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a nitrogen rich explosive
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Energetic amine salts
Synthesis and properties:
- Methylamine perchlorate
- EDA perchlorate
- Ethyl amine perchlorates
- Isopropyl amine perchlorates
And chlorates for the above (balls of steel.)
Would any other salts work (periodate, bromate etc.)
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PHILOU Zrealone
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This has already been discussed into the energetic forum...
--> search engine...
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a nitrogen rich explosive
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I have UTFSE.
Would this work with periodic/bromic acid?
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PHILOU Zrealone
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Good, so you got your answer, right?
Of course the search engine will work for those too 
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a nitrogen rich explosive
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There's nothing in the search engine on amine periodates or bromates...
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hyfalcon
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I bet you haven't searched Google as thoroughly as you think you have. Try this then "site:sciencemadness.org bromate". See if this doesn't help.
[Edited on 25-4-2016 by hyfalcon]
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PHILOU Zrealone
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Quote: Originally posted by a nitrogen rich explosive  | Synthesis and properties:
- Methylamine perchlorate
- EDA perchlorate
- Ethyl amine perchlorates
- Isopropyl amine perchlorates
And chlorates for the above (balls of steel.)
Would any other salts work (periodate, bromate etc.) |
So you found all needed info on the perchlorates...you see; this spared us a lot of work.
You noticed that the power goes down from EDA DIperchlorate > MA perchlorate > EA perchlorate
> IPA perchlorate...
Let us see if you have wel done your homework and fully understood the basics of energetic materials...
--> Why are those in that power order?
Tip: there are two main factors...
About amines periodates and bromates, if you haven't found info about those; then (its no secret and a good hint for you) they are good research
subject  ...so surprise us with your discoveries about those (with pictures,
protocols and scientific approach).
Tips:
1°) Bromates are less stable than chlorates towards heat while periodates are more stable than chlorates.
2°) Contemplating the stability order for the amine of all amines, ammonium (NH4(+)): NH4IO4 >> NH4IO3 > NH4BrO3 +/-= NH4ClO3
3°) NH4ClO3 exists but usually decomposes autocatalytically into NCl3, ClO2, NH4NO3 often with explosion and fire ...reason why mixing ammonium salts
and mineral chlorates into the same firework compositions has been banned.
--> Why did I wrote that to make EDA di-chlorate, one would need iron balls (btw you pastiched my own citation "iron balls" by using "balls of steel"  )
--> What may someone expect of the stability, sensitivity and power order of:
EDA di-, MA, EA, IPA
1°) chlorate between each other in its line
2°) bromate between each other in its line
3°) iodate between each other in its line
4°) perchlorate between each other in its line
5°) perbromate between each other in its line
6°) periodate between each other in its line
7°) between each other but crossing the lines
8°) now time to work and validate or invalidate the hypothesis...
That's how science works 
[Edited on 25-4-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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a nitrogen rich explosive
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Why are those in that power order? -->
OXYGEN BALANCE. The most powerful, EDA diperchlorate, is C2H10N2Cl2O8.
The least powerful, IPA perchlorate, is C3H9NClO4. See?
DENSITY. EDA has a density of 0.88g/cm3, whereas IPA has a density of 0.6g/cm3. More density = more energy packed into a smaller space.
Why would I need iron balls to make EDA dichlorate? -->
Chlorates are always less stable that perchlorates. Amine chlorates are notoriously unstable. In the case of NH4ClO3, NCl3 is a contact explosive,
ClO2 is a toxic, explosive gas and NH4NO3 is an oxidiser. Given EDADC's high OB and high explosive power, the fact that it is sensitive makes it very
dangerous.
Stability, sensitivity and power order of various energetic amine salts? -->
1) Amine chlorates: extremely low stability, very high sensitivity and high power.
2) Amine bromates: extremely low stability, very high sensitivity and slightly less power that amine chlorates due to the slightly worse OB due to
Bromine's higher atomic mass.
3) Amine iodates: Medium stability, medium sensitivity and medium-high power.
4) Amine perchlorates: High stability, medium-low sensitivity and high power.
5) Amine perbromates: Medium stability, medium sensitivity and high power.
