106 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c C h em i s t r y. Action of Carbon Bisulphide on Metals. By A. CAVAZZT (Ohern. Centr., 1887, 8&8, from Xem. R. Ace. Sc. Imt. Bologna [4], 7, 27-33).-Carbon bisulphide vapour when passed over the heavy metals in a fine state of division and heated to a high temperature yields metallic sulphides with separation of carbon in a graphitoidal form. Other compounds of carbon with sulphur seem not t o be formed in any case. Formation of Hydrates of Lithium Hydyoxide from Alcoholic Solutions : Quantitative Determination of Lithium, By C. Q i j ~ r 1 ' 1 ~ (Bey., 20, 29 12 -29 15) .-Lithium hydroxide generally sepa- rates from hot saturated soltitions in 96.8 percent. alcohol with 4 mol. H,O; when in contact with water, it ahows the movements pre- viously observed with crystals of potassium and sodium hydroxide (Alostr., 1887, 636).When lithium hydroxide is crystallised from 62.8 per cent. alcohol, a hydrate with 1 mol. H20 is obtained; the crystals do not move when placed in contact with watef. In determining lithium as sulphate, the sulphate must be ignited for a long time until of constant weight. Transformation of Ammonium Nitrate. By M. BELLATI and R. ROMANESE (Nuovo Cimento [3], 21, 5--24).-Frankenheirn, and, more recently, Lehmann 'have shown that ammonium nitrate crystal- lises in various forms, according to the temperature at which the V. H. V. N. H. M.INORGANIC CHEMISTRY. 107 crystallisation is effected. Thus at 36" it cryst'allises in the trimetric system, a t 87" in the rhombohedral, and at 120" in the monometric system.I n the present paper, it is shown that a t these various points the salt undergoes other physical modifications. Tbus, on warming, the temperature of the salt increases in direct proportion to the time up to a temperature of 35.67" ; so also the rate of cooling is regular up to 30.3", reaching a minimum at 30.07" ; it then increases to 31*05", at which point it remains constant for some time. Similar phenomena are also observable a t a temperature of 855" to 86.5" with ascending terriperature, and 82.2" to 82.6" with descending temperature, as also at 124.8" and 124.05'. The variations of volume corresponding with these crystalline changes is also determined in an accurately calibrated dilatometer containing oil of turpentine, a liquid whose expansion is regular, and which, when properly dried, does not dissolve the salt, Results show that the curve of coefficient of expansion has two points of inflection: one a t a temperature between 33 29" and 41.29", and another at about $5" ; the formula expressing the rate of expansion from 0" to the former of these points is vl = uo (1 i- 0.000339t + 0*000000346t2), whilst between 40" and 85" this becomes v1 = vo (1.04957 +- 0.00038756t + 0-0000M976ta + 0*0000000432t*).There is also an alteration in the value of the mean specific heat at the temperature of these crystalline transformations ; applying the method of mixtures and using oil of turpentine as t,he liquid, it is shown that the mean specific heat from 0-31" is 0,407, from 31" to 82.5" is 0.355, and from 82.5" to 124" is 0.426.Hence the following values are deduced for the heats of transformation at these points :- At 31.0" = 5-02 ,, 124.0 = 11.86 The values obtained for the specific heats of ammonium nitrate are compared with those of Kopp and Tillinger, and the methods of cor- rection applied by the latter are criticised. Ammonium Phosphites. By L. AMAT (Compt. ?*eizd., 105, 809- 811).-A solution of phosphorous acid mixed with ammonia until aentral to methyl-omnge, and then concentrated until the weight of the liquid is one-fourth or one-fifth more than the calculated weight of the salt, yields large, deliqnescent crystals which can be dried over sulphuric acid or at 100". Similar crystals are obtained if the liquid is concentrated i n a vacunm a t the ordinary temperature.The crystals have the composition NHa*H2P03, and seem t o be monoclinic prisms ; they melt at 123" and are very soluble in water. A t 145" they lose half their ammonia without evolution of hydrogen phos- phide, and yield a gummy mass which seems to contain crystals. At a higher temperature, ammonia and hydrogen phosphide are given off and phosphoric acid is formed. Hydrated diammonium phosphite, (NH,),HPO, + 2H,O, when kept in a dry vacuum a t the ordinary temperature or heated at loo", loses water aud ammonia, and yields the monammonium salt j u s t ,, 82.5 = 5-33 V, H. V.108 ABSTRACTS OF CHEMICAL PAPER,S. described. Both at the ordinary temperature and at loo", the water is given off before the ammonia.Monammonium phosphite has no appreciable action on ammonia gas at the ordinary temperature, but at 80" to 100" absorption is rapid, and the anhydrous diammonium salt is obtained as a white powder. The corresponding compounds of sodium and potassium have not yet been obtained. Effects produced by Small Quantities of Bismuth on the Ductility of Silver. By J. SCULLY (Clhem. News, 56, 224-926 ; 232-244 ; 247--248).-1t is observed that the Indian method of met assay is incidentally a delicate test for bismuth in presence of a large excess of silver. The bullion is dissolved in nitric acid, the solution diluted, excess of hydrochloric acid added, and tb e whole vigorously agitated to facilitate the aggregation of the silver chloride, which settles down and generally leaves a clear supernatant liquid; if, however, the liquid is turbid and the silver chloride on exposure to light, while still under the liquid, remains white, the turbidity is due to mercury, if on the other hand, the silver chloride becomes discoloured, the turbidity is due to bismuth ; tin and antimony having been proved t o be absent when dissolving in nitric acid.In such cases, to prevent the vitiation of the silver assay, the following modified method has proved successful :-The assay ponnd of bullion is dissolved in 5.5 C.C. of nitric acid, sp. gr. 1.200, the solution is mixed ;with 5 ozs. of wat'er and 10 C.C. of nitric acid, sp: gr. 1.320, then 2.5 C.C. of hydrochloric acid are added, and kbe method proceeds as usual. F o r the estimn- tion of the bismuth, having obtained a rough idea of the amount of bismuth present from the amount of turbidity in the trial assay, suflicient bullion to yield a weighable amount of bismuth is dissolved in a small quantity of nitric acid, the solution diluted and heated with excess of ammonium carbonate, which dissolves the silver and copper carbonates, but leaves the bismuth carbonate insoluble ; the latter is then washed, dried, ignited, and weighed. Jf lead or cadmium are present they would remain with the bismuth carbonate ; the latter, however, is not likely to be present, and the former may be separated by