Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  ..  23    25    27  ..  30
Author: Subject: Picric acid: different instructions
caterpillar
National Hazard
****




Posts: 472
Registered: 8-1-2012
Member Is Offline

Mood: No Mood

[*] posted on 29-11-2013 at 22:35


What Google exists for? Try "Jared Ledgard preparatory manual of explosives" and you'll get dozens of links. I do not remember, where I downloaded it from (but for free!). But be careful: this famous book contents really much BS. Read at this very forum "the worst book, ever written". For example, this wise guy wrote, that ammonium picrate is very sensitive and used as a primer.



Women are more perilous sometimes, than any hi explosive.
View user's profile Visit user's homepage View All Posts By User
Bot0nist
International Hazard
*****




Posts: 1559
Registered: 15-2-2011
Location: Right behind you.
Member Is Offline

Mood: Streching my cotyledons.

[*] posted on 2-12-2013 at 06:51


papaya.
Seriously, just follow roscos workup with ASA. The extra amount of. sulfuric (93%) aids in sulfanation of ASA, keeps reaction liquid, and the extra bit of water is benifitial to the sulfanation and nitration. Follow the temps and additions to the tee.
,
No more spoonfeeding. Go run the reaction, follow the writeup, and mind the NO<sub>x</sub>.

[Edited on 2-12-2013 by Bot0nist]




U.T.F.S.E. and learn the joys of autodidacticism!


Don't judge each day only by the harvest you reap, but also by the seeds you sow.
View user's profile View All Posts By User
papaya
International Hazard
*****




Posts: 597
Registered: 4-4-2013
Member Is Offline

Mood: reactive

[*] posted on 2-12-2013 at 11:40


Thanks guys, found Ledgard - should I trust someone who presents oxidation state and vallence as they were the same thing? I trust more "official" literature like Urbanski, etc (also some russian authors). Anyway one more question - Rosco describes synthesis that took him 5 hours, is this really the case for small batches (like 5g) or after one gradually adds nitrate and foaming is over + some 30 minutes at 110 °C is enough ? And pls, don't call this "spoonfeeding" I really checked literature before asking, here in forum one expects to hear real experience, a "recipe" is easy to find. I will see when (if) I try this.
View user's profile View All Posts By User
Bot0nist
International Hazard
*****




Posts: 1559
Registered: 15-2-2011
Location: Right behind you.
Member Is Offline

Mood: Streching my cotyledons.

[*] posted on 2-12-2013 at 11:53


Addition times should be adjusted in order to keep the temps as he recorded them in his larger scale writeup. Temps are vital to this nitration, in my experiance.

[Edited on 3-12-2013 by Bot0nist]




U.T.F.S.E. and learn the joys of autodidacticism!


Don't judge each day only by the harvest you reap, but also by the seeds you sow.
View user's profile View All Posts By User
caterpillar
National Hazard
****




Posts: 472
Registered: 8-1-2012
Member Is Offline

Mood: No Mood

[*] posted on 3-12-2013 at 01:27


Quote: Originally posted by papaya  
Thanks guys, found Ledgard - should I trust someone who presents oxidation state and vallence as they were the same thing? I trust more "official" literature like Urbanski, etc (also some russian authors). Anyway one more question - Rosco describes synthesis that took him 5 hours, is this really the case for small batches (like 5g) or after one gradually adds nitrate and foaming is over + some 30 minutes at 110 °C is enough ? And pls, don't call this "spoonfeeding" I really checked literature before asking, here in forum one expects to hear real experience, a "recipe" is easy to find. I will see when (if) I try this.


I described here my own experience. I'd made some mistakes before I found right "recipe", but I think this sort of experience has no interest. Yeah, temperature regime is just that thing which you have to keep under control, otherwise runaway is possible.




Women are more perilous sometimes, than any hi explosive.
View user's profile Visit user's homepage View All Posts By User
Bot0nist
International Hazard
*****




Posts: 1559
Registered: 15-2-2011
Location: Right behind you.
Member Is Offline

Mood: Streching my cotyledons.

[*] posted on 3-12-2013 at 06:22


Not just cascading runaway. but also undesirable oxidation products, resinous gunk, and low yields if the temperature is controled. poorly throughout the reaction.



U.T.F.S.E. and learn the joys of autodidacticism!


