656 INORGANIC AND THEORETICAL CHEMISTRY

P. Lebeau found that the specific gravity of the liquid is 2-93 ; M. Meslans gave3-0076, and he found that the gas liquefies at —30°. H. Moissan and P. Lebeaugave —32° for the boiling point, and 0. Ruff and K. Thiel, —30° for the b.p. at760 mm., and —110° for the melting point. When the gas is heated in a dry glassvessel to 400°, H. Moissan and P. Lebeau found that it decomposes 2S0F2+Si02=SiF4+2SO2 ; the action of the electric discharge from an induction coil on thegas in a glass vessel is similar to that of heat. O. Ruff and K. Thiel said that thegas is not changed when passed through a white-hot platinum tube filled with spongyplatinum. H. Moissan and P. Lebeau found that if sparked along with hydrogenin a glass vessel, the sulphur dioxide is reduced to hydrogen sulphide, sulphur,and water, and the latter reacts with the silicon tetrafluoride, forming hydrofluo-silicic acid. The presence of oxygen does not affect the decomposition of the thionylfluoride by the action of heat, but when the mixture of the two gases is sparked,a certain amount of a more volatile oxyfluoride is produced—vide infra, sulphury!fluoride. The gas is decomposed by water : SOF2+H2O=SO2+2HF. O. Ruffand K. Thiel observed that a mixture of thionyl fluoride and chlorine, in a sealedglass tube, in sunlight, or in the presence of carbon, reacts with the silica of theglass to form silicon tetrafluoride and sulphuryl chloride. Under ordinary con-ditions chlorine, and bromine are inactive. H. Moissan and P. Lebeau found thatwhen the gas is treated with hydrogen chloride over mercury, a gaseous mixtureis produced which attacks the mercury. The gas is not attacked by sulphur at500°, but, at high temp., hydrogen sulphide forms sulphur, water, and hydrogenfluoride; at ordinary temp., there is no reaction. M. Meslans found that thegas reacts with ammonia, forming ammonium fluoride and thionyl amide.F. Wunderlich represented the reaction: S02F2+4NH3=2NH4F+S02(NH2)2.With methylamine in place of ammonia, he obtained dimethylsulphamide,SO2F2+4CH3NH2=SO2(NHCH3)2+2CH3NH3F. Similarly, ethylamine furnishesdiethylsulphamide. H. Moissan and P. Lebeau showed that the first product ofthe reaction with ammonia is an orange-coloured thionyl hemipentamminofluoride,2SOF2.5NH3, and finally a white substance corresponding with thionyl hemiheptam-minofluoride, 2SOF2.7H2O, and when the latter is treated with hydrogen chlorideit forms sulphur, and sulphur dioxide. O. Ruff and K. Thiel said that thionylfluoride reacts with nitrogen trioxide and moisture, forming nitrosulphonic acid;and silicon tetrafluoride; but the gas does not react with nitric oxide. H. Moissanand P. Lebeau observed no reaction with phosphorus at 500°. Accordingto F. Wunderlich, one vol. of glycerol absorbs 0-12 vol. of the gas; petroleum,14 vols.; benzene, 2-3vols.; toluene, 2-9 vols.; ethyl alcohol,30 vols.; methylalcohol, 31 vols.; carbon tetrachloride, 34 vols.; chloroform, 40 vols.; andacetone, 4-9 vols.; while ether and carbon disulphide absorb only a little of thegas. H. Moissan and P. Lebeau also found that the gas is soluble in arsenictrichloride, and also in benzene, turpentine, and ether; and it is absorbed by moltensodium or tin. F. Wunderlich found that a soln. of potassium sulphide in absolutealcohol forms a little thiosulphate when treated with sulphuryl fluoride; and thereaction in an aq. soln. of calcium hydrosulphide is symbolized: SO2F2-f 2Ca(SH)2+H2O=CaS2O3+CaF2+3H2S.

J. Persoz and N. Bloch 2 first prepared thionyl chloride, SOC12, in an impureform, by the action of sulphur dioxide on phosphorus pentachloride; P. Kremersobtained it in a similar way, and named it schwefligsaures Phosphorsuperchloridbecause it was supposed to have the composition PC15.SO2 until H. Schiff preparedit in a fairly pure state and showed that its empirical composition is really SOC12.The work of L. Carius, C. A. Wurtz, and A. Michaelis demonstrated the chemicalcharacteristics of the compound. C. Schorlemmer has made some remarks on thehistory of thionyl chloride. L. Carius prepared thionyl chloride by heating calciumsulphite with phosphoryl chloride to 150°. He first employed the proportionsindicated in the equation: 3CaSO3+2POCl3=Ca3(PO4)2+3SOCl2, and heatedthe mixture to 150° in sealed tubes; but so much sulphur dioxide was developed

SULPHUR 657

that the tubes burst. Possibly the reaction is 6CaSO3+2POCl3=Ca3(PO4)2+3CaCl2+6SO2, but some thionyl chloride is also formed. L. Carius found, thatby raising the proportion of oxychloride until equal molecular proportions of thetwo substances were present, the proportion of thionyl chloride greatly increased,and that of sulphur dioxide became very small. Calcium sulphite can thusbe made to yield most of its sulphur as thionyl chloride, but only by using excess ofphosphorus oxychloride, since without this excess sulphur dioxide is the mainproduct. Now, this sulphur dioxide must be derived from thionyl chloride shouldphosphorus oxychloride really act on calcium sulphite, and then form thionylchloride by this action. E. Divers and T. Shimidzu said that phosphorus penta-chloride is itself without action on calcium sulphite, but at 150°, the pentachlorideis dissociated into phosphorus pentoxide and pentachloride: 10POCl3=2P2O5+6PCI5, the pentoxide takes calcium oxide from the sulphite, thus setting freesulphur dioxide : 6CaSO3-r2P2O5=2Ca3(PO4)24-6SO2, and. this with phosphoruspentachloride gives thionyl chloride and phosphorus oxychloride again:6SO2+6PCl5=6SOCl2-t-6POCl3—vide infra. Three-fifths of the phosphorusoxychloride begun with are thus regained. In practice, L. Carius found an extrahalf of the oxychloride to be excess enough to use. The large quantity of sulphurdioxide which forms when these proportions are greatly altered in favour of thecalcium sulphite, is to be traced to the action of the- phosphorus pentachloride uponthe excess of calcium sulphite instead of upon the sulphur dioxide, as is shown bythe following equation: 15CaSO3+6PCl5=3Ca3(PO4)2+6CaCl2+9SOCl2+6SO2.With the other 6SO2 liberated, but now not decomposed, there are thus obtained12SO2 to 9SOC12. The calcium chloride here shown is a necessary complement tothe sulphur dioxide, whatever version of the change be adopted. L. Carius alsoprepared thionyl chloride by the action of phosphorus pentachloride on sodiumsulphite; and on certain organic sulphonates on the alkali metals; A. Michaelis madeit by the action of phosphorus pentachloride on sulphuryl chloride; and K. Kraut,by its action on thiosulphates. J. Persoz and N. Bloch, P. Kremers, L. Carius,and H. SchifE prepared thionyl chloride by passing sulphur dioxide over phosphoruspentachloride—SO2+PCl5=POCl3+SOCl2—and separating the thionyl chloride—b.p. 82°—from the phosphoryl chloride—b.p. 110°—by fractional distillation.A. Michaelis said that chlorine and sulphur dioxide colour the product yellow, andthey can be removed by boiling the liquid in a flask with a warm reflux condenser,and rejecting the first fraction. This mode of preparation was employed byT. E. Thorpe, and was formerly the process generally employed. The ChemischeFabrik von Heyden recommended making thionyl chloride by the interaction ofphosphorus trichloride and sulphuryl chloride: SO2C12+PC13=POC13+SOC12;while the Chemische Fabrik von Buckan found that carbonyl chloride reacts withsulphur dioxide at temp, above 200° with the formation of thionyl chloride andsulphur tetrachloride according to the equations: SO2+COC12=SOC12+CO2and SO2+2COCl2=SCl4+2CO2. The first reaction predominates at lower temp,and with excess of sulphur dioxide, and by suitable adjustment of conditions oneor other of the reactions may be almost entirely excluded. The reactions arecarried out by passing the gases over a heated contact substance, such as woodcharcoal, and the carbonyl chloride may be partly or entirely replaced by a mixtureof carbon monoxide and chloride, or carbon monoxide and sulphuryl chloride may beemployed. This mode of preparation gives good results. The Farbenfabrikvorm. F. Bayer obtained thionyl chloride by heating a mixture of chlorosulphonicacid and sulphur monochloride or dichloride.

