Picric acid

[Mr Cool]

Exactly the same as when recrystalising from water, only you use ~2% HCl instead. Add picric acid to boiling 2% HCl until no more will dissolve, filter if you think it necessary, let cool while stirring, chill, filter, wash crystals with a little water, dry.

[Mendeleev]

Here's a picture of my picric acid yield from that liquid fire experiment from 250 tablets of aspirin, 325 mg ASA each. The floweasy drain cleaner gave me about a third or a fourth of this and it was brown.

[K'Luuppo]

I made today my first attempt to make TNP, but it didn't go as expected: I took 100ml of my boiled-down battery acid and heated it to 80-70 degrees. At this stage I added 21g ASA. When ASA came into contact with acid, it made big chunks instead of those small crystals it were in my container. I managed to crush some of the chunks, but they were still quite big (4-8mm by diameter).

Now the strange part: the liquid has now sitted more than six hours, all the time at 80-70 degrees, but there is still ASA crystals floating on top of the solution. There is also some crystals on bottom. Those crystals aren't very visible, but they can be seen.

Would someone please tell me which part is wrong? I would also appreciate if someone told me what are those crystals on the bottom. My guess is that my sulfuric acid wasn't concentrated enough, but it's really only a guess.

[K9]

Well there's that problem - which includes impurities in the sulfuric acid. Is the ASA pure, or are there impurities there too which may not dissolve? The way I add the ASA (purified from aspirin) is too dump in a bit at a time and stir until it dissolves. 25 grams dissolved in 135 ml of sulfuric acid at around 70 degrees celsius in ~5 minutes.

[Detonate]

Ive read that the Aspirin you can buy in germany contains ASS, NaHCO3 and Citric acid. Thats not good! The NaHCO3 should reakt with the ASA to form the Na salt. Thats better for your stomach. But in the TNP reaction it forms NaSO3, NaHSO3 and the salts of the citric acid and the ASA.
These ASA is from Bayer Aspirin. This source of ASA is expensive as hell! I dont know if other Aspirins contain these ingredients too.

[K'Luuppo]

I messed bit up when purifying it, but that led to loss of product instead of polluting with impurities. I only spilled half of the acetone/ASA mix but nothing went in. Only impurities I can figure out would have been came from the containers and I suppose there is way more undissolved stuff than it would have been possible to get that way.

Also there should be only water and H2SO4 in my acid, because it wasn't from old battery.

As for the Aspirin, I can't remember the manufacturer, but at ingredients it said only ASA and some corn/wheat thingy.

Does somebody know how would lower concentraton of acid affect the solubility?

[FUTI]

If someone know how this reaction can be stoped at the dinitro-salicilic acid I would be gratefull...this has noting with explosives just one of mine side projects. Some old procedure for precrystalisation are maybe better then pure acetone. Measure the solid, add small amount of alcohol warm alcohol until most of it dissolve ( at cold it takes 12ml for 1g of PA), then add warm water until cloudiness. Let it slowly cool to room temperature and it will make fine crystals. Maybe you will loose little PA compared to acetone procedure but it can help with extremely dirty reaction products.

EDIT: This thread is soooo long that I didn't have time to check did someone propose this crystalization procedure. Also at the begining of the thread everyone are talking about NO2 when regard to frothing. I know that it will make NO2 in some amount, but I think that CO2 coming out during decarboxilation is that is inevitable and mine first suspect when the frothing is mentioned.

EDIT2: The posts at the first page in this thread recomend recrystalisation of PA from aceton. I didn't check that procedure but I think that procedure I recomend will work fine. BTW none said anything about dinitro-SA.... :( does that mean I can't make it this way?

[Boomer]

Did you mix up the purification of the ASA in the beginning with that of the PA at the end?

IIRC the acetone is used for the tablets, and hot water later for the end product. :confused:

[K9]

I'm not quite certain of what your proposed method is. I know that I purify my ASA using acetone, and then the crude PA by dissolving in hot water. Could you clarify?

[R_Chemist]

I have synthesized picric acid before with the sulfuric acid/nitrate method before and it worked fine for me. However I have recently tried it with 70 % nitric acid and have had a few problems. 10g ASA was sulphonated with 20mL sulfuric acid for 1h at 100C. This was then cooled to below zero. 30mL of 70% nitric acid was slowly added at such a rate that evolution of NO2 was minimal. The mix was then allowed to sit untill no more NO2 was given off when stirring(about 5 days). This was then crashed into 150mL of ice/water. For some reason crystalls did not appear, the solution was just red. The solution must have contained picric acid as when I accidently spilled a drop of it on my finger, my skin was stained. Also, when cleaning up and dumping the red solution down the drain, while washing it down with a lot of water, the color changed to a familiar yellow color.

So my question is: Why was there no precipitation upon crashing with water?

Any ideas are apreciated
Thank You.

[FUTI]

I edited my post to clarify it. I hope that was good enough.

[Myrol]

To R_Chemist: Your problems was the heating wich you haven't done! Poly Nitrated Aromatics need often high Temperatures to form gently. I will try soon my firts attempt in making TNP.

I have 16,5g very pure A.S.A. and will sulphonate it like you with 35ml 96% H2SO4 for 30min. at 100°C and then Nitrate the mix with 40ml 65% Nitric Acid and 40ml 96% Sulphuric Acid. The Acid should be added slowly at 45°C with chilling until all components are mixed in the reaction vessel. I will heat it slowly to 120°C and hold that Temperature until 30min. are gone. Yield is below 70-80%, the KNO3 method seems to be also intresting....but my PN is just 13-0-46 Fertilizer grade so the purity is insufficient for preparative chemistry.

[K9]

You should test it with your KNO3 to see how well the reaction works. Or at least purify it and see how that is. It would be interesting to compare the products. When making TNP I've used only a higher grade KNO3 which seems to give a nice yield.

[Chris The Great]

Saturday I made a batch of picric acid, following the procedure on Douchermann's page: http://douchermann.a0tu.com/Highexplosivespictorials/picricacid.html

I used red coloured drain cleaner, recrystallized acetylsalicyclic acid and ammonium nitrate in prill form.

First, I put 220ml of drain cleaner in a 700ml jar, and began heating the water bath. As it was heating up, I added 40 grams of ASA (acetylsalicyclic acid) and stirred it. It all dissolved once the water bath reached boiling temperature, and during this time the solution turned from red to deep black. After the ASA finished dissolving, I continued heating in the boiling water bath for 25 minutes, with occasional stirring.
http://img355.imageshack.us/img355/6323/sulfonation1fl.jpg


I took it out of the boiling water, then proceeded to add ammonium nitrate very slowly, at a rate just slow enough to prevent orange fumes from forming. The mixture foamed uring this step.
http://img228.imageshack.us/img228/1858/nitration2cu.jpg


The rate of foaming varied, being strongest near the middle of the addition process then slowing down again near the end. The colour lightened until it had formed a clear red solution. The addition took a total of 40 minutes to complete.
http://img228.imageshack.us/img228/8941/finish3ux.jpg


This was allowed to sit for about 15 minutes, after which a layer of yellow picric acid had formed on top. I then stuck it in boiling water for another 6 minutes, and a bit more picric acid was formed. It did not turn black again like in douchermann's description.
http://img355.imageshack.us/img355/9273/finish27bn.jpg


I let it cool a bit, then helped it along with some cold water since it was getting late. I then poured the room temperature or therabouts solution in 1 liter of cold water, and then more water was used to rinse out the remaining picric acid out of the nitration jar.
http://img355.imageshack.us/img355/9690/diluted0nr.jpg


I filtered it out, but have not recrystallized yet. At the moment it's hard to heat anything, since I ran out of propane when boiling down a KNO3 solution I was purifying.
The yield looks pretty good.

[doedel]

Ive read that the Aspirin you can buy in germany contains ASS, NaHCO3 and Citric acid. Thats not good! The NaHCO3 should react with the ASA to form the Na salt. Thats better for your stomach. But in the TNP reaction it forms NaSO3, NaHSO3 and the salts of the citric acid and the ASA.
These ASA is from Bayer Aspirin. This source of ASA is expensive as hell! I dont know if other Aspirins contain these ingredients too.

Buy the ASS from Ratiopharm. It's 5 Euro for 50 grams (still expensive compared to USA, I think)

Zus.: 1 Tbl. enth.: Acetylsalicylsäure 300 mg/500 mg.
Weit. Bestandteile: Maisstärke, Mikrokristalline Cellulose, Cellulosepulver.
50 Tbl. (N3) 300 mg (FB 3,93) 2,60 PZN 3484719
100 Tbl. 300 mg 4,30 PZN 7602392
30 Tbl. (N2) 500 mg (FB 3,36) 2,30 PZN 4345931
50 Tbl. (N3) 500 mg (FB 4,79) 3,00 PZN 1830979
100 Tbl. 500 mg 5,00 PZN 4345948
source: www.rote-liste.de

[hashashin]

hey guys ive tried to make PA from salicylic acid and got some weired results.
ive mixed one part salicylic acid with 4 parts sulfuric and heated for half an hour to make phelon-4-sulfonic acid. and the weired part that i got a yellow solid( should it be a solid? ) anyway i continued the experiment, iv eadded 3 parts HNO3 and after several minutes got a vigorous reaction and a lot of NO2 was participated. after that i rinsed with cold water and filtered out the crystals.
still have to recristalize it.
the question is : should the phenol-4-sulfonic acid be a solid? and should the PA crystals appear before i pour the final mixture into water? because it crystalized out before i even added water.

[festergrump]

Advice: Consider the RS Forums an airplane and your posting anywhere here outside the Water Cooler as the act of jumping out. The SHIFT keys are your parachute's rip cords. You've got two to use just in case one doesn't work. Find at least one of them or go SPLAT! (http://www.roguesci.org/theforum/water-cooler/5150-beast-has-fed-upon.html)

[nbk2000]

And *SPLAT!* he went. :)

[megalomania]

At least he capitalized the molecular formulas :rolleyes:

[meyer25]

Most of you are reffering to rather short sulfonation times, i.e. 15-60min. Since this step involves actually three reactions (first, hydrolysis/deacetylation of ASA to SA, second, decarboxylation of SA to phenol, third, sulfonation of phenol to phenol-2,4-disulfonic acid), I would advise you heating the aspirin with sulfuric acid for longer periods, that is 2-3hours/100-110°C. You will see if you get more picric acid after the nitration step.
Even straight phenol, which is directly sulfonated and high reactive because of the free -OH group on the aromatic cycle, needs to be sulfonated for 1,5-2hours to obtain best yields.
Try it, you have nothing to lose, except for 1-2hours of your time.

[Cobalt.45]

Megalomania, may I ask a question? Your sites' procedure for making picric acid calls for adding 32.5g ASA ( unless the asprin are other than 325mg/ea) into 700mL sulfuric acid in a 1000mL beaker.

Is this correct?

[vod8750]

I'm thinking about making picric acid but I can't seem to get the usual Aspirin tablets in the shops!
All I can get is Disprin which contains Aspirin. Since Disprin is taken dissolved in water is there a danger that other ingredients other than acetylsalicyclic acid will be dissolved in the isopropyl alcohol giving me impurities in the endproduct? :confused:

Although if this is not a problem I can get 16 tablets of Disprin extra strength (containing 500mg acetylsalicyclic acid) for 2-3 euro. I don't know how this compares to other countries but I don't think it is that bad!
Any opinions on the matter would help a lot!

[megalomania]

Vod, no offense intended, but what kind of third world crap hole do you live in that you can’t even buy some aspirin?

Cobalt, the procedure as given is correct, but I cannot guarantee your specific numerical figure as being accurate. The particular source for the aspirin method is adapted from KIPE (Kitchen Improvised Plastic Explosives), which is the only non-scientific piece of literature I have resorted to using. Since KIPE is generally held to be reputable, and considering the overwhelming utility of such an OTC method, I opted to include the aspirin method of making picric acid. Indeed without a standard as to what constitutes a mean dosage of acetylsalicylic acid in a pill the procedure will give varying results.

[VolatileMatter]

What's the meaning of this, you cant`t buy aspirin ? A lot of shops have pills which contains acetylsalicylic acid. You can`t buy aspirin, by a simliar drug.
The KNO3 method works good but HNO3 will give a little better result.

Originally Posted by Meyer25
decarboxylation of SA to phenol
phenol to phenol-2,4-disulfonic acid

Can you post what chemicals was used in this process. I was first exposed this forum discussing explosives. Would you make PA with clinical grade ?

[vod8750]

Its ok I just found a different pill which contains acetylsalicylic acid. Its expensive though!
Im also quite used to not being able to get hold of chemicals easily seeing as I live in Ireland! The government banned the sale of a lot of the chemicals you guys might find really easy to get because the IRA were using them to make bombs during the Troubles in the 70's!
I cant get KNO3 or AN! No hardware shop that I have asked has even heard of using acetone as a paint thinner! There are more, I just cant think of them right now!

[c.Tech]

vod8750, your situation sounds really bad. May I ask which country you are from?

[nbk2000]

Oh Jesus...'what country are you from'? :rolleyes:

He quite clearly states Ireland. :p

[c.Tech]

:o Sorry I honestly didn't see.

[A.Scriabin]

Hi, today happened to me a strange thing: I wanted to make copper picrate by adding copper nitrate to an ammoniacal solution of picric acid(as I saw in a book,except it uses copper sulfate), but I've obtained a strange goldish precipitate(very similar to true gold!O_o), with a big yield. What it could be?ammonium picrate?

When I added one small piece of copper nitrate(idrated), the typical yellow solution turned dark, then blood-red, and finally it was completely converted in the precipitate that I described before @_@

[c.Tech]

I wanted to make copper picrate by adding copper nitrate to an ammoniacal solution of picric acid(as I saw in a book,except it uses copper sulfate)

ammoniacal solution? Mixing picric acid with ammonia makes ammonia picrate.

Now you need to know if ammonia picrate and copper nitrate would exchange ions to yield copper picrate and ammonium nitrate.

You probably can’t replace the copper sulfate with another copper salt IMO, I would try mixing picric acid with copper hydroxide/carbonate.

What book was this from?

[Rbick]

While we are on the subject of picric acid... I am currently having a problem with it. Out of 30g of ASA, I was able to get a yield of 20g of what looks like, and I am pretty sure is Picric Acid. It comes out as canary yellow crystals. I let it dry for about 4 days after washing it.

The problem comes in when I try to detonate it. I attempted to detonate 20g of PA with a 1g cap of AP pressed into a 7.62x39mm cartridge (I love my ak-47 :D ) The cap worked prefectly, but the PA did not detonate, only scattered from the cap.

