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ChrisWhewell
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[*] posted on 22-12-2009 at 13:44
Picric acid sensitivity


Around 1989 I went to an estate sale in Willowick Ohio, and in the garage were several boxes with chemical reagent amber bottles. Being a chemist I opened one of the boxes, as I had previously found a large bottle of silver nitrate crystals at a garage sale, which I reduced and sold at profit.

Well, in Willowick, the bottle I pulled out was labeled "picric acid", was about a pound in a clear glass bottle, and guess what ?

It was dry. In that state, my understanding is that its quite sensitive.

I slowly put the bottle down and attempted to inform the others at the sale to get out of the house immediately. Of course they didn't listen to a stranger.

So I left and called the fire chief. He sent the boys over, and they roped off the whole block and spent the afternoon there. No telling what all they found.

Imagine a little wrong percussion on that box - a pound of picrate is basically a pound of TNT.

As far as what you all should do in your home labs, that's up to you. If it were me, I'd avoid anything organic, other than known soap molecules. If you want to mess with other organics, sign up for some independent study credit at a college. You'll have better facilities, good guidance and access to instrumentation.

Besides, there is a ton of work to be done with inorganics. Working with solar cells or thermoelectric coolers or new welding compositions or rendering glass conductive, or trying to find a superconductor or a ton of other things etc. is a lot safer than messing around with anything organic. Back in the early 90's I invented and patented 5,156,721 Process for extraction and concentration of rhodium from catalytic convertors in my basement using salt water, a couple electrodes, HCl, a rectifier and an old catalytic convertor. While searching for a superconductor, I accidentally discovered a mixed oxide that has a variable Curie point around 32 deg. F that a group in China has recently reported on something similar. Point is, like Edison said, Nature teaches you if you keep your eyes open. A room temperature superconductor definitely exists, it just needs to be found. Over a period of over a year, I generated less than a pound of mixed inert oxide waste that all fit in one jar. Since it contained appreciable amount of silver, to dispose of it all I had to do was send it to a refiner.










[Edited on 22-12-2009 by ChrisWhewell]
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entropy51
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[*] posted on 22-12-2009 at 13:58


Quote:
If it were me, I'd avoid anything organic, other than known soap molecules.
Interesting point of view, Chris. It's the inorganics that scare the sheet out of me! Welcome to Science Madness!

Some members may not agree that the local community college has better facilities, guidance and instrumentation.
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[*] posted on 22-12-2009 at 15:14


Interesting patent too. . . although I haven't yet read it in depth.
Chris you're the only *real* inventor here that I know of and only the second member to use his full name.


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ChrisWhewell
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[*] posted on 22-12-2009 at 15:30


I love chemistry. Lately I'm into looking at improving the Graetzel solar cells, as I think the current config sucks insomuch as they require an electrolyte, although they've allegedly passed the accelerated 20-year testing. I got a kit from the Univ. of Wisconsin and made a few. I don't like the tri-iodide in glycol electrolyte though, I think in real life this is the weak link and they haven't yet learned it. What we need is a cheap, quick and reproduceable way to reduce a monolayer of SiO2 present on glass, to elemental silicon. I have a couple of ideas that probably won't work but I'm going to try them anyhow. All I need to see is a tiny shining spec of silicon.

Its pretty inert stuff, requiring super high temperatures for even carbon to reduce it. But I never let my schooling interfere with my education, since a few of my professors never amounted to much.

I have a colloidal silver generator at www.genouveau.com at the only working link in the left column at the top. It looks simple but was the result of a lot of work to get the gap and surface area right. There is one other factor, not described. What I find is that I can use that with two other tricks to lay a conductive layer of silver onto glass, that is very tenacious and retains conductivity after firing at red heat. I don't know where to go from here just yet, maybe some genius will come along and run with it. But I do note some groups reporting increased output of solar cell materials when coated with silver which you can probably find pretty quicly if you do a websearch.

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Rosco Bodine
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[*] posted on 28-12-2009 at 04:11


Quote: Originally posted by ChrisWhewell  
Around 1989 I went to an estate sale in Willowick Ohio, and in the garage were several boxes with chemical reagent amber bottles. Being a chemist I opened one of the boxes, as I had previously found a large bottle of silver nitrate crystals at a garage sale, which I reduced and sold at profit.

Well, in Willowick, the bottle I pulled out was labeled "picric acid", was about a pound in a clear glass bottle, and guess what ?

It was dry. In that state, my understanding is that its quite sensitive.


Incorrect, and it is a popular myth assuring neverending job security for people who appear to know what they are doing when they actually don't.
Quote:

I slowly put the bottle down and attempted to inform the others at the sale to get out of the house immediately. Of course they didn't listen to a stranger.

