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Author: Subject: Ethyl Perchlorate
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smile.gif posted on 13-12-2003 at 21:21


1,2- and 1,3-diperchloratopropane are perfect OB explosives!
C<sub>3</sub>H<sub>6</sub>Cl<sub>2</sub>O<sub>8</sub> <s>&nbsp;&nbsp;&nbsp;></s> 3CO<sub>2</sub> + 2H<sub>2</sub>O + 2HCl

is the diazotation product of p-phenylene diamine the p-phenylene <b>di</b>diazonium diperchlorate ?




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[*] posted on 25-12-2003 at 09:41


Yes, yes, I know I'm mad but I've tasted ethyl perchlorate!!!

After all its discoverers did and curiosity got the better of me! I used a standard food tasting strip - the ester has a very pleasant odour and a sweet taste that changes to a burning one like cinnamon as they describe. A very unusual sensation caused no doubt by hydrolysis on the tongue to ethanol and perchloric acid!

Brings a whole new meaning to "don't try this at home"!!!:o
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chemoleo
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[*] posted on 31-1-2004 at 09:37
Dichlorine Heptaoxide Cl2O7


I read something interesting today, in Advanced inorganic Chemistry by Cotton and Wilkinson:

Quote:

Dichlorine heptaoxide is the most stable chlorine oxide. It is a colourless liquid formed by dehydration of perchloric acid with P2O5 at -10 deg C, followed by vacuum distillation with precautions taken against explosion. It reacts with water and OH- to generate ClO4-. Electron diffraction shows the structure O3ClOClO3 (so the anhydride of perchloric acid). The reaction of Cl2O7 with alcohols yields alkyl perchlorates (ROClO3), which find use as intermediates in synthesis. It reacts (and this is cool) similarly with amines to yeild R2NClO3 or RHNClO3!!!!!


How cool is that? Blaster, fancy making some amine-perchlorates?

Besides, I am thinking that the distillation may not be necessary, possibly a mix of 99% perchloric acid and P2O5 will be enough, whereby the resulting phosphoric acid (??) hopefully does not interfere with the reaction...

[Edited on 31-1-2004 by chemoleo]




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[*] posted on 31-1-2004 at 18:46


If I'm not mistaken, can't Cl2O7 be generated in much the same way as Mn2O7? I think it may be the chlorate salt in this case. I'm quite confident that a mixture of Chlorate and fuel will ignite on contact with Sulfuric Acid. Quite similar to Permanganate and fuel.
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[*] posted on 1-2-2004 at 12:40


I'm quite confident that a mixture of Chlorate and fuel will ignite on contact with Sulfuric Acid.

That's because hypergolic ClO2 is formed.




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[*] posted on 7-2-2004 at 19:10


Amazing!



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[*] posted on 7-2-2004 at 20:02


Quote:

If I'm not mistaken, can't Cl2O7 be generated in much the same way as Mn2O7?


To an extent you're right. When potassium permanganate is added to concentrated sulfuric acid it becomes permanganic acid, which is then dehydrated to Mn2O7. With perchloric acid it is a bit more difficult. It would have to be done in two steps, the first would be the making of the perchloric acid with sulfuric acid and a suitible perchlorate, then distilling the perchloric acid with almost 6 times as much fuming sulfuric acid! This gives anhydrous perchloric acid which is actually an equilibrium mixture of Cl2O7 and HClO4 and H2O.

So some Cl2O7 could be created similarly to Mn2O7 but you would need a whole lot of H2SO4 and heat, and I believe that the distillation is what drives the reaction foreward, not to mention anhydrous perchloric acid is not a nice creature in the world of chemistry.




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[*] posted on 12-2-2004 at 15:46


I believe anhydrous HClO4 decomposes to various oxides of chlorine when stored, Cl2O7 being the principle oxide formed. This is the reason all the textbooks don't advise storage of the pure acid!

PS: I'm on a tour of the USA at the moment so my explosive exploits are on hold!
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[*] posted on 13-2-2004 at 11:11


In a book of hazardous chemicals and their reactions I ran across this for barium perchlorate:
Quote:
Alcohols
Kirk-Othmer, 1964, Vol. 5, 75
Distillation of mixtures with C1-C3 alcohols gives the highly explosive alkyl perchlorates. Extreme shock-sensitivity is still shown by n-octyl perchlorate.

