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woelen
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I have done the experiment of leading NOx over H5IO6. Nothing happens at all. The H5IO6 remains a dry powder.
Next, I heated the H5IO6, such that it just melts, while having it under un atmosphere of mostly NO2 (and some NO). Again, nothing happens. The solid
melts, a clear colorless liquid is formed, and no NO2 or NO is absorbed in it.
I left the whole thing alone for an hour and when I came back, the white liquid had solidified again, and now it was covered with a thin layer of
elemental iodine. Most likely, the periodate has oxidized some of the NOx to HNO3, itself being reduced to I2.
I also read some literature about the nitryl and nitrosyl ions. These ions need very strong acidic conditions and H5IO6 simply is not sufficiently
strong, in fact, it is a fairly weak acid, even for its first proton. So, nitrosyl- or nitryl periodate is not possible, at least not along this
route.
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Anders Hoveland
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madscientist:
"I wouldn't be suprised if nitrosyl perchlorate could be prepared from nitric acid and perchloric acid. That reaction may be dangerous if concentrated
reactants are used!
HNO3 + HClO4 ----> H2O + O2NClO4
O2NClO4 + 2HClO4 ----> ONClO4 + HClO4 + HClO3 "
There is no reaction, only some equilibrium.
2HClO4 + HNO3 <--> H3O(+)ClO4(-) + NO2(+)ClO4(-)
your second reaction does not balance
14oxygens ---> 12oxygens , you would not get any NO(+)
[Edited on 9-7-2010 by Anders Hoveland]
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Formatik
National Hazard
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Nitric and perchloric acid can be used to get some nitronium perchlorate.
A substance (H3NO3)[ClO4]2, was made by Hantzsch (Ber. 58 [1925] 946) by adding anhydrous HClO4 into conc. nitric acid. Described as an exothermic,
stable, non-explosive compound, recrystallizable from absolute perchloric acid. Later work by Goddard, Hughes, Ingold (J. chem. Soc. [1950] 2559) has
found this material could be separated into nitronium perchlorate and hydroxonium perchlorate by fractional recrystallization from nitromethane.
NO2ClO4 being obtained pure and structure verified by X-ray crystallography by Cox, Jeffrey, Truter (Nature, Lond. 162 [1948], 259).
Hantzsch also claimed to have made (H2NO3)ClO4 by adding conc. nitric acid into anhydrous perchloric acid. Describing this as stable, exothermic,
non-explosive compound, recrystallizable from absolute nitric acid. But work from the first previous authors could not make this compound, they say he
got a mixture.
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The WiZard is In
International Hazard
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I am a little late upon this. I would mention in passing that
Quote without the source .....
Another source (I am not going to quote it so I don't have
to tell you what it is, however, I'll give you a hint. Volume2
p.484) sez. essentially the same thing and references :—
K.A. Hofmann and A. Zedtwitz, Ber, 2031 (1909).
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Formatik
National Hazard
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Using equal volumes, and adding red fuming nitric acid (d= 1.52g/cc) to azeotropic conc. HClO4 under agitation gave me a white precipitate and left
the liquid colorless. The resulting mixed crystals and liquid which weren't separated was very violently reactive against turpentine in very small
amounts (but not towards DMSO, DMF which both just gave off white fumes at the same amounts). I'm not sure what this material is (comparisons in
spectra can narrow down if it is a crystal mixture). It would be interesting to use spectra to compare these and see what it really is. One drop of
the white crystals suspension on contacting about 2 drops turpentine which were spread out on a flat iron plate immediately thumped violently
producing a very visible orange fireball accompanied by thick carbon/soot smoke rings and a horrible smell. It looked as something out of Hollywood on
a minature scale. (Warning! Don't use more than a few drops or a very dangerous violent explosion can occur!). This violent reaction
and rapid rate is in strong contrast to experiments with a bit larger amounts of moist NOClO4 solid which had added to it dumped in an excess of
turpentine (hypergolics thread).
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kuro96inlaila
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Nitronium perchlorate, NO2ClO4, also known as nitryl perchlorate and nitroxyl perchlorate, is an inorganic chemical, the salt of the perchlorate anion
and the nitronium cation. It forms colorless monoclinic crystals. It is hygroscopic, and is a strong oxidizing and nitrating agent. It may become
hypergolic in contact with organic materials.
Nitronium perchlorate was investigated as an oxidizer in solid rocket propellants. Thomas N. Scortia filed for patent on such propellant in
1963.However its reactivity and incompatibility with many materials hindered such use. Coating of nitronium perchlorate particles with ammonium
nitrate, prepared in situ by passing of dry ammonia gas over the particles, was investigated and a patent was awarded.
Decomposition rate of nitronium perchlorate can be altered by doping with multivalent cations.
Nitronium perchlorate and ammonium perchlorate do not produce smoke when burned with fuels. Potassium perchlorate and other metal perchlorates
generate smoke as the metal chlorides are solid materials creating aerosols of their particles. Of all perchlorates, nitronium perchlorate is the most
powerful oxidizer. However it can be easily detonated.
Fierce compound,hehehe
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The WiZard is In
International Hazard
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Ahhhaaaa ... whats a coming out of the bottom of
the space shuttle boosters on launch?
Each booster engine "will burn the equivalent of 10,000 rubber tires"
C&EN 8 XII 89
djh
---
When you are courting a
nice girl an hour seems
like a second. When you
sit on a red-hot cinder a
second seems like an hour.
That's relativity.
AE
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Anders2
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"this material could be separated into nitronium perchlorate and hydroxonium perchlorate by fractional recrystallization from nitromethane"
Would that not mean that nitronium ions (the source of HNO3's oxidizing power) were not attacking the nitromethane? Why is this?
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