Inorganic chemistry


作者: H. Bassett,  


期刊: Annual Reports on the Progress of Chemistry  (RSC Available online 1932)
卷期: Volume 29, issue 1  

页码: 74-95




年代: 1932




出版商: RSC


数据来源: RSC



INORGANIC CHEMISTRY.IN reviewing the work on Inorganic Chemistry which has beenpublished during the past year it is perhaps allowable in the firstplace to take a somewhat wider view and to consider the main linesupon which investigations have run during the past few years.I. Discovery and Investigation of New Elements.This phase of chemistry has, of course, almost come to an end.Nevertheless, a great deal of work has been done on the compoundsof the element rhenium, which was only discovered as recently as1925.l Masurium,2 announced a t the same time as rhenium andillinium (At. No. 61), seems to have gone the same way as so manynew elements, but the search for these and for the missing alkalimetal (No. 87) and halogen (No, S 5 ) is being prosecuted with the aidof all the modern technique and appliance^.^ There is a tendencyto name these elements somewhat prematurely.It has been sug-gested that the highest possible at,omic number is 92.411. Investigation of Compounds of the Rarer Elements.Richer sources and improved methods of extraction of rarerelements, as well as the discovery of technical applications of manyof them, have been responsible for a greatly increased interest insuch elements as rubidium and c~esium,5 berylliumY6 gallium,' andgermanium .7III. Striking Developments with Old Elements.Applications of modern theories and refined physical methodshave shown that there is still much to discover about some of thebest known elements. The separation of ortho- and para-hydrogenmay be cited as a case in point,* and also the discovery of isotopesAnn.Reports, 1938, 25, 59; 1929, 26, 65; 1930, 27, 73; 1931, 28, 59;this vol., p. 88.Ibid., 1925, 22, 63.Ibid., 1929, 26, 43; 1931, 28, 49; F. Allison and E. J. Murphy, PhysicalRev., 1930, [ii], 35, 285; A., 1931, 1391; J . L. McGhee and M. Lawrenz, J .Amer. Chem. SOC., 1932, 54, 405; A., 355; F. Allison, E. R. Bishop, A. L.Sommer, and J. H. Christensen, ibid., p. 613 ; A., 317 ; F . Allison, E. R.Bishop, and A. L. Sommer, ibid., p. 616; A., 353.V. V. Narliker, Nature, 1932, 129, 402; A., 442.Ann. Reports, 1930, 27, 57. ' Ibid., 1929, 26, 51; 1930, 27, 63, 6s; 1931, 28, 55.Ibid., 1929, 28, 40.6 Ibid., 1929, 26, 44BASSETT. 75of hydr~gen,~ carbon,lo nitrogen,lo and oxygen,lo which until quiterecently had been regarded as simple elements.IV.Work: on the Older Elements and their Compou?zds.This, of course, includes the great majority of the inorganic workpublished and can be sub-divided as follows :-(i) Study of the valency stages. Numerous complex compounds ofbivalent silver have now been prepared.11 Several of the rare-earthmetals form well-defined bivalent compounds, notably samarium,europium, and ytterbium,12 which may be of great analyticalsignificance since the bivalent metals can be separated with greatreadiness from those which remain tervalent. The bromides ofter- and bi-valent zirconium have been prepared 13 and compoundsof univalent platinum and pa1ladi~m.l~(ii) Value of the co-ordination number and spatial character of theco-ordination and linkages.It is important to know, not only thevalencies of the elements in the old-fashioned sense, but also theco-ordination values, in Werner’s sense, with which they can act. Acertain amount of work now being done aims at determining theseva1~es.l~ The spatial arrangement of the co-ordinated atoms orgroups provokes investigations in connexion with the problem ofoptical activity associated with special elements. Optically active6-co-ordinated nickelous compounds were recently prepared.16 Itis, however, the problem of the 4-co-ordinated atom which arousesmost interest. Although the configuration is usually tetrahedral,it can apparently be coplanar in special circumstances. Telluriumand platinum compounds of the type PtX2Y2 have received muchattention in this connexion.17Three important theoretical papers have been published on thenature of chemical linkages.18 In the first paper several rules areformulated for electron-pair linkings, and the conditions specifiedunder which four strong linkings in one plane directed towards thecorners of a square become possible.In the second paper theconditions of stability of single- and triple-electron linkhgs aredefined. The conditions for single linking are found in the boronhydrides and for triple linking in nitric oxide, nitrous oxide, andThis vol., p. 77.l1 Ibid., 1931, 28, 51.l3 Ibid., 1931, 28, 55.Is Ibid., 1930, 27, 54; 1931, 28, 51; this vol., p. 78.l6 Ibicl., 1931, 28, 61.l7 I b d ., 1929,26,60,80; 1930,27,150, 164; 1931,28,62; this V O ~ . , p. 92.L. Pauling, J. Amer. Chern. SOC., 1931, 53, 1367, 3226; 54, 988; A . ,lo Ann. Reports, 1930, 27, 52.l2 Ibid., 1929, 26, 49; 1930, 27, 63.l4 Ibid., 1930, 27, 76.1931, 670, 1356; 1932, 56176 INORGANIC CHEMISTRY.oxygen. The third paper deals wiOh the transition from ionic toelectron-pair linkages.Much recent work l9 on the electrical conductivity, diffusivity,and reactivity a t high temperatures of a number of spinels, silicates,germanates, molybdates, and tungstates in the solid conditionappears to show that the structure of such compounds may be of twotypes. They may have an ionic lattice with conductivity of anionic nature and a relatively high diAusivity, or a double oxidelattice in which the conductivity is electronic and the diffusivitymuch lower.It would seem that some kind of equilibrium betweenthe two types of structure exists but that, at any rate in some cases,the double oxide type tends to become the more stable form a t highertemperatures. Thus, Mg,Ge04 has a transformation point at 1065".At lower temperatures it crystallises in a spinel type, and at highertemperatures it is isomorphous with olivine, Mg,Si04. The spineltype has a higher electrical conductivity which is a t least partlyionic, whilst the conductivity of the olivine type is electronic andassociated with, mainly, a double oxide lattice. In the case of doublehalides there is, similarly, a transition between complex salt anda'ggregate of simple halides.It is well known that salts, e.g., cobalt sulphate, which, from thepoint of view of low-temperature reactions, are best considered interms of Co" and SO," ions, behave a t high temperatures in afashion which is most conveniently interpreted on the old dualisticlines in terms of COO and SO,.The above results appear to havesome bearing on this matter.Manysuch compounds might be mentioned, but the oxides of fluorine andbromine are perhaps the most striking.20(iv) Phase-rule examination of various systems. An immenseamount of work is being done on these lines. Phase-rule methodsare frequently the only ones by which the existence or non-existenceof particular compounds can be decided with certainty. Much ofthis work relates to aqueous systems and has important bearings onmany industrial processes.Various non-aqueous systems have ofrecent years been examined in connexion with slag equilibria inmetallurgical processes. Much of metallurgy consists of the phase-rule examination of metal systems by special methods, among whichX-ray examination plays an increasingly important part. Referencesto practically all the systems examined in the last few years are given19 W. Jander, 2. angew. Chem., 1931, 44, 870; A., 1931, 1356; Z. anorg.Chem., 1930, 192, 286, 295; 1931, 190, 306; A., 1930, 1351; 1931, 1236;W. Jander and W. Stamrn, ibid., 1931, 199, 1G5; 1932, 207, 289; A., 1931,'399; 1932, 985.