For a second try, I again yielded about 20g of PA, and this time mixed it with 8g of AP (making a 60/40 mix). I cafefully mixed the two, and added a cap, again a 1g charge of AP. The cap worked fine, but again the PA did not detonate. From what I have read, PA shouldn't require a booster. Am I missing something here? Any help is appreciated, thanks guys.

[A.Scriabin]

ammoniacal solution? Mixing picric acid with ammonia makes ammonia picrate.

Now you need to know if ammonia picrate and copper nitrate would exchange ions to yield copper picrate and ammonium nitrate.

You probably can’t replace the copper sulfate with another copper salt IMO, I would try mixing picric acid with copper hydroxide/carbonate.

What book was this from?
The book is italian, and there are described some analitical methods to recognize picric acid. I've made some tests with the gold substance obtained: is difficult to dry, but if warmed on aluminium foil above a flame, it deflagrate with a white/green bright flash. I think that it isn't copper picrate because my substance are goldish instead green,but it cannot be ammonium picrate because it burn with green flash immediately on a contact with flame, and has metallic aspect(not like sand as yellow ammonium picrate).I think it could be cuprammonium picrate...

[209]

I have made Picric Acid from aspirin only once, I have only 500mL of H2SO4 left and I really want to avoid using it, It getting really hard to find now because of all these K3wls blowing themselves up.

This may sound stupid - Can you use HCl for making picric acid? Unless there is some method of obtaining Sulphuric it that I havent thought of, I am stuck.

[c.Tech]

NO you cannot use HCl for picric, because the sulfuric acid is needed to keep the water generated from the reaction out.

I was thinking of anhydrous magnesium sulfate being used in the place of sulfuric, enough to absorb the water generated, but the water would probably favour the HNO3.

I think I’m way off track because I’ve never heard of substitutes to sulfuric.

[akinrog]

Can you use HCl for making picric acid?

HCl and HNO3 shall create a very corrosive substance called Aqua Regia which shall attack even gold. So both acids are not compatible with each other in reactions. You need a dehydrating acid (i.e. concentrated Sulfuric acid). Regards.

[FUTI]

Some methods IIRC for nitration use heating substance with sulfuric acid to sulfonate compound then add nitric acid and heat again to make them "switch" place ;) so H2SO4 has few good bonus points for that reaction. As for HCl...bad idea man...mixing phenols with aqua regia...when heated aqua regia contains among other stuff Cl2 and NCl3 IIRC!!! I would like to watch that though...from safe distance:). NCl3...hmmm...if only I know is the yield is high enough...just joking I like my eyes and fingers. Cl2 or NCl3 would act as oxidant to almost anything not to mention phenols. I could put few bucks to uncontrolable reaction going on splashing and spilling everywhere.

[xenon24]

I did a quick search, and it seems to me that everyone has simply pressed their Picric Acid. Now, it has a boiling point significantly lower than its flash point, has anyone tried melting it to make a charge? I ask, because this seems as if it would yield the best density (better than simply pressing at least), and I would like to do it, but don't want to get myself blown up.

Is there a problem with melting it and pouring it into a plastic container to make a charge?

[Alexires]

Perhaps if your search was a little longer than "quick" you would have found that Picric Acid can, in fact, be cast.

Starting at wikipedia (the widely reknown source that it is :rolleyes:), I found that a man by the name of Eugene Turpin held the patent for pressed and cast Picric Acid. I then ran a search on google for the patent.

I didn't find it, but found that COPAE talks about casting picric acid. Those sources combined would be suitable enough for me. I would say that you would be pretty safe in casting it. I'm downloading a copy of COPAE onto this computer at the moment. If it talks about any dangers regarding cast picric acid ill edit this post.

Just beware metals and decomposition of the Acid/plastic.

I'm thinking that it might decompose giving of NO2 fumes which are never nice, but I don't know if that would happen just as it melts. Use a oil bath to melt it over a hotplate (not an open flame).

Be careful.

[209]

Cast Picric acid:confused: Thats a new one(for me at least). I have made Picric a few times but tend to stay away from it because it is so toxic. I have often used it as a main charge rather than a primary or secondary. Maybe I am just to chicken shit to make NG:) . Is it true though that Picric acid will form as fast on the threads of a container as AP?

[xenon24]

Well, I knew it could be cast (similar to TNT) I was just wondering if anyone on this forum had tried it and had first-hand knowledge. Because TNT can be boiled, but its safest to do it at a lower pressure so that it doesn't get too close to the temperature at which it decomposes (even though the BP is 20 degrees lower or something like that).
So my question was not so much "Can you cast picric acid?" as "Has anyone cast picric acid here, and are there any complications I should be aware of?" Thanks, btw, I'll check out that patent.

P.S. When I stated "Everyone has simply pressed PA" I meant everyone on the forum, not everyone in life. Maybe it's not worth the hassle, maybe it is...If I could, I would compare pressed and cast charges, but I don't have the proper equipment.

[nbk2000]

I believe TNP is usually mixed with a lower M.P. explosive or wax if it is to be cast, becuase it's very sensitive when melted, even more so if there is any trace of metal contamination.

[xenon24]

Thanks for that NBK. What would you recommend?

I was going to simply put some in a heat resistant plastic container and put that in an oil bath that I would heat to maybe 130 C...and then once the PA had melted I would take it out of the bath and let it cool. Once cooled I could take it out of the container or leave it in to make it less of a contamination hazard.

I suppose melting wax and mixing powdered PA into would be safer, and work just as well. (although I'm assuming I'd lose some power [VoD?])

A mix of PA and TNT might also be an interesting alternative to try, and I'm sure would not compromise the power as much. Small amount of TNT to a large amount of PA, since PA is by far the easier of the two to synthesize.

[Flamethrowa]

Beware mixing PA with all kinds of things; It is a strong acid. Normally since it is fairly insoluble it's probably not as big of a deal but once fused...well, be careful. I don't remember whether TNT is one of those explosives that dislikes being in acidic situations but I imagine that would be something to avoid.

A quick google shows that the old historical explosives Lyddite and Melinite are basically mixtures of NC and PA produced by dissolving both in an NP solvent. Upon evaporation, I'd imagine the NC would serve to bind everything nicely...however, I was under the assumption that NC becomes very unstable in acidic conditons.

Personally, I've always wanted to try AN/PA....drymixed on site of course. Though, who knows? HNO3/Ammonium picrate might be kinda nice...

It would have to be called "Amaphen" Heh..

[KrIsPy]

Yeah...AN/PA would be nice. With PA (if my source is correct) having an oxygen balance of – 45.4, AN would be a great source of oxygen for ANPA. Has anyone tried AN/PA mixtures...I suppose I could try it in tiny proportions once I make some PA this weekend. With AN at a +20 OB, would it be about 2:1 AN/PA?

I had one of the worst experiences synthesizing PA I have ever had in any synthesis. It had partially to do with the fact that I was tired and pressed for time.

First, when filling my hot water bath, I poured about 40ml of water into my 40ml of acid/ASA solution by mistake. It foamed up badly.

I should have quit then, but decided to keep stirring, and in an attempt to use a cheaply made electronic stirring mechanism (a VERY stupid idea), Sulfuric/ASA solution splattered, one of which drops hit me directly in the left eye, and I VERY stupidly was not wearing goggles.

I washed my eye for at least fifteen minutes and continued to wash it on and off for some time. It hurt and I thought I might go blind in that I, but thankfully, my vision is back to normal with my eye only slightly aching day later. I'm glad I spilled water in the solution to dilute the Sulfuric, or it could have been worse.

Anyway, I recovered, learned from my severe stupidity and possibly crippling accident.

Though I feel that PA is cursed for me, I am wondering if this diluted solution has been rendered useless, as I added probably about 1:1 water:sulfuric/ASA. Should I throw out my 40ml sulfuric and 22 aspirin tablets? Seems a shame, but at least it's not much. Thanks.

[peppovsky]

Just a quick question - I've done my first synth of picric acid yesterday (from ASA), and today I've purified it. Now it's a strong yellow colored - so either i've made it well, or I fucked the thing up real bad at some point. Is it the color it should have? (different sources claim different things)

[tomu]

Picric acid is of yellow colour. You can look at some photographs of the final product at:

http://www.powerlabs.org/chemlabs/picric.htm

[peppovsky]

The pictures at Sam's site are of low quality and it's not clear what is the exact color of the substance. My product was a REALLY yellow one - and stained half my house with yellow. :(

Update: I've managed to clean the stains from the picric acid by cleaning stuff (carefully) with hot concentrated NaOH solution. Just a note for anyone who might need cleaning PA stains in the future. ;)

[tomu]

Picric acid is yellow. What shade of yellow will mainly depend on the purity of it, I guess.

If you want to know how pure it ist analyse it, e.g. melting point etc..

[peppovsky]

Well, it melted at around 110-125 C , but I will do further analysis. Attached is a picture of the batch (wet), for sharing.

http://i167.photobucket.com/albums/u146/peppovsky/TNP.jpg?t=1177080775

[Charles Owlen Picket]

MP of Picric acid is 122-123 C. Explodes @ 300 C (Merck or E.C.H. 1998) Therefore oil bath cast / melts could be easily done. It HAS been done (see French & German ordinance, WW I) frequently. The point about metallic impurities is extremely important. However if the PA was synthn'ed in glass that may be a "non-issue".

The color of PA given by Merck and COPAE is light to very light yellow. There has been a great reference in A.E.E. (usenet) to the contamination of PA with H (via bases, or even air during synthesis, etc) as yielding a deeper yellow (Canary yellow) or orange. Olsen & Goldstein state that via re-crystallization PA can become close to white. It is generally accepted that the lighter, the better provided the mp is @ 122-3.

If however true trinitrophenol has been achieved there should be no problem with purifying this [& eliminating the discoloration] through re-crystallization.

Please reference US Patent 2455322 (1948 Allied Chemical) is key patent to most common as well as unique method of synthesis. Olsen & Goldstein - (Industrial Chem. Engineering) 1924 did the most extensive work with PA alone that is referenced in English during the 20th century.

[peppovsky]

As mentioned before in the thread - the picric acid refuses to get dryed from water, even after 2 days in the open air. I thought of putting it in the oven on 60-70 C for 2-3 hours, but I'm afraid of oxidation of some of the material. Are there any safety measures I can take, or is it not a problem at all?..

[nbk2000]

You can spread it out in a shallow layer in a glass or plastic jar/pan/tray, and put that inside a larger air-tight box filled with a dissicant, like Dri-Rite (Calcium Chloride), and leave it somewhere warm for a few days.

That should do the trick for you. :)

[peppovsky]

I will probably use one of those tupperware boxes (Still on my search for CaCl2, though this shouldn't be to much of a problem). Plus, I was thinking - recrystallization of TNP from Acetone - is it anything better then recrystallization from EtOH/MeOH or water?

[fiknet]

Perhaps your TNP has some residual Sulfuric Acid in it, try washing it again with distilled water.

[peppovsky]

ok, so I will recrystallize the TNP again, to purify it (I'm a bit parranoid concerning metal picrates - hopefuly, if there are any, they should go away with the water when filtered).

I'm also planning on making a brick test with my stuff - dropping a 2kg weight on 1 gram of TNP from different heights, until it detonates. I'm expecting less then 60 cm, since this is the height of drop for a 2kg weight on TNT for detonation, and TNP is more sensitive then TNT. I will share the results (and the images, if possible) with the forum after the test.

[Charles Owlen Picket]

I'm also planning on making a brick test with my stuff - dropping a 2kg weight on 1 gram of TNP from different heights, until it detonates.

Do not be surprised if it does not explode. If you are interested in impact testing, metal to metal contact is what was used by the old USBoM.

Some very effective and sensitive energetic materials require metal to metal contact to shoot. You would be very surprised what resists impact alone (wood, etc).

[peppovsky]

Thanks for the note, I will use metal surfaces (Is there any prefered metal for that use?).

btw, my TNP had grown to crystals of the size of 1-2 cm and I wish to powder them (so I can press them when making detonators). Can I use a ceramic mortar and pestle for that purpose, or do I risk a detonation (I will make sure they are wet, of course)?

[Charles Owlen Picket]

You know, that is a good question because you are proposing a different type of stimulus there (friction as opposed to impact). The USBoM has some great material on that as does both Federoff & Urbanski. IMO it's best to start a small library of research and resource material when dealing with any energetic material.

Putting aside all the mess of staining, I personally would not recommend grinding it. It is a rare thing but dry Picric Acid in the threads of glass containers have been known to "pop" on occasion. There are variables that need to be met however. Would this happen with gentle crushing not grinding, etc? No one can tell because the variances in such a description. That's why people get hurt from information where sources are not sighted and specific conditions are not outlined.

When old, dry PA is sometimes encountered in school labs there have been tendencies to over-react and call the police for disposal. To the best of my knowledge it is rare that PA will shoot from opening an old bottle with it in the threads but I believe it HAS occurred and people have been hurt. The conditions have to be right but I believe it can be initiated from friction. And it's happen enough so that it's common place to cause concern in most Chem depts.

Use safety with all energetic materials. Do not rely in internet sources alone but research from respected sources and read all you can concerning initiation of various secondaries. That way you maintain safety as a priority.

.

[peppovsky]

ok, so I've grind the crystals with a mortar and pestle, very very carefuly, one crystal at a time. It didn't detonate, nor "popped".

To anyone reading this - I should state again this is very dagnerous , and should be performed only with very small amounts (not more then 1/4 gram at a time), and never with a metal mortar! I've done it only because nothing else worked. Always try dissolving in warm water/ethanol and recrystallize, prior to crushing the crystalls.

...Now I shall get myself some CaCl2 (in a couple of days), dry it and test it ;)

[zeppelin69]

I just can’t figure this stuff out. I have tried the synth. 3 times now and I keep getting the same results. My end product is never crystals, but this back, tar like goo, that float to the top, and stick to my stirring rod. Does anyone have any idea what I’m doing wrong?

The last time I did it, I used 150ml sulfuric acid (95%), 60 aspirin tablets (325mg each) and 30g of potassium nitrate. I think I'm messing up somewhere during the addition of the nitrate, I added it slowly over an hour and a half, but towards the end I had lots of foaming (if that helps the diagnosis at all).

Thanks for your help to any one that might have any suggestions.

[peppovsky]

ok, TNP is dried (not completely though, will let it dry more in the next few days). In the mean time I'm planning the brick drop test - Just have to find a metal weight that will fit the cyllinder I have. Picture of 10g TNP is attached.

http://i167.photobucket.com/albums/u146/peppovsky/TNP2.jpg

[KrIsPy]

Looks nice pepp...That should be enough to do some pretty good damage.

Anyway, I know I already asked this, but I never got a response. I was curious to know if there is anything you can make from TNP besides DDNP and Ammonium Picrate, such as TNP/ammonium nitrate or something of this sort iin which TNP can be added to some cheaper compound?

