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Author: Subject: Exotic Primaries - Complex Salts
Axt
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[*] posted on 17-2-2005 at 01:36


I had this written down so I think its what I did:

36g 25% ammonia solution was added to A warm solution of 16g CuSO4.5H2O in 150ml water. To this was added a solution of 20g KMnO4 in 270ml water. The mixture was then chilled to 10°C and the fine sludgy precipitate filtered out and dried.

I dont know about the purity of the product, but the silver salt is nearly insoluble, thus easily extracted and its properites are no better, so I dont think much more can be expected.
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[*] posted on 17-7-2005 at 23:20
Trihydrazine Nickel (II) Nitrate


Hello,

I'm wondering, does anyone have experience with this compound?

There is a Wikipedia article about it here:

http://de.wikipedia.org/wiki/Nickelhydrazinnitrat

(It's in German, but you can easily translate it using the following).

http://babel.altavista.com/babelfish/

It seems to have many good properties, but I would like to know about long term stability in storage and compatability with metals, which the article doesn't say.
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[*] posted on 18-7-2005 at 06:57


For convienience: http://babel.altavista.com/babelfish/trurl_pagecontent?lp=de...

Interesting...

[Edited on 7-18-2005 by 12AX7]




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[*] posted on 18-7-2005 at 07:43


See

GB821586
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chemoleo
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[*] posted on 18-7-2005 at 14:57


Merged with this thread.
Please note that nickel hydrazine nitrate has been discussed already in the first post of this thread.

There is a paper from the Journal Propellants, Explosives, Pyrotechnics that deals with it (Title: Evaluation of a New Primary Explosive: Nickel Hydrazine Nitrate (NHN) complex ), if someone's got access to this journal please upload the article here!




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[*] posted on 18-7-2005 at 18:10


Thanks for the references.

I wonder about zinc vis-a-vis nickel. Has anyone any theoretical or experimental info? Seems to me it would be a little less toxic if nothing else.

Anyway, I've given up on TACC and TACN...I'm now looking for new bones to knaw on.

I got nowhere with TACN. I made one batch of successful TACC that detonated some picric acid, but it was not repeatable. Moreover, the TACC rapidly lost ammonia and became inert after sitting around for a few days.
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[*] posted on 19-7-2005 at 10:39


Can anyone tell me something about tetramminecopper perchlorate? Because ive HClO4 i could try it. How sensitive is it and how strong? It would be great if you could tell me something. The tetraminecopper persulfate is also very interesting.

[Edited on 19-7-2005 by Kinepak]
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[*] posted on 20-7-2005 at 20:27
TACP


You can find some information by following the link below (about 3/4 of the way down the page).

http://roguesci.org/theforum/showthread.php?t=161&page=5...

I would like to know if anyone has experimented with hexammine nickel perchlorate.
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[*] posted on 21-7-2005 at 13:17


Quote:
Originally posted by chemoleo
There is a paper from the Journal Propellants, Explosives, Pyrotechnics that deals with it (Title: Evaluation of a New Primary Explosive: Nickel Hydrazine Nitrate (NHN) complex ), if someone's got access to this journal please upload the article here!

Here:

Attachment: PEP97_06_317.djvu (36kB)
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[*] posted on 21-7-2005 at 13:47
PEP articals required


Artem, I think it will be very much appreciated, if you would be so kind as to uploade any PEP articals you may have to MadHatter's FTP. I don't want to burden you with any obligations, but maybe oneday when you have any spare time and some extra bandwidth available.....please !.
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[*] posted on 6-12-2005 at 01:47
Detonation of Nickel Hydrazine Nitrate???


I have made som Nickel hydrazine nitrate both by using Hydrazine sulphate and hydrazine solution. It is a nice substance that burns extremely fast. I also like the fact that it is easy to prepare if you just avoid breathing the hydrazine fumes and getting poisoned.

I have made many detonators containing about 0.8-1g of NHN but they don't detonate. I have made the detonators by rolling Al-foil around a pen.
I once stuffed a detonator into a wood log that I had drilled a hole into and it made a loud bang that shot the log into 5-6pieces. But I have still not managed to detonate any other explosive by means of NHN, I'd say it CAN NOT substitute Lead azide.

Anyone had any success?

I have been thinkin of using some sturdier tubing for the detos. but I don't like havin explosives in metallcontainers and then there is always the need for a hole for the fuse (if not using electrical ingnition)
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[*] posted on 6-12-2005 at 02:02
Tetramine copper perchlorate


Quote:
Originally posted by Kinepak
Can anyone tell me something about tetramminecopper perchlorate? Because ive HClO4 i could try it. How sensitive is it and how strong? It would be great if you could tell me something. The tetraminecopper persulfate is also very interesting.

