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Author: Subject: Styphnic acid and lead styphnate
SAM4CH
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[*] posted on 13-11-2004 at 06:41
Styphnic acid and lead styphnate


I tried to make styphnic acid but I faced many problems in preperation it,
1) when I disloved resorcinol in 90-95% H2SO4 I can not dislove all of it with out heating.
2) when I heated the solution to 50 degree I found two form of solidification of resorcinol sulfate, in some times it started to solodify when I heated for 30 minutes with was a yellow/brown color and in other experiment it still liquid during heating and solodify when it cold to room temp.
3) while I adding Nitric acid (very slowly-drop by drop) and my sulfate solution was cold under 10 degree, afetr few minutes I notice a high amount of NO2 gas suddenly released from my solution and its temp. rised (70-90 degree) and some times it was a strong gas which caused the solution to flowing out of beaker.

[Edited on 21-2-2005 by chemoleo]
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[*] posted on 13-11-2004 at 08:12


SAM4CH: 1-2) That's a typical mistake if you calculate the amount of sulfuric acid only to sulfonate both hydroxy-groups. But you need more acid, as it acts as solvent for the 1,3-Benzenedisulfonate. For 50 g Resorcinol, you need at least 226 ml concentrated sulfuric acid. This way you get a stirrable mixture and not a solid.

3) Better you add the nitric acid slowly, while the beaker is in a cold bath, so the temperature won't rise over 50 °C. Even if the temperature didn't rise after an adding, wait some minutes, before you add more nitric acid.

For all others, some pictures of the solidification of Resorcinol / 1,3-Benzenedisulfonate with not enough sulfuric acid.





BTW: German readers could visit the styphnic acid synthesis at LambdaSyn.tk.




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SAM4CH
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[*] posted on 13-11-2004 at 13:22


I was wonder about the best way for preparing Styphnic acid, in PowerLabs I read that 0.8grams of resorcinol are reacted for every 1.5ml of Nitric acid (68%) and 1ml of sulfuric acid (98%), but in Jonney post in energitic material he mention that 24 gram of resorcinol to 30 ml H2SO4 (95%) + (45 ml 72% H2SO4), 175 ml nitric acid (70%)!.

Other thing I notice in my experiments that it is true for (8 gram resorcinol gives 10 gram styphnic acid) but I found amazing thing when I mixed two flitrated solution, I mean that the first was styphnic acid filtrated solution (after geting styphnic acid) and the second was lead styphnate filtered solution which was washed with methanol, I noticed a precipitate and I tried to filter it, then I found that it was styphnic acid and I got about (35 gram) from this step and around (30 gram) from regular step (total 65 gram), please explian whats happened!!:(




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SAM4CH
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[*] posted on 17-11-2004 at 02:21


OKay.. No one replied!
in other subject what about the exactly amount of styphnic acid needed to make a sturated solution of methanl (at 65 degree) and ethanol (at its boiling boints), and what about amount of lead monoxide needed to make lead styphnate if I have 145 gram of styphnic acid.
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SAM4CH
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[*] posted on 21-2-2005 at 00:44
Lead Styphnate


How can I get a pure Lead Styphnate from Styphnic acid, Lead nitrate, and water or ethanol as solvent, I ment I need exact steps and amount for preparing 99.?% Lead Styphnate!?
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[*] posted on 21-2-2005 at 15:27
Lead Styphnate from COPAE


Lead styphnate is commonly prepared by adding a solution of magnesium styphnate at 70° C to a well-stirred solution of lead acetate at 70° (I guess nitrate should work too). A voluminous precipitate of the basic salt separates.
The mixture is stirred for 10 or 15 minutes; then dilute nitric acid is added with stirring to convert the basic to the normal salt, and the stirring is continued while the temperature drops to about 30°. The product, which consists of reddish-brown, short, rhombic crystals, is filtered off, washed with water, sieved through silk, and dried.

In terms of quantities - you could just add more Mg styphnate until no more precipitate occurs, or simply calculate the required amounts.

