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Smoer
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Thank you for the info and nice pics .
But I still have a few questions:
| Quote: | | in kaltem dagegen kaum (0.81 g in 100 g 10 °C kaltem Wasser |
Does this mean that in 100grams(=100ml)of water,only 0.81gram of Pa can be solved at 10°?
----------------------------------------------------
The synth in this topic says you have to heat the ASA+H2SO4 at 70°,then add the KNO3 en let it cool down to 5°.
But your(Mephisto's) synth says you have to heat it at 90°,then add the KNO3(temp below 45°) and then heat it for 15 min at 120°.
So what is the best way en why is heating necessairy(because brainfever doesn't heat it).
Thank you for answering.
cheerz
[Edited on 13-11-2004 by Smoer]
[Edited on 13-11-2004 by Smoer]
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Mephisto
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> Does this mean that in 100grams(=100ml)of water,only 0.81gram of Pa can be solved at 10°?
Yes. This information is from Urbanski (I), page 257.
> So what is the best way en why is heating necessairy(because brainfever doesn't heat it).
To complete the sulfonation and nitration, heating is necessary. Although I tested this way twice, the time and temperature aren't only my own
empirical realization. Since it's almost two years ago, when I write down my synthesis, I can't find today the original source of this
information.
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Smoer
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So,I made picric acid .
Synthese:
First I dissolved 8,4grams of ASA in 50 ml H2SO4 on a temperature between 80° en 90°.After that de solution turned black/brown.Then,I let it cool
down to 30° and started adding 18grams of KNO3 to the mixture slowly.First the solution turned orange and after all the KNO3 was added it was
red(took me about 40min to add all the KNO3.).I didn't let the temperature rise above 45°.
I heated the mixture up to 120° degrees for 20minutes.The mixture turned brown/yellow.Then I dumped the mixture in ice cold water and immediatly the
solution turned yellow.I filtrated the solution and I think its a >70% yield .
Pictures will follow.
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Smoer
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Hi,
Sorry for the dubble post....But does anyone knows were I can find the solubility of different Picrid Acid salts?(especially Sodium picrate).
BTW: PA yield is 50%  little dissapointed)
cheerz and thanks for answering.
[Edited on 11-12-2004 by Smoer]
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Quince
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I assume ammonium nitrate can be substituted for potassium/sodium, as in other nitrations?
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Bert
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Go here.. Yes, it will work. Sodium or potassium nitrates will work better.
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Quince
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When making a nitrate by neutralizing the easily obtainable weak HNO3 with a hydroxide, I remember I read somewhere that one of the common hydroxides
formed water of crystallization, so it's suboptimal for that use. I can't remember if it was caclium or sodium (I have both hydroxides).
Does anyone know which one it is?
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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froot
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Bert, in my experience I've found that substituting KNO3 with NaNO3 in the PA synth doesnt seem to work. The 'product' is yellow but it
completely dissolves in the in the water that's meant to precipitate the PA, whereas KNO3 works fine. The reason for this is beyond me so if
anyone knows please enlighten me.
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
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Quince
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Oh shit! I just spent time making NaNO3 by neutralizing dilute HNO3 with NaOH, not to mention that I fucked up two batches since I poured H2O2
instead of the acid (the bottles are almost identical) before I figured out why the fucking thing kept bubbling... 
I thought that the NH4+ ion behaved similarly to K+ in a lot of solutions, so wouldn't NH4NO3 be a better substitute for KNO3?
BTW, I read one of Rosco's posts at roguesci.org, and he suggests making dets with base of picric acid, primary of [4 (basic lead picrate-lead
nitrate-lead azide).12 lead azide), and initiator of lead nitrato-bis basic lead picrate. To make this one needs lead nitrate and sodium azide.
Where do I buy these two or how do I synthesize them?
[Edited on 4-3-2005 by Quince]
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Quince
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So just to be clear, Megalomania's method uses about three times too much acid?
Edit: I had already mixed the H2SO4 and ASA before I realized it was too much acid, so I just continued with that mix. The color began lightening
right away when I started NaNO3 addition (I made the nitrate yesterday, and it had already increased weight by 25% by absorbing water I guess), going
from dark reddish-brown to orange. The temperature stayed below 45*C during the ten minute addition, but there was still some undissolved solid. I
heated in the microwave to 120*C, which dissolved the solid completely and turned the solution to yellow. There's a good deal of bubbling and
acid vapors coming off, and maybe a bit of NOx (hard to tell). It's cooling outside now. I thought the mixture was supposed to turn black
again... BTW, my guess is that Megalomania specifies this much acid since it's easier to dissolve the ASA and nitrate in it.
