DeusExMachina - 5-1-2003 at 09:16
Has anyone tried making this? As soon as I get the chance, I am going to get a whole bunch of chems and make this and a few other stuff. I was
wonering if anyone here has tried making this. Please tell me about your experience with making/detonating TNP. To make it you need KNO3, H2SO4 and
ASA.
madscientist - 5-1-2003 at 12:57
Check out the thread in this section "Picric Acid and the Mystery of the Red Goo".
Haggis - 5-1-2003 at 20:11
This might help you a bit. I don't know what you're looking for though.
http://www.roguesci.org/ubb/ultimatebb.php?ubb=get_topic;f=6...
For some reason, this link was to a picric acid thread, but now leads to something on North Korea. Sorry!.
[Edited on 21-3-2003 by Haggis]
Darkfire - 5-1-2003 at 21:21
Keep in mind it is highly toxic and to wear the adiquit protection when making it.
CTR
I made it
trinitrotoluene - 5-1-2003 at 23:06
I had made TNP before. I used brainfevers methoh. First I took 10 grams of ASA and added it to 120ml of 93% H2SO4 then I heated it to 80*C. After that
it is dissolved. The color of the soloution changes color.Then I add 20 grams of KNO3. Gram by gram and after each addition HNO3 fumes is given
off.While you are adding and yuo are done the soloution turns brown. Then wait till the soloution cools to room temperatures and the soloution turns
orange. After its cooled I added it to 1000ml of cold water. Heat will be generated. Then I put the soloution in the fridge and let all the TNP
percipitate over night. After that I filter the TNP with filterpaper. This is the painful part. Then after that I let it sit outside in the sun to
dry. It takes a while to dry. My TNP had been sitting outside for 6 days now and it still moist.
Darkfire - 24-1-2003 at 15:23
Is it nessary to use ASA or can you just add the unpurified asprin?
CTR
madscientist - 24-1-2003 at 16:16
Aspirin is acetylsalicylic acid with small amounts of impurity (usually calcium phosphate and starch). When I prepare picric acid, I don't bother to
purify the acetylsalylic acid in the aspirin. I grind up the aspirin and use as-is.
Mongo Blongo - 24-1-2003 at 20:16
Yes the other binders and shit is a very small amount. They will get nitrated and the yield of TNP will be SLIGHTLY smaller but nothing to worry
about.
Here's my batch
Boob Raider - 21-2-2003 at 17:21
I made a batch recently with about 15 g Salicylic acid. It is way cheaper and easier than using ASA.
I am sorta confused
Boob Raider - 23-2-2003 at 20:05
On quite a few references I have seen ... Trinitrosalicylic acid and its salts (esp.Pb) to be explosive. So how do I know if I have TNP in that pic or
TNSA. Is there some sort of test, that someone can suggest, that I can perform, which will be accurate enough to tell me what it is ?
PHILOU Zrealone - 19-3-2003 at 08:55
TNASA should be HO-C6H(NO2)3-CO2H and weight 273g/mol
TNP is HO-C6H2(NO2)3 and weight 229g/mol
The first one is a biacid while the second one is a monoacid!
A simple titration of a known dry amount of the solid should answer!
Ex use a 20ml 0,01 mole solution of the acid and titrate with a 0,01 mole solution of NaOH!
If it is the first acid you will need nearly 40ml, while if it is the second one you will need 20ml!
Anyway since we don't know your process of making, a possible side product is dinitrosalysilic acid!
menchaca - 22-3-2003 at 06:57
i ve recently tried to do this i used 10grs salicilic acid 16 gr NaNO3 and 55ml 96%H2SO4 is still drying but i ve never try to detonate a high
explosive so im not sure about how will it work
Haggis - 22-3-2003 at 11:01
I would recommend not making any high explosives yet, menchaca, because you need a primary to 'detonate a high explosive'. This sounds like
your first time with a synthesis so I assume you don't have any primaries laying around. Also, I wouldn't want to store it. If you just
really like the chemistry part, make it, enjoy it, and destroy it. If you want to use it as an explosive, I reccommend that you get a stronger base
in high explosives first.
