Sciencemadness Discussion Board - Picric acid: different instructions

Picric acid: different instructions

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grndpndr - 5-8-2010 at 20:00

In retrospect wizard in one of the patent excerpts you posted I noted the simple LP would not det cast PA .Not a suprise,however it went on to say a small amt of crystaline PA atop the cast PA would cause the whole to detonate.This is more n line with what I had expected i dont know why i didnt mention that earlier.
Just as plain Ful of Merc 1gr plus pressed to perhaps 4500 mps 1.5 gr is successful in a composite cap with crystalinePA it seems thers little question LP possibly as a composite with K chlorate/AL will detonate PA in its crystaline form/ composite cap.Really all I was trying to get at is/isnt LP a reasonably energetic material capable of detonating many of the energetics used as secondarys in composite caps.Testings in order to determine quantities densities and tube diameter but I dont think thers really any question properly pressed to max densitys LP will detonate good crystaline PA.As to compatibility issues that shouldnt be a overly difficult problem.

[Edited on 6-8-2010 by grndpndr]

The WiZard is In - 6-8-2010 at 07:04

Quote: Originally posted by grndpndr

In retrospect wizard in one of the patent excerpts you posted
I noted the simple LP would not det cast PA

[snip]

You take this toooo seriously! My post(s) are/was not a comment nor
a criticism but merely an addition to the copious of knowledge.

Some will find this of interest :—

REPORTS OF INVESTIGATIONS
BUREAU OF MINES - - APRIL 1921 - -
DEPARTMENT OF INTERIOR

PICRIC ACID AS A BLASTING AGENT
By C E. Munroe (Chief explosives chemist, Bureau of Mines)
and
Spencer P. Howell, (Explosives engineer, Bureau of Mines)

http://tinyurl.com/2brwzsk

Rosco Bodine - 6-8-2010 at 07:19

Unqualified generalizations are too often made in scientific writings, then misunderstood by readers and taken as gospel truth, what should be understood more correctly in a qualified, sometimes highly qualified sense, so that "truth" gets lost in the actual meaning. Picric Acid and picrates are fine examples of the misunderstanding which is generated by "unqualified generalizations" which are mythical in their dimension for spreading ignorance masquerading as knowledge.

Believe what your own experiments show and compare that to the literature and it soon becomes very clear what is going on there. There is almost a nod and a wink given to the "lingo" used in scientific publication, and a lack of precision in description used in scientific literature, which may become generally worse in the older writings, but is too often imported ignorance transported as regurgitated myth brought forward into more modern writings, by "researchers" who perpetuate the errors stated before, either deliberately being vague, or for not checking their facts.

With regards to interpreting various tables which describe in general terms the properties of explosives, the quantity and conditions for the tests are definitively important for making any sense of what those numbers mean. The raw numbers
by themselves are so dependant upon the test conditions, that under different conditions, those numbers may be quite meaningless and no inference can be drawn from them which can be crossed over from one test condition to another. They are highly specific tests, and even device specific tests, comparable on a reasonable basis only in the context of that one specific test, and not reasonable to be interpreted as any unqualified generalization, which may or very well may not hold.

Efficient and reliable firing trains, no matter what materials are used, are systems which are deliberately engineered and specifically tuned devices, and they are not some abstract contraption where somebody read a chart and willy nilly tossed together some odds and ends thought would work okay together. Firing trains are highly specific and well tested systems of refined designed that are tuned like a piano.

Any of you folks who are reloaders of cartridges for firearms surely know how much effort goes into "working up a load"
that has particular accuracy and other performance, and how small variations have an observable difference. It is exactly the same for other firing trains, and applies to detonators in the same way as for ordinary cartridge ammunition. And what works perfect for .45 cal may not work so good for .50 cal. Maybe there is a world of difference there.

The inevitable conclusion is that loadings are device specific.
What you theorize may work or should work, in proof tests may or may not work as expected. The tests which you do specific to a specific device are definitive. All the rest is just theory.

[Edited on 6-8-2010 by Rosco Bodine]

The WiZard is In - 6-8-2010 at 07:40

Quote: Originally posted by Rosco Bodine

Unqualified generalizations are too often made in scientific writings,

[snip]

And they get carried on — unchallenged — verbatim from publication
to publication — in perpetuity. Like human anatomy which was
accepted unchallenged from that of the ancient Greeks up to the
Renaissance.

From Wiki-P

The number of ribs was noted by the Flemish anatomist Vesalius in
his key work of anatomy De humani corporis fabrica in 1543,
setting off a wave of controversy, as it was traditionally assumed
from the Biblical story of Adam and Eve that men's ribs would
number one fewer than women's.

The WiZard is In - 6-8-2010 at 14:55

Take good notes there will be a test.

Uber-die-Metallfalze-des.jpg - 658kB

grndpndr - 6-8-2010 at 23:05

if anything you misunderstood my reaction wizard i was not angry irritated in any way,I appreciate any information I can get.I was mildly interested to see what i believe to be true in print.The only thing that does disturb is as precise as everyone attempts to be on this forum and the consequences if one isnt as accurate as possible is at least called to thier attention if an honest mistake, at worst someone may be hurt.This is unnacceptable with can i say amateur chemists why then would it be acceptable for professional
chemists involved with energetic materials to be less accurate.That does bother me and frankly makes me wonder were these folks careless about thier fellows or am I missing something...

IIRC they did have the scientific method way back 100yrs ago (Edison maybe the exception( but perhaps accurate records doublechecking a colleages work seemed redundant.
maybe they didnt yet use the scientific method after all?Even the lists of todays VOD's/RB are allegedly filled with a very many errors copyed verbatim
from passed down 100yr old texts no one bothering to check the data
apparently!?Now that german shite does tee me off! LOL

wizard thanks for the link to'21' dept of interior and use of surplus wartime PA
with AN admixed with the eutectic PA/mononitronapthalene
is interesting.i havent as of yet finished the link though its saved.
Thanks again.I believe I have access to plenty of dead soft old lead plumbing pipe when i get the measurements \im thinking the lead test blocks couldnt be to difficult to make.And relatively accurately measure cavity volume and RB/VOD

Wizard can you enlighten me as to the nature of that artillery shell thats illustrated?

[Edited on 7-8-2010 by grndpndr]

The WiZard is In - 7-8-2010 at 07:29

Quote: Originally posted by grndpndr

Wizard can you enlighten me as to the nature of that artillery shell thats illustrated?

It a DP patent for the bursting charge in an shrapnel shell,
me thinks with a little help from several dictionaries.

Rosco Bodine - 7-8-2010 at 08:32

Context is important when interpreting the meaning of tabular data for energetic materials and also for weighing generalizations which are made with regards to performance, reactivity and dangers, which are things often affected by the scale of what is being described. There are not necessarily linear magnitude of 10 differences in parameters when comparing samples of 10 mg, 100 mg, 1 gram, 10 grams, 100 grams, 1 kilogram, 10 kilograms, 100 kilograms, 1 metric ton ...ect. of energetic materials. Algebra definitely applies. There is error that sometimes enters into reading data and tempted generalizations which are made without regards to peculiarities dependant upon scale and other parameters which are not linearly incremental for one material, nor for comparisons of different materials, or mixtures or complex combinations. There is a temptation to try to overtranslate or oversimplify actual meaning that may be reasonable for materials which can easily behave differently under differing conditions. There are "bumps" and transitions in performance curves for energetic materials.
There are case A,B,C,D ect. ....through the alphabet scenarios where you can't necessarily take the data from A
and say it is the same for C or D. It may be and it may not be that the properties for one case hold true in a differing case. There are things written as absolutes that are only "more or less true" depending on variables and generally the "lie" will get told erring on the side of safety, which then makes it something of a "white lie" given a nod and wink by those knowing better. People who don't know better will read this kind of stuff and blow right past it, not even recognize that kind of stuff in the literature. If I do
know better on some of what I read, then the professor will just have to pardon the hell out of me for believing results of my experiments instead of the academic propaganda.

For older references, these may be of interest

The unqualified statements about the dangers of accidental detonation of picric acid due to picrate salts also formed accidentally are statements which are true under only the most extreme conditions such as might appear in an industrial scale situation or a magazine storage situation where adverse and abnormal conditions also applied. Yet many people read such misleading statements as gospel truth applicable in all scenarios, including the laboratory, when it is simply false....and yet there is no dismissing the myth which has become "politically correct bad science" and thereby has become conventional wisdom that is simply bullshit and always was bullshit.

Attachment: M.C. Lea article picric acid solubility purification.pdf (271kB)
This file has been downloaded 757 times

Attachment: purification of picric acid pages from Chemical News 1878.pdf (383kB)
This file has been downloaded 863 times

Attachment: Picric Acid, Thorpe 1911, dictionary_of_applied_chemistry.pdf (687kB)
This file has been downloaded 1040 times

Attachment: the metallic picrates.pdf (1.2MB)
This file has been downloaded 824 times

[Edited on 7-8-2010 by Rosco Bodine]

The WiZard is In - 7-8-2010 at 09:42

Quote: Originally posted by Rosco Bodine

Context is important when interpreting the meaning of tabular data for

[snip]

Attachment: the metallic picrates.pdf (1.2MB)

Sorry, the scholar in me requires I add this :—

Silberrad and Phillips
Journal of the Chemical Society
[93] 1908

von Kast on Pikrat's

The WiZard is In - 7-8-2010 at 09:51

Byda I own v3 1911, v. 6 1911 and v. 8 1913 of
this journal, if'n anyone has need of a reference
from them.

Kast-Pikrit-1.jpg - 514kB

Rosco Bodine - 7-8-2010 at 10:09

You speak German, we get it. This is an English language forum however, so the file as an attachment would be entirely adequate, unless you just want to plaster and clutter the pages here with German to make a point. Do you also have the English editions ?