C. A. Wurtz observed that thionyl chloride is formed by the action of chlorinemonoxide on sulphur, but the reaction proceeds with explosive violence; it was there-fore found better to dissolve the sulphur in sulphur monochloride, and allow gaseouschlorine monoxide to act on the soln. at —12°, until nearly all the dissolved sulphuris consumed. The thionyl chloride and sulphur monochloride were separated byfractional distillation. C. A. Wurtz, and P. Schiitzenberger also obtained thionyl

VOL. x. 2 u

658 INORGANIC AND THEORETICAL CHEMISTRY

chloride by the action of chlorine monoxide on carbon disulphide: 3C12O+CS2=2SOC12+COC12. A. Michaelis and 0. Schifierdecker obtained an 80 per cent,yield of thionyl chloride by the action of sulphur trioxide on sulphur tetrachloride :SCl4+S03=S0Cl2+S02+Cl2 ; and A. Behal and V. Auger, and W. Majert, by theaction of sulphur trioxide on sulphur dichloride at a temp, below the b.p. of sulphurdioxide, or under press. : SO3+SC12=SOC12+SO2. The Chemische FabrikGriesheim-Elektron obtained thionyl chloride by adding sulphur trioxide to ordinarysulphur chloride at a temp, of 75°-80°, according to SO3+S2C12=SOC12+SO2+S.Chlorine is passed in continuously in order to reconvert the sulphur produced intosulphur chloride. In this way, an almost theoretical yield is obtained, and thepractical inconveniences attending the use of higher chlorides of sulphur are avoided.The Farbenfabriken vorm. F. Bayer found that the reaction proceeds smoothlyat ordinary temp, and press., in the presence of antimony trichloride, mercuricchloride, or chlorides of the heavy metals; and that sulphur or sulphur monochloridewith chlorine and chlorosulphonic acid, or sulphur dichloride and chlorosulphonicacid can be used with or without the addition of the catalyst.

According to C. A. Silberrad, thionyl chloride may contain traces of phosphorylchloride, stannic chloride, or sulphur di- or tri-oxide. The first of these contamina-tions was found by J. Ogier to be difficult if not impossible to remove. P. Luxdetected stannic chloride by producing a yellow coloration with triphenylmethylchloride, or a red coloration with ;p-triiododiphenylmethyl chloride—neitherreagent gives the coloration with thionyl chloride alone. The stannic chloridecan be removed by fractional distillation. H. Meyer and R. Turnau, and H. Meyerand K. Schlegel found that sulphur dioxide may be removed by distillation overdimethylaniline or quinoline, and colourless thionyl chloride may be obtained bydistillation over linseed oil and purified beeswax. Thionyl chloride can be destroyedin mixtures where it is not desired by adding sufficient formic acid to react:H.COOH+SOC12=2HC1+SO2+CO—a reaction discussed by C. Moureu, andH. Meyer and R. Turnau.

Thionyl chloride is a colourless, refractive liquid with a penetrating smellrecalling that of sulphur dioxide. K. Heumann and P. Kochlin found the vapourdensity at 154° is 3-95, corresponding with the. mol. SOC12 for which the theoreticaldensity is 4-11; at 444-5°, the vap. density is about two-thirds the normal value,indicating that the compound is dissociating, and when the vapour is passed througha red-hot tube, the dissociation products are sulphur dioxide and monochloride,and chlorine. H. Standinger and W. Kreis also observed that when the vapouris chilled from 1000° to —190°, sulphur monochloride is formed. According toG. Oddo and E. Serra, the molecular weight calculated from the effect of the salton freezing benzene is 108-110 ; and with boiling chloroform, 229-235, when thetheoretical value for SOC12 is 119. When corrected with the results of G. Oddoto allow for volatilization in boiling soln. a normal value is obtained for themol. wt. E. B. R. Prideaux represented the electronic structure :

A. F. O. Getman discussed thionyl chloride as a solvent. C. A. Wurtz gave 1-675for the specific gravity at 0°; G. Carrara and I. Zoppellari, 1-6577 at 1° ; E. Nasini,1-655 at 10-474°; T. E. Thorpe found 1-6763 for the sp. gr. at 0°/4°; andS. Sugden and co-workers gave 1-656 at 14-5°/4°, 1-622 at 32°/4°, and 1-593 at48°/4°, or at 0°/4°, sp. gr. =1-683+ 0001886/. T. E. Thorpe represented thethermal expansion «=1+O-OO1164190+O-O69141802+O-O8953603, where v repre-sents the vol. attained when unit vol. at 0° is heated to 6° up to 78-8°. Thesp. gr. at the b.p. is 1-52143, and the molecular volume 78-01. S. Sugden, andE. Rabinowitsch also studied the mol. vol. W. Ramsay and J. Shields obtained30-80 and 27-22 dynes per cm. respectively at 19-8° and 45-9° for the surface tension ;a2=3-83 and 3-50 sq. mm. for the specific cohesion respectively at 19-8° and 45-9° ;

SULPHUR 659

and 538-6 and 486-2 ergs, for the mol. surface energy at 19-8° and 45-9° respectively.H. A. Mayes and J. R. Partington gave —104-5° for the freezing point. C. A. Wurtzgave 78° at 746 mm. for the boiling point; L. Carius, 82°; and T. E. Thorpe,78-8°; S. Sugden and co-workers gave 76'9° to 77-1° at 772 mm. K. Arii gavelog 2?=7-60844—1648-21 I"1 for the vapour pressure. J. Ogier found the specificheat between 17° and 60° to be 0-2425 ; the heat of vaporization, 54-45 cals. pergram; and the heat of formation for liquid thionyl chloride 47-2 Cals. P. Waldenfound that thionyl chloride is an ionizing solvent. R. Nasini found that theindices of refraction for the F-, D-, and C-rays to be respectively 1-544, 1-527,and 1-522. H. Schlundt gave 9-05 for the dielectric constant at 22°.

