Flip
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Sodium Hyponitrite
So I've just been sitting around looking at my reagents and I was wondering if there is anything cool I can do with sodium hyponitrite?
I could use it to make (tertiary) organic hyponitrites, but to what end?
I need ideas for a cool experiment to quell my boredom. 
[Edited on 4/26/09 by Flip]
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DJF90
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I had not heard of "hyponitrite" before you had mentioned it, but based upon what I have read then what you have is NaNO right?
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panziandi
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there are many nitrogen-oxide derived acids and salts not only nitric/nitrates and nitrous/nitrites. I have an inorganic text (can't recall for the
life of me what it is) which has a nice section dedicated to their preparation, properties and reactions. I will try and have a look see what is
listed in there (it's not really an area I am clued up on or interested in!)
A quick search of JACS reveals a paper (I haven't read fully) which uses silver hyponitrite and reacts with t-alkyl bromides and trialklsilyl
chlorides to form the dialkyl hyponitrites etc.
Navamoney Arulsamy, D. Scott Bohle, Jerome A. Imonigie, and Elizabeth S. Sagan, 2000, "Correlation of the Product E/Z Framework Geometry and O/O vs
O/N Regioselectivity in the Dialkylation of Hyponitrite" J. Am. Chem. Soc., 122 (23), 5539-5549
[Edited on 27-4-2009 by panziandi]
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JohnWW
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That, NaNO, would be sodium nitrosyl, or nitroxide, containing the NO- anion, -N=O . It would probably be formed by direct reaction of Na metal with
gaseous NO, which contains an unpaired electron, although such a reaction would be highly exothermic. It could probably be used in organic synthesis
to introduce nitrosyl, -NO, groups into electron-deficient parts of molecules by nucleophilic addition.
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Flip
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Sodium hyponitrite I believe is Na2N2O2.
I'm just wondering if I should keep it around or if it could be useful someday. I would hate to throw it out only to find I could have used it. I'm
like a pack rat that way.
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Sauron
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How stable is it?
If it has a long shelf life, just keeping it is an option.
What brand is it?
Never heard of sodium hyponitrite before, and I have been at this 50 years.
Na2N2O2 you say?
[Edited on 27-4-2009 by Sauron]
Sic gorgeamus a los subjectatus nunc.
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UnintentionalChaos
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Odd. I've never heard of hyponitrites either, but they even have a wikipedia page.
It says that organic trans-hyponitrites can be used as a source of alkoxy radicals. I wonder if there is some interesting chemistry that can be done
with that.
The free acid trans-hyponitrous acid is said to form explosive crystals when dry, but is somewhat unstable in aqueous solution. Sounds like a topic
for energetic materials.
[Edited on 4-27-09 by UnintentionalChaos]
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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Jor
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Sodium hyponitrite is better described as Na2N2O2. This is the sodium salt of hyponitrous acid, H2N2O2. The anhydride of this acid is N2O.
IIRC, H2N2O2 is one of the strongest oxidisers out there, am I right?
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panziandi
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Jor: N2O should not be considered the anhydride of H2N2O2 since you can not form hyponitrites nor hyponitrous acid from it. It's less of an acid
anhydride than carbon monoxide! It is only an anhydride in as much that it is formed by dehydrating the acid but is not a conventional anhydride.
H2N2O2 -> N2O + H2O is irreversible
Hyponitrous acid and salts are very resistant to reduction (claims of reduction to hydrazine have since been disputed). Easily oxidised, however, to
nitrites by alkaline potassium permanganate, nitrites can then be further oxidised to nitrates.
Sodium hyponitrite is stable up to 260*C when it decomposes to sodium nitrite and nitrogen.
Sodium hyponitrite is stable dry. Since hyponitrous acid is a weak acid hydrolysis occurs in the presence of moisture quickly generating free
hyponitrous acid which quickly decomposes. Alkaline solutions of hyponitrites are stable by reducing hydrolysis.
"Inogranic Text Book For Advanced Students" E. de Barry Barnett and C. L. Wilson.
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Paddywhacker
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I wonder if it forms complexes with transition metals such as the complexes between Cu or Fe and CN- or Cl-
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woelen
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Indeed, hyponitrite is N2O2(2-), and this ion is fairly stable in acidic solutions. On addition of alkalies, it decomposes, the main product being
N2O, most likely there are other nitrogen oxides as well as side reactions (nitrogen-based compounds seldomly react cleanly and quantitatively in a
simple way).