So I left and called the fire chief. He sent the boys over, and they roped off the whole block and spent the afternoon there. No telling what all they found.

Imagine a little wrong percussion on that box - a pound of picrate is basically a pound of TNT.


It is impossible for either picric acid or TNT to just accidentally be initiated by anything less than a profound stimulus like a bullet impact or an intense fire or being shocked by a high order detonation of some other nearby material. Mundane
conditions are not a source of danger for these insensitive materials. It takes a hell of an energetic impact to set 'em off even deliberately.
Quote:

As far as what you all should do in your home labs, that's up to you. If it were me, I'd avoid anything organic, other than known soap molecules. If you want to mess with other organics, sign up for some independent study credit at a college. You'll have better facilities, good guidance and access to instrumentation.

Been there, done that. Have no "home lab", but do have a separate building.
Quote:

Besides, there is a ton of work to be done with inorganics. Working with solar cells or thermoelectric coolers or new welding compositions or rendering glass conductive, or trying to find a superconductor or a ton of other things etc. is a lot safer than messing around with anything organic. Back in the early 90's I invented and patented 5,156,721 Process for extraction and concentration of rhodium from catalytic convertors in my basement using salt water, a couple electrodes, HCl, a rectifier and an old catalytic convertor. While searching for a superconductor, I accidentally discovered a mixed oxide that has a variable Curie point around 32 deg. F that a group in China has recently reported on something similar. Point is, like Edison said, Nature teaches you if you keep your eyes open. A room temperature superconductor definitely exists, it just needs to be found. Over a period of over a year, I generated less than a pound of mixed inert oxide waste that all fit in one jar. Since it contained appreciable amount of silver, to dispose of it all I had to do was send it to a refiner.


You are fortunate that the local nanny state bureaucrats overlooked your alleged operation of an "unpermitted rhodium recycling facility in a location zoned residential" or some similar nonsense as their excuse to "redistribute wealth" from your pockets to theirs and some of the local attorneys.
Of course, I am presuming too much for not knowing if
you filled out all the requisite paperwork and handed over the necessary advances for "paying protection" to the local banditos....er, I mean respected government officials :P



[Edited on 28-12-2009 by Rosco Bodine]
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[*] posted on 29-12-2009 at 11:54


I don't know all the answers, but do know that commercial picric acid is supplied in a container that is filled with water, and presumably for a reason. I don't know about bullets being necessary to set it off but do know that 2kg and 5 kg weight drop test data exists from which one can compare its sensitivity to other materials to obtain some idea of its relative sensitivity. As I recall the centimeter drop of a 2 kg weight isn't much in the case of picric acid but don't forget that free picric acid crystals in a drop test are not the same as a solidified lump of the material in a jar, which I guarantee you contains stress faults within its bulk from when its water had evaporated, as well as regions of stress that may not require much further agitation at all in a tiny region in the bulk to piss it off and send one's head soaring in the direction of the stars. Explosives are an interesting area of chemistry, but outside my area of interests, and I like to discourage amateurs from playing with dangerous materials in the absence of proper supervision. I mainly read of them 20 years ago for the value in knowing what to NOT ever mix together, what materials are not compatible with one another, history of chemistry, the way an industry develops, etc. As far as local public officials are concerned, my opinion is that local governments generally like industry for the tax revenues and jobs it provides. I think that should be a goal of most chemists, to develop new products from which new industry can be based, especially in this economy. I didn't make a fortune from the Rh process but learned a few good business lessons which when coupled with lessons learned in other failures increases the chances of success for my next venture in photovoltaic cells. I'm confident that if I try hard enough and never give up, that eventually I'll get one that's a real winner.

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[*] posted on 29-12-2009 at 12:00


By "real winner" I mean one that causes a paradigm shift in an industry. Photovoltaics are a great area since current efficiency levels are only around 10%. This means that if you get it up to 15 - 20%, you can cause a beneficial change in the industry without disrupting already deeply-entrenched participants such as oil companies and their infrastructures and all they jobs they currently provide. The collective global industries comprise a big ship that can only be steered very slowly.
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Rosco Bodine
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[*] posted on 29-12-2009 at 15:21


Your guarantee about the potential sensitivity of dry picric acid is incorrect and is based upon faulty information which you have read and believed without subjecting the information to verification by actual tests. Test the material yourself and then you will have the same knowledge I have, that picric acid is definitely not a sensitive explosive under any ordinary conditions. Not even a bullet impact from just any caliber would provide sufficient impetus to initiate dry picric acid, it would take something very high velocity to do the trick.
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[*] posted on 29-12-2009 at 15:28


Quote: Originally posted by Rosco Bodine  
Not even a bullet impact from just any caliber would provide sufficient impetus to initiate dry picric acid, it would take something very high velocity to do the trick.


