INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 27 Chlorous Acid and Chlorites. G. BRUNI and G I,E;VI (Gctxicttcr 1915 45 ii 161-179).-The authors have prepared various clilorites and investigated certain of their physical properties. The analogy between chlorites and nitrites is shown by the methods of preparation and by the existence of the compounds AgClO,,NH AgC10,,2NH3 and AgC102,3NH3 which are similar to those formed from silver nitrite and ammonia. Barium chlorite may be obtained absolutely free from chloride by the action of a mixture of chlorine dioxide and carbon dioxide free from chlorine on barium peroxide suspended in hydrogen peroxide solution. The sodium salt may be obtained from barium chlorite and sodium sulphate the liquid being evaporated in a vacuum a t the ordinary temperature ; the ammonium and hydroxyl- amine salts are not obtainable in this way.The basic mercuric chlorite 3Hg(C102),,Hg0 ( ?) obtained from barium or potassium chlorite and mercuric nitrate forms a bright red crystalline pre- cipitate and explodes when dried ; the yellow mercurous salt reddens in the air and decomposes spontaneously on drying. A number of the known reactions for soluble chlorites have been confirmed and the following new o n a added. No precipitate with mercuric chIoride ; red precipitate with mercuric nitrate in neutral and not too dilute solution; with mercurous nitrate a yellow pre- cipitat’e becoming white with excess of the reagent ; with neutraI ferrous sulphate solution a brownish-yellow coloration and in the hot an ochre-yellow deposit and liberation of chlorous vapours ; oxidation of potassium ferrocyanide t o ferricyanide in acid solution ; brucine and diphenylamine show the same behaviour with chlorites as with chlorates ; with reagents for nit’rous acid chlorites slowly give colorations analogous t o those given by nitrites prob- ably owing t o the oxidising action exerted.With concentrated sulphuric acid solid chlorites deflagrate more energetically than the chlorates. Electrical conductivity measurements of potassium silver and barium chlorites give for the mobilitlv of the ion C10,’ a t 2 5 O the values 50*6-51.7 the mean being 51.0 which is less than that for the ion C10,’ and less still than that for C10,’. Similar measurements with sodium potassium and silver nitrites give the mean value 75.4 f o r the mobility of the ion NO,’ a t 25O this being greatelr than that for the ion NO,’.Cryoscopic investigation of potassium chlorite in aqueous solutioas gives the respective values 0.930 0.920 0.935 and 0.959 f o r a with solutions containing 1.0656 grams of the salt in 10 15 20 or 40 grams of water. The decomposition of barium chlorite was studied in the bomb calorimeter and found to take place according to the equation Ba(ClO,),=BaCl + 20,+ 48.6 Cal. From this follows the equa- tIons Ba -I- C3 + 20 =Ba(ClO,),(soIid) + 148.4 Cal. and BaClz +ii. 28 ABSTRACTS OF CHEMICAL PAPERS. 2O,= Ba(C10,) - 48.6 Cal. Ba(ClO,) + 02=Ba(C103) 4 22.8 Cal. and Ba(C10& + 0 = Ba(C10,) + 30.2 Cal. Consequently in com- pounds containing chlorine in different degrees of oxidation the formation is the less endothermic or the more exothermic the higher the degree of oxidation.This apparently paradoxical intro- duction of successive atoms of oxygen with continually increasing energy is in agreement with Angeli’s observations on oxygenated nitrogen compounds (Rend. Accnd. Lincei 1894 [v] 3 i 510). T H. P. Rhythmic Cry stallisation of Sulphur. FRITZ KOHLER (Kolloid Zeitsch. 191 5 17 10-1 I).-Micro-structures of rhythmic character are formed when thin layers of liquid sulphur are allowed t o crystaJlise. These are illustrated by photographs. The author does not agree with the explanation given f o r the formation of these structures by von Fischer-Treuenfeld (A. 1915 ii 553). I n his opinion the rhythmic character of the crystallisation process is due to the rate of crystallisation exceeding the rate of diffusion. This is consistent with the fact that the phenomenon is readily shown in the crystallisation of viscous liquids.H. M. D. Internal Temperature of Sulphur Furnaces. STEFANO PBGLIANI (Ann. chi??^. Applicata 191 5 4 268-270).-Reply to criticism appearing in L’Inrlitstriu (1915 No. 42 Milan) on the author’s work (A. 1915 ii 766). Preparation of Thionyl Chloride and Sulphur Tetrachloride. CHEMISCHE FABRIK BUCKAIJ (D R.-P. 284935 ; froni J Soc. Clzem. Id. 1915 34 1092).-Carbonyl chloride! reacts with sulphur dioxide a t temperatures above ZOOo with the formation of thionyl chloride and sulphur tetrachloride acccrding to the equations SO + COC1 = SOCI + CO and SO + 2COC1,= SCl + 2C0,.The first reaction predominates a t lower temperatlures and with excess of sulphur dioxide and by suitable adjustment of conditions one o r other of the reactions may be almost entirely excluded. The reactions are carried out by passing the gasea over a heated contact substance such as wood charcoal and the carbonyl chloride may bO partly or entirely replaced by a mixture of carbon monoxide and chlorine o r carbon monoxide and sulphuryl chloride may be employed. G. F. M. H. B. NORTH and C. B. CONOVER ( J . Anzw. Chenz. Soc. 1915 37 2486-2490).-The action of thionyl chloride on the sulphides of zinc cadmium silver arsenic antimony iron copper tin (stannic) and mercury has been studied. It is shown that a reaction occurs when the two substames are heated in a sealed tube a t 150-200° for several days.I n general the reaction may be represented by the equation MS + 2SOC1 =MCl -+ SO + S,Cl,. The case of ferrous sulphide presents a slight difference f o r here an oxidation occurs and ferric chloride is formed according t o the equation 6FeS + 16SOCl,= 6FeCls + $SO + 7$2c&. T. H. P. Action of Thionyl Chloride on Sulphides. J. F. S.lNORGANIC CHEMISTRY. ii. 29 Vapour-pressure Investigations of the Fusion Products of Iodine with Sulphur Silenium and Tellurium. ROBERT WRIGHT (T. 1915 107 1527-1531).