Mountain_Girl wasn't able to produce any SOCl
2 by the method of
Patent US1861900
-
Post 257083
(Mountain_Girl: "Cl2, S2Cl2, SOCl2 & acid chlorides", Novel Discourse). This was the only attempt reported to the hive that I know of. I think the impression that making thionylchloride is impossible should not prevail. If Liebig's contemporaries could do it, it can be done today.
Ber. 1883;483thionylchloride and pyrosulfurylchloride from sulfur monochloride, sulfur trioxide and chlorine22g S
2Cl
2, cooled to -19°C with an ice/salt mix, were completely saturated with Cl
2 and 50g dry SO
3 distilled thither from 100g oleum, while a Cl
2 stream was permanently conducted thru the liquid. Thereby first a crystalline mass formed that wasn't stable and reliquified when the ice/salt mix was replaced with water of 0°C. SO
2 only emerged at the end of the operation and not in considerable amounts. CO
2 was conducted thru the liquid, that was heated a little in the end, to remove any possibly absorbed Cl
2. The product was fractionally distilled. 56g colorless S
2O
5Cl
2 and 22g still slightly yellow SOCl
2 were thus obtained.
related ref:
Liebigs Ann.Chem. : 170.1873;1-42
Z.Chem. : 23,12.1983;436This one is promising, but cannot be more than a weird hint:
thionylchloride from sulfur monochloride and aluminium oxide Chlorination of
gamma-Al
2O
3 with S
2Cl
2 and Cl
2 in a ratio of S
2Cl
2:Cl
2=1:3 gives AlCl
3 and SOCl
2 above 100°C.
2 Al2O3 + 3 S2Cl2 + 9 Cl2 __> 4 AlCl3 + 6 SOCl2Reaction was conducted in pipe bombs, t
rxn wasn't specified in the article more precisley than between 3-80h, the Beilstein abstract however says 48h.
The references given in the article didn't deal with anything concerning the reaction in question.
Patent DE139455
thionylchloride from sulfur trioxide and sulfur dichloride1000kg sulfur trioxide are slowly added to 1000kg S
2Cl
2, that are contained in a vessel equipped with reflux condensor and stirrer. Temperature is held between 75 and 80°C. Chlorine is constantly introduced to chlorinate the S, that forms as reaction product, back to sulfur monochloride to prevent reaction with SO
3. Reaction products are rectified.
Patent DE275387
thionylchloride from SCl2 catalysed by SbCl3In an iron vessel fittet with a stirrer to 1000 parts SCl
2 and 10 parts SbCl
3 as catalyst, at 10 - 15°C the theoretical amount of SO
3 is distilled thereto. Purificatin by fractional distillation, high yield of thionylchloride.
Also of interest here:
Patent US2420623
and
Feher, F.; Brauer, G., Handbuch der praeparativen anorganischen Chemie, Stuttgart 1954, page 294
Patent US236057
thionylchloride from oleum, sulfur monochloride/sulfur dichloride and chlorine Heretofore thionyl chloride has been produced by reaction of sulphuric acid or sulphur trioxide with sulphur monochloride and chlorine or with sulphur dichlorlde. The reaction of sulphuric acid with these chlorides of sulphur is as follows:
4 H2SO4 + 3 S2Cl2 + 5 Cl2 __> 4 SOCl2 + 6 SO2 + 8 HCl (1)
4 H2SO4 + 6 SCl2 + 2 Cl2 __> 4 SOCl2 + 6 SO2 + 8 HCl (2)
The reaction of sulphur trioxide with these chlorides of sulphur is as follows:
2 SO3 + S2Cl2 + Cl2 __> 2 SOCl2 + 2 SO2 (3)
2 SO3 + 2 SCl2 __> 2 SOCl2 + 2 SO2 (4)
Reactions {1) and (2) are generally unsatisfactory because of the fact that for every molecule of SOCl
2 two molecules of HCl are produced.
