Sciencemadness Discussion Board

Organic chlorates and perchlorates

Vikascoder - 5-5-2012 at 03:15

Hello friends . I tried to search a lot on google but could not find any info on the organic chlorates or perchlorate which are considered as explosive . If you feel i have not searched a lot so please sorry for that .will you please tell me the synthesis of organic chlorates

AndersHoveland - 5-5-2012 at 03:29

This thread is going to be sent to detritus. You should have known that.

But I ska help you out:
http://www.sciencemadness.org/talk/viewthread.php?tid=1081

[Edited on 5-5-2012 by AndersHoveland]

Vikascoder - 5-5-2012 at 08:12

Thanks andres hoveland you are good person

Vikascoder - 5-5-2012 at 19:31

there are some threads which tell us about the hexamine diperchlorate but i could not find any thread which deals with the synthesis of hexamine chlorate

AndersHoveland - 7-5-2012 at 05:28

That is no doubt because it would be very unstable. Ammonium chlorate is unstable enough, it can start decomposing in sunlight, and this can end up in spontaneous explosion. Whereas ammonium perchlorate is much more stable, it essentially is not even an explosive when in small quantities not mixed with anything else. Organic amine perchlorates would tend to be even more unstable. There would just be no point in making them. It would not just be the dangerous sensitivity, it would also be the chemical instability, there would be the danger of spontaneous detonation in storage.

On a side note, not all explosives with chemical instability are sensitive. Trinitroaniline is very safe against impact (about as much as TNT), or can be thrown in a fire without any danger, but large quantities of it can begin to decompose in storage, and eventually this decomposition can lead to spontaneous detonation.

The reason perchlorate ions are more stable than chlorate is because of steric hindrance. Paradoxically, because there as so many oxygen atoms around the chlorine atom, an additional electron has more difficulty entering. We can also see this with sulfur hexafluoride SF6, which is almost completely unreactive with anything. It will not even react with hot molten sodium, even though sodium is so reactive it can explode in contact with water. Sulfur hexaflouride is not even poisonous, it is safe to breathe it in. But sulfur tetrafluoride SF4 is much more reactive, and very poisonous. SF4 will react with water.

So perchlorate is better, more oxygen and more stable.
Although sometimes chlorate is preferred in certain flashpowders because it decomposes at a lower temperature, and so the composition can potentially burn even faster.

But it can also be mentioned that while ammonium perchlorate is very insensitive, organic amine perchlorates tend to be fairly sensitive.

[Edited on 7-5-2012 by AndersHoveland]

simply RED - 7-5-2012 at 05:48

"The reason perchlorate ions are more stable than chlorate is because of steric hindrance."

The reason is the electronic structure of the ions and has nothing to do with steric or any other spatial effects! With other words, the 7 valent chlorine in this case is more stable than 5. Or reducing 7 valent chlorine in perchlorate has higher activation barrier than reducing 5 valent Cl in chlorate.

[Edited on 7-5-2012 by simply RED]

woelen - 7-5-2012 at 22:24

Yes, simply RED is right, steric hindrance is no reason for perchlorate's stability. The perchlorate ion is resonance-stabilized. This is only true for ionic perchlorates. In covalent perchlorates (like anhydrous HClO4) one of the oxygen atoms differs from the other three, but in the perchlorate ion all electrons are equally distributed over all oxygens and one cannot say which oxygen was carrying the H-atom and which oxygens were attached to the chlorine using a double bond.

For the above reason all ionic perchlorates are stable and even the organic ionic perchlorates like amine-based perchlorates are quite stable. I myself made quite a few of them and all of them were stable enough to keep them around in miniature quantities (less than 1 gram) for a few days. I never stored them for a longer time and always stored them in a glass bottle, contained in a larger thick-walled plastic can.

Perchlorate esters on the other hand are insanely unstable and exceptionally dangerous to work with. On this forum, however, there is a very interesting (somewhat older) thread by user 'axt' who made some of this and did impressive experiments with it. A nice read, but not something to repeat lightly. Only do so if you really have the equipment and experience to handle these things safely.

caterpillar - 7-5-2012 at 23:44

Hertz recommended organic salts of perchloric acid as very powerful primers, but most of them are too sensitive. Is there any salt of this acid that can be used more or less safely as a primer?

AndersHoveland - 10-5-2012 at 22:28

Quote: Originally posted by woelen  
Yes, simply RED is right, steric hindrance is no reason for perchlorate's stability. The perchlorate ion is resonance-stabilized.

The chlorate ion also has resonance. Perhaps you care to explain why it is much less chemically stable?
Quote: Originally posted by simply RED  

The reason is the electronic structure of the ions and has nothing to do with steric or any other spatial effects! With other words, the 7 valent chlorine in this case is more stable than 5. Or reducing 7 valent chlorine in perchlorate has higher activation barrier than reducing 5 valent Cl in chlorate.


KClO4 certainly is more stable than KClO3. Potassium chlorate has a heat of formation of -391 kJ/mol, while potassium perchlorate has a heat of formation of -430 kJ/mol. (the lower the value, the more stable it is)
Potassium chloride is -437 kJ/mol. So each oxygen in the chlorate ions add 15.3 kJ/mol of energy, while each oxygen in the perchlorate ions add 1.8 kJ/mol of energy.