[Enkidu]

@zeppelin: Which 'synth' did you try? You don't post many specifics, unless you refer to Alen's synthesis. Because picric acid can be produced so easily, many different 'recipes' have evolved. Most of these are erroneous. Not to pick on Brainfevert, but his TNP recipe is misinformed on several accounts. He himself has stated this in numerous posts (either here on RS or on SM).

Rosco Bodine has demonstrated that temperature and time of the acetylsalicylic acid (ASA) to TNP reaction, as in nearly all other explosive syntheses, cannot be left to chance. My personal advice is to look up all the threads on picric acid, both here an on SM. SM has some good advice on picric acid production. Unfortunately, the search function on SM isn't very good. You'll have to look to find what you need. Look here for Rosco's 'good ol' country recipe' in an archive thread and the details of his recrystallization procedure in SM (it's hiding in a long 'picric acid from phenol' thread, IIRC).

The 'foaming' you see is the effervescence of carbon dioxide from decarboxylation. This 'foaming' is normal and required.

Also, look in literature for different picric acid labs. Even labs that begin with a different starting material, e.g. phenol, can provide some valuable hints about the reaction. The forumites' ideas are never a substitute for actual science. A background in science and a true scientific understanding of the experiment you are performing is crucial. An understanding will help to prevent you from injuring yourself. Are you aware that picric acid is toxic?

---

@peppovsky: If your picric acid is as yellow as you claim, it is impure. It should be a very pale yellow after recrystallization. If it's a bright yellow, my personal opinion is that it's contaminated with DNP. Recrystallize from Rosco's procedure. (Yes, I like his work.) Impurities could also be the cause of your wet TNP. Pure TNP is absolutely not hygroscopic. In my experience, salicylic acid (SA) provides a less yellow product than ASA and it requires less sulfuric acid. You can make SA from ASA though saponification with sodium hydroxide.

From your picture, I don't believe your picric acid is very impure. (The colors are sometimes hard to judge in a photograph.) In my dreams, my picric acid is less yellow than yours. However, the picture does say that your crystals are in a somewhat less than desirable form. You have 'fluffy' crystals. This type of crystal won't work well in your drop tests. For starters, use slow cooling. Again, use Rosco's recrystallization procedure to get dense, pure crystals.

[zeppelin69]

Don't quote whole posts.

Thanks for all of the help I really appreciate it. I have read all of the threads I could find on this site when searching for picric acid, TNP, and trinitrophenol. I guess I'll go back and read them again. I also read all of the threads I could find at SM, except the one that said "from phenol", I saw it but in my ignorance I disregarded it because I didn’t think it would help me because I was using ASA instead of phenol. I understand know though that it would still have decent information that would be of use to me.

I thought the foaming was from the carbon dioxide, I just wasn’t sure, thanks for clearing it up for me.

One of the "recipes" I used was Brainfever's, but the other two I tried had the same pitiful results. Yes I was aware that TNP is toxic, I have been reading up on it as much as I could in the last couple of months.

I will look up Rosco’s version, give it a try, and try to post my results (a little more clearly, and with pictures next time). I do have one more question though, I know that my sulfuric acid is not pure, on the bottle it says “virgin sulfuric acid with 12 buffers”. These buffers never got in the way of making nitro cellulose, but could it be what is giving me all of this trouble?

Thanks again.

[peppovsky]

Enkidu: I've done 3 recrystallizations from boiling water already, so after reading what you've said, I'm beginning to suspect this isn't such a good product after all :/ Though it must be stated that it wasn't dried for too long, only a couple of hours in the sun (with nbk's suggestion of CaCl2). Some drier, whiter crystalls are there on the plate, so I hope there's still a chance ;)

BTW - Should the TNP stain water with a strong yellow color, or is it a tendancy of DNP?

[Enkidu]

@zeppelin: You're welcome. :) Most people seem to use drain cleaner sulfuric acid in nitrations, but I never have. I've read in other threads that the '12 buffers' variety works fine, at least for nitroesters. However, I don't believe that I've ever seen any comments about it's effectiveness in aromatic nitrations. Others have used unspecified drain cleaner brands and reported that they work for picric acid.

BTW, the 'black junk' that you've been getting reminds me of the result of the oxidation of phenol. See the SM threads for that. Don't get discouraged if at first you can't get the reaction to work. Keep trying, but try to learn about what is causing the problem.

---

@peppovsky: The bright yellow batches seem to color the water a slight red. Good (read 'purer') batches stain it a light yellow. So I'd imagine that your batch falls somewhere in the middle.

The boiling water method of recrystallization does not work well to purify contaminated batches without some extra work. In my experience, you can filter quite pure crystals at room temperature, but no colder.

There are differing opinions about what causes the range of colors in a picric acid product. Many times I have seen red crystals on my thermometer or stirring rod about half way through the addition of the nitrate. I had always assumed that they were product of an incomplete nitration. After looking briefly at PHILOU Z's remarks upon the subject of the red impurity (search 'red picric acid' at SM), combined with my own observations, I doubt that it is DNP as I first said (although it's possible I guess).

From PHILOU Z (English is obviously not his first language):

By the way you may end with mononitrophenol and dinitrophenol too if the nitratation is not efficient enough (enough HNO3/H2SO4 at a strong enough conc).
DNP is explosive too and also makes explosives primary heavy metal salts; they are just less powerful than TNP and TNP salts!

I can tell because I have pure paranitrophenol (4nitrophenol) and (2,4 dinitrophenol) and TNP (2,4,6) that they all looks the same!
Cristalline yellow, colourising everything in yellow!

On the red impurity that I think somehow colors the batch bright yellow:

Answer is nitronic acid rearangement!

CH3-C(OH)=C(CH3)-NO2 <--> CH3-CO-CH(CH3)-NO2
CH3-CO-CH(CH3)-NO2 <-OH(-)-> CH3-CO-C(CH3)=N(O)-OH
Thus beta nitro enols undergo enol-ceton [ketone] equilibrium to provide a alfa hydrogenated nitro derivative in tiny % that gives the yellow colour; the later upon the action of a base undergo the nitronic rearangement
cf NM:
CH3-NO2 + NaOH --> CH2-NO2(-) + Na(+) --> CH2=N(O)-ONa
The later compound is deep orange to deep red-brown!

This may or may not be the reason for the bright yellow color of some batches. I hope you understand some chemistry.

===

Edit: I in no way intended to imply that you are kewlish. The fact that you are attempting to perform the drop test with meaningful results proves that you are not kewlish and have an interest in science and safety. The statement that I hoped you understand 'some chemistry' was meant to be an understatement. I did not learn about tautomers until O. Chem. II. Few people take this course. (I don't comment on many threads. Your scientific aims merit some discussion.)

Just because you do not see any red crystals does not mean that the impurity is nonexistent. During the formation of your TNP crystals, some impurities are trapped within the crystal's structure. The purpose of recrystallization is to obtain a crystal without those impurities.

The above post goes a long way to explaining the 'over-yellowed' color.

[peppovsky]

Of course I understand chemistry, I would never go through dangerous synths without knowing exactly what I was doing. I do not consider myself to be kewlish ;)

Anyhow, the synth went along just as the instruction said, I used > 99% const H2SO4, Technical grade KNO3, and pure ASA from pills. After the addition of ASA to the H2SO4, the mixture was colored red when KNO3 was slowly added over an hour, while stirring on a magnetic stirrer and hotplate (temp was kept at 70 deg C). Even the known foam was formed when I added it all to a liter of ice-cold water (at this point, btw, the mixture became yellow immediately). The filtered material looks just like in the pictures, and I've got NO red crystals what-so-ever. The only two things which are weird are the over-yellowed color of the crystals, and the fact they stain everything in strong yellow - just like you'd expect from styphnic acid.

As I've said before, I'll let the powder dry for a couple of days before doing anything else with it.

[Charles Owlen Picket]

Should the TNP stain water with a strong yellow color, or is it a tendancy of DNP?


The stain coloration (all nitrated phenol is a dye) won't give give you clues to purity. Melting Point is perhaps the easiest and fastest method to determine what you have. It is the only method I would trust without having a good lab to work in to sort out the issue.

Impurities will alter toward darkening. Analytical grade PA is very rare but reagent grade material is available and when dry is such a very light yellow as to be close to white but with a bright yellow cast in the crystals.

Crystal shape MAY be helpful when determining purity. So a look in the microscope is worth a try. However, the shaving phenomenon of bulk material may yield altered forms and mostly crushed specimens. [See Crawford, Yardly, & Beard 1936 RCS]

[KrIsPy]

In my experience, salicylic acid (SA) provides a less yellow product than ASA and it requires less sulfuric acid. You can make SA from ASA though saponification with sodium hydroxide.

That sounds interesting Enkidu. I'm just curious if you could either fill me in or redirect me to another site or page for more information on the saponification of ASA with NaOH, as in the amounts of NaOH to ASA.

I also have a question about the use of NaOH in this process. Since saponification is basically putting an ester in basic conditions, and also since I have read that it can be performed with either NaOH or KOH, I was wondering if a mixture of NaOH and KOH would function in this hydrolysis.
-I ask because I have a drain opener which is a fairly pure mixture of KOH and NaOH.

Also, if you have any information on the altered synthesis of TNP using salicylic acid. Reducing the required amount of H2SO4 and increasing the impurities/unwanted coloring of the yielded TNP would be nice. :)

[Enkidu]

@Krispy: Hydrolysis of Esters. (http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch20/ch20-3-3-1.html) I think your drain opener will work fine. Just use a concentrated soln. of your hydroxides and add heat. If you try to work out proportions, remember that the carboxylic acid will be deprotonated first.

If you don't have a vacuum filtration apparatus, it will be difficult for you to filter the SA. After precipitation with an acid (presumably muriatic acid), you will get a very, very fine powder. You don't get crystals that settle to the bottom.

I generally don't use less acid even if I use SA as my starting point for picric acid. The mix can become quite thick and difficult to stir effectively. The only reason I could foresee that would make you want to use less acid is if you had difficulty acquiring it. I have some notes on proportions somewhere, but I don't know where they are. Sorry.

[peppovsky]

I've done a "melting point test" today that was actualy a shame to chemistry work - I put some "TNP" in an oven and slowly heated it until it melted, then measured the temp. At least, that what I expected to do - instead, the termo reading progress to slow, and I couldn't hold it there because the heat from the oven was too great for my hand. :(
Next time I shall put it in a test tube with a termometer and warm it slowly, until the melting point is reached, onto complete melting, then repeat it a few times to verify.

@ Charles Owlen Picket: As written above, I've tried to make a (shameful) melting point test, and will try to do it again (and again) better next time.

@ Enkidu: Thanks for the info and especially the link to the Organic Chemistry On-Line Learning Center. I've read the SM thread(s) and I now realize I actually know much less about TNP then I thought before. More reading shall be done!

...To my "TNP" favor, btw, I should mention that the more I crush the crystals, they still remain the same color. That doesn't mean a thing, but at least I don't have big-sized impurities trapped inside, only perhaps very small-sized ones. :D
More drying gained nothing in color change yet. Still a bright yellow instead of yellowish white. At lesat I've found today my long-lost tubes - 13 of them - all 5cm diameter, 1m height, so although my crystal shape is not that promising, I shall make the brick drop test in the next few days (hopefuly).

Just two last things. First, the "kewlish" remark was not a result of me getting offended or anything. I'm still a newby here after all, and I try to show I don't mean to stay one for long. ;)
Second, I don't study Chemistry, I study Physics. My knowledge in Chemistry comes from self tutoring and experiments, but this should change soon, since next semester I'm taking Organic Chemistry I course in my university, and after that - probably Org.Chem.II. To my belief Org.Chem. is the most interesting subject in all Chemistry, and I do not intend to miss my oppurtinity of learning it formally. :)

[peppovsky]

Just a quick note - I've found out that my (suspected) TNP is way whiter when pressed. Maybe this is a good sign.

Today was my first HE detonation - not that big or sofisticated, but as I'm in the pyrotechnics buisness for serveral years now, and always thought of advancing to HE - I'm very happy. I've mixed some Pb(NO3)2 and my suspected TNP (about 100 mg total), and poured them on an aluminum sheet (made of several layers, of course). Then I heated that mixture slowly, until it became reddish, and let it cool down. I then put it on the stove, lighted it, and BANG! wonderful small explosion, with a very nice pop sound. :) I repeated that about 15 times, 3 of them with Copper powder instead (made a smaller explosion - with lots of black smoke).

[KrIsPy]

I don't know how to shrink the picture size. It displays larger than normal on this forum. You can cut them if need be NBK or someone else.

I've completed a TNP synthesis for the second time. This time, I used a plastic stir stick, and at least a half inch of it dissolved (its that Japanese looking chopstick in one picture.) Also, I didn't purify my aspirin, using Bayer Genuine.

The final yield after letting it sit overnight was black goo, due to the plastic, aspirin or who know what.

Here's the photo documented procedure. Sorry for the large pictures.
http://aycu19.webshots.com/image/17458/2002361103564665420_rs.jpg (http://allyoucanupload.webshots.com/v/2002361103564665420)
Aspirin
http://aycu23.webshots.com/image/13982/2002325788276451628_rs.jpg (http://allyoucanupload.webshots.com/v/2002325788276451628)
http://aycu09.webshots.com/image/14488/2002373476742555561_rs.jpg (http://allyoucanupload.webshots.com/v/2002373476742555561)
Sulfuric Acid
http://aycu33.webshots.com/image/15672/2002313838063892629_rs.jpg (http://allyoucanupload.webshots.com/v/2002313838063892629)
H2SO4 + ASA
http://aycu33.webshots.com/image/15512/2002385685234120000_rs.jpg (http://allyoucanupload.webshots.com/v/2002385685234120000)
Ammonium Nitrate
http://aycu04.webshots.com/image/17163/2002385186518476616_rs.jpg (http://allyoucanupload.webshots.com/v/2002385186518476616)
http://aycu36.webshots.com/image/15435/2002353111716944754_rs.jpg (http://allyoucanupload.webshots.com/v/2002353111716944754)
http://aycu02.webshots.com/image/13961/2002345854905829986_rs.jpg (http://allyoucanupload.webshots.com/v/2002345854905829986)
http://aycu07.webshots.com/image/16606/2001106790365492484_rs.jpg (http://allyoucanupload.webshots.com/v/2001106790365492484)
Final TNP = Ice water
http://aycu14.webshots.com/image/17133/2001121795713913055_rs.jpg (http://allyoucanupload.webshots.com/v/2001121795713913055)

[209]

Nice pics! Thank god for high speed internet :D! Hmmm, wait a minute, is that a fricken dress-like shirt your wearing for a TNP synth??!! Were is that lab grade chemical resistant apron? :)

[nbk2000]

Poor form, ol' chap, to in-line giant pictures which bring dial-up connections to their knees.

