INORGANIC CIFEMISTRY. Ino rgani c Chemistry. Production of Ozone by the Pulverization of Water. By G. BE L LU c c I (Gazzetta chirnica itaZiana vi 88-9 7) .-Lender had noticed in the concentration of the brine springs of Kissingen by graduation that the air in the immediate neighbourhood of the columns gave the ozone reaction and Gorup-Besanez found that the quantity of ozone produced by the spray of water issuing under pressure was greater the more rapid the evaporation. Morin and Monte have also shown that in the pulverization of water as practised ABSTRACTS OF CHEMICAL PAPERS. at some thermal establishments ozone is produced in sensible amount. These facts induced the author to make observations in the neighbour- hood of the falls of Terni to ascertain if ozone was produced by the natural pulverization of the water especially as he had often noticed the characteristic odour of ozone there.He found that Schonbein’s paper was distinctly attacked in three hours the alteration being more marked in the immediate vicinity of the falls and especially at those seasons when the volume of water was greatest. Papers exposed at a distance from the fall within a radius of 80-100 meters were all more or less attacked but most strongly on the banks of the stream below the fall the current of air which invariably follows the course of a rapid stream closely shut in by rocks or in a narrow valley carrying along the ozone. The author infers from these results that ozone is generally pro- duced where water undergoes pulverization or is converted into finely divided spray whether this is effected by a cascade a torrent rushing over rocks the surf on the sea-shore or the rolling of the waves in the open ocean.It is noteworthy that the air over the surface of the ocean is richer in ozone than that collected on the land. After dis- cussing at length the various causes which might produce the ozone the author arrives at the conclusion that it is due to the electrical state induced by the friction of the minute drops of water against one another which is increased by the mineral matter suspended or even dissolved in the water. C. E. G. Prismatic and Octohedral Sulphur. By D. G E RN E z (COmpt. rend. lxxxiii 217-220) .-When the contact of solid particles is pre-vented fused sulphur may be indefinitely maintained in the liquid state at a temperature much below its point of fusion.Under these circumstances solidification may be induced without the introduction of a crystal of sulphur by either rapidly cooling a part of the liquid as by touching the exterior of the containing tube with a cold body or rubbing the interior of the tube with a glass rod left in the liquid. In either case the sulphur solidifies at temperatures above 60” in the prismatic form and at ordinary temperatures these prismatic crystals break up into minute octohedrons. The octohedral crystallisation may however be induced in the fused sulphur even at the tempera- ture at which the prismatic occurs spontaneously as just described.This result is obtained by the introduction of an octohedral crystal which determines a crystallisation in the octohedral form throughout the mass but at a much slower rate than when the prismatic forms are produced. On fusing sulphur in a U-tube with proper precautions the two kinds of crystallisation can be simultaneously set up by the introduction of different crystals into each branch. R.R. and The Atomic Weight of Selenium. By 0. PETTERSSON G. EKMAN (Deut. Chem. Ges. Ber. ix 1210-1212).-The authors have attempted to arrive at the atomic weight of selenium by a variety of methods of which two only proved practicable namely (1) heating silver selenite and weighing the residual silver and (2) reducing selenious anhydride dissolved in water by means of INORGANIC CHEMISTRY.sulphur dioxide and weighing the precipitated selenium. The atomic weight was found to be by the first method 79.01 and by the second 79.08. The authors place more reliance on the results obtained by the second method J. R. Action of Halogen Acids on Selenious Oxide. By A DITTE (Compt. red lxxxiii 223-225) .-The compound Se02. 