Esplosivo
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Hydrazinium Propellants
Hydrazine is very important in the production of propellants, especially of the mono-based type.
Hydrazinium Perchlorate is one of these. It is relatively easy to produce using Hydrazinium Sulphate (the production of which was mentioned a million
of times) and Barium Perchlorate. As far as I know the latter can only be bought from lab suppliers. A reflux set-up is prepared. Barium Perchlorate
is added drop-wise to the hydrazinium sulphate. The reaction is of a deouble decomposition/displacement type. Because of the Barium Perchlorate being
ionic I think that the reaction does not require any heating, probably only warming. The mixture is then filtered. Barium Sulphate being most
insoluble will be collected on the filter paper, and the hydrazinium perchlorate will result in the filtrate. I didn't find any solid info. about
the boiling point, melting point and temp at which decomposition takes place of this hydrazinium perchlorate.
ESA is also working on the production of Hydrazinium Nitroformate (HNF) as a propellant. The nitroformate is probabaly nitrated methanoic acid (not an
ester), The formula of this HNF is N2H5C(NO2)3. Any ideas on how this can be produced?!
What are commonly available sources of Barium Perchlorate?
Site on HNF:
http://www.appbv.nl/hnf.html
Site on production of Hydrazinium Sulphate (for the few which have no idea):
http://www.rhodium.ws/chemistry/hydrazine.sulfate.html
[Edited on 21-3-2004 by Esplosivo]
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Nick F
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Nitroform is the result of oxidation/nitration of many things, eg isopropanol. There was a tiny bit of info over at E&W a while ago, I would get
it for you but I've been caught up in an area ban and can't find a good free proxy yet...
But basically, any nitration that you fuck up normally produces nitroform, as well as a cloud of NO2...
It's a very strong acid, since the -ve charge of the conjugate base can be delocalised over three nitro groups, and so can form some nice
salts... hexamine dinitroformate, anyone? Not a bad OB...
I'm trying to figure out a way to seperate nitroform from all the excess nitric acid other than a distillation. Any ideas?
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Esplosivo
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I'm not sure but nitroform should crystallize out of the mixture if the mixture is cooled to about 0 deg celcius. The crystals can then be
filtered and collected. Am I correct?
[Edited on 24-3-2004 by Esplosivo]
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Nick F
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Yes, from what I've read it has a mp of around 20*C, so that should indeed work.
US patent 4122124 details nitroform's manufacture from isopropanol. I'm just about to check it out...
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Esplosivo
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Keep us updated. It would be nice to have some HNF lying out in the house 
Btw, which site do you use to search for the patents? Thanks
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axehandle
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site
http://www.uspto.gov/patft/index.html
My PGP key, Fingerprint 5D96 E09E 365D 1867 2DF5 C2FE 4269 9C19 E079 CD35
\"Verbing nouns weirds the language!\"
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The_Davster
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The patent detailing the production of nitroform from nitric acid and isopropanol mentions 2 patents on the extraction of nitroform form the reaction
mix. Unfortunatly one of those patents does not exist and the other only exists in quicktime not full text. My quicktime is messed for some unknown
reason and I cannot see the document. Can anyone else see it and post the main ideas here?
Also, does anyone have any info on the properties of the nitroform, expecially, is it an explosive by itself?, if so is at a primary, or secondary...?
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AndersHoveland
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A word of caution, unlike hydrazinium nitroformate, hydrazinium perchlorate is probably dangerously friction sensitive, that is from looking at the
properties of hydroxylamine perchlorate, and of hydrazinium cobalt perchlorate.
as for nitroform, hope this helps:
NITROFORM (trinitromethane)
Physical Properties
Trinitromethane melts at 15°C, and begins slowly decomposing above 25°C
At room temperature nitroform is a colorless, or slightly yellow, oily liquid.
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons (although this can be very dangerous).
