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Author: Subject: Ethyl Perchlorate
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[*] posted on 8-11-2003 at 00:02
Ethyl Perchlorate


Am I the only person to have made Ethyl Perchlorate outside a laboratory? I made it in my Garage!
I used Meyer and Spormann's 1936 preparation by dry distilling Barium ethyl sulphate (also home prepared) and Barium Perchlorate. I translated the text from the German and took heed of their warnings about loosing fingertips etc.
I wore a motorbike helmet, a piece of sheet steel over my torso and twin thick leather gloves and didn't suffer any unexpected explosions!
I've been making explosives on an amateur level for many years but this stuff is just unbelievable! NCl3 and nitroglycerin pale in comparison. A single drop blew a beer can in half, again a single drop heated briefly in a spoon blew a hole through the spoon and out of my hand across the room. The lightest shock is enough to detonate it - I would say its equivalent to NCl3 in sensitivity. I made about 1ml all told but it can't be stored for long as it hydrolyses within about a week.
Fascinating stuff - I agree with them about its explosive violence, nothing I've ever made comes close! I should point out I'm an insane but trained professional chemist so don't recommend anyone has a go-I'll forward the translation to anyone who wants it though!
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[*] posted on 8-11-2003 at 06:13


holy SHIT

youre a nut, alkyl perchlorates, NCl3, damn.

thats awesome though, thats jsut amazeing, the power. glad to hear you didnt get any unwanted explosions. thanks for shareing your experiances, its greatly apreciated.

edit: got pics? i owuld love to see a pic ofthe spoon or whateve else. if you cant provie a pic can you please provide some measuremeants of the hole and thicknessof the spoon, and the nature of the hole?

[Edited on 11/8/03 by Madog]
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[*] posted on 8-11-2003 at 14:53


Here's a picture of a can of beer after the minutest amount (less than a drop) was detonated on it - note the exit holes on the other side! Larger amounts just ripped cans apart.

The original texts of these researchers make entertaining reading! Here's a couple of quotes:
Hare & Boye (who discovered the ethyl ester) "we are induced to believe, that in explosive violence it is not surpassed by any substance known in chemistry";
Meyer and Spormann (the latter lost three fingertips in the course of his work!) "We know of no other substance that is as powerful or destructive. The unbelievable brissance of the explosions result in extremely loud detonations which makes work unpleasant .... we wore thick leather gloves, iron masks and thick glass goggles (pre-plastic era!), and held the receptacles with long holders"!

I can sympathise with them, the ester is frighteningly powerful even when you expect the explosion. The shock wave hits you pretty strongly with the tiniest quantities and ear defenders are a must - even with them my ears were still ringing.

On a more technical note - they compare the perchloric esters with the nitrate esters. They behave similarly eg. ethyl nitrate is explosive but very much less so than the perchlorate for thermodynamic reasons. A nitrate ester everyone here should be familiar with is of course nitroglycerin but no comparable glycerol ester of the perchlorates has been isolated due to the extreme instability. It is for this reason that most perchlorate esters are academic curiosities and not used on a wider scale for explosives even though they are far more brissant.

DSCF0020.JPG - 79kB
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[*] posted on 8-11-2003 at 15:22


Just found the spoon - enjoy!

Its about a 1mm thick stainless steel lab spoon.

DSCF0026.JPG - 47kB
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[*] posted on 8-11-2003 at 15:57


This is quite amazing and interesting at the same time. You must have some large cahone's to be playing with this stuff. Keep us updated with your experiments and pictures are always golden.

American dimes laying around a European's laboratory...heh.




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[*] posted on 8-11-2003 at 16:37


yes, definately keep us updated, we would love to hear abuout it.

those pics are AMAZEING, the spoon especialy, i couldnt have expected beautiful results like that! the cleaness of the hole, so bristant.

this makes me wonder about CH3ClO4 though, i guess it would be extremely unstable.




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[*] posted on 9-11-2003 at 01:39


Put a dime in there because the first reply was from the USA!

Anyhow, Meyer and Spormann did make the methyl and propyl esters too.