[Edited on 19-7-2005 by Kinepak]


TACP is an easy to prepare compound. I have made it by dissolving coppersubcarbonate into perchloric acid untill no gas develops anymore. The solution can be very concentrated but it is hard to dry. It may be a good idea to dilute it slightly before the next stepp and deffinitely let it cool before adding ammonia.
To the Cu(ClO4)2 solution carefully add (in some excess) ammonia solution. And some of the TACP will precipitate. To precipitate the rest add about 5 times the volume of ethanol (92%EtOH/8%acetone has worked fine) Filter (maybe wash with EtOH) and dry!

The explosive formed is first a blue fine crystalline powder but turns violet when dried. It is very sensitive compared to most other complexes and I think it is poweful too.
Hitting it with the pestle in a mortar will make it go bang very easily, I have luckily not had any accidents though. Neither have I managed to make any working detos. woth it. A tube with 1g resulted in a mini-rocket:)

(I don't remember exactly but I think i have used something around 3ml HClO4 (70-72%), maybe about 5g Cusubcarb. and 10ml 25% NH3 and the added about 1/2 dl of ethanol. The yield is then around 5grams.)
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[*] posted on 6-12-2005 at 08:24


Quote:
Originally posted by jlithen
I once stuffed a detonator into a wood log that I had drilled a hole into and it made a loud bang that shot the log into 5-6pieces. But I have still not managed to detonate any other explosive by means of NHN, I'd say it CAN NOT substitute Lead azide.


I think, there is no "ideal" primer. More safety - hard to initiate. Many complexes are of high safety, but very often, without appropriate confinement and initial impulse they tend to deflagration or low-velocity detonation (for NHN, see, for example, PATR H199). Probably, particle size also play role.
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[*] posted on 9-12-2005 at 16:58


Hello jilithen,

Can I ask, how did you prepare NHN from hydrazine sulfate?

BTW, with regard to its use in detonators, here is some relevant information from PATR 2700, p H200:

"The possibility of using Ni nitrohydrazinate
in commercial detonators was investigated
by loading Cu caps of 5mm diam with 2.5g of
Ni complex and trying to detonate them by
means of a fuse, or an electric igniter. No ‘
detonations were produced unless the substance
was primed by ca 1.5g of Black Powder.
In attempts to increase the detonability of
Ni hydrazinate, it was mixed with equal parts
of an easily ignitable initiating substance, such
as Pb- styphnate or Pb- picrate, and then ignited.
The best that could be obtained was a deflagration
but no detonation. Mixtures of the Ni
complex with RDX deflagrated and only in
one case detonated (Ref 3)."

Regards,
Joe

Quote:
Originally posted by jlithen
I have made som Nickel hydrazine nitrate both by using Hydrazine sulphate and hydrazine solution. It is a nice substance that burns extremely fast. I also like the fact that it is easy to prepare if you just avoid breathing the hydrazine fumes and getting poisoned.

I have made many detonators containing about 0.8-1g of NHN but they don't detonate. I have made the detonators by rolling Al-foil around a pen.
I once stuffed a detonator into a wood log that I had drilled a hole into and it made a loud bang that shot the log into 5-6pieces. But I have still not managed to detonate any other explosive by means of NHN, I'd say it CAN NOT substitute Lead azide.

Anyone had any success?

I have been thinkin of using some sturdier tubing for the detos. but I don't like havin explosives in metallcontainers and then there is always the need for a hole for the fuse (if not using electrical ingnition)
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[*] posted on 9-12-2005 at 21:35


There may be critical diameter >7mm and
a critical mass > 1.5 grams with strong confinement
for the DDT to high order detonation to occur
with samples of the complex which are not mixed
with other primaries having better self-accelleration .
A similar problem exists for lead styphnate ,
by itself it can take several grams to reach the
velocity needed for a detonator , unless a third
of the styphnate is replaced with something much
more rapid in small quantities , like lead azide .

The attached patent also mentions that copper and
perhaps other metal salts of other oxidizing acids besides nitric , can form explosive complexes not only with hydrazine ,
but also with semicarbazide , and " oxiamines " ?

There are some other possibilities for experiments with
complexes . It would be my guess that cobalt and zinc
would also possibly form such complexes .

Attachment: GB821586 Nickel Hydrazine Nitrate Complex Detonators.pdf (253kB)
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[*] posted on 11-12-2005 at 11:35


Hi joe!

