ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h e m i s t r y . Preparation of Chlorine in a Kipp's Apparatus. By J. THIELE (A?znden, 253, 239--'L42) .-Chlorine may be conveniently prepared in a Kipp's apparatus by the action of hydrochloric acid on bleaching powder. By means of a handpress, tbe bleaching; powder is compressed i n to a hard cake ; this is broken into small lumps and used in this f o r in. w. c. w. Automatic Apparatus for Evolving Gases from Liquids. By J. THIELE (AnnuZen, 253, 242-246).-A convenient apparatus f o r preparing hydrogen chloride from commercial hydrochloric acid or sulphurous anhydride from a concentrated solution of sodium hydrogen sulphite may he made from R three-necked Wo1fl"s bottle. This is provided with-(1) a delivery tube fitted with a stop-cock; (2) a small stoppered separating funnel with the stem drawn out to a fine point; and (3) a safety funnel with some mercury in the bend and a loose plug of cotton wool in the funnel.The Wolff's bottle is half filled with the solution of sodium hydrogen sulphite, for example, and the sulphuric acid is slowly introduced through the separating funnel. w. c. w. Reciprocal Displacement of Oxygen and the Halogens. By BRRTHELOT (Compt. rewd., 109,546-548 and 590--597).-'l'he author summarises his previous work on the reciprocal displacement of oxjgen and chlorine and describes some later results. Pure concentrated fuming hydrochloric acid is not decomposed by oxygen in presence of sunlight, but if some maiiganous chloride is present the liquid acquires it deep-brown colour, the atmosphere i n the flask becomes cliarged with chlorine, and the liquid has bleaching properties.Oxygen is absorbed and hydrochlorides of manganese perchloride are iormed. If the liberated chlorine is removed and hydrogen chloride and oxygen are introduced into the flask, a further quantity of chlorine is set free, and this process may be repeated several times. The decomposition ceases when the hydrates of the hydrochloric acid contain the maximum amount of wat,er ; dilute non-fuming hydrochloric acid is not decomposed even after long ex- p osure in presence of manganese chloride. Ferric chloride behaves i n the same manner as mariganous chloride, but the phenomena are very much less distinct. The heat of formation of dissolved hydrobromic acid is almost iden- tical with that of water, and hence i n presence of water, but under these coiiditions only, reciprocal decomposition may take place, In pre- sence of excess of water, oxygen readily decomposes hydrogen bromide under the influence of light.Similar decomposition takes place a t the ordinary temperatnre in the case of it fuming solution of hydrobromic acid, that is, hydrates of the free acid not saturated with water, but is arrested almost immediately by the formation of hydrogen perbrom-INORGANIC CHEMISTRY. 7 ide, HBr3; HBr conc. soh. + Br2 gas = HBr, diss. develop +9*2 Cals., the total heat of formation, +43.5 Cals., being greater than the heat of formation of water. Oxygen does not decompose dilute hydrobromic acid, that is, the saturated hydrates of the acid, nor a solution of potassium bromide acidified with hydrochloric acid .The formation of hydrogen perbromide explains the decomposition of water by bromine, but this change is limited by the dissociation of the perbromide in presence of water. Dilute solutions of hydriodic acid are readily decomposed by oxygen under the influence of light at the ordinary temperature, the change corresponding with the liberation of 15.9 Cals. for each atom of gaseous iodine. The heats of formation of dissolved potassium iodide and hydroxide arc practically the same, and slight variations in the conditions serve to turn the reaction in one direction or the other. The combination of iodine with potassium iodide in concentrat'ed solution to form potassium triiodide liberates f5.0 Cals.for each atom of gaseous iodine ; the action of iodine on dissolved potassium hydroxide with formation of hypoiodite or iodate liberates +4*1 Cals. and + 5.4 Cals. respectively for each atom of gaseous iodine. l t follows that oxygen will not displace iodine from potassium iodide except under conditions in which potassium triiodide is stable, that is, in very con- centrated solutions. Experiment showed that dilute solutions of potassium iodide remain quite colourless when exposed to light for a long time in presence of pure air ; very concentrated solutions soon become orange and the colour deepens with prolonged exposure. The liquid then gives a blue coloration with starch and has an alkaline reaction; if, however, it is diluted, it rapidly becomes colourless, owing to dissociation of the potassium triiodide and the action of the liberated iodine on the potassium hydroxide which has been formed.It is well known that even dilute potassium iodide solutions become yellow when exposed to ordinary air. This is due to the fact that the carbonic anhydride of the air takes part in the reaction. Carbonic acid does not displace hydriodic acid, but the simultaneous action of oxygen and carbonic anhydride on a dilute solution of potassium iodide produces potassium hydrogen carbonate and free iodine. the change being accompanied by the liberation of +13.5 Cals. for each atom of gaseous iodine. The colour of the liquid becomes deeper if the quantity of carbonic anhydride in the atmosphere above it is increased.The action of the oxygen is still greater in presence of acetic or hydrochloric acid, but in these cases the result is in part due to the displacement of some hydriodic acid. Acetic acid liberates verylittle hydriodic acid, but the action of the oxygen depends on the successive liberation of small quantities. Hydrochloric acid liberates more hydriodic acid and in this case the action of the oxygen is more marked. In presence of a large excess of air, a solution of potassium iodide acidified with hydrochloric acid is completely decomposed by the action of light in a few days. If manganous chloride is added to a highly concentrated solution of8 ABSTRACTS OF CHEMICAL PAPERS. potassium iodide and the mixture exposed to light, a higher oxide of manganese is precipitated and iodine is liberated ; dilute solutions show the same phenomena in a lower degree.All the reciprocal displacements of oxygen and the halogens under the influence of light are in agreement with the thermochemical determinations. C. H. B. Simultaneous Synthesis of Water and Hydrogen Chloride. By P. HAUTEFEUILLE and J. MARGOTTET (Oowpt. rend., 109, 641-644). --Mixtures which contained oxygen and hydrogen in the proportion required to form water, with varying proportions of chlorine ; and mixtures of hydrogen and chlorine in the proportions to form hydrogen chloride, with varying quantities of oxygen, were exploded by means of a spark, and the residual chlorine was determined by means of standard sodium arsenite. If p represents the total hydrogen which enters into combination, and p' the quantity which combines with oxygen, v - p' gives the ratio of the hydrogen converted into W water to thb hydrogen which forms hydrogen chloride.This ratio is independent of the initial pressure, and of the nature of the spark. It is always less than unity if the proportion of chlorine is more than half the volume of the hydrogen, and it varies with every alteration in the proportion of chlorine. When the volume of chlorine present is double the volume of the hydrogen, the quantity bf water formed becomes inappreciable. It is evident that the results do not agree with Bunsen's law. With equal volumes of hydrogen and chlorine and varying propor- tions of oxygen, the 'ratio is always less than unity and does not vary greatly when the ratio of oxygen to hydrogen varies from 0.25 to 3.With equal volumes of the three gases the change is re- presented by the equation 5C1, + 5H2 -t 502 = 8HC1 + H,O + C1, 402. C. H. B. P Equilibrium between Hydrogen, Chlorine, and Oxygen. By H. LE CHATELIER (Cornpt. rend., 109, 664--667).-The author dis- cusses'the results of Hautefeuille and Margottet (preceding Abstract) from the point of view of his own laws of chemical equilibrium. The agreement between the observed and calculated numbers is very close. He points out that the degree of moisture of the gases, which is very important, is not specified. The fornlula shows that a reduction of initial pressure should be accompanied by a reduction in the propor- tion of water formed, and the fact that this is not observed indicates that' the chlorine is pai*tially dissociated.The varying effects of chlorine and oxygen depend solely on their relative volumes and not on their chemical properties. C. H. B. Preparation of Oxygen in a Kipp's Apparatus. By J . VOLHARD (AnnaZen, 253, 246--24H).-Small quantities of oxygen can be con- veniently prepared in a, Kipp's apparatus by the action of hydrogcbitINORGANIC CHEXISTRT . 