 Pucherite from West Australia. E. GRIFFITES (J. Roy. Xoc. New South Vales 1908,42 251-252).-The concentrates from an oxidised quartz reef at Niagara 115 miles north of Kalgoorlie W. A. have been found to contain pucherite in the form of approximately cubical crystalline grains chrome-yellow in colour brittle and with a resinous lustre D 5.7. Analysis gave the following results Bi,O 73*77% V,O (including trace of P,O,) 25*31% Fe,O 0.36% residue insoluble in hydrochloric acid 0.8 1 %. H. 11. D. Connellite and Chalcophyllite from Bisbee Arizona. CHARLES PALACHE and H. E. MERWIN (Amer. J. Xci. 1909 [iv] 28 537-540).-A single small specimen from the Cdlumet and Arizona mine at Bisbee consists of groups of radiating needles of dark blue connellite together with cuprite melaiiochalcite and chalcophyllite.The connellite prisms are terminated by the unit pyramid and measurements gave CL c = 1 1.185 ; refractive indices o 1.724 B 1.746 ; D 3.396. HZO H,O H,O H,O Total(less0 Analysis (by Merwin) on 0.73 gram gave SOs. C1. CuO. (-=220"). (220-260"). (260-300"). (> 300"). for Cl). 3'43 6-37 75-96 0.25 12'06 2'10 1-66 100-41 This differs somewhat from the only analysis previously made of connellite (Penfield 1890 on only 0.074 gram) and corresponds with Cu,,C1,S0,,.20H20 or distributing the water in accordance with the temperatures a t which i t is expelled [ CuS0,,3Cu(OH),,H20],2[CuCI,,Cu(OH),~ ,14[Cu(OH),]. The crystals of chalcophyllite present many points of resemblance to spangolite but they were found to contain copper aluminium aud arsenic.Measurements gave u c = 1 2.671. L. J. S. The Earths of Euxenite. OTTO HAUSER and FRITZ WIRTH (Ber. 1909 42 4443-4447).-Specimens of euxenite from (I) Eitland (11) Arendal (111) Sietersdal (IV) South Carolina gave the following analyses Cb,O,. Taz05. Ti02 SnO,. W03. UOz. Tho,. Y,O,. I. 29.00 1.01 24.43 0.11 trace 5-64 4.50 27.32 -+ I I. 30-21 26.45 - I 5.28 3'20 28.47 111. 20.72 31'45 0.13 0 09 5-49 3.80 25.43 IV. 28.20 9.35 17'45 0-07 0.11 7.91 2.04 22-01 Loss on Ce(Sa,Di),O,. AI,O,. FeO. CaO. MgO. PbO. ignition. Total. I. 2.45 trace 1'37 0.85 0.08 0-43 2.87 100'16 11. 2-05 - 1'89 0.97 - - 2.01 100.64 111.2.58 - 4-94 0-66 0.14 0.46 3.88 99.76 IV. 6'93 - 2-04 - - 0-96 2.21 99.28 Of these I and I1 are typical euxenites I11 is to be regarded rather as a polycrase whilst I V diBers from both in containing an unusually large quantity of tantalic acid and a relatively small quantity of titanic acid. Of the yttrium group yttrium is always in excess. With increasingii. 48 ABSTRACTS OF CBEMICAL PAPERS. titanium holmium and dysprosium increase relatively t o neo-erbium. The components of ytterbium are abundant and scandium occurs especially in polycrase where it attains 0*060/ Samarium and praseodymium are absent from normal euxenites but samarium is found with increasing tantalic acid. Zirconium could not be detected in any of the specimens.P. P. PILIPEKKO (Bull. Acad. Sci. St. PStersbourg 1909 1116-11 18).-The author describes crystals of bertrandite occurring in the aquamarice deposits of the Altai mountains. The crystals have a glassy lustre are mostly colourlees and transparent and form either long plates or prisms elongated along the x axis; D*56 2.603 hardness 6. Their composition is as follows C. H. D. Bertrandite from Altai. SiO,. A1,Oj. Fe,O,. CaO G10. €120. Total. 50.12 trace trace trace 40.67 8.87 99.86 This bertrandite is formed as a result of the weathering of beryl and itself undergoes further change. Sardinian Minerals Species from the Province of Sassari. AURELIO SEKRA (Atti R. Accad. Lincei 1909 [v] 18 ii 348-350. Compare Abstr. 1909 ii 492 494).-,4 sample of heulandite in which the angle 110 IT0 had a value of about 47O was found to have the composition 810,.A1,0,. CaO. MgO. Na,O. K20. H,O. Total. 61'12 15.61 6.04 0.53 2.23 0-94 14.32 100.79 corresponding with the formula (Ca,';Mg,Na K)0,A1,03,Si0,,5 H,O. As typical heulandite contains SiO 59 2; Al,O 16.8 ; CaO 9.2 and H,O 14*8% the abnormal value of the angle 110 IT0 depands on the variations in chemical composition. T. H. P. A. sample of mesolite from 'L Su Marralzu " gave on analysis SiO,. A1,03. CnO. MgO. Na,O. K,O. H,O. Total. 50.85 21.95 12.02 0.08 1-72 trace 14-61 10123 and a sample of Smithsonite froin the Sos Enattos (Lula) mines ZnO. PeO. CaO. cop Total. 62'60 1 2 2 1.53 35.77 101'12 T. H. P. Lujaurites from Pilandsberg (Transvaal). H. A. BROUWER (Compt. rend. 1009,149 1006-100S}.-The analyses of two different kinds of lujaurite from the Transvaal are given.The one (I) is very similar to lujizurite from the Kola peninsula (Lapland),-whilst the other (11) is rich in aegyrine and eudialyte SiO,. TiO,. ZiO,. A1,0,. Fe,O,. PeO. MnO. CaO. I. 52.35 0 5 9 0.39 14.11 7.98 2.17 0'62 4'65 11. 51'35 2'75 0.54 11-45 9-40 2'41 1-25 3 27 MgO. Ii,O. Na,O. CO,. H,O. Total. I. 0.66 2.78 0 30 1 *50 3.20 100-30 11. 0'54 2.52 10*80 - 3.20 99-48MINERALOGICAL CHEMISTRY. ii. 49 As compared with other lujaurites these are rich in lime because of tho presence of calcite. The decrease in A1,0 and increase of Fe,O in (11) as compared with (I) is due to the former being rich in aegyrine. T. 8. P. Rhonite from Puy de Barneire at Saint-Sandoux. ALFRED LACROIX (Bull.SOC. fpanq. Min. 1909 32 325-331. Compare Abstr. 1907 ii 972; 1909 ii 587).-Large black crystals with a brilliant greasy to metallic lustre are present in a doleritic nephelinite at this locality. Under the microscope these resemble the rhonite of the Rhon mountains but owing to the depth of colour and intense pleochroism their optical characters could not be completely determined; D 3.56. The following analysis by F. Pisani gives the formula ( Na,E,H),Ca,(Fe,Mg)15( Al,Fe),,( Si,Ti)2109,,. SiO,. TiO,. A1,0,. Fe,O,. FeO. MgO. CaO. Na,O. K,O. H,O. Total. 30.90 8.04 17-65 6.80 15.20 9'08 12-20 0.76 0-61 0.20 100'64 L. J. S. Deposits from the Mineral Water of the Rohitach Springe Styria. HANS LEITMEIER (Zeitsch. Kryst. Min. 1909 47 104-123). -The waters of the springs at Rohitsch contain carbon dioxide with considerable amounts of magnesium carbonate sodium sulphate and carbonate and much less calcium carbonate etc.Fine crystal groups of aragonite have been deposited naturally by these waters and quartz crystals 4 cm. in length are also noted. The mineral water was allowed to evaporate slowly in the air at temperatures of 2O 13' and 20'. At the two higher temperatures acicular rhombic crystals of MgC0,,3H20 (anal. I) identical with the mineral nesque- honite were formed after some days; and later there was a deposit of indistinct crystals of aragonite. When however the evaporation took place at the lower temperature (2") there was after one-and- a-half months a deposit of large tabular monoclinic crystals of the pentahydrate MgC0,,5H20 (anal. 11). This salt is not formed at temperatures above 6'. It commences to lose water in the air a t 20° and at 60° four-fifths is lost; at 100' the loss is 44.68% and at 300° 5 1.69%. as the mineral lansfordite (3MgC0,,Mg(OH),,21H20) and as the supposed tetrahydrate of magneslum carbonate described by Marignac. These three thus appear to be identical the analyses of the last two having been made on partly dehydrated material These crystals have the same geometrical constants [a b c = 1,6079 1 0,9524 ; p = 78'36'1 MgO. CaO. co,. H,O. Total. Sp. gr I. 28.52 - [31-09] 40'03 99.64 1.854 11. 23'18 trace 25.21 51'69 100-08 1.688 L. J. S VOL. XCVIII. ii. 4

ISSN:0368-1769    

DOI:10.1039/CA9109805045

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 50 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry Asphyxia in the Spinal Animal R. KAYA and ERNEST Ha STARLING (J. Physiol. 1909 39 346-353). -In asphyxia the increased tension of carbon dioxide in the blood excites the brain centres including those in the bulb ; this produces exaggerated attempts to breathe and a rise of arterial pressure but no injurious action on the heart. The convulsions which follow are due t o excit- ation of the spinal centres by lack of oxygen and the heart failure which leads to a fall of pressure is also due to the same cause. W. D. H. *Supposed Preaence of Carbon Monoxide in Normal Blood and in the Blood of Animals Anzesthetised with Chloroform. GEORGE A. BUCKMASTER and JOHN A. GARDNER (Proc. Boy. Xoc. 1909 B 81 516-528).-For detecting carbon monoxide the authors use the spectroscopic test and the admittedly delicate method of H aldane.Carbon monoxide is not a normal constituent of blood-gases. Chloro- form is not decomposed in the blood with the formation of carbon monoxide. Chloroform vapour contained in the blood-gases of anaesthetised animals yields carbon monoxide when these gases are passed over potash. The small quantities of iodine found in Desgrez and Niclaux’s experiments in which the normal blood-gases are passed over iodine pentoxide a t 150° are probably due to the decomposition of this substance a t this temperature. G. S. W. Comparison of the Haemoglobin of certain Molluscs with that of Vertebrates. RAFFAELE PALADINO (Biocherrz. Zeitsch. 1909 22,495-505).-The hEmoglobin from various molluscs was compared with that obtained from ScyEZium and the dog.It did not differ essentially from these although certain minor differences were observed ; the mollusc blood for example is more readily changed by 10% acetic acid and less readily by 10% sodium hydroxide solution ; it is also more difficult to obtain in crystalline form. s. B. s. Effect of Temperature on the Dissociation Curve of Blood. JOSEPH BARCROFT and W. 0. R. KING (J. I’hysioE. 1909,39,374-384). -Dissociation curves of undialysed hzemoglobin solution in water are given at different temperatures in the presence and absence of carbon dioxide ; in a solution of potassium chloride the presence of carbon dioxide is relatively more powerful in the reduction of haemoglobin than in the removal of oxygen. I n low forms of animal life in which hsmoglobin is retained in store in muscles or nervous tissue the oxygen can be withdrawn in case of need for instance in partial asphyxia or great activity ; a favourable condition for the ready with- drawal of oxygen woulcl be rise of temperature or rise of carbon dioxide tension.The influence of temperature is evident also in the blood In muscular exercise with its accompanying rise of tempera-PHYSIOLOGICAL CHEMISTRY ii. 5 1 ture in fever and in inflammation the organism or part of it requires oxygen at a more rapid rate than usual; the rise of body-temperature enables the blood to meet this demand and is in fact the counterpart of vascular dilatation W. D. H. Hcemolysis. OSCAR GROS (Arch. exp. Path.Pharm. 1909 62 l-38).-Haemolysis is due to two factors (1) the death of the corpuscles ; (2) to physico-chemical changes which lead t o the passage of haemoglobin out of them. The second factor can be best studied if the changes occur rapidly as when caused by ammonia. The velocity of the change is then proportional to the concentration of the ammonia and inversely proportional to the concentration of the blood. Various salts were studied in the same way at different temperatures. Various ions favour hemolysis at 47-5' in the following order Na<Mg<K<Ca; C1<S04; and at 50° Mg<Na<K<Ca; Cl<SO,. The inhibitory action of serum on htemolysis is not destroyed by heating to 65'. W. D. H. The Disintegration and Life of Blood-platelets. H. DEETJEN (Zeitsch.physiol. Chern. 1909 63 1-26).-Blood-platelets from human blood can be isolated by collecting the blood between the object glass and cover slip and washing with physiological saline. In this way the other elements can be removed ; the platelets alone remain sticking to the glass. They rapidly disintegrate under ordinary conditions but remain however intact if quartz is used instead of glass and the saline solution is perfectly neutral. I n the presence of minute traces of alkali (CoH = and of somewhat larger quantities of acid (C = 2*10-4) they disintegrate. The action of the hydroxyl ions is indirect ; they either influence a ferment or cause the liberation of a ferment which causes the disintegration of the platelets. This statement is made in consequence of the fact that even in the presence of alkali the platelets can under certain con- ditions remain intact. Thus they are protected from disintegration by the presence of hirudin manganese salts Witte's peptone and peroxides.From the investigations with hirudin the conclusion is drawn that the platelets themselves secrete an enzyme which leads finally to their destruction. The platelets after treatment with hirudin are not disintegrated by alkali although they are by plasma. The destroying ferment is not identical with the blood-clotting ferment although it is possibly with the pro-ferment. Nanganese salts do not entirely inhibit the disintegration but only retard i t ; on the other hand they inhibit blood-clottings owing perhaps to action on the pro-ferment.Witte's peptone paralyses the platelets and thus inhibits the secretionof the ferment. Peroxides entirely inhibit t h e disintegration of the isolated ferments. The explanation of this fact is not obvious. By means of the peroxide method the action of the living platelets can be demonstrated. The presence of a nucleus nuclear membrane and amaeboid movement can then be shown. The disintegration of the platelets after removal from the blood-vessels is due to the evolution of carbon dioxide and the increased concentration of the 4-2ii. 52 ABSTRACTS OF CBEMICAL PAPEPS. hydroxyl ions. with those from man; those from the ape are very similar. The platelets from other animals are not all identical S B S. Spectro-photometry of Blood. EUGEN LETSCHE (Zeitsch.physiol. CAem. 1909 63 313-314).-Remarks on the usefulness of Hufner’s spectro-photometer. In spite of its faults i t gives good results in accustomed hands. W D. H. bfluence of Stereochemical Configuration on Certain Physico-chemical Properties of Organic Colloids. GIUSEPPE BUGLIA and L. KARCZAG (Atti R. Accud. Lincei 1909 [v] 18 ii 374-380).-The authors have determined the influence of d - 1- i- and r-tartaric acids in various concentrations on the time of coagula- tion by heating of normal blood-serum and of blood-serum dialysed until it has become neutral. All these acids have a marked influence on the coagulation at first accelerating it and subsequently retarding and even absolutely preventing it. &Tartaric acid which is diseociated to a less extent than the other acids also produces less acceleration of the coagulation and renders the serum non-coagulable in lower concentrations than with the active and racemic acids.With these three acids which are approximately equally dissociated the influences on the coagulation are about the same. T. H. P. The Laws of Digestion and Absorption. SVANTE ARRHENIUS (Zeitsch. physiol. Chem. 1909 63 323-377).-A mathematical discus- sion of the laws relating to the velocity etc. of digestive processes. The rule of the square root appears to play a dominating part. London’s work on the subject 1s on the whole corroborated. W. D. H. The Enzymes concerned in Nuclein Metabolism in Human Organs. ALFRED SCHITTENHELM. The Fate of Nucleic Acid contained in the Food of Normal Men. F ~ ~ A N Z FRANK and ALFRED SCHITTENHELM.The Occurrence and Importance of Allantoin in Human Urine. ALFRED SCHITTENHELM and KARL WIENER. The Enzymes Concerned in Nuclein Metabolism in Lupin Seed- lings. ALFRED SCHITTENHELM (Zeitsch. physiol. Chem. 1909 63 248-268 269-282 283-288 289).-The capacity of the human liver and other organs t o form uric acid is undoubted and can be readily demonstrated in extracts by their action on guanine. Com- menting on W. Jones’ statement regarding the absence of adenase in human organs it is pointed out t h a t unquestionably adenine dis- appears during life the urine containing only traces after abundant ingestion of that substance when sweetbread is taken as food. It is therefore doubtful whether the action of extracts is a true index of vital metabolism; if an extract gives a positive result it is no doubt of the same nature as that occurring during life; but if a negative result occur that does not necessarily mean that a positive result may not occur during actual metabolism in the living organ.It is quite true again that extracts of human organa contain no uricolyticPHYSIOLOGICAL CHEMISTRY. ii. 53 enzyme that is to say destruction of uric acid does not occur post- mortem ; it is unscientific to conclude from this that uricolysis does not occur during life. Both in animals and men nucleic acid given in the food is completely absorbed and undergoes metabolism and the end-products are excreted during the same day. This comes out quite clearly by a study OE nitrogen and phosphorus excretion.The proportion between the different end-products varies in different animals; in man the main one is urea the uric acid formed is small in amount and the purine bases of the urine are minimal. The uric acid formed is doubtless again largely destroyed and the nitrogen finally is contained in urea. The meaning of allantoin in the urine is far from clear; if uric acid precursors are administered the amount of allantoin does not increase in the urine. If allantoin is given by the mouth or sub- cutaneously about 30% is recoverable in the urine. It cannot there- fore be an important end-product of uric acid catabolism. The expressed juice or aqueous extracts of lupin seedlings contain an amidaee which converts guanine into xanthine. 'CV. D. H. The Elimination of Total Nitrogen Urea and Ammonia following the Administration of Amino-acids Glycylglycine and Glycylglycine Anhydride.PH~BUS A. LEVENE and G. M. MEYEE (Amer. J. Physiol. 1909 25 214-230).-The results of these metabolism experiments on dogs are given with full detail ; the extra nitrogen administered is usually excreted within twenty-four hours but this rate varies and the proportion of urea ammonia etc. also varies in different cases. I t is specially rapid after the ingestion of amino-acids. W. D. H. The Influence of Removal of Segments of the Gastro- intestinal Tract on the Character of Protein Metabolism. ISAAC LEVIN D. D. MANSON and PH~BUS A. LEVENE (Anlev. J. Physiol 1909 25 231-253).-After excision of portions of the alimentary canal an unexpected acceleration in the absorption and elimination of nitrogen is the most noteworthy result.W. D. H. The Influence of Certain Mercury Compounds on Meta- bolism. GUIDO IZAR (Biochem. Zeitsch. 1909 22 371-393).- Mercury when introduced directly into the circulation either in form of a hydrosol or of salts markedly stimulates the nitrogenous metabolism and the amount of nitrogen in the urine is considerably increased. Larger doses however of sublimate calomel hygrol and mercuric thiosulphate are necessary to produce the same effect as a given dose of the hydrosol. There is no difference between the actions of stabilised and non-stabilised colloids. The increase of urea and uric acid in the urine runs parallel with the increase in total nitrogen. 8. B. S. [The Permeability of Cells for Dyes.] W.RUHLAND (Biochem. Zeitsch. 1909 22 409-410).-The author objects to the attempted explanation of Hober (Abatr. 1909 ii 912) of the reason why wool-ii. 54 ABSTRACTS OF CHEMICAL PAPERS. violet-S and other dyes do not behave in accordance with the Overton lipoid theory. S. B. S. Nucleo-protein in the Yolk Platelets of the Frog’s Egg; and the Black Pigment. J. E. MC~LENDON (Amer. J. Physiol. 1909 25 195-198).-The nucleo-protein investigated is probably more properly to be considered a lecitho-protein or vitellin-like substance. It is termed batrachiolin; it contains Y 1*2% S 1*32% and N 15.14%. Analyses are also given of the black pigment which appears to belong to the melanins but it was not satisfactorily freed from impurities. The Catalase of Echinoderm Eggs before and a f t e r Fertilisation.ELIAS P. LYON (Amer. J. Physiol. 1909 25 199-203).-1f the eggs are treated with hydrogen peroxide much more oxygen is set free by eggs which have been fertilised than by unfertilised eggs. The maximum is reached in twenty minutes after fertilisation. The increase in catalase is due either to a kinase in the sperm cell or by an increase in the permeability of the egg so that peroxide and catalase come more easily together. W. D. H. W. D. H. [Analyses of Brains. Distribution of Sulphur in Brains.] WALDEMAR KOCH (J. Amer. Chern. SOC. 1909 31 1329-1335). WALDEMAR KOCH and FRED. W. UPSON (ibid. 1355-1364)-See this vol. ii 78 79. G. LILJESTRAND (Skand. Archiv. Physiol. 1909 22 339-348)- Magnesium sulphate and chloride paralyse the motor nerves of the frog but this occurs late and is preceded by a stimulating action.Weak F O ~ U - tions are not stimulating. Sodium chloride has a similar action. Zinc chloride acts in the same way but much more strongly. Influence of Different Substances on the Gaseous Exchange of the Surviving Muscular Tiesue of Frogs. I. and 11. TORSTEN TRUNBERG (&and. Archiv. Physiol. 1909 22 406-429 430-436).- I. The measurements were made by means of the author’s micro- respirometer generally in an atmosphere of oxygen. In the intact muscular tissue tbe gaseous exchange is less than that of muscular tissue which has been cut by scissors ; it is greater however than in muscular tissue which has been ground up with sand so as to destroy the cell structure.Previous extraction of t,he tissue with physiological saline caused n marked diminution of the gaseous exchange; with isotonic neutral potassium phosphate the diminution was less. The maximum of gaseous exchange takes place in isotonic saline ; increase in the salt concentration causes a rapid diminution. There is not much difference in the gaseous exchange when the measurement is made after treatment with solutions of chlorides of the different alkali metals; the chlorides of the alkaline earths on the other hand cause considerable diminution. The action of the potassium halide salts is similar with the exception of the fluoride which causes a markod diminution in the gaseous exchange. The Action of Certain Salts on Frogs’ Motor Nerves. W. D. H.PHYSIOLOGICAL CHEMISTRY ii.55 11. Oxalic malonic and succinic acids in the form of their potassium salts affect the gaseous exchange considerably diminishing more especially the carbon dioxide output. The respiratory quotient is con- sequently affected by these salts. Other acids investigated do not affect the respiratory quotient in this manner. S. B. S. The Formation of Carbon Dioxide in Surviving Tissues. OLAV HANSSEN (Biochem. Zeitsch. 1909 22 433-441).-The author gives a method for estimating the carbon dioxide evolved by surviving tissues (chiefly liver) when suspended in physiological Faline at 37”. The influence of antiseptics and other substances on the action was determined Certain substances such as sodium p- hydroxybutyrate caused increased carbon dioxide output.Sodium lactate caused a slight increase. Most other sodium and ammonium salts had but little action ; sodium glycollate however inhibited the output. S. B. S. Water Rigor in Frog’s Muscle. EDWARD B. MEIGS (J. Physiol. 1909 39 385-390).-The statement of du Bois Reymond that in water rigor of frog’s muscle as in other forms of rigor sarcolactic acid is formed was confirmed by the thiophen test. If the muscle is then placed in Ringer’s solution it loses acid and lengthens. This is regarded as a confirmation of the view that the acid is the cause not the result or accompaniment of the shortening. W. D. H. Action of Cinchona Alkaloids on Muscle. VICTOR H. ‘VELEY and AUGUSTUS D. WALLER (Proc. physiol. Soc. 1909 xix-xxi ; J. Yhysiol. 39).-The relative toxicity of poisons can be well studied by their effect on the direct excitability of the frog’s sartorius.In the case of the alkaloids examined the figures obtained are cinchon- amine 400 quinine 100 quinidine 50 cinchonine and cinchonidine 25. These figures agree very well with what would have been anticipated from physicochemical data. W. D. H. Extractives of Fish Muscle. FRIEDRICR KUTSCHER (Zeitsch. physiol. Chem. 1909 63 104-105).-A reply to Suzuki and Toshimura (Abstr. 1909 ii 9lO).-The base C,H,,O,N isolated from Ommastrephes sp. agrees in properties withLbetaine and not with 6-aminovaleric acid as stated by these authors. Furthermore other bases described by them such as arginine leucine lysine and proline have already been isolated in the author’s laboratory from extracts of sea and laud animals.S. B. S. The Occurrence of Inactive Lactic Acid in a Meat Extract. ERNST SALKOWSKI (Zeitgch. physiol. Chem. 1909 63 237-247).-Valentine’s meat juice has a minimal nutritive value. Its colour is due to a pigment which was not identified but is possibly a derivative of hsemoglobin. When kept it deposits a crystalline precipitate of magnesium salts among which lactate is present. The lactic acid is of the optically inactive kind. The freshly prepared juice contains sarcolactic acid but as time goes on this is convertedii 56 ABSTRACTS OF CHEMICAL PAPERS. almost completely into the inactive variety. the cause of the transformation did not yield any certain results. Attempts to determine W. D. H. The Nucleo-protein of Spleen.T. SATO (Biochem. Zeitsch. 1909 22 489-494).-The nucleo-protein was prepared by precipitating the hot-water extract of the organ with dilute acetic acid. The amount of iron in various preparations varied between 0.15 and 0.80%. The metal appears to be contained in the nucleoprotein in two forms namely in a labile form the part corresponding with which is remov- able from the substance by treatment with sodium carbonate and a more stable form. S. B. S. Chemico-physical Investigations on the Crystalline Lens. XI. Imbibition of the Lens in Water at Different Tempera- tures and in Acids and Alkalis. FILIPPO BOTTAZZI and No6 SCALINCI (Atti R. Accad. Lincei 1909 [v] 18 ii 32’7-339. Compare Abstr. 1909 ii 502).-The velocity and total amount of imbibition of the crystalline lens in water are greater a t high than at low tempera- tures.Imbibition in dilute solutions of an acid or an alkali increases with the concentration of the solution. I n solutions of various acids and of sodium hydroxide imbibition increases in the following order acetic acid sulphuric acid water hydrochloric acid and sodium hydr- oxide. Since in the concentrations employed these acids are completely dissociated the sulphuric and acetic anions must exert a specific depressing influence on the imbibition in opposition to the action of the hydrogen ions which increase the imbibition. X similar relation probably holds with solutions of different bases the accelerating influence of the hydroxyl ions on the imbibition being modified to varying extents according to the nature and valency of the cation.When immersed in the acid solutions employed the lens becomes opaque probably owing to the precipitation of the faco-protein which in its natural state is an electro-negative colloid by the hydrogen ions. This action is more marked with sulphuric and acetic acids than with hydrochloric acid which seems to be capable of transforming the alkaline faco-protein rapidly into acid. C hemico-ph ysical Investigations on the Crystalline Lens. G. QUAGLIARIELLO ( A t t i R. Accad. Lincsi 1909 [v] 18 ii 350-383). -The author has studied the influence of hydrochloric acid on the coagulation of the crystalline lens by the method previously employed with sodium hydroxide (Abstr. 1909 ii 1036). The curve cf the vslocity of coagulation in presence of hydrochloric acid is essentially similar to that obtained with sodium hydroxide the variation in the velocity gradually diminishing as the amount of acid is increased; in this case however the final value of the velocity differs far less from the initial value than is the case when sodium hydroxide is present. Whilst the latter up to a certain concentra- tion first increases and then sensibly diminishes the velocity of coagulation hydrochloric acid produces a continuous increase.The results indicate that the influence of chemical agents on the T. N. P.PHYSIOLOGICAL CHEMISTRY ii. 57 velocity of coagulation of the crystalline lens is a function of the superficial area of the lens. Chemical Investigation of Teeth. 11. TH. GASSMANN (Zeitsch. physiol.Chem. 1909 63 397-400. Compare Abstr. 1908 ii 609). -Teeth from prehistoric men (at least 2000 years old) were found to be well preserved. They contain 3% more organic substance than recent teeth and less magnesium and phosphoric acid. The percentage of calcium sodium potassium chlorine and carbon dioxide is the same as in recent teeth. W. D. H. T. H. P. Inorganic Constituents of Two Egyptian Mummies. PAUL HAAS (Chem. News 1909 100 296).-The constituents of the ash were as follows Mummy A 4’83 1-21 0’24 0’156 0.134 2-64 1.91 1.57 0 22 - percent. Mummy B 0.90 0.77 9-03 0.27 0.90 traces 2.99 0‘42 1’89 5.80 A hot-water extract of (‘A’’ had an acid reaction and the same material yielded to ether 9% of extract which was acid and soluble in potassium hydroxide solution.No arsenic antimony or mercury was present. The high percentage of lime in the ash from “ A ” may indicate that quicklime was added t o the coffin in which the body was placed. Material ‘‘ B,” unlike ‘‘ A,” was moist and lost 16% of its weight when dried at looo but the dry material rapidly increased in weight on exposure to air. The ether extract amounted t o 3.5%. I n this case the embalming material may have been “ natron,” or “ nitrum,” a mixture of sodium chloride sulphate and carbonate. Alumina has not been recorded previously as a constituent of mummy ash. T . A H CaO. K20. Na,O. Fe,O,. A1,0,. CO,. SO,. P,O,. C1. SiO,. Presence of an Anzeroxydase a n d Catalase in Milk. J. SARTHOU (Compt. rend. 1909 149 809-810.” Compare Bordas Abstr. 1909 ii 505).-The filtrate from milk curdled at 30’ gives a very distinct reaction with p-phenylenediamine but not with guaiacol or hydrogen peroxide.By treating the residue on the filter with water a liquid is obtained which gives distinct colorations with p-phenylene- diamine and guaiacol in presence of oxygen. The casein after having been freed from the ansroxydase by washing reacts with p-phenylene- diamine and hydrogen peroxide but not with guaiacol. The conclusions drawn are that milk contains a soluble aasr- oxydase as well as an insoluble catalase and that the excessive sensitiveness of p-phenylenediamine t o oxidation should be recognised Anzeroxydase and Catalase in Milk. FRED. BORDAS and TOUPLAIN (Compt. rend. 19c19 149 101 1-1012. Compare Abstr. 1909 ii 505).-The author considers the experiments of Sarthou (preceding abstract) indecisive since the colorations obtained were due to the presence of casein which is always present in milk filtered * and.J.Pharm. Chim 1910 [viiJ 1 20-23 in the study of oxidirsing ferments. w. 0. w.ii. 58 ABSTRACTS OF CHEMICAL PAPERS. through paper. When fresh or curdled milk is passed through the Chamberland filter the filtrate gives no coloration with Storch’s reagent. There is no evidence therefore of the presence of a soluble Can the Radium Emanations taken up by Drinking be Detected in the Urine? WALTHER LAQUER (Chem. Zentr. 1909 ii 854; from Zeitsch. expt. Path. TAW. 1909 6 868-878).-Ey the method employed emanations of less than 20,000 units cannot be detected in urine. The quantity of emanation in urine increases with the quantity in the water drunk.All the values found must be multiplied by 2. The urine voided in the first half hour contains only three-quarters to four-fifths of the total excreted in the urine. The ratio of the quantity of emanation excreted t o that ingested is about 1 4000. anseroxydase or insoluble catalase in cows’ milk. w. 0. w. S. B. S. The Origin of Ethereal Sulphates in the Organism. T. SATO (Zeitsch. physiol. Chem. 1909 63 378-396).-Rabbits were treated with phenol added to their diet (cabbage) and certain sulphur com- pounds also added. The nitrogen and sulphur (in various combina- tions) were estimated in the uriue. Isethionic acid only slightly raises the output of ethereal sulphatep and has no effect on nitrogen.It appears to be rapidly excreted. Cystine raises the total sulphatep and the amount of ethereal sulphate is parallel to this. Albumose prepared from egg-albumin has no action. Sulphidal (a colloidal sulphur preparation) enormously increases both total and ethereal sulphate excretion. Thiocarbamide is largely excreted as such ; the effect on the excretion of sulphates is doubtful; the urine does not show the reactions of thiosulphuric acid. W. D. H. The Origin and Destiny of Cholesterol in the Animal Organism. VI. The Excretion of Cholesterol by the Cat. G. W. ELLIS and JOHN A. GARDNER (Proc. Roy. SOC. 1909 B 81 505-515. Compare Abstr. 1909 ii 595).-The tendency for the change of cholesterol of food to coprosterol in faeces appears to be greater in cats than in dogs.I n experiments with two cats on a diet of sheep’s brain coprosterol free from cholesterol was recovered ; on a meat diet the change was not complete ; on vegetable diet and on an artificial diet as free as possible from cholesterol or phytosterol no faecal coprosterol was found. A discussion of the part played by the cholesterols in the animal economy follows. G. S. W. The Biological Significance of Lecithin. IV. The Blood- Content of Phosphorus and Iron in Lipoid Form in Cases of Polycythaemia rubra megalosplenica. W. GLIKIN (Biochem. Zeitsch. 1909 22 461-463. Compare Abstr. 1909 ii 1038).-The lecithincontent was found to be about 5 grams per 1000 C.C. in cases of this disease as compared with 2 to 3 grams per 1000 as found by Abderhalden in the blood of mammals normally.The phosphorus and total iron were also large as compared with t h a t found in normal cases. s 6. s,PHYSIOLOGICAL CHEIMISTRY. ii. 59 The Detection of Phosphorus and Hypophosphorous Acids in Organs after Phosphorus Poisoning. 11. RrcHARD EHRENFELD and WILHELM KULKA (Zeitsch. physiol. Chem. 19Q9 63 315-322. Compare Abstr. 1909 ii 345).-Further investigations showed t h a t during putrefactive processes the phosphorus is in part rapidly converted into phosphorous and hypophosphorous acids but after this the change progresses but little. The experiments recorded further indicate that the normal phosphorised constituents of the body do not give rise to the acids mentioned. W. D. H. &Suprarenine (&Adrenaline). N. WATERMAN (Zeitsch. physiol.Chem. 1909 63 290-294).-Pr~vious work on the superior physio- logical activity of &adrenaline is confirmed ; so also is Abderhalden’s work on so-called adrenaline immunity. Administration of the d-compound increases the resistance of mice towards the I-variety. W. D. H. The Antagonism between Adrenaline and the Chlorides of the Alkaline Earths and of Potassium. THEODOR FRANKL (Pfliiger’s Archiu 1909 130 346-352).-The action of adrenaline in stimulat- ing sympathetic nerve-endings is antagonised by the chlorides mentioned in the title of which the strongest is barium chloride. Sodium chloride has no such action. W. D. H. Mode of Action of Nicotine and Curare determined by the Form of the Contraction Curve and the Method of Tempera- ture-coefficients. A. V. HILL (J. Physiol. 1909 39 361-373). -From a mathematical considersttion of the curves of contraction and relaxation of muscles under the influence of curare and nicotine at different temperatures the conclusion is drawn that there is a combination between the drug and some constituent of the muscle. Evidence is also adduced for the existence of two or more types of fibres (or contractions) in tlhe muscle selected for experiment the rectus abdominis of the frog. W. D. H. Relative Toxicity of Various Salts and Acids towards Paramoscium. LORANDE Loss WOODRUFF and HERBERT HORACE BUNZEL (Arner. J. PhgsioT. 1909 25 190-194).-The experiments with some exceptions indicate a marked parallelism between the order of toxicity of various cations and their ionic potential. The high migration velocity of hydrogen ions will explain their unexpectedly high toxicity. Specific affinities of the living cell for certain ions will explain other exceptiooal cases for instance the low toxicity of copper. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9109805050

