Sciencemadness Discussion Board - ethylenediamine dinitrate

ethylenediamine dinitrate

Jor - 1-3-2008 at 09:04

Today I made some of this by adding 0,350mL (7 drops) of ethylenediamine (I hate this stuff, fumes badly and very corrosive) to 0,750mL water (15 drops), and do this I slowly add 1 mL of 62% nitric acid why cooling the solution. Still lots of fumes are evolved but they do not exit the test tube. After 5 minutes I add approx 7mL ethanol , and a white precitipate is formed (large volume) I filter off and wash with ethanol, and dry it with my alcohol burner on a petri dish , keeping the flame at least a few inches away.
Then I tried igniting the stuff with my burner. I got nothing except a few bubbles and then it made a small 'woosh' , and it was gone... . I expected this stuff te be quite energetic. Did I do something wrong in the synthesis (wich I highly doubt), or is this stuff just not a really exciting one? If yes, does this also count for hydrazine nitrate and urea nitrate? Ad yes , I used the USTSE , and I get preparations and stuff, but not how energetic it is. Hope you guys can help me.

Joris

Zinc - 1-3-2008 at 11:19

I believe you need a blasting cap to set it of. Flames wont do anything. I think so but I cant confirm.

And where did you find ethylendiamine?

[Edited on 1-3-2008 by Zinc]

Jor - 1-3-2008 at 11:52

I got 250mL for free.

When it is all used up I can still get it very cheap

500mL 15,00 EUR from Merck or 1L 22,00 EUR from JTBaker.
Im using the stuff pretty much, already used up like 30mL in 1 week.

chemoleo - 1-3-2008 at 19:50

To my knowledge it needs a decent charge (=big) setting it off, and probably compression of the EDDN.
Not only that, it needs a much greater mass, in the dozens of grams quantities, on a par with NH4NO3 and the like... critical diameters and all that come into play.
It is not a primary by any means, and by no means comparable to nitrate esters!!!

But I'm sure other members know way more about this than I do...

Sickman - 1-3-2008 at 21:15

Quote:

Originally posted by Jor
Today I made some of this by adding 0,350mL (7 drops) of ethylenediamine (I hate this stuff, fumes badly and very corrosive) to 0,750mL water (15 drops), and do this I slowly add 1 mL of 62% nitric acid why cooling the solution. Still lots of fumes are evolved but they do not exit the test tube. After 5 minutes I add approx 7mL ethanol , and a white precitipate is formed (large volume) I filter off and wash with ethanol, and dry it with my alcohol burner on a petri dish , keeping the flame at least a few inches away.
Then I tried igniting the stuff with my burner. I got nothing except a few bubbles and then it made a small 'woosh' , and it was gone... . I expected this stuff te be quite energetic. Did I do something wrong in the synthesis (wich I highly doubt), or is this stuff just not a really exciting one? If yes, does this also count for hydrazine nitrate and urea nitrate? Ad yes , I used the USTSE , and I get preparations and stuff, but not how energetic it is. Hope you guys can help me.

Joris

Joris,

There is a much more conveniant method of preparing EDDN which is to react ethylenediamine with ammonium nitrate in an aqueous solution. Details for the synthesis can be found in the patent US4353758.

Ethylenediamine Dinitrate's explosive properties commend it as a powerful explosive. According to Urbanski's references EDDN is a thermally and chemically stable compound. It's explosive strength is greater than that of TNT and picric acid, but slightly lower than that of tetryl. It has a value of 345 cm3 in the lead block test. At 6800 M/sec in a cardboard tube of 33 mm in diameter, EDDN's velocity of detonation is just 100 m/sec shy of TNT's calculated VoD.

That being said EDDN is in my opinion too hygroscopic too be of very practical use (unless you can find a way to eliminate the problem). Its addition to ammonium nitrate in a 50/50 ratio results in a eutectic having a rather high melting point. There are however many other energetic materials far more interesting than EDDN.