They said that the methyl ester was even more sensitive and frequently detonated when being taken up in a pipette. It hydrolysed within 2 hours.

The propyl ester could only be made very slowly as heating the retort in an oil bath to 200'C like the prep for the other esters caused a massive explosion (they found that the fragments of glass were covered in carbon). They had to reduce the temp!

Another unusual ester was made in 1930 - trichloromethyl perchlorate from anhydrous carbon tetrachloride and AgClO4. It was so explosive that it could only be made in minute quantities and couldn't be completely isolated as it detonated with extreme violence when the CCl4 was evaporated off.
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[*] posted on 9-11-2003 at 06:55
perchlorates of simple amines


On that note, does anyone have info on perchlorate amines (not hexamine etc, which has been covered), but say methyl/ethyl amine perchlorate, etc? I guess they would be more stable, but nonetheless nicely powerful!
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[*] posted on 9-11-2003 at 09:17


Well, funny you should mention it, but me!
Tetramethylammonium perchlorate - its a white solid powder and is very easy to make from TMA hydroxide and aqueous HClO4.
Its another very interesting compound having both fuel and oxidiser in the same molecule and is an ideal rocket fuel! In fact it is the sole constituent, to my knowledge, in mini-rockets (the whistling ones that are readily available in the UK).
It does not explode (unless confined) when ignited, but burns very quickly and cleanly leaving very little residue and making no smoke.
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[*] posted on 9-11-2003 at 20:09


First off "Praise to Blaster!"

Even though I'm really not into energetic materials you have raised the bar for us at science madness, that's not easy to do, congrats!

After hearing about some of these tests you performed I took a look through the net for other information and found that Bretherick described ethyl perchlorate in The Handbook of Reactive Chemical Hazards as "The most explosive substance known" So of course that raises the question of how is it the most explosive. Which brings me to wonder what is the VOD and the lead block expansion for this wondrous chemical. Most books just don't seem to list explosive properties for exceedingly unstable compounds, well, if they were ever tested to begin with.

One other thing. This question directed to Blaster. I was looking up some info on the synthesis of ethyl perchlorate and found that it is 'supposedly' easily made from ethanol and perchloric acid. I'm assuming that it was easier to control/make with the barium perchlorate and the barium ethylsulfate procedure but I was wondering if there were any other advantages. Thanks a lot.




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[*] posted on 10-11-2003 at 01:27


Praise indeed, thankyou!

I thought it was about time to raise the alkyl perchlorates out of obscurity. They have been very little studied and even most prefossional chemists are unaware of them. You are right in that the thermodynamic properties have never been studied. These days, very few people are prepared to put themselves at risk for the advancement of science and my guess is that they will never will. I'm going to put all my German translations on a website shortly but it'll take a while - watch this space!

As to other methods of synthesis of ethyl perchlorate, Meyer and Spormann tried several. Synthesis can be performed from ethanol and perchloric acid BUT it is not easy because it is crucial that both ingredients are truly anhydrous. This means vacuum distilling 70% HClO4 with 100% H2SO4, itself a very hazardous and technically difficult operation. Having done so, you cannot just add the absolute ethanol because it detonates on contact with the 100% acid. A tiny trickle down the side of the flask at a very slow rate is the technique. Then water can be added to precipitate the insoluble ester.

They also made the ester from anhydrous ethylbromide and AgClO4, again this was difficult because the AgClO4 is very hygroscopic - they dried it over Phosphorous Pentoxide for a month and the ethylbromide must be freshly distilled!

All in all, the barium ethyl sulphate method is by far the easiest, I can verify that - it can be done by amateurs but the utmost care is needed. For your info, the ethyl ester was discovered in 1841 by Hare and Boye, Americans no less! I will also post their entertaining but not very tecnical paper on my website soon!
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[*] posted on 10-11-2003 at 04:17


Mr. Blaster,

You are hereby officially awarded the

Medal of Honor

for most courageous actions in the field of amateur madscience.

May the gods of chemistry be with you in all your experimental endeavours, guiding you to the most obscure and controversial knowledge there is to be acquired.

