Siconic
Harmless
Posts: 10
Registered: 27-3-2009
Member Is Offline
Mood: No Mood
|
|
HDN Synthesis Problem
I recently tried to make HDN. This should have been pretty straight forward, and it was.... at first.
I mixed my chemicals, and got a precipitate. Since this was my first batch, it was small. (50ml of hexamine in water)
However, I set it aside, and took a break. When I returned, I swirled the mixture, and all the crystals disappeared!
So what happened? Is this normal? Is there a way to get them back without tossing the mixture? Does this mean that once you get your precipitate you
need to filter, or loose your product?
Any help is appreciated. 
|
|
|
Peroxid
Hazard to Self
Posts: 56
Registered: 23-8-2006
Member Is Offline
Mood: No Mood
|
|
You used the hexamin + HNO3 route to synth. HDN?
Anyway you need to filter the precipitated crystals and wash with aceton, and dry it (HDN decomposed to formaldehyde and ammonia when it is wet)
[Edited on 15-4-2010 by Peroxid]
|
|
|
hissingnoise
International Hazard
Posts: 3940
Registered: 26-12-2002
Member Is Offline
Mood: Pulverulescent!
|
|
HDN is soluble in water - slow evaporation of the solution will reprecipitate it but it won't be very clean.
If you used the correct amount of acid, fumes shouldn't be a problem.
[Edited on 15-4-2010 by hissingnoise]
|
|
|
greenpick
Harmless
Posts: 3
Registered: 10-8-2011
Member Is Offline
Mood: No Mood
|
|
I recently synthesized what I hope is HDN, but I have run into a few problems. My procedure was as follows:
-Mix 28.03 g of hexamine with 100 ml of water. Cooled in ice/salt/water bath to ~5C.
-Slowly added 40 mL of 67% HNO3 cooled in said ice bath, keeping temp of solution in the 9-12C range.
-After approximately half the HNO3 had been added, a precipitate began to form.
-Upon last addition of HNO3, 110 mL of acetone was added to the solution, as I believed this would help precipitate all of the HDN. (probably not
necessary, maybe even harmful?)
-Filtered mixture through paper towels, and rinsed with more acetone. (100-200 mL)
-Let paper towel with HDN folded inside sit under a fan until no more acetone could be smelled.
At this point, HDN appeared no different than moist, coarse table salt in all respects (sight, smell, etc)
-The paper towel with the HDN was then placed in a ziplock bag with a shallow bowl of calcium chloride and zipped up. This was left to dry overnight
for ~10 hours.
All right, so this is when the problems start. When I opened the bag in the morning, I noticed an extremely pungent, burning odor. I was quite taken
aback, and had to step away to take a few deep breaths (more out of surprise than any actual need). There are no visible fumes, but the odor is
present even after putting the "HDN" in a plastic bowl and letting it sit in the open air for some time. It doesn't appear to be lessening to a great
degree.
Does HDN normally have a pungent odor. The effects remind me of HCl or HNO3 fumes, but the smell is pretty unique. Hard to describe for sure. My
only theory is that something in the moist hexamine reacted with the calcium chloride (maybe residual nitric acid, creating HCl?) Any theories as to
what this odor is, and how dangerous it may be?
|
|
|
hissingnoise
International Hazard
Posts: 3940
Registered: 26-12-2002
Member Is Offline
Mood: Pulverulescent!
|
|
HDN, (C<sub>6</sub>H<sub>12</sub>N<sub>4</sub> • 2HNO<sub>3</sub> has as you see, 2HNO<sub>3</sub>, weakly bound.
The small quantity of evolved NOCl in the mix would account for the 'uniqueness' of the smell . . .
'Substantially the same as reacting HNO<sub>3</sub> with NaCl!
|
|
|
greenpick
Harmless
Posts: 3
Registered: 10-8-2011
Member Is Offline
Mood: No Mood
|
|
Interesting...so you think it's possible that the HDN and CaCl2 reacted even though they weren't touching? I would think it's more probable that
residual HNO3 vapors were the culprit. Oh well, different mechanism, same result.
After looking up NOCl on wiki, I can see how HNO3 would combine with any HCl that may have formed to produce NOCl by this reaction:
HNO3 + 3 HCl → Cl2 + 2 H2O + NOCl
A mixture of chlorine and nitrosyl chloride gasses would certainly explain the pungent, irritating nature of the vapor!
One more thing; how would this contamination affect an RDX synthesis, if at all? Would air drying the HDN be enough, or is HDN appreciably
hygroscopic? I plan on reacting 2.5 mL home distilled HNO3 per gram of HDN. (once I get my distillation setup, that is) I will try a small synthesis
(~10 g HDN), unless anyone can think of a reason it would be exceedingly dangerous.
|
|
|
quicksilver
International Hazard
Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline
Mood: ~-=SWINGS=-~
|
|
Did you check pH? Do you have access to melting point equipment? A quick check of some more modern authors doesn't make note of odor, but that doesn't
mean it couldn't exist (Cook, Meyer, etc don't note it). However You make mention of continued odor after exposure to atmosphere circulating air, etc.
hexamine is basic (ammonia) - to swing it over (your synthesis) would need a great abundance of acid. If nothing else do you observe deliquesce or
some physical feature of release?
Subjective interpretations of smells are just too tough to categorize.
[Edited on 10-8-2011 by quicksilver]
|
|
|
greenpick
Harmless
Posts: 3
Registered: 10-8-2011
Member Is Offline
Mood: No Mood
|
|
That was my exact thought when I was trying to describe the smell in my first post. There is nothing I can really compare it to, although (I know
this sounds crazy) it seems like I've smelled it before, but I just can't put my finger on it. That's probably the chlorine if the above reaction was
accurate to any extent.