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 60 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. The Degradation by Bacteria of the Ultimate Hydrolysis Products of Proteins. WALTHER BRASCH (Biochem. Zeitsch. 1909 22 403-406).-The degradation of various amino-acids by BaciZZw putrifcus and by mixed putrefying bacteria was investigated. Aspartic acid yields with mixed cultures propionic acid as chief product together with small quantities of succinic acid. The pure culture gave the same products together with small quantities of formic acid. Serine yielded both with pure and mixed cultures propionic acid with small quantities of formic acid. Tyrosine yielded with the pure culture p-hydroxyphenylpropionic acid. Glycine with the pure culture yielded acetic acid alanine yielded propionic acid and aminobutyric acid yielded butyric acid.S. B. S. Accumulation of Nitrogen in Soils by Free Bacteria. ALFRED KOCH (J. Landw. 1909,5’7 269-386. Compare Abstr. 1908 ii 56). -A continuation of the experiments made in 1905 and 1906 (Zoc. cit.) on the effect of sugar on fixation of nitrogen by Azotobactsr. The results show a considerable after-effect increased yields of buckwheat oats and wheat being obtained in 1907 1908 and 1909 and that the increased yields diminish regularly each year Experiments with sand inoculated with soil showed a gain of 7.2 mg. N per 100 grams in four months when sugar was added; and vegetation experiments with buckwheat grown in sand showed a very greatly increased production of dry matter (98.1 grams) in presence of sugar as compared with the amount obtained without sugar (23.7 grams) whilst the amounts of nitrogen in the produce were 409 and 54 mg.respectively. Further experiments in plots ($ square metre) with wheat rye and oats (in 1907 1908 and 1909) showed that the nitrogen fixed in the first year was only utilised to a slight extent whilst the yields were considerably increased in the second and third years. The examination of fifteen different soils showed that Azotobacter was present in seven of them whilst eight gave negative results. The latter included three light sandy soils peaty light and heavy soils and soil from a pine wood. Addition of sugar to three of these soils failed to produce an increase in the nitrogen content. Experiments are described in which manni tol dextrose calcium succinate glycerol calcium butyrate (10 grams each) and xylan (5 grams) were added to soil (500 grams) which was kept for a month a t 2 5 O .The soil with mannitol and with dextrose gained 12.3 and 6.9 mg. nitrogen per 100 grams respectively whilst the others lost nitrogen (0.8 to 5.3 mg.). N. H. J. M. Production of Citric Acid by Citromyces. PIERRE M A Z ~ (Ann. Inst. Pasteur 1909 23 830-833).-Citric acid is produced not only when there is a deficiency of nitrogen but also when any one of theVEGETABLE PHYS~OLOGY AND AGRICULTURE. ii. 61 indispensable substances (phosphorus potassium iron or zinc etc.) is absent or deficient. A mineral solution in which iron or zinc is wanting gives on addition of sucrose (1 0%) a very insignificant amount of growth.It will however produce in a few weeks relatively important amounts of citric acid. The mechanism of the formation of citric acid is discussed (compare Buchner and Wiistenfeld Abstr. 1909 ii 602). F u n g i which Produce Citric Acid. CARL WEHMER (Chem. Zeit. 1909 33 1281).-In 1892 the author discovered two moulds which can convert sugar into citric acid (Abstr. 1893 ii 591). Since then the number has been extended and he has now isolated five or six others morphologically much alike capable of effecting the same change. Citrornyces To&?ens~unus is characterised by its snow-white appearance in mass culture although microscopically i t differs but little from t h e others. Another species possesses the remarkable property of thriving in a saturated solution of oxalic acid (containing about 10% of acid) ; the hardiest mould previously known (Aspergihs miger) can only withstand about 1% whilst most organisms are adversely affected by a trace.Another organism gives rise to oxalic instead of citric acid but some oxalic acid (or rather its calcium salt) is always found in old cultures as a decomposition product of the citrate. E. J. R. N. H. J. M. Theory of Disinfection. I. The Disinfecting Action of Phenol 111. HEINRICH REICHEL (Biochem. Zeitsch. 1909 22 $01-231. Compare Abstr 1909 ii 1045).-The assumption is made that the disinfecting action depends on the coefficient of distribution of the disinfectant between the two phases namely the bacteria and the disinfecting solution. The disinfecting action of phenol in the presence of varying quantities of sodium chloride was determined suspensions of typhus bacilli and staphylococci being employed.The time of exposure to the solutions just necessary to kill the cultures was determined the method of sub-culturing being employed. The curves obtained were submitted to mathematical analysis and the factors influencing the distribution of the disinfectant between two phases such as imbibition of water by the protein etc. discussed. S. B. S. Influence of Varying Relations between Lime and Mag- nesia on the Growth of Plants. LUIGI BERNADINI and A. SINIRCALCHI (Chem. Zentr. 1909 ii 857 ; from Stax. sper. agrar. ital. 1909 42 369-386).-The injurious effect of an excess of calcium and the poisonous action of an excess of magnesium do not depend on the absolute amounts of calcium and magnesium ions taken up but on the relation of the amounts absorbed by the plant to each other.The assimilated phosphoric acid is a function of the relation C'aO/MgO in the nutritive medium and depends on the relation of the calcium and magnesium ions in which these are absorbed. Formation of Btarch from Sorbitol in Rolsaceae. 0. TBEBOWX (Bsr. Dsut. bot. Ges. 1909 27 507-511),-Experiments with N. H. J. M.ii. 62 ABSTRACTS OF CHEMICAL PAPEREI. numerous varieties of Pomoidece Pvunoidece Spiraeoidea showed that all of them are able to produce starch from sorbitol whilst negative results were obtained with two other sub-orders Rosoidem and Ruboidece and with the related orders of the Saxifi*agince and Leguminosce.None of the plants which produce starch from sorbitol are able to utilise mannitol and dulcitol. As compared with sugars and glycerol the production of starch from sorbitol is almost always much more vigorous. Sorbitol has up to the present only been found in fruits but further investigation will probably show that it occurs in leaves and other parts of plants. N. H. J. M. Influence of Aluminium Salts on the Colour of Flowers VALENTIN VOUK (Bied. Zentr. 1909 38 755-756; from Oesterr. bot. Zeitsch. 1909 58 336-243).-Plants of Hydrangea hortensis watered with a 3% solution of alum produced flowers of a fine blue colour; at the same time brown spots appeared on the leaves which died a t an early stage. The best results were obtained with 1% solutions which had no injurious effect whilst the production of blue flowers was nearly complete.When aluminium sulphate was employed the coloration was less strong. Experiments with Phlox decussatu gave negative results. N. H. J. M. Protective Action of Sodium f o r Plants. W. J . V. OSTERHOUT (Bied. Zentr. 1909 38 730-731 ; from Juhrb. wiss. Bot. 1908 46 121-136).-Water and soil culture experiments in which roots algae and moulds etc. were supplied with single salts and with mixtures showed that the poisonous action of calcium is diminished by addition of small amounts of a sodium salt. The antagonism between sodium and calcium salts is stronger than between sodium magnesium and potassium salts. The conclusion is drawn that sodium is not a nutrient but a pro- tective substance for plants and probably for animals.Salts of aluminium zinc and cobalt have a protective action for animals and salts of calcium for fungi. N. H. J. M. Molecular Complexity of Caoutchouc in the Milk. F. WILLY HINRICHSEN and ERICH KINDSCHER (Ber. 1909 42 4329-4331).-The form in which caoutchouc occurs in the milk of caoutchouc-yielding plants is still unknown Weber claiming that the milk contains a hydrocarbon which polymerises to caoutchouc during the technical preparation of the substance (Abstr. 1903 i 8451 whilst de Jong and Tromp de Haas (Abstr. 1904 ii 762) assert that caoutchouc occurs already prepared in the milk ; Harries also holds the latter view (Abstr. 1904 i 1038). The authors have centrifugalised Kickxia milk with pure benzene until an approximately clear solution is obtained containing the caoutchouc and the caoutchouc-reain. The depression of the freezing point of this solution is determined ; the residue is weighed after evaporation of the solvent and extracted with acetone to remove the resin.The mole-VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 63 cular weight of the latter in benzene is 426 and by calculation the molecular weight of the caoutchouc is found to be 3173 a result which does not support Weber's view. c. s. Influence of Anesthetics and of Cold on Coumarin- producing Plants. EDOUARD HECKEL (Compt. rend. 1909 149 829-531. Compare Guignard Abstr. 1909 ii 823 ; Mirande ibid. ii 834).-The odour of coumarin in plants such as Anthoxanthum odoratum or MeZiZotus oficinalis is only perceptible in the dried leaf but is rapidly developed in the living leaves when these are submitted to the action of anesthetics or of cold.The author confirms the generality of similar phenomena observed by Guignard in the case of Cruciferae and has extended the experiments to LepidiuTn Zztifoliurn and CocJdearia armoracia. w. 0. w. Ajuga Iva. Uao PONTI (Gccxxetta 1909 39 ii 349-353).-The plant Ajuga Im which is largely employed in the ceighbourhood of Sassari as a remedy for malarial fever contains no alkaloids buk on distillation in a current of steam yields a small quantity of a green oil having a characteristic aromatic odour. When treated with milk of lime the herb yields ferulic acid which probably exists in the plant in combination with phloroglucinol thus >C*OH ,C(OMe)*CH C(OH)*CH oH'C<CH==CH> C*CH CH* CO C<C(OH) c~ this structure being analogous to that of homoeriodic tyol (compare Power and Tutin Trans.1907 91 887). Presence of Aucubin in Different Varieties of Aucuba Japonica. C. LEBAS (J. Pharin. Cliim. 1909 [vi] 30 390-392).- Six garden varieties of this plant namely elegantiasiina Zatimaculata Zongifolia punctata salicifolia and vii'idis have been examined and found t o contain aucubin (Bourquelot and HBrissey Abstr. 1902 i 634) which was isolated in the manner desciibed already (Zoc. cit.). The quantity obtained varied from 0.3% for elegantissima to 1.9% for Zatimacukutu. T. A. H. T. H. I?. Occurrence of a Cyanogenetic Glucoside in Linaria Striata. $MILE BOURQUELOT (J. Pharm. Chim. 1909 30 3S5-389).-The plant was extracted with alcohol and the concentrated extract dissolved as far as possible in an aqueous solution of thymol.This aqueous extract contained (1) sucrose identified by its resolution into '' invert sugar " by the action of invertase and (2) a cyanogenetic glucoside hydrolysed by emulsin into benzaldehyde hydrogen cyanide and a reducing sugar probably dextrose. The amount of dextrose produced was in excess of that required for any known glucoside producing benzaldehyde so that probably a second glucoside was present in the extract. T. A. H. Existence of Two New Glucosides Decomposable by a Ferment in Primula officinalis. A. GORIS and MASCRE (Compt. rend. 1909 149 947-960). -The fresh roots of Primula ofiicinalis,ii. 64 ABSTRACTS OF CHEMICAL PAPERS.like those of other species of Primula emit a characteristic odour when bruised. This appears to be due 40 interaction between two ,glucosides and an enzyme for which the name primeverase is suggested. The new ferment has been shown not t o be identical with emulsin myrosin or betulase. Details are given of the method employed in isolating the glucosides primeverin and primulaverin. The former occurs in colourless crystals m. p. 172-173O [aID - 60*24O whilst the latter forms needles m. p. 160-161° [a] - 66-86' Both are hydrolysed by dilute sulphuric acid disengaging an odour of anise and furnishing a substance which in the case of primeverin develops a bright blue coloration with ferric chloride and a lilac-violet coloration in the case of primulaverin. IV. 0.w. Localisation of Proteolytic Ferments in Vaeconcellea quercifolia. The Rennet and Spontaneously Coagulable Latex. C. GERBER (Compt. rend. 1909 149 737-740. Compare Abstr. 1909 ii 512 824).-Unlike the majority of plants the foliaceous ribs of Vasconcellea quercifolia show greater rennet activity than the parenchyma. Other parts of the plant show similar divergence from the general rule. This appears to be connected with the proportion of latex in the organs since for example the ribs are richer in latex than the parenchyma. On the other hand the presence of a milky latex such as that of the chestnut is not invariably associated with marked proteolytic activity. - The rennet activity of V. pwrcifolia Funtumia elastics htocarpus incisa and A . integrifolia shows some proportionality to the readiness with which the sap undergoes spontaneous coagulation.w. 0. w. Action of Different Amounts of Copper in t h e Soil on tbe Growth of Plants. J. SIMON (Landw. Versuchs.-Stat. 1909 71 417-429).-Mustard and barley were grown in a mixed soil in sand in garden soil and in a clay soil to which small amounts of copper sulphate were added. In the mixed soil the yield of mustard was reduced by about 11-13% by 0.001 and 0.01% of copper sulphate and to 83 and 0.5% by 0.1 and 0.5% respectively whilst the plants were killed by 1%. Barley isless sensitive being unaffected by 0.001% of copper sulphate and remaining alive in presence of 1%. With regard to the sand and other soils the experiments showed that copper sulphate is most poisonous in sand and least in the garden soil.Experiments on the absorptive power of the soils shoved that 100 grams of the garden soil absorbed 1.252 grams of copper sulphate whilst the mixed soil and the clay soil absorbed 0.378 and 0.111 respectively and the sand none at all. N. H. J. M. Depositioc of Nitrogen in Full-grown Animals with Abundant Food. KURT FRISKE (Landw. Versuchs.-Xtat. 1909 71 440-482).-The results of the experiments of Lawes and Gilbert (Phil. Tmns. 1869 493) on the changes in the composition of animals when fattened showed that the gain is chiefly in fat (two-thirds) and water (one-fourth) and includes only a very small amount of nitro- genous matter. The experiments were made chiefly with youngVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 65 animals.More recent experiments with f ully-grown animals have also indicated on the whole that the gain in animals when fattened consists almost exclusively of fat. In the experiments now described eight full grown sheep (over four years old) were fed for six months on moderate amounts of hay. They were then shorn weighed and two of them killed and analysed. Two of them were then fed for about one hundred days on a nitrogenous diet of hay (450) beans (300) and sunflower cake (260 grams per day). The nutritive ratio was 1 2.88. Two others were fed with a less nitrogenous diet (1 5-02) consisting of hay (450) beans (270) and crushed barley (290 grams per day). The remaining two were reserve sheep which were not however required. At the commencement in the middle and at the end of the fatten- ing period the sheep were kept for ten to eleven days in stalls for the collection of urine and faxes which were weighed and analysed.Finally the animals were again shorn weighed and then analysed. The analytical results showed that during fattening the sheep put on considerable amounts of flesh the greater gain being in the sheep with the nutritive ratio 1 5.02. The results of the balance experi- ments indicated a greater deposition of nitrogenous matter than the direct analysis. The gain in fat was greater than the gain in flesh in both experiments. N. H. J. M. Soil Analysis. JAMES HARVEY PETTIT (J. Landw. 1909 57 237-267 ; from Inaug. Db. Gottingen 1909).-The method of Schloesing and von Sigmond mas employed with six different soils.The results showed very clearly a definite natural limit of solubility for phosphoric acid; and when the basicity of the soil is allowed for the concentration of acid which acts uniformly lies between fairly definite limits 400-800 mg. N,O per litre. The method also makes distinction between readily soluble and spar- ingly soluble potash but a uniformly acting concentration was only found in the case of the loam. The relation between the percentages of total phosphoric acid and total potash is not the same as the relation between the amounts soluble in dilute nitric acid. Muschechalk contains more total but much less readily soluble phosphoric acid than Buntsandstein. The results of vegetation experiments agreed with the soil analyses in the case of loam and Muschechalk soils. The amounts of phosphoric acid and potash assimilated by barley beans buckwheat and potatoes are not the same as the amounts dissolved by dilute nitric acid. The different plants moreover take u p very different amounts of these substances-buckwheat assimilated 3-5 times as much potash and twice as much phosphoric acid as barley; so that no one solvent can possibly indicate the amounts of nutritive substances available to all plants. It is therefore desirable t o employ the term “ readily soluble ” instead of “ available.” N. H. J M. VOL. XCVIII. ii. 5