Also, yellow kitchen gloves are made of latex, and hot acids eat latex for breakfast. Nitrile rubber gloves are what you need for handling any hot acids, especially mixed acids like nitration mix.

Did you read the 13 pages we have here, and the 8 pages over at SM.org, prior to your failure?

If you had, it's very likely that you wouldn't have failed so badly. Learn from other peoples mistakes, and don't repeat them yourself. :)

[peppovsky]

KrIsPy: Why didn't you extract pure ASA from the aspirin tablets? It's not a difficult process, and it will garantee better results - plus, it's the only step that is sure to work everytime. ;) Try using MeOH/EtOH or Acetone for that purpose.

UPDATE (my turn again) : I've dried a small ammount of "TNP" in my elaborated dissector - a tupperware box with a stand in the middle and CaCl2 for moisture absorption (see picture here: http://i167.photobucket.com/albums/u146/peppovsky/TNP_tupperware.jpg) . It does look better now, much whiter, but when looking from up-close one can see contaminations (or hopefuly undried parts). But hey, considering the fact it's my first TNP synth, and my 3rd HE synth (two tries of Styphnic acid that went wrong) - I'm considering this a success :) (provided it detonates in brick experiments that shall be done soon)

The dried TNP on a plate:
http://i167.photobucket.com/albums/u146/peppovsky/TNP3.jpg

An image that exaggerate the contrast to show the contaminations that are less easily visible in the normal pic:
http://i167.photobucket.com/albums/u146/peppovsky/TNP3_contaminations.jpg

[KrIsPy]

Sorry about the huge pics. I was either going to post them big or not at all since I didn't have time.

I know it is poor form to not wear appropriate lab gear, but I have neither Nitrile rubber gloves nor a chemical resistant lab coat. The last picture was not what I was wearing for the synthesis, just what I had on at the end when pouring. I was wearing a normal apron and those crappy little lab gloves under the kitchen gloves. At least I got some goggles.

As for reading before hand, I did read all 13 pages here, but not on SM. It was pure stupidity to use a plastic stirring rod, but I just misjudged how much would melt and how fast it would do so. As for not purifying my aspirin, last I didn't have time to let it air dry for an hour or two and last time burn the ASA after extracting it trying to quickly dry it. I just didn't bother.

I still don't know why it is black goo. I guess the plastic since most things turn black when contacted with sulfuric acid. So plastic + TNP = black goo.

[peppovsky]

Next time, prepare the pure ASA ahead, that way you'll have plenty of time to let it dry.

Edit: Actualy, if you filter it with EtOH you don't need to wait that much either.

[Enkidu]

I still don't know why it is black goo. I guess the plastic since most things turn black when contacted with sulfuric acid. So plastic + TNP = black goo.

Concentrated sulfuric acid plus just about anything (cloth, paper, plastic, wood, and probably your finger or eyes) makes black goo. More than likely the fillers that you neglected to remove caused the majority of your problem.

For future reference, pictures alone do not satisfactorily document an experiment. A detailed lab notebook must be kept. If you want help, post your notes along with your questions.

[KrIsPy]

Thanks.

Concentrated sulfuric acid plus just about anything makes black goo. Yeah, that's pretty much what I said. Therefore, it could be anything that turned the TNP black. :)

More than likely the fillers that you neglected to remove caused the majority of your problem.
Definitely could be, considering I used Bayer, which probably is filled with buffers. I have done a few burn tests on the "goo" however, and it does burn violently, but also sputters (contaminants).

For future reference, pictures alone do not satisfactorily document an experiment. A detailed lab notebook must be kept. If you want help, post your notes along with your questions.
I realize that, and would have posted detailed notes/observations from my procedure, but, again, I was pressed for time. In the future... ;)

Final question: By placing TNP in warm acetone, does the TNP dissolve, leaving the contaminants, which could be filtered out, leaving relatively pure TNP? Is this a time to UTSFE?

[peppovsky]

UTFSE is always the right choice. This time, though, I shall provide some info: http://www.chemicalland21.com/lifescience/phar/ACETYLSALICYLIC%20ACID.htm
(look down @ "SALES SPECIFICATION")

Just take the pills, crush them, dissolve this in warm Ethanol, Filter out the binders - and let it evaporate for the night. Again - the easiest part of this synth.
Bayer's product is filled, as far as I remember, with potato starch and Dextrin (I could be mistaken - read what is says in the paper inside of it). Both have almost no solubility in Ethanol. If in doubt - filter a couple more times.

[KrIsPy]

Ok, great. Thanks peppovsky. Next time I will definitely purify my aspirin.

I think when calculating the theoretical amount of ASA I should have had according to the fact that each tablet contains 325mg Aspirin (ASA), I discovered the small bottle I had should have 7.5-8g ASA. When I didn't purify it and weighed all the aspirin tablets, it was 10g. That leaves 2-2.5g of binders in the aspirin I used...plenty to trash the yielded TNP.

I am aware that aspirin can be purified as mentioned, but I was wondering whether TNP would dissolve in acetone, but the contaminants wouldn't.

Anyway, I already dissolved a small amount of my black goo TNP into acetone and it all dissolved, including the impurities, so I answered my question. There is now some light brown acetone. Since there is nothing to filter out, I don't see how this will help to purify my TNP.

Should I just evaporate off the acetone now, even though it can't be filtered?

[peppovsky]

...Errr, yeah - you said "TNP" not "ASA". My mistake.

I say - let the Acetone evaporate, then keep that batch aside (or throw it), and make another one that is purer, without binders or glove/stirring-rod parts.

[nbk2000]

2/3 alcohol-1/3 acetone makes for cleaner crystals, quicker.

[KrIsPy]

Thanks NBK and peppovsky. NBK, I assume you mean standard 99% isopropyl alcohol. Unfortunately, I ran out, but thanks for the advice. I'll do next time.

As for dissolving TNP in any solvent, is it the recrystallizing that causes the crystals to form separately from the contaminants, the evaporation of some of the contaminants (not quite sure how that would work), or some other process that purifies the TNP?

I just don't get why dissolving something in a solvent and then evaporating out the solvent could actually make the substance dissolved any purer. Then again, all kinds of stuff can happen with recrystallization, so what do I know.

In regards strictly to color, it seems others have gotten rid of color contaminants using this method of recrystallization. Is this true. Doesn't the color transfer to the solvent and then back to the TNP once the solvent is gone?

[Enkidu]

NBK, I assume you mean standard 99% isopropyl alcohol.

No, he means ethanol.

As for the rest of your post, get a chemistry book and learn about recrystallization. To put it plainly, you have no clue about that procedure. BTW, your TNP batch is ruined and should be discarded.

[fiknet]

KrIsPy: http://i167.photobucket.com/albums/u146/peppovsky/TNP_tupperware.jpg)

Is that a metal container your using with bits of CaCl2 spilt in it? That could be a source of contamination.

[peppovsky]

Of course not - the glass plate (seen from up-close in the TNP image), is sitting on that metal ring, so it doesn't come near metal and/or CaCl2 ;)

[Charles Owlen Picket]

I just don't get why dissolving something in a solvent and then evaporating out the solvent could actually make the substance dissolved any purer. Then again, all kinds of stuff can happen with recrystallization, so what do I know.

Here are some little clues: hot water is a damn fine solvent, you don't evaporate anything in standard RC purifications, purifications provide stability and thus safety for energetic materials, and finally... find and read these books: Organic Chem Lab Survival Manual -J. Zubrick & Advanced Practical Organic Chemistry -M. Casey

[KrIsPy]

Thanks Charles Owlen Picket!

Hot water is a damn good solvent...but it takes forever to evaporate because of its high specific heat 4.18 J/g vs. acetone's 2.14 J/g. Still, I guess I'm not really under any time restraints.

As for the books, thank you very much. I love it when someone, instead of criticizing and saying to read some chemistry books, (of which I have read plenty), gives a specific book on the topic which you desire to learn about.

[Enkidu]

You don't evaporate anything in standard RC [recrystallization] purifications

Hot water is a damn good solvent...but it takes forever to evaporate

Hot water is a damn good solvent, but you don't evaporate the water for this proceedure.

I love it when someone, instead of criticizing and saying to read some chemistry books, (of which I have read plenty), gives a specific book on the topic which you desire to learn about.

Please don't think that I was insulting your intelligence. If I was insulting your intelligence, I would have told you that you are a kewl and that it's hopeless for you to try to learn or I would have simply ignored you. If you remember your question about saponification, remember that I fully answered your questions. However, I didn't do the work for you, because that is part of the fun and the satisfaction in this hobby. The books that Charles has told you to read contain many valuable laboratory procedures, everything from basic safety (don't use flame around organic solvents) to more advanced principles, such as recrystallization and (I assume) thin layer chromatography. It would be beneficial (and indeed, is necessary) for you to read those or similar books in their entirety.

I will see if I have any worthwhile Lab Manual .pdfs; if so, I'll upload them. Check the 'Lots of Rapid Share Links' thread soon. A simple PM to me that says 'What books should I read? Can you please help me with this subject?' would have elicited the same response. I am happy to help anyone who wishes to learn. This offer extends to all other forumites as well.

Remember, ignorance on a subject is no reason to be ashamed.

[peppovsky]

Enkidu: About the picture I posted - although it is not easily judged from a photograph - is that closer to the shade of white/yellow TNP should have, from your experience?

[Alexires]

KrIsPy - You have said quite a few times that you "don't have time", etc.

Why exactly is that? Is it you want to go out with your mates on a Sat. night and you want to get it done before so you can show it off? Is it because you need it desperately for next weeks rag head attack against Scientology?

I advise that you MAKE time. Either read through the procedure and find break points (such as when you are waiting for the ASA to re-crystallize out, etc) and you don't HAVE to do anything in the next 10 minutes afterwards.

If you don't make time, you will rush, and then you will have an increased chance of ending up like your name, either with or without fingers.

We have helped you and pointed you to where you need to go, what you need to do, and what you need to read.

Go do it and learn something. Remember, you shouldn't be asking what The Forum can do for you, but what can you do for The Forum?

Also, I just would like to ream you out for those massive pictures. I have dial up and it took me 30 minutes to work out why everything was going so slow, and then I sat there and waited patiently for your pictures. Go search about the crop function. It even works in paint.

[Enkidu]

@peppovsky: The picture that exaggerates the yellow impurities is quite interesting. Good job with the pictures. The whiter parts appear to be very white indeed (like my picric acid). However, many times I think that I've got a relatively white batch, but, on comparison to a previous sample that I've saved, I realize that it's not as white as I originally thought.

Keep in mind, that we, as chemistry hobbyists, are unlikely to get ACS grade products, especially if you're using aspirin and drain cleaner. It's unfortunate, but it's a fact of life.

I don't know how much picric acid you've got left, but, if you do want pure TNP for your drop tests, do another recrystallization from boiling water. This time, don't add any additional cooling, but instead allow your solution to slowly cool to room temperature, and then filter those crystals. You should have whiter crystals. Then, after you've filtered that crop of crystals, you can put the mother liquor in the freezer for a bit to precipitate the rest of the yellower crystals. Even if they're yellow, they make a nice pop. :D

[Charles Owlen Picket]

I honestly believe that once you learn the concepts involved in re-crystallization you will snap to a heck of a lot of other issues related herein. Learn what a polar solvent is, etc, etc. Now picture this:

Water is a solvent; acetone is a solvent, ethyl acetate is a solvent, ethanol / methanol is a solvent, as are chloroform, toluene, & MEK, etc, etc, etc

Acetone is miscible in water! Toluene is not but acetone is miscible in toluene.....Start to get the idea? You can dissolve materials on one solvent to access another soluble in another which they both have in common.

Re-crystallization generally does not employ evaporation. The STANDARD method for RC TNP is to use HOT water; the TNP will become soluble in such 100% at a certain temp & at a certain ratio; the temp drops and out comes your purified TNP. No evap necessary.

You are on the threshold of the science end of things -> and that is what will give you more info than any single discourse could ever. I noticed that Enkidu set up a download for some good chem textbooks: I would grab 'em fast and read them IIWY.

[nbk2000]

Miscreants may be miscreable in boiling oil. Everything else though, is miscible.

[peppovsky]

Enkidu: recrystallization from boiling water to room temp gave some VERY nice crystals - they even shine a bit :D
I still have some more to filter, but the results speak for themselves - two images:

The batch (not completely dry, and partialy pressed, hence the color differentiation):
http://i167.photobucket.com/albums/u146/peppovsky/TNP4.jpg

The exagerrated contrast version, showing a unified color of the batch:
http://i167.photobucket.com/albums/u146/peppovsky/TNP4_contaminations.jpg

[peppovsky]

Btw, is TNP storable under Ethanol/Acetone as well as under water? That would probably dry faster when needed.

[nbk2000]

It would be dissolved in ethanol/acetone, so it wouldn't 'dry', so much as recrystallize when the solvent was evaporated off.

[nathan]

I just wasted a day and some precious chemicals trying to synthesize PA.

I used lab grade KNO3 and isopropyl alcohol purified ASA but my PA? Won’t detonate from shock or heat.
When I added the ASA to the H2SO4 and heated, instead of dissolving completely the mixture thickened. The miniature grains of ASA were visible in the mixture.
After I took it of the heat (a water bath),the mixture grew less thick and turned a dark brown or black. The ASA was still visible in the mixture. I went ahead and nitrated it slowly but even with miniscule amounts being added, the mixture started to foam up to the point of overflow.
After a while it stopped foaming and I added the Potassium Nitrate a little more quickly. After precipitating the crystals I dried and tested with no result. Instead of intensely bitter, the crystals tasted sour with a mild bitter aftertaste.

The only thing I can think of is that I used 80% Sulfuric acid instead of the stated 98%.
How would a lower concentration of H2SO4 effect the synthesis?

[Zajcek]

Instead of intensely bitter, the crystals tasted sour with a mild bitter aftertaste.


OMG, you actually tasted your product :eek: or you gave it to someone else (enemy)? True chemist never tastes chemicals.

Picric acid is carcinogenic and causes liver and kidney damage.

Small quantities will not detonate from heat, it will only burn with yellow-orange flame and black smoke. (If you heat it with lighter or matches), it will not even detonate from mild shock when free of metal picrates. When I did a "hammer test" on it, I had to hit it quite hard to detonate it.

There can be several reasons why it did not detonate, maybe your detonator was to small, or there was still some moisture in it, maybe it was not pure enough. When I made it for the first time, I was quite surprised how insensitive it was when moist. (I thought that it was very sensitive because of old chemistry books)

When I made picric acid last time, ASA + sulfuric acid thickened after some minutes of heating in oil bath, but then everything went into solution, which was dark brown-black colored. I think that this was normal, since I got nice light-yellow crystals. I detonated it with 1g of HMTD. (I know 1g is overkill, but I had to use it because it was sitting around for quite some time)

Please provide some more details on your testing method.
How many primary explosive did you used, which was it, how did you test it for shock sensitivity, what did the crystals look like, what was the temperature during the reaction....

