teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
pyrosulfuryl chloride
I think the pyrosulfuryl chloride S2O5Cl2 should be an interesting compound for anhydrous chemistry.
The main article I red about it is http://www.jstor.org/stable/20022774?origin=JSTOR-pdf
Also by google site:sciencemadness.org I found this interesting pdf about one method of preparation: http://www.sciencemadness.org/talk/files.php?pid=171099&...
But I didn't find any associated discussion.
Does anybody have first-hand experience with this compound / attempts of preparation etc?
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
In the article "Über das Pyrosulfurylchlorid S2O5Cl2" Prandtl, Borinski there is an interesting equation:
8SO2(OH)Cl + 2PCl3 = 3 S2O5Cl2 + P2O5 + 2SO2 +8 HCl
The amazing thing is that P2O5 is the result of the reaction. Just imagine how "anhydrous" it is.
I am wondering whether are there other anhydrous chlorides which can react with chlorosulfonic acid by the same route.
|
|
|
Bedlasky
International Hazard
Posts: 1219
Registered: 15-4-2019
Location: Period 5, group 6
Member Is Offline
Mood: Volatile
|
|
I found this synthesis from SO3 and CCl4:
https://books.google.cz/books?id=fIyZAwAAQBAJ&pg=PT157&a...
This synthesis can be also used for making sulfuryl chloride and other polysulfuryl chlorides.
Maybe also HSO3Cl + SO3 or P4O10 works???
This stuff would be really nasty. I don't have experience with it but I often read about its analogue S2O5F2 in superacid chemistry books/articles. So
I suppose that S2O5Cl2 in HSO3Cl would be interesting superacidic system.
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
SO3 and CCl4 is a "classical" route which any man will try to avoid of course (COCl2 is a byproduct).
SO3 and CHCl3 is much better (CO as a byproduct).
These routes are favourite routes if you want to skip the purification step.
There are many other routes which always give chlorosulfonic/pyrosulfuryl chloride mix, they are not convenient for preparation on industrial scale
but could be quite good for experiments. Like that with chlorosulphonic acid and phosphorus trichloride, sulfuric acid and [P|S]xOyClz compounds etc.
There are a lot of equation and reversible reactions in system of SO3 and compounds of oxygen/sulfur/chlorine/phosphorus.
The point of my interest to pyrosulfuryl chloride is that this compound looks not as nasty as other in this family - mixed with water it forms "oily
layer", so the reaction is not violent at all but produce a water-scavenger as a result of the reaction - it is very interesting because it is the
anhydride of chlorosulfonic acid. Also the boiling point is quite high comparing to SO2Cl2. Also the interesting property is ability to dissolve SO3
without evolution of heat (if I properly remember that, you can check the articles).
I suspect that fluorine derivatives are really nasty just because they give HF in contact with the moisture.
[Edited on 27-7-2021 by teodor]
[Edited on 27-7-2021 by teodor]
|
|
|
unionised
International Hazard
Posts: 5102
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by teodor  |
The point of my interest to pyrosulfuryl chloride is that this compound looks not as nasty as other in this family - mixed with water it forms "oily
layer", so the reaction is not violent at all
|
That would be... remarkable.
And there's a reference here
https://haz-map.com/Agents/6923
which says it reacts violently with water.
I know which one I believe.
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
I wouldn't take a safety sheet as a reference for compound properties. Which is still good as a precaution especially when you don't know which
purity/age of the reagent you have.
From the article I mentioned in the first comment:
"
Pyrosulphuryl chloride is a colorless liquid, fuming slightly in moist
air and becoming turbid when added to a small amount of water.
It sinks in water as an oil, gradually decomposing
into chlorsulphonic acid, which in turn gives sulphuric and hydrochloric acids as final products.
Chlorine and probably sulphur dioxide may be formed in small amount.
"
There are two routes actually how this substance can react with water. It can accumulate water slowly forming chlorosulfonic acid which then reacts
vigorously or it can react calm way if it is pure and just mixed with water.
But it is just something from texts, not from a real experience.