(iii) Isolation of previously unknown simple compounds.20 Ann.Reports, 1929, 26, 63; 1930, 27, 71BASSETT. 77in the Annual Reports. A great deal of Inorganic Chemistry stillrequires revision by phase-rule methods.(v) Mit3ceZZaneow.s. Most of the remaining work can be groupedunder the heads of new methods of preparation, preparation of newcompounds of well-known types, study of the course or mechanismof reactions, but none calls for special mention here with the exceptionof oxidation,which has been the cause of much work on the corrosionand " passivity " of metals.21Group 0.The formation of compounds of krypton with chlorine and brominehas been announced.22 It is clear that this requires confirmationand verification.Liquid helium continues to be used for obtaining temperatures inthe neighbourhood of the absolute zero.Carbides, nitrides, borides,and silicides of the heavier metals become superconductors a t verylow temperatures. 23 An interesting account and discussion ofsuperconductivity has been given by J. C. McLennan and hisco -workers. 24Group I .A hydrogen isotope of mass two appears to be well established 25and should be of great importance in the study of isotopes if thepreliminary account of the enrichment of the residues of electrolytichydrogen plants in this isotope should be confirmed by furtherwork.26 By the action of atomic hydrogen on oxygen a t low tem-peratures there is formed what is considered to be a new form ofhydrogen peroxide 27-possibly with the structure E>O:O. At- 115" it changes into the ordinary form with partial decomposition ;97% of the theoretical yield of hydrogen peroxide is said to beobtained when hydrazobenzene in alcoholic solutions is convertedinto azobenzene by the action of gaseous oxygen.2821 Ann. Reports, 1929, 26, 38; 1930, 27, 55.22 A.von Antropoff, K. Weil, and H. Frauenhof, Nuturwiss., 1932, 20, 6 8 8 ;23 W. Meissner, H. Franz, and H. West,erhoff, 2. Physik, 1932, 75, 521 ; A , ,24 Nature, 1932, 130, 879; A., 1193.25 H. Kallmann and W. Lasarev, Naturwiss., 1932,20, 472; A., 790; N. S .Grace, J . Amer. Chem. SOC., 1932,54, 2562; A., 790.26 E. W. Washburn and H. C. Urey, Proc. Nut. Acad. Sci., 1932, 18, 496;H. C. Urey, F. G. Brickwedde, and G. M. Murphy, PhysicaZ Rev., 1932, [ii],40, 1; A., 554:A., 1007.566.27 K.H. Geib and P. Harteck, Ber., 1932, 65, 1233, 1551; A., 1098.28 J. H. TVdton and G . W. Filson, J . Arner. Chern. Soc., 1932, 54, 3223;A., 109878 INORGANIC CHEMISTRY.The vapour pressures of normal hydrogen (the mixture of ortho-and para-hydrogen which is in equilibrium at room temperature)and of para-hydrogen have been measured up to 1 atm. The normalb. p.'s have been determined as - 252.754" and - 252.871"respe~tively.~~Apparatus has been described for preparing and handling alkali-metal hydrides without exposure to air. All members of the serieshave the sodium chloride str~cture.~" Excellent yields of lithiumaryls and of butyl-lithium are obtainable under essentially the sameconditions as those used for the related Grignard reagents .31Lithium chloride monohydrate forms solid solutions with2LiCI,CoC12,2H20 (= [Liz(H20),]"[CoC1,]").32 From this fact it isconcluded that the monohydrate is termolecular with the structure [.i H2° Li]" [ Li c13 1".The polymerisation is determined by theH2O H2Oneed for the lithium atom to become either 2- or 4-co-ordinated.The two lithium atoms in the complex kation are linked through theoxygen of the two water molecules.I n presence of moisture a 93% conversion of potassium chlorideto nitrate can be obtained by the action of nitrogen peroxidc.Nitrosyl chloride is formed a t the same time.33The polyhalogen compounds of the alkali metals continue to attractinterest. No anhydrous perbromide of potassium exists, but2KBr6,3H20 separates a t 0" from concentrated solutions.34CsBr, can be obtained however.34 KIBr2,H20 35 and KI,,3C6H26have been described ; also HI,,4C7H5N ; LiI,,4C7H5N ; KI,,2C7H5N.37Rubidium resembles cmium in being able to form a solid polyiodide,RbI,, whereas potassium cannot do so unless combined water,benzene, or other addenda are also pre~ent.~S RbFIC1, and CsFICl,have been prepared.3929 W.H. Keesom, A. Bijl, and (Miss) H. van der Horst, Proc. K. Akad.30 E. Zintl, A. Harder, and E. Husemann, 2. physikal. Chem., 1931, [B], 14,31 H. Gilman, E. A. Zoellner, and m7. M. Selby, J . Amer. Chem. SOC., 1932,32 H. Bassett and (Miss) I. Sanderson, J., 1932, 1855; A., 811.33 C. W. Whittaker, F. 0. Lundstrom, and A. R. Merz, Ind. Eng. Chem.,34 I. W. H. Harris, J., 1932, 1694, 2709; A., 822.35 G.H. Cheesman and J. H. Martin, ibid., p. 586; A., 350.313 H. W. Foote and W. M. Bradley, J. Physical Chem., 1932,36,673 ; A , , 48.37 J. H. Martin, J., 1932, 2640; A., 1205.38 T. R. Briggs and E. S. Patterson, ibid., p. 2621 ; A., 1216.39 H. S. Booth, C. F. Swinehart, and W. C. Morris, J . Amer. Chem. Soc.,Wetensch. Amsterdam, 1931, 34, 1223; A., 453.265; A., 1931, 1358.54, 1957; A., 728.1931, 23, 1410; B., 304.1932, 54, 2561 ; A., 823; J . Phpsical Chem., 1932, 36, 2779; A., 1219BASSETT. 79The dissociation pressures of silver oxide have been measuredbetween 173" and 192".40 The solution of oxygen in molten silverand the phenomenon of spitting on solidification are due to formationof ~ g ~ 0 . 4 1Group I I .Beryllium of such purity that it dissolves in ordinary reagents onlywith difficulty can be obtained by electrolysis of solutions of thechloride or nitrate in liquid ammonia.42 Many other metals can besuccessfully deposited from solutions in liquid ammonia.43The fluoberyllates as a class appear to be isomorphous with thecorresponding sulphates.Many of them have been prepared andexamined.44It is said that Mg(SH)OH, MgS,, and MgS, can be stabilised in theform of compounds with two molecules of hexamethylenetetramineand ten of water.45The calcium silicates and aluminates, owing to their importancein connexion with cement, continue to attract several workers.46Pure anhydrous zinc chloride can be conveniently prepared inquantity by the action of dry hydrogen chloride on pure zinc inanhydrous ether.47The true solubilities in mercury of the metals of atomic numbers22-29 and of molybdenum, tungsten, and uranium have beendetermined by am improved method.These are in all cases verysmall even though, as in the case of copper, it may be possible todisperse considerable amounts of metal in the mercury.48 A wholeseries of what may be called low-temperature alloys have beenprepared and investigated by a novel and interesting methodinvolving the use of solutions of metals in mercury.49 These alloysare prepared either by admixture of the separate amalgams or by40 A. F. Benton and L. C. Drake, J . Amer. Chem. Soc., 1932, 54, 2186; A.,41 J. H. Simons, J. Physical Chew., 1932, 36, 652; A., 457; N.P. Allen,42 H. S. Booth and G. G. Torrey, J. Physical Chem., 1931,35,3111; A., 129.43 H. S. Booth