Here's another old reference which goes into some detail about assaying and impurities typical to be found in picric acid.

Attachment: Picric Acid excerpt from Commercial Organic Analysis.pdf (515kB)
This file has been downloaded 1118 times

[Edited on 7-8-2010 by Rosco Bodine]

The WiZard is In - 7-8-2010 at 12:32

Quote: Originally posted by Rosco Bodine

You speak German, we get it. This is an English language forum however, so the file as an attachment would be entirely adequate, unless you just want to plaster and clutter the pages here with German to make a point. Do you also have the English editions ?

German speak me? No. However, this doesn't prevent others
here from speaking/reading it.

I would note in passing for all those who have directed their
criticism at me and believe that this is their private form,
and are therefor entitled to have it run to their specifications ...
Here @ Science Madness. Org I answer only to God or
her representatives on earth, i.e., the forms
moderators.

Rosco Bodine - 7-8-2010 at 12:50

What kind of response is gotten for a reasonable request to an unreasonable person ? See above.

File attachments are easier and less clutter, yet you go to extra trouble to post
inline images in German on an English language board, which doesn't make sense,

Why ?

The WiZard is In - 7-8-2010 at 13:05

Quote: Originally posted by Rosco Bodine

What kind of response is gotten for a reasonable request to an unreasonable person ? See above.

File attachments are easier and less clutter, yet you go to extra trouble to post
inline images in German on an English language board, which doesn't make sense,

Why ?

Why? Because if you post a PDF as an attachment it
get pasted into la post. I will think upon putting it/them into
a PDF which gets attached. I think/hope. However, there
maybe a problem w/ exceeding the file size limit.

What kind of response is gotten for a reasonable request
to an unreasonable person ? See above.

I have a jiffy reply to this, however, as you have contributed
more than I have — probable ever will, I will confine myself
to saying your suggestion has been noted.

[Edited on 7-8-2010 by The WiZard is In]

The WiZard is In - 7-8-2010 at 14:07

Quote: Originally posted by Rosco Bodine

Context is important when interpreting the meaning of tabular data for energetic materials and also for weighing generalizations which are made with regards to performance.....

[snip]

Attachment: Picric Acid, Thorpe 1911, dictionary_of_applied_chemistry.pdf (687kB)

Attachment: the metallic picrates.pdf (1.2MB)

The WiZard Is In - Drives off topic - crashes and burns.

Sorry this it tooooo good to pass up. It is my moral duty
to warn you that you have violated one of the secret rules
here @ Science Most Mad, one that I have been frequently
criticized for violating. You have posted info that the offend
member could have found by themselves by searching
Google there by wasting their time, and as they could
have found it on their own your information is useless.

Whatever happened to — Scholarship is knowing what question
to ask.

Could it be the inmates think they should run the asylum?!

Rosco Bodine - 7-8-2010 at 14:42

It's interesting isn't it how it is more convenient if someone excerpts the portion of interest and posts it in a relevant location, for the benefit of saving people with slower connections having to download an entire document and then edit and compile the excerpt themselves. It also archives the relevant information as a backup in the thread. Really it benefits more those people who are less than regular Einsteins like yourself, since not just everybody can hope to be such a wise guy like you.

quicksilver - 7-8-2010 at 15:17

Quote: Originally posted by grndpndr

I
My laymans question is how do iI square the reported performance of these various primarys were discussing with the alleged inadequacies of basic LP, even FM in its proven ability to high order det a PA base charge of crystaline PA pressed to less than max density 1.4/1.6.Low temp of LP det can be addresse as can its OB increasing brisance/power beyond its ballpark of 4400mps .67 RB the RB exceeds that of LA,MF etc and det vel is off by 800 mps compared to LA @ max density.How do I sqaure that with alleged performances or lack theroff? LP did seem to be a popular material perhaps with the addition of K chlorate and/or AL powder but MF also benefitted from this approach.Assuming one were operating on the KISS principle, very appropriate in my case!Why would I not assume that these materials were basically very similar at least in the advertised performance parameters?

We know each other fairly well and I feel comfortable saying that I really don't have the chops to answer that query with degree of authority or even more of a potent referral to material that you may not have not already read. So speaking just for myself I'd answer a question with a question.

From an empirical perspective I could venture certain discussion points based on what I've observed.
We know that density affects performance & addition of Al results in a greater heat yet lowers certain other areas of performance. So many questions regarding primaries become contingent on agenda & circumstance to which they are put & the complexities of how they are measured & then compared with others of their ilk.

We are often met with generalizations such as HMTD is a more effective initiator of certain secondaries than MF. But what if we have subtle differences that are not taken into account during such an examination [of performance]? Things like outside temperature or the freshness of the synthesis [of the particular primary] that may play a role & are not accounted for.
There are rarely a perfect set of comparative circumstances, so we may be at loss to say with authority that "A >B" as an initiator or always be more efficient, etc. Even though for a given situation we see that lead azide initiates PETN at a lower weight than HMTD; would this ALWAYS be true?
Here's where the rubber meets the road because we have to accept the test data even though it may be flawed by [what may seem like] insignificant circumstances. This may have impact because we would never have all bases covered nor have such a complete knowledge that we could construct such a perfectly equivalent testing situation.

edit:
A classic example is shooting at distance targets.
We hand-load our favorite round with weighed cases and the highest quality match bullets. We then have a powder that we know gives us great results & use a micrometer seating our bullet. We use match primers & clean the flash hole. We know the distance with a laser rangefinder. We use our favorite rifle and make sure its clean and dialed in for the single cold barrel shot.. One day we group very well; another day - we goof.
What changed? We find that one day was hotter than the other and the temp change made the rounds gain in pressure; throwing off our point of impact. We thought we had taken into account all the variables but the temp affected our chemical(s) & spoiled our day.

[Edited on 7-8-2010 by quicksilver]

Rosco Bodine - 7-8-2010 at 16:13

One thing that can really help a lot is when you understand and accept the *fact* that a lot of published "data" is pure bullshit. Do your own experiments and believe your own eyes. If your data doesn't square with "the book" data, rely upon your data ....believe your own eyes. Believe what you see yourself, not what some "authority" tells you to see.

As for detonating PA with basic lead picrate, the problem is scale. It can probably be done if you can accept a "cap" being 5/8" diameter and 6" long.

If a marginal primary is being considered for use, to attempt initiation of a nitrophenol type base charge, then probably it is better to use a base charge of styphnic acid because it is more sensitive to initiation and almost as powerful as picric acid. It is also possible that a small increment of the styphnic acid like a quarter gram, could be used as an intermediate between the initiator and a picric acid base charge, or a composite of styphnic and picric acid may have enhanced sensitivity, making it easier to initiate.

Awhile back we discussed the reenforcing cap configuration which can also be used to increase the effect of the initiator.
That reenforcement may be required to achieve reliable functioning for a device having an initiator that is marginal for the task.

[Edited on 8-8-2010 by Rosco Bodine]

grndpndr - 7-8-2010 at 22:12

I cant ignore the respected forum voices any longer.I was evidently so invested in the now suspect data that I took as gospel what was printed in the data.Forum member Experience trumps paper/pencil in this case most others.How
badly underpowered is the plain PB picrate compared to simple HG fulminate approximately?
I regularly would use 1 gr of ful merc in these composite caps using PA.Mainly due to the abundance of mercury and nitric at the time not really based on need.Theoretically would a gram/gram and 1/2 pressed to 2.8 paper max density succeed in detonating PA pressed to less than max density '1.5 'to ease detonation somewhat and still reach 6500 mps
min.Experimentation may be in order unless theres experience willing to be shared, alothough as stubborn as I now appear...
Thanks for hanging in there fellas its appreciated.
Ive located some what seems to be dead soft lead metal that was used in a near century old home/more was salvage as new plumbing was installed.Seems to me the metal should be satisfactory its as soft softer than any lead ive ever encountered, far softer than even lead .22 bullets.I plan on imp a set of lead test blocks for detonator and the 10gr test of energetic det measuring the hole accurately w/water.Im also synthesising a few grams of K chlorate hoping to find some fine AL based paint to filter off the AL mesh.
One final question? In a gov interior dept paper where ww1 wartime PA was being surplussed I saw a eutectic mix with PA/Mononitronapthalene/Ammonium Nitrate.Aside from the basic energetics no further info was included.
No %,parts per, or wieghts were listed.Could it be Mononitronaphalene was used to initially coat the AN to prevent acid contacting the AN and causing damage or decomposition from the PA?No instructions were included for the composition at all nor were any time lenghths for storage mentioned.It sounds promising on the face of it but any advice would be appreciated.I would hope for a 6500 MPS det vel and higher with this energetic.Being cast it may require a booster of PA/ETN but the should be no problem. Thanks for all the help and patience.Pndr

That shrapnel shell is a trip,a holdover from the BP muzzleoader/breechloader era early 20th cent.Shrapnel was born in
late 17th cent and survived until the mid 18th cent.His initail design for muzzleloading artillery was basically a large riot gun.The original lead/iron ball contraption that held a # of large caliber balls at least the wieght of the rated cannon likely 2x the wieght of a normal Iron ball.Muzzleloaders of the era firing balls that wieghed from a light 6lber up to a med cal of 24 to 36 lber double that wieght in lead balls and thats a viscous mass killer a single large diameter ball passing through several ranks x 100 balls plus.Later shrapnel was considered as not being what it was originally named for but any piece of ballistic metal from most any source/size steel artillery shell or grenade splinter etc.