Chemical Properties
Trinitromethane can form salts with a base, such as methylamine or ammonia, or it can dissolve in hydrocarbons. It can be mixed with either nitro
methane or nitro ethane, to form a powerful explosive binary mixture. The one with EtNO2 is somewhat more powerful, but it also requires a higher
ratio of HC(NO2)3, so if nitromethane is easily available in large quantities it may be preferable. (the 'Et' means the --CH2CH3 group)
Salts of trinitromethane are more stable (and somewhat less energetic) than perchlorates, although trinitromethane itself is fairly sensitive. The
C(NO2)3(-) anion is very stable because of the resonances, there being four additional electrons to resonate around the the six oxygen atoms. These
salts are also known as nitroformates and are bright yellow in color. Trinitromethane oxidizes ferrous ions (Fe+2) to ferric (Fe+3). Dinitromethane
can also oxidize the Fe+2 ion, but only if an alkaline solution of dinitromethane is added to an acidified solution of a ferrous salt. This is because
the transient "aci-form" tautomer O2NCH=NO2H, which only exists for a few seconds, is more reactive.
Toxicity
Trinitromethane, while still giving off mildly poisonous fumes, is far less toxic than tetranitromethane. You would be well advised to avoid ever
preparing tetranitromethane, which was once considered for use as a chemical weapon. Trinitromethane is somewhat poisonous: 800 mg/m3/2 hour
Inhalation Mouse LC50, compare this with 1230ppm (for 36min, LC50) for tetranitromethane.
It can be seen that tetranitromethane is far more toxic (it is highly recommended that the synthesis of this compound never be attempted), but
nitroform should still be assumed to give off toxic vapor, and so should be handled outdoors or behind a windowed fumehood. The boiling point is 175.1
°C so at least it is much less volatile than tetranitromethane. Moderately toxic by inhalation. Irritating to skin, eyes, and mucous membranes.
Inhalation can cause headache and nausea. Causes mild narcosis.
Explosion Hazard
A very dangerous explosion hazard; explodes when heated rapidly. Dissolution is exothermic and solutions of more than 50% can explode. Mixtures of 90%
trinitromethane + 10% isopropyl alcohol in polyethylene bottles have exploded. Frozen mixtures with 2-propanol (10%) explode when thawed. Can explode
during distillation. Mixtures with divinyl ketone can explode at 4°C. Trinitromethane itself is sensitive (about as much as picric acid), and
mixtures of it and other hydrocarbons are more sensitive than the dangerous nitrate esters. Such mixtures are thermally unstable, quickly decomposing
above 100degC, such decomposition can lead to detonation.
Salts of Trinitromethane
Ammonium nitroformate is much more stable than the sodium salt. Silver nitroformate slowly decomposes at room temperature, and is a very sensitive
explosive. The potassium salt, KC(NO2)3 is a lemon yellow crystalline solid that decomposes slowly at room temperatures and explodes above 95 °C.
Ammonium nitroformate deflagrates or explodes above 200 °C. Hydrazinium nitroformate is thermally stable to above 125 °C. Most salts of
trinitromethane derive from the aci-form. However, the silver and mercuric salts exist in two forms: colourless and yellow. This may indicate that two
forms of these salts - nitro and aci - can exist.
PREPARATION
There are several routes to prepare trinitromethane.
By direct substitution
Tetranitromethane has been obtained from iodopicrin I3CNO2 and silver nitrite AgNO2. Hantzsh, Chemische Berichte, 39, p2478, (year 1906)
Such yields would be expected to be low, less than 11%, since nitrite substitution on secondary and tertiary haloalkanes gives successively lower
yields than a primary haloalkane because a small proportion of nitrite gets substituted instead of nitro groups, which in this case would lead to
degredation of the molecules with such undesirable substitutions. Bromopicrin could alternatively be used, but the reaction rate for the substitution
of chloropicrin would be far too slow to be practical (although there do exist room temperature catalysts to speed up such substitutions). Even with
iodopicrin, the reaction will likely take several days for completion. Both starting chemicals must be first dissolved in appropriate solvents, for
example benzene. Use of propylene carbonate as a solvent might possibly enable sodium nitrite to be used instead of silver nitrite.
