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Author: Subject: Which oxidizers are explosives?
UncleJoe1985
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[*] posted on 24-12-2008 at 02:13
Which oxidizers are explosives?


Hi. I'm trying to comply with federal and state regulations for storing oxidizers for rocket motors. I already found that APCP and black powder are considered explosive and are limited to 62.5g propellant without a storage magazine.

However, is storing chlorates and perchlorates in plastic bottles by the kilogram OK? I know NH4ClO4 won't if the particle size is small enough, but I also saw a video showing pure chlorate decomposing when struck with a hammer, so I'm worried. The ATF regulations list "chlorate explosive mixtures" and "perchlorate explosive mixtures" as explosives, but that seems vague.
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[*] posted on 24-12-2008 at 02:44


I'm pretty sure chlorate/perchlorate salts on their own are not explosives, with the exception of ammonium salts (which you would have a hard time detonating even if you wanted to).

62.5g of propellant... that is unfortunate!
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Mr. Wizard
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[*] posted on 24-12-2008 at 16:33


A hard time detonating isn't the same as won't detonate. View this video of the Pepcon plant fire, in which the ammonium perchlorate was stored outdoors in polyethylene HDPE drums.
http://www.youtube.com/watch?v=HJVOUgCm5Jk

I have talked to people who worked there. One of the intermediate steps involved Ammonium Chlorate which would be in solution, and the mist of the solution would contaminate wood pallets, people's pants, shoes, and collect in quiet areas. Peoples pants and shoes would burst into flames while they were wearing them. Wooden pallets would bust into flames if touched.
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hissingnoise
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[*] posted on 25-12-2008 at 04:55


Quote:
Originally posted by Mr. Wizard

One of the intermediate steps involved Ammonium Chlorate which would be in solution


Given its reputation, I'm surprised they'd handle ammonium chlorate in any form.
I thought they produced NaClO4 as initial product and produced the required HClO4 from it.
The major detonation was something else---phew!
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[*] posted on 26-12-2008 at 12:22


as for ammonium perchlorate it is shock-stable. i have done this test with a very heavy hammer and striking a pile of AMClO4, it seams that i literature it requires rapid heating and pressure. chlorate i have no experience on
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Mr.M
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[*] posted on 18-1-2009 at 18:26


Wether it can be detonated or not is closely related to the overall purity of the chemical. Potassium chlorate is more prone to explode when it is contaminated with (of course) organic substances or even potassium chloride. It won't explode without being handled very rough however, so it isn't considered an explosive. The only oxidizer used for rocketry I would consider an explosive is ammonium perchlorate, but also for this chemical purity plays a major role in the chance of getting it to explode.

I'd think '(per)chlorate explosive mixtures' means compositions or mixtures of a fuel and oxidizer. I think it is obvious why storing such mixtures would be regulated by law.
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woelen
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[*] posted on 19-1-2009 at 00:04


Ammonium perchlorate does not explode when it is heated (and not confined to a small space). It slowly decomposes, giving Cl2, H2O and O2. I tried this in a test tube with 100 mg of solid. This is in strong contrast with ammonium periodate. The latter suddenly explodes when it is heated, giving a cloud of purple iodine vapor and other colorless gaseous products. With 100 ml of ammonium periodate, the test tube is broken in the explosion.



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hissingnoise
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[*] posted on 19-1-2009 at 07:36


Some explosives are oxidisers in their own right, eg, tetranitromethane; presumably any oganic nitrate with a positive OB could fall into this class.
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[*] posted on 19-1-2009 at 10:58


Quote:
Originally posted by woelen

With 100 ml of ammonium periodate, the test tube is broken in the explosion.


Woelen, are you not missing a decimal point there?
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[*] posted on 19-1-2009 at 16:31


I think he means 100mg, as I assume ammonium periodate to be a solid compound.
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woelen
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[*] posted on 20-1-2009 at 10:12


Yes, I must have been sleeping while posting that message. I meant 100 mg of solid.



