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PHILOU Zrealone
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You need a slight excess of TNP otherwise your Na picrate is in basic media and most of your precipitating Pb picrate will be polluted by Pb(OH)2!!!!
That's for sure what you had!
 
    
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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Madog
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yeah, but that conclusion was a result of all of my lead picrate experiments.
Most people outgrow their pyro tendencies, we are the ones who\'s tendencies outgrew us.
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osamafon
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what do you think obout Al or Pb4+ picrates?
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PHILOU Zrealone
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Both look good to me!
OB is improved in Pb(picrate)4 vs Pb(picrate)2 since PbO is the thermidynamically stable oxyde!But the first one may suffer of a slightly lower
density!
I also like...Al(N3)3
Al(N3)3 --> 9/2N2 + Al(atomic)+ heat
2Al(atomic)+ heat -air-> Al2O3 + a lot of heat
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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chemoleo
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hmm... u definitely won't be able to make pure Alpicrate in aqueous solution. after all, dissolve Al in HCL and u get some Al-OH-HCl complex.
AlCl3, in its pure form, is I think made by reacting chlorine gas with Al. THis type of AlCl3 is an extremely strong H2o binding compound, and thus of
interest to many organic reactions. .. probably the same applies to Al(N3)3, I would bet my money's worth that you can't prepare it in its
pure state in aqueous solution ... sorry 
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Smoer
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Wy do you need a salt/oxide of lead to make lead picrate??
TNP is an acid so shouldn't it react with Pb also?
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neutrino
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This doesn’t work because organic acids are generally very weak. Even TNP (a very strong organic acid because of the nitrate groups drawing the
electron cloud and allowing that one hydrogen to protonate) couldn’t attack the metal with any real speed, if at all.
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Bert
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Numerous accidents resulting from the contact of picric acid and Lead are reported. It certainly WILL attack Lead sufficiently to produce Lead picrate
in sufficient quantities to detonate the remaining picric acid! See Maxim's "Dynamite tales" for an early account-
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Rosco Bodine
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To put things in perspective about picrates ,
and SEE just how unlikely it is that picric acid would be detonated accidentally by the presence of metallic picrates which may form in situ from
reaction of picric acid with corrosion of metals , ......
TRY to DELIBERATELY detonate picric acid using a separately made and loaded metallic picrate of any variety , in any reasonable amount and see if you
can succeed in securing the detonation of the picric acid . I'll bet you either won't succeed or it will require some pretty extreme
conditions to get even a partial detonation of the picric acid
* deliberately * using a metallic picrate as an initiator . I have experimented with this and came to the conclusion it would probably require an
enormous amount of corrosion in some very large items of ordnance , subsequently subjected to very great mechanical stress or even exposed to very
high temperatures like
a * fire * for example , to produce such
" accidental " detonations associated with
picric acid . The danger of such an occurrence is greatly exaggerated by the literature .
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Bert
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Prior to the use of salycilate and benzoate fuels with perchlorate oxidizers for pyrotechnic whistles, Potassium picrate mixtures were used. Lead
ramming blocks were also typical pyrotechnic factory equipment at that time- In a fireworks factory, the difference between a low order explosion
incapable of detonating straight picric acid and a high order one so capable would not be meaningful as you'd have an explosion/fire/dead or
injured workers regardless. That's my background. Hiram Maxim's late 19th century report of an associate's accident resulting from a
leaking wooden keg of picric acid and a lead water line also would not have required a true detonation- 20kg of burning picric acid in an explosives
plant would be quite exciting enough...
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SAM4CH
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Lead styphnate
What is the exact ratio of lead monoxide/styphnic acid needed to make lead styphnate using Ethanol as solvent for Styphnic Acid?
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Bert
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Re: Dynamite Stories
Correction- Dynamite Stories was written by Hiram Maxim's BROTHER- Hudson Maxim. I hope nobody wasted time looking for it under the wrong name.
The book is available here if anyone is interested. It includes a first hand account of Hudson's blowing his hand off with Mercury fulminate
as well as other interesting errata. His secretary commented after- "You too are now a "shorthand" writer..."