Synthesis notes like those of a snipers shot logbook detail almost every imaginable variable from weather to equipment.Down to humidity,mirage, cloud cover,pulse,respiration all can affect shot placement or synthesis results.Where I used to be a compulsive notetaker the only notes I make are those made prior to the start of the synthesis a habit I need to break.

The WiZard is In - 8-8-2010 at 06:34

Quote: Originally posted by grndpndr

One final question? In a gov interior dept paper where ww1 wartime PA was being surplussed I saw a eutectic mix with PA/Mononitronapthalene/Ammonium Nitrate.Aside from the basic energetics no further info was included.

No %,parts per, or wieghts were listed.Could it be Mononitronaphalene was used to initially coat the AN to prevent acid contacting the AN and causing damage or decomposition from the PA?No instructions were included for the composition at all nor were any time lenghths for storage mentioned.It sounds promising on the face of it but any advice would be appreciated.I would hope for a 6500 MPS det vel and higher with this energetic.Being cast it may require a booster of PA/ETN but the should be no problem. Thanks for all the help and patience.Pndr

There dobe a number of US Patents using PA and DNN and or
1-MNN.

Her dobe two comps from PATR 2700 (Which can in theory be DL'd) page N8.

Jap Onayako

PA DNN 50/50 or 80/20

(DNN is not explosive)

Trironite

88-90 PA
10-12 1-MNN

This curious US Patent of 1893 by Bolmén (Bolménite)
for pictated naphthalene.

495 178

quicksilver - 8-8-2010 at 07:35

Booster test scenarios are even more variable. War-time claims are often fraught with government contract competitions.

I have a little ditty that I learned the hard way.....
We all will see stuff in print (& since I didn't read over your shoulder; I don't know exactly the specifics). So what I do is assume nothing & simply because the government says something doesn't make it true. The truth will always be in the pudding.

Remember "daylight savings time"? Occasionally we are forced to choose between our watch & a sun dial.

The WiZard is In - 8-8-2010 at 11:21

Quote: Originally posted by grndpndr

My ever useful copy of TM 9-1985-4 Japanese Explosive
Firing Devices and Sabotage Devices)
March, 1953

Sez - The Yellow Peril used as a main charge -
Onayaku - Picric acid 50% dinitrohapthalene 50%.

TM 9-1985-5
Japanese Explosive Ordnance (Army Ammunition, Navy Ammunition)
March 1953

Type 94 7-cm (75mm) High-Explosive Projectiles contained
Ona — Picric acid and dinitronaphtalene. No percentages
given.

They also used Heinei trinitophenetole [2,4,5-trinitrophenetol, Ethyl picrate?] and trinitroanisole [methy picrate].

TM9 -1985-6
Italian and French Explosive Ordnance
March 1953

French Bombs

M Mn — Trimonite (U.S.A.)

70% melinite (picric acid)
30% monotrinitronapthalene

M Dn [MDN] or MFDN

80% melinite
20% dinitronapthalene

D D—Shellite (British)

60% melinite
40% dinitrophenol

We got's two out of three....

The WiZard is In - 8-8-2010 at 11:49

This from a book I am not going to tell you the title
of as I own only 1 of its 2 (3?) volumes and I don't
need any competition looking for the missing volume(s).
However, I'll give you a hint - it is the book that
Fededoroff co-authored before he did PATR-2700.

....
The Explosive characteristics of metallic picrates are given
by J. D. Hopper, J. Franklin Inst., 225, 219-25, 1938....
H. Kast, Z. ges. Schiess-Sprengstofw., 6, 7, 31,67
describes the properties of different picrates and Silberrad
and Phillips, J. Chem. Soc., 93, 474, 1908, gives
their temperatures of ignition.

Hopper not found @ Google.com/books.

grndpndr - 8-8-2010 at 11:50

I was familiar with the eutectic trimonite using the mononitro/pa IIRC the mononitro having a lower melting temp than pa. for Safetys sake. 60/40 i think cliamed 7050 FWIW

I can't recall off hand but thought that MP of DNN was higher than PA!A potentially dangerous situation as it seems to me the MP of PA is within a few degrees of decomp.Any comment on the admixture of AN with a PA/MNN eutctic. likelyhood rapid Decomposition?THANKS
again! I have a hard copy of a portion of a paper entitled metallic picrates!its not at hand so I cant say if its the same but thanks all for the other leads.I have located quite a few but none I recall give a clear answer if a eutectic composition containing AN will be stable enough for @ minimum a few months to a year under good storage coditions..stable moderate temps,humidity.

[Edited on 8-8-2010 by grndpndr]

[Edited on 8-8-2010 by grndpndr]

[Edited on 8-8-2010 by grndpndr]

The WiZard is In - 8-8-2010 at 14:00

Quote: Originally posted by grndpndr

I was familiar with the eutectic trimonite using the mononitro/pa IIRC the mononitro having a lower melting temp than pa. for Safetys sake. 60/40 i think cliamed 7050 FWIW

Capt. Colver in his 1918 opus High Explosives —

Melting points.

Picric acid 50% 122o
Nitronapthalene [which one?] 50% 61o
Mixture 49o

Picric acid 50% 122
TNT 50% 80
Mixture 47

Picric acid 50% 122
Trinitrocresol 50% 107
Mixture 70

Picric acid 66% 122
Trinitrocresol 33% 107
Mixture 78

quicksilver - 8-8-2010 at 14:30

Quote: Originally posted by The WiZard is In

This from a book I am not going to tell you the title
of as I own only 1 of its 2 (3?) volumes and I don't
need any competition looking for the missing volume(s).
However, I'll give you a hint - it is the book that
Fededoroff co-authored before he did PATR-2700.

Could that be.....
A Manual for Explosives Laboratories, 1943???

Rosco Bodine - 8-8-2010 at 15:15

Quote: Originally posted by grndpndr

I cant ignore the respected forum voices any longer.I was evidently so invested in the now suspect data that I took as gospel what was printed in the data.Forum member Experience trumps paper/pencil in this case most others.How
badly underpowered is the plain PB picrate compared to simple HG fulminate approximately?
I regularly would use 1 gr of ful merc in these composite caps using PA.Mainly due to the abundance of mercury and nitric at the time not really based on need.Theoretically would a gram/gram and 1/2 pressed to 2.8 paper max density succeed in detonating PA pressed to less than max density '1.5 'to ease detonation somewhat and still reach 6500 mps
min.Experimentation may be in order unless theres experience willing to be shared, alothough as stubborn as I now appear...
Thanks for hanging in there fellas its appreciated.
Ive located some what seems to be dead soft lead metal that was used in a near century old home/more was salvage as new plumbing was installed.Seems to me the metal should be satisfactory its as soft softer than any lead ive ever encountered, far softer than even lead .22 bullets.I plan on imp a set of lead test blocks for detonator and the 10gr test of energetic det measuring the hole accurately w/water.Im also synthesising a few grams of K chlorate hoping to find some fine AL based paint to filter off the AL mesh.
One final question? In a gov interior dept paper where ww1 wartime PA was being surplussed I saw a eutectic mix with PA/Mononitronapthalene/Ammonium Nitrate.Aside from the basic energetics no further info was included.
No %,parts per, or wieghts were listed.Could it be Mononitronaphalene was used to initially coat the AN to prevent acid contacting the AN and causing damage or decomposition from the PA?No instructions were included for the composition at all nor were any time lenghths for storage mentioned.It sounds promising on the face of it but any advice would be appreciated.I would hope for a 6500 MPS det vel and higher with this energetic.Being cast it may require a booster of PA/ETN but the should be no problem. Thanks for all the help and patience.Pndr

With regards to the volume efficiency, and "critical mass" of initiators, there is a transition point for a given diameter, where the "self-accelleration" produces a
"bump" in the output that corresponds to the transition from low order to high order detonation. The difference between mercury fulminate and basic lead picrate, or normal lead picrate, or lead styphnate, or lead nitrato bis basic picrate, or basic lead picrate - lead nitrate - lead chlorate is a difference between about an order of magnitude roughly somewhere between 10 and 20 depending on diameter. By that I mean if the "bump" in output for mercury fulminate is around about a quarter gram quantity in self-accelleration, then the corresponding "bump" in the output for those other materials is in the range of two and a half to five grams depending on diameter. That's a ball park "guess" because I have not done a careful systematic study and charting of this transition based on self acceleration of materials which demonstrate low self-acceleration. My interest has been a whole lot more directed to materials which show an even better self-accelleration than mercury fulminate. There are ways you can improve the sluggish self accelleration of those primaries that are more generally useful as "primers" rather than initiators, by combining them with more rapid self-accellerating materials and / or using strong confinement, which helps "kick" them towards the transition to high order at an earlier point. Thereafter you still must have an additional charge quantity beyond the amount that is "burned off" during the "runup to high order", the additional quantity which will be the actual
"work performing portion" transferring its high order impulse to the target base charge to be initiated. I haven't seen this described anywhere in any literature, but this is simply my observation and interpretation of experiments. Some primaries are fine for primers, for "flash igniters" and they are dependable as "first fire" and low order compositions. Any "relative brisance" sort of figure would likely not reflect performance of such a material being used in its usual mode and quantity where brisance is not much of an aspect of that low order scheme. That "relative brisance" quantity is probably from a test where the material was not in small quantity undergoing self-accelleration, but was being used as a relatively large sample secondary charge and fired by a separate detonator. So the "relative brisance" of a material being tested under conditions different from its ordinary mode of operation does not provide useful information about the "unboosted" performance of the same material in smaller quantity.
Yeah if you put ten grams of basic lead picrate in a test block and detonate it with a compound detonator, the whole ten grams goes high order at once and has significant brisance. But if you simply stick a fuse in the sample, five of the ten grams may be burned off in the "runup" which was circumvented entirely by the
use of a cap to get it going. I hope this helps makes sense of how test data can be misleading unless you have all the details factored into interpreting the tests.

