Sciencemadness Discussion Board

Styphnic acid and lead styphnate

SAM4CH - 13-11-2004 at 06:41

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]

Mephisto - 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.

SAM4CH - 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!!:(

SAM4CH - 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.

Lead Styphnate

SAM4CH - 21-2-2005 at 00:44

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!?

Lead Styphnate from COPAE

chemoleo - 21-2-2005 at 15:27

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)?

Mephisto - 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.)

SAM4CH - 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!?

Axt - 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)
This file has been downloaded 1895 times


Rosco Bodine - 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)
This file has been downloaded 1487 times


Rosco Bodine - 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)
This file has been downloaded 1366 times


Making Styphnic

Ollie - 23-3-2006 at 12:26

Hi
I was wondering if anybody knows a way of making Styphnic acid from scratch?

sylla - 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 :)

Ollie - 24-3-2006 at 12:29

thanks sylla
That was just the kind of thing i wanted.

garage chemist - 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.

sylla - 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]

The_Davster - 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.

SAM4CH - 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?

quicksilver - 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.

Hennig Brand - 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]

Rosco Bodine - 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 1213 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 1017 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]

Hennig Brand - 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 1747 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]

The Lead Styphnate Jelly

Rosco Bodine - 15-11-2013 at 14:54

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



Attachment: The Lead Styphnate Jelly.pdf (285kB)
This file has been downloaded 951 times


Peroksit - 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

Antiswat - 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

otonel - 22-3-2015 at 08:55

I made lead styphnate and double salts of lead styphnate and lead acetate using just styphnic acid and lead acetate in solution at 55*C
My target was to get a sensitive explosive percussion and double salt obtained has a good sensitivity higher than simple lead styphnate.
I would like to further increase the sensitivity of lead styphnate and add an oxidant but do not know which direction to go with experiments

otonel - 26-3-2015 at 13:26

If I use double quantity of lead acetate and finally some lead nitrate with long time mixing ,the result double salt is more sensitive as the one before but not so strong.

Lead Styphnate from Carbonates

jharmon12 - 17-4-2015 at 19:29

Hello all. Thanks to Roscoe's method, I have a great end product of styphnic acid. I am wanting to make small batch of lead styphate just to say I can do it. In order to make "basic" lead styphnate, all the instructions I have seen call for Mg Carbonate to first be converted to Mg styphnate followed, of course, by the use of lead nitrate to produce the final product.

I have an ample supply of barium carbonate, copper carbonate, strontium carbonate, and calcium carbonate. I do not (surprisingly) have any Mg carbonate. Can any of these other carbonates be used as a substitute for Mg carbonate during the process of synthesizing "basic" lead styphanate?

Thanks,

Joel

jharmon12 - 17-4-2015 at 20:03

Also related to my quest to try out a batch of lead styphnate, I am going to be synthesizing my own lead (II) nitrate using nitric acid (of course) and metallic lead. I am not finding any information on how lead nitrate is purified so that the excess acid can be removed or neutralized. If you use any salts, or ammonium hydroxide, in order to try and neutralize the remaining acid in your lead nitrate, you will create other salts inadvertently. So, how do you neutralize something so easily dissolved in water and so easily converted to other salts in the presence of other compounds?

Thanks,

Joel

Microtek - 18-4-2015 at 00:15

You wash it with ethanol (or methanol).

About the Mg-carbonate: The reason you convert styphnic acid to Mg-styphnate is to get a soluble styphnate. If you didn't do this, you'd risk having lead styphnate formed as a shell around styphnic acid particles (if you reacted solid styphnic acid with a lead nitrate solution).

So, you need to find out whether any of the metallic ions you mentioned form a soluble styphnate. This you should do for yourself.

[Edited on 18-4-2015 by Microtek]

Bert - 18-4-2015 at 05:26

Metalic Lead/nitric acid is a very slow reaction. Check the Lead salts preparation thread(s), one of the Lead oxides may be an easier choice-

(About the merge)

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jharmon12 - 19-4-2015 at 20:07

Hello all. As I said before, I am using Roscoe's method and I have what appears to be a good quality of styphnic acid (crystals showed up hex, as described by Roscoe). I am now getting around to asking this: What do you all think of my filtrates? I filtered it the first time and ended up with red liquid. I then filtered it a second time and ended up with yellow liquid. I know the yellow is probably the acid in h2o, but wanted to be sure before I did anything with it (disposed of it). I put both of these containers in the freezer and brought the temperature down to -4 C, and didn't see but a few (not even 1/2 gram) crystals in the bottom of the yellow container. In the red fluid container, there are no solids. What is this red fluid and can any more crystals be squeezed out of it? Keep in mind this is my filtered liquid. The final clean, "crystaled" liquid batch is described below.

The other issue I have is that my yield does not look like it is going to be very good. I haven't had a chance to filter it yet, but it looks like I have less than 10 grams in my final h2o/styphic acid solution at room temperature (in about 700 ML of h2o). Where did I go wrong? Is Roscoe around on the board to answer questions about his method? Has anyone had these low yield issues? Please ask me questions to see if you can figure out where I am going wrong.