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freedompyro
holmes1880
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How stable is the anhydrous version of lead picreate? No spontaneous decomposition or anything like peroxides I would assume.
Also, what is the difference between lead picreate synthesized with lead monoxide vs lead trioxide?
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Pulverulescent
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| Quote: | | How stable is the anhydrous version of lead picreate? |
Valuing certain fairly essential bits of my anatomy, I sure wouldn't mess with it!!!
P
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grndpndr
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Quote: Originally posted by Rosco Bodine  | and SEE just how unlikely it is that picric acid would be detonated accidentally by the presence of metallic picrates which may form in situ from
reaction of picric acid with corrosion of metals , ......
TRY to DELIBERATELY detonate picric acid using a separately made and loaded metallic picrate of any variety , in any reasonable amount and see if you
can succeed in securing the detonation of the picric acid . I'll bet you either won't succeed or it will require some pretty extreme conditions to
get even a partial detonation of the picric acid
* deliberately * using a metallic picrate as an initiator . I have experimented with this and came to the conclusion it would probably require an
enormous amount of corrosion in some very large items of ordnance , subsequently subjected to very great mechanical stress or even exposed to very
high temperatures like
a * fire * for example , to produce such
" accidental " detonations associated with
picric acid . The danger of such an occurrence is greatly exaggerated by the literature . |
Most of us have seen the'black books ' that deal with a mech mixture of TN/Litharge being used as a detonator.
As well many of us have seen a paper I believe produced by
Remington Arms for Picatinny Arsenal in which 2gr of mech mixture of litharge /TNP
were placed in a cartridge case Im assuming with some BP or SP as an ignition mix.The 2gram improvised det caused 50gr
of strongly confined lightly pressed, TNP to detonate high order.The found pieces of the container proved that it was a high order det(a picture of
recovered steel pieces is included in report).Thats hard to argue with unless were to disbelieve Rem. Arms/picatinny arsenal official
reports-documents.
Forget about all that for a moment and those of you who are experimenting with these mixes of TNP/Litharge take about a 1/4 gr wrap the mix in AL
foil and place on a HP.If you value your HP place a piece of metal between the burner and packet of TNP or it could well destroy your electric HP.Ask
me how I know.I also tried filling a .22lr case with the TNP/PB0
mix and cooking that off.In order to catch any fragments I
placed the case inside a tin can.As always the mix detonated violently no part of the case could be found only about a dozen small holes in the tin
can from small case fragments.
I believe what this means is exactly what roscoe alluded to that it required extreme conditions for the lithage /TNP mixture to detonate TNP, like a
fire or extreme heat that could be provided by a good amount of an ignition mix.I dont believe the mech mixture produces lead picrate at all.What Ive
seen isnt sensitive to friction in the slightest and requires a very stout hammer blow to det.The same as plain TNP IMO.But confine the mix slightly
and heat itv to the point of TNP melting/mixing with PB0 and a violent det occurs.
I looked up the document I was referring to which I believe is somewhere on the forum.
AD410399, (TNP/Litharge USMIL Imp Det)
Monthly report, #2
'Development of explosives and Initiators for special operations warfare.' Remington arms co for Picatinny arsenal
Dover NJ, may 1963
Also in the report the researchers report success with nitrating 'zerex' antifreeze under field conditions using AN/boiled down battery acid!
[Edited on 13-1-2012 by grndpndr]
[Edited on 13-1-2012 by grndpndr]
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freedompyro
holmes1880
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Is Lead Picrate compatible in mixing with ETN, MHN and other nitrates or does it act to catalyze it's breakdown? Picric Acid being acidic leads me to
ask this question.
[Edited on 28-1-2012 by freedompyro]
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quicksilver
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| Quote: Originally posted by freedompyro | Is Lead Picrate compatible in mixing with ETN, MHN and other nitrates or does it act to catalyze it's breakdown? Picric Acid being acidic leads me to
ask this question.
[Edited on 28-1-2012 by freedompyro] |
The question would also have some conditional issues. Does the nitrated material have an anti acid, does it have a stabilizer? Is this a scenario of
shelf-life?
It's not a common practice to ever place a nitric ester with an acidic substance, regardless of the conditions.