[Edited on 9-8-2010 by Rosco Bodine]

franklyn - 8-8-2010 at 18:23

Quote: Originally posted by Rosco Bodine

" primaries that are more generally useful as "primers" rather than initiators "

You lost me there , if there be a semantic distinction in definition. I take it
from the implied context that " primer " you take to be what is set off by
fuze flame or heated wire, and " initiator " that subsequent part of the train
most proximately in contact with the main charge ( assuming no booster ).

Cap constituent formulation is very much an empirical art. Your layer cake
design will differ from another's jelly roll concoction. Field testing is the only
validation that matters.

.

Rosco Bodine - 8-8-2010 at 19:03

It is a bit of semantics, but generally a "primer" references a primary "explosive"
which would be used more as a pyrotechnic igniter composition involving an explosive combustion which is of lower order, as in the case of an ammunition primer, producing a sudden flame as for igniting gunpowder, but not directly producing a detonation.

On the other hand an "initiating explosive" or "initiator" in that context, would
be associated directly with only high order detonation, not a burning or pyrotechnic ignition effect, but only producing a detonation effect.

For some of the compositions which may be used for either purpose depending on quantity, composition, and what is the device operated upon, those other aspects will make the distinction whether the material is functioning as a primer
or as an initiating explosive. And to confound the semantics further, in some cases the same material may be both a primer and an initiating explosive,
so what is there to be confusing

grndpndr - 8-8-2010 at 23:17

Thanks for your patience Roscoe.I understand your reasoning Roscoe and of course appreciate the help.layer cakes were mentioned.some are concerned with the finest ingredients, smallest size.If I make one my concern is it works well det difficult HE's uses OTC ingredients not nescessarily how big it is.Again thanks for your input,I particularly appreciate the OTC synthesis ofetn posted for common energetic secondarys.Sincerely pndr

[Edited on 9-8-2010 by grndpndr]

[Edited on 9-8-2010 by grndpndr]

pentanitronaphthol (and possible salts ?)

Rosco Bodine - 9-8-2010 at 01:20

Here's an off the beaten path material that may be of interest. I have never made this one and references on it are obscure to non-existent. Hey Axt ! Hey Philou ! Hey Engager ! Lookee here what I found

Attachment: US1419027 pentanitronaphthole.pdf (115kB)
This file has been downloaded 1134 times

grndpndr - 9-8-2010 at 08:00

Interesting patent,thanks for bringing it to my/our attention.One of my first reactions upon reading its MP
and acidic nature was as a possible eutectic with PA.
Im sure it sounds as if Im near compulsive as regards PA but I assure you im also interested in other inexpensive OTC energetics.From those suitable for cutting steel to ditching dynamite.
And simple primary energetic materials capable of detonating even difficult secondarys.Simply put a main requirement is would this be relatively simple and inexpensive to synthesise using simple household and labaratory equipment and mainly OTC chemicals.

All theoreticall of course!

[Edited on 9-8-2010 by grndpndr]

[Edited on 9-8-2010 by grndpndr]

Rosco Bodine - 9-8-2010 at 09:30

It looks like a variation and extension upon the "catalytic process" of aromatic nitrations using mercuric nitrate to form an unstable addition compound as an intermediate in the nitration. Picric acid is made from benzene, and trinitrocresol is made from toluene via the "catalytic" process (not precisely catalytic although the mercuric nitrate is regenerated). Evidently naphthalene also forms a partially oxidized nitroaromatic compound more easily nitrated to a penta nitro derivative than is usual rigor of nitration required for the better known tetranitronaphthalene, and as a bonus the pentanitro compound is more powerful and has the acidity of a nitrophenol. Hmmmm, that's interesting because it may be something like tetryl in terms of power, while being thirsty for compounding with a metal like lead which should result in a primary having considerable impulse, probably greater than the impulse of styphnate or picrate salts. Such a "nitroaromatic acid" could be a useful substrate for various salts and double salts. PATR Vol.8 N-20 reports one research paper done by A.H. Blatt & F.C. Whitmore OSRD 1085, 74 (1942) , which was a WWII "scientists at war" kind of project having many branches one of which was the Manhattan project. And the fellow who invented and patented the compound is a recognizable name in the field, who wrote a little handbook we all know so well as COPE. So this is very intriguing. Is it a mono or di acid ? Googling the authors names for the OSRD reference turns up no hits for me, so that article must be buried in obscurity somewhere possibly hardcopy archived in a box and never yet digitized. We ought to fix that.

Do we know any librarian types who are given to scavenger hunts for obscure historical material ?
Hmmmm, let me think .....any wizards around here ? Or just pretenders ?

Now there's a document request, and I'll even add a pretty please with sugar on it.

[Edited on 9-8-2010 by Rosco Bodine]

The WiZard is In - 9-8-2010 at 10:01

Quote: Originally posted by Rosco Bodine

Googling the authors names for the OSRD reference turns up no hits for me, so that article must be buried in obscurity somewhere possibly hardcopy archived in a box and never yet digitized. We ought to fix that.

Do we know any librarian types who are given to scavenger hunts for obscure historical material ?
Hmmmm, let me think .....any wizards around here ? Or just pretenders ?

Now there's a document request, and I'll even add a pretty please with sugar on it.

A v/ very quick search turns up a reference to :—

A H Blatt Compilation of Data on Organic Explosives
O.S.R.D. 2014 (1944)

This evening I'll spend some time look for whatever turns up.

Rosco Bodine - 9-8-2010 at 10:08

Thanks Wiz ...I've been searching for two days. Evidently there was a declassification and reindexing of OSRD material under new PB numbers
so the catalog is required to cross reference original numbers which are
basically a "lost" filing system for the previously classified war related research. These research papers, there are about 600 odd thousand of them which were government funded research are now boxed in hard copy form in several historical archives. Whether or how much of it has ever been scanned is unknown. I think I read somewhere they spent nearly a trillion dollars to get those research findings.

[Edited on 9-8-2010 by Rosco Bodine]

The WiZard is In - 9-8-2010 at 10:15

Quote: Originally posted by Rosco Bodine

PATR Vol.10
N-20 reports one research paper done by A.H. Blatt & F.C.
Whitmore OSRD 1085, 74 (1942) ,

Vol. 8 N20 works for me.

I do not believe L Davis ever worked for the Gov. so you
are not going to find any OSRD &c. pubs w/ his name on
them.

Rosco Bodine - 9-8-2010 at 10:26

Yeah Vol.8 N-20 is correct. Right , Davis patented the material earlier, but the followup testing, review and research I would guess came later via OSRD.
There may be something in the journals subsequently or it may have fallen through the cracks and disappeared into obscurity.

The WiZard is In - 9-8-2010 at 12:55

Quote: Originally posted by grndpndr

And simple primary energetic materials capable of detonating even
difficult secondarys.Simply put a main requirement is would this be
relatively simple and inexpensive to synthesise using simple
household and labaratory equipment and mainly OTC chemicals.

The WiZard is In - 9-8-2010 at 13:12

Quote: Originally posted by Rosco Bodine

IPATR Vol.8 N-20 reports one research paper done by A.H. Blatt & F.C. Whitmore OSRD 1085, 74 (1942)

Department of The Army Second Army-Navy Research Conference
of New High Explosives
1 November 1949

Byda AHB was editor of the 1 and 2nd Collective Volumes of
Organic Synthesis.

Blatt.jpg - 345kB

Rosco Bodine - 11-8-2010 at 22:43

Quote: Originally posted by Rosco Bodine

As for detonating PA with basic lead picrate, the problem is scale. It can probably be done if you can accept a "cap" being 5/8" diameter and 6" long.

If a marginal primary is being considered for use, to attempt initiation of a nitrophenol type base charge, then probably it is better to use a base charge of styphnic acid because it is more sensitive to initiation and almost as powerful as picric acid. It is also possible that a small increment of the styphnic acid like a quarter gram, could be used as an intermediate between the initiator and a picric acid base charge, or a composite of styphnic and picric acid may have enhanced sensitivity, making it easier to initiate.

I was remiss in posting an example of the use of an "increment" of a more sensitive intermediate secondary to decrease the amount of initiator required. I found an example of this where a small charge of picric acid is used as a booster for a TNT base charge in a compound detonator.

US1502754 composite picric acid - TNT compound detonator

Also is attached another detonator configuration patent showing a general design that is readily adaptable for larger compound detonators for example as might use a test tube for a housing. There are available polypropylene test tubes of 5 or 6 ml capacity and approximately 3/8" ID which are adaptable for such use.

US2214721 DDNP-KClO3 75-25 PETN base detonator

US2842059 Special Capsule Design for Detonator

Attachment: US1502754 composite picric acid - TNT detonator.pdf (196kB)
This file has been downloaded 959 times

Attachment: US2214721 DDNP-KClO3 75-25 PETN base detonator.pdf (206kB)
This file has been downloaded 1187 times

[Edited on 12-8-2010 by Rosco Bodine]

Attachment: US2842059 Special Capsule Design for Detonator.pdf (283kB)
This file has been downloaded 1013 times

efficiency of detonators

Rosco Bodine - 15-8-2010 at 06:56

Here is a reference which may be useful for general information, even though it doesn't relate specifically to picric acid base charges, it does show the effect of some of the same variables as would tend to be generally true.

Attachment: Efficiency of detonators.pdf (759kB)
This file has been downloaded 1476 times

The Sand Test Storm and Cope 1916

Rosco Bodine - 13-12-2010 at 01:55

The sand test for determining the strength of detonators
Christian George Storm and Willard C. Cope 1916

http://sciencemadness.org/scipics/The_sand_test_for_determin...