I followed Roscoe's method and quantities EXACTLY. I reacted with H2SO4, 50 ML with 10 Grams of Resorcinol powder. It reacted into a "strawberry milk shake". I then followed to procedure to nitrate with 20 ML of 70% HNO3 and then another 20 ML of 95% HNO3. All the while I watched my temps. I got a lot of foam and stirred it down when the temp went down to 35 or 40, which caused it to rise again. This happened two times and then the temperature stayed at around 35, then as it sat, it dropped into the 20's and I let it sit another 30 minutes. I then followed the final parts as he describes for harvesting the material and cleaning it, and yet I have this pathetic yield.

Please help.

Thanks,

Joel

image.jpg - 767kB

jharmon12 - 19-4-2015 at 20:09

FYI, I will execute the lead styphnate processing at some later date. I have decided that I am more concerned with getting my styphnic acid synthesis down pat before moving on and fixing this problem with low yields.

Thanks.

Joel

byko3y - 19-4-2015 at 20:37

You can make styphnic acid, dinitrophenol and methylpicric acid using sodium nitrite and 60% nitric acid without any concentrated acids. However, it's quality will be lower then via conc sulfuric and fuming nitric acid. US Patent 3,933,926 for details.
Although this compound is pretty useless for an amateur exploder, because the acid is non-sensitive and you need something like #8 cap to make a definity detonation, and the lead salt explodes like nothing, can't even detonate PETN.

Rosco Bodine - 20-4-2015 at 04:03

Quote: Originally posted by jharmon12  
Hello all. As I said before, I am using Roscoe's method and I have what appears to be a good quality of styphnic acid (crystals showed up hex, as described by Roscoe). I am now getting around to asking this: What do you all think of my filtrates? I filtered it the first time and ended up with red liquid. I then filtered it a second time and ended up with yellow liquid. I know the yellow is probably the acid in h2o, but wanted to be sure before I did anything with it (disposed of it). I put both of these containers in the freezer and brought the temperature down to -4 C, and didn't see but a few (not even 1/2 gram) crystals in the bottom of the yellow container. In the red fluid container, there are no solids. What is this red fluid and can any more crystals be squeezed out of it? Keep in mind this is my filtered liquid. The final clean, "crystaled" liquid batch is described below.

The other issue I have is that my yield does not look like it is going to be very good. I haven't had a chance to filter it yet, but it looks like I have less than 10 grams in my final h2o/styphic acid solution at room temperature (in about 700 ML of h2o). Where did I go wrong? Is Roscoe around on the board to answer questions about his method? Has anyone had these low yield issues? Please ask me questions to see if you can figure out where I am going wrong.

I followed Roscoe's method and quantities EXACTLY. I reacted with H2SO4, 50 ML with 10 Grams of Resorcinol powder. It reacted into a "strawberry milk shake". I then followed to procedure to nitrate with 20 ML of 70% HNO3 and then another 20 ML of 95% HNO3. All the while I watched my temps. I got a lot of foam and stirred it down when the temp went down to 35 or 40, which caused it to rise again. This happened two times and then the temperature stayed at around 35, then as it sat, it dropped into the 20's and I let it sit another 30 minutes. I then followed the final parts as he describes for harvesting the material and cleaning it, and yet I have this pathetic yield.

Please help.

Thanks,

Joel




The flask I used for the synthesis described here

http://www.sciencemadness.org/talk/viewthread.php?tid=4457&a...

was a 250 ml Erlenmeyer. Stirring was simply done using the thermometer for what was appearing to be a trivial, uncomplicated synthesis that was almost self regulating. It could be that for the small reaction scale, the progress for the nitration is sensitive to the flask shape due to the low thermal mass, and the small effects of using a different shape or size flask are making a difference in the thermodynamic observed for a different reaction vessel which is adversely affecting the yield. I did not perform many repetitions or variations for the synthesis to see what may be the range of yields as an average.

It would be my guess that what likely went wrong is your cooling was too aggressive. The nitration is exothermic and should proceed from its own exotherm but could require gentle heating if the reaction isn't being pushed sufficiently by rate of addition. I didn't specify a drops per minute rate or detail the times involved. My description of what I did and what I got was accurate to the extent I included only what details I noted. So I don't really know what is changed that would would cause any repeatability issue, probably something that seems trivial but is affecting the time and temperature curve.

Nitration of resorcinol to styphnic acid requires a gentler touch than nitration of phenol to picric acid, milder conditions of temperature particularly, which can be reached by the natural exotherm in a small scale nitration of this scale. The same concept can be applied for the synthesis of picric acid but the higher required temperatures and longer holding times would require a hundred or more times the scale as for resorcinol to be able to use the natural exotherm of the nitration and the latent heat and longer cooling of a much larger reaction mass
to provide the needed heat sufficient to drive the nitration to completion.