9 peroxide on bleaching powder. quantity to neutralise the lime in the bleaching powder. Nitric acid is added in sufficient The oxygen contains a small quantit,y of chlorine. w. c. w. Action of Sulphur on Solutions of Metallic Salts. By G. VORTMANN and C. PADBERG (Ber., 22,2642-2644).--The authors find that with many proto-salts when their aqueous solutions are boiled with flowers of sulphur, about half the metal present is precipitated as sul- phide, the remainder being oxidised to the per-salt.When a strongly acid solution of stannous chloride WRS employed, no stannous sulphide was precipitated, but hydrogen sulphide was evolved, and the whole of the tin oxidised to stannic chloride. With an aqueous solution of stannous chloride, and with an acid solution of' cuprous chloride, laather less than half the tin was Precipitated as sulphide, a littie being oxidised in the same manner as with the strongly acid solution of tin. With mercurous nitrate, almost exactly halt of the mercury was precipitated as sulphide. Solutions of manganese, iron, nickel, zinc, and cadmium sulphates, and acid solutions of bismuth and antinionious chlorides, and of arsenious and arsenic acids, are not altered wlien boiled with sulphur.L. T. 'l'. Preparation of Nitric Oxide. By J. THIELE (Annulen, 253, 246) .--Nitric oxide is prepared in the apparatus previously described (t,his vol., p. 6) by adding a strong solution of sodium nitiite to a solution of ferrous chloride or sulphate in hydrochloric acid. I f the sodium nitrite contains carbonate, i t may be removed by precipit,at,ion with calcium chloride. w. c. w. Phosphonium Sulphate. By A. BESSON ( C O V Z ~ ~ . Tend., 109, 644-645) .-When hFdrogen phosphide is passed into sulplinric acid a t the ordinary temperatxre, there is considerable development of heat, sulphur separates, and sulphurous acid is formed. If the acid is previously cooled by means of ice and salt, the gas is somewhat largely nbaorhed, and the liquid remains limpid.After a time, how- ever, it begins to decompose in the manner indicated, the temperature rises, and deconiposition becomes very rapid. If the acid is cooled to -20" or -25" by the rapid evaporation of methyl chloride, a syrupy liquid is obtained, from which a white, crystalline, highly deliquescent, solid separates; this seems to be phosphonium sulphate. When thrown into water at the ordinary temperature, it dissolves w i t h a strident noise, and hydrogen phosphide is evolved, but the sulphuilic acid is not reduced. When exposed to air a t the ordinary tempera- ture, the phosphorus is oxidised to phosphoric, phosphorous, and hypo- phosphorous acids, whilst the sulphuric acid is reduced to sulphurous acid and sulphui., with a small quantity ot' hydrogen sulphide.The crystals may be dissolved in dilute sulptiuric acid, and if t'he solution is electrolysed a t -25" or -40" with a mercury cathode, there is only a very slight intumescence of the mercury, and hence, if phos- phonium amalgam exists, it is very unstable even at the freezing point of niercury. Tlie solution bas a high resistance, and ii' the10 ABSTRACTS OF CHEMICAL PAPERS. current is too strong the compound is decomposed with great rapidity in the manner already described. Hydrogen phosphide has no action 011 nitric acid at -23". Behaviour of Sodium Thiosulphate towards Acids and Metallic Salts. By W. VAUBEL ( B e y . , 22, 2703-27@4).-A reply to Vortman (Abstr., 1889, 1107) upholding the author's previous news C.H. B. (ibid., p. 943). Direct Production of Crystalline Sodium Carbonate and Chlorine from Sodium Chloride. By W. HEMPEL (Bey., 22, 2475--2478).-1n the electrolysis of metallic chlorides, which give readily soluble decomposition-products, the latter are further decom- posed as soon as the quantity produced reaches a certain limit. When, however, the compound produced is only sparingly soluble, this secondary decomposition does not take place, and the whole strength of the current is utilised. Potassium chloride and sodium chloride, f o r example, can be converted into the corresponding chlorate ; calcium chloride and magnesium chloride can be decomposed into chlorine and a solid hydroxide, by employing a diaphragm.Marx (D. R.-P., No. 46318) has shown that alkaline chlorides can be directly converted into clilorine and an alkaline hydrogen car- bonate, by passing carbonic anhydride through the solution during electrolysis, metal aud liquid diaphra,%ms being employed. The author, who has been engaged independently in making similar experiments, describes, with the aid of diagrams, an apparatus in which sodium chloride can be directly converted into chlorine and crystalline carbonate. The cathode is a perforated ircn disc, the anode a per€orated carbon disc, the perforations being about 4mm. in diameter, and bored in an upward direction to allow the gas to escape freely. A disc of ordinary asbestos-paper, placed immediately between the carbon and iron discs, serves as a diaphragm.The three discs are placed in the centre of a vessel made of porcelain and glass, which is thus divided into two chambers, each of which is provided with a conducting tube, in one case for carbonic anhydride, in the other for chlorine. If sodium chloride is added from time to time t'nrouph a suitable aperture, and the water which is removed with the crystalline carbonate is replaced, the apparatus can be worked continuously, sodium carbona,te m d almost chemically pure chlorine being obtained. A tension of 3.2 volts is required for decoruposing the sodium chloride, and a tension of 2.5 volts to overcome the polarisation current ; but the latter has only a slight tension when both electrodes are made of carbon. With a current of 1.73 amp&res 0.93 gram of chlorine per hour was produced, so that if a dynamo were employed it should give 64.5 grams of chlorine and 259.8 grams of Na2C0, + lOH,O per horse-power-hour.F. S. I(. Preparation of Crystalline Normal Lithium Phosphate and Arsenate. By A. DE SCHULTEN (Hull. 8oc. Chim. [3], 1, 479-480). -Fused lithium chloride dissolves the amorphous, normal phosphate, and on cooling and washing the melt, rhomboidal, tabular crystals ofINORQ ANIC CHE YIISTR Y 11 normal lithium phosphate, which have a sp. gr. 2.41 at 15", and are infusible at a white heat, are obtained. The normal arseiiate is similarly prepared ; it corresponds with the phosphate physically, and is of sp. gr. 3.07 a t 15". T. G. N. Cadmium Phosphates and Arsenates. By A. DE SCHULTEX (Rz;ZZ.Xoc. Chim. [3], 1, 473--4i9).-The normal orthophosphate, Cd,( POa),, falls as a voluminous, amorphous precipitate when normal sodium phosphate is added to the solution of a cadmium salt. Hydrogen disodium phosphake throws down from a, hot solution of cadmium chloride or sulphate an amorphous precipitate which quickJr becomes crystalline. After purification by dissolution in phosphoric acid and cautious reprecipitation by alkaline hydroxides, i t forms small, prisnintic hexagons of sp. gr. 3-98 at 15", having the composition H2Cd5(P04)d + 4H20 ; these, when dissolved in cold phosphoric acid (sp. gr. 1.1), are reprecipitated unaitered on warming or on heating 111 sealed tubes to 250", butr redissolve on cooling ; as thus produced, tlieir sp. gr. is 4.12 a t l5O.This phosphate loses its water at a red heat, and fuses at a white heat ; it is probably tbe compouiid described by S tromeyer as the noriiial phosphate. Monocadmium phosphate, H,C'd(P@,), + 2H,O, crystallises out after slow evaporation of a saturated solution of the previous salt in cold dilute phosphoric acid a t the normal temperature. It exists as large clino-rhombic prisms of sp. gr. 2742 a t 15", which lose their water of crystallisation at lOO", and are decomposed by water to form a flocculent phosphate, H?Cd5(P04), + 4H20. Cadmium ch1orapatite.-Normal cadmium orthophosphate and the second phosphate described above dissolve in fused cadmium chloride, aiid on slowly cooling the melt, long, hexagonal prisms of the salt, 3Cd,(P04),,CdC12, of sp. gr. 5.46 at 15", separate.A cadmium loromapatite, 3Cd3( PO4),,CdBr2, may be similarly pre- pared, but is a1 ways contaminated with cadmium pprophosphate, from which it may be separated by cold, dilute nitric acid, which dissolves only the bronrapatite ; the cadmium pyrophosphate, Cd2PZO7, exists as flattened oblique lamella: of sp, gr. 4.965 at 15". Cadmium arsenates.