Do you feel confident enough in your assertion to put it to the test?

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[*] posted on 29-12-2009 at 15:44


I don't need to do those tests which have already been exhaustively done by the military and have been well documented. The data is already published.
And the drop hammer impact tests which get a reaction from concentrated impact of a few crystals sandwiched in the pinch gap of steel on steel, are a reaction test only and that point initiation will absolutely not self accellerate to accomplish a
sustained detonation of a larger mass. In other words you could bury the
bottom of the drop hammer test aparatus in a pit of crystals of the material being tested, and for the insensitive explosives like picric acid, the reaction impulse
from the few crystals going bang between the steels would not have enough
driving power to initiate the larger mass of crystals which are not pinched between the steel plates. The reaction would quench at the edge of the steel
rather than continue as a detonation wave through the mass, which would
require probably thousands of times more impetus across a critical diameter area
of the bulk mass, than is produced by the sample reaction. In short, it would take a detonation wave from a blasting cap or a high velocity bullet to initiate the mass.
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[*] posted on 29-12-2009 at 16:26


Quote: Originally posted by Rosco Bodine  
Your guarantee about the potential sensitivity of dry picric acid is incorrect and is based upon faulty information which you have read and believed without subjecting the information to verification by actual tests. Test the material yourself and then you will have the same knowledge I have, that picric acid is definitely not a sensitive explosive under any ordinary conditions. Not even a bullet impact from just any caliber would provide sufficient impetus to initiate dry picric acid, it would take something very high velocity to do the trick.


Well, instead of arguing with me, why not just write to those in industry who have made and supplied the material and tell them how foolish they are for shipping it under water for the past 80 years, in view of your superior knowledge ?

All I friggin did was relate a story above, and am now faced with one who comes telling me how wrong I was for calling the fire department 20 years ago when I discovered what I perceived to be an explosive substance in a sensitive state at a garage sale. If I am wrong, there is no damage. If I am right, which I think I am, then I may have saved human life. I think you're wrong for advocating the storage of picric acid in the dry state, since its counter to current and historic industry practice, and nothing you write will change my mind.

I see no benefit in advocating practices that go counter to what is done in industry for decades. It might be good to consider what if someone heeds your advice and has an accident from dry picric acid, and god forbid experiences a loss of some sort or other, then what ? When I was a kid we poured gasoline into a cup and a neighborhood guy literally put his cigarette out in it, with no flames occuring. Haha he laughed. I'd never take that to mean that its safe to smoke around gasoline. Point is, whatever conditions you've experienced don't encompass all and picric acid is stored wet for a good reason that you obviously have yet to learn. Good luck on that.



[Edited on 30-12-2009 by ChrisWhewell]
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[*] posted on 29-12-2009 at 17:00


Quote: Originally posted by Rosco Bodine  
The data is already published.

Are they?
can you show us where?

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[*] posted on 29-12-2009 at 18:28


Quote: Originally posted by ChrisWhewell  
Well, instead of arguing with me, why not just write to those in industry who have made and supplied the material and tell them how foolish they are for shipping it under water for the past 80 years, in view of your superior knowledge ?
80 years?? Absolutely not! It was still shipped dry as a bone in the 1960's and 1970's. It was about 1980 that I heard of this new-fangled hazard and added some water to several bottles that I had on the shelf.

As for superior knowledge, there does happen to be a fair amount embodied in the members of this forum, especially the ones who've been members for longer than a week or two.:P
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[*] posted on 29-12-2009 at 18:43


Quote: Originally posted by ChrisWhewell  
Quote: Originally posted by Rosco Bodine  
Your guarantee about the potential sensitivity of dry picric acid is incorrect and is based upon faulty information which you have read and believed without subjecting the information to verification by actual tests. Test the material yourself and then you will have the same knowledge I have, that picric acid is definitely not a sensitive explosive under any ordinary conditions. Not even a bullet impact from just any caliber would provide sufficient impetus to initiate dry picric acid, it would take something very high velocity to do the trick.


Well, instead of arguing with me, why not just write to those in industry who have made and supplied the material and tell them how foolish they are for shipping it under water for the past 80 years, in view of your superior knowledge ?