2HBr ener-getically absorbs bydrobromic acid gas with evolution of heat giving rise to a crystalline compound corresponding with the formula 2Se02.5HBr. This is decomposed at 65" with formation of water and disengagemenh of bromine but at lower temperatures it is trans- formed into Se022HBrand hydrobromic acid. The following are the values of the tension of dissociation of the compound 2Se02.5HBr at various temperatures :-At -25'...... At 30'. .....287 mm. , -6" ......lo:"$' 1 , 41" ......335 , , 0"......135 , , 54". .....404 Traces of bromine , $11"......191 , , 62".. ....404 } vapour. , 14"......209 , , 70°.. .... Decomposition with i abundant vapour of bromine. Hydriodic acid reacts with selenious oxide even at -lo' the products being water iodine and selenium. Selenious oxide also combines with anhydrous hydrocyanic and hpdrofluoric acids. Selenious oxide and hgdroselenic acid in presence of water decompose each other with separation of selenium. This result is always the same whether the solutions be concentrated or dilute hot or cold; and no compound corresponding with pentathionic acid has been obtained.The re-action is a convenient means of obtaining selenium soluble in sulphide of carbon. R. R. Action of Halogen Acids on Tellurous Oxide. By A. DITTE (Compt. relid. lxxxiii 336).-Tellurous oxide whether crystallised or amorphous behaves in the same manner to hydracids. Anhydrous tellurous oxide absorbs hvdrochloric acid with extri- cation of heat. If the vessel in which the reaction is occurring be cooled to -lo" the absorption of the hydrochloric acid ceases after a while. The substance has become light brown and the quantity of hydrochloric acid absorbed is that which corresponds with the formula 2Te02.3HC1. A slight elevation of temperature decomposes this compound hydrochloric acid is evolved and a body having the formula Te02.HIC1 remains.When this substance is heated at about 110" drops of waterappear and are deposited on the cool parts of the vessel. These increase in quantity by increased heat; the liquid becomes darker and at about 300" the production of the water (which should be removed as fast as it forms) ceases and if the heat be stopped so soon as white vapours begin to appear indicating the volatilisation of the substance left in ABSTRACTS OF CHEMICAL PAPERS the vessel this on cooling solidifies to a crystalline mass which con- sists of tellurous oxychloride TeOCI,. The oxychloride melts to a deep-coloured liquid which when boiled gives off bromine-coloured vapours and these on condensing deposit white crystals which consist of tellurous chloride while a great portion of the substance is not volatile at about 400° and consists of tellurous oxide.The oxychloride therefore splits up under the action of heat in the manner shown by the equation- 2TeOC12= TeOz + TeC14. No compound of the formula Te02.2HC1 analogous to the selenium compound could be obtained. C. H. P. Thermic Formation of Hydroxylamine or Oxyammonia. By M. B ERTHELOT (Cowzpt. rend. lxxxiii 473-478).-This paper contains a study of the thermic and chemical phenomena attending the formation and decomposition of oxyammonia leading the author to the conclusion that this compound belongs to a special and hitherto unrecognised type to which among bodies already defined the oxide of triethylphosphine offers the nearest analogy.The thermic observa- tions confirm and specify the conditions which determine the insta- bility of the compound. R. R. Phosphorus Pentafluoride. By T. E. T H ORYE (Liebig’s Anmden clxxxii 201-205) .-When phosphorus pentachloride is added pa- dually to arsenic trifluoride (obtained by heating arsenic trioxide with fluor-spar and snlphuric acid) a violent reaction takes place resulting in the formation of arsenic trichloride and phosphorus pentafluoride in accordance with the equation- 5AsF3 + 3PCl5= 5AsC1 + 3PF,. Phosphorus pentafluoride is a colourless gas having a very pungent odour and attacking the mucous membranes. It fumes in the air reacting with water to form phosphoric and hydrofluoric acids. Its density was found to be 63.23 that o€ hydrogen being 1 (theory re- quires 63).Under the pressure of 12 atmospheres at 7” it exhibits no marked deviation from Boyle’s law. The gas neither burns nor supports combustion. It is not affected by the passage of electric sparks through it when pure nor when mixed with hydrogen or oxygen. It combines with dry ammonia to form a yellowish-white solid body represented by the formula 2PF5.5NH3. A solution of the gas in aqueous ammonia deposits on evaporation crystals of ammonium phosphate (H,NH,PO,) and ammo- nium and hydrogen fluoride (HF.NH,F). J. R. Formation of Phosphonium Iodide. By K. LISSEPU’RO (Dezd. Chem. Ges. Rer. ix 1313).