Sciencemadness Discussion Board - The Ultimate Energetic Compound

The Ultimate Energetic Compound

JustMe - 3-12-2003 at 16:08

Well, I've always been interested in the limits of chemistry. I was fascinated by xenon chemistry, chemical preparation of fluorine, exotic stuff like that that caused textbooks to be rewritten. But I've been following stories on another extreme compound and where it might lead... to some new allotropes of nitrogen... very highly energetic compounds indeed! Some of it it only theoretical, but here is a link to one of the articles:

http://pubs.acs.org/cen/topstory/8033/8033notw1.html

I've read some other stuff, and although N8 (N5N3) seems impossible, there is theoretical evidence that N10 (N5N5) would be stable enough to exist at room temperature, having the structure of two five-membered rings connected to each other by one bond.

But last night I read one researcher who has an entirely different goal... N60! A Buckminsterfulverene made entirely of nitrogen! (synthesized from N10). I know that there are now C60 compounds with up to, I think, four or five nitrogens, but imagine the energy of N60!

Anyway, just wanted to throw this extreme (energetic) chemistry idea out there, if you haven't heard of it.

Blind Angel - 3-12-2003 at 18:16

It has already been discuss (in surface) in an other thread.

http://www.sciencemadness.org/talk/viewthread.php?tid=81

and maybe there also:

http://www.sciencemadness.org/talk/viewthread.php?tid=126

P.S.: I just want to point that there are some info on the board, not that this thread is useless

DDTea - 3-12-2003 at 18:47

On the note of the extremities of Chemistry, I was thinking about random nitrates the other day, nitrated Fullerenes and the like, but in doing searches for information I came across a dead Yahoo Chemistry board. Someone there was discussing the synthesis of Dinitroacetylene, since he could find almost nothing about it... Here is a synthesis that I propose; it is similar to that of Dihalo-acetylene compounds.

The main precursor would be 1-Chloro-1,2-Dinitroethylene. The reaction apparatus would consist of an Addition funnel, a Boiling Flask, a two-holed stopper, and an apparatus to add Nitrogen Gas to the system. Due to the nature of these reactive variants of Acetylene, it would not be safe to try their synthesis in everyday apparatus. They tend to burn spontaneously in air, you see.

Anyhow, the 1-Chloro-1,2-Dinitroethylene is added to the boiling flask, and the flask is purged of air by the N2 gas. In the addition funnel is 82% NaOH (this is the solution suggested by "War Gases" in the synthesis of C2Br2). The contents are kept cool through the use of a water bath. The addition of the NaOH solution should take 2 hours, after which time air-free water is added. In theory, a layer of C2(NO2)2 should separate at the bottom...

Now, some questions. Could any inert or relatively unreactive gas provide an atmosphere for this reaction? Because CO2 would be much easier to get than N2. Also, an ice bath could be substituted for the water bath, right? Or would that be TOO cold for the reaction to occur? And, instead of 1-Chloro-1,2-Dinitroethylene (which looks to be a strong lachrymator, similar to Chlorpicrin), could 1,1,2-Trinitroethylene react with NaOH to produce C2(NO2)2 and NaNO2?

By the way, the Dihaloacetylene compounds also decompose explosively, if you fancy such exotic compounds

[Edited on 12-4-03 by Samosa]

JustMe - 3-12-2003 at 18:47

So sorry, then... I did search for the topic before posting, but apparently didn't use the right keywords. But having viewed the threads, I still think that the link would be of interest... THAT portion is not theoretical, but real! Cool stuff, to me.

BTW: here are the links regarding N60:

http://www.llnl.gov/str/June01/Manaa.html

http://www-cms.llnl.gov/s-t/ex_soccer.html

[Edited on 4-12-2003 by JustMe]

Blind Angel - 3-12-2003 at 18:52

Just Me: I didn't meant to say that you posted something already post, i just wanted to show you that there was maybe some other info that could interest you on other thread

JustMe - 3-12-2003 at 18:55

You're right, of course... thanks, then BA.

BromicAcid - 3-12-2003 at 19:34

Well.... let's make some pentanitrogen cation!

(N2F)+(AsF6)- (HF) + HN3 (HF) ---@-78 C--> (N5)+(AsF6)- (s) + HF (l)

It sounds like more trouble then it's worth, like trying to make perbromic acid, but it would make for some pretty good bragging rights.