ISSN:0368-1769    

DOI:10.1039/CA9109805060

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 66 ABSTRACTS OF CHEMICAL PAPERS. An alg t ical Chemistry . Improved Method of Collecting Gases from the Mercury Pump. FREDERICK G. KEYES (J. Amer. Chem. Xoc. 1909 31 1271-1273).-1n the ordinary metbod of collecting gases from the mercury pump in an inverted tube and transferring them to the gas analysis apparatus minute bubbles of air are liable to be trapped even when great care is exercised. The following arrangement has been devised in order to avoid this source of error. A wide tube for collecting the gases is sealed on to the up-turned end of the capillary tube of the pump The wide tube is provided a t the lower end with a side-tube which is connected to a reservoir of mercury by means of rubber tubing. The upper end of the wide tube bears a three-way stopcock furnished with capillary leads.Towards tbe end of an ordinary exhaustion the air in the wide tube can be expelled by raising the reservoir. On closing the stopcock and lowering the reservoir a vacuum is formed in the tube into which the bubbles passing down the pump capillary will be discharged. The method of employing the apparatus for the collection of gases is very simple and is described with the aid of a diagram. E. G. Automatic Filling Burette. R. FRAILONG (Bull. Assoc. Chim. sucr. dist. 1909 27 470-471).-A description of two kinds of automatic burettes one intended to deliver a definite quantity of reagent at once and the other for delivering the same drop by drop. The main parts of the apparatus are a reservoir with a tube supplying the burette a specially-constructed Mohr’s pinchcock which serves to open the outlet tube while closing simultaneously the supply tube and a capillary tube passing through the rubber cork of the burette and dipping slightly into the liquid; i t serves t o obtain the zero point automatically.L. DE I(. Apparatus for the Rapid Elec tro-analytical Separation of Metals. HENRY J. S. SAND (Trans. Furaday SOC. 1909,5,159-164). -A description of some developments made in the author’s apparatus for the rapid electro-analysis and separation of metals (compare Trans. 1907 91 373; 1908 93 1572). A special screw-cap has been provided which may be screwed down when the apparatus is not in use making it possible to transport it without taking out the mercury which is employed to make connexion between the stationary and moving parts in the electrolytic stand.A clutch arrangement has also been added which enables the operator to start or stop the rotation of the anode without stopping the motor. All the apparatus required for the measurement of the electrode potential is now fitted into a single box. The arrangement is so designed that by depressing a keg it will also allow the potential difference between the anode and the cathode to be read directly. TheANALYTICAL CHEMISTRY. ii. 67 capillary electrometer is retained as a zero instrument and a special portable form which is a modification of the Ostwald horizontal capillary electrometer has been designed. It is provided with an enclosed scale and will readily indicate one millivolt when observed with a lens T.S. P. Aluminium Dishes and other Appliances in Quantitative Analysis. JAROSLAV FORMANEE and FRANZ PEG (Chem. Zeit. 1909 33 1282-1283).-Dishes of aluminium may be substituted for those of platinum in electrolytical separations but it is necessary to have the inside of the dish plated with n very thin sheet of copper This may then in turn be coated electrolytically with tin or silver etc. according to circumstances A number of successful experiments are communicated. Several improved appliances for quick electrolytic estimations are also described. L. DE I(. Electrolytic Estimation of Chlorine in Hydrochloric Acid with the Use of a Silver Anode. FRANK A. GOOCH and H. L. READ (Amer. J. Xci. 1909 [iv] 28 544-552; Zeitsch. anorg. Cham. 1909 64 287-297).-The authors have shown by a large number of experiments that when using anodes of silver or silver-plated platinum gauze and currents of various strengths the results are not so satisfac- tory as might have been expected.This is caused by the fixing of oxygen as well as chlorine on the anode the removal of silver from the anode to the cathode and the formation of hypochlorous acid. Even when the anode is ignited to decompose silver oxides the results are still irregular and always low. L. DE I(. The Beilatein Reaction [for Halogens]. Hvao MILBOTH (Cham. Zeit. 1909 33 1249).-The author has shown that the Beilstein copper oxide flame test for halogens is not absolutely trustworthy as owing t o the formation of cupric cyanide a green coloration is occasionally noticed which although not quite 80 characteristic may be mistaken for the halogen colour.The reaction is given by picolinic acid quinolinic acid 2-methyl- picolinic acid dipicolinic acid methyl 2-hydroxynicotinate quinaldinic acid and nicotinic acid whereas no green flame was observed with quinoline isoquinoline isonicotinic acid cinchoninic acid cinchomeronic acid methylanthranilic acid apophylenic acid and papaveric acid. In the case of hydroxyquinoline the reaction is obtained even without the use of a copper oxide bead. L. DE SE(. Analysis of Mixtures of Halogen Acids. 11. WILLIAM M. DEHN (J. Amer. Chem. Xoc. 1909 31 1273-1275. Compare Abstr. 1909 ii 612).-The following method is recommended for the aaalysis of mixtures containing two halide ions. Silver nitrate is added in excess and the precipitated silver salts are collected and weighed.The solution containing the excess of silver nitrate is titrated with thiocyanate and ferric nitrate by the Volhard method. It is shown that if a is the weightl of silver nitrate required to precipitate both the halogens present and b is the weight of silver VOL. XCVIII 6ii. 68 ABSTRACTS OF CHEMICAL PAPERS. halides precipitated the quantities of the halogens can be calculated by the following equations For mixtures containing chlorine and bromine Cl=0"317a - 0.79763; Br= 1.79763 - 1.5166a.' For mixtures containing chlorine and iodine C1= 0 5 3 5 8 ~ ~ - 0.38773 ; I= 1.38773 - 1.1706a. For mixtures containing bromine and iodine Rr = 2 . 3 5 0 1 ~ ~ - 1.70043 ; I = 2.70073 - 2-9S51a.Mixtures containing three halide ions can be analysed by the same method if one of the halogens is estimated separately. Thus if iodine is estimated separately we have C1 = 0.S817a - 0 79763 (+ 0.2954 I) ; Br = 1.79763 - 1 . 5 1 6 6 ~ ~ ( - 1.2951 I). If the bromine is estimated separately C1 = 0 . 5 3 5 s ~ ~ - 0.38773 ( - 0 2280 Br); I = 1.38773 - 1-1706a (0.7720 Br). If the chlorine is estimated separately Br = 2.3501tc - 1-7004b ( - 0,4386 C1) ; I = 2.70073 - 2.9851a ( + 3.3557 Cl). E. G. Estimation of Perchlorates by means of Titanous Salts. VICTOR ROTHNUND and A. BURGSTALLER (Chem. Zeit. 1909 33 L245). -Contrary to Stahler's statement (Abstr. 1909 ii 699) that the estimation of perchloric acid by boiling with excess of titanous sulphate and then titrating with permanganate is unsatisfactory the authors find that the results are trustworthy provided the operation takes place in a flask fitted with a cooling arrangement and in an atmosphere of carbon dioxide. The chloride formed in the reaction may be estimated by way of a check but the use of the nephelometer cannot be recommended in this case.L. DE K. Simple Process for the Estimation of Iodine. ERNST WINTER- STEIN and E. EERZFELD (Zeitsch. physiol. Chem. 1909 63 49-57),- The apparatus consists of a 250 cc. round-bottomed flask with a narrow neck which is closed by means of a ground joint through which pass two tubes like those of an ordinary washbottle. The exit tube is also furnished with a ground joint by means of which it is connected with a short condenser.The end of the condensicg tube is connected with two absorption flasks filled half way with a 10% solution of potassium iodide. Fifty C.C. of the solution to be tested for small quantities of iodides (bromides or chlorides do not interlere) are placed in the flask together with 5 C.C. of phosphoric acid and 10-20 C.C. of commercial hydrogen peroxide. A current of air is drawn through the apparatus and the solution is heated gradually to boiling. After thirty minutes the iodine is expelled and absorbed by the potassium iodide and may be titrated. When applying the process to urine the results are only qualitative but the full amount of iodine present may be obtained by rendering the urine alkaline with sodium hydroxide evaporating to dryness and destroying the iodised organic compounds by ignition.L. DE I(. Estimation of Iodine in Organic Substances. VINCENZO PAOLINI (Mon. Xci. 1909 [iv] 23 648).-The following method is recommended for the estimation of iodine in such substances as blood,ANALYTICAL CHEMISTRY. ii. 69 urine brain-substance sea-weed thyroid glands etc. A particular instance is given of the estimation of iodine in iodoform-gauze. Ten grams of the gauze cut into small pieces are treated in a flask with 40 grams of zinc dust and 60 C.C. of 25% sulphuric acid. The mixture is heated by means of a water-bath in a reflux apparatus for about three hours a further 50 C.C. of sulphuric acid being then added and the heating continued for some hours. The iodine present is thus converted into hydriodic acid. The gauze is then mashed several times by decantation with water and the solution made up to a volume of 1 litre.One hundred C.C. of this solution are treated with a few c.0 of potassium nitrite solution and extracted with 100 C.C. of carbon disulphide. The carbon disulphide is then separated washed with water and the iodine dissolved in i t is titrated with standard thio- sulphate solution in the presence of sodium hydrogen carbonate. w. P. s. Estimation of Iodine in the Thyroid. ATHERTON SEIDELL (J. Amer. Ciiem. Xoc. 1909 31 1326-1329).-Riggs (Abstr. 1909 ii 6 0 9 ) has stated t h a t the estimation of iodine in the thyroid by Baumann’s method (Abstr. 1896 ii 487) is liable to error owing t o the formatiou of iodate during the fusion and he has therefore suggested a modification involving a reduction process.I n the present paper an account is given of experiments which indicate that Baumann’s method is satisfactory and that Riggs’ modification is not only unnecessary but actually leads to greater error than the original method since it is difficult to remove the whole of the iodine from the aqueous layer before applying the reduction process and any iodine remaining in solution renders the results inaccurate. E. G. Estimation of Sulphur Dioxide and Sulphuric Acid in the Gases of Sulphur Furnaces. HENRI PELLET (Bull. Assoc. Clhn. SUCT. dist. 1909 27 468-469).-The author described his sulphi- carbonimeter some ten years ago in a pamphlet issued for private circulation and now communicates some results obtained. The pro- cess is based on the fact that on passing the gases through water the sulphuric acid is removed the sulphur dioxide being absorbed by a Estimation of Dithionic Acid and Dithionates.HENRI BAUBIGNY (Compt. rend. 1909 149 1069-1071. Compare Ashley Abstr. 1906 ii 800).-Preliminary experiments showed that it was not possible to oxidise dithionic acid completely to sulphuric acid by heating with aqua regia either in open or closed vessels. The solution containing the dithionate is mixed with a sufficient amount (12 t o 15 times the quantity of dithionate present) of a mixture of sodium carbonate aad nitrate. If a precipitate is formed it is filtered off and washed; the filtrate and washings are then evaporated to dryness and the residue carefully fused during from ten to fifteen minutes. The sodium sulphate so formed is estimated in the usual way with barium nitrate in presence of nitric acid.suitable reagent contained in a second washbottle. L. DE K. T. A. H. 6-2ii 70 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Nitrogen in Soil Extracts. DENSCH (Chem. Zeit. 1909 33 1249-1251).-A reply to Mitscherlich (Abstr. 1909 ii 935).-The author upholds the accuracy of his process and prefers it to the more scientific method of Mitscherlich in the case of analysis of the aqueous extract of soils. For the reduction of the nitrates (any nitrite is first oxidised by means of permanganate) in acid solution a mixture of iron and zinc powder is recommended although iron alone Method of Estimating very Small Amounts of Nitrogen. T. ZELLEB (Landw.Verszcchs.-Stat. 1909 71 437-440).-The method described by Mitscherlich Herz and Merres (Abstr. 1909 ii 614) is considered impracticable owing t o the relativelx large and variable amounts of nitrogen unavoidably introduced in the reagents. may be used. L. DE K. N. H. J. M. New Distillation Arrangement for Ammonia Estimation. ADOLF BERTHOLD (Chem. I A%. 1909 33 1292).-By using this apparatus all loss of ammonia is avoided. The substance is placed in the flask d and the centre-piece b is put on. The receiver f which contains the standard acid is then raised by iz wooden block g until the delivery tube dips into the acid. The funnel c is now filled with alkali and by gently lifting the tube e the liquid is allowed to run into d but a little should be left in t h e funnel so as to form a seal; the remainin5 alkali is then removed by rinsing a few times with water still retaining the seal.Alter connecting the condenser a with the water supply the contents of d are heated over a Bunsen burner. When the dis- tillation is practically finished the wooden block is removed and the distillation con- tinued for a short time. When dealing with liquids contain- ing free ammonia these should be intro- duced through the funnel tube c after placing on the centre-piece and raising the receiver. Into e a drop catcher has been sealed. L. DE I(. Estimation of very Small Amounts of Ammonia in Large Quantities of Air. PAUL LIECRTI and ERNST &m!ER (Chem. Eeit. 1909 33 1265-1266).-The apparatus consists of a U-tube contain- ing diluted N-sulphuric acid one limb of which is attached to a vertical spindle-shaped tube which is connected to the first of two pipettes inclined at about 45' t o the vertical; the top pipette is attached to a second U-tube.By means of a ventilating fan the air is drawn very rapidly through the apparatus. The acid is sweptANALYTICAL CHEMISTRY. ii. 71 mainly into the spindle-shaped tube where it is churned violently by the air current and a good deal of the acid is converted into spray; this however settles on the walls of the two pipettes and flows back; it is found that practically every trace of ammonia is removed. L. DE K. New Arrangement for the Estimation of Nitric Osmpounds in Sulphuric Acid. K. LEO (Chem. Zed. 1909 33 1218-1220).- Instead of shaking the sulphuric acid with mercury (Lunge’s process) 50 C.C.of the sample are placed in a specially constructed bulb the remaining space being taken up with mercury. By means of a tube furnished with three openings and connected with a mercury pressure flask mercury is forced into the acid like a spray and the action soon starts. The mercury displaced runs into another reservoir and from there into a beaker and is afterwards emptied into the pressure flask. The nitric oxide liberated is then transferred to a gas volumeter and measured. For working details the illustrations in the original article should be consulted L. DE K. Reduction of Nitric Nitrogen to Ammonia; New Procem for the Estimation of Nitrates. M. XMMANUEL POZZI-ESCOT (Bull. Aseoc. China sucr. dist. 1909 27 457-4459 ; Ann.Chim. aml. 1909 14 445-446).-The nitrate is placed in a distilling flask fitted with a funnel safety tube 5 to 6 grams of aluminium cuttings and 2 C.C. of a saturated solution of mercuric chloride are added and also 150 to 200 C.C. of water. After connecting the flask with the condensing apparatus a brisk evolution of hydrogen will be noticed; a solution of sodium hydroxide is added and the ammonia formed is distilled off and collected as usual in standard acid. I n order to decompose traces of ammoniated mercury compounds a few C.C. of sodium bypophosphite solution are added towards the end. L. DE K. Modifbation of -the Gtrandval and Lajoux Process for the Estimation of Nitrates in Waters Charged with Chlorides. L. PAECY (Bull. SOC. chim.1909 [iv] 5 1088-1090).-The author stated previously that in the presence of chlorides the process used by Graodval and Lajoux failed t o give correct results and he con- structed correction tables. * By operating as follows and using an improved reagent the use of these tables may be avoided. One volume of a mixture of 37 parts of sulphuric acid and 3 parts of phenol is mixed with 1 volume and a-half of hydrochloric acid and 1 volume and a-half of water and heated for half an hour on the water-bath. The residue left on evaporation of the sample is moistened with 1 C.C. of the reagent and heated on the water-bath for fifteen minutes. The residue is then rendered alkalirie with ammonia and the coloration compared with that of a standard watar similarly treated. L.DE K.ii. 72 ARSTRACTS OF CHEMtCAL PAPERS. Influence of Nitrites on the Estimation of Nitrates by Grandval and Lajoux’s Process. L. FARCY (Bull. SOC. chim. 1909 [iv] 5. 1090-1091).-The author states that although nitrites do not themselves affect Grandval and Lajoux’s reagent the least trace of nitrate added gives a coloration far more powerful than would be expected. The nitrite should therefore be estimated separately by means of Griees’ reagent and before estimating the nitrate it should be oxidised with permanganate or else destroyed by means of carbamide. L. DE K. Influence of Chlorides on the Estimation of Nitrates. L. FARCY (Bull. SOC. chim. 1909 [iv] 5 1091).-The loss in nitrate observed when applying the Grandval and Lajoux colorimetric test for nitrates in presence of chlorine is due to the formation of nitro-hydro- chloric acid; this may be proved by passing the gaseous products of the reaction through a solution of potassium iodide when the amount of iodine liberated corresponds with the loss observed.A slight mechanical loss owing to effervescence is also unavoidable. L. DE K. Coloured Substances Produced in Grandval and Lajoux’s Reaction. MAURICE LOMBARD (Bull. SOC. chim. 1909 [iv] 5 1092-1096).-The coloration is mainly caused by a mixture of o-nitrophenol-p-sulphonic acid and o-nitrophenol. The latter substance gives a more intense red coloration with ammonia. L. DE K. Estimation of Mineral Constituents in Vegetable Substances. L. VUAFLART (Bull. Assoc china. sucr. dist 1909 27 454-456).- Polemical. A reply t o Pellet (Abstr.1909 ii 755) on the subject of the volatilisation of phosphoric compounds on incinerating vegetable substances. The errors are avoided by using the moist combustion process with suiphuric acid. The use of alcohol when estimating nitrates is also discussed also the possibility of some magnesium ammonium phosphate remaining on the filter when dissolving the yellow molybdate precipitate in dilute ammonia containing some citrate solution. L. DE K. Estimation of Mineral Constituents in Vegetable Substances. HENRI PELLET. (Bull. Assoc. Chim. sucr. dist. 1‘309 27 456-457).- Polemical. A further reply co Vuaflart (preceding abstract). The author did use citrate solution and not nitrate as reported erroneously. Attention is called to the fact that t h e application of alcohol in the eRtimatiorr of nitrates has already been advocated by Bouesingault Estimation of the Free Acid in Superphosphates.FREDERICK B. GUTHRIE and A. ALEXANDER RAMSAY (J. Roy. SOC. New South WaZes 1909 43 G9-74).-The methods recommended for the estimation of free phosphoric acid have been examined. Herzfelder’s method i u which the free acid is extracted with ether and titrated in aqueous solution with methyl-orange as indicator gives the best results but in 1865. L. DE I(.ANALYTICAL CHEMISTRY. ii. 73 the values obtained are rather low. A modification of this method in which sodium alizarinsulphonate is used as indicator will probably prove to be the best method of estimating free phosphoric acid in superphosphates. E. M. D. Estimation of Total Phosphoric Acid in Basic Slags and Native Phosphates by the '' Citro-mechanic Method." E.GUERRY and E. TOUSSAINT (Bull. SOC. chirn. Belg. 1909 23 454-457).-Twenty to twenty-five C.C. of sulphuric acid are intro- duced into a 250 C.C. Jena flask by means of a funnel tube so as not t o moisten the neck. 2.5 Grams of the powdered sample are added and after gently shaking the whole is boiled for ten minutes. When cold water is added a little at a time and when cooled down the solution is diluted to the mark well shaken and filtered. Twenty- five C.C. of the filtrate are placed in a beaker and neutralised with ammonia and when cold 30 C.C. of ammonium citrate solution (= 10 grams of citric acid) are added followed by 15 C.C. of ammonia. After starting the stirring machine 35 C.C.of magnesium mixture are added drop by drop and after twenty-five minutes the precipitate is collected washed with dilute ammonia and ignited. No correction need be made for the volume of the insoluble matter as this contains relatively the same amount of phosphoric acid as the solution. L. DE K Estimation of Hypophosphoric Phosphorous and Hypo- phosphorous Acids in Presence of One Another and of Phosphoric Acid. ARTHGR ROSENHEIM and JAEOB PINSKER (Zeitscl.. anorg. Chent. 1909 64 327-341).-A method was required for the analysis of the acid obtained from the action of moist air on yellow phosphorus. Hypophosphoric acid (the pure sodium salt way used) may be estimated by titration with permanganate if certain precautions are observed.The slightly acid solution with the addition of a small quantity of permanganate is heated to 80-go" titrated rapidly with oxalic acid more perrnanganate added and so on until a red coloration persisting for five minutes is obtained. The excess is then titrated with oxalic acid 10H2P03 + 2KMn0 + 3H,SO + 2H20 = 10H3P0,+ 2MnS04 + K,SO,. Iodine is without action on hypophosphoric acid. Uranyl salts give a yellow precipitate according to the equation 2NaHP0 + U02(N03)5 = UO,( HPO,) + 2NaN0,. Phosphorous acid may be estimated by means of permanganate under the same conditions as hypophosphoric acid. It reacts quanti- tatively with iodine when heated in a closed flask to form phosphoric acid and may thus be estimated in the presence of hypophosphoric acid. Hypophosphorous acid may be titrated with permanganate as above 5E3P0 + 4KMn0 + 6H2S04 = 5H3P0 + 4MnS0 + 6H,O + 2K,SO and also reacts quantitatively with iodine when heated in acid solution in a closed flask.In all cases the oxidation of any ono acid is unaffected by the presence of one or more of the other acids. A.ii. 74 ABSTRACTS OF CHEMICAL PAPERS. mixture containing phosphoric phosphorous hypophosphoric and hypophosphorous acids may be analysed by (1) oxidising with nitric acid and precipitating with magnesia thus estimating total phosphorous ; (2) titrating with permanganate which oxidises all but the phosphoric acid ; (3) titrating with iodine which oxidises only phosphorous and hypophosphorous acids ; (4) titrating with uranyl nitrate which precipitates only phosphoric and hypophosphoric acids. An application of this method of analysis to the product obtained by the oxidation of phosphorus in moist air a t 5 O shows that the solution contains principally hypophosphoric acid.Equations for calculating the proportions are given. C. H. D. Apparatus for the Estimation of Carbon Dioxide in Milk. A. BAR ILL^ (J. Pharm. Chim. 1909 [vi] 30 452-453).-The apparatus which is figured in the original consists of a flask con- nected with (1) washbottles containing potassium hydroxide solution through which air freed from carbon dioxide may be introduced at will and (2) washbottles containing ammoniacal bnryta water for the absorption of the carbon dioxide liberated. Eight hundred C.C. of milk are introduced into the flask heated at 50° and the last traces of carbon dioxide swept by a current of purified air into the baryta solution where it is estimated. The ‘ I combined ” carbon dioxide is then estimated by adding excess of tartaric acid t o the milk and proceeding as before.The apparatus gives results within 1% of the theoretical. T. A. H. Estimation of Potassium in Potassium Silicates. AART VERWEY (Zeitsch. anal. Chem. 1909,48 760-762).-A slight modifica- tion of Lawrence Smith’s well-known method. One gram of the finely- powdered silicate is intimately mixed with 1 gram of pure ammonium chloride and 5 grams of alkali-free calcium carbonate and the whole is introduced into a platinum crucible 4.5 cm. in height and 3.5 cm. in width. After covering the mixture with a layer of 3 grams of calcium carbonate the crucible is heated until the ammonia is expelled and after putting the lid on a strong heat is applied for an hour with a Teclu o r a powerful Bunsen burner.The mass is then boiled with water for fifteen minutes and when cold the liquid is made up to 200 c.c. and in 50 or 100 C.C. of the filtrate the potassium is estimated by acidifying with hydrochloric acid and evaporating with excess of platinic chloride as usual. L. DEK. Estimation of Zinc and Analysis of Zinc Ores. K. VOIGT (Zeitsch. angew. Chem. 1909 22 2280-2285).-Complete analyses are given of a few zinc ores by known methods. The author prefers precipitating $he zinc as zinc ammonium phosphate after removing any calcium with ammonium carbonate in ammoniacal solution. Sulphur is best estimated after a preliminary fusion with a mixture of 5 parts of anhydrous sodium carbonate and 3 parts of potassium chlorate.If the ore contains an appreciable amount of matterANALYTICAL CHEMISTRY. ii. 75 insoluble in acid this should be fused with sodium carbonate and then again treated with hydrochloric acid. L. DE K. The Most Rapid W e t Lead Assay. JULIUS F. SACHER (Chem. Zeit. 1909 33 1257-1258).-A slight modification of Alexander’s process (separation of lead as sulphate dissolution in ammonium acetate and titration of the slightly acidified solution with standardised ammonium molybdate with tannin as external indicator). The author finds the previous separation of the lead as sulphate unnecessary and titrates the nitric acid solution at once after adding first a sufficiency of ammonia and then an excess of acetic acid.Supposing 1 C.C. of the molybdate solution=0*01 gram of lead a Correction must be made depending on the final volume of the liquid. For 50 c.c. 0.18 C.C. of molybdate should be deducted; for 100 c.c. 0.3 c.c.; for 125 c.c. 0.40 C.C. ; for 150 c.c. 0.45 C.C. ; for 175 c.c. 0.50 c.c.; for 200 c.c. 0.54 C.C. ; for 250 c.c. 0.60 C.C. ; and for 300 C.C. of liquid 0.75 C.C. of molybdate solution. If iron is present to any extent it should be removed from the solution by heating this for some time on the water-bath. L. DE K. Detection of Mercury in Urine. WILH. BECKER (Pharm. Zeit. 1909 54 987).-Polemical. A reply t o Stich (Abstr. 1909 ii 1055). The method given by Almdn only yields approximate results but the processes communicated by Farup and by Schumacher-Jung allow the determination of 0.1 mg.of mercury in urine. Bunge’s balances provided with a glass micrometer and indicating 1/20 mg. are recommended. L. DE I(. Detection of Mercury in Urine. FRITZ GLASER and A. ISENBURU (Chem. Zeit. 1909 33 1258).-To 250 C.C. of the sample are added 5 grams of pure aluminium sulphate and the solution is heated and precipitated with ammonia. The precipitate is then collected dissolved in hydrochloric acid and heated on the water-bath for forty-five minutes in presence of a copper spiral. The deposit is then as usual sublimed and converted into the red iodide. L. DE K. Electro-analysis of Mercury Compounds with a Gold Cathode. F. MOLLWO PERKIN (B-ans. Paraday Soc. 1909,5 45-48).-Using a gold flag electrode a large number of estimations of mercury were made using mercuric chloride bromide and sulphate. The electrolytes employed were nitric acid sulphuric acid potassium cyanide and sodium sulphide. The results obtained were always high-from 0.5 to 2.5%. This was at first attributed t o occluded hydrogen but it was not found that the gold electrode increased in weight when made the cathode in dilute sulphuric acid and the current passed for twenty hours. When the electrode coated with mercury was treated in a similar manner it also showed no increase in weight. Since the electrode was cathode the increase in weight could not be due to oxidation and when a platinum electrode was run in series with it ehs mercury deposited on the platinum was always slightly less thanii.76 ABSTRAC rS OF CHEMICAL PAPERS. that theoretically required. The author cannot explain the results which show however that a gold electrode cannot be satisfactorily used for analytical purposes. A rotating silver electrode showed similar resirlts to the gold electrode. Usually the time required to deposit the mercury was from five to six hours but on stirring the electrolyte by means of a powerful magnetic field the time of deposition was reduced to fifty minutes ; the results were still too high. The author comes to the conclusion that the best electrode on which to deposit mercury is one of mercury the :deposition being very rapid if a rotatinganode is used (compare Smith and Kollocb Abstr. 1905 ii 859 ; 1906 ii 194).Two quartz vessels one of them fitted with a siphon side tube are described for use with a mercury cathode. T. S. P. Estimation of Manganese by Volhard and WOES Method. WALDEMAR M. FISCHER (Zeitsch. anal. Chem. 1909,48 751-760).-A slight modification of the Volhard-Wolff permanganate titration pro- cess. The sulphuric or hydrochloric acid solution (containing about 0.35 gram of manganese) is diluted t o 500 c.c. and aqueous sodium hydroxide is added until a slight precipitate forms which is then at once redissolved by a few drops of dilate sulphuric acid. One gram of freshly ignited zinc oxide and 10 grams of zinc sulphate are added and after heating the solution to boiling it is titrated with .AT/10 permanganate. One C.C. of pure glacial acetic acid is added and the liquid is again heated to boiling.This causes the precipitate t o coagulate and to settle rapidly and the pink coloration to disappear ; the titration is then continued until the pink colour is restored. L. DE I(. Separation of Manganese and Chromium. FEEDINAND FALCO (Arch. Yharm. 1909 247 431-436).-A modification of Kassner’s process by means of which good results are obtained when the amount of manganese does not exceed 0.015 gram The solution is placed in a covered beaker and sodium peroxide added in small portions. The liquid is then heated until the precipi- tate has separated in brown flocks. The liquid is decanted through a filter and the precipitate wached with boiling water and finally collected on the filter ; the filtrate contains the chromium as chromate.The manganese peroxide is dissolved off the filter by means of hot 20% hydrochloric acid and returned to the beaker. Excess of bromine water is added followed by an excess of ammonia and the liquid is heated to boilbg. The precipitate is then collected washed ignited and weighed as manganosomanganic oxide. The filtrate which may still contain traces of chromium is added to the main solution. L. DE I(. Quantitative Separations by Means of Ammonium ‘( Cup- ferron ’’ (Nitrosophenylhydroxylamine). OSCAR BAUDISCH (Chem. Zeit. 1909 33 1298-1 300).-Analysis of By*own Iron Ore.-Five grams of the ore are dissolved in 60 c.c of Btrong hydrochloric acid ; theAXALPTICAL CHEMISTRY. ii. 77 iron is fully oxidised by boiling with potassium chlorate and when cold the whole is diluted to 500 C.C.Twenty-five C.C. of the liquid are placed in a beaker and 20 C.C. of hydrochloric acid and 100 C.C. of cold distilled water are added. While stirring a solution of 3 grams of ‘‘ cupferron ” in 50 C.C. of water is added. The iron is completely pre- cipitated when a white precipitate begins to form. The precipitate is now collected and washed with cold water until the washings are no longer acid; the filtrate is used for the estimation of manganese. The filter is then washed with dilute ammonia (1 1) to remove the excess of ‘‘ cupferion,” and the precipitate is then washed once with water and finally converted by ignition into oxide and weighed as such. Andysis of Nickel Ore.-The iron and copper present are precipitaked jointly with ‘6 cupferron,” and in the liltrate the nickel is estimated by a suitable method.The copper is extracted from the washed precipitate with strong ammonia and the copper is then obtained as oxide by evaporating the solution and igniting the residue; the oxide may be reduced to metal and weighed as such. The precipitate insoluble in ammonia is then ignited and weighed as ferric oxide. The use of ‘6 cupferron ” in a number of other cases is suggested. L. DE I(. Rrtpid Electrolytic Estimation of Cobalt. PIERRE BRUYLANTS (Bull. SOC. chim. Belg. 1909 23 383-400).-A lengthy paper containing a large number of experiments recorded in sixteen tables. The electrolytic estimation of cobalt in ammoniacal solution gives good results with a cathodic potential of 1.35 volts.If the same process as for the rapid estimation of uickel is applied a spongy and partly oxidised metallic deposit is obtained In any case the metal is very readily oxidised and redissolved so that it must be washed without interrupting the current. Under proper conditions cobalt may like lead and manganese be deposited as peroxide at the anode. Electro- lysis from an oxalic acid solution cannot be recommended as the deposit then contains carbon. An approximate separation of cobalt from zinc may be obtained when operating in ammoniacal solution as directed above. If sodium sulphite is also added the cobalt although free from zinc contains an appreciable amount of sulphur. L. DE I(. Gravimetric Estimation of Chromium ; Quantitative Hydro- lysis of Sesquioxides.WALTER SCHOELLER and WALTER SCHBAUTH (Chem. Zed. 1909 33 1237).-The neutralised solution of the chromic salt which contains 0.1-0-2 gram of metal and is diluted to about 300 c.c. is heated to boiling and 3 C.C. of aniline are added in portions of 1 C.C. After boiling for five minutes the chromium has been precipitated quantitatively as hydroxide in a form which may be readily washed by decantation. Salts of aluminium zinc and ferric iron are also precipitated by aniline but whether the process is sufficiently accurate for these metals has not as yet beep decided The process may be used in the presence of manganous salts. L. DE &ii. 78 ABSTRACTS OF CHEMICAL PAPERS. Elstirnation of Titanic Acid in Ilmenite. ELISE ROEB (Chem. Zeit. 1909 33 1225-1226).-0*5 Gram of the finely-powdered ore is heated with 10 grams of anhydrous sodium carbonate finally over the blowpipe for half an hour.The liquid mass is poured into a platinum dish placed in cold water and when cold it is put together with the crucible into a spacious beaker containing 50 C.C. of cold water. The portion left undissolved is washed on a filter then transferred to an Erlenmeyer flask of one litre capacity and heated with dilute hydro- chloric or sulphuric acid until quite dissolved. When cold the solution is rendered slightly alkaline with sodium hydroxide and then again slightly acidified with sulphuric acid. One hundred C.C. of strong sulphur dioxide solution are added and enough water t o obtain a volume of 700 C.C. The whole is now boiled on an asbestos plate for one hour and another 20 C.C.of sulphur dioxide solution are added. After remaining for a few hours in a slanting position the precipitate is collected washed with boiling water ignited and weighed as titanium peroxide. L. DE K. Estimation of Thorium in Monazite. Colorimetric Estima- tion of Small Amounts of Platinum. JOHN C. H. MINGAYE (Records Geol. Survey 8. S. Wales 1909 8 276-286).-Estimatiom of Thorium irt Monccxite.-Samples of Carolina monazite have been analysed by several methods. The precipitate obtained with sodium thiosulphate must be redissolved precipitated with oxalic acid and extracted with ammonium oxalate. Precipitation with moist lead carbonate (Giles Abstr. 1905 ii 615) gives good results if the precipi- tation is repeated. Precipitation as basic acetate (Haber Abstr.1898 ii 295) is rapid and sufficiently accurate. Several Australian monazites have also been examined the richest being a sand from Black Swamp Torrington New South Wales contbining 4.1 2% of thoria. Colorimetric Estimution of Platinum-The small quantities of platinum occurring in beach sands or alluvial deposits may be estimated by fluxing with litharge and charcoal to obtain a lead button cupelling with the addition of silver and parting with nitric acid D 1.28 which dissolves platinum and silver leaving gold and iridosmine. The silver i E precipitated as chloride and the filtrate evaporated twice to dryness with hydrochloric acid. The hydrochloric acid solution filtered from traces of lead and silver chlorides is treated with stannous chloride or potassium iodide and the coloration obtained compared with that of a standard solution containing 0.065 gram platinum per litre. Quantities of platinum as small as 0.06 gram per ton may be estimated in this way.C. H. D. Methods for the Quantitative Chemical Analysis of Animal Tissues. I. General Principles. WALDENAB KOCH (J. Amer. Chem. Soc. 1909 31 1329-1 335).-A discussion of the general principles on which accurate methods of analysis of animal tissues depend and of the manner in which the analytical data should be applied in order to yield results of value t o the physiologist. The difficulties attending such work are pointed out. It is suggested that the constituents of the cell may be conveniently arranged in theANALYTICAL CHEMISTRY. ii.79 following classes (1) lipoids including phosphatides cerebrins and cholesterol ; (2) extractives such as creatine taurine and hypo- xanthine ; (3) inorganic constituents represented by the ash ; (4) proteins ; (5) fats ; (6) carbohydrates namely! glycogen. Very few of the methods at present employed for estimating these various groups are at all satisfactory and it is therefore considered more useful to study the distribution of the three elements nitrogen phosphorus and sulphur which are of special interest as they are invblved in somewhat different phases of cell activity. From a physiological standpoint it is desirable t o study the same tissue under different conditions of which the three most important are (1) the period of growth or development ; (2) conditions of pathological change; and (3) conditions of starvation the first of these being the most favourable for a study of the chemical transformations in the cell.As an illustration analyses are given of (1) a very young brain (2) an adult brain and (3) a brain from a case of dementia prscox. The young brain contained a larger quantity of extractives than the adult brain whilst the latter contained a greater proportion of lipoids. The brain from the case of dementia prscox resembled the normal brain but contained a smaller quantity of partly oxidised sulphur compounds soluble in water. E. G. Methods for the Quantitative Chemical Analysis of Animal Tissues. 11. Collection and Preservation of Material. WALDEMAR KOCH and SIDNEY A. MANX (J.Amer. Chem. Xoc. 1909 31 1335-1341. Compare preceding abstract).-An account is given of the precautions to be observed in order to obtain uniform and representative samples for analysis and of the methods of preserving the material. The chief methods of preservation are (1) immersion in alcohol (2) drying and (3) the addition of a dehydrating agent such ag sodium sulphate or gypsum The relative advantages and disadvantages of these three methods are discussed. E. G. Methods for the Quantitative Chemical Analysis of Animal Tissues. 111. Estimation of the Proximate Constituents. WALDEMAR KOCH and EMMA P. CARR (J. Amer. Chem. Soc. 1909,31 1341-1 355. Compare preceding 'abstracts).-Methods are described for effecting the separation and estimation of the six classes of constituents referred to by Eoch and the results of the analysis of a sample of meat by these methods are tabulated.Methods for the Quantitative Chemical Analysis of Animal Tissues. IV. Estimation of the Elements with Special Reference to Sulphur. WALDEMAR KOCH and FRED. W. UPSON (J. Amer. Chem. Soc. 1909 31 1355-1364. Compare preceding abstracts).-Methods are described for estimating the total sulphur in animal tissues and its distribution in the lipoids extractives proteins and inorganic sulphates. I n the lipoids extractives and proteins the sulphur exists in both the oxidised and non-oxidised condition the former being represented by the ethereal or R*SO,*OH type and the E. G.ii. 80 ABSTRACTS OF CHEMICAL PAPERS. latter by the cystine or R*S*H type.Methods are given for the estimation of the sulphur in each of these states of combination. The results of a study by these methods of the distribution of sulphur in brains of three different ages are tabulated. The per- centage of total sulphur does not show any great variation. The results indicate however that the lipoid sulphur increases at first with age and decreases later and the organic sulphur compounds soluble in water decrease with age. E. G. Volumetric Estimation of Phenol by Lloyd’s Method. Tribromophenol Bromide and Hexabromophenoquinone. S. C. J. OLIVIER (Rec. trav. chim. 1909 28 354-367).-1n the author’s experience Koppeschaar’s process for the estimation of phenol does not as Lloyd states (Abstr. 1905 ii 209) give inaccurate results and on the contrary the modified form described by Lloyd (Zoc.cit.) gives results less trustworthy than those given by the original process. In this investigation the author prepared tribromophenol bromide and hevabromophenoquinone and records certain new data regarding these substances. Tribromophenol bromide when heated in an atmosphere of carbon dioxide begins to evolve bromine even below looo and it is to this decomposition that the different melting points ascribed to this substance are due. Mixed with excess of potassium iodide and hydrochloric acid the bromide liberates 99.6% of the theoretical quantity of iodine so that the anomalous results recorded by Lloyd cannot be due as he suggests to the formation of this substance in the titration of phenol by Koppeschaar’s process.Hexabromophenoquinone was prepared by Benedikt’q process ( A bstr. 1879 717) but could nob be obtained crystalline. This substance is not formed when excess of bromine is allowed to react with phenol under the conditions prescribed by Koppeschaar so that Lloyd’s anomalous results with this process are not due to this cause. In using Koppeschani’s process the time of action of the bromine on the phenol may be reduced to five minutes if not more than 0.09 gram of phenol is used and if the solution of sodium bromide and bromine is about 0.8 decinormal. The addition of sodium bromide inhibits the formation of t r i bromophenol bromide. The end reading is clearer if chloroform is added as suggested by Lloyd (Zoc. cit.). T. A. H. Application of Arsenious Acid in Volumetric Analysis.I. FRANZ M. LITTERSCHEID and J. BORNEMANN (Zeztsch. angew. Chem. 1909 22 2423-2427).-Estimu,tion of Dextrose [in Urine].-Fifty C.C. of copper sulphate solution (49.848 grams per litre) are placed in a 200 C.C. measuring Bask 20 C.C. of the usual alkaline tartrate solution are added and the liquid is heated to boiling. Twenty-five C.C. of the dextrose solution (urine) not exceeding 1% in strength are added and the boiling is continued for two minutes. To the hot liquid are then added 50 C.C. of arsenious acid solution (9.9 grams per litre; this is equivalent t o the copper solution) and also 30 C.C. of 96% acetic acid. When cold 7 grams of potassium iodide are added i n six t o eightANALYTICAL CHEMISTRY. ii. 81 portions. When all the copper inchding the reduced oxide has passed into cuprous iodide the liquid is diluted to the mark and filtered the first portion of 10 C.C.being rejected. One hundred C.C. are theu nearly neutralised with 20% sodium hydroxide and after adding 5 grams of sodium hydrogen carbonate and diluting t o 400-500 c.c. the free arsenious acid is titrated with N/lO-iodine as usual. Or the liquid may be nearly neutralised with pure ammonia and diluted to 400-500 C.C. without addition of hydrogen carbonate. The arsenious acid found is equivalent to the copper reduced by the dextrose. A table is given showing the amount of dextrose corresponding with the C.C. of iodine used. L. DE K. Simple Distilling Apparatus for the Estimation of Pentosans by Tollens’ Method. JOHANN TISCHTSCHENKO (J.Landw. 1909 5’7 229-230).-The usual apparatus consists of a flask fitted with a tap funnel and a Kjeldahl distilling bulb to which the condenser is attached. This is now simplified by making the funnel and bulb in one piece the funnel passing down through the middle of the bulb ; the double boring of the cock is thus avoided. A sketch ir given. N. H. J. M. [Estimation of Glycogen.] KARL GRUBE (PfCgep’s Archiu 1909 130 322-3 24). EDUARD PFLUUER (ibid. 3 5-32?) .-Polemical. Quantitative Estimation of Lactic Acid in Cheese. SHIGEHIRO SUZUKII and EDWIN B. HART (J. Amel*. Chem. Soc. 1909 31 1364-1367).-1n connexion with a study of the chemical changes which take place during the ripening of cheese i t was necessary to find a trustworthy method for estimating lactic acid.Palm’s method (Abstr. 1887 307) depending on the formation of basic lead lactate 3Pb0,2C,H603,-has been found to be inaccurate. Partheil’e method (Abstr. 1903 11 189) in which the lactic acid is distilled in a current of superheated steam when applied to i-lactic acid must not be carried out below 1304 and the distillation must be continued until 750 C.C. of distillate have been collected. This method however cannot be used in presence of other acids :such as malic citric tartaric oxalic or succinic and is therefore unsuitable for cheese analysis. The usual method of estimating lactic acid by adding dilute sulphuric ;acid t o the cheese extracting with^ ether and afterwards separating the acid in the form of its zinc salt gives fairly satisfactory results when carefully carried out.E. G. Estimation of Cinnamic and Benzoic Acids in Mixtures of the Two Acids. ANNE W. K. DE JONG (Roc. trav. chim. 1909 28 342-348. Compare Abstr. 1908 ii 993).-The methods already described such as those of de Jong (Abstr. 1906 ii 315) and Scberinga (Abstr. 1907 ii 823) give good results for the volumetric estimation of these two acids but are unsuitable in cases where other acids are present or where the constituents must also be isolated and identified. I n the process now described cinuamic acid is converted intoii. 82 ABSTRACTS OF CHEMICAL PAPERS. dibromophenyIpropionic acid whioh can be separated quantitatively from benzoic acid and identified. Preliminary experiments with mixtures of the two acids by (1) fractional crystallisation ; (2) extraction by solvents ; (3) sublimation and (4) precipitation of metallic salts did not give promising results.The process eventually discovered consists in dissolving the mixture under examination in carbon disulphide and determining either by titration or weighing the bromine necessary to convert the cinnamic acid present into dibromophenyl propionic acid. This may then be separated quantitatively from benzoic acid by extracting the latter with carbon tetrachloride or by removing it by sublimation. T. A. H. Sodium Phosphotungstate as a Reagent for Uric Acid and other Reducing Substances. CARLO CERVELLO (Arch. exp. Puth. Pharm. 1909 81 434-437).-The reaction in urine with sodium phosphotungstate described by Richaud and Bidot depends on the presence of uric acid which reduces the reagent and forms a blue colour.Other reducing substances (dextrose hydroxylamine morphine etc.) give the same reaction. The blue colour which ferrous salts give with the tungatate passes in the presence of atmos- pheric oxygen into a green and then a red colour as lower tungsten oxides are formed. Reducing agents produce analogous changes in molybdic salts. W. D. H. LUDWIG KRAUSS (Biochem. Zeitsch. 1909 22 131).-A question of priority. The author claims that the reaction with iodic acid described by Frankel and Allers (hbstr. 1909 ii 628) mas previously described by himself (Apoth. Zeit. 1908 701). Estimation of Morphine in Opium; Extract of Opium and Tincture of Opium. HEINRICH PRERICHS (Chena. Zentr. 1909 ii 1499-1500 ; from Apoth.Zeit. 1909 24 592-596).-Helfen- berger’s process is recommended using 5 grams of dilute ammonia (17 + S3)and water saturatedwith ether. Aconvenient separating funnel for washing the morphine crystals is described. The process is also applicable to the extract and the tincture of opium ; the latter should be concentrated to about one-third. Opium may be reduced to a d e h i t e morphine content by addition of starch; for the extract P. W. GILL F. G. ALLISON and HARRY 8. GRINDLEY (J. Amer. Chenz. Xoc. 1909 31 1078-1093).- A modification of the hydrolysis method. The resulting solution after heating the urine with hydrochloric acid in an autoclave is mixed with an excess of sodium carbonate and the ammonia formed from the urea is then expelled in a current of air and absorbed in standard acid.Under these conditions no ammonia is yielded by the products of the hydrolysis of creatinine uric acid or hippuricacid. A The Iodine Reaction of Adrenaline. W. D. H. lactose may be used. L. DE K. Estimation of Urea in Urine. special aeration apparatus is described. L. DE I(.ANALYTICAL CHEMISTRY. ii. 83 Estimation of Urea Allantoin and Amino-acids in Urine. DOROTHY E. LINDSAY (Bio-Chem. J. 1909 4 448-454).-Nitrogen is estimated by (a) Bohlaad’s method ; this gives the nitrogen of amino- acids hippuric acid creatinine allantoin and urea. Estimation by Folin’s method (6) gives the nitrogen of urea allantoin and ammonia ; estimation by the Morner-Folin method (c) gives the nitrogenof urea and ammonia. Ammonia and creatinine are estimated separately by Folin’s method.The difference between (a) and (6) gives the nitrogen of amino-acids (including hippuric acid) and of creatinine ; the differ- ence between (b) and (c) gives the dlantoin nitrogen. This combina- tion of methods was found to give good results with artificial mixtures. W. D. H. Estimation of Purine Bases in Urine. ERNEST L. KENNAWAY (J. Physiol. 1909 39 296-310).-When urine is treated by the Camerer-Arnstein method for the estimation of total purines uric acid loses ammonia; this loss occurs when the precipitate of silver- magnesium urate is boiled. The purine bases do not undergo this loss. The method is therefore only correct when employed for the estima- tion of purine bases in urine from which the uric acid has been removed.W. D. H. Vanillin &s a Test for Antipyrine and Kryogenine ; Detection of Antipyrine in Pyramidone. CHAELES PRIMOT (Chem Zentr. 1909 ii 479 ; from BUZZ. Sci. Pharmacol. 1909 16 270).-If a small crystal of antipyrine is moistened with 2 C.C. of a reagent consisting of 1 gram of vanillin 6 grams of dilute hydrochloric acid (1 I) and 100 grams of 95% alcohol and the whole evaporated on the water-bath a dark orange-yellow ring is formed first and afterwards a similar stain on the bottom of the dish is noticed. The test shows the presence of even 0.00095 mg. of antipyrine. Pyramidone does not give the test and even 0*005 mg. of antipyrine may thus be detected in 0.1 gram of pyramidone. Rryogenine gives a distinct greenish- yellow coloration when this test is applied.L. DE I(. Attempt to Estimate Indoxyl in Urine. L. A. MENNECHET (Chem. Zentv. 1909 ii 1499; from Bull. Sci. Pharmacol. 1909 16 458-460).-The urine is defecated by 10 vol. % of basic lead amtate and a portion of the filtrate representing 50 C.C. of the urine is mixed with an equal voliime of pure hydrochloric acid. After shaking for five minutes 5 C.C. of chloroform are added and the shaking is continued; if the chloroform remains colourless 2 to 3 drops of hydrogen peroxide solution are added. The chloroform is drawn off and the liquid is shaken repeatedly with fresh portions of chloroform. The united chloroform extracts are shaken first with water containing a few drops of sodium hydroxide and then with water and the indoxyl is titrated by means of standard hypobromite.The chloroform does not become quite colourless at the end of the titration but retains a slight lilac colour. L. DE K.ii. 84 ABSTRACTS OF CHEMICAL PAPERS. Cause of the Vanillin Hydrochloric Acid Reaction for Camphor. 0. TUNMANN (Chem. Zentr. 1909 ii 1010 ; from Schwedz. Wocbschr. Chem. Pharm. 1909,4'7 617-519),-'J!he active substance contained in commercial camphor to which the reaction with vanillin and hydrochloric acid is due is only an impurity and is not derived from the oil cells of the camphor tree but exists in the parenchyma cells It is probably closely related to the phloroglucotannoids and it seems t o play an important physiological rSle. L. DE K. A Colour Reaction for Gelatin. R. ED. LIEBEGANG (Zeitsch. Chem. 2nd.Kdloids 1909 5 248).-RIixed aqueous solutions of cupric chloride and excess of tripotassium phosphate give in the presence of gelatin a violet coloration instead of the usual whitish-green precipitate. G. S. W. The VaIue of Benzidine for the Detection of Minute Traces of Blood. E. J. MCWEENEY (Sci. Proc. Roy. Dubl. Soc. 1909 12 216-223).-The reagent is made by dissolving a pinch of benzidine in 3-4 C.C. of glacial acetic acid just before use for the mixture itself turns blue after about a minute 0.5 C.C. is transferred to a test- tube and 2 C.C. of 10% hydrogen peroxide are added. To the white opaque mixture is added the material to be examined for blood and its presence is denoted by an immediate blue coloration. The material requiring investigation consists nearly always of suspected' stains and may be usually obtained as a fine dust by scraping. Should it be found impracticable to obtain a scraping the fabric may be treated with a drop of normal saline solution the stained fibres removed to another slide and treated between slide and cover-glass with a drop of the reagent when the presence of blood reveals itself bF the brilliant blue coloration of the affected fibre. The mass may then be treated on the slide with a drop of 32% potassium hydroxide so as to render visible the outlines of the individual red cells. None of the secretions and excretions hitherto tested by the author (saliva nasal mucus urine etc.) has been found to behave towards benzidine in the same way as blood but precisely similar results are given by many freshly-cut vegetables and fruits (potato and apple for instance) but these no longer give the reaction when boiled for some time whereas the reaction given by blood solutions is unimpaired by boiling for ten minutes. A positive result with the benzidine test should not be looked on as absolutely positive proof of the presence of Mood although i f the result is negative the absence of blood may be safely assumed. No regard should be paid to colour ,changes occurring after the lapse of one minute and a blank test should be made to make sure thst the ,paterials and the test-tubes to be used are satisfactory. L. DE I(.

