J.S.C.I.

, 6g, March, 1950 BARTON A N D MUGDAN-VINYL CHLORIDE FROM ACETYLENE A N D HCl 7

' Table V
Coniparisorr of the preserrt dnra with those of Hcriy and Gritidley%1
Ociirrrcrrr kilirrrartdsc/raricririr Euphorbia ca@cirm Eriplrorbia eyrlrraeae Chrozopirora plicata
Present Henry and Present Henry and Present Henry and Present
work GrindlcyJ work Grindlep work Grindlep work Grindlcy'
Weight of 100 seeds, g.
Oil content of seed, ?$,
.. .. .. .. 0.04 0.049 I -76
o'74
I -24
32.3 t'22 2'20 t .98
12.5 16.2 20.8
Oil, iodine valuc
Cornnoncnt acids :
. . . . . . 192.6 __
195.6
25.2
189.4 192'3 177'7
33 '0
179.2
39'2
111.7 .
38.5
107.2
Saiunted . . . . . . 14 8
229
.. .. .. .. .. .. .. ..
9 20 I3 23 -0 24 '0
Olcic 5 1-1 19 9 7 24'9 27.1
Linolcic 16 14
Linolcnic ...... 65 61 66
I2
60
18
53
39
41 -
52'1 48.9
-
the seed oil of Etiplrorbia erytliraeae has a close resemblance Hcnry, A. J., and Grindlcy, D. N., J SOC. clrerii. h d . 1g4,63,188
in fatty acid composition to linseed oil and should be usable ' Grindley, D. N., ibid. 1948, 67, 230
Anon., Bull. irirp. hist. ~ g ~39t, ,97
for the same purposes. 'Patwnrdhn, V. A., Thesis, University of Bombay, 1930
The Clirozophora plicata seed oil is not a ' drying ' oil in the ' Barker, C., Crossley, A., and Hilditch, T. P., If. SOC.clretrr. Ind.
accepted sense, but closely rcsembles cottonseed oil in its Iwo.
_ _ 69.16
~ ,
component acids, especially in its proportions of oleic and Bark&C. and Hilditch, T. P.. ibid. Iwo. 69. IC
Hilditch, T. P., Morton, R. A: and Rilgy,. J. P.,-Arrab.sr 1945,70, 68
linoleic acid. Indeed, the only significant difference in fatty lo Gunstone, F. D. and Hilditch, T. P., -7. Soc. cherrr. frrd. 1946,65, 8
acid composition is that its z3-z4y0 of saturated fatty acids Hilditch, T. P.and Riley, J. P., ibid. 1946,65,74
include more stearic than palmitic acid, whereas in cottonsced 12 Bertram, S. H., Z.Brsrli. Of- ti. Eeri- Itid. rgti,..15, 733
oil palmitic acid forms about go"/, of the total saturated acids.
It is noticeable that different species within the genera
Ociiiiirtii and Eiiphorbia yield seed oils with very different pro- THE SYNTHESIS OF VINYL CHLORIDE
portions of the major component acids. Thus linolenic acid FROM ACETYLENE AND HYDROGEN
forms over 60% of the fatty acids in the oil of E. calyciira, but CHLORIDE
little over 50% of the fatty acids in the oil of E. eryfhracae;
the differences recorded in the fatty acids of the oils of Ociiirrim By D. H. R. UARTON and (the Iatc) M. MUGDAN
basilicririi,6 0. viride and 0.kiliiirandscharicrirtt are even greater : The usc of solid catalysts in the synthesis of vinyl chloride from
the contents of linolenic acid are z1,39 and 65% and of linoleic hydrogen chloride and acetylene has bccn investigated. The sdvan-
acid 60, 32 and 160/,,respectively. tagcs of employing catalysts in the finely powdered form has been
From the standpoint of practical cultivation, for the reasons demonstrated, and the valuc of granular pumice as support indi-
cated. Alumina pel and silica gel have bccn tried as altcmativcs to
already indicated, it is doubtful whether any of the four active charcoal ;alumina gel proved successful.