and M. Menahem, ibid., p. 3303; A., 129.44 N. N. Ray, 2. anorg. Chem., 1931, 201, 289; 1932, 205, 257; 206, 200;4s A. Tettamanzi, Gazzetta, 1932, 62, 597 ; A., 1098.4 6 H. Ehrenberg, 2. physikal. Chem., 1931, [B], 14, 421; A., 131; E. T.Carlson, Bur. Stand. J . Res., 1931, 7, 893; A., 131; S. Nagai, J . SOC. Chem.Ind. Japan, 1931, 34, 4 1 8 ~ ; 1932, 35, 1 8 2 ~ , 3 2 0 ~ , 3 8 0 ~ , 3 9 4 ~ ; A., 131, 707,1008, 1217 ; idem, 2. anorg. Chem., 1932,206, 177; 207, 313; A., 707, 1008.4 7 R. T. Hamilton and J. A. V. Butler, J., 1932, 2283; A., 1008.4* N. M. Irvin and A. S. Russell, ibid., p. 891; A., 457.49 A. S. Russell, P. V. F.Cazalet, and N. M. Irvin, ibid., pp. 841, 852; A.,456; A. S. Xussoll and H. A. 11. Lyons, ibid., p. 857; A., 456; A. S. Russell,T. R. Kennedy, J. Homitt, and H. A. 31. Lyons, ibid., p. 2340; A., 1082.810.Inst. Metals, Sept. 1932, Advance Copy; A., 1090.A . , 131, 582, 70680 INORGANIC CHEMISTRY.interaction of one amalgam with an aqueous solution of a salt of theother metal. The character of the compounds formed is deducedfrom their behaviour with acidified permanganate or other oxidisingagents.The compounds obtained are in many cases entirely different fromthose found in alloys prepared by the usual high-temperaturemethods and this was to be expected. The compounds found inordinary alloys were, however, also obtained. A very large numberof new intermetallic compounds have been found by the new method,some of which contain mercury.Many of the compounds do notobviously belong t30 any class known to metallurgists but all of themfollow the simple rule that their empirical formulz correspond tototal valency electrons equal to 6, 9, or 12 or some simple multipleof these numbers.Group I I I .Crystallised boron of metallic appearance and 99% purity isobtained by passing very condensed high-frequency sparks betweenelectrodes of molybdenum or tungsten in a mixture of hydrogen andboron trichloride v a p o ~ r . ~ ~ New methods have been described forpreparing B,H,, B,H,Br, and B5H9,51 and reasons given for assign-ing B,N,H, a str~icture-nTH<BH.NH>BH-recalling BH*NH that ofbenzene.52 The compounds BBr,,HCN and BBr,,AgCN have becriprepared.53A convenient method for preparing anhydrous aluminium bromidehas been given.54 Aluminium chloride forms a white compoundAlCl,,BHCN with hydrogen cyanide.55 Tensimetric and othermeasurements have been made on the numerous ammines of alumin-ium chloride, bromide, and iodide.56 The mono-ammines in all casesare unimolecular non-ionic compounds [AlX,,NH,].Alkali oralkaline-earth permutites become blue when treated with alkalisulphide or polysulphide solution in presence of air. In absence ofair, only the polysulphides cause formation of the blue compoundsince the sulphide adsorption complex or compound is colourless.If the blue polysulphide permutites are prepared a t temperatures50 L.Hackspill, A. Stieber, and R. Hocart, Compt. rend., 1931, 193, 776;51 H. I. Schlesinger and A. B. Burg, J . Amer. Chem. SOC., 1931, 53, 4321 ;52 A. Stock and R. Wierl, 2. anorg. Chem., 1931,203, 228; A., 215.53 E. Pohland, ibid., 201, 282; A., 132.54 R. P. Bell, J., 1932, 338; A., 239.5 5 L. E. Hinkel and R. T. Dunn, J., 1931,3343; A., 132.5 6 W. Iqlemm and E. Tanke, 2. anorg. Chem., 1931, 200, 343; A., 1931,A., 1931, 1377.A., 350.1380; W. Klemm, E, Clausen, and H. Jacobi, ibid., p. 367; A., 1931, 1380BASSETT. 81above about 200" they are much more stable and yield the sameX-ray diagram as ultramarine.57 Base exchange by zeolites(permutites) can be applied so as to afford almost quantitativeyields of salts by double decomposition even whefi the ordinaryreaction between the solutions is in~omplete.~~A dark brown sublimate of Ga,O is obtained by heating a mixtureof the metal and the trioxide in a stream of hydrogen at 500-700".GaO could not be prepared.59GsBr3,6NH, and GaI,,6NH3, stable a t room temperature inabsence of moisture, are formed by the action of liquid ammoniaon the halides.60 GaN, which sublimes without decomposition above800°, can be prepared by the action of ammonia on gallium a t 900-1000".61The alloys of lanthanum with Pb, Sn, T1, Mg, Cu, Ag, and Au havebeen studied and several compounds were found in each case.62La, Ce, Nd, and Pr form compounds with mercury of the typeM,Hg,.G3Conductivity measurements on solutions of the normal and acidsulphates, and determinations of the degree of hydrolysis of thenormal sulphates, have been utilised to determine the basicity ofa number of the rare-earth metals.64Measurements of the solubility products of the hydroxides undersuitable conditions have been used for the same purpose 65 and, onthe assumption that the solubility product is proportional to thebasicity, the relative values of the latter for the metals Y, La, Pr,Nd, Sm, Gd, and Dy are found to be 1 : 1300 : 80 : 47 : 8 : 3 4 : 0.5.It is difficult to believe that there is so much difference betwcculanthanum and praseodymium.A full account has been published of the preparation, properties,and reactions of ytterbium di- and tri-halides.Reduction ofanhydrous tri-chloride or -bromide by hydrogen is the best methodfor preparing the dihalides, but the di-iodide can be prepared bydissociation of the tri-iodide in a vacuum a t 600".The dichloride and dibromide on strong heating break up into5 7 E.Gruner and E. Hirsch, 2. anorg. Chem., 1932, 204, 232, 247 ; A., 350.5 8 G. Austerweil, Bull. SOC. chim., 1932, [iv], 51, 729; A., 1007.59 A. Brukl and G. Ortner, 2. anorg. Chem., 1931,203,23; A., 238.60 W. C. Johnson and J. B. Parsons, J . Amer. Chem. SOC., 1932, 54, 2588 ;61 W. C. Johnson, J. B. Parsons, and M. C. Crew, ibid., p. 2651 ; A ., 1218.e2 G. Canneri, Met. Itul., 1931, 23, 803; Chem. Zentr., 1931, ii, 3035; A . ,63 P. T. Daniltschenko, J. Gen. Chem. RUSS., 1931, 1, 467; A., 1931, 1381.64 B. Brauner and E. Svagr, Coll.Czech. Chem. Comm., 1932, 4, 49, 239;85 G;. Enders, 2. anorg. Chem., 1932, 205, 321; A,, 69G.A., 1218.455.A., 470, 89482 INORGANIC CHEMISTRY.metal and the trihalide. Aqueous solutions of the dihalides areyellowish and slowly evolve hydrogen-the more rapidly the greaterthe acidity.Anhydrous chlorides of the cerium group metals have been pre-pared from the anhydrous benzoates by the action of a saturatedsolution of hydrogen chloride in dry ether.67The iodide oxidises most slowly.66Lanthana appears to form both a tri- and a mono-hydrate.68Group I V .Metallic sodium reacts sinoothly with warm xylene solutions ofphenyl or alkyl carbonates t o yield pure dry carbon monoxide.69The preparation and properties of carbonyl sulphide and selenide 70and of cyanogen fluoride 71 and osycyanogen, (OCN),,72 have beenexamined.Support has been found for four of the five silicic acids describedby earlier and conclusions have been drawn as to the p ,under which SiO,” and Si,O,” ions can exist in solution.74 Silicavolatilises in supercritical steam (365-410”, 200-350 atm.) andthen attacks various metallic oxides.A number of silicates havebeen synthesised in this way and the process appears to be of con-siderable mineralogical significance. 7 5 Several papers have beenpublished on germanium dioxide, on the hydrated dioxide, and onthe germanates.s6 The behaviour found recalls that of the siliconcompounds.Several salts of 10-tungstogermanic acid have been de~cribed.’