Resorcinol is much more easily nitrated than phenol so a small scale nitration can proceed on its own exotherm, unless the reaction is quenched by excessive cooling.

Phloroglucinol nitration would require an even gentler condition for nitration than resorcinol. With phenol there is one hydroxyl on the benzene ring which makes it more easily nitrated than benzene but also makes it more susceptible to oxidation. With resorcinol, the two hydroxyls makes it still easier to nitrate but also makes it much more susceptible to oxidation. With pholorglucinol, the three hydroxyls has still more greatly the trend to easier nitration yet much more susceptibilty to oxidation.

The nitrations of such materials is generally stepwise and gradual and is exothermic, but obviously the scale and method will be different for each where the rate of addition and temperature and holding times are well matched to that nitration scenario. These batch process nitrations on a small laboratory scale can be difficult to keep "in the groove" with regards to the "window" of reaction conditions so that there is exact reproducibility. Everything that may seem like it should not matter like the type and size of the flask, the method of stirring, the depth of the flask in the ice bath, can make a difference.



[Edited on 20-4-2015 by Rosco Bodine]

jharmon12 - 20-4-2015 at 07:35

Thanks for responding, Roscoe. Let me give you more information. One of these things could be causing the problem (I think you might have figured it out). I did the nitration outside and the winds were high and the air temperature was 50 F:

1. When adding the initial 20 ML of 70% Nitric drop by drop, I got a temp rise because my reaction mixture was not in an ice bath. The temp went up and I got a little nervous at around 70 C, so I put it in an ice bath and let it calm down a little. Once the temp went down it started going down pretty fast and I increased the HNO3 drop rate such that the mixture really didn't exceed around 30 C. In fact, it stayed around the same temp the whole time (30 C) once it was placed in the ice bath and stayed in the ice bath.

2. When adding the 20 ML of 95% Nitric drop by drop, the starting temperature was 10 C (as specified in your instructions), and what amazed me was that the temp never went up from 10 C EVEN AFTER adding all the fuming HNO3. Yes, I kept it in the ice bath when adding the fuming HNO3.

2a. Note: I used a magnetic stirrer during the entire nitric acid addition. I only eliminated the stirrer after the acid was all added.

3. I then took it off the ice bath and waited for the reaction temp to rise. It did not rise very fast, so I heated it on the hot plate and once it hit 60 C, it started to thicken up and I got foam. So, I took it off the hot plate and let it go on it's own. I stirred it once it went down and it went back up again. But it stayed up and was climbing above 80 C. I remember your instructions saying that it didn't go past 75, so I panicked and placed it in the ice bath before I got a runaway nitration. Should I be using much higher temperatures here? Please specify. I know quicksilver was using temps in excess of 100 C!! But he didn't use concentrated HNO3, either.

4. Once the temp went down a little, I took it out and stirred it again and the temp went up a little but finally went down to around 25 C and stayed there.

5. I let the mixture stand for about 45 minutes (could it be overnitrated because you specified 30 minutes)? Can the mix become "overnitrated", in general.

6. I then placed it on ice and then flooded it with ice cold water and filtered it, as you see in the photos above...my filtered water.

My conclusion is that I didn't nitrate it either A) Long enough or B) Hot enough or C) Both. Any further information is welcome. That raises another question: Do I add the nitric acid at such a rate that I hover around the max temps you specify during HNO3 addition, or is it more important to get the temp up after all the acid is added? Or do you have to do both???

BYKO3Y, I know about teh method that uses sodium nitrite. I have the book The Preparatory Manual of Explosives by Ledgard.

Thanks,

Joel

[Edited on 20-4-2015 by jharmon12]

Rosco Bodine - 20-4-2015 at 10:19

Quote: Originally posted by jharmon12  
Thanks for responding, Roscoe. Let me give you more information. One of these things could be causing the problem (I think you might have figured it out). I did the nitration outside and the winds were high and the air temperature was 50 F:

1. When adding the initial 20 ML of 70% Nitric drop by drop, I got a temp rise because my reaction mixture was not in an ice bath.


There is a problem there at the very start. The initial nitration needs to occur with a slow dropwise addition with ice cooling while stirring, rate limiting the addition to keep the reaction temperature just under 35C.

Quote:

The temp went up and I got a little nervous at around 70 C, so I put it in an ice bath and let it calm down a little.


Here is a second problem in that you overshoot the 35C limit temperature for the initial addition. You should instead get the nitration started more gently and be more patient with the additions, watching the temperature rise effect which is delayed for the addition. You should be able to pace the addition so that you get a controllable but steady rise to 35C without the reaction spiking early like you have described.

Quote:

Once the temp went down it started going down pretty fast and I increased the HNO3 drop rate such that the mixture really didn't exceed around 30 C. In fact, it stayed around the same temp the whole time (30 C) once it was placed in the ice bath and stayed in the ice bath.