I had once read a patent for a "container-less" detonator, yet it was sealed within a shell of polymer (PBX). This may also be one of the utilitarian
aspects of polyester in smokeless powder.
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freedompyro
holmes1880
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No anti-acid. This is a scenario of picrate salts catalyzing the breakdown of nitrated materials rendering them storage unstable.
I just attempted to synthesize lead picrate with 10g 95% Ethanol and 1.2g of Pb3O4 and then a second synthesis with 1.2g PbO.
The Pb304 synthesis failed for some reason... The resulting product is still red. The issue may be that ethanol does not work with Pb304 or that the
product was not heated for long enough.
The Lead Picrate from the PbO synthesis won't go high order when initiated by flash... Are you guys sure about the 1.2g PbO? Both megalomania and
powerlabs say 1-1 ratio of picric acid to PbO... It won't sustain deflagration either. It just melts and goes POP with a small flame then goes out
before it all is burned. Further heating with a torch gets the rest to deflagrate.
[Edited on 29-1-2012 by freedompyro]
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freedompyro
holmes1880
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Confirmed that this synthesis is correct. Plate dent tests are exactly twice as deep as with the 1.2-2 synthesis as with the powerlabs/megalomania
synth with everything else done identically. Also, the coloration wasn't quite correct with the 1-1 synthesis.
I agree with the thread author... Very weak primary. Only suitable for the initiation of something like MHN. Without metal confinement you have a hell
of a time getting it to go high order without flash initiation.
I am trying to convert that synthesis for Pb3O4 from PbO... With my bad chemistry skills... Lets see what I come up with a quick approximation!
PbO = 223.20 g/mol x 3 = 669...
Pb3O4 = 685.6 g/mol
Looks like the extra oxygen takes up some weight. 685.6/669 = 1.0248. Multiply that times 1.2.. = 1.2297. Approximately 1.3g Pb3O4 is required? That
correct?
[Edited on 29-1-2012 by freedompyro]
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quicksilver
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| Quote: Originally posted by freedompyro | No anti-acid. This is a scenario of picrate salts catalyzing the breakdown of nitrated materials rendering them storage unstable.
I just attempted to synthesize lead picrate with 10g 95% Ethanol and 1.2g of Pb3O4 and then a second synthesis with 1.2g PbO.
The Pb304 synthesis failed for some reason... The resulting product is still red. The issue may be that ethanol does not work with Pb304 or that the
product was not heated for long enough.
The Lead Picrate from the PbO synthesis won't go high order when initiated by flash... Are you guys sure about the 1.2g PbO? Both megalomania and
powerlabs say 1-1 ratio of picric acid to PbO... It won't sustain deflagration either. It just melts and goes POP with a small flame then goes out
before it all is burned. Further heating with a torch gets the rest to deflagrate.
[Edited on 29-1-2012 by freedompyro] |
This is the old "military" synthesis for normal lead picrate and it really is a poor synthesis. Many people have attempted it because it was commonly
seen in a military technical manual.
Do a SEARCH for "basic lead picrate" and you will find a synthesis that yields a product. Normal lead picrate can be synthesized as well.
Storage conditions for long term shelf life are somewhat opposite to stimulus conditions for initiation. You must remove heat, impact, friction,
impact, exposure to oxygen & UV. The most frequent and sound approach is to re-crystallize at least twice; this starts you out with minimal
contaminants. In some conditions cold (substantially lower than room temp) is very helpful. The deprivation of oxygen is one reason why some materials
are stored with a solvent.
Nitric esters however demand purity. Therefore the synthesis must begin properly and carefully for any storage issues to have effect.
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freedompyro
holmes1880
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Thanks a lot quicksilver. Yea, this synthesis is a little sketchy and it's VERY hard to nearly impossible to purify in my experience. But, I did
discover the picrate salts are far too insensitive to be used for noisemakers. The silver salts and red phosphorous are the way to go. Silver is
getting expensive nowadays...
Here is where I found the basic synthesis if anyone needs it.
https://www.sciencemadness.org/whisper/viewthread.php?tid=50...
Need to make some lead nitrate...