~A number of ammines of germanium iodide have been described,78G o G.Jantsch, N. Skalla, and H. Jawurek, 2. anorg. Chem., 1931, 201, 207 ;8 7 P. Brauman and S. Takvorian, Compt. rend., 1932, 194, 1579; A., 584.c 8 G. F. Huttig and M. Kantor, 2. anorg. Chem., 1931, 202,421 ; A., 125.69 S. T. Bowden and T. John, Nature, 1932,129, 833 ; A., 707.7o T. G. Pearson and P. L. Robinson, J . , 1932, 652; T. G. Pearson, P. L.71 V. E. Cosslett, 2. anorg. Chem., 1931, 201, 7 5 ; A., 31.7 3 H. Hunt, J . Amer. Chem. SOC., 1932, 54, 907; A., 482.73 A. Simon and P. Rath, 2. anorg. Chem., 1931, 202, 191; A., 122; Ann.’* G. Jander and W. Heukeshoven, 2. anorg. Chem., 1931, 201,361 ; A., 124.7 5 C. J. van Nieuwenburg and H. B. Blumendal, Rec. trav. chim., 1931, 50,129, 989; A., 322, 1381.7 G A.W. Laubengayer and P. L. Brandt, J . Amer. Chem. SOC., 1932, 54,549, 621 ; A., 483 ; A. W. Lsubengayer and D. S. Morton, ibid., p. 2303 ; A . ,905; R. Schwarz and E. Huf, 2. anorg. Chem., 1931, 203, 188; A., 117; R.Schwarz and F. Heinrich, ibid., 1932, 205,43; A., 584; R. Schwarz and G.Trageser, ibid., 208, 65 ; A., 1099.A., 30.Robinson, and J. Trotter, ibid., p. 660; A., 329.Reports, 1929, 26, 50; 1930, 27, 64.77 A. Brukl and B. Hahn, iMonatsh., 1932, 59, 194; A . , 351.7 * T. Karantnssis and L. Capatos, Conrpt. rend., 1931, 193, 1187; A . , 133BASSETT. 83but no evidence is given that they are definite compounds and thatno reactions have occurred such as those between ammonia andgermanium chloride. 79The reactions and decompositions of stannous nitrate have beeninvestigated,80 and evidence obtained for a tri- and a mono-hydrateof stannic oxide.81The action of ammonia on the tetrachlorides of tin and lead is verycomplex.82 A number of compounds formed in the reaction withthe former or by further treatment of the products have beenisolated, such as SnC14,2NH,, which appears to be a true ammine,the triamino-chloride Sn( NH,),Cl, the nitrilo-chloride SnNC1, andthe nitride Sn3N4.Lead also yields the nitrilo-chloride, PbNC1, anda very explosive compound derived from this by loss of lead chloride.There is still difference of opinion as to whether lead suboxidereally exists.83 All the other oxides of lead have a definite crystalstructure with the exception of the sesquioxide which isand there seems some doubt whether Pb,O, represents a definitecompound.The absorption and removal of oxygen in the reactionsPbO=Pb,O,ZPbO, have been followed by means of oxygen-pressure measurements and X-ray examination of the crystallattices.85 With absorption of oxygen, the lattice of lead oxide ortriplumbic tetroxide persists up to a definite oxygen content,whereupon red lead or the peroxide appears as a second phase.Similarly on removal of oxygen the lattice of PbO, or Pb30, persistsover a certain range without any indications of Pb,O, or Pb,O,.There does, however, appear to be a second, black, modification oft riplum bic tetroxide.Several intermediate stages have been detected in the decomposi-tion of lead nitrate in molten potassium nitrate.86All the alkali-metal fluotitnnates have been prepared and described,and their reactions and solubilities determined.87 A number ofcomplex iodates of titanium have also been described.88Black crystals of Th,N, were prepared by electrically heating to79 Ann.Reports, 1930, 2'7, 65.81 A. Simon and P. Rath, 2. anorg. Chern., 1931, 202, 200; A., 122.82 R. Schwarz and A. Jeanmaire, Ber., 1932, 65, [B], 1443; A., 1100.83 P. Pascal and P. Minne, Compt. rend., 1931, 193, 1303; A., 132; M. LeBlanc and E. Eberius, 2. physikal. Chern., 1932,160, 129; A., 823; R. Frickeand P. Ackermann, ibid., 161, 227; A., 1100.J. A. Darbyshire, J . , 1932, 211 ; A., 326.C. Montemartini and E. Vernazza, Ind. chirn., 1931, 6, 632; A., 351.8 5 M.Le Blanc and E. Eberius, 2. physikal. Chem., 1932, 160, 69; A., 697.86 K. Laybourn and W. M. Madgin, J., 1932, 1360; A., 707.H. Ginsberg and G. Holder, 2. anorg. Ckem., 1931, 201, 193; A., 31; €I.Ginsberg, ibid., 1932, 204, 225 ; A., 351.88 P. R. Ray and H. Snlia, ibid., 208, 200; A . , 109984 INORGANIC CHEMISTRY.2220-2600" a compressed mixture of thoria, grayhi te, and tungstenin a non-oxidising atmosphere containing nitrogen.89Qroup V .The nitric oxide liberated at the anode in the early stages of theelectrolysis of fused sodium nitrite results from the secondaryreaction NaNO, + NO, NaNO, + NO, but although nitritewas completely oxidised to nitrate in 3 4 hours in a current ofnitrogen peroxide a t 315450", only about 5% of nitrate wasreduced by nitric oxide in 6-7 hours a t 315".90 Nitric oxide isabsorbed by alkaline sulphite solutions to yield compounds whichreact like M2S04,N20 since they decompose slowly in cold, andrapidly in hot, water to yield sizlphate and nitrous oxide.Very purenitrous oxide can be obtlained by the action of dilute sulphuric acidon solutions of K,S0,,N20, the gas being washed with 4N-potassiumhydroxide and water. By addition of K2S04,N20 to solutions ofsuitable manganese, cobalt, zinc, or cadmium salts, complex saltswere formed of the type K4M(S04,N,0)3,2H20 or, in the case ofcadmium, IC,M(S04,N,0)2,2H20.g1Phosphorous acid alone is formed when phosphorous oxide isshaken vigorously with excess of cold water. If there is no shaking,local overheating of the acid leads to formation of phosphine, whileinteraction between the acid and thc oxide yields phosphoric acidand yellow, so-called, phosphoriis suboxide.92Both in neutral and in acid solutions, sodium metaphosphatctcombines with water to give orthophosphate only.(NaPO,), iiineutral solution aIso gives rise only to orthophosphate, but in acidsolution pyrophosphate also is formed.93 A incthod for preparingthe well-crystallised hexametaphosphate Na,(PO,),,lOH,O has beengiven.94 The equilibrium €€,PO, + HF H2P0,F + H20 hasbeen studied at 20". H,PO,F is also formed by the action ofhydrogen fluoride on potassium dihydrogen phosphate and on sodiumpyrophosphate, but potassium fluoride and potassium dihydrogenphosphate do not react either in dilute or in concentrated s o l ~ t i o n .~ ~NH,PF, and KPF, can be obtained in good yield by the actionof phosphorus pentachloride on ammonium or potassium fluoride.89 W. Diising and M. Hiiniger, Tech. tuiss. Abh. Osram-Konx., 1931, 2, 367 ;90 J. Szper and K. Fiszman, 2. anorg. Chem., 1932, 206, 257; A., 823.91 H. Gehlen, Ber., 1931, 64, [B], 1267; 1932, 65, [B], 1130; A., 922, 919.92 L. Wolf, W. Jung, and M. Tschudnowsky, Ber., 1932,65, [B], 488; A . , 483.93 S. S. Dragunov and A. N. Rossnovslraja, 2. anorg. Chem., 1931, 200, 321 ;94 P. Pascal and (Mme.) Itkchid, Compt. rend., 1932, 194, 762; A., 483.95 \V. Lange and G . Stein, Ber., 1931, 64, [El, 2772; A., 132.Chem. Zentr., 1932, i, 203; A., 584.A., 1931, 1372BASSETT.85With sodium fluoride reaction is much slower so that only a 5--6y0yield of NaPIF', is obtainable. Ammonium chloride and phosphoruspentachloride yield (PNC12),.g6The mechanism of the thermal conversion of arsenite into arsenateis invariably based on the reaction 5As203 --+ 3As,05 + 4As anddoes not involve direct oxidation by atmospheric oxygen. I n airarsenious oxide is formed, subsequently, from the