Sciencemadness Discussion Board

Walkaway synthesis / safest material

chief - 13-3-2009 at 11:17

First: I'm not doing it, I'm just asking the opinions of all the knowing people here ...

Wouldn't the safest explosive/EM (for many purposes) be one, which can be manufactured while the application is going on: Just set the relatively harmless reagents into the blasting hole, together with the igniter, and then walk away ...

After the known amount of time the stuff would be ready to blast ...

So the idea would be: To make the synthesis happen in place, not having to handle any explosive materials manually ...

I'm quite sure that out of the many EM at least some might be manufactured this way ; (eg. let the cooling of the nitration be done by some calculated quantity of ice/dry ice/enough metal to keep everything in temp-range)

Or another idea: Generate the HNO3 in place:
==> Ba(NO3)2, more or less finely milled, to meet the exothermicity
==> mixed with the to-be-nitrated solid material
So far only a burning/gunpowder stuff

But now: Adding H2SO4; the Ba(NO3)2 gives: HNO3 (100 % !), + BaSO4; the nitration would go on, and any residual acid would make sure the stuff auto-decomposes after a while if not used ...

How about those ideas ? Any other ones ? Could safe a lot of people their health, maybe

Leander - 13-3-2009 at 12:52

Having to carry concentrated H2SO4 to the blast side is problably more dangerous than handeling a well made charge of PETN.

Adding H2SO4 to any nitrate salt generates heat. Having easily oxidised material in the acid at that point, you're almost begging to get a runaway reaction.

Further it involves taking liters of icewater or ice along with glassware, thermomether etc to make such an experiment go reasonably safe. Not mentioning the need of filtration of your BaSO4 and excess sulfuric acid.

This kind of approach one works well when handeling binary explosives such as ANNM, NM/HNO3 or AN/Hydrazine nitrate, or charges that involve multiple stages (detonator, booster, main charge).

chief - 13-3-2009 at 15:59

I was reasoning that the H2SO4 could just stay in place, to destroy everything if the charge somehow fails ; also I thought the BaSO4 could stay in place, as with some sorts of dynamites ... ; also it would provide, by it's high density, some sort of kinetic confinement ...

Also: If the Ba(NO3)2 is in a shape of sufficiently big crystals the thermal runaway would become sort of impossible or at least less probable ? So then there just could go a nitration on, peacefully, with the option of self-destruction by too much acid in case of not using it ...

Well: Maybe those ideas are not too practicable ... , thats why I was asking: I'm not an expert in this, and will not attempt it, but maybe it's useful ... ...

[Edited on 13-3-2009 by chief]

not_important - 13-3-2009 at 16:20

Know as Sprengel explosives, specific examples are Rackarock and Cheddite. The subset based on liquid oxygen and a fuel (oxyliquits) saw some applications. Panclastite/anilites uses liquid N2O4 in place of LO2, and is rather sensitive to shock, plus being corrosive and poisonous NO2 being really bad to breath.

497 - 13-3-2009 at 18:00

I like the idea of N2O4 based explosives. It's sad there's so little information about them..

Frozen N2O4 can be handled relatively safely (mp. -11*C), and has a relatively high enthalpy of fusion (about half that of water).

N2O4 and toluene can make some extremely powerful mixtures when used at the right ratios. Power approaching or above (depending on who you ask) that of pure NG.. N2O4 and gasoline is a little less powerful, but not bad at all, still better than TNT AFAIK.

Drill your hole, dump appropriate amount of frozen N2O4 pellets down it, dump in appropriate amount of gasoline, attach detonator, walk away, wait a little while for the N2O4 to thaw, detonate. And did I mention that N2O4 on a large scale is super cheap?

vulture - 14-3-2009 at 11:46

Highly concentrated hydrogen peroxide mixtures, Mn2O7 formed in situ, Perchloric esters formed in situ, chloric acid,...

hissingnoise - 15-3-2009 at 08:07

Quote:
Originally posted by 497
I like the idea of N2O4 based explosives. It's sad there's so little information about them..


AFAIK, panclastite-type mixtures are notoriously shock-sensitive and this might explain the paucity of info. . .
It's probably just as well that NO2 is practically unobtainable (for the hobbyist) and difficult to prepare in quantity since careless individuals would be attracted by its reputation.
I've often thought of preparing it by decomposing Cu or PbNO3 as an exercise, but I have better uses for HNO3.
A two compartment container with a remotely controlled valve/mixer might do.
Such mixtures detonate from the spit of a fuse, IIRC.