Hubert - 19-11-2003 at 11:00
http://www.powerlabs.org/chemlabs/picric.htm
carbolic acid
froot - 24-11-2003 at 10:48
Phenol, C6H5OH, is also commonly known as carbolic acid. Well I found a disinfectant at a supermarket called 'Jeyes Fluid' which on the
container states; 'CARBOLIC ACID COEFFICIENT 4 TO 6'
It's a black liquid with a tar-like odour. When mixed with water it goes milky white. I was wandering if anyone has encountered such a product
and if it is possible to extract the phenol, if it is phenol??
unionised - 24-11-2003 at 14:37
That means that it is 4 to 6 times better at killing bacteria than phenol. That, in turn means it isn't phenol. IIRC it's a mixture of
cresols and soaps.
There may well be some phenol in it but it would be tricky to isolate it.
TNP production
JDP - 24-11-2003 at 15:41
well, lately I've been producing alot of piceric acid useing the method posted above, powerlab's method, but I scale it up a bit to suit my
applications - 40 grams of ASA are disolved in 80mls of hot 95% H2SO4 and once its disolved, chill it down to 10*C, then add 120mls of 70% HNO3, a big
reaction will happen, once the reaction has ended you should mix it to get all the NO2 out then dump in an equal amount of H2O this will precipitate
the picric acid which is filterd and washed with a bit of water. this synthasis yields around 46g of TNP after pureification. 
Mendeleev - 25-12-2003 at 15:44
I would purify the apirin anyway, you just dissolve it hot alcohal, filter it, and evaporate the filtrate. Not too much trouble, but yields are bit
better.
Haggis - 25-12-2003 at 16:14
JDP getting high TNP yields are always fun like that...getting a nice fluffy layer of stuff on the bottom. Your TNP looks pretty crystaline. Mine
has always been soft fluffy powder. Is it because of your purification steps?
Mendeleev-homestarrunner.com is damn funny.
JDP - 25-12-2003 at 19:41
Yeah, that TNP batch was quite crystaline, and as you guessed it is because of my pureifaction procedure - recristalisation from a solution of acetone
and water. Moastly I was going for the highest pureity, for picerate salts. upon cristalition from the acid mix it was a finer product aswell as
larger cristals.
blazter - 28-12-2003 at 21:02
This project has been resting for a while only because of the great dissappointment which it was.
10g ASA was dissolved in 33ml conc. H2SO4. In retrospect this was probably too little acid since at ~10 mins under heating fine crystals started to
appear at the surface of the solution. To attempt to remedy the situation an addition 7ml acid was added. From here the KNO3 was slowly added, with
no real noticible change other than the evolution of HNO3 vapors. The mix was heated to 50C and stirred for about 1hr. 20 min by hand until foaming
was no longer noted. The color gradually changed from black to dirty yellow. The mix was precipiated and recrystalized which gave a final yeild of
5g after recrystalization from 1:2 ethanol/H2O.
Now the problem is that the flame test of this material does hardly anything. No flames or drama as shown in the powerlabs videos. It simply glows
red for a bit and evolves large quantities of black ash resembling very much those lame "Black snake" fireworks. The appeareance seems to
be right, though it seems to be a slightly darker shade than the pics which have been posted.
My guess is that it consists of mononitrophenols and dinitrophenols, anyone care to hazard a guess of what happened?
Mendeleev - 28-12-2003 at 22:06
1. Did you purify your asa in alcohal?
2. You need more sulfuric acid per acetylsalysylic acid. The ratio of sulfuric acid in mL to grams of asa should be at least 4:1 from the start,
maybe even more like 5:1 or 6:1 (this is most likely your problem, you did not have enough sulfuric acid to catalyze the reaction thus the incomplete
nitration).
3. Before adding the asa to the sufuric acid did you heat it to 60-70 degrees?
4. How much potassium nitrate did you add? Ratio of potassium nitrate to asa should be ~ 2:1 by mass(temperature should rise above 70 during the
addition, without additional heating).
5. 1 hour and 20 minutes might be too long, add 1 gram potassium nitrate per minute which would give you about 20 minutes, then don't keep it
sitting for one hour, cool it to room temp and dump it in water, no additional heating is needed after all the potassium nitrate dissolves.
