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Axt
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You will get HNO2 from water + N2O3, which then decomposes from the exotherm. You'll get some from N2O4 as well.
R-Salt needs concentrated acid solution @ pH1, HNO2 is a weak acid. R-salt is also decomposed by strong acid solutions, thus the reaction isn't
as merry as it first looks.
[Edited on 28-11-2005 by Axt]
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Rosco Bodine
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R-salt reportedly has 125% the output of TNT and yet it is made under fairly mild conditions . That alone makes it interesting and even better if
the yield could be increased over the 50% without too much added difficulty . I hope someone will get a look at those 1951 articles in Memorial of
the Powders .
The reference in PATR to the 90C heat test
for an R-salt and NG mixture is also intriguing , and it makes me wonder what may be the result of mixtures with other nitroesters like ethylene
glycol dinitrate ,
and erythritol tetranitrate , IF of course the information in PATR is accurate and
not a misprint like some others we have seen .
In the thread about HMX there was a high yield reported for DNPT by a reaction scheme which may be adaptable to R-salt using different proportions and
pH . An experiment by a forum member BASF was unable to confirm the method for DNPT ,
which seemed to be a low temperature variation on something similar to the
K process for RDX , but intended for a nitrosamine product . Such a
" no hexamine " method for R-salt from
reaction scheme which proceeds from a mixture of NH4 and CH2O providing
" nascent hexamine " as the precursor for the nitrosamine would be an interesting simplification , similarly as is the case for those of us
who make out own hexamine anyway and never drop it out of solution as hexamine free base , but rather as the dinitrate .
R-salt is a chemically reactive material and
I have wondered also what is its reactivity towards an organic peroxide , such as MEKP , or a liquid MEKP / AP mixture , or in an AP melt 
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K9
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Just to clarify, the "60g 35% HCl in 100ml water" would be ~51 ml of the HCL in 100 ml water to give ~12% HCl in solution? Thank you in advance.
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Axt
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Yes 60g 32% (actually checking bottle, its 32% not 35 as I previously said) HCl was added to 100ml H2O, which makes it 160g of 12% HCl. I hate volume
measurements of impure liquids.
This has been a bit touchy, and it may be advantageous to lower the HCl percentage making sure to keep the HCl:hexamine ratio >6:1 & pH ~1.
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K9
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Ok then one more thing. At 160 grams of 12% HCl, that works out to 0.526 moles (unless I screwed that up somewhere) to 0.14 moles of hexamine - or a
3.75:1 ratio which wouldn't be 6:1. Did I just screw that up somewhere or was that right?
I've tried adding NaNO2 at the end twice before resulting in total loss of product. I'm planning now to attempt this method with 17 grams KNO2 in 30
ml water, 7 grams hexamine, and I guess whatever concentration I dilute my 31.45% HCl down to.
EDIT: From here - http://www.basf.de/basf/img/produkte/farbmittel/leder/pdf/pb... 31.45% HCl is at a density of 1.1600 g/ml. So if I were to go with 12% I guess I
would be using roughly 21g HCl in 35g H2O or 18.4 ml HCl in 35 ml water.
[Edited on 4-12-2005 by K9]
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Axt
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OK, you scared me there for a while. Punching buttons on the calculator scratching my head  You forgot the other HCl/hex solution.
| Quote: | | Three solutions were made, one containing 60g 35% HCl in 100ml water, one containing 40g NaNO2 in 80ml water and one containing 20g hexamine and 60g
HCl in 100ml water |
Its 120g 32% HCl all up, so ~7.5 HCl to 1 Hexamine. This was done before I read that article, so dropping it back to 6:1 may prevent the decomposition
that sometimes occurs.
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K9
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Oh whoops I completely forgot that. Sorry.
Now after reading the article, it seems that their preferred method of reagent addition is of HCl and NaNO2 to a hexamine/water solution in one
instance and addition of NaNO2 solution to a hexamine/HCl solution in another. But from what I understand the order makes no difference at all, just
the pH.
