656

INORGANIC AND THEORETICAL CHEMISTRY

P. Lebeau found that the specific gravity of the liquid is 2-93 ; M. Meslans gave
3-0076, and he found that the gas liquefies at 30. H. Moissan and P. Lebeau
gave 32 for the boiling point, and 0. Ruff and K. Thiel, 30 for the b.p. at
760 mm., and 110 for the melting point. When the gas is heated in a dry glass
vessel to 400, H. Moissan and P. Lebeau found that it decomposes 2S0F 2 +Si0 2
=SiF 4 +2SO 2 ; the action of the electric discharge from an induction coil on the
gas in a glass vessel is similar to that of heat. O. Ruff and K. Thiel said that the
gas is not changed when passed through a white-hot platinum tube filled with spongy
platinum. H. Moissan and P. Lebeau found that if sparked along with hydrogen
in a glass vessel, the sulphur dioxide is reduced to hydrogen sulphide, sulphur,
and water, and the latter reacts with the silicon tetrafluoride, forming hydrofluosilicic acid. The presence of oxygen does not affect the decomposition of the thionyl
fluoride by the action of heat, but when the mixture of the two gases is sparked,
a certain amount of a more volatile oxyfluoride is producedvide infra, sulphury!
fluoride. The gas is decomposed by water : SOF 2 +H 2 O=SO 2 +2HF. O. Ruff
and K. Thiel observed that a mixture of thionyl fluoride and chlorine, in a sealed
glass tube, in sunlight, or in the presence of carbon, reacts with the silica of the
glass to form silicon tetrafluoride and sulphuryl chloride. Under ordinary conditions chlorine, and bromine are inactive. H. Moissan and P. Lebeau found that
when the gas is treated with hydrogen chloride over mercury, a gaseous mixture
is produced which attacks the mercury. The gas is not attacked by sulphur at
500, but, at high temp., hydrogen sulphide forms sulphur, water, and hydrogen
fluoride; at ordinary temp., there is no reaction. M. Meslans found that the
gas reacts with ammonia, forming ammonium fluoride and thionyl amide.
F. Wunderlich represented the reaction: S0 2 F 2 +4NH3=2NH 4 F+S0 2 (NH 2 ) 2 .
With methylamine in place of ammonia, he obtained dimethylsulphamide,
SO2F2+4CH3NH2=SO2(NHCH3)2+2CH3NH3F. Similarly, ethylamine furnishes
diethylsulphamide. H. Moissan and P. Lebeau showed that the first product of
the reaction with ammonia is an orange-coloured thionyl hemipentamminofluoride,
2SOF2.5NH3, and finally a white substance corresponding with thionyl hemiheptamminofluoride, 2SOF2.7H2O, and when the latter is treated with hydrogen chloride
it forms sulphur, and sulphur dioxide. O. Ruff and K. Thiel said that thionyl
fluoride reacts with nitrogen trioxide and moisture, forming nitrosulphonic acid;
and silicon tetrafluoride; but the gas does not react with nitric oxide. H. Moissan
and P. Lebeau observed no reaction with phosphorus at 500. According
to 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.; methyl
alcohol, 31 vols.; carbon tetrachloride, 3 4 vols.; chloroform, 4 0 vols.; and
acetone, 4-9 vols.; while ether and carbon disulphide absorb only a little of the
gas. H. Moissan and P. Lebeau also found that the gas is soluble in arsenic
trichloride, and also in benzene, turpentine, and ether; and it is absorbed by molten
sodium or tin. F. Wunderlich found that a soln. of potassium sulphide in absolute
alcohol forms a little thiosulphate when treated with sulphuryl fluoride; and the
reaction in an aq. soln. of calcium hydrosulphide is symbolized: SO2F2-f 2Ca(SH)2
+H 2 O=CaS 2 O 3 +CaF 2 +3H 2 S.
J. Persoz and N. Bloch 2 first prepared thionyl chloride, SOC12, in an impure
form, by the action of sulphur dioxide on phosphorus pentachloride; P. Kremers
obtained it in a similar way, and named it schwefligsaures Phosphorsuperchlorid
because it was supposed to have the composition PC15.SO2 until H. Schiff prepared
it 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 chemical
characteristics of the compound. C. Schorlemmer has made some remarks on the
history of thionyl chloride. L. Carius prepared thionyl chloride by heating calcium
sulphite with phosphoryl chloride to 150. He first employed the proportions
indicated in the equation: 3CaSO3+2POCl3=Ca3(PO4)2+3SOCl2, and heated
the 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

