DDNP procedure

[stanfield]

I was trying to make DDNP but, there are some problems...

1. I dissolved 10g of NaOH in 100 mL of H2O. Easy http://theforum.virtualave.net/ubb/smilies/smile.gif

2.I added 10g of sulfur then I heated the solution during 6-7 min at 85-90°C (until "it gently boil") ==> the solution became brown red but there is an excess of sulfur on the top of the solution and, after cooling, I can see some powder (sulfur ?) low in the beaker, is it normal ? Do I need to heat again and again the solution to dissolve all the sulfur ?

3. I made the solution of NaOH, picric acid and water. Easy http://theforum.virtualave.net/ubb/smilies/smile.gif

4. In this step, I must add the solution I heated (sodium sulfide ?) in 5 times... ok, but, the sodium sulfide must be hot or cool ? (room temp.)

thanx to answer all my questions...

[Tony Montana]

If I understand your post correctly, you have two different solutions: 1'st=Picric acid/Sodium hydroxide/Water and the 2'nd=Sulfur/Sodium hydroxide/Water.
Alright, your on the right track!
The solution of Sodium hydroxide/Water/Sulfur you heated, you are meant to gently heat until until solution turns dark red. Then allow to cool to room temperature. Then slowly stir the red water/sulfur/sodium hydroxide mixture into the water/picric acid/sodium hydroxide mixture. Let this new mixture stand (at room temperature) for 30 minutes, stirring every 5 minutes. Filter this mixture through filter paper, reddish crystals will collect on the paper. Keep the crystals and discard the liquid. Then the crystals are dissolved in a pre-determined amount of boiling water. The mixture is filtered, but this time the liquid is kept and the filtrate is discarded.
Hopefully you know the rest Stanfield, if not just let me know and ill post the whole recipe!

[stanfield]

thanx but why there is an excess of sulfur, even after heating ?

see ya !

[Mr Cool]

The ratio of Na:S is wrong if the product formed is Na2S. You have too much sulphur, so just filter the solution and then use it. You have 0.25 moles of sodium and 0.3125 moles of sulphur, whereas you should have 0.25 moles of sodium (10 grams of NaOH) for every 0.125 moles of sulphur (4 grams of sulphur).
I haven't worked out how much sodium picrate you'd need when using 10g of NaOH and 4g of sulphur, I will do if you want.

[stanfield]

If you have some time, work on it, it will be very nice but the "recipe" says 10g/10g !

see ya !

[Mr Cool]

When using 10 grams of NaOH and 4 grams of S (or 10 grams of Na2S), you'll need 31.4 grams of C6H2(NO2)3ONa. That can be made from 28.6 grams of TNP and 5 grams of NaOH. This is, of course, assuming 100% reaction at every stage. This will make 24.9 grams of picramic acid. This will need to be reacted with 10.6 grams of KNO2 or 8.6 grams of NaNO2 to make 26.3 grams of DDNP.

Actually, I've just thought: the reaction for the Na2S must be (I think) 4NaOH + 3S --> 2Na2S + 2H2O + SO2. So in order to get the 10 grams of Na2S needed in the reaction above, you'd need 10 grams of NaOH and 6 grams of sulphur, not 4 grams.

How does that compare with the ratios in your "recipe"?

[stanfield]

I saw the "recipe" in the Kitchen Improvised Blasting Cap, next, I posted a topic on the Forum and one guy (I can't remember, do a search...) said he suceed making DDNP with 10g/10g

here is his topic :


Ok guys I'm back, I just had to get a few explosives precursors from the local grocery before they closed up shop at 9pm. Will append the results to this post...