-The author believes that this compound is formed by the action of hydriodic acid on hypophosphorous acid for when the latter is fused and saturated with hydriodic acid a pro-duct is obtained which when heated in a current of carbon dioxide yields non-inflammable hydrogen phosphide hydriodic acid and phos- Ih'ORQANIC CHEMISTRY.47 phonium iodide while phosphoric acid remains behind. When 1part of phosphorus and 2 parts of iodine are dissolved in carbon sulphide and the latter distilled off a red mass is obtained which is a mixture of several compounds. On adding water the odour of hydrogen phosphide is given off and the solution first contains hypophospho- rous acid but on standing also phosphoric acid. The orange residue which remains appears to be solid hydrogen phosphide. c. s. Action of Hydrochloric Acid on Potassium Chlorate. By G. Sc HA c K E R L (Liebig's Annah clxxxii 193 -201) .-Pebal showed that the action of hydrochloric acid on potassium chlorate results in the formation of chlorine and hypochloric acid (C102) in varying pro- portions (see this Journal 1875 1157).The author's experiments on this subject have led to the conclusion that the action is represented primarily by the equation- 1CC103+ 2HC1 = CIOz + C1 + KCl + H20; or when sulphuric acid and potassium chloride are employed by the equation-KC103 + KC1 + 2H2SO4 = ClOz + C1 + 2KBSO4 + HZO; but that in most cases there occurs a secondary action of free hydro- chloric acid on the hypochloric acid first formed whereby the pro- portion of chlorine is increased. The extent to which this secondary action takes place was found to depend upon the amount and strength of the hydrochloric acid preseiit in the liquid from which the gases were evolved.Thus when a solution of potassium chlorate was run into hot hydrochloric mid of sp. gr. 1-19 the proportion by volume of the hypochloric acid and chlorine evolved was 2 35.6 ; but when finely-triturated potassium chlorate was decomposed with hydrochloric acid diluted with twice its bulk of water the two gases were in the proportion of 2 1.71. Again when a mixture of 1mol. of potassium chlorat'e and 5 mol. of potassium chloride was decomposed by sul- phuric acid the hypochloric acid and chlorine evolved were in the proportion of 2 5.54; but when a mixture of 4 mol. of chlorate and 1mol. of chloride was decomposed in the same manner the two gases were in the proportion of 2 1.27.Numerous other experiments were made all leading to the same conclusion. In no case was pure chlorine obtained. The gases were analysed by Pebal's method. J. R. The Dissociation of the Vapour of Calomel. By H. DEBRAY (Compt. rend. lxxxiii 330) .-The results of the author's experiments upon the dissociation of the vapour of calomel at 440" do not coincide with those of Odling and Erlenmeyer according to whom the disso- ciation is complete as determined from the vapour-density and the fact that a strip of gold plunged into the vapour becomes amalga- mated and also incrusted with corrosive sublimate. This experiment with the strip of gold can only be of use if it is established that at 440"the tension of dissociation of the amalgam of gold is inferior to ABSTRACTS OF CHEMICAL PAPERS.one-half an atmosphere which is the tension of the vapour of mercury in the mixture of equal volumes of mercury and corrosive sublimate supposed to exist by Odling's hypothesis if it is beyond half an atmosphere the strip of gold could not amalgamate in such a mixture ; but it is shown by direct experiment that a strip of gold heated to 440° does not become whitened in the vapour of mercury at the ordi nary atmospheric pressure ; it could not therefore become amal-gamated in the globe used for determining the vapour-density. When calomel is heated to 440"in a platinum vessel and a curved silver-gilt tube through which cold water is circulating is plunged for a few seconds into the vapour it becomes coated with a greyish deposit consisting of a little mercury interspersed in a powder of calomel PO fine that the mercury has not been able to attack the gold.Therefore althongh calomel heated to 440° and maintained at that temperature for some time suffers some decomposition it cannot be considered as established that the dissociation is complete. c. H. P. A New Process for the Extraction of Gallium. By LECOQ DE Bo ISBAUDRAN (Cornpi. h end. lxxxiii 636-638).