| Pages:
1
2
3
4
5
6 |
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
The reaction mix is supposed to be milky and it does tend to take up alot of volume and froth, especially if the temp it to high since DNU decomposes
exponentially faster at high temps into water and laughing gas which I think is the cause of the frothing(photo attached is just after some of the
hexamine has been added from my old synth)
[Edited on 17-12-2021 by fredsci93]
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
It's good that I didn't see anything I shouldn't. So everything was going well until I made the mistake of dumping the last remaining bit of hexmaine.
So the next time I will know (and review these posts). I will make sure I have a 500ml beaker. so I will have enough space for the expansion... or
just halve my amount of acids and hexamine and call it a day.
| Quote: | | Also the nitration mix after a runaway didn’t seem to have any RDX/keto-RDX when I dumped mine into water, the high temps seem to cook the
keto-RDX/RDX, but there’s no harm in dumping the mix into water just to see if anythings in it |
Yeah but not with this runaway that I had! I noticed that the tempt went from what I assumed to be 15C to 50 C and it started to turn yellow and
bubble. My spidey senses said 'this is going to blow!' and I immediately let go of the entire thing and fled. There was no explosion, but the
resulting gas cloud was spectacular. I am pretty certain that if I caught even the smallest whiff of that stuff I would be in serious danger.
Thankfully I got away and was completely safe.
The thing burned and boiled until there was nothing left was a black residue in the bottom. I guess that's whatever was supposed to be my RDX yield.
[Edited on 18-12-2021 by ManyInterests]
|
|
|
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
wow, that's even more intense than my runaway, after the mix spewed gas and acid all over the walls (the gas was probably mostly N2O and nitric acid
vapour rather than NO2 since it was uncoloured), a small amount of yellow liquid was left over, my runaway occurred ~1/2 way though my synthesis
though, so it must have not generated enough energy to boil everything off since not all the hexamine was added
what sort of burning happened, just charing or full fledged flames?
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
There was massive boiling and gasses spewing out. No flames, no lasting charring (my 1000ml beaker was 100% intact. You gotta love borosilicate
glass!!) but imagine something boiling but in ultra fast-motion and it goes from full to empty in a few seconds. That was one hell of an ultra
dramatic runaway and my single most dramatic runaway!
I did hear something popping, I thought my beaker busted, but what actually happened was my glass thermometer was what popped. I don't mind... that
glass thermometer was already destined for the trash. The first runaway I had had worn out almost all of the numbers so I had no idea what it was
indicating other than zero (which was the only number to survive). I had already ordered another 0-100C glass thermometer, but what I will be doing
before continuing my experiments in a year or so is order a set of -30-100C thermometers from Aliexpress. They're not that expensive. I will have
plenty of spares, and the greater range will tell me just how cold it is when I am at sub-zero temperatures.
This is a pity because based on what you said how the synthesis go, I was doing mostly fine until I dumped the remaining hexamine. The next time I do
this if I feel like adding anymore is risky I will just call it a day. The one thing I learned about nitrating stuff is that you can undernitrate
things, but you can't overnitrate something. This is why in my ETN synthesis I always put a little less erythitol to the nitrating mix. While this
does mean I need to wash the end product more thoroughly, that is a small price to pay for a safer reaction.
|
|
|
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
Right, I find the hexamine addition my first time around was super difficult, but on my last run it was much easier and the urea step was the awful
part, not sure why, probably down to cooling, or any range of other factors, the reaction is pretty unpredictable and hard to tame, some time in a
month or so I'll try another few synths at the scales quoted in the paper, this time with overhead stirring because I noticed there are alot of local
heating maxima during the synth which will lower the yield alot.
|
|
|
MineMan
National Hazard
Posts: 996
Registered: 29-3-2015
Member Is Offline
Mood: No Mood
|
|
Fred? Why not use a slushy of dry ice and isopropyl or ethanol?
|
|
|
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
The main reason I haven’t tried dry ice/ethanol is because where I live the only place to get dry ice is a BOC gas facility an hour away, it's
inconvenient for me and salted ice baths are sufficient for the reaction so long as you replenish them often. It's an interesting idea, if I'm near
the dry ice facility I'll grab a bit for a test run.
|
|
|
MineMan
National Hazard
Posts: 996
Registered: 29-3-2015
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by fredsci93  | | The main reason I haven’t tried dry ice/ethanol is because where I live the only place to get dry ice is a BOC gas facility an hour away, it's
inconvenient for me and salted ice baths are sufficient for the reaction so long as you replenish them often. It's an interesting idea, if I'm near
the dry ice facility I'll grab a bit for a test run. |
Doooooooooooo ittttttttttttt!
|
|
|
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
I looked a bit, I’ll probably be a very long time before I try a dry ice reaction, the smallest amounts I can seem to find are 10kg boxes for nearly
90USD, which is a very frivolous purchase for a single reaction, which is a shame, I remember only 2 years ago they used to sell by the kilo  , oh well maybe they'll start selling by the kilo again soon (could have switched
during covid?) or maybe I'll get some in a package.