OK I wiped the beaker completely dry... At first with an ordinary towel, then with a soft paper towel. Then I placed it in the oven for 10 minutes to drive off the remaining moisture, the usual procedure in every recipe Then 3ml of water were carefully measured out into the beaker... I added 7.5g sulphur and 7.5g NaOH. There was no reaction. I put it on the hotplate. Soon I realised that there is no way this is gonna work. All of the NaOH dissolved, and some sulphur too, the solution indeed turned yellow-red (which I assume to be Na2S and Na2S4), some yellow-green oily liquid formed on the top of the mixture, which I assume to be molten sulphur. But, on cooling (which they suggest) the sulphur solidifies, so it's neither dissolved nor reacted. Some S remains unreacted. The red solution started boiling and smelling like hell, I fear it's decomposing. OK so tell me (with a straight face) how many of you guys have actually attempted DDNP according to the Tim Lewis' recipe...
Now adding 297ml H2O. At first solution turned yellow-green. After a while the red stuff started dissolving. I stirred it, solution turned orange. Small bubbles formed on the sulphur. Now I am cracking up the solidified sulphur, it still takes ages to dissolve it... After some time solution is about the color of tea. Now there are huge bubbles on the sulphur pieces, and I can't crack them up, because they're flying around, funny... The volume of the solution was reduced to 270ml by boiling! Reduced the heat, now it's at lowest heat. The 3ml experiment was a fuckup in that it turned the sulphur to big pieces, which don't dissolve. So when you do this, start with a fine sulphur powder. Solution is brown, 250ml. After some more ages it starts turning red. Refilled to 320ml. Finally, it all dissolved, by the time it was boiled down to 120ml. Solution is reddish brown, but stains paper in yellow-green. Some fine insoluble residue appears in the liquid, but I assume this to be an impurity from the sulphur.
The 100ml batch took a lot of time too, I haven't crushed it properly, but finally it dissolved, some residue appears - the amount is negligible, but it's a bit coarser than in the previous batch. After cooling nothing precipitates, so 100ml should be OK.
10fingers suggested the Lewis formula is correct so I tried the controversial stuff again... Trying with 1ml, 2x 2.5g. Upon addition of the NaOH to the 1ml water there is a violent reaction and heating, some of the NaOH cakes. Put it on the hotplate. The 1ml water is quickly boiled away, it's difficult to keep replacing it so that the volume is constant. When heated, the mixture is brick red. Then it starts to fizzle, decompose and gives off some irritant gas (feels kinda like tear gas). After cooling it forms the sulphur lumps same as before, color is reddish brown. I cycled through this 3 times, and allowed to cool. It definitely doesn't form a solution, but rather a thick mass. So my conclusion is: This way it is difficult to moderate the reaction, it gives off nasty fumes, cannot be poured out the reaction vessel, and does not behave the way it's described in the books (I cannot imagine how this could be poured in three portions). I can't help it but I keep thinking the 3ml or 1ml formulas, must be wrong. And why would they use a 500ml beaker?

The recipe: Crush 10g of sulphur to a fine powder. Into a 250ml beaker or jar place 100ml distilled water. Dissolve 10g NaOH in the water, stir to prevent caking. and keep replacing what is being boiled away, until everything had dissolved. Solution should be a reddish brown color. This is a mixture of sodium sulfides in water. Let it cool down. If an insoluble residue remains in the solution, pour in the sulphur powder and heat the mixture so that it gently boils. Stir occasionally , do not filter, it will be removed later in the process. Into another 500ml beaker or jar put 90ml distilled water and 1.5g NaOH and stir until the lye had dissolved. Dissolve 12g of PA in the solution with stirring. Add the cooled sodium sulfide solution in five portions, to the PA solution. Stir with a teflon rod while the liquid is being added. Again allow the solution mixture cool. Filter this mixture through filter papers (coffee filter, paper towels). Small red particles will gather on the paper. Discard the liquid. Dissolve these red particles in 180 ml of boiling water. Remove and filter this hot liquid through a filter paper (coffee filter, paper towels). Discard the particles left on the paper and save the liquid.
Now if you just wanted to make %SUBJ% (why??? Silly idea! It's toxic!) just evaporate the liquid to dryness (do not overheat, dry in an oven with precise regulation at 150°C, or on an oil bath, do NOT exceed this temperature) and you should get red crystals of pure picramic acid. You should evaporate this and weigh it out anyway, at least for the first time, to ascertain the yield of picramic acid. Theoretical yield is 11,26g.
10g of picramic acid is dissolved with strong stirring (or magnetic stirrer) in 120ml of 5% HCl in a 250ml beaker placed in an ice bath. 3.6g of NaNO2 is dissolved separately in 10ml water and added in one portion to the picramic acid solution, with stirring. Let the mixture stand for 20 minutes. The mixture will turn a brown color. Filter the brown solution through a filter paper (paper towel, coffee filter). Wash the particles left on the paper with 60 ml of ice cold water. The DDNP is then purified by dissolving in the smallest amount of acetone possible. The acetone should be preheated to 40-45°C. With stirring this solution is slowly dumped into ice cold water, the precipitate is filtered and allowed to dry. Leave a small amount of water for safety.
I will keep updating this recipe and will write a note here if anything changes. Recently I adjusted amounts so that amount of picramic acid matches second step. Now I found out that the "second step" is virtually identical to Megalomania's procedure. Any input is welcome.