-A simple method is described f o r the measurement of the pressure of tile iodine vapour in equilibrium with the solid products which result from the fusion of iodine with sulphur selenium and tellurium.Products which contain a large excess of iodine have in all three cases the same vapoar pressure as pure iodine a t the same temperature. With excess of sulphur and selenium the same result was obtained but with excess of tellurium the iodine vapour pressure is very small up t o 1 5 0 O . The results show that in no case are solid solut.ions formed that sulphur and selenium do not combine with iodine on fusion but that tellurium forms a compound TeI,. H. M. D. Metallographic Study of the System Tellurium-Selenium YASUKIYO KIMATA (Mew. CoZZ. Sci. Kyoto 1916 1 119-121).- Tellurium and selenium form two series of solid solutions. These meet a t 95% Se and 130° a t which temperature the liquid and solid phases have the same composition. The two branches of the liquidus and solidus curves intersect a t a sharp angle suggesting a eutectic but all the alloys are microscopically homogeneous.Whether a compound is fosmed a t this point is undetermined. C. H. D. The Imide Character of Hydronicric Acid (Azoimide). I. Synthesis of Lizidoaithiocarbooic Acid. FRITZ SOAIMER (Ber. 1915 48 1833-1841).-1n accordance with its usual formulation as an imino-compound azoimide behaves in the same manner as a secondary amine towards carbon disulphide; analogous t o the formation of the compound NE&*CS*SH,NHEt from diethylamine and carbon disulphide sodium azoimide and carbon disulphide react with formation of the sodium salt of azidodithio- carbonic acid N,*CS*SNa. Sodium azidoclithiocarbonate N,*CS2Na,4H,0 is obtained by the interaction of carbon disulphide and an aqueous solution of sodium azoiinide a t 40-50° a pale yellow solution being obtained which yields colourless prisms on evaporation; the salt is fairly pernian- ent if kept below loo in a closed vessel.It explodes when heated being more explosive in the anhydrous condition. The corresponding potassium salt obtained in a similar manner is a crystalline solid which explodes violently when pressed. The barium salt was also prepared forming hexagonal tablets (N3CS,),Ba,513,0 which were comparable with the sodium salt in explosive nature the anhydrous ,salt being somewhat more explosive. Salts of certain of the heavy metals were prepared by precipita- tion from solutions of the sodium salt. The fact that the colour of the products in some cases deviated from the usual colour of the salts of the metal and their occasional solubility in organic solvents indicate t h a t in common with the xanthic acids azidodithio- carbonic acid bends to form complex salts of abnormal dissocia-ii.30 ABSTRACTS OF CHEMICAL PAPERS. tion. Most of these salts of the heavy metals were exceedingly explosive. SZZ u e ~ salt amorphous; cupric salt yellow ; mercuric salt colourless crystals soh ble in ether carbon disulphide and ethyl acetate ; mercurous salt colourless ; lead salt yellowish-white ; tlwdlium salt yellowish-white ; cadmium salt colourless needles ; bismuth salt yellow ; zinc salt colourless. The addition of ferric chloride to the solution of the sodium salt instead of effecting the precipitlation of the ferric salt of the acid caused oxidation to the disulphide S2(CS*N& which separated in needles; a similar result was obtained with other oxidising agents.This compound is so explosive that even on warming in aqueous suspension a violent explosion may ensue. By treating the concentrated solution of sodium azidodithio- carbonate with hydrochloric acid i t is possible to obtain free azido- dithiocarbonic a c i d ; this by oxidation can be converted into the corresponding disulphide. Details of these compounds will be published later. D. F. T. Explosive Mixture of Phosphorus and Liquid Air. ARNALDO PIUTTI (Atti. R. Accad. Lincei 1915 [v] 24 ii 25%-2.53).-Yellow phosphorus does not comb'ine with liquid oxygen but after removal from the liquid explodes with extreme violence if struck t'ouched with hot iron or subjected t o the action of an electric spark.This property is conferred on the phosphorus only by actual contact with the liquid oxygen. With highly compressed red phosphorus o r with ordinary sulphur no explosion occurs under the above condi- tions but the substance burns vigorously. T. H. P. Fibrox. E. WEINTRAUB (Trans. Amer. Electrocliem. SOC. 1915 27 267-284).-When silicon is heated in a graphite crucible a t 1400-1500° in a gas furnace a small quantity of calcium fluoride being present the crucible becomes filled in a few hours with a fibrous mass of silicon oxycarbide. After breaking away the slag and re-heating a further quantity may be obtained. This material known as fibrox is made up of very fine amorphous threads some- times carrying minute beads of vitreous silica.It is formed by reactions in the s t a b of vapour and experimelnts in an electric furnace show that the presence of carbon dioxide is necessary. The density varies from 1-84 t o 2.2 increasing with the percentage of silicon. The apparent density of the fibrous mass is only 0*0025-0.0030 or 2.5-3-0 grams per litre. Ths thermal resist- ance in the loosely packed condition is very high but diminishes with rising temperature. C. H. D. The Temperature of Reaction between Acheson Graphite and Magnesia. 