In my books it is mentioned as a mild reductor, stable in dry air and fairly stable in acidic solutions. I can imagine that this is interesting as a
compound for making complexes and/or metal precipitates. Some of these may have energetic properties, so be careful when playing around with this,
only use small quantities.
Do not throw away the stuff. Keep it, it does not introduce a strong storage hazard, and if you throw it away you might regret later.
Edit: I accentally exchanged acidity with alkalinity and this compound is fairly stable in acidic solution, while being unstable at high pH.
[Edited on 27-4-09 by woelen]
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panziandi
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I would imiagine it to be interesting as a ligand. But I would agree with woelen, that some complexes maybe quite energetic so would edge on the side
of caution scale-wise. And I have seen a few sources mention organic hyponitrites as radical sources etc, obviously these compounds would need some
care, I haven't looked up safety information but would imagine photosensitivity and explosive hazards. Certainly do do get rid of the sodium
hyponitrite but at the same time don't waste it. I'm sure you'll find something of interest for it.
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JohnWW
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Quote: Originally posted by woelen  | | Indeed, hyponitrite is N2O2(2-), and this ion is fairly stable in acidic solutions. On addition of alkalies, it decomposes, the main product being
N2O, most likely there are other nitrogen oxides as well as side reactions (nitrogen-based compounds seldomly react cleanly and quantitatively in a
simple way).(cut) |
The structure of that anion would probably be -O-N=N-O- . If it were to be tried as a ligand for metal cations, particularly those of transition
metals, there would be a question of exactly how it would bond. Transition metal cations preferentially bond to N atoms over O atoms, but in this case
it may result in complexes with highly-strained 3-membered rings.
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Formatik
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Alkyl hyponitrites are more hazardous and unstable than alkyl hypochlorites. Some of the heavy metal salts are explosive, e.g. as characterized by A.
Kirschner in Z. anorg. Chem. 16 [1898] 429: the basic lead salt, Pb(NO)2.PbO, is whitish yellow and amorphous, but the normal salt builds small yellow
crystals. Both are insoluble in water. The basic lead salt is reported to deflagrate on heating, but the normal salt, (Pb(NO)2), explodes in the same
instance; with both leaving behind bright lead oxide. Scattered daylight dec. the basic salt with brown color dec. quickly so it has to be handled in
the dark. Conc. H2SO4 will decompose the hyponitrous acid and its salts under formation of N2O, I remember reading somewhere that N2O is only
considered the theoretical anhydride of the acid.
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panziandi
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No indeed as I mentioned furher up N2O isn't considered a true anhydride since you can not form the hyponitrites nor hyponitrous acid from it. It is
therefore even less of an anhydride than carbon monoxide is!
I could imagine that the heavy metal hyponitrites would have been explosive.
I personally wouldn't try any organic chemistry of hyponitrites unless you opertated on a small scale, note the silver hyponitrite required is likely
explosive, and not to mention the alkyl hyponitrites would be unstable explosive light stable etc etc etc. Also I'd expect that operating under a
filtered light, i.e. yellow light dark room.
JohnWW - would the metals co-ordinate via the O- forming a bi-dentate 5-member ring system as opposed to through the N? This would be interesting to
explore... I don't suppose woelen has any or can get any hyponitrites... I'm sure he would be able to chuck out a few nice pictures 
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woelen
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No, I have no hyponitrites nor do I have a source where I can purchase some 
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Jor
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Well woelen, we have a source! Aldrich, we can buy there through our local supplier. But the stuff is too expensive!
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Paddywhacker
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Indeed, $241 for 10g. How much do you have, Jor?
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MadHatter
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Hyponitrite ?
That's a new one even for me. It's been said that you learn something new everyday.
Even chemsavers website, who supplies a good deal of obscure, my term, compounds
at unreasonable prices doesn't carry it.
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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Taoiseach
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http://jupiter.chem.uoa.gr/pchem/lab/pubs/XX_26A(1961)70.pdf
You need sodium metal to form hyponitrites from NaNO2. I wonder if there is also an organic route starting from pseudonitrosites.
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Jor
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Yes, I have seen this method in Brauer as well. Problem is you need a LOT of nasty mercury to form the sodium amalgam.
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