Don't judge each day only by the harvest you reap, but also by the seeds you sow.
View user's profile View All Posts By User
papaya
International Hazard
*****




Posts: 597
Registered: 4-4-2013
Member Is Offline

Mood: reactive

[*] posted on 3-12-2013 at 09:10


Thanks a lot, temperature is important, though what if one conducts synthesis on the boiling water bath (a little lower temperature than needed), and only heat higher at the very end? Also, any notes on salicylic acid usage instead of ASA, how to adjust quantities then, just on 1 to 1 molar basis ? Hope not bored everybody yet.
View user's profile View All Posts By User
Bot0nist
International Hazard
*****




Posts: 1559
Registered: 15-2-2011
Location: Right behind you.
Member Is Offline

Mood: Streching my cotyledons.

[*] posted on 3-12-2013 at 09:22


The ASA sulfanation will break the ester anyway. I used a simmering brine bath to heat the sulfuric acid during ASA additions, and again to keep the.nitration heat up durring the first small additions. Then it may have to be removed from the bath as the exotherm from nitrate salt.additions picks up. Good mag stirring is vital. Think vortex...



U.T.F.S.E. and learn the joys of autodidacticism!


Don't judge each day only by the harvest you reap, but also by the seeds you sow.
View user's profile View All Posts By User
papaya
International Hazard
*****




Posts: 597
Registered: 4-4-2013
Member Is Offline

Mood: reactive

[*] posted on 3-12-2013 at 12:27


Thing is I found rather pure salicylic acid (reagent), so don't want to bother with tablets, etc...
View user's profile View All Posts By User
Bot0nist
International Hazard
*****




Posts: 1559
Registered: 15-2-2011
Location: Right behind you.
Member Is Offline

Mood: Streching my cotyledons.

[*] posted on 3-12-2013 at 13:19


Just run it as if it were ASA. Sulfanate and nitrate, and record your results for possible improvments.



U.T.F.S.E. and learn the joys of autodidacticism!


Don't judge each day only by the harvest you reap, but also by the seeds you sow.
View user's profile View All Posts By User
caterpillar
National Hazard
****




Posts: 472
Registered: 8-1-2012
Member Is Offline

Mood: No Mood

[*] posted on 3-12-2013 at 13:57


Go ahead. Your own experience is the most valuable. And learn chemistry- pure theory is useful thing too.



Women are more perilous sometimes, than any hi explosive.
View user's profile Visit user's homepage View All Posts By User
roXefeller
National Hazard
****




Posts: 463
Registered: 9-9-2013
Location: 13 Colonies
Member Is Offline

Mood: 220 221 whatever it takes

[*] posted on 9-12-2013 at 15:35


I found to avoid a great deal of the NOx emissions was to split the sulfuric acid in two, the first part reacts with the ASA, while the second part, roughly in excess of stoichiometric amounts, was mixed with the nitrate salt. Then this is added the same way as the nitrate salt originally. There was a sweet spot for the addition rate that could be dialed in with the sep funnel. Beyond this spot would bring about the fumes again, but still not as bad as before.
View user's profile View All Posts By User
barley81
National Hazard
****




Posts: 481
Registered: 9-5-2011
Member Is Offline

Mood: No Mood

[*] posted on 14-12-2013 at 08:38


If it helps, I typeset/edited Rosco's original procedure (Dec 9, 2003, E&W forum). Note that this is <b>not the same</b> as the original. Any corrections or improvements would be appreciated. LaTeX and PDF files are both attached.

Has this been done already? If so, then *oops.*

Attachment: roscopicric.pdf (89kB)
This file has been downloaded 4741 times

Attachment: roscopicric.tex (7kB)
This file has been downloaded 1230 times

[Edited on 14-12-2013 by barley81]
View user's profile View All Posts By User
Hennig Brand
International Hazard
*****




Posts: 1284
Registered: 7-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 17-4-2014 at 10:34


For a long time I was off and on questioning the purity of the picric acid I was producing from ASA. Here is a couple of articles I found a while back which helped convince me that picric acid is the usual and only product from the direct sulfonation and nitration of ASA or salicylic acid.


Attachment: 4-Sulfo Salicylic Acid Nitration.pdf (1.1MB)
This file has been downloaded 976 times

Attachment: 4-Sulfo Salicylic Acid Synthesis.pdf (424kB)
This file has been downloaded 583 times





"A risk-free world is a very dull world, one from which we are apt to learn little of consequence." -Geerat Vermeij
View user's profile View All Posts By User
Rosco Bodine
Banned





Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 8-11-2014 at 08:52


Quote: Originally posted by ordenblitz  
Working from Roscoe's good old country recipe as was posted in another thread, I made some TNP this weekend.

