Picric acid from asprin

[Madog555]

i had an interesting dream today, this is what happened:

I took 200ml of battery acid and boiled it down to about 1/2 its original volume. then i measured out 70ml and started heating it. then added 10 powdered asprins. after stirring and disolving most of the asprin i added 2 grams of KNO3, red fumes were produced. after the reaction subsided i repeated the addition of the KNO3 until my 9 grams of KNO3 was gone. i shut off the heat and let the dark-orange liquid cool. after that i added 150ml of cool water, a small amout of dark orange-brown crystals formed. it was kinda hot so i put it in a big ice bath. after it cooled down pretty good some more crystals precipitated. i filtered the very small amount of crystals out, and now their drying in my basement.

i have a couple questions:

1. are the crystals picric acid?
2. why are their so little of these extremely small crystals
3. did i do anything wrong? f yes what?


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"True freedome is not without anarchy"

[CodeMason]

Well the first thing I notice is that you only boiled the acid down to half its original volume. That's only 50% sulfuric.

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[Madog555]

that is probaly it : (

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"True freedome is not without anarchy"

[nbk2000]

Acid was too weak, if you used standard battery acid (30%) than you only had 60% acid. It has to be boiled till fuming.

You didn't use alchol to wash the aspirin to remove the fillers and binders. This gets oxidized too, taking away from the phenol.

Next, too much acid in relation to the aspirin, you're carbonizing it.

Was the aspirin/acid mix heated and allowed to react for 15 minutes before cooling? NO. This means the acetylsaliyic acid wasn't given time to be converted into phenol.

You added the water to the acid. THAT'S A NO-NO! NEVER add water to acid, always add the acid to water. Otherwise you risk splash back.

Did you pour the mix into crushed ice slush? NO. This means that a lot of the picric acid was dissolved in the water, since it is water soluble.

Water must be ice cold, and immediately filter through a fine filter (coffee).

When I did it (followed BB#1 procedure) I got about a quater to half ounce from 40 tablets. Didn't have a scale at the time so I'm estimating the weight.

Also, the crystals should be BRIGHT yellow. Like a canary. Dark brown means it's dirty and should be disposed of.


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[Madog555]

ok, i didn't pureify the asprin because when i tried to do it earlier with 70% ethyl-alchohol all of it disolved so i didn't bother this time. i will buy 91% and try that. and the acid to asprin ratio was out of megas recipe, his uses 100 asprin and 700ml of acid.

i will have to try this again...

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"True freedome is not without anarchy"

[mongo blongo]

Guess what! In a dream I was having similar problems!
I had just run out of phenol so I have to use asprin from now on.
I scaled down from mega's procedure.
When I added the acetylsalicylic acid to the H2SO4 it turned a pink colour and started to solidify.
When I heated it to about 90 C (Mega said heat to dissolve crystals but gave no temp)it started to dissolve.
When I added the NaNO3 it instantly turned a dark brown colour.
After doing the rest of the procedure + purifying I had a load of brown crystals which would not change colour after numerous purification procedures!
The product has the same appearance as acetylsalicylic acid but dark brown in colour. I am guessing that for some reason it didn't nitrate!
All chemicals used were pure! It would help if someone could outline the temps and colour changes that should occour.

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AAARRRRRHHH! My beautiful eyes! It burns!
The goggles do nothing!AAARRRRRHHH!

[shooter3]

When I made mine(a long time ago, it came out a very light yellow. It didn't look like it was supposed to, so I stuffed it into a tomato past can(about a third full)with about 10 grams of MF. Set it out into the middle of the field(ground was frozen)and lit the fuse. I didn't think it would do anything, but what a hole it made! And from 200 yards away it made an incredible noise! My understanding is now that the color can very quite a bit, depending on the impurities and crystal size. By the way, I burned rubber getting out of there! Don't do your stuff in a box canyon!

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The truth shall set you free!

[DBSP]

I've also had similar problems. I tried making PA about a month ago using the procedure in kibc The first problem was that the acetylsalisylic acid wouldn't dissolve after a lot of heating it dissolved, but I belive that some of it carbonized because the solution got black. I thought I would give it a try anyway so I started adding KNO3 in small ammount at a time but nothing happened it just sank to the bottom of the beaker. My biggest problem is that my KNO3 doesn't dissolve I simply can't get it to dissolve. I tried making nitro starch but I never got to add any starch because there was a thick layer of KNO3 on the bottom, I just left the beaker as it was and I had a look about a week later it still hadn't dissolved. What do you think the problem is?

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¤monte¤

[CodeMason]

In fact, a dirty yellow colour is normal for nitroaromatics.

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[Madog555]

DBSP, my asprin did the same thing but the reaction was fierce when i did the nitrate addition. maybe it wasn't hot enough when you added the nitrate. next time i do this im going to heat it in an oil bath or double boiler, that should protect the asprin powder.

BTW, codemason, i got a quick question for you. i know this is off topic but im afraid to post a topic on it.
How is KNO2 synthisised from KNO3?

i want to know this so i can give r-salt an atempt

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"True freedome is not without anarchy"

[This message has been edited by Madog555 (edited 11-22-2001).]