dissolving the bismuth carbonate in nitric acid, and evaporating down with sulphuric acid ; the lead sulphate is treated in the usual manner and weighed, whilst the bismuth is reconverted into carbonate and estimated as described above.Fine silver, or silver cont'aining 10 per 1000 of copper, alloyed with 1 to 5 per 1000 of bismuth and cooled rapidly, had its ductility, as tested by rolling, sensibly but slightly impaired, the straps having jagged edges ; with 6 per 1000 of bismuth, the decrease in ductility was more evident, whilst fine silver with 9 to 11 per 1000 of bismuth was so brittle as to brenk with a mere tap. When, however, the cooling was gradual, 4 per 1000 of bismuth was sufficient to make the silver or silver-copper alloy mentioned above highly brittle, the fracture being crystalline in the case of fine silver and granular in the silver- copper alloy. With Indian standard d v e r containing 83.4 per 1000 of copper, 2 per 1000 of bismuth produced red shortness and jagged straps : as the quantity of bismuth increased the evidence of diminished C.H. B.INORGANIC CHEMISTRY. LO9 ductility is more decisive, and with 10 per 1000 of bismuth the alloy was very brittle and had a granular fracture ; the mode of cooling bad no appreciable effect on the ductility of these alloys. Other experi- ments with Indian coinage bars show that the ductility of bullion is not materially affected by the presence of 0.5 per 1000 of bismuth. As the refining fine silver containing bismuth is both tedious and attended with loss of silver, the author suggests dilntion with silver free from bismuth as a, practical means of overcoming the brittleness. The anthor remarks on the concordance of his results with those of Gowland and Koga (Trans., 1887, 410-416), as regards the question of brittleness.The discrepancy in reference to refining bismuth silver he suggests is possibly due to the Japanese silver containing more base metals than the Indian silver ; it consequently supplied more slagging material and greater facilities for refining. D. A. 11. Combination of Silver Chloride with Metallic Chlorides. By M. C. LEA (Anter. J. Sci., 34, 38&387).-1f hydrochloric acid is mixed first with ferric chloride and then with silver nitrate, the silver chloride which forms is not white but buff-coloured. The ferric chloride cannot be removed by washing, and is only partially removed by treatment with hydrochloric acid. The presence of the minute quantity of ferric chloride makes the silver chloride remarkably less sensitive to light. Cobalt chloride and hydrochloric acid give a silver chloride which is pink and contains cobalt ; but the reduction in the sensitiveness to light is very much less than when iron is present.Nickel and manganese behave similarly, but cupric chloride seems to have no tendency to combine with silver chloride. The tendency of gold chloride to combine with the silver chloride is, however, well marked, and the precipitate has a reddish shade, but the influence on the sensitiveness is not easily determined, since the gold is rapidly reduced to the metallic state, and the silver chloride darkens to black instead of to chocolate or violet. as would be the case if it were pure. In analytical determinations, it is important to digest the silver chloride for a considerable time with hydrochloric acid, and even then i t is doubtful if the foreign chloride is entirely removed, especially if it is ferric chloride.These observations show that silver chloride has a great tendency t o combine with small quantities of other chlorides, and supports the author’s view as t o the nature of the ‘‘ photo-salts ” (this vol., p. 1). They also explain the fact that a small quantity of mercuric chloride very greatly reduces the sensitiveness of silver chloride to light. In order to ascertain the presence of mercury in the silver chloride, the anthor employs a solution of stannous chloride in hydro- chloric acid which has no action on silver chloride if light is carefully excluded, but gives a brown or brownish-black colour t o the precipi- tate if mercury is present. The author was unable to remove mercuric chloride from silver chloride even by very prolonged washing.Poitevin’s observation that his coloured photographic images resisted the action of light better after they were treated with dextrin and110 ABSTRACTS OF CHEXICAL PAPERS. lead chloride is explaincd by the tendency of the lead salt to prevent alteration of silver chloride. C. H. B. Silver Potassium Carbonate. By A. DE SCHULTEN (Compt. rend., 105, 811--813).-When silver carbonate is formed by the action of an alkaline cabonate on silver nitrate, the precipitate is sometimes white, sometimes yellnw, but always becomes yellow when washed. If silver nitrate is added to an excess of a concentrated Solution of potassium Carbonate containing some hydrogen carbonate, a white precipitate is formed which changes to microscopio crystals of the oomposition AgKCOs.This compound is decomposed by water, with removal of the potassium carbonate and formation of yellow silver carbonate. 150 grams of potassium carbonate is dissolved in 150 C.O. of water, cooled and agitated with 15 grams of potassium hydrogen carbonate. When the liquid is sahurated with the latter salt a t the ordinary tem- perature, it is filtered and mixed with a solution of 1 gram of silver nitrate in 25 C.C. of water. In order to obtain large crystals, the liquid contaiuing the precipitate is heated with continual agitation. The precipitate dissolves, and when the l i p i d is cooled it deposits long, transparent crystals with a brilliant lustre ; sp.gr. 3.769. They do not blacken when exposed to light except in the presence of orpnic matter, and when treated with water, the silver carbonate which remains retains the form of the osiginal crystals. When heated, the compound loses carbonic anhydride, and a t a higher tem- perature the silver oxide which i s formed gives off oxygen. The crystals are microscopic, rectangular lamell= with a terminal angle closely approaching 90". The refraction is almost identical with that of apatite ; the extinction of parallel polarised light takes place longitudinally ; twinning plane parallel with the plane of the optical axes ; sign of elongation positive ; maximum birefractir-e power approximately 0.0216.C, H. B, Lead Aluminium Sulphate, By G, H. BAILEY (J. XOC. Chem. Ind., 6, 415).-The author has examined some crystals whioh have been noticed in a mordanting liquor (aluminium nitroaoetate) pre- pared by dissolving up alum, lead acetate, and lead &rate in water and allowing to settle. The crystals form octahedra crystallising in cruciform aggregates like alum. They are, however, not transparent and are quite unaltered by exposure to air. The substance is a lead alum, Pb,A1,(S0J6 + 20H20, formed under speoial conditions of concentration and temperature. D. B. New Oxide of Thallium. By A, PICCINI (Gazzetta, 17,450-452).