DDNP

[stanfield]

A few days ago in my dreams, I made some DDNP with the following method :
1) Dissolve 10g of picramic acid in 80mL of water
2) Add a solution of 3.2 g of sodium nitrite and 20 mL of water
3) prepare a solution of 60 ml of HCl at 5-6%
4)add the HCl solution to the solution with picramic acid over a period of 2 minutes...

works well...
All steps were made at room temperature.

I posted this because I tried many times to make DDNP with megalomania's method but its synthesis doesn't work at all !

Do you think an ice bath could help me to increase the yield ? (which is already good...)

thanx.

<small>[ April 22, 2002, 12:40 PM: Message edited by: megalomania ]</small>

[Madog555]

sounds good, i have never made DDNP but as soon as get some nitrite i probaly will.

can you please weigh the yield when it dries?

maybe if you cool the final solution more will precipitate out but i cant realy say sience i have never made it.

did you use low conc. HCl because thats all you have? or does it call for it.

[stanfield]

I have 33% HCl so I did a dilution to 5% ...

[stanfield]

I just weighted out the yield : 5 g
hummmm... very bad, next time I will try to add an ice bath...

any other reply is more than welcome

[Dhzugasvili]

I have made DDNP successfully and with a relatively good yield for my purposes (sorry i forgot to weigh it), NOT using the picramic acid route, instead, the bright and colorful reaction using pottassium nitrite, NaOH, picric acid, etc...im assuming you are familiar with this procedure if not i can post it. However there is an ambiguity in this procedure, how the fuck much sulphuric to add...but i solved this problem by making sure i added enough to the mix to ensure a bright color change of solution from dark brown to orange. it took about 25ml of 98% H2s04. However the first time i made this i added to little H2so4 and this resulted in a very low yield...with this batch i did proper detonation tests with the material, and found that it has to be confined completely to detonate properly when initiation is attempted, UNLESS the charge is greater than six grams, which in case detonation is achieved by the mere mass of the charge.

[stanfield]

during your procedure, you're making picramic acid :)

[Dhzugasvili]

oh, oops, i forgot! Slip of the mind, you're right Stanfield.

[stanfield]

I think that DDNP is the best primaty ever made but picric acid is hard (& very expensive) to get and his manufacture really boring me...

Next time, I must use an ice bath to see if I could increase the yield. I will try tomorrow maybe...

see ya later

[stanfield]

I just re-made some DDNP with the same procedure and I increased the yield ! it's 8g of DDNP whereas 5g to my first attempt (so, yield is 80%)

I repeated exactly the same procedure but I put the beaker with picramic/water/nitrite in an ice bath with acetone then I slowy added the HCl (The temp. didn't rise above 0°C)

I have heard that making little quantity of HE like here always decrase the final yield, do you think I could get the 84% practical yield by increasing the amount of chemical ?

thanx !

[Microtek]

When I try to make DDNP from the picric acid etc, etc route, I have problems getting the picramic acid to crystallize. I try to follow the recipe exactly, except for scaling it down, but in many recipes there are obvious flaws such as the Blackbook: " Add 2.5 g sulfur and 2.5 g lye to 1mL water and boil until it turns red...".
I do get the colour changes, but when I add the red NaOH/S soln to the PA/NaOH it becomes dark red, the slurry is dissolved and that's it. The recipe says to let the solution cool, but the temp hasn't risen at all, and no precipitate is formed on standing.
Any ideas as to what is the matter would be appreciated.

[stanfield]

I posted the recipe of picramic acid on my web site, but he is optimized to 1280*1024, so, you may experience some trouble...
otherwise, the recipe works well...
<a href="http://stanfield.150m.com" target="_blank">http://stanfield.150m.com</a>

see ya !

[stanfield]

ok, I revisited my site, now he's optimized for 1024*768. thanx

At the end of my picramic production, there are always some yellow particle which are picric acid... Could I solve this problem ? maybe by increasing the amount (and not the concentration)of sodium sulfide solution, no ? or maybe by extending the time of picric acid in the solution of sodium sulfide ?

see ya !