You seem to be the one who wishes to argue a point that isn't a point because it has no factual basis. Flammability and dusting are reduced by keeping some materials damp,
and not "under water", which is another incorrect piece of information you are sharing.
Quote:

All I friggin did was relate a story above, and am now faced with one who comes telling me how wrong I was for calling the fire department 20 years ago when I discovered what I perceived to be an explosive substance in a sensitive state at a garage sale. If I am wrong, there is no damage. If I am right, which I think I am, then I may have saved human life. I think you're wrong for advocating the storage of picric acid in the dry state, since its counter to current and historic industry practice, and nothing you write will change my mind.


My hero ! You saved the day. Frankly I care more about what I know than your opinion which is based on ignorance rather than having factual basis. You won't accept good information, so believe whatever you like. Nothing you say after advocating some bright line distinction about he safety of inorganic chemistry versus organic chemistry has much credulity anyway. You can practice your art any way you please but don't come here to school me about things I know a hell of lot more than you.
Quote:

I see no benefit in advocating practices that go counter to what is done in industry for decades. It might be good to consider what if someone heeds your advice and has an accident from dry picric acid, and god forbid experiences a loss of some sort or other, then what ?


The difference between me and you is that about picric acid I know what I am talking about while you do not, and that is no minor difference. So please stop trying to be an expert
about something which you are so obviously ignorant.
Quote:

When I was a kid we poured gasoline into a cup and a neighborhood guy literally put his cigarette out in it, with no flames occuring. Haha he laughed. I'd never take that to mean that its safe to smoke around gasoline. Point is, whatever conditions you've experienced don't encompass all and picric acid is stored wet for a good reason that you obviously have yet to learn. Good luck on that.

Your point here is a fire safety and ease of ignitability nonsequitur, which has nothing to do with detonability of picric acid in a single jar sized quantity where it would not have sufficient mass to ever burn to a cooking off scenario.
Even for that concern being unrealistic in a jar sized amount, it is a real concern for magazine or bulk storage where dusting concerns are also alleviated by damp storage.
The product in bulk is stored damp and is likely cased in
many bottles per box where then the protocol of damp storage may have some validity. It is easier to bottle the material in the same form as the bulk storage anyway.
But for a single bottle on a storage shelf, the protocol
is not the same. A bottle of dry picric acid is not hazardous
to any extent which requires intervention to abate the hazard. You don't believe that because you haven't had the experience handling the material or studying its energetic properties to understand that what I have stated has factual basis.
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ChrisWhewell
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[*] posted on 29-12-2009 at 19:01


How did you come to know just exactly what my experiences and knowledge are ?

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


[Edited on 30-12-2009 by ChrisWhewell]
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entropy51
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[*] posted on 29-12-2009 at 19:09


Quote: Originally posted by ChrisWhewell  

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


Is there a literature reference to that having disemboweled someone?

I did it many times prior to hearing that I should fear for my life.
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[*] posted on 29-12-2009 at 19:16


Then that makes you a brave man too.
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[*] posted on 29-12-2009 at 19:25


Quote: Originally posted by entropy51  
Quote: Originally posted by ChrisWhewell  

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


Is there a literature reference to that having disemboweled someone?

I did it many times prior to hearing that I should fear for my life.



I have also untwisted a jar of picric acid which had the material on the threads, in a university lab no less! Then again, my instructor did advocate washing hands with benzene :-)

I was always told that chief danger of picric acid was in its salts formed with various metals. The second danger to it was its propensity to dye your clothes!




Neither flask nor beaker.


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[*] posted on 29-12-2009 at 19:29


Quote: Originally posted by ChrisWhewell  
How did you come to know just exactly what my experiences and knowledge are ?

It was my reasonable conclusion that you lack experience with the material because from your advice concerning the material it was clear enough you didn't know much about the subject matter.
Quote:

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


Okay, that's me then , a brave man. Alternatively, and just maybe... I know a fair amount about the subject matter and you can verify from authoritative literature as well as by experiment that what I have been trying to tell you is correct.
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[*] posted on 29-12-2009 at 19:30


Quote: Originally posted by ChrisWhewell  
Then that makes you a brave man too.
Well things that are extremely dangerous now were a lot safer before the advent of the Institutional Health & Safety Officer.
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[*] posted on 29-12-2009 at 19:44


Quote: Originally posted by entropy51  
Quote: Originally posted by ChrisWhewell  

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


Is there a literature reference to that having disemboweled someone?

I did it many times prior to hearing that I should fear for my life.