Edit: plenty of precipitate when dumped into cold water, but it went right through the coffee filter. WTF? All I have to show for this are some
yellow stains, which especially sucks because I had to synthesize the nitrate too -- basically a heartbreaking disappointment...
PowerLabs says the dinitro- and mononitrophenols are more soluble in water, so perhaps my mix didn't nitrate enough. Or, perhaps it's due
to the too much H2SO4 from Megalomania's instructions, making for too much liquid overall, thus more of the PA dissolving. Or it has to do with
that I used NaNO3. Has anyone here used this salt instead of the potassium with success in this procedure?
[Edited on 5-3-2005 by Quince]
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Bert
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If you didn't throw away the batch- Chill the filtrate liquid that went through your filter to near freezing. You will see the precipitate
re-form. Use several coffee filters in a stack. Don't wash the filtrate with more than a bare minimum of ice cold water. Pre-chill the equipment
so it doesn't warm up your mixture to the point that the picric acid can dissolve.
How small was your experiment?
Powerlabs is not a very good source for proper ratios. Sodium nitrate works just fine. Trust Mega.
[Edited on 5-3-2005 by Bert]
[Edited on 5-3-2005 by Bert]
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Quince
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| Quote: | | If you didn't throw away the batch |
I had second thoughts halfway through purging, but...down the sink it went.
My size was 10 tablets. I used acetone instead of alcohol, as in my first try with 99% isopropanol, heating it to evaporate faster made some of the
alcohol react with something in the tablets and resulted in some sticky gummy shit.
Is the heating Mephisto writes to 120*C really necessary? Megalomania's procedure doesn't mention it, nor does Brainfever's.
As to which procedure, in an earlier post here the admin says to trust the PowerLabs instead. I'm confused by contradictory recommendations.
[Edited on 5-3-2005 by Quince]
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Bert
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That batch size is so small that you would have very little left after inefficiencies and losses, and could easily have the whole remaining batch
dissolve in the water at the end of the procedure with a minor positive error in measurement of the water and/or a slightly too warm water temp.
Heating is necessary. Read the whole PA thread on E&W and carefully note who claims to have what yields with which procedure. I should perhaps
have said E&W, not Mega
Tiny batch sizes have their place, assuming one is set up to measure accurately. Microtek size batches require microtek precision... Just ask
Microtek..
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J_O_H_N_Q
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Why don't you just work it out stochiometrically for yourself?
That way you know it'll be accurate because you didn't just take someone who you've never met before's word on it.
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Quince
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| Quote: | | That way you know it'll be accurate because you didn't just take someone who you've never met before's word on it.
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By that logic: Do you really know the view that the Earth is round is accurate? After all, what if you haven't met any astronaut that has seen
it with his eyes?
Plus, my numbers are different from every procedure, so I'm missing something here:
According to PowerLabs, H2SO4 breaks down ASA to acetic and salicylic acids, but it doesn't say any H2SO4 is consumed, so I'm assuming
it's just a catalyst. 1 mol ASA makes for 1 mol salicylic acid. This is sulfonated with 1 mol H2SO4, and then it takes 1 mol H2SO4 to make 1
mol HNO3 when NaNO3 or KNO3 is added. So, for 1 mol ASA that's 2 mol H2SO4. With H2SO4 being 1.87 g/mL, that gives with 95% acid about 110 mL
for 180 g ASA (that's 554 tablets)! So, since my numbers are so far from everything else (or perhaps this javascript calculator is fucked, http://environmentalchemistry.com/yogi/reference/molar.html), I'm doing it wrong and I have no choice but to pick someone else's ratios.
[Edited on 7-3-2005 by Quince]
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Mephisto
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Quince: Your calculation will give an almost dry reaction-mixture. To avoid the formation of solids in the mixture, the surplus of
sulfuric acid is used. Megalomania exaggerates this a little bit. 50 g of ASA in 250 ml of sulfuric acid is a fine ratio.
Here the translation of this method from www.LambdaSyn.tk (German):
******
Add 50 g of dry acetylsalicylic acid and 250 ml of concentrated sulfuric acid to a 600 ml beaker. Heat the mixture 10 minutes to 90 °C, to dissolve
the acetylsalicylic acid. Let the mixture cool down and add 87.5 g of dry potassium nitrate or 74 g of sodium nitrate. Add a few grams at a time then
wait for the reaction to subside before adding more. During the addition the mixture will turn orange and nitrous gases (!) and CO2 will escape. At
this point it should be avoided to let the temperature rise above 45 °C (foaming gets uncontrollable at higher temperatures). Heat the mixture after
all nitrate is added and no more foam occurs 15 minutes to 120 °C to complete the reaction. Allow the mixture to cool to room temperature and pour it
into 1500 ml of ice water to precipitate the picric acid. Filter the solution to collect the picric acid crystals and wash them with cold water to
remove sulfuric acid traces.
