Sciencemadness Discussion Board

hydrazine nitrate and hydroxylamine nitrate

chemoleo - 4-8-2003 at 04:13

Has anyone ever made these (i.e. (NH2NH2)(NO3)2 and (NH2OH)NO3)? routes for synthesis, without any other interfering salts?? (all I could find were synthesis pathways that would leave you with a soluble salt that one couldnt purify away...). Also, anyone knows their properties in terms of MP, BP, flammability, detonatability etc.?

[Edited on 5-3-2006 by chemoleo]

Hydrazine nitrate

Mephisto - 4-8-2003 at 06:09

density: 1,64 g/cm³
lead block test: 408 cm³
melting Point: 72 °C
explodes at 360 °C
explosive velocity: 8690 m/s at max. density
sensitivity: 7,4 Nm

from: Köhler u. Meyer, Explosivstoffe, 9. Aufl., Weinheim: VCH Verlagsges. 1998

[Edited on 4-8-2003 by Mephisto]

franklyn - 15-9-2010 at 01:28

Adducts of Hydroxylamine which is itself energetic appear promising
candidates for propellants or explosives.

Hydroxylamine has been considered as a monopropellant a possibility is the
borane salt , 3 HONH2 • BH3 => B2O3 + BN + N2 + 9 H2

Hydroxylammonium Methylenedinitroamine is one I have not seen nor heard about.
CH2(HNNO2)2 • 2H2NOH => CO + 5 H2O + 3 N2

Hydroxylammonium Nitroamine is another compound of interest
4 HONH2 • H2NNO2 => 10 H2O + 6 N2 + O2
particularly with 36 % Aluminum
4 HONH2 • H2NNO2 + 8 Al => 4 Al2O3 + 6 N2 + 10 H2

There may be some question whether these can form at all , similar doubt
has been expressed regarding an azide salt here _
http://www.sciencemadness.org/talk/viewthread.php?tid=1146#p...

.

ScienceSquirrel - 15-9-2010 at 02:46

Quote:
Hydroxylamine has been considered as a monopropellant, a possibility is the
borane salt ;
3 HONH2 • BH3 => B2O3 + BN + N2 + 9 H2


That is not a salt but a Lewis adduct.

Rosco Bodine - 15-9-2010 at 12:28

Double decomposition of hydrazine sulfate with calcium nitrate or barium nitrate or lead nitrate, or the perchlorates, should precipitate the insoluble metal sulfate, and leave the soluble hydrazine nitrate or perchlorate in aqueous solution which may be evaporated to crystallize out the hydrazine salt.

Anders2 - 15-9-2010 at 14:12

Hydrazinium Nitrate is very difficult to dry. Hydrazine Hydrate with dry Ammonium Nitrate, when mixed, forms a liquid layer, and a precipitate, which seems to be Hydrazinium nitrate, or the hydrate of it, and the solution foams/ bubbles with ammonia gas.

Dry hydrazine sulfate and calcium nitrate do not dissolve in alcohol, but when when the two powders are finely crushed and mixed, and alcohol then added, the alcohol slowly dissolves some anhydrous hydrazine nitrate into it, the alcohol can then be removed at warmed to leave the dry hygroscopic powder.

Engager - 16-9-2010 at 02:27

Quote: Originally posted by Rosco Bodine  
Double decomposition of hydrazine sulfate with calcium nitrate or barium nitrate or lead nitrate, or the perchlorates, should precipitate the insoluble metal sulfate, and leave the soluble hydrazine nitrate or perchlorate in aqueous solution which may be evaporated to crystallize out the hydrazine salt.


Yes - they are quite easy to make in such manner, however some things should be remembered. Heating salts of hydrazine with oxidant nature acids can produce strong explosion. Then working with hydrazine salts, especialy those witch can be source of oxygen, one should be cautious, since redox systems due to reductant nature of hydrazine at elevated temperature or in melted state and are quite unstable. Literature describe preparation such salts as chlorate and perchlorate, but work with this salts should be carried out with great care. Dibasic salts of hydrazine are thermally unstable and decompose with intermediate formation of corresponding monobasic salt and free acid. Heating of hydrazine dinitrate leads to formation of hydrogen azide among other products, so evaporation of solution with slight overheat can lead to nasty results. Monobasic salts of hydrazine are generally more stable in solution and are VERY soluble in water, often have low melting point and are difficult to crystallize.

YSome long time ago i made both N2H4*HNO3 and N2H4*HClO4, both are components of astrolite explosive. Here is some more information about this salts.


Hydrazine mononitrate (N2H4*HNO3): White or slightly yellowish crystalline solid with melting point at 70C, is excessively soluble in water (175g at 100 ml at 10C, 266 at 20C and 2127 at 60C). Substance begins to volatize without decomposition at 140C, not showing significant decomposition up to 300, decomposition of solid residue begins at 180 and becames explosive at ~270C. Easily inflames on the air, causing strong explosion then confined. Then dissolved in strong sulfuric acid decomposes with formation of nitrogen oxides, then heated with delute acid forms hydrogen azide as one of reaction products. Contact with oxidizers such as KMnO4, chromates and hydrogen peroxide causes inflamation. Melted salt at 70C explodes with 8500 m/sec velocity, 5640 m/s at 1.25 g/cm and 8510 at 1.59 g/cm. Non compressed sample containing 0.5% moisture detonates from cap with 0.25g of mercury fulminate, compressed to 1.6 g/cm3 requires 1.5g. Sensitivity to impact is 50% with 200-150 kg/cm. Brisance is 82% of TNT, Trauzl block test is 120.4% vs picric acid, TNT equivalent is 1.42.


