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Rosco Bodine
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Here are a couple of additional articles of interest.
Attachment: nhn1.pdf (175kB) This file has been downloaded 1754 times
Attachment: JSIR 63(8) 677-681.pdf (70kB) This file has been downloaded 1471 times
[Edited on 21-2-2013 by Rosco Bodine]
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franklyn
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Metal Hydrazine Complexes , Patents
US 5970703 , US 6481746
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franklyn
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Apparently co-crystallized compounds of Cyanides with Nitrites have been noted
but out of sight and earshot of the mainstream , as mentioned halfway down here _
www.guidechem.com/reference/dic-15333.html ( See " Reactivities and
Incompatibilities " )
( Just as I said in my post above here )
" Mixtures of Sodium Nitrite and various Cyanides explode on heating, including Potassium Cyanide,
Potassium Hexacyanoferrate(III), Sodium Pentacyanonitrosylferrate(II), Potassium Hexacyanoferrate(II),
or Mercury(II) Cyanide. Such mixtures have been proposed as explosives, initiable by heat or a detonator.
A mixture of Sodium Nitrite and Potassium Thiocyanate explodes on heating.
There is no interaction between Sodium Nitrite and Sodium Thiosulfate in solution, but evaporation
of the mixture gave a residue which explodes on heating. The mixed solids behave similarly."
__________________________________________
- and now for something completely different
Na2NO2 , Disodium Nitrite ? Huh
http://sodium.atomistry.com/disodium_nitrite.html
See bottom of page " 10 Miscellaneous Cathodic Reductions "
http://books.google.com/books?id=6ghTyzzOzM8C&lpg=PA74&a...
An excerpt from " Reduction of Inorganic Substances "
http://tera-3.ul.cs.cmu.edu/NASD/4dcb85c3-9fee-4c83-9e6d-fe6ce5522b59/China/disk1/46/31004737/PDF/00000119.pdf
Disodium Nitrite, an Additive Compound of Sodium Nitrite and Sodium
http://pubs.rsc.org/en/content/articlelanding/1917/CT/ct9171...
Electroreduction of Nitrate to Nitrite to Hydronitrite
http://jes.ecsdl.org/content/101/5/229.abstract
Mellor 8: Supp. 1, 546 (1964) obtained this from NH4NO3 with sodium
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Rosco Bodine
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trimethylammoniumpentazidodicuprate
A similar complex to Diazidodiamminocopper(II) described on page 8 of this thread is a related Trimethylamine complex or compound salt
trimethylammoniumpentazidodicuprate
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...
Quote: Originally posted by Taoiseach | was prepared according to
CuSO4*5H2O + 2NH3 + 2NaN3 ---> [(NH3)2(N3)2Cu] + Na2SO4 + 5H2O
NH3 was added to a solution of CuSO4 until the precipate of Cu(OH)2 redissolved. A saturated warm solution of NaN3 was added. Upon cooling and
addition of an equal volume of ethanol, a nice crop of [(NH3)2(N3)2Cu] precipated.
Green-blue glistering crystals. Unlike copper azide these are not friction sensitive. Explodes upon flame contact.
Obviously the compound is oxygene-deficient, so addition of a strong oxidizer should increase its power. |
trimethylammoniumpentazidodicuprate is a similar compound about which I can find very little information. It is unclear to me if this type complex
or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with copper azide, or if other trimethylamine salts
such as the perchlorate may also form a complex or mixed salt with copper azide. It would seem possible that different metals may also form analogous
compounds as does copper.
See attached excerpt from PATR for description of
trimethylammoniumpentazidodicuprate
(CH3)3N-HN3-2[Cu(N3)2]
Attachment: TMA - PATR Vol. 9 Q-T.pdf (103kB) This file has been downloaded 1091 times
[Edited on 17-3-2013 by Rosco Bodine]
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AndersHoveland
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Quote: Originally posted by Rosco Bodine | It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with
copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide.