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
I didn't think of the dry ice and alcohol... I think I can get some in my area. I'll keep that in mind the next time around.
|
|
|
Microtek
National Hazard
Posts: 827
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
Be aware that it is not always safer to cool a reaction excessively. It is possible to essentially stop some reactions if the temp is too low. This
means that when you have added all of your reactants and at some point stop the cooling, the mix will heat up naturally. Then when it gets warm enough
to begin reacting, the exotherm will warm it faster and faster --> runaway.
Also, don't freeze your beaker into a block of ice. A stirred cooling bath is much more effective for removing heat, even if the temp of the bath was
higher than that of the block of ice.
|
|
|
fredsci93
Hazard to Self
Posts: 84
Registered: 29-12-2017
Member Is Offline
Mood: No Mood
|
|
that's true, dry ice could be detrimental, the ideal reaction temp during urea additions is between 5C and 0C so dry ice could very easily be
detrimental for making the DNU, however the hexamine additions should be done ideally between -5C and 0C and in that case dry ice/ethanol could be
useful, but even then it could also lower it to low fairly easily, definitely worth a try if anyone has good access to dry ice.
[Edited on 22-12-2021 by fredsci93]
|
|
|
caterpillar
Hazard to Others
Posts: 472
Registered: 8-1-2012
Member Is Offline
Mood: No Mood
|
|
it seems to me that urea nitrate and hexamine dinitrate would be useful- the process won't be very exothermic. And these organic salts already contain
some nitric acid.
Women are more perilous sometimes, than any hi explosive.
|
|
|
Herr Haber
International Hazard
Posts: 1236
Registered: 29-1-2016
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by fredsci93 | the hexamine additions should be done ideally between -5C and 0C and in that case dry ice/ethanol could be useful, but even then it could also lower
it to low fairly easily, definitely worth a try if anyone has good access to dry ice.
[Edited on 22-12-2021 by fredsci93] |
You can easily maintain -5 to 0c just with ice and salt. How long depends on how much ice you have and local temperatures.
You can get gel packs that freeze at all kind of temperatures to help manage your cooling. They are also very useful in distillations (just replace)
Check the different color / temperatures and check how low your freezer will go before purchasing.
Normal freezers will go down to -16c which for me is the blue gel.
That, and good brine can really help. Water will of course freeze around the packs.
They're a good alternative, are reusable (just rinse and put back in freezer).
Oh... and dont put them in acetone 
The spirit of adventure was upon me. Having nitric acid and copper, I had only to learn what the words 'act upon' meant. - Ira Remsen
|
|
|
Uriel
Harmless
Posts: 14
Registered: 28-1-2017
Member Is Offline
Mood: No Mood
|
|
Hello guys,
I just fail to produce Keto-RDX via the 2008 Chinese paper route with H2SO4/NH4NO3 way :-(
1-I mixed 50g of 98% clear H2SO4 + 31g of recrystallized NH4NO3 and putted it in the freezer.
2-Then I've added 5.25g of urea to the cold mixture, unfortunately, I guessed the tiny pearls would dissolve... But don't all of them, 20% remain in
pearls...
Probably the temperature was to far below zero...
The reaction is very strange, at first, the mixture is firstly like a soft past, and in 4 secondes, become hard like hard butter ! So strange ! And
endothermic furthermore ! Then I managed to hit
this bloc and back it to soften butter with lot of efforts.
3- At -20°C the precedent paste is kneaded again to bring it to very thick slurry.
4- I've added 5g of hexamine wile the mixture was more easy to stir, like a hard paste. First by 0.5grams, then, like the temperature remain to
-15°C, all the 5g of hexamine remained.
5- the temperature after 40 minutes was to -2°C (in a ice bath) then, I putted it in 20°C water and stir it again during 10minutes.
6- As the temperature was near 15°C, I poored it in 500mL 5°C water.
7- Almost nothing was precipitaed, only some pearls of urea wasn't still not dissolved...
Sad experiment, but cheap !
Conclusion: even the fact that the temperatures was not exactly the same than the paper, I guess that this route H2SO4/Nitrate is not a functioning
way for RDX/K-6 BUT with a really strict method, maybe... Someone could succeed. Maybe.