For a reaction being controlled by rate of addition, you should be able to see a gentle oscillation in temperature that is a little delayed in response to the addition. Falling temperature is nudged upward again by addition of more acid, but because of the delay affect, you can anticipate the falling temperature will continue and resume addition cautiously, waiting for the delayed "correction" effect. It is easy to overshoot because of the delayed response. You have to develop a "feel" for the
delay response and anticipate the effect of the delay to
"dampen" the temperature oscillation and keep the reaction near to the limiting temperature. It will vary a few degrees, but should not be tens of degrees out of spec.
Quote:

2. When adding the 20 ML of 95% Nitric drop by drop, the starting temperature was 10 C (as specified in your instructions), and what amazed me was that the temp never went up from 10 C EVEN AFTER adding all the fuming HNO3. Yes, I kept it in the ice bath when adding the fuming HNO3.


IIRC the fuming HNO3 addition was begun when the initial reaction from the concentrated HNO3 addition had subsided and temperature had fallen to 10C. The addition of fuming HNO3 was rate adjusted to allow for temperature increase to near 25C through the end of the d 1.5 HNO3 addition, with stirring and cooling continued through that addition. Then the stirring was stopped and the mixture simply allowed to sit in the cooling bath for a few minutes.

I didn't describe this before but likely what I was doing is just watching the thermometer and seeing how steady would
the temperature hold near the 25C. When any perceived falling of temperature was observed, then the cooling would have been reduced or removed to keep from diminishing the natural exotherm that should sustain the reaction temperature.

Quote:

2a. Note: I used a magnetic stirrer during the entire nitric acid addition. I only eliminated the stirrer after the acid was all added.


That was correct to stir during the acid additions and stop when completed.

Quote:

3. I then took it off the ice bath and waited for the reaction temp to rise. It did not rise very fast,


It shouldn't matter if the temperature rise was slow, the noted changes and what seemed to be "waypoint" temperatures for monitoring the reaction I described what I saw. Did you watch for any of those "markers" at ~28C, ~38C, or the reaction rate jump at ~45C which should carry it to peak at ~75C? It may have been a different curve followed because you got the temperature spike early in the nitration where that should not have occurred that soon.

Quote:

so I heated it on the hot plate and once it hit 60 C, it started to thicken up and I got foam. So, I took it off the hot plate and let it go on it's own. I stirred it once it went down and it went back up again. But it stayed up and was climbing above 80 C. I remember your instructions saying that it didn't go past 75, so I panicked and placed it in the ice bath before I got a runaway nitration. Should I be using much higher temperatures here? Please specify. I know quicksilver was using temps in excess of 100 C!! But he didn't use concentrated HNO3, either.


It looks like you got impatient with pacing the addition and rushed the initial nitration which resulted in the exotherm exceeding the cooling needed to limit to 35C. Accumulation of unreacted HNO3 added too quickly at too low a temperature caused an avalanche, a little "runaway" when things should have been methodically controlled early in the addition of the first regular concentrated 1.42 d HNO3.

Higher temperature isn't needed using the stronger 1.5 d HNO3. Avoiding the higher temperature and larger amounts of less strong acid was precisely the idea, to avoid oxidation, and "kick" the nitration to completion at a lower temperature, low water content mixture.

Quote:

4. Once the temp went down a little, I took it out and stirred it again and the temp went up a little but finally went down to around 25 C and stayed there.

5. I let the mixture stand for about 45 minutes (could it be overnitrated because you specified 30 minutes)? Can the mix become "overnitrated", in general.


The extra 15 minutes would have been better spent during the initial addition of the 1.42 d HNO3. You are plotting a different reaction curve where the natural exotherm is not being used to advantage. Due to the reaction temperature oscillations it is hard to know what should be the holding time, but no I don't think you over nitrated it. I think you may have oxidized some of the resorcinol in the first runaway you quenched, and then you quenched a second "spike" in an already compromised nitration mixture. This is like scraping the carbon off burned toast and trying to cover up the mistake with extra strawberry jelly ;)
Quote:

6. I then placed it on ice and then flooded it with ice cold water and filtered it, as you see in the photos above...my filtered water.

My conclusion is that I didn't nitrate it either A) Long enough or B) Hot enough or C) Both. Any further information is welcome.


I think you rushed the initial reaction and did not pace the additions to achieve and maintain a smooth nitration at about ~35C.
Quote:

That raises another question: Do I add the nitric acid at such a rate that I hover around the max temps you specify during HNO3 addition, or is it more important to get the temp up after all the acid is added? Or do you have to do both???


It is more nuanced "algebra", what you are trying to do is to steadily ramp the temperature from the low end to near the limit but not overshoot the mark, and dampen the temperature swings to near the upper limit. Because of the delay effect, the oscillations must be anticipated because of the time lag. You don't wait for the falling temperature to go all the way back down to resume addition. Exploit the trend. You learn by observing how much delayed temperature rise three drops of HNO3 will cause so you can guess when the reaction is subsiding how much to add to predict suspending that fall and swing it back up where it was without overshooting. It is like a fly by wire kind of effect where the control responses will be delayed by two or three minutes, so you can't do something and when nothing happens in ten seconds then do something else to see if that "works" when there hasn't been time to realize the effect of what you are impatient to see. A nitration is like a dog leash that is a long rubber band. The information "feedback" is sluggish and elastic so it requires finesse.