- Carstanjen has observed that when a rapid current of chlorine is passed through a concentrated solution of potash in which thallium sesquioxide is suspended, the solution acquires a violet colour which is considered to be due to a potassium thallste. The same liquid is also formed when thallium hydroxide is submitted to electrolysis, using a plate of thallium as an electrode, as also on adding potassium hypo- chlorite to a quarter of its weight of caustic potash to which thallium sulphate is subsequently added.On digeetinp the whole and addipg barium nitrate, a violet precipitate is finally obtained. The results ofINORGANIC CHEMISTRY. 111 analyses made to determine the relation between thallium and baiium in this precipitate led to discordant results, but sufficient evidence was afforded to point to a formula, TIOz, for the oxide of Bhallium. The isolation of this oxide brings out a further point of analog7 of the thallium compounds to those af lead.Experiments made to pre- pare the corresponding sulphur compound have not as yet been successful, although substances have been obtained which contain a proportion of sulphur greater khan that required for the trisulphide. V. H. V. Constitution of Basic Salts. By S. U. PICKERING (Chem. News, 56,210-212).-1n the author's opinion, those basic compounds, which although seemingly of indefinite composition can scarcely be regarded as mere mixtures, are preoisely analogous to the complex hydrates, which he contends conskitnte a solution of a salt in water. Hydrated basic salts of copper may be obtained of a composition come. fiponding with that of an anhydrous salt of the formula ~ ~ C U O , S O .~ , but the most basic definite sulphate known is 4Cu0,S03, therefore if these higher basic salts are to be regarded as mixtures, they must be mixtures of a basic salt with copper hydroxide and not mixtures of two different basic salts. To investigate this point, a aeries of basic copper salts were pye- pared by diluting a solution of ammonio-copper sulpha-te with increasing quantities of water; the precipitates were dried in a vacuum, and analysed. The results, although not decisive, bend to show that free copper hydroxide is not present in these compounds, for on comparing any two preparations of different basicity, the excess of copper oxide present in the more basic one is not accompanied by a constant pro- portion of water. D. A, L. Crystallisad Mercurous Iodide and Bromide.By A. STROMAN (Bey., 20, 2818-2823) .-If a saturated solution of mercuroue nikrato, as free as possible from oxide and slightly acidified with nitric acid, is heated to boiling with iodine, the latter becomes covered with a, yellow powder, which partially dissolves, and Che solution, after decantation into a warm dish, deposits, in the dark, lustrous, yellow, transparent, tetragonal scales of' mercurous iodide ; these must be dried in the dark a t the ordinary temperature. When the merourous nitrate solution is treated wihh an alcoholic solution of iodine in the cold, small, yellow spangles of mercurous iodide are obtained, but the product formed by the old methods of prepapation, that is, by rubbing together molecular proportions of mercury and iodine, and by adding patassium iodide in solution to a solution of a mercurous salt, have a green colour, and are impure, although the pure yellow compaund can be obtained by reversing the last process and adding an exoesa of a dilute solution of mercurous nitrate to potassium iadide in solution. Tbe crystallised compound shows t8he same colour- ohange as observed by Yvon (this Journal, 1873,1105), but the change does not begin at 60", as stated by him, since the salt is still a pure yellow at loo", and only passes from this colour through dark yellow and orange to garnet-red at higher temperatures.Sublimation commences at 110-120", not at 190" as stated by Yvon, and the112 ABSTRACTS OF CHEMICAL PAPERS. salt fuses at 290" with decomposition. Towards acids and solvents, the crystalliskd compound behaves like that precipitated by potassium iodide ; ammonia and caustic alkalis render it green, and on heating convert it into the corresponding alkaline iodide and metallic mercury.The crystallised iodide is less sensitive to light than the precipitated yelIow compound, which rapidly becomes black even in diffused daylight. When mercurous nitrate solution is treated with bromine under similar conditions, small, white, nacreous, tetragonal scales of mer- curous bromide are obtained, and the same compound separates in yellow, crystalline spangles when an alcoholic or aqueous solution of bromine is employed. It sublimes at 340-350" in small scales, is less sensitive to light than the iodide, dissolves in hot sulphuric acid with the evolution of sulphurous anhydride, becomes black and graduaIly decomposes when heated with dilute and concentrated hydro- chloric acid, dissolves slowly in hot nitric acid (sp.gr. = 1*42), and decomposes with the formation of the corresponding bromides when treated with ammonia and caustic alkalis. TQ. P. W. Atomic Weight of Yttrium Metals in their Natural Com- pounds: Gadolinite. By C. RAMMELSBERG (Ber. Akad. Ber., 1887, 549-556) .-According t o Nordenskiold (Abstr., 1887, log), the oxides of the yttrium metals occur in their natural compounds in proportions so nearly constant that he suggests the term gadolinium oxide for this mixture of yttrium, erbium, and ytterbium oxides. The author shows from the results of 29 analyses of minerals from different sources and by various chemists, that this mixed oxide, so far from being constant, would give atomic weights Yarying from 97.5- 132.5" for the mixture of metals. Analyses of gadolinite from Hittero and Ptterby gave the following results :- Hittero.Ytterby. Silica ............... 24.36 25-53 Yttrium earths. ....... 45.5 1 38.13 Cerium oxide. ........ 7.01 13.55 Ferric oxide .......... 2.85 4.07 Ferrous oxide ........ 11.50 7.47 Lime ................ 0.36 0.5 7 Beryllium oxide ...... 8.58 10.03 Loss on ignition ...... 0.50 1.34 100-67 100.51 N. H. M, Water of Crystallisation of Alums. By J. JUTTEE (Qh.em. Cerztr., 18, 777).--Potash alum, in a, vacuum over sulphuric acid, loses 19 mols. H20, chromium alum 12-13, and iron alum, 20-21 mols. H,O. Potash alum, heated at 100" in a current of dry air, loses 15 mols.H20 readily, but the remainder only after prolonged heating, end breaking up of the dry crust, which retains the water. At a temperature of 20-30" potash alum gives off no water, at 42" 11 mols., at 65-91" 19 mols., and att 100" the remaining 5 mols. of water areIN0 RGANIG OHELCIlSTRY. 