+3CaCl 2 +6SO 2 , but some thionyl chloride is also formed. L. Carius found, that
by raising the proportion of oxychloride until equal molecular proportions of the
two substances were present, the proportion of thionyl chloride greatly increased,
and that of sulphur dioxide became very small. Calcium sulphite can thus
be made to yield most of its sulphur as thionyl chloride, but only by using excess of
phosphorus oxychloride, since without this excess sulphur dioxide is the main
product. Now, this sulphur dioxide must be derived from thionyl chloride should
phosphorus oxychloride really act on calcium sulphite, and then form thionyl
chloride by this action. E. Divers and T. Shimidzu said that phosphorus pentachloride is itself without action on calcium sulphite, but at 150, the pentachloride
is dissociated into phosphorus pentoxide and pentachloride: 10POCl3=2P2O5
+6PCI5, the pentoxide takes calcium oxide from the sulphite, thus setting free
sulphur dioxide : 6CaSO3-r2P2O5=2Ca3(PO4)24-6SO2, and. this with phosphorus
pentachloride gives thionyl chloride and phosphorus oxychloride again:
6SO2+6PCl5=6SOCl2-t-6POCl3vide infra. Three-fifths of the phosphorus
oxychloride begun with are thus regained. In practice, L. Carius found an extra
half of the oxychloride to be excess enough to use. The large quantity of sulphur
dioxide which forms when these proportions are greatly altered in favour of the
calcium sulphite, is to be traced to the action of the- phosphorus pentachloride upon
the excess of calcium sulphite instead of upon the sulphur dioxide, as is shown by
the following equation: 15CaSO3+6PCl5=3Ca3(PO4)2+6CaCl2+9SOCl2+6SO2.
With the other 6SO2 liberated, but now not decomposed, there are thus obtained
12SO2 to 9SOC12. The calcium chloride here shown is a necessary complement to
the sulphur dioxide, whatever version of the change be adopted. L. Carius also
prepared thionyl chloride by the action of phosphorus pentachloride on sodium
sulphite; and on certain organic sulphonates on the alkali metals; A. Michaelis made
it 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 phosphorus
pentachlorideSO2+PCl5=POCl3+SOCl2and separating the thionyl chloride
b.p. 82from the phosphoryl chlorideb.p. 110by fractional distillation.
A. Michaelis said that chlorine and sulphur dioxide colour the product yellow, and
they 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 by
T. E. Thorpe, and was formerly the process generally employed. The Chemische
Fabrik von Heyden recommended making thionyl chloride by the interaction of
phosphorus trichloride and sulphuryl chloride: SO2C12+PC13=POC13+SOC12;
while the Chemische Fabrik von Buckan found that carbonyl chloride reacts with
sulphur dioxide at temp, above 200 with the formation of thionyl chloride and
sulphur tetrachloride according to the equations: SO2+COC12=SOC12+CO2
and SO2+2COCl2=SCl4+2CO2. The first reaction predominates at lower temp,
and with excess of sulphur dioxide, and by suitable adjustment of conditions one
or other of the reactions may be almost entirely excluded. The reactions are
carried out by passing the gases over a heated contact substance, such as wood
charcoal, and the carbonyl chloride may be partly or entirely replaced by a mixture
of carbon monoxide and chloride, or carbon monoxide and sulphuryl chloride may be
employed. This mode of preparation gives good results. The Farbenfabrik
vorm. F. Bayer obtained thionyl chloride by heating a mixture of chlorosulphonic