Mg- stypnate itself is prepared by adding magnesium oxide to a suspension of styphnic acid in water until a clear solution results and only a very small portion of the
styphnic acid remains undissolved.


Nice pics btw, Mephisto. Did you convert some of the styphnic acid to the lead salt (& test it)?




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[*] posted on 21-2-2005 at 16:37


No, I didn't have prepared the lead salt at all.

The lead styphnate preparation on my page is taken from US 1,942,274. Maybe it's worth a look for SAM4CH. (You'll need a TIFF-plugin to see the patent-image.)




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SAM4CH
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[*] posted on 13-1-2006 at 05:29


I need to know more about adding sodium nitrite in this German forum:

http://www.lambdasyn.com/synfiles/styphninsaeure.htm[/url]
how can I add NaNO2, to H2SO4 direct or with resorcinol!?
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[*] posted on 14-1-2006 at 00:59


Quote:
Originally posted by SAM4CH
How can I get a pure Lead Styphnate from Styphnic acid, Lead nitrate, and water or ethanol as solvent, I ment I need exact steps and amount for preparing 99.?% Lead Styphnate!?


Of that purity, try the following article.

Quote: <i>"The present investigation was undertaken because of our need for a reproducible source of pure lead styphnate. preparations carried out under directions available to us did not yield a satisfactory product. As a result, a new preparative method, which gave an easily-reproducible, highly crystalline material, was developed."</i>

Uses ethanolamine instead of NaOH, includes synthesis of pure basic lead styphnate as well.

Attachment: lead salts of trinitroresorcinol.pdf (533kB)
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[*] posted on 14-1-2006 at 08:26


The same chemist who disclosed the azo-clathrates also
had a patent related to a simple method for cubical crystals
of normal lead styphnate .

A patent was later issued to the US Navy regarding the use of glycerol as the solvent in processes for the synthesis of
lead styphnate .

No experiments have been done by me concerning this , but it would seem worthwhile combining the techniques of the two patents .

And perhaps also of interest is investigating the effect of using magnesium oxide or carbonate for obtaining a possibly more soluble magnesium styphnate intermediate , as well as using acetic acid , and/or nitric acid to adjust the pH to acidic before addition of the lead nitrate or acetate . Some interesting results in crystal form and size variations may be obtained from such experiments .

Attachment: US2589703 Cubical Crystals Lead Styphnate.pdf (212kB)
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[*] posted on 14-1-2006 at 08:29


A patent was later issued to the US Navy regarding the use of glycerol as the solvent in processes for the synthesis of
lead styphnate .

Attachment: US3041361 Lead Styphnate using Glycerol Solvent.pdf (96kB)
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[*] posted on 23-3-2006 at 12:26
Making Styphnic


Hi
I was wondering if anybody knows a way of making Styphnic acid from scratch?
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[*] posted on 24-3-2006 at 10:25


What do ya call "from scratch" ? From resorcinol ? phenol ? benzene ? carbon ? From nitric acid ? a nitrite ? an amine ?

or maybe just from starch ;) It has already been discussed here several times from different materials. Here is a popular one :

1/ one gram resorcinol is dissolved in ten ml forty percent nitric acid.

2/ Slowly add this solution to twenty ml conc sulfuric acid keeping it under fifty °C.

3/ Dump three hundred ml very cold water to precipitate the crystals.

You might now want to UTFSE to see the difference between red and yellow form :)
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[*] posted on 24-3-2006 at 12:29


thanks sylla
That was just the kind of thing i wanted.
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[*] posted on 24-3-2006 at 13:43


There is no way that this synthesis could generate Styphnic acid.
It will make some mono- and maybe dinitrated resorcinol.

Direct nitration of resorcinol cannot produce Styphnic acid.
The conditions required for this will rupture the aromatic ring.

For Styphnic acid, the resorcinol first has to be sulphonated by heating with conc. H2SO4.
THEN it can be nitrated under controlled conditions with 70% HNO3 or better a HNO3/H2SO4 mix which is slowly added to the resorcinoldisulphonic acid.
The reaction also needs some heating after the initial reaction has subsided.