I made NHN by dissolving about 50 grams of Hydrazinesulfate and 1xx grams of Ba(OH)2*8H2O in water (stochiometric ratio, can't remember exact ammounts) and then vacum filtering it for about 2h...to get the water sol. which contained about 4% H4N2... to this I adder ethanol and then the solution of Ni(NO3)2...
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[*] posted on 12-12-2005 at 11:05


As mentionned in the first post...Ni(NH2-NH2)3(NO3)2 might be mixed with Ag2C2.xHNO3

The original idea came to my mind because I had the info...that THNiN complex was better than mercury fulminate on many points but that it suffers from a lack of detonation propagation reliability. So I had the idea to mix 1/3 to 1/2 of the silver acetylide nitric acid complex to it and it was a succes...With 5g of the 2/1 mix I did detonate 70 g of hydrazine nitrate in a pipe bomb (5mm wall thickness) detonator was made of copper 4 cm long and 5 mm diameter (wall thickness was 1.5 mm)...

The THNiN was made by the use of 80% NH2-NH2 (100% NH2-NH3OH) dissolved in 97% ethanol and with green solid nickel (II) nitrate saturated in ethanol 97%.
The complexation produces a lot of heat beause of the concomitant precipitation...matter contraction always heats up!

Attempt with Cobalt delivered the same way a compound of comparable properties...Beautiful orange-brown precipitate.

After a few attempts I isolated a copper salt but it is unstable and most batches had turned into a black lump with N2 evolution...I stil had the chance to get a mittiged reaction wich was a mix of two compounds a black one (certainly colloidal copper) and a trukoise blue precipitate...upon drying on the filter (hopefully in tiny quantity)...filter had burst into flame...but a part of the truquoise precipitate was dry and stil intact...I had the ability to test it and it made a beautiful blue flash upon contact with a flame...why it remained intact after the filter had burned is a mystery...hereby I confirm that the copper is quite hazardous and an unpredictible compound (or a mix of compounds)...

Based on a experienced incident I suspect hydrazine nitrate to be able to react with copper to deliver the unstable truquoise compound...
NH2-NH3NO3 + Cu --> NOx + N2H4 + CuO + Cu(OH)2 + Cu(NO3)2... --> Cu(NH2-NH2)4(NO3)2

Warning about NH4NO3 with Cu powder must thus be taken seriously in the case of Hydrazine nitrate.
And even more with perchlorate...Ni(NH2-NH2)4(ClO4)2 is indeed said to be shocksensitive even if dissolved in water...

NH2-NH3ClO4 is rather fun stuf and isn't too sensitive to heat...catches the moisture from the air...much more than NH...
And because of its properties better keep it away from complexing metals...

[Edited on 12-12-2005 by chemoleo] - removed quote/unedited original.

[Edited on 12-12-2005 by chemoleo]




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[*] posted on 14-12-2005 at 23:13
silver salts


I've tried to form some silver salts, the only success was ethylenediaminesilver (I) bromate. Which detonates in very small quantities when ignited. It also seems uneffected by sunlight.

It was made by precipitating silver bromate (very insoluble ~0.2g/100ml) by combining solutions of AgNO3/NaBrO3. Filtering, washing and drying. 5ml distilled water was added to 3g AgBrO3 then 0.8g ethylenediamine which took the AgBrO3 into solution. This was then poured into a tray and left overnight where it formed chunky crystals of Ag(C2H8N2)BrO3.

If 2mol ammonia was used instead of 1mol ethylenediamine it also went into solution and formed feathery crystals on evaporation, but they had very feeble explosive properties, melting and sometimes going "puff", perhaps it loses NH3 on drying.

I also tried AgClO2 instead of AgBrO3, but it also forms a very soluble complex with NH3, on evaporation it started looking suspiciously like fulminating silver so it was disposed of it. Never tried ethylenediamine/AgClO2.

<center><img src="http://www.sciencemadness.org/scipics/axt/silver-bromate-complexes.jpg">
Ag(C2H8N2)BrO3 on left, Ag(NH3)2BrO3 on right.</center>

Regarding permanganate complexes (Ag(NH3)2MnO4 ignited in sunlight) The Cu(NH3)4(MnO4)2 complex that I posted before is improved on in the attached reference, it mentions that it must be combined and precipitated at low temperatures to avoid decomposition to NH4MnO4 & MnO2.

Attachment: tetraaminecopper (II) permanganate.pdf (129kB)
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[*] posted on 15-12-2005 at 06:33


Quote:
Originally posted by Ium
You will want Ammonium Persulfate not the Potassium salt. Solubility of Ammonium salt is many times higher according to references.