By reducing tetranitromethane
Hantzsch and Rinckenberger obtained the ammonium salt of trinitromethane by treating tetranitromethane with aqueous ammonia.
It is well known that tetranitromethane can be reduced to nitroformate salts using an alkaline solution of hydrogen peroxide. This is the most usual
route for preparing trinitromethane. Prepare a solution of 168 g of potassium hydroxide in 350 mL of water in a round-bottomed 1000-mL Florence flask,
and cool to 5 °C with a salt-ice bath. While stirring, add 108 mL of 30% hydrogen peroxide to the solution. Next, add 117 mL of tetranitromethane at
a rate which keeps the temperature at 20-25 °C, add while stirring. The temperature is then allowed to rise to 30 °C over 15 minutes. The bright
yellow solid, that should have formed, is filtered to collect it using glass filter paper because of its high acidity, washed with anhydrous methyl
alcohol, then anhydrous ethyl ether, and finally air dried to give 100% of the potassium salt of trinitromethane. The salt is suspended in anhydrous
ethyl ether and anhydrous hydrogen chloride gas is passed in until the yellow color disappears. The white precipitate of potassium chloride is
filtered off and washed with anhydrous ethyl ether. The ethyl ether is evaporated from the filtrate and additional washings at reduced pressure give
85-90% of crude trinitromethane which can be purified by sublimation.
Although usually an oxidizer, in some reactions hydrogen peroxide can act as a reducing agent. For example, it reacts with hypochlorite to form
chloride and oxygen gas. Similarly, an alkaline solution of H2O2 reduces Cl2 to Cl- ions.
From Trinitroacetonitrile
Trinitroacetonitrile can be synthesized by the nitration of cyanoacetic acid with a solution of sulfur dioxide and 98+% concentrated nitric acid in
carbon tetrachloride, with 73-77% yields. The trinitroacetonitrile can be stored as a solution in the carbon tetrachloride, and need not be isolated
for further use on other reactions.
NCCH2C(=O)OH + (3) HNO3 + (3)SO2 -- > NCC(NO2)3 + CO2 + (3) H2SO4
Trinitroacetonitrile is a colorless, camphor-like, crystalline compound melting at 41.5 °, and detonating violently at 220°. It hydrolyzes to carbon
dioxide and the ammonium compound of nitroform by water or alcohol at ordinary temperatures.
"Nitroacetonitrile has been prepared by treating methazonic acid with thionyl chloride SOCl2 in ether. That the compound so obtained is
nitroacetonitrile follows from the fact that it yields a-nitroethenylamino-oxime with hydroxylamine, and gives the nitrolic acid reaction. Its
formation from methazonic acid proves the correctness of the formula. (methazonic acid has the formula HON=NCHCH2NO2, and is well discussed elsewhere
on this forum). Nitroacetone, NCCH2NO2 ,is obtained as a fairly stable yellow oily liquid. Wen pure, it may be distilled under reduced pressure
(boiling point 96 ° under 14mmHg reduced pressure). It does not seem to be explosive, neither is the ammonium salt, which crystallizes in slender,
yellowish-white needles, decomposing at 130-135°. The silver salt, obtained as a brown precipitate, however, is a sensitive explosive.
A-Nitroethenylamino-oxime (NO2)CH2C(NH2)=NOH, obtained by the action of hydroxylamine on nitroacetonitrile, forms yellow crystals and decomposes
suddenly at 108°."
Journal of the Royal Society of Chemistry (Great Britain), Volume 94. p.327 (year 1908)
It is known that dinitroacetonitrile can be nitrated to trinitroacetonitrile, so nitroacetonitrile probably can be similarly nitrated.
Shishkov (and later Steiner) claimed to have obtained trinitroacetonitrile by treating the sodium salt of fulminuric acid with a mixture of nitric and
sulphuric acid, but it was later shown that the compound which is obtained from this reaction is not identical to trinitroacetonitrile.
“Nitroform (Trinitromethane), CH(N03)3, is obtained in the form of its ammonium salt by the decomposition of trinitroacetonitrile with water.” (L.