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[*] posted on 24-3-2006 at 14:14


I do not agree. Nitric acid is added prior to prevent NO2 erruption but it acts the same way as it always does. Heating is done by the water/H2SO4 reaction. It is in NO WAY a direct nitration !

Note that this is not my synthesis but one posted on roguesci long times ago by... can't remember... Mr Cool (?)

It is quite similar than the common synthesis one can read in Urbanski or even with pictures on powerlabs. Why would in that case work and in the other case not ?

The only point is that the former produces a red form while the later produce a yellow one. Following philou's investigations red form would be more energetic.

Though this kind of topic has already been discussed to death here... seems I'm wrong :)

EDIT: I've done some searchs on the forum and it was posted by Microtek in early 2003, direct link : http://www.roguesci.org/theforum/showthread.php?t=386

[Edited on 24-3-2006 by sylla]
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[*] posted on 24-3-2006 at 17:23


This is the way I have done it, from COPAE. I have wanted to try the method that Rosco posted a while back, using 98% acid to finish off the nitration. I did this with 70% and got ~18g from 10g resorcinol.

Styphnic acid of high purity
Sulphonation. 100 parts of resorcinol are introduced in small increments during
a period of half an hour into 1000 parts of sulphuric acid (93-98%) under stirring.
The temperature rises to 50°C and is maintained then for 15 min, when the mixture
is ready to be nitrated.
Nitration. 200 parts of concentrated nitric acid (90% HNO3) are added to the
sulphonation mixture in such a way that the first 110 parts are introduced relatively
quickly (within 30-50 min), and the temperature is kept between 50° and 55°C.
After that, the rate of stirring and the rate of introducing nitric acid is reduced (3-
5 times) to maintain the temperature at 55-60°C. Styphnic acid begins to crystallize.
From this moment the rate of adding nitric acid is gradually increased and
cooling is so arranged that the temperature finally reaches 60-65°C.
The whole is stirred for half an hour at this temperature, cooled, filtered, washed
with cold water until the wash water is neutral to Congo paper and dried at 60°C.
The yield of the product with m. p, 176°C is 180-185 parts.




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[*] posted on 8-5-2007 at 17:28


How can I prevent formation high sensitivity needle crystals of lead styphnate in styphnic acid/MgO lead nitrate method?

what about drying lead styphnate? if it clot during drying how can I get powder?
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[*] posted on 9-5-2007 at 06:12


I have never had such needles form and I have samples from 7 years ago! I am very interested in crystal structure and growth and I can tell you honestly that I have never had an alteration of shape from the dry product. I have used both methods of nitration but neither leans toward the alteration of crystal structure. - However to be fair I don't leave the samples in 30% water either. I wrap the threads of a small plastic bottle with Teflon tape and keep the samples, cool, clean, & dry. LS is sensitive but not similar to "touch" explosives.. If a small lump forms you can place these between pieces of paper and roll it gently and the powder will become consistent. Ideally you will have very tiny rhomboids. You can also dextrinate the material with a simple wash of 1.5 grams of dextrine in 100ml hot water solution. That will stop most all crystal shaping and maintain very tiny particulate matter. but then it's important that you don't breath the dust......that is what made lead azide a dust issue.
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[*] posted on 8-8-2011 at 15:50


Here is a little Styphnic Acid and Lead Styphnate I made on the weekend. On the left is TNR and on the right is LS.

I used the Davster's method to make the TNR, and Microtek' s method to convert it to LS.

This stuff is very neat. It is definitely more powerful than my lead picrate, though my lead picrate is probably not the best sample around. It takes such a small amount to make DDT.

Is using Magnesium Carbonate the best way to make Lead Styphnate? I did use MgCO3 to make the LS in the picture.

I just got my Resorcinol recently, so I am experimenting a bit.

TNR, Lead styphnate.JPG - 327kB

[Edited on 8-8-2011 by Hennig Brand]
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[*] posted on 8-8-2011 at 18:00


To see something truly astonishing as crystallizations go, you should try the reaction of US2150653 The properties of the product are excellent too, but it is a bit tricky to get it to work as described.

http://www.sciencemadness.org/talk/viewthread.php?tid=6395&a...