[CodeMason]

<font face="Verdana, Arial" size="2">BTW, codemason, i got a quick question for you.</font>This has been discussed before. By heating it with lead.

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[Madog555]

ok, thanks man

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[nbk2000]

You don't need the lead either. Just heat it till it melts and stops bubbling. That leaves the nitrite.

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[Madog555]

Thanks nbk, I think I see a good dream in my near future : )

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"True freedome is not without anarchy"

[Madog555]

i just melted about 10 grams of KNO3, it was clear when molten and didn't bubble, is this good?

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"True freedome is not without anarchy"

[nbk2000]

It's good that it was clear, but it doesn't sound like you heated it hot enough to cause it to break down.

This takes a bright red heat, like from a propane torch.

If you were to do it in a test tube, you could connect a stopper with a piece of tubing that you could pass into water to see when it stops bubbling. That would show when the reaction was done.

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[CodeMason]

Common steel wool is a good substitute for lead.

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[nbk2000]

Any metal that's easily oxidized would work I'd imagine.

Aluminum, copper, lead, zinc, iron, etc.

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[rikkitikkitavi]

I just make a guestimate here , but isnt the point of using lead that it isnt as reactive as aluminium, zink and iron ? Copper could probably do to. Mixing nitrate and Al and heating it hoping that you would get nitrite...

/rickard

[Lagen]

... yeah, BOOOOMM!

I would think that the point in using lead is that at roughly 350°C both of the reactants are in liquid phase thus able to react easily, and still stable, so the reaction would be well defined. With zinc or any higher melting metal the nitrate would start decomposing at 400°C with the metal being still solid (and the product as well). Now does anybody know what are the byproducts of thermal decomposition of KNO3? Nitrite decomposes at 500 something. With lead there are still side reactions leading to plumbite etc. but the impurities are relatively easy to separate. The impure nitrite usually doesnt work for DDNP, R-Salt, NM and the like... Just my 0.02$, anyway.

This is a bit OT, but I am a bit confused. I remember posting something on making nitrite in the "sodium nitrite" thread, now its 404, not found in the archives, and I cant find the overflow site, have I missed something here? (Edit: SNIP and posting in Forum Matters)

[This message has been edited by Lagen (edited 12-10-2001).]

[Madog555]

thats strange,

the decomposition byproduct for kno3 would be O2, am i right? but if you heat it with lead it would be PbO, am i right?

these should be the reactions:

with lead

KNO3 + Pb --> KNO2 + PbO

without lead

2KNO3 --> 2KNO2 + O2

are these correct?




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"To live is to suffer, to survive... well thats to find meaning into suffering." -DMX

[Lagen]

No. KNO3 forms nitrogen oxides and potassium oxide upon decomposition, the K2O reverting to KOH and K2CO3. What I was not sure about, if there are any other byproducts, like nitrogen compounds and maybe others, formed by interactions of the NOx, KOH etc. with the metal at 400°C.

Edit: Of course a lot of KNO2 and O2 is formed as well (not a BYproduct...)

[This message has been edited by Lagen (edited 12-10-2001).]

[Madog555]

is the lead one correct

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"To live is to suffer, to survive... well thats to find meaning into suffering." -DMX

[Lagen]

With lead you got the same situation, the KOH which is present in small amounts (cause the temp. is not that high) reacts with the litharge (PbO) to form potassium plumbite (K2PbO2) (this is the industrial method of making plumbite). Believe me, this is not a marginal issue. In my cupboard I keep a beaker from a failed R-Salt attempt two years ago, as a memento. The nitrite didnt work. It is all green with sodium plumbite and other byproducts (litharge is orange).

[CodeMason]

I'll test it with steel wool today or tomorrow. I got the info from a reliable source.

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[Mr Cool]

You don't need any lead or any other metal. If you heat pure KNO3 you'll get KNO2 and O2, but if you get it too hot then you'll get NO2, K2O and O2. I think omitting the metal would be a good idea, to reduce impurities...
Slightly on topic: anyone tried CH2Cl2 + 2NaNO2 --> CH2(NO2)2? Or has anyone read anything about it?

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"Nothing makes a man fear much, more than to know little." - Francis Bacon.

[CodeMason]

Mr Cool: I don't think it would work, dichloromethane being fairly unreactive, and even if it did, it would require a phase transfer catalyst and some hefty reaction conditions at the very least.

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[Madog555]

ahh, just woke up from a nap

i had another dream like the one that i posted before, i think this is a re-acurring dream.

here is what happened in it:

i crushed up 10 asprins and disolved them in 70ml of H2SO4 drain opener. then i gently heated the mix to help disolve the asprin. after it was all disolved i added 9 grams of KNO3 in sevaral parts. there was no NOx fumes. but the solution turned bright red. after letting it react for a couple minnutes i poured it into a beaker full of cracked ice-water. it turrned yellow and there was some precipitate in it. i filtered out the yellow-gold crystals and put them on a table in my lab. there was a good amount of crystals in this dream (unlike the last one i had)

this is indeed a very strange dream because i would never do anything dangerous like make explosives. or work with an acid ;)

[ January 12, 2002: Message edited by: Madog555 ]</p>

[Alchemist]

Hello all, 031402

OK on Picric Acid (from Asprin) there seems to be some variations on how long to leave the Asprin in the H2SO4 and then also how long to heat it before adding the NO3! Reading the MANY procedures around I have seen
from right away to as long as an hour before the heating. As far as the heating goes it should be just long enough to dissolve the Asprin (is this correct?).