It's kind of hilarious. I have lead oxide, lead tetraoxide, and no plain lead for dissolving into HNO3... Sheesh! My lead monoxide was even made from
reducing lead tetraoxide with heat.
[Edited on 29-1-2012 by freedompyro]
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quicksilver
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| Quote: Originally posted by freedompyro | Thanks a lot quicksilver. Yea, this synthesis is a little sketchy and it's VERY hard to nearly impossible to purify in my experience. But, I did
discover the picrate salts are far too insensitive to be used for noisemakers. The silver salts and red phosphorous are the way to go. Silver is
getting expensive nowadays...
Here is where I found the basic synthesis if anyone needs it.
https://www.sciencemadness.org/whisper/viewthread.php?tid=50...
Need to make some lead nitrate...
It's kind of hilarious. I have lead oxide, lead tetraoxide, and no plain lead for dissolving into HNO3... Sheesh! My lead monoxide was even made from
reducing lead tetraoxide with heat.
[Edited on 29-1-2012 by freedompyro] |
You're not stuck because if you don't want a large amount You may be able to work that out in several ways. You'll need common HNO3 - Check out:
http://www.sciencemadness.org/talk/viewthread.php?tid=9495#p...
OR.....you can get into some fun stuff with experimentation because I believe it Pb(NO3) may be formed by electrolytic means. If you only want about
250 grams, you won't have too much trouble.
A source for lead can be tough in some areas. Environmental issues have made many sources tough to get a pure element...however some fishing weights
may be pure. Many sources have some antimony but are convenient size for dissolving in acid (#8 shot from shot-shells). Some hardware stores have near
pure for roof flashing. Old automobile batteries have two lugs that may be pure (take them off with care or drain the battery - THEN use the hammer).
Search "PbNO3" or similar..... I do remember a Hg nitrate to oxide: perhaps there's a oxide to nitrate w/ Pb that's workable. If you have acid, you'll
have no trouble w/ a small amount. You won't need much. I know the electrolytic thread may be a fun experiment.
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freedompyro
holmes1880
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I just reduced lead tetraoxide with heat to lead oxide. I then added 25g of my high concentration HNO3 to 75g H2O, and then added 25g PbO. The
solution was then boiled off and the Lead Nitrate collected. Note: All of the PbO dissolved and the solution turned clear during heating with a little
mixing.
I my yield was eight grams with the Basic Lead Picrate synthesis. Half a gram or so was just left stuck to the glassware and washed off with H2O then
H2SO4 and Acetone. Kind of bizarre how the picric acid/NaOH solution is bright orange to red. The resulting powder appeared to be around 400 mesh with
possibly dust as small as 600 mesh. Ignore the small stuck together chunks. That occurred during drying. It was dried for merely 20 minutes at 103C.
At first it showed promise of having superior initiatory properties. When 300mg was ignited it would deflagrate with enough violence to make a pop
sound. However, it proved to be even harder to DDT when consolidated and compressed. It is conclusive that lead picrate needs metal confinement to
reliably DDT.
Perhaps with less agitation crystals of a better sensitivity and acceptable stability could be attained. I'm not quite sure what an acceptable largest
crystal size is for lead picrate though. Perhaps it could be wet granulated and dried with 4% of a pyrotechnic binder and that would give a powder
with easier DDT but lower VoD.
If lead picrate is not soluble in alcohol a alcohol based binder would make things simpler.
[Edited on 31-1-2012 by freedompyro]
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quicksilver
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There was a discussion on Basic lead picrate some time back and try as I might, I couldn't find it. The material is "demanding" (similar to lead
styphnate / styphnic acid) in that slight alterations in temp, scale, & purity levels affect the final material. I know we have the thread
however. Check threads for 04-06 year dates It may have started thereabouts (old thread perhaps).
There are some synthesis that don't do well scaling up or down - or that are very sensitive to appropriate Ph levels. I don't want to get off track
here but a microscope a very fine tool for determining how you final product is doing. When I explored picrate salts, the most energetic had finely
delineated crystalline formation.
Lead picrate is not a great initiator - but you can get some that is substantially more energetic than others. This is a VERY good example of working
with a few methods and the needs to keep notes. I found SOME stuff. But I would have to re0-type the individual successes and failures.