acid and sulphur monochloride or dichloride.
C. A. Wurtz observed that thionyl chloride is formed by the action of chlorine
monoxide on sulphur, but the reaction proceeds with explosive violence; it was therefore found better to dissolve the sulphur in sulphur monochloride, and allow gaseous
chlorine monoxide to act on the soln. at 12, until nearly all the dissolved sulphur
is consumed. The thionyl chloride and sulphur monochloride were separated by
fractional 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+S0 3 =S0Cl 2 +S0 2 +Cl 2 ; and A. Behal and V. Auger, and W. Majert, by the
action of sulphur trioxide on sulphur dichloride at a temp, below the b.p. of sulphur
dioxide, or under press. : SO3+SC12=SOC12+SO2. The Chemische Fabrik
Griesheim-Elektron obtained thionyl chloride by adding sulphur trioxide to ordinary
sulphur chloride at a temp, of 75-80, according to SO 3 +S 2 C1 2 =SOC1 2 +SO 2 +S.
Chlorine is passed in continuously in order to reconvert the sulphur produced into
sulphur chloride. In this way, an almost theoretical yield is obtained, and the
practical inconveniences attending the use of higher chlorides of sulphur are avoided.
The Farbenfabriken vorm. F. Bayer found that the reaction proceeds smoothly
at ordinary temp, and press., in the presence of antimony trichloride, mercuric
chloride, or chlorides of the heavy metals; and that sulphur or sulphur monochloride
with chlorine and chlorosulphonic acid, or sulphur dichloride and chlorosulphonic
acid can be used with or without the addition of the catalyst.
According to C. A. Silberrad, thionyl chloride may contain traces of phosphoryl
chloride, stannic chloride, or sulphur di- or tri-oxide. The first of these contaminations was found by J. Ogier to be difficult if not impossible to remove. P. Lux
detected stannic chloride by producing a yellow coloration with triphenylmethyl
chloride, or a red coloration with ;p-triiododiphenylmethyl chlorideneither
reagent gives the coloration with thionyl chloride alone. The stannic chloride
can be removed by fractional distillation. H. Meyer and R. Turnau, and H. Meyer
and K. Schlegel found that sulphur dioxide may be removed by distillation over
dimethylaniline or quinoline, and colourless thionyl chloride may be obtained by
distillation over linseed oil and purified beeswax. Thionyl chloride can be destroyed
in mixtures where it is not desired by adding sufficient formic acid to react:
H.COOH+SOC12=2HC1+SO2+COa reaction discussed by C. Moureu, and
H. Meyer and R. Turnau.
Thionyl chloride is a colourless, refractive liquid with a penetrating smell
recalling that of sulphur dioxide. K. Heumann and P. Kochlin found the vapour
density at 154 is 3-95, corresponding with the. mol. SOC12 for which the theoretical
density 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 through
a red-hot tube, the dissociation products are sulphur dioxide and monochloride,
and chlorine. H. Standinger and W. Kreis also observed that when the vapour
is chilled from 1000 to 190, sulphur monochloride is formed. According to
G. Oddo and E. Serra, the molecular weight calculated from the effect of the salt
on freezing benzene is 108-110 ; and with boiling chloroform, 229-235, when the
theoretical value for SOC12 is 119. When corrected with the results of G. Oddo
to allow for volatilization in boiling soln. a normal value is obtained for the
mol. wt. E. B. R. Prideaux represented the electronic structure :

