Author Topic: Vesp's Random Expirement Thread  (Read 823 times)

Vesp

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Vesp's Random Expirement Thread
« on: June 08, 2009, 11:03:45 PM »
I figured a thread like this is a good idea. Sedit has one as well, and you guys are more then welcome to create your own.

I've decided to create one since I've been getting back into the lab lately and this might encourage me to do more things.

Recently I attempted making some crude phenol. It was a total failure and I think I ended up with only Salicylic acid and some black carbon like material.

I mixed ~20 grams of NaOH with 18 grams of ASA. The ASA  was purified from aspirin w/ denatured alcohol. I ground the two together, mixed them in a flask and heated with a torch. Water came off as the mixture was molten. I continued to heat it and it became solid, white fumes started to come off (which, the phenol should have been in the form of sodium phenolate, so I don't think this should have happened!) and it started to char and turn black in some areas. I decided that it was probably done, and so I dissolved some in water, added an acid and found a very fluffy white substance to form. Heating it was hoping it would melt at the temperature around which phenol would, and it didn't. It remained a solid until I tossed it.

So I've concluded that heating Sodium hydroxide and ASA together doesn't make phenol. I should have added less NaOH, and attempted to distill the phenol that would form. This would likley still lead to significant charring but it should work. I'll try it some other time.


Even more recently, I've broken apart 3-4 (can't remeber) D sized batteries, extracted the MnO2, ground it in a mortar and pestle and then heated with strong sulfuric acid and some sulfur.
The idea was to get MnSO4 with this reaction:

MnO2 + SO2 = MnSO4

H2SO4 + S = H2O + 2 SO2 ( or really, H2SO3 + SO2 but heat decomps the acid)

Also hot sulfuric acid tends to dissolve MnO2 anyways.
This reacted fumed off lots of white smoke, even (if not especially) before the addition of sulfur, and a decent amount of MnO2 seemed to dissolve. I added HCl to see if any was left, and there was a ton. Chlorine gas was evolved, though bubbles were not noted until vigorous stirring. The chlorine formed for a good hour before I decided to put in an air bubbled to encourage the Cl2 to leave the solution. The air bubbler was originally used for fish, or something like that.

The solution is sitting outside, about 1L worth, with the air still bubbling though it. I'll leave it till tomorrow or the next day to boil it a bit more to get some of the HCl, or chlorine out.

MnO2 + 4 HCl = MnCl2 + Cl2 + 2 H2O
Since there is an excess amount of H2SO4 in the solution.. the following occurs..

MnCl2 + H2SO4 = MnSO4 + 2 HCl

The HCl is either going to be reacted with more MnO2, or get kicked out of the solution, especially when I boil it in the next couple of days.

So, soon I should be left with a lot less MnO2, and a bunch of MnSO4 (or other sulfates of Mn) in a solution of sulfuric acid. Likely with carbon at the bottom. The top will just be separated, titrated, and then used for some oxidation thing I have in mind ;)

Soon, I will try a Nickel/Copper extraction from a solution of 25% Ni and 75% Cu - in their Nitrates that I have prepared.  (nickels were dissolved in dilute HNO3)
This will be a bit tricky, but I think it can be done, and for me at least, will be useful to be able to get Ni powder fairly cheaply. Ni powder could be used for Hydrogenation itself, electroplating onto materials for hydrogenation, or to get Ni hydroxide/oxide complexes with ammonia (probably forms?) which could be absorbed onto very fine activated, or reactivated carbon, reduced to leave very small Ni powder with a high surface area - again for hydrogenation.. of course.

Any suggestions on the best how to go about these things? or how to make that phenol?



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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #1 on: June 08, 2009, 11:18:45 PM »
For those playing with Mn compounds, dust, etc be careful of this:

http://en.wikipedia.org/wiki/Manganism

Seems pretty scary to me...

Quote
In initial stages of manganism, neurological symptoms consist of reduced response speed, irritability, mood changes, and compulsive behaviors.[2] Upon protracted exposure symptoms are more prominent and resemble those of idiopathic Parkinson's disease, which it is often misdiagnosed as, although there are particular differences in both the symptoms (nature of tremors, for example), response to drugs such as levodopa, and affected portion of the basal ganglia. Symptoms are also similar to Lou Gehrig's disease and multiple sclerosis.