May the gods of chemistry also have pity for your limbs and health, ensuring you a fruitful career filled with exciting and most useful discoveries.

With the utmost respect,

Vulture

[Edited on 10-11-2003 by vulture]




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[*] posted on 10-11-2003 at 07:38


Maybe the text could also be hosted in the Science Madness Library, which is well started but a bit tiny :(



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[*] posted on 10-11-2003 at 08:09


Ok, here's the link to my webpage. Note that the information contained within was very time consuming and difficult to obtain.

I had to look up the references in a comprehensive 1950's tome entitled "The Chemical Elements and their compounds" by Sidgewick, travel to one of the largest historical chemical libraries in the world in Imperial Collage, London to get them and translate most of them from German.

Hare and Boye's journal was in the rare books dept and I had to obtain special permission to look at it!

Feast your eyes on this:

http://homepages.tesco.net/cdodgyd/perchloric.htm
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[*] posted on 14-11-2003 at 00:21


The site has been updated for faster loading pages, my thanks to chemoleo for the suggestion. Always happy to hear from anyone on the subject of explosives, especially the perchlorates!
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[*] posted on 14-11-2003 at 07:06


I would be VERY interested to see experiments with nitroniumperchlorate...:D



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[*] posted on 20-11-2003 at 18:55


Ethyl Perchlorate is quite the interesting molecule. Ive been looking up all I can in my library and found some other alkyl perchlorates that seem to have a nice ring to them.

Peroxyacetyl Perchlorate CH3COOOClO3 yeah, that one seems kind of unstable. And then Ethylene Diperchlorate, supposedly it's capable of detonation by the addition of a few drops of water.




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[*] posted on 21-11-2003 at 00:35


Excellent! Can you post references / scans? Must admit I haven't heard of these and I'm very interested.

Amazing to think ethyl perchlorate was discovered way back in 1841, before the discovery of nitroglycerin (1847)etc. Can you imagine their surprise, they can't have known what hit them!!!
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[*] posted on 21-11-2003 at 16:15


I found them in "Handbook of Reactive Chemical Hazards" it give some references. For Peroxyacetyl Perchlorate it lists
Quote:

Yakovleva, A. A. et al., Chem. Abs., 1979, 91, 210847

And for Ethylene diperchlorate
Quote:

Schumacher, 1960, 214 "A highly sensitive, violently explosive material, capable of detonation by addition of a few drops of water."

Also under the general heading of Alkyl Perchlorates it lists the following references:
Hofmann, K. A. et al., Ber., 1909, 42, 4390
Meyer, J. et al., Z. Anorg. Chem., 1936, 228, 314
Schumacher, 1960, 214
Burton, H. et al., Analyst, 1955, 80, 4
Hoffman, D. M., J. Org. Chem., 1971, 36, 1716
I believe that you collected your information from some of these. Im going to try and find one or two of them to find some more info, I will help any way I can.




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[*] posted on 22-11-2003 at 03:17


Thank you, that's wonderful! I will visit Imperial collage library next time I'm in London!
I 'missed' the latter references because my main reference text book dates from the late 50's! Perhaps I'd better update it - trouble with more modern text books is they miss out on the interesting obscure compounds and concentrate on orbital theory and all that theoretical stuff. All well and good but not of much use to the amateur!
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[*] posted on 28-11-2003 at 05:09


Just signed up for Brethericks' online database. Great resource though not entirely correct about the alkyl perchlorates being "easily" made from the alcohol and HClO4!

As to whether ethyl perchlorate is the most explosive compound known I'm not too sure either - I'd have thought the methyl ester was more so because it has an oxygen excess in the molecule!

Another interesting perchlorate mentioned is the trifluoromethyl ester - its (almost) stable due to the immense strength of the C-F bonds!

There is a great section on the perchlorate salts of nitrogenous bases both organic and inorganic, most of them have found use as rocket propellants or are explosive.

