Hydrazine

[inton]

Would it be possible to use another inert gas other than nitrogen for the first distillation?
the second distillation you need to use nitrogen though.
??

[megalomania]

Any inert gas should work at any stage. The reaction acts badly to oxygen, and presumably other reactive gasses like halogens, perhaps even CO2. Nitrogen would be the top choice if you can get it for mere economic reasons. Helium of course would be fine, as would neon or argon. These are a bit pricy, but if thats what you have then use em. I can't really say what either CO2 or hydrogen would do with hydrazine. The literature says it is "reactive with air." Actually it says it explodes if traces of air are present... I take that to mean oxygen, but who wants to find out the hard way eh?

<small>[ September 25, 2002, 11:57 PM: Message edited by: megalomania ]</small>

[NoltaiR]

How can nitrogen be the top (economic) choice or even a choice at all if the compound reacts with air which is approximately 78% nitrogen? (well I guess maybe it doesn't react to air itself, but rather the oxygen that is in it).. anyways I was just curious.

[Microtek]

Well hydrazine is strongly reducing, so likely it reduces the oxygen. Maybe it is strong enough to reduce CO2 to CO but I doubt it. It would certainly not reduce N2.

[nbk2000]

Small tanks of helium gas are available at Toys R Us, Wal-Mart, and other places for inflating party balloons. These tanks are quite cheap too, only about $10. Use one of these for your distillation. :)

[Marvin]

Balloon helium is almost always a mixture of helium and oxygen. Try welders nitrogen. If the distillation can be worked under vacuum this would be much better.

On the subject of hydrazine I am very interested in the xylene method on megas site. From the looks of things the xylene is being used as an entrainer, to produce a tertiary heterogeneous azeotrope which removes the water and some hydrazine. This being the case it seems likley that it requires the binary azeotrope as its input, ie 60% hydrazine, rather than 60% hydrazine hydrate as stated. Any more water will affect the system adversely in terms of yeilds. To be really useful we need more information on the heteroazeotrope, specifically its composition, and the phases it seperates into for recovery of xylene and hydrazine.

The page is wildly optamistic in terms of its yeilds from the raschig synth. Raschig was an excellent experimental chemist and modifying the synth is probably unwise. Ive read the thread that resulted in the adjustments, the product is a small amount of hydrazine in a very large amount of salt water. Removing the sulphate and treating it with base is likley to save a lot of time and effort. I will work out some probable yeilds based on existing data and the ammonia - hyperchlorite ratio, but as a rule of thumb one of my books states this synth will yeild a solution containing up to 2% of hydrazine in the resulting solution. Assuming you lose no hydrazine in the reduction in volume the maxamum concentration in the resulting brine is 6% hydrazine. Concentration and seperation from the brine is likley to be non trivial, remebering also that reasonable concentrations of hot hydrazine attack glass.

Its worth mentioning that the process uses a massive excess of ammonia to get even a half decent yeild of hydrazine based on hyperchlorite. The excess ammonia is liberated during the boiloff and poses a serious heath hazard. Arguably much more than the hydrazine the reaction produces.

[nbk2000]

Stuff a section of glass pipe with copper scrubber, heat to near redness, then pass through the heliox gas. Oxygen combines with copper to form black copper oxide, leaving pure helium gas. :)

[NoltaiR]

Marvin is right about 'balloon helium' being a mixture of helium and oxygen; this is done for two reasons in particular:
1) cheaper.. in fact there are still traces of other gases as well
2) safety.. balloons are most always associated with children, and in the instance that a child accidently or purposely inhales the mix; the only obvious effect is a momentary high-pitch voice and maybe a few dead brain cells.. but nothing serious

In industrial and lab grade helium, however, if you were to try to inhale it, you would most likely suffucate if you couldn't exhale all the gas fast enough because it would flush out all the oxygen in your lungs. Also, you would most likely need a permit or have your own business to be able to purchase industrial grade helium.

[the_unbound]

Hi,
I worked in a factory which sells 'balloon helium' and in such
small tanks are normaly only 5%-10% helium the rest is normal air.

[xyz]

I know inton, he was asking to see if he could use the argon based inert gas mixture that is used for mig welding as he (or someone he knows, I'm not sure) has a mig welder.