<small>[ April 14, 2002, 03:28 PM: Message edited by: stanfield ]</small>

[andreas]

people I may have found a source of sodium nitrite,but before they will ship me anything they want to know what I am going to use it for.
I told them I am interested in chemisty and do lab experiments at home. But what do you use sodium nitrite for ither than diazo reactions. I could make up a lab about indigo preparation and ask them for both fenol(for tnp) and sodium nitrite(for ddnp)
But maybe you have a beter suggestion the fenol isn't nessecery so I could try an other strory

[stanfield]

Maybe you could find some informations <a href="http://www.nsc.org/ehc/ew/chems/sodinitr.htm" target="_blank">there</a>
or maybe <a href="http://www.soilassociation.org/sa/saweb.nsf/848d689047cb466780256a6b00298980/80256ad800554549802569f40040113b?OpenDocument" target="_blank">there</a>
and ofcourse <a href="http://www.google.com/search?q=sodium+nitrite&hl=fr&start=0&sa=N" target="_blank">there</a>

see ya !

<small>[ April 17, 2002, 07:53 AM: Message edited by: stanfield ]</small>

[10fingers]

It's used for curing and preserving meat. Tell them that you make your own sausages. Or you can just order from a Pyro supplier with no questions asked for about $5.00 per lb.

[stanfield]

or do it yourself : search for my old topic :)

[andreas]

Well I tried it today after some calculations.
20gram's with 16 grams of Pb.
Heated it till al had melted and than for 5 minutes.
I will try it after extracting it from the filtrate.
The thing I'm worried about is lead contamination.
That would make the ddnp a lot more unstable.
It is not much used for meat curing here in holland.
My best shot would be for anti-corrosion metall plating

[mr.evil]

i think heating it 5minuts isn't long enough, i guess there must be formed brown PbO to form Na/KNO2.

[mongo blongo]

It takes quite a long time for it to convert! It will turn a brown/red/yellow colour (PbO).
When you have extracted the xNO2 I would advise you to heat it with some more Pb again.I have had to do this many times because for some reason xNO3 didn't totally convert.
Also, to remove the impurities, you could pass a strong stream of CO2 through a solution of the xNO2 for about 5 mins. The solution will turn milky and precipitate out lead carbonate. Filter the ppt out and then you should have pure xNO2.
You can test it by mixing some distilled vinegar and iron sulphate and add some xNO2 and the solution will turn dark brown.
good luck. :)

[Microtek]

What are the products of thermal decomposition of KNO2 ? If one were to mix stochiometric amounts of lead and KNO3, heated until all was melted and then stirred until all the lead had been converted, wouldn't that be an indicator that all the KNO3 had been converted to KNO2 ? It seems that when I do this, I get the lead converted to two kinds of compound; one that is white or yellow and one that is grey like the surface of lead ingots. Any ideas what the difference is?

[mongo blongo]

When the xNO3 is heated (before the Pb is added) it will slowly start to decompose into xNO2 and will give off small amounts of oxygen. This means that after the Pb is added and reacted, there will always be small amounts of unreacted Pb (if you used stochiometric amounts).
As for your products, you should end up with a very thick bubbly liquid which is dark orange in colour with a small amount of molten Pb which rests at the bottom. You may also see some small beads of Pb in the liquid when you stir it. At this point there is so much PbO (your orange product)in the mix that it may get in the way of the reaction, which I think may be the reason why not all of the xNO3 is converted due to the slow reaction rate near the end.
This grey stuff you talk about; Is it like some shiny stuff which rests on top of the mix? I have a small amount of this stuff but I don't know what it is sorry.

[Anthony]

Don't forget that when you weigh out your lead, it's not pure Pb, there's also PbO on the surface.

I'm fairly sure the grey floating stuff you mention is the dross you often get when melting metals, it should be PbO. So dunno why it doesn't appear the same as the PbO formed in the reaction.

<small>[ April 20, 2002, 02:13 PM: Message edited by: Anthony ]</small>

[stanfield]

I just re-made DDNP, the product is filtering and the yield seems to be good as expected...

Sodium nitrite is available at all chemical supplier, try to buy this stuff before trying to make your own which will contain lots of impurities...

see ya !

[Microtek]

Yes I tried ordering it from a chem supply, but they called me back ( thinking they were talking to a company scientist ) saying that they needed a copy of my license to work with poisons ( I didn't think KNO2 was that toxic ). I said that we hadn't been issued one of those yet so we'd have to abort the order for now.
Has anyone of you actually succeded in making DDNP using both homemade nitrite and picramic acid from homemade picric?

