Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
Fructose trinitrate
Fructosan trinitrate a, C6H7O2(ONO2)3, is produced by the
action of mixed acid at 0-15° on d-fructose or on laevulosan,75
colorless, quickly effluorescing needles from alcohol, which melt
at 139-140° and decompose at about 145°. It is readily soluble in
methyl and ethyl alcohol, acetic acid, and acetone, and insoluble
in water. It is relatively stable at 50°. It reduces hot Fehling's
solution. The alcoholic mother liquors from the a-form yield
fructosan trinitrate /3, crusts of white crystals which melt at
48-52° and decompose at 135°. The material decomposes slowly
at 50°. It reduces Fehling's solution rapidly on warming.
That was all I could find about it (copied from COPAE).
Does anyone have any more information about it (sensitivity, VOD)? I would like to try it as I have fructose so can anyone please tell me in what
ratios should I use H2SO4/AN to make it?
|
|
|
Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
Well I tried it. To 80 ml of H2SO4 I added at once 88 g of ammonium nitrate. After it cooled to around 17 C I started to slowly add 13 g of fructose
with stirring. After I added all the fructose I stirred the mix for around 10 min and then drowned it. Nothing precipitated. Does anyone know why?
|
|
|
hinz
Hazard to Others
Posts: 200
Registered: 29-10-2004
Member Is Offline
Mood: No Mood
|
|
Maybe because not all OH-groups are nitrated in fructose trinitrate and thus the product has a higher solubility than full nitrated alcohols like MHN
or PETN.
Did it work good? I've always avoided to nitrate sugars with an aldehyde or keto-group because they like to oxydise and than to runaway.
|
|
|
gregxy
Hazard to Others
Posts: 421
Registered: 26-5-2006
Member Is Offline
Mood: No Mood
|
|
Zinc, didn't you have the same problem with your NG?
Maybe you should check the density of your H2SO4.
If it contains too much water then these reactions will
not work.
Did the temp go up at all when you added the fructose?
|
|
|
Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
Yes I had the same problem with NG. Well I am sure that the acid is highly concentrated, It charrs paper and wood instantly and is very dense and
syrupy (I heat it until thick white SO3 fumes start to come off and after they start I still heat it for some time to make sure all water is gone).
The temp didn't go up at all.
|
|
|
Leander
Harmless
Posts: 28
Registered: 23-2-2008
Member Is Offline
Mood: No Mood
|
|
Because the temperature didn't went up while adding the sugar, I guess fructose isn't really reactive, and no estrification occured at all. You really
need to let your batch react a lot longer to get a nitrated product. You should also keep in mind that H2SO4/AN is a less reactive acid mixture than
H2SO4/98% HNO3, because of the KHSO4 diluting the mix, and because the mixture is much less stirrable, slowing down the reaction. This is even worse
when nitrating sugars/polyoles, since they tend to thicken the mixture even more. Longer reaction times are in this case really a must! 
I always nitrate MHN with H2SO4/AN over multiple days in the freezer. When I bring back my reaction time to 15 minutes, like you did, the yield is
much, much lower.
It also helps to raise the temperature at the end of the reaction to approx. 40-50 oC for ~30 min, before quenching it. This way the acid is much more
reactive, giving higher yields. You must make sure that when you start heating, >90% of the product is allready nitrated, if not, heating will
simple result in a nasty runway! 
[Edited on 25-3-2008 by Leander]
[Edited on 25-3-2008 by Leander]
|
|
|
garage chemist
chemical wizard
Posts: 1803
Registered: 16-8-2004
Location: Germany
Member Is Offline
Mood: No Mood
|
|
Nitration times should be more like 10 hours than 10 minutes.
Were the AN and fructose finely powdered? Crystalline precursors really don't work well in such reactions, because they don't dissolve. You need fine
powders.
I remember doing the nitration of cellulose a few times with H2SO4/KNO3 and H2SO4/AN mix when I got my first concentrated H2SO4 many years ago.
After I switched to H2SO4/HNO3 (the latter self distilled from H2SO4 and KNO3) I was very impressed what a difference that made. The nitrocellulose
products simply weren't comparable, the quality of the material made with real HNO3 was so much better.
If you frequently do nitrations and can't buy HNO3, a simple distillation setup should be the first thing on your list of things to get. Don't buy
anything else until you have the money for it.