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donlaszlow
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[*] posted on 4-8-2009 at 09:48


You need to mix an oxidizer with a fuel to get an explosion. No mixture no explosion. Keep it sealed and be careful at all times when handling explosive mixture components. As long as you don't mix it with metal powders or any small granulated organic material it should be safe.
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[*] posted on 4-8-2009 at 10:12


No. Some oxidizers are themselves explosive. Some additional examples are Mn2O7 which is an oxidizer and an unstable explosive. The entire series of the oxidizing chlorine oxides are violent explosives. With some compounds it's questionable wether if you should call, or classify it "an explosive". KClO3, conc. HClO4 are among those. These are not classified as such as far as I know, e.g. in the USA there is DOT classification system (for transportation), KClO3 and 70% HClO4 are both class 5.1 oxidizer, the latter also class 8 because of it's corrosive nature. Compare this to TNT. Though there might be additional restrictions and even these classifications can change. I believe it's the declared classification the thread author is interested in.
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[*] posted on 4-8-2009 at 11:23


There are more explosive oxidizers. I made K3CrO8 and by simply heating it it violently explodes. I also made CrO2(NH3)3 and this compound burns like fast flash powder when ignited. No mix needed, just the fine powder. K3CrO8 also explodes when hit with a hammer. I tried this by wrapping some of the material in some Al-foil, putting that on a concrete tile and hitting it with a hammer. With just 50 mg of the solid you get a very loud report. Quite impressive.



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[*] posted on 6-8-2009 at 05:59


A lot of oxidizers are explosive by semself, simply because they are not very stable and release a lot of gaseous products when they decompose.

All chlorates are explosive. With a strong initiation even pure KClO3 will explode. Literature says that hg fulminate will accomplish that.

There are some heavy metal chlorates/perchlorates which are said to be explosive. Cobalt perchlorate I once read can be detonated by a strong hammer blow. Lead perchlorate is said to be explosive as well.

Most chlorites are explosive too, at least their anhydrous form. Lead and titanium chlorite are said to readily explode from a hammer blow.

Zinc peroxide is said to explode if rapidly heated. I can confirm it gives a flash and a hiss sound when thrown onto a red hot heating plate. Bigger amounts under confinement may well detonate.

Some safety papers say that zinc permanganate is explosive too.

Generally, the bigger the cation the less stable these compounds are. Lead and mercury salts of strong oxidizing anions are thus potentially dangerous.

Calcium persulphate is said to be explosive altough I doubt that.

Most ammonium salts with oxidizing anions are explosive: chlorate (unstable), perchlorate, chlorite (very unstable), nitrate, nitrite, bromate (unstable too), permanganate, dichromate, chromate. The chromate is said to be more sensitive than the dichromate (I tried to detonate it with a hammer but failed).

These salts however aren't "pure" oxidizers because the NH+ ion itself can be oxidized by the anion.
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[*] posted on 7-8-2009 at 15:15


Reference for cobalt perchlorate (Co(ClO4)2.6H2O) exploding from impact is Salvadori, Gazz. 40 II [1910] 9, 42 I [1912] 458 who also says it burns without explosion if quickly heated. AgClO4 explodes if heated to around 800ยบ (Hill, J. Am. Soc. 43, [1921] 256). Another one is chromyl perchlorate CrO2(ClO4)2 which is a red liquid that dec. at regular temps., especially by light, occasionally also exploding. And the list goes on. :P

Attachment: CrO2(ClO4)2.pdf (504kB)
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[*] posted on 8-8-2009 at 06:55


CoII and CoIII also gave very energetic and sensitive ammino complexes in my experiments, however both were slightly hygroscopic.

Acetato perchlorate complexes are definetly worth a try. There might be some compounds out there which can be made from just vinegar, a soluble metal salt and Na/K perchlorate. There was mention of a CrIII acetato perchlorate complex with low solubility somewhere but I never came across a preparation.
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[*] posted on 29-1-2010 at 00:33


Even copper sulfate and potassium permanganate are said to be capable of explosively decomposing, though not detonating.

H2O2 would be another example ...
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