The reason your flame test for EDDN didn't result in a detonation is that EDDN is thermally stable and not subject to detonation from flame (at least not without confinement).

As for hydrazine nitrate and urea nitrate. They by themselves are not that "exciting" because they have their own problems. Namely, hydrazine nitrate: a low VoD and urea nitrate: it's "corrosive acidity" in the prescence of moisture.

In spite of the problems, if we are clever, keeping all their properties in mind, we can find a proper use for all these explosives. This idea may not be exciting , but I do find it at least encouraging if better materials cannot be employed for any purpose and for any reason.

artem - 2-3-2008 at 01:14

Quote:

Originally posted by Sickman
... Namely, hydrazine nitrate: a low VoD...

hydrazine nitrate - D=8.69(1.626d/cm3) - is it a LOW VoD?

Sickman - 2-3-2008 at 14:08

Quote:

Originally posted by artem

Quote:

Originally posted by Sickman
... Namely, hydrazine nitrate: a low VoD...

hydrazine nitrate - D=8.69(1.626d/cm3) - is it a LOW VoD?

Yes, according to Urbanski in his Chemistry and Technology of Explosives, volume 2, pages 464-465. Which basically points out that even though casting the hydrazine nitrate produces a density of 1.62, a high VoD seems to never be realized. The VoD for hydrazine nitrate is a bit strange when you look at a table of density vs. VoD. The VoD for HN @1.0 is just 3900 M/sec. The VoD of HN peaks @ a density of 1.25 with a VoD of 5640 M/sec. Strangely, as the density increases more than 1.25 the VoD decreases. For example HN @ 1.57 has a VoD of 3250 M/sec which is even lower than than that for the earlier mentioned VoD of HN @ 1.0

This same sort of phenomenon of a peaking of VoD at a certain density and then VoD decreasing with increasing density also seems to be seen in some Cheddites. See COPAE for details and tables.

franklyn - 3-3-2008 at 03:05

Sickman you neglect to consider the charge diameter for the data you cite is 3 mm
as such your observations on variations in density are without any context.
As - chemoleo - observed above " critical diameters and all that come into play."
Urbanski provides a mere abstract, read also the entry in Federov PATR 2700 vol 7
I myself was under the misimpression that dry Hydrazinium Nitrate is a sensitive
primary and it happens on closer reading that it is about the same as Tetryl.

Hydrazinium Nitrate is known more for it's common name of Astrolite G which is a
solution of it prepared by adding 2 units of weight of Ammonium Nitrate to one of
anhydrous Hydrazine, 4 NH4NO3 + 5 N2H4 , which displaces the ammonia to form the
compound in situ, for this form in bulk as the main explosive charge the accepted value
for detonation velocity is as - artem - stated ~8.7 km/sec , though not as dense.
See - Principle Characteristics of the Liquid Explosive Astrolite G
S. Levmore & S.J. Lovell - PATR 3633 ( Aug 1967 )

According to Federov,
on page H193 bottom left column, quote :
" The water content is varied to control the detonation velocity. For example a
solution containing N2H5.NO3 70%, N2H4 7%, and NH3 14% has a density of
1.31, detonation rate 8100 m/sec "

on page H197 lower right column, quote :
" Detonation velocity : Bureau of Mines determined detonation velocity of molten
Hydrazine Nitrate at 75 ºC in thin film experiments to be 8500 m/sec " ( ref. 21 )
Immediately following are results of tests by Medard and others which indicate
that VOD only achieves high values in cylinder diameters in excess of 2.5 inches
( ~ 6 mm , in keeping with what - artem - wrote ).
[21] H.K.James et.al, Physical and Explosion Characteristics of Hydrazine Nitrate,
US Bureau Of Mines Information Circular 8452 ( March 1970 )
( This quote above illustrates what I pointed out to you before in regard to casting
picrates, generally the properties of explosives differ greatly from liquid to solid form.
on page H192 middle left column, following the heading of chemistry , hydrazine is shown
to have various isomeric forms in solution which differ from that of the solid nitrate. )

