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Author: Subject: HELP! need thionyl chloride(SOCl2) synthesis
navarone
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sad.gif posted on 31-1-2004 at 14:16
HELP! need thionyl chloride(SOCl2) synthesis


zzup bros?
look guys....does any body of u know how to make thionyl chloride SOCl2?
i would really need it man!
and possibly with easy getting chemicals.
u know dont come out with crasy substances like cyan,palladium,arsenic or others stricted chems.
u know a recipe that even a kid would be able to do.
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[*] posted on 31-1-2004 at 14:33


If you looked hard enough online Im sure you could come up with a preparation but here is the basic one. Not OTC chems but oh well, maybe you could build off it. Next time though try and word your post so it seems like you're actually interested in it and not just like you expect immediate gratification.

Thionyl Chloride

PCl5 + SO2 -----> POCl3 + SOCl2


A well-dried, 250-ml., two-neck, round-borrom flask, equiped with a reflux condenser is connected to a CaCl2 tube, is loaded with 100 g. of PCl5. Sulfur Dioxide is intorduced though a gas inlet rube extending to the bottom of the flask. The SO2 is carefully dried by allowing it to bubble though two wash bottled containing H2SO4. The reaction which can be acceletated by shaking the flask, is completee after several hours when all the PCl5 dissolves. The products
are seperated by repeated careful fraction using an efficent collum. BP of SOCl2 77C and BP of POCl3 108C This preparation is generally not free of phosphorus compounds. The yeild of SOCl2 is 30g (50% of theroretical)

From Inorganic Preparations book I




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[*] posted on 31-1-2004 at 18:36


There's another method, on this site no less posted my Solo. The title is Thionyl Chloride.

You pass SO3 into SCl2 to make SO2 and SOCl2. I've never tried it, but it looks like it would work. Perhaps you should consult the other thread. Those can be made from Sulfur, Chlorine, and some NaHSO4. All quite easy to obtain/make.

It's obvious you didn't search. This could of easily gone in that thread. Or you could of completely avoided making the thread by finding both answers provided thus far there.
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[*] posted on 1-2-2004 at 23:52


Quote:
Originally posted by navarone
HELP! need thionyl chloride(SOCl2) synthesis

No you don't. Trust me, you really don't.
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meselfs
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[*] posted on 7-2-2004 at 16:15


IIRC, this is how you make it:

Pass a mix of sulpfur dioxide & chlorine through activated carbon or camphor catalyst.

Note that this stuff is slowly hydrolyzed to H2S04.




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[*] posted on 7-2-2004 at 22:50


Quote:
Originally posted by meselfs
Note that this stuff is slowly hydrolyzed to H2S04.

Actually, it hydrolyses to SO2 and HCl
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[*] posted on 8-2-2004 at 18:29


Right.. I was thinking SO2Cl2 . Sorry.



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[*] posted on 9-2-2004 at 20:05
interesting patents


US 4,337,235 Purification of thionyl chloride
US 4,388,290 Purifying thionyl chloride with AlCl3 catalyst
US 4,759,826 Process for purifying thionyl chloride
US 5,498,400 Preparation of thionyl chloride and phosphorus oxyhloride from sulfur dioxide




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[*] posted on 24-10-2004 at 10:37


Hi mfs,

SO2 + Cl2 --> SO2Cl2 with camphor catalyst at 20°C! (this reaction looks so great)
do you have already tried it ?
i think i am gonna try it

SO2Cl2 + H2O --> H2SO4/HCl oleum

[Edited on 24-10-2004 by acx01b]

[Edited on 24-10-2004 by acx01b]
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[*] posted on 25-10-2004 at 08:52
Ref: thionyl chloride synthesis


try reading post [537708] over at the hive.....