[Enkidu]

@nathan: Because you don't post any detailed notes at all, no one really knows what could have gone wrong.

Have you read ALL the threads here on RS and SM? If not, go do that. If you had, you'd know that the dark color after you dissolve the ASA is normal.

Picric Acid is hard to detonate. The fact that it didn't detonate could easily have been your fault, as opposed to the fault of your explosive. (I.e., not enough confinement or not enough primary.)

One thing that the low concentration of sulfuric acid could cause is an incomplete nitration of the ASA. Then you'd have DNP (or maybe even 2,4-dinitrosalicylic acid, which I suppose is possible). Picric Acid contaminated with DNP would be harder to detonate.

[nathan]

I tasted a miniscule amount of the substance but your right, that was pretty stupid….

I read all the threads on the subject and I was aware that the dark color was normal when the ASA is dissolving, but I didn’t see anyone else mention uncompleted dissolving of the ASA (after 20 mins on a water bath) and the maintained thickening of the mixture. I could have missed something however…

I tested the chemical with shock from a hammer and a weak detonator (300mgs AP) I would have used a more powerful detonator but I was under the impression that PA was pretty sensitive to shock.

I put a very small amount over the flame of a burner and it only melted, turned black, and started to burn with a yellow flame. I later tested it with some BP with AL mixed in with no results, the chemical didn’t even burn.

The crystals are extremely fine, almost a dust. They are a reddish brown color. They are also very soluble in water, originally when I added water the second time ( ALENGOSVIG1’s Picric Acid 1: step 13) and precipitated the crystals I lost more than half my original yield. During the nitration I kept the temperature below 100deg. F.

[Bert]

Dring the nitration I kept the temperature below 100deg. F.

The reaction finishes at a temperature in the vicinity of 120 C.

[Enkidu]

@nathan: I have stained my fingers with Picric Acid, and then I tasted that. It's very bitter. I don't think it's that terrible for you. IIRC, the guys over at SM said that Picric Acid is a mutagen (and therefore also a carcinogen). You might not experience any trouble, but your kids could. :eek:

You've stated you used isopropyl alcohol. If you used standard 70% rubbing alcohol, then you will have many impurities (binders and fillers) in your ASA.

Also, like Bert said, the reaction FINISHES at about 120*C. Don't try to start out at that temperature.

You seem to have loosely followed Alen's method. I think that the standard method for making Picric Acid is Rosco Bodine's. Read my previous posts in this thread for information on his method.

[209]

I am going to make some TNP in the near future, but don't intend to use it right away. I would like to store it underwater but they say that TNP is readily soluable in water. Can put it in water and store it on a shelf in my lab in a glass jar?

I understand that the shelf life can be quite high if it is stored correctly. So If I put it in water would it not all dissolve? I guess you could filter it out when you are ready to use it by putting the container in the freezer. Would the TNP percipitate for filtering?

[Enkidu]

@209: The standard method of storing Picric Acid is under water. It's only 'readily soluble' in water at high temperatures. If you're worried about getting every last gram out of solution, you could use fractional crystallization.

To store your TNP, put it in a jar, then just cover it with water.

Wasn't this just covered on this page or the last one? :rolleyes:

[209]

I am such a dumbass :mad: .

I was completly walking around in the fog this morning while I was making some TNP. I already have purified almost 500 grams of ASA and I decided to put some to use. I completly forgot that picric stains skin yellowy.

FUCK! Now I look like a damn clown because my hands are all fucking YELLOW:mad: :mad: . Does anyone know a trick to remove the yellow stains? If not, how long does it take for them to disappear??

[Cindor]

Uhh man thats highly toxic ! Don't you wear gloves ?!?!?

You may tray with concentrated Hydrogen Peroxide...

[zeppelin69]

Does anyone know a trick to remove the yellow stains? If not, how long does it take for them to disappear??

I have tried many different ways of getting rid of the stains. 30% hydrogen peroxide didn't work for me, in fact I haven’t found anything else that works other than something that dries your skin out, and makes it peel off. If you don’t feel like going that route (and I wouldn't blame you) you can wait about a month for your skin you peel off on the stains, on its own. Any stains on your fingernails will take even longer.

By the way, the best excuses I have found so far (because you can't exactly tell everybody why your are really yellow) are that you were: painting, doing a project with yellow markers or highlighters, or if it just so happens to be that time of year, you were dying easter eggs :D

[209]

Yeah, thats the primary reason why I have stayed away from picric acid for some time, but sensitive primaries really begin to wear on the nerves. I am kinda freaked, is anything going to come of the stains, its not like my pubes are going to fall out and my internal organs are going to dissolve right? :eek: :eek:

This isn't going to impare or contradict my health is it? There are only a few stains, don't want to be an alarmist here, but nothing is going to come of this right?

[Enkidu]

As I've said before, Picric Acid is a mutagen and therefore also a carcinogen. The amount you got on your skin probably won't have any effect on you or your kids. If, by chance, it does make all your pubs drop out... let me know immediately. I could do with a few fewer pubs. :rolleyes:

[zeppelin69]

Yeah, thats the primary reason why I have stayed away from picric acid for some time, but sensitive primaries really begin to wear on the nerves. I am kinda freaked, is anything going to come of the stains, its not like my pubes are going to fall out and my internal organs are going to dissolve right? :eek: :eek:

This isn't going to impare or contradict my health is it? There are only a few stains, don't want to be an alarmist here, but nothing is going to come of this right?


I had the same problem a few months ago.. and I am still here to tell about it. Albeit on crutches, but that is another story...

Honestly though, I wouldn’t be worried at all. My main concern would be how to make your hands less noticeable in public so that people don't think you have a crazy skin disease :p

Just learn from your mistake, wear gloves next time, and I highly doubt anything will come of it.

[209]

Ahh, life, it feels good! :D :D. The stains are small and arn't particularly noticeable. I went on an MSDS on TNP and It was sayin shit about how it's a mutagen and highly toxic (not that it isn't true). Pretty scary stuff, not to be fucked with.

It's funny how when your freaked about something (maybe its touching a chemical, or thinking you breathed in a harmful gas) you begin to think every little thing that you sense on your body you think your dying or something. You end up thinking your head is throbbing and you hand begins to twitch..... Oh man, you can begin to overreact way to much. At this rate, I am only going to have another 75 or so years left to live :D

[Bert]

Picric acid was used as a topical treatment for burns at one time. It's not going to kill you too quickly in small ammounts on unbroken skin.

The first time I saw some, I was at a pyro shop of someone very traditional. He was making pyrotechnic whistles the good old fashioned way, with Potassium picrate. I asked if it was as nasty tasting as Weingart and Lancaster mentioned, and he said "try some!" I did, and he got a good laugh at me spitting yellow trying to get the taste out of my mouth. I haven't died yet, and the extra eyeballs and scales I've grown make it easier to approach reef fish while SCUBA diving.

[Zajcek]

You can speed up skin peeling process with Alpha hydroxy acids if you do not want to wait for the skin to restore itself by its natural way.

Some examples what you can use:
fruit acids
Azelaic acid
DL-mandelic acid
citric acid
salicylic acid
lactic acid
glycolic acid
phenol
combinations of the above

Here are some examples and information.
http://www.plasticsurgery.org/patients_consumers/procedures/ChemicalPeel.cfm
http://en.wikipedia.org/wiki/Chemical_peel
http://www.healthyskinportal.com/procedure/Chemical%20Peels/
http://www.atsofusa.com/gpage7.html
I hope I am not advertising, because some pages are commercial, but they do tell us some information on chemical peeling and some formulations.

For you safety do not use phenol, because it is too strong.

My experience:
When I was working something with DL-mandelic acid dissolved in ethanol, my whole hands and fingers started peeling in couple of days. There was also some sulfuric acid in the mixture.
I use azelaic acid for acne treetment. It is 15% solution in ethanol. My skin was iritated and was peeling of a bit until it got used to it.

[Rbick]

Reading some of this stuff kind of worries me. I think your best bet is just to ware gloves while making Picric Acid and avoid touching it at all, since as mentioned above, it is highly toxic and mutagenic... I would recommend lab gloves you can buy off the internet and many stores. Don't think about improvising with your dish washing gloves, H2SO4 eats though latex like nothing! Ever since I researched about PA after already getting my hands stained, I realized it was a bad idea not to be wearing gloves, and have worn them ever since.

Point being, I wouldn't feel more comfortable knowing I can remove skin stains by adding MORE chemicals to my skin. You actually want to cause your skin to come off faster? Don't worry about your skin color, worry about your health and avoid touching it at all. Well, unless you want cancer or a 6th finger growing out of your palm.

EDIT: I just read that PA was used as an antiseptic and for skin dyes. So why are people saying its mutagenic? Is it in large quantities that it is dangerous? And if so, what would be considered a dangerous amount? I'll do some more reading. Either way, my statement still stands, I would rather just avoid touching it at all.

[Enkidu]

'Doctors' also used leeches as the 'remedy' for many illnesses.

From a J.T. Baker MSDS,

Hazard Information: CAUSES SEVERE EYE IRRITATION. HARMFUL IF SWALLOWED, INHALED OR ABSORBED THROUGH SKIN. CAUSES IRRITATION TO SKIN AND RESPIRATORY TRACT. MAY CAUSE ALLERGIC SKIN REACTION. AFFECTS LIVER, KIDNEYS AND BLOOD.

Toxicology Information: Oral rat LD50: 200 mg/kg. Investigated as a mutagen.

That means you'd have to ingest (and hold down) quite a bit of it to die on the spot, but that doesn't mean it's not bad for you.

[Zajcek]

They used picric acid because they did not have enough information about its toxicity or because the benefits the usage were greater than risks.
Their resources were probably limited during the war, so they had to use what they had.

It is probably the same as with the Chloramphenicol, an antibiotic which has been used quite often in our country, but now its use is limited.
They did not knew that it can cause aplastic anemia, leukaemia and bone marrow suppression, but they do now, so they prescribe it only if the benefit of treatment is greater than risk and if nothing else helps. It is now used in eye drops and creams to treat eye infections.

And I agree with you. Acid resistant gloves are the best solution. You should avoid contact with chemicals in the first place, but if you do come in contact and stain your skin, it is good to know how to get it of as soon as possible, especially if you did something with that chemical, that is against the law....
In that case, applying some chemicals with minimal toxicity to your skin, to make it peel off is better than going to jail.

[megalomania]

I deal with concentrated acids all the time wearing latex gloves and they don't get eaten right away, or at all. I will change them quick, but that's because I am worried about transferring conc. acid to the items I am touching. Having conc. sulfuric on your gloves makes everything feel oily and slippery, the easier to drop expensive glassware full of acid onto my shoes. The only thing I have found that eats through latex quick is dichloromethane.

Don't take everything to heart that a MSDS tells you. They predict dire doom and gloom for every chemical. Many of the toxic effects of chemicals are cumulative, i.e. after chronic use in the workplace. Yes, it may be mutagenic, tetragenic, carcinogenic, cause organ failure, the whole nine yards, but only after years of dealing with the stuff at the factory all day, every day.

The problem is the MSDS won't tell you if the chemical you are using can kill you in hours, or after a decade of chronic exposure. Telling the difference is something you learn from experience in the chemical trade.

[209]

This new batch of picric acid is really weird. It doesnt react at all to flame, the only thing it does is melt. How much AP or primary do you use to detonate your picric? I also couldn't manage to detonate it with a hammer, how much force does it take?!! After all this is a secondary with a medium sencitivity, shouldn't it detonate when struck sharply?

[Rbick]

All of the picric acid this guy that I know has made has always melted when exposed to flame. Have your past batches acted differently? The point of decomposition for PA is 300 C degrees. While butane from a lighter burns hotter than this, heating the PA to over 300 degrees would take some time.

While detonating, this guy usually uses .5g AP, which may be too much, but he always uses too much in his caps. Or, even though it is a bad idea, he uses PA mixed with AP as a booster. Mixing an acid with an organic peroxide can't be safe... Not sure on that though :p

As for the hammer test, he has never tried that with PA, so I couldn't tell ya. I assume it would go off if hit hard enough?

[209]

I was absolutly wacking the shit out of it, I put a damn hole in the floor of my garage, so I would say that it is pretty darn safe to handle, pack and detonate without fear of premature detonation. I am glad I didn't chuck it out, I dried it, tried to make it do something and was going to chuck it because It didnt do anything. I dont have any AP right now ( I never store it) and am too lazy to make any so I will try detonating it tomorow.

[Enkidu]

All of the picric acid this guy that I know has made has always melted when exposed to flame. Have your past batches acted differently?

If I lay a match on top of a small pile of my TNP, it burns after a few seconds with a big whoosh.

[Rbick]

Strange thats never happened to me. Perhaps it was because when the flame was put onto the TNP, it was still slightly wet. So I guess make sure your stuff is dry.

And TNPs impact sensitivity is about 7.4 Nm, which is equal to that of HMX and RDX. TNT is at about 15. So as you can see, it isn't all that sensitive to impact and your hammer might not be doing the trick.

[Flamethrowa]

Guys, guys! Intentionally peeling your skin off??

I don't know how badly you've been stained, but previously I've managed to attain a few small yellowy patches on my skin. Washing with bicarbonate as quickly as possible helps, as well as using hot soapy water. I also have found a heavy duty hand cleaner with little bits of pumice and lots of petroleum distillates. Yes, it's abrasive, but it doesn't leave your skin chapped and raw.

I'm not sure how much bicarbonate helps, but my theory would be it either neutralizes and produces a more soluble sodium salt, or by raising the pH at the surface of your skin you can prevent with PA from reacting with the keratin in your skin (which will turn your skin weird orangey brown colour AFAIK).

[Exothermic]

Just referring back to a topic mentioned in the archives, about turning Trichlorophenol into Trinitrophenol from TCP.
Use
Although people came to the conclusion that TCP does not contain enough pure Trichlorophenol to actually use, theoretically if it was pure then I believe it would be possible.
Paragraph
By nitrating Trichlorophenol you could convert the chlorine molecules into NO2 and ONO2 molecules, to give a similar structure to Trinitrophenol (most probably form-Trichloro-trinitrophenol). I believe this could be done, because it’s the similar process used in the manufacturing of TATB. In the production of TATB trichlorobenzene is converted into 1, 3, 5-Trichloro-2, 4, 6-trinitrobenzene by nitrating it with nitric and sulphuric acids.
Breaks
Is this theoretically possible, if the Trichlorophenol was pure in TCP? Or have I got my facts wrong?
nbk2000

[Enkidu]

Nice try. As nbk says, chemistry isn't 1 + 1. You need to know something about aromatic activators and deactivators to propose the synthesis of anything that involves attaching functional groups to an aromatic ring.