Schischkoff, Ann., 1857, 10 3, p. 364).
Direct nitration of acetonitrile?
I am unsure, but I think it may be possible that trinitroacetonitrile could be prepared by nitration of acetonitrile using nitronium
tetrafluoroborate. Although acetonitrile is commonly used a solvent for the nitration of other reagents by nitronium tetrafluoroborate, apparently
without significant reaction of the acetonitrile, it may likely be that the acetonitrile does in fact slowly react, but much less rapidly than the
nitration of the other reagent being nitrated. There is a reaction, which was developed by Olah, in which alkanes, which are generally fairly inert at
room temperature, can be nitrated using nitronium salts. Thus it seems probably that acetonitrile could be similarly nitrated.
From Nitric Acid and Isopropanol
A 250 ml three-necked flask was fitted with a mechanical stirrer, a thermometer and a dropping funnel. 140 ml (3.33 moles) of 98% nitric acid was
introduced into the flask. The acid was warmed to about 60.degree. C. and 20 ml (0.26 mole) of isopropyl alcohol was added dropwise over a 10-minute
interval. External cooling was used to maintain the temperature at 60°C. The solution was then heated to a temperature of about 70°C. and held at
this temperature for 2 hours. Substantial quantities of brown gaseous fumes evolved during this nitration. The solution subsequently was cooled to
ambient temperature and analyzed for nitroform content. The yield of nitroform was determined to be 9.8 gm (approximately a 25% yield).
To obtain significant yields of the desired trinitromethane it is essential that the isopropyl alcohol be introduced into an excess of nitric acid.
Thus, the molar ratio of nitric acid to isopropyl alcohol will be in excess of about 8:1. Too great an excess of nitric acid will, of course, increase
the cost of the method, and will require an unnecessary amount of nitric acid to be distilled and recycled to the process. Thus, the molar ratio of
nitric acid to isopropyl alcohol generally is maintained within a range of from about 10 to 25, and preferably within a range of from about 15:1 to
20:1.
The reaction temperature is not particularly critical, provided, of course, that the temperature must be sufficiently high to maintain the mixture of
reactants in a liquid phase. In addition, the temperature should not be too high, otherwise substantial gas evolution takes place with little or no
formation of nitroform. Therefore, the temperature generally has been maintained within a range of from about 25° to 85°C. and preferably within a
range of from about 40° to 70°C. The time required for the reaction will vary with temperature, pressure ratio of reactants, etc. Generally, a time
of from about 1 to 5 hours is sufficient to react substantially all of the isopropyl alcohol to form the desired trinitromethane. Yields of up to
50-58% have been obtained from a modification of this procedure.
From 4,6-dihydroxypyrimidine
Nitration of 4,6-dihydroxypyrimidine using mixed nitric and sulfuric acids yielded nitroform as the sole product, although gas evolation was also
observed.
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AndersHoveland
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hydrazinium perchlorate melts at 137degC.
hydroxylamine perchlorate, hygroscopic solid
melting point between 87.5 and 89degC. Decomposes at 120degC. Drop height value of only 2cm, meaning very sensitive to impact. addition of small
ammounts of hydroxylamine perchlorate to several propellents could roughly double their burning rates
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AndersHoveland
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one of the moderators might want to save this attachment and put it in the SM library
[Edited on 22-1-2012 by AndersHoveland]
Attachment: HNF.pdf (55kB)
This file has been downloaded 1348 times
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AndersHoveland
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Hydrazinium nitroformate has a sensitivity to friction value above 20 Newtons, and sensitivity to shock value above 2 Joules.
Another source describes hydrazinium nitroformate as having a friction sensitivity between 14-36 N, an impact sensitivity of 2-15 Joules. Density:
1.85 g/cm3. Melting with decomposition at 110-124°. The salt may have thermal stability problems above 71°C.
Aminoguanidine nitroformate has a sensitivity value not below 10 J, friction value 144 N, and is hygroscopic, with density of 1.77 g/cm3. The
nitroformates of di- and tri-aminoguanidine are much more sensitive, suggesting that the sensitivity comes from the reactive reducing nature of the
hydrazine towards the oxidizing anion.