Excerp
Summary

The oxidation of SCl2 by atmospheric oxygen has been investigated using activated charcoal as the catalyst. The reaction has been discussed in terms of two reactions. Firstly, the irreversible oxidation of SCl2 to SO2Cl2 :
SCl2 + O2 __> SO2Cl2

and secondly, the reversible reaction between the SCl2 and the SO2Cl2 to form SOCl2 :

SCl2 + SO2Cl2 <__> SOCl2

This oxidation has been investigated at the temperatures 193°C, 138°C and 320°C, and the equilibrium constant of the reversible equilibrium reaction has been determined for each temperature. From the temperature dependence of this equilibrium constant it is found that the reaction is exothermic to the extent of 18 kcal.

(Yield of SOCl2 at 193°C : ~73%)

..............




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[*] posted on 9-11-2004 at 10:51


Well I know a way... unfortunatly in Canada under the CanadaChemical Weapons Convention Act thionyl compounds are illegal.

I would assit if I could...but bound by Canadian Laws and George Bushs' reelection I wouldn't want to assist any terrorist organization

Edit by Chemoleo: That's good to know, but what's the point of your post? :o:o

[Edited on 9-11-2004 by chemoleo]
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[*] posted on 9-11-2004 at 14:25


It's doubtful whether anyone will come after you for telling a bunch of harmless hobbyists how to synthesize one simple chemical. You could always give us a reference to it or just tell one person who may or may not take it upon himself to break the anti-knowledge laws for the good of mankind. If they’ve made exchange of knowledge an international offence, then we all have much bigger things to worry about.
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[*] posted on 10-11-2004 at 10:09


I am quite interested in that synthesis using a camphor catalyst, could you perhaps post a patent number or something to that?



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[*] posted on 18-12-2004 at 18:18


Taken from Handbook of Preperative Inorganic Chemistry, Volume 1, Second Edition, pages 382 to 383.

Thionyl Chloride
SOCl2


I.
SCl2 + SO3 = SOCl2 + SO2
102.98 80.07 118.98 64.07

Flask A of the apparatus in Fig. 166 is charged with pure 65% oleum, flask B with 100g of SCl2 (see p. 370). Flask A is slowly heated in an H2SO4 bath, while B is cooled with an ice water bath. The stoichiometric quantity of SO3 is thus gradually distilled onto the SCl2. The reaction proceeds with SO2 evolution (use a hood!). Partial solidification of the flask contents feqeuntly occurs at the beginning. However, the contents should again be completely liquid when the addition is completed. If necessary, the flask is heated at the end for a short time on a water bath. Flask A is then disconnected, the ground joint at C is stoppered, and the mixture is slowly distilled in a column (use a hood!). The mixture must be protected from contact with atmospheric moisture. The middle fraction is further porified by repeated careful fractionation, with S added to the distillation charge in order to convert all sulfur chlorides present to S2Cl2. The contents are distilled through an efficient column until a completely colorless product, coming over at 76-77C, is obtained. The yeild is about 80% of theoretical.

Fig.166

II.
PCl5 + SO2 = POCl2 + SOCl2
203.37 65.07 153.35 118.98

A well-dried, 250mL, two neck, round bottom flask, equipped with a reflux condenser connected to a CaCl2 tube, is loaded with 100g of PCl5. Sulfur dioxide is introduced through a gas inlet tube extending to the bottom of the flask. The SO2 is carefully predried by allowing it to bubble through two wash bottles containing concentrated H2SO4. The reaction, which can be accelerated by shaking the flask, is complete after several hours, when all the PCL5 dissolves.
The products are seperated by repeated careful fractionation, using an efficient column. Bp. Of SOCl2, 77 C; of POCl2, 108C.
This preparation is generally not completely free of phosphorus compounds. The yeild of SOCl2 is 30g (50% of theoretical).

PROPERTIES:
Colorless, highly refractive liquid with an unpleasant, SO2-like odor. Mp. -104.5 C, bp. 77 C; d. 1.64. Significant dissociation to S2Cl2, SO2 and Cl2 occurs just above the boiling point. Hydrolyzes inwater to SO2 and Hcl; soluble in benzene and chloroform.