A. F. O. Getman discussed thionyl chloride as a solvent. C. A. Wurtz gave 1-675

for 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; and
S. Sugden and co-workers gave 1-656 at 14-5/4, 1-622 at 32/4, and 1-593 at
48/4, or at 0/4, sp. gr. = 1 - 6 8 3 + 0001886/. T. E. Thorpe represented the
thermal expansion =1+O-OO1164190+O-O69141802+O-O8953603, where v represents the vol. attained when unit vol. at 0 is heated to 6 up to 78-8. The
sp. gr. at the b.p. is 1-52143, and the molecular volume 78-01. S. Sugden, and
E. Rabinowitsch also studied the mol. vol. W. Ramsay and J. Shields obtained
30-80 and 27-22 dynes per cm. respectively at 19-8 and 45-9 for the surface tension ;
a 2 =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. Wurtz
gave 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 gave
log 2?=7-608441648-21 I"1 for the vapour pressure. J. Ogier found the specific
heat between 17 and 60 to be 0-2425 ; the heat of vaporization, 54-45 cals. per
gram; and the heat of formation for liquid thionyl chloride 47-2 Cals. P. Walden
found that thionyl chloride is an ionizing solvent. R. Nasini found that the
indices 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 easily
by soln. of alkali hydroxides, forming hydrochloric and sulphurous acids; while
L. Carius said that warm water, or no more than an equal vol. of cold
water, furnishes sulphur and sulphuric acid. For the heterogeneous system
G. Carrara and I. Zoppellari found the reaction between water and thionyl
chloride at 1 could be represented by (ljst) \og{aj(ax)}=ah, where s is the surface
area of the liquids in contact; a, the quantity of decomposable liquid; x, the
quantity 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+2HC1
is reversible, since H. S. Tasker and H. O. Jones found that when thionyl chloride
acts on mercaptans at a low temp., 0 to 70, hydrogen chloride and sulphur
dioxide are evolved, and water is found among the residual products. H. B. North
and A. M. Hageman found that sodium dioxide reacts violently with thionyl
chloride at ordinary temp.: 2Na2O2+2SOCl2=2NaCl+Na2SO4+SO2CI2, and
Na2O2+2SOCl2==2NaCl+SO2+SO2Cl2, according to the proportions of reagents
employed. With barium dioxide and a large excess of thionyl chloride in a sealed
tube at 150, the reaction is symbolized: BaO 2 +2SOCl 2 =BaCl 2 +SO 2 +SO 2 Cl 2 ;
but when mol. proportions are used: 2BaO2+2SOCl2=BaCl2-}-BaSO4+SO2Cl2 ;
lead dioxide and manganese dioxide act in a similar manner. Thionyl chloride is
an active reducing and chlorinating agent. C. A. Silberrad said that the chlorine
usually attaches itself to some portion of the substance acted upon, and the sulphur
appears in combination with oxygen or chlorine. A. Besson found that thionyl
chloride reacts with dry hydrogen bromide, forming thionyl bromide: SOC12
+2HBr=2HCl+SOBr 2 ; and with dry hydrogen iodide, cooled by a freezing
mixture, forming hvdrogen chloride, sulphur dioxide, iodine, and sulphur: 2SOC12
+4HI=4HC1+2I 2 +SO 2 + 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 not
replaced by sulphur; rather does the thionyl chloride behave like a mixture of
sulphur dioxide and tetrachloride. O. Ruff said that thionyl chloride is indifferent
towards sulphur even in the presence of alumimum chloride, and this behaviour can
be used to separate it from sulphuryl chloride (q.v.). H. B. North and C. B. Conover
represented the reaction above 150 by 2SOC12+3S=SO2+2S2C12. H. B. North and
J. C. Thomson obtained similar results at 150-180. H. Prinz found that hydrogen
sulphide does not react at ordinary temp., but at 60, the reaction 2SOC1+2H2S
=4HC1+SO 2 +3S occurs. A. Besson said that this reaction occurs slowly even
when cooled in a mixture of ice and salt, and at a higher temp., the main reaction is
2SOC12+H2S=S2C12+SO2+2HC1. O. Ruff said that the reaction between
hydrogen sulphide and thionyl chloride is greatly accelerated if aluminium chloride
be present. C. Moureu found that thionyl chloride does not at first mix with
sulphuric acid, but after a time, hydrogen chloride and sulphur dioxide are given
oH ; and when the mixture is heated between 138157, chlorosulphonic acid,