[Edited on 20-4-2015 by Rosco Bodine]

jharmon12 - 21-4-2015 at 06:09

Sorry for the delay in reply.

So my first mistake was the initial nitric addition and the spike that occurred. The next time, during the FIRST NITRIC ADDITION, I want to bring the nitration temp up to 35 and hold as close to this as possible. True statement?

Other things I will note/ask based on your response:

I didn't allow for the temperature increase to near 25C through the end of the concentrated HNO3 addition. It did not rise because I kept it in a cold bath even after I cooled it back down to 10C after the first nitric addition. Next time, I will need to remove/add the cold bath back in as the temperature goes up/down so I can try and regulate the mixture appropriately to stay as close to 25C as possible during the concentrated nitric addition. Is this a true statement?

I take it, from your response, that after you stopped the nitric addition (concentrated), you stopped stirring and simply watched the thermometer and held the temp near 25C in the cooling bath for a few minutes. You would adjust the cooling to sustain close to 25 C for a few minutes. Is this a correct assumption? I can tell you that my reaction was around 15 C or so after the end of the concentrated acid addition, and I let it fall to 10 C, which only took a few minutes, and then I pulled it out of the ice bath to see if it the temp would rise. When it wouldn't, I put it on the hot plate.

The markers you mention at 28/38/45 and peak at 75 didn't happen for me. I put my mixture on the hot plate and when it got to about 60 I started to see solidification and foam. I removed it from the heat and watched it until it got to around 80 and then placed it in the cooling bath for a short time to bring the temp down below 75. How high will it go safely, to maximimize yield? Can it go to 80 or 90? Once it hits 75, do I cool it right away? How do I know how long to put the mix in the ice bath before I take it out so I don't over cool? This seems complicated, but it is an artform that I want to accomplish.

I also want to add that it was a very windy day and 10C outside when I did this. I really think the wind cooled things off as well, and this might have made it harder for me to control the temps because it seems like my temps, with the exception of the first small runaway, overall were very low.

Thanks for all the help so far.

Joel

[Edited on 21-4-2015 by jharmon12]

Rosco Bodine - 21-4-2015 at 07:36

You need to start the reaction correctly and then see how things proceed.

Other business requires my time for now so I can't really analyze this further or help you with the reproduction of the synthesis beyond what I have already described. Obviously if the temperature curve I described was not observed and yours was lower, then your cooling is more aggressive for having a deeper or colder bath, or better stirring. You should be able to see these variations and make adjustment to your conditions to get the same temperatures I described.


jharmon12 - 23-4-2015 at 08:38

Well, I want to thank Roscoe for posting his method and answering my questions. I was able to filter and dry my styphnic acid crystals and I ended up with 12.45 grams of dry material from 10 grams of Resorcinol. It didn't look like that much at the bottom of the beaker, but these crystals are heavy. It was slightly disappointing, because it is short of the roughly 20 grams I was expecting. I will watch my temperatures more closely next time and see if I can get closer to 20 grams of finished material.

Thanks,

Joel

Rosco Bodine - 25-4-2015 at 09:19

As best I recall about this nitration done over ten years ago, there was nothing elaborate about it. I think it was a very simple setup, like about a two liter slab of ice having been freeze molded in a rectangular poly food storage tray, and left in the same tray to serve as a heat sink for the bottom of the 250 ml Erlenmeyer flask which was simply set on the surface of the small block of ice. A lab thermometer was inserted and leaned against the opening of the flask, and a ringstand supported a small addition funnel for the HNO3 additions. There was used no magnetic stirring, so the mixture was simply done manually with the thermometer or picking up and swirling the flask. So if you use magnetic stirring it needs to be very slow and if you are using a bath, the depth of immersion for the flask needs to be minimal so as to not provide too much of a heat sink. The idea is to work with the natural exotherm and limit the temperature climb, but not too much cooling which quenches the reaction.

It is general technique for manipulation of reaction conditions where your starting temperature and rate of addition and stirring intensity, and the thermal behavior is something you must calibrate for the conditions peculiar to your combination of flask and method of cooling and stirring because those things are interactive and vary according to your individual setup. The size of the flask and thickness of the glass, the depth of the flask in the bath, and the stirring rate are things in combination that affect the amount of heat being sinked away from the reaction. For this nitration you want the cooling not to be too aggressive so the reaction should proceed slowly. Using too little cooling the reaction time would be greatly extended and the task would become tedious for the length of time it would require to make the acid additions. Using too much cooling then the reaction is rushed and does not have sufficient "holding time" at the warmer temperatures provided by the natural exotherm. This nitration must be allowed to "cook" awhile from its own heat of reaction in that time where the foaming tends to make it self regulating, which should be observed after the addition of the fuming HNO3 and after the reaction has been moderated some for awhile by continued cooling, finally removing the cooling and letting the temperature climb to complete the nitration.