(for example, I reach 95% yield for ETN since 7 years with this route (1/4/10) and 80% for ETN with 1/5/12 with KNO3)
[Edited on 3-4-2022 by Uriel]
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
I did more reading from the paper, especially the last part where they discuss that Keto-RDX (K6) is more sensitive than RDX. I still have a hard time
following on just how sensitivity scales work. I know that RDX is an exceptionally insensitive energetic material, but Keto-RDX being more sensitive
than RDX means what? I assume it means more stable than PETN (which is quite stable) and ETN (not as stable as PETN, but still very safe to handle)?
I also read on a sciencedirect article (https://www.sciencedirect.com/science/article/abs/pii/S03043...) that it is only usable in phlematized form. Would that mean just mixing a bit of
melted paraffin wax in it before using it or storing it?
| Quote: Originally posted by Uriel | Hello guys,
I just fail to produce Keto-RDX via the 2008 Chinese paper route with H2SO4/NH4NO3 way :-(
1-I mixed 50g of 98% clear H2SO4 + 31g of recrystallized NH4NO3 and putted it in the freezer.
2-Then I've added 5.25g of urea to the cold mixture, unfortunately, I guessed the tiny pearls would dissolve... But don't all of them, 20% remain in
pearls...
Probably the temperature was to far below zero...
The reaction is very strange, at first, the mixture is firstly like a soft past, and in 4 secondes, become hard like hard butter ! So strange ! And
endothermic furthermore ! Then I managed to hit
this bloc and back it to soften butter with lot of efforts.
3- At -20°C the precedent paste is kneaded again to bring it to very thick slurry.
4- I've added 5g of hexamine wile the mixture was more easy to stir, like a hard paste. First by 0.5grams, then, like the temperature remain to
-15°C, all the 5g of hexamine remained.
5- the temperature after 40 minutes was to -2°C (in a ice bath) then, I putted it in 20°C water and stir it again during 10minutes.
6- As the temperature was near 15°C, I poored it in 500mL 5°C water.
7- Almost nothing was precipitaed, only some pearls of urea wasn't still not dissolved...
Sad experiment, but cheap !
Conclusion: even the fact that the temperatures was not exactly the same than the paper, I guess that this route H2SO4/Nitrate is not a functioning
way for RDX/K-6 BUT with a really strict method, maybe... Someone could succeed. Maybe.
(for example, I reach 95% yield for ETN since 7 years with this route (1/4/10) and 80% for ETN with 1/5/12 with KNO3)
[Edited on 3-4-2022 by Uriel] |
I don't think that is going to work. RDX is not a simple nitrated ester like ETN or nitrocellulose. You need a very high concentration of nitric
acid/HNO3 in order to get RDX or K6. Like WFNA at 98%+ or more.
[Edited on 16-7-2022 by ManyInterests]
[Edited on 16-7-2022 by ManyInterests]
|
|
|
Herr Haber
International Hazard
Posts: 1236
Registered: 29-1-2016
Member Is Offline
Mood: No Mood
|
|
Unless you intend to subject the container of your energetic material to thousands of g's then it's doubtful you'll need to phlegmatize it.
And ugh...
RDX is a simple nitrated ester ? What is the nitro group attached to ?
Please comment on the image on the following webpage:
https://www.researchgate.net/figure/Molecular-structures-of-...
The spirit of adventure was upon me. Having nitric acid and copper, I had only to learn what the words 'act upon' meant. - Ira Remsen
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
Arrrghh! I hate these embarassing typos (I corrected it) I mean that RDX is NOT a simple ester. My apologies.
Also that's good, so I don't need to do anything special in terms of handling or storage. I will, of course, treat K6 with the same utmost respect I
treat any high explosive material. Just in case the gods of chemistry frown upon me and give that specific thing I am holding the stability of
azidoazide azide...
|
|
|
Hey Buddy
Hazard to Others
Posts: 384
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
KETO RDX FAILURE Via H2SO4+AN
| Quote: Originally posted by Uriel | Hello guys,
I just fail to produce Keto-RDX via the 2008 Chinese paper route with H2SO4/NH4NO3 way :-(
1-I mixed 50g of 98% clear H2SO4 + 31g of recrystallized NH4NO3 and putted it in the freezer.
2-Then I've added 5.25g of urea to the cold mixture, unfortunately, I guessed the tiny pearls would dissolve... But don't all of them, 20% remain in
pearls...
Probably the temperature was to far below zero...