The materials…
http://img58.imageshack.us/img58/9658/asacrystals7bj.jpg
http://img58.imageshack.us/img58/4581/h2so48hp.jpg

93.75 grams of ASA were sulfonated in 375ml 80º, ~96.5% H2SO4
http://img58.imageshack.us/img58/8198/hotsulfasa8lv.jpg

Strangely enough, upon cooling overnight the solution remained clear with no sulfonated material precipitating.
http://img58.imageshack.us/img58/6996/coldsulfasa4gw.jpg

The mixture was placed in a 1000ml flask and the temperature raised to 95º. The additions of granular sodium nitrate commenced. The NaNO3 was obtained from a commercial fireworks chemical supplier and is of high quality but the actual purity is unknown.
http://img58.imageshack.us/img58/1463/beginnitra0wo.jpg
http://img58.imageshack.us/img58/9098/1stadd6oj.jpg

The solution began to slightly darken with each subsequent addition.
http://img58.imageshack.us/img58/627/3rdadd3sl.jpg
http://img58.imageshack.us/img58/9339/7thadd2jo.jpg
http://img58.imageshack.us/img58/2308/10thadd1uv.jpg

As the crystals of TNP formed the mix began to thicken and lighten again.
http://img58.imageshack.us/img58/5044/14thadd6gb.jpg

At this point there was considerable foaming upon the addition of the solid nitrate and the timing between same had to be greatly increased as was suggested.
http://img58.imageshack.us/img58/6453/22ndadd9zj.jpg

Stirring was very difficult and the viscous mix moved but slowly with my poor 2" stir bar. Roscoe mentioned a big 3"oval stir bar and It's surely needed! Next time I will use more sulfuric to lower the viscosity. No sense being stingy.
http://img58.imageshack.us/img58/6875/26thadd8se.jpg

Although it looks like foam, it’s a viscous crust of TNP sitting on the top of the acid. It was making the additions of the nitrate almost impossible to work into solution. This was the final addition of the nitrate.
http://img58.imageshack.us/img58/5117/28thfinal9bd.jpg

An evil looking brew as 500ml of water was being added from a wash bottle as the dilution began.
http://img58.imageshack.us/img58/7987/startdilution9mq.jpg

Some ice and some time and viola'
http://img58.imageshack.us/img58/634/dilutedandcooling4nd.jp...

Filtering out the raw TNP crystals. I cooled quickly, so the result is a voluminous fine crystal.
http://img58.imageshack.us/img58/8335/filteringtnp2kq.jpg

The raw material was suctioned well and dissolved in 2200 ml of boiling water and then allowed to cool again.
http://img58.imageshack.us/img58/7097/recrycooling2uk.jpg

The first crop was dried and weighed in at 84.2 grams or 70.5% of theoretical.
http://img58.imageshack.us/img58/2767/firstcrop6ff.jpg

The mother liquor was boiled down to ~500ml and a second crop was obtained. After filtering and drying a further 24.16 grams was obtained.
http://img58.imageshack.us/img58/9192/secondcropcooling9df.j...

The remaining TNP in solution was neutralized with K2CO3 then chilled and the crystals of potassium picrate were collected. They were then re-crystallized from acetone which yielded 3.56 grams, corresponding to 3.053 grams of picric acid in the final liquor.
http://img58.imageshack.us/img58/6001/ktnp7um.jpg

Final tally was 111.41 grams of C6H3N3O7, 93.38% based on ASA.
It was a good day. Thanks Roscoe.


Kinda perty aint she?


For those who may be looking for the other thread referenced for this synthesis

picric acid from ASA , NaNO3 and 92% H2SO4

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

Also attached are the ordenblitz images which have dead links



Attachment: ordenblitz pictures picric acid synthesis.pdf (663kB)
This file has been downloaded 575 times

View user's profile View All Posts By User
Hawkguy
National Hazard
****




Posts: 326
Registered: 10-10-2014
Location: British Columbia (Canada eh!)
Member Is Offline

Mood: Body is Ready

[*] posted on 26-1-2015 at 19:48


2, 4, 6 – Trinitrophenol [Picric Acid]

Picric Acid is a light yellow solid of bitter taste, hence its name. It was discovered in 1742 (earliest documentation), although it could have potentially been synthesised earlier by the nitration of organic materials. Picric Acid’s applications remained solely to use as a chemistry reagent and as a dye until 1830, when its properties as a secondary explosive were realized. The First World War saw extensive use of Trinitrophenol. Explosive action ceased however, because of its reactivity towards metals, forming unstable or hygroscopic salts. By the time World War Two came around, Picric Acid was only used as a Picratol precursor. Today the explosive is obsolete as to military application, but is sometimes used in fireworks for whistle mixes.
Preparation
Although 2, 4, 6 – Trinitrophenol was most often synthesized from Phenol, it is much easier to do so from Acetylsalicylic Acid. This is also a lot safer, as free Phenol, a potent carcinogen, is not handled directly through the ASA route.