--When the amorphous powder, H2Cd5( As04)4 + 4H20, which is precipitated on the addition of hydrogen disodium arsenate to the solution of a cadmium salt, is dissolved to saturation in a cold solution of arsenic acid of sp. gr. 1.3, and, subjected to heat, crystals of the salt HCdAsO, + H,O, having a sp. gr. of 4.164 a t 15" are deposited. Monocadmium arsenate, H4Cd(As04)2 + 2H20, crystallises out when a saturated solution of the compound H2Cd,(P04)4 + 4H20, in arsenic acid solution (sp.gr. 1.3), is allowed to evaporate at the ordinary temperature. It forms large, clino-rhombic prisms of sp. gr. 3.241 at 15", which are isomorphous with those of the corresponding phosphate. At 70-80", they lose their water of hydration, and are partly decomposed; with excess of water, they form a flocculent substance, H,Cd5(As0,)r + 4H20. Cadmium chlorarsenioapatite, 3Cd:,(AsO4),,CdCI2, is produced by fusiiig either normal ammonium arsenate or the salt HzCd,(As04), +12 ABSTRACTS OF CHEMICAL PAPERS. 4H20, with excess of cadmium chloride. Its sp. gr. is 5.865 at Is", and its physical properties correspond with those of the chlor- apatite. Cadmium bromaraenioapatite, 3Cd3(AsOl).?,CdBr,, is similarly pre- pared, and exists as long yellow prisms of sp.p. 6.017. Cadmium pyroarseriate, CdrAsoO,, is prepared by f'using a mixture of cadmium bromide (22 parts) with potassium bromide (5 parts), and adding to the fused mass iiormal ammonium arsenate (9 parts) ; after washing the melt, the colourless crystals of the pyroarsenate are separated from the yellow brorliarsenioapatite Ins treatment with dilutJe nitric acid, which dissolves the latter compound only. This pyroarsenate forms crystals of sp. gr. .5*474 at 15", corresponding in physical properties with the pyrophosphate. T. G. N. Action of Sodium Thiosulphate on Metallic Salts. By G. VO~WXANN and c. PADBERG (Bw., 22, 2637 --2641).-The authors have extended Vortmann's work on copper salts (Abstr., 1898, 787) to ot,hcr metallic salts.When a concentrated solution of sodium thiosulphate is added to a strong solution o i lead acetate until thc lead thiosulphate first precipi- tated has been just redissolved, and alcohol is then added, an oily liquid separates, which when rubbed with absolute alcohol solidifies to a crystalline mass of the formula PbY20,JSa,Sz03 + 12H,O. Thallious sulphate under similar treatment yields small needles of the formula T1,S20,,2Na,SL0, + 8H,O. When molecular proportions of cadmium sulphate and barium thiosulphate are rubbed together with a little water, the insoluble barium sulphate formed filtered off, and alcohol added to the filtrate, cadmium thiosulphate, CdS,O, + 2H,O, separates as an oil, which gradually solidifies to a yellowish-white, crystalline mass.When equal molecular proportions of sodium thiosulphate and cadmium nitrate in aqueous solution are mixed together and alcohol added, yellowish-white needles of the formula 2CdE,O3,NalS20, + 7H20 are formed. If a large excess of the thiosulphate is used, the compound CdS20,,3Na,S,03 + 9H,O separate., as an oil. This gradually solidifies to sinall, yellow scales, which lose 4 mols. H,O over sul- phuric acid. On mixiiig strong solutions of zinc iodide and sodium thiosulphate and adding alcohol, an oil separates, wliicli after long exposure over sulphuric acid solidities tci a gum-like mass of t h e formula 2ZnS,03,3Na2S,0, + 1 OH20. I t is deliquescent, and decomposes gradually with formation of zinc sulphide. Ferrous tliiosulphate, PeS20, + 5Hy0, forms green crystals easily soluble in water.A double salt, FeS2O3,3Na2S2O3 + HH,O, was ob- tained by precipitating a mixed solution of ferrous iodide and sodium thiosulphate with alcohol. It forms bright-green crystals, soluble in w a t 61'. Rlanganese t,hiosulphate, MnS,O, + 5H20, is crystalline but un- stable. A pale, rose-coloured double salt, hlnS20,,2N%S,0, + 16H20, was obtained. The cobalt double salt, CoS,0j,3NaLSLOj + 15H20, forms a Iilue,INORGANIC CHEMISTRY. 13 gum-like mass, soluble in water. No corresponding nickel salt could be prepared, though a crystalline salt, NiS203,6NH3,3H20, was obtained. L. T. T. New Method of Preparing Anhydrous Aluminium Chloride. By C. F. MABERY (Ber., 22, 2658).-The author finds that dry hydrogen chloride extracts the whole of the aluminium from an alloy of copper and aluminium without attacking the copper.The reaction is most energetic a little below a red heat. The alloys containing 15 to 40 per cent. of alaminium are hest powdered, .mixed with powdered charcoal (to prevent the fusion of the remaining copper), put into a graphite retort, and when heated just below R red heat a current of hydrogen chloride is passed through. The aluminium chloride distils over, and may be condensed in suitable vessels, the liberated hydrogen passing on. L. T. T. Alkali Aluminium Silicates. By A. GOEGEU Zeit. Kryst. Min., 15, 646, from BdZ. SOG. fran. win., 10, 278).-On melting kaolin with alkali haloid salts in the presence of moist air, silicates are formed, having the composition AlR'SiO,.B.7 melting kaolin with potassium carbonate or caustic potash at a dull-red heat, an amorphous salt, A1KSi04, is obtained, whilst a t a more intense heat octahedra are obtained, having the composition Al2K2Sio6, o r else a more basic silicate also cr.ystallising in the regular sjstem. The sodium-corn- ponnds prepared in a similar way are alm~~ys basic, and form doubly refracting crystals. B. H. B. Mercuricobaltarnmonium Salts. By G. VVRTMANN arid E. MORGULIS (Rer., 22, 2644--2648).-When solntions of the mercuric double salts of cobaltammonium chlorides are treated with potash or soda, rsd precipitates are formed, which appear to be cobalt-ammo- nium chlorides, in which part of the hydrogen is replaced by varying proportions of the univalent radicles (HgCl) or (HgOH).A solution of the salt CO~(NJH,)~~C~,,~H~C~,, or a mixture of one part by weight of lut,eocobalt chloride and three parts of mercuric chloride, when treated with 6 mols. of soda yields the salt ; or with excess of soda, the salt Co,N12Hz8(HgOH)8C16. Both compounds are bright-red, and decompose quickly when moist, slowly when dry. Equal weights of luteocobalt chloride and mercuric chloride with excess of soda yield a slightly more stable, red salt, Co2N12H3,( Hg0H),CI6. Pirrl7ureocobaZtdecamin~ salts.-1 mol. of purpureocobalt chloride, 6 niols. of mercuric chloride, and 6 mols. of soda yield a dark-red, flocculent salt, Co2Nl,H,2(HgC1),(H~oH),C16 ; with excess of ~ o d a , the salt CO,N,,H~~(H~OH)~CI~ is formed. RoseocohaZtdecamine saZts.-1 mol.of roseocobalt chloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield a violet-red precipitate, Co2NlOHZ4( HgOH)&I, ; with excess of soda, a salt, Luteocobalt salts. coz"JL( HgOH)6C14( OH)*, is formed. Both salts are very unstable.14 ABSTRACTS OF CHEMICAL PAPERS. Pur~ureocobaltoctaminu snlts.-l mol. of purpureocobaltoctamine chloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield the d t , Co2N6Hl6(HgCl),( HgOH )&16 ; with excess of soda, the salt Co,N,H,, (HgOH),Cl, is formed. Equal weights of the cobalt and mercuric salts with excess of soda yield the salt Co,N,Hls(HgOH),Cl,(OH),. Roseocobultoctamine salts.-Under like conditions as with the pur- pureo-salts, the three salts, CO,NBH~~(H~CI),(H~OH)~C~~, Co2N8HM( HgOH)SCh, and CO~N~H,~(H~OH)EC~,(OH),, are formed.All three are rio:et-recl, and decompose at ordinary atmospheric temperature, as do also the corresponding purpureo-compounds. L. T. T. Cobaltoctamine Salts. By G. VORTMANN and 0. BLASBERG (Be,.., 22, 2648-2655) .-When cobalt nitrate, sulphate, or chloride is dis- solved in a small quantity of water and added to a mixture of ammonia and ammonium carbonate, violet-red solutions are formed. If these are oxidised by a current of air, decamine salts are formed, but on evaporation these are decomposed, octamine salts crystallising o u t . The following salts are described :- CO,(NH,)~~(NO~>~(CO~)~,~H,O ...... Crystalline. Co,(NH3) SO,) ,C 03,4H ,O ......... Crystalline. ~ o , ( N H , ) , ( ~ ~ ~ ) , C ~ ~ ~ ~ H ~ O ..........Long, thinneedles. CO,(NH,)~SO,(CO~),,~H,O. ......... Dark red, prismatic Co,(NH3),CI,C0,,2 H-0. ............ Crgstalline. Co2( NH3) (X O&( CO,) 2,H20 ........ Cherry red crystals. crystals. CV? (NH,),Cl,( CO3)2,H,O ........... 9 7 CO,(NH~),(NO~)~(SO~)~,~H,O ....... 7 , CO,( NH3) 8 (“0,),,2H,O. ............ CO,( NH,),(N03),C14,4H?O. .......... 7 7 C‘O~(NH,),(NO~)J~,~H~O ........... 9 7 Co,( NH,) ,Br2( SO,) ............... 99 Co2(NH3),1,(SO4),. ................ 9, 1 , CO~(NH,)~I,CI~,~H,O .............. Brown scales. Co2(NH3),(OH)2C1,,2H20 .......... Dark green powder. CO~(NH~),(OH),C~,,~H~C~, ......... C O ~ ( N H ~ ) ~ ( OH),CI,,PtCI,,H?O ...... L. T. T. Action of Sulphurous Acid on Cobaltammonium Salts. By G. VORTMANN and G. MAGDEBURG (Ber., 22, 2630--2637).-The authors have obtained the following compounds :- CO,(NH,),(SO,A~)~,~OH~O ........Yellowish-brown needles. Co,(NH3),( S03)6Ba377H20 ........... Golden-yellow scales. C O ~ ( N H ~ ) , ( S ~ ~ ) , B ~ ~ A ~ , , ~ H , G . ...... Golden-yellow scales. Co2(NH,),(S03),Co~vi7~6H,0 ........ Orange crystals. Co2( NH3),( So3)6c02v’,~4H,0 ........ Orangc crystals.ISORQANIC CHERIISTRY. 