0. L. KOWALKE and D. S. GRENFELL (Trans. Amer. Electrochem. Soc. 1915 27 221-239. Compare Slade T. 1908 93 327; Lebesu A. 1907 ii 460).-When electrically fused mag- nesium oxide is powdered and heated in a granular carbon resist- ance furnace in contact with graphite the temperat8ure being measured by an optical pyrometar sighted on a hollow graphiteINORGANIC CHEMISTRY. ii.31 ‘‘ black-body,” the reaction MgO + C = Mg + CO begins slowly a t 1950° and becomes very violent a t 2030O. This temperature is sufficiently constant to serve as a fixed point for the calibration of optical pyrometers. When a vacuum furnace is used observa- tions are difficult on account of the fumes produced in the reaction. L. BALBIANO (AWL. Chim. Applicatn 1915 4 231-245) .-Investigation of preparations of graphitic acid and graphitic oxide obtained from three different samples of graphite shows that the compositions of these products vary with the method of preparation and with the quality of the graphite employed.Brodie’s method (Phil. Trans. 1859 149 249) gives a graphitic acid which contains C = 57.35 H = 1-47 and 0 = 41.17 these figures corresponding with the formula C13H407; for the product obtained by Sbaudenmaier’s method (A. 1898 ii 472 ; 1899 ii 481) the composition is C=59.2 H=1*4 and 0=39.4 and the formula CI4H40,. With graphitic oxide the analytical numbers also correspond with the1 formula C,,H40 o r C14H407. Them graphitic products which deflagrate when rapidly heated and vary in colour with the nature of the original graphite and t’he method of preparation are found however to be merely adsorption products of graphite water carbon monoxide and dioxide varying in composition between narrow limits. They have no acidic o r quinonic functions and it is suggested that they be termed yellow green or black hydrocarboxygraphites instead of graphitic acid and oxide.The System Sodium Sulphate-Sodium Chromate-Water. ISAKICHI TAKEUCHI (Mem. CoZZ. Scz. Kyoto 1915 1 249-255).-The equilibrium of this system has been determined a t 1 5 O and 25O. The decahydrates of sodium sulphate and chromate are miscible in all proportions at 15O. A t 25O the solubility curve consists of three branches corresponding with decahydrate solid solution from 0 to 34 mol.% of chromate anhydrous sulphate and sodium chromate hexahydrate respectively. The limit of miscibility of the decahydrate crystals coincides approximately with but the existence of a double salt has not been definitely proved. C. H. D. C. H. D.Graphitic Acid. T. H. P. 2Na2S0,,Na2Cr 0,,30H20 Allotropy of the Ammonium Haloids. I. F. E. C. XCHEFFER (Proc. K. Akad. Wetensch. Amsterdam 1915 18 446--458).- According t o Wallace (A. 1910 ii 208) ammonium chloride and ammonium bromide are enantiotropic having transition tempera- tures a t 159O and 109O respectively. Further experiments with ammonium chloride have shown that the cooling-curve method which was used in the determinations referred to gives a much lower temperature than the true transition temperature in conse- quence of the retarded transformation. I n presence of glycerol o r mannitol which act as catalysts the thermal method yields much better results in that the temperatures indicated by cooling andii. 32 ABSTRACTS OF CHEMICAL PAPERS. heating curves are in fairly close agreement.The value thus obtained f o r the transition t’emperature is 184.5O. The same result has been arrived a t on the basis of measurements of the solubility of ammonium chloride in water between 160° and 205O. If x represents the number of mols. of salt in one mol. of saturated solution then it is found on plotting logz against 1/T that two straight lines are obtained which intersect at 184*5O. The equation for the solubility of the modification which is stable a t the lower temperatures is - logx = 464.5 / T - 0’5400 and for that stable a t higher temperatures - logx = 3 2 7 q T - 0*2412. I n a discussion of the nomenclature of isomerism the author considers that. allotropy may be1 conveniently used to include all cases of isomerism and polymorphism.Where two or more solid modifications occur the allotropy would be distinguished as phase allotropy t o distinguish it from molecular allotropy. H. M. D. Solubility of Calcite in Water in Contact with the Atmos- phere and its Variation with Temperature. ROGER C. WELLS (J. Washington Acad. Sci. 1915 5 617-622).-The solubility of calcite in water exposed t o the air has been determined a t a series of temperatures. The method consisted in placing powdered calcite in water in Jena flasks and bubbling air of average content 3-18 parts of carbon dioxide per 10,000 through it until saturation occurred. The content of calcium carbonate was then estimated by titration with 0*02N-sodium hydrogen sulphate. Saturation required usually about eighty days.The following results expressed in parts of calcium carbonate per million were obtained a t lo 82; 21° 60; 22” 57; 2 3 O 57; 30° 55. The rate a t which saturated solutions deposit calcite on keeping was also determined. The results of the decreased solubility with increase in temperature are discussed from a geo-chemical point of view in connexion with the deposits of the Mississippi and the presence of marble in certain coral islands in the Philippines. J. F. S. The Reactions between Several of tne Salts contained in [Natural] Wa~ers at the Soiling Point. P. PETIT (iVon. Sci. 1914 [v] 4 537-541).