Xenon compounds are pretty interesting explosives, acutally anything with high nitrogen content attracts my intrest even NH4N3 is captivating to me.

Theoretic - 5-12-2003 at 08:09

Samosa:
The alkali-metal hydroxide dehydrohalogenation method is said to give "very low yields".
You might want to try calcium oxide (not to be confused with calcium hydroxide), which is a base more powerful that alkali hydroxides. Or calcium ethoxide, prepared by reacting cacium oxide with ethanol. It seems a better option, since it is soluble in some solvents and does not have such a strong crystalline lattice, which might hinder the reaction.
The precursor could also be 1,2-dichloro-1,2-dinitroethane, although it would require double dehydrohalogenation.

unionised - 5-12-2003 at 14:46

Just a thought, Octaazacubane. (N8)

Theoretic - 31-12-2003 at 08:48

Another idea on preparation of C2(NO2)2:
I think it could be prepared by reacting calcium carbide and nitryl chloride (NO2Cl) to make calcium chloride and the desired compound. Nitryl chloride is made from anhydrous sulfuric acid and chlorosulfuric acid at 0 C. Chlorosulfuric acid is made by reacting dry hydrogen chloride and sulfur trioxide.

Mumbles - 31-12-2003 at 09:32

Just curious, but how does Sulfuric acid and chlorosulfuric acid make nitryl chloride?

H2SO4 + HSO3Cl ---> NO2Cl ?

I think you might have a reagent mixed up as you have no nitrogen at all on the reactant side, unless it reacts with air maybe. Did you mean anhydrous nitric acid maybe? If so, that reaction works yielding Nitryl chloride and sulfuric acid.

HNO3 + HSO3Cl ---> NO2Cl + H2SO4

[Edit] Ahhh, I see from another post you did mean nitric.

[Edited on 12-31-2003 by Mumbles]

KABOOOM(pyrojustforfun) - 2-1-2004 at 13:43

Theoretic: I first read about your dinitroacetylene idea on Kewls welcome, have I got recipes for you! I thought you were joking (u were but...), nitrychloride explosively reacts with some organic compounds (I would say not just organic compounds). IF the reaction could take place at all it would be an explosive one, making caclium chloride nitrogen CO2 and other byproducts from side reactions

Theoretic - 3-1-2004 at 06:08

Kaboom:
A solution would be to cover calcium carbide with an inert solvent such as carbon tetrachloride (not chloroform) and slowly drop in nitryl chloride. It would dissolve, and slowly reach the carbide, thus the reaction would be moderated. A problem is that dinitroacetylene (let's say DNA from now on) is likely to be soluble in carbon tetrachloride and could react with nitryl chloride...
My concept was that the nitryl ion (NO2+) that results from an ionisation equilibrium in nitryl chloride (I assume) would react with the carbide ion (C2--):
2NO2+ + C2-- => C2(NO2)2.

Mendeleev - 7-1-2004 at 20:00

Currently, the main strategies employed for strengthening explosive compunds is the addition of furoxan groups instead of nitro groups to hydrocarbons, making strained cage compounds, and, making nitro ureas. Currently the most powerful explosives are dinitroazofurozan(DNAF) vod = 9700-10000, octanitrocubane(ONC) vod = 9800-10000, and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexazatricyclo(7,3,0,0)dodecane-5,11-dione(HHTDD) vod= 9700. Keto RDX is also pretty damn decent with a vod of 9500. The three highest ones have problems DNAF is very sensitive, HHTDD is decomposed easily by water, and they haven't yet made the densest all powerful isomer of ONC. Keto-RDX however is powerful as hell and quite insensitive, unfortunately its not something you could do with over the counter chemicals, however there are a few good companies who sell to individuals. Once I get the needed funds it could be promising synthesis...

Nick F - 8-1-2004 at 05:07

Mendeleev: extract triazone from N-Sure or Blend-Plus or other slow-release nitrogen fertiliser (many contain triazone, but perhaps not all. Check first!), react with anhydrous nitric acid, you get K-RDX...