[Edited on 29-12-2003 by Mendeleev]
froot - 28-12-2003 at 22:33
The first time I tried TNP it worked great. And then the tries after that not so great. Now that you mentioned it Mendeleev I was using as little
H2SO4 as possible, but why the excess acid?
I notice that the ratios you give for the SA and ASA are not in accordance with what powerlabs states;- 0.5g ASA per 1ml H2SO4. I'm sure both
ratios would give different yields. There must be an optimum.
The last batch I made was BRIGHT yellow and it burns but I don't think it's pure TNP.
[Edited on 29-12-2003 by froot]
blazter - 29-12-2003 at 12:51
The ASA was painstakingly purified using hot acetone. The sulfuric was heated for at least 10 minutes when the ASA dissolved, and heating was
continued until the acetic acid odor was not noticible. The temp only increased slightly when the KNO3 was added and heating was continued even
after, with stirring since the evolution of gas continued, as the color slowly changed to a dirty yellow.
This was a long time ago and am only following notes, I guess it can be chalked up to not enough H2SO4 being used. It seems like an excessive amount
to use, would there be any way of recycling it after the rxn? Boiling it back down to reconcentrate it and filtering through glass wool would seem to
work, but does this seem like it would be safe because of the residual TNP in the boiling acids?
Mendeleev - 29-12-2003 at 14:13
Froot:
Sulfuric acid due to its hygroscopity serves as a catalyst in nitration reactions, because it takes away the water produced and thus maintains a high
concentration of nitric acid in the system so that the system does not reach equilibrium due to low nitric acid concentrations. Nitrations of
aromatic hydrocarbons are more problematic than nitrations of other hydrocarbons(I think it has something to do with the high electron density inside
the ring) and thus require more nitric acid/catalyst, and so you just need a lot of sulfuric acid for their nitrations. Even so its lucky phenol can
be trinitrated through one nitration unlike benzene, toluene, and xylene. Furthermore in using acetylsalicylic acid, some of the sulfuric acid is
used to split of acetic acid and sulfonate the asa. Also this nitration proceeds at higher temperatures then say nitroglycerine, so more nitric acid
decomposes into NO2 and water. I am not very familiar with powerlab and where they got their ratios, but it seems to me they don't have enough
sulfuric acid.
blazter:
Your dissolved TNP would contaminate other nitrations if you attempted to reuse it for that purpose, however if you decided to use it to distill
nitric acid, the picric acid would not distill over, and yet you would still be getting use out of your sulfuric acid.
froot - 30-12-2003 at 09:29
Apologies if this has been discussed, but Mendeleev, in your experience, have you found the optimum amount of water to dump the complete reaction in?
TNP being soluble in H2O, you will obviously lose some yield to solution. I speculate that if you use too little water you'll end up with
sodium/potassium sulfate in your yield if you use the corresponding nitrates, and if you use too much H2O, obviously more of the TNP will dissolve and
escape extraction. There must be an optimum here again and would this be calculated against the amount of H2SO4 used?
I've also found that after filtration I almost freeze the mother liqour and a second batch of crystals form, slightly different in appearence to
the first batch. Would I be correct in assuming the second batch is contaminated with sulfates, DNP and MNP?
Mendeleev - 1-1-2004 at 18:51
I usually use 10 mL cold water and 15g of crushed ice per 1 gram asa nitrated. I am not sure if this is the optimum ratio, but it gives satisfactory
yields.
Keep Picric acid wet Dangerous when dry
FloridaAlchemist - 3-1-2004 at 23:12
Picric acid is Dangerous when dry.
Should be stored wet,or under water until needed.
Mendeleev - 4-1-2004 at 18:13
Thanks for your concern Florida Alchemist, but I usually store my picric acid in a cool dry place, and I haven't really had any problems. In
World War I all the artillery shells full of picric acid were stored dry, they didn't have too many problems.
sylla - 13-1-2004 at 05:05
I've done TNP resulting in pale yellow crystals.
When I tried to drop TNP into ammonia to make Ammonium Picrate they immediatly turned deep-yellow when the NH3 gaz touched them.
So I've done Ammonium Picrate and kept half of the original amount of TNP to see what happend when I put NH3 on them.