Also, just wondering does anyone know exactly what you have if you did NOT add the NO3? Is it aPhenolSulfonic Acid or ?

<small>[ March 14, 2002, 10:22 AM: Message edited by: Alchemist ]</small>

[Kalium]

Hmmm. You got picric acid. But may be in solution with 2,4-dinitrophenol(it looks like picric acid, but more yellow when it dry)...

[andreas]

I've tried the asprin procedure once and I think I carbonized the phenol. My question would be how much sulphuric-acid to use for say 100 tabs of asprin.By the way I used mega's recipe(where did his site go) Well I finally succeeded. Before now I always used paracetamol of wich I thought contained acethylsalicilic acid as well.
It does not. But this time I used asprin.
I took 40grams ac-acid and added it to 250ml sulphuric acid and when it al had dissolved I added 140 grams of ammonium nitrate no NOx was formed and with the final few grams a yellow precip was already vissable. During the addition the collor of the solution was light red.
It's now driing, that takes ages.

What an awsome dream :D

<small>[ April 09, 2002, 06:44 AM: Message edited by: andreas ]</small>

[mr.evil]

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> i crushed up 10 asprins and disolved them in 70ml of H2SO4 drain opener. then i gently heated the mix to help disolve the asprin. after it was all disolved i added 9 grams of KNO3 in sevaral parts. there was no NOx fumes. but the solution turned bright red. after letting it react for a couple minnutes i poured it into a beaker full of cracked ice-water. it turrned yellow and there was some precipitate in it. i filtered out the yellow-gold crystals and put them on a table in my lab. there was a good amount of crystals in this dream (unlike the last one i had) </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Madog, didn't you purified your Aspirin? :confused:

[Madog555]

no, i didnt have any ethly alcahol, that was a long time ago.

[mr.evil]

this evening i've tried it again, still no succes :(
the first time i made it, i used Phenol... but that was of a friend and i haven't a good source for it.

i will do some other Expiriments, because TNP makes me angry as it takes alot of acids and ASA :mad:

[Einstein]

I´m just adding that car battery acid is 37% H2SO4, so when boiled to half of it´s volume it should be 74%. But when you boil it until white thick fumes are given off, it should be around 98% :D

[Yi]

*Someone* I know just tried a method that was an amalgamation of Mr Cool's, Brainfever's, and Megas method and it worked perfectly :) ! Used 60ml 98% H2SO4, 21g KNO3, 10g ASA to produce lovely bright (and I do mean bright) yellow crystals :D Still need to weigh the yield once its dry though.

<small>[ July 31, 2002, 04:27 PM: Message edited by: Yi ]</small>

[kingspaz]

Yi, just a quick note. you must make sure the TNP is completely free of nitrating mixture otherwise it won't dry as H2SO4 is hygroscopic. the problem is that TNP is also soluble! if you wash it with a small amount of ice cold water then you shouldn't lose much of it.

[Yi]

Yep its been washed with 500ml distilled ice water....so max I could of lost is 7g (solubility 1.4g per 100ml according to Chemfinder) at room temp but less was lost as the temp was low (obviously). Does anyone have a solubility curve for TNP ? The liquid was kept for evaporation to get some sort of idea how much was lost altough it's probably not a signifigant amount.

EDIT: oops just realised what was ment now...I'll go wash it now with some more :)

<small>[ July 31, 2002, 05:09 PM: Message edited by: Yi ]</small>

[mr.evil]

But then, you can dry the TNP solution to get crystalls again :rolleyes:

[kingspaz]

i recovered 5g of TNP from the filtrate (after filtering the TNP) and the washing water. i let it evaporate until only about 20% of it was left and filtered out the crystals that had formed. definately worth doing in my opinion. no point in wasting it. so Yi, save the washing water!

[Yi]

Yeah am keeping it..There is already a large amount of crystals there and its only been overnight. It looks quite nice with long needles floating around in clumps.