-Whilst the precipitation of calcium carbonate from dilute solutions of the hydrogen carbonate is but little influenced by external conditions t’he similar precipitation of magnesium is greatly dependent on the method of heating and the size of the vessel and the condition of its walls.After one hour’s boiling the quantity of calcium carbonate remaining in solution is about 17 mg. per litre and is independent of the initial concentration. With magnesium carbonate on the other hand the percentage precipitated decreases with decrease in initial concen- tration and for concentrations of about 110 mg. per litre 50% a t most is eliminated by an hour’s boiling in clean vessels. Water containing both calcium and magnesium hydsogen carbonates loses nearly all its calcareous matter when the calcium considerably predominates; the magnesium is precipitated as if it were alone. Sodium chloride diminishes the precipitation of calcium carbonate,INORGANIC CHEMISTRY.ii. 33 and also of magnesium carbonate except in minute quantities in which case the precipitation of magnesium carbonate is increased by about 10%. From a water containing calcium hydrogen carbonate and magnesium sulphate with a preponderance of calcium the precipitation of calcium carbonate is almost unaffected by the presence of the magnesium salt but with a preponderance of magnesium precipitation of calcium carbonate is diminished and in neither case is much magnaium carbonate eliminated. Calcium sulphate in excess facilitates the precipitation of mag- nesium carbonate and with a pmponderance of 21 1 92% of the lather is eliminated. With increasing 0xcess of magnesium hydro- gen carbonate increasing quantities of calcium carbonate are precipitated from a sulphate solution G.F M. Formation of Magnesium Suboxide in the Electrolytic Preparation of Magnesium. FRANCIS C FRARY ahd HARRY C. BERMAN (Trans. Amer. Electrochem. Soc. 1915 27 209-219).- When magnesium and potassium chlorides ar0 electrolysed in a graphite crucible small mame5 of a dark substance which evolves hydrogen with water are found in the mass after cooling. The gas so obtained contains 95% of hydrogen the remainder being nitro- gen. The dark solid oxidises so rapidly that it has not been found possible t o make an analysis. It is without action on a solution of anhydrous nickel chloride in absolute alcohol whilst metallic magnesium powder rapidly precipitates nickel. The dark sub- stance is not formed when oxygen is completely excluded from the electrolyte by melting in a stream of hydrogen chloride and con- tinuing the passage of the gas during electrolysis.Adding a little magnBium oxide to this electrolyte results in the formation of suboxide. C. H. D. Atomic Weight of Cadmium. W CECESNER DE CONINCK and G&RARD (Compt. rend. 19 15 16 1. 676- 677).-The substance used was cadmium carbonate which was prepared by dissolving metallic cadmium in sulphuric acid and passing a current of hydrogen sulphide for several hours; the precipitata after washing was dissolved in concentrated hydrochloric acid the excess of acid evaporated off and a large excess of a concentrated solution of ammonium carbonate added cadmium carbonate alone being pre- cipitated. This process was repeated three times. A definite weight of the dried cadmium carbonate was ignited in a special crucible in a current of pure hydrogen and from the ratio CdC03:Cd the atomic weight of cadmium was calculated.The mean of five determinations was 112.32. W. G. Red Lead. JAROSLAV MILBAUER (Chenz. Zezt. 1915 39 858-859). -The presence of silver in lead oxide has a Tavournble eff ecb on thO formation of red lead a t low temperatures; a t 300° 27% of Pb304 was obtained against 9% in the absence of silver. At higher temperatures no effect was observed on the formation of red lead. Bismuth is also indifferent but zinc and antimony cause an appre- VOL. CX. ii. 2ii. 34 ABSTRACTS OF CHEMICAL PAPERS. ciable reduction in the amount of the higher oxide formed. Iron and copper likewise have no accelerating effect and they tend t o influenm the colour unfavourably.The formation of red lead is accelerated by using amorphous preparations of lead oxide and by employing air or oxygen under pressure (Austrian Pat. 58167). The equilibrium conditions semain thereby unaltered. The prepara- tion of pure red lead by fusion of lead oxide with potassium nitrate (A. 1914 ii 464) is not possible owing to the reversibility of the reaction. A new wet method f o r the preparation is suggeded namely by boiling lead peroxide (3 mols.) and lead oxide (2 mols.) with concentrated aqueous potassium hydroxide. The product is 100% pure and its colour varies from purplish-red t o bright red with increasing concentration of the alkali. G. F. M. MASAO KINURA (Mem.CoZZ. Sci. Kyoto 1915 8 149-152. Compare Fay and Gillson A 1902 ii 260).-This system is of a simple type the only compound melting a t 904O with one eutectic point a t 412O and 24% Pb the other eutectic practically coinciding with pure lead. Solid solutions are not formed to any appreciable extent. The micro-structure is simple and accords with the thermal diagram. C. H. D. Alloys of Tellurium with Lead. Metallography of the System Thallium-Selenium. TAKEJIRO MURAKAMI (Mem. CoZZ. Sci. Kyoto 1915 1 153-159).-The equili- brium diagram of this system is complex. There are three com- pounds of which two present themselves as maxima on the freez- ing-point curve whilst the third decomposes below its melting point. There are three eutectic points a t 281° 283O and 150° respectively.These correspond with alloys containing 1% 21% and 52% of selenium respectively. Tl,Se decomposes a t 265O and undergoes a transformation a t 165O. There are two gaps of miscibility in the liquid state extending from 4 to 14.5% Se and from 55 to 97.5% Se. All the compounds are brittle and the micro-structure is in accordance with the thermal diagram. T1,Se melts a t 368O and TlSe a t 310O. C. H. D. The Structure of Electrolytic Copper. M. VON SCHWARZ (Intern. Zeitsch. Metallographie 1915 7 124-173. Compare Faust A. 1912 ii 1173).