******
This method was carried out successfully. If some is interested, there are some pics taken during the method (see attachment).
Attachment: 14pics.rar (467kB)
This file has been downloaded 1914 times
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Quince
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I'm going to try again then.
Has anyone here had success with NaNO3? No one has yet commented on froot's post above:
| Quote: | | Bert, in my experience I've found that substituting KNO3 with NaNO3 in the PA synth doesnt seem to work. The 'product' is yellow but it
completely dissolves in the in the water that's meant to precipitate the PA, whereas KNO3 works fine. The reason for this is beyond me so if
anyone knows please enlighten me. |
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Bert
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Rosco Bodine quite specifically recommends Sodium nitrate in his procedure. Go do a search of his posts on E&W for the whole post. Picric acid archive file page 2
Once again: more searches = posting less (frequently!) previously answered questions
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Cloner
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The problem with using salts and not nitric is that the already viscous and nasty stuff gets even viscouser and nastier! Among salts, I think KNO3 is
the worst choice in solubility. I just tried NH4NO3 and KNO3 and not NaNO3 but for these two salts it is most definitely true. Nitric acid is better,
although it is also capable of producing a nasty viscous mass that forms bubbles which do not burst and just come out of the container.
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Quince
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I just used my DIY magnetic stirrer in its first synthesis, picric acid. There was no problem dissolving the nitrate (sodium). Also, I had no
problem with sodium nitrate as someone else on this thread did. I used Rosco's procedure that someone linked to above, and even with my tiny
scale of 5 g ASA I got about 70% of the stoichiometric yield.
One thing bothers me, though: when boiling down the liquid for the second crop of PA, I did not get any molten red precipitate of impurities, so I
just let it crystallize at that point. I wonder if I have a lot of impurities left in that second crop because of that, in terms of anything that may
increase sensitivity.
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Rosco Bodine
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No problem . Even with a batch that is 20 times the scale as your reaction ,
the residue of impurity would only amount to about a gram . The way this impurity
is separated out is to boil down the solution left from the first crystallization until a precipitate is observed in the boiling solution . Most of
the precipitate is actually picric acid , but it carries with it most of any impurites which form a melt and settle as a globule of red material .
This globule will solidify almost immediately as the heat is reduced ,
and will stick fast to the bottom of the vessel as the hot remaining solution is decanted . The decanted solution on cooling will precipitate clean
light colored crystals of picric acid free from any " red goo " or impurities which would darken the color .
The second crop of crystals is only about
ten percent of the total yield , so unless
you are working with a fairly large batch ,
the second crystallization is hardly worth the effort .
As for the impurity causing sensitvity issues , probably not .
Any melt compositions of this sort are likely less sensitive than pure picric acid .
Sodium nitrate has been used on a medium industrial scale for batch nitrations producing picric acid in good yield , so it is a well proven method ,
even though the literature references may be obscure since that method was obsoleted by more modern methods nearly a hundred years ago . Even so ,
the primitive method can produce yields of 85-90% picric acid from recrystallized aspirin .
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The_Davster
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Has anyone ever gotten a picric acid that is bright yellow(more so than regular picric acid), forms no actuall crystals after recrystallization, does
not stain filter paper severly yellow and most importantly burns incredibly fast? I used Mr. Cool's procedure, only 1/10th the scale. Only
other difference was that it was crashed into cold water, not ice and water. Could it have formed potassium picrate somehow? It reminds me of
potassium picrate when it burns.
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Quince
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One more thing...how do I get PA yellow stains off skin? I mostly used gloves, but at one point I forgot, and it was the worst one to do so --
squeezing out the filter. Washing with water and several solvents didn't do much, and my fingertips are still yellowish...
At least I'm not worried about licking them, as the stuff is incredibly bitter.
[Edited on 13-3-2005 by Quince]
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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Smoer
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You can't wash it away...It will stay on your skin for about a week..
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BrAiNFeVeR
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Please bear in mind that at the time the picric acid synth at my site was made, I knew allmost nothing about chemistry.
I clearly state at the entry page that it is probably not the best way to get what you desire.
Now that I have cleared myself of all possible blame and waste of acetylsalicylic acid I think I actually DID heat the H2SO4 and phenol to make the latter dissolve.
I don't quite remember where I got my procedure from, but I suspect a thread on the old E&W forum.
If I ever have time again  I'll redo all improper synths on my site, and
filter it's contents a bit. (like that AP electric detonator ... that HAS to go!!)
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