and pyrosulphuryl chloride are the main products: SOC12+H2SO4=SO3H-HC1
+C1HSO3; and 3SOC12+2H2SO4=3SO2+4HC1+S2O5C12. y. Lenher and
H. B. North represented the reaction with selenium: Se+2SOCl2=SeCl4-f SO 2 +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 tetrachloride is formed when an excess of thionyl chloride acts on tellurium or on
tellurium dioxide, if not in excess, tellurium dichloride is formed.
H. Schiff at first thought that thionyl chloride reacts with ammonia to form
thionyl amide, but later, A. Michaelis found that a mixture of nitrogen tetrasulphide,
and ammonium chloride, sulphide, and polythionate is formed ; and F. Ephraim
and H. Piotrowsky observed that if thionyl chloride be slowly dropped into liquid
ammonia, an intensely red soln. is formed which furnishes ammonium imidodisulphinate, (NH4)N(NH4SO2)2?"an<i it is a result of the hydrolysis of the
imidosulphonamide, HN(SONH2)2, first formed. Some observations on the action
of ammonia on thionyl chloride were made by M. Gurewitsch. According to
F. 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 hydrazine
N 2 H 4 +2S=N 2 +2H 2 S. With a dil. soln. of hydrazine, an unstable sulphurous
hydrazide appears to be formed, but it has not been isolated. A. Mente found that
an imidosulphonate is formed by the action of thionyl chloride on ammonium
carbamate. C. Moureu observed that thionyl chloride reacts violently with nitric
acid with the development of heat, and the formation of nitroxyl chloride, sulphur
dioxide, and hydrogen chloride ; nitrogen oxides and sulphuric acid are also formed
in consequence of secondary reactions between the hydrogen chloride, the excess of
nitric acid, and sulphur dioxide. T. E. Thorpe gave for the reaction with silver
nitrate : SOCI2+AgNO3=AgCl+CI.SO2.O.N : 0. H. B. North and J. C. Thomson
found 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, some
phosphorus pentachloride is formed as indicated below. A. Besson said that
gaseous phosphine, at ordinary temp., reacts with thionyl chloride causing an evolution of hydrogen chloride, the liquid after some time forms two layers, the upper
of which, on distillation under reduced press., yields, first, thionyl chloride, then
phosphoryl chloride, and, finally, thiopbosphoryl chloride, PSC13 ; a syrupy liquid
from which no definite compound can be obtained remains in the retort. The lower
layer is viscous, and contains chlorine, sulphur, phosphorus, oxygen, and hydrogen.
C. Moureu found that ortho- and meta- phosphoric acids are at once attacked by
thionyl chloride, but with metaphosphoric acid the reaction is incomplete, and
orthophosphoric acid furnishes chlorinated condensation products which are not
further attacked by thionyl chloride. D. Balareff found that boiling thionyl
chloride converts orthophosphoric acid into a mixture of the pyro- and meta-acids.
L. Carius represented the reaction with phosphorus pentasulphide at 150:
58OCI2-f P 2 S5=5S 2 Cl2+P 2 O 5 , but H. Prinz showed that the reaction is more probably : 2P2S6+6SOC12=4PSC13+3SO2+9S, at temp, below 150, and A. Michaelis
found that the reaction, at 160. with phosphorus trichloride : 3PC13+SOC12
=PCl5+POCl3-f-PSCl3, is slow but completeH. B. North and J. C. Thomson said
incomplete in 16 hrs. at 80-160 : possibly with an excess of thionyl chloride, there
is a secondary reaction : 3PC1S+4SOC12=3PC13+2SO3+S2C12. H. B. North and
A. M. Hageman represented the reaction with arsenic : 2As+4SOCl2=2AsCl3
+S2C12+2SO2 ; and with arsenic trioxide, the trichloride is formed. H. B. North
and C. B. Conover represented the reaction with arsenic trisulphide : As2S3+6SOCl2
=2AsCl3+3SO2+3S2Cl2, and similar remarks apply to orpiment. K. Heumann
and P. Kochlin represented the reaction with powdered antimony in the cold :
6Sb-j-6SOCl2=4SbCl3+Sb2S3+3SO2. H. B. North and A. M. Hageman agreed
with this statement provided the antimony is in excess, and the reaction occurs with
violence at ordinary temp. If heated in a sealed tube with a large excess of thionyl
chloride, 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 antimony
trisulphide : 6SOCl 2 +2Sb 2 S 3 =4SbCl s +9S+3SO 2 . This was probably below 150

