Sciencemadness Discussion Board

metallic peroxy salts

IodineForLunch - 9-11-2002 at 14:22

In my never-ending quest for stronger oxidizers, I was thumbing through my CRC handbook a while ago, in the inorganic nomenclature section, when I ran across peroxynitric acid. HNO4. I spent a while thinking about it but decided it would be too unstable to be preactical for anything. However, a few nights ago I was joking around with madscientist on AIM and he mentioned HOOClO3 for some reason. I immediatly snapped back to reality, and we talked about chemicals such as this for a long time. Why not take normal oxy mineral acids, oxidize them even further with H2O2, and then convert them to metal salts through the addition of hydroxides? Here's what I've come up with so far:

Peroxyperchlorates - active group of -OOClO3 (XClO5)

Peroxynitrates - active group of -OONO2 (XNO4)

Diperoxymanganates - active group of -OO(MnO2)OO- (X2MnO6)

Peroxyperiodates - active group of -OOIO3 (XIO5)

Anyone got any more? Tips, comments, suggestions? Any brave soul out there actually willing to mix perchloric acid with concentrated hydrogen peroxide??

David Hansen

vulture - 9-11-2002 at 15:22

I fear they are too unstable too exist, except for HNO4.

How about O-ClO2-O-O-ClO3 and similar? You get the idea, a peroxide chain between two central atoms...

IodineForLunch - 9-11-2002 at 15:48

Sounds good to me!

David Hansen

vulture - 10-11-2002 at 07:44

BTW, I hereby volunteer to mix perchloric acid and hydrogen peroxide. IF someone get's me the perchloric acid.....:D

IodineForLunch - 10-11-2002 at 09:44

The compound you mentioned can exist wtih a single oxygen between the chlorine atoms. That would be Cl2O7, chlorine heptoxide, a violently explosive oil. Perhaps reacting it with H2O2 would put a peroxy chain inbetween the two chlorines.... But I wouldn't mix Cl2O7 with ANYTHING unless I had a death wish.

David Hansen

madscientist - 10-11-2002 at 12:34

Mixing Cl2O7 with H2O2 would probably result in an equimolar mix of HClO4 and HOClO4 (sounds like a very dangerous experiment).

I highly doubt any compound containing just chlorine and oxygen, containing a peroxide chain as well, will be stable enough to exist at realistic temperatures.

bonemachine - 10-11-2002 at 12:49

vulture you said that HNO4 is stable and i wonder if something like kno4 could be prepared.

vulture - 10-11-2002 at 14:01

I have no idea....

bonemachine - 11-11-2002 at 01:46

Maybe the action of H2O2 to KNO3 would form KNO4 with some way?

How about

Boob Raider - 11-11-2002 at 13:25

Electrolysing a solution of NaNO3 in conc. HNO3. This should result in NaNO4 along with a mix of HNO3 and HNO4, since most oxy anions can be peroxidized this way. I might try this as soon as I get some Ca(NO)3 and NaNO3. I have H2SO4. I need to make some HNO3 first.

KABOOOM(pyrojustforfun) - 21-11-2002 at 18:57

I remember a thread on E & W forum, the topic was something like H2O2 bp. someone had wetted his black powder and when dried it was surprisingly faster than his other batches I remember they gussed silly causes for it. may be the KNO3 had turned into KNO4 (although I have doubt).
I'm going to react proxynitrous acid(the nitric acid isomer) with hexamine to see if RDX could form. I will do it like R salt synth except that I will add excess amount of H2O2

vulture - 22-11-2002 at 04:12

I think that blackpowder story has a more simple explanation. The KNO3 probably catalyticly decomposed the H2O2 and the escaping oxygen gas got caught in bubbles in the blackpowder. When dry, the blackpowder had a low density with lots of bubbles which contained pure oxygen. This would ofcourse speed up the burn.

I don't think you can make KNO4 by KNO3 + H2O2 since KNO3 will decompose H2O2.

KABOOOM(pyrojustforfun) - 23-11-2002 at 18:31

neutrale or slightly acidic solutions of dichromate salts of K ,NH4 & Tl if react with H2O2 will produce bluish purple salts which are explosive. these salts are suggested to have [CrVIO(O2)2OH]- ion so they are related to CrO5

Microtek - 24-11-2002 at 03:08

These peroxychromates are very unstable and fragile substances. The blue colour is used in analytical chemistry to identify chrome, but you have to observe the solution carefully because the complex is often destroyed very quickly.

PHILOU Zrealone - 13-3-2003 at 06:15

KMnO4 decomposes H2O2!

vulture - 13-3-2003 at 15:27

I know that.
Unless I am mistaken, I thought most salts speed up the autocatalytic decomposition of hydrogenperoxide?

PHILOU Zrealone - 26-3-2003 at 06:43

N2O5 + HO-OH (conc) --> HO-NO2 + HO-O-NO2

HNO4 = peroxonitric acid
The free acid is said to be unknow and solid salts are unknown but strangely they say :
"UNSTABLE EXPLOSIVE CRISTALS" --> unknown but isolated ????

HO-O-NO is unstable isomeric with HO-NO2 some salts are more stable; it is made by in situ reaction between HNO2 and H2O2.Its oxidation power is higher than H2O2 or HNO3 alone!!!
Alkaline solutions are more stable but the yellow peroxonitrites MOONO have never been isolated pure!

AndersHoveland - 20-9-2011 at 11:49

Solutions containing up to 10% peroxynitric acid, HOONO2, have been prepared. Such solutions are unstable, gradually decomposing with a half-life of about 30 minutes. Peroxynitric acid quickly decomposes under alkaline conditions, and salts have never been prepared.

It may be prepared by reacting nitrous acid with excess H2O2, or by reaction of nitronium tetrafluoroborate with concentrated H2O2.

Peroxynitrite salts have been prepared, NaOONO, and they readily decompose on being acidified, being extremely reactive oxidizers. There are two decomposition routes, about 66% of the HOONO decomposes by the first route, to form hydroxyl radicals, while the remaining 34% decomposes to form transient nitronium ions. Peroxynitrous acid has actually been used to add nitro groups to aromatics.

PHILOU Zrealone - 10-10-2011 at 12:18

Stange that one of the major decomposition route for not the production of the stabler nitrates...via an intramolecular (eventualy intermolecular) oxydoredox (2 oxygen atoms going from -1 to -2 oxydation level and one N atom going from +3 to +5 oxydation level)
Na-O-O-N=O --> Na-O-NO2

Too bad those are not more stable...otherwise NH4-O-O-N=O or NH2-NH2-O-O-N=O would have been interesting unstable molecules to study; alternatively peroxynitrate salts of amines or esters with boosted OB and enhanced densities...but sadly those are dreams until otherwise proven :(