EDIT: Pictures
<a href="http://incoherent.topcities.com/TNP.jpg" target="_blank">http://incoherent.topcities.com/TNP.jpg</a>
<a href="http://incoherent.topcities.com/TNPfiltrate.jpg" target="_blank">http://incoherent.topcities.com/TNPfiltrate.jpg</a>

<small>[ August 01, 2002, 01:31 PM: Message edited by: Yi ]</small>

[Boob Raider]

Each time I have tried preparing PA using phenol I have got brownish yellow crystals which don't seem flaky. But if I didn't heat the H2SO4 phenol mix .... the crystals seemed closer to normal. Although with Salicylic acid (not ASA) .... I always got bright yellow flaky crystals with the normal PA properties. I have never tried using ASA or methyl salicylate. Oh and the nitration of salicylic acid seemed less violent as far as heat evolved and NOx goes compared to phenol. My suggestion ... using phenol takes a lot of practice and is wasteful on a small scale. Although my sulfonated mixtures used to sit around for a couple of days before I nitrated them. As first I'll prepare a multiple of small batches of sulfonates, and then nitrate them in a similar fashion.
Anybody know of any subsitutes for resorchinol, that can be bought easily in Canada, so I can make some styphanic acid. (ASA subsituting phenol for making PA sort of idea)

[shooter3]

You can get resorcinol as a 2 part marine glue. The other part is formaldehyde(2 for one!). Look for the weldwood brand.

[ShockWave]

I searched a lot about setting off TNP, does it really need a shockwave to detonate? or can it be set off by a very strong firecracker? I'm almost sure that it needs a shockwave but maybe that someone here has tryed it with something that deflagrate ?

[nbk2000]

Shockwave, your question is bordering on the idiotic.

A high explosive like picric acid REQUIRES a detonator, not a firecracker, to be detonated. Hence the "DETONATOR". :rolleyes:

Read more before you post questions of such a basic nature otherwise you'll be banned. We don't have time to explain such basics anymore. We're moving forward, not backwards, in our sophistication.

[ShockWave]

well sorry about that, but I thought it was possible and that maybe someone had done this.

[ShockWave]

I didn't know what was in my firecracker, but a few minutes ago I read that it is Flashpowder, And I thought that flashpowder can detonate NG, PETN, so maybe TNP too, but I'll guess not than.

[Kalium]

Certainly, any powder CAN'T detonate high explosives!! Even, some primaris, like lead styphnate and some picrates, can't be used in blasting-caps.

[ALENGOSVIG1]

Actually, Low explosives like flash etc. can be used in detonators. There are many patents on this and I believe its been talked about here too.

[Boob Raider]

It depends on the explosive ..... most of the nitrated aromatics are very stubborn and don't detonate easily. Like TNT needs a C-4 booster for complete detonation. Whenever I have used TNP in a detonator, it has only spilled out if the casing is Al, on the other hand when I used a steel tube (AAA or 9V battery casing), the detonator worked. Nitrated esters on the other hand are quite sensitive. NG might be slightly more sensitive than AP, RDX is reletavely insensitive compared to NG although it can be set off from a wack with a hammer (A pinch of RDX). So shockwave .... a firecracker won't detonate TNP ... only spill it all over the place.

[Trinitrotoluene]

I few days ago I had made some picric acid from asprain.I used brainfevers method 10grams of acetylsalicylic acid 120ml of H2SO4 93% and 20 grams of KNO3.I dissolved the acetylsalicylic acid in the H2SO4 by heating it to 80*C when all wa dissolved I slowly added the NKO3 gram by gram white fumes was given off. The soloution turned brown after i was done i let it sit there till it had cooled to room temperature and the color had changed to orange.Then i added the soloution to 1000ml of cold water. Large amounts of heat was generated and it converted to a yellow color. Then let it sit in the fridge overnight. The next day ive seen a huge mass or picric acid crystals.I then filtered the soliution. This is the part i hate the most about picric acid production because its a pain to filter those crystals.When i was filtering i had spilled some soloution in my lab it was such a pain to clean up.But all the crystals are filtered now and its taking forever to dry.

[kingspaz]

its takes such a long time to dry because it will still be contaminated with the nitrating acids. a good way to reduce this is to recrystalise the TNP from boiling water. the problem with this is that you will lose some TNP in the solution left over. its worth this step in my opinion though, but maybe not to you as you don't have that much TNP.

<small>[ January 01, 2003, 06:44 AM: Message edited by: kingspaz ]</small>

[Keyser Soze]

What a coincidence, this topic is being brought back up and i just made TNP for the first time last night using Mr. Cools synth. I thought picric acid was supposed to be odorless, but mine reeks! It is also a dirty yellow so i will probably purify it.

[Mr Cool]

The smell is probably ethanoic acid, from the hydrolysis of the aspirin.
In what way is the yellow dirty? If you let the aspirin oxidise (ie, let it get too hot in the reaction when there is HNO3 present) then you can get dark, tar-like products which might be contaminating your product. If you got significant NO2 then this is quite a likely cause for the discolourisation (I'll assume you used nice H2SO4, not the brand of drain cleaner that is black!).
See what it looks like after recrystalisation from boiling water, with a very small amount of HCl added. It should end up ranging from a bright but light yellow to a fairly intense yellow.
I find that sometimes, when first ppted, the TNP has almost a pink colouration, but becomes the usual colour after recrystalisation. I think it's to do with the shape and size of the crystals, whenever it's the strange pinkish colour it's always very thin, flat plates.

[Keyser Soze]

Sorry, you assumed wrong, i used the crappy black/brown H2SO4 drain cleaner.