-Very large crystals 5 cm. or more in length may be obtained from an ordinary sulphate bath for the electrolytic deposition of copper the temperature being 1-7O and all agitation being avoided. The crystals are repeatedly twinned octahedra and their orientation is confirmed by etching.The growth of crystal grains in massive electrolytic copper on annealing is also described. The larger grains absorb the smaller excep't where the metal has been locally strained. The very small grains produced by straining grow much more rapidly than the others a t first but this difference only persists for a short time of annealing. Electrolytically deposited crystals grow parallel to the surfaceINORGANIC CHEMISTRY. ii. 35 of the cathode oiie octahedral face being in contact with the cathode and elongation taking place along a trigonal axis. Twin- ning occurs when these crystals are annealed but again disappears after prolonged annealing. The effect of pressure on isolated crystals in causing the forma- tion of new crystal centres is also shown by the experiments and the observations are utilised for a discussion of the hypothesis of an a,morphous modification produced by flow and also present a t the crystal boundaries in cast metals.Micro-structural Changes accompanying the Annealing of Bronze. HENRY S. RAWDON (J. Washiizgtoii. Acud. Sci. 1915 5 589-591).-Specirnens of bronze containing 88% of copper 10% of tin and 2.4 of zinc have been annealed a t various temperatures. The cast a.lloys lose their dendritic structure a t 800° but without any change in the form of the crystal grains. Bronze which has been deformed in the cold recrystallises completely the depth of the layw affected by the deformation remaining constant as the crystals increase in size.Cerium Alloys. I. The Constitution of Cerium-Copper Alloys. FRANZ HANANAN (I?zter?z. Zeitsch. AletaZlogruphie 1915 7 174- -212).-Tlie metallic cerium used contains cerium 96.71% iron O.SO% the remainder being cerite metals. It melts a t 715O and as a small quantity of an iron eutectic is undoubtedly present the true melting point of cerium must be close to 720O. The metals are melted in unglazed porcelain crucibles under a layer of sodiurn chloride or mixed potassium and sodium chlorides. The cerium is best added t o molten copper except for alloys containing morethan 80% Ce for which the reverse process is used. The thermo-couple is pro8tected by a very thin tube of unglazed porcelain and the cooling curves are determined by the inverse-rate method. The freezing-point curve has two well-marked maxima corre- sponding with a compound Cu6Ce which melts a t 935O and Cu2Ce melting a t 820O.There are also two compounds which are formed by reactions between solid and liquid thus giving rise to breaks in the freezing-point curve; Cu,Ce a t 780° and CuCe a t 514O. There are three eutectic points a t 875O 757O and 415O occurring at 1776 44% and 84% of cerium respect'ively. Solid solutions are not formed. The alloys richest in cerium contain traces of a ternary eutectic of copper cerium and iron. The hardness curve of the alloys determined by Brinell's method has two pronounced maxima corresponding with the compounds Cu&e and Cu,Ce the former being nearly four times as hard as copper. The micro-structure of the alloys is described in detail and illustrated.The colour of the alloys resembles that of copper as far as the first eutectic; from that point t o the third eutectic i t resembles that of bronze and then becomes steel-grey. Only those which lie between 55% and 85% Ce are pyrophoric. Those containing less than 30% Ce are stable and retain their colour in air ; richer alloys soon disintegrate. C. H. D. C. H. D. C. H. D. 2-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. Calorising Metals. W. E. RUDER (I'ra7z.s. Amer. Electrochem Soc. 19 15 2 7 253- 266) .-The process of '' calorising " consists in heating the metal a t 700-950° in a mixture of powdered alumia- iuin and alumina with the addit'ion of about 1% of ammonium chloride Copper and brass are heated a t 700-BOOo iron and steel at 9QQ-950° a larger proportion of metallic aluminium in the mixture being required by the latter metals.The time is usually two t o three hours. Aluminium alloys supesficially with the metal and gradually diffuses inwards. When heated for a long time a t or above 1000° the greater part of the layer of alloy disappears owing to diffusion and a thin layer of oxide. remains on the surface. Nickel wire or ribbon may be coated with a layer sufficiently thick t o resist oxid& tion without injuring its flexibility. The stages in the diffusion are illustrated by photo-micrcgraphs. C. IX. D. Manganese-Bismuth Alloye. E. BEKIER ( I a t e m Zeitsch. ~Ietullogrc~phie 1914 7 83 -92 Compare Parravano and Perret A. 1915 ii 565).-Powdered manganese may be dissolved in molten bismuth by heating very cautiously in unglazed porcelain tubes around which a reducing atmosphere is maintained.There is a eutectic point very close t o pure bismuth. Only a single com- pound is formed the composition of which lies between MnBi and Mn,Bi. Partial miscibility in the liquid state extends from 39% t o practically 100% of manganese the horizontal part of the curve being a t 1240O. C. H. D. The Iron-Carbon Equilibrium Diagram. OTTO RUFF (Ferrunz 1915 12 121-123. Compare A. 1913 ii 56).-The cementite which is decomposed wibh formation of graphite during the cool- ing of liquid iron-carbon alloys is that which is in excess of the equilibrium concentration but below the saturation concentration. Any excess above this latter concentration separates as free cementite.The true eutectic temperature is 1125O or possibly nearly 1 I3O0 ; the pseudo-eutectic te'mperature is higher about 1138O. C. H. D. The Pseudo-eutectic Temperature of the Iron-Carbon Alloys. OTTO RUFF and WALTER BORMANN (Ferrzmz 1915 12 124-126. Compare preceding abstract).