[stanfield]

maybe the final DDNP will contain some Pb but there must be a way to eliminate this... On the other hand, will Pb make DDNP super unstable, very reactive, harder to detonate or something like that ? I don't think...

see ya !

[mongo blongo]

Lead picrate may form?

[10fingers]

I have tried making sodium and potassium nitrite via reduction with lead. In my experience it does not work well. Sodium nitrite works a little better because it is easier to isolate, it is more soluble in alcohol than potassium nitrite. Yields are poor also.
I know a couple people who have tried using the homemade nitrite for DDNP and R-Salt synthesis with poor results.

[Pu239 Stuchtiger]

Pb isn't very hard to eliminate from the DDNP, simply dissolve your NaNO2 in water, and filter out the Pb... recrystalize the filtered NaNO2 solution. Pb will then no longer be a problem.

[Microtek]

Considering the apparant problems with manufacturing good grades of XNO2, maybe azides would be better. In the FEMFEP synthesis for sodium azide, XNO2 is needed for making isopropyl nitrite, but this is done in an aqueous phase and the IP-nitrite then separates as an oily layer according to the recipe. Wouldn't this part of the procedure be easy to carry out, even with low purity of XNO2 ?
Once you have the isopropyl nitrite, you need hydrazine hydrate which is a little tricky, but hydrazine sulfate is not so hard to make if you take proper safety precautions. Could you then react the sulfate with NaOH in the minimum amount of water to get the hydrate, and would the solution be sufficiently concentrated ?
Sorry about the straying.

[Pu239 Stuchtiger]

React hydrazine sulfate with sodium hydroxide, I think this would occur:

N2H4*H2SO4 + 2NaOH --> N2H4 + Na2SO4*2H2O

[Microtek]

I've found an alternative way of synthesizing silver azide without making sodium azide first. It seems to be well-suited to small scale improvised manufacture ( in theory ).
In "The Chemistry of Powders and Explosives" it is noted that a white precipitate of insoluble silver azide is obtained by mixing saturated solutions of silver nitrite and hydrazine sulfate and allowing it to stand in the cold for a short time.
Now, silver nitrite can be made by mixing a solution of sodium nitrite ( or presumably KNO2 ) and silver nitrate and allowing to stand for an hour, the silver nitrite being insoluble in cold water.
In this reaction, some KNO3 in the KNO2 should not cause any trouble, so homemade KNO2 should be usable.

[kingspaz]

also silver azide is better primary than lead azide :D

[mongo blongo]

I am thinking of making silver azide from sodium azide but I could have a problem. I would have to make the silver nitrate myself. It's easy enough to make BUT I would have to find some very pure elemental silver. This a problem because in jewelry, it may contain other metals eg copper, as you should know is not good! <img border="0" title="" alt="[Eek!]" src="eek.gif" />
I'm not sure if any other metals are present but I think there could be.
Sorry for straying.

[Microtek]

Usually you can buy pure silver, either from a jeweler ( though some places their union won't allow them to sell un-worked metals ) or from a hobby shop ( for making necklaces etc. ).
Silver is not all that expensive; about 5 g for a dollar, though it may be more expensive when not bought directly from the national reserves. Still, you don't need very much primary in your caps; I find that when using MHN as an intermediate between primary and base charge, only 0.06 mL of pressed HMTD ( thats about 0.05 g depending on pressure ) with a single speck of silver acetylide is neccessary.
With these numbers one dollar worth of silver would give you enough silver azide for more than a hundred caps.

[Idiot]

What About Silver Azide stabillity ? I have heard it's very unstable. It's true ? Some info about SA would be good. Of course if you can and/or have it.

[Idiot]

What About Silver Azide stabillity ? I have heard it's very unstable. It's true ? Some info about SA would be good. Of course if you can and/or have it.

[Idiot]

What About Silver Azide stabillity ? I have heard it's very unstable. It's true ? Some info about SA would be good. Of course if you can and/or have it.