113 given off. Potassium, chromium, and ammonium iron Flum heatcld at 100" are completely dehydrated, without becoming insoluble in water, and without undergoing any decomposition. Action of Hydrogen Sulphide on Cobalt Salts. . By EL BAUBIGNY (Compt. rend., 105, 751-754, and 806--809).-The action of hydrogen sulphide on solutions of cobalt salts varies, as in the case of nickel salts (Abstr., 1882, 1031), with the concentration of the solu- tion, the nature of the acid in the salt, the ratio between the weight of acid and metal present, the ratio of free acid to the water present, the degree of saturation with hydrogen sulphide, or in other words the tension of the gas, and also with certain other Conditions, includ- ing the temperature and the duration of the experiment.Solutions of the normal sulphates of cobalt and nickel were satu- rated with hydrogen sulphide, and hermetically sealed in glass flasks, the liquid occupying about five-sixths of the volume of the flask. After standing for some days, *precipitation is always more complete in the case of nickel than with cobalt. This, however, is only ft special result. Under comparable conditions the formation of cobalt sulphide from a solution of a cobalt salt is always more rapid than the formation of nickel sulphide from the corresponding nickel salt.This is observed, for example, if the solutions saturated with hydrogen sulphide only partially fill the vessels. It follows that the tension of the gas exercises a considerable influence on the result. Precipitation of the cobalt sulphide is prevented by the presence of free acetic acid, the proportion required to produce this result being greater the greater the concentration of the solution. More acetic acid is necessary to prevent the precipitation of cobalt than to prevent that of nickel. With sulphuric acid and similar acids, however, the differences between the two metals tend to disappear. In both cases, there is no precipitation even after several days at the ordinary tem- perature if the proportion of free sulphuric acid is equal to half that in Combination with the metal, provided that the quantity of salt present exceeds 0.15 gram per liti-e.If the solutions are more dilute, some precipitation takes place, the quantity of sulphide formed being greaterin the case of cobalt than in the case of nickel. The presence of the precipitated sulphide accelerates the reaction in both cases. Rise of temperature accelerates precipitation from solutions of cobalt sulphate, but precipitation is not as complete as with nickel sulphate under the same conditions. The precipitation of nickel iii fact takes place more readily than the precipitation of cobalt as the acidity of the solution increases. The more concentrated the original solution of the neutral salt, and consequently the greater the quantity of acid liberated during the reaction, the greater is the precipitation of the nickel as compared with that of cobalt.I t follows that, a smaller quantity of free acid is required to prevent the precipitation of cobalt than to prevent that of nickel. With weak acids, the dif- ference is still distinct. In a solution containing only a small propor- tion of free acetic acid, the precipitation is greater i n the case of colalt, but if the proportion of free acid is increased the precipitation of nickel becomes the greater of the two. V. H. V. C. H. B. VOL. LIV. i114 ABSTRACTS OF CXERIICAL PAPERS. Action of Vanadic Anhydride on Potassium Fltioride. By A. DITTE (Compt.rmad., 105,1067-1070).-When excess of vanadic anhydride is fused with potassium fluoride in a platinum crucible, care being taken to prevent access of air, a brick-red, crystalline mass is formed on cooling, and when tlhis iR treated with water, a residue of vanadic anhydride is left, and a red solution is obtained. The solu- tion first deposits a small quantity of potassium bivnnadate, formed in consequence of accesB of air, and then orange-red plates of the com- pound W205,2KE + 5H20, which melts easilyto a black liquid. The mother-liquor on fiirther concentration deposits red, transparent prisms of the composition 4V2O5,2KF + 8H20. Contact with air is more completely avoided by heating the crucible at the bottom of a, long glass tube. Under these conditions the aqueous solution first deposits the compound 3Vz05,'2KF + 5H20, then ruby-red prisms of the composition 3V205,2KF + 6Hz0, and less soluble, lemon-yellow crystals of the composition 3 V205,4KF.All these compounds are soluble in concentrated sulphuric acid, with evolution of hydrogen fluoride and formation of a red solution which becomes pale-green when diluted with much water. When an excess of potassium fluoride is employed, the residue is pale-yellow, and on treatment with cold water first yields a saturated solution of potassium fluoride, in which the vanadium compounds are practically insoluble. A further quantity of water forms a yellow solution, which deposits small plates of the composition 2V205,2KF + 8H20, and the mother-liquor when concentrated in a vacuum yields the compound W205,2KF + 4H,O.The portion of the residue least soluble in water has the cornposition V205,4KF + 3H20. With a large excess of potassium fluoride, the solution yields suc- cessively large, thin, brilliant, orange-yellow lamella of the compound 3V205,2KF + 5H20, white c~ystals with a greenish-yellow tinge of the compound V205,8KF + 3H20, and finally yellow crystals OP the compound V205,4KF + 2H20. If air has free access and vanadic anhydride is in excess, the residue is an orange-red mass with a vitreous fracture, and whon treated with hot water some vanadic anhydride remains undissolved. The solution first deposits potassinm bivanadate, and afterwards lemon- yellow crystals of the composition V205,4KF. Similar results are obtained with excess of potassium fluoride.Water first dissolves the excess of fluoride, and the solution obtained by further treatment deposits yellowish-white crystals of the compound V205,8KF + The action of potassium fluoride on vanadic anhydride yields the compounds 2V205,KF; 3Vz0,,2KF; V205,KF ; 3V205,4K3' ; V205,4KE ; V205,8KB, which may be regarded as analogous to potassium chloro- chromate. Their solutions give no coloration and no precipitate with ammonia. If these compounds are regarded as derived from an oxg- fluoride, the latter must be V20aF2. Possibly the compounds do not actually exist in the fused mass, but the aqueous solution contaics several different compounds, giving rise to conditions of equilibrium ih which the crystallisable salts described are formed.A solution of potassium duoride dissolves vanadic anhydride, and the liquid deposits 2H2O.MINERALOGICAL CHEMISTRY. 