[Edited on 16-2-2012 by AndersHoveland]
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Adas
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CH(NO2)3 should not be called nitroformic acid, because nitroformic acid is: O2N-C(=O)-OH - a very unstable derivate of formic acid.
Rest In Pieces!
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AndersHoveland
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The naming can be somewhat confusing.
Trinitromethane is often referred to as nitroform, similar to the name chloroform for CHCl3.
Thus, a salt of nitroform is called "nitroformate", although occasionally it is referred as "trinitromethanate".
Formic acid is named after the Latin word for ant, but is sometimes referred to as "methanoic acid". Chloroform was so named because of its molecular
similarity to formic acid, but also because this compound seemed to inexplicably "form" from the reaction between ethyl alcohol with alkaline
hypochlorite.
[Edited on 16-2-2012 by AndersHoveland]
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quicksilver
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Quote: Originally posted by Adas  | | CH(NO2)3 should not be called nitroformic acid, because nitroformic acid is: O2N-C(=O)-OH - a very unstable derivate of formic acid.
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The gentleman I know who has more information on Hydrazine and related materials in Roscoe Bodine. Some material he had posted some years back was
extremely insightful (& some of it rare). If I am correct he had quite a few posts regarding it in various synthesis and applications.
If you're of a mind to do any background, check a "search" under his name as "author". It IS nasty stuff but I do know there had been some
developments as a propellants. However in a generalist perspective it had been used as an oxygen scrubber in boilers, etc. - One job I would not
particularly enjoy.
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AndersHoveland
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Perhaps it is somewhere in here:
http://www.sciencemadness.org/talk/viewthread.php?tid=15091
see Rosco Bodine's post, ninth down:
http://www.sciencemadness.org/talk/viewthread.php?tid=1128&a...
Here is the ketazine process to prepare hydrazine, from nurdrage's video:
| Quote: |
Start with 250mL of ammonia and add to it 100mL of methyl ethyl ketone. Stir and then slowly add 1/4 mole equivalent of sodium hypochlorite based
bleach. if using 10% bleach then about 186g is needed. If using 6% household bleach about 310g is needed. As the bleach is added the reaction will
heat up and bubble vigorously, slow down the addition if it’s bubbling too much. After all the bleach is added, keep stirring until the mixture
stops bubbling. Then stop stirring and allow it to stand for a few hours until so until it separates into two clear layers. The top layer is methyl
ethyl ketazine. Separate it using a seperatory funnel or by careful decantation. In a separate container, add 20mL of concentrated sulfuric acid to
100mL of water and stir. Then add the hot solution directly to the ketazine and keep stirring. The hydrolysis will generate crystals of hydrazine
sulfate.
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He mentions that acetone could potentially be used instead of methyl ethyl ketone, but that the resulting ketazine would have too much solubility to
separate out from solution, so would have to be cautiously distilled out.
[Edited on 17-2-2012 by AndersHoveland]
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AndersHoveland
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from E+W forum archive:
| Quote: |
Hydrazinium nitroformate, N2H5.CN3O9
yellow-orange solid
Density: 1.86 g/cm3
Ignition point: 165 ºC
Melting point: 123 ºC
Molecular weight: 183.09 kg/kmol
Friction sensitivity: 14-36 N
Impact sensitivity: 2-5 N/m
Detonation velocity: 8400 m/s, releasing 5044 J/g.
brisance value slightly higher than RDX, but lower than HMX
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If you want to make hydrazinium nitroformate, you will have to do it by displacement, because trinitromethane is a fairly reactive oxidizer and
hydrazine is a reducing agent. For the same reason, hydrazinium nitroformate is likely to violently decompose in acidic solution.
Probably the easiest way would be to react ammonium nitroformate with hydrazine hydrate (ammonolysis, displacing NH3).
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DubaiAmateurRocketry
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I think ammonium nitroformate might be more stable than HNF ? Is there any link about ammonium nitroformate ?? i cant find it at all
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