I could have just made a big mistake with it though. I wasn't thinking and i put the filter on an aluminum pan to dry. I know picric acid is incompatible with most metals, and is it incompatible with alumninum? If it is i have a big problem.

I just looked at it again and it looks only yellow/brown in some spots so i will purify it soon and see if that changes anything. Do you recommend leaving it in the fridge or an ice bath after i've boiled it so more will precipitate out?

[Mr Cool]

Ah, that could explain it! Unfortunately I've never used that kind of acid, so I don't know what the colouring agent is, nor how it could be removed. I doubt it will be dangerous to leave it in though, it should be pretty inert.

I don't think Al is very dangerous with TNP, but if you recrystalise it from water with a small amount of added HCl then it should be fine, HCl being a much stronger acid than TNP.

Yeah, get it as cold as you can without freezing it to ppte as much TNP as possible after dissolving it in the least possible quantity of boiling water.

[Keyser Soze]

Phew! I almost shit myself when i realized i had 30 grams of TNP sitting in a metal container but it turns out i was ok.

I have it sitting in the fridge now and when i checked it i can already see that more crystals have precipitated out of it.

Another quick question: Were the red fumes produced when adding the KNO3 nitric acid vapors? How harmful are these?

EDIT: Thanks for all the help so far!

<small>[ January 01, 2003, 04:52 PM: Message edited by: Keyser Soze ]</small>

[kingspaz]

if red fumes are produced when you add the KNO3 to the H2SO4 it means you have added it too fast and the mixture has got too hot. hot = HNO3 decomposition and NO2 production. NO2 is red and very toxic <img border="0" title="" alt="[Frown]" src="frown.gif" />

[THe_rEaL_dEaL]

A bit of a survey

To this day who has had good yield and decent quality crystals and from which method was this from? (Megas, Mr.Cools, Brainfevers or a different one)

[Al Koholic]

Well...I have never had any problems at all making TNP. In fact, I always get an 84% yeild with my method too.

I purify ASA from aspirin tablets with denatured alcohol.
I use technical grade KNO3.
I use 93% H2SO4 drain opener that is completely clear and very slightly brown/yellow. I do not boil it down as 93% is satisfactory as a dehydrating agent in this reaction.

This would be a sample procedure by my method.
1) Weigh out 10g ASA. Add this to 220 grams of 93% H2SO4.
2) With a glass stirring rod, stir the mixture as you heat it to around 80 degrees celcius. The exact temperature is not totally critical. You can do it just above 60 I believe, but it'll take much longer (the higher the heat, the shorter your seat! (to a point)). While stirring and light crushing of larger ASA crystals, watch the mixture....it will change to a very very dark red/brown. It should not be turbid either.
3) If heating at 80 degrees, continue the heating for about 25 minutes or until it is clear that the solution is not changing in color or quality.
4) Remove the beaker from the heat source. There is no need to let it cool, you may proceed right to step 5.
5) Slowly add 22.5g KNO3 to the mixture. And when I say slowly...I mean slowly. It should take you about 15-20 minutes to add an amount of 22.5g. When you first start adding, go very slow. The solution will still be dark from the 4-phenol sulfonic acid. You will notice some foaming when adding but not much....just stir it in and keep that mix stirring (helps to have a magnetic stirer). As you add more KNO3, nothing will be happening (except for the foaming) until a point when you will see the solution change from the dark brown/red to a lighter tone of brown/red. This is right at the point where the color change will occur on the next (or second next) addition of KNO3. Add a little more with vigorous stirring and all of a sudden the solution should go bright/deep red/orange. This change will be accompanied by a strong degassing of the solution which is why you must proceed to this point slowly so as to not let the rising foam overflow. Once the color change has happened, you can go a little faster with the addition but not a lot because you do not want to see NO2 vapor coming off...if it does you are going too fast.
6) Continue stirring and adding until done. Let the mixture cool to room temp.
7) Add the mix to around 450 or 500 grams of ice water. Crushed ice slush works great.
8) Place the whole deal in a fridge. You will notice that the TNP is forming more of a foam on the top of the solution rather than being nice crystals at the bottom of the liquid (there will be some down there don't get me wrong). Just filter like normal and ignore the fact that it is foaming. This I believe is because of CO2 and other gasses which were dissolved in the acid mix.
9) Scrape any last remains of TNP in the beaker into the filter and wash it with COLD water.
10) You can recrystallize from boiling water if you want to (probably a good idea if you're looking for high purity product) or just wash a couple times with COLD water. Something I like to do is make a saturated solution of pure TNP for the washing portion. Then you won't lose any of your product b/c none will dissolve and then you can use the saturated solution for more recrystalization or making Explosive D. Whatever....
11) Dry this on an inert tray with a heat fan blowing on the crystals to speed things along.
12) Collect dried product, weigh it and store in ground glass stopper bottles.

Sorry for the long post and all since I probably reitterated some things that have been talked about but I like this idea of a survey with detailed descriptions because more often than not, fucking up a chemical procedure is very easy if you have no "feel" for the reaction. Getting it to work finally is a great feeling because you have learned things which could not have been revealed to you until you made a successful solo attempt at the reaction. Now that I have done this reaction many times it is second nature...

