chlorites from chlorates [Archive] - The Explosives and Weapons Forum

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jimwig

November 9th, 2002, 04:35 PM

been reading the nitrites from nitrates post

just wondering if the same methodology could be used to remove an atom of oxygen from chlorates to form the oh so desirable chlorites?

As in NaClO3 ===> NaClO2

i know this works NaClO3 ===> ClO2 =====> NaClO2 (fill in the blanks)

sodium chlorate chlorine dioxide sodium chlorite

just curious a more direct method

maybe using electrochemistry to rip off that O.......????

vulture

November 9th, 2002, 06:52 PM

Where do you want chlorites for? Most of them are dangerously unstable and explosive. But if you want, I could look up a synth, but not today anymore....tired....

Marvin

November 10th, 2002, 10:51 PM

"Most of them are dangerously unstable and explosive."

What part of this sentance are we not interested in. :D

jim, N (V) is as high as nitrogen goes, and nitrite is the only possible alternative at this temperature which is why it forms.

Cl(V) is not as high as chlorine goes however, and hyperchlorite and chlorite are not stable at elevated temperatures, which is why when you heat it, chlorate disproportionates into perchlorate and chloride. In the presence of catalysts or at higher temperatures it will go direct to chloride releasing oxygen.

Edit,
Ok, noones continued this, so I'll do it.
The chlorine dioxide method will work, most of the refs I have use hydroxide.

Chlorine dioxide is highly toxic, highly reactive, and oh yes, it explodes when it feels like it. The safest way of prepairing it involves heating sodium chlorate intimatly mixed with an organic acid (suggested acids are oxalic, citric, tartaric I dont have specific details on each one) which produces chlorine dioxide diluted by up to 2/3rds with carbon dioxide. There does not seem to be any danger of detonation of the solid or the gas by this process, but bear in mind it could ignite if the heating is not done carefully.

Action of this on a metal hydroxide will produce a mixture of chlorites, chlorates and carbonate/bicarbonate which should be easily seperable by fractional crystalisation. Absorbing the gas with carbonate from the start will probably work. This may seem like a pain but generating ClO2 on its own is simply not safe. One of the demos I tried (using another method for fairly pure ClO2) involves filling a glass container with it, and taking a flash photograph at close range.

Edit,
Adding an equation to clarify the reaction of chlorine(IV) oxide with sodium hydroxide (a disproportionation).
2NaOH + 2ClO2 => NaClO2 + NaClO3 + H2O

[ November 14, 2002, 08:38 PM: Message edited by: Marvin ]

jimwig

December 20th, 2002, 04:01 PM

thank you sir!!!

i get that same question a lot. but your response is dead on the bullseye as to what this board is all about. and with your permission i am gonna plagerize that very answer.

kabooom

January 26th, 2003, 11:00 PM

the following reaction comes from my "industrial inorganic chemistry" :
2ClO2 + 2NaOH + H2O2 => 2NaClO2 + 2H2O + O2

there is sever spontaneous explosion hazard for chlorites, and of course their O is less than chlorates and perchlorates so its salts ain't good oxidizers. if you are looking for explosives like AgClO2, the chlorate salt should be a better choice.

don't try the composition on ISP explosives <blockquote>quote:<hr /> Sodium Chlorate Explosive(M,AHC): Mix 50% red phosphorus with 50% sodium chlorite(don't substitute with potassium chlorate because will spontaneously explode when mixed with phosphorous. <hr /></blockquote>from ANAR(Accidents and Near Accident Reports):
<blockquote>quote:<hr /> For God's sake DO NOT mix Sodium Chlorite (NaClO2) with anything. ESPECIALLY not sulphur, but it is also friction, and I would imagine impact, sensitive to sugar, carbon and probably most other stuff - I didn't check that far. Burned my hand quite bad with Sulphur (the slightest touch in my mortar set it off) and nearly did so again with the sugar. Should you come into posession of any, not that it's that common - mine was still a bit 'warm' when I used it - don't bother with it. If it's possible to convert to (per)chlorate, then do it...don't trust the Chlorite or you'll end up getting burned.
duncan
England
Age: 23, Experience: Educated Novice, - Thursday, June 10, 1999 at 09:21:28 (EDT) <hr /></blockquote>