linolenic-rich seed oils are capable in the immediate future of A brief account o f th:: study of the mechanism of the vinyl
exploitation on a scale sufficient to be of technical commercial chloride reaction, made by the late Dr. Mugdan, has bccn includcd.
interest. The Eripliorbia species possess seeds of attractive Introduction
size and oil-content, but at present only grow in the wild state
in somewhat inaccessible regions. Hyptis spicigera and Ociiiiiiai It is well known that vinyl chloride can be made by three
being dwarf annuals with very minute seeds,
kil~iiiaiidsl~arictiiii, main methods: (i) The union of acetylene and hydrogen
are primarily less attractive as fatty-oil sources ; if, however, chloride in the presence of a suitable catalyst ; (ii) the decom-
0. kilirirairdslrariciiii; becomes cultivated on a sufficient scale
for the sake of the camphor content of the leaves and stalks,
the superlative drying properties of the seed oil would form
CJ-I4CI2 --
position of ethylene diehloride, according to the equation :
CH&HCI +
HCI; (iii) the reaction of tri-
chloroethane with various bivalent metals such as zinc or iron,
an important reason for harvesting the seed also on as large a or ten~alentmetals like aluminium,
scale as possible. The main purpose of the present paper is Two processes for the formation of vinyl chloride from acety-
not so much to recommend the immediate consideration of lene are available. The first involves the reaction of gases at
the cultivation of any of the four species mentioned for the a solid catalyst surface, but in the second process the gases
production of linolenic-rich seed oils, but to draw attention arc passed through a solution or suspension of the catalyst in
to the fact that such species exist, probably in greater numbers an inert liquid medium. The starting gases are acetylene and
than is yet realized. It may well happen, as further oilseeds hydrogen chloride, but it may be noted in passing that Wackerl
are submitted for study, that it will be found that still other uses a mixture of acetylene and chloroethanes at a high tempcra-
potential substitutes for linseed oil, equivalent or superior to ture in the presence of a solid catalyst.
it, are available from the many tropical and semi-tropical plants The earliest known process for the gas-solid reaction is that
whose seed oils have not yct bccn examined. of Griesheim," in which a mixture of acetylene and hydrogen
chloride is passed over mercuric chloride supported on pumice
Acknowlcdgmcnts or coke. Later processes are all modifications of this, using
We wish to record our indebtedness to the Director of Agri- different catalysts. Consortium3 employ activated charcoal or
culture, Ibadan, Nigeria, and to Mr. D. N. Grindley, Sudan silica gel impregnated with mercuric chloride, whereas I.G." use
Medical Scrvice, Khartoum, for the help given by the provision charcoal activated with phosphoric acid at a temperature of
of the six species of seeds discussed in this paper. \Ve thank 180' c. I.C.I.5 use activated charcoal alone a t a temperature
the Colonial Products Research Council for authority to of 100-300" c., the catalyst being previously treated with
publish these results, and for grants to two of us (C.B., H.C.D.). hydrogen chloride gas at 20c-600° c. Another variationo is to
pass the reacting gases over activated charcoal periodically
The University supplied with mercury, either by adding drops or passing the
Liverpool Rccei\.cd:April 1 2 , 1449 reactnnts through the heated metal. In this last process, using
References an impure, 16% acetylene, a 95% yicld is claimed at 130' c.,
Gunstone, F.D., Hi!ditch, T. P.,J. SOC. clrerri. Irrd. 1g47,66,293 the production being 16 g. vinyl chtoride/l. catalyst/hr.
'Hilditch, T. P.,J. Oil Cal. Clrcrr~.Ass. 1948,31, 1 ; 1949,32,5 Numerous catalysts containing activated charcoal are mentioned
C6
76 BARTON AND MUGDAN-VINYL CHLORIDE FROM ACETYLENE A N D HCI
in the literature, but charcoal impregnated with mercuric
chloride seems to be the best.
