"anything that precipitates isn't MnSO4 and thats all I want. "

No this is not the case. The pink/white/orange shit at the bottom is MnSO4 thats why I was explaining a means of getting it out of the black stuff. The solution can only hold so much and you started with black Mn(IV) and droped it down an oxidation state to Mn(II) so some of the MnSO4 will more then likely not dissolve the way you want in the cold H2SO4 and precipitate as a solid. What ever the case try to save the light precipitate. That will be purple after running in the cell.

Sorry my explenation of science is way worse then my understanding of it but you get the point.

This explains why MnO2 didn't react with my bisulfite/hydrosulfite mixture:

Sulfur dioxide, in the presence of sulfuric acid, reduces the precipitated manganese dioxide to the soluble sulfate; the removal of this large quantity of flocculent material greatly facilitates separation of the heptanoic acid. The addition of sulfur dioxide requires about two hours; an excess is to be avoided. Sodium bisulfite may be used if sulfur dioxide is not available.

-- http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2p0315

I didn't have any sulfuric acid in it. this might be a decent way to make MnSO4.

I'll add pictures of what I did. The SO2 method seems to work pretty decently with what I had left over, which was probably activated MnO2 since it had reacted quite a bit with acids, etc.

I got a water bottle, added my mixture of H2SO4/MnO2 and the other shit, tossed in Rust out, or whatever it is called - containing Sodium bisulfite and sodium hydrosulfite as the only ingredients, and screwed on the lid as fast as I could. It wasn't fast enough and I got a good face full of SO2. The bottle built up pressure and started to scare me a bit since this bottle was so flimsy, I wish I could have found a coke bottle, and then I just let it sit for a while and I shook it often.

The black water started to turn milky white, and after a while I poured it into a beaker and let it separate. black on the bottom, and white on the top. I'll get a picture of that soon - apparently it couldn't hold anymore MnSO4 and that was probably the white precipitate.

Anyways, I was a bit resistant to use much of my rust out despite it being super easy to get and pretty cheap since I have plenty of MnSO4 right now. about 200ml of a wet white powder, 150ml of a yellow saturated solution of MnSO4, and a little bit more in another beaker, maybe 50ml of the wet powder - but with carbon dust in it.

its solubility at 24*C is almost 40grams per 100ml so I probably have 150+ grams or more something like that, I don't know.

I think I might wash the crystals with alcohol to get rid of the remaining acids and so they dry more easily.


Oh also I have extracted some impure Ni, but i think it is mostly Ni from the Ni/Cu powder using my magnets.
sure was a messy process.

Also my Al foil in my ball mill has actually gotten larger from when I first put it in so thats not even cool.
 

First Picture:
 H2SO4 added to a melted, but now cooled mixture of random amounts of KNO3, NaHSO2, Na2S2O4, and NaHCO3.
The reaction with heating probably went something like this:

NaHSO3 + NaHCO3 = Na2SO3 + H2O + CO3
Na2SO3 + KNO3 = KNO2 + Na2SO4
Not sure how the Na2S2O4 reacted, but it didn't seem to prevent the chemicals from making KNO2.


Second Picture:
H2SO4 added to impure KNO2 that was prepared by heating a 2:1 KNO3:C mixture on the stove till autoignition. This wasn't a horribly fast reaction (most all of the contents, remained in the metal container. The mixture that was decently powdered, and probably would give more pure KNO2 if it were ball milled for a while. I have about 115, but now likely more close to 110 grams of KNO3/C mixture with a bit of excess KNO3. I figure excess KNO3 is better then carbon, but I'm not to sure why.

Third Picture:
I've also rinsed my MnSO4 with alcohol to cause any left in solution to precipitate, to free it off unwanted acids, and to encourage it to dry - since it helps pour out the water.  I think it will be dry soon and only be slightly acidic from left over junk acids.

Once it is dry, I'll dehydrate it a bit and then heat it with the correct amount of H2SO4 (~93%)

Question: What is the best way to electroplate lead metal on to some other metal?
Would copper sulfate work with a lead electrode? It seems like it may.