ISSN:0368-1769    

DOI:10.1039/CA9109805066

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

85 General and Physical Chemistry. Refraction and Dispersion of Air Oxygen Nitrogen and Hydrogen and their Relations. CLIVE CUTHBERTSON and MAUDE CUTHBERTSON (Proc. Roy. Soc. 1910 83 A 151-171).-0n account of the discrepancies exhibited by existing data the authors have redeter- mined the refractivities of the four gases for the wave-lengths X=6563 5790 5461 and 4561. I n all cases it is found that Cauchy’s formula p - 1 =a( 1 + b/X2) is inadequate for the expression of the dispersion data the value of b increasing as the wave-length diminishes. Much better agreement is obtained when a formula of the Sellmeier type is employed to represent the results The constants involved i u the Sellmeier formula are calculated for each of the four gases examined and also for phosphorus sulphur and mercury.H. M. D. Refraction‘and Dispersion of Sulphur Dioxide and Hydrogen Sulphide and t h e i r Relation to those of their Constituents. CLIVE CUTHBERTSON and XAUDE CUTHBERTSON (Pmc. Roy. SOC. 1910 83 A 171-176).-Measurements of the dispersion of sulphur dioxide and hydrogen sulphide are recorded and the data are expressed in terms of Sellmeier’s formula for which the constants involved are calcul a t ed. The refraction data for sulphur dioxide acd hydrogen sulphide are compared with those of the component elements a n d . i t is shown that the refractivity does not follow an additive law. For sulphur dioxide the refractivity is IS% and for hydrogen sulphide 6% less than that required by the law of addition. Whereas the number of dispersion electrons in sulphur dioxide appears to be equal to the sum of the dispersion electrons in sulphur and oxygen this relation- ship does not hold in the case of hydrogen sulphide.H. M. D. Refraction and Dispersion of Neon. CL~VE CUTHBERTSON and MAUDE CUTHBERTSON (Proc. Zoy. Soc. 1910 83 A 149-llil).-The refractive index of neon a t 0’ and 760 mm. was found to be 1*00006716 for the green mercury line (X=5461). From this and values obtained for the red and blue lines of cadmium the dispersion has been calculated. Previous measurements having shown that the refractivities of the inert gases are very nearly in the ratio of whole numbers it was anticipated that the refractivity of neon would be exactly twice as large as that of helium. The experi- mental value is however less than this to the extent of 4%.H. M. D. Distribution of the Ultimate Rays in the Spectrum of Different Regions of the Sun. ANTOINE DE GRAMONT (Compt. reend. 1910 150 37-40. Compare Abstr. 1908 ii 645).-This paper contains a tabular statement of the wsve-lengths for the VOL. XCVIII. ii. 7ii. 86 ABSTRACTS OF CHEMICAL PAPERS. ultimate rays of great persistency found in the sun. The fact that metalloids such as tellurium phosphorus arsenic antimony and boron have never been recognised in the sun is probably to be explained by the absorption of their ultimate rays by the terrestrial atmosphere. The author considers that Lockyer's enhanced lines are not due to dissociation but that they are ultimate rays and that their appearance gives some indication as to the proportions in which the Critical Study of Spectral Series.I. The Alkalis Hydrogen and Helium. WILLIAM M. HICKS (Proc. Roy. Xoc. 1910 83 A 226-228*).-The experimental measurements of the spectral lines of the alkali metals hydrogen and helium have been analysed with the object of determining the relationships between the wave- length numbers. For any one series of lines the wave numbers can practically all be represented by a modified Rydberg formula. The relationships between certain constants for the series (lithium sodium potassium rubidium cmium) are expressible by the integers 1 2 4 5 and 6 and these integers are also involved when the atomic volumes of the respective alkali metals are compared. Line Spectrum of Calcium given by the Oxy-acetylene Burner.GUSTAVE A. HEMSALECH and CHARLES DE WATTEVILLE (Compt. rend. 1909 149 11 12-1 115).-Using the method described previously (Abstr. 1908 ii 336 445 547 745) the authors have investigated the spectrum of calcium in the oxy-acetylene flame. The flame contains a very brilliant blue cone which shows not only the bands which are obtained with R Burisen burner but also a series of supplementary bands which are distiibuted over the whole length of the spectrum. All the calcium lines do not exist a t the base of the flame but are only formed some distance above the orifice of the burner. Even the strongest lines although visible are only very faint at the base of the flame ; they become very intense just above the blue cone. A table IS given showing that with flames of different temperatures the number of lines between X 3900 and X 5000 increases with increas- ing temperature.It is also shown that the number of lines given by that portion of the flame which extends to the top of the blue cone decreases with rise in temperature. The Yellow Orange and Red Regions of t h e High Tempera- ture Flame Spectrum of Calcium. GUSTAVE A. HEMSALECH and CHARLES DE WATTEYILLE (Compt. rend. l909,149,1369-1372).-The authors compare the less refrangible part of the calcium spectrum obtained by them in the oxy-acetylene dame (preceding abstract) with the spectrum obtained by King ( A ~ o p h y s . Journ. 29 190) with the electric furnace. With the exception of the line A = 6708.18 which is present in the latter spectium and not in the former the characters of the spectra are the same and the causes which produce them are therefore probably thermal.I n order to produce the red lines in the * and Phzl. Trans. 1910 A 210 57-111. elements producing them are present. IV. 0. w. H. M. D. A full list of wave-lengths and intensities is given. T. S. P.ii. 87 GENERAL AND PHYSICAL CHEMISTRY calcium spectrum a high temperature such as that given with the oxy-acetylene flame is necessary. The line A = 6108.18 which is present in the spectrum of the electric furnace is probably due to lithium (A= 6705 OS).‘ This same line is found in the sun-spot spectrum and therefore lithium is present in the sun. T. S. P. Series Systems in the Spectra of Zinc Cadmium and Mercury. T. ROYDS (Ann. Phpsik 1909 [iv] 30 1024).-In refer- ence to Paschen’s paper (this vol.ii 3) the author poiots out that he has alreadymeasured the Zeeman effect for certain lines in the spectra of zinc and cadmium. I n a magnetic field the lines 6438.7 (cadmium) 6362.6 (zinc) 5528:7 and 4703.3 (magnesium) appear as symmetrical triplets. The magnetic displacement observed for these lines corresponds with values of elm in good agreement with the value for cathode rays. H. M. I). The Spectrum of Antimony. A KRETZER (Zeitsch. wiss. PAoto- graph. PhotophysiE. Yhotochem. 1910 8 45-79).-The spark arc and flame spectra of antimony have been investigated. The wave-length measurements of the lines and bands are recorded in detail and compared with the data of previous observers. H. M. D. Absorption Spectrum of Potassium Vapour.P. V. BEVAN (Phil. Hug. 1910 [vi] 19 195-200).-It has been found that t h e principal series lines of potassium appear in much greater numbers in the absorption spectrum of potassium vapour than in any form of emission spectrum which has as yet been examined. This result is analogous to that obtained by Wood in the case of sodium vapour. The method of experiment consisted in heating potassium in a steel tube the ends of which were closed by quartz plates. A beam of light was passed through the tube and the emergent beam was examined by means of a quartz spectrograph. I n this way the author was able to measure the wave-lengths of the principal lines of potass- ium up to the line corresponding with n=26 in the Kayeer and Runge formula. Hitherto the members of the series LIP to w = l l have been observed so that fifteen new lines have been added to the list.A comparison of the absorption spectra of sodium and potassium vapours shows a close correspondence between them and this is regarded as evidence that the mechanism involved in the two cases is the same. H. M. D. The wave-lengths of these range from 2928.0 to 2870.0. Absorption Spectra of Various Salts in Solution and the Effect of Temperature on Such Spectra. XXVI. HARRY C. JONES and W. W. STRONU (Amer. Chem. J. 1910 43 37-90).-A detailed account is given of an investigation of the absorption spectra of various potassium uranium and neodymium compounds by the methods employed by Jones and Uhler (Abstr. 1907 ii 147 211 212) and by Jones and Anderson (Abstr.1909 ii 197 359). The absorption epectra of potassium ferricyanide ferrocyanide chromate 7-2ii. 88 ABSTRACTS OF CHEMICAL PAPERS. and dichromate and of uranyl acetate bromide chloride nitrate and sulphate in aqueous solution of uranyl acetate nitrate and chloride in methyl alcohol and of uranyl nitrate and chloride in ethyl alcohol are recorded. The effect of dehydrating agents such as calcium and aluminium chlorides has been determined. Photographic records have been obtained of the absorption spectra of uranous chloride and sulphate and the absorption spectra of neodymium chloride in glycerol and in mixtures of glycerol and water have been studied. The effect of changes of temperature of solutions of various salts at different concentrations has been investigated and spectrograms for a given concentration of a salt have been made a t Oo 15O 30° 4 5 O 60° 75" and 90' for a layer of constant thickness.The absorption spectra of the uranyl salts contain a series of bands in the blue and violet which are usually diffuse. The position of the uranyl bands is not affected by dilution. I n methyl and ethyl alcohol the bands of each particular salt occupy different positions. A new set of fine bands in the green has been discovered in the spectrum of aqueous solutions of uranyl chloride; the presence of a small quantity of aluminium or calcium chloride causes them to disappear. The absorption spectra of the uranous salts are quite different from those of the uranyl compounds. The absorption spectrum of neodymium chloride in glycerol differs entirely from that of an aqueous solution.The intensity of the phosphorescence of the same uranyl saits obtained from different solvents by evaporation is found to vary greatly. Monochromatic stimulation fails to excite phosphorescent bands until the wave-lengths reach the region of the uranyl bands. The NO group has a great influence on the frequency of the uranyl and uranous absorption bands and of the uranyl phosphorescent bands. E. a. A Relation between Absorption and Phosphorescence. L. BRUNINGHAUS (C'ompt. rend. 1909 149 1124-1 127).-The absorption and phosphorescence spectra of the rare earths are dis- continuous consisting generally OF narrow bands. I n the absorption spectra groups of absorption bands are separated by regions of trans- parency whereas in the phosphorescence spectra the regions of emission are separated by dark regions.Taking the spectra of praseodymium erbium dysprosium terbium and samarium as examples the author shows (1) that the mean regions of emission are generally little separated from the mean regions of absorption and (2) that the regions of emission do not coincide with the regions of absorption but with the transparent regions (either those between the groups of absorption bands or those outside them). There is thus an alternation between the groups of absorption bands and those of phosphorescence. The results obtained with compounds of the common elements such as manganese chromium iron copper etc. confirm those given above. In general these substances phosphoresce with a colour which is little different in shade from their colour by reflected or transmitted light.For example chromium sesquioxirle when dissolved in alumina givesGENERAL AND PHYSICAL CIIEMISTRY. ii. 89 the ruby which phosphoresces with a red light; when dissolved in lime it is green and the phosphorescence is green. It seems as if the light emanates from “ phosphoragenic ” molecules in the interior of the phosphorescent substance. This light under- goes absorption in the superficial layers and the radiations observed at the surface are only those for which the “phosphorogenic” substance is relatively transparer,t. T. S. P. Theory of the Law of the Optimum of Phosphorescence L. BRUNINOHAUS (Compt. Tiend. 1909 140 1375-137‘i.)-Making use of the ideas put forward in a previous paper (preceding abstract) the author develops a relation connecting the intensity ( I ) of the radiatiou comprised between two wave-lengtbs X and h+dX which are very close together and the concentration (c) of the phosphorogenic sub- stance in a phosphor.The relation is I=kce-Bc where k and B are constants B depending on the phosphorescent substance. T. S. P. Electrolytic Conductivity of Fluorescent Solutions. A. RASSENFOSSE (Bull. Acod. roy. Belg. 1909 995-1 lO?).-According to the theory of do Heen the conductivity of a fluorescent solution should depend on the light to which it is exposed. Experiments on solutions of fluorescein and eosin show that the conductivity is a maximum when they are submitted to the action of light which is absorbed by them green in the case of fluorescein and yellow in the ’case of eosin.Blank experiments on solutions of potassium chloride proved that the conductivity does not vary under the action of light of different colours and also that the observed variation in the case of the fluorescent solutions is not a thermal effect. T. S. P. Luminescence of Crystals. ALFREDO POCHETTINO (Nuovo Cimento 1909 [v] 18 245-300. Compare Abstr. 1905 ii 430).- The phenomenon of luminescence has been investigated for 227 specimens of crystals representing 78 kinds of minerals. Several methods of exciting luminescence were used ; the more important results mere obtained with cathode Xuminescence but the anodic luminescence fluorescence phosphorescence and thermoluminescence of the crystals were also investigated when they occurred.In many cases the nature of the luminescence depends upon the method of excitation thus for distene the ordinary phosphoregcence and the cathode luminescence are of different colours and in the case of calcite the ordinary fluorescence is polarised and the cathode lumines- cence is not. The nature of the spectra of the cathode luminescence is in many cases independent of the Z.kf.F. applied to the vacuum tube but the intensity of the luminescence is generally greater the greater the applied E.M.F. provided the crystals undergo no permanent changes under the influence of the rays. There does not appear to be any definite connexioc between the luminescence of crystals and their mineralogical relationships ; even crystals of the same substance from different sources may show luminescence of different colours and some specimens of quartz show luminescence whilst others do not.ii.90 ABSTRACTS OF CHEMICAL PAPERS. Many observations have been made on the orientation of the plane of polarisation of the polarised part of the luminescence. The mineral milerite is dichroic greenocite shows double cathodic luminescence and the light emitted from the face of crystals of cassiterite parallel to the x axis is totally polarised. With one exception the lumines- cence emitted from crystals of the rhombohedric system is not rectilineally polarised. The greater the exhaustion of the vacuum tube the more completely is the luminescence polarised and in general all causes which tend to diminish the total intensity of the light emitted diminish the degree of polarisation of the light.Mauy minerals become brown under these conditions and on the face of a crystal directly exposed to the rays a stain made up of differently coloured concentric rings is sometimes observed. On continued exposure to cathode rays the capacity of a crystal to become luminous by excitation of the rays diminishes and this diminution may be temporary or permanent. Fewer substances are rendered luminous by anode rays than by cathode rays and every mineral so far examined which shows anodic luminescence can also be rendered luminous in some other way. I n all cases the luminescence due t o anode rays is weakest less durable and less polarised than that produced by cathode radiation under corresponding conditions.The effect of cathode rays on the minerals is discussed. G. S. Dependence of the Photo-electric Effect of the Alkali Metals in Polarised Light on the Wave-length. ROBERT POEIL (Ber. Deut. phpiknl. Ges. 1909 7 15-722).-Experiments with an alloy of potassium and sodium and ultra-violet radiation of short wave-length show that the photo-electric behaviour of the alkali metals in polarised light is the same as that observed in the case of other metals. H. M. D. Theory of the Ripening Process of the Silver Haloids. A. P. H. TRIVELLI (Zeitsch. wiss. Photocher~z. 1910 8 17-24).-As the result of a microscopic examination of ripened silver haloid plates of high sensitireness the author concludes tbat the ripening process is due to the development of definitely recognisabla crystalline structure.I n consequence of this structural change the silver haloid is in a condition of strain and in consequence is less stable than in the unripened condition. The smaller degree of stability is supposed t o be the cause oI the greater photo-sensitiveness. H. M. D. New Determinations of the Radioactivity of the Thermal Waters of Plombieres. ANDR~ BROCHET (Compt. rend. 1910,150 145-148).-The author has redetermined the radioactivity of the waters of Plombihres (compare Abstr. 1908 ii 143). The radio- activity of the gases spontaneously liberated from the various waters was measured and then the latter mere agitated with a n equal volume of air and the radioactivity of the latter measured in the apparatus of Chheveau-Laborde.The tabulated remlts give theGENERAL AND PHYSICAL CHEMISTRY. ii. 91 altitude of the spring the outflow per twenty-four hours mean temperatures in 1859-1861 Sept. 1908 and August 1909 the total solids per litre the radioactivities in milligram-minutes per 10 litres of the gases and the waters and the total radioactivity for twenty- four hours. The waters are strongly radioactive the radioactivity being due to radium emanation. The total radioactivity of the 22 springs is 74620 milligram-minutes for an average outflow of 67244 cubic metres of water per twenty-four hours. The average radioactivity is 1.11 milligram-minutes per 10 litres the Lambinet water being the most active (2.18). It is calculated that 55-60 mgms. of radium bromide are contained in the total output of water per minute (507 litres).This quantity is defined as the radioactive power of the Plombihres waters. T. 5. P. The Recoil of Radium-C from Radium-B. WALTER MAKOWER and SIDNEY Russ (Phil. Mag. 1910 [vi] 19 100-115. Compare Abstr. 1909 ii 455).-The active deposit of radium on a platinum plate was mounted opposite a metal disc in a n exhausted tube for some minutes so that the disintegration products recoiling from the plate would be received on the disc. The plate mas first freed from adhering emanation and from radium-8 by heating a t 360' in a vacuum for half an hour before use. It mas found that in general. both radium-B and -C were radiated to the disc but if three hours elapsed between the preparation of the active deposit and the recoil experiment only radium4 was obtained.They consider that the radiation of radium4 may not in all cases be a primary recoil effect but due to mechanical disturbance produced by the recoil of radium-D. The amount of radium4 recoiled varies with the same plate with the time in an unexplained manner and is always small compared with the amount of radium-B recoiled. Since radium-B gives only a /3-particle i t is t o be expected that radium4 will recoil with far less energy than radium-& which results from the recoil of the a-ray- expelling radium-A. But the energy of the recoiling radium-B atom is apparently far greater than theory would indicate. Its power oE penetrating air is about 1/40th of that of recoiling radium-B. Attempts to detect an electric charge on the recoiling radium4 atom have failed (compare Makower Abstr.1909 ii 456; Le Radium 1909 6 50). F. S. Disengagement of Emanation from Radium Salts. L. KOLOWRAT (Le Radium 1909 6 321. Compare Abstr. 1907 ii 729).-The paper is devoted to a detailed reconsideration of many of the points previously discussed. The anomaly encountered in that the disengagement of emanation from radiferous barium chloride decreases with rise of temperature from 830' to a minumum at 920° and then increases again quickly to the m. p. at about 950° is probably explained by Plato's observation of the existence of two forms of barium chloride with transformation point 34.4' below the m. p. (Abstr. 1907 ii 239). Similar behaviour of barium fluoride indicates a similar polymorphic transformation between 1000° and 11 00'.ii.93 ABSTltACTS OF CHEMICAL PAPERS. Additional salts studied comprise potassium nitrate silver chloride and czesium nitrate. Nineteen series of experiments have been made on the growth with time of the amount of emanation retained by the salts at varying temperatures after complete initial removal of the emanation by fusion both when the temperature is maintained and also when during part of the time the salt is not heated. The results are interpreted on the view that a definite temperature different for differ- ent molecules exists for each molecule of emanation formed within the salt below which it is retained. The amount of emanation retained at any temperature is the sum of all the molecules the temperatures of disengagement of which are above that temperature.No evidence of any want of homogeneity of the emanation disengaged at different temperatures was obtained (compare Rutherford AbGtr. 1909 ii 457 ; Debierne ibid. 534). F. S. Nature of the Ionisation of a Molecule by an a-Particle. R. D. KLEEMAN (Proc. Roy. Soc. 1910 83 A 195-199).-1f the energy of ionisation is derived from the kinetic energy of the a-particle the electrons ejected from molecules should on the whole possess a a motion in the direction of the a-particles. I n the experiment designed to test this a-particles from a plate covered with polonium were passed through a very thin aluminium foil and fell on a parallel aluminium plate in hydrogen and also in air a t a low pressure If the emergent electrons from the foil are more numerous than the incident electrons from the plate when an electric field is applied between the foil and plate the current should be larger with the foil negative than vice versa and this difference should be the more marked as the potentials are increased.Experiments in hydrogen at 0.8 mm. pressure show a well marked difference increasing rapidly as the voltage is increased above the point a t which the expelled electrons acquire sufficient velocity to ionise by collision. The experi- ments support the view that the energy of ionisation is derived from the ionising agency not by ‘‘ trigger ” action from an internal store in the molecule ionised. F. S. The Number of a-Particles Expelled from the Actinium and Thorium Emanations. H. GEIGER and E.MARSDEN (Physikccl. Zeitsch. 1910 11 7-11. Compare Bronson Abstr. 1908 ii 792).- By a further developnient of the method of counting a-particles by the scintillations produced i n zinc sulphide interesting confirmation and extension have been obtained of Bronson’s conclusion that the thorium emanation must give a t least four a-particles and the actinium emanation a t least two a-particles on disintegration. The number of scintillations produced by the emanation and active deposit together in equilibrium and by the active deposit alone after the supply of emanation has been stopped and the emanation allowed to decay is as 3 to 1 both for thorium and actinium showing that the emanation produces twice the number of a-pdrticles produced by the active deposit.The thorium active deposit is known to produce two a-particles. [A similar conclusion in the case of the actinium active deposit (compare Blanquies Abstr. 1909 ii 634) is not referred to.]GEIVERAL AND PHYSICAL CHEMISTRY. ii. 93 Emanation was allowed to diffuse between two parallel zinc sulphide Bcreens placed close together film side inwards an6 the number of scintillations on exactly opposite portions of the two screens counted simultaneously by two observers with two microscopes. For actinium emanation a very large proportion of the scintillations up to 66% occurred in pairs showing that two particles are expelled simultan- eously or a least with less than 0.1 second between them With radium emanation and active deposit in equilibrium only 2 to 4% of pairs was observed.For thorium emanation it was established that the four a-particles expelled were not simultaneous. A large number of cases of successive scintillations in similar parts of the field were observed with a time interval between the two scintillations from half a second to an unmeasurably short time. This occurred even when extremely few scintillations were produced. The existence of at least one >short-lived a-ray product in the thorium series with a period of average life of about 0.2 second is indicated but full elucidation of this case is not yet arrived at. F. 5. The Absorption of Cathode Rays of Different Velocity in Helium. JAMES ROBINSON (Physikal. Zeitsch. 1910 11 11-13).- The cathode rays obtained by the action of ultra-violet light on a negatively charged plate were employed.The velocity of the rays was varied by varying the charge on the plate. With decreasing velocity of cathode rays the absorption by gases attains a maximum. In hydrogen the maximurn is reached more suddenly and at lower velocity than in other gases. I n helium the absorption with decreasing velocity increases a t first only very slowly down to far smaller velocities than for other gases. The absorption then rises with great abruptness to the maximum. Helium thus resembles hydrogen but the peculiarities shown by the latter gas are even more marked in helium. F. 5. Contact Electrification. ALBERT GRUMBACH (Compt. rend. 1909 149 846-848. Compare Gouy Abstr. 1906 ii 662).-According to Helmholtz the contact potential of a liquid with glass is proportional to pP/$Z where E is the E.H.F.acquired by the liquid of viscosity q- and resistivity p in passing through a glass capillary tube under pressure P. The author finds that in a N/lOOO-solution of potassium chloride in water E is strictly proportional to P. The addition of 5.6% of phenol to the solution increases the viscosity r] in the ratio 1 1.09 but does not alter the conductivity. The capillary E. M.F. however undergoes a marked reduction. In two series of experiments the addition of phenol altered the contact potential in the ratios 1 0.80 and 1 0.78 respectively. R. J. C. Dielectric Properties of the Elements. DIMITRI K. DOBROSERDOFF (J. Russ. Phys. Chem. Soc. 1909 41 llG4-1171).-As usually determined the dielectric capacity X refers to large wave-lengths and the index of refraction n to very small wave-lengths and in order to test Maxwell’s law n2 = K it is necessary to obtain values of n and K referring to comparable conditions.The value nm of n for very largeii. 94 ABSTRACTS OF CHEMICAL PAPERS. wave-lengths may be calculated by means of Cauchy’s formula r(r = A + BA-2 + CX-4 where m = A. But this process of extrapolation gives results agreeing with the experimental values only when X varies within narrow limits so that the values of n thus obtained must necessarily be somewhat inaccurate and it is found that (n2tro and K have identical values only in exceptional cases. A list is given of the values of d and K for such elements as have been previously investigated and in all cases the differences between the two are considerably less than those observed for complex liquids and solids.These results confirm Schmidt’s view (An%. Physik 1902 [iv] 9 919) that in the elements the molecules have an especially simple structure. The dielectric constants of the non-metals increase with the valency in any horizontal row of the periodic system and with the atomic weight in any vertical column. For helium ?a=1.0000375 or (n2= 1.000075 whilst K has the value 1.000074. For the other rare gases of the atmosphere the calculated values of K (n2) show a continuous increase with the atomic weight. Determinations of the dielectric constants of the metals are insufficient in number to allow of any similar regularity being observed. T. H. P. Quantitative Relations between the Dielectric Constants and other Properties of Substances.DIMITRI K. DOBROSERDOFF (J. Russ. Pl~ys. Chem. Xoc. 1909 41 1385-1406).-The author has investigated the validity of various relations between the dielectric constant and other physical constants which have been suggested by various investigators. It was shown by Obach (Abstr. 1892 158) that for the members of certain homologous series of organic compounds proportiouality exists between the dielectric constant and the latent hea% of evaporation or p/K=const. the actual magnitude of the ratio being different for different series. The author has calculated the value of the ratio for organic compounds belonging to nine homologous series the mean and limiting values found being as follows (1) propionic esters 15.20 (14-84-15.39); (2) butyric esters 15.41 (15*04-15.78) ; (3) valeric esters 15.56 (15.03-16.27) ; (4) ketones 6-00 (4.95-7-1) ; (5) alkyl derivatives of benzene 31.0 (29.73-33.02) ; (6) aliphatic acids 39.55 (39*06-40.05) ; (7) nitriles 5.65 (4.7-7.31) ; (8) amines 25.47 (25*0-26*0) ; (9) alkyl halogen compounds 6.61 (6.32-6-95).The values obtained by Obach were (10) formic esters 11-85 (I 1-03-12.78) ; (11) acetic esters 13.72 (13*26-14*30); (12) ethyl esters of fatty acids 13.34 (11*15-14*20) ; (13) monohydric alcohols and water 7.41 (6.22-7*91) the values for isopropyl (6.14) and cetyl (9.1) alcohols being of doubtful accuracy. The mean of the values obtained for groups (13) (7) (4) and (9) is 6.46; for groups (lo) (ll) (l) (2) (3) and ( l a ) 14.18; for group (S) 25.47 ; for group ( 5 ) 31 and for group (6) 39.55 these numbers 6.46 14.18 25.47 31 and 39.55 being approximately in the ratios of 1 2 4 5 and 6.When a11 the other compounds (inorganic as well) for which the values of p and K are known are included the values of the constant have the approximate proportionate magnitudes 0.5 1 2 3 4 5 6 . The chemical nature of any particular compoundGEKERAL AND PHYSICAL CHEMISTRY. ii. 05 seems to have no appreciable influence in determining t o which group it belongs members of one group being compounds completely different as regards their chemical characters. The relationship between dielectric constant and chemical constitu- tion of a dielectric given by Thwing (Abstr. 1894 ii 374)' and expressed by the equation K= d(a,K1 + a2K2 + .. .)/A4 (where d is the density and M the molecular weight of the compound a1,cc2 . . . the atoms or atomic groups of the same kind oomposing the molecule and Kl,K2 . . . . the dielectric constants of the atoms or groups) is not confirmed by the experimental numbers collected by the author. The relation discovered by Lang (Abstr. 1896 ii 144j for gases namely ( K - 1)106/S=const. = 123(116-145) (S being the sum of the valencies of the atoms constituting the molecule of the gas) holds only,as far as can be ascertained a t 0' and 760 mm. pressure for the six gases obeying Maxwell's law E=n2. T. H. I?. The Conductivity of Mixtures of Dilute Solutions. J. A. GARDINER (Trans. Roy. SOC. Canada 1908 [iii] 2 iii 37-52).