on page H198 top left column, quote :
" Kurbangalina ( in a russian journal ) found that critical diameter increases with
increasing water content, and that molten Hydrazine Nitrate and its aqueous solutions
can detonate with different velocities ( 2 - 8 km/sec ). Low velocity detonations are
less dependent on critical diameter than high velocity detonations. " ( as one would expect )
The Velocity of detonation may vary greatly and thus affect brisance, yet compares
with and exceeds trinitrophenol and trinitrotoluene in power. As you yourself said :
" if we are clever, keeping all their properties in mind, we can find a proper use for all
these explosives "

on page H199 lower right column, Nickel Nitrohydrazinate is discussed and there is
a dedicated thread to it here _ http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

.

artem - 3-3-2008 at 09:40

Quote:

Originally posted by Sickman
...Which basically points out that even though casting the hydrazine nitrate produces a density of 1.62, a high VoD seems to never be realized. The VoD for hydrazine nitrate is a bit strange when you look at a table of density vs. VoD. The VoD for HN @1.0 is just 3900 M/sec. The VoD of HN peaks @ a density of 1.25 with a VoD of 5640 M/sec...

This results are typical for unconfined and cardboard tubes charges at diameters up to ~30mm. For charges > 40mm VoD vs density continuously increases . For example, figure 8.51km/s at 1.59g/cm3 was recieved for 2.5inch-charge (1th Symposium on Detonation, 22).
On my experience, in steel tubes and powerfull initiation HN gives exceptional brisance at diameter 20-25mm or more.

Sickman - 3-3-2008 at 12:49

The numbers I gave for Hyrdrazine nitrate were from Urbanski and they are for hydrazine nitrate in 30mm diameter charges in cardboard.

I'm very glad that I was wrong about hydrazine nitrate not being capable of a high velocity of detonation. It may actually be a more interesting material than I had at first thought, and since it is castable it seems like it may be utilized for some interesting applications.

PHILOU Zrealone - 4-3-2008 at 09:35

Quote:

Originally posted by Sickman
The numbers I gave for Hyrdrazine nitrate were from Urbanski and they are for hydrazine nitrate in 30mm diameter charges in cardboard.

I'm very glad that I was wrong about hydrazine nitrate not being capable of a high velocity of detonation. It may actually be a more interesting material than I had at first thought, and since it is castable it seems like it may be utilized for some interesting applications.

It does detonate with a very high VOD (I did a test with 70g or so).During a test of mine it blew the 5mm thick iron pipe in pieces (2.5cm diameter and 20 cm long) and the cement block that was above the charge was cut in three pieces of 20*20*20 cm...the block was lifted 1.5m in the air.

Sole problem is the drying! Hydrazine nitrate, ethylene diamine dinitrate and hydrazine perchlorate are quite hygroscopic.
Water and below critical diameter for detonation can account for bad performances or weird VOD....while above critical diameter,VOD at a given density always increases.
About HN at 1g/ccm, there must be a lot of air...like for ammonium nitrate it might help at the beginning and contribute for weird VOD vs density plots...

Ethylene diamine dinitrate is a HE with a VOD (6.8-7.3 km/s) and sensitivity about equal to TNT.

In a comparative study between amine nitrate, perchlorate, nitramines and nitric esters, I have started...amine nitrates are not far behind the nitric esters regarding VOD but full conclusion are not made yet since I need to get some experimental data based on own synthesis.

[Edited on 4-3-2008 by PHILOU Zrealone]
*********************************************
Just for the fun of it:

Ethylenediamine dinitrate:
O3NH3N-CH2-CH2-NH3NO3
density (g/ccm): 1.577
Melting Point (°C): 188
Deflagration Point (°C): 370-400
Lead block test for 10g: 350 ccm
Impact sensitivity: 10 N/m
VOD(velocity of detonation) (m/s)@d: 6800@1.53 (*)
VODG(volume of detonation gases (L/kg at STP): 1083
(*) at max density it must be 7200-7100.