Quote
The current mainstay of manganism treatment is levodopa and chelation with EDTA. Both have limited and at best transient efficacy. Replenishing the deficit of dopamine with levodopa has been shown to initially improve extrapyramidal symptoms,[21][22][23] but the response to treatment goes down after 2 or 3 years,[24] with worsening condition of the same patients noted even after 10 years since last exposure to manganese.[25] Enhanced excretion of manganese prompted by chelation therapy brings its blood levels down but the symptoms remain largely unchanged, raising questions about efficacy of this form of treatment.[26][27]
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Sedit

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Re: Vesp's Random Expirement Thread
« Reply #2 on: June 08, 2009, 11:53:20 PM »
Quote
MnCl2 + H2SO4 = MnSO4 + 2 HCl


This is claimed to not work well either. The MnCl2 will have to be precipitated as the carbonate from what they say over at SciMad. This does work very well and I have done it a few times to get a peach powder that turns brown after a while in the air. Personaly for ease I dont mind just heating the MnO2 strongly with H2SO4 even if it does yeild low. I think I may go and work up some of the left over shit though to recover and loses. The sulfur don't sound like a bad idea though I may give this a try.

What is the reaction of fusing MnO2 and sulfur directly?
------------------------------------------------------------------------------------------

Destructive distillation of paracetamol with NaOH is a standard for the home synthesis of phenol. You mix correct portions of ASA+NaOH and dry distill the Phenol off. Them white fumes you seen where more then likely the phenol you wanted leaving behind carbon. I have never done it but read many discussions on it.

--------------------------------------------------------------------------------------------------------------------


I did the Ni/Cu thing not to long ago. I did not use the nitrate though. You can make an oxidising acid by mixing 35% H2O2/HCl and the nickles will also dissolve. Nitrates would more then likely be a better bet but its always an option. I took this to dryness to leave green/blue crystals to rid the left over HCl and then dissolved them in H2O again. Added Al foil and the solution eats it and drops out copper and I assume nickle because there is a darker material then when normal copper is precipitated.

Is there a means of selective precipitation for just the copper to leave the nickle in solution? Im sure someone here knows the electromotive series off the top of there head. That would be nice because you can filer the copper and then make nickle oxide and pass it to a reducing enviroment. This could make very fine Nickle powder perfect for a catalyst.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #3 on: June 09, 2009, 12:24:31 AM »
I see no reason why HCl wouldn't be kicked off with H2SO4 when added to MnCl2. I bet it is, are you sure they don't think its a good method?

Quote
What is the reaction of fusing MnO2 and sulfur directly?

I thought about doing that, but I also thought it might end up being some sort of horrible flash powder so i didn't. I was afraid I might see some sort of ignition (flames, or det) with the H2SO4/MnO2 mix, but I did not.

MnO2 + S = MnS + SO2 would be my guess, but I bet it is actually pretty difficult to ignite, or get it to react properly.


Quote
Destructive distillation of paracetamol with NaOH is a standard for the home synthesis of phenol. You mix correct portions of ASA+NaOH and dry distill the Phenol off. Them white fumes you seen where more then likely the phenol you wanted leaving behind carbon. I have never done it but read many discussions on it.

Paracetamol? You mean Aspirin?
I'll distill some phenol in a while if that method works well. I'll add only enough NaOH to decarboxylate instead of also form the phenolate salt.

------------------------------------------------------------------------------------------

I did the Al foil separation with a Ni/Cu solution. The damn thing made water catalytically reacted with the Al also producing lots of hydrogen or something. Al hydroxide fell out, and the solution remained a light blue color - total bitch to extract so I decided Al doesn't work well for me to get Cu or Ni out of soln. I think I'll attempt Iron powder soon.

H2S is supposed to ppt Cu sulfide in an acidic solution, while Ni salts remain in solution IIRC. Only slightly acidic though. I tried this when it was really acidic and it didn't work. I don't want to mess with a lot of H2S either, so if I have to use this method I'll just forget about it.

Thanks for the input though, I hope to make phenol for making methoxybenzene using NaCH3SO4. In doing so, I hope it will create a greater interest in Sodium Methyl Sulfate for making mescaline, etc.






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Sedit

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Re: Vesp's Random Expirement Thread
« Reply #4 on: June 09, 2009, 01:16:49 AM »
No not Aspirin, Acetaminophen is what the destructive distillation is done on IIRC. Dont take my work for it but im 95% sure. There are some threeds at SM on this.