what do you think ?
if possible, post YOUR recipe...

see ya !

[Mr Cool]

Sounds like you use too much sulphur and not enough water to me. I'll post more in the morning.

[Tony Montana]

The way that works!
CHEMICALS REQUIRED:
Picric acid=3 units by weight(UBW)
Sulfur (powdered)=2.5 UBW
Sodium hydroxide=3 UBW
Potassium nitrate=1.8 UBW OR Sodium nitrate=1.8UBW
Sulfuric acid=2.5 UBW
Water

MANUFACTURE:
1. Pout 30 UBW (units by weight) of warm water into the first container.
2. Stir 0.5 UBW of sodium hydroxide into the water in the first container.
3. Stir 3 UBW of picric acid into the water/sodium hydroxide mixture. Set this mixture aside.
4.IN A NEW CONTAINER: Pour 1 UBW of of water into the second container.
5. Stir 2.5 UBW of powdered sulfur and 2.5 UBW of sodium hydroxide into the water.Stir this mixture for one minute.
6. Place the water/sulfur/sodium hydroxide mixture on the heat source. GENTLY heat the mixture until it turns a dark red color. Remove the mixture from the heat source and allow it to cool to room temperature.
7. Slowly stir the red water/sulfur/sodium hydroxide mixture into the water/picric acid/sodium hydroxide mixture from step 3. Let this mixture stand for 30 minutes, stirring every 5 minutes.
8. Filter this mixture through filter paper. Reddish crystals will collect on the paper. Keep the crystals and discard the liquid.
9. IN A NEW CONTAINER: Pour 60 UBW of water into a new container.
10. Heat water to a low boil, turn off heat.
11. Dissolve red crystals from step 8 in boiling water.
12. Filter the mixture through filter paper. This time, keep the liquid and discard the material that collects on the filter paper.
13. IN A NEW CONTAINER: Pour 6 UBW of water into the new container. Slowly stir 3 UBW of sulfuric acid into the water. This water/acid mixture will be referred to as diluted sulfuric acid.
14. Stir ONE DROP at a time of the diluted sulfuric acid into the liquid (from step 12) until the liquid turns aa orange-brown color. Be sure to add the acid one drop at a time so only the minimum amount necessary to change the liquids color is used. Let this mixture stand for 5 minutes.
15. Stir in an additional 2.5 UBW of diluted sulfuric acid into the above mixture. Let this mixture stand for 30 minutes.
16. IN A NEW CONTAINER: Pour 80 UBW of water into a new container. Stir 1.75 UBW of potassium nitrate into the water. Stir until potassium nitrate dissolves.
17. Stir potassium nitrate/water mixture into the mixture from step 15. NOTE: The crystals that settle out of this new mixture are DDNP. Handle with care.
18. Filter DDNP out of the mixture using filter paper.
19. The DDNP must now be dried. Hope you now how to do this, if not let us now and I will post a few good ways.