(CH3)3N-N3-2[Cu(N3)2]
dark red crystals, explodes at 201°
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I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The
compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as
an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.
I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably
also be too electron-withdrawing.
Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:
[(CH3)3N]3Ni+1(N3)3 •
(ClO4−)
The nickel center can only complex to 6 ligands, so that would leave a +1 ionic charge, so that perchlorate could be part of the complex salt also.
The electronic configuration of the nickel in this proposed compound would correspond to the nickel complex NiF62−, which has been described in the literature.
It could perhaps be prepared by reacting nickel(II) perchlorate with trimethylamine in excess hydrazoic acid.
[Edited on 17-3-2013 by AndersHoveland]
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Rosco Bodine
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Quote: Originally posted by AndersHoveland | Quote: Originally posted by Rosco Bodine | It is unclear to me if this type complex or compound salt is strictly limited to the example of trimethylamine azide forming a complex salt with
copper azide, or if other trimethylamine salts such as the perchlorate may also form a complex or mixed salt with copper azide.
(CH3)NH-N3-2[Cu(N3)2]
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I think perhaps you mean (CH3)3N-N3-2[Cu(N3)2] |
You are correct ....my typo above has been edited to show "3" for the trimethyl and I see it would also be better to show the trimethylamine as
hydro-azide analogous to TMA hydrochloride...which is what I think is probably the case here. If I am on the right track then an anlogous compound
may be possible with chlorides as is showing for the azides.
Quote: |
I think I know exactly what the structure of this salt is. 3 azide ligands are complexed to the copper center, along with the trimethylamine. The
compound can be seen as a sort of adduct, with the trimethylamine being electron donating towards the azide groups, or alternatively it can be seen as
an additional azide anion complexed to Cu(N3)2. The copper can be seen to lie somewhere between the +2 and +3 oxidation states.
I am fairly certain none of the azides could be substituted with perchlorate. Perchlorate does not act as a ligand, and furthermore would probably
also be too electron-withdrawing.
Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:
[(CH3)3N]2Ni+2(N3)4 2(ClO4-)
The nickel center can only complex to 6 ligands, so that would leave a +2 ionic charge, so that perchlorate could be part of the complex salt also.
[Edited on 17-3-2013 by AndersHoveland] |
I'll have to do some reading on these complexes to be sure.
My first inclination would be to disagree about the metal being "complexed" by the azide, as it would be more my inclination to expect the
complexation involves the substituted ammonia with the metal to form the complex which then forms a mixed salt or compound salt with the uncomplexed
metal salt. The complexation of the metal by the substituted ammonia would seem to be analogous for what happens with complexation by hydrazine or
semicarbazide, where an "ammonia value" is present as some multiplier. However that value is 0 for trimethylamine, which does not form a complex with
copper. It seems almost as if part of the compound is trimethylamine "hydro"-azide which exists or can exist as a distinct compound, cocrystallized
as a double salt with 2 copper azides.
This behavior may be peculiar because trimethylamine does not form a complex with copper as does ammonia.
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AndersHoveland
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The article listed the possible formulas as either:
Quote: |
(CH3)2NH[(N3)2CuN3Cu(N3)2 or
(CH3)3N.HN3.2[Cu(N3)2]
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It seems they were not entirely sure what the structure actually was. I think the name "trimethylammoniumpentazidodicuprate" is therefore probably
very misleading.
Perhaps I am just overthinking this too much, and the salt just consists of trimethylammonium cations and
Cu(N3)3− complex anions.
[Edited on 17-3-2013 by AndersHoveland]
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Rosco Bodine
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Yeah it is intriguing huh. It sort of looks like a complex ...but not exactly, and may simply be a multiple salt.....which is what my impression was
that led me to speculate even other multiple salts could form as series. But it may not follow at all that way because it could just be a peculiar
anomaly that is true for only this one case. Clearly some other investigators were definitely scratching their heads looking at this one ......and we
can agree it is red.
And it is energetic ...but what are its properties?
Anyway it's a possible "green energetic" so it caught my notice.