The reaction between acetylene and hydrogen chloride is
strongly esothermic, and control of temperature in the gas-
solid processes is difficult. Uniform heating can, however, be
ensured by the employment of catalyst dissolved or suspended
in a liquid medium: such a process was first mentioned in
the Gricsheim patent.2 Nevertheless, production is higher
with solid than with suspended catalysts, and the work in this
paper is confined to a study of the formation of vinyl chlorjde
from acctylcne and hydrogen chloride under the influence of
various solid catalysts.
Experimental
The acetylcne and hydrogen chloride gases were dried by
passage through calcium chloride, mised, and allowed to
react in a U-tube containing the catalyst and suspended in a
liquid bath. T h e reaction products were washed with water
to remove hydrogen chloride and (after drying) condensed in a
bath at - Soo c, ; unrcacted acetylene passed on to waste.
The hydrogen chloride gas rate was dctermincd by titration
and checked with a flowmeter, and acetylene rate was measured
with the aid of a \vet gas meter.
Mercrrric chloride oiitl carhorr or silica gel cnialJlsis
(a) EJecr of tciiiperacitre O ~ Iyield.-Several different cata-
lysts were uscd successively in the preliminary tests carried out
to study the eff'cct of temperature on the yield. I n each case
the results were analogous t o those set out below, which are
for 57 C.C. of granular (4-8 mesh) charcoal from Messrs.
Sutcliffe, Speakman and Co., impregnated with I O ' ~ of
mcrcuric chloride by weight ; the rates of flow of acetylene and
hydrogen chloride were 0.45 mole per hr. and 0.30 mole per
hr. respectively. The yield rose to a maximum at 150' c. and
then remained fairly constant.
Temp., C. 60 go 120 150
Condensate,g./hr. 5 . 5 6.4 8-3 12.9 11.1
(b) EJect of teii~perntirreon stability oJcara.$sr.-During
runs it was observed that, whereas no sign of mercuric chloride
sublimate could be detectcd a t 150OC., a slight trace appeared
after 2 hours a t 18oOc. At higher temperatures mercuric
chloride sublimed in quantity, the catalytic activity being
destroyed at 120 ' c.
The most efficient operational temperature for nearly all the
catalysts appeared to be 150' C.
(c) Use of fitrely powdered carboir or silica &.--As it seemed
that a great saving in the initial outlay on the catalyst could be
effected by replacing the usual granular carbon or silica gel
with the comparatively finely powdered material possessing
approximately the same surface area, catalysts consisting of
mercuric chloride supported on carbon or silica were prepared
i n fine powder form and then mounted on a carrier. The
method of preparation was (i) to stir the requisite amount of
carbon into a solution of mercuric chloride in methanol and
evaporate to dryness, or (ii) to run anhydrous silicon tetra-
chloride into an aqueous solution of mercuric chloride, erapor-
ate, dry and grind the residue. The prepared .catalyst was
carried by granular pumice of about the same size as the
granular carbon. Various means of attachment of catalyst to
pumice were investigated, but i n the majority of tests the pumice
was merely moistened with water, thoroughly mixed with the
catalyst, and the whole dried at 150"c. in a current of air.
The effect of using powdered carbon or silica gel is shown in
Table I (Experiments 1-6)- T h e use of sticking agents is dealt
with later.
( d ) EJecf of silica, silver clrloriile, e/c.,. (1s proiiioters.-These
catalysts were prepared (i) as in (c) (11) above, except that
J.S.C.I., 69, March, 1950
powdered charcoal was added before evaporating off the water;
(ii) by dissolving silver nitrate in water and stirring in the
powdered charcoal already impregnated with the mercuric
chloride. I n each case the water was evaporated off with con-
tinuous stirring. (Experiments 7-1I.)
(e) Eflect of rntio of carhoir/i~iercitricchloride.-Several runs
were made at 150" C. using different ratios of carbon to mercuric
chloride in the catalyst. The results, experiments 12-17
inclusive, show that the ro?/" mercuric chloride catalyst is by
far the most effcctiae per g. mercuric chloride employed.