Of particular interest are the perchlorates of ethanolamine and ethylene diamine, the latter being considerably more powerful than TNT! Preparation in most cases must be fairly straight forward acid-base reactions like the TMA salt I mentioned in an earlier posting. There's a whole world of possibilities with these salts! ;)
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[*] posted on 11-12-2003 at 21:11


I borrowed the Schumacher book though an interlibrary loan program and read it front to back. It was a bit of a dissapointment as it only devoted about 12 pages to organic perchlorates. The most interesting section was on the Diazonium Perchlorates:
Quote:

A number of diazonium perchlorates were prepared by Hofmann and Arnoldi. These salts are sparringly soluble in water and are extremely explosive. The authors report that benzenediazonium perchlorate, a crystalline salt, is so explosve that a few centigrams of the compound, if allowed to fall on hard wood, will tear a deep hole in it. o-Toluenediazonium perchlorate will explode with great severity from the slightest pressure of a porcelain spatula, even when the compound is moist with ether. The (alpha)- and (beta)-naphthalenediazonium perchlorates also exploded violently when dry. The diazonium perchlorate of p-phenylenediamine was reported in 1910 to be the most explosive substance known. Their coupling power show them to be normal diazonium derivatives.

The sections on Nitroxyl Perchlorate and Nitrosyl Perchlorate were quite the let down. Regardless, these substances sound quite insane and I figured they deserved mention here.




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[*] posted on 12-12-2003 at 15:15


Very interesting - I must have a go at making these salts. Presumably they are made by the usual diazotization process but substituting HCl etc with HClO4? Like other diazonium salts they probably start decomposing unless the temp is kept low too?

Did Schumacher give a synthesis of Ethylene diperchlorate (or a reference to it) as mentioned in Bretherick's database? This compund sounds spectacularly explosive and I'm curious as to how it is synthesised!
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[*] posted on 12-12-2003 at 22:37


Additional information on the diazonium salts included:
Quote:

The diazonium perchlorates are particularly hazardous, being exploded by the slightest shock when dry. Hoffman and Arnoldi found that a few centigrams of benzenediazonium perchlorate falling on hard wood tore a deep hole in it, although the explosion was so localized as to leave intact a thin glass vessel 20 cm away. Even when wet with ether, o-toluenediazonium perchlorate exploded with great violence under slight pressure from a porcelain spatula. p-Toluenediazonium perchlorate was less sensative then the preceeding two salts, but both the a- and b-naphthalenediazonium perchlorates exploded violently when dry, m-Nitrobenzenediazonium perchlorate exploded spontaneously when heated to about 154 C, and was also sensitive to shock or to a blow. For use as primers, the maximum detonating power of the aromatic diazoperchlorates was obtained by the mononitro compound.

So since such a high temp is used to detonate the nitrobenzene derivative I guess some of the diazonium salts are somewhat more resilliant to heating then expected. On the note of perchlorate esters of ethylene glycol or glycerine the book had this to say.
Quote:

Partial and complete esters with ethylene glycol, glycerine and pentaerythritol were prepared by Zinov'ev by incremental addition of the alcohol to cooled (-75 to -78 C) anhydrous perchloric acid, followed by heating to 60 to 80 C. These reaction mixtures could not be diluted directly with water, since even a few drops of water caused violent explosions. Dilution was effected by first adding the constant boiling mixture of perchloric acid and water, after which, on addition of water alone, the heavy ester seperated from the aqueous solution.

Sorry I can't give exact references, they were footnoted in the text and I failed to make photocopies of the pages that relayed them. Although the procedure involving anhydrous perchloric acid seems a bit out of reach of the average mad scientist.... or right up his alley, depends on how you look at it. Good luck!:D




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[*] posted on 13-12-2003 at 02:43


I have made m-nitrobenzenediazonium perchlorate as well as the dinitro ( most likely 2,4-dinitro ) derivative. They are both powerful primary explosives with an incredibly high initiating power ( at least as good as undextrinated pressed lead azide; even on a volumetric basis ), but the mononitro compound is a little too sensitive, being exploded by vigorous rubbing with a ceramic pestle on a steel anvil. The dinitro compound is much less sensitive, about as much as HMTD.
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