You asked about the upper limit of 75C, and I would try to keep it about there.
I would say if it goes much higher then you should probably cool it but not below 40 to 45C, and let it climb again to see if it limits itself by the dilution effect of the foaming. The temperature should become better behaved in response to the natural exotherm and tend to self regulate by foaming, on the next cycle if it overshoots the 75C mark on the first excursion and you intervene. If you cool it too much then the reaction will quench and you will have to gently warm it to get it going again. I think if the temperatures and reaction profile I described are reproduced fairly closely the yield should be very near the same 90% that I got.

jharmon12 - 4-6-2015 at 06:20

I was finally able to make a batch of Pb styphnate using lead nitrate and the TNR I made. To save time explaining what procedure I used for the LS, I will just say that I used the procedure outlined in Jared Legard's book on producing Basic Red Lead Styphnate. I followed the procedure exactly and got a lemon yellow product. It doesn't matter that I didn't get the red product I bargained for because testing small quantities reveals it is definitely LS which is at least dry enough to explode in very small quantities out in the open.

The yield looks pretty good, but I don't know yet as I haven't weighed it. Part of the reason I haven't weighed it is because I am not 100% sure it is dry.

I have been allowing the washed and neutralized lemon yellow product to air dry at room temperature around 30-40% humidity now for over five days. The material seems wet still. But it might be the crystal shape/structure/size that is causing it to stick together and act "wet". It almost seems rubbery in its consistency. I can tell the crystals are very, very fine. If I rub a small amount between my fingers, I get a pure yellow streak. There is no discerning any particulate there (amorphous?).

I did some research and discovered that basic LS will hold onto water in its crystals. The only way to release this water is to break the crystals open using elevated temperatures, and allowing the water to evaporate. I don't want to do this because they are talking about heating this stuff up to 200 C to get it completely dry. I am trying to figure out how to get this stuff so that it is something easy to work with and somewhat free flowing, as it still seems to work even though it has this rubbery, pulpy consistency. I am sure someone here has worked with this and knows what I am dealing with. That leads me to my questions:

1. Why is it rubbery/pulpy?
2. Is this a problem for using it as an exploding (cap) end product or does other processing need to be executed?
3. If this form is okay for final use, how do I get it workable (flowable)? I could granulate it through a screen, but it would probably stick pretty bad and it might not be safe to push this through a screen (not sure).

Thanks,

Joel

Rosco Bodine - 4-6-2015 at 10:25

If your intended application is a detonator then basic lead styphnate is not going to be helpful for what you want to do, even when you have successfully performed a synthesis for that material, it will not serve as an initiator in a detonator.
Basic lead styphnate is an igniting or priming charge easily ignited for transferring ignition to something else. It won't be used to detonate anything because it lacks power for doing the job of an initiator. So does normal lead styphnate lack sufficient power to be a good initiator, which even so is still a lot more powerful than the basic salt.


You should be skeptical and do your homework and carefully fact check anything that is written by Jared Ledgard. He is not reliable as a source of information. The patents he does not directly or incorrectly references that are relevant to the section are US1942274 and US2275169 attached. Also attached for different interest for the normal salt is another Brun patent US2202647. Maybe there will be a better insight going by the original information than dealing with the interpretation of another author who is a dubious source of information not always helpful.

Obviously you have not produced a pure sample of what you were intending to produce, based upon your description. It is impossible to troubleshoot without exact and detailed information.

Attachment: US1942274 basic lead styphnate.pdf (361kB)
This file has been downloaded 529 times

Attachment: US2275169_MANUFACTURE_OF_STYPHNIC_ACID_SAL.pdf (116kB)
This file has been downloaded 548 times

Attachment: US2202647 MANUFACTURE_OF_LEAD_STYPHNATE.pdf (85kB)
This file has been downloaded 574 times

[Edited on 6/4/2015 by Rosco Bodine]

jharmon12 - 4-6-2015 at 13:17

Read all three of these. Unfortunately, it doesn't really give me any ideas on why my filter cake is so fiberous. The LS does work as advertised (explodes in the open), so I know it is basic yellow LS. I am not sure what other details I could give that would help anyone here tell why my cake is so rubbery/fiberous. I was just assuming that some experimenters here may have come across this issue already and had already dealt with it.

Regards,

Joel

Rosco Bodine - 4-6-2015 at 14:42

The patent describes the yellow form as amorphous and low density. A similar thing can happen for lead picrate which precipitates as a fluffy low density fibrous form or as a fine dense crystalline form which gravity filters easily. The same thing occurs for the basic or the normal salt. The level of dilution and temperature and pH and the concentration of unreacted precursor in excess, and the order of addition can affect the crystal development of precipitates. More coarse and dense crystals are favored by more slow precipitation from more dilute and more hot solutions, and more amorphous and low density precipitates are favored by just the opposite conditions, as a general rule. The general rule does not always hold and sometimes a particular range of concentration provides a "window" condition where best crystal development occurs. That occurs in this particular reaction which is a peculiarity that is basis for the US1942274 patent for the red crystal form.

