Anders Hoveland
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Question: hydroxylamine superoxide?
The ozonide and superoxide of ammonia exist. I wonder if hydroxylamine superoxide could be made?
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JohnWW
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If any of those exist, they would be dangerously explosive!
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DJF90
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Brainfarts like this should be posted in the "Short questions thread (2)".
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franklyn
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No less a luminary than Linus Pauling said it best, " The way to have a good idea , is to have
lots of ideas. " This does not however grant you license to open a new thread here on every
random notion that passes through your head , in particular only one line devoid of references
and to top it all placed in the wrong section for a proposed energetic material. Various members
of this forum have already pointedly told you as much
The Inorganic ozonides and superoxides have been barely spoken of here , so to save this
thread from detritus I'll start it properly.
Alkali Superoxides and Ozonides are known , and also an Alkaline , that of Calcium
6 KOH + 4 O3 => 4 KO3 + 2 KOH • H2O + O2 , , 2 KO3 slowly decomposes into 2 KO2 + O2
apparently it is reversable.
Synthesis of potassium ozonide from potassium superoxide suspended in Freon-12
http://www.springerlink.com/content/v2u7532p22j02762
Potassium Ozonide
http://www.pnas.org/content/49/1/1.full.pdf
Derivatives of Ozone , ( KO3 ) - abstract only
http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...
http://www.dtic.mil/srch/doc?collection=t3&id=AD0257921
Ammonium Ozonide , is only stable below −126 ºC
4 NH4O3 => 2 NH4NO3 + O2 + 4 H2O
Ammonium Ozonide - J. Am. Chem. Soc., 1962, 84 (1), pp 34–36
Irvine J. Solomon, Kiyo. Hattori, Andrew J. Kacmarek, Gerald M. Platz, Morton J. Klein
Ozone - Horvath M., Bilitzky L., Huttner J. , pp. 44–49
Elsevier ( 1985 Monograph - Topics In Inorganic and General Chemistry )
A solution of Calcium in Ammonia reacts with Ozone to give Ammonium Ozonide
3 Ca + 10 NH3 + 6 O3 => Ca·6NH3 + Ca(OH)2 + Ca(NO3)2 + 2 NH4O3 + 2 O2 + H2
Thermochemical and Structural Studies on Alkali Metal Ozonides - abstract only
http://oai.dtic.mil/oai/oai?verb=getRecord&metadataPrefi...
http://www.dtic.mil/srch/doc?collection=t3&id=AD0427772
( a one page article appears on .pdf page 34 ) Inorganic Ozonides
http://handle.dtic.mil/100.2/AD296544 , redirects to :
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=AD296544&Locatio...
The Inorganic Ozonides ( J. Chem. Ed.) - including Tetramethylammonium Ozonide
http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/1963000...
Forum member ' solo ' has kindly made available the following paper in the references section
Two Potential Energetic Compounds: Ammonium Superoxide and Ammonium Ozonide
- Quote -
With regard to the feasibility of preparation of NH402 and NH4O3, some encouragement
can be obtained from the fact that Tetraalkylammonium superoxides and ozonides, NR402
and NR403, are well known [ 11-14 ]. Perhaps the observed acidity of the hydroperoxy
radical, HO2 ( pK, = 4.7 [ 15 ]), could be exploited. The predicted properties of NH402
and NH4O3 suggest that some exploration of synthetic routes may be warranted.
Melikow and Pissarshewsky ( Chem. Zeit.)
Obtained Ammonium Superoxide by a saturated solution of Ammonia in Ether ,
poured in excess into a saturated solution of H2O2 in Ether. On cooling to
-40 ºC , crystals separate out , which , on washing with Ether were found
to have a composition ( NH4 )2 O2 • H O.
At ordinary temperature , this Ammonium Superoxide is decomposed with
the production of free Ammonia , and trifling quantities of Ammonium Nitrate.
Us Patent 3102140 , ( On Tetramethylammonium Superoxide )
Quarternary Ammonium Superoxide Compounds and Their Preparation
By example , Ammonium Carbonate can be made , but is it stable ?
Hydroxylamine is a much weaker base than Ammonia, Superoxide acid is a weak acid
that decomposes immediately. Ozone also oxidizes Hydroxylamine into Nitric acid ,
H2NOH + O3 => H2O + HNO3
Condensed-phase reactions of O3 with NH3 and NH20H ( append extension *.pdf to read )
http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?issn=1480-3...
http://en.wikipedia.org/wiki/Superoxide
http://mattson.creighton.edu/KO2/KO2.html
Chemical Reactivity of Hydrogen , Nitrogen and Oxygen Atoms at Temperatures Below 100 °K
( On *.pdf page 82 mentions Ammonium Ozonide , Hydrogen Superoxides H2O3 , H2O4 , on page 96 )
http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/1966002...
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Anders Hoveland
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I read that ozone will not oxidize NH4+ cations. And superoxide salts apparently do not tend to be especially oxidizing unless the pH is raised. So
Ammonium peroxide ironically does not exist because the peroxide is not electron withdrawing enough to ionize and take an electron from a hydrogen
that would then stick onto NH3 and protect it from oxidation. Interesting that superoxide is so oxidizing that, in holding its extra electron so
strongly, it ends up protecting the ammonia from being oxidized. hydroxylamine cations are weaker reducing agents than NH2OH, but I cannot find
sources about how powerful of a reducing agent/oxidizer NH3OH+ and O2- are.
Obviously hydrazine superoxide has a next to null chance of existing.
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franklyn
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These compounds can only find application as special purpose reagents.
I cite the example of noble gas compounds which after 50 years have yet
to become other than laboratory curiosities.
Pay attention - I'm quoting myself from above , quoting the source literature.
" Ammonium Ozonide , is only stable below −126 ºC "
" At ordinary temperature , Ammonium Superoxide is decomposed "
A compound of a weaker base if it can be made will not exist isolated
above cryogenic temperatures. Peroxynitrite for example , can be
maintained only as a solute in cold basic solution.
Peroxonitrite Physical Properties Data
http://www.caymanchem.com/pdfs/81565.pdf
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Anders Hoveland
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Peroxy-nitrite is indeed fascinating. It decomposed (when the pH is lowered) two separate ways, making NO2+ ion 2/3's of the time, and making hydroxyl
radicals the other third. Since NaOONO can be made by simple cold H2O2 on NaNO2, and strong base added right after, this might be a way to somehow do
a nitration. Unfortunately, my first instinct to use AgOONO in benzene would not work, as Ag2O2 (the I,III oxide) would precipitate out. And the NO2+
would almost certainly hydrolyze in water solution before it could nitrate anything. NaNO2 is not soluble in methanol.
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