Just adding more information to the thread, I don't know how well this works in realation to the Barium ethylsulfate with Barium perchlorate method but it does sound interesting.




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[*] posted on 20-3-2004 at 10:51


Here is a kind of funny addition to this thread:

http://www.engin.umich.edu/~cre/04chap/html/ahp04-a.htm

Here are some highlights:

"A rather sinister-looking gentleman sidles up to you one night and in a sibilant whisper asks you to make him some methyl perchlorate."

"You're not too comfortable with this situation, but times are hard, and you need the money."


But there is also pertinent information contained within, such as a rate constant for this reaction in benzene:

MeI + AgClO4 ---> MeClO4 + MgCl

It's a fairly slow reaction by the way.




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[*] posted on 18-4-2004 at 08:11


Except that your oxygen balance is bad to start off with. Adding more combustibles surely won't help.
Plus the inherent instability of EtClO4, I certainly wouldnt try it.
It's like asking, how about mixing NI3:NH3 with a few other nasties...




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[*] posted on 26-4-2004 at 00:13


Halogen,
You need to (re)-read my website. The alkyl perchlorates are so inherantly unstable they can only be made by a few methods. In almost all cases, hydrolysis will be the dominant reaction. Dry distillation is really the only viable route for the home chemist.
Perchloric esters
The manufacture of pure Cl2O7 is difficult and hazadous needing advanced equipment, so that route (even if possible) just isn't worth it.
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[*] posted on 26-8-2004 at 08:19
New web page address


New address for my webpage (changed due to a broadband upgrade):

PS: anyone had a go at ethyl perchlorate yet?!!!

http://www.cdodgyd.f2s.com/perchloric.htm
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[*] posted on 26-8-2004 at 16:51


No go at it yet, but what about you? You were really active making ethyl perchlorate and tetranitromethane in the course of a few weeks, then nothing of your other exploits, are you still actively experimenting?



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[*] posted on 27-8-2004 at 03:18


Thanks Bromic. I haven't done any more with Ethyl Perchlorate since but to assist those of you who might want a go at making it, here's a pic of the apparatus:



Firstly, note how small everything is. The condenser measures about 3" in length.

The aluminium bowl below the flask is filled with oil (I used Sunflower oil) and heated with a standard lab heater. You MUST monitor the temp though - no more than 200'C. I used a thermocouple (the wire you can see) attached to a multimeter, although a high temp thermometer would be just as good.

The flask is more or less filled with BaClO4 (foreground) and BaEthylSO4. Remember this is a dry distillation - see my webpage for details. Not shown is some heatproof cloth I used to keep the heat away from the condenser.

The receptacle should be positioned so that it actually touches the end of the condenser and doesn't drip (it might explode!). Both the receptacle and the red ice tray below are plastic in case of explosion.

The Ethyl Perchlorate comes over with water from the distillate and being denser, sits below it in the receptacle. The EP can then be taken up in a (preferably plastic) pipette.
The ester has a pleasant sweet smell.

I should also add that I wore safety specs INSIDE a motorbike helmet/visor and covered my torso and neck with a piece of sheet steel!!! I also wore two pairs of thick leather gloves. I couldn't wear these when using the pipette, so when the distillation was finished I moved the receptacle away from the apparatus and put it behind a wooden screen and sort of reached around that to take up the ester for testing!
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[*] posted on 27-8-2004 at 07:56


Blaster, how would you go about making Ba-ethylsulphate? What is it structurally, actually?



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[*] posted on 27-8-2004 at 09:12


Barium ethyl sulphate is stucturally just as you'd expect it to be, namely the barium salt of ethyl sulphuric acid:
[H3C-CH2-O-SO2-O]2 Ba
or more simply Ba(C2H5SO4)2

The synthesis of Barium propyl sulphate is given on page 6 of Meyer&Spormann's paper on my webpage and I adapted that using ethanol instead of propanol. You can use higher temps than they quote because the ethyl salt is more stable than the propyl.

Firstly you make ethylsulphuric acid by adding 10 ml ethanol (I used 96%purity) dropwise to 20ml conc. H2SO4. Its crucial to keep the temperature low (below 20'C) otherwise you end up with diethyl ether!

Leave it for two hours at that temperature then neutralise the whole thing with BaCO3 until no more CO2 is evolved, again keeping the temp below 20'C.