[stanfield]

Thanx Tony Montana but what's this "unit by weight" (UBW) I'm french and here, we don't use this unit...
example :
for 5g of picric acid, I'll need 4.16 of sulfur right ??

To dry it, I've heard about and oil bath or in an oven (both at 150°C)

Let's see the Mr Cool's Recipe now http://theforum.virtualave.net/ubb/smilies/smile.gif !

see ya and thanx again for all !

[Mr Cool]

Well I've never heard of nitrates being used, only nitrites. It's not a nitration remember, it's an azotisation.
I wouldn't dry it at above 100*C just to be extra safe but 150*C should be OK.
I'd use the same method as Tony, but by my calculations he has 5 times too much sulphur and 2.5 times too much NaOH. He's using the usual 1:1 ratio, which from what you've told me doesn't work. I'm sure it would work though, becuase the excess sulphur is filtered out, and the fact that you have an excess of sodium sulphide means that you won't be wasting any of your TNP.
After you filter it out, you should recrystalise it from acetone.

[stanfield]

two questions :
- what about Unit By weight ? (is my calculation right ?)
- couls you tell me more about recrystalisation from acetone (especially measurement (ratio DDNP : Acetone ...)

thanx for all !

[Tony Montana]

Units by weight means it is measured by weight instead of volume. The easiest way to go about figuring this out is to just multiply all by ten for example 5 units by weight picric acid and 2 units by wieght water: is easily worked out to 50grams picric acid and 20 grams of water.
Picric acid=3 units by weight(UBW)
This from above:
Sulfur (powdered)=2.5 UBW
Sodium hydroxide=3 UBW
Potassium nitrate=1.8 UBW OR Sodium nitrate=1.8UBW
Sulfuric acid=2.5 UBW
Water
Is easily converted to:
Picric acid=30 grams or grains
Sulfur (powdered)=25 grams or grains
Sodium hydroxide=30 grams or grains
Potassium nitrate=18 grams or grains OR Sodium nitrate=18 grams or grains
Sulfuric acid=25 grams or grains
Water
It is basically the ratio (by weight) of the ingredients.
DRYING FINISHED CRYSTALS:
1'st method: Using a hot water bath. Place a small amount of finished product in a suitable container. Fill a pan with hot (90* C/194*F) water and then place the container in the pan. Refill the pan with hot water as it cools.
2'nd method: Using an oven, first preheat the oven to 100* C(212* F). Then turn the oven off and wait 10 minutes. Place a small amount of finished product in a suitable container. Place the container into the oven. Let the material sit in the oven until either it is completely dry or the oven cools below 50* C(122* F). If the oven has cooled but the material is not dry, take the material out of the oven and reheat the oven to 100* C. Again turn it off and wait 10 minutes before placing back in the oven. Reapeat this process untill material is completely dry. Also such things as DDNP should not be dried in direct sunlight.

[This message has been edited by Tony Montana (edited August 17, 2001).]

[Mr Cool]

You should take into account the difference in relative molecular mass between NaNO2 and KNO2. Otherwise some will be wasted and you will therefore have an inefficient reaction. The same number of UBW for each will not work as well as if adjust them.
I don't have exact measurements for the recrystalisation, but just heat the acetone to 50*C and dissolve in as much DDNP as you can (maybe 10g per 100mL of acetone). Filter it if necessary, and dump it into 3 times it's volume of cold water to precipitate the DDNP.

[stanfield]

thanx for acetone...
but I have sodium nitrite, what will it change here ? What will be the new mass of NaNO2 ?

see ya !

[Mr Cool]

I've actually just looked at the ratios again and they are quite similar, so don't bother adjusting them. When using 3 UBW of TNP, you'll need about 1.3 UBW of KNO2 or 1.1 UBW of NaNO2. That is allowing for a slight excess.

[stanfield]

thanx for all, I will try these recipes when I will receive more picric acid. My reseller, sell 25$ for 250 g of picric acid, is the price good ?

see ya !

[Mr Cool]

Yeah, that's pretty good. I wish I could just buy it!