There is also the matter of the ratios. From what I can understand, the best ratio seems to be about 1:6:4.3 of hex:HCl:nitrite.
As for the order of addition, I guess I'll go with adding HCl/NaNO2 to the hexamine/water solution since that seems to give good yields unless there's
some reason that I'm missing for which the hexamine should be dissolved in HCl first. Again, I know that all that really matters is the pH level
maintenance, but I don't quite know how well I will be able to control the pH during reagent addition.
Aside from the addition discrepancy (which again as far as I know makes no difference) I'm prepared for this procedure to finally work after the
failures. I'll report back with the results which will probably be nearer the end of the week.
Thanks again for all the help.
[Edited on 5-12-2005 by K9]
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K9
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Sorry for the double post but here's the results. Finally a success!
First I added 30 ml of 31.45% HCl to 50 ml water and this was mixed with 18 grams KNO2 in 30 ml water. I then added 7 grams hex to 50 ml water.
http://img.photobucket.com/albums/v78/wolfhound/ct1.jpg
At < 0C I added the nitrous acid to the hexamine solution. At first I thought nothing was happening but then it foamed up quite a bit, almost to
the top of the reaction vessel. Then the foam went down as the gas escaped.
http://img.photobucket.com/albums/v78/wolfhound/ct2.jpg
http://img.photobucket.com/albums/v78/wolfhound/ct3.jpg
This was then filtered and now it's drying. I don't know how great the yield is since it's a big air filled blob of wet product still, but I'll
measure when it's dry. Either way I'm just happy that it worked.
http://img.photobucket.com/albums/v78/wolfhound/ct4.jpg
I think the first time I tried it I actually did get something but it was an uncontrolled foaming with lots of NO2(?) coming off. So now all that's
left is drying and weighing. Just one more question, is there any reason to wash the product to neutralize it? Thank you for the help and I
appreciate any input.
[Edited on 7-12-2005 by K9]
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chloric1
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HMMM
Hey I cannot wait until I can do the experiment! That nitrous acid solution looks pretty, kind of like blue koolaid.
Fellow molecular manipulator
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Deceitful_Frank
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Well done! This is also on my to-do list, I beleive that this CTMTNA has a density of around 1.6 and velocity in the order of 7800m/s, stablises NG
and forms a more powerful composition due to synergy of oxygen balance. Toxic but an excellent explosive
I wanted to make it as I saw it as a potentially easy route to RDX though I am aware that the overall yeild from hex to RDX will be no more than 25%
of theory.
I posted a thread about converting this to RDX both on totse and on APC but without alot of interest. If you were to try to do this would you be using
the xNO3/H2SO4 bath to nitrate or to oxidise? Ime not sure how the reaction would procede even after etensive searching on the net. It would be good
to know the correct ratios of reactants to use if only to increase that abbysmal yeild though I fear you may end up having to just use a large excess
just to be sure.
EDIT:
Just walked my GF to work and upon walking back in the freezing foggy air, I've had a couple more thoughts regarding the above.
At first I assumed that CTMTNA would be VERY oxygen defficient... in the order of TNT and PA but it seems that It has the same theoretical detonation
products as HMTD... CO, N2 and H2, some carbon would obviously form but I would not expect to see black smoke upon firing. More a grey mist like from
HMTD.
Also I remember reading that CTMTNA forms a low melting point and easily castable eutectic in a 50:50 ratio with RDX though I'm not sure what defines
a "low melting point" IMO this would be have slightly more power than composition B and be of similar balance.
Also, if your nitration/oxydation to RDX is not to be and you can perfect your yeild and ecomany when synthesising CTMTNA, you could try plastisisng
it with a 20% mix of 4:1 by mass NG/MHN. Although the heat output would be lower than than RDX/NG/MHN plastique I'd bet the velocity would still be
around 7800m/s for a fully plastisised though TOXIC mass... (gloves)
[Edited on 7-12-2005 by Deceitful_Frank]
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K9
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I think I do want to try the conversion to RDX just to see if it does work and I would be using xNO3/H2SO4. I'm not really sure how to figure out what
the ratios should be (any help would be appreciated there) but I wouldn't be using a very large amount now anyways.