15 C O ~ ( NH3),( SO3),(NH3) ,,Co.,"'.SH,O . . CO,(NH,),(SO,),(SO~A~),,~H.?~. .... CO~(NH~)~SO~[SO~)~CO~",~~H~O ..... Coz(NH3) (NH3),( SO3)?C1?,4H:.?O . . . C ~ ~ ~ ~ H , > ~ , ( s o , ~ a ) ~ , ~ H ~ o .......... *Co2(NH,) lo( S03)6C02Vi,8H,0 ......... Coz( NH,) S03)zC12. ............... CO~(NH,),,(SO,),,~H,O. ............ CO~(NH,)~~(SO,)~C~~,~H,O .......... Orange powder. Yellowish- bro w n needles .Yellow crystalline powder. Dark brown crystals. Light brown crystals. Brom.nish-yellow powder. Brown crystalline powder. Yellow needles. The authors consider that these salts show the exist.ence of f o u r series of salts. New case of Isomorphism of Uranium and Thorium. By C . RANMELSBERG (Zeit. K~yst. Nifl., 15, 640-641 ; from Sitzber. preuss. Akad. Wiss., 1886, 603).-The author shows that the thorium sulphate described by Nordenskiijld and others, and the uranium sul- phate hitherto regarded as rhombic, have a similar composition, namely :- (SO,)zTh + 9H,O, (so*),u -k 9H2.0. The crystals of the latter are only seemingly rhombic in conse- quence of twin-formation ; in reality they are monosymmetric, like the thorium sulphate. The axial ratios of the two minerals are: uranium sulphate, a : b : c = 0.597 : 1 : 0.6555, /3 = 82" 11'; thorium sulphate, a : b : c = 0.598 : 1 : 0.658, /3 = 81" 30'.Fluorine-compounds of Vanadium and its Analogues. By E. PETERSEN ( J . p. Chenz. [a], 40, 271-296 ; compare Abstr., 188:4, 107).-The following double salts of vanadium oxyfluorides and potassium fluoride have been obtained :- 2KF,VOF3: a white, crystalline precipitate, is obtained by adding a solution of potassium fluoride to one of vanadic acid in hydrofluoric acid ; when dried over sulphuric acid, it becomes reddish-brown, and has the above formula. 4KF.VF,,VOF3 separates as a white precipitate from the mother- liquor of the above salt. HB',3KF,2VOF3 crystallises from a hot solution of either of the preceding salts in hydrofluoric acid in beautiful, colourless prisms, which lose very little weight at 100".3KF,VOF3,V0,F is the white, crystalline residue left when the precipitate obtained by adding a solution of vanadium pentoxide in hydrofluoric acid to a solution of potassium fluoride is treated with water at the ordinary temperature; if hot water is used and the solution is poured into a hot solution of potassium fluoride, a crystal- line precipitate is obtained, cf uncertain composition, but approaching * Probably Kunzc.l's penttlmineclicobaltic sulphite. B. H. B.1 li ABSTRACTS OF OHENICAL P-1PERS. the formula 4KE',VOF3,V02F ; or if the first-mentioned precipitate is heated with water for some minutes, a salt having nearly the coin- position VOF,,VO,F is obtained. 2KP,VO,F separates from a warm solution of vanadium pentoxide in hydrofluoric acid when i t is nearly neutralised with potassium hydroxide.It crystallises in yellow, six-sided, truncated prisms. When reci*ystallised from water, it yields the salt 3KF,2V02F. 3HF.9NH4F,5VOY3, obtained by adding ammonium fluoride in slight excess to the solution of vanadium pentoxide in hydrofluoric acid, crystdlises in larqe, colourless, four-sided prisms. SNH,F',VO,F cryst allises from a solution of vanadium pentoxide in hpdrofluoric acid wheii it is nearly neutralised with ammonia. The crystallography of the salt is given. HF,7NH4F,4V02F separates in white crystals from the solution of the last-nxmed salt in warm water. 2Nbp0,,3KF,5H,0 is obtained by melting niobium pentoxide (1 part) with potassium fluoride (3 25 parts) and treating the melt with water, when the salt remains undissolved as a crystalline powder.Nb20,,KF,3H,0 is a prismatic, crystalline powder, obtained by fusinq niobium pentoxide (1 part) with potassium fluoride (1*.3-1*5 parts). The author reviews the work already done on the vanadium double fluorides, and concludes his paper with the followinq directions for extracting vanadic acid from the finery slag of Taberg:--.300 grams of the finely-powdered slag is mixed with 400 C.C. of hydro- chloric acid (sp. gr. 1.18) and shaken. After 24 hours, water is added to make the bulk up to 1i litres, and the whole filtered through linen. Iron is then addpd, and, after the evolution of hydrogen has ceased, sodium acetate until the liquid is reddish-brown; finally, acetic acid and sodi nm phosphate are added until all iron, chromium, aluminium, and vanadium are precipitated as phosphates.The precipitate is mixed with sodium carbonate (0.5 part) and heated on an iron plate for i-2 hour ; the mass is treated with water, hydrochloric acid nddecl to nearly neutralise the solution, which is then heated, filtered, and made acid with acetic acid ; solid ammonium chloride is now added, when a red, crystalline ammonium vanadate, (NH&0,2V2O5,4H20, separat,es ; this is heated and the residual vanadium oxide treated with hot nitric acid at 110-120", and converted into ammonium mets- vanadate by evaporating off the nitric acid, dissolving in ammonia, and cr~+stallising ; pure vanadic acid is obtained from this salt by igniting and repeating the nitric acid treatment.Vapour-density of Antimony Pentachloride. By R. ANSCH~TZ A. G. B. and N. P. EVANS (Annnlen, 253,95--105).-By means of a modification of La Coste's apparatus, the authors have attempted to determine the density of the vapour of antimony pentachloride under reduced pressure. As antimony trichloride boils at 143-144" under 70 mm. pressure and antimony pentachloride boils a t 102-103" under 68 mm. pressure, the determinations were made under 58 mm. pressure a t a temperature of 218". The mean of four determinations gave the \ d u e 10, the theoretical density being 10.33. It was impossible toIKORGANIC CHENISTRY. 17 exclude all traces of moisture from the apparatus and avoid the formation of minute quantities of the monohydrate of antimony penta- chloride.w. c. FV. Atomic Weight of Palladium. By E. H. KEISER (Amer. Chew. ,J., 11, 398--403).-Attempts were at first made to use the double chlorides of palladium with ammonium and with sodium, but they had to be abandoned, a s these compounds contain water, from which i t is almost impossible to completely free them ; moreover, the dried salts are very hygroscopic, and absorb water rapidly while being weighed. Finally, the yellow, cry stadline palladiodiammonium chloride, PdN,H6C12, was used ; this is formed whenever hydrochloric acid is added to a solution of palladium chloride in excess of ammonia ; it is R stable compound, and can be obtained very pure. It contains no water of crystallisation, c:m be dried completely, and is not hygro- bcopic.When heated in a current of pure hydrogen, the colour changes from yellow to black, hydrogen being absorbed, and metallic palladium and ammonium chloride formed. On raising the tempera- ture, the ammonium chloride volatilises, and spongy palladium is left behind ; this is cooled below a red heat in a current of hydrogen, and then the hydrogen is displaced by air; in this way the occlusion of hydisogen is prevented. The weight of palladium obtained from a known weight of the chloride is thus ascertained, and from this the atomic weight of palladium is calculated, assuming N = 14.01, H = 1, C1 = 35.37. Two series of experiments were made; the palladammonium chloride used in the second scries was prepared from the metallic ptiliadium obtained in the first.The results give a s mean value Pd = 106.35:- Atomic weight. r----h.---- - Series. Experimenta. Mean. Maximum. Minimum. I. 11 106.352 106.459 106-292 11. 8 106.350 106.455 106.286 C. F. B. Ruthenium Potassium Nitrites. By A. JOLY and M. VEZES (Compt. rend., 109, 667-670 ; compare Abstr., 1889, p. 352).-If ruthenium chloride is added to a boiling solution of potassium nitrite until the precipitate which forms a t first is redissolved, and the liquid is concentrated and allowed to cool, it deposits dichroic, orange-red, monoclinic prisms of 90" 10'. They are very soluble in water, can be purified by repeated recrystallisation without under- going a1 teration, and have the composition RuZOL( N,0,)a,4KN0, or When the potassium nitrite is in excess, and prolonged ebullition is avoided, a pale-yellow, crystalline precipitate is obtained of the composition $uz02, (N203),,8KN02 or Ru?O,( NO)2,N,03,8KN0,.Sepa- ration of the ruthenium is never complete, and the mother-liquor, OIL concentration, yields crystals of the first compound. The second salt is converted into the first by prolonged ebullition with wat8er, and the reverse change is effected by the addition of potassium nitrite. A t a voc. LVIII. C RU~O,(NO),,(N?O~),,~KNO~.I S ABSTRACTS OF CHEMICAL PAPERS. low temperature, the second salt crystallises with 2 mols. H,O. Other double nitrites seem to be formed, but are relativelyvery unstable. If the double nitrites are heated with ammonium chloride and hydrochloric acid, only part of the nitrogen is evolved and one atom of the nitrogen remeins i u combination with each atom of ruthenium.The solution wh '11 concentmtc.d yields the potassium ruthenium nitrosochloride previous1 y described (Zoc. cit.). No compound was obtained corresponding with that to which Claus attributes the formula Ru(N0,),,3KNO2. C. H. B.ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h e m i s t r y .Preparation of Chlorine in a Kipp's Apparatus. By J. THIELE(A?znden, 253, 239--'L42) .-Chlorine may be conveniently preparedin a Kipp's apparatus by the action of hydrochloric acid on bleachingpowder. By means of a handpress, tbe bleaching; powder is compressedi n to a hard cake ; this is broken into small lumps and used in thisf o r in. w.c. w.Automatic Apparatus for Evolving Gases from Liquids. ByJ. THIELE (AnnuZen, 253, 242-246).-A convenient apparatus f o rpreparing hydrogen chloride from commercial hydrochloric acid orsulphurous anhydride from a concentrated solution of sodium hydrogensulphite may he made from R three-necked Wo1fl"s bottle. This isprovided with-(1) a delivery tube fitted with a stop-cock; (2) asmall stoppered separating funnel with the stem drawn out toa fine point; and (3) a safety funnel with some mercury in thebend and a loose plug of cotton wool in the funnel. The Wolff'sbottle is half filled with the solution of sodium hydrogen sulphite, forexample, and the sulphuric acid is slowly introduced through theseparating funnel. w. c. w.Reciprocal Displacement of Oxygen and the Halogens.ByBRRTHELOT (Compt. rewd., 109,546-548 and 590--597).-'l'he authorsummarises his previous work on the reciprocal displacement ofoxjgen and chlorine and describes some later results.Pure concentrated fuming hydrochloric acid is not decomposed byoxygen in presence of sunlight, but if some maiiganous chloride ispresent the liquid acquires it deep-brown colour, the atmosphere i nthe flask becomes cliarged with chlorine, and the liquid has bleachingproperties. Oxygen is absorbed and hydrochlorides of manganeseperchloride are iormed. If the liberated chlorine is removed andhydrogen chloride and oxygen are introduced into the flask, a furtherquantity of chlorine is set free, and this process may be repeatedseveral times. The decomposition ceases when the hydrates of thehydrochloric acid contain the maximum amount of wat,er ; dilutenon-fuming hydrochloric acid is not decomposed even after long ex-p osure in presence of manganese chloride.Ferric chloride behavesi n the same manner as mariganous chloride, but the phenomena arevery much less distinct.The heat of formation of dissolved hydrobromic acid is almost iden-tical with that of water, and hence i n presence of water, but underthese coiiditions only, reciprocal decomposition may take place, In pre-sence of excess of water, oxygen readily decomposes hydrogen bromideunder the influence of light. Similar decomposition takes place a t theordinary temperatnre in the case of it fuming solution of hydrobromicacid, that is, hydrates of the free acid not saturated with water, but isarrested almost immediately by the formation of hydrogen perbromINORGANIC CHEMISTRY.7ide, HBr3; HBr conc. soh. + Br2 gas = HBr, diss. develop+9*2 Cals., the total heat of formation, +43.5 Cals., being greaterthan the heat of formation of water. Oxygen does not decomposedilute hydrobromic acid, that is, the saturated hydrates of the acid,nor a solution of potassium bromide acidified with hydrochloricacid .The formation of hydrogen perbromide explains the decompositionof water by bromine, but this change is limited by the dissociation ofthe perbromide in presence of water.Dilute solutions of hydriodic acid are readily decomposed byoxygen under the influence of light at the ordinary temperature, thechange corresponding with the liberation of 15.9 Cals.for each atomof gaseous iodine.The heats of formation of dissolved potassium iodide and hydroxidearc practically the same, and slight variations in the conditions serveto turn the reaction in one direction or the other. The combinationof iodine with potassium iodide in concentrat'ed solution to formpotassium triiodide liberates f5.0 Cals. for each atom of gaseousiodine ; the action of iodine on dissolved potassium hydroxide withformation of hypoiodite or iodate liberates +4*1 Cals. and + 5.4Cals. respectively for each atom of gaseous iodine. l t follows thatoxygen will not displace iodine from potassium iodide except underconditions in which potassium triiodide is stable, that is, in very con-centrated solutions.Experiment showed that dilute solutions ofpotassium iodide remain quite colourless when exposed to light fora long time in presence of pure air ; very concentrated solutions soonbecome orange and the colour deepens with prolonged exposure. Theliquid then gives a blue coloration with starch and has an alkalinereaction; if, however, it is diluted, it rapidly becomes colourless,owing to dissociation of the potassium triiodide and the action ofthe liberated iodine on the potassium hydroxide which has beenformed.It is well known that even dilute potassium iodide solutions becomeyellow when exposed to ordinary air. This is due to the fact that thecarbonic anhydride of the air takes part in the reaction.Carbonicacid does not displace hydriodic acid, but the simultaneous action ofoxygen and carbonic anhydride on a dilute solution of potassiumiodide produces potassium hydrogen carbonate and free iodine. thechange being accompanied by the liberation of +13.5 Cals. for eachatom of gaseous iodine. The colour of the liquid becomes deeper ifthe quantity of carbonic anhydride in the atmosphere above it isincreased. The action of the oxygen is still greater in presence ofacetic or hydrochloric acid, but in these cases the result is in part dueto the displacement of some hydriodic acid. Acetic acid liberatesverylittle hydriodic acid, but the action of the oxygen depends on thesuccessive liberation of small quantities.Hydrochloric acid liberatesmore hydriodic acid and in this case the action of the oxygen is moremarked. In presence of a large excess of air, a solution of potassiumiodide acidified with hydrochloric acid is completely decomposed bythe action of light in a few days.If manganous chloride is added to a highly concentrated solution o8 ABSTRACTS OF CHEMICAL PAPERS.potassium iodide and the mixture exposed to light, a higher oxide ofmanganese is precipitated and iodine is liberated ; dilute solutionsshow the same phenomena in a lower degree.All the reciprocal displacements of oxygen and the halogens underthe influence of light are in agreement with the thermochemicaldeterminations. C. H. B.Simultaneous Synthesis of Water and Hydrogen Chloride.By P.HAUTEFEUILLE and J. MARGOTTET (Oowpt. rend., 109, 641-644).--Mixtures which contained oxygen and hydrogen in the proportionrequired to form water, with varying proportions of chlorine ; andmixtures of hydrogen and chlorine in the proportions to form hydrogenchloride, with varying quantities of oxygen, were exploded by meansof a spark, and the residual chlorine was determined by means ofstandard sodium arsenite. If p represents the total hydrogen whichenters into combination, and p' the quantity which combines withoxygen, v - p' gives the ratio of the hydrogen converted intoWwater to thb hydrogen which forms hydrogen chloride. This ratio isindependent of the initial pressure, and of the nature of the spark.It is always less than unity if the proportion of chlorine is more thanhalf the volume of the hydrogen, and it varies with every alterationin the proportion of chlorine. When the volume of chlorine presentis double the volume of the hydrogen, the quantity bf water formedbecomes inappreciable.It is evident that the results do not agreewith Bunsen's law.With equal volumes of hydrogen and chlorine and varying propor-tions of oxygen, the 'ratio is always less than unity and doesnot vary greatly when the ratio of oxygen to hydrogen varies from0.25 to 3. With equal volumes of the three gases the change is re-presented by the equation 5C1, + 5H2 -t 502 = 8HC1 + H,O + C1,402. C. H. B.PEquilibrium between Hydrogen, Chlorine, and Oxygen. ByH. LE CHATELIER (Cornpt. rend., 109, 664--667).-The author dis-cusses'the results of Hautefeuille and Margottet (preceding Abstract)from the point of view of his own laws of chemical equilibrium.Theagreement between the observed and calculated numbers is very close.He points out that the degree of moisture of the gases, which is veryimportant, is not specified. The fornlula shows that a reduction ofinitial pressure should be accompanied by a reduction in the propor-tion of water formed, and the fact that this is not observed indicatesthat' the chlorine is pai*tially dissociated. The varying effects ofchlorine and oxygen depend solely on their relative volumes and noton their chemical properties. C. H. B.Preparation of Oxygen in a Kipp's Apparatus. By J . VOLHARD(AnnaZen, 253, 246--24H).