11/04
Lead Picrate. 2,4,6-Trinitro-lead-phenolate basic
Molecular weight: 452.303
Procedure:
Place 80 milliliters of a 4% sodium hydroxide solution into a flask, then quickly add 9.2 grams of picric acid. Then dissolve 15 grams of lead nitrate
into 600 milliliters of water, and heat this mixture to 80 Celsius. Then add drop-wise, the picric acid mixture to the lead nitrate solution over a
period of one hour. During the addition rapidly stir the lead nitrate solution and mantain it's temprature at 80 Celsius. After the addition remove
heat source and allow the mixture to cool to room temprature. rapidly stir the mixture while it's cooling to room temprature. When cool filter-off the
precipitated lead picrate and wash with several hundred milliliters of cold water then vacuum dry or air dry the product. Check structure: broken
crystals appeared well formed but easily shaved in bulking intimate contact.
80 C -appears to be the "magic temp number". {end} Always do your math first: it will make or break a synthesis & can be a safety factor in some
instances.
Check stoichiometry in both normal and basic is critical: not a "fast" synthesis if you want to determine if you product is a di-basic lead picrate.
The above was an experiment note but it yielded something of note-worthy value because when I have some significant issue I write in that it "appears
to have 'low stimulus threshold'" or was a "poor product energy as compared to....". Always check math first: then compare it to a source you believe
to be quality (like PATR). but "little things" can mean a great deal. With styphnate salts you can change the crystal shape in it's final portion of
the synthesis from broken polygonal to cuboid (in the presence of graphite if I am correct). That's quite unique. It may also be accomplished with a
picrate. I'm confident about the 80 C temp but the other material is simply notes. Let's say that the above is a productive lab. Ph will be very
significant so if you need a 4% sodium hydroxide solution; that should be a #1 priority. #2 should be keeping track of temp, 3rd should be maintaining
scale and 15gr in 600ml hopefully is as exact as possible. If you have doubts about the purity of your TNP or whether it may contain DNP they will
both create picrate salts....But they may require more exposure time. This is why notes become SO valuable over time as you may discover some
materials have 3 very significant variables while others may have 4 or more. If time issues are a serious priority you won't often hear expression
like "one hour", you'll read, 50 minutes with no additional heat exposure until solution solids have altered; approx on hour / or until below 35 C.
There is a great deal to discover with energetic heavy metal salts. They can be altered in physical crystal make-up, they can shed light on strong
lab technique. & they can be simple to synthesize. However they can be somewhat misleading. If the experiment yielded particulate instead of well
formed crystal, the level of sensitivity & speed may be lowered. Differing metals can have decidedly different initiation thresholds (Cu, Hg, Ag,
& Pb -being classics). If you feel comfortable with Picrates, there is a great deal to learn from them. but whenever you are working with an
unknown scale down the experiment.
____________edit:
Hey, I drank a lot of coffee when I wrote that but is the paper brown also?
Was the product as dark as it appeared?
Did it precipitate as a granular material or was there some crystalline element to it?
[Edited on 9-2-2012 by quicksilver]
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freedompyro
holmes1880
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| Quote: Originally posted by quicksilver |
Hey, I drank a lot of coffee when I wrote that but is the paper brown also?
Was the product as dark as it appeared?
Did it precipitate as a granular material or was there some crystalline element to it?
[Edited on 9-2-2012 by quicksilver] |
Sorry, the light sucks royally... That was a video camera frame also and it didn't have a light mode for "incandescent halfway across the room". LoL!
The paper was pure white. It was pretty dark... About 1/3rd less dark than it appears in that picture though.
It precipitated as a purely granular material with zero sign of crystals at all. I had used too much agitation for safety reasons and addition was
completed too fast at merely 30 minutes.
In my opinion it may be possible to improve it's properties to a primary by granulating it with a binder... The way it was it's behavior was of a
secondary and could not be initiated high order by fuse even in standard metal tubing at any density in 1g amounts... Ill leave someone else to test
granulation. I may work on LP again next year when I get free time.
[Edited on 12-2-2012 by freedompyro]
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