My first all-glass still cost me less than 50€ since it was a small one with a 25cm liebig condenser. I used it almost every day in the lab for five
years.
|
|
|
Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
Yes they were finely powdered.
So next time I will let it stand longer.
Today I got some sorbitol and will try to nitrate it to get SHN. It is interesting as at first you get a liquid explosive which consists of SHN and
lower nitrates. Purifying that by recrystallization you can get solid SHN.
|
|
|
Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
This time I tried to make SHN. I mixed 100 ml of H2SO4 with 66 g of AN. After it cooled down to around 20 C I started to slowly add 23 g of sorbitol.
After I added it all I waited for around 30-45 min. A oil separated above the acids (I believe SHN). Then I added water to the mix. The SHN sank. Then
I decanted the above layer of water, added some fresh water and added powdered sodium hydrogen carbonate to neutralize the aced. After the fizzing
stopped the oil disappeared!!
|
|
|
enthalpy
Harmless
Posts: 6
Registered: 12-3-2008
Member Is Offline
Mood: No Mood
|
|
some things simply don't work with boiled down battery-acid and ammonium nitrate (moist I think, because getting and especially keeping it really dry
is not that easy!). Maybe your sulfuric acid (which is hygroscopic too!) is "only" 93% and then your ammonium nitrate contains another 3% of water and
whoops you have a lot of water in your mixture and esterifications arent that tolerant towards water. Maybe you have some lead salts (from battery) in
your acid which hinder the nitration in some way. Or your neutralisation step is not recommendable because basic solutions easy destroy the esters.
Then the reaction time is important too. You still let it react for 30? oder 45 minutes (difference if you ask me). Maybe it should react for at least
an hour. You know what I mean? There are some energetics which are easily synthesized out of OTC stuff and you need no special control of reaction
conditions. But I think nitric esters of fructose and sorbitol need advanced control/materials. Urbanski wrote that they precipitated the hexanitrate
of sorbitol with 30% oleum. Thats no boiled down battery acid. And they used nitric acid with a density of 1.52g/ccm which is no ammonium nitrate.
They worked at really low temperatures (-10°C). I dont say that it isnt possible to get the nitrates of fructose/sorbitol with the H2SO4/XNO3 method.
But maybe it needs a bit testing. And be careful, these solid esters of higher alcohols arent alway fun. They are sensitive and probably chemically
and physically unstable! Dont give up, but change your method/conditions and maybe your chemicals.
|
|
|
Zinc
Hazard to Others
Posts: 472
Registered: 10-5-2006
Member Is Offline
Mood: No Mood
|
|
Thank you very much for the detailed post
I am definitively going to change my chemicals. I have to order H2SO4 and HNO3 (only 67 % but better than nothing) from a chem. company and the
chemicals are expensive (22 dollars for a liter of H2SO4 and 30 dollars for a liter of HNO3 plus shipping charges around 8-10 dollars) so I wanted to
see if I could use boiled battery acid and ammonium nitrate (which contains a little calcium nitrate and around 5% magnesium nitrate).
And I again tried to make SHN with the same method. This time I didn't neutralize the mixture (only diluted it with water) and I will let it stand
some hours to see if the oil will disappear or perhaps better separate from water.
|
|
|
Boomer
Hazard to Others
Posts: 190
Registered: 11-11-2005
Member Is Offline
Mood: No Mood
|
|
Two points: See my comment about car batteries in the nitro thread.
And apart from long times (a night in the freezer is minimum), it is vital to stirr the mix in a very thin stream into lots of water (10+ volumes).
Too little water and it decomposes back into crap.
Another thing, when making the acid/AN mix just dump all the AN in at room temp, then swirl with a nearly closed glass stopper. It heats up +
dissolves easily, and can be put in the freezer for some hours and stays as a solution, while mixing it in the ice bath may give a porridge instead of
a solution. Plus, you waste no time waiting for it to cool down. Just mix at bedtime, add half your glycerine/polyol/sugar after breakfast, mix really
well and put back. At noon add the other half, mix + put back. In the evening crash into water. It helps to shake the living shit out of it a few
times in between, but basically you invest 3 x 3 minutes, the fridge does the rest. Beats the hell out of babysitting the reaction for hours with
dropwise additions.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