497 - 15-3-2009 at 12:44

^ Source for any of that?

Even if it is relatively sensitive, that's the whole point of mixing on site.

Quote:

NO2 is practically unobtainable


You have to be kidding me? There are many ways to NO2/N2O4. Calcium nitrate decomposes into it on heating, NaHSO4+NaNO3 dry distilled works. There are other ways to make Pb(NO3)2 besides directly with HNO3.. The hardest part of the whole deal is condensing the shit, which could easily be done with dry ice or a CaCl2+ice bath, etc. If you live in a cold climate, it gets even easier. I'm not saying it's safe stuff to deal with, but it can be done.

chief - 15-3-2009 at 13:14

Even a standard refrigerator (deep-cooler) will go to -34 [Cels] if the temp-regulation is disabled or defect ... ; I have 2 of the sort. -55 [Cels] can be obtained with NH4NO3 + ice-bath, even lower than CaCl2 (if I remember right ...)

hissingnoise - 15-3-2009 at 14:32

Quote:
Originally posted by 497

Quote:

NO2 is practically unobtainable

You have to be kidding me?

"Practically unobtainable for the hobbyist" means it's definitely not OTC---something you'd have realised had you given the post a second's thought.
And while it can be prepared from a plethora of nitrate salts, its preparation in large quantities is a real pisser.
In anilites the ratio of fuel to oxidiser is ~27% to 73%, so even for a fairly small charge you'll be collecting NO2 till the cows came home, and longer. . .
As for "relatively sensitive",---relative to what?
Nitrogen trichloride, perhaps. . .

497 - 15-3-2009 at 16:28

I guess I mistakenly figured "unobtainable" was not the same thing as non-OTC.. lots of things must be "unobtainable" to you then.

Hmm lets see... 55 pounds of [5Ca(NO3)2.NH4NO3.10H2O] costs about $25. Heated with a propane burner in a disposable metal container and condensed by the usual means, that comes to about 10kg of N2O4, which when mixed with a few kilos of toluene will make about 12.5kg of near NG equivalent liquid explosive. Very unobtainable indeed...

Come on man, this stuff isn't that sensitive. Read the damn patents before you go pretending to know so much about it. A 10 pound weight falling 7.5 feet won't even detonate it unless the mixture is very near stoiciometric.

PS. The only mixture I've seen that was very shock sensitive was the original CS2+N2O4 mix that Turpin came up with, maybe that's what you're thinking of. Hell, the patents for "improved" N2O4 binary explosives don't even state the prior art mixtures (N2O4+gasoline, etc.) are particularly sensitive. And you know how patents like to state every disadvantage of the prior art they can possibly find..

[Edited on 15-3-2009 by 497]

[Edited on 15-3-2009 by 497]

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hissingnoise - 16-3-2009 at 06:22

You seem to think extracting NO2 from a deliquescent mass is *easy*.
Where do you think H2O from thermolysis of NH4NO3 will go?
So try it---and be prepared for a long series of nasty surprises. . .
Stoichiometric mixtures are powerful *and* sensitive but explosive performance is reduced, often unacceptably, in non-stoichiometric binaries.
But you go ahead regardless. . ."Superman". . .

[Edited on 16-3-2009 by hissingnoise]

497 - 17-3-2009 at 00:07

Actually it works fine, I've tried it. Have you? First the waters of hydration boil off, then the NH4NO3 decomposes (the double salt is less than 8% NH4NO3), releasing a little NOx and H2O which is neutralized or vented, and then at a considerably higher temperature the remaining Ca(NO3)2 begins to decompose fairly cleanly in into NO2 and O2, this is when you would attach the appropriate condenser. I'm sure there is some water contamination, but a zeolite or MgSO4 column can take care of that.

Quote:

Stoichiometric mixtures are powerful *and* sensitive


I still wonder where the hell you're getting this exclusive information. From everything I've seen, the stoiciometric mixtures are not a lot more sensitive than non-stoiciometric. By extrapolating from graphs in the patents, a stoic mixture might be up to twice as sensitive as the a non-stoic mix (that will not det from 1000 kilogram-centimeters in their rig.) I wouldn't call that extremely sensitive.

hissingnoise - 17-3-2009 at 05:37

Quote:
Originally posted by 497
I wouldn't call that extremely sensitive.