arsenic liberatedand then undergoes further decomposition.97 Salt-like polyanti-monides or polybismuthides Na,Sb7,xNH, (Na,Bi,,xNH,) are formedby extracting sodium-antimony or -bismuth alloys with liquidammonia.98 When ammonia is removed, the complex anions breakup and a mixture of metallic phases, Sb with NaSb or Bi with NaBi,results.Thesubstance regarded as SbC13,3NH, is really a mixture of ammoniumchloride and, probably, Sb(NH)Cl.The latter yields SbN onextraction with liquid ammonia to remove the ammonium chloride.9gI n the equilibrium 2Bi20, + Bi2S, z3 6Bi + 3SO,, evolution ofsulphur dioxide begins at 150--200" and reaches a pressure of 1 atm.a t 519". Absorption of sulphur dioxide in the reverse reaction ismeasurable at 400O.1A number of internally complex organic derivatives of tervalentvanadium have been prepared and compared with those of thecorresponding iron compounds.2 Conductometric and potentio-metric titrations of solutions of potassium niobate with causticalkali or hydrochloric acid gave no indications of the existence ofortho- or pyro-niobates but only of meta- compound^.^Antimony trichloride gives no ammine with ammonia.Group V I .A nearly quantitative yield of fluorosulphonic acid is obtained bydistilling a mixture of oleum with potassium hydrogen fluoride.The dry acid does not attack gIass.4The m.p.'s, b. p.'s, densities, and surface tensions of selenium andtellurium hydrides have been re~orded.~9 6 W. Lange and G. von Krueger, Ber., 1932, 65, [B], 1253; A., 1100.97 G. G. Reissans, 2. angew. Chem., 1931,44,959; A., 130; E. R. Rushton,'* E. Zintl and W. Dullenkopf, 2. physikal. Chem., 1932, [B], 16, 183; A.,O9 R. Schwarz and A. Jeanmaire, Ber., 1932, 65, [B], 1662.J . Physical Chem., 1932, 36, 1772; A., 810.455 ; Ann. Reports, 1929, 26, 42.R. Schenck and F. Speckmann, 2.anorg. Chem., 1932,206,378; A., 810.A. Rosenheim, E. Hilzheirner, and J. WOE, ibid., 1931,201,162; A., 31.H. T. S. Britton and R. A. Robinson, J., 1932,2265; A., 999.J. Meyer and G. Schramm, 2. anorg. Chem., 1932, 206, 2 4 ; A., 708.P. L. Robinson and W. E. Scott, J., 1935, 972; A., 45486 INORGANIC CHEMISTRY.Selenium dioxide has been found to be a useful oxidising agentfor the preparation of EL number of organic compounds.G Solubilitiesof the normal and acid selenites of sodium and potassium have beendetermined and the composition of the salts and their hydratesestablished - 7Pure chromous iodide has been prepared by heating electrolyticchromium with an excess of iodine in nitrogen or vacuum a t 1150-1200" and removing excess of iodine from the product by heatinga t 2OOO.8The specific action of chromates in inhibiting corrosion of ironis due to the fact that CrO," ion precipitates Fe" ion completely ; theprecipitate consists of the hydrated sesquioxides and has considerableprotective action owing to its gelatinous nature, high specific volume,close adhesion to the iron, etc.Similar protective films form onchromium steels .9The blue " perchromic acid " has hitherto been regarded as a trueperoxidic acid H*O*O*CrO,, of which the pyridine and ammoniacompounds were true salts. It was, however, difficult to understandhow chromium could have the valency of 7 which is required by sucha structure. Strong evidence has now been brought forward forbelieving that the blue compound is not an acid at all but a non-ionicco-ordination complex of the peroxide CrO,, O=Cr<$, with-pyridine, ether, etc., in which the chromium still has a valency of six,with co-ordination number 4.The pyridine compound, on this basis,MolybdGnum sesquisdphide must be prepared by heating thedisulphide under ordinary pressure, not in a vacuum.11 The com-plex cyanide of tervalent molybdenum K4Mo(CN),,2H,0 l2 and thered permolybdates &MOO, and Zn(NH,),MoO, have been prepared,13while the preparation and reactions of the red K,[Mo(CN),( OH),]have been discussed.14 Methods have been given for preparingH. L. Riley, J. F. Morley, and N. A. C. Friend, J., 1932, 1875; A.,533; H. L. Riley and N. A. C. Friend, ibid., p. 2342; A., 1108.J.Janitzki, 2. anorg. Chem., 1932, 205, 49; A., 584.F. Hein and I. Wintner-Holder, ibid., 1931, 202, 81 ; A., 133.T. P. Hoar and U. R. Evans, J., 1932,2476; A., 1093.lo R. Schwarz and H. Giese, Ber., 1932, 65, [B], 871; A., 708; E. H.l1 Guichard, Bull. SOC. chim., 1932, [iv], 51, 563; A., 708.l2 R. C . Young, J . Amer. Chem. SOC., 1932, 54, 1402; A., 584.K. Gleu, 2. anorg. Chem., 1932, 204, 6 7 ; A., 484.l4 W. F. Jak6b end E. Turkiewicz, Rocz. Chem., 1931, 11, 669; A., 1931,1382; W. F. Jak6b and C. Michalewicz, ibid., 1932,12, 667; A., 1100.Riesenfeld, ibid., p. 1868BASSETT. 87several sodium salts of phosphomolybdic and phosphotungsticacids.15 WOC1, is best prepared by passing chlorine over anequimolecular mixture of tungsten and its dioxide at 700-800".It is purified by distillation in vacuum or in a stream of carbondioxide at 200".Careful measurements of a number of its physicalconstants have been made.16 Some reactions of tungsten hexa-chloride have been described.17Mixtures of WC and W2C are formed when the elements are heatedtogether a t temperatures between 1600" and 2500". The former canbe separated from the reaction products by heating in chlorine below600" since the metal and the other carbide are converted into volatilechlorides while WC remains unaffected.18A number of complex salts and ammines of quadri- and sexa-valent uranium have been described, as well as a number of per-uranates .I9Group V I I .Various physical properties of boron and bromine trifluorides andarsenic pentafluoride have been measured.20 A number of complexfluorides of tervalent vanadium and chromium of the typesi&[V(or Cr)F,] and q[V(or Cr)P,,H,O] have been prepared.21They all form cubic crystals.Bromine pentafluoride has been obtained by heating the trifluoridewith fluorine at 200".It is a colourless fuming liquid, b. p. 40.5".Its physical properties and reactions have been examined.22Preliminary details have been given for preparing hypofluorousand fluoric acids.23 Chlorine and bromine form the hydratesCl,,6H20 and Br,,lOH,O, and BrC1,4H20 is more stable than eitherof these.24 It is considered that there is little if any I' ion in aqueousl5 A. V. Rakovski and E. A. Nikitina, J . Gen. Chem. Russ., 1931, 1, 240,l6 W. Reinders and J.A. M. van Liempt, Rec. trav. chim., 1931, 50, 997;l7 A. J. Cooper and W. Wardlaw, J., 1932, 635; A., 352.l8 I. Iitaka and Y . Aoki, Bull. Chem. SOC. Japan, 1932, 6, 108; A., 708.R. RLscanu, Ann. sci. Univ. Jassy, 1930, 16, 32, 459; A,, 1931, 1382;A. Rosenheim and M. Kelmy, 2. anorg. Chem., 1932, 206, 31; A., 708; A.Rosenheim and H. Daehr, ibid., 208, 81; A., 1100.2O 0. Ruff, A. Braida, 0. Bretschneider, W. Menzel, and H. Plaut, ibid.,206, 59; A., 707.21 L. Passerini and R. Pirani, Gazzetta, 1932, 62, 279, 289; A., 795; R.Pirani, ibid., p. 380; A., 902.22 0. Ruff and W. Menzel, 2. anorg. Chem., 1931, 202, 49; A., 133.23 L. M. Dennis and E. G. Rochow, J . Amer. Chem. Soc., 1932,54, 832; A.,24 S. Anwar-Ullah, J., 1932, 1172, 1176; A,, 586; I.W. H. Harris, ibid.,247; A., 1931, 1382.A., 1931, 1382.486.pp. 582, 2709 ; A., 36288 INORGANIC CHEMISTRY.iodine monochloride, but that in hydrochloric acid solution there isconsiderable formation of IC12' i0n.25 It has been stated 26 thatiodine dissociates in ethyl-alcoholic solution to yield uni- and ter-valent ions. The former are precipitated by alcoholic silver nitrate,leaving I(NO,), in solution, and this, with excess of iodine, yieldsINO,. Pyridine and quinoline compounds of these nitrates aredescribed.The isobaric dissociation curve of manganese oxide at about10 mm. shows the successive formation of Mn203, Mn304, and MnO ;nIn,O;;ppears to give the dioxide directly without any intermediatestage. Several manganic dithiocarbamates have been preparedwhich are very similar t o the corresponding ferric compounds.28Evidence is given for the view that Re,O, is thc highest oxide ofrhenium stable under ordinary condition^.