But you say you have produced the amorphous yellow form. Both the red and the yellow forms are compared in the patent, and how the production of each differs.


Good stirring is helpful for producing uniform crystals and for low solubility crystals it may be required to have stirring vigorous enough that the crystals remain in suspension in the hot liquid through the entire reaction. A peculiarity for the styphnates can be the formation of a gel intermediate. It can occur that a longer time of heating and stirring can cause break up and conversion of the low density form to the higher density form. If everything else is ruled out as the problem it could be as simple to resolve as raising the temperature and increasing the stirring rate.

The patent US1942274 describes a coprecipitated mixture of the basic and normal salt which would probably be easier to make and would be more fault tolerant in manufacture, and still provide a useful product even if the composition did not turn out to be exactly 50% of each the basic and the normal salt.

The patent explicitly describes the difference between the yellow and the red forms and how to produce the more dense red form is the subject matter of the patent. You mentioned your product was "rinsed and neutralized" but there is nothing to be neutralized or described as being neutralized in the patent. The end product material is basic to a controlled extent by its chemical nature as "basic" lead styphnate and is not neutral, as would be normal lead styphnate. And the byproduct water from which the end product is filtered contains sodium nitrate which is hygroscopic. Rinsing on the filter with distilled water should eliminate that source of hygroscopicity for the basic lead styphnate. The end result should be like fine dry beach sand.

[Edited on 6/4/2015 by Rosco Bodine]

Styphnic Acid An its Lead Salt

Keith Fletcher - 15-10-2015 at 05:36

I recently made a video on the synthesis Of Styphnic acid and Its Lead salt.

https://youtu.be/fnwgJWn42SA

I hope you find it informative.

[Edited on 15-10-2015 by Keith Fletcher]

Detonationology - 15-10-2015 at 05:44

Quote: Originally posted by Keith Fletcher  
I recently made a video on the synthesis Of Styphnic acid and Its Lead salt.

https://youtu.be/fnwgJWn42SA

I hope you find it informative.

[Edited on 15-10-2015 by Keith Fletcher]

Are you Primary?

Primary

Keith Fletcher - 15-10-2015 at 06:17

Indeed

Tdep - 15-10-2015 at 06:23

I already watched the video, great work, really good content and quality as always, big fan of the channel you're running there keep it up

Keith Fletcher - 15-10-2015 at 06:39

Thank You

Any suggestions for future videos.

Tdep - 15-10-2015 at 06:50

Quote: Originally posted by Keith Fletcher  

Any suggestions for future videos.


The DDNP thread looks interesting recently, and theres some nice writeups on making the two slightly different versions, what is it DDNP and iso-DDNP. Would be interesting to compare them and see a nice video of their formation.

Keith Fletcher - 15-10-2015 at 07:12

I will do so work with DDNP

nitro-genes - 15-10-2015 at 07:54

Or DDNR...:) Stannous chloride can be made from dissolving tin in concentrated hydrochloric, I think Rosco posted a patent for the reduction of TNR to dinitro amino rescorcinol this way in the DDNP thread. The potassium salt is very energetic reportedly, though very sensitive as well...

TNR salts

Keith Fletcher - 15-10-2015 at 08:26

Im thinking about making the Mercury, Nickle, Cobalt, Cadmium and Chromium salts of TNR. Has anyone had any expirance with these compounds?

Herr Haber - 24-7-2016 at 11:30

Hey all,

I just got a new (and better!) magnetic stirrer / heater and was wondering what to do with it when it struck me: Magnesium Styphnate then Lead Styphate !

So I weighted 2 grams of TNR, added them to an Erlenmeyer flask with 500 ml water (then added 300 more during the course of the experiment) and cranked the heat up to 70°c with stirring on.
So far, so good. The TNR had dissolved and I started adding Magnesium Carbonate.
And then I added more. And more. And turned the heat up to 80°c but still no color change. The solution with now a good amount of Magnesium Carbonate was still yellow. A magnesium styphnate solution should be clear right?

Seing that a good number of Sodium salts can be used (hydroxide, bicarbonate etc). I was pretty certain using MgCO3 instead of MgO would be ok.

Then I noticed the label on this food grade Magnesium Carbonate : 4MgCO3*Mg(OH)2*5H20

Was I wrong in assuming the carbonate could replace MgO or is it my food grade Magnesium Carbonate who's to blame?

Thanks for your input.

PHILOU Zrealone - 25-7-2016 at 03:34

Maybe that Magnesia (4MgCO3*Mg(OH)2*5H20) is more basic than MgCO3 and as such is responsible of the yellower tinge of your trinitroresorcinate salt.

This is observed with trinitrophenates too basic a media and the colorfull nitronic form of the salt is present.
-C(-NO2)=C(-OH)- <--base==> -C(=N(O)-OH)-C(=O)-
So the proton switches from the phenol to the nitrogroup.