[Boob Raider]

I am not too sure if this would work but .... lets say I prepare a batch of Hydrazine Sulfate using NaOCl and NH4OH and H2SO4 method and let it sit on a hot plate and get the HydraSulf crystals .... Then to a soln of this in anything but H2O ... say Acetone I add fine Zn dust or Mg or something like that. Shouldn't that remove the sulfate from Hydrazine and form the metal sulfate and ppt out of soln which can be filtered out leaving behind a soln of Hydrazine in Acetone ..... which can be distilled rather easily :D . Maybe using ether will work better as it boils at ~35*c but its structure is very similar to H2O which might give some problems by forming compounds. Well its an IDEA so lets see what the experts think. :p

[Marvin]

I can see what you are trying to get at B.R. but a metal wont do that, its in the wrong oxidation state. Metals will kick out hydrogen in acids to get the right oxidation state, but hydrazine sulphate isnt very acid, its a salt of a strong acid and a half decent base. Something like zinc hydroxide is probably a much weaker base than hydrazine and is largly insoluable all bad traits to compete for the sulphate. Secondly, in order to do a metathesis, you need an ionising solvent, water works well, but you get the hydrate, ammonia works (and doesnt require a base, it is one) but its rather beyond home methods. Alkali hydroxides work well, being much stronger than hydrazine, but form water in the process. You can distill the product from (previosly) fused KOH, which is a good dehydrating agent. Theres a sizable loss in this process though and with most other hydrazine distillation methods.

Acetone isnt a useful solvent with hydrazine, as ketones and aldehydes form addition products (Hydrazones). Carbon dioxide cant be used because it is an acid oxide, and so forms salts with hydrazine of its own. Anything synthetically useful can be done with hydrazine hydrate, the difficulty, the extreme loss, not being able to use glass, aluminium, steel or most other transition metals and the perminant health risks really dont justifiy the tiny amount of astrolite youd be able to make at the end.

[Boob Raider]

The reason I thought so is the chem formula of HydraSulf is N2H4*H2SO4 and not (N2H4)2SO4. I am not too sure of how different the bonding is. I might be wrong but thats where the idea originated.

[Marvin]

Ammonia has 3 hydrogen around the nitrogen, but its not planar becuase it has a lone pair, its distorted tetrahedral. Molecules with lone pairs are lewis bases and can form ions with a proton. H3N: + H+ =&gt; NH4+ which is tetrahedral. NH4Cl is a salt with ions NH4+ and Cl-, though you can write it as NH3.HCl but its not what happening becuase of the lewis base. Hydrazine is very similar, there is a lone pair on each of the nitrogens and so its a fairly strong mono base, or a rather weaker di base. You can write the molecular forumla as NH2NH2.H2SO4, but whats really present are NH3NH3 2+ and SO4 2- ions to all intents and purposes.

Edit: Damn, last in the thread, thus robbing me of my 50th post. <img border="0" title="" alt="[Wink]" src="wink.gif" />
Finally did the math for the synthesis on megs page as promised a short eternity ago.

Based on,
1500 mL of 28-29% ammonium hydroxide
1200 mL of normal sodium hypochlorite solution

Yeild should be about,
1.8% hydrazine after reduction to 1/3rd volume.
2.7% hydrazine hydrate after reduction to 1/3rd volume.
or 78 grams of hydrazine sulphate.

Edit: Clarification, the percentages arnt the reaction yeild, which is actually quite high owing to the larger than normal excess of ammonia, its the concentration of hydrazine in brine at the end of the reaction.

<small>[ October 24, 2002, 04:03 PM: Message edited by: Marvin ]</small>

[Boob Raider]

Here's a method to prepare anhydrous Hydrazine that I came across.
Anhydrous hydrazine is prepared by heating under reflux 100% hydrazine hydrate with an equal weight of sodium hydroxide pellets for 2 hours, followed by distillation in a slow stream of nitrogen introduced through a capillary leak. (Caution! Distillation in air can lead to explosion.) The distillate boils at 114–116° and the yield is 95–97%.