^^ Further work has beenpublished on the oxides and other compounds of ter-,30 q ~ a d r i - , ~ ~q~iinque-,~~ s e ~ a - , ~ ~ and septa- 33 valent rhenium, but much of this isin the nature of confirmation of earlier work.Some thermochemicalmeasurements have been made on a few of the septavalent com-pounds . 34Group VIII.The study of the corrosion of iron and other metals has beenplaced on a much more quantitative basis by measuring the absorp-tion of oxygen and evolution of hydrogen which occur during theprocess. Important results have already been obtained in this way.Thus, it is found that when iron or steel corrodes in potassiumA ., 467 ; Ann. Reports, 1930, 27, 72.25 J. H. Faull, jun., and S . Baeckstrom, J . Amer. Chenz. SOC., 1932, 54, 620;26 M. I. Uschakov, J. Qen. Chem. RUSS., 1931, 1, 1258; A., 809.2 7 A. Simon and F. Fehdr, 2. Elektrochem., 1932,38,137 ; A., 468. See alsoI?. Krull, 2. anorg. Chem., 1932, 208, 134; A., 1204.28 L. Cambi and A. Cagnasso, Atti R. Accad. Lincei, 1931, [vi], 14, 71; A . ,133.2s H. V. A. Briscoe, P. L. Robinson, and A. J. Rudge, Nature, 1932, 129,618; A., 585.30 F. ICrauss and H. Steinfeld, Ber., 1931, 64, [ B ] , 2552; A . , 1931, 1382;W. Manchot, H. Schmid, and J. Diising, ibid., p. 2905; A . , 133; F. Kraussand H. Dahlmann, ibid., 1932, 65, [B], 877 ; A., 71 1 ; H.V. A. Briscoe, P. L.Robinson, and A. J. Rudge, J . , 1931, 3218; A., 133; E. Turkiewicz, Rocz.Chem., 1932, 12, 589; A . , 1101.31 W. A. Roth and G. Becker, Ber., 1932, 65, [B], 373; A . , 353.32 W. Biltz, G. A. T,chrer, and K. Meisel, Nach. Ges. Wiss. Cdttingen, 1931,191; Chem. Zcntr., 1932, i, 1070; A., 708; idem, 2. anorg. Chem., 1932, 207,113; A . , 1008.33 H. V. A. Briscoe, P. L. Robinson, and A. J. Rudge, J., 1932, 1104; A . ,685; A. Brukl and K. Ziegler, Ber., 1932, 65, [B], 916; A., 708; W. Biltzand F. Weibke, 2. anorg. Chem., 1931, 203, 3 ; A., 239.34 W. A. Roth and G. Becker, 2. physikal. Chem., 1932, 159, 2 7 ; L4., 4.69BASSETT, 89chloride solutions the proportion of metal which corrodes owing toliberation of hydrogen is considerable for solutions more concentratedthan O-OOlN.35By the interaction of ferric chloride with alkali-metal thio-cyanates in alcoholic solution, complex ferrous thiocyanates only arc'obtained, of the type R,[Fe(CNS),],xH,O. In aqueous solutionferric compounds are obtained and a large number of complex ferricthiocyanates have been boiling with pyridine is reduced to [Fe(C5H5N)4(CNS)2], which,on atmospheric oxidation in chloroform solution, yields[Fe,(C,H,N),,(CNS),] corresponding with Fe,0,.36 The two ferricdithiocarbamates [Me,N*CS,],Pe and [C,H,oN*CS,]3Fe have beenprepared. These are stable towards oxygen and nitric oxide, butthe corresponding ferrous compounds each combine with one mole-cule of this gas.,' Under the influence of sodium ethoxide, ironpentacarbonyl reacts to form ethyl carbonate and Fe(CO)4Na,.38The latter gives the ether-soluble Fe(CO),H, with acid, and this,with concentrated mineral acid, decomposes into tetracarbonyl andhydrogen. It is pointed out that the production of Fe(CO),H, andcarbon dioxide from the pentacarbonyl may be regarded as a form ofhydrolytic water-gas reaction taking place a t room temperature.The' reactions of iron pentacarbonyl with alkali or with organicbases seem to be often very complex, and a number of papers inaddition to the one just cited deal with the matter.39Several iron csrbonyl halogen compounds have been prepared ,derived by substitution either from Fe(CO),X, (X = C1, Br, or I),e.g., (EtS-[CH2],*SEt)Pe(C0)212, or from [Fe(C0)4]3, e .g . ,[Fe(CO),Br,]3.40Carbon monoxide is lost by [Co(CO),], at 55-60', with formationof [Co(CO),],. The cobalt carbonyls show a great tendency towardsThe compoundC5H,N[Fe(C5H5N),(CNS),135 C. D. Bengough, J. M. Stuart, and A. R. Lee, Proc. Roy. SOC., 1930, [ A ] ,127, 42; A., 1930, 712; G. D. Bengough, A. R. Lee, and F. Wormwell, ibid.,1931, [ A ] , 134, 308; A., 27.36 A. Rosenheim, E. Roehrich, and L. Trewendt, 2. anorg. Chem., 1933,207, 97; A., 1009.37 L. Cambi, A. Cagnasso, and A. Tanara, Atti R. Accad. Lincei, 1931, [ui],13, 254; A., 1931, 1382.38 H. Hock and H. Stuhlmann, Chem.-Ztg., 1931, 55, 874; A., 32.39 3'. Feigl and P. Krumholz, Monatsh., 1932, 59, 314; A., 485; W.Hieberand F. Leutert, Ber., 1931, 64, [B], 2832; A., 134; W. Hieber, F. Leutert,and (Frl.) E. Schmidt, 2. anorg. Chem., 1932, 204, 145; W. Hieber, H. Vetter,and H. Kaufmann, ibid., p. 165 ; A., 485; W. Hieber and F. Muhlbauer, Ber.,1932, 65, [B], 1082 ; A., 920.40 W. Hieber, G. Bader, K. Ries, and E. Becker, 2. anorg. Chem., 1931,201, 329; A., 13490 INORGANIC CHEMISTRY.polymerisation and high chemical reactivity. Nickel tetracarbonylis considerably more stable than the iron or cobalt carbonyls. Anumber of derivatives of the cobalt and nickel compounds have beenprepared .41A critical review of recent work on the equilibrium of systemsinvolved in the production of steel has been p~blished.*~ Thesystems Fe-0, Fe-FeO-CaO, Fe-O-C, Fe-Si-0, Fe-MnO, andothers involving phosphorus and sulphur are considered, and atabulated summary is given of the equilibrium constants obtainedby the various workers.The equilibria concerned in the cementation of iron have been thesubject of a careful study.It is concluded from the results thatcarbon vapour is monatomic and that the distribution of free carbonbetween the vapour and the solid phase follows Henry's law.43 Theequilibria between ferrous oxide and silica have been examined inelectrolytic iron crucibles in a vacuum and in pure nitrogen a ttemperatures below 1523". The very interesting fact emerged thatall melts in equilibrium with iron contain some ferric oxide, thepercentage weight of which decreases rapidly from 11.5 as silica isadded.This is presumably owing to an equilibrium 3Fe0 zzFe + Fe203 of the well-known type to which lower valency stagesare subject. On account of this, synthetic and natural fayalite(Fe,SiO,) and all FeO-SiO, mixtures melt incongruently, withseparation of iron. The bearing of the results obtained on petrologyand the problems of slag formation and furnace linings is disc~ssed.~*The distribution of manganese between molten iron and slagowing to the equilibrium FeO + Mn Fe -t MnO has beenexamined, and also the influence of additions of silica and lime.45Two calcium ferrites exist, CaO,Fe,O, and 2Ca0,Fe,03 ; they can beformed from calcium carbonate and ferric oxide a t temperaturesabove 500". 