While organic amine perchlorate salts certainly are surprisingly stable for something that contains so much oxygen in one group, they are still much more sensitive than the organic amine nitrate salts.
Quote:

"Organic perchlorates, in which the oxidant is already present in the same molecule, are in general much more violent in their explosive action than mechanical mixes in which the organic material and oxygen carrier are present as separate solid phases. Manuelli and Bernardini patented the use of perchlorates of biguanide and of guanidine for use as explosives, while Rintoul and Beckett covered the use of dicyanodiamine perchlorate as a blasting explosive. The compound is stated to have an explosive force equal to TNT, but to be insensitive to shock. When slowly heated, it begins to melt with slight decomposition at around 200 °C, completely melting at 300 °C, and finally exploding at 378 °C. It is relatively soluble in water, but less hygroscopic than potassium nitrate.

The perchlorates of aniline, phenylenediamine, aminoazobenzene, pyridine, and quinoline are supposedly suitable for use as explosives. patented methylamine perchlorates, all of which are stated to be stable, and substancially insensitive to moisture, with the exception of (CH3)2NH2(ClO4). (Lungsgaard and Herbst)

The ammonium and hydrazine compounds of several bivalent metals have been investigated as possible initiating explosives for use in detonators. It was found that these compounds had explosive properties between primary, such as fulminate of mercury, and booster explosives,such as tetranitromethylanaline. The chlorate salts were found to be deliquescent and to hydrolyze rapidly. They are much more sensitve than the corresponding perchlorate salts. (Friederich and Vervoorst)

An explosive has been prepared from ethylenediamine perchlorate, by forming an addition compound with picric acid or other polynitro aromatic body containing hydroxyl groups. (Vogl) Such explosives have high detonating velocities, stated to be suitable for use in booster charges."
CHAPTER: PERCHLORATES IN EXPLOSIVES AND PROPELLANTS p138, 139
"Perchlorates: Their Properties, Manufacture And Uses"


Pyridine-perchlorate has a lead block rating of 95% TNT and is about as sensitive as PETN. It has a low solubility in ethanol so the salt may be precipitated from a water solution with ethanol.
Encyclopedia of explosives and related items, Vol. 9, PATR 2700, Seymour M. Kaye, article by Dr. W. Klöhn


As for chemical stability, even ammonium perchlorate is known to slowly degrade after many years in storage.

[Edited on 11-5-2012 by AndersHoveland]

woelen - 10-5-2012 at 22:53

Quote:
The chlorate ion also has resonance. Perhaps you care to explain why it is much less chemically stable?
Chlorate is less resonance stabilized than perchlorate, due to the free electron pair on the chlorine atom in chlorate. This free electron pair destabilizes the perfectly symmetric distribution of electrons as is present in perchlorate. This effect is very common for the elements in the upper right part of the periodic table:

- nitrite is less stable and much more reactive than nitrate
- hypochlorite is less stable than chlorite is less stable than chlorate is less stable than perchlorate
- hypobromite and bromite are extremely unstable and cannot be isolated as solid salts, bromate is somewhat less stable than perbromate
- dithionite is less stable than sulfite is less stable than dithionate is less stable than sulfate
- phosphite is less stable than phosphate

It is less pronounced in the lower right part of the periodic table:
- tellurite is of approximately same stability as tellurate
- iodate is somewhat less reactive than periodate
The simple pure symmetry of the maximum oxidation state ions does not exist for those heavier elements, due to the big size of the central atom. Periodate usually wants to be in orthoperiodate form (e.g. H3IO6(2-)), except for periodates of larger cations, such as KIO4 and CsIO4. Tellurate exists as H6TeO6 and salts of this.
Quote:
As for chemical stability, even ammonium perchlorate is known to slowly degrade after many years in storage.
Is this true? I have ammonium perchlorate, 10 years old and I received it from someone, who may have had it before me for many many years. It still is in perfect condition, no decomposition at all, free of chloride and free of chlorate. Ammonium perchlorate indeed decomposes on heating (above appr. 150 C), but I do not think it decomposes when stored at room temperature in the solid state in a decent container.

caterpillar - 11-5-2012 at 20:36

Ridiculous, but many years ago I read one article (it was popular magazine "Chemistry and live") about ammonium perchlorate. Been added to pig's food, it makes them very quickly increase in weight. But I do not know, if such method is in use somewhere.

AndersHoveland - 11-5-2012 at 21:03

Quote: Originally posted by caterpillar  
But I do not know, if such method is in use somewhere.

Probably in China, I would not be surprised. If they find ethylene glycol cheaper than glycerin to use in toothpaste and cough medicine, and think that melamine makes a good additive to milk, I do not see any reason why they would not find ammonium perchlorate as an acceptable hormone regulator for pigs.

caterpillar - 12-5-2012 at 12:22

It was Russian magazine. But I'm not sure, that AP been added to food, makes pig's meat really dangerous. About ethylene glycol- on one same day I saw news. there was two similar reports. Diluted ethylene glycol was stolen from some plant and was sold by one woman (it happened in former USSR). 14 people dyed, all alcoholics except one girl. Sentence was 6 years in prison. Similar incident in China- death sentence (excuse me, boys, it is not about explosives).

caterpillar - 12-5-2012 at 12:27

One of the most powerful composition for blasting rocks: RDX + AP + Al + few percents of desensitizator (I do not remember which in particular- may be some wax).

quicksilver - 15-5-2012 at 06:52

We need to get back to sighting documentation in this (Energetics) section. Discussion is great ~IF~ the concepts discussed are based in fact. Documentation allows independent opinion to be based upon those issues which peer-reviewed science outlines.
Opinion based on simple observation of an individual phenomenon is too open to misinterpretation or short-cuts in logic.

The "Rules" are there for several very important reasons.