H. Schiff said that thionyl chloride is decomposed by water, and still more easilyby soln. of alkali hydroxides, forming hydrochloric and sulphurous acids; whileL. Carius said that warm water, or no more than an equal vol. of coldwater, furnishes sulphur and sulphuric acid. For the heterogeneous systemG. Carrara and I. Zoppellari found the reaction between water and thionylchloride at 1° could be represented by (ljst) \og{aj(a—x)}=ah, where s is the surfacearea of the liquids in contact; a, the quantity of decomposable liquid; x, thequantity of this liquid decomposed at the time t; and k is a constant, 0-0152.W. Wardlaw and F. H. Clews assume that the reaction : SOC12+H2O^SO2+2HC1is reversible, since H. S. Tasker and H. O. Jones found that when thionyl chlorideacts on mercaptans at a low temp., 0° to —70°, hydrogen chloride and sulphurdioxide are evolved, and water is found among the residual products. H. B. Northand A. M. Hageman found that sodium dioxide reacts violently with thionylchloride at ordinary temp.: 2Na2O2+2SOCl2=2NaCl+Na2SO4+SO2CI2, andNa2O2+2SOCl2==2NaCl+SO2+SO2Cl2, according to the proportions of reagentsemployed. With barium dioxide and a large excess of thionyl chloride in a sealedtube at 150°, the reaction is symbolized: BaO2+2SOCl2=BaCl2+SO2+SO2Cl2 ;but when mol. proportions are used: 2BaO2+2SOCl2=BaCl2-}-BaSO4+SO2Cl2 ;lead dioxide and manganese dioxide act in a similar manner. Thionyl chloride isan active reducing and chlorinating agent. C. A. Silberrad said that the chlorineusually attaches itself to some portion of the substance acted upon, and the sulphurappears in combination with oxygen or chlorine. A. Besson found that thionylchloride reacts with dry hydrogen bromide, forming thionyl bromide: SOC12+2HBr=2HCl+SOBr2; and with dry hydrogen iodide, cooled by a freezingmixture, forming hvdrogen chloride, sulphur dioxide, iodine, and sulphur: 2SOC12+4HI=4HC1+2I2+SO2 + S.

H. Prinz observed that when thionyl chloride is heated with sulphur at 180°,sulphur monochloride is formed. Here the oxygen of the thionyl chloride is notreplaced by sulphur; rather does the thionyl chloride behave like a mixture ofsulphur dioxide and tetrachloride. O. Ruff said that thionyl chloride is indifferenttowards sulphur even in the presence of alumimum chloride, and this behaviour canbe used to separate it from sulphuryl chloride (q.v.). H. B. North and C. B. Conoverrepresented the reaction above 150° by 2SOC12+3S=SO2+2S2C12. H. B. North andJ. C. Thomson obtained similar results at 150°-180°. H. Prinz found that hydrogensulphide does not react at ordinary temp., but at 60°, the reaction 2SOC1+2H2S=4HC1+SO2+3S occurs. A. Besson said that this reaction occurs slowly evenwhen cooled in a mixture of ice and salt, and at a higher temp., the main reaction is2SOC12+H2S=S2C12+SO2+2HC1. O. Ruff said that the reaction betweenhydrogen sulphide and thionyl chloride is greatly accelerated if aluminium chloridebe present. C. Moureu found that thionyl chloride does not at first mix withsulphuric acid, but after a time, hydrogen chloride and sulphur dioxide are givenoH ; and when the mixture is heated between 138°—157°, chlorosulphonic acid,and pyrosulphuryl chloride are the main products: SOC12+H2SO4=SO3H-HC1+C1HSO3; and 3SOC12+2H2SO4=3SO2+4HC1+S2O5C12. y. Lenher andH. B. North represented the reaction with selenium: Se+2SOCl2=SeCl4-f SO2+S;and with selenium dioxide : SeO2+2SOCl2=SeCl4-f 2SO2 ; the reaction was also

660 INORGANIC AND THEORETICAL CHEMISTRY

studied by B. von Howath. V. Lenher and C. W. Hill found that tellurium tetra-chloride is formed when an excess of thionyl chloride acts on tellurium or ontellurium dioxide, if not in excess, tellurium dichloride is formed.