-Small quantities of oxygen can be con-veniently prepared in a, Kipp's apparatus by the action of hydrogcbiINORGANIC CHEXISTRT .9peroxide on bleaching powder.quantity to neutralise the lime in the bleaching powder.Nitric acid is added in sufficientThe oxygencontains a small quantit,y of chlorine. w. c. w.Action of Sulphur on Solutions of Metallic Salts. By G.VORTMANN and C. PADBERG (Ber., 22,2642-2644).--The authors findthat with many proto-salts when their aqueous solutions are boiled withflowers of sulphur, about half the metal present is precipitated as sul-phide, the remainder being oxidised to the per-salt. When a stronglyacid solution of stannous chloride WRS employed, no stannous sulphidewas precipitated, but hydrogen sulphide was evolved, and the wholeof the tin oxidised to stannic chloride. With an aqueous solution ofstannous chloride, and with an acid solution of' cuprous chloride,laather less than half the tin was Precipitated as sulphide, a littiebeing oxidised in the same manner as with the strongly acid solutionof tin.With mercurous nitrate, almost exactly halt of the mercurywas precipitated as sulphide.Solutions of manganese, iron, nickel, zinc, and cadmium sulphates,and acid solutions of bismuth and antinionious chlorides, and ofarsenious and arsenic acids, are not altered wlien boiled with sulphur.L. T. 'l'.Preparation of Nitric Oxide. By J. THIELE (Annulen, 253,246) .--Nitric oxide is prepared in the apparatus previously described(t,his vol., p.6) by adding a strong solution of sodium nitiite to asolution of ferrous chloride or sulphate in hydrochloric acid. I f thesodium nitrite contains carbonate, i t may be removed by precipit,at,ionwith calcium chloride. w. c. w.Phosphonium Sulphate. By A. BESSON ( C O V Z ~ ~ . Tend., 109,644-645) .-When hFdrogen phosphide is passed into sulplinric acida t the ordinary temperatxre, there is considerable development ofheat, sulphur separates, and sulphurous acid is formed. If the acid ispreviously cooled by means of ice and salt, the gas is somewhatlargely nbaorhed, and the liquid remains limpid. After a time, how-ever, it begins to decompose in the manner indicated, the temperaturerises, and deconiposition becomes very rapid. If the acid is cooled to-20" or -25" by the rapid evaporation of methyl chloride, a syrupyliquid is obtained, from which a white, crystalline, highly deliquescent,solid separates; this seems to be phosphonium sulphate.Whenthrown into water at the ordinary temperature, it dissolves w i t h astrident noise, and hydrogen phosphide is evolved, but the sulphuilicacid is not reduced. When exposed to air a t the ordinary tempera-ture, the phosphorus is oxidised to phosphoric, phosphorous, and hypo-phosphorous acids, whilst the sulphuric acid is reduced to sulphurousacid and sulphui., with a small quantity ot' hydrogen sulphide. Thecrystals may be dissolved in dilute sulptiuric acid, and if t'he solutionis electrolysed a t -25" or -40" with a mercury cathode, there isonly a very slight intumescence of the mercury, and hence, if phos-phonium amalgam exists, it is very unstable even at the freezingpoint of niercury.Tlie solution bas a high resistance, and ii' th10 ABSTRACTS OF CHEMICAL PAPERS.current is too strong the compound is decomposed with great rapidityin the manner already described.Hydrogen phosphide has no action 011 nitric acid at -23".Behaviour of Sodium Thiosulphate towards Acids andMetallic Salts. By W. VAUBEL ( B e y . , 22, 2703-27@4).-A replyto Vortman (Abstr., 1889, 1107) upholding the author's previous newsC. H. B.(ibid., p. 943).Direct Production of Crystalline Sodium Carbonate andChlorine from Sodium Chloride. By W. HEMPEL (Bey., 22,2475--2478).-1n the electrolysis of metallic chlorides, which givereadily soluble decomposition-products, the latter are further decom-posed as soon as the quantity produced reaches a certain limit.When,however, the compound produced is only sparingly soluble, thissecondary decomposition does not take place, and the whole strengthof the current is utilised. Potassium chloride and sodium chloride,f o r example, can be converted into the corresponding chlorate ; calciumchloride and magnesium chloride can be decomposed into chlorineand a solid hydroxide, by employing a diaphragm.Marx (D. R.-P., No. 46318) has shown that alkaline chlorides canbe directly converted into clilorine and an alkaline hydrogen car-bonate, by passing carbonic anhydride through the solution duringelectrolysis, metal aud liquid diaphra,%ms being employed.The author, who has been engaged independently in making similarexperiments, describes, with the aid of diagrams, an apparatus inwhich sodium chloride can be directly converted into chlorine andcrystalline carbonate.The cathode is a perforated ircn disc, theanode a per€orated carbon disc, the perforations being about 4mm. indiameter, and bored in an upward direction to allow the gas to escapefreely. A disc of ordinary asbestos-paper, placed immediately betweenthe carbon and iron discs, serves as a diaphragm. The three discsare placed in the centre of a vessel made of porcelain and glass, whichis thus divided into two chambers, each of which is provided with aconducting tube, in one case for carbonic anhydride, in the other forchlorine. If sodium chloride is added from time to time t'nrouph asuitable aperture, and the water which is removed with the crystallinecarbonate is replaced, the apparatus can be worked continuously,sodium carbona,te m d almost chemically pure chlorine being obtained.A tension of 3.2 volts is required for decoruposing the sodiumchloride, and a tension of 2.5 volts to overcome the polarisationcurrent ; but the latter has only a slight tension when both electrodesare made of carbon.With a current of 1.73 amp&res 0.93 gram ofchlorine per hour was produced, so that if a dynamo were employedit should give 64.5 grams of chlorine and 259.8 grams of Na2C0, +lOH,O per horse-power-hour. F. S. I(.Preparation of Crystalline Normal Lithium Phosphate andArsenate. By A.DE SCHULTEN (Hull. 8oc. Chim. [3], 1, 479-480).-Fused lithium chloride dissolves the amorphous, normal phosphate,and on cooling and washing the melt, rhomboidal, tabular crystals oINORQ ANIC CHE YIISTR Y 11normal lithium phosphate, which have a sp. gr. 2.41 at 15", and areinfusible at a white heat, are obtained.The normal arseiiate is similarly prepared ; it corresponds with thephosphate physically, and is of sp. gr. 3.07 a t 15". T. G. N.Cadmium Phosphates and Arsenates. By A. DE SCHULTEX(Rz;ZZ. Xoc. Chim. [3], 1, 473--4i9).-The normal orthophosphate,Cd,( POa),, falls as a voluminous, amorphous precipitate when normalsodium phosphate is added to the solution of a cadmium salt.Hydrogen disodium phosphake throws down from a, hot solution ofcadmium chloride or sulphate an amorphous precipitate which quickJrbecomes crystalline.After purification by dissolution in phosphoricacid and cautious reprecipitation by alkaline hydroxides, i t forms small,prisnintic hexagons of sp. gr. 3-98 at 15", having the compositionH2Cd5(P04)d + 4H20 ; these, when dissolved in cold phosphoric acid(sp. gr. 1.1), are reprecipitated unaitered on warming or on heating111 sealed tubes to 250", butr redissolve on cooling ; as thus produced,tlieir sp. gr. is 4.12 a t l5O. This phosphate loses its water at a red heat,and fuses at a white heat ; it is probably tbe compouiid described byS tromeyer as the noriiial phosphate.Monocadmium phosphate, H,C'd(P@,), + 2H,O, crystallises outafter slow evaporation of a saturated solution of the previous salt incold dilute phosphoric acid a t the normal temperature.It exists aslarge clino-rhombic prisms of sp. gr. 2742 a t 15", which lose theirwater of crystallisation at lOO", and are decomposed by water toform a flocculent phosphate, H?Cd5(P04), + 4H20.Cadmium ch1orapatite.-Normal cadmium orthophosphate and thesecond phosphate described above dissolve in fused cadmium chloride,aiid on slowly cooling the melt, long, hexagonal prisms of the salt,3Cd,(P04),,CdC12, of sp. gr. 5.46 at 15", separate.A cadmium loromapatite, 3Cd3( PO4),,CdBr2, may be similarly pre-pared, but is a1 ways contaminated with cadmium pprophosphate, fromwhich it may be separated by cold, dilute nitric acid, which dissolvesonly the bronrapatite ; the cadmium pyrophosphate, Cd2PZO7, exists asflattened oblique lamella: of sp, gr.4.965 at 15".Cadmium arsenates.