115 greenish-white crystals of the compound V,O,,bKF, which is but slightly soluble in excess of the alkaline fluoride. As the colourless solution cools it becomes yellow, and deposits lemon-yellow crystals of the compound V,05,4KF. C. H. B.106 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c C h em i s t r y.Action of Carbon Bisulphide on Metals. By A. CAVAZZT(Ohern. Centr., 1887, 8&8, from Xem. R. Ace. Sc. Imt. Bologna [4], 7,27-33).-Carbon bisulphide vapour when passed over the heavymetals in a fine state of division and heated to a high temperatureyields metallic sulphides with separation of carbon in a graphitoidalform. Other compounds of carbon with sulphur seem not t o beformed in any case.Formation of Hydrates of Lithium Hydyoxide from AlcoholicSolutions : Quantitative Determination of Lithium, By C.Q i j ~ r 1 ' 1 ~ (Bey., 20, 29 12 -29 15) .-Lithium hydroxide generally sepa-rates from hot saturated soltitions in 96.8 percent.alcohol with 4 mol.H,O; when in contact with water, it ahows the movements pre-viously observed with crystals of potassium and sodium hydroxide(Alostr., 1887, 636).When lithium hydroxide is crystallised from 62.8 per cent. alcohol,a hydrate with 1 mol. H20 is obtained; the crystals do not movewhen placed in contact with watef.In determining lithium as sulphate, the sulphate must be ignitedfor a long time until of constant weight.Transformation of Ammonium Nitrate.By M. BELLATI andR. ROMANESE (Nuovo Cimento [3], 21, 5--24).-Frankenheirn, and,more recently, Lehmann 'have shown that ammonium nitrate crystal-lises in various forms, according to the temperature at which theV. H. V.N. H. MINORGANIC CHEMISTRY. 107crystallisation is effected. Thus at 36" it cryst'allises in the trimetricsystem, a t 87" in the rhombohedral, and at 120" in the monometricsystem. I n the present paper, it is shown that a t these various pointsthe salt undergoes other physical modifications. Tbus, on warming,the temperature of the salt increases in direct proportion to the timeup to a temperature of 35.67" ; so also the rate of cooling is regularup to 30.3", reaching a minimum at 30.07" ; it then increases to 31*05",at which point it remains constant for some time.Similar phenomenaare also observable a t a temperature of 855" to 86.5" with ascendingterriperature, and 82.2" to 82.6" with descending temperature, asalso at 124.8" and 124.05'.The variations of volume corresponding with these crystallinechanges is also determined in an accurately calibrated dilatometercontaining oil of turpentine, a liquid whose expansion is regular,and which, when properly dried, does not dissolve the salt, Resultsshow that the curve of coefficient of expansion has two points ofinflection: one a t a temperature between 33 29" and 41.29", andanother at about $5" ; the formula expressing the rate of expansionfrom 0" to the former of these points is vl = uo (1 i- 0.000339t +0*000000346t2), whilst between 40" and 85" this becomes v1 = vo(1.04957 +- 0.00038756t + 0-0000M976ta + 0*0000000432t*).Thereis also an alteration in the value of the mean specific heat at thetemperature of these crystalline transformations ; applying the methodof mixtures and using oil of turpentine as t,he liquid, it is shown thatthe mean specific heat from 0-31" is 0,407, from 31" to 82.5" is 0.355,and from 82.5" to 124" is 0.426. Hence the following values arededuced for the heats of transformation at these points :-At 31.0" = 5-02,, 124.0 = 11.86The values obtained for the specific heats of ammonium nitrate arecompared with those of Kopp and Tillinger, and the methods of cor-rection applied by the latter are criticised.Ammonium Phosphites.By L. AMAT (Compt. ?*eizd., 105, 809-811).-A solution of phosphorous acid mixed with ammonia untilaentral to methyl-omnge, and then concentrated until the weight ofthe liquid is one-fourth or one-fifth more than the calculated weightof the salt, yields large, deliqnescent crystals which can be dried oversulphuric acid or at 100". Similar crystals are obtained if the liquidis concentrated i n a vacunm a t the ordinary temperature. Thecrystals have the composition NHa*H2P03, and seem t o be monoclinicprisms ; they melt at 123" and are very soluble in water. A t 145"they lose half their ammonia without evolution of hydrogen phos-phide, and yield a gummy mass which seems to contain crystals. Ata higher temperature, ammonia and hydrogen phosphide are given offand phosphoric acid is formed.Hydrated diammonium phosphite, (NH,),HPO, + 2H,O, whenkept in a dry vacuum a t the ordinary temperature or heated at loo",loses water aud ammonia, and yields the monammonium salt j u s t,, 82.5 = 5-33V, H.V108 ABSTRACTS OF CHEMICAL PAPER,S.described. Both at the ordinary temperature and at loo", the wateris given off before the ammonia.Monammonium phosphite has no appreciable action on ammoniagas at the ordinary temperature, but at 80" to 100" absorption israpid, and the anhydrous diammonium salt is obtained as a whitepowder. The corresponding compounds of sodium and potassiumhave not yet been obtained.Effects produced by Small Quantities of Bismuth on theDuctility of Silver.By J. SCULLY (Clhem. News, 56, 224-926 ;232-244 ; 247--248).-1t is observed that the Indian method of metassay is incidentally a delicate test for bismuth in presence of a largeexcess of silver. The bullion is dissolved in nitric acid, the solutiondiluted, excess of hydrochloric acid added, and tb e whole vigorouslyagitated to facilitate the aggregation of the silver chloride, whichsettles down and generally leaves a clear supernatant liquid; if,however, the liquid is turbid and the silver chloride on exposure tolight, while still under the liquid, remains white, the turbidity is due tomercury, if on the other hand, the silver chloride becomes discoloured,the turbidity is due to bismuth ; tin and antimony having been provedt o be absent when dissolving in nitric acid.In such cases, to preventthe vitiation of the silver assay, the following modified method hasproved successful :-The assay ponnd of bullion is dissolved in 5.5 C.C.of nitric acid, sp. gr. 1.200, the solution is mixed ;with 5 ozs. of wat'erand 10 C.C. of nitric acid, sp: gr. 1.320, then 2.5 C.C. of hydrochloricacid are added, and kbe method proceeds as usual. F o r the estimn-tion of the bismuth, having obtained a rough idea of the amount ofbismuth present from the amount of turbidity in the trial assay,suflicient bullion to yield a weighable amount of bismuth is dissolvedin a small quantity of nitric acid, the solution diluted and heated withexcess of ammonium carbonate, which dissolves the silver and coppercarbonates, but leaves the bismuth carbonate insoluble ; the latter isthen washed, dried, ignited, and weighed.Jf lead or cadmium arepresent they would remain with