(/) Reprodrtcibilify of resrrlts.-It was found that the catalyst
tended to fall off the pumice during experiments, and that
uncertainties were introduced by the considerable solubility
of acctylene in vinyl chloride a t temperatures around - 80" c.
Some tests were therefore made and it was demonstrated that,
by reducing the acetylene rate from 0.45 molelhr. to 0.26
mole/hr., using a rcflur head at -80' C. and keeping the liquid
vinyl chloride thereby condensed just at the boiling point, and
also by not allowing the catalysts to b e subject to any mcchani-
cal shock, constant results could b e obtained. T h e effect of
shock on the dry catalyst is shown in the results of experiments
15 and 20-22, in which the catalyst was dried in the usual way
at 150" c. and examined, then removed from the heating bath,
gently tapped scvcral times, and subsequently replaced and
examined again.
(g) Attachtiwit o j catalyst to pwrtice.-Mcntion has already
been made of attempts to attach the powdercd carbon-mercuric
chloride catalyst to the granular pumice, Many sticking agents
were tried, including destrin, gelatin, starch, sugars, liquid
paraffin and waterglass ; all were ineffectire, owing either to
~ their lack of adhesive power under the given circumstances or
to the estent by which the activity of the catalyst was reduced.
Results are shown in the following series of experiments :
(i) 2-4, (ii) 14, 18, 1 5 and 19,and (iii) 23 and 24. I n the case of
experiment 24, 0.8 g. water glass (density I .7) dissolved in
180 water, was used.
It \\,as then thought that some improvement in the adhesion
of the powdered catalyst to pumice might be effected if the
these mixing of the pumice moistcned with water and the powder
were carried out mechanically instead of by hand. Accordingly
the moist pumice was packed into a long-necked R.B. flask,
the powder introduced and the flask slo\vly rotated about a
horizontal axis with the aid or an electric motor for 4 hr. With
carbon-mercuric chloride catalysts the product appeared
exactly like granular carbon; until the water was removed the
catalyst was mechanically stable and the attachment \vas good.
On drying, the attachment was better than with the catalyst
prepared by hand. I t \vas found that catalysts prepared by
hand were usually slightly more active than those prepared by
the procedure above (experiments 25 and 26). All the catalysts
of the type powder supported by solid prepared for the espcri-
ments described below were made with the aid of the machine.
(II) Use OJ wire gairze aid poroiis plate as catahst siippor1,-
It was suggcsted that iron wire gauze might be a suitable
support for the powdered catalyst. Some trials were made,
the material being mixed into a paste with benzene and painted
on to the gauze. Broken porous plate, roughly equivalent in
surface area to the pumice, was also tried. (Experiments 27-3 I).
Corboir-~i~crctrr~~ cata(ys1
This catalyst was prepared by heating togcther the carbon
and mercury iir vaciio at 210' C. One experiment only was
made (no. 32). On passing chlorine over this catalyst, the
activity fell to zero.
Carboii-iircrcrrroits chloride catalyst
Two runs were made with catalysts consisting of mercurous
chloride on granular Sutcliffe Speakman charcoal. For the
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IdICIE3
 78 BARTON A N D MUGDAN-VINYL CHLORIDE FROM ACETYLENE A N D HCI
first (experiment 33) the charcoal, impregnated with 10%
mercuric chloride, was heated with excess of metallic mercury
at 200' c. This catalyst contained an indefinite amount of
escess mercury which, as shown in experiment 32, is slightly
active. For experiment 34, granular Sutcliffe Speakman
charcoal was impregnated with 20% of its weight of mercurous
chloride in the dry by heating the two carefully in an evacuated
flask, the vapours of mercurous chloride being rapidly and
quantitatively adsorbed by the carbon.
AliiiNiira-iirercriric chloride cotnlysts
Alumina was precipitated from aluminium sulphate solu-
tion with ammonia, filtered off and boiled with distilled water
until free from all ammonium salts, chloride and sulphate.