Thank you, and I may try to test using Pb, but I was just going to fractional crystallize some shit, and maybe to a weird gas titration thingy with an ammonium salt. I honestly don't care that much though since I have enough nitrite for what I plan to be doing with it. Close to say 200 grams of the impure stuff?

Anyways for what I did today:
Out of 116 grams of KNO3/C mixture I obtained 93 grams of solid white material after heating it on the stove forever -then I ignited it since it was to stressful to watch and I filled the shed white a white smoke that smelled of burnt black powder.

It was a 110grams KNO3 to 6 grams carbon. I split a lot since I took it from my mortar and pestle, to my ball mill which leaked powder like a son of a bitch, to the funnel, to a mesh thing to separate the metal balls, and finally to the pot. After it had reacted and cooled, I lost a few crumbs again.

2 KNO3 + C =  CO2 + KNO2

I used 9 grams excess KNO3, and the stoichiometric amount of carbon needed to reduce 101 grams of KNO3 to KNO2 - the theoretical yield being about 85 grams.

85+9 = 94 grams

I'm sure I lost more mixture to have lowered my yield, also the dust was kicked into the air, and K2CO3 likely formed which could account for some of the mass.

I dissolved this in boiling water along with my other nitrites I had made and noticed that a shit load of iron from my walmart special crucible had went into the mixture, and was a bit disappointing since some how the solution was lightly green with flocculation brown material.

Picture 1: The mixture after ball milling felt like recently fluffed up flower. I put it in the metal bowl and heated it up on my stove.

Picture 2: A video of the reaction, I put a pan over it, to prevent much smoke and loss of stuff, but I recorded this first with my camera.

Picture 3: The pan over the reaction, holds in junk, holds in heat, blah blah

Picture 4: Last little bits of carbon bubbling but not flaming, etc.

Picture 5: It being cooled in a pan of water. If you cool it, it can cause the solid KNOx to crack since the pan apparently has big difference when it comes to thermal expansion and it makes it easier to get out. Poping up off some of the KNOx will probably happen on the edges.

No picture of the solution made, or the test of it. The test was positive and similiar to the other nitrites I have with orange brown fumes.

That MnSO4 looks mightly fine there vesp. Alot more then I have at the moment. Now throw that shit into a Ecell and let me know how happy you are when it starts to turn pink Grin

I will soon! As soon as a construct my sexy Ecell. Do you know how to electroplate lead?
I have a lot of lead chunks, but I'd like to have a lot of surface area, and not deal with melting it into the shapes I want. I was thinking of just electroplated a bunch copper wire, or perhaps even a screen? idk I guess surface area doesn't really matter does it? I was thinking it did.


I have mostly dried all of my purest MnSO4 and weighted it to be 270 grams. It smells of acid, alcohol and other things so tomorrow it should be totally dry and probably a bit less.
I wanted to see how much MnSO4 I get so I can calculate yield and try to make a really nice cell. Hence the process of getting it out of solution and all that shit just to put it back in again.

Oh and I'll let you know how happy I am when it turns pink or black or whatever color it is supposed to turn.  You can also count on a unnecessary amount of photo's also - since I think people enjoy photos of stuff.

I am using KNO3.
So 101.1g/mol
vs 85g/mol KNO2

EDIT: Oh also I used 110 grams of KNO3, and the mix was about 116 grams. I like this method because it could be scaled up really big for cheap and it is easy to and safe to do from what I can tell.

Heh, excess will lead to lots of carbonates so only add a little excess since it will be plenty hot for the KNO2 to get reduced more so. I think slower reacting carbon - pet store activated carbon perhaps, might be better doing it your way. I like to have it mixed though really fine. I think that is important to prevent to much carbon in a single place, which wouldn't produce XNO2 at all and just carbonates.


According to my quick calculations 300 grams of MnSO4 (roughly what I expect to get everything combined) will produce almost 470 grams of Mn(SO4)2, which should produce about 190 grams of benzaldehyde or 190mls of it. These figures were mostly rounded up so it is probably closer to 180 something, and of course it would produce  the molar equivalent of whatever aldehyde you'd want to make at the time from a methyl group, and I guess it would make twice as much from an alcohol, eh?

Acetaldehyde has been on my list of things to make for a while.