Google books link
http://books.google.com/books?id=EdfHxMJtIBUC&printsec=f...

A bit of interesting history about Mr. Cope, is that he was an explosives expert who was involved in the construction of the Panama Canal. He was also an expert witness called by the official inquiry regarding the Halifax Explosion of Dec. 6, 1917. The Halifax Explosion was a result of a harbor collision between ships causing fire aboard one of the ships which was loaded with munitions and exploded less than an hour later, killing 2000 people and injuring 9000. Fragments of the munitions ship S.S. Mont Blanc were scattered for miles by the tremendous explosion.
2653 tons of munitions were involved in the explosion and most of that cargo was picric acid.

http://en.wikipedia.org/wiki/Halifax_Explosion

[Edited on 13-12-2010 by Rosco Bodine]

K.I.S.S. extremus — The nail test for detonators

The WiZard is In - 13-12-2010 at 13:05

US Bureau of Mines 1915

http://tinyurl.com/266pkr5Text

quicksilver - 13-12-2010 at 13:52

Aaahhhhh; beat me to it.

Personallly I have no problem with the idea of basic lead picrate initiating real reagent grade picric acid.

Rosco Bodine - 13-12-2010 at 14:48

It isn't impossible for basic lead picrate to initiate picric acid, it would just require
an inconveniently large amount and special confinement in a relatively large detonator in order for it to be possible. So it is not technically infeasible, it is simply an impractical and awkward arrangement compared to more efficient alternatives. It may well be that an increase of sensitivity to initiation can also be obtained depending upon the solvent and the method used for crystallization. It is not unusal for different crystal forms to be possible and some may be more sensitive than others.

quicksilver - 14-12-2010 at 06:15

I had just recently bought a "add-on" for taking pictures via a microscope but it wasn't up to par. So I couldn't get what I really wanted, which were quality pictures (w/ sizing lens) of alteration in crystal structure (especially in the "picric-genre'"). Sometime back we had a discussion on the alteration of the crystal in Basic Lead Picrate (& some other materials as well) and there was some patent material in alteration of (IIRC) lead styohnate into granular cuboids. There are also growth procedures to lead picrate;normal & basic, that can make them substantially larger, well formed, & possibly more sensitive Testing their utility would be pretty interesting.

Rosco Bodine - 14-12-2010 at 06:19

Actually it was the picric acid and styphnic acid that I was more thinking about in recalling perhaps some reference that more sensitive crystals easier to initiate were possibly gotten from solvent crystallizations other than water,
alcohol may have been one of them. I never tested this
to see if there is any significant difference in sensitivity
for organic solvent crystallizations.

grndpndr - 21-12-2010 at 11:15

Quote: Originally posted by Rosco Bodine

Quote: Originally posted by grndpndr

I have deleted a majority of my own post for brevitys sake and keep this post somewhat on topic.
Roscoe's reply verbatim

"With regards to the volume efficiency, and "critical mass" of initiators, there is a transition point for a given diameter, where the "self-accelleration" produces a
"bump" in the output that corresponds to the transition from low order to high order detonation. The difference between mercury fulminate and basic lead picrate, or normal lead picrate, or lead styphnate, or lead nitrato bis basic picrate, or basic lead picrate - lead nitrate - lead chlorate is a difference between about an order of magnitude roughly somewhere between 10 and 20 depending on diameter. By that I mean if the "bump" in output for mercury fulminate is around about a quarter gram quantity in self-accelleration, then the corresponding "bump" in the output for those other materials is in the range of two and a half to five grams depending on diameter. That's a ball park "guess" because I have not done a careful systematic study and charting of this transition based on self acceleration of materials which demonstrate low self-acceleration. My interest has been a whole lot more directed to materials which show an even better self-accelleration than mercury fulminate. There are ways you can improve the sluggish self accelleration of those primaries that are more generally useful as "primers" rather than initiators, by combining them with more rapid self-accellerating materials and / or using strong confinement, which helps "kick" them towards the transition to high order at an earlier point. Thereafter you still must have an additional charge quantity beyond the amount that is "burned off" during the "runup to high order", the additional quantity which will be the actual
"work performing portion" transferring its high order impulse to the target base charge to be initiated. I haven't seen this described anywhere in any literature, but this is simply my observation and interpretation of experiments. Some primaries are fine for primers, for "flash igniters" and they are dependable as "first fire" and low order compositions. Any "relative brisance" sort of figure would likely not reflect performance of such a material being used in its usual mode and quantity where brisance is not much of an aspect of that low order scheme. That "relative brisance" quantity is probably from a test where the material was not in small quantity undergoing self-accelleration, but was being used as a relatively large sample secondary charge and fired by a separate detonator. So the "relative brisance" of a material being tested under conditions different from its ordinary mode of operation does not provide useful information about the "unboosted" performance of the same material in smaller quantity.
Yeah if you put ten grams of basic lead picrate in a test block and detonate it with a compound detonator, the whole ten grams goes high order at once and has significant brisance. But if you simply stick a fuse in the sample, five of the ten grams may be burned off in the "runup" which was circumvented entirely by the
use of a cap to get it going. I hope this helps makes sense of how test data can be misleading unless you have all the details factored into interpreting the tests.

[Edited on 9-8-2010 by Rosco Bodine]

With the above in mind 3.75grains of PB picrate was detonated in a layer of tin foil(enclosed) by means of heat from a hotplate with an aluminum plate .110 thick to protect the H/P element.The detonation was very energetic.Not having a method to measure decibels Id say it was equivalent to a .32 automatic pistol fired indoors.The Aluminum plate that absorbed the untamped detonation dented the approx 1/10in thick(unknown alloy) AL plate to a diameter of perhaps 3/4 in and using straightedge and feeler gauges,
as I dont have to hand a depth micrometer. A rough measurement indicates .080 thousandths dent depth.Wouldnt that indicate a detonation? And a detonation of 3.75grains (243 mg) Of 'KEWL' PB picrate.I prefix the PB picrate with KEWL as its made using a KEWL's recipe or synthesis along with some less than kind,mature observations(perhaps warranted)by some ,members.TNP/Methanol/Pb0,although an excess of TNP was used but no other additives such as nitrates / chlorates/Al were incorporated.Im curious as to the explanation for such a vigorous reaction.With respect . sincerely,grndpndr.

PS;In the interests of complete information, I strongly suspect this lead picrate was made using a poor quality TNP as the TNP itself doesnt det from a hammer blow.Steel on steel with the TNP enclosed with foil as well.
Also the alleged PB picrate isnt sensitive to friction or impact of the type described.Just a few sparks from a hammer blow!?

[Edited on 21-12-2010 by grndpndr]

[Edited on 21-12-2010 by grndpndr]

Rosco Bodine - 21-12-2010 at 13:02

You will get low order detonation even below 100 mg. Think of that as DDT for low order. It could take tens of times more to make the transition from low order to high order.

grndpndr - 21-12-2010 at 18:54

I appreciate the insight Roscoe. Thanks!

PS; It would be interesting/enlightening to test a variety of primarys using the same test plate,duplicating the first test parameters.

[Edited on 22-12-2010 by grndpndr]

grndpndr - 10-1-2011 at 02:47

Theoretically If it did take 10x approx 1/4gram to reach full detonation that would = approx 2.5grams.IIRC approx 2.8 gr fills 1ml3 @ its highest density/vod. that doesnt amount to much volume in a .25 ID cap
given PB picrates density.Ballpark IIRC thats about a 1 3/4 in long cap with 1 gram PA also pressed to its optimum density.

Forgive my stubborness but I think that how edison maDE his breakthroughs.Im not claiming to be an edison simply possesing a stubborn streak.No offense!

hiperion42 - 10-4-2011 at 12:55

Attachment discusses the mix of picric acid with litharge for use as a initiator capable of detonating the nitrated phenol.

Attachment: AD410390.pdf (206kB)
This file has been downloaded 983 times

Blasty - 11-4-2011 at 13:21

Quote: Originally posted by hiperion42

Attachment discusses the mix of picric acid with litharge for use as a initiator capable of detonating the nitrated phenol.

Is there a continuation to that interesting paper? It seems the author was planning more tests of the improvised detonator, and whether or not it could be used with ammonium nitrate and oxidizer-fuel explosives.

quicksilver - 11-4-2011 at 16:10

One of the difficulty in commercial study papers of this type (Remington Arms Corp submitted for Gov't review) is that occasionally they are offshoots of accidents or studies of "concept methods". Picric acid had been subject to periodic tragedies via the (accidental) emergence of picric - metal salts in storage conditions. However when submitted, expressions such as "squib" are often used to describe items that have a direct bearing on the utility and efficiency of the technique. The reader then does not fully know what was the composition of the initiator.

Truly high quality Picric acid would initiate with the basically same circumstances as many other benzene-ring nitrated materials. In fact TNP is one of the more sensitive of that group and equivalent of the "standard #6" fuse cap: compressed mercury fulminate would substantially fill the need. Because we don't know what is meant by "squib" when used to describe the initiation of the possible lead picrate; we might even have a minor explosive charge in train. These unknowns put us at a disadvantage for evaluation.