Mendeleev - 8-1-2004 at 17:36

Yeah, the exotic chemical is the result of condensing formaldehyde, nitroguanidine, and tert-butylamine. This product, 2-nitrimino-5-tert-butyl-hexahydro-1,3,5 triazine. It is then subjected to chloride assisted nitrolysis, and poof! Mono-keto-RDX. NH4Cl addition improves the yield. And thanks for the fertilizer idea Nick F, I didn't expect to find triazine in fertilizers.

Edit: Scratch that first thing about the exotic chemical, it is tert-buytlamine, I was thinking of another similar nitrourea when I was talking about the condensation and NH4Cl.

[Edited on 14-1-2004 by Mendeleev]

verode - 31-7-2006 at 12:42

Quote:

Originally posted by Nick F
Mendeleev: extract triazone from N-Sure or Blend-Plus or other slow-release nitrogen fertiliser (many contain triazone, but perhaps not all. Check first!), react with anhydrous nitric acid, you get K-RDX...

franklyn - 31-7-2006 at 17:37

Quote:

Originally posted by JustMe
Well, I've always been interested in the limits of chemistry.
I've been following stories on an extreme compound and where
it might lead. imagine the energy of N60!

I tried previously to suggest a way in which something more modest
might be achieved. Since I am not taken seriously it went unnoticed.

see -> http://www.sciencemadness.org/talk/viewthread.php?tid=6027

.

Sickman - 31-7-2006 at 23:13

Speaking of allotropic explosives perhaps:

Magnesium Nitride + Deuterium Oxide (heavy water)--->

Mg3N2 + 2H20 ---> NH6 + Mg(OH)?

The idea is this: normally magnesium nitride reacts with normal H2O to form ammonia gas and magnesium hydroxide.

However in our reaction we substitute normal water for heavy water (deuterium oxide). In hopes that we may form the dueterium analog of ammonia with a content of six hydrogen atoms instead of three.

This deuterium ammonia is then nitrated to dueterium ammonium nitrate. Which may be represented by the formula: NH7NO3?

Of course if such an explosive analog of ammonium nitrate could be synthesized, it would be very oxygen deficient. However the excess hydrogen would simply be extra gas in the explosion which could react with atmospheric oxygen to further enhance performance.

Perhaps, the deuterium ammonia analog cannot be formed or nitrated, although it seems like a reasonable idea to me, I thought I'd just throw it out there!

I just had another thought! It maybe that the extra hydrogen in the analog would not come out as loose H2, but rather may once again form heavy water upon detonation, meaning an oxygen positive explosive once again!
The result would be an explosive with greater density and with a higher temperature and energy content.

[Edited on 1-8-2006 by Sickman]

Nerro - 31-7-2006 at 23:22

Sickman; no. NH7 is never ever ever going to happen. There are not enough valence electrons on the N atom to bind seven protons.

You will just have this reaction:

Mg3N2 + 6D2O -> 3Mg(OD)2 + 2ND3

Sickman - 31-7-2006 at 23:39

So Nerro, what is 2ND3 and can it be nitrated?

YT2095 - 1-8-2006 at 00:14

I seem to remember hearing about another explosive that seemed rather exotic, involving liquid nitrogen and specialy prepared Silicon, don`t quote me, but I think it was something like 7 times the power of TNT.
and apparently discovered purely by accident.

Sickman - 1-8-2006 at 00:43

Is not 2ND3, the deuterium ammonia analog I was hoping for by my reaction of magnesium nitride with heavy water (deuterium oxide)?

Would it not form upon nitration exactly the deuterium ammonium nitrate analog I had in mind?

I think my mistaken formula is what threw Nerro off.

What I was trying to represent by my formula was the extra hydrogen atoms in the deuterium molecules + the hydrogen from the nitrate group representing the total number of hydrogen atoms in the new compound, not that 7 hydrogen atoms would bond to a single nitrogen atom.

[Edited on 1-8-2006 by Sickman]

Nerro - 1-8-2006 at 00:50

2ND3 means 2 molecules of ammonia, the hydrogen atoms on the ammonia molecules are all replaced by deuterium atoms which are 1 proton and 1 neutron in the core and 1 electron in the shell rather than the usual 1 proton and 1 electron in the shell.

Obviously it can be nitrated, add DNO3 or HNO3 and evaporate the water (preferably D2O

) to yield either ND4NO3 or ND3HNO3

Sickman - 1-8-2006 at 01:58

So is my idea new or has this deuterium analog of ammonium nitrate been prepared before and described in the literature?