2Ca0,Fe203 does not decompose below 1400", thoughferric oxide evolves oxygen a t 1380".Lime also forms a compoundwith ferrous oxide which is probably 2Ca0,Fe0.46Mixtures of metal and several phosphides are obt,ained by the*l F. Reiff, 2. anorg. Chem., 1931, 202, 375; A . , 239; vCT. Hieber and H.Kaufmann, ibid., 1932,204,174 ; A., 485 ; W. Hieber, F. Miihlbauer, and E. A.Ehmann, Ber., 1932, 65, [B], 1090; A . , 920.42 F. Sauerwald and W. Hummitzsch, Arch. l~isenkiitlenw., 1931-1032, 5,355; A., 340.43 A. Bramley and H. D. Lord, J., 1932, 1041; A., 811.44 N. L. Bowen and J. F. Schairer, Anier. .T. Sci., 1932, [v], 24, 177 ; A., 997.4 5 W. Krings and H. Schackmann, 2. nnorg. Chem., 1931, 202, 99; 1932,206, 337; A., 125, 811; E. Maurer and W. Rischof, I r o n and Rteel I n s t . , May1932, Advance Copy; B., 60%.4 6 J.Konarzewski, Rocz. Cltetn., 1931, 11, 510, 607; A . , 1031, 1010, 1373BASSETT . 91action of hypophosphite on solutions of cobalt or nickel salts.47Crystalline Nip is obtained by the interaction of phosphorus vapourand nickel tetracarbonyl a t 50". An amorphous black solid, prob-ably Nip,, is obtained by bubbling the carbonyl vapour throughphosphorus, either liquid or dissolved in turpentine .48Several new cobaltic ammines have been described,49 and a verylarge number of ruthenium compounds. 50Rhodium dioxide cannot be obtained anhydrous, but in hydratedform it may be obtained pure by the electrolysis of a solution preparedfrom Na,RhCl, and potassium hydroxide. Dark green hydratedRho, separates a t the anode, but attempts to dehydrate it alwaysresult in the formation of Rh203.51 At 210" [BrRh(NH3)5]Br, isquantitatively converted into [Br3Rh(NH,),].The correspondingchlorine and iodine compounds do not behave in this way.52 Aninorganic compound containing no carbon but showing opticalactivity has a t last been found in sodium diaquo-rhodium disulph-amide, Na[ (H20),Rh(NH*S0,*NH),], the cis-form of which has beenresolved into a d- and anNickel, ruthenium, rhodium, and palladium can apparently bereduced to the univalent state when suitable cyanide solutions arewarmed with alkali and 907; sodium hypophosphite solution.54Palladous chloride with many purines and alkaloids forms almostinsoluble compounds from which the bases are easily regenerated.The caffeine and theobromine complexes have the formula R2PdC12.55Much work published during the past year has centred round thequestion whether the valencies of 4-covalent compounds of themetals of Group VIII are planar or directed towards the corners of atetrahedron.The conditions under which a planar configurationis possible have been deduced and can occur with bivalent nickel,palladium, a n d p l a t i n ~ r n . ~ ~ A case of the kind appears to occur withthe glyoximes of nickel, since the benzylmethylglyoxime has beenobtained in two isomeric forms 'of the same molecular weight whichare interpreted as cis- and t~ans-forms.~~4 7 R. Scholder and H. L. Haken, Bey., 1931, 64, [B], 2870; A., 13-1.4 * C. M. W. Grieb and R. H. Jones, J., 1932, 2543.*@ H.J. S. King, J., 1932, 1275; A., 586; T. Das-Gupta and P. B. Sarkar,J . Indian. Chem. SOC., 1932, 9, 79; A., 709.5 1 L. Wohler and K. F. A. Ewald, 2. anorg. Chem., 1931, 201, 145;52 E. Birk and H. Kamm, Siebert Festschr., 1931, 12; A., 2-10.53 F. G. Mann, Nature, 1932, 130, 368; A., 1101.64 W. Manchot and H. Schrnid, Ber., 1931, 64, [ B ] , 2672; A., 32.fi6 J. M. Gulland and T. F. Macrae, J., 1932, 2231; A., 1052.56 L. Pauling, J. Amer. Chem. SOC., 1931, 53, 1367; A , , 1931, 670.6 7 5. Sugden, J., 1932, 246; A., 272.R. Charonnat, Ann. Chim., 1931, [XI, 16, 123; A., 1931, 1383.A., 3202 INORGANIC CHEMISTRY.Investigation 58 of the supposed cis- and trans-isomerides ofPdhX, (where A is an amine and X an acid radical) appears to show,however, that in these cases such isomerism does not occur.Thepink compounds are considered to have the formula [PdAJPdX,,while the yellow compounds are [PdA,X,]. Other workers 59 agreethat there is no cis-trans-isomerism in the case of Pd(NH3),C12 butconsider that both the yellow and the pink form are bimolar.From an X-ray examination of [Pf(NH3),]Cl2,H,O it is deducedthat the four ammonia molecules have a planar configuration roundthe platinum atom. The water molecule is regarded as being at thecell centre and not midway between two platinum atoms as part of asix-point system round the platinurn.6O The solid solution formationsaid to occur between [Pt(NH,),]CI,,H,O and4(Pt(NH3),C1,}Pt (NH,),CI,was not confirmed. X-Ray investigations of the green salt ofMagnus [Pt(PJH,),][PtCl,] show that the two complex ions have thesame structures as those present in [Pt(NH3),]C1,,H20 and inK,PtCl,; both are therefore considered to be planar.The corre-sponding pink salt of Magnus was shown to be very unstable anclits precise nature is still uncertain.62The problem of the isomeric diamminoplatinous chlorides has beencomplicated by the discovery of a third i~orneride.~~ All threeforms are considered to be, probably, structural isomerides and t obe unimolecular and non-ionic. Only one form is supposed to havefour groups arranged round the platinum atom, with no evidenceavailable at present to show whether the arrangement is tetrahedralor planar. For the other two isomerides the early types of structuresc1'H3N>Pt and H3NhPt,+"H3c1 have been revived.The evidenceCl*H,N c1/advanced for this is lengthy, but to the reviewer it seems a retrogradestep. I n the groups *NH,C1 the chlorine is considered to be attachedt o nitrogen which is &covalent with a decet of electrons. It isdifficult to believe that such a structure would have the stabilitxnecessary to account for the behaviour of the compounds, anclweightier evidence seems called for before discarding Sidgwick'scovalency rule for nitrogen. It seems more likely that the threeisomerides are not all monomeric.I n order to account for the remarkable isomerism found amongst5 8 H. D. K. Drew, F. W. Pinkard, G. H. Preston, and W. Wardlaw, J.,59 F. Krauss and K.Mahlmann, Siebert Festschr., 1931, 215; A., 240.Go E. G. Cox, J., 1932, 1912; A., 797.G1 Ann. Reports, 1930, 27, 76.G2 E. G. Cox, F. W. Pinkard, W. Wardlaw, andG. H. Preston, J., 1932, 2527.63 R. D. K. Drew, F. W. Pinkard, W. Wardlaw, and E. G. Cox, ibid., p.1932, 1895; A., 824.988; A., 56%BASSETT. 