-The true eutectic tem- perature is that a t which the iron solid solution and cementite solidify in the same ratio as that in which they are present in the liquid. The pseudo-eut'ectic temperature is that a t which the liquid is simultaneously saturated for cementite and graphite. Experiments t o determine thel latter temperature must be made with hypereiltectic alloys ; otherwise the absence of graphite nuclei causes great undercooling. An iron containing carbon 4.13 silicon 0.074 sulphur 0.006 manganese 0.15 phosphorus 0.02 and copper 0.005% is melted in a graphite crucible the atmosphere of the electric carbon furnaceINORGANIC CHEMISTRY. ii.37 containing about 30% of carbon monoxide. The pseudo-eutectic temperature is found quite sharply 1138.8O +_ lo. It is slightly raised by addition of silicon and lcwered by that of manganese. C. H. D. Can the Dissociation Theory be Applied to Solid Solutio s in Steels 3 EDWARD D. CAMPBELL (J. Anze?.. Chem Soc. 1915 37 2522).-Owing to an ammeter used in the experiments described previously reading too high (A. 1915 ii 779) a correction of from 0.42 to 0.48 microhms is to be applied to the figures there given. This correction does not effect the significance of the figures o r the deductions drawn from them. J.F. S. The Behaviour of Slag Enclosures in Acid Steel. F. GIormn and S. ZURLENA (Ifbtem. Zeitsch. Illetallogrnphie 191 4 7 35 - S3. Compare Giolitti and Tavanti A. 1915 ii 57).-Specimens are cut from the sound central portion of an ingot of acid open-hearth steel containing carbon 0*38% manganese 0*60% silicon 0*22% sulphur O*OOS% phosphorus 0.02% and nickel 2.02%. I n all cases the enclosures of grey sulphide slag are found in the central part of the ferrite masses completely separated from the pearlih. When heat'ed for four hours a t a constant temperature of 1060O in carbon dioxide slight decarburisation takes place and the slag enclosures are now frequently in contact with pearlite. The effect is more marked a t llOOo. In carbon monoxide a t l l O O o the carburised portion shows the1 ferrite and slag completely independent.This occurs whenever carburisation takes place whilst ferrite formed during an oxidising process encloses the slag. The results are attributed to the influence of the slag on the oxidation of the carbide and consequent liberation of ferrite. Repeating the experiments with a steel containing carbon 0*40% manganese 0*58% silicon 0*20c;/ sulphur 0*006% phosphorus 0.03"/ and nickel 1*98% also of acid open-hearth origin the same changes are found t o take place still more readily. The only slag enclosures which exert an influence on the distri- bution of ferrite are those of light grey colour usually regarded as manganese sulphide. LESLIE AITCHISON (T. 191 5 107 1531-1538).-The influence of molybdenum on the corrodi- bility of '' high-speed " steels has been investigated by comparative experiments with a standard pure carbon steel and a series of steels containing approxiniately the same percentage of carbon and quantities of molybdenum varying from 2.5 t o 20%.The results obtained with 3% sodium chloride and 1 t o 10% sulphuric acid sohitions show that the addition of small quantities of molybdenum i3 accompanied by a considerable increase in the corrodibility ol' the steel. I n the salt solution the corrosion increases somewhat with further increase in the molybdenum content but in the acid solutions this is accompanied by a diminution in the corrodibility. I n tap-water molybdenum first produces a slight diminution and then a slight increase.C. H. D. Corrosion of Molvbdenum Salts.ii. 38 ABSTRACTS OF CHEMTCAL PAPERS. The results obtained in the investigation of the action of 10%) sulphuric acid on the steels shows that no trace of molybdenum dissolves until the proportion of molybdenum exceeds t h a t required’ for the formation of carbide (19-20%). This is in agreement with the micro-structure of the samples. H. M. D. An Acid-resisting Alloy to Replace Platinum in the Con- struction of a Bomb Calorimeter. S. W. PARR ( J . Amer. Chenz. SOC. 1915 37 2515-3522).-After a large number of experiments an alloy has been obtained which on account of its high tensile strength resistance to acids and closely-grained structure has been used for making calorimetric bombs. This alloy which melts a t 1600° renders the use of a platinum lining quite unnecessary.It. has the following composition; 6.42% Cu 0.98% Mn 1*04% Si 3.13% W 60.65% Ni 1.09% Al 0.76% Fe 21.07% Cr and 4.67% No. J. F. S. The Monoclinic Double Sulphates containing Ammonium. Completion of the Double Sulphate SQries. *4. E. H. TUTTOR (Phil. Tm?zs. 191 5 A. 216 1-62) -The crystallographic and optical properties of the double sulphates of the series R,M( S0,),,6H20 i n which R is ammonium and M represents magnesium zinc and iron have been described in previous papers (compare T. 1905 87 1123; A. 1913 ii 603). The present paper gives an account of the properties of the five remaining double salts in which M represents nickel cobalt manganese copper and cadmium. The densities of the corresponding potassium rubidium and msium double sulphates have been redetermined by the immersion method the values previously obtained by the pyknometer method being rather low.The chief experimental data of interest t o the chemist are given in the following summary Ammonium nickel sulphate-monoclinic [a b c = 0.7373 1 0.5000 p= 106’57’1 ; Di’ 1.923. 