The reaction is very strange, at first, the mixture is firstly like a soft past, and in 4 secondes, become hard like hard butter ! So strange ! And
endothermic furthermore ! Then I managed to hit
this bloc and back it to soften butter with lot of efforts.
3- At -20°C the precedent paste is kneaded again to bring it to very thick slurry.
4- I've added 5g of hexamine wile the mixture was more easy to stir, like a hard paste. First by 0.5grams, then, like the temperature remain to
-15°C, all the 5g of hexamine remained.
5- the temperature after 40 minutes was to -2°C (in a ice bath) then, I putted it in 20°C water and stir it again during 10minutes.
6- As the temperature was near 15°C, I poored it in 500mL 5°C water.
7- Almost nothing was precipitaed, only some pearls of urea wasn't still not dissolved...
Sad experiment, but cheap !
Conclusion: even the fact that the temperatures was not exactly the same than the paper, I guess that this route H2SO4/Nitrate is not a functioning
way for RDX/K-6 BUT with a really strict method, maybe... Someone could succeed. Maybe.
(for example, I reach 95% yield for ETN since 7 years with this route (1/4/10) and 80% for ETN with 1/5/12 with KNO3)
[Edited on 3-4-2022 by Uriel] |
I also attempted this route of preparation using H2SO4 drain cleaner and NH4NO3. AN was recrystallized from agricultural AN prills, and was in a
powdered form. Initial temperature was at min -5c and rose to max 5c during duration of whole experiment. Stirring was done with an overhead stirrer
w/PTFE paddle stirrer.
H2SO4/AN mix was prepared and allowed to cool for 30min, Urea was added and allowed to react for 1 hour, then hexamine was added and reacted for 2
hours.
It "felt" promising but upon crashing into dH2O and filtering I was left with nothing.
|
|
|
ManyInterests
National Hazard
Posts: 837
Registered: 19-5-2019
Member Is Offline
|
|
I just want to note that I made two attempts at producing Keto-RDX and both ended up with runaways. At this point I decided I will simply go to the
simple method of making simple RDX (with adding a little bit of potassium nitrate to the fuming nitric to increase possible HMX yields) I had a
successful RDX yield (very small, using HDN as a starting material) and I didn't find making RDX to be any more difficult than making ETN.
Maybe one day I will try to go with a Keto-RDX synth since I now have a electronic thermometer that will not have it's graduations fade away due to
the fumes.
|
|
|
Hey Buddy
Hazard to Others
Posts: 384
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
I just attempted this reaction per the Iranian paper. Imagine someone grabbing an industrial fire extinguisher, then discharging it into the air but
it's all NO2. --The run away complaints are no joke. It is a deceptive reaction. I had massive cooling, -10 most of the time. Had teeny weeny run away
for a few seconds on first additions of hexamine, easily controllable. Moved right along. When the temp climbed, I just took a break and let it cool.
No big deal. A little over half way through hexamine addition, the temp climbed closer to zero and I got over confident. I heard a fizz for about
three seconds, and the beaker just had foggy white haze, and then there was no recovery.
I could barely see the thermometer through the NO2 but it looked like one of those whack-a-meters at a carnival. I will reattempt this reaction with
more tact, beware: do not let the temp go anywhere near zero. I use a PID overhead stirrer with paddle for this kind of stuff, and a sodium salt/ice
bath, it stirs very strongly, I would have had difficulty managing the hexamine additions without automated strong stirring. My runaway began under 0
C or perhaps right at zero. It was not above zero though.
Honestly, if you wanted to impress someone on the dangers of runaways, this is the method to use. If you thought you knew what a good runaway was
like, I guarantee you this is a good one.
[Edited on 17-11-2022 by Hey Buddy]
|
|
|
underground
National Hazard
Posts: 692
Registered: 10-10-2013
Location: Europe
Member Is Offline
|
|
Hey Buddy can you also try another synthesis of keto-RDX but this time use nitroguanidine instead of nitrourea ?
[Edited on 17-11-2022 by underground]
|
|
|
Hey Buddy
Hazard to Others
Posts: 384
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
| Quote: Originally posted by underground | Hey Buddy can you also try another synthesis of keto-RDX but this time use nitroguanidine instead of nitrourea ?
[Edited on 17-11-2022 by underground] |
Sure, with fuming nitric/ sulfuric 50:50? like the K-6 iranian paper? Sure. I will try it and record it for you.