SULPHUR

661

and without excess of thionyl chloride, because H. B. North and C. B. Conover

showed that the thionyl chloride reacts with the sulphur above this temp., and
between 150 and 200, the reaction in symbolized: 6SOCl2+Sb2S3=2SbCl3
+3SO2+3S2CI2. Similar remarks apply to stibnile. The reaction with bismuth
at 200 is symbolized: 2Bi+4SOC]2=2BiCl3+S2Cl2+2SO2.; and with bismuth
trioxide : Bi2O3-f 3SOCl2=2BiCl3+3SO2. C. Moureu found that the action of
thionyl chloride on boric acid resembles that with orthophosphoric acid.
H. S. Tasker and H. O. Jones found that the reaction of thionyl chloride with
nickel carbonyl results in the vigorous evolution of sulphur dioxide and carbon
monoxide 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 mixture
of sulphur dichloride, SC12, and sulphuryl chloride, SO2C12. The reactions of thionyl
chloride with organic compounds have been summarized by C. A. Silberrad. He
classifies the reactions: (i) The replacement of various radicles or of oxygen or hydrogen
by chlorine. Thus, the replacement of hydroxyl, OH, was observed by G. Barger
and 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 and
P. F. Ahmann, G. Darzens, L. Euzicka and F. Liebl, H. Wieland and P. Kappelmeier, 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- or
N02-group, by H. Meyer ; the sulphonic- or HSO3-group, by H. Meyer, J. Pollak
and 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) The
introduction 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 and
G. Wagner, A. Rosenheim and W. Sarow, A. E. Arbusoff, H. Hunter, L. Ruzicka
and F. Liebl, A. McKenzie and G. W. Clough, M. M. Richter, and A. Green; the
formation of thionyl derivativessulphoxidesby 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. Storbeck, G. Schroter and E. Linow, A. Michaelis and G. Schroter, A. Michaelis
and G. Erdmann, A. Michaelis and J. Ruhl, A. Michaelis and P. Grantz, and
A. Francke ; the formation of anhydrosulphites, by K. Moers, M. M. Richter, and
E. E. Blaise and M. Montagne; and the replacement of hydrogen by sulphur to
form a sulphide, by A. Michaelis, A. Michaelis and E. Godchaux, A. Michaelis and
B. Philips, A. Michaelis and P. Schindler, C. T. Sprague, G. Tassinari, and
H. 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. Bergmann
and A. Miekeley. (iv) Dehydrogenation by the removal of hydrogen. E.g., B. Holmberg, H. S. Tasker and H. 0. Jones, J. A. Smythe and A. Forster, and K. A. Hofmami
and K. Ott. (v) Condensations. E.g., S. Smiles and R. le Rossignol, G. Barger and
A. J. Ewins, A. Michaelis and G. Erdmann, and P. Freundler. (vi) Catalytic
actions. 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 coworkers, 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 and
G. W. Clough, G. W. Clough, and P. Karrer and W. Kaase. (vii) Other reactions
have 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. Bottinger, etc.
Thionyl chloride reacts with many of the metalscold or hotforming 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 in
excess, 3M+2SOC12=2MC12+MS+SO2. They found that gold is not attacked
at 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 and
J. de Seixas-Palma found that the reaction with zinc dust can be represented by
2SOCl 2 +2Zn=2ZnCl 2 +SO 2 +S. H. B. North found that mercury with thionyl
chloride in a sealed tube at 150 reacts either Hg+4SOCl 2 =HgCl 2 +2SO 2 Cl 2 +S 2 Cl 2 ,
or 3Hg+4SOCl2=3HgCl2+2SO2+S2Cl2 according to the proportions of the
reagents. The reaction with tin furnishes stannous chloride: 3Sn+2SOCl2=2SnCl2
+SnS+SO 2 , but in the presence of an excess of thionyl chloride some stannous
Chloride 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 are
converted into chlorides or oxychlorides with the evolution of sulphur dioxide.
G. Darzens and F. Bourion said that at temp, below 400, thionyl chloride behaves
towards metal oxides like a mixture of chlorine and sulphur monochloride, but it
is less advantageous in practice as a chlorinating agent owing to the difficulty
of obtaining it free from phosphorus compounds. H. B. North and A. M. Hageman
said that at 150-250, the metal oxides react: MO+SOCl2=MCl2-f-SO2; and
with a metal forming two chlorides, the lower chloride is first formed, and this is then
oxidized to the higher chloride: 3MC12+4SOC12=3MC14+2SO2+S2C12. They
found that cupric oxide reacts : CuO-f-SOCl2=CuCl2+SO2 ; and cuprous oxide :