Attachment: US2150653 NORMAL_LEAD_STYPHNATE_AND_A_METHOD.pdf (193kB)
This file has been downloaded 816 times

US2295104 is also attached. It describes an intermediate colloid or gel forming stage speculated to possibly be an acid styphnate. Additionally see example 3 which describes a subsequent double salt formation of Lead Styphnate with Lead Acetate. I would have to check my old references but
I am pretty sure that likewise Lead Picrate can form a double salt with Lead Acetate. So an interesting experiment would be to see if a double salt of Normal Lead Styphnate and Normal Lead Picrate can be formed by conversion of the double salt of example 3, accomplished by adding 2 equivalents of Picric Acid and boiling the mixture for an hour or two, hoping to convert the Acetate to Picrate while preserving the anhydrous double salt structure. If this works, the anhydrous double salt could have properties superior to either Lead Styphnate or Lead Picrate. This may or may not work ...it is purely my hypothesis and may be novel as I can find no reference to it. Different approaches
might be required or might work to produce such double salt
if it does exist or is possible.

Attachment: US2295104 Lead Styphnate Gel Intermediate and double salts.pdf (235kB)
This file has been downloaded 701 times

The nickel styphnate - potassium styphnate double salt may also be interesting
http://www.sciencemadness.org/talk/viewthread.php?tid=11105&...

[Edited on 9-8-2011 by Rosco Bodine]
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[*] posted on 9-8-2011 at 05:15


Thanks, the first patent has a nice method in there which uses sodium hydroxide instead of magnesium carbonate. I think I will need to give it a try.


Here is something I thought was kind of interesting.
NORMAL LEAD STYPHNATE SUITABLE FOR AUSTRALIAN
PRODUCTION OF LOW SENSITIVITY CC PRIMERS

Attachment: Lead Styphnate for military primers.pdf (786kB)
This file has been downloaded 1170 times


It seems there are many ways to make Lead Styphnate. Which method is best depends on which product is most suitable for a given application, and also depending on what materials are on hand.

edit:
Rosco, I just read through some of that stuff from your post as well as from the other thread you linked to. Yeah, I thought it was a screw up on my part. Both times I have made LS, I got a gelled mass, then when I wasn' t looking it changed to fine crystals. In that link you posted, I believe Quicksilver said that he had a similar experience, not knowing what was happening at first.


[Edited on 10-8-2011 by Hennig Brand]
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[*] posted on 15-11-2013 at 14:54
The Lead Styphnate Jelly


This article is something I thought I had already posted but was perhaps overlooked.



Attachment: The Lead Styphnate Jelly.pdf (285kB)
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[*] posted on 13-1-2014 at 11:18


How can I make L.Azide and L.Styphnate in same batch ? I read a patent but I couldn't calculate the ratio
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[*] posted on 4-4-2014 at 06:24


neutralizing styphnic acid with ammonium hydroxide results in a sludge of ammonium styphnate
this compound will when heated up on an aluminium plate give off a thick cloud of yellow smoke, this smoke can be settled on a surface, not sure what it is, but the compound that settles is DEEPLY bright yellow
not entirely sure if the fact that its a sodacan plate cut out of the soda can body could explain this smoke, but its doubtful
it leaves behind some weird black carbonized sugar like mass after decomposition
at one point the ammonium styphnate was possible to be ignited with a slightly sooting flame when it was heated

neutralizing styphnic acid with H2SO4 still in the product results in ammonium sulfate being stuck in the powder, solution and slurry, not sure how this could be removed, using sodium hydroxide/carbonate could be one way if it could be seperated as sodium sulfate and sodium styphnate

however styphnic acid has a solubility of 5g/100mL, not sure if it was 0*C or 20*C, so washing the precipitated acid is not an option, its salts seems fairly soluble aswell, sadly




~25 drops = 1mL @dH2O viscocity - STP
Truth is ever growing - but without context theres barely any such.

https://en.wikipedia.org/wiki/Solubility_table
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