-The gelatinous precipitate obtained by treating acid solutions of the gallium-bearing mineral with excess of zinc is dissolved in hydrochloric acid; sul-phuretted hydrogen is passed through the liquid; and after the gas has been expelled from the filtrate the latter is fractionally precipitated by sodium carbonate until gallium ceases to be thrown down and the precipitate no longer yields the characteristic spectrum of the metal.The precipitates are dissolved in sulphuric acid and the solution is evaporated until vaponrs of sulphuric acid cease to be evolved. The residue is treated with cold water and after dilution the solution is heated to boiling when a sub-salt of gallium is precipitated and separated by filtering while the liquid is hot. This basic salt is dis-solved in a small quantity of sulphuric acid a slight excess of caustic potash is added and the filtrate is treated for some time with a current of carbonic acid gas by whkh gallium oxide is precipitated. This is dissolved in the smallest possible quantity of sulphuric acid a small excess of slightly acid ammonium acetate is added and sulphuretted hydrogen is passed through the liquid which is then filtered diluted and heated to boiling.The greater part of the gallium is now pre-cipitated and is separated by filtering the hot liquid. The precipitate is dissolved in sulphuric acid caustic potash is added in slight excess and the solution is filtered and submitted to electrolysis. The metallic gallium is easily separated from the platinum pole by pressing with the fingers under warm water and the product is purified by treatment with nitric acid free from chlorine. R. R. On the Physical Properties of Gallium. By LECOQ DE BOISBAUDRAN (Conzpt. rend. lxxxiii 611-613).-The author has prepared more than half a gram of gallium; when liquid it has a silver-white liistre but when crystallised it shows a tinge of blue and loses its brilliancy.Its crystalline form is octohedral. Its melting-point averaged from six determinations is 30.15. It is hardly acted INORGANIC CHEMISTRY. on by nitric acid diluted with its om volume of water. Its specific gravity is 5.956 ;when crystallised under water it decrepitates slightly when melted. W. R. 2RC1 . PtCI,. 2TlC1 . PtC1,. BRbC1 . PtCl,. 2NaC1. PtCl2 4-4H,O. 2csc1 . PtCI,. 2LiC1 . PtC12 + 6HzO. 2AmCl . PtC1,. 2AgC1. PtCI2. BeC1 . YtCl + 5H,O NiCl . PtCl + 6H20. MgCI . PtCl + 6H,O. CUCI . PtCl + 6HZO. MnC1 . PtCI + 6H,O. ZnCl . PtC1 + 6H,O. CoC1 . PtCl + 6H20.PeCl .PtCl f 7H20. ITI. Tehad iwetals. ZrOC1,. PtCl + 8H20. I 2ThC14 .3PtC12 + 24 HZO. IV. Heread Netab. A12C16 . 2PtC1 + 21H,O. I ErzGl6 . 2PtC1 + 27H,O. Y,C& La2CI6 . SPtCI + 24HzO. . 3PtC1 -+-18Hz0. I Di2CI . 3PtC1 + l8H,O. CezC16 .4PtC1 + 20H20. 1 Di,Cl . 4PtC1 + 20H,O. The chloroplatinit,es of the monad and dyad metals are all normal salts ; the mercuric salt and that of cadminm could not be obtained. The metals having a higher quantivalence form chiefly basic salts and a few also acid salts and it is very remarkable that in the case of the VOL. XXXI. E ABSTRACTS OF CHEMICAL PAPERS. cerite and gadolinite-metals the normal salts crystallise only from basic and the acid salts from normal solutions. Ferric chromic and indium chloroplatinites could not be obtained.The following chloroplatinates were also prepared :-SnC14+ PtC14 + 12H,O forms glistening thin four-sided yellow plates. ZrOC1 + PtC1 + 12H20 crystallises in sma,ll oblique four-sided honey-yellow plates. Clet-e has already described the salt ThC14 + PtCl + 12H20,which is further proof that thorium is a tetrad. c. s. The Specific Heats and Atomic Weights of Cerium Lan- thanum and Didymium. By W. F. HILLEBRAND (Pogg. Ann. clxiii 71-87).