-Burton has recently shown that a fall in the conductivity of the solution occurs when dilute hydrochloric acid is added to a colloidal solution of silver or to a dilute solution of silver nitrate. I f the ordinary law of electrolysis were followed a rise in the conductivity should occur.The author's experiments show that as a N/lO,OOO solution of hydrogen chloride is added to water there is a t first very little change in the conductivity of the solution but as the acid solution becomes more concentrated the conductivity gradually increases. On the addition of hydrochloric acid to silver nitrate of various dilutions a drop in the conductivity was observed. When however a 39.5 x 10-7 normal silver nitrate solution was reached this effect disappeared. A similar drop in the conductivity was observed when a dilute nitric acid solution was added to a dilute silver chloride solution. The conductivity of a silver nitrate solution steadily increased with the concentration. It is suggested that the abnormalities here recorded may be due to (1) the absorption of hydrogen by the platinum electrodes ; (2) the hydrogen ion attracting to itself the neutral silver chloride and becoming loaded so that its mobility falls below that of the silver ion which it displaces.E. J. R. Cadmium Chloride Concentration Cells. EUGEN VON BIROF and B. P. APHANASSIEFF (J. Buss. Phys. Chem. Soc. 1909 41 1175-1182).-The authors have measured the E.M.F. of cadmium chloride concentration cells with and without transport of the cation. In the first case silver chloride electrodes prepared by Jahn's method were used and one of the solutions had the same concentration and the other different concentrations for the different cells.The curve connecting the log. of the number of grams of salt per 1 gram of water in the variable solution with the E.H.F. calculated for 1 equivalent of salt per litre in tho constant solutioq exhibits a spread-out maximum for solutions containing 6-8 equivalents of salt. This maximum corresponds with solutions in which the transportii. 96 ABSTRACTS OF CHEMICAL PAPERS. number of the cation is zero. A line drawn parallel to the axis of log. concentrations cuts the curve in two concentrations which would give a cell having a zero E.M.F. although diffusion would occur. If the concentrations of the two 5olutions are below the maximum point on the curve the positive electricity is directed from the more con- centrated t o the more dilute solution; that is with the diffusion current whilst if the concentrations are greater than the maximum the reverse is the case.With cells without transport the curve connecting E.M.F. and log. of the concentration is approximately linear for solutions containing 1-3 equivalents of cadmium chloride but for higher concentrations it becomes mere complex. The curve does not however show any of the peculiar bends observed by Godlewski (Abstr. 1902 ii 445) whose observations are inaccurate owing to irreversible processes at the electrodes of which he took no account. The transport numbers for the anion arid cation are calculated the values for the former agreeing well with those obtained by Hittorf’s method (compare Abstr.1908 ii 145 250). Concentration cells with concentrated solutions hence show the same diffusion phenomena as are observed in those with dilute solutions and Nernst’s theory of diffusion of electrolytes is justified as well for concentrated as for dilute solutions (Zoc. cit.). T. H. P. Rapid Formation of Positive Lead Accumulator Plates. GERHARD JUST PAUL ASKENASY and B. MITROFANOFF (Zeitsch. EZektro- chem. 1909 15 872-892).-The effect of iepeatedly charging and discharging lead plates immersed in sulphuric acid and in mixtures of sulphuric and nitric acids is investigated. I n presence of nitric acid the attack on the plates is much more rapid lead sulphate being first formed.This is subsequently oxidised to lead peroxide. With smooth plates however it appears to be impossible to obtain a sufficiently adherent coating of lead peroxide ; with plates built up of a large number of small lead sheets so as to give a large surface good results were obtained. I n the solutions containing nitric acid lead nitrate is formed at the anode and this is converted into lead sulphate a t some distance from the surface of the plate. This distance increases as the concentration of the nitric acid increases and that of the sulphuric acid diminishes. When it is sufficiently small an adherenk deposit is obtained; when it is greater a loose deposit is formed and when it is greater still a precipitate of lend sulphate is produced in the solution.A solution containing 30 grams of potassium nitrate and 218 grams of sulphuric acid per litre appears to give the best results. T. E. Volatilisation of Cathodes. VI. VOLKMAR KOHLSCHUTTER (Zeitsch. Elektrochem. 19U9 15 930--937).-Tn reply to the criticism of Starck and Fischer (Abstr. 1909 ii 718) the author says that between the value of the cathode fall of potential at which volatilisation begins and the higher value a t which it ceases to increase proportionally to the cathode fall the volatilisation is quite a definite reproducible quantity ; the relation of the quantity volatilisedGENERAL AND PHYSICAL CHEMISTRY. ii 97 to the atomic weight of the metal is too striking to be regarded as accidental. He inclines to regard Starck’s theory of the phenomena as a distinct advance.New experiments with gold and platinum in oxygen and with platinum in air are described. Satisfactory measurements could not be made in these gases with other metals because they react with the gas in circumstances which cannot be controlled. The chemical reaction causes the discharge to become intermittent which is indicated by a telephone in the circuit. In oxygen the regular volatilisation is observed between 440 and 1200 volts cathode fall for gold and between 500 and 900 volts for platinum. T. E. Electrode for Determining the Concentration of the CO,” Ion and the Condition of Silver Carbonate in Solution. JAMES F. SPENCER and MARGARET LE PLA (Zeitsch. anorg. Chem. 1909 65 lO-l5).-Pure silver carbonate is best prepared by adding a dilute solution of sodium hydrogen carbonate to a concentrated solution of silver nitrate stirring continuously.A silvered platinum wire covered with the freshly precipitated carbonate has a constant potential. With pure sodium carbonate solution as the electrolyte the value Ag.Ag2C0,.N/1-C0,” = + 0.7545 volt is found and the concentration of the CO,” ion c’ is found in any solution by tho relation E = 0.7545 -0.029 log. c’. The solubility of silver carbonate in water at 25” is thus found to be 1.16 x 10-7 mol. per litre (compare Abegg and Cox Abstr. 1904 ii 256) and the salt is almost completely hydrolgsed. C. H. D. Investigation of Electrolysis with the Ultramicroscope. J. J. KOSSONOGOFF (PhysikaZ. Zeitsch. 1909 10 976-986).-An arrangement is described by means of which the author has applied the ultramicroscope to the examination of solutions through which an electric current is passed.When a current is started through a solution of silver nitrate or copper sulphate a very considerable increase in the number of bright points in the field of view of the ultramicroscope is at once observed. The view is put forward that these are associated with the ionic carriers of the electric current. I n support of this it is found that ultramicroscopic effects of a special kind are observed when the potential difference between the electrodes is raised to that which corresponds with the tension of decomposition. I n the case of the above-mentioned solutions the attainment of the critical potential difference is accompanied by a very special dis- tribution of the bright points in the neighbourhood of the cathode.A t a short distance from this electrode and parallel to it a zone can be distinguished in which the bright points are very closely crowded together. Between this special zone and the electrode itself is a region which is almost entirely free from bright points. This is supposed to correspond with the dark cathode space in gaseous discharge. The appearance of this effect at a particular voltage affords an -optical method of determining decomposition tensions. Similar effects have also been observed at the anode in other cases. H. M. D.ii. 98 ABSTRACTS OF CHEMICAL PAPERS. Electrolytic Oxidation of Ammonium Carbonate. FRITZ FICHTER and HANS KAPPELEH (Zeitsch. Ekktroclzem.1909 15 937-943. Compare Brochet and Boiteau Abstr. 1909 ii 657).- A solution of ammonium carbonate containing 3.669 gram-molecules of ammonia and 2.494 molecules oE carbon dioxide per litre was electrolysed between platinum electrodes a t temperatures from 20' to 60' and with anodic current densities between 0.027 and 0.731 amperes per sq. cm. Ammonium nitrate is the principal product; neither carbamide nor nitrite could be detected. The experiments were always stopped when a comparatively small quantity of the ammonium carbonate was oxidised. The gases evolved contained carbon dioxide ammonia oxygen and hydrogen; nitrogen W ~ S not found. In an open vessel the yield increases with the current density and with the temperature. I n a closed vessel however very much worse yields were obtained; this is due to the fact that in an open vessel the solution loses ammonium carbonate rapidly and dilute solutions give better yields than more concentrated ones.The best results were finally obtained with a current density of 0.4 to 0.6 ampere per sq. cm. a temperature of 50-60° and a solution containing about 2 mols. of ammonia per litre the ratio COJNH being 0.27; in these cir- cumstances the current eficiency is from 82% to 97%. A solution of ammonium tetraborate gives very similar results. T. E. Electro-catalysis. D. ALEXJ~EFF (J. Buss. Phys. Chern. Soc. 1909 41 1155-116O).-By the electrolysis of ammonium sulphate with lead peroxide electrodes nitrogen oxygen and nitrous oxide are evolved but neither nitrite nor nitrate is formed in the solution.Hence the oxidation of the ammonia does not proceed further than the stage NH(OH) the anhydride of which is nitrous oxide hydroxylamine forming an intermediate oxidatib product. The evolution of nitrogen occurs according to the equation NH,*OH + KH(OH) =N + 3H,O. That the nitrogen and nitrous oxide developed do not arise by the formation and subsequent decomposition of ammonium nitrite and nitrate is shown by experiments on the oxidation of hydroxylamine (vide i..fi*u). With solutions of ammonium sulphate containing sulphuric acid electrolysis with lead peroxide electrodes yields only nitrous oxide and oxygen whilst if the ammonium sulphate solution contains ammonia pure nitrogen is obtained. I n the latter case the form- ation of NH,*OH predominates over that of (NOH) the reaction 2NH,*OH + (NOH) -+ 2N + 4H,O occurring in preference to (NOH) -+ 24-20 + H20.The reaction between lead peroxide and hydroxylamine proceeds according to one or the other of the two equations 2NH,-OH+ PbO = PbO + N + 3H20and2NH,*OH + 2Pb0 = 2Pb0 + N,O + 3H20 according to whether the hydroxylamine or the peroxide is in excess. I n practice as is shown by a study of the products obtained when the reaction takes place in absence of air a mixture of the two gases is always obtained; the amounts actually formed in two cases were (1) 22% N,O and 78% N and (2) 30% N20 and 70% N,. Thus lead peroxide is a typical catalyst with the peculiarity thatGENERAL AND PHYSICAL CHEMISTRY. ii. 99 one-half of its action is a chemical and the other a physical process The formation of nitrogen and nitrous oxide a t lead peroxide electrodes is hence a typical electro-catalytic process.T. H. P Manganese Aluminium and Copper. FRIEDRICH HEUSLER and FRANZ XICHARZ (Zeitsch. anorg. Chem. 1909 65 110-1 12. Compare Ross and Gray Abstr. 1909 ii 859).-The fact that certain manganese-aluminium bronzes heated above 200' and slowly cooled become strongly magnetic but have considerable hysteresis has been observed previously by Heiisler and by Asteroth. C. H. D. Magnetic Dichroism of Siderite in Liquids. GEORGES MESLIN (Comnpt. rend. 1909 149 855-S57. Compare Abstr. 1909 ii 529). -Siderite suspended in carbon disulphide or aniline exhibits magnetic dichroism t o such a high degree that the phenomena can be seen with an ordinary permanent magnet or the raidual magnetism of an electromagnet. The suspensions are also slightly dichroic spontaneously.A method of demonstrating dichroism by the optical lantern is described. R. J. C. Nagnetism of Solutions. PAUL DRAPIER (J. Chim. Php. 1909 7 385-404. Compare Pascal Abstr 19OS ii 927)-The author has examined the behaviour of a number of solutions when placed in a flat vertical cell between the pointed poles of a powerful electro- magnet. If the liquid has paramagnetic properties it tends to move radially in a plane perpendicular to the lines of force and thus forms a tumulus or convexity at the surface. This convexity is much accentuated in aqueous solutions when the surface-tension is lowered by addinga layer of ether or benzene. An aqueous solution of ferric alum or ferric chloride shows a convexity even when only 1% of ferric salt is present but n solution of the same concentratiorl in ether is unaffected.Ferric ammonium oxalate is but slightly affected and colloidal ferric hydroxide potassium ferrocyanide and potassium ferricyanide are unaffected . If a solution ol ferric chloride in ether is floated on water a striated layer is produced which in the field bends downwards into the water the striae being displnced horizont,ally. Displacements are also observable if precipitated ferric hydroxide or air bubbles are suspended in the p warnapetic fluid. Dilute manganese sulphate gives a marked convexity but potassium permanganate none. When ether is poured on the latter solution an intermediate layer is formed containing ether water manganese sulphate and precipitated manganese dioxide which is extremely sensitive to the magnetic field owing to manganese sulphate and perhaps to free oxygen occluded in the precipitate. Cobalt and nickel hydroxides precipitated by ammonia are also very sensitive to the magnetic field.Chromium sulphate cobaltous chloride and nickel nitrate areii. 100 ABSTRACTS OF CHEMICAL PAPERS. paramagnetic ; potassium dichromate potassium cobulticyanide titanium sulphate and platinum chloride are not. The author's observations confirm the conclusion arrived at by Pascal by a different method that as a magnetic metal becomes more and more removed from its normal (ionised) state it loses its para- magnetism. The magnetic capillary rise of solutions of ferric alum and ferric chloride of 5 7$ and 10% strengths was investigated.On increasing and decreasing the exciting currents between 0 and 10 amperes marked hysteresis was found in the capillary rise apart from the usual hysteresis of the magnet. This effect is supposed by the author to be true liquid hysteresis. R. J. C. Use of the Magnetic Field as a means of Determining Con- stitution in Organic Chemistry. 11. and 111. PAUL PASCAL (BUZZ. Xoc. clhim. 1909 [iv] 5 1110-1118 ; 1910,7 17-28. Compare Abstr. 1909 ii 487 788 859).-Part of this work has been published already. From comparisons of the magnetic susceptibility of oxygen in a series of oxygenated carbon compounds the conclusion is drawn that the value is - 48 x 10-7 where oxygen is joined to two different carbon atoms - 35 x 10-7 where it is doubly linked to a carbon atom the latter being itself joined to two oxygen atoms (as in carboxylic acids) and + 1s x 10-7 where a single oxygen atom is doubly lioked to carbon (as in aldehydes and ketones).A compara- tive list of (1) experimental molecular magnetic susceptibilities and of (2) values calculated from the data given above shows close con- cordance. The application of these rules to the case of paraldehyde lends support to the KekulB formula for this substance. Apart from the above effect due to the method of linking of oxygen the value of the magnetic susceptibility of the latter is also influenced by the general structure of the rest of the molecule and especially by the presence of (1) tertiary or quaternary carbon atoms (2) double linkings.The first of these effects is marked when the disturbing atom is in position a or y and more so in positions 6 and c but is very small in p t or 7 and ceases beyond position 8. The presence of a double linkage shows itself in an analogous manner and a table of corrections for the effect of double linkings in several positions is given. The second group of conclusions lends support to Bayer's strain hypothesis provided the carbon chain is regarded as having a roughly spiral form. The influence of the hexamethylene nucleus on the magnetic suscep- tibility is estimated at +31 x 10-7 and with this correction the calculated value for cineol according to Briihl and Wallach's formula agrees with that determined experimentally.and retains this in most of its organic derivatives but in thioacetic acid the atomic susceptibility of the oxygen atom is - 15 x lo-' as against - 35 x 10-7 for the same oxygen atom in acetic acid the greater effect in the former case being due to the presence of the sulphur atom. The normal value for nitrogen is - 58 x lW7 but in a cyanogen group Sulphur has the value - 156 xGENERAL AND PlXYSICAL CHEUISTRY. ii. 101 or where nitrogen is directly attached to a benzene nucleus the value becomes - 48 x I n closed chains containing carbon and nitrogen the latter has the same value as in aromatic amines and for purposes of calculation the value for one CH (or CK) group is replaced by t h a t for NH (or N) with the usual total correction for the influence of the nucleus.This rule is not applicable in the case of pyridine. T. A. H. Thermometers as Thermo - regulators. ERRARD GLASER (Biochem. Zeitsch. 1909,23,5-9).-1nto the thermometer which is used as thermo-regulator platinum wires are fused at certain definite points corresponding with temperatures the constancy of which it is desired to maintain. The lowest platinum wire is always in contact with the mercury when the thermometer is immersed in the apparatus the temperature of which is to be regulated. By means of this and another platinum wire corresponding with the temperature which is to be maintained in the thermostat an electric circuit is made with a coil in which is immerded a Hahn regulator. As soon as the mercury reaches the higher poict and the circuit is closed an iron core in the Hahn regulator is drawn down by the current and shuts off the supply of gas t o the burner heating the thermostat.As the latter cools the gas is automatically lighted again by means of a by-pass. The apparatus is figured in the paper. S. B. S. Krafft’s Boiling - point Estimations and his Theory of Volatilisation. C. VON RECHENBERG (J. pr. Chem. 1909 [ii] 80 547-555. Compare Abstr. 1909 ii 544).-Largely polemical in reply to Krafft (Abstr. 1909 ii 969 and Hausen ibid. 969). It is pointed out that the expression used by Krafft b. p./O mm. is a contradiction as if sufficient vapour is present for the temperature to be determined there must be a vapour pressure. The effects which are attributed by Krafft to the influence of gravity are regarded by the author as due to the condensation of vapour by external cooling.J. J. S. Preparation of a Mixture of Constant Boiling - point and Maximum Vapour Pressure by Distillation. D. D. GADASKIN and A. E. MAKOVETZKI ( J . Buss. P/ys. Chern. Soc. 1909 41 1160-1 163).-The authors describe experiments on the distillation of various aqueous solutions of the ether of methylene glycol under ordinary and reduced pressure (compare Abstr. 1908 i 753 ; 1909 ii 215). The resulbs obtained are discussed by Ma ovetzki (see following ex tract). Determination of the Composition of Constant Boiling-point Mixtures having Maximum Vapour Pressures and their Quantitative Separation by Distillation. A. E. MAKOVETZKI (J. h?uss. Phys. Chenz. Soc. 1909 41 1171-1175.Compare preceding abstract).-The author adduces further evidence in support of his view that a binary liquid mixture for which a maximum or minimum vltpour pressure exists may be regarded as consisting of two components one T. H. P. VOL. XCVIII. ii. 8ii. 102 ABSTRACTS OF CHEMICAL PAPERS. Deing the mixture of maximal or minimal vapour pressure and the other the component present in excess. By means of aqueous solutions of the ether of ethylene glycol it is shown that the mixture of maximum vapour pressure can be separated quantitatively by one distillation in a suitable fractionating apparatus. The quantity and composition of the mixture with maximum vapour pressure are not altered by the addition t o the solution of a nou-volatile substance which effects the separation of the liquid into layers but does not give a solid phase.T. H P. An Electrical Apparatus for the Direct Determination of the Water Value of a Calorimeter. W. ~WIFTOS~AWSKI (Bull. Acad. Sci. Cracow 1909 548-555).-The principle of the method consists in using two calorimeters which are heated by means of a n electric current. The one calorimeter (chief calorimeter) is filled with the solution the water value of which is required and the other (water calorimeter) with water. The heating is accomplished by means of a platinum wire spiral which is fused in between two concentric layers of glass. The two vessels are of tho same construction. The heat coefficient a is calculated from the formula a = A/l,(500 -t c1 + cl’)/AF2(500 + c2 + c2’) where AT and AT denote the increases in temperature c1 and c2 the water values of the calorimeter with stirrer and thermometer cl’ and c2’ the water values of the heating apparatus and where each calorimeter contains 500 grams of water. The sp.heat K of any liquid can then be calculated from the equation I<= aAT2/Al; where the increases in temperature of the two calorimeters are AT and AT;. Atomic Volume of Allotropic Modifications at Very Low Temperatures. EKNST COHEN and J. OLIE jun.* (Proc. K. Akud. Wetensch. Amsterdam 1909 12 437-445).-1n order to obtain information relating t o the densities of allotropic modifications at absolute zero measurements of the densities of diamond and graphite and of white and grey tin mere made at a. series of temperatures by a dilatometric method.The graphite was subjected t o pressures of 1000 to 5000 atmospheres until the sp. gr. remained constant after repeated compression. ‘l’he ratios of the specific gravities of diamond and graphite were found to be 1.585 1.583 and 1.582 at 1 8 O - 3S0 and - 164O respectively; those of white a n d grey tin 1.266 and 1.274 a t 78’ and - 164’. These numbers indicate that the specific volumes of the allotropic forms do not converge as the temperature falls. H. M. D. Associated Liquids. W. A. KURBATOFF and G. G. ELISEEFF (J. Russ. Plqs. Chem. SOC. 1909 41 1422-1425. Compare Abstr. 1909 ii 117 120).-In order to throw light on the abnormal values of the Ramsay-Shields constant given by certain apparently normal liquids the authors have examined acetic anhydride and ethyl malonate in this connexion.* also Zcitsch. yhysikcd. Cllem. 1910 Vl 385-400. J. J. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 103 Acetic anhydride for which Trouton’s constant has the high value 22.9 is stated to give the normal value of the Ramsay-Shields constant K = d(yNw2’’)/dt = 2.129 corresponding with a non-associated liquid. This value of IT is confirmed by the authors’ measurements which give the mean result 2.12 +_ 3%’ in open and closed vessels. A whole series of esters are known which are normal as regards their thermal data and their values of Trouton’s constant but give abnormally high values for the Ramsay-Shields constant. This is also found to be the case with ethyl malonate which gives values of K varying from 2.20 to 2-56? The results obtained indicate that the value of the Ramsay-Shields constant varies for different homologous series.T. H. P. Association of Glycerol. G. G. ELISI~EFF and W. A. KURBATOFF (J. Rzcss. Phys. Chem. Soc. 1909 41 1426-1427).-The values of the Ramsay-Shields constant for glycerol at various temperatures are as follows 0.63 at 35*2-66-S0; 1-10 at 64%-74*3°; 1.50 at 74.3-101°40 snd 1.20 at 101.4-123.4” the alteration with tempera- ture being almost identical with that exhibited in the case of ethylene glycol. It hence appears that the degree of association of glycerol is not less than that of ethylene glycol. These results give no reason for expecting that the molecule of sugar is a simple one But if the sucrose molecules are associated as indeed all molecules containing hydroxyl groups appear to be then the laws of osmotic pressure derived from a study of sucrose solutions should be modified and there is exhibited also a possibility of an explanation of the coefficient i other than that given by Arrhenius.T. H. P. Adsorption of Ions. V. BOURNAT (Compt. Fend. 1909 149 1366-1368).-Dilute solutions of binary electrolytes excluding acids have a higher surface-tension than water; acids however lower the surface-tension. The action of acids is probably due to the accumula- tion of hydrions in the superficial layer giving the same effect as in the capillary electrometer. I n sopport of this explanation it is shown that the addition of a hundredth molecular weight of potassium ferro- cyanide t o a litre of NIS-nitric acid increases the surface-tension to a considerable extent whereas when added to a N/5-solution of a binary salt the increase is only very slight.Perrin has shown that multi- valent ions diminish considerably the charge in a double layer that is that they accumulate in the surface layer and in the experiment mentioned above they displace the hydrions and thus raise the surface- tension. Comparing equimolecular solutions the curve showing the relation between the molecular weights (abscissze) of binary salts and the diff ereiices in the surface-tension (ordinates) of their solutions from that of water is a straight line Monobasic acids also give a straight line lying below and parallel to that for the salts the difference in the ordinates being 0.35 absolute unit for N/lO-solutions.Sodium and potassium hydroxide raise the surface-tension of water but not t o the same extent as binary salts; in this case also a sbraight line is 8-2ii. 104 ABSTRACTS OF CHEMICAL PAPERS. obtained the difference in the ordinates being 0.25 unit. These differences are apparently proportional t o the molecular concentrations of the solutions. Assuming that the diminution in the surface-tension is due to the accumulation of ions in the surface layer it is shown that the number (n) of ions absorbed per unit surface is given by the formula ~ = u c ! where c is the concentration and p is a constant depending on the ion. This formula is analogous to the general adsorption formula of Freundlich. T. S. P. Adsorptive Power of Hydroxides of Silicon Aluminium and Iron.111. Adsorption by Clay. 11. PAUL ROHLAND (Zeitsch. anorg. Chern. 1909 65 108-109 ; Biochein. Zeitsch. 1909 23 278-280 Compare Abstr. 1909 ii 27 55l).-A property of a Fraustadt clay the analysis of which is given is to adsorb unsaturated hydrocarbons when it has imbibed its maximum quantity of water. It is however impermeable to saturated hydrocarbon. By means of this clay the unsaturated hydrocarbons can be separated from the saturated in American petroleum. The hydroxides of clays of this description (silicon aluminium iron and titanium) can adsorb organic substances containing oxygen such as alcohol and acetone but prevent the diffusion of organic substances such as carbon disulphide toluene etc. and hydrocarbons which do not contain oxygen with the exception of the unsaturated hydrocarbons. S.B. S. Chemical Dynamics and the Colloidal State. I 11 and 111. ALBERT REYCHLEK. (J. Chim. Phys. 1909 7 365-368 497-510. Compare Biltz Abstr. 1904 ii 324 393).-The experi- ments made by Biltz on the removal of arsenious acid fromits solution by shaking with colloidal ferric hydroxide led to the conclusion that the amount of acid removed (x) was related to the amount remaining in solution (a - x) by the equation x5 =]<(a - x). The phenomena were attributed to adsorption but were not further investigated mathematically. The amounts of ferric oxide used by Biltz in all his experiments were sufficient to form a normal arsenite with 1.4 grams of arsenious oxide whereas the amount of arsenious oxide actually adsorbed never exceeded 0.824 gram even when almost four equivalents were available.If a normal arsenite is produced its concentration would be represented by xl1.4 that of the free ferric hydroxide by (1.4 - x)/1.4 and of the free arsenious oxide (a - 2)/3. Assuming that normal ferric arsenite is hydrolysed in the usual manner for a salt of a weak acid and a weak base the eqoilibrium will be (~/1*4)~ = X3((1.4 - ~)/1*4)~(a - x)/3,whence If on the other hand only two of the basicities of arsenious acid are exercised the constant is 1C2 = Jx"(a - x) It is shown that K satisfactorily expresses Biltz's values up to the point where about one-half of the theoretically possible arseriious oxide is combined and that above this K2 gives a constant pointing to the formation of some acid arsenice.K,= ~Z'/(CG-Z) + (1.4-x). (2 x 1.4 - x).GENERAL AND PHYSICAL CHEMISTRY. ii. 105 If the equivalent amount of arsenious oxide in Biltz’s experiments is taken as 3.2 instead of 1.4 an even better constaat (K3) is obtained. It is not certain whether alumina has a similar a6nity for arsenious oxide. The author suggests that all so-called adsorption phenomena regu- lated by equations of the form d / ( u - x) = K may eventually be made amenable to the ordinary laws of chemical dynamics. The experiments of Freundlich on the adsorption of various acids etc. by blood-charcoal (Abstr. 1907 ii 155 939) can be considered as cases of chemical combination. Since however the basicity of charcoal is unknown i t is necessary to assume that 1 gram of charcoal is capable of combining with n-milli-equivalents of acid m-Grams of charcoal can therefore combine with mn-milli-molecules of a monobasic acid. If x milligram-molecules of acid be adsorbed the degree of saturation of the charcoal is elinn and the unsaturated charcoal is (mn - x)/mn.If cc is the initial concentration in the solu- tion (a - x) is the final concentration. Assuming that the adsorption compound is hydrolysed like a salt of a weak acid with a weak base (x/mn)2= K,(rnn - x)/rnn x (a - x) whence Kl = ( ~ / r n ) ~ / ( a - x)(n - x/m). By choosing a suitable value for n a very satisfactory constant K can be obtained. The values are Acetic acid ............... Propionic acid ........... Dichloroacetic acid.. ... Formic acid ............... Butyric acid ............Chloracetic acid ......... Benzoic acid ............ Sulphanilic acid ......... n=6 n = 5 n=6 n=S 71 = 6 n=4 12=4 n=5 K~ = 0.043 irl = aeoza K,= 0.30 K1=0*139 Kl = 0.21 Kl =0*33 K1 = 24 Kl = 0 -21 The strong acids trichloroacetic acid and benzenesulphonic acid do not give satisfactory constants ; it is supposed t h a t their adsorpticin compounds are not hydrolysed according to the same law. I n the case of dibnsic acids with only one active valency R= ( ~ / m ) ~ / ( a - 2)(2n - x/m) whereas if both valencies be active X2 = J / ( ~ / r n ) ~ / ( a - x) 4 (n - z/m). With succinic acid both valencies are active n= 10 and K2=0.32. Citric acid acts as a tribasic acid R = 0.16 when n = 15. Bromine appears to follow the same adsorption lnw as monobasic acids whereas methy lamine follows a simple partition law.Adhesion dissolution etc. mas in many cases superpose their effects on chemical adsorption. The author’s hypothesis is based on the theory that a large number of colloidal solutions may be considered as strongly basic or acidic salts. For instance the small proportion of hydrochloric acid which stabilises a solution of ferric hydroxide acts by combining with all the hydroxyls in turn thus preventing tbe hydroxide from forming large complexes which on dehydration would be precipitated. For every degree of dilution of the colloid sol there is a correspond- ing minimum of acid to prevent precipitation. All the known agentsii. 106 ABSTRACTS OF CHEMICAL PAPERS. for precipitating ferric hydroxide can be explained to act by disturbing the chemical equilibrium of acid water and ferric hydroxide. Colloidal silica can be considered as a very acidic.sodium silicate and its properties can all be explained on chemical grounds. The phenomena of cataphoresis and anaphoresis the precipitation of colloids byelectrolysis may be due to the transfer of water to anode or cathode respectively the colloid appearing to travel in the reverse direct ion. R. J. C. Adsorption of Arsenious Acid by Ferric Hydroxide. WILHELM BILTZ '(L Chim. Phys. 1909 '7 570-574).