The WiZard is In - 11-4-2011 at 16:55

Quote: Originally posted by Blasty

I did a Vulcan Mind Meld with la Net, and yes, however, only the July report can be DL'd gratis. The others
can be had from the NTIS. [$$$]

1. Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL OPERATIONS
Personal Author: Johnson, Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CT
Source Code: 301600
Page Count: 8 page(s)
AD Number: AD0410390
Report Date: 01 MAY 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL OPERATIONS.
Personal Author: Johnson,Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CONN
Source Code: 301600
Page Count: 1 page(s)
AD Number: AD0416303
Report Date: 10 JUL 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL WARFARE OPERATION...
Personal Author: Johnson,Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CONN
Source Code: 301600
Page Count: 3 page(s)
AD Number: AD0425772
Report Date: 01 SEP 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL OPERATIONS
Personal Author: Johnson, Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CT
Source Code: 301600
Page Count: 6 page(s)
AD Number: AD0425771
Report Date: 31 AUG 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL WARFARE OPERATION...
Personal Author: Kenney,J F Johnson,Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CONN
Source Code: 301600
Page Count: 3 page(s)
AD Number: AD0425773
Report Date: 01 OCT 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

Title: DEVELOPMENT OF EXPLOSIVES AND INITIATORS FOR SPECIAL OPERATIONS.
Personal Author: Johnson,Theodore B
Corporate Author: REMINGTON ARMS CO INC BRIDGEPORT CONN
Source Code: 301600
Page Count: 2 page(s)
AD Number: AD0416302
Report Date: 01 JUN 1963
Distribution Code: 01 - APPROVED FOR PUBLIC RELEASE
Report Classification: U - Unclassified
Collection: Technical Reports

---------
Dr. Dupre [1889] made the interesting observation that a mixture of two
parts by weight litharge (oxide of lead) with one part picric acid
detonates violently when heated. I will heat one grain of this
mixture on this piece of tin-plate, and this quantity will be sufficient
to give a very sharp explosion.

http://tinyurl.com/3sc5fb8

The WiZard is In - 12-4-2011 at 09:14

Quote: Originally posted by Blasty

Quote: Originally posted by hiperion42

Attachment discusses the mix of picric acid with litharge for use as a initiator capable of detonating the nitrated phenol.

Well ... the small arms cartridge case detonator
made it into the Low Albedo Book(s), however, use
litharge and PA in it did not.

Blasty - 13-4-2011 at 00:32

Quote: Originally posted by The WiZard is In

Well ... the small arms cartridge case detonator
made it into the Low Albedo Book(s), however, use
litharge and PA in it did not.

It seems the author of those reports was working along these lines, noticed at least as far back as the 1890s:

"A very crude admixture of metallic oxides or nitrates, notably litharge, lime, and the nitrates of lead, and strontium, with picric acid, will, on the application of heat, detonate, and such detonation will extend to contiguous masses of the unmixed acid. The heat first induces the formation of picrates, and its continued application causes their detonation."

http://books.google.com/books?id=_4lBAAAAIAAJ&pg=PR38&am...

It would be interesting to read what explosives he managed to successfully detonate with these litharge-picric acid mixtures + pure picric acid booster.

[Edited on 13-4-2011 by Blasty]

quicksilver - 13-4-2011 at 07:10

Some elements of this issue rest in the level of efficiency of the stated primary. A great many things can eventually develop a detonation wave (or energy transmission in general) strong enough to transmit energy from primary to secondary. The contingency is amount (weight/volume) of the primary in question. Use enough of many materials and you could develop a train of enough energy to initiate the secondary; the question is how much is enough? Additionally, is this the best or appropriate example of method(s)?
What's more if we examine a simplistic technique to synthesize a salt it may not necessarily be the most effective example of that salt.
A very good example is lead picrate. Carefully synthesized basic lead picrate is decidedly more efficient than poorly or haphazardly made normal lead pirate, etc.

Blasty - 13-4-2011 at 11:36

Quote: Originally posted by quicksilver

Some elements of this issue rest in the level of efficiency of the stated primary. A great many things can eventually develop a detonation wave (or energy transmission in general) strong enough to transmit energy from primary to secondary. The contingency is amount (weight/volume) of the primary in question. Use enough of many materials and you could develop a train of enough energy to initiate the secondary; the question is how much is enough? Additionally, is this the best or appropriate example of method(s)?
What's more if we examine a simplistic technique to synthesize a salt it may not necessarily be the most effective example of that salt.
A very good example is lead picrate. Carefully synthesized basic lead picrate is decidedly more efficient than poorly or haphazardly made normal lead pirate, etc.

There's several things to consider as to why the author of those reports is choosing these methods. He seems to have been interested in improvising detonators + explosive charges from relatively common & available materials and without requiring too complicated processes or apparati (a kind of "MacGyver" thing.) Also, it seems from the descriptions of these picric acid + litharge/lime/nitrate mixtures that they only mention their explosion with heat, apparently not with friction or impact, or at least not easily enough to make a pertinent note of it. Since the picrates do not seem to form until heat is applied to such mixtures, this might have to do with their more relative safety over using the actual picrates already prepared.

quicksilver - 13-4-2011 at 12:02

Good point. An interesting experiment would be an "exposure level" experiment. Wherein the tri-nitrated (or lower for that matter) material is simply exposed to a metallic salt in various conditions and from that, determined what (if any) resultant picate would be synthesized. Indeed, we could go beyond a focused synthesis & test whether (not to lead this discussion astray but expound upon a theme) time, heat, solvency, mother liqueur, pressure / density, etc...contribute to a synthesis? Improvisational techniques may benefit from "accidental" synthesis analysis in things of this nature.
Such experiments could answer what level of heat, solvency, pressure, density are required to bring about a resultant primary (in this case). It could lead further to a look at other benzene-ring nitrated materials in their capacity to serve in the same context in the synthesis of a primary. Is picric acid the most efficient candidate for such a thing, etc?

Hades_Foundation - 14-4-2011 at 23:28

Quote: Originally posted by hiperion42

Attachment discusses the mix of picric acid with litharge for use as a initiator capable of detonating the nitrated phenol.

Forgive my ignorance, but isn't this just research for TM31-210 Improvised Munitions (section 1 No 20)?
http://cryptome.org/tm-31-210-pdf.zip

sorry if I'm stating the obvious.

[Edited on 15-4-2011 by Hades_Foundation]

497 - 30-6-2011 at 18:29

Well this picric acid synth is different all right. So I thought this looked like the appropriate thread.

According to the this paper, boiling various p-substituted phenols is pretty dilute HNO3, sometimes with vanadium oxide as a catalyst will yield picric acid. This is new to me.

The best option if you can get it looks to be p-hydroxybenzoic acid. They boiled it in excess "4N or 8N" HNO3 for 1-3 hours and got around 70% yields of picric acid. The main byproduct is oxalic acid which they remove from the solution by addition of Ca(NO3)2.
p-OH-benzoic acid can be made in >90% yields by thermal rearrangement of the dipotassium salt of salicylic acid at around 220*C for a 2-3 hours. Or you could just buy "methyl paraben" and hydrolyze to p-OH-benzoic acid (in situ possibly?), its pretty cheap and available in quantity.

Alternatively you can go with an even easier to get substrate, tyrosine. To oxidize the side chain to the benzoic acid intermediate you have to add some vanadium pentoxide catalyst though. But it is like $40/lb and tyrosine is under $20/pound.. They boiled it in 8N(~40%) HNO3 for an hour and then raised the concentration to about 9.5N and boiled for a further 2 hours to get a 45% yield of picric acid.

They tried it on phenylalanine and got p-nitrobenzoic acid in 40% yield. Maybe useful for other purposes?

Also worth noting that they got 95% yield of picric acid from dinitrohydroxybenzoic acid by boiling in 10 times its weight of plain old 8N HNO3.

It doesn't look like any of these reactions were optimized much. I'm pretty sure you could improve the yields substantially. I would also be very interested to see what happened to salicylic acid or aspirin in these conditions..

One thing I like about this route is that the acid is very reusable and you can avoid mixtures with H2SO4 if desired. Just cool the solution after the reaction, separate the precipitated crystals of PA, precipitate oxalic acid as its calcium salt, and you're good to start again. Once the water formed dilutes it too much, you can just boil it out, maybe even continuously during the reaction. If reused extensively it seems good yields based on HNO3 could be obtained. If using tyrosine NH4NO3 will eventually build up in the acid solution.

I would assume that a solution made by filtering the precipitated sulfate salt from a mixture of dilute H2SO4 + XNO3 and boiling it down to the correct concentration would provide an effective alternative to distilled HNO3.

I'm not trying to say that this is a superior method to Rosco's aspirin sulfonation/nitration procedure, at least until someone tests it

But it's at least another alternative which may be advantageous in certain situations for a number of reasons, such as no need for H2SO4, easier reaction conditions (avoids foaming, stirring, exotherms, gradual additions of reagents) and no waste mixed acids. Another possible advantage is its lack of ability to detonate since no solid PA is present until cooling, and the liquid phase should always have far too much water to be detonable. Maybe it is more amenable to scale up than a traditional mixed acid nitration?

I've never seen anything similar to it for PA synthesis, though I haven't read this whole thread. What do you think?

P.S. On a less related note, I'm curious what you guys think are the best or most interesting energetic derivatives of PA? Sadly I don't have any means available to chlorinate it to picryl chloride, so derivatives based on that aren't an option.
Wow, never knew TATB was this easy! React PA with urea to get 88% yield picramide, the aminate that with hydroxylamine + NaOEt in DMSO for a 50-74% yield of TATB! Cool! Too bad I'm not drilling oil wells...

[Edited on 1-7-2011 by 497]

quicksilver - 1-7-2011 at 07:25

I found this quote interesting:
"Morner (1915) (2) has obtained p-nitrobenzoic acid, picric acid, and
oxalic acid as well as the several other substances by oxidising protein
with nitric acid, and he pointed out that the parent substance of nitrobenzoic
acid was phenylalanine and those of picric acid were tyrosine and
phenylalanine which arose from the protein during the treatment with
nitric acid."

Remembering many of those very old protein-acid synthesis for picric acid ( such as horn, wool, etc), the concept of tyrosine makes sense. What's more the refluxing was only taking place for 2 hours (re: small yields).