And no, there doesn't appear to be any visual signs of release. The HDN looks uncannily like table salt: a.k.a. it is a perfect, glittering white
substance with large, slightly flattened crystals. Unfornutely I don't have access to melting point equipment, but I will check the pH with some pH
paper later today. I will continue to leave the HDN out in open air, as it continues to slowly lose weight. If my calculations are correct,
theoretical yield would be around 50.4 grams, and I have about 51 g of material.
edit:
I checked the pH by just sticking aquarium pH paper into the crystals, and I got a result of ~7.5! Now there is no doubt that this isn't a 100%
accurate result, but you would think the pH paper would stay its normal color, rather than go through the work of showing a basic result. This tells
me that it is atleast somewhat basic. Shouldn't it be nuetral, or even slightly acidic though?
I'm thinking of dissolving my HDN in the minimum amount of water, and adding 67% HNO3 until the solution is acidic. (~6 pH) This shouldn't take much.
I will then filter and rinse as before, but omit the CaCl2, and see if I get better results.
[Edited on 8/11/2011 by greenpick]
|
|
|
hissingnoise
International Hazard
Posts: 3940
Registered: 26-12-2002
Member Is Offline
Mood: Pulverulescent!
|
|
| Quote: |
One more thing; how would this contamination affect an RDX synthesis, if at all? |
RDX is most conveniently prepared by adding hexamine, in small portions, to strong HNO<sub>3</sub> at <30°C . . .
Forget HDN; it's an unnecessary complication!
|
|
|
quicksilver
International Hazard
Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline
Mood: ~-=SWINGS=-~
|
|
I will try to find detailed info on HDN characteristics. So far I have only found the most general material. It is a puzzle - I haven't heard of a
"strong odor" issue previously.
|
|
|
Microtek
National Hazard
Posts: 871
Registered: 23-9-2002
Member Is Offline
Mood: No Mood
|
|
HDN often decomposes, producing formaldehyde if the temperature gets too high at some point, or sometimes if impurities are present. Formaldehyde
certainly has a pungent smell but of course, so does a number of other compounds.
I suggest recrystallizing the salt from dilute nitric acid and leaving out the acetone. There is no problem with using CaCl2 in the desiccator, but
make sure that you don't place it somewhere warm (especially while it is still moist).
|
|
|
Phantom
Harmless
Posts: 43
Registered: 26-4-2011
Member Is Offline
Mood: AUDENDUM EST,FORTES AUDIUVAT IPSE DEUS
|
|
Try to make HDN with 30% HCl instead of HNO3. I made my HDN with HCl. I dissolved some AN in water then I added hexamin and HCl and a little
denaturated alcohol.
|
|
|
Hey Buddy
Hazard to Others
Posts: 430
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
I have had the same issues with recent HDN production. Precipitation is normal, washing with acetone goes normally.
On drying, batches sometimes appear to release one of the nitrates. Here is a picture of two batches, the orange one was prepared by dumping in 2x mol
68% HNO3 in one shot, at 0 C resulting in instantaneous 30 C jump. The orange batch started as white normal HDN and became orange drying on gentle
heat for 24hr..The normal white color batch was made by dripping in 68% HNO3 <15 C as the traditional literature recommends. I attempted to dry the
white batch at gentle 40 C heat and it is also resulting in a strong smell and putting off color change.
To be honest, everytime Ive used HDN, I washed with acetone and left it on a coffee filter, then it air dried over a week or so, just sitting exposed
to ambient room temp. Then it was used that way. The weight of using that was probably added to by water, making it less accurate but there were never
any issues of decomp.
I reviewed some literature. I havent found any mention of this anywhere. Urbanski describes that on boiling HDN it results in a methylhexamethylene
mono nitrate. Is it possible that under even gentle heat this HDN is dropping a nitrate and converting to this mono nitrate? It seems to be a common
occurrence.
What procedures are people using to dry HDN successfully? Are people using HDN and achieving bone-dryness? Or just using it "pretty dry" and it's good
enough?
Heating to assist in drying doesnt seem to go well. Perhaps an interaction with the acetone? I havent attempted heated drying without acetone wash
first... According to literature its thermal degradation is only known to occur at much higher temps, like 170C at prolonged heating IIRC...
|
|
|
Hey Buddy
Hazard to Others
Posts: 430
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
Quote: Originally posted by Phantom  | | Try to make HDN with 30% HCl instead of HNO3. I made my HDN with HCl. I dissolved some AN in water then I added hexamin and HCl and a little
denaturated alcohol. |
This is interesting. For HNO3 the yields are pretty high >90%. What sort of yield does HCl method give? May have to experiment...
|
|
|
Hey Buddy
Hazard to Others
Posts: 430
Registered: 3-11-2020
Location: Bushwhacker Country
Member Is Offline
|
|
I have been updating an HDN procedure. There certainly appears to be different product from nitrating <15 C versus allowing temp to jump on dumping
in all HNO3 at once. The later seems to be popular because it's recommended by Ballard and it has a dramatic positive appearance in reaction. The high
temp procedure makes an HDN that is more sensitive to decomposing and releasing a red color, with strong smell. Below 15 C addition gives an HDN that
is more stable at elevated temperature. Although HDN seems to be tested to withstand high temperatures in literature, I have found that HDN becomes a
fluid at even moderate elevated temperature. The high temp HDN in an elevated temperature state appears to release acid or decompose to possibly
formaldehyde but I'm not sure what is taking place. The low temp HDN at elevated temp becomes fluid but becomes solid again after removal from heat,
without apparent decomposition. For now I have found that acetone wash of HDN, followed by open air evaporation of several hours, followed by
prolonged room temperature dehydration with silica gel works well at getting a dry HDN.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