T h e pure, powdered alumina was impregnated with mercuric
chloride by means of methanol and dried a t 100' C. The
material was then tested; no catalyst activity was observed
even at 150' c., at which temperature rapid loss of mercuric
chloride took place. Alumina for chromatography was similarly
found to be quite inactive.
Alutiriira gel-niercriric chloride cntdysfs
T h e alumina gel examined was the American Alorco ' G Z
A ' product, 4-8 mesh, which may be dried by heating to
175-375' c. The catalyst was prepared by impregnating the
material with mercuric chloride (i) as a solution in methanol,
(ii) as a solution in water (experiment 39, or (iii) by a dry method
as in the impregnation of granular carbon with mercurous
chloride (experiment 36). T h e methanol method is unsuitable,
since droplets of mercury appear during the drying. There
would seem to be little difference in the activity of catalysts
prepared by the wet or dry method.
Esperiment 37, performed with a catalyst containing 2%
mercuric chloride and prepared in the dry way, showed that
the percentage of mercuric chloride could be lowered with
advantage.
These catalysts are, initially, rigorously active at oo c., but
soon decline and eventually become totally inactive. The
results shown for esperiment 38 are the optimum values,
obtained after 1 4 - 4 hr. At xoo0 c., none of the poisoning
effects which occur at oo C. has been detected, although cata-
lysts have been examined for operational periods as long as
30 hr.
Altinrina gel-rtrerciiroiis chloride raf alyst
Alumina gel was dried by heating at 310' c. for 20 hr. and
impregnated in the dry with 10% of calomel. At 0' c. the
catalyst behaved exactly similarly to the corresponding
mercuric chloride catalyst; at 100" C. the results were as
given in Table I for experiment 39.
Miscellaneoris catalysts
Silica gel was found to hare no catalytic activity a t all up to
temperatures of zooo C. Catalysts of silica gel-zinc chloride
(esperiment 40) and alumina gel (experiment 41) showed a
slight activity a t 200' C. Some alumina gel-cupric chloride
catalysts were also prepared with the aid of water and dried at
1x0' c. : they were found to lose their small activity rapidly
(experiments 42-45).
Results a n d conclusions
T h e results of the experiments described above are shown in
Table I. From them the following facts emerge:
(a) Finely powdered active carbon impregnated with 10%
of mercuric chloride and distributed over granular pumice of
8-20 mesh has a similar activity to 7-8 times its weight of the
correspondingly sized granular Sutcliffe Speakman charcoal,
Powdered Sutcliffe Speakman charcoal and Super-norit have
almost the same activity.
J.S.C.I., @, March, 1950
(b) The optimum temperature for the reaction seems to be
150' C. (measured i n the cooling bath). At this temperature
the yield is a maximum in all cases and the loss of mercuric
chloride due to sublimation is small. The amount of mercuric
chloride lost depends on the ratio of mercuric chloride to
carbon, but with low concentrations like 10% mercuric chloride
the loss is negligible.
(c) In testing the effect of ratio of mercuric chloride to
carbon it appears that the IOYA mercuric chloride catalyst is
the most effective per gram of mercuric chloride present.
(4 Addition of silver chloride to the mercuric chloride has
no marked promoting effect.
(e) Silica containing 10% mercuric chloride and prepared
from silicon tetrachloride and a solution of mercuric chloride
in water by evaporation and drying at 100' c. is as active as the
corresponding carbon catalysts with 10% mercuric chloride.
This silica has no adsorptive power towards the mercuric
chloride and does not promote the carbon-mercuric chloride
catalysts. If the silica is dried at 370" c. it seems to become
almost inactive, whilst still remaining a non-adsorbent.
Powdered carbon catalysts hare been attached to pumice
without any sticking agent by a mechanical device j all attempts
to find an adhesive were unsuccessful.
(g) Mercury itself is a very poor catalyst; mercurous
chloride-carbon catalysts seem to be just as active as the
corresponding mercuric catalysts.