What's interesting about the paper from a historical perspective is that it was published in 1941 (war years).

497 - 4-7-2011 at 09:52

Based on this old book and other references boiling of salicin in nitric acid eventually yields picric acid. I assume it would be formed by oxidation to (nitro)salicylic acid then decarboxylation and further nitration. One book even said picric acid of "remarkable purity" was obtained by boiling salicin in nitric acid.

This would seem to indicate that simply boiling acetyl salicylic acid in HNO3 of similar concentrations to the above japanese paper would give at least moderate and possibly good yields of PA under the right conditions. It may be worthwhile to hydrolyze ASA into SA before nitration if it turns out that the acetic acid from ASA increases the solubility of PA in HNO3 solutions appreciably.

Jimbo Jones - 5-7-2011 at 00:44

I think SA is also OTC and may be found dirty cheap (compared to ASA) in the local pharmacy store.

Interesting found 497.

Rosco Bodine - 5-7-2011 at 10:17

Hey even Rosco said his tried and true good old country organic synthesis was not necessarily optimized and could probably be improved, but is a good starting point if you don't have another method that works better ....red goo complications loom large as a potentially big one

Actually aspirin is hard to beat for a precursor in terms of price and availability, but sure there are a dozen different potentially useful precursors and several of them are better than phenol in economy and convenience. I think it is probably possible to make picric acid using a slow dripped addition of the nitrating material as a concentrated aqueous
solution or possibly a low temperature melt from a heated funnel, consisting of one or several nitrates in a mix with either water or nitric acid. I'm just not sure what is the mix of conditions and concentrations peculiar to such anticipated schemes which will produce optimum results. The variables are there to make the final nitration a bit finicky about temperatures and times and concentrations and they are interactively interdependant on what curve the reaction follows so any process is likely to require some process modeling and fine tuning of reaction parameters to get the best result. Certainly scaleup will be favored by the nature of which process is worked out with that end in mind. Many of the nitrations reported are scale dedicated and work fine until you start changing the scale up or down. Then you get differing thermodynamics and reaction rates which leads to a lot of process algebra to work things out for the differing batch size. Actually that is generally true for more things than just nitrations. So anybody having a go at scale changes should be prepared for surprises which may be small or not so small.

The WiZard is In - 5-7-2011 at 11:03

Quote: Originally posted by Jimbo Jones

I think SA is also OTC and may be found dirty cheap (compared to ASA) in the local pharmacy store.

Another Kitchen Tested receipt from one of my Uncle's
Low Albedo Books

At no extra charge - One Hundred Years of Asprin
from The Lancet.

Attachment: Chem asprin.pdf (70kB)
This file has been downloaded 1017 times

djh
----
Turn you yellow dye into
a brown dye.

Very sensitive to impact and friction —
violently explosive potassium purpurate
is prepared using KCN and PA.

Bot0nist - 5-7-2011 at 13:45

Nice recipe Wiz. Who is the 'Official Use Only" for?

BTW, I love how you wield language. "low albedo" I quote you often in the real world.

[Edited on 5-7-2011 by Bot0nist]

The WiZard is In - 5-7-2011 at 14:05

Quote: Originally posted by Bot0nist

Nice recipe Wiz. Who is the 'Official Use Only" for?

BTW, I love how you wield language. "low albedo" I quote you often in the real world.

[Edited on 5-7-2011 by Bot0nist]

Official Use Only

Is the lowest level of US Gov classifications followed by;

Confidential
Secret
Top Secret

Gov. Telephone book are often Official use only.

In years gone by - The CIA would have paid you a pile
of money for a Kremlin one!

djh
----
Where everything is secret -
Nothing is secret.

Anon.

caterpillar - 8-1-2012 at 05:22

I love this acid, and made it many times. This nice compaud can be readely prepared without HNO3- one may use KNO3 (or NaNO3) instead. Phenol 250 gr plus sulphuric acid 800 gr (I took acid for accumulators, it was probably 92-94%). Put phenol into acid an keep one our at 100 Celsius by means of simple water bath. Put 1600 gr of sulphuric acid into a flask and add 1000 gr of KNO3. Cool this mixture down to 20 Celsius and slowly add cooled phenol, diluted in H2SO4. This mixture must not be hot. This process took some ours for me (I couldn't cool this mixture, because I used simple glass bottle). When all phenol has been added, wait for one night. At the next day slowly increase temperature up to 100 and keep at this temperature for one our. Finally put reaction mixture into large volume (10 liters) of cold water with crushed ice. Picric acid will precipitate. Wash with mall amount of cool water. Use gloves!!! My parents knew, when I made such experiments because yellow color cannot be removed from hands for one week. It would be better to convert picric acid to ammonium salt. It is less sensitive and do not corrode metals.

Bot0nist - 8-1-2012 at 06:31

caterpillar, Welcome to SciMad!

I also think TNP is a very interesting compound. Such beautiful crystals, and all the brisance one could need. Here in the bowels of the forum it has been discussed to death, and a search of TNP, picric acid, picrates, etc will yield so much good information that you'll be reading for days. In one of my past searches I uncovered a wonderful write up done by our very own Rosco Bodine. This write up has been scaled down a bit and ran multiply times, always with a beautiful product free of red and brown oxidized trash and superior yields when working from recrystallized acetylsalicylic acid.

<a href="http://www.sciencemadness.org/talk/viewthread.php?tid=4457#pid53029">picric acid from ASA , NaNO3 and 92% H2SO4</a>

quicksilver - 8-1-2012 at 09:49

DNP and TNP can visually construct similar crystallization architecture. The simplest method to determine if the product is TRI-nitrated is impact. 50mg in a small foil enclosure when struck, steel against steel will explode with violence (-=goggles=- foil flies, etc). The majority of nitrated products contain a percentage of lower nitration. When this lower nitrated percentage is substantial (especially w/ TNP) there will be no impact detonation. Benzene-ring nitration (especially those which utilize sulfonization) have few sensitive products that can be tested in this way. but fortunately TNP does respond to impact. Blurring the distinction is the use of DNP to form picrates (which it will). Impact test should always be kept at a very small level (50mg) as some products have a superior brisance (NC) and can possibly chip one of the steel surfaces. (USBoM 1914 "Commercial Impact Testing")

caterpillar - 8-1-2012 at 20:03

As I know, even during WWII shells of large calibers was been loaded with TNP (with small addiction of nitrophenole, probably to decrease melting point). In Germany it was called "sprengstoffe 88". kalium salt of TNP is the remarkable compound too. Small piece of ti, been ignited, flyes like a rocket leaving behind black smoke. But if same compound is ignited in restricted volume it explodes without primer and leaves no smoke. I read once about a rocket propellant: 45% of ammonium picrate, 45% of NaNO3 and 10% of come organic binder, but I never tested it.

chem77 - 22-6-2012 at 11:48

I don't know if threads ever die here, but seeing as this one spans 9 years, I assume they don't.

I've successfully made picric acid in the past, but today, my synthesis didn't work at all. I used the ASA + H2SO4 + KNO3 method, and I realized something was horrible wrong when I poured the acid mixture into the ice bath. This was always my favorite step because the dark red solution would burst into a brilliant yellow solution when it hit the cold water, but this time, the color never changed. I just poured the black/brown solution into the water and nothing happened.

I figured that maybe this discoloration would go away when I recrystallized the picric acid, but as I added the thick brown sludge to my boiling water, the water simply turned black. I decided that I wouldn't be able to salvage the picric acid because I was pretty sure I had more of this black/brown sludge than I had picric acid, though, I do know picric acid was produced because when I poured the stuff down the drain, as I diluted it, the water partially turned the classic yellow of picric acid.

Now, I'm tying to figure out what this stuff is. I tried burning it and it didn't burn, but it expanded like those pyrotechnic carbon snakes. There was only one step that seemed strange when I was making the picric acid, and that was when I mixed the ASA and the H2SO4. Rather than letting the alcohol evaporate off, I usually just boil down the mixture until the temperature rises to > 100C, that way I know all the alcohol is gone. But this time, since I didn't want to deal with the solidified block of ASA, I added in 1/3 of my H2SO4 (due to measuring device size) to the ASA while it was still hot (potentially > 100C).

After I added this bit of H2SO4, the mixture let off a bunch of gas and turned rather black. I figured it was just CO2 and I thought, "Screw de-esterfication, the H2SO4 simply ripped the acid group off the aspirin." But, is it possible the the acid actually destroyed the ASA? I'm not exactly sure what might have happened, but could it be something similar to the H2SO4 + sugar snake?

I have a feeling this step is where it all went wrong, but could the acid actually have turned the ASA to carbon (or similar)?

Kalium - 23-6-2012 at 04:49

Have you ruled out the possibility that some sort of soluble additive was added to the aspirin? I don't think that the acid decomposed the ASA but I'm no expert. Personally I'd rather buy pure SA (used for homemade cosmetics), knowing that there shouldn't be any complications.

Oh, and the threads never die. People here get really worked up if you start a new one with a topic that already exists.

S.C. Wack - 23-6-2012 at 08:25

Doesn't sulfuric acid sulfonate and hydrolyze aspirin? I'd just as soon hydrolyze aspirin with base, acidify, and get nice crunchy salicylic acid, to avoid guessing games, but I'm just a clown on the internet.

chem77 - 2-7-2012 at 11:26

Well, I tried it again with cool ASA, and I got the exact same results.

I'm pretty sure the trouble is that I'm letting the sulfonation get way too hot. Both times I tried to bring the temperature to 120C and then hold it there, but due to residual warming, it ended up going to about 145C. I figured more heat would be better, but it may have broken something.