-1t is shown that Reychler's explanation (preceding abstract) of the author's observations relating to the absorption of arsenious acid by ferric hydroxide is untenable. This explanation is based on the assumption of the formation and hydrolytic decomposition of ferric arsenite.New experiments have been made in which varying quantities of the hydroxide were shaken up with the same volume of a solution of arsenious acid of determined concentration. IF x denotes the quantity of arsenious oxide taken up by rn grams of the hydrogel and x is the quantity which remains in solution the observed results can be satisfactorily represented by the equation log z/m = 0937 log x + log k. From this the author concludes that the removal of arsenious acid from the solution by the ferric hydroxide is a pure adsorption phenomenon. H. M. D. Thermodynamics of the Capillary Layer. GERRIT BAKKER (Zeitsch. physikal. Chem. 1909 68 684-692).-8 mathematical paper. The author indicates certain errors very often committed in applying thermodynamical considerations to the capillary layer.When the capillary layer is considered by itself instead of the usual equation d& = d e - Hds (where dQ is the heat absorbed in varying the surface d e is an energy difference H is the surface-tension and ds the change of surface) the equation d& = d e +pNdv - Hds must be used where p is the vapour pressure and v the specific volume of the capiilary layer. The last equation is the correct expression for the specific heat of the capillary layer per unit of mass. Nothing is known as to the variation of this speci6c heat with temperature. The energy equation obtained when a vessel filled with liquid vapour and the capillary layer as transition layer is considered differs from that deduced for a thin sheet.G. 5. Relationship between Physical Properties of Solutions. I. Density aad Electrical Conductivity of Aqueous Solutions of Salts. ADOLF HEYDWEILLER (Aim. Physik 1909 [iv] 30,873-904). -From an examination of the data for a large number of aqueous solutions of electrolytes it is shown that a connexion exists b$ween the density of a solution and that of the solvent which can be expressed by the equation A = B + ( A - B)i. I n this equation A denotes the percentage change in density per gram-equivalent of the dissolvedGENERAL AND PHYSICAL CHEMISTRY ii. 107 electrolyte i is the ratio of the equivalent conductivity of the given solution to the conductivity at infinite dilution and A and B are constants. A and B represent respectively the percentage changes in density which are caused by one gram-equivalent of ionised and non- ionised electrolyte ; A - B represents the influence of ionisation on the density of the solution. The values of A and B are tabulated for a number of electrolytes.For certain electrolytes the values of 3 indicate that the volume of the undissociated electrolyte in solution is the same as that of the salt in the solid State. I n other cases changes in volume take place on solution. The contractions which are found in the case of salts which form hydrates in the solid state indicate that hydrated molecules are also present in the aqueous solutions. Ionisation of the electrolyte is always accompanied by an increase in density and this is found to become greater as the sum of the mobilities of the constituent ions increases.The observed contrac- tion is shown to be probably due to a diminution in the volume of the water. The values of A exhibit additive relationships and ionic moduli are calculated by means of which it is possible t o calculate the influence of the ionised portion of any electrolyte on the density of its aqueous solution. Certain electrolytes are abnormal in t h a t they do not agree with the relationship A = B + ( A - B)i. The anomalous behaviour is traced in some cases to the formation of complex ions in the more concentrated solutions and to the large affinity of the dissolved salts for water. H. M. D. Condition of Equilibrium between a Dilute Solution and the Pure Solvent Separated by a Semi-permeable Diaphragm or by the Vapour of the Solvent.GIOVANNI GUGLIELMO (Atti R. Accad. Lincei 1909 [v] 18 ii 536-544).-Making use of two relations which mere obtained by van der Waale (see Die Continuitat des Jussigen und gasformigert Zustccndes) and which express the condition of equilibrium of a large number of molecules (considered as material points) in perpetual motion and attracting one another the author derives (1) in two forms the condition of equilibrium of the molecules of a chemically homogeneous liquid and (2) the equilibrium conditions for a chemically heterogeneous liquid-solvent and solute ; (3) the condition of equilibrium between pure solvent and solution separated by a semi-permeable surface. With the aid of the results thus obtained the following questions are discussed independence of the molecular attraction on the mass of the molecules and a hypo- thesis on the nature of this attraction; causes of the lower vapour pressure of solutions compared with the solvents and of the equality of vapour pressure for equimolecular solutions ; influence of the curvature of the surface of a liquid on its vapour pressure.T. H. P. Remarks on THOMAS S. PATTERSON (Zeitsch. physihl. Chem. Compare Dolezalek Abstr. 1909 ii 22).-It is Binary Mixtures and Concentrated Solutions. Doleartlek’s Paper. 1909 67 572-574.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. shown that the theoretical densities of mixtures of chloroform and acetone calculated by Dolezalek are incorrect as they were obtained by multiplying the respective densities of the components by the molecular fraction of the component in the mixture instead of by the usual method The observed density of n particular mixture of chloro- form and acetone only differs very slightly from the theoretical value ; the deviation is only one-ninth of that given by Dolezalek and the conclusions of the latter investigator therefore require revision.G. S. Existence and Properties of Disperse Systems in the Region Separating Colloidal and Crystalloidal Solutions. THE SVEDBERG (Zeitsch. Chern. Ind. Kolloide 1909 6 3 18-325. Compare Abstr. 1909 ii 389).-Experiments are described which show that the absorption of light by a gold hydrosol increases as the size of the colloidal particles increases. By raising the temperature of a ruby- red hydrosol or by the addition of electrolytes the particles were caused to coagulate and measurements of the colour intensity showed a gradual increase in the absorptive capacity of the hydrosol.The addition of a non-electrolyte was found to be without influence on the absorption. By the reduction of a solution of gold chloride by means of hydrazine in presence of gelatin (free from electrolytes) as protective colloid gold hydrosols consisting of extremely small particles can be obtained. The intensity of the colour of the hydrosol obtained in this way is much smaller than that of the hydrosol obtained under similar conditions in the absence of the protective colloid. The action of this consists in reducing the rate of coagulation of the hydrosol and it is shown that the activity of the gelatin is approximately pro- portional to its concentration.Gold hydrosols prepared in different ways exhibit considerable differences in respect of the position and the intensity of the absorp- tion maximum. This is found to depend on the size of the colloidal particles. As the size diminishes the absorption maximum shifts to- wards the region of smaller wave-lengths. For the most highly disperse hydrosols this maximum is in the ultra-violet and approxi- mates to the position of the maximum for a solution of gold chloride. H. M. D. Theory of Colloids. JACQUES DUCLAUX (J. Chim. phys. 1909 [vii] 405-446. Compare Duclaux Abstr. 1909 ii 303 ; Malfitano ibid. 473 ; Pappada ibid. 473)-The author develops the theoretical ideas already put forward by him into a complete theory of colloids.The physical theory which postulates that the stabilising ions in a colloidal solution are permanently combined with the colloid particles and that the whole osmotic pressure is due t o colloid particles acting as molecular units fails to explain the difference in properties when one stabilising ion is substituted for another. According to the chemical theory put forward by the author colloid particles are very large multivalent ions forming salts with the stabilising ions which surround them but which are capable of super-adding their osmoticGENERAL AND PHYSICAL CHEMISTRY. ii. 109 pressures conductivities etc. t o that of the nucleus granules or micella (compare Reychler this vol. ii 105). The degree of ionisation will vary with the nature of the stabilising ion.For instance ferric hydroxide stabilised with sulphuric acid has a much lower oemotic pressure than the same colloid stabilised with hydrochloric acid. It is shown that if the colloidal micella is assumed to be exactly comparable to an ionisable salt the osmotic pressures calculated from the conductivities and ionic mobilities of the solutions are about double the experimental osmotic pressures. The measurements mere all made on solutions with a very pure intergranular liquid (compare however Malfitano Zoc. cit.) and a small correction was subtracted for the con- ductivity of the intergranular liquid. The ionic mobilities of the colloid granules were determined by passing a direct current through the solution and afterwards analysing the liquids in the anode and cathode chambers it being assumed that no transference of water had occurred.The ultramicroscope is not available here because colloids with an appreciable osmotic pressure are so small as to be almost invisible. When a colloidal solution is dilute the micella are so widely separated that the ions surrounding each one are never attractad from it but the whole comprises a stable almost neutral sphere. On establishing an electric field the ions all crowd to one side of the sphere and the parent granule to the other. Since the voltages required for electrolysis are small it follows that only a few of the ions become detached. When the solution is concentrated the micella approach each other and ultimately their neutral spheres intersect.Each micella will then facilitate the ionisation of its neighbours a kind of Grotthus’s chain being set up. It follows that as a colloidal solution is concentrated its ‘‘ molecular ” conductivity increases. This is showri to be the case with ferric hydroxide and gum arabic. The degree of ionisation of a colloid does not mean the proportion of granules ionised but the average extent to which each granule is ionised. Knowing the number of stabilising ions the degree of micella ionisation can be calculated. It varies in the author’s experi- ments from 0-008 in copper forrocyanide to 0.88 in gum arabic. If the intergranular liquid contains electrolyte this must have an ion in common with the micella and will influence its ionisation. When the degree of ionisation of the micella the ionic velocity and the viscosity are known the radius of the micella can be calculated with the aid of Stokes’ theorem.This varies from 0 . 5 5 ~ ~ in tungstic acid to 5 . 2 ~ ~ in Prussian-blue the number of free ions per micella being 2.9 and 24 respectively. These values are in accord with the relative retoention of the colloids by collodion acd are also of the same order as the radius < l p p found by Zsigmondy for colloidal gold particles. The molecular weights of the colloids calculated from their micella radii are tungstic acid 1900 thorium hydroxide 7000 gum arabic 16,000 ferric hydroxide 115,000 copper ferrocyanide 700,000 Prussian-blue 1,000,000. The neutral sphere probably has a radius about ten times that ofii.110 ABSTRACTS OF CHEMICAL PAPERS. the micella that is to say on an average an ion does not move further than 10pp from the micella. Direct measurements have been made of the osmotic pressures of ferric hydroxide copper ferrocyanide Prussian-blue thorium hydr- oxide gum nrabic and caramel with collodion membranes. The results confirm those obtained by the filtration method (Abstr. 1909 ii 303) and clearly show that the osmotic pressure of a colloid increases more rapidly than the concentration. In very dilute solution each micella with its ions complete acts osinotically as one molecular unit. As the concentration increases it may attain by splitting off of ions an osmotic value of S or more. R. J. C. General Equation of State. KARL DRUCKER (Zeitsch. physikal. Chem.1909 68 616-636).-A theoretical paper. A general equation of state is deduced on the assumption that the gas laws hold for gases and pure liquids in general and that the deviations are to be accounted for on purely chemical grounds that is on the formation of complex molecules (polymerides). On this basis the general gas equa- tion pv = RT.8n leads to the equation p/RT= 8n/v = Sc = el + c2 + c3 + . . . . (l) where 8 c = c1 + k,c12 + k,cI3 + . . . . I n this equation cl c2 etc. represent the respective partial concentrations of the simplex and complex molecules ; k k etc. represent the respective equilibrium constants and the other symbols have the usual signi- ficance. It is assumed in deducing this equation that equilibrium between simple molecules and their polymerides is established instantaneously.I n equation (1) the coefficients are necessariIy positive and it appears at first sight as if it applies only to cases where the com- pressibility is too great. Although this difficulty can theoretically be got over it has been considered advisable to insert a volume correction (analogous to that of vim der Waals) in equation (1). The equation is then tested by application to the data for ethyl ether methyl alcohol and other vapours given by ltamsmy and Young and others and simplified forms of it are found to give satisfactory results. The application of these considerations to liquids leads to the con- clusion t h a t a liquid under ordinary conditions consists of a dilute solution of unimolecules in complex molecules.The fact that this result is in apparent conflict with the method of determining the molecular complexity of liquids due to E6tvos-Ramsay-Shields based on surface-tension measurements is not regarded as an insuperable objection as the method in question has no purely thermodynamic basis. The author considers that liquids such as water usually regarded as complex are really comparatively simple. Provisional suggestions are made for determining the partial concentrations in liquids. G. S. Demonstration of the Phase Rule. R . BOULOUCH (Compt. rend. 1909 149 1377. Compare Abstr. 1909 ii 802).-The author maintains his criticisms of Miiller's demonstration of the phase rule,GENERAL AND PHYSICAL CHEMISTRY. ii. 111 pointing out that Muller has confused three things which are essenti- ally distinct namely (1) the actual changes taking place in a system not in equilibrium; (2) the virtual changes which one imagines to take place in a system in equilibrium ; (3) the atomic interchanges occurring according to the atomic theory in a system in equilibrium.T. S. P. Invariant Systems and the Regularity of Composition of Certain Eutectics. ALEX. GORBOFF (J. Buss. Phys. Chem. Xoc. 1909 41 1241-1300).-The author discusses the phase rule and the composition of eutectic mixtures a large number of examples from the work of various investigators being considered. The principal results arrived at are as follows. One of the fundamental propositions of chemical mechanics is that the laws ‘by which material systems are characterised are determined not by the number of their components but by the number of effective degrees of freedom.Examination of the compositions of eutectics formed by the elements and by chemical ‘‘ molecular,” and ‘‘ complex ” compounds shows that the composition of any eutectic corresponds with a chemical compound formed by the elements occurring in the eutectic which may hence be expressed by a chemical formula with rational indices. So that eutectics obey not only the law of constant composition but also the law of multiple proportions. Not only may the composition of a eutectic formed by two independent components capable of giving chemical compounds melting without decomposing be expressed by a chemical formula but this formula is often constructed according to a simple rule-equal masses of one of the two components being distributed in both solid phases of the eutectic.Thus if the two components A and B form the compounds A + xB and A + yB melting without decomposing then the eutectic between A and A +xB is expressed by the formula 2 A +xB and that between A + x B and A + y B by the formula ( g A + x y B ) + (d + q B ) or ( x + g ) A + 2xgB and so on. Excluding the limiting eutectics answering to the general formula 2A +xB in all the others expressed for example by (x + y)A + 2xyB in both solid phases that independent component is distributed in equal masses which possesses the more basic chemical character. The latter in the euiectics formed by crystallo-hydrates of sulphur dioxide hydrogen chloride hydrogen icdide nitrogen pentoxide copper nitrate magnesium chloride ferrous nitrate and ferric chloride is water and in the metallic eutectics the more alkaline metal.I n every case where a chemical compound of two components does not melt without decomposing but exhibits a transition point below the melting point its solubility in one of the components is lower sometimes very considerably lower than is required by the above rule; in such cases this component consequently occurs in excess in the eutectic. For the large numbers of experimental data from which these conclusions are drawn and for references given the original must be consulted. T. H. P.ii. 112 ABSTRACTS OF CHEMICAL PAPERS. Influence of Centrifugal Force on the Equilibrium of Chemical Systems. A.V. DUMANSKY (J Buss.Phys. Chem. Soc. 1909 41 1306-1308).-When a concentrated solution of cadmium iodide is subjected to centrifugalisation in a tube closed with a cork a brown precipitate containing cadmium and iodine is deposited whilst aqueous hydrogen iodide under similar conditions gives a deposit of iodine. The author's results seem to indicate that the cork acts as a catalyst. Also centrifugalisation of solutions of ferric chloride and mercurous nitrate produces a marked increase in the electrical conductivity of the solutions the increased values persisting after removal of the centrifu- gating force and mixing of the liquids. Since all the compounds used in his experiments are readily decomposed by water the author suggests that such decomposition may occur to a slight extent and that one of the products of the decomposition being the heavier may be readily removed from the sphere of action by the centrifugalisation.Thus with ferric chloride the ferric hydroxide formed by the hydrolytic dissociation would pnss to the periphery of the centrifuge and thus permit of the hydrolysis of further quantities of ferric chloride ; the hydrochloric acid formed by the hydrolysis would cause the increased conductivity observed. Colloidal solutions of antimony sulphide and ferric hydroxide deposit precipitates when subjected to centrifugalisation. T. H. P. Chemical Affinity. 111. Solution-affinity of Binary Systems. 11. Sulphuric Acid and Water. J. N. BRONSTED (Zeitsch. physikal. Chem. 1909 68 693-725).-The theoretical conclusions discussed in the previous paper (compare Abstr. 1909 ii 29) are now tested by application to the system sulphuric acid-water. The heat of admixture of sulphuric acid and water has been determined over the whole range of concentrations and as large amounts of the substances mere used the results are probably very accurate ; they are represented in tabular form in various ways.The heat of formation of 1 mol. of monohydrate is 6710 cal. The m. p. of pure sulphuric acid on the hydrogen scale is 10.49". The results obtained are in good agreement with those of Pfaundler and of Pickering (Trans. 1890 57 94) but not with those of Thomsen (Thermochemische Untersuchungen) ; i t is probable that Thomson's "pure" acid contained a little water. From the results the differential curves for the heats of admixture are determined by means of the equations given in the earlier paper.The solution-affinity of the components throughout the whole range of concentrations is then determined from the combined results of i7.M.X measurements of vapour-tension measurements and of freezing-point determinations. The reaction the E.M.F. of which has been determined is the formation of sulphuric acid by the reduction of mercurous sulphate by hydrogen the cell being built up as follows H I H,SO I $g,SO I Hg. Measurements have been made between 15" and 80" with varying proportions of acid and the affinity is calculated from the results by means of the Helmholtz equation in the usual way.GENERAL AND PHYSICAL CHEMISTRY. ii. 113 As regards vapour-pressure measurements the results of Tammann (Zeitsch.physihl. Chern. 1888 2 42) at loo" and of Dieterici (Ann. Phys. Chern. 1893 [ii] 50 47) at O" have been supplemented by measurements at 20' and 30" with a special form of apparatus. In connexion with the calculation of solution-afinity from freezing- point determinations with the help of thermal constants it has been found that the heat of fusion of sulphuric acid is 2485 + 6 - l t calories per mol. and that of the monohydrate 4290 + 18% calories. From these results the differential solution-affinity curves for water and acid respectively have been obtained and for comparison are plotted on the same diagram with the corresponding curves for the heat of admixture. The forms of the curves are very different from the ideal type due to chemical reaction between water and acid.As regards the sulphuric acid curve A the solution-affinity is greater than U the heat of admixture for x= 1 (x is the molar pro- portion of acid in the mixture) ; the curves intersect at x = 0.53 where A = U= 1400 cal. beyond which the A-curve is lower than the U-curve until they again intersect at x = 0*006,~~tvhen A = U= 17,000 cal. FOP water the affinity and heat of reaction curves practically coincide for concentrations between 0.1 and 0.3. The values found are throughout in accord with the general thermodynamic equation A - U= T x dA/dT (where the symbols have the usual significance). G. S. PAUL TH. MULLER (J. Chim. Phys. 1909 7 534-539).-The theorem recently published by Nernst (Abstr. 1907 ii 153) correlating affinity with temperatlure in condensed systems is applied to the affinity of sodium phosphate for water.The affinity of the hydrate Na2HP0,,12H,0 for its water is given by the formula A = 1*985T'log,f/f' cd. where J' andf' are the vapour pressures of pure water and hydrate respectively a t temperature 1'. Nernst's equation gives A = Qo - UP - P P / 2 where Qo is the heat of hydration at absolute zero. The values of A in the first formula are calculated from Frowein's measurements of the vapour pressure of the hydrate between 6.8" and 27*00°. I f Qo= 1200'58 cal. a = 0.01 19827 and /3 = 0 Nernst's formula gives values agreeing with Frowein's within 0.35%. The heat of hydration at any temperature is equal to Qo+uT2+pl'3. Hence the heat of hydration of sodium phosphate at 18" should be 2215.3 cal.whereas Thomsen and Pfaundler obtained the values 2234 cal. and 2244 cal. by direct measurements. When the affinity for water ( A ) is zero (@-aT2)=0 whence 5!'=316.5O abs. It follows that at 43.5O the phosphate becomes anhydrous. Extrapolation of Frowein's results indicates that at about this temperature the vapour pressure of the phosphate begins to exceed that of water OTTO SACKUH. (Zeitsch. Elektrochem. 1909 15 865. Compare Trautz Abstr. 1909 li 651).-Trautz'a equations for the velocity of a reaction are obtained essentially by dividing the well known equation d log K/dI'= Q/RP into the two equations d log k1/d2'= q1/12Tz and d log k,/dT= q2/&P where k and k are the Affinity of Sodium Phosphate for Water. R. J. C. Chemical Kinetics.ii.114 ABSTRACTS OF CHEMICAL PAPERS. I. 11. Calcium platinichloride ........ 1 2 6 Zinc platinichloride ........... 11 7 Copper platinichloride ......... 18 6 Cadmium platinichloride ...... 18 6 Cobalt platinichloride ........... 12 10 Nickel platinichloride ......... 12 10 Sodium platinochloride ......... 4 3 Sodium platinibromide ......... t i 5 Barium platinichloride ......... 6 5 Manganese platinichloride ...... 11 7 I. 11. Ammonium palladiochloridc 5 4 Palladious iodide ........... 6 (at 0”) 2 Rhodium chloride ........... 4 3 Ruthenium chloride ......... 3 . 3 Ruthenium bromide ......... 3 2 Cuprous chloiide.. ............. 3 1 Cuprous iodide .............. 3 0 Silver nitrate .................. 3 2 Chronious chloride ............ 6 3 Uranium tetrachloride ......3 3GENERAL AND PHYSICAL CHEMISTRY. ii. 115 Neither hydrogen chloride nor phosphine combines with any dry inorganic salt. Acetylene is absorbed only by cuprous chloride. Ethylene gives no additive products; its absorption by ferrous and platinous chloride in ethereal or hydrochloric acid solution only takes place when these chlorides are formed by reduction of the correspond- ing ferric and platinic chlorides. Carbon monoxide was not absorbed by any of the salts investigated under the particular conditions of experiment . T. s. P. Eder’s Solution. I. CHR. WINTHER (Zeitsclh. wiss. Yhotochern. 1909 7 409-441).-The rate of the photochemical reaction between mercuric chloride and ammonium oxalate in aqueous solution is increased by ceric salts and potassium ferricyanide and decreased by cupric salts potassium tin chloride and many organic colouring matters.Potassium iodide in small quantity accelerates the reaction but when this is present in excess the velocity‘of the reaction diminishes. I n order to obtain information relative to the nature of the catalytic effect the author has examined the behaviour of chlorine potassium permanganate and more especially ferric salts. I n the case of chlorine the catalytic phenomenon is traced to the inducing effect of the reaction between chlorine and ammonium oxalate on that between the mercuric salt and the oxalate. The action of potassium permanganate is found to be accompanied by a period of induction during which the permanganate is reduced to a manganic salt which then accelerates the photochemical change.The mode of action of this is in all probability similar to that of ferric salts. The numerous experiments made on solutions containing iron salts show that the catgltic effect is very largely dependent on the asmount of oxygen which is present. I n the absence of oxygen the catalytic process can be resolved into two stages in one of which the rapid photochernicaJ reduction of ferric oxalate is involved whereas the other consists in the inducing effect of the oxidation of the ferrous oxalate formed in the photochemical reduction process. I n presence of oxygen the process is complicated by reason of the action of the oxygen on the reduced ferric salt. In support of this view it is found that the rate at which mercurous chloride is precipitated from a solution containing a given amount of ferrous salt increases as the amount of oxygen in the solution diminishes.For a given quantity of ferrous salt the total amount of mercurous chloride precipitated increases as the oxygen concentration diminishes. Ferric salts diminish the rate of the reaction. For a given ratio between ferric and ferrous salts the retarding effect increases rapidly with the total amount of iron in the solution. These observations are in accord with the fact that maximum photo-sensi- tiveness is obtained for a particular iron concentration. Since the retarding action of ferric salts increases when the amount of oxygen in the solution diminishes the iron concentration corresponding with maximuq sensitiveness diminishes with the oxygen concentration.The rate of precipitation of mercurous chloride from Eder’s solutionii. 116 ABSTRACTS OF CHEMICAL PAPERS. is recommended as a means of estimating small quantities of dissolved oxygen. H. M. D. Vacuum Correction of Weighings Applied to Atomic Weight Determinations. PHILIPPE A. GUYE and N. ZACHARIAD~S (Compt. rend. 1909 149 1122-1123. Compare Abstr. 1909 ii 989).-The authors have determined previously the magnitude of the error made in reducing weighings to vacuum values through the presence of condensed air on the surface of the substance. These calculations have now been revised after taking into account another source of error. The new numbers together with the results of fresh determinations for other common substances are given in tabular form.The results were obtained by weighing a flask in air (u) exhausted of air ( b ) full of air (c) containing air and the substance ( d ) containing the substance only. The apparent weight of the salt in air is reduced to the vacuum value by the usual method and compared with the “actual weight in vacuum” given by ( d - cc) - p where p is the loss of weight in the air of the standard weights. A further correction should be made for the air condensed on the surface of the standard weights. The “actual weight in vacuum” was in each case found to be higher than the calculated value the difference ranging from 1 mg. in the case of silver bromide to 25 mg. in the case of sodium chloride per 100 grams. I n the case of silver however the numbers were the same. w. 0. w. The Fundamental Constant of Atomic Vibration and the Nature of Dielectric Capacity. WiLLIAM SUTHERLAND (Phil. Mag. 1910 [vi] 19 1-25).-0n the assumption that positive and negative electrons are associated in pairs and are revolving round one another in such a way that each pair has an average electric moment it follows that if these moments are similarly directed the atom as a whole mill have an electric moment and can be investigated as a uniformly electrised sphere. It is shown that the internal electric fields cause atomic vibrations and that the atomic vibrator can be regarded as the single electron which is involved in the explanation of the Zeeman effect. The common constant which appears in Rydberg’s formuh for the series lines of many elements is discussed in terms of this conception of the atomic vibrator. An explanation of dielectric capacity in terms of the electron theory is given and it is shown that Balmer’s formula relating to spectral structure can be interpreted on a kinematical basis. H. M. D. Molecular Diameters. WILLIAM SUTHERLAND (Phil. Mug. 19 10 [vi] 19 25- 26).-0n the basis of the value 2.77 x obtained by Rutherford for the number of molecules in 1 C.C. of a gas under standard conditions the author has recalculated a series of molecular diameters with the following result H2 2.17 He 1.02 CO 2.74 C,H 3.31 N 2.95 NO 2.59 0 2.71 A 2-66 CO 2.90 N,O 3-33 C1 3.76 x lo-* em. H. M. D.INORGANIC CHEMISTRY. ii. 117 Liquid Extraction with the Aid of Soxhlet’s Apparatus. TADASU SAIKI (J. Biol. Chem. 1909 7 21-22).-9 modification of Soxhlet’s apparatus is described and figured for the extraction of liquid material with ether. W. D. H. Apparatus for Evaporating Ethereal Solutions. GILBERT P. GIRDWOOD (Analyst 1909 35 16)-The one end of an inverted siphon has the shape of a funnel and the other end projects several inches below the level of the ethereal solution to be evaporated. The watch-glass containing this is placed under the funnel-shaped opening and by applying suction to the long arm the ether vapour siphons over and the residue is finally deposited in a small space in the centre of the watch-glass. The same means may be adopted for concentrating an ethereal solution in a test-tube or beaker by gradually lowering the funnel of the siphon as the ether evaporates. L. DE I<.

