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Author: Subject: Exotic Primaries - Complex Salts
jlithen
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[*] posted on 15-11-2006 at 13:03


I just have to say one thing related to my previous post on this thread (long time ago now).
LNP (Lead nitrato phosphite) is actually very sensitive to friction...when I noticed it I got very frightened as I have handled it rather uncarefully. It say on megas site that it is "stable" of course not necessarily meaning insensitive.
How stupid of me to not immediately check the sensitivity of a substance that I have been using for years. Anyway the detos seem to work relatively well, even after months of storage, but I would like to change the LNP to something more powerful and maybe even less sensitive. Although senitivity has not been a problem in the caps.
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[*] posted on 23-12-2006 at 11:12


I tried making a complex Triethanolamine(TEA) of my own. I first made copper (II) nitrate by reacting copper sulfate and potassium nitrate in 30mL of water(1/10 mol scale). I fucked up though and added half as much KNO3 as I should have(christ this is the 2nd time I have neglected the fact that SO4 is a -2 ion). Well anywho I added in 20mL of TEA into the CuSO4/Cu(NO3)2 solution. The solution turned a dark turquiose(SP) color. After swirling the solution for a few seconds the color intensity went down a bit. I added 30mL of ethanol and a blue/turquiose perciptate formed. The perciptate is really fine. I assume its about >200 mesh easy. Right now the perciptate is drying off in the air.


I wonder if Copper (II) Nitrate would form a complex with nitrosoamines like NitrosoEthanolamine or Dinitrosoethanol amine. These complexes would probably be more energetic due better OB.

Anywho Copper(II) Nitrate TEA complex should be more stable* than the tetramine variant. By stable I mean the complex won't fume off ammonia and become useless after a few days. TEA has a much higher boiling point.

[Edited on 23-12-2006 by DeAdFX]
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[*] posted on 24-12-2006 at 13:13


UPDATE:

The complex has dried off and still has the same turquiose color. I burned a small sample of the complex. The sample turned from a turquiose color to a black color indicating the complex decomposed to copper(II) oxide. The decompisition was not violent nor was there any flame. To verify that I had a copper complex I burned the sample with some Ammonium Perchlorate in a paper cup. The resulting flame was a very pretty blue.
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[*] posted on 25-12-2006 at 08:34


Copper (II) nitrate is SO hygroscopic that there would be some water in the crystals unless special efforts were taken and that would effect the outcome to a degree that it would deflagrate. Under other circumstances it may well detonate but the water would present a problem. Copper (II) nitrate has often had this as a stumbeling block. The issue has arisen with many primaries. Even lead-based materials, if water still existed within the final product, they did not respond well. Really -=DRY=- material often tests far differently. Determine if any water existed before making a final assesment.



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[*] posted on 15-1-2007 at 07:13


Quote:
Originally posted by quicksilver
Copper (II) nitrate is SO hygroscopic that there would be some water in the crystals unless special efforts were taken and that would effect the outcome to a degree that it would deflagrate. Under other circumstances it may well detonate but the water would present a problem.


You mean that copper (II) nitrate can detonate?
If yes do you know anything about its properties(stability,VOD and how to dehidrate it)?




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quicksilver
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[*] posted on 17-1-2007 at 06:19


No it does not. It is a nitrate salt that is very hygroscopic but that in use, it brings with it so much water that unless steps are taken to deal with the water - the compound / resultant will have that issue. Some primaries are desensitized by water to a greater degree than others., etc.



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[*] posted on 17-1-2007 at 17:26


DeadFX what I really wonder is why you think TEA is an appropriate complexing agent. I mean, for one Cu ion there are two molecules of TEA, and 2x NO3. If you calculate the oxygen balance, you'll note it is appalling. No way this will ever make it into some sort of energetic material.
Try hydrazine, hydroxylamine (although I think that I tried that before, and it doesn't work-> decomposition in solution), guanidine, and other small nitrogen containing bases, these are feasible targets! Or even tetrazole, I think Nick F may have tested that.




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[*] posted on 14-2-2007 at 12:01


Would it not be one molecule of TEA per copper atom?