93the mixed tetrammino-dihalides, e.g., [Pt (NH,),py,JCI,, it has beensuggested 64 that the four linkings to the ammino-groups of thetetrammines are differentiated into two equivalent pairs whichfunction independently, a closer relationship existing between themembers of a pair than exists between either member of one pairand either member of the other. All four linkings are, however,supposed to be of the same kind, and precisely equivalent to oneanother in the sense of the equivalence of the six linkings to hydrogenin the benzene ring.Time alone can show whether such a, viewwill be found satisfactory, but it has been found useful in interpretingthe formation and reactions of a number of c o m p o ~ n d s . ~ ~ ~ 65The view appears to be gaining ground that in 4-covalent platinumthe groups may be grouped tehahedrally about the platinum atomin some cases and be planar in others. To investigate this pointstill further, the two isomeric diquinolinoplatinous chlorides havebeen prepared for the first time in a pure condition.66Systems and Equilibria.Ag-Cu-Mn 67 ; potassium phthalate-phthalic acid-water 68 ; Fe-0, 69 ; CO-N,-H, and the component binary systems 70 ; Pr,(SO,),-TI,SO,-H,O 71 ; Pr2(S04)3-Na,S04-H,0 72 ; Li,SO4-Bi,(S0,),-H,O 73 ; Na2(K,,Rb2,(NH4),,T1,> SO4-Mg(Co,Ni,Zn,Cd)SO,-H,O 74 ;K,(Rb,,Tl,)SO,-CdS0,-H,O 75 ; CaO-Al,03-H,0 76 ; MgCl2-NaNO3-H20 77 ; SrO-As,O,-H,O ; PbO-As,O,-H,O 78 ; Fe-Ni-P 79 ; HCI-S,CI, ; H20-C0,-NH, 8l; K,CO,-KHCO,-H,O 82 ; Fe-Zr 83 ;64 H.D. K. Drew, F. W. Pinkard, W. Wardlaw, and E. G. Cox, J., 1932,6 5 H. D. H. Drew, ibid., p. 2328; A., 1101.66 E. G. COX, H. Saenger, and W. Wardlaw, ibid., p. 2216; A., 1039.6 7 M. Keinert, 2. physikal. Chem., 1931, 156, 291; A., 1931, 1364.6 8 S. B. Smith, J. Aneer. Chem. SOC., 1931, 53, 3711; A., 1931, 1365.6s H. Schenck and E. Hengler, Arch. Eisenhiittenw., 1931-1932, 5, 209;70 T. T. H. Verschoyle, Phil. Trans., 1931, [ A ] , 230, 189; A., 1931, 1370.71 F.Zambonini and S. Restaino, Atti R. Accad. Lincei, 1931, [vi], 13, 650;72 Idem, ibid., 14, 69; A., 132. 73 L. Malossi, ibid., 13, 775; A., 32.74 A. Benrath, 2. anorg. Chem., 1931, 202, 161; 1932, 208, 169; A., 13.3,75 A. Benrath and C. Thonessen, ibid., 1932,203, 405; A., 229.76 G. Assarsson, ibid., 1931, 200, 385; A., 1931, 1370.7 7 A. Sieverts and E. L. Muller, ibid., p. 305; A., 1931, 1370.7 8 H; V. Tartar, M. R. Rice, and B. J. Sweo, J . Amer. Chem. SOC., 1931,R. Vogel and H. Barn, Arch. Eisenhiittenw., 1931-1932,5,269; A,, 221.E. Jiinecke aad E. R d f s , 2. Ekktrochm., 1932,38, 9; A., 229.1004; A., 562.A . , 1931, 1369.A , , 1931, 1381.1205 ; A. Benrath and W. Thiemann, ibid., p. 177 ; A., 1205.53,3949; A., 125.8o H.Terrey and H. Spong, J . , 1932, 219; A., 228.82 Z. P. Staxkova, J . Cen. Chem. RUSS., 1931,1, 747; A . , 229.8a R. Vogel and W. Tonn, Arch. Eisenhiittenw,, 1931-1932,5,387 ; A., 33094 INORGANIC CHEMISTRY.Fe-Co-W ; Fe-Co-Mo 85 ; NH,-H,S 86 ; Na,SiO,-NaF *' ; Fe-GO, 8 8 ; systems SiO,, CaO, and A120, with C S9; Na,O-B,O,-H,O ; Na2S04-A12(S0,),-H,0 91 ; Mg(10,)2-Na103-H,0 ; NaIO,-KIO,-H,O ; KI0,-KC1-H20 ; KI0,-K,SO,-H,O 92 ; KI0,-KN0,-H20 ; Ca(103)2-NaI0,-H20 93 ; KMn04-KBF4-H,0 94 ; Pb(NO,),-(Na,K,Ag,Tl)NO, 95 ; CdC1,-KC1-H,O 96 ; CdBr,-KBr-H,O 97 ;Mg(NO,),-H,O 98 ; Na,S04-H,S0,-H,0 99 ; LiN0,-TlNO, ; CaO-Na20-Al,03 ; SiO,-ZnO-Al,O, ; Ag-Cu-Zn ; MgO-C0,-H,O ;K2C0,-NH3-H20 ; ZnSO,-NH,-H,O ; CuC1,-LiC1-H,O andNiC12-LiC1-H,0 ; CoC1,-LiCl-H,O ; CuSe0,-H,SeO,-H,O lo ;La,(SeO,),-H,O l1 ; Pr,(SeO,),-H,O l2 ; Ni-Zn l3 ; KRe0,-H,O l4 ;NaN0,-KNO, l5 ; KF-AlF, ; LiF-AlF, l6 ; Ca(ClO,),-H,O l7 ;s 4 W. Koster and W.Tom, Arch. Eisenhiittenw., 1931-1932,5,431; A., 456.86 L. Schleflan and C. R. McCrosky, J . Arrber. Chem. Soc., 1932, 54, 193;8 7 H. S. Booth and B. A. Starrs, J . Physical ChenL., 1931,35, 3553 ; A., 340.89 R. Brunner, 2. Elektrochem., 1932, 38, 55; A., 341; E. Baur, ibid., p. 69;Idem, ibid., p. 627; A., 801.A., 340.E. Jiinecke, 2. anorg. Chem., 1932,204, 267; A., 340.A., 341.U. Sborgi, Cfazxetta, 1932, 62, 3; A., 341.91 J. T. Dobbins and R. M. Byrd, J . Physical Clzeuz., 1(331,35,3673; A., 341.92 A. E. Hill and J. E. Ricci, J. Amer. Chem. Xoc., 1931, 53, 4305; A., 341.O3 A.E. Hill and S. F. Brown, ibid., p. 4316; A., 341.94 R. C. Ray and K. K. Chatterji, J., 1932, 384; A., 341.O 5 H. M. Glass,K.Laybourn,and W.M.Madgin,ibid.,pp. 826, 2713; A., 468.H. Hering, Compt. rend., 1932, 194, 1157; A., 469.97 Idem, ibid., p. 1348; A., 574.A. Sieverts and W. Petzold, 2. anorg. Chem., 1932, 205, 113; A., 573.99 T. Okuno andK. Miyazaki, J . SOC. Chem. I n d . Japan, 1932,35,97; A., 57 .1 H. V. A. Briscoe, C. Evans, and P. L. Robinson, J., 1932, 1100; A., 574.2 L. T. Brownmiller and R. H. Bogue, Bur. Stand. J. Res., 1932, 8, 289;3 E. K. Bunting, &id., p. 279; A., 5'74.4 1%. Keinert, 2. physikal. Chew!., 1932, 160, 15; A., 687.5 (Mme.) Walter-LBvy, Compt. Tend., 1932, 194, 1818; A., 697.6 M. P. Applebey and (Miss) M.A. Leishman, J., 1932, 1603; A., 697.7 M. P. Applebey and M. E. D. Windridge, ibid., p. 1608; A., 697.8 H. Benrath, 2. anorg. Chenz., 1932, 205, 417; A., 697.9 H. Bassett and (Miss) I. Senderson, J., 1932, 1856; A., 811.10 G. B. Macalpine and L. A. Sayce, ibid., p. 1560; A., 698.11 J. A. N. Friend, ibid., p. 1597; A., 707.1 2 l d e m , ibid., p. 2410; A., 1083.13 K. Tamaru, Bull. Inst. Phys. Chem. Res. Tokyo, 1932,11, 90; A., 801.14 N. A. Pushin and D. Kovatsch, Bull. SOC. chim. Yougoslav., 1931, 2, 2 5 ;15 J. Ettinger, Rocz. Chenz., 1932, 12, 362; 2. anorg. Chem., 1932, 206, 260;1 6 P. P. Fedot6ev and K. Timoiiev, ibid., p. 263; A,, 810.17 V. S. Egorov, J . Ben. Chew&. Russ., 1931,1, 1266; A., 810.A., 574.A., 801.A., 809, 810BASSETT. 95KC1-PbC12-H20 '8 ; KNO3-NH4NO3-HZO l9 ; CUSO~-COSO~-H20 2o ; carbamide-H202-H20 21 ; Al-Mg-Si 22 ; Al-Mg-Cu 23 ;Al-Cu-Si 24 ; Al-Cu-Fe 25 ; HgBr2-KBr-H20 26 ; Mg0-MgCl2-H20 27 ; NiS0,-CaS0,-H20 2* ; Fe-Mi 29 ; PbO-SiO, 30 ; Fe-Co-C 31 ; Fe-Co-Cr 32 ; Fe-Fe,C-FeS 33 ; KCl-NaC1-H20 34 ;MnSi0,-Fe,Si04 ; FeS-Fe2Si0, 35 ; CaCI2-MgCl2-H2O 36 ; (m4)2s04-Th(SO&-H,O 37 ; MnSOg-Th(SO4)2-H20 38 ; AgNCS-NH3-HZO 39 ;AgNCS-Na"S-H20 ; AgNCS-KNCS-H,O ; AgNCS-NH4NCS-H20 40 ; CaC12-Ca(N03)2-H,0 ; CaC12-Ca( C1O3),-H2O ; SrC1,-Sr(NO,),-H20 ; KN0,-Pb(N03),-H20 41 ; Na20-CaO-B,O,-SiO, 42 ;K2Si03-Na2Si03Si02 43 ; NaN03-KN03-Pb(N03)2.44Is L. J. Burrage, Trans. Faraday SOC., 1932, 28, 529; A., 810.lo E. Janecke, H. Hainacher, and E. Rahlfs, 2. anorg. Chem., 1932,206,357 ;2o H. D. Crockford and D. J. Brawley, J . Physical Chem., 1932, 36, 1594;21 E. Janecke, Rec. trav. chim., 1932, 51, 579; A., 811.L. Losana, Met. Itul., 1931,23,367; Chem. Zentr., 1932, i, 1425; A., 907.z3 A. Portevin and P. Bastien, Cornpt. rend., 1932, 195, 441 ; A., 989.24 G. G. Urazov, S. A. Pogodin, and G. M. Zamoruev, Ann. Inst. Anal. Phys.25 K. Yamaguchi and I. Nakamura, Bull. Inst. Phys. Chem. Res. Tokyo,26 (Mlle.) M. Pernot, Compt. rend., 1932, 195, 238; A,, 913.27 C. R. Bury, E. R. H. Davies, and G. Grime, J., 1932, 2008; A., 913.28 A. N. Campbell and N. S. Yanick, Trans. Faraday SOC., 1932, 28, 657;29 A. KM and F. Pobofil, Iron and Steel Inst., Sept. 1932, Advance copy;30 K. A. Krakau and N. A. Vakhrameev, lieram. i Steklo, 1932, 8, No. 1,31 R. Vogel and W. Sundermann, Arch. Eisenhuttenw., 1932-1933, 6, 35;32 W. Koster, ibid., p. 113; B., 1035.33 T. Sat& Tech. Rep. Tbhoku, 1933, 9, 119; A., 1090.34 E. Cornec and H. Krombach, Ann. Chirn., 1932, [s], 18, 5; A., 1091.3G J. H. Andrew and W. R. Maddocks, Iron and Steel Inst., Sept. 1932,36 C. F. Prutton and 0. F. Tower, J . Amer. C'hem. Soc., 1932,54, 3040; A.,37 A. Rosenheim and J. Zickermann, 2. anorg. Chem., 1932, 208, 95; A.,A., 810.A., 811.Chirn., 1931, 5, 157; A., 907.1932,11, 815; A., 907.A., 913.A., 990.42; A., 1090.A., 1090.Advance Copy ; A., 997.1091.1091.It. M. Caven, J., 1932, 3417; A., 1091.30 F. J. Garrick and C. L. Wilson, ibid., p. 835; A., 457.4O V. J. Occleshaw, ibid., p. 2404; A., 1091.41 W. F. Ehret, J . Amer. Chem. SOC., 1932, 54, 3126; A., 1091.42 G. W. Morey, J . Arner. Ceramic SOC., 1932, 15, 457; B., 1029.43 F. C. Kracek, J . Physical Chem., 1932, 36, 2529.44 I<. Laybourn and W. 31. Madgin, J., 1932, 2582; A., 1205.H. BASSETT


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