Quote
I see no reason why HCl wouldn't be kicked off with H2SO4 when added to MnCl2. I bet it is, are you sure they don't think its a good

Thats whats claimed. I also see no reason that O2 should not react either but thats what they say may be a matter of yeilds but if Mn carbonate reacts as quick as people say then theres no reason to not just add some bicarb to the MnCl2 solution to precipitate esspecially when it will leave behind your impuritys. Im pretty sure in that other threed in that dark place I posted the link for MnSO4 synthesis discussion.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #5 on: June 09, 2009, 07:11:10 AM »
I'll just have to see tomorrow. I'll read up on the link posted in the dark place.
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zzhuchila_clocker

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Re: Vesp's Random Expirement Thread
« Reply #6 on: June 09, 2009, 05:50:40 PM »
I dont remember if Mn(OH)2 is sensetive to oxidation and thus can hardly be obtained pure(or it concerns to some other metal hydroxide), but i think if you simply basify your MnCl2, decant the residue several times washing with water, and then acidify with H2SO4, you can obtain MnSO4.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #7 on: June 10, 2009, 06:12:52 AM »
I don't want to waste all that base just to make the salt that will form if given enough heat/time.

I've never reacted HCl with MnO2, but it turns out heating makes it react, while at room temperature it hardly creates chlorine at all. I was going to boil away the left over HCl today, but upon heating tons of chlorine was produced. I wasn't prepared, and it was very annoying.

I'll just let the MnO2 fall out, boil away the HCl in soln and then recycle the remaining MnO2. I might distill the HCl in the solution right now just to conserve chemicals, and to prevent Mn compounds getting kicked into the air. I don't want Parkinson disease or anything like it. 

Right now this is what the horrible solution looks like. The first picture is a bit of it being heated, can you see the chlorine gas?

The bottom is the solution recently agitated so it appears almost completely black.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #8 on: June 10, 2009, 09:55:30 PM »
I've boiled more of the MnO2/MnSO4/H2SO4/HCl mixture and lots of chlorine was let off, the solution now is much more clear, but still pretty dark. I'll wait longer to see if a significant amount of MnO2/other crap will fall out.


Right now though, I am going back with my mess of Al(OH)3, Ni, Cu, + various salts in solution that I messed up with a long time ago and I am going to attempt to physically extract the Ni from the metal powders I am extracting from the mixture right now.

I was thinking about the "gold penny" experiment that coats a copper penny with zinc. This is done by adding a clean penny to a solution of NaOH and zinc in it. That is when heated and the Zn and Cu alloy.
http://www.chemistrylecturenotes.com/Brass_Penny_Lab.htm

Well, figuring how Ni and Cu are just to damn similar, I think you could coat Ni powder with Zn in the same way, The powders could be heated in an inert atmosphere forming an Ni/Zn alloy.

It seems like this alloy, which is probably a nice powder could then be reacted with hydrochloric acid to form some sort of raney nickel material. However, if it were possible I think I should be able to find a lot of information on Zn/Ni alloys for producing sponge metal catalyst, right?
Well, I can't find anything on it, can you? It seems useful, but maybe there is a reason it might not work.

I guess the alloy might react with hydrochloric acid. However if it is a powder with already a decent amount of surface area, it should.

The other thing might be some weird electrochemical cell forms and dissolves the Ni. I doubt this also.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #9 on: June 10, 2009, 10:53:50 PM »
Here is a picture of the stupid Mn solution boiling, and then the solution was it was allowed to cool and have everything fall out of it.

Now it is a light brown/tan murky color. I'm not sure what is turning it light brown, any idea?
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Sedit

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Re: Vesp's Random Expirement Thread
« Reply #10 on: June 10, 2009, 10:56:46 PM »
Not sure if you will be able to achieve the Ni/Zn alloy but if so that would be awsome. The idea that it would make a form of randy nickle is intreaging and something I woundered about other Ni alloys so keep us updated. If it burst into flames when you try to dry it then im going to have to make some ;D.