Please give references to patents etc.

Is there any information on explosive power and characteristics compared to regular ammonium nitrate, I would assume a greater velocity of detonation and quantity of gas per kilogram of explosive?

I would also assume that the interesting ammonium picrate analog is also possible by reacting picric acid with the deuterium ammonia analog!

In fact I can think of many possible explosive substances possible using deuterium as a substitute in just about every high explosive imaginable that contains the light H2 molecule!

We can increase both density and energy content, however the cost of heavy water (deuterium oxide) is a draw back for sure, although it is very much OTC if we are wanting it!

[Edited on 1-8-2006 by Sickman]

Marvin - 1-8-2006 at 05:10

Deuterium is just a different isotope, the performance in an explosive will be less by a miniscule amount.

DeAdFX - 1-8-2006 at 06:24

Quote:

Originally posted by Sickman
So is my idea new or has this deuterium analog of ammonium nitrate been prepared before and described in the literature?

Please give references to patents etc.

Is there any information on explosive power and characteristics compared to regular ammonium nitrate, I would assume a greater velocity of detonation and quantity of gas per kilogram of explosive?

I would also assume that the interesting ammonium picrate analog is also possible by reacting picric acid with the deuterium ammonia analog!

In fact I can think of many possible explosive substances possible using deuterium as a substitute in just about every high explosive imaginable that contains the light H2 molecule!

We can increase both density and energy content, however the cost of heavy water (deuterium oxide) is a draw back for sure, although it is very much OTC if we are wanting it!

[Edited on 1-8-2006 by Sickman]

I recall reading an article talking about radioactive ammonium nitrate as a way to detect people who use it for illegimate purposes...

Sickman - 1-8-2006 at 10:05

Deadfx, I wasn't exactly thinking radioactive

Tritium ammonium nitrate dirty bomb

YT2095 - 1-8-2006 at 10:43

here we go, this is an item regarding the post I made previously: http://www.newscientist.com/article.ns?id=dn1103

I knew I wasn`t dreaming

neutrino - 1-8-2006 at 12:33

Ah yes, LOX-porus silicon explosives. These were discussed here and at roguesci.org a few years back.

hinz - 1-8-2006 at 15:26

Ammoium dinitramide looks interesting.

http://enermat.org.ru/ammomium.html (found it while looking for pka of tetranitrocubane)

Wonder if it's further nitratabe to trinitramide to N(NO2)3 would be quite interessting, but I think it's impossible due steristic issues and electronic issues, central N is quite possitive charged, poor nucleophile on NO2+, but NI3 is also existent and if the oxygen atoms of each NO2 are standing straight (not in the same plane as the central N atom), the NO2 wouldn't need to much place.

Does anyone know if nitromethane is further nitratable to tetranitromethane since it's a weak acid, thus a potentially weak nucleophile on NO2+ and once its nitrated to dinitromethane the molecule will be nitrated completly to TeNM due it's acidity. Since it works also with a chlorination agent forming chloropicrin, but under basic conditions which eliminate a proton and producing a higher concentration of the nucleophile, I think the whole reaction needs some (long?) time. I've ordered 5l of CH3NO2 and these 5l need an application together with my fuming nitric acid. And TeNM balanced on CO/H2O/Al2O3 in a mix with Al and low melting parafine (to prevent the separation of the Al dust/ acting as a binder) would be quite interesting like a flash with VoD of 8km/s

Nick F - 1-8-2006 at 17:28

Please, do some reading. TeNM is often discussed.

JohnWW - 1-8-2006 at 17:48

Someone asked on this thread about octaazocubane, N8, i.e. cubane in which all the CHs are replaced by Ns. Even more energetic wou;ld be Octaazidocubane, C8(N3)8, in which all the Hs in cubane are replaced by azide groups, and in which the strained carbon rings add to the energy available. This compound has actually been made, and papers about it and other azidocubanes have appeared as attachments in this part of sciencemadness.org.
Also dodecaazidododecahedrane, C12(N3)12, i.e, dodecahedrane, C12H12, in which the Hs have been replaced woth azido groups. I doubt that this has been made, though. Other possibilities include hexadecaazidobuckminsterfullerene, in which the C60 is saturated by having azido groups added, C60(N3)60.
More simply, also with a highly strained carbon ring adding to the energy, one could have triazidocyclopropane, C3(N3)3, and the corresponding cyclobutane derivative, C4(N3)4. I am not sure whether they have been prepared.
Because such azido derivatives are likely to be dangerously explosive, the nitro derivatives would be safer to handle.