Rosco Bodine was the one that mentioned the mix (in page 1 of this thread) with RDX. That too sounds interesting. And the plasticized CTMTNA also
sounds good.
As far as improving the yield, I don't really know how I would go about that. I still have to weigh my yield but whatever I do get, lowering the HCl
concentration to allow better formation of nitrous acid (which is what I'm told would help it) might possibly increase my yield. In the paper they
also mentioned allowing about 1/2 hour time to pass before filtering. I let about 15 minutes go by before filtering off the foam. That may help too.
But it just seems like anytime the yield increases by a considerable amount it is simply due to having more dinitroso product.
EDIT:
Just weighed the dry product. Bang on at 50% yield.
[Edited on 7-12-2005 by K9]
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Rosco Bodine
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The conversion of R-salt to RDX is an idea which seems
to offer no advantage over the usual nitrolysis of HDN ,
and is much more dangerous . The Simecek article which
describes the reaction conditions is covered in the thread
started by BASF about HMX without acetic anhydride .
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Axt
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| Quote: | Originally posted by Rosco Bodine <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=4937#pid57468">here</a>
Anybody have access to these R-salt articles ?
P. Aubertein , Mem. Poudres 33 , 227 ,
( 1951 )
H. Ficheroulle and A. Kovache , Mem. Poudres 33 , 241 ,
( 1951 ) |
The second one is attached. Wait a <i>little</i> longer for the first.
Attachment: R-salt-Mem Poudres 33 241.pdf (823kB)
This file has been downloaded 1964 times
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Axt
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Heres the first.
http://ww1.ft100.net/~64671/xfiles.ft100.net/images/rsalt_me...
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Rosco Bodine
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Excellent get . Thanks for these references Axt .
These articles are another first on the web ,
so far as I know anyway .
Now pdb has something worth the work
From what I can understand of it the H2SO4
appears to be producing the increased yield .
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pdb
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I might help if you wish, provided I could access the document, but the server is out of reach. Is it so big that you can't attach it to your message
?
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Rosco Bodine
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The server is blocking the unsplit file so I have
split it up into four files attached in sequence .
[Edited on 2-2-2006 by Rosco Bodine]
Attachment: Pages 1 thru 4 from rsalt_mem_poudres_33_277.pdf (715kB)
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Rosco Bodine
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Here's the second file .
Attachment: Pages 5 thru 7 from rsalt_mem_poudres_33_277.pdf (891kB)
This file has been downloaded 1703 times
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Rosco Bodine
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Here's the third file .
Attachment: Pages 8 thru 10 from rsalt_mem_poudres_33_277.pdf (595kB)
This file has been downloaded 1589 times
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Rosco Bodine
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Here's the fourth and last file .
Attachment: Pages 11 thru 13 from rsalt_mem_poudres_33_277.pdf (687kB)
This file has been downloaded 1694 times
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pdb
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Memorial des Poudres (vol 33) - in English
Here you are...
Attachment: TRIMETHYLENE TRINITROSAMINE - (Memorial des Poudres - vol 33) (english).pdf (87kB)
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Rosco Bodine
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Thank you for the excellent translation of this important
and enlightening reference . More productive experiments
are foreseeable having this reference as a guide .
There are a couple of ideas which I have considered with
regards to the production of R-salt . I always make my
own hexamine from the reaction of paraformaldehyde mildewcide crystals and 28% ammonia blueprint developer
in excess , bringing the completed reaction to boiling after
all is in solution to drive off any unreacted ammonia and
leave a strong solution of pure hexamine in nearly quantitative yield , based on the 96% purity of the paraformaldehyde crystals used for the
synthesis .