(11) Alumina gel has been shown to give exceedingly active
catalysts with mercuric chloride, operating at a lower tempera-
ture than any other material studied. Although the catalysts
became inactive at 0" c. after an operational period of about
IZ hr., they retained their activity unchanged after 30 hr. when
employed a t 100' c. Mercurous chloride catalysts behave
similarly to the mercuric chloride catalysts on this medium.
T h e alumina gel retains the mercuric chloride well on heating,
and has almost as high an adsorptive power towards mercuric
chloride vapour as carbon. Silica gel is by comparison only a
poor adsorbing medium.
( j ) T h e miscellaneous catalysts studied were found to give
very poor results up to 200' c.
Mechanism of the v h y l chloride process
The exact mechanism of the vinyl chloride synthesis is still
uncertain. It is interesting, however, to speculate that an
intermediate compound may be formed between the mercuric
chloride and one or both of the reactants, and that this sub-
sequently decomposes giving vinyl chloride. There is some
support for this view in the discovery of Fierz-David and
Zollinger' that a volatile mercury compound is always found,
although in very small concentration, in vinyl chloride prepared
using a mercury-containing catalyst.
The obvious intermediate compound, the formation of which
might provide B mechanism for the vinyl chloride synthesis,
is p-chlorovinyl mercurichloride (CHCl:CH*HgCl). This com-
pound was first obtained by BiginelliR and was investigated
later by Brame.O A convenient method of preparation was
described by Chapman and Jenkins1" who passed acetylene
into an ethanol solution of mercuric chloride containing some
hydrogen chloride. T h e reaction was, however, a slow one,
only about 7 ~ %of the mercuric chloride being converted
in rG hr.
Recently the chemistry of j3-chlorovinyl mercurichloride
has been extensively 'investigated. It has been shown l1-Ia
to exist in both fratis and cis forms, the former having m.p.
124" c. and the latter 79" c. T h e material obtained in our
investigations which are outlined below had a m.p. of about
roo" c. with decomposition and was prcsumably a mixture of
the two forms.
J.S.C.I., 6g, March, 1950 WILSON AND STRAW-SULPHUR
In the absence of hydrogen chloride the formation of
,%chlorovinyl mercurichloride was very slow in ethanol,
acetone, dioxan, acetic acid, benzene and pentachloroethane.
I n the presence of active charcoal the rate of formation was
increased in the three last named solvents, though not much
affected in the others. A possible mechanism then for the
vinyl chloride synthesis would be
+-
(i) GHZ HgCI, -> CHCkCHHgCI
(ii) CHCI:CH*HgCI 4-HCI ---> CHC1:CHZ HgCI, +
with the active charcoal speeding up the first of these
reactions. In apparent agreemcnt with this view treatment
of ,Gchlorovinyl mercurichloride with hydrogen chloride at
100"C. gave vinyl chloride, a discovery confirmed by Varshav-
skii." The latter worker has also shown that reaction with
hydrogen bromide gives vinyl chloride (and HgCIBr), thus
proving that the reaction is not the catalytic union of acetylene
and hydrogen chloride on mercuric chloride.
Various liquids, containing dissolved mercuric chloride,
were then tried for their power to bring about the vinyl chloride
synthesis. In each case equal rates of acetylene and hydrogen
chloride were passed through the liquids in which was sus-
pended finely divided active charcoal. Temperatures up to
100' c. were employed. Pentachloroethane, p-diisopropyl-
benzene and C&I, were fairly effective, but the other solvents
tried were of little use. The replacement of the charcoal by
alumina or silica gel was likewise without effect.
The formation of /I-chlorovinyl mercurichloride without
the aid of liquids was then investigated. Charcoal with 20%
mercuric chloride was treated with acetylene at room tempera-
ture and excess acetylene was then removed in 'L'UCIIO at 6 5 O C.
When hydrogen was passed over the charcoal at 100' c. vinyl
chloride was formed in about one third of the theoretical
amount. A similar result was obtained when a mixture of
finely powdered active charcoal was intimately admixed with
an excess of mercuric chloride.