People not knowledgeable with respect to the inherent properties and hazards of these materials would do well to avoid them. I suspect that in most states making and storing picric acid is probably a criminal offense, and for good reason since even those believing themselves knowledgeable, aren't always. Here's three references relating to the relative instabilities of the dry vs. wet from the days long before what you refer to as "the advent of the Institutional Health & Safety Officer" in your smartypants remark

Kast, in Z. ges. Scheiss- u. Sprengstoff 6, 7, 31, 67 (1911)
Will, ibid., I, 209 (1905)
Silberrad and Phillips, J. Chem. Soc. 93, 474 (1908)



[Edited on 30-12-2009 by ChrisWhewell]
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Rosco Bodine
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[*] posted on 29-12-2009 at 20:06


Quote: Originally posted by ChrisWhewell  
Quote: Originally posted by entropy51  
Quote: Originally posted by ChrisWhewell  

If you're comfortable with twisting off an encrusted frozen tight lid on an old bottle of dry phenolic trinitro material, then you're a brave man.


Is there a literature reference to that having disemboweled someone?

I did it many times prior to hearing that I should fear for my life.


People not knowledgeable with respect to the inherent properties and hazards of these materials would do well to avoid them. I think that in most states making and storing picric acid is probably a criminal offense, and for good reason since even those believing themselves knowledgeable, aren't always. Here's the reference you requested, in fact, three

Kast, in Z. ges. Scheiss- u. Sprengstoff 6, 7, 31, 67 (1911)
Will, ibid., I, 209 (1905)
Silberrad and Phillips, J. Chem. Soc. 93, 474 (1908)



[Edited on 30-12-2009 by ChrisWhewell]


Urbanski and PATR are going to be more authoritative, along with possibly Mem Poudres ......but better than any are the direct observations from experiments. There are occasionally disputes which can arise with literature references where described properties and processes do not square with what is found by direct experiment or described
otherwise more accurately in other literature.

As for your interpretation of the law concerning energetic materials themselves, that is probably incorrect also, as
most regulations concern the assembly of components into destructive devices which are used unlawfully as the point at which laws are broken. I'm sure from your sentiments and
the true ignorance on which they are based, that you are no friend of science, except that which is regulated to death
in deference to alleviating your own unfounded safety concerns which actually are a political agenda now recognized for precisely what it is.

Chris is a NARC .

[Edited on 30-12-2009 by Rosco Bodine]
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[*] posted on 29-12-2009 at 20:24


I suspected that I cited a reference some of the argumentative types would come in and attack it, so I chose to cite three. If you don't like J Chem Soc. , Rosco Bodine or whatever your name is, that's fine. If you want to call me names like NARC or whatever and it makes you feel good, then have at it, for name calling changes nothing, nor contributes anything, just like the other two name callers I experienced on this board in the past week. There's no way in he77 you could have even looked at those references in such short time and its clear your agenda is neither geared towards knowledge sharing or learning, but rather is insipid and habitual attacks, which makes you no friend of science, in my book.

If you look at my message above, I said "I suspect....." and that is all I wrote. If possessing picric acid (a high explosive) by know-nots in the general public isn't unlawful, then maybe it should be made so. I've got about a dozen issued patents under my belt in several areas of chemistry, some of which generate money. What have you ever published ? I came here to possibly share some of my knowledge and experience with inventing and commercializing, as I also have an MS from www.ic2.org

But since I've only met attacks, I won't be returning to this website. Good evening.



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[*] posted on 29-12-2009 at 20:26


To the moderators - please delete my account.

Thanks,

Chris
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[*] posted on 29-12-2009 at 20:48


Cannisters of smokeless powder are higher explosive and far more sensitive
and dangerous than picric acid. They are not needed nor required to be stored wet either, although bulk storage quantities of raw unstabilized nitrocellulose very well should be. You could cite three hundred references and it wouldn't matter. Picric acid and TNT alike have been used as a filler in artillery shells, mortars, grenades and other ordnance. Do you have the first clue what sort of shocks are required to be endured by energetic materials suitable for military use
to allow for their not just "going off accidentally" from any rough handling ?
Bottom line is that these materials are extremely insensitive to unintended detonation and are actually pretty difficult to cause deliberately to detonate.
These materials are not like nitroglycerin or worse sensitive materials, so the
alarm over the sensitivity of dry picric acid is simply bullshit and it will still be bullshit whether you cancel your account and take your leave or not.

Maybe go do some transmutation experiments and patent that. A "NARC" is
a term that goes back to the sixties, referencing "undercover agents" who
pretend to be of like mind with various groups of persons thought to be
"subversive" in order to infiltrate and "gather evidence" for criminal prosecutions
which those "moles" bring about. Don't expect a warm reception at any
amateur science forum where you come to talk about how experimentation by
amateurs should be limited to only what you think is safe or legitimate,
because no matter what are your credentials or accomplishments, you will be told to get lost and go find yourself a nice stuffy professional forum where all of
you can review your great accomplishments and exchange attaboys for how smart you think you are.
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