In principle the nitronic colored form is slightly more sensitive to shock and heat than the normal phenic form...

[Edited on 25-7-2016 by PHILOU Zrealone]

Herr Haber - 17-8-2016 at 13:43

Well... As I kept the TNR with the magnesia settled in the bottom I thought "Why not play with it a bit and test Philou's theory?"
I didnt have what I wanted and I have a bit of lead nitrate so this is what I did:

- Filter out the excess magnesia that had settled in the bottom.
- Heat the filtrate to 70°c as if I was going to proceed with the normal synthesis
- Dissolve and heat 1g of lead nitrate
- Add the lead nitrate to the assumed magnesium styphnate solution.

Lo and behold! A precipitate appeared !

Since I was curious, I pipetted a few ml of 69% HNO3 and started adding it drop by drop to my not so scientific experiment.
- First some fizzing was observed therefore confirming Philou's theory that the solution was basic
- Then, while adding drop by drop all of a sudden all the precipitate vanished further confirming that theory.
It would have been interesting to know what was the PH when this happened.
At this point, I wanted confirmation and grabbed some NAOH. I added some tiny pearls and got back a precipitate.

I filtered out everything, let it dry and unsurprisingly the precipitate doesnt react to the flame.

In a few days I might try lead styphnate "the right way" through sodium styphnate.
I've been wondering though what would happen if instead of MgO I couldnt use straight powdered Mg.
And in that case, what would be the dynamics of the reaction?
Would it be straight to Magnesium Styphnate or would it go through Magnesium hydroxide first?
Or am I totally wrong? :)

PHILOU Zrealone - 18-8-2016 at 06:11

Magnesia is MgCO3 mixed with Mg(OH)2.
It is "unsoluble" but stil a little --> the MgCO3 is a little more soluble than the Mg(OH)2...
Solubility is defined by the solubility product even for "unsoluble" products.
MgCO3(s) <==H2O--> Mg(2+) + CO3(2-) (cations and anions are solvated /aqueous)
Mg(OH)2(s) <==H2O--> Mg(2+) + 2 OH(-) (cations and anions are solvated /aqueous)

Trinitroresorcinol (2,4,6-trinitro-1,3-dihydroxybenzene) is a diacid
(O2N)3C6H(-OH)2 <--H2O-->(O2N)3C6H(-O(-))2 + 2 H(+)
As such it should have fizzed a bit with the MgCO3 unless the Mg(OH)2 has reacted faster with it.
H(+) + OH(-) <--==> H2O (neutralization)
2 H(+) + CO3(2-) <--==> H2CO3 <--> H2O + CO2(g) (another kind of neutralization)
So
(O2N)3C6H(-OH)2 + Mg(OH)2 --> (O2N)3C6H(-O-)2Mg + 2 H2O (in fact (O2N)3C6H(-O(-))2 + Mg(2+))
(O2N)3C6H(-OH)2 + MgCO3 --> (O2N)3C6H(-O-)2Mg + H2O + CO2(g) (in fact (O2N)3C6H(-O(-))2 + Mg(2+))

If there was exces MgCO3/Mg(OH)2 as proven by the remaining precipitate then you have into the media after filtration:
Mg(2+), CO3(2-), OH(-) and (O2N)3C6H(-O(-))2

Adding Pb(NO3)2 will precipitate traces PbCO3, Pb(OH)2 aswel as (O2N)3C6H(-O-)2Pb all less soluble (= more unsoluble).

Adding HNO3 will fizz from CO3(2-) and PbCO3 by setting CO2(g) free and neutralize OH(-) and Pb(OH)2...but it will also solubilise them by forming the soluble Pb(NO3)2
PbCO3 + 2 HNO3 --> Pb(2+) + 2 NO3(-) + H2O + CO2(g)
Pb(OH)2 + 2 HNO3 --> Pb(2+) + 2 NO3(-) + 2 H2O
Then the HNO3 will act further and solubilise the lead styphnate/trinitroresorcinate because HNO3 is a stonger acid than TNR and as such it will displace the weaker acid from their salts.
(O2N)3C6H(-O-)2Pb + 2 H(+) --> (O2N)3C6H(-OH)2 + Pb(2+)
If too much acid is added then TNR will be dropped out of solution because the later equation is an equilibrium
(O2N)3C6H(-OH)2 <--H2O-->(O2N)3C6H(-O(-))2 + 2 H(+).

The neutralization pH must close to 7 and more than certainly between 6 and 8.

Adding NaOH will precipitate only Pb(2+) and Mg(2+) as unsoluble white Pb(OH)2 and Mg(OH)2...the nitrate and TNR will remain solubilized as Na(+) salts...thus normal that the precipitate doesn't react to flame!

Mg metal will be probably too reductive to allow for direct reaction with TNR so some reduction of the nitro into amino (or intermediary nitroso, hydroxylamino groups, diazo oxyde)