[totenkov]

DDNP 2
Materials:
1) Picric acid
2) 50% Sulphuric acid
3) Potassium Nitrate
4) Sodium hydroxide
5) Distilled water
6) Sulphur
Procedure:
1) In a beaker add 1g of sodium hydroxide to 60 ml of warm distilled water and stir until dissolved.
2) While stirring the water/sodium hydroxide solution, add 6g of picric acid and stir until dissolved.
Set this solution aside.
Picture of the sodium hydroxide/water/picric acid solution:
3) In another beaker, add 5g of sodium hydroxide and 5g of sulphur to 3 ml of distilled water while
stirring.
4) Heat the sodium hydroxide/water/sulphur on a simmering water bath until it turns dark red then
remove it from the heat.
Picture of the sulphur/water/sodium hydroxide solution:
5) While stirring the solution made in step 2, slowly add the solution made in step 4 and let sit for 2
hours then filter off the precipitate and discard the liquid. Set the precipitate aside.
Picture of Both solutions mixed together ready for filtration:
Picture of precipitate:
6) In another beaker, boil 120g of distilled water and remove from the heat source.
7) After removing the beaker from the heat source, quickly add the precipitate collected in step 5 to
the hot water and stir for one minute.
8) While the liquid is still hot, filter it and discard any solids collected. Keep the filtrate.
9) Drop by drop, add 50% sulphuric acid to the filtrate from step 8 until the liquid turns
orange/brown then let it sit for 10 minutes. Stir occasionally.
10) Add an additional 5g of 50% sulphuric acid to the filtrate and let the solution sit for 30 minutes.
11) In another beaker, dissolve 3.5g of kno3 in 160 ml of distilled water.
12) While stirring the solution made in step 10, add the solution made in step 11. Let the solution sit
for 24 hours and filter off the DDNP precipitate.
13) Wash the precipitate with distilled water.


This is a method of making DDNP that I got from Alen's page. I am curious if anyone has tried this synth. I was under the impression that you need a nitrite and a nitrate wouldn't work, If it does, please share!

[Charles Owlen Picket]

Silver azide is an industrial/military primary and EXTREMELY stable....I know that an OLD query but I don't want anyone to think that the standard for Apache Powder Company's ms delay caps was anything but well thought out. Silver azide showed a bit more resistance to static than lead azide under similar test conditions. Azides were (& to a degree still are) the standard stable primary; where primaries are still utilized.
__________________________________________________ _

@totenkov: the process calls for a NITRITE. Please see "Preparation of
Picranzic Acid" By HERBERHT. HOEGSOAN D EDWARRD. WARD. 1945 or any informed source such as Federoff or Urbanski. The actual synth of Diazodinitrophenol is a diazotisation, not a nitration in the simplest sense of the word.

[totenkov]

I have just tried to make Picramic acid. I used the NaOH S mix and TNP. It went ok, but the reaction didn't turn dark red/black like it was supposed to. I threw it on the hotplate and it turned a nice dark red at 60C. I then filtered it however the stuff caught in the filter paper was more of an orange color then red, is this picramic acid that I have made?

The next step is to use this stuff, but I am not sure if I have done it right. What color is your picramic acid?

[The_Duke]

Can you be more specific about the procedure you used...

Remember guys, the more details you give the easier it is for us to spot any problems there might be.

[totenkov]

Good point, I will be more specific:

http://stanfield.150m.com/

I used Stanfield's method, everything seemed to go OK, but the sulfur/ NaOH mix didn't mix all that well and never turned the dark color it was supposed to.

Eventually I just said screw it and dumped it into the TNP/ NaOH solution and let it sit, stirring every 5-10 minutes. Then the solution separated into two distinct layers. A bottom that appeared to be a yellowy picric acid that had settled and the middle layer that was a very dark red color. and then the top of yellowy S.

I'm not trying to bake a cake! I want picramic acid! The only thing that was changed was the amount of reactants because I had used a fair bit of my TNP.

[megalomania]

Two things, what is the condition of your sulfur and sodium hydroxide, and how long did you let the reaction sit? If you are using old hydroxide that has been exposed to the air for some time it might have formed sodium carbonate. As for the reaction time, Stanfield does not specify a time, only to let it sit until it turns red. Did you give it an hour and get impatient, or did you let it sit overnight?

[Charles Owlen Picket]

One of the ways to achieve a decent yield is to not use the mil-manual methods but to make sodium picramate first and go from there.