the bismuth carbonate ; the latter,however, is not likely to be present, and the former may be separatedby dissolving the bismuth carbonate in nitric acid, and evaporatingdown with sulphuric acid ; the lead sulphate is treated in the usualmanner and weighed, whilst the bismuth is reconverted into carbonateand estimated as described above.Fine silver, or silver cont'aining 10 per 1000 of copper, alloyedwith 1 to 5 per 1000 of bismuth and cooled rapidly, had its ductility,as tested by rolling, sensibly but slightly impaired, the straps havingjagged edges ; with 6 per 1000 of bismuth, the decrease in ductilitywas more evident, whilst fine silver with 9 to 11 per 1000 of bismuthwas so brittle as to brenk with a mere tap.When, however, the coolingwas gradual, 4 per 1000 of bismuth was sufficient to make the silveror silver-copper alloy mentioned above highly brittle, the fracturebeing crystalline in the case of fine silver and granular in the silver-copper alloy. With Indian standard d v e r containing 83.4 per 1000of copper, 2 per 1000 of bismuth produced red shortness and jaggedstraps : as the quantity of bismuth increased the evidence of diminishedC. H. BINORGANIC CHEMISTRY. LO9ductility is more decisive, and with 10 per 1000 of bismuth the alloywas very brittle and had a granular fracture ; the mode of cooling badno appreciable effect on the ductility of these alloys.Other experi-ments with Indian coinage bars show that the ductility of bullion isnot materially affected by the presence of 0.5 per 1000 of bismuth.As the refining fine silver containing bismuth is both tedious andattended with loss of silver, the author suggests dilntion with silverfree from bismuth as a, practical means of overcoming the brittleness.The anthor remarks on the concordance of his results with those ofGowland and Koga (Trans., 1887, 410-416), as regards the questionof brittleness. The discrepancy in reference to refining bismuthsilver he suggests is possibly due to the Japanese silver containingmore base metals than the Indian silver ; it consequently suppliedmore slagging material and greater facilities for refining.D. A.11.Combination of Silver Chloride with Metallic Chlorides.By M. C. LEA (Anter. J. Sci., 34, 38&387).-1f hydrochloric acid ismixed first with ferric chloride and then with silver nitrate, the silverchloride which forms is not white but buff-coloured. The ferricchloride cannot be removed by washing, and is only partially removedby treatment with hydrochloric acid. The presence of the minutequantity of ferric chloride makes the silver chloride remarkably lesssensitive to light.Cobalt chloride and hydrochloric acid give a silver chloride which ispink and contains cobalt ; but the reduction in the sensitiveness tolight is very much less than when iron is present. Nickel andmanganese behave similarly, but cupric chloride seems to haveno tendency to combine with silver chloride.The tendency of goldchloride to combine with the silver chloride is, however, well marked,and the precipitate has a reddish shade, but the influence on thesensitiveness is not easily determined, since the gold is rapidly reducedto the metallic state, and the silver chloride darkens to black insteadof to chocolate or violet. as would be the case if it were pure.In analytical determinations, it is important to digest the silverchloride for a considerable time with hydrochloric acid, and even theni t is doubtful if the foreign chloride is entirely removed, especially ifit is ferric chloride.These observations show that silver chloride has a great tendencyt o combine with small quantities of other chlorides, and supports theauthor’s view as t o the nature of the ‘‘ photo-salts ” (this vol., p.1).They also explain the fact that a small quantity of mercuricchloride very greatly reduces the sensitiveness of silver chloride tolight. In order to ascertain the presence of mercury in the silverchloride, the anthor employs a solution of stannous chloride in hydro-chloric acid which has no action on silver chloride if light is carefullyexcluded, but gives a brown or brownish-black colour t o the precipi-tate if mercury is present. The author was unable to remove mercuricchloride from silver chloride even by very prolonged washing.Poitevin’s observation that his coloured photographic images resistedthe action of light better after they were treated with dextrin an110 ABSTRACTS OF CHEXICAL PAPERS.lead chloride is explaincd by the tendency of the lead salt to preventalteration of silver chloride.C. H. B.Silver Potassium Carbonate. By A. DE SCHULTEN (Compt. rend.,105, 811--813).-When silver carbonate is formed by the action of analkaline cabonate on silver nitrate, the precipitate is sometimes white,sometimes yellnw, but always becomes yellow when washed. If silvernitrate is added to an excess of a concentrated Solution of potassiumCarbonate containing some hydrogen carbonate, a white precipitate isformed which changes to microscopio crystals of the oompositionAgKCOs. This compound is decomposed by water, with removal ofthe potassium carbonate and formation of yellow silver carbonate.150 grams of potassium carbonate is dissolved in 150 C.O.of water,cooled and agitated with 15 grams of potassium hydrogen carbonate.When the liquid is sahurated with the latter salt a t the ordinary tem-perature, it is filtered and mixed with a solution of 1 gram of silvernitrate in 25 C.C. of water. In order to obtain large crystals, theliquid contaiuing the precipitate is heated with continual agitation.The precipitate dissolves, and when the l i p i d is cooled it depositslong, transparent crystals with a brilliant lustre ; sp. gr. 3.769. Theydo not blacken when exposed to light except in the presence oforpnic matter, and when treated with water, the silver carbonatewhich remains retains the form of the osiginal crystals.Whenheated, the compound loses carbonic anhydride, and a t a higher tem-perature the silver oxide which i s formed gives off oxygen.The crystals are microscopic, rectangular lamell= with a terminalangle closely approaching 90". The refraction is almost identical withthat of apatite ; the extinction of parallel polarised light takes placelongitudinally ; twinning plane parallel with the plane of the opticalaxes ; sign of elongation positive ; maximum birefractir-e powerapproximately 0.0216. C, H. B,Lead Aluminium Sulphate, By G, H. BAILEY (J. XOC. Chem.Ind., 6, 415).-The author has examined some crystals whioh havebeen noticed in a mordanting liquor (aluminium nitroaoetate) pre-pared by dissolving up alum, lead acetate, and lead &rate in waterand allowing to settle.The crystals form octahedra crystallising incruciform aggregates like alum. They are, however, not transparentand are quite unaltered by exposure to air. The substance is a leadalum, Pb,A1,(S0J6 + 20H20, formed under speoial conditions ofconcentration and temperature. D. B.New Oxide of Thallium. By A, PICCINI (Gazzetta, 17,450-452).