6) Amine periodates: High stability, low sensitivity and medium-high power.
If a saturated solution of nitroform is acidic enough, I will also try nitroformate:
7) Amine nitroformates: Very low stability, high sensitivity and extreme power.
Point me out if I got anything wrong!!
[Edited on 25-4-2016 by a nitrogen rich explosive]
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PHILOU Zrealone
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| Quote: Originally posted by a nitrogen rich explosive | Why are those in that power order? -->
OXYGEN BALANCE. The most powerful, EDA diperchlorate, is C2H10N2Cl2O8.
The least powerful, IPA perchlorate, is C3H9NClO4. See?
When I get home, I will post a full detail of my synthesis, with pictures and scientific methods.
Why would I need iron balls to make EDA dichlorate? -->
Chlorates are always less stable that perchlorates. Amine chlorates are notoriously unstable. In the case of NH4ClO3, NCl3 is a contact explosive,
ClO2 is a toxic, explosive gas and NH4NO3 is an oxidiser. Given EDADC's high OB and high explosive power, the fact that it is sensitive makes it very
dangerous.
Stability, sensitivity and power order of various energetic amine salts? -->
1) Amine chlorates: extremely low stability, very high sensitivity and high power.
2) Amine bromates: extremely low stability, very high sensitivity and slightly less power that amine chlorates due to the slightly worse OB due to
Bromine's higher atomic mass.
3) Amine iodates: Medium stability, medium sensitivity and medium-high power.
4) Amine perchlorates: High stability, medium-low sensitivity and high power.
5) Amine perbromates: Medium stability, medium sensitivity and high power.
6) Amine periodates: High stability, low sensitivity and medium-high power.
If a saturated solution of nitroform is acidic enough, I will also try nitroformate:
7) Amine nitroformates: Very low stability, high sensitivity and extreme power.
Point me out if I got anything wrong!!
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I'm very pleased to read that!
You succeded the test
The last parameter you forgot is the density... what has more impact on VOD than chemical energy (OB related) (see Kamelet-Jacobs équations)
--> EDA diperchlorate > MA perchlorate
--> I > Br > Cl for density but IO4 is probably less good than BrO4 owing to poor energy
--> BrO4 > ClO4 (> IO4? place to be verified)
--> BrO3 > ClO3 (>IO3? place to be verified)
Good idea for nitroform!
If you have adamantium balls (diamond or carborundum will also do the trick)...
You could go for EDH diperchlorate (EDH = ethylenedihydrazine), EDHA diperchlorate (EDHA = ethylenedihydroxylamine) or diperbromate or diperiodate...
But the hydrazine or hydroxylamine counterpart may not survive to oxydative power of periodate or perbromate...
Note that there are two EDHA!
H2N-O-CH2-CH2-O-NH2 (very basic O-hydroxylamine) and HONH-CH2-CH2-NHOH (less basic N-hydroxylamine)
Final notes:
-many transition metals do form energetic complexes with such amines, so there is a chance an insensitive compound becomes an utterly sensitive
primary...I think to iodates and periodates here
See Axt report about Cu(EDA)2(BrO3)2...
-EDH may not survive some metal cations like hydrazine is uncompatible with Cu(2+)...
[Edited on 25-4-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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a nitrogen rich explosive
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If my balls truly are tungsten carbide:
EDH and EDHA nitroformate.
HMTD perchlorate? Would it survive the strongly acidic HClO4?
[Edited on 25-4-2016 by a nitrogen rich explosive]
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PHILOU Zrealone
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If picric acid is acid enough to make EDA, EDH or EDHA dipicrate, they would be unsensitive and with VOD < 7200 m/s (probably close to 6500
m/s)...while all proposed compounds must display VOD > 7500 m/s (certain above 9000 m/s)...
Even nitroform may have some troubles if not acidic enough for second protonation of the proposed diamines...
PH Z (PHILOU Zrealone)
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a nitrogen rich explosive
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HMTD salts?
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Endo
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One note... Bromates and Hydroxylamine have already been explored by Woelen in this awesome thread.
http://www.sciencemadness.org/talk/viewthread.php?tid=27139
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a nitrogen rich explosive
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Thanks Endo!
