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underground
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[*] posted on 16-12-2017 at 10:17


From what shops you can buy it that cheap?
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JJay
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[*] posted on 16-12-2017 at 10:20


Walmart.

https://www.walmart.com/ip/Equate-Mineral-Oil-Intestinal-Lub...

[Edited on 16-12-2017 by JJay]




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[*] posted on 16-12-2017 at 10:25


I see. Anyway i found tha there is a paraffin oil used as "lamp oil" Is that the same ? It costs 3€ per 1L
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[*] posted on 16-12-2017 at 10:30


If unscented, that would probably work fine for protecting sodium.



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[*] posted on 16-12-2017 at 10:45


Yea it is colourless and odourless
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[*] posted on 22-12-2017 at 08:28
Uses for "red water" waste from sulfite wash of TNT?


I recall reading a patent or other process information on reclaiming and recycling into either subsequent batches of TNT (or other explosives synthesis?) the non symmetrical water soluble nitrotoluenes separated from TNT by the sulfite wash process. The "red water" which otherwise would be a loss of fixed Nitrogen, toluene precursor and an environmental hazard If wasted.

A quick Google of this site has not found this again for me, do any recall this being posted here?

[Edited on 22-12-2017 by Bert]




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[*] posted on 24-12-2017 at 03:40


Yeah I think so, I was the one who asked about that - quite some time ago. I had that red water sitting around for ages but only recently got rid of it. I evaporated most of the water and absorbed what was left onto paper towels before incinerating it. As was suggested to me.
I just checked back on that thread and you did mention a process but didn’t have a follow up patent or anything. There was a few other patents there relating to the purification of TNT but I’m unsure if they deal with the recycling of waste water or not I don’t have the time to read through them right now but it is toward the bottom of the page: https://www.sciencemadness.org/whisper/viewthread.php?tid=29...




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[*] posted on 10-1-2018 at 18:21


Is there any difference between bubbling Cl gas vs adding hcl acid into a base solution to make a hcl salt ?
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[*] posted on 10-1-2018 at 18:32


Quote: Originally posted by underground  
Is there any difference between bubbling Cl gas vs adding hcl acid into a base solution to make a hcl salt ?


Yes, because it's Cl gas, not HCl gas.

Cl gas is lousy for making HCl salts because it is lacking in H.

HCl gas works like HCl solution though, as long as it's going into something aqueous.




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[*] posted on 10-1-2018 at 22:13


Thank you for your reply but my english are not that good to understund despite i used google translate :D

What do you mean by "lousy" ? Can you give me an example ?
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[*] posted on 10-1-2018 at 22:21


Lousy is slang for terrible.

Cl is terrible for making hydrochlorides.

HCl is good for making hydrochlorides.

People said lousy a lot 50 years ago but not so much now.

I talk like an old man sometimes, sorry.




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[*] posted on 13-1-2018 at 22:48


How can I obtain small grain-ish crystals that have high density during recrystallization?
The explosive I'm trying to recrystallize is Picric Acid. In fact, its drying outside. I've just filtered it, but the idea of using it as is doesn't make me happy.

I will recrystallize it, but I want high density, but at the same time, small crystals, almost like powder.
I've managed to successfully achieve small crystals by dissolving ETN in hot ethanol and then adding distilled water drop-wise to the solution. The problem is that PA is soluble and recrystallized from water. What should I do, gently boil the water? Crash it somehow in another solvent?
I don't have much time before it dries out. LOL.




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[*] posted on 14-1-2018 at 08:32


Quote: Originally posted by joseph6355  
How can I obtain small grain-ish crystals that have high density during recrystallization?
The explosive I'm trying to recrystallize is Picric Acid. In fact, its drying outside. I've just filtered it, but the idea of using it as is doesn't make me happy.

I will recrystallize it, but I want high density, but at the same time, small crystals, almost like powder.
I've managed to successfully achieve small crystals by dissolving ETN in hot ethanol and then adding distilled water drop-wise to the solution. The problem is that PA is soluble and recrystallized from water. What should I do, gently boil the water? Crash it somehow in another solvent?
I don't have much time before it dries out. LOL.


The faster you boil or dry it, the smaller crystals will be, and the denser it will be. At least we weirdos learned that in chemistry.
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[*] posted on 14-1-2018 at 14:00


Very small scale experiment without much details, but any ideas what was produced? :) Seems an interesting reaction, since it appears to produce a very specific product in, what seems to be, a very good yield.