++++++++++++++++++++++++++++++++++++++++++++++

This isn't exactly news you know. Anybody who's read the merck index knows this. :rolleyes:

<small>[ October 23, 2002, 07:07 PM: Message edited by: nbk2000 ]</small>

[Marvin]

Ive just corrected my use of the word 'yeild' in my last post, Boob, is the 'yeild' in your post the concentration of hydrazine produced at the end of the reaction, or the total amount produced?

I would expect the process boiling for 2 hours to result in loss of considerable amounts of hydrazine. So I would expect 95-97% to be the concentration, as over 95% is considered 'anhydrous' in my books.

IVe also read that if the temperature of the distilling flask drops below 60C, NaOH.H2O crystalises out, which is a problem in vacuum distillation, it does make me wonder if we could form this and then decant to quickly concentrate.

Does the merk say anything about containers? We cant use glass, we cant use aluminium, we cant use steel, silver is damn expensive. I'm wondering if we could coat the inside of a quickfit system with a layer of silver to try this sort of experiment. Electroless silver plating is fairly easy and a lot cheaper than solid silver containers.

[Boob Raider]

Sorry about that NBK :( ... I for one haven't read the merck index so I didn't know it is there. Anyways Marvin ... I got this from an organic synth site under the preperation of Acetone Hydrazone. One doesn't heat the NaOH and Hydrazine Hydrate mix for 2 hrs ..... its just allowed to sit followed by distilation at the specified temp. I don't quite know what is implied by the word "yeild" but I am assuming it to be yeild. I suppose the last 5% of the Hydrate is destroyed during distillation or remains in the NaOH syrup.

[nbk2000]

You can use glass, just not ground glass joints. The NaOH will react with the glass flask, but pyrex does so rather slowly. Pure quartz flasks are very expensive, but are (I believe) immune to attack by NaOH. They're also thermal shock proof. You can take them red-hot from a furnace and dunk them in ice water without shattering. :o

[Polverone]

Quartz isn't immune to attack by NaOH. But in all cases, the rate of attack of NaOH in aqueous solution on glass is relatively low. Molten NaOH is a different story. Your glassware isn't going to be particularly stressed by this reaction - relatively low temperatures, no vacuum - so I'd just go with the cheapest vessel you have lying around and if it's somewhat etched by the NaOH, too bad. Of course that presumes that you already have hydrazine hydrate and that you really want anhydrous hydrazine. I wouldn't want it. Not even if it were a free gift from DuPont under my Christmas tree. I don't have the facilities to work safely with anhydrous hydrazine.

[Marvin]

My understanding of pyrex is that is reacts faster with sodium hydroxide than soda glass does. I forget where I read this, but this is presumably due to the boric acid content making the glass more acidic. I havnt tested this yet, I plan to keep all my pyrex away from concentrated hydroxides.

Also hydrazine hydrate itself attacks glass, and the etched surface of the glass is going to be a much better catalyst for decomposition of the hydrazine.

Add all of this the high temperature, and I dont think these are suitable conditions to use. I agree with polverone, I wouldnt try this without much better facilities than I have at home, needs a fume hood with a chimney high enough to get the vapour out of the way of people.

An easy way of making hydrazine hydrate, which is just as unfreindly but vastly useful would be a big help, and the conditions are essentially the same. I cant seem to get round needing aperatus that will distill hydrazine. Maybe some sort of teflon coating would work.

Ive read a few rather old reports of concentrating hydrazine, and even those that used silver aperatus ended up with less than half of the hydrazine they started with as sulphate.

The organic nitrite process for azide is very clever if you can get hydrazine hydrate. Maybe we need to find a process that doesnt use it. Preferably one that doesnt require a lot of fractional crystalisation.

[Boob Raider]

When the first sample of Hydrazine was prepared .... some dude did a whole bunch of reactions and obtained Hydrazine Hydrochloride. He then mixed with N2H4*HCl, a soln of CH3ONa in CH3OH. The NaCl precepitated and a mix of N2H4 and CH3OH was obtained which was later distilled.
And I also read that one of the newer methods of making CH3ONa is electrolytic. And the so called electrolyte consists of NaCl and CH3OH. There might be some other things in it but the article didn't specify. So one doesn't need Na metal for making the methoxide. :D

[Mr Cool]

There's another method that I found on the Hive, that involves mixing a metal hydroxide with an alcohol and adding excess CaO, to form the metal alkoxide and Ca(OH)2. CaO shifts the equilibrium towards M-O-R and H2O. Equilibrium is reached after a few days at room temperature.