But would it work with potassium or sodium Persulphate?

I'm woundering because it's kind of hard finding a reasonable price on ammoniumpersulphate here in Sweden.
Ammonium is 50USD per kilo (shipping included) while Sodium is 9USD per kilo and is widely available.
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[*] posted on 16-12-2005 at 16:53


Out of the tread about picrates

I have made a mix of Ni(NH2-NH2)3(NO3)2 (usually pale lilas-pink) coprecipitate with NH2-NH3O-C6H2(NO2)3 (hydrazine picrate-pale yellow).....the original pink complex had turned that way pale brown.
In the mix probably Ni picrate, Hydrazine picrate and nickel trihydrazine dinitrate complex...properties not very wel studied owing to the lack of made material (a few mg)...burns fiercely but difference with the original nickel nitrate hydrazinate not noticeable at that quantity...
I'll certainly come back on that study since I have plenty of Ni(NO3)2 at home, about 300g TNP, and about a kilogram of hydrazine sulfate...
And then I'll try to set a testing up to compare:
1)Ni(NH2-NH2)3(NO3)2 (pink)
2)Ni(OC6H2(NO2)3)2 (?colour?)
3)(Ni(NH2-NH2)3(NO2)3)x.(NH2-NH2-O-C6H2(NO2)3)y.(Ni(OC6H2(NO2)3)2)z (pale brown)

The idea of the mix came to the fact I discovered hydrazine picrate to precipitate upon the mixing of saturated ethanolic solutions of hydrazine monohydrate and saturated ethanolic solution of picric acid...I decided to make an hybrid of the usual proces of the pink complex by mixxing three saturated solutions from which I had to get 2 or 3 coprecipitates...

Hydrazine picrate has proven to be very strange stuf...said to be less sensitive than the ammonium salt in litterature...while making a confinement test in aluminium foil in a flame...it puffed and smoked yellow :o without burning...looks like it sublimates...

[Edited on 17-12-2005 by PHILOU Zrealone]




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[*] posted on 16-12-2005 at 17:42


Axt,
I think you used not enough amine...silver is a tetracoordinating metal core...Thus Ag(NH3)4BrO3 and Ag(EDA)2BrO3
Because of its single oxoanion Ag is a poor choice vs other metals

**********************************
I have an idea...what if we all gather here all the interesting complexating and precipitation ability we can find about metals...
The aim would be to have idea of potent combination of precipitate that would allow coprecipitation, cocristallisation or cocomplexation of mixed energy fuels (CN, SCN, C2O4,NH3, N2H4, ....) and oxydisers (BrO3, IO3,....) of potentially interesting metals....meaning thus the mixing on a molecular level of oxydisers and fuel on catalytic core or vicinity :):):):)

As the field of investigation is nearly infinite...it would provide a good starting material for testings...:cool::cool::cool:


My complexation tables lists:
Co(NH3)6(2+) Kco= 1.3*10-5
Ag(CN)2(-) Kco1= 4*10-6 Kco2= 1*10-20
Cd(NH3)6(2+) Kco= 1.9*10-7
Ag(NH3)4(+) Kco= 5.9*10-8
Ni(NH3)6(2+) Kco= 2*10-9
Zn(NH3)4(2+) Kco= 2.6*10-10
Cu(NH3)4(2+) Kco= 7.1*10-14
Cd(CN)4(2-) Kco= 7.8*10-18
Fe(CN)6(4-) Kco= 1*10-24
Cu(CN)3(2-) Kco= 5*10-28
Fe(CN)6(3-) Kco= 1*10-31
Co(NH3)6(3+) Kco= 1*10-33
Hg(CN)4(2-) Kco= 4*10-42

My precipitations tables lists:
Co(IO3)2 Ks= 1.21*10-2
Pb(SCN)2 Ks= 2.11*10-5
Ca(IO3)2 Ks= 6.47*10-6
Zn(IO3)2 Ks= 4.29*10-6
Mn(IO3)2 Ks= 4.37*10-7
AgIO3 Ks= 3.17*10-8
Ba(IO3)2 Ks= 4.01*10-9
CaC2O4 Ks= 2.34*10-9
PbC2O4 Ks= 8.51*10-10
CuC2O4 Ks= 4.43*10-10
AgSCN Ks= 1.03*10-12
Pb(IO3)2 Ks= 3.68*10-13
CuSCN Ks= 1.77*10-13




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[*] posted on 17-12-2005 at 16:36
5-HYDRAZINOTETRAZOLE-MERCURY (II) PERCHLORATE [Hg(CH4N6)](ClO4)2


Just in case anyone is interested, I came across a Russian patent regarding the preparation of this compound, apparently for use as a primary. The abstract is in English, but unfortunately the rest of it is in Russian.