Thank you.
Is there any advantages to using MAA over just MnSO4? Is it able to oxidize more or does it just get rid of the need for a partitioned cell? That alone is enough, but I am curious if it has a higher oxygen content or whatever?


This is a little snippet from CycloKnight on SM.

I use approximately 1Kg of manganese ammonium alum, made by adding manganese sulfate to sulfuric acid (60%+) which already has an excess of ammonium sulfate dissolved in it. The molar ratio for MAA is 2 moles manganese sulfate to 1 mole ammonium sulfate. It is a orangy-yellow precipitate. When you pass a current through it - it oxidizes and turns dark red. Its really cool to watch, you see the dark red pouring off the anode, gradully turning the yellow mix dark red. It lasts a long time, I've never worn it out - getting used over and over and over again!
The ratios (from the patent, scale down accordingly) are: 47.5 Kg mangano-ammonium sulfate, 45 Kg water, 79Kg of 98% sulfuric acid.
The reaction mix is heated to 50 C, and with stirring 4Kg toluene are added. When the dark red solution has turned yellow again - reaction is finished!!! The solution REAKS of cherries!
The patent says steam distil, but don't. Use solvent extraction, the steam will leach out your acid from the mixture. The product (from 4kg toluene) is 3.7Kg benzaldehyde, 0.6 Kg toluene, of course if you are using 1Kg of oxidant instead of 47.5 then you will get about 100ml or so.
My experience is that this is a little on the high side, but that may be due to the impurity of the MAA I'm using (i didn't isolate the yellow precipitate before making up my electrochemical solution, I just added molar ammount of manganese sulfate to excess of ammounium sulfate in sulfuric acid)

also heres a shitty picture of a lead plate I made.. uhh BFD I know, but whatever, surface area is good, right?

I think I will make the MAA. I'll need to recrystallize and purify some ammonium sulfate fertilizer soon then.

Also my KNO2 solution now has nice white crystals that I need to grow just a bit bigger (getting soln. colder) and then I should have some decently pure material for testing.

Oh by the way, it is mentioned that eugenol can be oxidized using MAA. Do you think Resveratrol could be oxidized to 3,5-dihydroxybenzaldehyde along with another aromatic.

If so, I could imagine resveratrol being useful, especially if the 2 OH groups would encourage halogenation to occur at the 4 position? Eh, just thinking out loud.

Is there any advantages to using MAA over just MnSO4? Is it able to oxidize more or does it just get rid of the need for a partitioned cell? That alone is enough, but I am curious if it has a higher oxygen content or whatever?

Yeilds. 10% higher and up reported in patants ect.. IIRC. I think it was somewhere along the lines of MAA 80%-85% while the Mn(SO4)2 reports quantitive so it must be 95% and up. The ammonia sulfate is there to protect the charge and prevent it from reacting with the cathode. The divided cell is not much of a problem at all if you ask me and its more then likely just a fear of the unknown your experiancing at the moment. I had the same thing before swithich to divided cells because I thought that they where a whole different creature then an undivided cell but in all reality they are just as user freindly as the next.

Carbon also should work in both of them divided or not. Maybe even stainless steel but lead was the best thing I had on hand and its known to give repeated results. When batching sodium persulfate carbon electrods get degraded rather quickly compaired to the lead electrods that can just keep going and going with no sign of corrosion. I would like to start experimenting with DLC electrodes but I feel these are a bit out of my leage at the moment. This may also just be another case of fear of the unknown though also.

Extreamly high density currents in methanol and some people talk about DMSO but I dunno. But the idea of synthesising a form of diamond is just fucking cool. Plus they can withstand everything damn near.

Carbon MIGHT work here I dunno. You can with ease take that circle of Lead you have there and cut it into shape if ya want also.

I want to try to screw with DLC(Diamond Like Coating) Electrodes just to get my dick wet and try to brush away some of the fear of it being out of reach. Almost every thing I have ever thought that about has proven to be atlest a little bit within my grasp so its worth a shot.

So your going to put the MnSO4 solution on the outside compartment correct?

Is that a carbon rod in the pot there?

Looks good. Very large, How much oxidiser will you be working with at a time?