H. Schiff at first thought that thionyl chloride reacts with ammonia to formthionyl amide, but later, A. Michaelis found that a mixture of nitrogen tetrasulphide,and ammonium chloride, sulphide, and polythionate is formed ; and F. Ephraimand H. Piotrowsky observed that if thionyl chloride be slowly dropped into liquidammonia, an intensely red soln. is formed which furnishes ammonium imidodi-sulphinate, (NH4)N(NH4SO2)2—?•"•—an<i it is a result of the hydrolysis of theimidosulphonamide, HN(SONH2)2, first formed. Some observations on the actionof ammonia on thionyl chloride were made by M. Gurewitsch. According toF. Ephraim and H. Piotrowsky, sulphur is produced by the action of a cone. soln.of hydrazine on thionyl chloride, the sulphur then reacts with the excess of hydrazineN2H4+2S=N2+2H2S. With a dil. soln. of hydrazine, an unstable sulphuroushydrazide appears to be formed, but it has not been isolated. A. Mente found thatan imidosulphonate is formed by the action of thionyl chloride on ammoniumcarbamate. C. Moureu observed that thionyl chloride reacts violently with nitricacid with the development of heat, and the formation of nitroxyl chloride, sulphurdioxide, and hydrogen chloride ; nitrogen oxides and sulphuric acid are also formedin consequence of secondary reactions between the hydrogen chloride, the excess ofnitric acid, and sulphur dioxide. T. E. Thorpe gave for the reaction with silvernitrate : SOCI2+AgNO3=AgCl+CI.SO2.O.N : 0. H. B. North and J. C. Thomsonfound that with an excess of thionyl chloride, phosphorus reacts: 2P+4SOC12=2PC13+2SO2+S2C12 after 2 hrs.' heating at 125°; if the temp, be 180°, somephosphorus pentachloride is formed as indicated below. A. Besson said thatgaseous phosphine, at ordinary temp., reacts with thionyl chloride causing an evolu-tion of hydrogen chloride, the liquid after some time forms two layers, the upperof which, on distillation under reduced press., yields, first, thionyl chloride, thenphosphoryl chloride, and, finally, thiopbosphoryl chloride, PSC13 ; a syrupy liquidfrom which no definite compound can be obtained remains in the retort. The lowerlayer is viscous, and contains chlorine, sulphur, phosphorus, oxygen, and hydrogen.C. Moureu found that ortho- and meta- phosphoric acids are at once attacked bythionyl chloride, but with metaphosphoric acid the reaction is incomplete, andorthophosphoric acid furnishes chlorinated condensation products which are notfurther attacked by thionyl chloride. D. Balareff found that boiling thionylchloride converts orthophosphoric acid into a mixture of the pyro- and meta-acids.L. Carius represented the reaction with phosphorus pentasulphide at 150°:58OCI2-f P2S5=5S2Cl2+P2O5, but H. Prinz showed that the reaction is more pro-bably : 2P2S6+6SOC12=4PSC13+3SO2+9S, at temp, below 150°, and A. Michaelisfound that the reaction, at 160°. with phosphorus trichloride : 3PC13+SOC12=PCl5+POCl3-f-PSCl3, is slow but complete—H. B. North and J. C. Thomson saidincomplete in 16 hrs. at 80°-160° : possibly with an excess of thionyl chloride, thereis a secondary reaction : 3PC1S+4SOC12=3PC13+2SO3+S2C12. H. B. North andA. M. Hageman represented the reaction with arsenic : 2As+4SOCl2=2AsCl3+S2C12+2SO2 ; and with arsenic trioxide, the trichloride is formed. H. B. Northand C. B. Conover represented the reaction with arsenic trisulphide : As2S3+6SOCl2=2AsCl3+3SO2+3S2Cl2, and similar remarks apply to orpiment. K. Heumannand P. Kochlin represented the reaction with powdered antimony in the cold :6Sb-j-6SOCl2=4SbCl3+Sb2S3+3SO2. H. B. North and A. M. Hageman agreedwith this statement provided the antimony is in excess, and the reaction occurs withviolence at ordinary temp. If heated in a sealed tube with a large excess of thionylchloride, the antimony trichloride first formed reacts: 3SbCl3+4SOCl2=3SbCl5-f S2C12+2SO2. With antimony trioxide at ordinary temp., antimony trichloride,and with an excess of thionyl chloride, heated in a sealed tube at 150°-250°,antimony pentachloride is formed. H. Prinz represented the reaction with antimonytrisulphide : 6SOCl2+2Sb2S3=4SbCls+9S+3SO2. This was probably below 150°

SULPHUR 661

and without excess of thionyl chloride, because H. B. North and C. B. Conovershowed that the thionyl chloride reacts with the sulphur above this temp., andbetween 150° and 200°, the reaction in symbolized: 6SOCl2+Sb2S3=2SbCl3+3SO2+3S2CI2. Similar remarks apply to stibnile. The reaction with bismuthat 200° is symbolized: 2Bi+4SOC]2=2BiCl3+S2Cl2+2SO2.; and with bismuthtrioxide : Bi2O3-f 3SOCl2=2BiCl3+3SO2. C. Moureu found that the action ofthionyl chloride on boric acid resembles that with orthophosphoric acid.

H. S. Tasker and H. O. Jones found that the reaction of thionyl chloride withnickel carbonyl results in the vigorous evolution of sulphur dioxide and carbonmonoxide accompanied by a fall of temp.: 2Ni(CO)4+2SOCl2=2NiCl2+SO2+8CO-4-S. In many reactions thionyl chloride behaves as if it were a mixtureof sulphur dichloride, SC12, and sulphuryl chloride, SO2C12. The reactions of thionylchloride with organic compounds have been summarized by C. A. Silberrad. Heclassifies the reactions: (i) The replacement of various radicles or of oxygen or hydrogenby chlorine. Thus, the replacement of hydroxyl, OH, was observed by G. Bargerand A. J. Ewins, A. Stahler and E. Schirm, A. McKenzie and T. M. A. Tudhope,A. McKenzie and F. Barrow, A. McKenzie and G. W. Clough, L. McMaster andP. F. Ahmann, G. Darzens, L. Euzicka and F. Liebl, H. Wieland and P. Kappel-meier, P. F. Frankland and F. II. Garner, A. Green, E. E. Blaise and M. Montagne,etc. The replacement of thiol, SH, was observed by O. Silberrad; the nitro- orN02-group, by H. Meyer ; the sulphonic- or HSO3-group, by H. Meyer, J. Pollakand B. Schadler, and J. Pollak and Z. Rudich; of hydrogen, by A. Michaelis,G. Schroter and E. Linow, J. Pollak and Z. Rudich, and H. Meyer ; and of oxygen,by H. Hunter, P. Horing and F. Baum, and F. Loth and A. Michaelis. (ii) Theintroduction of sulphur alone or in combination with oxygen to form SO-groups. E.g.,the formation of sulphurous esters was observed by L. Carius, A. Michaelis andG. Wagner, A. Rosenheim and W. Sarow, A. E. Arbusoff, H. Hunter, L. Ruzickaand F. Liebl, A. McKenzie and G. W. Clough, M. M. Richter, and A. Green; theformation of thionyl derivatives—sulphoxides—by C. E. Colby and C. S. McLoughlin,H. C. Parker, S. Smiles and A. W. Bain, S. Smiles and R. le'Rossignol, E. Schiller,P. F. Frankland and F. H. Garner, W. S. Denham and H. Woodhouse, A. Michaelis,A. Michaelis and R. Herz, A. Michaelis and W. Jacobi, A. Michaelis and 0. Stor-beck, G. Schroter and E. Linow, A. Michaelis and G. Schroter, A. Michaelisand G. Erdmann, A. Michaelis and J. Ruhl, A. Michaelis and P. Grantz, andA. Francke ; the formation of anhydrosulphites, by K. Moers, M. M. Richter, andE. E. Blaise and M. Montagne; and the replacement of hydrogen by sulphur toform a sulphide, by A. Michaelis, A. Michaelis and E. Godchaux, A. Michaelis andB. Philips, A. Michaelis and P. Schindler, C. T. Sprague, G. Tassinari, andH. Voswinckel. (iii) Dehydration by the removal of the elements of water. E.g.,E. de B. Barnett and I. G. Nixon, A. Michaelis and H. Sieber, H. Meyer, G. Lasch,B. von Pawlewsky, A. Wohl, A. McKenzie and T. M. A. Tudhope, C. Moureu,P. Horing and F. Baum, "W. Herre, G. Schroter and M. Lewinsky, and M. Bergmannand A. Miekeley. (iv) Dehydrogenation by the removal of hydrogen. E.g., B. Holm-berg, H. S. Tasker and H. 0. Jones, J. A. Smythe and A. Forster, and K. A. Hofmamiand K. Ott. (v) Condensations. E.g., S. Smiles and R. le Rossignol, G. Barger andA. J. Ewins, A. Michaelis and G. Erdmann, and P. Freundler. (vi) Catalyticactions. The presence of thionyl chloride was found to favour a number of reactions—F. G. Mann and co-workers, A. Shimomura and J. B. Cohen, R. S. Bly and co-workers, R. Wolffenstein and F. Hartwich, H. Meyer, K. H. Meyer and K. Schuster.G. Egerer-Seham and H. Meyer, S. Jaroschy, C. L. Horton, A. McKenzie andG. W. Clough, G. W. Clough, and P. Karrer and W. Kaase. (vii) Other reactionshave been investigated by J. Klieeisen, H. McCombie and H. A. Scarborough,H. Meyer and K. Schlegel, H. Meyer and R. Turnau, G. Sachs, R. Stiimmer,B. Singh and J. F. Thorpe, E. de B. Barnett and J. W. Cook, H. Leuchs, C. Bot-tinger, etc.