2.586 czsium 2.872. For corresponding potassium salt D;’’ = 2.237 rubidium Ammonium cobalt sulphate-monoclinic [a b c = 0.7386 1 0.4975 ; p = 107’2’1 ; r)? 1.901. Potassium salt DF =2*219 rubidium 2.567 caesiuni 2.844. Ammonium manganese sulphate-monoclinic [a b c = 0.7400 1 0.4931 ; 0 = 106’51’] ; UiO 1.831. Rubidium salt DT’ =2*461 caesium 2.740. [a b c = 0.7463 1 5066 ; /3 = 106’9’1 ; DT 1.926. Potassium salt D:” =2.233 rubidium 2.574 caiuni 2.858.Ammonium copper sulphate-monoclinic Ammonium cadmium sulphate-monoclinic [a 71 c = 0.7364 1 0.4931 ; /3 = 106°41’] ; Uy) 12.061. Rubidium salt DY 2.695 cxsium salt 2.957. The results obtained for the above five amnioniuni salts are per- fectly in line with those yield-ed by the three! salts examined.INORGANIC CHEMISTRY. ii. 39 previously. The close similarity of the crystal angles the axial ratios the volume constants and the optical constants indicates that the ammonium salts of the double sulphate series are fully entitled t o be considered as truly isomorphous with the correspond- ing potassium rubidium and caGum salts. The ammonium salts do not however exhibit the eutropic relations which are found to exist between the salts of the three alkali metals.I n spite of the departure of the ammonium and also the thallium salts from the law which in the eutropic series expresses the connexion between the crystallographic properties and the atomic weight of the alkali metal i t has been clearly established that non-eutropic replacement may occur with extremely small alterations in the crystalline structure. These changes are almost vanishingly small when rubidium is replaced by either ammonium or thallium. H. M. D. Metallographic Study of the System Antimony-Tellurium. YASUKIYO KIMATA (Mem. CoZZ. Sci. Kyoto 1915 1 115-128. Compare Fay and Ashley A. 1902 ii 266).-The freezing- point curve of this system has a maximum a t 620° correspond- ing with the compound Sb,Te,.There are two eutectic points a t 540° and 28% Te and a t 420° and 89% Te respectively. There is no indication of the formation of solid solutions. The flatness of the curve in the neighbourhood of the eutectic point on the bismuth side led Fay and Ashley to assume that solid solutions were formed on this side the curve passing through a minimum. Microscopical examination confirms the' existence of the two eutectics. C. H. D. Nitrogen Compounds of Gold. ERNST WEITZ (AnnuZen 1915 410 117-222).-Explosive nitrogenous compounds of gold are obtained not only from the salts or oxides of gold and aqueous ammonia or ammonium carbonate but also from auric hydroxide and the ammonium salts of strong acids. I n 1840 Dumas assigned t o the substance obtained from chloro- auric acid and ammonia the formula 4 ( AuN ,NH,) ,2 (A u C1,2 N H,) ,9H,O and to another prepared from auric hydroxide and ammonia the formula 2(AuN,NH3),3H,0.Raschig in 1886 regarded the latter as goldamidine NH:Au-NH ; another compound obtained from ammonia and an excess of chloroauric acid was defined as gold- iminochloride NH :AuCI whilst the former of Dumas' compounds was stated t o be a mixture of these two. These formulz have been generally accepted without further evidence of constitution and no attempt has hitherto been made t o formulate the nitrogen compounds of gold in accordance with the co-ordination theory. The compounds described by the author &re generally obtained only under definite conditions of concentration of the reagents and most of them have been analysed in the wet state on account of their explosiveness and decomposition by washing ; the names are The paper deals with these two points,ii.40 ABSTRACTS OF CHEMICAL PAPERS. determined by the ratio Au:N. From the numerous data re- corded in the paper the following summary may be made By treating an aqueous solution of chloroauric acid with ammonia (5 mols. o r more) precipitates are obtained containing gold nitrogen and chlorine; as the amount of ammonia is increased the quantity of chlorine in the precipitate diminishes the ratio Au:N however remaining constant a t 1 1.5. These precipitates which are called by the general name " explosive gold-chloride," are mix- tures of two substances t o which after drying the compositions Au203,,3NH3 (.sespz~iammipzect.lIric oxide) and NH(AuCI*NH& (diamznoiminodiauric clhloride) are given.The chlorine-free con- stituent has been isolated. When air-dried it has the composition 2Au(OH),,3NH3 and is relatively harmless but after drying a t 105-110° or in a vacuum over phosphoric oxide it loses water and then explodes very violently by mere rubbing or pressure with a spatula . Other mixtures (explosive gold-nitrate -bromide etc.) have been prepared by another method; the ratio Au N is still 1 1.5. When N / 5-chloroauric acid containing ammonium chloride is added t o a cold saturated solution of ammonium chloride saturated wit 11 ammonia an individual compound diaminoauric chloride Au(NH,),Cl is obtained which contains 1H,O. This is a dense yellow powder which is not explosive and is decomposed by washing with water yielding ultimately a substance ( ? Au3N2,zH,0 or 3Au0,2NH3,yH20) which is explosive.Explosive gold-chloride and diaminoauric chloride are each con- verted by continued treatment with aaueous ammonia into seaqui- ammineauric hydroxide. This is changed t o diamminetriaurozis oxide ;-Au2Q,2NH3 a very explosive black substance by heating a t 115-120° and into a more explosive monoammineauric oxide Au203,2NH3 by hot water. Sesquiammineauric hydroxide is con- verted by warm dilute hydrochloric acid into chloroauric acid explosive gold-chloride being an intermediate product. The hydr- oxide is scarcely attacked by dilute sulphuric