I hope that helps some of you who may be experiencing problems...
It is what I do and I get about 84% yeild every time I do it....even when I do larger amounts. My last attempt (a week or 2 ago) was a batch of 30g ASA. Last week I also made 273g ASA from 1000 325mg Aspirin tablets....I know it is a bad yeild from such a simple extraction...I used the right amt of alcohol but the problem was in my crushing job...the grinder left some not so fine pill pieces which I can only imagine contain the residual ASA...oh well! I've got some nitrating to do!
Al

<small>[ January 15, 2003, 03:33 PM: Message edited by: Al Koholic ]</small>

[1337bomber]

I bought a bottle of protex max drain opener and I cannot find a company MSDS to find out the concentration or if there are any other chemicals in it. Is there a typical concentration for H2SO4 drain openers, and does anybody know if or what other chemicals are added to H2SO4 drain openers? I REALLY don't want to take a sample to my school lab and do a titration to find the conc.

[Mic]

I think that drain opener sulfuric is something like 93% concentration.

[1337bomber]

Hey, thanks Mic. Do you know if there are any other chemicals in it that would affect AP synth? I am new at this and I would like it if my first HE synth was not my last.

[Al Koholic]

There shouldn't be anything that would compromise the stability of the AP in the kind of H2SO4 drain cleaner I'm thinking of. However you might be using the dyed kind...this really has probably been discussed in the 'other explosives section'...Not really on topic here. Try a search.
Also, if you have KNO3 or NaNO3, or even NH4NO3, TNP is a really easy first HE synth and unless you mistreat the product in very bad ways, you won't be exposed to a detonation...

<small>[ January 23, 2003, 01:21 PM: Message edited by: Al Koholic ]</small>

[Anthony]

The various drain opener H2SO4 that I have used has ranged from 91-97%.

Please try to keep the threads on topic. We're currently discussing the impurities in drain opener H2SO4 in the "NG is red" thread.

[nbk2000]

You say you get an 84% yield.

84% of what? Based on the amount of ASA used? Or calculated yeild?

[Al Koholic]

ASA 180.16g/mol
TNP 229.11g/mol

From 1 gram of ASA, in theory you would get 1.27 grams of TNP with 100% efficency. I would obtain 1.07 grams with my procedure.

I basically end up with a weight of TNP very close to the weight of the ASA I use....

I have 273 grams of ASA waiting....:-)

[vonK]

From my method using methyl salicylate I have got a 92% yeild.
The method is really a take off of Mr Cool's, using an equimolar amount of methyl salicylate instead of acetylsalicylic acid.
My calculations could be wrong, they always were my biggest downfall.
From 27.5g of methyl salicylate I got 38g of TNP.
Looking back at my old notes, this was one of only about three experiments I ever made notes for, I seem to have said
"1mol MeS =&gt; 1mol TNP". One benzene ring in each molecule, it made sense. From that I calculated a theoretical yeild of 41.2g.
38/41.2 gives 92.2%

I have pretty much given up on TNP. It seems to never dry. Even after recrystalisation it is still an incredibly fine powder.
I tried recrystalising it from meths once and it seemed to consolidate into a golden putty that also would not dry.

The reaction between TNP and aluminium appears harmless.
I once had about 10g of TNP sitting on an aluminium dish for weeks. It turned a lustrous browny-gold and no amount of burning, bashing, grinding or attack with primaries could cause it to do anything remotely spectacular.

Personally I think TNP is too much of a mess.
Its tendency to stain everything in sight has resulted in relentless jeering from my peers and numerous fights with my mother, she was worried about the bathroom sink, not me.

Does anyone regularly use TNP?
I can make shitloads of it, but the stuff is such a pain in the arse.

[Al Koholic]

Vonk, without looking at the actual molar mass of methyl salicylate, I can at least tell you that you're using the right method for calculating yield.

It's odd that your TNP never dries...
All I do is sit mine out on a sealed fiberglass tray while still wet from the washings I give it and blow a fan on it on low speed. Sometimes I use a heater fan but it dries just fine for me with a regular fan as well. Get a nice powder and all...

I never "regularly" use anything at all. I'd say I make TNP more often than anything else because it is storage stable and useful in other reactions...like my DDNP attempts... I live in a city now and have school going on all the time so it's hard to concentrate on chemical reactions when you have an MCAT to study for.

Once I obtain a good vacuum distillation setup (about june 10th or so) this will change drastically as I will add unlimited HNO3 to my arsenal. This will pretty much alleviate the need to ever make TNP except for the purpose of explosive D, and picramic acid...

BTW, when you say I tried recrystallizing from meths...do you mean methyl alcohol? Odd that from such a volatile solvent it never dried...

[Keyser Soze]

Yes, I also feel that TNP can be a bitch with the constantly yellow fingers and its toxicity. VonK, try putting your TNP right next to a dehumidifier(sp?). This works great for drying AP also. Stuff usually dries in 12 hours.