[Edited on 2-8-2006 by JohnWW]

franklyn - 5-8-2006 at 10:33

Quote:

Originally posted by YT2095
here we go, this is an item regarding the post I made previously: http://www.newscientist.com/article.ns?id=dn1103

I knew I wasn`t dreaming

Well, rub your eyes some more _
I'm astonished that a semi reputable magazine as New Scientist
would publish something that is so blatantly stupid through and through.
I quote "The substance - an exotic form of silicon - releases seven times
as much energy as TNT, and explodes a million times faster."
Given that the reaction time is proportional to the velocity of detonation,
and for T.N.T. this is 7.8 kilometers per second, a million fold increase is
7 million plus kilometers per second. The speed of light is 300,000. Duh
Even if this is just a wave involving no mass transport, no information,
detonation wave, or anything else can exceed 300,000.

As if that wasn't enough let me also run this by you.
The energy product of T.N.T. is 930 Kilogram Calories per Kilogram of T.N.T.
The energy product of Silicon Dioxide formed from its elements Silicon and
Oxygen, is some 3800 Kilogram Calories per Kilogram, or just 4 times as much, not 7 times.

[Edited on 5-8-2006 by franklyn]

not_important - 5-8-2006 at 17:03

Well, New Scientist has been going downhill, although they've managed to avoid Page 3 girls so far.Looks like he's sold someone on it as an explosive

http://www.newscientist.com/article/mg18024243.300.html

He has continued messing about with porous Si and O2, although not explosively

http://www2.kobe-u.ac.jp/~fujii1/Journal/68_2004_APL_Kovalev...

But he did give a talk that included the porous silicon explosive, last year

http://matsci.iw.uni-halle.de/nanosec/

(the speaker after him, Pacholski, has been doing some interesting work)

Here's a bit more recent information

http://www.trnmag.com/Stories/2002/022002/Chip_provides_more...

Engager - 29-8-2006 at 18:18

I've heard that inhert gas compounds such as XeO3 are extremly poverfull explosives, because of extremly high energy release on Xe-O bond breakage. I've also heard that XeO3 has unbeliveable brisance as well. I wonder how powerfull will be explosive mixture of XeO3 + active metall (Al for example), it will probably detonate on contact of reagents.

Germans in WW2 tried to make a superbombs mixing liquid C2H2 with liquid ozone. All planes with such kind of bombs were exploded on takeoff, so the stuff was forgotten. I think this mix will be far more powerfull that any of imaginable nitro compounds. Mixture of liquid (CN)2 with liquid ozone will be even more powerfull, at normal conditions this mixture burns with temperature of 10000K - that is the highest temperature achiveable in chemical combustion.

The third candidate is a ethyl perchlorate, that was considered as most powerfull explosive compound known for almost century (until first inhert gas compounds vere found). Glycerin triperchlorate is pretty much the same but more powerfull and unstable in pure state.

[Edited on 30-8-2006 by Engager]

franklyn - 29-8-2006 at 20:37

The problem with binary or sprengel mixtures is that at least one component if
not both need to be liquid in order to get an intimate molecular mix, otherwise
you have just a low velocity pyrotechnic. A liquid phase mix of Acetylene and
Cyanogen is of interest because the products of detonation are all combustable
in air, hence there is an additional thermobaric effect. But for a handful of
exceptions ( Astrolite, PLX, Kinepak ) such materials are not used because
almost all are dangerously shock sensitive, thus they will detonate upon impact
precluding deep penetration of a target and timed initiation by a fuze.

I have thought that the binary gas artillery shell design could be applied to
binary or sprengel type explosives. The mixing is done during flight thus there
is no risk from recoil and setback upon firing. Such a munition would be safer
than anything in use now.

[Edited on 30-8-2006 by franklyn]

not_important - 29-8-2006 at 20:57

And the problem with liquid O3 is that it tends to go off when a door slams, or a butterfly flaps its wings, or it feels like it. Adding hydrocarbons to liquid ozone is a Bad Idea.