[Edited on 27-7-2021 by teodor]
[Edited on 27-7-2021 by teodor]
|
|
|
unionised
International Hazard
Posts: 5102
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
Chlorosuplhonic acid reacts violently with water so...?
In any event, I suggest you start by assuming I'm right; if you later prove that I'm wrong, only my feelings get hurt...
|
|
|
Bedlasky
International Hazard
Posts: 1219
Registered: 15-4-2019
Location: Period 5, group 6
Member Is Offline
Mood: Volatile
|
|
I agree with Unionised. I doubt that pyrosulfuryl chloride would react peacfully with water. Rather more violently than HSO3Cl or SO2Cl2.
|
|
|
woelen
Super Administrator
Posts: 7976
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
Sometimes the reactions of compounds like these discussed here are surprising. I have SO2Cl2 and I have SO2(OH)Cl. SO2(OH)Cl is regarded as an
intermediate compound between SO2Cl2 and H2SO4 (which actually is SO2(OH)2). But when you look at reactions of these, then things are surprising:
- SO2Cl2 only reacts with water very slowly. If you add this to water, it form an oily layer at the bottom and it takes hours for a layer of just a
few mm thickness to dissolve in a large excess amount of water.
- SO2(OH)Cl reacts with water EXTREMELY violently. The reaction between sodium and water is tame, compared to that between SO2(OH)Cl and water.
- SO2Cl2 and H2SO4 do not mix and do not form SO2(OH)Cl. I ampouled 100+% H2SO4 and SO2Cl2 together and kept this sealed ampoule around for several
years already, and I shaked it vigorously several times. There still are two separate layers in the ampoule of the same size as when I made the
ampoule (I marked the line where the interface between the two liquids is).
Heating SO2(OH)Cl can lead to decomposition, with formation of H2SO4, SO2Cl2, S2O5Cl2 and loss of HCl. The resulting mix is much less reactive towards
water than SO2(OH)Cl.
So, I tend to go with teodor on this one. I expect the reaction of S2O5Cl2 with water to be fairly tame. I read that S2O5Cl2 is an undesirable
side-product in synthesis of SO2(OH)Cl and that it is very hard to obtain SO2(OH)Cl in a really pure state.
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
| Quote: Originally posted by woelen |
I ampouled 100+% H2SO4 and SO2Cl2 together and kept this sealed ampoule around for several years already, and I shaked it vigorously several times.
There still are two separate layers in the ampoule of the same size as when I made the ampoule (I marked the line where the interface between the two
liquids is). |
From the very informative article "Smoke-forming chemicals" by K.E. Jackson (1937) :
"At 170C the reaction
2ClSO3H <-> SO2Cl2 + H2SO4
is a reversible one, and after 72 hr the equilibrium mixture contains 1 mole of SO2Cl2, 1 mole of H2SO4 and 2.5 moles of ClSO3H"
Based on what I have red I would expect reaction between SOCl2 and H2SO4 with formation of ClSO3H / S2O5Cl2 / SO3 mixture, probably without heating.
And I think you already have proved that, woelen, if I remember it properly you have some demo of K2Cr2O7 + H2SO4 + SOCl2 on your website with forming
chromyl chloride which is usually formed when ClSO3H reacts with CrO3.
[Edited on 28-7-2021 by teodor]
[Edited on 28-7-2021 by teodor]
|
|
|
Bedlasky
International Hazard
Posts: 1219
Registered: 15-4-2019
Location: Period 5, group 6
Member Is Offline
Mood: Volatile
|
|
Woelen: That's interesting behaviour. I would guess that SO2Cl2 react with water violently, this really surprised me.
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
Based on the data of SO2 solubility in SO2Cl2 (solubility data series, vol. 12) - 32% my mass or 187 volumes in 1 volume of SO2Cl2 I would predict
that S2O5Cl2 should also do it pretty well, probably by forming -S-O-S- bonds.
The ability of dissolve SO2 as good as SO3 is a very interesting property of the solvent.