Just for giggles Google
trimethylammoniumpentazidodicuprate
What do you get ?
Consider the possibility that a compound salt could form between Trimethylamine Perchlorate and Copper Azide , now that would be interesting.
All right Klapotke, enough loafing, time to get back to work
[Edited on 17-3-2013 by Rosco Bodine]
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Rosco Bodine
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metal carbohydrazide complexes
With regards to my post on the preceding page
http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...
there is information in the hydrazine thread which has bearing upon preparation of carbohydrazide from hydrazine cyanurate but this is uninvestigated
and will require experimental confirmation.
http://www.sciencemadness.org/talk/viewthread.php?tid=1128&a...
Also one of the articles which was posted previously as an attachment evidently has too long of a name and is not downloading true as a pdf so I am
attaching the name edited file here.
Attachment: Talawar Studies on Lead free initiators metal complexes of carbohydrazide.pdf (415kB) This file has been downloaded 2208 times
In my earlier post is a typo which I need to correct or clarify
Where I wrote "semicarbazide" should be corrected to read "carbohydrazide" as is the context for the attached article.....even though the same may be
true for the semicarbazide complex analogue, I have not yet found references for the semicarbazide complex to verify this.
"With regards to the semicarbazide [should read carbohydrazide] complex of nickel perchlorate or in the alternative the more
expensive cobalt perchlorate, these compounds appear to be very promising as fairly easily made initiators."
Attached is an article of interest Thanks to gsd
Chemistry of carbohydrazide and thiocarbohydrazide
Frederick. Kurzer, Michael. Wilkinson
pp 111–149
Publication Date: February 1, 1970 (Article)
franklyn mentions that carbohydrazide is also known as diaminourea ( DAU )
http://www.sciencemadness.org/talk/viewthread.php?tid=15455&...
Attachment: THE CHEMISTRY OF CARBOHYDRAZIDE AND THIOCARBOHYDRAZIDE.pdf (850kB) This file has been downloaded 8915 times
Attachment: Explosives Based on Diaminourea (carbohydrazide).pdf (240kB) This file has been downloaded 1411 times
[Edited on 22-3-2013 by Rosco Bodine]
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AndersHoveland
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I just had an idea, I thought I would mention it here.
Take a look at the structure of Manganese(III) acetate. It has a surprisingly complicated inter-coordination structure. Each cluster consists of 3
manganese atoms, 6 acetate groups, a central oxygen atom, and each cluster has a positive charge, typically with an extra outside acetate ion
associated with it. The bonding in the cluster is very delocalized, I would draw an analogy to acetylacetone with copper ions (copper acetylacetonate
is almost aromatic).
So would it be possible to use dinitrosomethanate in place of the acetate? (dinitrosomethane has an aci-tautomer)
That would leave a positively charged cluster, and then presumably some other oxidizing anion like perchlorate or nitroformate could be associated
with it.
Mn3O[CH(NO)2]3+ C(NO2)3‒
The cluster also has 3 water molecules of hydration, not shown, but those could possibly be replaced with NH3.
resonance diagram of dinitrosomethanate ion:
O=N‒CH=N‒O‒ <--> O‒‒N=CH‒N=O
resonance diagram of formate ion:
O=CH‒O‒ <--> O‒CH=O
similar to acetate ion
[Edited on 11-6-2013 by AndersHoveland]
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papaya
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While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're
instable or just no information?
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PHILOU Zrealone
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Quote: Originally posted by papaya | While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're
instable or just no information? |
The facts are that...
Zn nitrate forms a stable hydrazine complex
Ni (II) nitrate forms a stable hydrazine complex
Cd(II) nitrate forms a stable hydrazine complex
Co (II) nitrate forms a stable hydrazine complex
But...
Cu (II) nitrate forms an unstable hydrazine complex
Hydrazine and iodine or iodate are uncompatible...
Silver nitrate is unstable towards hydrazine...
So watching closely to the oxydoredox potential table
There must be an electrochemical explanation to this...