ISSN:0368-1769    

DOI:10.1039/CA9109805085

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 117 Condition of Dissolved Iodine. PERCY WAENTIG (Zeitsch. physikal. Chem. 1909 68 513-571. Compare Beckmann Abstr. 1907 ii 340).-The investigation of solutions of iodine in a large number of solvents has led to the conclusion that in all the solutions iodine is partly combined with the solvent according to the reversible equation SoI f So + I (So = solvent) ; for the violet solutions the spectra of which approximate to that of iodine vapour the amount of combination is much less than for the brown solutions. These conclusions are mainly based on spectroscopic observations and in particular the effect of change of temperature on the spectra has been fully investigated. On heating the violet solutions the absorption band becomes displaced towards the red end of the spectrum in other words towards that of iodine vapour and is displaced in the opposite direction on cooling.The spectra of many of the brown solutions tend to become permanently altered on heating a result which speaks in favour of considerable association between iodine and solvent. The view that there is only a difference in degree between violet and brown solutions is further supported by the fact that brown solutions in thiophen and in sulphur dioxide become violet on heating and regain the original colour on cooling. The conclusion to be drawn from the displacement of the equilibrium with temperature that the heat of formation of the compound must be positive is supported by observations on the effect of temperature on the solubility of iodine and on its heat of solution in different solvents.Although the heat of solution is negative in all the solvents examined except pyridine the heat absorption is much less for brown than for violet solutions. Moreover cryoscopic investigations with iodine and a ‘ 6 solvent ” dissolved together in an indifferent solvent show that the VOL. XCVIII. ii. 9ii. 118 ABSTRACTS OF CHEMICAL PAPERS. depression is so much the smaller the greater the degree of combin- ation according to the above considerations (compare Hildebrand and Glascock Abstr. 1909 ii 225). A cornpound with pyridine of the formula PyI has been isolated. The influence of dilution on the absorption spectra has been measured for two kinds of light and it was found that contrary to the requirements of the law of mass-action the ratio of the absorption for both kinds of light increases with dilution.This is probably con- nected with ionisation of the additive compound as many of the solu- tions have a considerable molecular conductivity which increases with the dilution. The observations on the nature of the absorption bands and of their displacement with temperature are satisfactorily accounted for on the assumption that there is a maximum of absorption for the additive compound in the ultraviolet and that the absorption due to the compound is more or less affected by the absorption band due to free iodine. The partial vapour pressures of the components in boiling solutions of iodine in ether carbon disulphide chloroform carbon tetrachloride and benzene have also been determined and the results considered from the point of view due to Dolezalek (Abstr.1909 ii 22) support the above conclusions. Even at the boiling point there is considerable association between iodine and solvent in the brown solutions. The molecular freezing-point depression for carbon tetrachloride is 299. G. S. Production of Ozone by Ultraviolet Light. EDMOND VAN AUBEL (Compt. Tend. 1910 150 96-9S).-The following correction should be made in the previous paper (this vol. ii 2s). I n the experiments where water was used to absorb the ozone produced the resulting solution contains hydrogen peroxide the presence of which was detected by its action on a photographic plate. The presence of hydrogen peroxide in the water proves the formation of ozone in the air by the action of the ultraviolet light.T. S. P. Dissociation Isotherms of Sulphur between 3003 and 850". GERHARD PREUNER and W. SCHUPP (Zeitsch. physikal. Chem. 1909 68 129-156).-By means of the quartz-glass manometer described by Abegg and Johnston (Abstr. 1908 ii 157) the authors have determined the density of sulphur vapour at nine temperatures between 300° and 850' and within wide limits of pressure. The results cannot be reconciled with the assumption that only S and Sa molecules are present but indicate that above 30 mm. pressure only S S and S molecules are present. A t pressures lower than 30 mm. it is possible that S molecules are also contained in the vapour. From the displacement of the different equilibria with temperature it is calculated that in the reaction 35,=4S 29,000 calories are absorbed and in the other reaction S = 3S2,64,000 calories are absorbed.Similarly the change of gaseous S8 .to 45 absorbs 95,000 calories. From the most trustworthy results on the variation of the vapour pressure of sulphur with the temperature i t is calculated t h a t the heatINORGANIC CHEMISTRY. ii. 119 of vaporisation 8S[solid] -+ S&gaseous) is 20,000 calories hence for the reaction 8S,[solid] -+ 4S2(gaseous) 115,000 calories are absorbed. Otherwise expressed it requires about 115,000/4 = 28,800 calories t o transform 64 grams of solid sulphur into gaseous S,. On the assumption that S is identical with Sp the modification of sulphur insoluble in carbon disulphide the proportion of Sp in saturated sulphur vapour is calculated from the density results at different temperatures and compared with the values determined directly by Gal (Abstr.1893 ii 455) and by Kruyt (Abstr. 1908 ii 1028). The authors’ results are in excellent agreement with those of Gal but not with those of Kruyt. G. S. Action of Hydrogen on Sulphur or Selenium in Presence of Another Element. HENRI P~LABON (.I Cl&~t,. Phps. 1909 7 447-463).-Excess of pure sulphur or of sulphur containing less than 2/3 atomic proportion of arsenic when heated a t 610’ in hydrogen gives a gaseous mixture containing about 98% of hydrogen sulphide. When the proportion of arsenic is increased until the sulphur is saturated at approximately the composition SAs the amount of hydrogen sulphide decreases regularly to 78%.Further addition of arsenic which remains as a separate phase does not decrease the amount of hydrogen sulphide produced. Tho uaiphase solutions of arsenic in sulphur give a greater proportion of hydrogen sulphide the less the pressufe of hydrogen but mixtures containing a free arsenic phase always give 78% of hydrogen sulphide. The results obtained with mixtures of arsenic and selenium are analogous but the proportions of hydrogen selenide are in all cases much lower. Addition of selenium or tellurium to mixtures of sulphur and arsenic promotes the formation of hydrogen sulphide but to a less extent than an equivalent amount of sulphur itself. Selenium produces a similar effect on mixtures of sulphur and antimony b u t tellurium is here without influence.The addition of antimony to sulphur makes no change at first in the amount of hydrogen sulphide (98%) but when 43-90 atoms of antimony are present per 100 of sulphur the liquid consists of two phases antimony sulphide saturated with antimony and antimony saturated with its sulphide. Whilst these two phases are present the proportion of hydrogen sulphide produced is. about 60%. With larger proportions of antimony the hydrogen sulphide rapidly decreases towards zero. The phenomena with mixtures of selenium with antimony bismuth tin and thallium are similar to those obtained with selenium and arsenic. Silver and copper on the other hand which form stable selenides solid at the temperature employed entirely prevent the formation of hydrogen selenide when their proportions exceed Ag,Se and Cu,Se.R. J. C. Preparation of Colloidal Solutions of Selenium. ALFREDO POCHETTINO (Atti R. Accad. Lincei 1909 [v] 18 ii 544-551).-1n preparing colloidal solutions of selenium by the method of Muller 9-2ii. 120 ABSTRACTS OF CHEMICAL PAPERS. and Nowakowski (Abstr. 1906 ii lS) the author finds that at the same time as a red coloration forms in the liquid near the cathode the current intensity exhibits a continuous increase which begins immediately the circuit is closed. If the liquid in the cell is shaken the current intensity falls sharply but rises to the original value as soon as the shaking ceases and then continues t o rise to a certain limiting value which may be as much as ten times the initial current ; if the liquid is kept continually agitated a longer time is required for the current to increase to the limiting value.By this method if the duration of the current is sufficient to allow of the liberation from the cathode of more than about 0.24 gram of selenium per litre of water present a deposit of red selenium begins to form at the bottom of the cell. If a solution prepared in this way is filtered and subjected to an E.MF. of 40 volts between polished platinum electrodes the current increases gradually from about 40 milli-amperes at the beginninglto about 60 milli-amperes after two hours; if the current is interrupted for some time and then re-applied the initial value is again about 40 milli-amperes and the same gradual increase takes place. The increase of current seems t o be due to a diminution in the resistance of the liquid present in the cell.When a dilute solution of selenions anhydride is electrolysed with platinum electrodes the phenomena observed vary with the E. M.F. employed. With 3 volts a red deposit forms on the cathode and the current gradually falls; with 17 volts the deposit forms almost instantaneously and increases in thickness the current remaining sensibly constant ; whilst with 48 volts the current gradually increases whilst the liquid appears red in reflected and blue in transmitted light a colloidal solution of selenium and a black cathodic deposit of selenium being formed. The internal friction of such colloidal selenium solutions is sensibly identical with that of the distilled water from which they are prepared the same being the case with solutions prepared by Gutbier’s method (Abstr.1902 ii 652). T. H. P. Chemical Reactions in Gases Submitted to very High Pressures ; Decomposition of Nitric Oxide ; Formation of Nitrosyl Chloride. E. BRINER and A. WROCZYNSKI (Compt. rend. 1909 149 1372-1374. Compare Abstr. 1909 ii 557).-Nitrosyl chloride is formed when a mixture of nitric oxide and hydrogen chloride is submitted to a pressure of 300 atmospheres. When nitric oxide is allowed to remain a t high pressure in a sealed tube i t is colourless at first but after a day appears bluish-green. If the tube contains a large quantity of the gas drops of a blue liquid appear. The reaction is supposed to be represented by 6N0 = 2N20 + N ; the synthesis of nitrosyl chloride would then be explained by the action N203 + 2HCl= 2NOCl+ H20.No action occurs unless the nitric oxide is above a certain minimum pressure. I n experiments in which the pressure in the tubes was gradually increased the blue gaseous phase was first noticed a t 28 atmospheres. The rate of formation of nitrosyl chloride increases with the pressure. w. 0. w.INORGANIC CHEMISTRY ii. 121 A New Chloride of Phosphorus. ADOLPHE BESSON and A. FOURNIER (Compt. rend. 1910 150 102-104).-0n submitting a mixture of phosphorus trichloride and hydrogen to the action of an electric discharge (compare Abstr. 1909 ii 663) a colourless liquid holding in suspension a yellow solid is produced. After filtration and purification by distillation under diminished pressure in an inert atmosphere the liquid has a composition corresponding with that of phosphorus dichloride P,~l,.It is a colourless oily and strongly fuming liquid. The fuming is not only caused by the action of moisture but also by oxidation and under certain conditions the liquid takes fire spontaneously. It has b. p. about 180°/760 mm. (decomp.) 95-96’/20 mm. without decomposition m. p. - 28O. It is decomposed by water with the formation of phosphorous acid and a yellow solid of indefinite composition. It decomposes slowly at the ordinary temperature and more quickly when heated to phorphorus trichloride and a yellow to red solid of indefinite composition which is possibly a mixture of amorphous phosphorus with other chlorides. Attempts to prepare phosphorus dibromide in a similar manner and also by the action of hydrobromic acid on the dichloride were not successful. A yellow to red solid of indefinite composition mas obtained which in the light of the results obtained with the dichloride may have resulted from the decomposition of a dibromide.T. 5. P. Phosphorus Suboxide. ALFRED STOCK (Chem. Zeit. 1909 33 1354. Compare Burgess and Chapman Trans. 1901 79 1235).- Gutbier has stated (Sitxungsber. physik.-med. Soc Erlccngen 1909 40 176) that the existence of phosphorus suboxide (P,O) may be con- sidered as proved ,by the work of Weidner (Znaug. Diss. Erlangen 1909) who hsts repeated Michaelis and Pitsch’s experiments (Abstr. 1900 ii 137) and found in agreement with them that the substance in question does not contain hydrogen which is attached to phosphorus any hydrogen present being due to moisture.The author points out that Michaelis and Pitsch’s experiments are not conclusive and that Weidner has adduced no fresh experimental evidence in support of the existence of phosphorus suboxide. T. S. 9. Formula of Hypophosphoric Acid. I. and 11. E. CORNEC (Bull. SOC. chim. 1909 [iv] 5 1081-1084 1121-1126).-1n the first paper the author reviews the evidence so far brought forward in favour of the simple H,PO and double H4P,06 formulze for this acid. It is pointed out that the five sodium salts prepared by 8alzer (Abstr. 1886 420) can all be regarded as derived from an acid represented by the simple formula and that evidence furnished by (1) the decomposition of the salts by heat (Salzer and Joly) and (2) the electrical conductivity (Rosenheim Stadler and Jacobson Abstr.1906 ii 744 and by Parravano and Marini ibid. 744 848) is not conclusively in favour of either although the latter by analogy with the case of sodium pyrophosphate to a certain extent supports the double formula. Ebullioscopic determinatioiis of the molecular weight of the methyl ester are in favour of the simple formula (Rosenheim Stadler and Jacobson Zoc. cit.).ii. 122 ABSTRACTS OF CHEMICAL PAPERS. I n the second paper the author gives the results of measurements of the lowering of freezing point of solutions of hypophosphoric acid its potassium salts and of solutions of the acid progressively neutralised with potassium hydroxide sodium hydroxide or ammonia (Abstr.1909 ii 972). These all afford evidence in favour of the double formula H4P206 for this acid (compare Parravano and Marini Zoc. cit.). The only valid argument for the simple formula H,PO still remaining is drawn from the esters of this acid and these will now be further investigated. Extinction of Flames. WILLEM P. JORISSEN and N. H. SIEWERTSZ VAN REESEMA (Chern. Weekblad 1909 6 1053-1062).-An investiga- tion of the power of various gaseous mixtures to extinguish flame and a review of previous work on this subject. Inner Cone of the Bunsen Flame. FRITZ HABER and BURRITT S. LACY (Zeitsch. physikal. Chenz. 1909 68 726-’762).-The paper consists largely of a recapitulation and discussion of results already published by Haber’s students and others (compare Haber and Richardt Abstr.1904 ii 166; Davidson Abstr. 1906 ii 325 ; Tufts Physical Review 1906 22 193 ; Lacy Abstr. 190s’ ii 1033). The experiments of Davidson and of Tufts on the electrical con- ductivity of flames have been repeated by Lacy but are only briefly described as Epstein and Krasoa have since made extended observa- tions by an improved method; the results of which are shortly to be published. All the observations indicate that with a plentifuI supply of air the electrical conductivity of the inner green zone of the Bunsen flame is relatively high and much exceeds that in the neighbouring non- luminous regions. Further the velocity with which the water equiiibrium is established is much less outside than inside the luminous zone. Reasons are advanced in favour of the view t h a t these two phenomena are connected both being due to the influence of gas ions in the green luminous zone.I n this case the ions are produced as a consequence of the chemical changes taking place in the luminous zone. The effect of ionisation in accelerating the establishment of equilibria has already been investigated for the carbon monoxide flame by Haber and Coates (compare Abstr. 1909 ii 997). G. 8. LUDWIG WEISS and THEODOR ENGELHARDT (Zeitsch. anorg. Chem. 1909 65 38-104).-A review of previous work on the ill-characterised silicon nitrides is given. Pure silicon is best prepared by reducing potassium silicofluoride with massive aluminium a better regulus being obtained than when aluminium powder is used. The regulus is crushed and extracted successively with hydro- chloric concentrated sulphuric and hydrofluoric acids.The product even after repeated boiling in a state of fine powder with hydrofluoric acid contains 0-3-0*5:! Fe 0.1% Cu and 0.72% SiO,. It forms brown crystalline particles 13 2.30 and is not oxidised by oxygen at 700’. Heated in pure nitrogen in a porcelain tube combination begins near 1240” the velocity of reaction increasing rapidly with the tempera- T. A. H. A. J. W. Nitrogen Compounds of Silicon,INORGANIC CHEMISTRY. ii. 123 ture. The product is amorphous and bulky resembling cork and is seen under the microscope t o consist of several different substances. About 4% of the silicon volatilises and forms a sublimate. The composition of the residue varies with the means of purification adopted.If boiled with potassium hydroxide solution followed by hydrofluoric acid a product having the formula Si,N is obtained mixed with silica which it is impossible to remove. If the free silicon is removed by boiling with a mixture of nitric and hydrofluoric acids and the residue ignited and washed with hydrochloric acid the compound SiN is obtained. By heating silicon in nitrogen at 1300-1400" until saturated a nitride of the approximate formula Si,N is formed and is only slightly decomposed by treatment with potassium hydroxide and hydrofluoric acid or with a mixture of nitric and hydrofluoric acids. The nitride SIN is white and has D 3.17; the nitride Si,N has D 3.64 and the nitride Si,N D 3.44 after allowing for the silica present. All the compounds are more or less decomposed by alkalis and by hydrofluoric acid.Heating silicon in the flame of a coke fire gives a product containing carbon and nitrogen corresponding approximately with the formula Si,C,N. The estimation of nitrogen in the products is performed by heating with a mixture of equal parts of lead oxide lead chromate and lead peroxide in a porcelain tube in an atmosphere of carbon dioxide increasing the temperature from 600 t o 1000". Kjeldahl's method gives less than half the total nitrogen. Silicon is estimated by fusion with potassium and sodium carbonates as in the analysis of silicates. Commercial silicon is best analysed by fusion with potassium and sodium carbonates and potassium nitrate in a platinum crucible which is first coated with a lining of the salt mixture before introducing the silicon.Any csrborundum present is completely dissolved by these means. C. H. D. Action of Metals on Fused Sodium Hydroxide. I. MAX LE BLANC and L. BERGMANN (Bey. 1909 42 4728-4747).-The action of various metals on fused sodium hydroxide at temperatures ranging between 400' and '720" has been investigated all the experi- ments being carried out in an atmosphere of nitrogen. Preliminary experiments having shown that gold is the only metal which is no5 attacked by anhydrous fused sodium hydroxide the latter was always contained in a gold crucible which was placed at the bottom of a silver tube surrounded by a porcelain tube. This tube could be heated to any desired temperature by an appropriate furnace arrangement.Pure dry nitrogen was passed through the reaction tube and the extent of any reaction taking place was measured by determining the amount of water and hydrogen present in the issuing gas. Sodium hydroxide can be readily dehydrated at a temperature of 400° and undergoes no further loss in weight on heating to 720° so that a dissociation corresponding with the equation 2NaOH = Na,O + H,O does not take place between these temperatures. Silver and sodium react with fused sodium hydroxide underii. 124 ABSTRACTS OF CHEMICAL PAPERS. evolution of hydrogen ; platinum copper iron nickel aluminium zinc and magnesium enuse an evolution of hydrogen and a t the same time water is eliminated. The simplest explanation of this double reaction is that the compound M(ONa) which is formed according t o the equation M + xNaOH = M(ONa) + xH where M is a metal forms a more or less complex compound with Na20 resulting from the loss of water from two molecules of the sodium hydroxide.The valencies of the metals mere calculated from the amount of hydrogen evolved and found to be normal in the case of sodium magnesium copper iron aluminium and zinc. Silver nickel and platinum gave abnormal values as for example tervalent silvbr. When the gold crucible containing sodium hydroxide and copper turnings was heated a t 700° i t absorbed a not inconsiderable quantity of copper forming an alloy. This alloy is not formed at this tempera- ture i n the absence of sodium hydroxide. When silver was used in place of copper the silver became alloyed and at the same time the silver tube containing the gold crucible took up some of the gold.The latter phenomenon was also noticed with nickel but with none of the other metals. Magnesium also formed a gold-magnesium alloy. T. S. P. Alkali Hydrogen Garbonates. ROBERT DE FORCRAND (Compt. rend. 1909 149 825-829).-Hydrogen carbonates of the formula R,CO 2RHC03,xH20 such as natural trona have only occasionally been obtained in the laboratory. Dry potassium carbonate when left exposed to the air attains the composition K2C03,2KHC0,. When dilute solutions of potassium rubidium and czesium carbonates are exposed at room temperature for several weeks carbon dioxide is absorbed until the composition corresponds with the formule SK2C0,,2KHC0 ; 3Rb2C0,,2RbHC03 and 4Cs2C03,2CsHC0,.Although the amount of cdrbonic acid absorbed depends on the dilution temperature and pressure of carbon dioxide in the air the results are held to indicats the formation of definite compounds. When solutions of hydrogen carbonates are boiled for prolonged periods they are found to contain hydrogen carbonates of the same composition as the above but the crystals deposited on evaporation have the composition 5(K2C0,,1~H20),4KBC0 ; 3(hb2Co~,l~H20),2RbHC0 ; 5(Cs,C0,,3~H20),2CsHC0,. The last is converted on the water-bath into 5(Cs2C'0,,2H20),2CsHC0,. The heats of formation of these hydrogen carbonates are negative and small in value. R. J. C. Hydrates of Rubidium and Caesium Kydroxides. ROBERT DE FORCRAND (Conapt. rend. 19U9 149 13 41-1344. Compare Abstr.1906 ii 445).-When an aqueous solution of rubidium hydroxide is allowed to evaporate at 15O crystals of the hydrate RbOH,2H20 are deposited ; these have m. p. 45-46' and heat of solution - 0.646 Cal. at 15". The thermal properties of rubidium hydroxide and its hydrates are closely analogous with those of the corresponding potassium compounds.INORGANIC CHEMISTRY. ii. 125 The monohydrate of czesium hydroxide already studied (Zoc. cit.) is more stable than those of the rubidium and potassium hydroxides. Although thermochemical measurements indicate the probable exist- ence of a dihydrate this has not yet been isolated the crystals deposited when a solution of cssium hydroxide is allowed to evaporate being those of the monohydrate contaminated by mother liquor.A saturated solution of rubidium hydroxide a t 15' contains 64.17% of RbOH whilst a saturated solution of the czesium compound contains 79.41% of CaOH. w. 0. w. Acid Sulphates. V. JOH. D'ANs (Zeitsch. anorg. Chem. 1909 65 228-230. Compare Abstr. 1909 ii S85).-Determinations of the solubility of ammonium sulphate in mixtures of sulphuric acid and water at 25" indicate the separation of three solid phases ammonium sulphate and the acid salts (NH,),H(SO,) and NH,HSO,. The com- position of the second salt was confirmed by isolation and titration. Washing with alcohol or ether is impracticable on account of decom- position of the salt and mechanical separation of the acid must there- fore be employed. Unlike sodium and potassium sulphates the solubility of which increases with increasing sulphuric acid concentration that of ammonium sulphate falls to a minimum and then rises only very slightly to the limiting solution (NH4)&30 - (NH,),H(SO,),.The curve for (NH,),H(SO,) also has a minimum. C. H. D. Action of Heat and Light on Silver Sulphite and its Alkali Double Sulphites. Amount of Dithionate Obtained. HENRI BAUBIGNY (Compt. rend. 1909 149 858-860. Compare Abstr. 1909 ii 1004).-Analysis of the products obtained by decomposing silver sulphite under various conditions shows that as much as 89.84% may be converted into dithionate whilst the remainder is converted into sulphate. Sodium silver sulphite may give as much as 9'7.5% of sodium dithionate. Silver sulphite is perfectly stable in the dark but in diffused light it is slowly decomposed giving dithionate and a small proportion of sulphate.R. J. C. [Action of Heat on Sulphites.] HENRI BAUBIGNY (Compt. rend. 1909 149 1378).-Polemical against Colson (compare this vol. ii 34) pointing out that nowhere in the literature is there the statement ascribed by Colson to Berthier that the double sulphites of the alkali metals and of silver decompose with the formation of sulphate. Necessity f o r Exactness in Describing Reactions. T. S . P. New Preparation of the Second Anhydrous Modification of Calcium Sulphate. PAUL ROHLAND (Zeitsch. anorg. C'hem. 1909 65 10b-l07).-When either gypsum or the hemihydrate is dissolved in hot concentrated sulphuric acid an anhydrous salt separates on cooling which proves t o be the second anhydrous calcium sulphate known as Estrich gypsum.There are in addition to the naturally occurring anhydrite four anhydrous modifications of calcium sulphate.ii. 126 ABSTRACTS OF CHEMICAL PAPERS. (1) Kraut's anhydride obtained a t 100' ; (2) van't Hoff's anhydride also prepared at looo and hydrating very rapidly; (3) dead-burnt gypsum prepared above 130" incapable of hardening; (4) a modif~ca- tion prepared by heating above 530° or by the action of sulphuric acid hydrating very slowly. C. H. D. Decomposition of Calcium Carbonate. ERNST H. RIESENFELD (J. Chirn. phys. 1909 7 561-569).-New measurements of the dissociation pressure of calcium carbonate hare been made with the object of explaining the discrepant results obtained by Brill (compare Abstr. 1905. ii 522). 'l'he following values are recorded in mm.of mercury 700" 50 ; 750" 99 ; 800° 195 ; 850'' 370; 900° 700. These data are in good agreement with the thermodynamic equation of Nernst and by means of this equation the dissociation pressures are calculated for every 100' between 600' and 1500O. H. M. D. Solubility of Cadmium Sulphide in Light Petroleum Con- taining Oil. G. C. A. VAN DORP and J. RODENBURG (Chenz. Weekblad 1909 6 103S).-A colloidal solution of cadmium sulphide is obtained by triturating this substance with oil and adding light petroleum. A. J. qT. [Formation of Alloys by Pressure.] WALTHERE SPRING (Zeitsch. Elektrochem. 1909 15 984).-The author agrees with Tammann'a view (Abstr. 1909 ii 669) that the formation of alloys under pressure is a result of diffusion which is not accelerated by the pressure.T. E. Constitution and Heat Contents of Lead-Tin Alloys. W. GIJERTLER (Zeitsch. Blektrochern. 1909 15 953-965).-The recent investigations of Rosenhain and Tucker (Abstr. 19OS ii 1038) and of Degens (Abstr. 1909 ii 888) leave the question of the cause of the development of heat at about 150' undecided; it may be due to decomposition of mixed crystals of lead and tin (Guertler Abstr. 1909 ii 319) or t o the formation of a compound of about the composition Sn,Pb,. Using measurements of the quantity of lieat given out by mixtures of lead and tin in cooling from 380' to 100' made by Spring in lSS6 and the melting-point curve determined by Rosenhain and Tucker and Degens the author has calculated the heats of fusion of different alloys of tin and lead.The values obtained are very much larger than those calculated on the assumption that the heat of fusion of the alloy is the mean of the heats of fusion of its constituents This shows that liquid tin and lead must give out a considerable quantity of heat when they are mixed together. T. E. Peroxidiaed Compounds. LUIGI MARINO (Zeitsch. anorg. Chew&. 1909 65 25-31).-l'he isolation of a salt Pb,Se,07 (Abstr. 1909 ii 575) proved lead sesquioxide to be a true ieebly-basic oxide and not a salt of the dioxide. I n the attenupk to prepare other sesquioxides the liquid obtained by the addition of an acid solutionINORGANIC CHEMISTRY. ii. 127 of potassium permanganate to a mixture of hydrogen peroxide and sulphuric acid a t - 15' supposed by Berthelot to contain the compound H203 has been examined.The solution is capable of oxidising sulphurous acid completely to sulphuric acid. It is probable that the compound present is a higher acid of manganese as the curve connecting volume of oxygen evolved in the absence of sulphurous acid with time has exactly the same form as that obtained with a mixture of chromic acid and hydrogen peroxide in which perchromic acid is known to be present. It is shown that the oxidation of the sulphurous acid is not due to the action of free oxygen in supersaturated solution. Relation of Thallium to the Alkali Metals a Study of Thallium Zinc Sulphate and Selenate. ALFRED E. H. TUTTON (Proc. Roy. Xoc. 1910 83 A 211-226).