Ethanolamine dinitrate:
O3NH3N-CH2-CH2-ONO2
density (g/ccm): 1.53
Melting Point (°C): 103
Deflagration Point (°C): 192
Lead block test for 10g: 410 ccm
Impact sensitivity: ? N/m (*)
VOD(velocity of detonation) (m/s)@d: ?@1.53 (**)
VODG(volume of detonation gases (L/kg at STP): 935
(*)As a good assumption must be between 1 and 5 N/M based on the nitric ester and on the amine nitrate being half constituent of it.
(**)As a good assumption between EGDN and EDADiNitrate, must be arround 7300-7200

Ethylene dinitramine:
O2N-HN-CH2-CH2-NH-NO2
density (g/ccm): 1.71
Melting Point (°C): 176.2(decomp)
Deflagration Point (°C): 180
Lead block test for 10g: 410 ccm
Impact sensitivity: 8 N/m
VOD(velocity of detonation) (m/s)@d: 7570@1.65 (*)
VODG(volume of detonation gases (L/kg at STP): 908
(*)At maximum density VOD must be 8200-8000

Ethyleneglycol dinitrate:
O2NO-CH2-CH2-ONO2
density (g/ccm): 1.48
Melting Point (°C): liquid
Deflagration Point (°C): 217
Lead block test for 10g: 620 ccm
Impact sensitivity: 0.2 N/m
VOD(velocity of detonation) (m/s)@d: 7300@1.53
VODG(volume of detonation gases (L/kg at STP): 816

Just out of this serie one can see that nitrates of amines are not bad considering their high heat resistance and the ease of fabrication. Sole problem is to dry them completely and corrosivity.
************************************************
Just for the maths:
Impact sensitivity of 10 N/m is roughly equivalent to the fall of 1kg from one meter high.
So
10 N/m = 1kg from 1m = 10kg from 10cm = 100g from 10m

This must be compared with the tiny value of 0.2N/m for EGDN:
0.2 N/m = 20g from 1m = 200g from 10cm = 2g from 10m

Note also that there is some statistic behind and that IS values are the energy to make 50% of the tested samples to explode.

[Edited on 5-3-2008 by PHILOU Zrealone]

[Edited on 5-3-2008 by PHILOU Zrealone]

franklyn - 7-3-2008 at 10:38

Amine base + Acid , adducts are readily made and powerful compounds but due to inherent acidity
and resulting decomposition have not been investigated in depth. Except for EDDN of this thread,
ED with nitromethane ( PLX ) and in situ prepared formulas utilizing hydrazine, methyl or dimethyl
hydrazine, adducts of Hexamine, even Urea nitrate has seen limited use, Guanidine nitrate is only
applicable to propellants if at all, but no other compounds have found practical application. I would
think that Nitrourea with Hydrazine merits consideration. CO(NHNO2)2: (N2H4)2 => CO + 4 H2O + 4 N2 + H2

I had posted on a suggested compound of this type here _
scroll down to Possible new organic perchlorate salt
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
Editng option lapsed so I have not been able to correct the very unbalanced equation shown for
detonation products in the attached image of CycloTrimethyleneTrihydraziniumTriperchlorate
should actually be 1 mol => 3 CO2 + 6 H2O + 3 HCl + 3 N2

From the SciMad Library Formaldehyde J. Frederic Walker , page 123
http://www.sciencemadness.org/library/books/formaldehyde.pdf
By addition of a molecular proportion of formaldehyde to one mol of hydrazine hydrate,
Stolle, R., Ber„ 40, 1505 (1907) obtained Formalhydrazine, a soluble product believed to be
the trimer Methylenehydrazine, (CH2:N-NH2)3. The same product was also given by heating
formaldehyde polymer ( Paraformaldehyde ? ) with hydrazine hydrate in a sealed tube at 100°C.
This compound is a colorless powder which explodes with a flash on strong heating.