REFERANCES
I.A, Michaelis, Liebigs Ann. Chem. 274, 173 (1893).
II.H. Grubitsch, Anorganisch-praparative Chemie, Vienna, 1950, p. 294.


Much of the fancy glassware can probably be left out, and just distilled etc. with what you have on hand, as every synthesis in the book is on how to get super-uber-absolutely pure chemicals, which we don't need for most things.
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[*] posted on 19-12-2004 at 12:30


Quote:
[quoteMuch of the fancy glassware can probably be left out, and just distilled etc. with what you have on hand, as every synthesis in the book is on how to get super-uber-absolutely pure chemicals, which we don't need for most things.


Yes but that applies if we only need to go one or two steps. You see if one is attempting a several step proceedure(advanced members) then the product at each step will be of a little less purity as the previous. Then again, if you are taking hydrated metallic chlorides and wanting to convert them to anhydrous chlorides then the phosphorus compounds impurites are helpfull if anything. Purity is application specific.

[Edited on 12/19/2004 by chloric1]




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[*] posted on 3-1-2005 at 14:58


Quote:
Originally posted by solo
try reading post [537708] over at the hive.....

Excerp
Summary

The oxidation of SCl2 by atmospheric oxygen has been investigated using activated charcoal as the catalyst. The reaction has been discussed in terms of two reactions. Firstly, the irreversible oxidation of SCl2 to SO2Cl2 :
SCl2 + O2 __> SO2Cl2

and secondly, the reversible reaction between the SCl2 and the SO2Cl2 to form SOCl2 :

SCl2 + SO2Cl2 <__> SOCl2

This oxidation has been investigated at the temperatures 193°C, 138°C and 320°C, and the equilibrium constant of the reversible equilibrium reaction has been determined for each temperature. From the temperature dependence of this equilibrium constant it is found that the reaction is exothermic to the extent of 18 kcal.

(Yield of SOCl2 at 193°C : ~73%)

..............


Seeing as how the hive is currently unavailable, might you have all the details mentioned in that post? Or is that it? We have the temperature, but what about an actually example detailing reactant (and catalyst) amounts and a general description of the set up. Boiling S2Cl2 in a stream of air through a glass tube with activated carbon heated to 193c? If you have the details (inc. original ref.), please post them, many thanks to you.




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[*] posted on 3-1-2005 at 16:41
Ref: thionyl chloride synthesis


I haven't the posted thread , but I do have an article I can share......solo

Attachment: synthesis of thionyl chloride (trans_faraday_soc_43.).djvu (170kB)
This file has been downloaded 1402 times





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[*] posted on 3-1-2005 at 20:06


Ah, thank you very much good sir. That information is most helpful. I dont know if I will get around to attempting it (going to try SO3 from NaHSO4 first), never the less it is good to know. :cool:



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[*] posted on 6-1-2005 at 10:06


Something about this document has been bothering me. They show the use of SCl2, which is represented as chemically distinct from S2Cl2 (differing bp, etc), which in itself makes sense to my limited knowledge. However, I cannot find one single reference to SCl2 anywhere, not in the Merck, my textbooks, or any of a numerous amount of vendors with online catalogues. The implication in thier purity description from the lot obtained from a chem supply house is that SCl2 was made from S2Cl2 via either reaction with HCl or catalytic hydrogenation (oh, or maybe excess Cl2?). Either way, it does make this synth not quite as conveinent and useful as it might be. I guess the real question now is how easy and viable is a synthesis of SCl2 from S2Cl2?

PostScript : Put SO3 attempts on hold, this just seems too interesting. ;)




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[*] posted on 6-1-2005 at 14:56


SCl2 certainly does exist. In Sidgwick's <i>Chemical Elements and their Compounds</i> it is said to be prepared by adding Cl2 to S2Cl2 and distilling.



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[*] posted on 7-1-2005 at 08:24


SCl2 is mentioned on WebElements (not the best resource for compounds, but good for some).