Had some left over ascorbate and copper(II)sulfate solutions from a DBX-1 synthesis and decided to see if Cu(I) picrate would exist and would be less water soluble than Cu(II)picrate. So I added a spatule of picric acid and ~3 ml 0.4M copper(II)sulfate solution and heated until everything dissolved. Then I added 3 ml of 0.21M sodium ascorbate solution, but nothing precipitated.Thinking that maybe the sodium ascorbate solution had air oxidized, I added 1 drop of very dilute NaCl, immediately producing a white copper(I) chloride precipitate, so Cu(I) was present. Upon adding another 3 ml of ascorbate solution and heating harder to boiling (covered with cling wrap) slowly the solution went to a yellow, then dark greenish brown and finally brown. An abundant yellow-brown precipitate started to form as small (but well defined) crystals. After filtering and drying it is a yellow-brown coloured compound, burning slightly energetic with green flame and producing a lot of carbon (so definitely a picric derived compound). Thinking the colour could be from copper powder, I added a few drops of 70% nitric, which dissolved the compound to a colourless solution (no NOx produced), diluting this with water produced a beautiful bright orange glistening precipitate, barely soluble in water. It melts sharply at around 150-155 deg C. Any ideas? I'm guessing a partial reduction product of TNP itself, but which? :P Alternatively maybe some condensation product of ascorbic or dehydroascorbic and a nitroso/hydroxylamine intermediate (one would think these would be fairly water soluble)?

TNP ascorbate copper(II) reaction.jpg - 72kB

[Edited on 15-1-2018 by nitro-genes]
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[*] posted on 15-1-2018 at 04:46


Quote: Originally posted by ShadowWeirdo  
Quote: Originally posted by joseph6355  
How can I obtain small grain-ish crystals that have high density during recrystallization?
The explosive I'm trying to recrystallize is Picric Acid. In fact, its drying outside. I've just filtered it, but the idea of using it as is doesn't make me happy.

I will recrystallize it, but I want high density, but at the same time, small crystals, almost like powder.
I've managed to successfully achieve small crystals by dissolving ETN in hot ethanol and then adding distilled water drop-wise to the solution. The problem is that PA is soluble and recrystallized from water. What should I do, gently boil the water? Crash it somehow in another solvent?
I don't have much time before it dries out. LOL.


The faster you boil or dry it, the smaller crystals will be, and the denser it will be. At least we weirdos learned that in chemistry.

I must be very stupid. I swear that I've read somewhere that the melting point of PA was 92 C and it would melt.
I just checked COPAE and it states 122 ºC. Thank god.

The batch I synthesized is gone though. I already blew it up.
Thanks and sorry for not double checking it.




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[*] posted on 15-1-2018 at 12:35


Quote: Originally posted by nitro-genes  
Very small scale experiment without much details, but any ideas what was produced? :) Seems an interesting reaction, since it appears to produce a very specific product in, what seems to be, a very good yield.

Had some left over ascorbate and copper(II)sulfate solutions from a DBX-1 synthesis and decided to see if Cu(I) picrate would exist and would be less water soluble than Cu(II)picrate. So I added a spatule of picric acid and ~3 ml 0.4M copper(II)sulfate solution and heated until everything dissolved. Then I added 3 ml of 0.21M sodium ascorbate solution, but nothing precipitated.Thinking that maybe the sodium ascorbate solution had air oxidized, I added 1 drop of very dilute NaCl, immediately producing a white copper(I) chloride precipitate, so Cu(I) was present. Upon adding another 3 ml of ascorbate solution and heating harder to boiling (covered with cling wrap) slowly the solution went to a yellow, then dark greenish brown and finally brown. An abundant yellow-brown precipitate started to form as small (but well defined) crystals. After filtering and drying it is a yellow-brown coloured compound, burning slightly energetic with green flame and producing a lot of carbon (so definitely a picric derived compound). Thinking the colour could be from copper powder, I added a few drops of 70% nitric, which dissolved the compound to a colourless solution (no NOx produced), diluting this with water produced a beautiful bright orange glistening precipitate, barely soluble in water. It melts sharply at around 150-155 deg C. Any ideas? I'm guessing a partial reduction product of TNP itself, but which? :P Alternatively maybe some condensation product of ascorbic or dehydroascorbic and a nitroso/hydroxylamine intermediate (one would think these would be fairly water soluble)?

[Edited on 15-1-2018 by nitro-genes]


http://www.sciencemadness.org/talk/viewthread.php?tid=433&go...

Curpous salts and sodium ascorbate are each capable of reducing picric acid to picramic acid.

Picramic acid is the probable reduction product and you could have sodium picramate or free picramic acid depending on pH. Diazotize it and see if DDNP results.

