12AX7
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Oxidizing amines?
I've got to believe there's a thread applicable but searching is in vain...
I was thinking of taking something with NH groups, like an ammonium salt, or urea, or whatever, and oxidizing it with manganese, (III) or (IV). I
don't have any Mn(7) on hand. Else, I could try something else, like CrO4-- (which I haven't crystallized yet, so don't have any pure ATM), or OCl-,
though that would tend to make chloramine (or hydrazine), huh? Or what if I put urea in an anode cell with say, 20% sulfuric acid solution?
Tim
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DeAdFX
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I have potassium permanganate, some ammonia compounds and a bulk urea(40LBs+ left). What did you have in mind perhaps I could be of some help. By
chance are you trying to oxidize NH2 to NO2?
Edit: I forgot I also have glycine(NH2 CH2 COOH)...
[Edited on 5-5-2006 by DeAdFX]
[Edited on 5-5-2006 by DeAdFX]
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12AX7
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Yeah, something like that. Odd, I forgot to explicitly note that I want to make nitric acid without copper catalyst and brown gasses. Well now you
know.
Any N-H thing should do, but I do happen to have a couple pounds of urea on hand, so that would be a good candidate.
Hum.. lemme see...
Assuming it all "burns":
H2N-CO-NH2 + KMnO4 = 2NO3- + CO2(g) + 2H2O + K+ + Mn(2+)
Lots of oxygen, 9/4ths mol KMnO4 looks right?
H2N-CO-NH2 + 9/4(KMnO4) = 2NO3- + CO2(g) + 2H2O + 9/4[K+ + Mn(2+)]
Slightly more than two moles, so from neutral, if it proceeds, it should end up basic with a little MnCO3, some CO2 gas, and mostly KNO3 in solution.
I'm guessing it'll have to be acidic to drive the KMnO4 towards oxidizing, especially down to (2+), instead of 3 or 4. If it were acidic, the 3 or 4
state might still react, so it shouldn't be prone to running away, knock on wood.
Molecular weight, 2*14 + 4*1 + 12 + 16 = 60g/mol urea, and 39 + 55 + 4*16 = 158g/mol KMnO4, so 158/60ths is the ratio. Plus a few bits of sulfuric
acid to get it going.
I would appreciate using your laboratory vicariously, thank you 
If it reacts, after it seems to be done reacting (not much purple?), test the gasses for N2 or CO2, and the solution for nitrate.
Tim
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DeAdFX
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Plan/procedure
I will try this over the weekend in the mean time I have some homework to do.
Hmm... I think what I will do a 1.58 grams of potassium permanganate to .6grams of urea ratio. I recently acquired some volumetric flask so I will
put those to some use. I will make a 1molar solution of both chemicals. The
experiment will be conducted at out door temp (summer so that will be about 20-25c dpending on time of day).
Questions...
I have slightly discolored rooto sulfuric acid. I am under the assumption it is 90-98% conc. Should I dilute the acid and add it to the KMnO4/Urea
mix or just pipette in the conc sulfuric acid via straw. I think 1/4 ml might be good enough for the starting ratios. This will be difficult to
measure as the only good small mL measuring peice of glassware I have is is a 25mL graduated clyinder.
Misc comments.
By "vicariously" I'll assume you will want pictures. Second off I think that if this experiment is conducted at higher temperatures a small portion
of Ammonium Nitrate might form (assuming the equation is correct). Urea is hydroylsis is increased(not by much I believe) at higher temperatures. At
lower temps I assume potassium nitrate to be dominate.
[Edited on 6-5-2006 by DeAdFX]
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12AX7
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I think diluted acid, maybe 20% would be good, just to drop the pH.
If anything interesting happens I'd like to see pictures, sure.
Yeah if it hydrolyses, it would tend to get more basic, all the more reason for acid needed for this reaction.
Tim
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Madandcrazy
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Surely a couple of amines can oxidized when it is the correct
oxidizer/solvent to the reaction and the amin component is not decomposed or is stable for this.
I belive any different methods existing, when a amin should oxidized i a aromatic ring  with H2SO4/H2O2, it is certainly more easy as when a azin component should oxidized.
What should you do when for instance the reaction with the glycin and the chloroamin should oxidized to the follow ?
COOH-CH2-NH2
-->
COOH-CH2-NHNH2
-->
COOH-CH2-NHNO2
It would possibly give not the desired end-product, but it would give maybe glycin anhydride.