I still might experiment with HMTD salts...
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Laboratory of Liptakov
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HMTA
Hexamethylene tetra amine is almost universal compound and precursor for almost all explosives. I think, that HMTA not says last word still. As
example can be examination tetra amine copper perchlorate (TeACP) as clathrate with hexamine. According last attempts this clathrate is possible
using, as replace ETN in detonators. 0,3g of this clathrate can fully replaced 0,25 ETN. Estimated VoD at 1,85 g/cm3 is 7500 m/s. Critical diameter 3
mm in solid cover. Deflagration-detonation transfer (DDT) is possible in diameter 4mm and more. Confirmed stability in copper cavity detonators are 3
months at 15 Celsius storage. Without changes of properties, of course...LL...
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a nitrogen rich explosive
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That clathrate does sound pretty cool as a detonator... It is used in the synth of copper hexamine perchlorate isn't it?
I wasn't talking hexamethylene tetraamine, I was talking hexamethylene triperoxide diamine... Azeotropic perchloric acid might be enough for a second
protonation, giving hexamethylene triperoxide diamine diperchlorate
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PHILOU Zrealone
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Already discussed into your tread "Experimental explosives"!
Anyway an hybrid complex of TeACuP (tetramine copper(II) perchlorate - Cu(NH3)4(ClO4)2) mimicking the hybrid complex Cu(NH3)3(HMTA)(ClO4)2 (HMTA =
hexamethylenetetramine (tetraazaadamantane) C6H12N4) with HMTD instead of HMTA would be very dangerous initiator
--> Cu(NH3)3(HMTD)(ClO4)2 (HMTD = hexamethylendiaminediperoxyde (1,6-diaza-3,4,8,9,12,13--hexaoxa-bicyclo-[4.4.4]-tetradecane) C6H12N2O6)
The dangerosity and risk would come from the uncompatibility of peroxydes with Cu(2+) so sticking on a molecular level an unstable sensitive primary
compound like HMTD on a catalytic metallic core fixed to a powerful secondary...this is hot!
But maybe HMTD is not basic enough to allow complexation by the free N doublet...this might stil happen by the O doublets of the peroxydic
link...destabilizing or stabilizing the unstable molecular edifice...
Has anyone pKa's or pKb's values for HMTD?
PH Z (PHILOU Zrealone)
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a nitrogen rich explosive
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This is indeed getting very warm! I shall boldly go where no man in his garage
has ever gone before.
If you're suggesting a compound that mimics LL's CHP with HMTD, this is going to get very interesting... Can you get me a synthesis for CHP so I can
do some tests, and, before you ask, I have used the search engine with 'copper hexamine perchlorate' under 'Laboratory of Liptakov.'
The problem that I have had with, just to make a start, calculating the pH is the fact that HMTD is only sparingly soluble in water, meaning that I
can't do a litmus test or use my electronic pH measuring tool. It would possibly dissolve in pure ethanol, but I have neither the time nor the money.
I will tell you if I work anything out.
How sensitive would CHMTDP be (are we talking nitroglycerin or copper nitrotetrazole?) I think I need to get my blast shield out.
[Edited on 27-4-2016 by a nitrogen rich explosive]
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Laboratory of Liptakov
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I am afraid that this thread will be torn unexpected explosion. Coming soon. You will see on Science Madness......LL
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a nitrogen rich explosive
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34 year old man blown up by extremely touchy explosive complex...
Coming Soon
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PHILOU Zrealone
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Woelen's work refers to HONH3Cl with NaBrO3, thus hydroxylamine in contact with acidic HBrO3 in solution.
There is big chance HONH3BrO3 might not exist.
But maybe Cu(BrO3)2.xNH2OH or other transition metal complexes wel.
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a nitrogen rich explosive
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This is the synth I am preparing for to do EDADP. Can you vet it?
10ml of concentrated perchloric acid is added to a small beaker. A small amount of UI is also added. 1ml of 10% EDA in water is then added. The EDA
solution is then gradually added dropwise until there is an excess of EDA (shown by UI.) The mixture is left, then filtered, to form EDADP.