Thionyl chloride reacts with many of the metals—cold or hot—forming chlorides

662 INORGANIC AND THEORETICAL CHEMISTRY

with the evolution of heat. H. B. North and A. M. Hageman said that at temp,up to about 250°, the reaction with bivalent metals is symbolized: 3M+4SOC12=3MC12+2SO2+S2C1<>, if the thionyl chloride is in excess, and if the metal is inexcess, 3M+2SOC12=2MC12+MS+SO2. They found that gold is not attackedat temp, up to 150°, but at 200° it slowly forms auric chloride; magnesium,zinc, and cadmium are not attacked by thionyl chloride at 200°; but B. Fromm andJ. de Seixas-Palma found that the reaction with zinc dust can be represented by2SOCl2+2Zn=2ZnCl2+SO2+S. H. B. North found that mercury with thionylchloride in a sealed tube at 150° reacts either Hg+4SOCl2=HgCl2+2SO2Cl2+S2Cl2,or 3Hg+4SOCl2=3HgCl2+2SO2+S2Cl2 according to the proportions of thereagents. The reaction with tin furnishes stannous chloride: 3Sn+2SOCl2=2SnCl2+SnS+SO2, but in the presence of an excess of thionyl chloride some stannousChloride is converted into stannic chloride: 3SnCl2+4SOCl2=3SnCl4+2SO2+S2Cl2.Neither lead nor chromium is attacked at 200° ; the reaction with iron is symbolized:2Fe+4SOCI2==2FeCl3+2SO2+S2Cl2, and with an excess of metal: 3Fe+2SOCl2=2FeCl2-hFeS-J-SO2; nickel is not attacked at 200°. Several metal oxides areconverted into chlorides or oxychlorides with the evolution of sulphur dioxide.G. Darzens and F. Bourion said that at temp, below 400°, thionyl chloride behavestowards metal oxides like a mixture of chlorine and sulphur monochloride, but itis less advantageous in practice as a chlorinating agent owing to the difficultyof obtaining it free from phosphorus compounds. H. B. North and A. M. Hagemansaid that at 150°-250°, the metal oxides react: MO+SOCl2=MCl2-f-SO2; andwith a metal forming two chlorides, the lower chloride is first formed, and this is thenoxidized to the higher chloride: 3MC12+4SOC12=3MC14+2SO2+S2C12. Theyfound that cupric oxide reacts : CuO-f-SOCl2=CuCl2+SO2 ; and cuprous oxide :Cu2O+3SOCl2=2CuCl2+SCl2+2SO2. Only a trace of chloride is produced whenthionyl chloride reacts with silver oxide under these conditions; calcium, strontium,and barium oxides are not attacked by thionyl chloride at 200°, nor is berylliumoxide attacked; magnesium OSJde reacts : MgO+SOCl2=MgCl2-f SO2 ; and zincand cadmium oxides react in an analogous manner. In a sealed tube at 160°,H. B. North found that mercuric oxide reacts: HgO+3SOCl2=HgCI2+SO2Cl2+S2C12, but if the thionyl chloride be not present in large excess: Hg0+S0Cl2=HgCl2+SO2. H. B. North and A. M. Hageman found that aluminium andchromic oxides are not attacked by thionyl chloride at 200° ; G. Darzens andF. Bourion found that at a higher temp, chromic oxide forms the chloride and withlanthanum, samarium, zirconium, and thorium oxides, the anhydrous chloride isalso produced, but with tungstic and vanadic oxides, oxychlorides are formed ; andwith titanic oxide, a sulphochloride was formed, and with gadolinium oxide, amixture of chloride and oxychloride was formed. H. B. North and A. M. Hagemansaid that tin dioxide is not attacked at 200°. H. B. North and C. B. Conover saidthat the reaction with metal sulphides at 150°-180° can generally be represented byMS+2SOC12=MC12+SO2+S2C12; for example, this reaction applies to copper,silver, zinc, cadmium, and mercuric sulphides ; similar remarks apply to covellite,argentite, sphalerite, and cinnabar and to galena or lead sulphide ; with stannicsulphide the reaction is SnS2-f-4SOCl2=SnCl4+2SO2+2S2Cl2; and with ferroussulphide there is a complication owing to the oxidation from the ferrous to ferricstate: 6FeS+16SOCl2=6FeCl3+8SO2+7S2Cl2. They found that while the mineralsargentite, molyhdenite, and cobaltite were not attacked by thionyl chloride in a sealedtube at 150°-175°, a few hours' heating decomposes galena, pyrites, cinnabar, orpi-ment, stibnite, and. arsenical pyrites, while pyrargyrite, proustite, covellite, sphalerite,and tetrakedrite require one to two days for their decomposition.