You end up with a thick paste, to which you add approx 200ml H2O and filter or centrifuge it. (I used the latter method which is much quicker). The solid BaSO4 and any unreacted BaCO3 can then be discarded and the Ba(C2H5SO4)2 in solution then needs to be evaporated down.
However, you cannot heat it to more than about 40'C as the product will decompose. For speed I used a vacuum dessicator, but I'm sure gentle warming in a current of air would do the trick, perhaps putting it in a normal dessicator when most of the liquid has gone because its quite hygroscopic.
When dry you end up with white flakes which can be ground up for use.

[Edited on 27-8-2004 by Blaster]
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[*] posted on 27-8-2004 at 10:46


Very interesting, thanks. Surprising how easy this is! I wondered - how is the formation of Diethyl sulphate avoided?

Also - when you made the ethylperchlorate - by mixing barium ethylsulphate with barium perchlorate, at what temperature does it form? Is distilling ultimately necessary? Or couldn't the two just be mixed, and utilised with a BaSo4 contamination?


[Edited on 29-8-2004 by chemoleo]




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[*] posted on 27-8-2004 at 12:42


I'm not an organic chemist (inorganic is my specialty) but I know that the reaction of sulphuric acid and ethanol gives all sorts of products entirely dependent on temperature. If the temp is low you get ethyl sulphuric acid, higher than that diethyl sulphate, higher still diethyl ether and if its heated like hell eventually ethylene gas!
I'm sure I've read that diethyl sulphate is actually made by heating ethyl sulphuric acid, so the answer to your first question is keep it cold!

I don't know the exact temperature at which the ethyl perchlorate is formed but nothing happens until steam starts coming off and explosions were reported above 200'C, so its between those temps.

Since ethyl perchlorate boils at 89'C, I can't really see any way of retaining it - refluxing would be extremely dangerous. You have to let it distill away really. I reckon a small retort would be suitable for simplicity although you might reduce the yield a bit.
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[*] posted on 27-8-2004 at 15:26


A point about perchlorate and substituted ammonium esters and salts - the most "efficient" ones as explosives, in terms of energy liberated, would be those in the molecules of which the number of bonds that can be oxidized (i.e. C-H, C-C, N-H, N-C) is closest to 8, noting that the Cl is reduced from the +7 to the -1 oxidation state on ignition. So the best low-molecular-weight perchlorate ester explosives would be cyclopropyl perchlorate (8 such bonds), 1,2 or 2,3-propenyl perchlorate (8), iso- or n-propyl perchlorate (9); and for amine salts, methylammonium perchlorate (7), cycloethylammonium and vinylammonium perchlorate (9), and dimethylammonium and ethylammonium perchlorate (10).

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[*] posted on 28-8-2004 at 16:42


JohnWW,

Organic perchlorate compounds, with the exception of salts are far too unstable to have any use as explosives.

The rest of the post is completely incorrect and displays fundamental misunderstandings about chemistry.

You do not oxidise bonds, bonds are where the electrons go, oxidation states are about formal charges, where the electrons would be if the molecule was ionically bonded, ie entirley about atoms.

Counting bonds is completely pointless, for N-H for example, the N will end up at oxidation state 0. The H will end up at oxidation state +1. For C-H, C will end up with oxidation state +2, or +4, the H will again end up +1. It makes no sense to treat these as the same.

Even the term "efficient" is completely meaningless on its own. What are you refering to, maximum energy per unit mass? Maximum energy density per unit volume? Perfect oxygen balence? Highest detonation velocity? Maximum energy yeild per molecule? None of these can be satisfied by adding up bonds.

8 bonds because the chlorine is dropping 8 oxidation states is misunderstood at a very basic level.

Blaster, its a very nice thread and the picture is perfect the size is currently is.

As I recall Rhodium has some ethylsulphate preperation methods on his page. They might be linked with the preperation of nitroalkane methods.
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[*] posted on 18-1-2005 at 01:00
more


Why bother with all of the large, heavy aromatics on the diazonium perchlorate instead of cycloalkanes or especially the newer cubane? Will anyone try an octaperchlorocubane? How does one find the octane rating of that?

Why is there still fear about blowing off fingers when it's the 21st century? Can't anyone just put together a CVD or PVD factory (slow and small, but many isolated flows) and have any desired substance waiting for you like a vending machine? Use wire-, laminate-, etc.-screens over the critical chambers. The thoughtful should be able to make alkyl perchlorates more useful than the stable explosives, even to make some on the spot and clock.