Eventually I'll have to try this again without ever letting the temperature climb over 100C. Hopefully then I'll get some nice yellow crystals.

quicksilver - 2-7-2012 at 14:31

Quote: Originally posted by S.C. Wack

Doesn't sulfuric acid sulfonate and hydrolyze aspirin? I'd just as soon hydrolyze aspirin with base, acidify, and get nice crunchy salicylic acid, to avoid guessing games, but I'm just a clown on the internet.

Actually I had heard the same thing for some time.

caterpillar - 2-7-2012 at 14:37

Is phenol a problem to you? When I was young, this compound could be obtained in a special shop without problems. I never tried to make picric acid from ASA, but the route from phenol is clean and convenient.

chem77 - 7-7-2012 at 19:37

At this point, I've never found phenol, but I'm a little tired of making this stuff. My only chance to really test it without suspicion (July 4th) has already passed, so I'm not quite as motivated to make it. Someday I'll definitely try this again with lower temperatures, but I'm going to wait a while before finally attempt to defeat this reaction.

In the mean time, I'll try to extract some gold from an old computer in my basement.

Kalium - 7-7-2012 at 20:18

Quote: Originally posted by caterpillar

Is phenol a problem to you? When I was young, this compound could be obtained in a special shop without problems. I never tried to make picric acid from ASA, but the route from phenol is clean and convenient.

It isn't as easy as it used to be. Watch this:
http://www.youtube.com/watch?v=HVFo44JPbMM

chem77 - 25-6-2013 at 09:20

1 year update:

I finally managed to make picric acid. It turns out that the brown sludge I talked about in my previous posts was the filler in the aspirin pills. I was heating my iso up to make the ASA more soluble and since I didn't want it all to crystallize out in my filter, I just quickly decanted it. This apparently didn't do a good job of separating it because as I later saw, it just turned into a brown sludge ruining everything.

I just wanted to leave my solution here in case anyone else ever runs into this same problem. But, here's my bright yellow picric acid in the step that had gone wrong every time before.

Ral123 - 25-6-2013 at 11:36

Great, now detonate it and upload it in YT. Make sure to record well, not just the burning of the fuze, the boom and done.

chem77 - 30-6-2013 at 12:45

I would, but logic tells me I shouldn't upload videos that might get me labeled as a terrorist.

Ral123 - 30-6-2013 at 13:47

Haha and what are you doing in this site? You've just publicly announced you're into energetics. You even uploaded a picture. Google gives you 10gb of space for free, how much do you think it would cost the NSA to store some of your data like ip and some pictures and messages? If you would worry about being known with energetics, you better start working like a real T, as stealthy as possible. You can start here:
http://www.businessinsider.com/nsa-prism-keywords-for-domest...
otherwise video, or it didn't happen

papaya - 24-11-2013 at 15:37

A question to those here, who intimately knows the subject : is this procedure here
http://www.sciencemadness.org/talk/viewthread.php?tid=4457&a...

the "best" one known here (derived during these years) in terms of yields, quality and economy of reagents, or some else writing exists?
Because I see it uses too much sulfuric acid compared to the double excess of what is theoretically needed, or there are other things that don't let to use any less? Same about the nitrate quantity...
Multiple picric acid threads (though this is longest) make it difficult to differentiate initial experimental results from the final "recipe" (I even think the final optimized version deserves an article in prepublications, from author of course

), so I wanted someone to confirm that what I found is what is thought to be the best so far. Thanks.

papaya - 25-11-2013 at 09:03

Great, now nobody is going to confess that ever made this compound.. Then I will show you one small trick on picric acid purity testing: I went through this thread and people offer to blow with hammer and listen carefully for echo, or to look at color and guess - not against it, but to my opinion the best test would be melting point determination (pure picric acid melts at 122.5 °C according to wiki). Only problem for amateur here is that this must be done accurately and with precision thermometer use... unless you know how to overcome that part! A possible solution that came to my mind I wanted to share is to use another PURE substance side by side with the sample under question which melts at nearly the same temperature and which is easy to come by - meet benzoic acid with m.p. of 122.41 °C. Seems easy, isn't it?

plante1999 - 25-11-2013 at 09:08

Lambdasyn got some good preparation for it.

Many, many people mde some, not many will tell tough.

papaya - 25-11-2013 at 09:19

I saw lambdasyn - waste of acids, as well as strange differences in quantities if different precursors are use - compare ASA / H2SO4 with others (sooo much sulfuric) - it seems these "recipes" are collected from different origins there. The problem is that one anyway will obtain SOME picric even with wide variations of reagent quantities, but this has no value unless the synthesis gets "optimized" in some sense (quality, safety, economy, etc.). I even think that if one comes with a good polished procedure where only dilute nitric acid is used it will be substantial contribution (I read industry loves strong acids mostly beacuse they are less corrosive to equipment, not that it's impossible).
I think there are people here with enough (first hand) experience who could answer my original question, I hope so.

caterpillar - 28-11-2013 at 03:22

I made TNP many times. Procedure is described at this very tread. Phenol, KNO3 (or NaNO3) and H2SO4. Simple and convenient (if you can get phenol). Very few NOx was generated. I suspect, that preparation, based on diluted HNO3, gives very dirty product.

papaya - 28-11-2013 at 11:41

Quote: Originally posted by caterpillar

Procedure is described at this very tread.

Could you point out which one exactly gave best results for you (among many pages)? Also phenol or ASA ? Cannot ASA replace the phenol ONLY by recalculating for different molecular weight?

Bot0nist - 28-11-2013 at 12:17

IIRC, Rosco Bodine's TNP from ASA in this thread used to be regarded as optimized and easily reproducable. Moniter temps well with additions. Using KNO<sub>3</sub> make the workup harder so stick with sodium nitrate.

papaya - 28-11-2013 at 12:35

Quote: Originally posted by Bot0nist

IIRC, Rosco Bodine's TNP from ASA in this thread used to be regarded as optimized and easily reproducable. Moniter temps well with additions. Using KNO<sub>3</sub> make the workup harder so stick with sodium nitrate.

Agree on NaNO3, but do you speak about Rosco's procedure I pointed out above (actually it's in other thread) or to which one you refer ? (put the link). Sorry, this type of asking questions (myself) appears stupid already.

Bot0nist - 28-11-2013 at 14:58

Im on a phone so i cant do the legwork for you right now. If your interested in TNP, please read this whole thread. In it rosco posts a very detialed writeup using ASA. You will know it when you see it. And then go find his and hennigs work on BASIC lead picrate. Read read read. No spoonfeeding or lazyness for you, since your into EM its a good habit to learn.

[Edited on 28-11-2013 by Bot0nist]

http://www.sciencemadness.org/talk/viewthread.php?tid=4457&a...

If that link doesnt work, UTFSE, like this. :p
http://www.sciencemadness.org/talk/search.php?token=&src...

That writeup needs desperatly to be in the new compendium. Best I have found. That and the work on basic lead picrate...

[Edited on 28-11-2013 by Bot0nist]

caterpillar - 29-11-2013 at 01:15

Quote: Originally posted by papaya

Quote: Originally posted by caterpillar

Procedure is described at this very tread.

Could you point out which one exactly gave best results for you (among many pages)? Also phenol or ASA ? Cannot ASA replace the phenol ONLY by recalculating for different molecular weight?

As BotOnist wrote to you, read, read and read. Page 23 at this very tread. There are two methods- from ASA and from phenol. During conversion of ASA to TNP some parts of ASA will be most likely destroyed, therefore this way will require more HNO3 (KNO3, NaNO3) than the route, starting with phenol. You may read Ledgard's famous book as well.

papaya - 29-11-2013 at 07:59

Thanks for the answers, and yes, I've read whole thread before asking.
In Rosco's method when you calculate molar ratios, result is ASA:H2SO4:NaNO3 = 1 : 12.37 : 3.815 !
Well some excess of nitrate I understand, but more than 12 moles of sulfuric to ASA ? No doubt it will work well, but what if for example it can be done equally well just with 6-7 moles only, any experience ?

plante1999 - 29-11-2013 at 09:24

I'm seriously deceived by papaya attitude. There is reasons to use more sulphuric acid, we don't waste reagent for fun. If we don't the decarboxilation and acetate group degradation will not go well, and will become an hard, impossible to stir mass.

It seams to me that if you want to have a perfect "receipe" that work for all substrate using the less reagents possible without changing anything with different substrate, you want to make very large quantity of it, which is both agains the law mostly everywhere and has not link with amateur chemistry what so ever.

I'm definetly not agreeing on the way the last few posts worked.

caterpillar - 29-11-2013 at 11:25

According to dear Jared Ledgard (procedure 18-04B) ASA 50 gr, H2SO4 350, KNO3 115 (or NaNO3 95). Now I think, that I could take less H2SO4 than I did.

Ral123 - 29-11-2013 at 11:52

Does anyone know if not separating the isomers will effect the storage stability? I feel like TNP is the most storage stable EM one can make readily. May be more stable would be DNB, but DNB is invalid by itself.

papaya - 29-11-2013 at 12:50

Quote: Originally posted by plante1999

It seams to me that if you want to have a perfect "receipe" that work for all substrate using the less reagents possible without changing anything with different substrate, you want to make very large quantity of it, which is both agains the law mostly everywhere and has not link with amateur chemistry what so ever.

I'm definetly not agreeing on the way the last few posts worked.

Not really, it's my habit to check procedures myself on paper before I even consider to experiment(or not) and the question I raised is related to chemistry, so please don't speak for me next time or make incorrect deductions. If I ever test this synthesis I will start from salicylic acid instead of ASA, so quantities must be recalculated somehow, I guess equimolar salicylic instead of ASA must be correct amount, unless you take into account that... hydrolysis of ASA CONSUMES water (this may be beneficial), ever thought about it?
Also, where is that Ledgard book, link please ?

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