F. de Lalande and M. Prud'homme showed that a mixture of boric oxide and sodium chloride is decomposed in a stream of dry air or oxygen at a red heat with the evolution of chlorine.
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[*] posted on 15-2-2007 at 00:50


Quote:
Originally posted by chemoleo
DeadFX what I really wonder is why you think TEA is an appropriate complexing agent. I mean, for one Cu ion there are two molecules of TEA, and 2x NO3. If you calculate the oxygen balance, you'll note it is appalling. No way this will ever make it into some sort of energetic material.
Try hydrazine, hydroxylamine (although I think that I tried that before, and it doesn't work-> decomposition in solution), guanidine, and other small nitrogen containing bases, these are feasible targets! Or even tetrazole, I think Nick F may have tested that.


The reason I thought TEA would be a more suitable complexing agent is because it has a way higher boiling point than ammonia[liquid vs gas]. The TEA complex should be more stable in the sense of having a somewhat longer shelf life with a major sacrifice in power. However my experiment was a failure because I had a miscalculation so the power is yet to be determined. The perchlorate variant would probably show more promise.

The nitrogen bases that I posses are urea and hexamine[yeah yeah big molecule..]. Technically I could also posess ammonia, guanidine and methyl amine if I weren't so god damn lazy/bogged with work. I also have azide however my time is limited in my home lab so I can't synthesize tetrazole and even then my knowledge in high explosives is rather limited.

Even if the compound is only capable of a simple burn it will still be of practical use for me atleast. Somewhat off topic but I am working on a blue star composition involving Ammonium Nitrate( I hear it burns a lot cooler than Perchlorates] as the primary oxidizer. So far I have very little success.
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[*] posted on 15-2-2007 at 06:46


OT remark:

Blue is a tough color to get right. However I have had some success. The problem is that metal fuels (other than copper) will drown it out very fast. Ammonium nitrate could work just fine if you used something like: ammonium nirate 33% nickle or cupric nitrate 20% copper powder (325 mesh) 13% chlorine doner 20%, burn rate enhanser 7% binder 6% - The burn rate enhancer is needed due to ammonium nirate's slower burn and less O than the perchlorate. It's a problem and a good thing as well.

[Edited on 15-2-2007 by quicksilver]




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[*] posted on 13-3-2007 at 17:26


Haven't seen any mention of nitrato/nitrito-metal complexes for energetic complex salts in this thread (or I have overlooked them :)). Some would be pretty promissing, like the hexanitritocobaltate(III) ion. The sodium salt is one of the few well soluble salts, while it readily precipitates with K+ or even NH4+...

Forming a salt with methylamine, urea, hexamine, etc could give interesting results, no idea what it's properties, or how stable they would be, as most NO or NO2 ligand metal complexes are not very stable...

Are there even any known nitrito/nitrato complexes that have been reported to have primary explosive properties? I seem to remember this nitrato-Hg(II) aldehyde complex, though it was a rather feeble explosive IIRC...

[Edited on by nitro-genes]
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Rosco Bodine
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[*] posted on 13-3-2007 at 20:17


Joeychemist got this file from solo ,
and hasn't posted it here so I will .

Attachment: Explosive Properties of Metal Ammines.pdf (273kB)
This file has been downloaded 2272 times

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[*] posted on 13-3-2007 at 22:12


Thanks for posting that article! :)

Ammonium hexanitrocobaltate(III) goes out the window as it seems concerning it's potential as a primary. Hydrazine hexanitrocobalate still seems pretty spicy though, if it would exist that is...

Most of the used oxidizers seem to stable to accellerate fast enough to behave like a primary, like the perchlorates or nitrates. On the other hand the chlorates are capable of doing so, but are not very storage stable. For that matter would the peroxo chromates Woelen posted about be a good starting point, since it was pretty obvious that it is a very powerfull oxizer, but seemingly stable in storage...

[Edited on by nitro-genes]
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[*] posted on 6-8-2007 at 11:59


[Edited on 24-12-2007 by Ballermatz]
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[*] posted on 6-8-2007 at 13:21


Nitrito-?



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[*] posted on 6-8-2007 at 13:46


[Edited on 24-12-2007 by Ballermatz]
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[*] posted on 6-8-2007 at 14:45


Quote:
Originally posted by 12AX7
Nitrito-?
nitrite as a ligand ;)



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[*] posted on 6-8-2007 at 15:50


Yes; he spelled "nitrato" is all. I wasn't aware NO3- formed ligands, but I've heard of the NO2 cobalt complex.

Tim




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[*] posted on 6-8-2007 at 17:03


Why shouldn't nitrate form ligands? It does, it even forms reasonably stable eta-2 ligands (bridging ligands with 2 hapticity).