BTW, what do nonorganic and nonmetallic perchlorates smell and taste like?
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[*] posted on 18-1-2005 at 09:01


*They* already had enough on their hands making octanitrocubane.

See this link: http://physical-sciences.uchicago.edu/research/2002/articles... or search for octanitrocubane on Google.

Octaperchlorocubane? Maybe you meant octaperchloratocubane. Perchlorocubane and octachlorocubane are identical.

I wouldn't bother about the octane rating. This is too expensive and, IMHO, too energetic to put in a car engine.

With regards to your idea, my two cents worth on this is that this factory of yours can blow up as well. Shrapnel is painful. You never know. ;)

I am not at all aware of existing nonorganic/nonmetallic perchlorates. Even if there were, I'd give it a second and third thought to smell them, and I would never seriously consider tasting them.

Nothing else to add.

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[*] posted on 25-1-2005 at 13:19


I've seen the ethylsulfate method before. Could it perhaps be used to make Et-O-NO2? or other things like it? EtN3, EtIO3, EtIO4, EtBrO3, EtBrO4 and Et-O-CO-O-Et come to mind...

It might be a good way to make such interesting chemicals.




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[*] posted on 26-1-2005 at 19:33
Time to look up references...


J. Org. Chem. 1971 36 1716
Page 1
Page 2
Page 3

This article details the preperation of alkyl perchlorates in situ by reaction of a alkene with lithium perchlorate in sulfuric acid and extracting with an inert hydrocarbon. Fun stuff!

Chem. Abs. 1979 91 210847
Quote:
91: 210847m Low-temperature electrochemical method of preparing alkyl peroxyperchlorates. Yakovleva, A. A.; Bairamov, R. K.; Veselovskii, V. I. (Nauchno-Issled. Fiz.-Khim. Inst., Moscow, USSR). Elektrokhimiya 1979, 15(8), 1114-18 (Russ). RCO2OClO3 (I; R = Me, Et) were prepd. by electrolysis of the corresponding carboxylate salts in 4 - 8 N HClO4 at -20 deg and >3.5V,. I were oxidizing agents and exploded on detonation or friction. A mechanism of I formation involving the interaction of adsorbed carboxylate radical anions and perchlorate radicals was proposed.,

Also from references in the first article I found more journals, I looked up:
H. Burton, D.A. Munday, and P. F. G. Prail, J. Chem. Soc., 3933 (1956)
Titled "Acylation and Allied Reactions catalysed by Strong Acids. Part XV. Some Reactions of Simple Alkyl Perchlorates." With the abstract
Quote:
Alkylation of anisole and benzene by methyl, ethyl, n-propyl, and the four butyl perchlorates has been studied. Two types of reactoin appear to be taking place: (1) nuclear alkylation occruing almost simultaneously with the fomration of alkyl perchlorate in solution, (2) subsequent alkylation by the alkyl perchlorate in certain cases. Detailed mechanisms have not been determined. The possible importance of these types of reactions in the more conventional Friedel-Crafts reactions is discussed.
It was an interesting article but it did not have any good infomation on the preperations of alkyl perchlorates that is not covered in other places, although they do appear to be very useful in organic synthesis.
J. Randell, J.W. Connolly, and A.J. Raymond, J. Amer. Chem. Soc, 83, 3958 (1961).
Quote:
[Contribution from Research and Development Group Frankford Arsenal, Philadelphia 37, Pa; Aeronautical Research Lab., Wright-Patterson Air Force Base, Ohio and the Research Division of the Wyandotte Chemicals Corp., Wyandotte, Mich.]
n-Alkyl Perchlorates: Preparation, Study and Stabilization
By Jack Radell, J.W. Connolly and A. J. Raymond
Received April 22, 1961
Abstract: The previously unreported normal pentyl, hexyl, heptyl and octyl perchlorates were prepared from the corresponding alkyl iodide and silver perchlorate. The pure esters of perchloric acid were stabilized as the endocyte of a urea inclusion compound. The infrared spectra and some physical properties are reported for the n-alkyl perchlorates
Although the prepartions are a little tough in this one, the stabilization and other physical information make a good read, I will probably scan this in the future.

Enjoy!

BTW: How long has Blasters page been down? I think I was just there a week or two or three ago but it's not loading today, it doesn't have his e-mail anyway, I just wanted to tell him I had more information.

[Edited on 1/27/2005 by BromicAcid]




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