- 6 grams of pure Acetylsalicylic Acid are dissolved in 60ml of 18M Sulphuric Acid at 20°C. The solution is heated over the course of 3 minutes to 110°C, and the Acetylsalicylic Acid will hydrolyse to Acetic and Salicylic Acid. The colour of the solution will change from clear, to yellow, to black. The Salicylic Acid will decarboxylate to Phenol and Carbon Dioxide, and Phenylsulphonic Acid will be formed.
- Potassium Nitrate is added in small portions over the course of the next 10 minutes. With every addition, the temperature will rise to 120°C. It is important to keep the temperature below 130°C, so a thermometer must be carefully monitored at all times. At this point the Phenylsulphonic Acid is undergoing a triple nitration to produce water, Sulphuric Acid, and 2, 4, 6 – Trinitrophenol. The temperature is dropped, and the colour will become an orange – red.
- After 5 minutes since the solution was removed from heating, it can be added to 300ml crushed ice, and a yellow precipitate will immediately form. This is the product, and it can be collected.
- [Purification] The product must undergo two water washes, rinses with water to remove acid and other residual contaminants. As well, a recrystallization from Ethyl Alcohol helps remove insoluble contaminants.


View user's profile View All Posts By User
Bert
Super Administrator
*********




Posts: 2815
Registered: 12-3-2004
Member Is Offline

Mood: " I think we are all going to die. I think that love is an illusion. We are flawed, my darling".

[*] posted on 26-1-2015 at 21:00



Quote:

By the time World War Two came around, Picric Acid was only used as a Picratol precursor. Today the explosive is obsolete as to military application,


I beg to differ.

During WWII, the Japanese used picric acid in shell fillers extensively, and the Germans used picric acid as a booster charge for some rather large TNT charged ordnance (500kg TNT parachute deployed naval mines with 1kg pelletized picric acid as a booster?!).

So... What do you have to contribute from personal experience.




Rapopart’s Rules for critical commentary:

1. Attempt to re-express your target’s position so clearly, vividly and fairly that your target says: “Thanks, I wish I’d thought of putting it that way.”
2. List any points of agreement (especially if they are not matters of general or widespread agreement).
3. Mention anything you have learned from your target.
4. Only then are you permitted to say so much as a word of rebuttal or criticism.

Anatol Rapoport was a Russian-born American mathematical psychologist (1911-2007).

View user's profile View All Posts By User
caterpillar
National Hazard
****




Posts: 472
Registered: 8-1-2012
Member Is Offline

Mood: No Mood

[*] posted on 27-1-2015 at 02:47


Shellite, what was used during WWII in large caliber shells by Britons, was as a matter of fact picric acid with few percents of something like nitrophenole. Ammonium picrate ("dunnite" or compound "D") was used in anti-tank shells due to its low sensibility (lower than of the TNT).



Women are more perilous sometimes, than any hi explosive.
View user's profile Visit user's homepage View All Posts By User
Hawkguy
National Hazard
****




Posts: 326
Registered: 10-10-2014
Location: British Columbia (Canada eh!)
Member Is Offline

Mood: Body is Ready

[*] posted on 27-1-2015 at 08:30


Sorry about that... Yeah you're right then.. I totally though that Picric was starting to be replaced by more modern nitrated explosives by then...
View user's profile View All Posts By User
Rosco Bodine
Banned





Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 29-3-2015 at 16:26


Quote: Originally posted by Hennig Brand  
For a long time I was off and on questioning the purity of the picric acid I was producing from ASA. Here is a couple of articles I found a while back which helped convince me that picric acid is the usual and only product from the direct sulfonation and nitration of ASA or salicylic acid.



This is the article I think will be most helpful. See first sentence at top of second page of article journal page 2040. This applies to the case involving 5-sulfosalicylic acid

Datta and Varma, J. Amer. Chem. Soc., 1919, 41, 2039

(article attached)



Attachment: JACS Vol 41 pg2039.pdf (414kB)
This file has been downloaded 544 times

[Edited on 30-3-2015 by Rosco Bodine]
View user's profile View All Posts By User
Hennig Brand
International Hazard
*****




Posts: 1284
Registered: 7-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 29-3-2015 at 17:11


Thanks for locating that. We have a nice collection of old articles now (pieces of the puzzle).

It is the first paragraph from the first article of the two that I posted above, where your article is referenced, which immediately got me very interested at the time.