Ammonium Picrate crystals were very deep yellow, TNP through NH3 yellow and original TNP pale yellow.
What is the color of -normal- TNP ? yellow or pale yellow ? What happened exactly with the NH3 gaz ?
Thx for your reply
Mendeleev - 12-3-2004 at 20:38
As I mentioned I have been storing my picric acid dry up until now, however http://en.wikipedia.org/wiki/Halifax_Explosion . What was Florida Alchemist saying about wet storage?
Bert - 13-3-2004 at 06:47
Every couple of years I hear about some high school's chemistry lab store room blowing up from a jar of picric acid stored dry for too long. Not
sure of the specifics, but I understand it undergoes a change in crystaline form on standing a long time dry. This is NOT a short term storage issue,
but you shouldn't be storing HE anyways.
Mendeleev - 16-3-2004 at 08:23
Does anybody know if one of those paint respirators that one can buy at Lowes or Home Depot (not the dust mask, the actual half-face respirator with
filters) will filter NO2 fumes?
Haggis - 16-3-2004 at 10:06
The one I have, the purple banded P100, will filter nitrogen dioxide. Make sure on the package, it lists acid gas as one of the substances it is able
to filter.
For general nitrations, you shouldn't need a respirator as long as you keep upwind and outside.
Darkfire - 16-3-2004 at 15:45
Always keep a respirator nearby though, i can think of serveal times i was happy i did, or wishing i had.
thunderfvck - 11-6-2004 at 00:32
Okay. I give up.
Sorry to bring up a dead topic but I have a question!
Okay. The chemical equation. I can't find it ANYWHERE, and I need it! I want to work at the mechanism and such but cannot without the equation.
From, phenol, it is no problem. I found it in vogel:
PhOH + H2SO4 ---> o-phenolsulphonic acid & p-phenolsulphonic acid + HNO3 ---> TNP
Quite straight forward!
But with aspirin, hmmm...I just don't know.
Acetic acid would make a nice leaving group from aspirin, especially considering all the acid to protonate the carbonyl orxygen, then water can attack
the carbonyl carbon and acetic acid can leave. Obvious hydrolysis. Then you can have the lone oxygen pick up a proton and there's the hydroxyl.
Is this correct? I'm not so sure considering the solvent is 95% H2SO4, and not water with a catalytic amount of H2SO4.
Then there's that damned actyl group. How the hell is he dealt with?The only way I can think of is just as the former was dealt with. The water
attacks and out comes carbonic acid. But what the hell. This sounds so wrong!
And from there it would be just phenol reacting with the usuals.
But this seems quite wrong. I need assistance!
Another thing, I take it that adding the KNO3/whichever nitrate salt just creates HNO3 in situ?
Thanks guys!
AngelEyes - 11-6-2004 at 03:10
This is what I got from www.powerlabs.org
Aspirin (Acetyl Salicylic Acid) is mixed with Sulphuric Acid.
The sulfuric acid breaks down the acetylsalicylic acid to acetic and salicylic acid.
C9H8O4 -------> C2H4O2 + C7H4O2
Then with gentle heating the Salicylic acid hydrolyses (with the little water in the Sulphuric) to Carbon Dioxide and Phenol.
C7H4O2 + H2O ---> C6H6O + CO2
You now have Phenol, Sulphuric and you then add your xNO<sub>3</sub> to the mix.
C6H5OH + H2SO4 => (HO.C6H4.SO3H + H2O) + HNO3(aq) => C6H3N3O7
Any good to you?
Marvin - 11-6-2004 at 04:41
This is what happens when people dont use structural formulae for working things out. You end up with a pile of shit that just makes sense in terms
of conservation of atoms.
I'm very glad you got this elsewhere Angel, because it alows me to rant, and thats always fun.
Asprin, C6H4(OOCCH3)(COOH)
Which would be C9H8O4, so thats correct.
Salicylic acid, an OH, and a COOH next to eachother on a benzene ring.
C6H4(OH)(COOH)
Which would be C7H6O3, not C7H4O2
Asprin is an ester, you can see that from the structure and esters need to be hydrolysed to get the alcohol and the acid. So its acid catalysed
hydrolysis to get to salicylic acid.