[Marvin]

Very interesting indeed, and points my books are very much missing on. I suspect forming NaCl is much prefered to forming sodium sulphate, but I cant think why that would be. I have another fragment I can throw into this puzzle I think. If you take dry ethanol or methanol and magnesium turnings, add a trace of something to start the reaction, an alkyl halides, eg carbon tet, the magnesium will react and convert completely to magnesium ethoxide/methoxide.

With this twist, we arnt relient on the hydroxide forming for the effective dehydration (as it loses hydrogen directly), so we might be able to use this with the hydrazine salt itself, rather than remove magnesium/calcium hydroxide to replace the base. Alkali earth hydroxides are pretty crappy bases, maybe if you added sodium hydroxide youd get a ppt of the hydroxide or oxide and sodium ethoxide/methoxide left even though its a stronger base. The same way calcium hydroxide caustifies potash by exploiting low solubilities. This is almost exactly what MrCool is saying, except you dont have to worry about the oxide/hydroxide equilibrium to achive the dehydration. This is very confusing, becuase its making a very strong base, from a strong base, by precipitating a weak base.

As for making sodium methoxide electrolytically, Ive no idea how conductive a salt in methanol would be. I wonder if sodium hydroxide in methanol would be preferable to sodium chloride, and how youd prevent the oxidation products at the anode interfering. I read somewhere that the following reaction works for producing sodium oxide, Na2CO3 + C =&gt; Na2O + 2CO, but I dont know what temperature is needed for the reaction to go, and Ive since failed to find any other information. Sodium oxide should react with an alcohol to produce the ethoxide also.

I'm not sure in my mind how all the bits fit together, but this may well end up as the cunning process we need to produce an alcohol solution of hydrazine with low water content directly from the salt.

[aster]

i had hydrazine hydrate 80%, i can increasing the concentration by dehidrating them using KOH, but what the difference of the reaction by mixing this with AN, compared to mixing the anhydrous form with AN? anyone knows? thanks

[Mr Cool]

Well, it is my understanding that Astrolite explosives have hydrazine nitrate as the explosive component, mixed with Al or whatever.
This is because
N2H4 + NH4NO3 &lt;--&gt; N2H5NO3 + NH3
The ammonia gas escapes, shifting the equilibrium to the right and producing hydrazine nitrate in high yield, perhaps dissolved in hydrazine if it is used in excess.
Water will not interfere with this equilibrium, but the product will be hydrazine nitrate dissolved in, or wetted with, water (and any excess hydrazine). So it will need to be dried out before use in order to make it cap sensitive. This will be quite hard, since hydrazine nitrate is apparently quite hygroscopic, but leaving it in a warm oven should do it. Don't get it too hot, obviously...
So the result will be crystals of HN, rather than the traditional Astrolites which are liquids, but it will still be a powerful, cap sensitive explosive.

A similar method can be used to make hexamine dinitrate, although it is slower since hexamine is a pretty shit base, but it failed when I tried it with 5-ATZ. Pitty.

<small>[ January 01, 2003, 10:14 AM: Message edited by: Mr Cool ]</small>

[nbk2000]

Making hydrazine salts is fairly simple. It's getting the anhydrous hydrazine from the salt that's dangerous.

Now, if you can react sodium methoxide with hydrazine hydrochloride, to form salt and pure hydrazine in MeOH solution, than you could probably use that solution as-is in a reaction with ammonium nitrate to form hydrazine nitrate, without previously distilling it off.

Vacuum concentration of the solution to form a saturated solution of HN in MeOH would be fairly safe to do since it could be done remotely without heating. The remaining liquid would still be explosive without being too sensitive since the alchol dilutes it somewhat.

I did a quick Google search but, not surprisingly, failed to find anything about the solubility of HN in MeOH.