The short answer is no, I don't think you could make TNP from trichlorophenol. However, industry starts with monochlorobenzene to avoid the oxidation losses incurred when using a feedstock of phenol. If you want to know more about why you can't use trichlorophenol or about the monochlorobenzene process, send me a PM.

Erm... now permit me to tear apart your post...

By nitrating Trichlorophenol you could convert the chlorine molecules into NO2 and ONO2 molecules, to give a similar structure to Trinitrophenol (most probably form-Trichloro-trinitrophenol).

One moment you say that you going to convert the -Cl to -NO2, while the next you say that it would probably form a 'trichloro-trinitrophenol' compound. Pose your theories as questions, especially if you have two contradicting ideas.

Second, you say that you want to convert the -Cl into a '-NO2 or -ONO2.' Considering that you are not synthesizing a nitric ester, why the -ONO2? That isn't even a functional group.

Please post your question in the appropriate thread. This thread is about TNP from aspirin (or maybe phenol), not trichlorophenol. As long as you have a reasonable question or idea, it's not necromancy to pull up an old thread.

Try to throughly think through your idea before you post it. Rough drafts and sitting on it for a few minutes help.

[rangegal]

Does anybody know if I can use acetone (instead of isopropyl, since all I have is 70%) as the solvent to purify the ASA?

Because I just tried it... and barely anything dissolved, theres still a big layer of wet white stuff under a layer of acetone so either theres a shit load of binders and stuff in my aspirin, or it's just not dissolving.

CAN it work? Did I not use enough acetone possibly? Or am I a newb about to hear a rant about the solubility of ASA?

[totenkov]

Yes!!

Acetone works far better for purifying ASA than IP. Just dump the the crushed up aspirin into the acetone using only enough acetone to cover the aspirin. Then heat it slowly till about 30 degrees. Just enough to dissolve as much ASA as possible.

Next is to filter it. Throw away the collected white stuff (its all binders and crap you don't want) and keep your filtered liquid. Set it in the sun to evaporate off all the remaining acetone. You will be left with pure ASA. Make sure its nice and dry before you use it (I am assuming you want it for PA)

With IP follow the same steps, but IP is quite an oily alcohol. You are going to need to heat it up nice and hot (just below boiling) and then dump the solution into cold water to precipitate the ASA.

[rangegal]

DAMN! Thanks for the info!
The thing is I only have a gas BBQ grill side burner for heating things up outside, no hotplate. I don't think heating acetone with an open flame is the safest thing to do, plus I can't control the temperature very well, let alone keep it down around 30.

I guess I'll just try making PA with unfiltered asprin... seems to have worked for some other people.

[Bert]

DAMN! Thanks for the info!
The thing is I only have a gas BBQ grill side burner for heating things up outside, no hotplate. I don't think heating acetone with an open flame is the safest thing to do, plus I can't control the temperature very well, let alone keep it down around 30.
1. Boil a pot of water several times the volume of the solvent to be heated.
2. Turn off flame.
3. Immerse container, such as a canning jar with lid screwed on, filled with solvent and powdered aspirin in hot water.
4. Check temperature every few minutes, shake jar occasionaly and wait for solution to take place. If you do not have a thermometer, wait untill you aquire one before attempting dangerous chemical processes requiring precise temperature control.

[rangegal]

I do have a thermometer, actually my science teacher just gave it to me the other day, which is why I'm finally attempting my first nitration.

Thanks for the idea bert, I'll try it tomorrow. :)

[Hinckleyforpresident]

Why not just purchase a $5-10 hot plate at wal-mart? They are pretty much disposable if they get ruined and they work well enough for PA.

That way you don't need to contain the hot acetone in a shatter prone mason jar. You can just boil the acetone open in a water bath.

Just don't smoke or light anything on fire around the boiling acetone and you will be fine. DON'T do that on the burner though, it will light the fumes and start a fire.

[rangegal]

So I just attempted the synthesis of picric acid. I followed the procedure put up by somebody on the first page of this thread (sorry, forgot who you were), except using ammonium nitrate in place of potassium nitrate.

Everything went well, no NOX was produced, and nothing broke or bubbled over. So I cooled the solution, got a jug of ice/water (didn't crush the ice because the baby is sleeping and the blender is loud as hell) and tried to precipitate the picric.

Instantly all this red crap floated to the top of the water, and the whole thing started to foam a bit. The foaming stopped, so I poured it through a coffee filter. And what collected on the filter? The red crap. "Isn't picric acid yellow?" I asked myself. I removed the filter and poured the yellow filtrate on my driveway, leaving a big (and probably incriminating) yellow spot.

So heres my question, is the red stuff picric acid?

EDIT- Uhmmmm... never mind. I re-read this thread and found the answer. Sorry for not checking it again before I posted. Guess I have a couple hundred grams of picric acid on my driveway now... what to do about that?

[nbk2000]

One thing you learn early in chemistry to to never throw away anything until you are sure you don't need it anymore.

You succeeded in filtering out the crap, only to throw away your product.

Didn't the intense yellow of the solution make you wonder? You could have boiled off a bit of it in a spoon to see if you got yellow crystals, eh?

[Charles Owlen Picket]

I honestly don't mean to sound flippant but depending upon your age, neighborhood, activities, and associations a "big yellow stain" on your driveway
is a "red flag" to certain law enforcement agencies (no pun intended). I would get that stain off of there, pronto!

However, as previously mentioned, you may have had a successful reaction. Studying basic organic chemical re-crystallization would be very beneficial at this juncture.
The "red goo" issue is a well known issue with PA and will help a great deal when studying nitro-phenols. Time, temp, & addition controls will yield surprising results.
Check out: Organic Chem Survival Manual, James W Zubrick, 1984. It's got fantastic techniques for just that agenda!

[rangegal]

I guess I learned my lesson last night nbk. I will not make that mistake again.

The intense color did raise my eyebrow, but it was 10:00 at night and I just got back from a party. So I guess my sleepiness/impatience/stupidity made me look the other way.

Charles Owlen Picket: You need not worry, my "incriminating?" comment was just sort of a joke. I live far out in the mountains of a small town in Vermont, since I've lived here I've only seen one cop. But I would like to get rid of those stains... I guess the rain will wash away the residual PA, but is there a way to remove the stains from the gravel?

[totenkov]

You're going to have a hell of a time trying to get that Picric stain off your driveway. I have done it a few times myself, cursing ever time because I know I wont be able to get it off. It doesn't stain, if you look closely it actually bleaches the concrete.

Your best option would be to use dilute HCl to get rid of the yellow and then lightly bleach around the area of the stain so it won't stand out so badly. The two times I did it, the solution overflowed over the beaker on the the concrete, frying my hotplate while it was at it :mad:. I rewired the hotplate and it works fine now but the stains are still pretty bad, they do fade with time though. :)

As for the red "picric acid" I have had dye carry over into my NG so it is a possibility that the red may have been carried over from your drain opener, what color is it? That never happens to me though (I hate picric acid, making it and using it, that horrid yellow color is just unavoidable). My drain cleaner is dark brown almost black and when the synth is done there is plenty of fumes coming off a deep blood red solution, is this the color of your end product?

[rangegal]

Oh well, I'll just rake up the gravel and spread it around the rest of my driveway.

I almost had mine overflow also; with every tiny spoonful (those tiny ones used for putting sugar in tea) of AN the solution gained about 1/4 its volume. Which is why it took 4 damn hours of adding then waiting for the foam to settle before the addition was complete.

My drain opener looks slightly yellow in the bottle, but was clear when I measured it in my cylinder. It turned bright red right when I put the aspirin in it though, and it got even deeper red by the end of the reaction.

My "product" is indeed bright red, but it's nothing like I've read PA is supposed to look like. It's sort of a slimy clay. It burns vigorously as I've read PA does, but leaves a very puffy ash behind. So I guess it does have some PA in it, but it's mostly binders and crap from my unpurified aspirin (I ran out of acetone). Almost all of my PA was left behind in the solution, which I then stupidly threw out.

[leander]

I made some picric acid succesfully, and filtered it. I thried to dry the filtrate, but there was to much H2SO4 contimination, and it remained a red/yellowisch goo. Then I decided to recristalise it. I dissolved al my picric acid (approx 20 grams) in 100-150 ml of boiling water until everything just dissolved, and put it in the freezer. After 5 hours @ -5 oC, no yellow participate formed. The only thing I filtered out was 1-3 grams of dark brown goo. This might be iron(II or III)picrate-x-hydrate, since i stirred with a stainles spoon.

After that I added some hydrochloric acid to help participation, and waited for a little longer. No participate formed.

I know the solution has to be saturated with PA, but noting participated, it just seems gone! Does anyone knows what to do?

(I'm sure this question was asked before, but I'm not going to check 34 pages for the ansfer.)

[The_Duke]

The “red goo” is lower nitrated phenol compounds, unsymmetrical nitro bodies, and other decomposition products caused by side reactions during nitration. The amount of these decomp products is dependant on many factors such as starting materials, time and temperature of nitration, etc.

All of the answers you sought were right in front of you and you couldn’t even bother yourself with reading the previous pages, you wanted us to do all the work for you, but I’ve got a change of tune for you boy! :mad:

You have failed to UTFSE and to use spell check, you posted this crap seven times, and you couldn’t even be bothered to read the rest of the thread, I believe that makes you…. Food. :D

[totenkov]

Recently I obtained 300g of Phenol! :).

I am planning on making more picric cause the last bit was used up in a DDNP synth. I am going to use the nitrate salt method because I can afford to use up more HNO3 that I already am running very low on. Any special procedures or can I go ahead and make TNP the same way I would make it using purified ASA?

[Enkidu]

You can't make TNP from phenol the same way you make TNP from ASA; look for a phenol --> TNP synthesis.

[paldor]

Here is a good reputable site with a TNP synthesis from phenol:

http://www.powerlabs.org/chemlabs/picric.htm

[Charles Owlen Picket]

I believe I can give some tips on phenol. It nitrates "hotter" than ASA (but both have a related benzene ring of course). By this I mean both time and strength of nitration. Phenol sublimes and is quite reactive to the nitration process. The timing is extremely important. Phenol TNP-synthesis works well with a sulphonation mechanism in it's initial phase. Treat a phenol-TNP like you would a Stephnic acid from resorcinol lab and you'll do well and have a good yield.

[totenkov]

I think I will try the Powerlabs method, saw it a few years back but didnt have any phenol to try it. The Phenol that I got is probably older than I am and is a purple colour. I'm not sure if it will work but may as well give it a shot.

[Aristocles]

TNP musings:

I viewed a friend trying this as his first synthesis.

Observations:

1) He found the 'experiment' to be very aesthetically pleasing.

2) He spent a great deal of effort being careful to avoid NOx fumes. (He opened both garage doors, fully. He cracked both windows for air flow; then he sat a box fan on a table, placed vessel in front. He sat at the side and stirred his fucking ass off.)

3) He found the 'precipitation reaction' one of the more interesting aspects.

4) He learned a good deal about filter failure.

5) He much enjoyed seeing his final dried yellow crystals, although an inefficient yield due to the filter error.

He noted that everything was precisely as laid out here. I think he's hooked.

;)

[Charles Owlen Picket]

A lot has been said about rigging up a good magnetic stirrer (there is a thread here somewhere as well). Buying one may be simpler but they are not cheap unless you get used stuff from university sell-offs. Stir-bars can be tough to get as they walk off from labs all the time.

Along time back folks used to use an air jet to stir NG is various labs. Even in early industry air had been used to stir NG. If one were to get a bit creative and want to spend $5 for an aquarium air pump, that person could buy two or three and arrange the hoses to create a vortex to stir one's experiments..... (yes indeed!)

It works and is a Hell of a lot better than stirring one's ass off. Depending upon the density of the solution you may have to buy a few of them but you have the advantage of not having to fetch the fucking stir-bar or having it plop into your filtrate. Once upon a time I didn't have a magnetic stirrer and made this thing to work with some pretty thick solutions. It used to look like a toilet flushing.

When you set up your filters, wet the filter first before you pour and use two or three, brown paper coffee filters will be fine if wet. Kruger unbleached coffee filters: the choice of dirt poor amateur chemists!

[Aristocles]

A lot has been said about rigging up a good magnetic stirrer (there is a thread here somewhere as well). Buying one may be simpler but they are not cheap unless you get used stuff from university sell-offs. Stir-bars can be tough to get as they walk off from labs all the time.

Along time back folks used to use an air jet to stir NG is various labs. Even in early industry air had been used to stir NG. If one were to get a bit creative and want to spend $5 for an aquarium air pump, that person could buy two or three and arrange the hoses to create a vortex to stir one's experiments..... (yes indeed!)

It works and is a Hell of a lot better than stirring one's ass off. Depending upon the density of the solution you may have to buy a few of them but you have the advantage of not having to fetch the fucking stir-bar or having it plop into your filtrate. Once upon a time I didn't have a magnetic stirrer and made this thing to work with some pretty thick solutions. It used to look like a toilet flushing.

When you set up your filters, wet the filter first before you pour and use two or three, brown paper coffee filters will be fine if wet. Kruger unbleached coffee filters: the choice of dirt poor amateur chemists!

"5 dollars for for an aquarium air pump"? Shit Charles, I'm an uptown kind of guy! I bought two of the 10 dollar Walmart specials, brother! :D ;) Yesterday, my friend was stirring some NG (it was his first attempt at such, thus he was properly scared shitless- not that it's not a simple synthesis, it's just that he fears being blown up, he's strange that way...) This guy is funny, he took a broken "candy thermometer" and removed the small glass thermometer inside, stripped it, and taped it with teflon plumber's tape. He reason that the small magnitude of the 'bar' mass combined with the buffer of the tape would render it relatively safe. Thusly armed he stirred/swirled with less trepidation. This is where it got funny...

Now, our green friend filled his newly purchased burette with glycerin the day before. Guess what? Yep, the shit was so thick (from the cold) it released one drop every 3-5 minutes. He soon tired of this, so he took the burette and rigged it where it was laying on its side with the thick gel pouring (hyperbole, actually slowly dripping) out the top. No sooner had this begun, than I witnessed a tirade of profanities that would make a sailor run away, screaming STOP! I peaked in and there lay his brand new burette, broken... Being pissed, he scraped up the remnants and dumped, the almost completely not spilled, glycerin into an Erlenmeyer flask, and finished his addition.