OK, so show me where I called it extremely sensitive 497?

vulture - 17-3-2009 at 13:49

Tone it down you two and don't start nitpicking. Time for some experimentation.

hissingnoise - 17-3-2009 at 15:18

Sorry vulture.
It wasn't intended to sound bellicose. . . but it does!

497 - 17-3-2009 at 17:01

Quote:

As for "relatively sensitive",---relative to what? Nitrogen trichloride, perhaps. . .


Are you going to try to tell me that's not implying it is extremely sensitive?

Sorry vulture, I just get annoyed when he makes a bunch of statements with absolutely nothing to back them up...

grndpndr - 17-3-2009 at 18:03

Kinepack,simple solution for us dummies.:)

Seriously as a powder monkey/seismograph driller the difficulties of getting a charge down a 200ft deep supposed 5-in dia.hole IIRC was quite difficult what with the hole collapsing and more often than not being undersize. as well as filled with drilling mud a premixed charge was w/o doubt a nescessity both waterproof and encased in a strong conatainer most often thick plastic.5lb sticks slightly under bore diameter theaded at each end so any size charge could be made up as needed similar to very large bangalore torpedoes but plastic and larger diameter.Dual caps with a delay depending on the string secured with half hitches often requiring assistance in the form of wooden poles that could be threaded together to 'encourage' the charge to bottom out.If we failed we lost the HE and the $ for drilling the hole.To rambunctious ramming the charge and it could be worse,premature detonations at 20-40ft with 20lbs of HE could still make old faithful look silly and with a man standing in the way very inconvenient for the worker!:(
Since we used 20lb lenghths of HE and 2 detonators it happened occasionally that a hole would be lost, contain a 20lb 'stuck' charge and 2 det,in other words irretrievable. LOL
Sucks to be an independent contractor no HE in hole no $!
Back on topic even kinepack wouldnt work for obvious reasons nor would any explosive that was intended to be poured down the hole with a cap following.So thats the realitys of the problem sometimes it helps to know the logistical problems as well as the technical.Im not much of a chemist but a respectable backyard experimenter/fabricator with some experience with the practical side of the use of HE.
So the binary or others would likely work only in 6/30ft deep
holes dry of course and many places even out here in this arid part of the country 30 ft will often get you a wet hole.Not a well by any imagination but lots of moisture.
Just something to ponder for the genuine chemists among you who despite myself Ive learned a great deal.Much appreciated.:D

[Edited on 17-3-2009 by grndpndr]

[Edited on 17-3-2009 by grndpndr]

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[Edited on 17-3-2009 by grndpndr]

hissingnoise - 18-3-2009 at 03:49

Yeah 497, it was mostly hot-air; I don't even know how sensitive nitrogen trichloride is. . .do you?

grndpndr - 18-3-2009 at 05:00

Pleasant as ever,the individual doesnt seem to matter just the scrap.Must be sad/lonely to be so angry. Maybe just needs some strange poon -tang?:)

[Edited on 18-3-2009 by grndpndr]

hissingnoise - 18-3-2009 at 05:44

That little comment, grndpndr, says a lot more about you than it does me.
If that's how you really feel you must be very thin-skinned indeed. . .

grndpndr - 18-3-2009 at 06:32

So thin skinned I dont need a moderator to tell me to "tone it down"

Yep Im a thin skinned former paratrooper stationed in the canal zone and with the 82nd
as a comp. sniper.Oil field roughneck, bridgebuilder heavy equip operator married 25years with 3 kids.You bet im thin skinned..:D
So what in fact is your excuse with arguing with every other poster on the site?
[Edited on 18-3-2009 by grndpndr]

[Edited on 18-3-2009 by grndpndr]

hissingnoise - 18-3-2009 at 13:59

A counter-riposte, grndpndr, being off-topic, would put me way above quota, sorry!

grndpndr - 18-3-2009 at 15:47

Being a bore never bothered you before.Nevermind.I am inclined to cease and desist.

[Edited on 18-3-2009 by grndpndr]