This hear states that no reaction occurs between HCl and Ni.
http://jchemed.chem.wisc.edu/JCESoft/CCA/CCA3/MVHTM/VOLTAGE/VOLTAGE1.HTM


Thats it vesp. The bottom one is what the solution of MnSO4 looks like the top is a form of Mn(IV) I think. Thats what the Neograviton looks like and after the Mn(IV) is hydrolysised by boiling in 60% H2SO4 it turns into the pink Mn(II). If you toss that mixture right now into the anode of the electro chemical cell it will turn pink---purple----Black. I say boil it down and try to get it to crystalize to the pink MnSO4 so you know exactly how much H2O is in your cell. I feel that may be one problem Im having at the moment amongst other so Im going to do the same with my solution... right after I make some paraformaldahyde with it because its already dark purple ;D
« Last Edit: June 10, 2009, 11:01:47 PM by sedit »
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #11 on: June 10, 2009, 11:11:51 PM »
Yeah, Ni doesn't react with HCl, so I guess it should work assuming the alloy forms and THAT reacts.

Ah that must be the problem! well, that is if there is one. Nickel and Zinc must not dissolve in each other very well to form an alloy with decent Ni concentration . I will hopefully still try it if I can get the damn Ni and Cu to separate.

I'm afraid the Ni and Cu powder might start allowing back together.

Instead maybe what should be done since Al and Ni obviously dissolve each other easily is to get a solution of Nickel sulfate and add Al powder. I think you would want the aluminum particles to be kind of coarse so that they get coated in Ni instead of completely dissolved by the Ni sulfate. Then you would want to figure out how much aluminum to use for a certain amount of nickel sulfate.

Quote
The most common starting alloy used in industry contains an equal amount per weight of nickel and aluminum, incidentally, the same ratio Murray Raney used in his discovery of Raney nickel.
- wiki

I'll do the math later to figure out how much Al to add to Ni Sulfate to get the weight ratio of 1:1 Al:Ni but you get what I mean.
I would probably end up using blenderized aluminum foil anyways, since I don't have more then 10 grams of Al powder.

Is there a decent way of powdering aluminum from foil? Perhaps mortar and pestling blenderized Al "powder" with sand, and then physically separating? Eh I'll worry about it when it is a problem I guess.

Either way, it seems pretty exciting. woelen from SciMad demonstrated that the gold penny forms after 2 years at room temperature.




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Sedit

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Re: Vesp's Random Expirement Thread
« Reply #12 on: June 11, 2009, 12:01:46 AM »
Quote
Is there a decent way of powdering aluminum from foil? Perhaps mortar and pestling blenderized Al "powder" with sand, and then physically separating? Eh I'll worry about it when it is a problem I guess.

Ball mill.

Take some Al foil and put it into a rock tumbler with some ball barings. Works like a charm. Careful though I have heard reports that this can ignite but I never had a problem with it. I also did small batches so just be careful expecialy when opening it because when it hits oxygen all hell can possibly break loose.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #13 on: June 11, 2009, 12:07:39 AM »
Yeah, I only have a rock tumbler that holds maybe 500ml. I guess that would work pretty well actually.
I'll try that, noisy little sucker though.
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #14 on: June 11, 2009, 01:36:06 AM »
Talking about the possible need for alumium powder was enough for me to grind some in a little blender, got it down to about the size of an ant, and then turn on my rock tumbler with a handful of metal balls about 1/4inch in size.

Hopefully this will be a decent way for me to get aluminum powder.
Sedit, how long does it take for you to get aluminum powder using a ball mill?

Given we use different grinding media and RPM's as well as other variables, but is it days or weeks?
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Re: Vesp's Random Expirement Thread
« Reply #15 on: June 11, 2009, 01:40:39 AM »
Yeh that will work, just get some steal barrings and let it run for a while. Im not joking though when I say that it can explode under the wrong conditions and where as I have never had a problem you can feel it heat up especialy when the powder hits air. Just keep this thing out of the way of things that can catch on fire. When done you will be left with a VERY fine black Al powder that is highly reactive. I got the idea from roguesci and they have a few threeds there on it. They use this for thermite IIRC.

Hmm I wounder if done in a solvent if this could work to make Organoaluminum materials. Maybe a future topic of my random experiment threed when I get everything else on my plate cleaned off.