[Al Koholic]

Ummm..."constantly yellow fingers"?

From what I've been reading here...it sounds like I ought to mention that one can purchase a box of 100 latex gloves from Wal-Mart for like 6 bucks. They are extremely easy to get and will do alot to protect against TNP toxicity. It really is not something you want to come in contact with at all.

Uncoupling the proton gradient from oxidative phosphorylation in your mitochondria has a way of leading to a rapid death...

DNP was sold as a weight loss drug (which it actually does work as) but people started dying because of its tendency to accumulate in the adipose tissue....leading to toxic levels.

Seriously though, TNP is no better and I would just try and stay out of contact with the stuff as much as possible...A little won't kill you but its just safe lab procedure to always be wearing gloves.

[Mic]

Well, this is not about making TNP with aspirin but with sodium salicylate.
Somebody actually make this experiment? If yes I would like to hear your method and the quality of the final product. Thank you.

I will be doing soon experiment but i'm not very good in chemistry .. well I'm learning... So I will be trying to achieve to make TNP from sodium salicylate

BTW my Sodium salicylate is a medication against muscular pain. On the bottle it just says that it is sodium salycilate. Do you think that it contains impurities or something else ?

Thanx again.

<small>[ February 05, 2003, 09:56 PM: Message edited by: Mic ]</small>

[kingspaz]

yes, they can't give out medicines in concentrated form otherwise it would be waaaaaay too easy to overdose and die.
sodium salicylate is a salt of salicylic acid. the salicylate anion is more basic than an SO₂^2- so will accept H⁺ ions from sulphuric acid. this mean is you mix sodium salicylate with sulphuric acid you'll get salicylic acid and sodium sulphate (if low concentration acid is used). so basically it should work if you use a load more acid. of coruse you'd have to work out the best amount to use from the reaction equations.

[Al Koholic]

Yesterday I made some more TNP just because...
Anyway, when I went to pour out the required amount of H2SO4, I noticed that the acid was very milky coloured. I had used it just 4 weeks ago for some TNP and for some reason in that time it had gone kind of cloudy.

It had been shaken a little probably during transport of the acid from home to school when I moved back for this semester. The acid is drain opener acid and is clear, straight from the bottle normally.

I proceeded to dissolve the ASA in the acid and then began to heat it. I went and studied while it heated, periodically checking on it. The hotplate I was using kept shutting off by itself so I moved the beaker to another hotplate that was not digital so I couldn't closely monitor the temperature. Well, I set it on low and went and studied a little more. It was magnetically stirred this whole time and when I came back to it about 5 or 10 minutes later, I immediately noticed whitish/metallic swirls in the now dark sulfonated phenol solution. I thought "uh oh....I heated it too hot" but when I checked the temp the solution was only 93 C. Soooo...I proceeded to shut off the magnetic stirrer and then I became amazed. Stirring the solution with the thermometer produced an unbelievably beautiful swirl/mosaic/whatever pattern in the liquid. It was almost metallic looking! Like some kind of silvery colloid was suspended in the dark solution. It looked like something you would see in a CGI special effects movie...totally unlike anything I have ever seen. Quite possibly one of the most beautiful and perplexing things to look at. It looked like silver plasma rippling and twisting through the liquid. It did not settle out and never mixed with the black like you would expect upon stirring.It was just kind of like....part of the solution and just kept producing the effect!

I hypothesize that the effect was produced by the cloudiness of the acid but I cannot think of what could have gotten in there to cause the change in transparency. The bottle was not opened or disturbed greatly in the time since I last used it. I still have a little bit of the acid left.

Has anyone ever overheated the sulfuric/asa mix? I'm going to try doing that to see what happens. I still proceeded with the nitration and all throughout the process, the silvery swirls were present. The yeild was exactly the same as always...an almost perfect 30g ASA = 30g TNP conversion (84% yield).

Has anyone else ever experienced this?

[EP]

So I decided to give TNP a shot today. The crushed aspirin tablets were added to heated acetone and stirred. This was then filtered, leaving a considerable amount of solid (several grams from using ~30g crushed aspirin). It seems that some of the ASA may have recrytalized and been filtered out because it doesn't seem like it would have that much binder... Anyway, I put the beaker of acetone/ASA solution back on hotplate and once it heated up (using Mr. Cools synth, it says to heat it to evaporate off some of the acetone then let it sit to evaporate the rest) it started popping! <img border="0" title="" alt="[Eek!]" src="eek.gif" /> I could hear it popping and see the acetone bubble up each time there was a pop. I've never heard of this happening, whats going on and is it a problem? I took it off the heat because I was rather worried about it...

Maybe I shouldn't bother purifying the aspirin. Any ideas/suggestions?

[Al Koholic]

What sort of heat source were you using? If it was too hot, you'll get popping from the acetone boiling. Like when boiling water in a pyrex beaker without bump chips....