Cu2O+3SOCl2=2CuCl2+SCl2+2SO2. Only a trace of chloride is produced when
thionyl chloride reacts with silver oxide under these conditions; calcium, strontium,
and barium oxides are not attacked by thionyl chloride at 200, nor is beryllium
oxide attacked; magnesium OSJde reacts : MgO+SOCl2=MgCl2-f SO2 ; and zinc
and 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+S0Cl 2
=HgCl 2 +SO 2 . H. B. North and A. M. Hageman found that aluminium and
chromic oxides are not attacked by thionyl chloride at 200 ; G. Darzens and
F. Bourion found that at a higher temp, chromic oxide forms the chloride and with
lanthanum, samarium, zirconium, and thorium oxides, the anhydrous chloride is
also produced, but with tungstic and vanadic oxides, oxychlorides are formed ; and
with titanic oxide, a sulphochloride was formed, and with gadolinium oxide, a
mixture of chloride and oxychloride was formed. H. B. North and A. M. Hageman
said that tin dioxide is not attacked at 200. H. B. North and C. B. Conover said
that the reaction with metal sulphides at 150-180 can generally be represented by
MS+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 stannic
sulphide the reaction is SnS2-f-4SOCl2=SnCl4+2SO2+2S2Cl2; and with ferrous
sulphide there is a complication owing to the oxidation from the ferrous to ferric
state: 6FeS+16SOCl2=6FeCl3+8SO2+7S2Cl2. They found that while the minerals
argentite, molyhdenite, and cobaltite were not attacked by thionyl chloride in a sealed
tube at 150-175, a few hours' heating decomposes galena, pyrites, cinnabar, orpiment, 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 action
of bromine on thionyl aniline : C6Hs.N : SO+3Br 2 =C 6 H 2 Br3NH 2 .HBr+SOBr 2 .
He said that the brown liquid product is difficult to purify. This was confirmed by
H. A. Mayes and J. R. Partington. P. J. Hartog and W. E. Sims prepared it by
the 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 of
solid renders the first distillation in vacuo very awkward. A. Besson found that
while dry hydrogen bromide has no action on thionyl chloride in the cold, the
reaction at the b.p. results in the partial substitution of the chlorine by bromine.
The fractional distillation of the product under reduced press, furnished thionyl
bromide, and chlorobromide. H. A. Mayes and J. R. Partington prepared thionyl
bromide by this process. A. Besson later obtained the same products by the action
of aluminium bromide on thionyl chloride. The reaction is vigorous, and when the
soln. is cooled, crystalline complex compounds of aluminium chloride and bromide
with thionyl chloride are deposited. When the product is distilled under reduced
press, it furnishes thionyl bromide. A better yield is obtained by the action of dry
hydrogen bromide on thionyl chloride at a temp, not exceeding 100. When the
product is distilled under reduced press., it furnishes thionyl bromide, boiling at
68 under a press, of 40 mm.; the higher boiling fraction, thionyl chlorobromide; and
sulphur bromide are also separated by fractional distillation. A. Besson said that
thionyl bromide is not formed by the action of sulphur dioxide on phosphorus
pentabromide. H. A. Mayes and J. R. Partington found that the reaction which
occurs on adding the calculated quantity of sulphur trioxide to cooled sulphur
bromide results in a violent effervescence: S2Br 2 +SO3=SOBr 2 +SO2+S. The
distillation of the product furnishes unchanged sulphur monobromide, and so little
thionyl 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 crimson
liquid ; A. Michaelis, a brown liquidbut these liquids were probably contaminated
with sulphur bromides, and bromine, since A. Besson found it to be a pale yellow
liquid. P. J. Hartog and W. E. Sims said that the sp. gr. of the hygroscopic liquid
is 2-6 at 18, and A. Besson, 2-61 at 0. H. A. Mayes and J. R. Partington said that
the yellowish-orange liquid has a sp. gr. 2-697 at 15/4, 2-692 at 17/4, and 2-672
at 25/4:0. The surface tension at 17 is 43-71 dynes per cm., and at 25, 43-08 dynes
per cm. The results are in agreement with a small degree of association. A. Besson
added that the liquid does not solidify at 23, but does so at 50 ; H. A. Mayes
and J. R. Partington gave 52 for the f.p. A. Besson found that thionyl bromide
boils at 68 under a press, of 40 mm. H. A. Mayes and J. R. Partington found
for the b.p. at different press., p mm.,
p
B:p.