It would be interesting to see if the cuprous / ascorbate system would also partially reduce styphnic acid to provide a diazotization precursor for DDNR. It may work similarly as does the stannous chloride reduction and would be more economical using a cuprous / ascorbate scheme instead of the tin salt. Ascorbate could be useful for recycling regeneration of the spent oxidized metallic salts in either case, and the ascorbate may faciliate use of the metallic salt in catalytic amounts to perform the reduction, with the spent oxidized catalyst being regenerated in situ by incoming additions of ascorbate. This may be done also with iron and manganese salts, and probably cobalt and nickel salts also.

[Edited on 1/15/2018 by Rosco Bodine]
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[*] posted on 15-1-2018 at 13:05


It is some reduction/codensation product, probably immediately precipitated by copper(I) or (II) present, preventig further reaction (Ascorbic is capable of fully reducing TNP IIRC). Picramic crossed my mind as well, it burns fairly similar. Then again, the photo attached doesn't represent the colour right, it is more of a bright orange (like orange peel) instead of the bright red for picramic and although the melting point was taken on a hotplate, it usually is fairly accurate (picramic = 165-170 C) and the compound melted incredibly sharp.

I'll do some more tests, see how the colour changes with changes in pH, solubility in other acids and maybe diazotization indeed.

[Edited on 15-1-2018 by nitro-genes]
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[*] posted on 15-1-2018 at 13:07


It is interesting. Try different things and see what results.

Gotta love this basic textbook stuff that for some reason isn't in any of the modern textbooks as specific "student lab" examples particularly for these basic color change pH sensitive dyes.

pH dyes and redox indicators are very cool chemistry all by themselves, and can become essential spectator and reaction condition monitors for a great many other reactions.

[Edited on 1/15/2018 by Rosco Bodine]
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[*] posted on 15-1-2018 at 14:40


Is there anyplace that sells round metal tubing that is divided in half down the center, something around 3 cm in diameter, more or less? Or what place might use such tubing?
Something like this concept ...
Info if you scroll down to the second photo. This stuff is too small though and it's quartz so a pretty penny too.
http://www.qsil.com/en/products-solutions/twin-an-septum-tub...

[Edited on 15-1-2018 by Morgan]
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[*] posted on 15-1-2018 at 17:00


Quote: Originally posted by Morgan  
Is there anyplace that sells round metal tubing that is divided in half down the center, something around 3 cm in diameter, more or less? Or what place might use such tubing?
Something like this concept ...
Info if you scroll down to the second photo. This stuff is too small though and it's quartz so a pretty penny too.
http://www.qsil.com/en/products-solutions/twin-an-septum-tub...

[Edited on 15-1-2018 by Morgan]


What kind of metal? What temps does it need to withstand, any acids/bases? Does it need to be round or can square tube with a divider in the center?

How long does it have to be? Could 2 tubes nested inside one another be possible like 3cm ID of large one and inner one of about 2cm which would give about equal volume of each tube (of the same length) but we'd have to calculate wall thickness of the inner tube for total accuracy.


*Note = Why does it say the word "center" is mispelled on this forum? There are alot of words like this that say that which are not mis-spelled..
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[*] posted on 15-1-2018 at 20:35


It doesn't have to be anything exotic, it could even be aluminum but preferably some ordinary steel if such a thing exists. Maybe a strip of stiff thin metal could just be slid down a tube as a prototype if the thing would stay in there straight and true. If you could cut a channel on the inside for the strip of metal to fit into on both sides maybe ...

Or cut a slit down one side the length of a tube and slide in a partition flush with the outside walls of tube but seal it from leaking about the cut portion somehow.

I just want to get around using 2 tubes which can't be swagged neatly into a single round hole of a predetermined size. Maybe mash 2 tubes flat on one side and put the two faces together?

I've also considered a tube within a tube with spars or screws to set the spacing but it might create more drag or turbulence for airflow.

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[*] posted on 16-1-2018 at 14:36


Ok, so I made the orange-peel-insoluble-in-water-stuff again, trying to determine better the conditions for it's formation.

0.25 grams (~1 mmole) of picric were added to a 25 ml beaker, together with 0.27 grams of copper(II)sulfate pentahydrate (~1 mmole) and heated in 20 ml of distilled water to near boiling, upon which everything dissolved. NaOH solution was added to a pH of 7 to neutralize the picric. Then I weighed out 0.6 grams (~3.2 mmoles) of ascorbic acid and slowly started adding this to the picric/copper sulfate solution. When about 0.27 g was added (1.5 mmoles), a greenish-yellow precipitate started to form abundantly, the pH at this point was about 3-4. This was filtered off and washed thoroughly. The precipitate was resuspended in 10 ml of water and NaOH solution was again added at room temperature (pH of 10-12 or so), upon which it turned to a deep red-orange suspension. Upon acidifying again (this time using dilute HCl, instead of nitric) the bright orange precipitate formed slowly.