The'next step was to examine the effect of acetylene on pure
dry mercuric chloride. Initially at 100' c. the reaction was
very slow, but the velocity of absorption increased rapidly with
time. The product of the reaction was a sintered black mass
containing 8-chlorovinyl mercurichloride and unchanged
mercuric chloride. The increase in the velocity of the reaction
with time suggested the formation of some catalyst ;a similar
result was observed in the presence of finely divided charcoal.
I t was shown, howcver, that 6-chlorovinyl mercurichloride
was not the catalyst in the reaction since, when admixcd
initia!ly with the mercuric chloride, it caused no increase in the
reaction rate.
The experiments so far described indicated that vinyl
chloride could be obtained via P-chlorovinyl mercurichloride
and that the rate of formation of the latter compound was
increased by the presence of charcoal. Although this evidence
might be taken to support the intermediate theory of catalysis
outlined in equations (i) and (ii) above, the rate at which hydro-
gen chloride reacted with P-chlorovinyl mercurichloride was
very small below 100' c., whereas the vinyl chloride synthesis
reaction may be made to proceed rapidly at much loier
temperatures (sce p. 76). More decisive evidence against the
intermediate compound theory was obtained by consideration
ofthe properties of mercurous chloride. As we have mentioned
on P. 78, this substance is equally as effective as mercuric
chloride in the vinyl chloride synthesis, a result confirmed by
Fierz-David and Zollinger,i yet d l ntfcnipts to obtain a com-
pound from mercurous chloride, analogous to fi-chlorovinyl
mercurichloride, have failed. The mechanism of vinyl chloride
synthesis and the unique role played therein by mercury
compounds has not therefore yet received an adequatc
explanation.
IN ORGANIC COMPOUNDS 79
Acknowledgments
This investigation was supervised by Professor Sir Ian
Heilbron, D.S.O., F.R.S., whose constant interest and
encouragement are gratefully acknowledged. Thanks are also
due to the Directors of The Distillers Company, Ltd. for
permission to publish this paper. The work was carried out
during the period 1940-1941 in the Department of Organic
Chemistry at Imperial College.
The Distillers Company Ltd.
Research and Development Department
Great Burgh
Epsom, Surrey Received April 13, 1949
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~ -~_ ___ _
_ ___ ___
___.
THE DETERMINATION OF SMALL
AMOUNTS OF SULPHUR IN ORGANIC
COMPOUNDS
By 11. N. N'ILSON and H. T. STRAW
A recently described apparatus for the determination of tnces
of sulphur in organic compounds has been investigated. T h e
original mcthod described B vertical tube hcatcd to 830' C.
and packed with silica, on to which the sample was allowed to fall
drop by drop, and burnt in a npid current of air. The silica
packing was quite unsatisfactory, but by substitution of an oxida-
tion catalyst such as vanadium pentoxide on alumina, very satisfac-
tory results me obtained, The apparatus rcquircs little skilled
attention, is npid, and u n be applied to a very wide vmicty of
substances ranging in volatility from petrol to sperm oil.
Introduction
The determination of minute traces of sulphur in many
kinds of organic materials has become of very great importance ;
the corrosive properties of many compounds are much modified
by very small amounts of sulphur, and since the introduction
of sulphur-sensitive catalysts in various synthetic processes,
knowledge of the sulphur content of certain intermediates is
essential. The problem of the determination of a few parts
per million of sulphur is an old one. Sulphur in methanol or
ethanol can be fairly easily determined by burning about zoo g.
of the solvent in a lamp with a wick of purified cotton or silica
fibre, then scrubbing the sulphur dioside and trioxide from the
combustion products with either hypobromite or peroxide
solution j however, the time necessary for the combustion is
between one and three da s. Petrol or benzene can be burnt
in lamps of special design,Y but owing to the difficulty of pro-
ducing a smokcless flame combustion is slow, and in practice
samples larger than 25 ml. are seldom burnt in this way. This
automatically puts a limit to the sensitivity of the method, as
C8