--When the amorphous powder, H2Cd5( As04)4 + 4H20, which is precipitated on the addition of hydrogen disodiumarsenate to the solution of a cadmium salt, is dissolved to saturationin a cold solution of arsenic acid of sp. gr. 1.3, and, subjected toheat, crystals of the salt HCdAsO, + H,O, having a sp. gr. of 4.164a t 15" are deposited.Monocadmium arsenate, H4Cd(As04)2 + 2H20, crystallises outwhen a saturated solution of the compound H2Cd,(P04)4 + 4H20, inarsenic acid solution (sp. gr. 1.3), is allowed to evaporate at theordinary temperature. It forms large, clino-rhombic prisms of sp.gr.3.241 at 15", which are isomorphous with those of the correspondingphosphate. At 70-80", they lose their water of hydration, and arepartly decomposed; with excess of water, they form a flocculentsubstance, H,Cd5(As0,)r + 4H20.Cadmium chlorarsenioapatite, 3Cd:,(AsO4),,CdCI2, is produced byfusiiig either normal ammonium arsenate or the salt HzCd,(As04), 12 ABSTRACTS OF CHEMICAL PAPERS.4H20, with excess of cadmium chloride. Its sp. gr. is 5.865 at Is",and its physical properties correspond with those of the chlor-apatite.Cadmium bromaraenioapatite, 3Cd3(AsOl).?,CdBr,, is similarly pre-pared, and exists as long yellow prisms of sp. p. 6.017.Cadmium pyroarseriate, CdrAsoO,, is prepared by f'using a mixtureof cadmium bromide (22 parts) with potassium bromide (5 parts),and adding to the fused mass iiormal ammonium arsenate (9 parts) ;after washing the melt, the colourless crystals of the pyroarsenateare separated from the yellow brorliarsenioapatite Ins treatment withdilutJe nitric acid, which dissolves the latter compound only.Thispyroarsenate forms crystals of sp. gr. .5*474 at 15", corresponding inphysical properties with the pyrophosphate. T. G. N.Action of Sodium Thiosulphate on Metallic Salts. By G.VO~WXANN and c. PADBERG (Bw., 22, 2637 --2641).-The authorshave extended Vortmann's work on copper salts (Abstr., 1898, 787)to ot,hcr metallic salts.When a concentrated solution of sodium thiosulphate is added to astrong solution o i lead acetate until thc lead thiosulphate first precipi-tated has been just redissolved, and alcohol is then added, an oilyliquid separates, which when rubbed with absolute alcohol solidifiesto a crystalline mass of the formula PbY20,JSa,Sz03 + 12H,O.Thallious sulphate under similar treatment yields small needles ofthe formula T1,S20,,2Na,SL0, + 8H,O.When molecular proportions of cadmium sulphate and bariumthiosulphate are rubbed together with a little water, the insolublebarium sulphate formed filtered off, and alcohol added to the filtrate,cadmium thiosulphate, CdS,O, + 2H,O, separates as an oil, whichgradually solidifies to a yellowish-white, crystalline mass.Whenequal molecular proportions of sodium thiosulphate and cadmiumnitrate in aqueous solution are mixed together and alcohol added,yellowish-white needles of the formula 2CdE,O3,NalS20, + 7H20 areformed.If a large excess of the thiosulphate is used, the compoundCdS20,,3Na,S,03 + 9H,O separate., as an oil. This graduallysolidifies to sinall, yellow scales, which lose 4 mols. H,O over sul-phuric acid.On mixiiig strong solutions of zinc iodide and sodium thiosulphateand adding alcohol, an oil separates, wliicli after long exposure oversulphuric acid solidities tci a gum-like mass of t h e formula2ZnS,03,3Na2S,0, + 1 OH20. I t is deliquescent, and decomposesgradually with formation of zinc sulphide.Ferrous tliiosulphate, PeS20, + 5Hy0, forms green crystals easilysoluble in water. A double salt, FeS2O3,3Na2S2O3 + HH,O, was ob-tained by precipitating a mixed solution of ferrous iodide and sodiumthiosulphate with alcohol.It forms bright-green crystals, soluble inw a t 61'.Rlanganese t,hiosulphate, MnS,O, + 5H20, is crystalline but un-stable. A pale, rose-coloured double salt, hlnS20,,2N%S,0, + 16H20,was obtained.The cobalt double salt, CoS,0j,3NaLSLOj + 15H20, forms a IilueINORGANIC CHEMISTRY. 13gum-like mass, soluble in water. No corresponding nickel salt couldbe prepared, though a crystalline salt, NiS203,6NH3,3H20, wasobtained. L. T. T.New Method of Preparing Anhydrous Aluminium Chloride.By C. F. MABERY (Ber., 22, 2658).-The author finds that dryhydrogen chloride extracts the whole of the aluminium froman alloy of copper and aluminium without attacking the copper.The reaction is most energetic a little below a red heat.The alloyscontaining 15 to 40 per cent. of alaminium are hest powdered, .mixedwith powdered charcoal (to prevent the fusion of the remainingcopper), put into a graphite retort, and when heated just below Rred heat a current of hydrogen chloride is passed through. Thealuminium chloride distils over, and may be condensed in suitablevessels, the liberated hydrogen passing on. L. T. T.Alkali Aluminium Silicates. By A. GOEGEU Zeit. Kryst. Min.,15, 646, from BdZ. SOG. fran. win., 10, 278).-On melting kaolin withalkali haloid salts in the presence of moist air, silicates are formed,having the composition AlR'SiO,. B.7 melting kaolin with potassiumcarbonate or caustic potash at a dull-red heat, an amorphous salt,A1KSi04, is obtained, whilst a t a more intense heat octahedra areobtained, having the composition Al2K2Sio6, o r else a more basicsilicate also cr.ystallising in the regular sjstem.The sodium-corn-ponnds prepared in a similar way are alm~~ys basic, and form doublyrefracting crystals. B. H. B.Mercuricobaltarnmonium Salts. By G. VVRTMANN arid E.MORGULIS (Rer., 22, 2644--2648).-When solntions of the mercuricdouble salts of cobaltammonium chlorides are treated with potashor soda, rsd precipitates are formed, which appear to be cobalt-ammo-nium chlorides, in which part of the hydrogen is replaced by varyingproportions of the univalent radicles (HgCl) or (HgOH).A solution of the salt CO~(NJH,)~~C~,,~H~C~,, ora mixture of one part by weight of lut,eocobalt chloride and threeparts of mercuric chloride, when treated with 6 mols. of soda yieldsthe salt ; or with excess of soda, thesalt Co,N12Hz8(HgOH)8C16. Both compounds are bright-red, anddecompose quickly when moist, slowly when dry.Equal weights ofluteocobalt chloride and mercuric chloride with excess of soda yielda slightly more stable, red salt, Co2N12H3,( Hg0H),CI6.Pirrl7ureocobaZtdecamin~ salts.-1 mol. of purpureocobalt chloride,6 niols. of mercuric chloride, and 6 mols. of soda yield a dark-red,flocculent salt, Co2Nl,H,2(HgC1),(H~oH),C16 ; with excess of ~ o d a ,the salt CO,N,,H~~(H~OH)~CI~ is formed.RoseocohaZtdecamine saZts.-1 mol. of roseocobalt chloride, 6 mols.of mercuric chloride, and 6 mols.of soda yield a violet-red precipitate,Co2NlOHZ4( HgOH)&I, ; with excess of soda, a salt,Luteocobalt salts.coz"JL( HgOH)6C14( OH)*,is formed. Both salts are very unstable14 ABSTRACTS OF CHEMICAL PAPERS.Pur~ureocobaltoctaminu snlts.-l mol. of purpureocobaltoctaminechloride, 6 mols. of mercuric chloride, and 6 mols. of soda yield thed t , Co2N6Hl6(HgCl),( HgOH )&16 ; with excess of soda, the saltCo,N,H,, (HgOH),Cl, is formed.Equal weights of the cobalt and mercuric salts with excess of sodayield the salt Co,N,Hls(HgOH),Cl,(OH),.Roseocobultoctamine salts.-Under like conditions as with the pur-pureo-salts, the three salts, CO,NBH~~(H~CI),(H~OH)~C~~,Co2N8HM( HgOH)SCh,and CO~N~H,~(H~OH)EC~,(OH),, are formed. All three are rio:et-recl,and decompose at ordinary atmospheric temperature, as do also thecorresponding purpureo-compounds.L. T. T.Cobaltoctamine Salts. By G. VORTMANN and 0. BLASBERG (Be,..,22, 2648-2655) .-When cobalt nitrate, sulphate, or chloride is dis-solved in a small quantity of water and added to a mixture of ammoniaand ammonium carbonate, violet-red solutions are formed. If theseare oxidised by a current of air, decamine salts are formed, but onevaporation these are decomposed, octamine salts crystallising o u t .The following salts are described :-CO,(NH,)~~(NO~>~(CO~)~,~H,O ...... Crystalline.Co,(NH3) SO,) ,C 03,4H ,O ......... Crystalline.~ o , ( N H , ) , ( ~ ~ ~ ) , C ~ ~ ~ ~ H ~ O .......... Long, thinneedles.CO,(NH,)~SO,(CO~),,~H,O. .........Dark red, prismaticCo,(NH3),CI,C0,,2 H-0. ............ Crgstalline.Co2( NH3) (X O&( CO,) 2,H20 ........ Cherry red crystals.crystals.CV? (NH,),Cl,( CO3)2,H,O ........... 9 7CO,(NH~),(NO~)~(SO~)~,~H,O ....... 7 ,CO,( NH3) 8 (“0,),,2H,O. ............CO,( NH,),(N03),C14,4H?O. .......... 7 7C‘O~(NH,),(NO~)J~,~H~O ........... 9 7Co,( NH,) ,Br2( SO,) ............... 99Co2(NH3),1,(SO4),. ................ 9,1 ,CO~(NH,)~I,CI~,~H,O .............. Brown scales.Co2(NH3),(OH)2C1,,2H20 .......... Dark green powder.CO~(NH~),(OH),C~,,~H~C~, .........C O ~ ( N H ~ ) ~ ( OH),CI,,PtCI,,H?O ......L. T. T.Action of Sulphurous Acid on Cobaltammonium Salts. ByG. VORTMANN and G. MAGDEBURG (Ber., 22, 2630--2637).-Theauthors have obtained the following compounds :-CO,(NH,),(SO,A~)~,~OH~O ........Yellowish-brown needles.Co,(NH3),( S03)6Ba377H20 ........... Golden-yellow scales.C O ~ ( N H ~ ) , ( S ~ ~ ) , B ~ ~ A ~ , , ~ H , G . ...... Golden-yellow scales.Co2(NH,),(S03),Co~vi7~6H,0 ........ Orange crystals.Co2( NH3),( So3)6c02v’,~4H,0 ........ Orangc crystalsISORQANIC CHERIISTRY. 15C O ~ ( NH3),( SO3),(NH3) ,,Co.,"'.SH,O . .CO,(NH,),(SO,),(SO~A~),,~H.?~. ....CO~(NH~)~SO~[SO~)~CO~",~~H~O .....Coz(NH3) (NH3),( SO3)?C1?,4H:.?O . . .C ~ ~ ~ ~ H , > ~ , ( s o , ~ a ) ~ , ~ H ~ o ..........