This guy is a fucking brute, he breaks everything... ;)

Re: the coffee filters

I guess I've been using Kroger "bleached" coffee filters. I'll have to find some unbleached and wet them prior to use. I have tried taping them to the vessel as well as rubber banding them, but I keep fucking up. I think I'm gong to try putting the filter over a huge funnel and then place funnel over vessel.

Many thanks for the post, Charles.

I can see this being an expensive hobby for me... :p

Remember ole Thomas Hobbes' summation of life in a 'state of nature'? "Nasty, brutish, and short"? Actually, it physically describes my friend to a "T". :D

[Charles Owlen Picket]

There are a lot of those friends around. They will mellow with age like a fine wine. He really doesn't have to have deep worries about NG _IF_ he keeps his synths at the 40gr level or below. The reason I say this is that at that level the run-a-way phenomenon is very controllable and hot-spots (the true culprit) are minimized. The shit mixes more completely at smaller batch levels so the amateur chemist is given the opportunity to learn where and how to keep the material moving within the nitration.
However, I knew a guy who lost a fucking eye and thumb. Folks could say that he was dumb. He wore not goggles or gloves that one....He paid for his mistake: forever glum. His right hand - less and forever numb. Mind ye safety, lest ye succumb!

When your friend starts doing direct nitrations with expensive acids (distilled 90% +) you really want your hot spots minimized to maintain the highest yield possible in direct nitrations of amines (RDX - via hexamine) and high yield nitrations of solid alcohols (mannitol). That takes actual experience and a "touch". Picric acid & NG is actually a good training ground. Just remember that NG will bite if not treated with serious respect. Even the headache is not something to shrug off (you fucking can't; it's unbelievable!).

Tell him to start taking pics of good yields or poor; interesting stuff or problems. At very minimum; keep serious notes! The notes can contain that one concept that is key to making a lab work. - Notes are vital! Even if the notes begin with very simple observations, in time they will contain much more. Keeping them in a undergrad chem text book is a good idea. Keep the pics very neutral / nothing in the background, etc.

[Charles Owlen Picket]

disregard this edit: I fucked up.
-=-=-=-=-=-=-=-=-=-=-=-=-
But check out Mega's last post:
http://www.roguesci.org/theforum/showthread.php?t=3448&page=11
This is the sort of stuff your friend wants to start doing. Getting SOURCES. Sources for labware add-ons, chemicals, surplus, all sorts of stuff. in a very short time you will have the skills that will start to multiply upon themselves and you will start to know what you want to hoard. Weather they are chemicals and simple lab equipment or just common household materials that blend in with the surroundings. If you are creative - no one can take the knowledge and basics away via ridiculous legislation. I collect books and very simple materials. It allows the hobby to blossom and continue. Frankly now it's been some decades of related hobby's all interwoven. IMO it's actually the books that are the key to this hobby. You may find that undergrad organic chemistry text books are a damn good source for opening up new vistas. The "Organic Chem Lab Survival Manual" Zubrich - and "Advanced Practical Organic Chemistry" - Casey, are lab work manuals that teach technique! You may just find them incredibly valuable.

[Rbick]

IMO it's actually the books that are the key to this hobby. You may find that undergrad organic chemistry text books are a damn good source for opening up new vistas.

Actually Charles, I've kept my organic chemistry/chemistry related (ie Anatomy and Physiology) text books from my former college classes for that very reason. The books themselves have very few, if any information on explosives specifically, but the concepts are there, and it is easy to apply them to energetic materials. Not to mention you learn seemingly useless, at first anyway, information such as why acetone is also known as dimethyl ketone. It links a lot of things together.

I also agree with the household products approach. A little drain cleaner in the kitchen, some fertilizer in the garage (any nitrate salt), and some healthy sugar replacement (erythritol) seems harmless enough to the untrained eye. If that bitch Hiliary gets in, we are all going to have to be a lot more careful...

As far as PA, I wouldn't recommend it for a first nitration. It is simple, but not as easy or safe as say a Nitrocellulose or ETN synthesis. And although NG is quite easy, I don't think its a good first explosives lab either. PA was actually the first secondary I attempted to make. I got a lot of stains everywhere, almost destroyed my basement vinyl floor, and used a lot of Sulfuric Acid. I eventually got it, but I think messing up with cellulose would be less costly and less dangerous. Just my opinion :)

[Aristocles]

My friend's order has gone thusly:

1) TNP
2) Black Powder (lol... hey fuck it, he just wanted to)
3) NC
4) NS
5) AP
6) NG

No raging successes and no abject failures. However, I guess one could 'say' that his scaled down experiments were very successful in that no accidents were incurred.

He's passed 40 and tends to be cautious. Hopefully, mellowness and being more careful with glassware will follow shortly, but the guy has fingers the girth of sausages and hands like paws...

I think it's methyl nitrate next...

He has already managed to basically destroy his order from pellet lab- yes, I neglected to state that he managed (somehow) to break the sidearm on the RBF while setting it up- but has received his UGT order and is also awaiting this (he says it slated for delivery today):

Pyrex 500 mL round bottom flask
Ace Glass side-arm adapter with 10/30 thermometer joint
Pyrex Liebig condenser with 35 cm jacket
Guaranteed new and unused Ace Glass angled adapter
Guaranteed new and unused Ace Glass vacuum take-off adapter with extended
length drip tip
Pyrex 500 mL flat-bottom flask
Pyrex 300 mL flat-bottom flask
Kimax 125 mL flat-bottom flask
Pyrex 50 mL round bottom flask

via ebay (along with 2 RBF (500 & 1000).

So far TNP has been his most enjoyable, besides that damn yellow 'dye'! Geez, that shit is like duct tape, it has a life of its own.

[Grapes Of Wraith]

I have had many problems with this synthesis. I tried to make it twice, using brain fevers method: http://www.geocities.com/brainfevert/index4.html

I did half of what it said as to not waste chemicals on my first try. Everything goes accordingly until the last part. When I dump in the ice water, the reddish brown solution that is supposed to contain the picric turns yellow. Nothing precipitates and when I filter it the yellow mixture just passes through my coffee filter.

at first I thought it was the ASA so i made a new batch and tried again.
I had the same problem.
then I thought it was my sulfuric acid, I knew it was >90% maybe >85% at the least. it made the solution turn the right colors at the right time and made white fumes as I added the nitrate and stirred, I monitored the temperature and everything else. I do not know what is wrong, please help. Thanks in advance.

[Charles Owlen Picket]

Actually Charles, I've kept my organic chemistry/chemistry related (ie Anatomy and Physiology) text books from my former college classes for that very reason.

+1 !
... a 10th edition Merck index (I love that thing)....I didn't sell them back as they were going to give me shit money for them and I had a partial (scholarship) so it came out of pocket. I didn't have a screaming pack of liberals in ancient times so my Humanities materials were wonderful also.

Actually I have heard of an ETN run-a-way from a reliable source! The fellow didn't have a stir bar of any size and it clumped after a time, I suppose. No big deal, but it did happen. Just my opinion but PA is not an easy nitration. My hats' off to a guy who can get a good clean white-yellow crystal with very little hydrogen discoloration on his first few times. I've heard that phenol PA synths are actually a bit touchier than related materials (possibly because it nitrates faster). I have actually tried the old time nitrations of horn and wool! That's a real fuck-mess (even outdoors) but IT WORKS if you go heavier on the nitric acid and watch your material introductions. The yield sucks and the reactions vessels don't clean up that pretty; but it actually can be done.

I don't want to Shanghai this thread but if Hillery gets in you better buy some stock in RCBS, Dillion, & Lee. ... 'Betcha' reloading equipment will sell off the shelves!

Aristocles:
Hey, I don't tell anyone how to live but when you get your glass; take some time and get something to pack them away in! Even if it's the boxes you got them from for awhile.....I have broken more stuff than I care to relate because I didn't think about how to clean up! My little distillation rigs and expensive shit have little briefcases. I have some glass that was real money when it was new and I had some of the condensers and fittings for years after I had some stupid breaks. You can go to Home Depot and buy for $10 a foam lined case for stuff that you cut out the shape. Looks clean and allows you to pack stuff up and clean up right.

[Man Down Under]

Grapes, the fact that the water turned yellow showed that you had product!

If it doesn't precipitate, you can try cooling it down in a freezer, or boil it to reduce the volume by half or more, then cooling it. It'll precipitate out then.

[Rbick]

Grapes,

Also make sure you are using distilled water. Apparently water containing ions and other impurities (the water out of your kitchen faucet) can destroy your yield. Also, as man down under said, make sure it is cold enough. I usually had crushed ice in the bath to make sure it was cold enough.

[Enkidu]

Grapes, don't use that method. Brainfevert himself said it isn't any good. LOW fucking yields. You need to let if react much longer or much hotter. Also, the synth uses too much H2SO4. However, if you'd read this thread, you'd know that.

[Charles Owlen Picket]

There are some wonderful parallels between PA and styphnic acid. I was not much for starting with acetylsalicylic acid.
I've done it a few times and have a source for veterinary material that allows a low price for pure material. I've tried salicylic acid and it nitrated much smoother. Veterinary sources are available for resorcinol also! Styphnic acid is prettier and I really enjoy the way things look under microscopes at this point....
I noticed that the sulphonation period is critical in both styphnic and PA. I had my notes on the table with this computer and exacting temp (I've narrowed it to within 10 C), time and length of sulphonation is just about the key to getting a premium product in both instances (benzene ring nitrations). If you get bored of those two the toughest one was Cresol!
The product there is termed methylpicric acid and is no light feat to get down consistently.

[Grapes Of Wraith]

Thank you for your replies, I will read this thread, try a new method and use distilled water.
If I get this to work I will be very grateful.

[megalomania]

I have considered making an overhead stirrer from one of those cordless screwdrivers and a plastic spatula. This is for my pudding fix; I like cooked pudding, but I hate wasting my time stirring like mad over the pot while my hand gets flame broiled. I can't use my magnetic stirrer on the stove. I have little else to do while stirring (cook pudding needs ~10 min, constant rapid stirring) except think of how to automate the process.

Those cordless screwdrivers, similar to cordless drills but not as fast, can drive a paddle arrangement for chemical reactions as well. I have used overhead stirrers for large batches of things when I used to do that kind of work. A dremel, possibly torqued up and slowed down, may work, especially one with the flex attachment.

A simple (tiny) motor, pulley, and rubber belt arrangement could also provide slow and steady stirring.

If you are willing to build such a system, and do it right, you can likely do it much cheaper than buying a magnetic stirrer. Overhead stirring does not work well in all situations, but, like with my pudding, neither does magnetic stirring.

[peppovsky]

I intend to synthesis a new batch of TNP sometime son. I wasn't here lately (actually - I was here, just reading), for several, personal reasons (house, money and girl issues, of course ;) ).

I managed to find a good source of Salicylic Acid for around 30$ a pound (which is around 5 times cheaper then Aspirin for me). Now of course I wish to use the SA for the TNP synthesis - so I wonder, can I use the same method for TNP from ASA, and just replace ASA with molaric equivalence SA?

The reason I'm asking this is that it was stated here that when using SA one should do a double nitration with HNO3. The problem is that I have a phobia of HNO3 since a few months ago it got spilled pretty nasty and suddenly when I tried synthesizing Styphnic Acid. Since Resorcinol and SA are somewhat similar (both are Phenol derivatives), and since I managed to get some pretty nice batches out of the old ASA to TNP synth (which seems safer and doesn't use direct HNO3) - I prefer this method, even if it means lower yields and more purification to be done.

One further question - There was an unanswered issue that was raised in this thread, a few years back - can NaNO3 be used instead of KNO3? Someone said that it didn't work for him, yet I see no reason for that plus no one answered about it. (And now it's time to finally go to sleep ;) )

[Charles Owlen Picket]

I think you'll have no problem. As you may know some phenol-type materials nitrate better than others. I remember when folks were attempting the nitration of Methyl-Salicylate in the form of oil or wintergreen. It worked because of the care shown in temp exposure as well as that it nitrated easily itself. I've attempted wool, horn and all sorts of "old time" crud.....they all made PA. The easiest however was always phenol.

I believe what you are taking about in your description of styphnic acid synths is termed sulfonation and it does allow for a smoother nitration. If you've gotten a good product from resorcinol then you are on the right track and should use the technique that is producing good SA with other Phenol derivatives. Temp, acid concentration, etc need to all hook up and if you're getting good SA; you're on track!

One thing I use personally to determine if I have made real TNP is an impact test. I used to have access to a melting point machine but it's in town and a problem to get to. But good TNP will pop. All PA will have ratios of DNP to TNP but if you have good product a small match-head sized amount of material in a foil enclosure WILL produce an loud explosion when struck with a hammer on an anvil! I always do that if I have the chance. Dinitrophenol won't "crack"; only TNP will.

[peppovsky]

My last try at Styphnic acid synth wasn't successful - it failed due to sudden run-away and sputter (The stains are still there, on the wall, more then six months after that shitty accident...). That is why I never tried it again since. Now I got some Salicyclic acid, but I will first go on to Nitrate the ASA I filtered and dried a few days ago, since this had worked for me last time. Yet, I do have this damn fear of heating conc. H2SO4 to 70oC, and to keep it there while adding NaNO3 for an hour or so.
(And to think the NaNO3 might also not work at all...)

[Charles Owlen Picket]

Please understand something about the nitrations of benzene ring materials: they will spew fumes! That is NORMAL in the nitration process. In nitric esters that is a serious warning sign but with benzene-ring materials that is part of the nitration! It is VERY difficult to have a true run-a-way reaction with the above due to the demand for high temp synths to begin with.

There is really very little to fear with the above agenda. They won't come close to temp needed to be volatilized: seriously! One of the safer nitrations. The issues are primarily toxicity....not explosion.

[peppovsky]

I see. Thanks for the encouragement ;) Well then, I will try to overcome my fear and do the nitration like I once did successfully. Further more, I will try to make Styphnic acid later on this month, but I'm really scared of that, since the last two times I tried (with HNO3 and Resorcinol... we discussed it here (http://roguesci.org/theforum/showthread.php?t=386&page=5) ) it sputtered terribly.

And do you have any idea about the NaNO3 instead of KNO3 issue?..

[Charles Owlen Picket]

And do you have any idea about the NaNO3 instead of KNO3 issue?..

By issue I assume you mean - why some nitrates appear to be more efficient than others in solid nitrate - nitrations. And if the use of nitrogen from a solid nitrate is the function why is not Urea used as it have 40% nitrogen in it's composition (quite a bit more than the alkali metal nitrates).

Actually I don't have an educational background in chemistry so I can only conjecture. And I may be dead wrong. I would defer to Mega or someone who has actually had some upper division chemistry or chemical engineering.

[peppovsky]

ok then, I will try to just nitrate it with NaNO3 and see what happens. Hopefully it will work just fine (My past experiment tells me that both NaNO3 and KNO3 react the same for a lot of things, but organic chemistry has its own special... ways ;) ).