See hydrazine at potential at +0,11... Zn, Ni, Cd, Co are above in the negative potential...while Cu, Ag, Iodine and Iodate are below...
Cr(3+) and Cr(2+) seems to be on the safe side!
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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papaya
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Quote: Originally posted by PHILOU Zrealone | Quote: Originally posted by papaya | While reading this thread I didn't see something like chromium (III) nitrate complexes with hydrazine or ethylenediamine, is the reason that they're
instable or just no information? |
The facts are that...
Zn nitrate forms a stable hydrazine complex
Ni (II) nitrate forms a stable hydrazine complex
Cd(II) nitrate forms a stable hydrazine complex
Co (II) nitrate forms a stable hydrazine complex
But...
Cu (II) nitrate forms an unstable hydrazine complex
Hydrazine and iodine or iodate are uncompatible...
Silver nitrate is unstable towards hydrazine...
So watching closely to the oxydoredox potential table
There must be an electrochemical explanation to this...
See hydrazine at potential at +0,11... Zn, Ni, Cd, Co are above in the negative potential...while Cu, Ag, Iodine and Iodate are below...
Cr(3+) and Cr(2+) seems to be on the safe side! |
Well, once I tried to mix dilute Cr(NO3)3 + HNO3 solution with 50% hydrazine hydrate (few ml scale) and immediately obtained green precipitate which
didn't burn and actually was metal hydroxide. However supernatant liquid turned into pink color which indicate something more interesting happened
there besides that classical acid-base reaction. There was no formation of gas observed, so hopefully no worries about hydrazine decomposition. I
didn't investigate it further because I have no source of decent quality chromium nitrate (pure solid salt), perhaps with a proper synthesis method
this is doable. It may be fun for anyone here to try and report results and properties here for a first time before it get's published in academic
journals (if it's really new)!
Also as there are 3 nitrate anions - more oxygen is available and it must be worth to try to prepare some (insoluble) complex with organics like
acetonitrile, real pain is that many of these things may be soluble in water and require anhydrous conditions (as well as anhydrous chromium salt).
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papaya
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Hi, a long thread so I might miss something - did anyone actually try to synthesize bis- nickel hydrazine azide, that is mentioned on p.13 here? How
stable is it (to storage, humidity, etc.), ? Is it a "real" primary with a short DDT, or merely deflagrates/explodes? It's characterized as even less
sensitive than tris- hydrazine nickel nitrate in Ilyushin's paper attached there, which is counter-intuitive (azide!). What about other azide
complexes(Zn, Co,..) - was any tried here? Thanks.
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DraconicAcid
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Quote: Originally posted by papaya |
Well, once I tried to mix dilute Cr(NO3)3 + HNO3 solution with 50% hydrazine hydrate (few ml scale) and immediately obtained green precipitate which
didn't burn and actually was metal hydroxide. However supernatant liquid turned into pink color which indicate something more interesting happened
there besides that classical acid-base reaction. There was no formation of gas observed, so hopefully no worries about hydrazine decomposition. I
didn't investigate it further because I have no source of decent quality chromium nitrate (pure solid salt), perhaps with a proper synthesis method
this is doable. It may be fun for anyone here to try and report results and properties here for a first time before it get's published in academic
journals (if it's really new)! |
Chromium(III) is a very non-labile ion. Once you've got [Cr(H2O)6]3+ in solution, the water ligands don't really
want to come off very rapidly. If you let your solution mixture of chromium(III) nitrate and hydrazine stand for extended periods of time, you might
form the complex.
If the solution is basic, that can speed it up (a base can catalyze it by forming a hydroxy complex, which is more labile), or you can sometimes
catalyze it by reducing chromium(III) to chromium(II), which is much more labile.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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papaya
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Thanks Draconic, so perhaps I had to keep that Cr(OH)3 formed in contact with solution for a long time until it converts to the desired product.
And what about bis- nickel hydrazinium azide ?