Intersted is maybe when chloromethane should treated with
ammonium acetate and dilute HCl to aminomethane, is it not eventually the endproduct Cl-CH2-NH2 ?
Should this way walk too when some components was easyer threated with bromin, maybe
the glycin anhydride should brominated to
dibromoglycin anhydride -->
diaminoglycin anhydride -->
2,5-dinitrogylcin anhydride
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12AX7
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...What the hell do chloramine, azin [sic] and bromo- products have to do with the subject? Alright Madandcrazy? Just what is your point? Do you
have *anything* on topic to add to this thread?
Tim
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DeAdFX
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| Quote: | Originally posted by Madandcrazy
Surely a couple of amines can oxidized when it is the correct
oxidizer/solvent to the reaction and the amin component is not decomposed or is stable for this.
I belive any different methods existing, when a amin should oxidized i a aromatic ring with H2SO4/H2O2, it is certainly more easy as when a azin component should oxidized.
What should you do when for instance the reaction with the glycin and the chloroamin should oxidized to the follow ?
COOH-CH2-NH2
-->
COOH-CH2-NHNH2
-->
COOH-CH2-NHNO2
It would possibly give not the desired end-product, but it would give maybe glycin anhydride.
Intersted is maybe when chloromethane should treated with
ammonium acetate and dilute HCl to aminomethane, is it not eventually the endproduct Cl-CH2-NH2 ?
Should this way walk too when some components was easyer threated with bromin, maybe
the glycin anhydride should brominated to
dibromoglycin anhydride -->
diaminoglycin anhydride -->
2,5-dinitrogylcin anhydride |
I don't believe glycine has an anhyride counterpart/analog(sp) to acetic acid. That would elminate the amino acids unquie ability of being
base/acid(amphoteric) [sp].
Anyways 12AX7 stated he wants the NO3-. This will be use for nitric acid. Unless the R-NH-NO2 can be hydroylsised(sp) to R-NH2 + NO3-?
I will try the experiment right now while I still have a few hours of light left.
Carried out experiment... Jack shit happened. Woohoo purple water. How long is this reaction suppose to take? Will get pictures sometime
[Edited on 7-5-2006 by DeAdFX]
[Edited on 7-5-2006 by DeAdFX]
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DeAdFX
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Ok here are two pictures(lazy). They are a comparison of when all the chemicals were added together(5 or so mins in) and about 18 hours later(half
assed guess). Second off it is taking forever to upload images. Fucking Comcast.
http://img55.imageshack.us/img55/559/oneforth2gv.jpg
http://img363.imageshack.us/img363/441/oneforth29ad.jpg
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12AX7
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Thanks.
Does it smell like anything? Did it ever say, heat up?
You might try more (or stronger) acid.. not so much to make Mn2O7, but getting close might push up the oxidation power...
Tim
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DeAdFX
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I did not notice a heat increase or smell. I am not familiar with Mn2O7 so I am cautious of adding more sulfuric.
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chemoleo
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I am not sure what you are expecting from this.
Synthesis of nitroalkanes is possible using KMnO4, but normally the NH2 is attached to a tertiary carbon for this to work properly. Primary amines
won't work, you'll get full oxidation to the acid, and gasses. (https://sciencemadness.org/talk/viewthread.php?tid=2995)
The same is likely true for dichromates.
About lower manganates - I don't know. I don't think it will work regardless. If you are questioning on such a level, I suppose you should test
Fe2+/Fe3+, Pb2/4+ etc... of which none will work for sure...
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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12AX7
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Well, I would think Pb4+ would work, it's pretty strong ain't it? Strong enough for Fe6+ I read?
If you look up, you'l note acid is exactly what I want.  Not nitro-anything.
(I wouldn't expect "dinitrocarbonyl" (O2N-CO-NO2) to be too stable, anyway.. although it sounds like an interestingly explosive oxidizer if it can
exist.) I want the (- or =)NHx part completely oxidized to NO3-. It seems to me urea should be a good choice, since the -CO- is already pretty
reactive and should be pushed to CO2, leaving NH2 radicals to suck up the oxygen around. Second in line I would pick ammonium compounds.
Tim
[Edited on 5-7-2006 by 12AX7]
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Madandcrazy
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Something to my last replay. 
Is it maybe possible oxidizing a amin in a aromatic ring with perchloric acid and sodium amide without forming a chlorate to form eventualy a -N=NH2
compound when the process with a substitution of a dinitramide salt and a carbonate is combinued ?
[Edited on 16-5-2006 by Madandcrazy]
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