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[*] posted on 7-8-2007 at 01:27


Getting the anions of strong oxy-acids like NO3-, SO4--, ClO4-, BrO4-, IO4-, and similar, and of strong fluoro-acids like PF6-, SbF6-, BF4-, to act as ligands is very difficult, if not impossible, because of their high symmetry and steric crowding reasons, and, in the case of the oxy-acids, their resonance-stabilization which results in the negative charge being evenly distributed over the oxygens.
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[*] posted on 7-8-2007 at 04:33


Which makes it impractical for an amateur chemist but not impossible on the whole.



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[*] posted on 7-8-2007 at 10:45


I'm almost 100% sure that the yellow material, mentioned here is ammonium hexanitritocobaltate (III). So, nitrite as ligand and not nitrate. I have the sodium salt of this complex ion and indeed it forms beautul precipitates with ammonium salts and even better results are obtained with potassium salts. I know of nitrato complexes, e.g. UO2(NO3)2 and also some cerium compounds, such as (NH4)2[Ce(NO3)6].



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[*] posted on 7-8-2007 at 12:04


Are those the nitrito complexes (-O-N=O) or the nitro complexes (with the bond being made by the lone pair on the N)?

And how feasible is it to make a complex like ferrocene but with N<sub>5</sub><sup>-</sup>? (the structure of which being similar to that of the cyclopentadienyl ion). Is anything known of such complexes and their stability?

-Edit-
The complex would be called bis-pentazolido iron(II).

Quote:
source
Abstract : The pentazole anion has been generated from para-hydroxyphenylpentazole and identified by electrospray ionization mass spectrometry. Whereas at low collision voltages the para-phenoxypentazole anion undergoes stepwise N2 elimination generating the corresponding azide and nitrene, at high collision voltages the N5(-) anion is formed. Fragmentation of the pentazole anion produces the N3(-) anion as the principal negative ion. These experiments provide the first experimental proof for the existence of the pentazole anion. They also demonstrate that under suitable reaction conditions the C-N bond in a phenylpentazole can selectively be broken with conservation of the pentazole ring, thus providing a potential synthetic route to the pentazole anion.

Doesn't sound like a very usefull synthesis... I remember synthesizing the cyclopentadienyl ion by letting a saturated solution of KOH with excess KOH at the bottom react with C<sub>5</sub>H<sub>6</sub>, why shouldn't something similar work on HN<sub>5</sub>? A stronger base will probably be needed...

Could an oxidizing agent be applied to synthesize N<sub>10</sub> (+2H<sup>+</sup> and two electrons)? Sounds like a pretty dangerous substance to me but perhaps at -80°C it might be stable enough?

And I also read that phenylpentazole is much more stable than just pentazole. Could para-dipentazolebenzene be synthesized somehow? And how is phenylpentazole synthesized anyway?

[Edited on 7-8-2007 by Nerro]

[Edited on 7-8-2007 by Nerro]




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[*] posted on 8-8-2007 at 16:51


Hey Nerro: if find out more stuff about ferrocenes please post 'em! I'm interested also and have had little luck......
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[*] posted on 8-8-2007 at 17:38


I have done minor looking into of pentazoles
Phenylpentazole is formed by the reaction of benzenediazonium chloride with sodium azide, this is analogous to the making of tetrazoles by the reaction of cyanides, 5-phenyl -1H-tetrazole being formed from phenylacetonitrile and sodium azide.

I have seen a paper somewhere about the free pentazoles, it was posted on this site years ago. I forget one very important thing, whether it was theoretical, or had been done before. It was on a 'pentazolium pentazolate' compound which could cyclize into a nitrogen flavour of buckyballs.


1H,5H-tetrazole can be formed from anhydrous HCN and HN3, problem is finding a nitrogen analogue of HCN that would be substitutable here. Acetylides/acetylene(forget which exactly) also react with HN3/NaN3 making the triazoles, but no such easy lab analogues exist for N. I wonder if under extreme conditions nitrogen gas would react with HN3? Some sort of exotic excitation would likely be necessary,and under pressure.



EDIT:
Quote:

And how feasible is it to make a complex like ferrocene but with N5-? (the structure of which being similar to that of the cyclopentadienyl ion). Is anything known of such complexes and their stability?


There is something close, nitrotetrazolate CN4NO2-, ion would seem to be similar to a substituted cyclopentadiene, but its complexes are not eta5, all I have seen is eta1. A tetrazolate might make a ferrocene type compound, but I have seen nothing on it as a ligand.



[Edited on 8-8-2007 by The_Davster]




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