-Carstanjen has observed that when a rapid current of chlorine ispassed through a concentrated solution of potash in which thalliumsesquioxide is suspended, the solution acquires a violet colour which isconsidered to be due to a potassium thallste. The same liquid is alsoformed when thallium hydroxide is submitted to electrolysis, using aplate of thallium as an electrode, as also on adding potassium hypo-chlorite to a quarter of its weight of caustic potash to which thalliumsulphate is subsequently added. On digeetinp the whole and addipgbarium nitrate, a violet precipitate is finally obtained.The results oINORGANIC CHEMISTRY. 111analyses made to determine the relation between thallium and baiiumin this precipitate led to discordant results, but sufficient evidencewas afforded to point to a formula, TIOz, for the oxide of Bhallium.The isolation of this oxide brings out a further point of analog7 ofthe thallium compounds to those af lead. Experiments made to pre-pare the corresponding sulphur compound have not as yet beensuccessful, although substances have been obtained which contain aproportion of sulphur greater khan that required for the trisulphide.V.H. V.Constitution of Basic Salts. By S. U. PICKERING (Chem.News, 56,210-212).-1n the author's opinion, those basic compounds,which although seemingly of indefinite composition can scarcelybe regarded as mere mixtures, are preoisely analogous to the complexhydrates, which he contends conskitnte a solution of a salt in water.Hydrated basic salts of copper may be obtained of a composition come.fiponding with that of an anhydrous salt of the formula ~ ~ C U O , S O . ~ ,but the most basic definite sulphate known is 4Cu0,S03, thereforeif these higher basic salts are to be regarded as mixtures, they mustbe mixtures of a basic salt with copper hydroxide and not mixtures oftwo different basic salts.To investigate this point, a aeries of basic copper salts were pye-pared by diluting a solution of ammonio-copper sulpha-te with increasingquantities of water; the precipitates were dried in a vacuum, andanalysed.The results, although not decisive, bend to show that freecopper hydroxide is not present in these compounds, for on comparingany two preparations of different basicity, the excess of copper oxidepresent in the more basic one is not accompanied by a constant pro-portion of water. D. A, L.Crystallisad Mercurous Iodide and Bromide. By A. STROMAN(Bey., 20, 2818-2823) .-If a saturated solution of mercuroue nikrato,as free as possible from oxide and slightly acidified with nitric acid, isheated to boiling with iodine, the latter becomes covered with a,yellow powder, which partially dissolves, and Che solution, afterdecantation into a warm dish, deposits, in the dark, lustrous, yellow,transparent, tetragonal scales of' mercurous iodide ; these must bedried in the dark a t the ordinary temperature.When the merourousnitrate solution is treated wihh an alcoholic solution of iodine in thecold, small, yellow spangles of mercurous iodide are obtained, butthe product formed by the old methods of prepapation, that is, byrubbing together molecular proportions of mercury and iodine, andby adding patassium iodide in solution to a solution of a mercuroussalt, have a green colour, and are impure, although the pure yellowcompaund can be obtained by reversing the last process and addingan exoesa of a dilute solution of mercurous nitrate to potassiumiadide in solution. Tbe crystallised compound shows t8he same colour-ohange as observed by Yvon (this Journal, 1873,1105), but the changedoes not begin at 60", as stated by him, since the salt is still a pureyellow at loo", and only passes from this colour through dark yellowand orange to garnet-red at higher temperatures. Sublimationcommences at 110-120", not at 190" as stated by Yvon, and th112 ABSTRACTS OF CHEMICAL PAPERS.salt fuses at 290" with decomposition.Towards acids and solvents,the crystalliskd compound behaves like that precipitated by potassiumiodide ; ammonia and caustic alkalis render it green, and on heatingconvert it into the corresponding alkaline iodide and metallicmercury. The crystallised iodide is less sensitive to light than theprecipitated yelIow compound, which rapidly becomes black even indiffused daylight.When mercurous nitrate solution is treated with bromine undersimilar conditions, small, white, nacreous, tetragonal scales of mer-curous bromide are obtained, and the same compound separates inyellow, crystalline spangles when an alcoholic or aqueous solution ofbromine is employed.It sublimes at 340-350" in small scales, isless sensitive to light than the iodide, dissolves in hot sulphuric acidwith the evolution of sulphurous anhydride, becomes black andgraduaIly decomposes when heated with dilute and concentrated hydro-chloric acid, dissolves slowly in hot nitric acid (sp.gr. = 1*42), anddecomposes with the formation of the corresponding bromides whentreated with ammonia and caustic alkalis. TQ. P. W.Atomic Weight of Yttrium Metals in their Natural Com-pounds: Gadolinite. By C. RAMMELSBERG (Ber. Akad. Ber., 1887,549-556) .-According t o Nordenskiold (Abstr., 1887, log), the oxidesof the yttrium metals occur in their natural compounds in proportionsso nearly constant that he suggests the term gadolinium oxide for thismixture of yttrium, erbium, and ytterbium oxides.The author shows from the results of 29 analyses of minerals fromdifferent sources and by various chemists, that this mixed oxide, so farfrom being constant, would give atomic weights Yarying from 97.5-132.5" for the mixture of metals.Analyses of gadolinite from Hittero and Ptterby gave the followingresults :-Hittero.Ytterby.Silica ............... 24.36 25-53Yttrium earths. ....... 45.5 1 38.13Cerium oxide. ........ 7.01 13.55Ferric oxide .......... 2.85 4.07Ferrous oxide ........ 11.50 7.47Lime ................ 0.36 0.5 7Beryllium oxide ...... 8.58 10.03Loss on ignition ...... 0.50 1.34100-67 100.51N. H. M,Water of Crystallisation of Alums. By J. JUTTEE (Qh.em.Cerztr., 18, 777).--Potash alum, in a, vacuum over sulphuric acid, loses19 mols. H20, chromium alum 12-13, and iron alum, 20-21 mols.H,O. Potash alum, heated at 100" in a current of dry air, loses15 mols. H20 readily, but the remainder only after prolonged heating,end breaking up of the dry crust, which retains the water.At atemperature of 20-30" potash alum gives off no water, at 42" 11 mols.,at 65-91" 19 mols., and att 100" the remaining 5 mols. of water arIN0 RGANIG OHELCIlSTRY. 