"It has been found by the previous workers that the sulphonic acid group
in either 3-sulpho- or 5-sulpho-salicylic acid can easily be substituted by
the nitro group, and if the reaction is carried further, the -COOH group is
removed and picric acid is the usual and the only product. Thus Datta
and Varma obtained picric acid by the action of nitrous gases on 5-sulphosalicylic
acid. Meldrum and Hirwe obtained 3 : 5-dinitrosalicylic acid by
controlled nitration of 5-sulphosalicylic acid."

3 : 5-dinitrosalicylic acid is the intermediate just before decarboxylation and addition of the last nitro group forming picric acid.




"A risk-free world is a very dull world, one from which we are apt to learn little of consequence." -Geerat Vermeij
View user's profile View All Posts By User
Rosco Bodine
Banned





Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 29-3-2015 at 17:47


The sulfonate group is more stable than the carboxyl so the "steering effect" on substitution by the first entering nitro will I believe cause the decarboxylation and substitution of the nitro to occur for the first entering nitro group.
View user's profile View All Posts By User
Hennig Brand
International Hazard
*****




Posts: 1284
Registered: 7-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 29-3-2015 at 18:49


I am just an amateur experimenter, not a professional chemist, but I did asked Philou to explain this to me well over a year ago now and this is what I was told:

"Salicylic acid is very closely related to phenol and the hydroxy group is a very strong activator in ortho and para while the carboxy is an activator in meta... both effects are thus additive and favoring ortho and para position to the OH.
Once those two places are nitrated, the nitro groups are dropping the CO2 away from the aromatic ring and the rest of the reaction follows the course of normal nitration of 2,4-dinitrophenol"

5-Sulphosalicylic acid structure taken from Wiki.

5-Sulfosalicylic acid.png - 4kB


I think you must be forgetting, or just recently saw something that made you re-question some of this. The following was taken from "Rosco's Good Old Country Recipe for TNP":

"When about 2/3 of the sodium nitrate has been added, the reaction product is largely dinitrosalicylic acid, which will acquire a third nitro group while evolving carbon dioxide and thereby be converted to picric acid as the reaction proceeds."


[Edited on 30-3-2015 by Hennig Brand]




"A risk-free world is a very dull world, one from which we are apt to learn little of consequence." -Geerat Vermeij
View user's profile View All Posts By User
Rosco Bodine
Banned





Posts: 6370
Registered: 29-9-2004
Member Is Offline

Mood: analytical

[*] posted on 29-3-2015 at 19:36


It isn't really a substantive issue what is the mechanism, or if different paths are occurring simultaneously when all reactions in sum lead to the same 2,4,6-trinitrophenol as the end result in the same reaction mixture. All roads lead to Rome there.

For the case of phenol the hydroxyl on the ring strongly promotes ring substitution, much more than a ring hydrogen on ordinary benzene, but an added sulfonate group hinders further substitution relative to a ring hydrogen. For salicylic acid the carboxyl further hinders substitution even more than a sulfonate. In the case of 5-sulfosalicylic acid there is the promoting hydroxyl of phenol and BOTH the inhibiting sulfonate and further there is the even more inhibiting carboxyl.

My interpretation is the inhibiting groups would themselves be subject to substitution preferentially to the unsubstituted #6 position ring hydrogen which would be nitro substituted dead last if the nitration was steered according to my guess what happens. My understanding may be wrong but I would have supposed the carboxyl would be first to nitrate, the sulfonate would be second, agreeing with the intensity which they hinder substitution relative to a ordinary ring hydrogen, making the plain ring hydrogen at 6 the last to nitrate.

That is my guess how the reaction may proceed. Whether the guess is correct or not I don't know. I would trust what Nicodem may say about this more than Philou :D

BTW I do not even like the naming convention for 5-sulfosalicylic acid

When I look at the molecule I think of this name:

2-carboxyl-para phenolsulfonic acid

[Edited on 30-3-2015 by Rosco Bodine]
View user's profile View All Posts By User
Hennig Brand
International Hazard
*****




Posts: 1284
Registered: 7-6-2009
Member Is Offline

Mood: No Mood

[*] posted on 29-3-2015 at 19:45


As long as all roads do in fact lead to Rome I am satisfied, which was my main interest before when I decided to do a little investigating. I found the naming of 5-sulfosalicylic acid a bit confusing myself.



"A risk-free world is a very dull world, one from which we are apt to learn little of consequence." -Geerat Vermeij
View user's profile View All Posts By User
 Pages:  1  ..  23    25    27  ..  30

  Go To Top