According to A. Michaelis,3 thionyl bromide, SOBr2, is produced by the actionof bromine on thionyl aniline : C6Hs.N : SO+3Br2=C6H2Br3NH2.HBr+SOBr2.He said that the brown liquid product is difficult to purify. This was confirmed byH. A. Mayes and J. R. Partington. P. J. Hartog and W. E. Sims prepared it bythe interaction of sodium bromide and thionyl chloride. H. A. Mayes and J. R. Part-

SULPHUR 663

ington said that the action with potassium bromide is slow, and the large bulk ofsolid renders the first distillation in vacuo very awkward. A. Besson found thatwhile dry hydrogen bromide has no action on thionyl chloride in the cold, thereaction at the b.p. results in the partial substitution of the chlorine by bromine.The fractional distillation of the product under reduced press, furnished thionylbromide, and chlorobromide. H. A. Mayes and J. R. Partington prepared thionylbromide by this process. A. Besson later obtained the same products by the actionof aluminium bromide on thionyl chloride. The reaction is vigorous, and when thesoln. is cooled, crystalline complex compounds of aluminium chloride and bromidewith thionyl chloride are deposited. When the product is distilled under reducedpress, it furnishes thionyl bromide. A better yield is obtained by the action of dryhydrogen bromide on thionyl chloride at a temp, not exceeding 100°. When theproduct is distilled under reduced press., it furnishes thionyl bromide, boiling at68° under a press, of 40 mm.; the higher boiling fraction, thionyl chlorobromide; andsulphur bromide are also separated by fractional distillation. A. Besson said thatthionyl bromide is not formed by the action of sulphur dioxide on phosphoruspentabromide. H. A. Mayes and J. R. Partington found that the reaction whichoccurs on adding the calculated quantity of sulphur trioxide to cooled sulphurbromide results in a violent effervescence: S2Br2+SO3=SOBr2+SO2+S. Thedistillation of the product furnishes unchanged sulphur monobromide, and so littlethionyl bromide that the method is useless as a mode of preparing thionyl bromide.Thionyl bromide was said by P. J. Hartog and'W. E. Sims to be a deep crimsonliquid ; A. Michaelis, a brown liquid—but these liquids were probably contaminatedwith sulphur bromides, and bromine, since A. Besson found it to be a pale yellowliquid. P. J. Hartog and W. E. Sims said that the sp. gr. of the hygroscopic liquidis 2-6 at 18°, and A. Besson, 2-61 at 0°. H. A. Mayes and J. R. Partington said thatthe yellowish-orange liquid has a sp. gr. 2-697 at 15°/4°, 2-692 at 17°/4°, and 2-672at 25°/4:0. The surface tension at 17° is 43-71 dynes per cm., and at 25°, 43-08 dynesper cm. The results are in agreement with a small degree of association. A. Bessonadded that the liquid does not solidify at —23°, but does so at —50° ; H. A. Mayesand J. R. Partington gave —52° for the f.p. A. Besson found that thionyl bromideboils at 68° under a press, of 40 mm. H. A. Mayes and J. R. Partington foundfor the b.p. at different press., p mm.,

pB:p.

. 22

. 45°4762-5°

10481-5°

138-590°

219101-5°

315-5111°

471123-5°

680136°

773138

The ratios of the b.p. at different press, indicates a little dissociation. The mol.wt., calculated from the action of thionyl bromide on the f.p. of benzene, agreeswith the assumption that 25 per cent, exist as doubled molecules. The mol. heatof vaporization is 10-4 Cals., and Trouton's coefficient, 25-2 points to someassociation of the liquid. Unlike P. J. Hartog and W. E. Sims, H. A. Mayes andJ. R. Partington were able to keep thionyl bromide in a stoppered bottle withoutdecomposition for a few weeks; but decomposition does occur, and the thionylbromide acquires a red colour owing to the formation of free bromine. Aboutone-third decomposes: 4SOBr2=2SO2+S2Br2+3Br2, when the liquid is dis-tilled at ordinary press. At a temp, a little above its b.p.—at 136°, according toA. Michaelis, and at 150°, according to P. J. Hartog and W. E. Sims—it decom-poses into sulphur monobromide, bromine, and sulphur dioxide. H. Staudingerand W. Kreis observed that when the vapour is suddenly chilled from 100° to—190° bromine, sulphur, and sulphur dioxide appear. A. Besson added thatthionyl bromide is rapidly decomposed by water; and in contact with mercuryit yields sulphur, sulphur dioxide, and mercurous bromide. H. A. Mayes andJ. R. Partington said that thionyl bromide is a very reactive liquid attacking bothcork and rubber very readily. It is soluble in the more inert organic solvents—e.g. benzene, carbon disulphide, carbon tetrachloride, and chloroform. It reactsvigorously with acetone, forming; a vapour which has a very irritating effect on the

664 INOEGANIC AND THEOEETICAL CHEMISTRY

eyes ; with organic acids it forms acid bromides just as thionyl chloride gives acidchlorides. The corresponding thionyl iodide, 8OI2, has not been prepared.

A. Besson reported thionyl chlorobromide, SOClBr, to be formed as justindicated. It is described as a pale yellow liquid which boils and slightly decom-

poses at about 115° under normal press., and doesnot solidify at —23° ; the sp. gr. =2-31 at 0°. Ata temp, a little above its b.p., it decomposes intosulphur dioxide, thionyl chloride, bromine, andsulphur bromide, and the same decomposition takesplace slowly in the cold. The chlorobromide israpidly decomposed by water. In contact withmercury, thionyl chloride and mercurous bromideare formed, sulphur is liberated, and sulphur di-oxide is given off. H. A. Mayes and J. E. Part-ington measured the f.p. of mixtures of thionylchloride and bromide, and the results are illustratedby Fig. 144. The simple mixed-crystal curve shows

20Percent B°S0 sf ' >0° a minimum, but no eutectic. They were alsoFIG. 144.—Freezing-point Curves unable to establish the existence of thionyl chloro-

of Mixtures of Thionyl Chloride bromide as a bromination product of thionyland Bromide. chloride because (i) it is impossible to separate any

constant-boiling liquid, other than thionyl chlorideand thionyl bromide, from the product of bromination of thionyl chloride withhydrogen bromide, (ii) The freezing-point curve shows that no intermediatecompound is present in mixtures of thionyl chloride and bromide, (iii) Physicalproperties show that the product of bromination of thionyl chloride is exactly thesame as mere mixtures of thionyl chloride and bromide.

-50°

- 60'

-70"

-80'

-90

-100'

-110

JW;S"^109°

//

y/

-52°i

_j

~J_

1

0

REFEEENCES.

1 M. Meslans, Bull. Soc. Chim., (3), 15. 391, 1896; H. Moissan and P. Lebeau, Oompt. Bend.,130. 1436, 1900; K. Thiel, Versuch zur Darstellung eines Schwefeltetrafluorids, Berlin, 1905 ;O. Ruff and K. Thiel, Ber., 38. 549, 1905; O. Ruff, H. Graf, W. Heller, and M. Knoch, ib., 39.4310, 1907 ; W. Steinkopf and J. Herold, Journ. prakt. Chem., (2), 101. 79, 1920 ; F. Wunderlioh,Ein Beitrag zur Kenntnis der fluorsulfonsauren Salze und iiber eine neue Darstellungsweise desSulfurylfluorids, Berlin, 1919.