Phenol, C6H5OH
We only need a decarboxylation to get this from salicylic acid.
These arnt trivial mistakes chemically, esters hydrolyse we all know that, its clueless atom counting. Use structural formulae!
AngelEyes - 11-6-2004 at 07:03
My apologies if that was not as accurate as it should have been - I was a little busy and didn't check it as I should have done. Powerlabs is
usually pretty good...
Aside from the errors in the formulae, though, does it accurately illustrate the reaction process? ie how you get from ASA to TNP?
thunderfvck - 11-6-2004 at 12:25
Well son of a bitch. I thought I looked at that site and found nothing, but evidently it's right there before my face!!
So I had it partly right then, ester hydrolysis to salicylic acid then decarboxylation. Excellent!
But is this a useful way in making phenol? I guess not, as the phenol would now take on an SO3H (o or p) group which would direct the NO2's
(meta!!) from coming in, then the SO3 would leave and the final NO2 would strike.
And of course the concentrated H2SO4 converts the NO3 into NO2 which is easily accepted. But sulphonation can only occur in dilute acid, no? Otherwise
the equilibrium is strongly shifted towards product. But I have no choice here. Unless much of the acid is reacted with by this point.
Yes, this is how the reaction takes place! Much more interesting and rewarding to know it this way!
Thanks for the help!
[Edited on 11-6-2004 by thunderfvck]
thunderfvck - 13-6-2004 at 02:00
Well I tried it twice now.
THe first time I used about 4.5 g of ASA in 40 ml of H2SO4, 9 g of NH4NO3 was added slowly. Nothing special, NO2 vapours, yes, about a 3 g yield of
TNP.
But I did it again tonight, on a larger scale. It was much more exciting. 19 g ASA, 50 ml of H2SO4, 28 g of NH4NO3. MAD NO2 vapours. My god, it was
intense. The bubbling was furious, I'm glad I used my 250 ml RB flask. I got the red goo as madscientist had reported, but I no longer see it
having dumped about 350 ml of water in it. The heat was hard to control. THe higher the temperature, more NO2 vapours, which is what I had been aiming
for the whole time. I equated that with a more thorough reaction though I doubt this is the case. Acetic acid began to boil off at one point and
jesus, did it stink. I'll post my yields tomorrow but I was wondering, maybe the red goo formation is due to using less H2SO4? I had no problems
with it the first time by using a lot more H2SO4. The temperature didn't get out of hand as much either the first time around.
In either case, it was a very fun experiment!!
thunderfvck - 13-6-2004 at 12:44
Alright, well in both cases I let the mix sit in the fridge overnight to fully crystallize out. The first time I got about a 40 something % yield.
Poor! But this time, using less acid, I got a 63% yield! I also expect to get more as I usually obtain a bit more after filtering and letting it sit
for some time. So close to 70%! I think this is very good. However I am very uncertain as to it being entirely TNP, I recall Philou stating that other
products can be formed, all of which are yellow. Well, I'll be recrystallizing tonight and I'll take a melting point to ensure what I got is
the real deal.
BTW, this stuff STAINS REALLY BAD! My god. It looks like I've mutated! My hands are yellow all over!
Oh, and I take it the NO2 vapours are due to the decomposition of HNO3 which evidently takes place at higher temperatures. I wonder if I dissolved all
the NH4NO3 at low temperatures (where I noticed practically no foaming whatsoever), how my yields would look, hmmm....
thunderfvck - 13-6-2004 at 23:45
FINALLY.
I've just spent three hours putting together the mechanism in chemdraw.
<a href="http://lobstertales.tripod.com/lab/TNP/tnpmech1.jpg">Part 1</a>
<a href="http://lobstertales.tripod.com/lab/TNP/tnpmech2.jpg">Part 2</a>
<a href="http://lobstertales.tripod.com/lab/TNP/tnpmech3.jpg">Part 3</a>
<a href="http://lobstertales.tripod.com/lab/TNP/tnpmech4.jpg">Part 4</a>
Good?
What happens to the SO3H cation? I know in dilute acid it reforms H2SO4, will the same apply in concentrated acid? Seeing as how it doesn't have
anywhere else to go...
[Edited on 14-6-2004 by thunderfvck]