-The paper describes the method by which the author determined the specific heats of cerium lanthanum and didymium operating with masses of the metals electrolytically prepared by Norton and himself. The figures obtained for the specific heats were cerium ,04479 ; lanthanum *04485 ; didymium -04653.Mul-tiplied by the hitherto-accepted atomic weights the respective pro-ducts are 4.12 4.15 and 4.40 by which the elements would appear as exceptions to the law of Dulong and Petit. But as these atomic weights have been estimated by indirect methods based upon hypo- thetical assumptions the author prepared the several oxides and sub-mitted them to a rigorous analysis. The results show that when instead of CeO Lao and DiO as heretofore the formulae of these compounds are taken as Cez03 La203 and Di203 the atomic heats exhibit a satisfactory accordance with Dulong and Petit’s law; for they severally become 6.18 6.23 and 6.60. The atomic weights as thus determined are Ce = 138; La = 139; Di = 144.78.X R.R. New Salts of Bismuth and their Use in the Detection of Potash.By A. CARNOT(Cowyt. rend. lxxxiii 338).-The new salts are the double thiosulphates of bismuth and alkalis. When to a faint’ly acid solution of bismuth chloride a rather strong solution of sodium thiosulphate is added the liquid becomes yellow but remains clear ; water may then be added in any quantity without producing any alteration if the amount of tbiosulphate which should be about three times as much as the bismuth is sufficient. This double salt with sodium is also soluble in alcohol. The aqueous solution decom- poses on standing the more rapidly in proportion to its concentration ; heat also assists the decomposition the double salt splitting up into bismuth sulphide and sulphuric acid.Potassium chloride added to an alcoholic solution of the sodium * Mendelejeff from considerations deduced from the “ periodic law ” of the ele- ments likewise regards the oxides of cerium aid didymiuin as sesquioxicles Ra03 assigning to both these metals the atomic weight 138. He has also made a deter-miiiatioii of the specific heat of cerium for which he finds the number 0.050 agree-ing nearly with that found by Hillebrand. On the other hand he regitrds Ianthanuni oxide as Lao, and estimates the atomic weight of lantliai~ulvat 180. (See this Journal rol. xsvi p. 1004.)-[E~.] INORGANIC CHEMISTRY. salt affords a yellow precipitate which rapidly coheres on agitation. The reaction succeeds equally well with a mixture of potassium chloride and nitrate but not with sulphate.No precipitate is formed by the chlorides of ammonium and the ordinary metals which are not precipitated by sulphuretted hydrogen but the chlorides of barium and strontium afford a white precipitate in either aqueous or alcoholic solutions of the double salt. The potassium precipitate is soluble in water but nearly insoluble in alcohol; it keeps well when dry but rapidly alters when moist particularly when in contact with the mother-liquors which themselves soon decompose bismuth sulphide being ia all cases deposited. The composition of the potassium salt is expressed by the formula Bi,03.3S,0 + 3K2S,03+ 3H,O. It is crystalline the crystals being the more marked in proportion as they are more slowly produced.Some very good crystals were obtained by redissolving in water some of the precipitated salt (after filtering off the mother-liquors) and adding alcohol till precipitation was on the point of occurring and then plunging into the solution a dialyser containing strong alcohol. As the alcohol diffused the salt slowly crystallised out chiefly on the membrane of the dialyser. These crystals keep in the air without alteration. C. H. P. Researches on the Solution of Gases in Iron Steel and Manganese. By L. TROOSTand P. HAUTEFEUILLE (Am. Chinz. Phys. [5],vii 155-1i"7).-This is a reprint of several papers which have appeared in the Comptes mndus de Z'dcade'rnie des Sciences and in abstract in this Journal (1873 729 ; 1875 610 and 790). Appended is the following summary of the general results arrived at :-1.Whenever cast iron is kept in fusion in contact with silica or silicates it evolves carbon oxide resulting from the action of iron carbide on silica ; the iron consequently becoming poorer in carbon and richer in silicon. 