[PEROMAN]

I've found a patent( <a href="http://www.uspto.gov/patft/" target="_blank">http://www.uspto.gov/patft/</a> ) about producing ketazine (and then hydrolysing it to hydrazine) - No 6,482,383

The ketazine is made by reaction of ketone , NH3 and (!)H2O2
in a presence of catalyst( nitriles , amides , and ammonium salt of the acid , and sodium phosfates, or mixtures thereof)
Maybe, because of my bad english, i did not understand some parts of the patent (mostly about catalyst)

But this seems a very easy method - they use methylethylketone(but in another patent they use acetone) , 25%NH3(or less) , and 30%H2O2(or less) can be used . The reaction goes in room temperature (also in higher t) The yield is 70-90%
see also pat.: 3,972,878, 3,972,876, 3,948,902, 4,093,656

Ketazine can by hydrolysed by H2SO4(not concentrated) to hydrazine sulphate Then, for example, we add 100ml of water to 30 g N2H6SO4
and add CaCO3 - after the reaction ,we filter off CaSO4 and unreacted CaCO3 , and we get a solution of (N2H5)2SO4
Then we add Ca(NO3)2 (solution) to (N2H5)2SO4 and we get a solution of N2H5NO3 And then we dry the water out . So i think it is not necessary to destillate hydrazine

Also see patent 5,241,117 - about producing semicarbazide from "manochlorourea sodium salt" and ammonia The catalyst is
Zn(2+) or Cd(2+)
NH2CONCl(-) + NH3 = NH2CONHNH2 + Cl(-)
Monochlorourea is made from sodium hypochlorite and urea

Then , i think, it is possible to add acetone to semicarbazide solution and filter off semicarbazone(NH2CONHN=C(CH3)2)(not soluble) , and then we add nitric acid to it and obtain NH2CONHNH2*HNO3 (i think it is rather good explosive , but it can be hydroscopic)

[nbk2000]

Looks interesting.

[Mr Cool]

Do you have information on semicarbazide nitrate's explosive properties, or is it just supposition when you say it'd be a good explosive?
While it may be good compared to other salts like AN, I'm sure it will fall behind the common HE's like PETN or TNP. Hydrazine nitrate is a powerful explosive salt, but it is a somewhat anomalous case. In general, it can be said that the more hydrogen an explosive contains, the lower its density (this is a very rough rule and is not applicable in all cases). Also, it is almost a straight chain molecule, and will probably be less dense than the cyclic molecules of aromatic nitrocompounds, cyclic nitramines etc. Few nitrate salts' VoD's exceed 4 km/sec, which is pretty shabby for a HE.
If you have semicarbazide, it is a MUCH better idea to convert it into NTO. Nitro compounds also have the advantage over nitrate salts that they are not acidic (well they might be, but you know what I mean).
Thanks for the reference to hydrazine via ketazine, I'll check it out. It could be a very nice procedure...

[nbk2000]

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">Then we add Ca(NO3)2 (solution) to (N2H5)2SO4 and we get a solution of N2H5NO3 And then we dry the water out.</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">So then, once you have the hydrazine sulphate solution, you add Calcium nitrate which would form HN + calcium sulphate precipitate?

I wonder, could an aqueous solution of HN be used as a sensitizer, like NM, or would the water render it impotent? I know that once the HN reaches 95%+, that the solution is explosive, but what about lower concentrations?

Also, I saw urea for sale as a deicer for $12/Kg, at the local hardware store.

<small>[ February 02, 2003, 03:48 PM: Message edited by: nbk2000 ]</small>

[PEROMAN]

No, i dont have any info on semicarbazide nitrate . But i think it is not bad .. For example , the maximum VoD of urea nitrate is about 5000.

I dont know the VoD of hydrazine nitrate , somebody told me that it is about 8000 (but in some books(as i remember Urbanski) they write (!)4-5km(!) - i dont believe it , because astrolite , based on HN , has high VoD) .

I think the heat of explosion of semicarbozide nitrate, must be rather close to the heat of exp of hydrazine nitrate, besides, SN has a better oxygen ballance than HN
So its VoD seems to be at least more then 7000(seems to me) ,
Of course , it is better to make NTO , bust firstly i need to obtain any semicarbazide salt.