So no reduction to picramic, which would have required at least 6 electrons and 3 mmoles of ascorbic (3.5 if you don't count the copper reduction), though IIRC it's also only able to reduce nitro groups under more basic conditions. Curious what this stuff is exactly though. :)

[Edited on 16-1-2018 by nitro-genes]
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[*] posted on 16-1-2018 at 17:03


Tried recrystallizing some of the orange precipitate from boiling 10% HCl, but it only formed a colourless solution from which nothing precipitated on cooling. When base was added, the orange stuff formed again, though slightly duller in appearance, maybe at high ph it was oxidized again, or the boiling hcl hydrolyzed something off.

Also diazotized some of the orange-peel stuff (after boiling hcl recryst attempt) it immediately formed a yellow compound, flashing like DDNP. Hmmmm, this requires some thinking through of what exactly is the greenish-yellow stuff?! :o

The copper-ascorbic reduction system may be interesting to study it seems. @rosco, you mentioned Cu(I) mediated nitro reductions, any references would be interesting to read.

[Edited on 17-1-2018 by nitro-genes]
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[*] posted on 16-1-2018 at 20:27


Copper Picramate is greenish yellow. Picramic acid is the likely reduction product using the copper sulfate / ascorbic acid reagent, where curpous sulfate or hydroxide formed in situ would be reducing towards the copper picrate or sodium picrate also formed in situ.

A double sodium picramate - copper picramate is also a possible product, in any case would be converted to free picramic acid by moderate acid concentration such as added HNO3, and the low solubility free picramic acid would likely precipitate. With further added acid the picramic acid would redissolve via formation of picramic nitrate, so the solubility would be pH dependent....parallel behavior as you have observed for the iso-picramic acid, also showing color changes with pH that mark the transitions in pH where conversions are complete for these amphoteric compounds having changed states and composition.

In the highly acidified state, where the picramic nitrate is dissolved in sufficient excess HNO3 for supplying the NO2 for diazotization as a byproduct from formation of Cu(NO3)2 you could probably add the pieces of copper wire to achieve the diazotization very gradually and get good crystal development.

Using copper acetate with ascorbic acid should also work and eliminate any sulfate impurity. Basic copper carbonate could be easily formed from copper sulfate and filtered out and dissolved in acetic acid or white vinegar.

This is interesting because other divalent salts like iron and manganese and nickel and cobalt should also work, but the economy for the iron and manganese is good.

Should probably get a moderator to export these posts to the DDNP thread.

The picramic from picric thread has a lot of references I'll have to review and see what is already posted to know if I have any other references to add.

https://books.google.com/books?id=PshJAQAAMAAJ&pg=PA407&lpg=...
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[*] posted on 17-1-2018 at 03:36


Thanks for looking up the colour of the copper picramate, yellow greenish amorphous matches the precipitate obtained. "Detonates slighty" also sounds interesting. :) I used HCl this time, since unlike HNO3, it is non-oxidizing and doesn't have solvent properties towards nitroarenes like 70% nitric might have, so it indeed seems to behave amphotheric, like would be expected from picramic acid.

Very interesting this, I've attempted the reduction of picric before using ascorbic and catalytic amounts of Fe(II), and didn't get any picramic or precipitate in general. Maybe the copper(I) or (II) is complexing the ascorbic as a ligand in such a way that it forms ideal circumstances to preferentially attack a single ortho nitrogroup, even when the reaction is performed in water, or it may be a property of Cu(I) itself. Would be interesting to test if a catalytic amount of Cu(II) would have a similar effect, guessing not since the copper may be required to precipitate the picramic resulting in a high yield and very pure product. It's possible the acid pH was limiting in the amount of the greenish yellow stuff that was able to form indeed, maybe adding a sodium ascorbate/ascorbic buffered solution at pH of 7 instead of ascorbic acid itself would result in higher yield. Not sure yet the greenish yellow stuff is a copper picramate itself, it may be a different product than that of the first reaction due to a possibly higher pH the first time.

Maybe getting ahead of myself, since this may never exceed the economy of a hydrosulfide reduction, it may however offer some advantages in terms of recycling, waste waters produced and may additionally be advantagous for the reductions of other nitroarenes bearing more sensitive functional groups.

[Edited on 17-1-2018 by nitro-genes]
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