2 C. A. Wurtz, Bull. Soc. Chim., (2), 5. 243, 1866 ; Oompt. Bend., 62. 460, 1866 ; P. Schutzen-berger, ib., 69. 352, 1869; A. Besson, ib., 122. 320, 1896; 123. 884, 1896; A. Besson andL. Fournier, ib., 150. 1752, 1910; E. E. Blaise and M. Montagne, ib., 174. 1173, 1553,1922; P. Freundler, ib., 142. 1153, 1906; R. Marquis, ib., 143. 1163, 1906; G. Darzens,ib., 152. 1314, 1601, 1911; G. Darzens and F. Bourion, ib., 153. 270, 1912; J. Persoz andN. Bloch, ib., 28: 86, 1849 ; J. Ogier, ib., 94. 82, 1882 ; C. Moureu, ib., 119. 337, 1894; Bull.Soc. Chim., (3), 11. 767, 1068, 1894; A. Behal and V. Auger, ib., (2), 50. 594, 1888 ; L. Carius,Journ. prakt. Chem., (2), 2. 262, 1870 ; Liebig's Ann., 70. 297, 1849 ; 106. 291, 1856 ; 110. 209,1859 ; 111. 93, 1859 ; 122. 73, 1862 ; 131. 165, 1864 ; A. Michaelis and O. Schifferdecker, Ber.,6. 993, 1873 ; A. Michaelis and W. Jaoobi, ib., 26. 2158, 1893 ; A. Michaelis and G. Wagner, ib.,7. 1073, 1874 ; A. Michaelis and B. Philips, ib., 23. 559, 1890 ; A. Michaelis and E. Godchaux,ib., 23. 553, 1890 ; A. Michaelis and R. Herz, ib., 23. 3480, 1890 ; A. Michaelis and G. Schroter,ib., 26. 2155, 1893 ; G. Schroter and M. Lewinsky, ib., 26. 2171, 1893 ; A. Michaelis, G. Schroter,and E. Linow, ib., 26. 2162, 1893 ; F. Loth and A. Michaelis, ib., 27. 2540, 1894; A. Michaelisand G. Erdmann, ib., 28.2192,1895 ; A. Michaelis and P. Grantz, ib., 30.1009,1897 ; A. Michaelisand O. Storbeck, ib., 26. 310, 1893 ; Liebig's Ann., 274. 187, 1893 ; A. Michaelia, Jena. Zeit., 6.79, 1871 ; Zeit. Chem., (2), 6. 460, 1870 ; Ber., 5. 875, 1872 ; 24. 745, 1891; Liebig's Ann., 170. 1,1873 ; 274. 200,1893 ; A. Michaelis and J. Ruhl, ib., 270. 114, 1892 ; A. Michaelis and H. Sieber,ib., 274.312, 1893 ; A. Miehaelis and P. Schindler, ib., 310.137,1899 ; H. Wieland and P. Kappel-meier, ib., 381. 306, 1911 ; P. Kremers, ib., 70. 297, 1838 ; K. Kraut, ib., 118. 95,1961; H. Schiff,ib.,102. I l l , 1857; H. Prinz, ib., 223. 355,1884 ; B. Holmberg, ib., 359. 81,1908 ; V. Lenher andC. W. Hill, Journ. Amer. Chem. 8oc, 30. 737,1908 ; V. Lenher and H. B. North, ib., 29. 33, 1907;A. F. O. Getman, ib., 44. 2461, 1925 ; T. E. Thorpe, Journ. Chem. Soc, 37. 141, 1880; 41. 297,1882 ; H. A. Mayes and J. R. Partington, ib., 2594, 1926 ; S. Sugden, ib., 1780, 1786, 1927 ;S. Sugden, J . B. Reed, and H. Wilkins, ib., 127. 1525, 1925; W. Ramsay and J. Shields,ib., 63. 1089, 1893; Zeit. phys. Chem., 12. 433, 1893; A. Mente, Amer. Chem. Journ.,10. 332, 1888; Liebig's Ann., 248. 232, 1888; Ueber einige anorganische Amide, Tubingen,