2. Melted cast iron dissolves considerable quantities of hydrogen the solubility of the gas being diminished by the presence of silicon and much increased by the presence of manganese. 3. Carbon oxide is much less soluble than hydrogen in the different varieties of cast iron. Its solubility is diminished or even annulled by the presence of manganese. 4. Pig iron after cooling retains gases which may be extracted by heating the metal to a temperature not exceeding 800'. Hydrogen is always more abundant than carbon oxide both in the solid and the fused metal and is more persisteutly retained by the metal.Man-ganiferous iron retains more hydrogen than does ordinary cast iron. 5. Steel dissolves less gas than cast iron hydr0g.n predominating over carbon oxide and being more forcibly retained by the metal. 6. Soft iron on the contrai-y dissolves more carbon oxide than hydrogen and retains it more forcibly. 7. Finely-divided pure iron deprived of gases decomposes water slowly at the ordinary t'emperature and rapidly at loo" the decom- position being more rapid the finer the state of division of the iron. J. R. E2 ABSTRACTS OF CHEMICAL PAPERS. Salts formed by Manganese Peroxide. By E. FRE MY (Cornpi. rend.Ixxxii 1231-1237) .-Manganese peroxide in the anhydrous state is very commonly considered as an indifferent oxide ; sometimes however it behaves like a saline oxide and less frequently as a metallic acid ; in the present instance the author wishes to show that it is also capable of functioning as a trne base. He has succeeded in combining the peroxide with sulphuric acid by acting directly on the hydrate Mn02.2H20 ; but the best method of operating seems to consist in decomposing potassium permanganate with a considerable excess of sulphuric acid. 100 grams of perman-gannte are treated with a cold mixture of 500 grams of sulphuric acid and 150 grams of water whereupon an oily layer of permanganic acid separates which gradually decomposing forms at the end of a few days a deep yellow liquid from which crystals can be obtained.This salt the author first!regarded as a sulphate of the sesquioxide but the following considerations induced him to alter his opinion and to look upon it as a salt of the peroxide. It is deliquescent soluble in sulphuric acid and decomposed by water forming at the same time a hydrate of the peroxide MnO2.2H2O. The liquor resulting from this decomposition contains no manganese. The yellow liquor exposed to the air or saturated with potassium snlpbate deposits a black subsulphate of the composition Milo2.SOS which when redissolved in sulphuric acid reproduces the yellow sul-phate. Certain salts such as manganous sulphatle potassium sulphate &c. combine with the yellow sulphate and form well-crystallised double salts The analysis of the new compound was effected by making it react upon an acidulated solution of ferrous chloride of known strength and then titrating the residual iron by means of a solution of perman-ganate.Experiment. Theory. Manganese. ................... 63.62 63.28 Oxygen ...................... 37-00 36.72 Five new compounds have been prepared from the yellow liquid before mentioned an amorphous hydrate ; a crystalline hydrate ; two subsulphates ; and a double sulphate containing both protoxide and peroxide of manganese the analyses of this latter salt led to the formula MnOz(S03)2.Mn0( S03).9H,0. This double salt may be pro- duced by the careful addition of reducing agents such as alcohol to the solution of the yellow sulphate ; it is of a rose colour and easily decomposed by water.It is possible of course to regard this compound as containing manganese sesquioxide but the existence of a corresponding potassium salt and the fact that when decomposed by an alkali it gives a pre-cipitate which yields a quantity of msnganous oxide to ammonia leaving a residue of peroxide are sufficient to show that the manganese exists in the salt in two different states of oxidation. Manganese sesyuioxide does not break up under the action of ammonia. Manganese peroxide does not appear to be the only oxide of the MINERALOGICAL CHEMISTRY. formula RO which can unite with acids to form salts inasmuch as the author has obtained several definite combinations of stannic oxide Sn02,with sulphuric nitric and hydrochloric acids. J. w.