o r nitric acid in the cold but by warming ammonia is eliminated and explosive pro- ducts (Au N = 1 1) are obtained. Cold conesntrated nitric or sulphuric acid does n o t decoinposd the sesquiammineauric liydr- oxide a salt only being formed.Te tru-n m mineauric nitrate [Au (NH,),](NO,) colourless needles is obtained when about N/5-chloroauric acid saturated with ammonium nitrate is added t o a cold saturated solution of ammonium nitrate the mixture treated with gaseous ammonia a t the ordinary temperature and the precipitate washed with water. The salt can be crystallised from warm water. I n not too dilute solution itl is precipitated unchanged by almost all nitrates but with potassium sodium or ammonium nitrate in sufficiently con- centrated solution it yields double nitrates [Au(NH,),](N03),,MN0 crystallising in needles. By double decomposition tetra-ammine- ainric nitrate has been converted into other salts containing theINORGANIC CHEMISTRY.ii. 41 cation [AU(NH~)~] (represented by R in the formulze; the phos- phate RPO,,H,O fkely crystalline colourless precipitate; oxalate nitmte NO,*R(C,O,) ; .perchlorate R(ClO,) stout prisms (specially suited by reaction with potassium salts for the preparation of other soluble tetra-ammineauric salts) ; oxalate perchlorate C10,*R(C20,) very small leaflets; chlorate R(C10,),,2H20 tufts of very thin leafy needles; iodate; two sulphate nitrates NO,*R*SO,,H,O and R4( S0,),(N0,)2,2H,0 ; a complex hydrogeu sulphate R,H,(SO,) ; sulphate perchlorate ; and chromate R,(CrO,) have been prepared. These salts are very stable in the solid state and retain their ammonia even against the attack of concentrated acids. The salts of the strongest acids have a neutral reaction.Tetra-ammineauric hydroxide has not been isolated but its existence is indicated by the facts that the nitrate is distinctly more soluble in aqueous alkali hydroxides or ammonia than in water and that from these alkaline solutions the nitrate is again precipitated by the rapid addition of nitric acid; when the alkaline solutions are kept they become brownish-yellow and yield yellow explosive precipitates which appear to be mixtures (explosive gold- nitrate etc.) constituted similarly to explosive gold-chloride or such mixtures containing also monoammineauric oxide. Tetra-ammineauric salts of the halogen acids cannot be obtained a t all events in solution; when the colourless solutJon of tetra- ammineauric nitrate is treated with f o r example aqueous potassium chloride a yellow colour is produced and a yellow ex- plosive precipitate (explosive gold-chloride nitrate) is obtained..Bromides iodides cyanides and thiocyanates produce similar changes; potassium fluoride does not produce any coloration o r precipitate. Constitutional formulz of the preceding nitrogen compounds of gold are discussed and attempts are made t o extend the formula to the explosive nitrogen compounds of other noble metals and of mercury. c. s. Organosols of Metals and Metallic Hydroxides of the Platinum Group. 111. CONRAD AMBERGER (Kolloicl Zeztsch. 1915 17 47-51. Compare A. 1912 ii 1053 1059; 1914 ii 60). -Colloidal osmium dioxide may be obtained by the method which has been used previously f o r the preparation of organosols of platinum and palladium.Lanolin is impregnated with a solution of potassium osmate and the mixture relduced by the addition of hydrazine hydrate The product is dissolved in light petroleum and can be precipitated by the addition of alcohol. It consists of colloidal osmium dioxide in admixture with lanolin as protective colloid. I f the precipitated organosol is heated in a current of hydrogen a t 50° to 60° the oxide is reduced to metal and the metallic organosol dissolves readily in ethyl ether benzene light petroleum and other organic solvents. An organosol containing 21% of metallic osmium has been obtained in this way. H. M. D. 2*ii. 42 ABSTRACTS OF CHEMICAL PAPERS.The Hydroxylammonia Complexes of Bivalent Platinum. L. TSCEIUGAEV and I. TSCIIERNJAEV (Compt. rend. 1915 161 637-639).-The authors have succeeded in preparing all the members of the series of compounds [Pt(NH2*OH).(NH,) - n]C12 namely [ P t (NH,. OH) 4] C1 [Pt (NH,*OH),(NH,)ICI (1.1 (11.) [OH*NH,>pt<NH NHJ c1 2 [ OH*NH N H ~ > P t < ~ ~ ~ * O l I ] C 1 2 OH-NH (IIIA ) (IIIB.) [P t (NH,* OH) (NH3)31 c1 [Pt(NH3)&1 (IV. 1 (V. ) Of these only I and V were previously known and IIIB very imperfectly. Starting with Yeyrone’s chloride this when digested with hydroxylamine in aqueous solution gives the compound IIIA which yields the mixed complex N ~ > P t < ~ ~ ~ . o 1 4 on treatment with hydrochloric acid at the temperature of a water-bath. This complex easily fixes two molecules of hydroxylamine t o give the compound 11 o r two molecules of ammonia t o give the compound IV. The compound IIIB is readily prepared by the action of hydroxylamine in aqueous solution on the chloride of Reiset’s basel 11 the1 latter chloride being regenerated by the action of hydrochloric acid. All the members of this series of compounds are colourless and more or less soluble in water being ionised. The molecular con-. ductivities lie between 240 and 260 which corresponds exactly with electrolytes of the type (Pt,4A)X2. They yield platinochlorides palladochlorides and picrates. Of these the platinochlorides pre- pared by precipitation with potassium platinochloride are the most characteristic those of the compounds I 11 and IIIA being rose- violet in colour and those of IIIB IV and V being green. This reaction readily distinguishes between the isomerides IIIA and IIIB. The chloride [Pt(NH,),NH,*OH]CI gives when heated with hydrochloric acid Clew’s salt (Yt,SNH,,Cl)Cl. W. G.