The solution may be boiled down until crystals of hexamine
just appear and then the heating stopped . Upon cooling the hexamine will redissolve due to the inverse solubility
curve of hexamine with regards to temperature , leaving
a cold saturated solution . Hexamine dinitrate can be
precipitated from the freezing cold solution by just neutralizing with HNO3 in no great excess . The residual
solution contains some dissolved hexamine dinitrate which
is generally lost since the solution cannot be evaporated
by boiling at ordinary temperature . But the solution
from filtration of HDN can be further used directly in synthesis instead of simply being discarded as waste .
The HDN solution can be mixed with a 15% excess of theory
of hydrogen peroxide and kept in the freezer for the precipitation of HMTD which is complete after a couple of days . And it seems likely that the
cold HDN solution could also be used for the production of R-salt by reducing the amount of H2SO4 somewhat for one of the Aubertein
syntheses , to adjust the pH accounting for the HNO3 present in the HDN which is in solution . A useful byproduct
would thus be salvaged from a waste solution from the
synthesis of the HDN precursor for RDX , improving the economy of the process . Also the R-salt produced would
be of value because of its ability to form useful eutectics with
any RDX ultimately made from the HDN which was recovered
as crystals earlier in the process . This production of R-salt
as a byproduct would offset the losses which are inherent in the relatively inefficient nitrolysis of HDN to RDX . A further
improvement in efficency may be obtained by using the diluted nitrolysis mixture from filtration of the RDX , which
contains fairly concentrated HNO3 , for neutralization of
subsequent batches of concentrated hexamine solution to
produce more HDN and R-salt . By this scheme otherwise
wasted byproducts are recycled in the process , which would be of significant value in any large scale production .
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Fulmen
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Wonderful work guys, this really seems like a real alternative to the much more complicated RDX-synthesis. And wouldn't you know, I found both
hexamine and sodium nitrite in the basement the other day :-) But I would like to know more about the toxisity before I start, I don't have a real
lab and toxic materials give me the heebies-jeebies. Like the kilo or so of DNT I have, I'm sure it would be a valuable compound if I only could bring
me to ever use it...
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Douchermann
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Sorry to bring up an old thread, but I can not find a reaction diagram for this for the life of me. All of the reactions I thought of did not give
11.6grams of theoretical yeild for 7grams of hexamine (as in Mr. Cool's procedure). Does anyone know it, or can they figure it out? It would be
interesting to see it.
It\'s better to be pissed off than to be pissed on.
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Rosco Bodine
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| Quote: | Originally posted by Douchermann
Sorry to bring up an old thread, but I can not find a reaction diagram for this for the life of me. |
Now that I think about it , I have never seen the reaction stated either , so here is what I suppose is most likely .
(CH2)6N4 + 3 HNO2 ----> (CH2)3N6O3 + NH3 + 3 CH2O
m.w. 140.19 hexamine --------- m.w. 174.13 TMTN
100% yield of TMTN would be 1.2421 grams
per each 1 gram of hexamine .
The best yield reported by Aubertein in Experiment 19 was
64.9% of theory which amounts to .806 grams of TMTN
per each 1 gram of hexamine .
| Quote: |
All of the reactions I thought of did not give 11.6grams of theoretical yeild for 7grams of hexamine (as in Mr. Cool's procedure). Does anyone know
it, or can they figure it out? It would be interesting to see it. |
The equation I provided above is probably correct .
Evidently the yield figure of 84% attributed to Aubertein by Urbanski on page 122 of volume 3 , is an error .
It may be worthwhile also to experiment with nitric acid
as the acid used in whole or in part in the process for producing TMTN , and using Hexamine Dinitrate as the form of hexamine . My first experiment
for TMTN will likely be
of that nature , simply to satisfy my curiosity . I have a
hunch , an intuition that this could work fine also , and it would be interesting to discover what the effect would be on the yield .
[Edited on 8-7-2006 by Rosco Bodine]
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