The HCl comes off mixed with SO
2 from which it must be separated, and there is not always a sufficient demand for this byproduct. Sulphur trioxide as such is expensive and Reactions (3) and (4) are commonly carried out by means of SO
3, evolved from oleum. As the heat of reaction is considerable and SO
3, boils at about 46° C., it is reacted in gas phase. In the case of Reaction (3) chlorine is passed in at the same time to avoid production of sulfuryl chloride and pyrosulfuryl chloride.
I have now discovered that instead of-evolving SO
3 from oleum, for use in the above reactions, the oleum itself may be advantageously used directly in the reactions. Assuming oleum containing 70 per cent SO
3, the reactions are as follows:
6 (H2SO4 + 2.83 SO3) + 13 S2Cl2 + 16 Cl2 __> 22.98 SOCl2 + 25.98 SO2 + 12 HCl (5)
6(H2SO4+2.83 SO3) + 26 SCl2 + 3Cl2 __> 22.98 SOCl2 + 25.98 SO2 + 12 HCl (6)
It is to be understood, that Reactions (5) and (6) may be combined by using a mixture of sulphur monochloride and dichloride.
It should be noted that in these reactions the SO
3 is reacted in liquid phase. This results in more intimate contact and a consequent reduction of about one half in the time of reaction, namely from 100 hours to from 45 to 50 hours. It also results in a better yield with respect to the SO
3. Moreover it will be observed by comparison of Reactions (1) and (2) with Reactions (5) and (6) that the quantity of byproduct HCl is decreased from a ratio of two molecules of HCl to one of SO
2 to a ratio of one molecule of HCl to nearly two of SOCl
2; or, in other words, the molecular proportion of HCl produced for a given quantity of SOCl
2 is decreased to a little more than one quarter of that produced in the reaction with sulphuric acid alone, which is the only reaction of the prior art that is practicable for carrying out in liquid phase. Besides the saving in time, improved yield and reduction in byproduct HCl. a further practical advantage as compared with the process in which SO
3 is evolved from the oleum is that no H
2SO
4 is left over to be shipped back to the manufacturer of the oleum.
Reactions (5) and (6) are preferably carried out in a glasslined, jacketed, iron reactor, equipped with an agitator, manometer, thermometer well exits for SO
2 and HCl and a reflux condenser. There must also be a chlorine inlet tube, which should extend to near the bottom of the reactor. The oleum should have as high a content of SO
3 as practicable and should preferably be liquid. In order to minimize production of higher oxides of SCl
2 e. g., sulfuryl and pyrosulfuryl chloride, and afford better control of the reaction, which is otherwise quite violent, the oleum is preferably added gradually to a body of the' chlorides of sulphur, so that the latter may be in large excess until near the finish of the reaction. The sulphur monochloride or dichloride is therefore first charged into the reactor. If desired, antimony trichlorlde may be added to serve as catalyst. With the agitator working and cooling water flowing in the reactor jackets, the oleum is added at such a rate that the temperature is kept below 45°C and preferably at substantially 25°C. The admission of chlorine may be started at the same time or later, depending upon whether sulphur monochloride or dichloride is the other reagent. At the finish it is desirable that there should be a slight excess of both oleum and chlorine in the mixture over the theoretical quantity.
After the optimum quantities of oleum and chlorine have been added the charge is heated by passing steam through the reactor jacket and refluxed until the refluxing temperature has became stabilized at substantially 75° C., which is the boiling point of thionyl chloride. The product is then distilled away from residual reagents and high boiling oxides and other impurities and further treated by any of the known ways to purify it.
Z.Anorg.Allg.Chem. : 233.1937;385-400 and Z.Anorg.Allg.Chem. : 211.1933;150-160 S2O + 2 Cl2 __> SOCl2 + SCl2S2O
Z.Anorg.Allg.Chem. : 319.1963;337-349
Z.Naturforsch. b : 19.1964;535-536
Z.Naturforsch. : 20b.1965;809
Can.J.Chem. : 43.1965;2357-2362
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