[Edited on 29-7-2021 by teodor]
|
|
|
woelen
Super Administrator
Posts: 7976
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
| Quote: |
"At 170C the reaction
2ClSO3H <-> SO2Cl2 + H2SO4
is a reversible one, and after 72 hr the equilibrium mixture contains 1 mole of SO2Cl2, 1 mole of H2SO4 and 2.5 moles of ClSO3H"
|
This is at 170 C. I did not heat my ampoule, it always has been at room temperature.
| Quote: |
Based on what I have red I would expect reaction between SOCl2 and H2SO4 with formation of ClSO3H / S2O5Cl2 / SO3 mixture, probably without heating.
And I think you already have proved that, woelen, if I remember it properly you have some demo of K2Cr2O7 + H2SO4 + SOCl2 on your website with forming
chromyl chloride which is usually formed when ClSO3H reacts with CrO3. |
You probably meant SO2Cl2 instead of SOCl2...
In my experiment, however, I did not add a mix of H2SO4 and SO2Cl2, but I added SO2(OH)Cl. The latter reacts vigorously with K2Cr2O7 and many other
salts.
https://woelen.homescience.net/science/chem/exps/HSO3Cl/inde...
I also did an experiment with SO2Cl2 and K2Cr2O7 (and also with CrO3). That reaction leads to a nice red solution, but nothing vigorous.
[Edited on 29-7-21 by woelen]
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
No, I mean that I suspect SOCl2 would require less heat to chlorinate/dehydrate H2SO4 to S2O5Cl2 / (OH)SO2Cl mix comparing with SO2Cl2 based on its
greater affinity to -OH groups.
But there is another surprise from this compound family. Dichlormethane also quite easily chlorinates H2SO4 to (OH)SO2Cl.
[Edited on 29-7-2021 by teodor]
|
|
|
woelen
Super Administrator
Posts: 7976
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
That latter thing is really interesting. Do you have a practical method of letting CH2Cl2 react with H2SO4 and getting SO2(OH)Cl? What is the CH2Cl2
converted to? CH2(OH)Cl does not look like a stable compound. Do you get CH2O (methanal) and HCl? The production of CH2O would also surprise me. That
compound is quite strongly reducing and SO2(OH)Cl is fairly strongly oxidizing, comparable to concentrated H2SO4 and I can imagine that this oxidizes
CH2O.
[Edited on 29-7-21 by woelen]
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
woelen, the article is attached.
I didn't try yet and I am a bit afraid of COCl2 formation. Reaction of CCl4 with hot oleum gives phosgene, but I suspect that small quantity is still
possible to get with CHCl3 (as you know, light can play some role) and, by this logic CH2Cl2 should be much safer in this sequence, but I have no any
reliable data for this yet.
Attachment: saljoughian1985.pdf (125kB)
This file has been downloaded 184 times
|
|
|
unionised
International Hazard
Posts: 5102
Registered: 1-11-2003
Location: UK
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by woelen | That latter thing is really interesting. Do you have a practical method of letting CH2Cl2 react with H2SO4 and getting SO2(OH)Cl? What is the CH2Cl2
converted to? CH2(OH)Cl does not look like a stable compound. Do you get CH2O (methanal) and HCl? The production of CH2O would also surprise me. That
compound is quite strongly reducing and SO2(OH)Cl is fairly strongly oxidizing, comparable to concentrated H2SO4 and I can imagine that this oxidizes
CH2O.
[Edited on 29-7-21 by woelen] |
I rather hope the formaldehyde is oxidised- (presumably to CO and /or CO2)
One alternative is the reaction given here.
https://en.wikipedia.org/wiki/Bis(chloromethyl)_ether
which says "It was produced industrially from paraformaldehyde and a mixture of chlorosulfonic acid and sulfuric acid."
|
|
|
teodor
National Hazard
Posts: 872
Registered: 28-6-2019
Location: Heerenveen
Member Is Offline
|
|
Reaction of SO2(OH)Cl with (paraformaldehyde) depending on conditions can give:
1. Methylene sulfate (dimer)
2. dichloromethyl ether (low temperatures, ~0C)
3. chloromethyl chlorosulfonate
4. dichloromethyl sulfate
For detailed description of the reaction paths and conditions for these reactions see the available (in the Internet) book "Chlorosulfonic acid. A
versatile reagent" R.J.Cremlyn (thanks, Bedlasky).
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
