Sciencemadness Discussion Board - The most efficient method to prepare Hydrazine Nitrate

The most efficient method to prepare Hydrazine Nitrate

Astroboy - 10-5-2003 at 07:49

Does anyone have a suggestions as to which method is the most efficient (yield) to produce hydrazine nitrate?

I have tried the hydrazine + AN method, 2 moles AN for one H2N H2N and on several tries, I was never able to remove the amonia completely and large crystals formed out of the solution. Is it possible I had dissolved ammonia in my comercial hydrazine?

Also found that French patent (FR2,276,261) from 1976 were AN is not used but only nitric acid, hydrazine and methylene chloride. This method is also similar to the method used by Rocketdyne in 1966 to make HN out of nitric acid (70%) and hydrazine.

I need to find an efficient way to prepare it that would give the purest yield.

Thanks,

Astroboy

FadeToBlackened - 11-5-2003 at 06:05

If you follow the hydrazine sulfate synth that is in FEMFEP and other places, react it with calcium nitrate, calcium sulfate will precipitate since it is poorly soluble. Solution will be of hydrazine nitrate.

FrenchPyro - 11-5-2003 at 13:01

Comercial hydrazine nitrate can be prepared by the nitration of fatballs

Krypton - 13-5-2003 at 16:45

Pyro,

to this theme here little pic

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PHILOU Zrealone - 4-6-2003 at 02:38

I have made sucessfully pure hydrazine nitrate cristalls from 80% hydrazine and 70% HNO3...but you need to cool them in freezer prior to reaction to avoid excessive heat and vapourisation of HNO3 / NH2-NH2 in the air.
Dillution with distillated water is also a possibility to reduce the heat of reaction since anyway an evaporation step is needed to get the maximum yield of cristals.

Cristals of HN are hard to dehydrate completely.
Depending on your most valuable reactant, you can add an excess of HNO3 or an excess of NH2-NH2..they are both volatile and will leave the system upon evaporation to cristallisation.

Beware of transition metal (copper is bad news in contact with HN since it is decomposed quite fast)...HN remains weakly acidic being the salt of a strong acid and a weak base.

Plain hydrazine can be used to make Ni(NH2-NH2)3(NO3)2 by mixing NH2-NH2 in ethanol with Ni(NO3)2 in ethanol... the media heats a lot since a complexation occur and a precipitation of blue and then upon further agitation of a pinkish claylike precipitate (abundant- yield is near 100%).
This can be water washed because unsoluble in water, then washed with ethanol and dried.
Once dry it displays excellent primary properties, infinite storage, moderate sensitivity to shock, deflagrate from flame in the open and detonate at 7km/s when confined...very high lead block test for a primary (400 ccm/10g), good brisance superior to TNT.

Megalomanias website expose a similar salt based on Zn(NO3)2; but I have never tried that one and I have seen no reference elsewere.

PHILOU Zrealone - 6-6-2003 at 09:42

By the way:
:cool:

Silver azide can be done from hydrazine and Ag nitrite.

NH2-NH2 + AgONO --> AgN3 + 2 H2O

Beware of AgN3...hell sensitive primary and in concentrated NH2-NH2 (endothermic fuel)...it is a wich for an explosion.

fritz - 30-11-2003 at 03:58

What about mixing concentrated hot solutions of Hydrazine-sulphate and Barium-nitrate? Barium-sulphate will precipiate. After filtrating it may be possible to remove the remaining water by
azeotropic destillation. Perhaps whith Xylene??
Access to Barium-nitrate should be easy by extracting sparklers. And by repeated recrystallisation it should be possible to achieve to get it in a good purity.
I think precipiating the sulphate whith barium should be slightly better than precipiating whith Calcium because the solubility of Ba-sulphate is much smaller than the solubility of Calcium-sulphate.

solvent preciptiation

chemoleo - 1-12-2003 at 18:28

Alternatively, is there a solvent that is water miscible such as Ethanol, and in which the hydrazin nitrate does not dissolve in?
For instance, in the case of hydrazin sulphate (which is water soluble), one can precipate it completely by mixing it with ethanol. Doing this twice removes all the water. This is then easy to dry, i.e. under vacuum or on the radiator in case of a non-hygroscopic substance.
Anyway, give it a shot and mix a bit of your hydrazine nitrate solution with an excess of ethanol, or acetone, and hope it will precipitat.
If it does you are on the money

KABOOOM(pyrojustforfun) - 4-12-2003 at 13:50

such solvent would also be useful to get fine crystalls (mix the sols while stiring vigorously)

Hydrazine nitrate from N2H4.H2SO4

SAM4CH - 11-12-2004 at 09:14

Can I get HN from Hydrazine sulfate using Nitric acid or ammonium nitrate (Molten AN)!!?

neutrino - 11-12-2004 at 09:30

Molten AN would be suicide (as well as not working) and the other method wouldn’t work well, either. I suggest adding calcium nitrate and letting the calcium sulfate precipitate out.