[stanfield]

www.jeulin.fr (http://www.jeulin.fr) => (very good) french industry but I think they sell all over the world... try to see on the web page...
they sell picric acid with 40% water to delete the explosive danger

see ya !

[Ezikiel]

I am still confused.
From what I know NaNO2 or KNO2 (only Nitrites) can be used.
So my question is will Nitrates work too ?

------------------
"Go out in a BLAZE OF GLORY"

[stanfield]

never heard this...

[Lagen]

Nitrates cannot be used. As Mr Cool said, it's a diazotisation reaction. BTW have a look at the new topic (http://theforum.virtualave.net/ubb/Forum1/HTML/000486.html) in the HE section on synthesis of picramic acid. The guy raises some good questions. I hope someone will clear up the "sodium sulfide" thing once for all.

[This message has been edited by Lagen (edited August 19, 2001).]

[Mr Cool]

Thanks for that link, I'll have a look.
It doesn't matter whether it's Na2S, NaHS or Na4S2 - you use the same amount of sulphur for each to reduce the same amount of TNP, e.g. 31g of sodium picrate will need 6 grams of sulphur in the sulphide. Na2S and Na4S2 both need 10 grams of NaOH when using 6 grams of sulphur, NaHS needs 5 grams of NaOH but if you use 10 grams then if the NaHS is made then you'll just have an excess of NaOH, which won't matter. And if one of the other sulphides is made, then you'll have a complete reaction.
You need nitrites.

[Tony Montana]

Shit, the book I was quoting out of:
FMX The revised black book, by William Wallace.
ISBN=0-87364-853-6 by paladin press.
Does have a mistake in it, page 46 DDNP it states to use NaNO3 or KNO3! After cross refenrencing, it is wrong -NO3 ion is not needed -NO2 is!

[stanfield]

What about picramic acid ?
is it dangerous ? explosive ?
could you tell me more about this one especially safety...

thanx...

[Mr Cool]

I can't find much info on toxicity or exact explosive characteristics, sorry.
Treat it like TNP - explosive and toxic.

[EventHorizon]

Merck only states that it has toxic symptoms similar to 2,4-dinitrophenol, which are:

LD 50 orally in rats: 30 mg/kg (Schafer) for 2,4-dnp

and

Caution: Highly toxic material. Readily ab sorbed through intact skin. Vapors absorbed through respiratory tract. Produces marked increase in metabolism and temp, profuse sweating, nausea, vomiting, collapse, death. May cause dermatitis, cataracts, wt loss, granulocytopenia, polyneuropathy, exfoliative dermatitis, Clinical Toxicology of Commercial Products, R. E. Gosselin et al., Eds. (Williams and Wilkins, Baltimore, 4th ed., 1976) Section III, pp 134-137

probably not what you are looking for but maybe it will give an idea.

[stanfield]

thanx,
I especialy wanted to know if this acid is explosive...
see ya !

[PHILOU Zrealone]

Basically a diazotation is an organic reaction between a primary amine and nitrous acid!Thus noway it works with nitrate salts what produces nitric acid...HONO is not HONO2 even if they seem quite similar (a O can make the difference in chemistry just as in a ones person name!).
So:
R-NH2 + HO-N=O --> R-NH3O-N=O --> H2O + R-N=N-OH
R-N=N-OH + HCl --> R-N=N-Cl (diazonium chloride salt)
R-N=N-OH -25C-> R-OH + N2
(that's why you get alcools from non aromatic amines spontaneously and why you may get phenol from aromatic amines).

In the DDNP the acid comes from the nearby neightbourg OH and thus you create a ring closure R-OH + HO-N=N-R--> R-O-N=N-R
As a resume:
HOC6H2(NO2)3 -reducer-> HOC6H2(NO2)2NH2
HOC6H2(NO2)2NH2 + HONO --> HOC6H2(NO2)2N=NOH
HOC6H2(NO2)2N=NOH --> H2O + C6H2(NO2)2N=NO

------------------
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"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"