-A detailed crystallc- graphic examination of the double salts TI,S0,,ZnS04,6H,0 and T1,Se0,,ZnSe04,6H,0 has been made.The various crystallographic data and the morphological angles are tabulated. The double sulphate was found to have D 3-7204 by the author's pyknometer method ; consistent results could not be obtained for the double selenate. From a comparison of the thallium salts with the corresponding potassium rubidium ammonium and czxium salts the author concludes that the morphological and physical properties of the crystals of the thallium double salts are such as quite entitle them to places in this isomorphous series but not to places in the more exclusive eutropic series obeying the law of progression according to the atomic weight oE the interchangeable metals. The position of thallium in either the simple or double salt series is very close to that of arrimonium and therefore also to that of rubidium. This does not hold however for the refractive power.I n respect of this property the thallium double salts are quite exceptional in that they exhibit abnormally high refraction and a larger amount of dispersion and of double refraction. The mean refractive index of thallium zinc sulphate for sodium light is 1.6064 whereas the values for the other four double sulphates range from 1.4859 to 1.5054. Acid Sulphates. VI. JOH. D'ANs and 0. FRITSCHE (Zeitsch. anorg. Chem. 1909 65 231-232. Compare this vol. ii l25).- Thallium sulphate and dilute sulphuric acid form two acid salts TI,H(SO,) and TlHSO the limits of existence of which at 25' have been determined.The curves differ from those of the alkali sulphates the solubility increasing almost continuously with the sulphuric acid concentration. C. H. D. The System Mercuric Chloride and Mercurous Chloride. W. P. A. JONKER (Chem. Weekblad 1909 6 1035-1038).-Mercuric chloride has m. p. 2 7 7 O and b. p. 301'. Addition of mercurous chloride lowers the rn. p. to the eutectic point 271'. A saturated solution of mercurous chloride in mercuric chloride contains 12% of the former and has b. p. 304O. Mercurous chloride sublimes at 373'. C. H. D. H. M. D. A. J. W.ii. 128 ABSTRACTS OF CHEMICAL PAPERS. Resolution of Ytterbium. CARL AUER VON WELSBACH (~Monatsh. 1909 30 695-700 + i-vi).-Polemical (compare Welsbach Abstr. 1908 ii .591). Disputes Urbain's claim of priority (compare Abstr.1907 ii 956; 1908 ii 849). W ITOLD BRONIEWSKI (Compt. rend. 1909 149 853-855. Compare Pushin Abstr. 1907 ii 774).-Determinations were made of the electrical conductivity temperature-coefficient of resistance solution potential and thermoelectric power of a complete series of alloys of copper and aluminium. Alloys containing more than 12% of either metal which are very brittle bad not been investigated previously. The electrical properties in question were often greatly modified by annealing but the inferences drawn from the curves of both tempered and annealed alloys are the same. The annealing was carried out in an electric furnace for four to five hours a t a temperature somewhat below the solidus of each alloy. The curves indicate the compounds Al,Cu AlCu Al,Cu AlCu,.The compound Al,Cu bas not been detected previously but the other three were found by Le Chatelier and by Guillet (Abstr. 1905 ii 712). Carpenter and Edwards (1907) found no evidence for the compound AlCu but on the other hand their compound AlCu could not be detected by the author. The compound AlCu is depolymerised above 500° when the larger crystals are split up into finely crystalline masses and the electrical resistance is doubled. Crystalline Structure of Iron at High Temperatures. WALTER ROSENHAIN and J. C. W. HUMFREY (PTOC. Boy. Soc. 1910 83 A 200-209).-The structural changes which accompany the deformation of iron at high temperatures have been investigated. The material employed for most of the experiments was a pure form of commercial iron of very low carbon content.To remove oxygen the metal was heated to about 900" in a current of pure dry hydrogen. A strip of this iron the surface of which had been polished previously was then placed in a specially designed piece of apparatus in which it could be electrically heated in a vacuum and subjected to stress whilst at a high temperature. By means of comparative observations on specimens which were heated without straining the changes in the structure which resulted from the rise of temperature could be distinguished from those which were a consequence of the applied stress. Under the conditions of the experiments the strips of metal were not uniformly heated and whereas the temperature of the central portion exceeded lOOO" the metal at and near the ends did not reach a visible red heat.Corresponding with the distribution of temperature the micro-structure exhibits three distinct regions when the strips are examined from the central portion towards either end. The structural differences lead to the conclusion that pure iron between the ordinary temperature and 1000" exists in three distinct modifications possessing widely different mechanical properties. The temperature ranges in which these modifications exist are consistent with E. F. A. Electrical Properties of Aluminium Copper Alloys. R. J. C.INORGANIC CHEMISTRY. ii. 129 the view that they are identical with the a- p- and y-forms of Osmond and Roberts-husten as indicated by cooling curves. The deformation observations also indicate that p-iron although existing at a higher temperature is harder and stronger than a-iron and that the reversible transformation of these forms is accompanied by a change of volume.The y-iron obtained in the case of approximately pure iron exhibits the structure and properties of the ‘‘ y-iron ” alloy steels. H. M. D. Passivity of Iron. P. KRASSA (Zeitsch. EZektvochem. 1909 15 981-984).-8 reply to Muller and Konigsberger (Abstr. 1909 ii 1016). The author maintains his former criticism (Abstr. 1909 ii 738) and insists further that the potentials of Miiller and Konigs- berger’s mirrors were SO abnormal that their behaviour cannot be regarded as proving anything about ordinary iron. T. E. Retardation of the Oxidation of Iron by Chromic Chloride. PAUL ROHLAND (Zeitsch. Elektrochem. 1905 15 865-866).-Chromic chloride retards the oxidation of iron ; an increase of the concentration of the hydrogen ions in the solution causes the protection t o disappear.The action persists in presence of chlorine ions and to a less extent in presence of bromine ions. Ferric chloride is however an exception ; possibly the hjdrogen ions formed by hydrolysis account for this. Chromic ions protect ironin presence of sulphates but not in presence of nitrates. T. E. Carbon Monoxide in Steels. E. GOUTAL (Compt. rend. 1909 ’ 149 1129-1 131)-The author has shown previously (Abstr. 1909’ ii 519) that when steels are dissolved in solutions of copper sabts’ gases are evolved which contain carbon dioxide and monoxide. The percentage of carbon monoxide mas estimated by making use of the oxidising action of iodine pentoxide at 75” and found to have a mean value of 0.014%.These results are now confirmed as follows. The evolved gases were swept by a current of nitrogen through a series of tubes each containing 25 C.C. of a 1% solution of defibrinated guinea- pig’s blood. Each tube could absorb a known quantity of carbon monoxide and by determining the number of tubes which showed the characteristic absorption spectrum of carbon monoxide-hsmoglobin t he percentage of carbon monoxide could be found. The percentages thus determined are independent o f (1) the amount of steeltaken; (2) the duration of the experiment; (3) the acidity of the copper solution used; (4) the substitution of cupric chloride by a solution of iodine in potassium iodide ; (5) the gas (air or nitrogen) employed for sweeping out the evolved gases.Analyses of different steels show that the percentage of carbon monoxide does not appreciably exceed 0.01 4. This percentage (0.014) remains approximately constant for ordinary steels containing more than 0.3% of carbon. Nickel steels contain a much less and chromium steels about the same percentage of carbon monoxide as ordinary steels of the same carbon content. Samples of steel mere taken from a Siemens Martin furnace oneii. 130 ABSTRACTS OF CHEMICAL PAPERS hour and then forty-five minutes before tapping and also just before and just after the addition of ferro-manganese. The percentage of carbon monoxide remains practically constant during the period of decarburisation ; it then falls considerably just before the addition of ferro-manganese t o rise to its final value after the ferro-manganese has been added.This is true for both soft and hard steels in which the percentages of carbon monoxide are respectively 0*0063 and 0.0137. T. S. P. Oxygen Evolved from Ferric Oxide at High Temperatures. SIEGFRIED HILPERT (Bey. 1909 42 4893-4895).-1n -contradistinc- tion to Walden (Abstr. 1908 ii S52) theauthor has not been able to determine the temperature at which the pressure of oxygen over ferric oxide is equal to that of the atmosphere. The results vary considerably with the method of preparation and previous treatment of the ferric oxide and the velocity with which equilibrium is attained is extremely slow. I n general the amount of ferrous oxide formed by heating ferric oxide in the air to 1300' did not exceed 5'; only above 1350' was there further loss of oxygen.In one experiment heating the ferric oxide to 1600' only increased the percentage of ferrous oxide from 2.95 to 3.1%. It is pointed out that thermodynamical calculations according to Nernst's theorem are totally untrustworthy when the dissociation of such substances as ferric oxide is taken as the basis. T. S. P. Phosphorus Compounds of Iron. N. S. KONSTANINOFF (J. Rzcss. Phys. Chem. Xoc. 1909 41 1220-1240).-The alloys of phosphorus aod iron were divided by Stead (J. Iron and Steel Inst. 1900 58 60) into five classes (I) those containing 0-1.7% of phosphorus and consisting of solid solutions of Fe,P in iron; (2) alloys with 1*7-10.2% of phosphorus which form solid solutions of Fe,P in iron and give a eutectic alloy (10.2% P) consisting of a definite solid solution and the phosphide Fe,P ; (3) those with 10.2-15.58% P also consisting of the eutectic and Fe,P the m.p. of the latter (15.58% P) being 1060'; (4) alloys containing 15.58-21*6% P and consisting of Fe,P and Fe,P ; ( 5 ) those with more than 21.6% P and containing Fe,P and another phosphide richer in phosphorus. These results were confirmed by Saklatwalla (J. Iron and Steel Inst. 1908 77 92-103) who gave a melting-point diagram for these alloys. The author's investigations of iron-phosphorus alloys containing up to 2100% (32.4 atom.%) of phosphorus show that the solidification- point diagram consists of three branches (1) AB falling from 1514O the m.p. of iron to 1020' corresponding with 10.2% F e ; (2) BC rising continuously from B t o C and corresponding with the separa- tion of crystals of the phosphide Fe,P. The separate solidification curves exhibit two halts one showing a regular rise corresponding with the separation of crystals of the phosphide and the other at a constant temperature corresponding with separation of the eutectic and gradually diminishing in magnitude as C is approached. Micrographic examination of these alloys shows the presence of rhomboidal plates of Fe,P surrounded by the eutectic ; (3) CD rising at first rapidly andINORGANIC CHEMISTRY. ii. 131 afterwards more slowly to the point D corresponding with the phosphide Fe,P (compare Gercke Abstr. 1908 ii 1041 ; Le Chatelier and Wologdine Abstr.1909 ii 1017). A list is given of the known phosphides arsenides and antimonides of the metals of the iron series of the eighth group in the periodic system. With the typical metals of this series iron cobalt and nickel these compounds are more varied in type than with the initial members manganese and copper. With the metals of the other groups of the periodic system these compounds are in the great majority of cases derived from the hydrogen phosphides PH and PH,. With phosphorus the most stable compounds are those rich in metal such as M,P,. whilst with arsenic and especially with antimony compounds relatively poor in metal such as MSb are the most stable. T. H. P. Iron Phosphides. OTTO KUHN (Chem. Zeit. 1910 34 45-46).-Le Chatelier and Wologdine (Abstr. 1909 ii 1017) state that there are only four iron phosphides namely Fe,P Fe,P FeP and Fe2P3 and further that the existence of the last two has not been proved with absolute certainty. I n the course of an investigation on the preparation of copper phosphide by heating a mixture of bone ash powdered quartz wood-charcoal and granulated copper the author obtained a product which on solution in nitric acid left a small residue of glistening needles which were practically insoluble in hot or cold concentrated nitric acid or in dilute sulphuric acid although readily soluble in aqua regia. The results of analysis agree approximately with the formula Fe5P2 the iron coming from the impure quartz used in the preparation. These needles cannot be con- sidered as a solid solution of Fe,P and Fe,P since the former com- pound is readily soluble in nitric acid.Electromotive Forces of Cobalt Alloys. F. DUCELLIEZ (Compt. rend. 1910 150 98-101. Compare Pushin Abstr. 1907 ii 325 618 774 S37).-From the curves showing the relation between the composition of the alloy and the potential with respect to a normal solution of cobalt sulphate the existence of the following compounds has been deduced CoSn CoSb CoSb,. Alloys of cobalt and bismuth form two phases the one rich in cobalt and the other and heavier rich in bismuth. Bismuth lowers the melting point of the cobalt which when liquid is capable of dissolving some bismuth. From liquid alloys containing 0-94 (approx.) % Bi the cobalt separates in a pure state on cooling.The results obtained with lead and cobalt are similar to those with bismuth and cobalt. Cobalt and copper do not form compounds with each other but give either homogeneous solid solutions or two phase systems of solid solutions. T. s. P. T. S. P. Absorption of Carbon by Metals Especially Nickel in the Electrolysis of Aqueous Solutions. GUSTAV LAMBRIS (Zeitmh. Elektrochem. 1909 15 973-981).-The nickel which is deposited from a solution containing ammonium oxalate contains up to 4% of carbon; the smaller the quantity of nickel deposited and the largerii. 132 ABSTRACTS OF CHEMICAL PAPERS. the quantity of ammonium oxalate used the greater is the quantity of carbon *in the deposit. The carbonaceous residue obtained by dissolving the nickel by copper chloride and chlorine contained ammonium chloride which could not be completely removed.The percentage of carbon in the residue increased as greater precautions were taken to free it from ammonium salts. The ammonium salts of glgcollic formic and acetic acids also yield nickel containing carbon but if a diaphragm is interposed between the anode and cathode carbon-free nickel is obtained if the cathode solution contains free ammonia but not if it is kept slightly acid. Carbon dioxide also gives carbonaceous nickel (from nickel ammonium sulphate solution) but in presence of a little free ammonia carbon-free metal is obtained. Since the metal obtained from ammonium oxalate solution contains carbon even in presence of a large excess of free ammonia the anodic carbon dioxide cannot be the source of the carbon.The same applies to carbon monoxide which behaves in the same way as carbon diqxide. Methane ethane and ethylene give carbon-free nickel but acetylene passed into the cathode solution gives carbonaceous nickel both i n neutral and strongly ammoniacal solutions. It is shown that acetylene is formed in small quantities a t the cathode when ammonium oxalate is electrolysed with platinum and nickel cathodes but not with iron copper or t i n ; some ethane is also formed by further reduction of the acetylene. The carbon is contained in the nickel in the form of a carbide ; when the metal is dissolved in hydrochloric acid the whole of the carbon is evolved in the form of hydrocarbons. Iron at which no acetylene is formed is deposited from ammonium oxalate solutions quite free from carbon.It appears therefore quite clear that the carbon is contained in the nickel as carbide formed from acetylene during the deposition of the nickel. Alloys of Nickel and Copper. EMILE VIGOUROUX (Compt. rend. 1909 149 1378-1380. Compare Kurnakoff Abstr. 1907 ii 525 ; Guertler Abstr. 19013 ii 557).-From an examination of the action of acids on alloys of copper and nickel and by determinations of the X.M.F. produced in cells when one of the metals constitutes one of the electrodes and an alloy of the two the second electrode the author is led to the conclusion that no definite compounds of nickel and copper exist. w. 0. w. T E. Two New Nickel Phosphides. PIERRE JOLIBOIS (Compt. rend. 1910 150 106-108).-Twenty-one grams of an alloy of tin and nickel containing 5% of nickel were heated with 1-4 grams of phosphorus in a vacuous sealed tubo to 700'.On cooling and dissolving the lower part of the ingot obtained in warm concentrated hydrochloric acid small prismatic crystals OE metallic appearance were left having a composition corresponding with the formula Nip and DlS = 4.62. They are soluble in nitric acid decomposed by fused sodium hydroxide and lose their phosphorus at 650'. I f the proportion of phosphorus in the reaction mixture is increased to 7-10 grams hydrochloric acid leaves a mixture of tin phosphideINORGANIC CHEMISTRY. ii. 133 (SnP3) with another nickel phosphide having the formula Nip,. These are separated by heating the mixture in a vacuum t o 360" whereby the compound SnP loses phosphorus giving the compotlnd Sn,P (compare Abstr.1909 ii 319) which is then readily soluble in hydrochloric acid. This second phosphide of nickel forms microscopic crystals of metallic appearance which are readily soluble in nitric acid and is decomposed with incandescence by fused sodium hydroxide ; t h e phosphorus is lost at 580" ; DlS = 4.19. T. S. P. Mixed Halogen Compounds of Tin. VICTOR AUGER (Compt. rend. 1909 149 860-862).-Numerous compounds of the types SoCI,Br SoC12BrzI SnClBr have been described all of which are said to decompose on distillation into the simple stannic salts SnX SnY,. The author shows that mixtures of SnEr and SnI give a normal f reezing-point curve with a eutectic at the composition SnBr3.21,,.8.The supposed compound SnEr2T2 melting at 54' is identical with a n equimolecular mixture of SnBr4 and SnI and may be separated by a series of ten fractional crystallisations into fractions melting a t S8O and 2 7 O of compositions SnBr,.212.s and SnBr2.?11. respectively. Similarly the supposed compounds SnBrI (m. p. 103') and SnBr,I may be partly resolved by crystallisation. The cooling curve of SnBr21 from 5 5 O is an unbroken line such as is given by a mixture although the crystals are brilliant and apparently homogeneous. The author suggests that in all molten mixtures of the composition SnBr,T(,-, the halogen atoms are perfectly mobile. The same is suggested for t h e chlorobromides and iodochlorides. R. J. C. Natural Zirconium Dioxide. LUDWIG WEISS [and in part RICHARD LEHMANN] (Zeitsch.anorg. Chem. 1909 65 178-227).- Native zirconium dioxide baddeleyite instead of being isomorphous wit ti rutile and cassiterite is monoclinic. If artificially crpstallised from borax however it is quadratic and isomorphous with rutile. Several hundred kilograms of the native mineral from Brazil have been used for the investigation. It contains SS-O9% ZrO 7.39% SiO 0.74% TiO and 3.78% Fe,O,. About one-half of che impurities q a y be removed by boiling with hydrochloric acid and rather more by heating with sodium sixlphate salt and carbon. Pure zirconia is obtained by heating the mineral with potassium hydrogen fluoride and crystallising the double fluoride. For analysis the mineral is fused with sodium hydrogen sulphnte. Iron is separated with aluminium if present in small quantity by precipitation with ammonium sulphide from a hot solution containing ammonium oxalate and tartrate.After removal of organic salts from the filtrate the zirconium hydroxide is precipitated with sodium hydroxide and hydrogen peroxide titanium being left in solution. The following analyses represent dense fragments ZrO,. Fe,O,. Al,O,. TiO,. SiO,. H,O. Total. I. 92.07 2-73 1-17 trace 2'73 0.88 99'58 11. 84'96 7.01 3 '99 trace 1'57 1'04 98-57 VOL. XCVIII. ii. 10Ti. 134 ABSTRACTS OF CHEMICAL PAPERS. Pure zii-conia is obtained by a long process which is desokibed in detail. Repeated fractionation does not produce any indication of a separation of the zirconium into two constituents. 8mall qnan tities of rare earths have been recognised spectroscopically but scandium is present only in faint traces.The specific gravity varies even of pure samples and is apparently dependent on the extent of the previous heating. After compressing to form rods under a pressure of 8000 kilograms per sq. cm. it may be fused by a powerful arc using 500 amperes’or more and then has D1* 50 5.48. The linear coefficient of expansion is a = 0*00000084 very near to that of fused quartz. Crucibles etc. may be made by mixing the zirconia with 10% of magnesia or clay. Platinum may be rendered completely liquid by heating in a zirconia crucible with an oxy-hydrogen flame. Quartz may also be melted without destruction of the crucible. Other technical applications are described. C. H. D. Thorium.H VON WARTENBERG (Zeitsch. Elektrochem. 1909 15 866-872).-Thorium is prepared by electrolysis of thorium chloride dissolved in a mixture of fused potassium and sodium chlorides (Abstr. 1906 ii 678). The action of the electrolyte on the porcelain crucible is avoided to a great extent by using a graphite crucible which fits closely into the porcelain crucible both as anode and as containing vessel for the fused salts. The cathode is a graphite rod and the electrolysis is carried out as rapidly as possible in an atmosphere of nitrogen. The metal is obtained in the form of crystals mixed with carbon from which it is separated by means of methylene iodide. Careful analyses gave 87+6 to 88.9% thorium 0.06% iron 0004% sodium 0.03% silicon and 0.15% carbon (mechanically admixed).The remainder mas oxide. Microscopic examination showed this to be mixed with the metal; it is left in the form of a felted mass when the metal is dissplved in acid Experiments with mixtures of lead and thallium with their oxides show that mechanically-admixed oxides do not affect the ductility of these soft metals very seriously so that the ductility of thorium cannot be used as an argument in favour of its purity (Abstr. 1909 ii 53). The heats of formation of thorium oxide and chloride were determined and corrected for the impurities present Th + 0 =Tho + 326.0 f 0.5% Gal. Th + 2C1 = ThCl + 300.2 & 0.67% Gal. The results are given in kilogram calories. The metal melted at 1700° but the carbon in it combined with it forming about 2% of carbide which would lower the melting point very considerably.Thorium sulphide has been prepared and its formula is shown t o be ThS,. T. E. The Atomic Weight of Vanadium. WILHELM PBANDTL and BENNO BLEYER (Zeitsch. anorg. Chem 1909 65 152-165)- Vanadium oxy-trichloride VOCl is the only vanadium compound capable of being obtained in a state of sufficient purity for atomic weight determinations. Ammonium metavanadate is three times precipitated from its boiling solution with ammonium chloride ignited,MINERALOGICAL CHEMISTRY. ii. 135 heated with hydrofluoric acid and then mixed with carbon and ignited first in a current of hydrogen and then in one of chlorine. The product is fractionally distilled and then has b. p. 124*4O/723 mm. (corr.). When no longer changed by further fractionation it has D:5'5 1.8362.The liquid is distilled into glass bulbs and weighed ; the bulbs are broken in glass flasks containing water and zinc. After acidifying with nitric acid and filtering the chlorine is precipitated with silver nitrate. The mean result of nine determinations obtained is V = 51.0 (Ag = 107.880 ; C1= 35*460) which is lower than the previously accepted value 5!*2. The difference is explained by a criticism of Roscoe's method C. H. D. Solution of Platinum in Sulphuric Acid and the Producta of Reaction. MARCEL DEL~PINE (Compt. rend. 1910,150,104-106).- Quennessen (Abstr. 1906 ii 551) has attributed the solvent action of sulphuric acid on platinum to the intermediate action of oxygen of the air. The author shows that all Quennessen's results can be explained by assuming that the reaction as represented by the equation 2Pt + 7H,S04 20H*Pt(S04H) + 380 + 4H,O is reversible. Sulphuric acid and spongy platinum were boiled up together in a flask whilevarious gases were passed through the liquid. With carbon dioxide the reaction proceeded according to the above equation. When air was used twice as much platinum dissolved and less sulphur dioxide was evolved owing to the oxidation of the sulphur dioxide to trioxide under the influence of the platinum. With oxygen four times as much platinum dissolved and less still sulphur dioxide was evolved. When a mixture of carbon and sulphur dioxides was used no solution of platinum took place and in some cases platinum was precipitated from solution. The compound of platinum mentioned above can be isolated in the form of the potassium salt OH*Pt(SO,H)*SO,K by adding a dilute solution of a potassium salt to the orange-yellow liquid. If the platinum is boiled with sulphnrio acid for a long time the liquid becomes darker and darker in colour finally almost black and after thirty hours may contain more than 20 grams of platinum per litre From this solution a brown compound can be obtained having the formula Pt(OH),*S04H,H,0 and crystallising in rectangular prisms which are very soluble in water concentrated sulphuric acid alcohol and acetone. The compounds can also be obtained by the oxidation of platinum dioxide with nitric acid. The vnpour density proves it to be undecomposed. At 100" it loses 1*5H,O. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805117

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Min era 1 ogi c a1 C h e mi s t ryl ii. 135 Volcanic Gases. ALBERT BRUN (Bec22. Soc. china. 1910 [iv] 7,4). -It is Dointied out that tbe use of the word ‘‘ fumarole ” in Gautier’s re-stateLent (Bull. Xoc. cfiinz. 1909 [iv] 5 982; compare Abstr. 10-2ii. 136 ABSTRACTS OF CHEMICAL PAPERS. 1909 ii 744 745) of the author's argument in favour of the view that aqueous vapour is of little importance in volcanic explosions (Abstr. 1907 ii 33) is confusing. T. A. H. Gas from Thermal Springs Presence of Krypton and Xenon. CHARLES MOUREU and A. LEPAPE (Compt. Tend. 1909 149 1171-1 174).-The authors have recognised the presence of krypton and xenon in twenty-six Prench thermal springs. The fact was established t h a t the gases did not come from the atmosphere in the w.0. w. Dawsonite a Sodium-Aluminium Carbonate. RICHARD P. D. GRAHAM (Trans. Boy. Soc. Canada [iii] 2 iv 165-177).-This mineral is found in two dykes in Montreal a t Thee Algeria and in Tuscany. Terminated crystals are very rare but the author found a few beloDging to the orthorhombic holosymmetric class [a b c = 0.6475 1 053391. Some very pure crystals on analysis gave vicinity of the springs. The optical properties mere studied. A1,0,. Na,O. CaO. MgO. co,. H,O. 35-70 21'62 1'59 trace 31-56 11.51 agreeing with the formula Al,P3,Na20,2C0,,2EI,0. A small amount of calcium was present as admixed calcite. Neither water nor carbon dioxide is lost at 140' ; long heating at high temperature is necessary to expel these constituents completely. Two constitutional formul~ are suggested ONa*Al(OH)*O*C!O*OH and Al(OH),*G*CO*ONa the first of which is considered the more probable.Chemical Investigation of a Uranium Mineral from Borneo. G. P. TSCHERNIK (Bull. Acad. Sci. Xi?. PGtersbourg 1909 [vi] 3 1203-1212).-This mineral occurs in well-formed iron-black crystals D16 9.057 hardness 5-6 exhibiting marked radioactive properties. The analytical results of two different specimens are as follows SiO,. UO,. UO,. PbO. Tho,. Y,O etc. CaO. FeO. 0.77 40.95 4124 8'51 5'03 1.56 0.18 0'91 0-76 40*58 41 15 8'49 5.00 1.57 0'18 0.90 trace trace - 0-52 99.67 9-059 - trace trace 0.52 99'45 9.056 These numbers show that the mineral consists of broggerite the corresponding formula being 4Si02,45U03,48U0 1 2Pb0,6Th0,,SY,03,C~0,4Fe0,9H,0.E. J. R. Bi,O,. MgO. Cud. H,O. Total. D'6. Further analysis of the rare earth constituent shows that it contains ytterhia and ceria in the proportion Y20 Ce,03 = 5 1 the cerin fraction containing oxides of cerium lanthanum neodymium and praseodymium in the proportioris Ce,03 La203 Nd,O Pr,O = 8 5 1 2. T. H. P. Isomerism in the Group of Alumino- and Ferri-silicates. WLADIMIR I. VERNADSKY (Bull. Acad. Sci. St. PZtersbourg 1909 [vi] 3 118~-1~02).-1n addition to alumino-(or ferri-)silicates having thePHYSIOLOGICAL CHEMISTRY. ii. 137 Rtructure of kaolinite (derivatives of clay) chloritoids (derivatives of M,AI,Si06) and chlorites [derivatives of A12Si2+m08+2m-fi( OH)2n or A1,Si0,,(OH)2,) a group of alumino-silicates is possibly derived from orthosilicates and having the general formula (M,SiO,),,qA where A =MA1,Si,08 (or MFe2Si20,) or MAl,SiO,. To this group belong (1) melilite (Ca,Si04)p,qCaA12Si,0s where p = 3.5 and q = 1.2 ; (2) gehlenite Ca,Si0,CaAl,Si06 and (3) ilvaite H,O - (Fe2Si0,)p - CaFe2Si20 where p = 2. In their properties these compounds differ from the compounds MAl,Si208 and approximate to the minerals M2Si0,. This series of silicates is analogous to the kaolinite series and to the granites isomeric with them. Isomerism in the kaolinite series is of three kinds (1) symmetry isomerism ; (2) transposition isomerism an example of which is shown by the granite CttA12Si20,(nucleus),Ca2Si04 and the member of the melilite series Ca2Si0,(nucleus),CtrAl2Si20 ; (3) isomerism of rearrange- ment as seen in lawsonite CaA12Si20 2H20 and Gibbsite H,A1,Si20,,Ca0,H20. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805135

出版商:RSC    

年代:1910

数据来源: RSC