--While we are talking about modified procedures, I should mention I tried a modification of the H2SO4 method of TMTN preparation, and added a molar
equivalent urea to hexamine, and it precipitated a "keto-TMTN" version that was slightly whiter than TMTN. I have learned that Nitroso compounds
introduce a yellow color and as you add oxygen to the molecule, it becomes whiter and whiter. TMTN is the most yellow, keto tmtn is a little whiter,
NTNT is lighter whiter than keto TMTN. Furthermore, I believe I was able to oxidize the keto TMTN to keto RDX by using a glacial acetic acid/ammonium
nitrate solution over about an hour, the yield is low but this oxidation solution turns from yellow on addition of TMTN to a fizzy foam when it
converts with heat, and then becomes white. Im assuming the change in color is the oxidation taking place and it takes place with heat generation,
typically from room temp to ~70c in a matter of 30 seconds or a minute. I have tried the same oxidation solution on an attempt to oxidize TMTN to
plain RDX and it results in a foam volcano but at the end of the volcano, the solution changes from yellow to white, the beaker I was using is too
small to contain the foam volcano, but a different method or a catch bowl around the beaker would contain it all. I also experimented with nitrite and
nitrate and peroxynitrite oxidation attempts, and they resulted in volcanos as well, but it was a few years back and I took no notes. I think there is
a route to Keto rdx through oxidation of keto-tmtn.
Additionally regarding this chinese/iranian synth in this thread on keto-rdx preparation, I believe this preparation is too long due to the
sensitivities of hexamine addition, fredsci93 reprted an addition of 5 hours. If the hexamine could be added in a timely manner without runaway, then
this preparation method would be really amazing.
I think the runaway probability is sensitized by climbing temperature, but the mass of reagents is too great to prevent runaway easily by the end of
hexamine additions. I think this iran/china procedure could be potentially managed and runaway probability minimized by reducing reagents by one half
and simply executing the reaction twice for the same yield. I suspect the addition of hexamine being halved would speed up the entire reaction
duration. Other benefits, If there was a run away, losses would halved. --The beginning of the hexamine additions go smoothly and the problems only
begin beyond half-way point of hexamine addition. In the prescribed procedure, The urea is already added before hexamine even begins. So by the time
the runaway problem begins, the mass of hexamine and urea have already surpassed the would-be halfway mark of a theoretical version with half
reagents. Of course there could be unforeseen complications by halving the reagents, but that seems to be an acceptable risk compared to 80%
probability of outrageous runaway. If it worked, you could run the procedure cut down by one half, two times back to back, maybe even in the same
amount of total time as the original procedure, and if you runaway your losses are only half.
Those are my thoughts on this issue, been thinking over since last night.
|
|
|
Hey Buddy
Hazard to Others
Posts: 384
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
| Quote: Originally posted by underground | Hey Buddy can you also try another synthesis of keto-RDX but this time use nitroguanidine instead of nitrourea ?
[Edited on 17-11-2022 by underground] |
Underground, just finished synth of compound from NQ +Hexamine +HNO3 +H2SO4. I modeled the chinese/iran keto-rdx procedure but took some liberties to
make it more successful. Hexamine additions are still very hot, but halving the reactants keeps it manageable. I had no issues with runaway at all,
the exothermic rise between urea addition versus NQ is practically the same, exotherm rate with hexamine addition is about same. Going to hack the
keto RDX quick mix procedure to half and it will really become a quick mix procedure.
NQ .04 mol 4.16 g
Hexamine .035 mol 4.90 g
HNO3 16.25 ml
H2SO4 16.25 ml
Added acids to beaker on salt/ice bath, added NQ at ~0 C, cooled to -10 C added hexamine slowly, stopped to cool anytime it got near -5 C. Let stir
for half hour after hexamine addition, then took it off ice and letting it sit another half hour now. Recorded it, will edit a video later. 250 ml of
crushed ice are ready to get reaction dumped on. I can't imagine this wouldnt be applicable to Urea keto rdx version as well, in terms of avoiding
notorious keto rdx runaway. Will try soon.
EDIT: After I posted this I poured off reaction mix on crushed ice. It went well at first but the ice wasnt enough and it started fuming and heating.
I keep a dump bucket for this purpose, and so I just dropped it in thinking I blew it, but the reaction was already finished so all the dump bucket
did was quench it and then I just scooped up what was recoverable in filter. I will have to analyze the compound after drying and see if it can be
determined which molecule is actually formed from that order of reactants.
[Edited on 18-11-2022 by Hey Buddy]
|
|
|
underground
National Hazard
Posts: 692
Registered: 10-10-2013
Location: Europe
Member Is Offline
|
|
Thanks a lot. Looking forward for your analysis.
|
|
|
| Pages:
1
2
3
4
5
6 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