SAM4CH - 11-12-2004 at 10:23

Okay.. I could not use Calcium nitrate as a solid and Hydrazine sulfate as a solid to start the reaction!?

if I dissolve Ca(NO3)2 in water I will get dilluted HN Sol.

what about using 96% Ethanol as a solvent for Ca(NO3)2?

and what about exactly amount of reactants in experimental work?

BromicAcid - 11-12-2004 at 13:16

If you were looking for a fool proof method to hydrazine nitrate from hydrazine sulfate:

Mix hydrazine sulfate with 5 x weight excess of sodium hydroxide, distill from a silver vessel preferably under reduced pressure, hydrazine will eat glass and may explode on ground glass or metal joints or from contact with light at this temperature.
Distill your resulting crude hydrazine with a 3 x by weight excess of barium oxide to removing clinging water, again preferably under reduced pressure.
From the two previous reactions you should achieve close to a 50% yield of anhydrous hydrazine with respect to the original weigh of hydrazine sulfate used. Mix the resulting viscous liquid with an equimolar quantity of anhydrous nitric acid with much stirring and keeping the solution cold.

Congradulations, if you managed to survive the various distillations and adding anhydrous nitric acid to your hydrazine, you should now be left with anhydrous nearly pure hydrazine nitrate. I think ..... Uhhhh... don't try this at home.

(BTW, isn't hydrazine nitrate only slightly exotic at best?)

Very little amount of!

SAM4CH - 15-12-2004 at 06:06

I got Hysrazine sulfate (N2H4.H2SO4) and I tried to get hydrazine nitrate (N2H4.HNO3), I let 250 mL of 65% Ca(NO3)2 solution to react with 130 gram of hydrazine sulfate in cold bath and I filtered the solution so hardly and I added Alcohol to the clear Sol. and I saw ppt. I filtered it and when I dried it, I found its weight was 5 gram only!!
Please what's wrong with my work!?

[Edited on 15-12-2004 by SAM4CH]

SAM4CH - 15-12-2004 at 06:13

How can I test my hydrazine sulfate and hydrazine nitrate?
and what about Hydrazine nitrate crystals as an explosive, is it like or the same of liquid Astrolite!?

[Edited on 15-12-2004 by SAM4CH]

Tweenk - 30-12-2004 at 09:42

Quote:

Originally posted by neutrino
Molten AN would be suicide

Molten AN doesn't exist, you get loads of N2O and other nitogen oxides before melting it.

SAM4CH - most of hydrazine nitrate was left in the soln, after filtering off the calcium sulfate you should evaporate it to dryness with careful heating as hydrazine nitrate is very, very soluble in water (just as AN is).

artem - 9-1-2005 at 01:07

Quote:

Originally posted by SAM4CH
I got Hysrazine sulfate (N2H4.H2SO4) and I tried to get hydrazine nitrate (N2H4.HNO3), I let 250 mL of 65% Ca(NO3)2 solution to react with 130 gram of hydrazine sulfate in cold bath and I filtered the solution so hardly and I added Alcohol to the clear Sol. and I saw ppt. I filtered it and when I dried it, I found its weight was 5 gram only!!
Please what's wrong with my work!?

[Edited on 15-12-2004 by SAM4CH]

Such a way you get N2H6(NO3)2, not a mononitrate; N2H6(NO3)2 is more unstable and sol. in ethanol. In order to prepare N2H5NO3 you may use the mixture Ca(NO3)2+Ca(OH)2.

Centimeter - 3-2-2005 at 18:04

Can you explain yourself a little bit more Artem?

I conducted a small test run of converting hydrazine sulfate into hydrazine nitrate. I added a concentrated solution of Ca(NO3)2 to a solution containing a small amount of hydrazine sulfate. I then filtered off the precipitate and added acetone. A white precipitate was observed. I am not sure, but I think some heat was evolved and there may have been some bubbles. Did the acetone react? I was under the impression that it was difficult to oxidize ketones. Did I get the dinitrate form? Would this not work for sodium azide production? I don't see why it wouldn't personally. CRC does not list any other solvents other than water for the dinitrate form where as it reports a slight solubility in ethanol for the mononitrate form. Perhaps I could purify it by adding a lot of ethanol, filtering, then evaporating?