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[*] posted on 8-1-2005 at 21:42


Thanks for the info guys. It made sense to me, but I feel better having other solid references to it.

Whilst I was perusing all the various posts on this site concerning thionyl chloride, I came upon this (http://www.sciencemadness.org/talk/viewthread.php?tid=790) thread. The procedure yet undisclosed (anybody ever find this ref?) states that thionyl chloride may be made by the action of SO2 on a saturated solution of HCl. Well, having some time on my hands (I ran out of MAPP gas for SO3 experiments :mad: ), I came up with this idea for a methodology in lieu of the details from the reference.

Saturate room temp anhydrous DCM (say, 500mL) with HCl. Set up for a distillation with a gas inlet reaching to the bottom of the DCM solution. Bring the DCM solution to a gentle boil, and begin a slow, steady flow of SO2 gas. Continue the gas flow until nearly all the DCM has distilled over (or the level of the DCM drops below the end of the gassing tube), cut the gas flow, but finish distilling off the DCM. If all goes well and the beanstalk grows, there should be thionyl chloride left in the flask. Change recieving flasks and distill the thionyl chloride for decent purity.

After looking at all the solvents available to me, I decided DCM would probably be the best based on several factors. One, its bp (40C) is well below that of thionyl chloride (76C), two, it doesnt react with thionyl chloride, and three, the azeotrope it forms with water (1%H2O) boils at 38.8C. The other solvent possibilities considered are CS2, isopropyl chloride, chloroform, and diethyl ether. Not that I have access to CS2, just that it has properties that would probably work in this reaction.

Anyways, just thought I would share some brainstorming. Criticism welcome.

Sincerely,
Nature's Natrium

EDIT: Oh wait, I just realized something. A 1% azeotrope means that disitlling 500mL of DCM would only remove a mere 7g of H2O, less than .5 moles. There has to be a better solvent...

EDIT2:500mL of propyl chloride or isopropyl ether would remove 15.4g. Interesting that because of density and azeotrope differences, they just happen to come out to removing the same amount of H2O per volume of solvent. Nevertheless, thats not even a mole of water. I am beginning to see the value of a dean-stark trap. On the other hand, in a perfect magic universe, .85 mol of water removal ought to equal 101g of thionyl chloride. It is becoming clear that in this variation of the idea, the amounts of HCl and SO2 would have to be tightly controlled to ensure a decent yield.

FINAL EDIT:Oh oh oh, chloroform would be even better for this. 500mL should be able to remove up to 36.75g of H2O, or roughly 2 moles. Also, its azeotrope has a lower bp than with isopropyl ether. If the chloroform is thoroughly saturated with HCl, and then about 2-2.5mol of SO2 bubbled in, the theoretical yield would be 237.9g (2 mol) of thionyl chloride. I think it is probably safe to say that is a lovely, vivacious day dream somewhat removed from reality though. :D


[Edited on 9-1-2005 by Natures Natrium]

[Edited on 9-1-2005 by Natures Natrium]

[Edited on 9-1-2005 by Natures Natrium]




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[*] posted on 9-1-2005 at 08:41


Ok, got a question about activated C, since I have never really used such as a catalyst for anything. The carbon I have on my hands is preactivated (aquarium carbon) and claims to contain less than 2% water. Thus, is the soak in CaCl2 solution really necessary? Would doing so anyways help or hinder the catalysts activity? I intend to heat it under vacuum to drive off water either way.

Thanks,
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[*] posted on 9-1-2005 at 17:19
Need to find reference for Thionyl Chloride


Excess sulfur dioxide in conc Hydrochloric acid yields thionyl chloride.

SO2 + 2HCl = SOCl2 + H2O

Ref. JCS, 117, pg 1103, 1920
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[*] posted on 9-1-2005 at 17:28
Just an Idea


Perhaps if dry HCl is led into dichloromethane or chloroform then excess dry sulfur dioxide led into this mixture , the DCM distilled off, leaving the thionyl chloride.:o
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