...Now seriously, I need some sleep :p

[Enkidu]

You should start the reaction with salicylic acid at a VERY low temperature. Then increase the temp for the final nitro group.

http://www.sciencemadness.org/talk/viewthread.php?tid=8815

[Sweeper]

Salicylic acid is cheap, you should spend small parts to the H2SO4/HNO3 mixture and noting more by chilling the mixture in a cold water bad.

This mix should be always stirred and the reaction comming up with horrible fumes. Might you increase a better yield by adding the salicylic acid into H2SO4 and the dropping the HNO3 into the H2SO4.

[tiac03]

Question for anyone, I found a plastic clear Pill case of picric acid that I had misplaced a while ago, (it is open with the lid sitting on top of the container but not completely covering it.) Stupid I know but now I was wondering how I can safely dispose of it. I`m sure there is no crystals formed on it but I can`t be sure of how PH neutral it is. My Idea was to immerse it in a bucket of cold water. It is a relatively small quantity but still don't want to take any more chances with it.

Any thoughts?

Again I know I'm an idiot for forgetting about it, it was Made to be tested right away but never had the time with school and work. I also know that I deserve any flames that are coming to me, but I figured my best bet was to ask those with more experience before doing anything possibly limb threatening.

[Enkidu]

It won't spontaneously explode. Picric acid is acidic by nature, and the alkali metal salts are very sensitive. If you tried to neutralize it, you have a problem because of the sensitive salts formed. I don't think you should mix it with water because you will have a terrible dye on your hands. As long as you have fairly pure TNP, just pour it on the ground and light it with a match... it will ignite with a poof.

[tiac03]

Sorry I wrote that badly. I meant I don't know how well "Washed it is" Seeing as it isn't canary yellow but more pale. Corresponding to the pictures I've seen from the just prior to the final dumping in ice water.

[Charles Owlen Picket]

I've said this a few times but I'll offer it up again. If a melting point machine is unavailable, use impact or friction. There is often a bit of DNP in picric acid but obviously the majority of the product SHOULD be TNP. I place a few mg in a fold of aluminum foil and strike it with a hammer on a metal surface. It should yield a report and slight flash; if it does not, you have not made TNP as DNP is not very impact sensitive. Friction sensitivity is not too high....so there is not that much to be aware of outside of common sense storage dynamics: it's an energetic material! Don't expose it to stimulus!!!

The problems with picric acid in older containers is with glass, thin thread screw tops (or ground glass stoppers) where the material has solidified into the thread over the course of years and the top is turned down quite well. Keep Teflon tape on all containers, use plastic, wide threads, do not "crank down" the tops, & don't use ground glass at all and there should be little problems.

Take your TNP outside and place a few mg (about half the head of a match) in a fold of foil, on an anvil and smack it with a hammer (wear eye protection)....you should get a "cap-gun" type report, slight flash and the foil should "puff" all over....If you are NOT getting a report....it's DNP (at best - as I've heard of some absolute crap labs). Test it first so you know what you have!!

[Zajcek]

I noticed that if hot picric acid solution is recrystallized from very cold water, or cold water containing some HCl is more pale.
The reason for this is crystal size and shape.

You can dispose your picric acid by simply detonating it in some remote area, where you are not putting other people to risk.
another option is (if you manage to open the cap) to neutralize it with ammonia, this will give you ammonium picrate which is quite insensitive. (similar sensitivity as ammonium nitrate)

[Charles Owlen Picket]

tiac03:
Neutralizing it may be the best idea of all. If you can do so, get a copy of Federoff and look at the various methods of doing so. However the specific instances of friction stimulus initiating nitrophenols is not too great in terms of common occurrences.

[tiac03]

Thanks everyone for the answers. The cap wasn't put on possibly to avoid friction issues when I first put it in the container. I'll tell y'all how the EOD-ing goes when I get it done. Thanks again.

[noelboy121]

Here where I am from we don't get conventional aspirin, we get Disprin. The problem I am having is that when it dissolves in acetone it seems to dissolve everything. After letting the dissolved solution (aspirin and acetone) stand for a few minutes it appears that all the Disprin has settled on the bottom leaving a murky acetone solution. It is not working as the aforementioned methods say it should, therefore I wonder if anyone has any experience with this product and perhaps an alternative method for removing the ASA from Disprins.






Moderator note:

Please check spelling & capitalize brand names so that post communicates more effectively. You may want to alter your solvent as well .

[Emil]

Why are you making a problem out of this situation? The very thing you are using to communicate with us is the answer. It doesn't matter where on earth you are, you will be able to get aspirin. eBay is one site that I know will sell it, and that is without even checking it.

It is possibly one of the most common tablet around. Even if your country doesn't sell it. Buy it from elsewhere.

[Cobalt.45]

The problem I am having is that when it dissolves in acetone it seems to dissolve everything. After letting the dissolved solution (aspirin and acetone)...

So, is this what it's coming to?

I have never been one to pine for "the good old days", but once upon a time this noob would have been fodder for the beast (uselessness, spelling, grammar, UTFSE, spoonfeeding)- no questions asked.

Time y'all mods step up and when it's needed, drop the GD axe!

[-=HeX=-]

Ah jesus this guys a classic. Either he is retarded and cant figure out that whats happened in his dissolving reaction is exactly whats supposed to happen, or he is just a fucking troll like that jolly roger guy. In the good ol days his ass would currently be reamed but lets go easy on him.

What country are you in? Because I have visited a few and every one I have been in I have been able to get generic aspirin.

Now use your head and filter your fucking mixture and continue as the synthises tells you to.

[Cobalt.45]

Hay-zoose fucking christ. Re-read the first sentence of his quote in my post above. I will not spoonfeed this delinquent- it's called (at the very least) U T F S E!!!

As evidence of his uselessness, here's his first post from "Newbies: How did you find The Forum?" : After doing extensive research into the prep of ammonium nitrate from fertilizer, a member of science maddness (believe it or not) suggested that rogue had a couple of good posts on the topic. Also when searching google for ap recipes rogue poped up, and the rest is history. Btw great new look for the forum

THAT in itself should've gotten him HED, but instead it's allowed to breed.

Even from a humanitarian standpoint:rolleyes:, is this someone you would feel is safe handling HE's?

++++++++++++++++

He's gone now - The_Duke

[Thermiteisfun]

Anybody ever try to do this from Potassium Benzoate for Potassium Picrate?

Sulfonation of the benzene followed by displacement with a nitrate salt to make PA with K2SO4 in solution which in turn reacts to make Pott. Picrate?

I really do not know much about what the reaction is favoring and why it does (although I have some suspicion it's elctronegativity, please correct me if I'm wrong)

I'm more into pyrotechnics than HE and I saw somewhere that this is used in a whistle comp.

Edit: also, how should I store this? I have HDPE, LDPE, PP and Pyrex.

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Merged post - totenkov
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Well...at least the post function is still working :(

I was going to edit this into my post in the picric acid thread but it seems Megas internet is broken :(

http://books.google.com/books?id=7b5GkvnYlrgC&pg=PA162&lpg=PA162&dq=potassium+picrate+whistle+composition&source=web&ots=p2rQ_MUP5R&sig=O82RP3sJ7eDhie15Is1Oh0HBuqc&hl=en&sa=X&oi=book_result&resnum=1&ct=result

I just wanted to post this here as I will not have time to do this or anything really as I'm going on a vacation to Mexico. If it would not trouble a moderator too much please append this to my post.

Thank you.

[al93535]

I have a question for you guys, if anyone has any idea what the deal is.

I made a batch of TNP from purified aspirin. I used 75.4 grams of ASA and dissolved it into 450 ml of H2SO4. It sulfonated for 30 minutes at 70 degrees. I added 150 grams of KNO3 over about 40-45 minutes. The temperature was increased to about 105 degrees at which point I added 10 ml of 98% HNO3.

Everything went well, I got nice crystals while the solution was cooling. I decanted, and added cold water, filtered and washed. I dried the TNP and it weighed in at 142 grams. It might have still had some sulfuric in it as well.

I wanted to purify the picric acid, so I used boiling water, dissolved the TNP then precipitated it by cooling the solution to 4 degrees and filtering.

Here is where my question comes in. I had too much water to fit into one container to let it cool, so I divided it up into two containers. The first one had more in it then the second. I filtered the first container, (which was the first container to be filled with the hot solution) and got a dark yellow almost orange TNP. When i went to filter the second container I got a bright pretty yellow TNP like I am used to from before.

So how did I get two different purities (that is what I am assuming the darker yellow is from) from the same batch??

Here is a picture.

Edit: Would it be wise to just mix the two and use? Keep them separate and re-crystallize the darker crop another time? I will be using the TNP for some attempts at DDNP.

[-=HeX=-]

I would advise Recrystalizing again on the dark batch. Keep the 'Contamination' away from your other portion. Just recrystalize again and it should be like the others. Just curious but where did you get that synth? I have neve seen one that adds 98% nitric after the potassium nitrate.

[Lewis]

I divided it up into two containers. The first one had more in it then the second. I filtered the first container, (which was the first container to be filled with the hot solution) and got a dark yellow almost orange TNP

If they are from the same batch, they are going to have the same composition... The only thing it can be is that one of your containers was unclean or reacted with your product.:cool:

[Alexires]

I think what Lewis has said is probably correct. Grasping at straws, it might have been that when you dissolved it in boiling water, you didn't give it time to mix through the entire solution/not enough water, so there might have been a greater concentration at the bottom, causing a difference in colour.

Or your shit was dirty and its contaminated.

Either way, clean it again.

[al93535]

I am going to recrystallize the darker lot.

After the powders have dried I did a test burn on them. The lighter powder, which I am sure is TNP melts then burns rather lazily with a sooty flame/smoke.

The darker batch is pretty energetic. Almost like a little nugget of slow flash powder. But it has the same sooty characteristic. Could I have a picrate?

The only thing different about the darker batch is that I had to use a plastic PETE container to cool the solution down in. It was clean, and I rinsed it with distilled water.

I recrystallized the darker batch, I got back just about exactly what I started with. I had 42 grams of crystals, I used 640 ml of boiling water to dissolve them. They all dissolved and there was no solids present. I cooled to 5 degrees and filtered out the needle like golden yellow crystals. They appear almost identical to the picture I posted above, except slightly lighter.

After some drying the powder has the same properties as before. No melting when exposed to a flame. Instead they pop and hiss, and burn rather violently with a sooty smoke.

I suppose I will just dispose of the lot, and start again with a fresh batch. I ended up with 11.42 grams of beautiful TNP in the end.

The next batch will be about the same, except with a single large glass cooling beaker.

[fluoroantimonic]

It sounds to me like you have a picrate salt contaminating it, from the sounds of K or Na, but I suppose it could be lots of others. That would explain the more energetic combustion, the color, and the failure to go away with recrystalization (except for a little bit getting lost with the cold solution and lightening the color). Try it again, this time acidify it a little. Maybe try it with a fraction of the batch this time in case it doesn't work. I would imagine something like acetic acid would be better than a strong inorganic acid, probably less likely to screw with the TNP molecule.

[tranquillity]

I think it would be necessary to use a strong acid to effectively protonate a picrate salt. Picric acid has a pKa of 0.38 and you need something with a lower pKa than that (or a huge excess of acid) to get a reaction I believe. I would suggest HCl; H2SO4 being the catalyst which attaches the nitro groups would probably detach them again.

[fluoroantimonic]

You are correct, I assumed picric acid was a weaker acid than that. HCl seems like a pretty good choice, since it shouldn't affect the picrate ion and is easy to remove by evaporation.

[al93535]

Thanks!

I recrystallized from boiling water with the HCl. I noticed a bright yellow solution forming, then immediately a bright yellow precipitate formed in the droplets of HCl as I added them. I decided to keep adding from a pipette and at 27 ml there was no more reaction noticed. I put in an additional 5 ml. It was quite pretty as the acid was added, and I got lots of crystals forming in the solution.

I got a much better yellow product, but not quite what I expect. It burned ALOT better, just like my previous batch except a few hisses and a faster burn at the end.

I re-crystallized one more time, with HCl. I added to boiling water, and this time not everything dissolved, so I filtered the solids off. Next I had to add 8 ml more HCl, with the same result as before. All the picric precipitates even in hot water when the HCl is added. I washed with 50 ml ice cold distilled water and I got the same pretty yellow crystals I expected. I will do a burn as soon as they dry.

Thanks for all the input, I do appreciate it.


I believe I will always add some HCl in all of my TNP recrystallizations from now on.

[fluoroantimonic]

All the picric precipitates even in hot water when the HCl is added.

Assuming it is pure picric acid, I do believe that would be your common ion effect, increasing the H+ concentration seems to greatly reduce the solubility of the TNP. That looks like it could have some interesting uses. It certainly would help with the yield in recrystalizations, precipitating a little extra picric acid in the cold solution. You might want to be careful though, adding tons of HCl could also precipitate the very dissolved chloride salts you're trying to get rid of. For "desalting" purposes you'd never need to add more than .4 mol HCl per 100g of questionable TNP, probably much less would be necessary. If the TNP was contaminated with a salt the precipitation could also be partially due to the lower solubility of TNP than the salt.

That is interesting that it burned so energetically.. I'm not quite sure why that would be, there's no way there is a picrate salt still contaminating it. Maybe it is pure and the stuff you tested earlier was actually not? Or maybe it was just a little damp or something, slowing it down. I suppose you'd need to do a direct comparison with known pure TNP to really get an idea. One could also try recrystallizing known pure TNP with HCl to make sure it doesn't change its properties.

You might be able to get rid of picrate salts a different way. Recrystallizing it from fairly dry alcohol should do the trick, I assume the salts are insoluble, while TNP is 1g per 12ml.

To confirm the purity of your TNP a solubility test may be in order. Merck Index says 1g TNP dissolves in 78ml water at room temp or 15ml boiling water. Alcohol solubility would be another good test.

[al93535]

I tried to detonate 41.5 grams of TNP today. I used one of my aluminum case detonators with 1.5 grams PETN and .50 grams mercury fulminate. I don't know if I got a partial detonation, or none at all. There was a big cloud of yellow floating away from the blast site. Not much damage was noticed in the area except from what would be expected from the det case.

I pressed the TNP lightly with a press into a 2.5" ID tube, and made a 3/8" OD hole in the center for the detonator. This gave me a column about 1" high.

Seems pretty insensitive. Maybe next time I will use a booster, and better confinement.

Anyways, I just finished another batch of TNP. 100 grams of ASA to start, I ended up with 89.12 grams of pure, recrystallized picric acid. This time I got a beautiful light yellow product. I did however add some HCl to the recrystallization water after it cooled quite a bit. This helped precipitate all the TNP and get a good dense crystal.