About HN:
(N2H5)2SO4 solution can be made by reacting N2H6SO4(called "hydrazine sulphate") with CaCO3(mixed with water) :
2N2H6SO4 + CaCO3 = (N2H5)2SO4 + CaSO4 + H2O + CO2

(N2H5)2SO4 is very good soluble in water (not N2H6SO4) ,
and Ca(NO3)2 too , but CaSO4 is not..

Then it is possible to crystallize N2H5NO3 by drying the solution on the air (without heating) , then mix it with Al
So i think destillation is not necessary
As for HN solution , i think it is not (a good) explosive(not sensinive) , and the VoD is very low

In Russia(Moscow) , urea costs about 50Cents (half dollar) per 1kg
(NH4NO3 is 30-40 cents per kg) - in fertilizer shops

[Microtek]

When reading this discussion I get the impression that many of you believe that hydrazine nitrate is unstable at elevated temperatures or perhaps too sensitive to risk heating. I don't think this is the case.
HN is sometimes used in cast charges with HMX when a very high VOD is desired because these generally have higher density than the pressed variety. HN melts at about 60-70 C so it can be used as a substitute for TNT but of course has much better VOD and OB. Anyway, I've seen a comparison of thermal decomposition data for various explosives and I think HN had 260 C no reaction written next to it. I'm not absolutely positive that that was what it said, but I can say for sure that I have made some HN myself by reaction of hydrazine sulfate in hot aqueous solution with Pb(NO3)2 soln. PbSO4 was filtered off and the water evaporated under heating. The HN melted but did not decompose.

[PEROMAN]

Somebody told me that the sensivity of HN is like RDX , but HN (as somebody said) does not decompose till 200c (and at higher t it decomposes without explosion ) - it is hard to believe this
I read ,that N2H5ClO4 is very shock sensitive and dangerous

[Microtek]

Yes I've heard that the perchlorate is quite sensitive too, but that is an entirely different compound. After all, the difference in anion makes the difference between Pb(NO3)2 and Pb(N3)2.

[cutefix]

Hydrazineperchlorate will sensitize the binary explosive made with hydrazine hydrate,ammonium nitrate .
Without the perchlorated hydrazine it will be difficult to initiate a hydrazine nitrate in water solution.
Now to practically do that they will add a small quantity of ammonium perchlorate to the ammonium nitrate/hydrazine hydrate mixture.

[aster]

i got 2 litre of hydrazine hydroxide, because ammonium nitrate is hard and expensive to get in my country, it cost about 20 bucks for 500 gram! damn:mad: for that fertilizer...:eek: , what the difference if i use HNO3 68% to nitrating them, in order to get hydrazine nitrate? i think i should cooling the hydrazine hidroxide and bring the HNO3 dropwise, will it be safe? because i think the water content of the 60% hydrazine hydroxide will makes difference from anhydrous hydrazine that stated will explode in contact with HNO3:rolleyes: thanks for reply:D

[vulture]

Carefully neutralize your HNO3 (which is alot cheaper than NH4NO3 were you live I assume?) with an ammonia solution. Collect the AN by boiling of the water.
That seems alot safer to me than nitrating hydrazine.

BTW, which country are you from? Did you ask for NH4NO3 at the apothecary? Because they'll charge you 500% of the usual street price.

[aster]

yes in my country, HNO3 70%, and the ammonia sol 30% cost about $1 for a litre, i live in "beautiful country" have you ever been in bali? :D thanks

[tmp]

To aster:

I wouldn't mix hydrazine and nitric acid together.
It might blow up in your face.

I understand that during World War II, the Germans
used this mix to power their V-2 rockets.

ANY input on this mixture is more than welcome

[aster]

did anyone knows, whether hydrazine nitrate grouped in primary or secondary explosives? since i think it's easy to set off, i guess the hydrazine nitrate is a primary explosives, right?

[knowledgehungry]

70% NA and 30% NH3 for 1$ a liter??? no wonder there are terrorist attacks there:D

EDIT: no Hydrazine Nitrate is not a primary, Hydrazine perchlorate is IIRC.

[aster]

yeah, so cheap, but i think terrorist prefer a huge amount and readily build material, nitric acid is a pain in huge amount, especially when reacting them together in nitration process or concentrating them :D, it's not their first choice, they prefer potassium chlorat here:D thanks for the info