Microtek - 4-2-2005 at 00:48

Hydrazine nitrate is extremely soluble in water. With about 100 ml water in the solution, I don't think you can get it to precipitate even with a large excess of ethanol. If I were you, I would evaporate most of the water first. If you don't like boiling it, you could just place the soln in a dish and blow dry air over it.

artem - 4-2-2005 at 11:32

Quote:

Originally posted by Centimeter
Can you explain yourself a little bit more Artem?

I conducted a small test run of converting hydrazine sulfate into hydrazine nitrate. I added a concentrated solution of Ca(NO3)2 to a solution containing a small amount of hydrazine sulfate. I then filtered off the precipitate and added acetone. A white precipitate was observed. I am not sure, but I think some heat was evolved and there may have been some bubbles. Did the acetone react? I was under the impression that it was difficult to oxidize ketones. Did I get the dinitrate form? Would this not work for sodium azide production? I don't see why it wouldn't personally. CRC does not list any other solvents other than water for the dinitrate form where as it reports a slight solubility in ethanol for the mononitrate form. Perhaps I could purify it by adding a lot of ethanol, filtering, then evaporating?

Esplosivo - 4-2-2005 at 11:36

Quote:

On mixing the hydrazine with the acetone you probably formed the hydrazone of propanone - that accounts for the heat generated. Hydrazine reacts with the C=O present in both aldehydes and ketones (such as acetone). [So too does hydroxylamine to give the respective oxime.]

[Edited on 4-2-2005 by Esplosivo]

artem - 4-2-2005 at 12:28

N2H5NO3 sol. in water -76.6g/100ml(25C), sl.sol. in cold ethanol and methanol. But when you mix N2H6SO4 + Ca(NO3)2 in solution you receive N2H6(NO3)2, which is not very stable (bubbles?). So, the correct way is: 2N2H6SO4 + Ca(OH)2=CaSO4+ (N2H5)2SO4, (N2H5)2SO4+Ca(NO3)2=CaSO4+N2H5NO3.
There is some complexity in multiple washings to get maximum N2H5NO3 from mix; as a result, the concentration of solution is not high. To increase, you may evaporate it at a room temperature, or at heating. The resulting subj is not pure, but detonate and burn very well.

Theoretic - 6-2-2005 at 10:35

"Molten AN doesn't exist, you get loads of N2O and other nitogen oxides before melting it."

From various people's experiences, it can exist and does exist.

A variation of the precipitation theme is reacting hydrazinium carbonate with calcium nitrate. The chalk precipitate is more manageable than the CaSO4 precipitate.

Also, HN isn't the best explosive possible, this is why. The reaction between N2H4 and HNO3 gives out energy, which isn't useful as this energy now can't be released in an exlosion. The nitrate ion isn't the best oxidant, as if you put in a large amount of energy and remove an oxide ion, you get a nitryl cation - lighter and much more energetic. But you can't have that go with N2H5+, as they are both charged positive. Nitrohydrazine is much better. It can be prepared by reacting a nitryl salt with anhydrous hydrazine, under controlled conditions. Being a molecule of water lighter than a molesule of HN, and compensating for the loss of reducing ability on the hydrazine part and oxidizing ability on the nitro part of the molecule by having an energetic N-N bond, I predict it will be more powerful and with a higher VoD (due to the N-N bond, which means the molecule will disintegrate faster than a N2H5 ion with a NO3- ion).

artem - 7-2-2005 at 22:37

Quote:

Originally posted by Theoretic
...Nitrohydrazine is much better. It can be prepared by reacting a nitryl salt with anhydrous hydrazine, under controlled conditions...

but can you tell us something about its propeties, stability; or about "under controlled conditions"?

AndersHoveland - 6-1-2013 at 16:48

Hydrazinium nitrate can be made by reacting hydrazine (either anhydrous or "hydrazine hydrate") with ammonium nitrate. The reaction gives off ammonia. It is not a good idea to mix more than small ammounts at one time, since the ammonia gas can form microbubbles that greatly sensitize the liquid mixture to detonation.

N2H4 + NH4NO3 --> N2H5NO3 + NH3

Hydrazinium di-nitrate also exists, and can be prepared by reacting a solution of nitric acid diluted in anhydrous methanol or ethanol (no water) with anhydrous hydrazine, or with dry hydrazinium nitrate. Hydrazinium di-nitrate is somewhat acidic and readily hydrolyses in water back to the mono-nitrate and nitric acid, so hydrazinium di-nitrate cannot be formed in the presence of water. The di-nitrate is also explosive, but has a slightly lower detonation velocity.