SULPHUR 665

1888; W. Majert, German Pat., D.R.P. 136870, 1901; Chemiache Fabrik von Heyden,ib., 415312, 1924 ; Chemische Fabrik von Buokan, ib., 284935, 1915; Chemische FabrikGriesheim-Elektron, 139455, 1902 ; Farbenfabriken vorm. F. Bayer, ib., 275378, 1915 ; 338851,1919 ; Brit. Pat. No. 27830, 1913; G. Oddo, Gazz. Chim. Ital., 31. ii, 222, 1901; G. Tas-sinari, ib., 20. 362, 1890; G. Oddo and E. Serra, ib., 29. ii, 318, 1899; G. Carrara andI. Zoppellari, ib., 26. i, 483, 1896 ; G. L. Ciamician, Atti Accad. Lincei, (5), 10. ii, 221, 1902 ;I. Guareschi, Atti Accad. Torino, 51. 4, 59, 263, 1916; K. Heumann and P. Kochlin, Bar., 16.1625, 1883 ; E. Fromm and J. de Seixas Palma, ib., 39. 3317, 1906 ; O. Ruff, ib., 34. 1749, 1901 ;E. Besthorn, ib., 41. 2003, 1908 ; P. Horing and F. Baum, ib., 41. 1914, 1908 ; E. Rabinowitach,ib., 58. B, 2790, 1925; G. A. Barbagliaand A. F. Kekule, ib., 5. 875, 1872; C. E. Colby andC. S. McLoughlin, ib., 20. 195, 1887 ; H. C. Parker, ib., 23. 1844, 1890 ; J. Klieeisen, ib., 27. 2549,1894 ; R. Anschiitz and W. Posth, ib., 27. 2751, 1894 ; W. Herre, ib., 28. 593, 1895 ; A. Francke,ib., 31. 2179, 1898 ; A. Rosenheim and W. Sarow, ib., 38. 1298, 1905 ; A. Wohl, ib., 40. 4698,4712, 1907 ; K. A. Hofmann and K. Ott, ib., 40. 4030, 1907 ; R. Horing and F. Baum, ib., 41.1914, 1908; O. Schmidt, ib., 41. 233, 1908; E. Schiller, ib., 42. 2017, 1909; A. Stahler andE. Schirm, ib., 44. 314, 1911 ; H. Pietrowsky, Ueber die Einwirkung von Ammoniak und Hydrazinauf Verbindungen des Schwefels, Bern, 1911 ; F. Ephraim and H. Piotrowsky, Ber., 44. 379, 386,1911 ; H. Leuchs, ib., 46. 2200, 1913; R. Wolffenstein and F. Hartwich, ib., 48. 2043, 1915 ;M. M. Richter, ib., 49. 1026, 2339, 1916 ; G. Sachs, ib., 53. B, 1737, 1920 ; P. Friedlander andA. Simon, ib., 55. B, 3969, 1922 ; K. H. Meyer and K. Schuster, ib., 55. B, 819, 1922 ;C. Bottinger, ib., 11. 1407, 1878; R. Nasini, ib., 18. 254, 1885; Atti Accad. Lincei, (4), 1. 76,1885; P. Walden, Zeit. anorg. Ohem., 25. 209, 1900; E. B. R. Prideaux, Journ. Soc. Chem.Ind.—Chem. Ind., 42. 672, 1923 ; H. Schlundt, Journ. Phys. Chem., 5. 503, 1901; C. Schorlemmer,Proc. Chem. Soc, 1. 52, 1885; Chem. News, 51. 199, 1885; E. Divers and T. Shimidzu, Journ.Chem. Soc., 49. 589, 1886; E. Divers, ib., 47. 206, 1885; C. T. Sprague, ib., 59. 329, 1891 ;S. Smiles and R. le Rossignol, ib., 89. 697, 1906; 93. 745, 1908 ; M. Gazdar and S. Smiles, ib.,97. 2249, 1910; S. Smiles and A. W. Bain, ib., 91. 1118, 1907; G. Barger and A. J. Ewins,ib., 93. 735, 2086, 1908; W. Wardlaw and F. H. Clews, ib., 117. 1093, 1920; B. Singh andJ. F. Thorpe, ib., 123.118,1923 ; H. S. Tasker and H. O. Jones, ib., 95.1910,1909 ; G. W. Clough,ib., 113. 342, 1918 ; A. Mackenzie and G. W. Clough, ib., 97. 1021, 2566, 1910 ; 101. 390, 1912 ;103. 687, 1913 ; A. Mackenzie and F. Barrow, ib., 99. 1910, 1911 ; J. A. Smyth and A. Forster,ib., 97. 1197, 1910; M. O. Forster and S. H. Newman, ib., 97. 2575, 1910; H. McCombie andH. A. Scarborough, ib., 103. 57, 1913 ; W. S. Denham and H. Woodhouse, ib., 103. 1861, 1913 ;P. F. Frankland and F. H. Garner, ib., 105. 1101, 1914; F. G. Mann, W. J. Pope, andR. H. Vernon, ib., 119. 644,1921 ; A. Shimomura and J. B. Cohen, ib., 119.1821,1921 ; A. Green,ib., 125. 1450, 1924; 129. 1428, 2198, 1926; H. Hunter, ib., 125. 1392, 1924; T. Yabuta, ib.,125. 575, 1924; O. Silberrad, ib., 119. 2029, 1921; C. A. Silberrad, Journ. Soc. Chem. Ind.—Chem. Ind., 45. 36, 55, 1926 ; H. Voswinckel, Pharm. Ztg., 40. 241, 1895 ; H. Meyer, Rev. Trav.Chim. Pays-Bas, 44. 323, 1925; Liebig's Ann., 433. 327, 1923; Monatsh., 22. 109, 415, 777,1901; 23. 897,1902 ; 25.443,1904 ; 28.1211, 1907 ; 34. 69,1913 ; 36. 719, 723,1915 ; H. Meyerand R. Turnau, ib., 28. 153, 1907 ; Ber., 42. 1163, 1909 ; H. Meyer and K. Schlegel, Monatsh.,34. 561, 1913 ; H. Meyer and H. Tropsch, ib., 35. 781, 1914; R. Stummer, ib., 28. 411, 1907 ;P. Lux, ib., 29. 763, 1908 ; G. Egerer-Seham and H. Meyer, ib., 34. 69, 1913 ; G. Lasch, ib., 34.1653, 1913 ; J. Pollak and B. Sohadler, ib., 39. 129, 1918 ; J. Pollak and Z. Rudich, ib., 43. 209,1922; S. Jaroschy, ib., 34. 1, 1913; D. Alexeeff, Journ. Chim. Phys., 23. 415, 1926; B. vonPawlewsky, Bull. Acad. Cracow, 8, 1903 ; A. E. Arbusoff, Journ. Buss. Phys. Chem. Soc, 41. 447,1909 ; K. Moers, Zur Kenntnis des Glycerinaldehyds, Berlin, 1907 ; H. B. North, Journ. Amer.Chem. Soc, 32. 184, 1910 ; H. B. North and A. M. Hageman, ib., 34. 890, 1912 ; 35. 352, 543,1913 ; H. B. North and J. C. Thomson, ib., 40. 774, 1918 ; H. B. North and C. B. Conover, ib.,37. 2486, 1915 ; Amer. Journ. Science, (4), 40. 640, 1915 ; S. G. Powell, Journ. Amer. Chem. Soc45. 2708, 1923 ; R. S. Bly, G. A. Perkins, andW. L. Lewis, ib., 44. 2896, 1922 ; L. McMaster andF. F. Ahmann, ib., 50. 145, 1928; C. L. Horton, Chem. News, 108. 37, 1913; E. de B. Barnettand I. G. Nixon, ib., 129. 121, 1924; E. de B. Barnett and J. W. Cook, ib., 129. 121, 1924 ;P. Karrer and W. Kaase, Helvetica Chim. Ada, 2. 436, 1919 ; L. Ruzicka and F. Liebl, ib., 6.267, 1923 ; M. Bergmann and A. Miekeley, Zeit. physiol. Chem., 140. 128, 1924 ; A. McKenzieand T. M. A. Tudhope, Journ. Biol. Chem., 62. 551,1924 ; B. von Horvath, Zeit. anorg. Chem., 70.408, 1911 ; M. Gurewitsch, Ueber einige Amidoderivate der Schwefelsaure, Bern, 1910;H. Stavdinger and W. Kreis, Helvetica Chim. Ada, 8. 71, 1924; D. Balareff, Zeit. anorg. Chem.,67. 234, 1910; 102. 34, 1917; K. Arri, Bull. Inst. Phys. Chem. Research Tokyo, 8. 719, 1929.

3 A. Michaelis, Ber., 24. 745, 1891; P. J. Hartog and W. E. Sima, Chem. News, 67. 82, 1893 ;Proc. Chem. Soc, 19. 10, 1893 ; A. Besson, Compt. Rend., 122. 320, 1896 ; 123. 884, 1896 ; Bull.Soc. Chim., (3), 15. 909, 1896 ; H. Staudinger and W. Kreis, Helvetica Chim. Ada, 8. 71, 1924 ;H. A. Mayes and J. R. Partington, Journ. Chem. Soc, 129. 2594, 1926.

§ 51. Sulphuryl Halides

H. Moissan and P. Lebeau 1 prepared sulphuryl fluoride, SO2F2, ty passingfluorine into an apparatus containing sulphur dioxide so disposed that the former