XeO3 around and above its melting point is similarly unstable, I believe.

franklyn - 1-9-2006 at 20:02

Reasons militating against introduction of more energetic compounds
to subplant those in current use are cost, necessarily caused by the
complexity of their manufacture. http://www.llnl.gov/str/Pagoria.html
consider whats involved just to obtain the precurser for octanitrocubane
http://www.chem.ox.ac.uk/dhtml/default.html

It seems conterintuitive that almost polymeric forms of nitrogen have
a more realistic prospect of implementation
http://www.afrlhorizons.com/Briefs/Dec01/PR0106.html

I have wondered if the Oxygenyl ( O2 +) cation radical could be coupled
with the Superoxide ( O2 -) anion radical into a stable molecule by the
double replacement of their salts O2SbF6 and KO2
Without quenching this reaction by itself would be quite energetic.
following this idea _
NitroniumTetrahydroAluminate NO2AlH4 or the Borate NO2BH4
or
TetraFluoroammoniumTetrahydroBorate NF4BH4 or the Aluminate NF4AlH4
would be interesting if it could be formed at all.

.

Mr. Wizard - 1-9-2006 at 23:27

Doesn't the formation of diatomic H2 from two monatomic H atoms release more energy than any other combination? If the monatomic atoms could be held apart with say a magnetic or electric field or magic or whatever, then it would make a great fuel or energy storage device. What are the spin directions of the atoms of H2? My physics is a little weak in that area.

artem - 17-9-2006 at 08:19

Quote:

Originally posted by Mendeleev
Yeah, the exotic chemical is the result of condensing formaldehyde, nitroguanidine, and tert-butylamine. This product, 2-nitrimino-5-tert-butyl-hexahydro-1,3,5 triazine. It is then subjected to chloride assisted nitrolysis, and poof! Mono-keto-RDX...
[Edited on 14-1-2004 by Mendeleev]

Here is the article about keto-RDX.

Attachment: PEP1994-5-232.djvu (117kB)
This file has been downloaded 900 times

nitro-genes - 17-9-2006 at 09:57

This article also mentions an acid hydrolisis route from hexamin, followed by condensation with dinitrourea. Not sure if this has been mentioned before, though I'm pretty sure I have seen dinitrourea and keto-RDX been discussed on roguescience somewhere, without results for the synthesis of either of them IIRC...

[Edited on 17-9-2006 by nitro-genes]

Attachment: Synthesis, characterization and thermal studies of keto-RDX or k-6.pdf (113kB)
This file has been downloaded 2161 times

Axt - 17-9-2006 at 21:54

The triazone fertiliser mentioned in the PEP article as the most convenient precursor is patented US4778510. Note the same "triazone corporation" responsible for fertiliser used in PEP article, and the patent. Gives correct pH, temp, time ratio of ammonia:formaldehyde:urea to form triazone urea mixture with minimal hexamine. Bit annoying to read though.

Also I'll attach an article, give synthesis of keto-RDX via potassium sulphamate:urea:formaldehyde. Only 18% yield though.

Attachment: use of potassium sulfamate in the synthesis of heterocyclic nitramines.pdf (271kB)
This file has been downloaded 1340 times

The_Davster - 17-9-2006 at 22:21

Is anyone else downright aroused by the product formed when aminotetrazole is used instead of urea?

Product V. Too bad chromatography is needed for purification.

Microtek - 18-9-2006 at 01:52

Personally, I prefer the nitrated condensation product with DAF. They mention a melting point of 151 C, so depending on decomposition temp it might be a candidate for a castable material. The yield also seems quite good.

nitro-genes - 20-9-2006 at 06:46

I wonder if the triazone precursor for the manufacture of keto-RDX could be made with higher purity using formic acid. Could a 3:2:1 molar ratio of ammonia/formaldehyde/formic acid yield 1,3,5 triazone upon evoparation to dryness and/or heating slightly?

formic acid + ammonia yields ammonium formate:

HCOOH + NH3 → NH4+HCOO-

Which upon heating forms formamide according to:

NH4+HCOO- → HCONH2 + H2O

Since the first step is the acid/base reation of the ammonia with formic acid, very little hexamin should be expected in the final product...

[Edited on 20-9-2006 by nitro-genes]