113given off. Potassium, chromium, and ammonium iron Flum heatcld at100" are completely dehydrated, without becoming insoluble in water,and without undergoing any decomposition.Action of Hydrogen Sulphide on Cobalt Salts. . By ELBAUBIGNY (Compt. rend., 105, 751-754, and 806--809).-The actionof hydrogen sulphide on solutions of cobalt salts varies, as in the caseof nickel salts (Abstr., 1882, 1031), with the concentration of the solu-tion, the nature of the acid in the salt, the ratio between the weight ofacid and metal present, the ratio of free acid to the water present,the degree of saturation with hydrogen sulphide, or in other wordsthe tension of the gas, and also with certain other Conditions, includ-ing the temperature and the duration of the experiment.Solutions of the normal sulphates of cobalt and nickel were satu-rated with hydrogen sulphide, and hermetically sealed in glass flasks,the liquid occupying about five-sixths of the volume of the flask.After standing for some days, *precipitation is always more completein the case of nickel than with cobalt. This, however, is only ftspecial result.Under comparable conditions the formation of cobaltsulphide from a solution of a cobalt salt is always more rapid than theformation of nickel sulphide from the corresponding nickel salt.This is observed, for example, if the solutions saturated with hydrogensulphide only partially fill the vessels.It follows that the tension ofthe gas exercises a considerable influence on the result.Precipitation of the cobalt sulphide is prevented by the presence offree acetic acid, the proportion required to produce this result beinggreater the greater the concentration of the solution. More aceticacid is necessary to prevent the precipitation of cobalt than to preventthat of nickel. With sulphuric acid and similar acids, however, thedifferences between the two metals tend to disappear. In both cases,there is no precipitation even after several days at the ordinary tem-perature if the proportion of free sulphuric acid is equal to half thatin Combination with the metal, provided that the quantity of saltpresent exceeds 0.15 gram per liti-e.If the solutions are more dilute,some precipitation takes place, the quantity of sulphide formed beinggreaterin the case of cobalt than in the case of nickel. The presenceof the precipitated sulphide accelerates the reaction in both cases.Rise of temperature accelerates precipitation from solutions ofcobalt sulphate, but precipitation is not as complete as with nickelsulphate under the same conditions. The precipitation of nickel iiifact takes place more readily than the precipitation of cobalt as theacidity of the solution increases. The more concentrated the originalsolution of the neutral salt, and consequently the greater the quantityof acid liberated during the reaction, the greater is the precipitationof the nickel as compared with that of cobalt.I t follows that, asmaller quantity of free acid is required to prevent the precipitationof cobalt than to prevent that of nickel. With weak acids, the dif-ference is still distinct. In a solution containing only a small propor-tion of free acetic acid, the precipitation is greater i n the case of colalt,but if the proportion of free acid is increased the precipitation ofnickel becomes the greater of the two.V. H. V.C. H. B.VOL. LIV. 114 ABSTRACTS OF CXERIICAL PAPERS.Action of Vanadic Anhydride on Potassium Fltioride. ByA. DITTE (Compt. rmad., 105,1067-1070).-When excess of vanadicanhydride is fused with potassium fluoride in a platinum crucible,care being taken to prevent access of air, a brick-red, crystalline massis formed on cooling, and when tlhis iR treated with water, a residue ofvanadic anhydride is left, and a red solution is obtained.The solu-tion first deposits a small quantity of potassium bivnnadate, formed inconsequence of accesB of air, and then orange-red plates of the com-pound W205,2KE + 5H20, which melts easilyto a black liquid. Themother-liquor on fiirther concentration deposits red, transparentprisms of the composition 4V2O5,2KF + 8H20.Contact with air is more completely avoided by heating the crucibleat the bottom of a, long glass tube. Under these conditions theaqueous solution first deposits the compound 3Vz05,'2KF + 5H20,then ruby-red prisms of the composition 3V205,2KF + 6Hz0, and lesssoluble, lemon-yellow crystals of the composition 3 V205,4KF.All these compounds are soluble in concentrated sulphuric acid, withevolution of hydrogen fluoride and formation of a red solution whichbecomes pale-green when diluted with much water.When an excess of potassium fluoride is employed, the residue ispale-yellow, and on treatment with cold water first yields a saturatedsolution of potassium fluoride, in which the vanadium compounds arepractically insoluble. A further quantity of water forms a yellowsolution, which deposits small plates of the composition 2V205,2KF +8H20, and the mother-liquor when concentrated in a vacuum yieldsthe compound W205,2KF + 4H,O. The portion of the residue leastsoluble in water has the cornposition V205,4KF + 3H20.With a large excess of potassium fluoride, the solution yields suc-cessively large, thin, brilliant, orange-yellow lamella of the compound3V205,2KF + 5H20, white c~ystals with a greenish-yellow tinge ofthe compound V205,8KF + 3H20, and finally yellow crystals OP thecompound V205,4KF + 2H20.If air has free access and vanadic anhydride is in excess, theresidue is an orange-red mass with a vitreous fracture, and whontreated with hot water some vanadic anhydride remains undissolved.The solution first deposits potassinm bivanadate, and afterwards lemon-yellow crystals of the composition V205,4KF. Similar results areobtained with excess of potassium fluoride. Water first dissolves theexcess of fluoride, and the solution obtained by further treatmentdeposits yellowish-white crystals of the compound V205,8KF +The action of potassium fluoride on vanadic anhydride yields thecompounds 2V205,KF; 3Vz0,,2KF; V205,KF ; 3V205,4K3' ; V205,4KE ;V205,8KB, which may be regarded as analogous to potassium chloro-chromate. Their solutions give no coloration and no precipitate withammonia. If these compounds are regarded as derived from an oxg-fluoride, the latter must be V20aF2. Possibly the compounds do notactually exist in the fused mass, but the aqueous solution contaicsseveral different compounds, giving rise to conditions of equilibriumih which the crystallisable salts described are formed. A solution ofpotassium duoride dissolves vanadic anhydride, and the liquid deposits2H2OMINERALOGICAL CHEMISTRY. 115greenish-white crystals of the compound V,O,,bKF, which is butslightly soluble in excess of the alkaline fluoride. As the colourlesssolution cools it becomes yellow, and deposits lemon-yellow crystalsof the compound V,05,4KF. C. H. B