[edit]

it varys but Couple days at the most. I have only ever done it a couple of times so experimental data just aint there to give ya.
« Last Edit: June 11, 2009, 01:42:25 AM by sedit »
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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #16 on: June 11, 2009, 02:01:03 AM »
I see thanks. I think I am going to upload lots of pictures to the various things I do. Its easy, and I think it'll make it more exciting. I'll add pictures to this Al process later for kicks and giggles but right now I am working on blenderizing a lot of aluminum foil.
I don't think it is possible to have to much Al powder. It is a reactive metal and has lots of uses. Practical uses and noob type uses such as mixing it with a strong oxidizer.  :D

I used to be into pyro (before I had the rock tumbler) and had read a lot about the process of making aluminum powder. It is starting to come back to me a bit.

It becomes pyrophoric when it is ground to long, I think oils might be added to make it safer.

It might be interesting to mix in a little wax/kerosene to prevent oxide layers from forming causing it to become more reactive. The waxy material could be washed off with hot dry acetone or something to get a really reactive form of Al powder that may be good for organoaluminium reactions.

I'll have to read about organoaluminium reactions, I know at least with the grignard reaction using magnesium you can make a carbon-carbon bond. Since Mg oxidation state is +2, with organo-Al, do you get 3 carbons to bond forming since Al is +3?


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Vesp

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Re: Vesp's Random Expirement Thread
« Reply #17 on: June 11, 2009, 03:56:30 AM »
Some out of focus shitty pictures (as always  :-\)  just for the hell of it, hopefully they are self explanatory... despite the fact I am going to type up crap anyways..

First Picture:
 My black solution is now yellow tan - wtf is the white stuff on top of the black stuff?

Second Picture:
Seemingly very fine aluminum powder that I collected on my finger after blenderizing a bunch.

Third Picture:
Aluminum foil after it met the blender

Forth Picture:
 My little piece of shit rock tumbler that was broken and over heating for a while until I fixed it. Notice the size by comparing it the plug in the picture.

Firth Picture: The inside of the ball mill/rock tumbler with all of the Al foil and metal balls.

Yep that is it for today! I would have pictures of my attempts of extracting Ni powder from Copper powder using a few gnarly neodymium magnets, but I was a clever little soul and forgot to bring them over. They were most of the reason why I went there to begin with! Either way, I guess today was pretty productive.

I attempted to make flash powder using some Al crap I mortar and pestled for a while, and then mixing with a 5:3:2 ratio of KNO3:S:Al - I added excess Al since it was very coarse and it totally failed - didn't even hardly burn, which was to be expected considering the Al sucked, and  I got the ratio off some stupid youtube video that kept popping up.





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Sedit

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Re: Vesp's Random Expirement Thread
« Reply #18 on: June 11, 2009, 04:10:36 AM »
That looks just like my two rock tumblers.

The black tan solution thats the MnSO4 right?

Your black is more then likely either Carbon or MnO2.

Since what ever it maybe is denser you could always agitate it till its all suspended and then as it settles wait till the white started to drop and then right away slowly decant it as to not disturb the layer to much. Its a bit tricky but works for many substances.
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Re: Vesp's Random Expirement Thread
« Reply #19 on: June 11, 2009, 04:31:53 AM »
Nice to know that the rock tumbler will work then! :D .. unless you use something else, and them for actually rocks? haha

Yeah, I'm not to worried about it, anything that precipitates isn't MnSO4 and thats all I want.
I'll just purify the solution, grow some crystals, and then re-dissolve in some water and begin electrolysis.

I'll keep the bottom stuff since I believe it is mostly MnO2 with some graphite.

With the left over MnO2 I have a little experiment I think I might do If SO2 reacts with MnO2 to form MnSO4 in decent time and yield.
  I think I will get a bucket and put some wet MnO2 on a stand, and below it a decent amount of sulfur. I'll ignite the sulfur, but the bucket lid on, and wait till the sulfur hopefully uses up most of the oxygen, and produces an atmosphere strongly of SO2. This will get dissolved in the water, which is absorbed onto the MnO2 and then react.  It is kind of a stupid way to go about it, but for some reason this little simple chemistry is a lot of fun and I figure it is better then heating the shit out of sulfuric acid till it fumes.

After it sits for a few hours, I'll just add more fresh air, re-ignite the sulfur and get more MnSO4.

Except for I am not to sure SO2 reacts with MnO2 at least at the conditions I would like it to. I added a mixture of Sodium Bisulfite and Sodium hydrosulfite to a solution with MnO2 suspended and absolutely nothing happened. I could smell SO2 though. The hydrosulfite/Dithionite could have messed things up a bit though.
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