*Co2(NH,) lo( S03)6C02Vi,8H,0 .........Coz( NH,) S03)zC12. ............... CO~(NH,),,(SO,),,~H,O. ............CO~(NH,)~~(SO,)~C~~,~H,O ..........Orange powder.Yellowish- bro w n needles .Yellow crystalline powder.Dark brown crystals.Light brown crystals.Brom.nish-yellow powder.Brown crystalline powder.Yellow needles.The authors consider that these salts show the exist.ence of f o u rseries of salts.New case of Isomorphism of Uranium and Thorium.ByC . RANMELSBERG (Zeit. K~yst. Nifl., 15, 640-641 ; from Sitzber.preuss. Akad. Wiss., 1886, 603).-The author shows that the thoriumsulphate described by Nordenskiijld and others, and the uranium sul-phate hitherto regarded as rhombic, have a similar composition,namely :-(SO,)zTh + 9H,O, (so*),u -k 9H2.0.The crystals of the latter are only seemingly rhombic in conse-quence of twin-formation ; in reality they are monosymmetric, likethe thorium sulphate.The axial ratios of the two minerals are:uranium sulphate, a : b : c = 0.597 : 1 : 0.6555, /3 = 82" 11'; thoriumsulphate, a : b : c = 0.598 : 1 : 0.658, /3 = 81" 30'.Fluorine-compounds of Vanadium and its Analogues. ByE. PETERSEN ( J . p. Chenz. [a], 40, 271-296 ; compare Abstr., 188:4,107).-The following double salts of vanadium oxyfluorides andpotassium fluoride have been obtained :-2KF,VOF3: a white, crystalline precipitate, is obtained by adding asolution of potassium fluoride to one of vanadic acid in hydrofluoricacid ; when dried over sulphuric acid, it becomes reddish-brown, andhas the above formula.4KF.VF,,VOF3 separates as a white precipitate from the mother-liquor of the above salt.HB',3KF,2VOF3 crystallises from a hot solution of either of thepreceding salts in hydrofluoric acid in beautiful, colourless prisms,which lose very little weight at 100".3KF,VOF3,V0,F is the white, crystalline residue left when theprecipitate obtained by adding a solution of vanadium pentoxide inhydrofluoric acid to a solution of potassium fluoride is treated withwater at the ordinary temperature; if hot water is used and thesolution is poured into a hot solution of potassium fluoride, a crystal-line precipitate is obtained, cf uncertain composition, but approaching* Probably Kunzc.l's penttlmineclicobaltic sulphite.B.H. B1 li ABSTRACTS OF OHENICAL P-1PERS.the formula 4KE',VOF3,V02F ; or if the first-mentioned precipitate isheated with water for some minutes, a salt having nearly the coin-position VOF,,VO,F is obtained.2KP,VO,F separates from a warm solution of vanadium pentoxidein hydrofluoric acid when i t is nearly neutralised with potassiumhydroxide. It crystallises in yellow, six-sided, truncated prisms.When reci*ystallised from water, it yields the salt 3KF,2V02F.3HF.9NH4F,5VOY3, obtained by adding ammonium fluoride inslight excess to the solution of vanadium pentoxide in hydrofluoricacid, crystdlises in larqe, colourless, four-sided prisms.SNH,F',VO,F cryst allises from a solution of vanadium pentoxide inhpdrofluoric acid wheii it is nearly neutralised with ammonia.Thecrystallography of the salt is given.HF,7NH4F,4V02F separates in white crystals from the solutionof the last-nxmed salt in warm water.2Nbp0,,3KF,5H,0 is obtained by melting niobium pentoxide (1 part)with potassium fluoride (3 25 parts) and treating the melt with water,when the salt remains undissolved as a crystalline powder.Nb20,,KF,3H,0 is a prismatic, crystalline powder, obtained byfusinq niobium pentoxide (1 part) with potassium fluoride (1*.3-1*5parts).The author reviews the work already done on the vanadium doublefluorides, and concludes his paper with the followinq directionsfor extracting vanadic acid from the finery slag of Taberg:--.300grams of the finely-powdered slag is mixed with 400 C.C.of hydro-chloric acid (sp. gr. 1.18) and shaken. After 24 hours, water is addedto make the bulk up to 1i litres, and the whole filtered through linen.Iron is then addpd, and, after the evolution of hydrogen has ceased,sodium acetate until the liquid is reddish-brown; finally, acetic acid andsodi nm phosphate are added until all iron, chromium, aluminium, andvanadium are precipitated as phosphates.The precipitate is mixedwith sodium carbonate (0.5 part) and heated on an iron plate for i-2 hour ; the mass is treated with water, hydrochloric acid nddeclto nearly neutralise the solution, which is then heated, filtered, andmade acid with acetic acid ; solid ammonium chloride is now added,when a red, crystalline ammonium vanadate, (NH&0,2V2O5,4H20,separat,es ; this is heated and the residual vanadium oxide treated withhot nitric acid at 110-120", and converted into ammonium mets-vanadate by evaporating off the nitric acid, dissolving in ammonia, andcr~+stallising ; pure vanadic acid is obtained from this salt by ignitingand repeating the nitric acid treatment.Vapour-density of Antimony Pentachloride.By R. ANSCH~TZA. G. B.and N. P. EVANS (Annnlen, 253,95--105).-By means of a modificationof La Coste's apparatus, the authors have attempted to determine thedensity of the vapour of antimony pentachloride under reducedpressure. As antimony trichloride boils at 143-144" under 70 mm.pressure and antimony pentachloride boils a t 102-103" under 68 mm.pressure, the determinations were made under 58 mm. pressure a t atemperature of 218". The mean of four determinations gave the\ d u e 10, the theoretical density being 10.33. It was impossible tIKORGANIC CHENISTRY.17exclude all traces of moisture from the apparatus and avoid theformation of minute quantities of the monohydrate of antimony penta-chloride. w. c. FV.Atomic Weight of Palladium. By E. H. KEISER (Amer. Chew.,J., 11, 398--403).-Attempts were at first made to use the doublechlorides of palladium with ammonium and with sodium, but theyhad to be abandoned, a s these compounds contain water, from whichi t is almost impossible to completely free them ; moreover, thedried salts are very hygroscopic, and absorb water rapidly whilebeing weighed.Finally, the yellow, cry stadline palladiodiammonium chloride,PdN,H6C12, was used ; this is formed whenever hydrochloric acid isadded to a solution of palladium chloride in excess of ammonia ; it isR stable compound, and can be obtained very pure. It contains nowater of crystallisation, c:m be dried completely, and is not hygro-bcopic. When heated in a current of pure hydrogen, the colourchanges from yellow to black, hydrogen being absorbed, and metallicpalladium and ammonium chloride formed. On raising the tempera-ture, the ammonium chloride volatilises, and spongy palladium is leftbehind ; this is cooled below a red heat in a current of hydrogen, andthen the hydrogen is displaced by air; in this way the occlusion ofhydisogen is prevented. The weight of palladium obtained from aknown weight of the chloride is thus ascertained, and from this theatomic weight of palladium is calculated, assuming N = 14.01,H = 1, C1 = 35.37. Two series of experiments were made; thepalladammonium chloride used in the second scries was preparedfrom the metallic ptiliadium obtained in the first. The results givea s mean value Pd = 106.35:-Atomic weight.r----h.---- - Series. Experimenta. Mean. Maximum. Minimum.I. 11 106.352 106.459 106-29211. 8 106.350 106.455 106.286C. F. B.Ruthenium Potassium Nitrites. By A. JOLY and M. VEZES(Compt. rend., 109, 667-670 ; compare Abstr., 1889, p. 352).-Ifruthenium chloride is added to a boiling solution of potassiumnitrite until the precipitate which forms a t first is redissolved, andthe liquid is concentrated and allowed to cool, it deposits dichroic,orange-red, monoclinic prisms of 90" 10'. They are very soluble inwater, can be purified by repeated recrystallisation without under-going a1 teration, and have the composition RuZOL( N,0,)a,4KN0, orWhen the potassium nitrite is in excess, and prolonged ebullition isavoided, a pale-yellow, crystalline precipitate is obtained of thecomposition $uz02, (N203),,8KN02 or Ru?O,( NO)2,N,03,8KN0,. Sepa-ration of the ruthenium is never complete, and the mother-liquor, OILconcentration, yields crystals of the first compound. The second saltis converted into the first by prolonged ebullition with wat8er, and thereverse change is effected by the addition of potassium nitrite. A t avoc. LVIII. CRU~O,(NO),,(N?O~),,~KNO~I S ABSTRACTS OF CHEMICAL PAPERS.low temperature, the second salt crystallises with 2 mols. H,O. Otherdouble nitrites seem to be formed, but are relativelyvery unstable.If the double nitrites are heated with ammonium chloride andhydrochloric acid, only part of the nitrogen is evolved and one atomof the nitrogen remeins i u combination with each atom of ruthenium.The solution wh '11 concentmtc.d yields the potassium rutheniumnitrosochloride previous1 y described (Zoc. cit.).No compound was obtained corresponding with that to whichClaus attributes the formula Ru(N0,),,3KNO2. C. H. B