Since we know that Perchloric acid is high explosive on it's own, the neutral adduct of both
yielding MethylenehydrazineTriperchlorate ( another name for it ) gives zero oxygen balance
and looks interesting. Given that Trioxane the trimer of formaldehyde is disassociated by
acidity and hydrazine readily forms hydrazones with ketones as just mentioned in the above
article, the proposed compound should readily form from Trioxane and Hydrazine perchlorate
as I outlined, obviating the route of Perchloric acid acting on Methylenehydrazine.

Another possible compound similar to this, TriaminobenzeneTriperchlorate, I posted on here _
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
2 mols C6H3(NH2)3.(HClO4)3 => 3 CO2 + 9 CO + 9 H2O + 6 HCl = 6 N2

.

Zinc - 7-3-2008 at 15:50

Is there any OTC source of ethylenediamine?

PHILOU Zrealone - 12-3-2008 at 03:28

Quote:

Originally posted by franklyn
Amine base + Acid , adducts are readily made and powerful compounds but due to inherent acidity
and resulting decomposition have not been investigated in depth. Except for EDDN of this thread,
ED with nitromethane ( PLX ) and in situ prepared formulas utilizing hydrazine, methyl or dimethyl
hydrazine, adducts of Hexamine, even Urea nitrate has seen limited use, Guanidine nitrate is only
applicable to propellants if at all, but no other compounds have found practical application. I would
think that Nitrourea with Hydrazine merits consideration. CO(NHNO2)2: (N2H4)2 => CO + 4 H2O + 4 N2 + H2

I had posted on a suggested compound of this type here _
scroll down to Possible new organic perchlorate salt
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
Editng option lapsed so I have not been able to correct the very unbalanced equation shown for
detonation products in the attached image of CycloTrimethyleneTrihydraziniumTriperchlorate
should actually be 1 mol => 3 CO2 + 6 H2O + 3 HCl + 3 N2

From the SciMad Library Formaldehyde J. Frederic Walker , page 123
http://www.sciencemadness.org/library/books/formaldehyde.pdf
By addition of a molecular proportion of formaldehyde to one mol of hydrazine hydrate,
Stolle, R., Ber„ 40, 1505 (1907) obtained Formalhydrazine, a soluble product believed to be
the trimer Methylenehydrazine, (CH2:N-NH2)3. The same product was also given by heating
formaldehyde polymer ( Paraformaldehyde ? ) with hydrazine hydrate in a sealed tube at 100°C.
This compound is a colorless powder which explodes with a flash on strong heating.

Since we know that Perchloric acid is high explosive on it's own, the neutral adduct of both
yielding MethylenehydrazineTriperchlorate ( another name for it ) gives zero oxygen balance
and looks interesting. Given that Trioxane the trimer of formaldehyde is disassociated by
acidity and hydrazine readily forms hydrazones with ketones as just mentioned in the above
article, the proposed compound should readily form from Trioxane and Hydrazine perchlorate
as I outlined, obviating the route of Perchloric acid acting on Methylenehydrazine.

Another possible compound similar to this, TriaminobenzeneTriperchlorate, I posted on here _
http://www.sciencemadness.org/talk/viewthread.php?tid=1081&a...
2 mols C6H3(NH2)3.(HClO4)3 => 3 CO2 + 9 CO + 9 H2O + 6 HCl = 6 N2

.

Funny to see you get same good ideas as the ones I have had

afew years ago

, amines and hydrazines have plenty of possibilities...
Stangely hydrazine perchlorate is less powerfull than the nitrate, in the other cases perchlorates are always higher performers on all aspects; maybe does-it come from its over oxygen contain.