Abstract of RU2225840

FIELD: inorganic chemistry, chemical technology. SUBSTANCE: invention relates, in particular, to methods for preparing mercury (II) compounds used as initiating explosive substance, in film charges for devices generating flat impact waves and others. Invention provides preparing 5-hydrazinotetrazole-mercury (II) perchlorate with the yield of the end product 50%, not less. Method for preparing involves mixing mercury (II) compounds as mercury (II) salt or mercury (II) oxide with 5-hydrazonotetrazole or its salt in 5-70% perchloric acid solution at temperature 10-70 C in the mole ratio 5-hydrazinotetrazole or its salt : mercury (II) compound = (0.8-2.0):1. Precipitate of 5-hydrazinotetrazole- mercury (II) perchlorate is filtered off, washed with water and alcohol and dried. Mercury (II) perchlorate is used as a mercury (II) salt. EFFECT: improved preparing method. 2 cl, 3 ex
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[*] posted on 19-12-2005 at 04:42


Quote:
Originally posted by Rosco Bodine
and " oxiamines " ?


Oxiamines would be the somewhat energetic compounds R-O-NH2, I guess you could include hydroxylamine in that group.

Quote:
Originally posted by PHILOU Zrealone
Axt,
I think you used not enough amine...silver is a tetracoordinating metal core...Thus Ag(NH3)4BrO3 and Ag(EDA)2BrO3 Because of its single oxoanion Ag is a poor choice vs other metals.


Google argues against "tetraamminesilver" in favour of "diamminesilver" by a 1:149 vote :cool:

And this, regarding the nitrate:

<i>Diamminesilver nitrate and (diammine-d6)silver nitrate were formed by dissolving silver nitrate in concentrated ammonium hydroxide (or ND4OD) at room temperature. The white crystalline products were separated by direct drying in a desiccator containing molecular sieves. Anal. Calcd for Ag(NH3)2NO3: Ag, 52.9; NH3, 16.7. Found: Ag, 53.0; NH3, 17.0. Calcd for Ag(ND3)2NO3: Ag, 51.4; ND3, 19.0. Found: Ag, 51.0; ND3, 18.7. These compounds are quite stable if stored in subdued light in a dry atmosphere. They lose ammonia rapidly if heated to about 70".</i> Inorg. Chem.; 1969; 8(4); 802-807.

Heres a <a href="http://ww1.webtop100.net/~62552/xmovies.webtop100.net/banners/ethylenediaminesilver-bromate.mpg">movie</a> of a crystal of Ag(C2H8N2)BrO3 being ignited.

On paper Ag(N2H4)ClO2 would be hard to beat, AgClO2 being explosive in itself, a high energy fuel and perfect OB. Though in practice .... dunno.
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[*] posted on 19-12-2005 at 06:03


AgNO2 + NH2-NH2 --> AgN3(s) + 3 H2O
Interesting :)

AgNO3 + NH2-NH2 --> Ag(s) + N2 + H2O
Sadly this is unstable :(

Axt,
In place Ag(N2H4)ClO2...which is interesting to test of course...I would suggest Ag(N2H4)2ClO4...also perfect OB ...

About diamino silver nitrate...
:o:o:o
I find really stange that no mirror Ag or Ag3N,Ag2NH and AgNH2 did form...do you see any explanation to this phenomenon?
AgONO2 + NH4OH --> NH4NO3 + AgOH/Ag2O -NH4OH-> AgxNyHz + Ag(s).
NH4OH conc is 33% by weight NH3 in water or so...
I could understand the reaction to succeed with dry liquid NH3 flowing on dry AgNO3 ... but with NH4OH???...They seem to mean that water is a problem for the stability...
Is there something said about this silver mirror problem or risk of explosion?




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[*] posted on 20-12-2005 at 02:19


You'll need a reducing agent to get silvering, I silvered a beaker trying to precipitate the chlorite with ethanol. The fulminating silvers would need heating or extended periods to form. There no mention of explosive properties for Ag(NH3)2NO3 in the article, though no doubt it is energetic.

Ag(N2H4)ClO2 didnt work, vigourous clear odourless bubbling on addition of AgClO2 to N2H5OH, dark grey precipitate, solution neutral. Precipitate not explosive :(

[Edited on 1-11-2007 by Axt]
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