. 22
. 45

47
62-5

104
81-5

138-5
90

219
101-5

315-5
111

471
123-5

680
136

773
138

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, agrees
with the assumption that 25 per cent, exist as doubled molecules. The mol. heat
of vaporization is 10-4 Cals., and Trouton's coefficient, 25-2 points to some
association of the liquid. Unlike P. J. Hartog and W. E. Sims, H. A. Mayes and
J. R. Partington were able to keep thionyl bromide in a stoppered bottle without
decomposition for a few weeks; but decomposition does occur, and the thionyl
bromide acquires a red colour owing to the formation of free bromine. About
one-third decomposes: 4SOBr2=2SO2+S 2 Br 2 +3Br 2 , when the liquid is distilled at ordinary press. At a temp, a little above its b.p.at 136, according to
A. Michaelis, and at 150, according to P. J. Hartog and W. E. Simsit decomposes into sulphur monobromide, bromine, and sulphur dioxide. H. Staudinger
and W. Kreis observed that when the vapour is suddenly chilled from 100 to
190 bromine, sulphur, and sulphur dioxide appear. A. Besson added that
thionyl bromide is rapidly decomposed by water; and in contact with mercury
it yields sulphur, sulphur dioxide, and mercurous bromide. H. A. Mayes and
J. R. Partington said that thionyl bromide is a very reactive liquid attacking both
cork and rubber very readily. It is soluble in the more inert organic solvents
e.g. benzene, carbon disulphide, carbon tetrachloride, and chloroform. It reacts
vigorously 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 acid
chlorides. The corresponding thionyl iodide, 8OI2, has not been prepared.
A. Besson reported thionyl chlorobromide, SOClBr, to be formed as just
indicated. It is described as a pale yellow liquid which boils and slightly decomposes at about 115 under normal press., and does
not solidify at 23 ; the sp. gr. =2-31 at 0. At
-50
-52i
a temp, a little above its b.p., it decomposes into
1 sulphur dioxide, thionyl chloride, bromine, and
- 60'
_j
sulphur bromide, and the same decomposition takes
~J_ place slowly in the cold. The chlorobromide is
-70"
/
rapidly decomposed by water. In contact with
-80'
mercury, thionyl chloride and mercurous bromide
y
are formed, sulphur is liberated, and sulphur di-90
oxide is given off. H. A. Mayes and J. E. Part/
ington measured the f.p. of mixtures of thionyl
/
-100'
chloride and bromide, and the results are illustrated
JW;S"
by Fig. 144. The simple mixed-crystal curve shows
^109
-110
0
20
Percent BS0 sf ' >0 a minimum, but no eutectic. They were also
FIG. 144.Freezing-point Curves unable to establish the existence of thionyl chloroof Mixtures of Thionyl Chloride bromide as a bromination product of thionyl
and Bromide.
chloride because (i) it is impossible to separate any
constant-boiling liquid, other than thionyl chloride
and thionyl bromide, from the product of bromination of thionyl chloride with
hydrogen bromide, (ii) The freezing-point curve shows that no intermediate
compound is present in mixtures of thionyl chloride and bromide, (iii) Physical
properties show that the product of bromination of thionyl chloride is exactly the
same as mere mixtures of thionyl chloride and bromide.
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3
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51. Sulphuryl Halides

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