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PHILOU Zrealone
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| Quote: Originally posted by a nitrogen rich explosive | This is the synth I am preparing for to do EDADP. Can you vet it?
10ml of concentrated perchloric acid is added to a small beaker. A small amount of UI is also added. 1ml of 10% EDA in water is then added. The EDA
solution is then gradually added dropwise until there is an excess of EDA (shown by UI.) The mixture is left, then filtered, to form EDADP.
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Please at least once in your post explain abreviations for convenience of reading.
Universal Indicator = UI
Ethylenediamine diperchlorate = EDADP
To me there is a big gap between 10 ml concentrated HClO4 and 1ml 10% EDA...I think you need to redo the stoechiometric! You are off by a lot with
your EDA if your HClO4 is the azeotropic concentrate --> Back to chemistry basics.
Please write chem equations, molar masses, introduce % of your reactants, write number of moles and conclude how much EDA(10%) you need to fully
neutralize 10 ml conc HClO4.
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a nitrogen rich explosive
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With the following being correct:
- The pH of perchloric acid is 1
- The pH of pure EDA is 12
2HClO4 + C4H8N2 = C4H8N2Cl2O8 + H2
It therefore follows that 2 mol of HClO4 is needed for every 1 mol of C4H8N2.
HClO4 = 100g/mol
C4H8N2 = 84g/mol
Using these calculations, 20g of HClO4 is needed for 8.4g of ethylenediamine.
HOWEVER, if the pH figures are correct, HClO4 is ten times as acidic as ethylenediamine is basic. Therefore, 84g of ethylenediamine is needed to
neutralise 20g of pure HClO4.
Round up to 90g for an excess of EDA - an excess of HClO4 will stop any reaction from occuring.
However, I will use 30% HClO4. Therefore, I will need to use 66g of 30% HClO4 to contain 0.2 moles of HClO4 to react with 0.1 moles of EDA.
Scale down calculations to 6.6g 30% HClO4 and 9g pure EDA.
I think that this is right?
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PHILOU Zrealone
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| Quote: Originally posted by a nitrogen rich explosive | With the following being correct:
- The pH of perchloric acid is 1
- The pH of pure EDA is 12
2HClO4 + C4H8N2 = C4H8N2Cl2O8 + H2
It therefore follows that 2 mol of HClO4 is needed for every 1 mol of C4H8N2.
HClO4 = 100g/mol
C4H8N2 = 84g/mol
Using these calculations, 20g of HClO4 is needed for 8.4g of ethylenediamine.
HOWEVER, if the pH figures are correct, HClO4 is ten times as acidic as ethylenediamine is basic. Therefore, 84g of ethylenediamine is needed to
neutralise 20g of pure HClO4.
Round up to 90g for an excess of EDA - an excess of HClO4 will stop any reaction from occuring.
However, I will use 30% HClO4. Therefore, I will need to use 66g of 30% HClO4 to contain 0.2 moles of HClO4 to react with 0.1 moles of EDA.
Scale down calculations to 6.6g 30% HClO4 and 9g pure EDA.
I think that this is right? |
All wrong! 
1°) If you want to work with pHs values...pH of HClO4 is 1 only at a very specific % but not the one you listed. pH of EDA is 12 only at a very
specific % too.
2°) EDA is not C4H8N2, maybe you should write molecules in extension H2N-CH2-CH2-NH2, your MW is thus wrong.
3°) EDA is not an electropositive metal, as such it doesn't set H2(g) free upon contact with acids...it forms an aminium cation and even a diaminium
dication.
4°) If HClO4 has a pH of 1, then its pOH is 13; and if EDA has a pH of 12 then its pOH is 2...because pKa+pKb=pH+pOH=14
So HClO4 is not 10 times as acidic as EDA is basic ...there is a 11 pKa or pKb factor between the two and that is 100*1000*1000*1000 difference in
acidity or basicity!
5°) You wrote you have EDA 10% solution and not 100% so you have to take this into account too.
6°) Working with EDA 100% would be very bad idea because the batch will heat a lot (heat of neutralization) and maybe boil off or worst in the case
of such a sensitive powerful HE like EDA diperchlorate.
[Edited on 29-4-2016 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
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