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DraconicAcid
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Nickel(II) is quite labile- if it forms, it should form quickly.
I'm not sure how well azide works as a ligand, though- I don't have much experience with azides.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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DraconicAcid
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Quote: Originally posted by AndersHoveland |
Likely other azide complexes of the same type are possible with other transition metals. It's rather speculative on my part, but I was thinking:
[(CH3)3N]3Ni+1(N3)3 •
(ClO4−)
The nickel center can only complex to 6 ligands, so that would leave a +1 ionic charge, so that perchlorate could be part of the complex salt also.
The electronic configuration of the nickel in this proposed compound would correspond to the nickel complex NiF62−, which has been described in the literature.
It could perhaps be prepared by reacting nickel(II) perchlorate with trimethylamine in excess hydrazoic acid.
[Edited on 17-3-2013 by AndersHoveland] |
Sorry, but that's not going to work. Azide is an anionic ligand. To get [NiL3(N3)3]ClO4 (where L is a
neutral ligand, such as ammonia or trimethylamine), you would have to have nickel in the +4 oxidation state, which is not preferred for nickel.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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papaya
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http://www.tandfonline.com/doi/abs/10.1080/00945719608004763...
This might help if somebody has access...
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Rosco Bodine
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Thanks to Dany for the following article attached
Synthesis and Characterization of Some Cobalt(II), Nickel(II), Zinc(II) and Cadmium(II) Hydrazine Azides
K. K. Naranga, M. K. Singh (Mrs), K. B. Singh & R. A. Lal
Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry
Volume 26, Issue 4, 1996, pages 573-589
Also attached is a related article of interest
Attachment: Metal Hydrazine azide complexe.pdf (508kB) This file has been downloaded 1059 times
Attachment: Hydrazine complexes of transition metals as explosives chemik_2011_65_1_24-27.pdf (193kB) This file has been downloaded 1349 times
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papaya
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Lately I managed to prepare and test some 0.2-0.3g of Ni[N2H4]2(N3)2 complex - it's a very fine light blue powder, that readily catches fire (flashes)
when exposed to fire, I didn't notice it to be highly sensitive and can be handled without too much risk in my opinion (was a small quantity and I
never tried to see how it behaves under different mechanical stimuli). However that 0.2g did NOT detonate when confined(slightly hand-pressed) into
soft PVC tube having about 4mm of internal diameter and 1mm of wall thickness and lit from open side. So not a first class primary
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DubaiAmateurRocketry
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Quote: Originally posted by AndersHoveland | Perchlorate complex salts of hydrazine are dangerously friction sensitive. Hydroxylamine perchlorate is very sensitive, having a drop height value of
only 2cm. |
Can I have a reference for the 2cm drop height value ?
That sounds very extreme! I've never seen a explosive with an positive OB of +42% can have such a sensitivity.
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DubaiAmateurRocketry
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Di-dinitramide salt of this also seems to be interesting derivative.
[Edited on 14-12-2013 by DubaiAmateurRocketry]
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franklyn
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Hydrazine complexes of transition metals as prospective explosives
www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf
Coordination explosives
www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf
.
Techniques to Disrupt, Deviate and Seize Control of
an Internet Forum In case you wonder W T F ! is going on here
?
www.zerohedge.com/contributed/2012-10-28/cointelpro-techniques-dilution-misdirection-and-control-internet-forum https://web.archive.org/web/20120814124000/www.washingtonsblog.com/2012/08/the-15-rules-of-internet-disinformation.html
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Rosco Bodine
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Quote: Originally posted by franklyn | Hydrazine complexes of transition metals as prospective explosives
www.chemikinternational.com/pdf/2011/01_2011/chemik_2011_65_1_24-27.pdf
Coordination explosives
www.chemikinternational.com/pdf/2010/01_2010/chemik_01_2010_023_024.pdf
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Here attached is the second linked file and the first is a few posts above.
Attachment: chemik_01_2010_023_024.pdf (173kB) This file has been downloaded 1098 times
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