[EP]

What are bump chips? I guess I'll just try it on lower heat, the hotplate can be seen here a few pics down:
<a href="http://www.geocities.com/extremepyro3/updateteaser.html" target="_blank">http://www.geocities.com/extremepyro3/updateteaser.html</a>

[NERV]

I think he meant boiling chips. Boiling chips are just chunks of broken glass that allow more surface area for bubbles to form on. This prevents them from forming in the middle of the solution, which is the cause of the "bumping".

[Al Koholic]

Yeah thats what I meant...I have seen them referred to as either bump or boiling chips. The only thing I think the source of your popping could be is heating too hard with no boiling chips. This causes a rather large bubble to form very rapidly. This can be quite violent at times especially when heating too strongly.

BTW, I think the solubility of ASA is higher in alcohol than acetone. I could be wrong about this but I do know that 1 gram ASA dissolves in 5 ml of alcohol. Anyone know what its solubility in acetone is?

Al

[EP]

Well I tried it without purifying this time, I don't know if it worked properly...

here are some pics:
<a href="http://www.geocities.com/extremepyro3/tnp.html" target="_blank">http://www.geocities.com/extremepyro3/tnp.html</a>

So my question is what is this nasty slime? It floats to the top and when I skim it off more forms. Is it just crap from not purifying the aspirin tablets? It's not TNP is it? From the pictures I've seen I don't think it can be, but who knows... Should I just skim it off and toss it? I tried filtering the liquid, it was going very slow so I'm going to try and set up something better...

[Al Koholic]

Wow...that sure is some foaming there!!! How fast were you adding KNO3?

The red stuff is NOT TNP... I have never run into it before in this procedure so my best guess is that it is some sort of byproduct from not purifying the ASA. I would say it would be in your best interest to just skim it and chuck it unless you are realllllllly curious and want to have a go at characterizing it with some experimenting...

What type of drain cleaner are you using? IE: Is it the black kind or clear stuff?

Its quite odd that it got all hard and lumpy like that! If we had some numbers as to the amounts used it may help deduce this debacle!
Anyway, it looks like the reaction might have worked with low yield judging from the way the precipitation looks...

If you can, rig up some sort of aspirator and do a vacuum filtration to save time. When you are done separating out the product, check it's solubility, flammability (with a small amt) etc... You could even try recrystalizing it to get a better idea of how contaiminated the reaction was...

[EP]

I added the KNO3 in bits half a gram at a time, stirring for 5-10 between each addition. There was no NO2 given off, but there was a white vapor give off after stirring in each addition (HNO3?).

I was actually using some technical grade H2SO4 I recently got, not drain cleaner. I used the amounts on Mr. Cool's site, following his directions except skipping the purification.

I went back and filtered the stuff after skimming of most of the slime on the top, there wasn't much, but hopefully it's actually TNP. I'll post a couple pics once I get a chance. I filtered it through a square of cloth cut from an old shirt because the coffee filters were too slow and didn't fit very well into my funnel made from a 2L pop bottle, it probably let a bit through. What should the crystals look like once they are added to the cold water? Are they like powder or are the crystals large enough to see?

[EP]

I'd edit but it won't let me... :confused:

Anyway, here are some pics of the solid filtered out. I got rid of the liquid... The solid isn't the bright yellow I suppose it should be, perhaps its that slimy crap just coating it.

the new pics are below the hr line:
<a href="http://www.geocities.com/extremepyro3/tnp.html" target="_blank">http://www.geocities.com/extremepyro3/tnp.html</a>

[NERV]

That goo is most likely just the binder from the aspirin. The binders in my aspirin are dicalcium phosphate dihydrate, glyceryl triacetate, hypromellose, starch, and talc. If your aspirin is similar to mine it probably contains nitrated starch, and some other gunk.

<small>[ February 18, 2003, 09:16 PM: Message edited by: NERV ]</small>

[rjche]

As to the topic posters fighting contamination of their aspirin here is a suggestion:

If you buy your aspirin in the bulk powdered form from places that sell mailorder cattle and horse farm products it has no pilling fillers in it.
Costs about $6.50 usa a pound.
One of several easy sources in usa is jeffers, phone 1 800 jeffers.

Farmers round here buy it to treat cattle and horses when they have fevers running too high or are in pain from falls or strains etc. Basicly the same reasons humans use it, but a 1500 lb animal takes 2 oz. at a dose , every 4 to 8 hours, so human size pills are out of the question. Its often put in their drinking water, so they get the right dose as they drink their daily water ration.

They also sell huge pills (100 human tablets worth in one bolus).

50 boluses weigh 5 lbs, and cost about 20$. That's $4 a pound but you are back to the contamination problem again.

For large animals it takes 5 boluses a day.

By mail no questions are asked. In a local store you might need the above info to sound knowledgeable about why you are buying it.

It is a common product among animal farms especially horse farms.

[Genital-Warfare]

You have the messyest lab set up ive seen, im only comenting on that because of the high toxicty of PA. Really you should not have suff like that all saturated in PA i would clean up each beaker before i continued the experiment. Really im not trying to nag just trying to give some good advice.

How long did you let the asprine sulfinate for before you added the kno3? Im guessing that could be a flaw, look at sciencemadness.org and look for the thread on the mysterious red goo.

CTR