Hydrazine dinitrate (N2H4*2HNO3): Solid witch melts at 104C then fast heated. As dibasic salt it is much more unstable then mononitrate. Then heated slowly, approximately at 80C it begins to decompose without melt, forming hydrogen azide along with other products. Even in dessicator with H2SO4 drying is accompanied by formation of HN3, residue consists of hydrazine mononitrate and ammonium nitrate. Good soluble in water, but solutions containing more than 30% of salt decompose on heating. More powerful explosive then Tetryl but less powerful then PETN.


Hydrazine perchlorate (N2H4*HClO4): Can be produced by neutralizing dilute solution of hydrazine with dilute perchloric acid. Compound formed is N2H5ClO4*0.5H2O it is stable up to 60C. Anhydrous salt can be prepared by crystallization from ethanol. It is crystalline solid with melting point at 137-138C forming colorless liquid. Decomposition begins at 145C and is finished at 230C (on cautious heating), fast heating causes strong flash. Impact or friction cause violent detonation. Sensitivity of anhydrous salt is similar to primary explosives, but hydrate is much less sensitive. Solubility is 23.6g in 100 ml H2O at 0C and is 93.1g at 75C. Almost insoluble in ethanol at room temperature but at 60C it is 69g in 100 ml. Unsoluble in ether, benzene. Attempt to produce hydrazine nickel perchlorate from nickel perchlorate in water solution in 5 days lead to formation of bluish solid, witch exploded violently then glass stirring rod was introduced to the mixture. Trauzl test for hydrazine perchlorate gives 113% of picric acid, and 122% of TNT.


[Edited on 16-9-2010 by Engager]

Possibly more interesting reaction

Rosco Bodine - 16-9-2010 at 09:27

@Engager ....Please share your thoughts on this:

There has been for many years speculation concerning a possible method of forming azides in aqueous solution via reaction of hydrazine sulfate with a metal nitrite, and the reaction does seem to work fine on paper and in theory, and yet it appears to be a pH sensitive reaction or an otherwise sensitive reaction where the predicted and desired azide is not produced. I posted years ago about this possible method which seems to not produce the desired product when experiments have been done.

Two British patents issued concerning the dubious method, described in the Hodgkinson patents GB128014 and GB129152 found here:

http://www.sciencemadness.org/talk/viewthread.php?tid=1987&a...

Perhaps a double decomposition of Hydrazine Sulfate with Calcium Nitrite Ca(NO2)2 or a Basic Calcium Nitrite , or a buffered Calcium Nitrite solution, perhaps in the presence of alcohol or polyol, would lead to a precipitation of Calcium Sulfate from a residual solution of Calcium Azide. If workable this would represent a greatly simplified route to Azides.

Attached is a patent US4294813 which relates to the synthesis of Calcium Nitrite and also a Basic Calcium Nitrite gotten from Sodium Nitrite plus Hydrated Lime.

Attachment: US4294813 Calcium Nitrite from Sodium Nitrite.pdf (103kB)
This file has been downloaded 1293 times

[Edited on 16-9-2010 by Rosco Bodine]

Engager - 16-9-2010 at 13:47

Well, actually i know about this process. It works - but only with silver azide, witch may be produced by reaction of hydrazine sulphate with sodium nitrite and silver nitrate, this patents was many times rechecked by many researchers and found to be true - yield can be as high as 82%. Regrettably this path seem to work exclusively for silver azide, since it is quite stable vs acid.
Luckily you don't need this process for azides, there are more useful metods, you can use hydrazine to react with urea to form semicarbazide witch can be reacted with nitrous acid (sodium nitrite/acid) to form corresponding azide witch is easy hydrolized forming azides:

1. NH2-CO-NH2 + N2H4 => NH2-CO-NH-NH2 + NH3 (this is generic form of equation, process may be work with hydrazine salts - try to dig up some patents)
2. NH2-CO-NH-NH2 + HNO2 => NH2-CO-N3 + 2H2O (product is unstable and is readily hydrolized to azide in aqueous basic media).

There is another maybe more interesting way, then diethylcarbonate is reacted with hydrazine carbonyldyhydrazide is formed, this can be reacted with nitrous acid to form exotic explosive substance carbonylazide (i can also give some references if you are interested), this one also hydrolizes readily forming azides:

1. CO(OC2H5)2 + 2N2H4 => CO(NH-NH2)2 + 2C2H5OH
2. CO(NH-NH2)2 + 2HNO2 => CO(N3)2 + 4H2O
3. CO(N3)2 + 2H2O => [H2CO3 + 2HN3] => H2O + CO2 + 2HN3

Also one can remember that such processes are very common, and will perfectly work for example with aminoguanidine (witch is structualy similar to semicarbazide):

1. NH2-C(=NH)-NH-NH2 + HNO2 => NH2-C(=NH)-N3 + 2H2O (formation of guanylazide).
2. NH2-C(=NH)-N3 + NaOH => NH2-CO-NH2 + NaN3

One also can use very known lab method for azides with hydrazine and very easy to make organic nitrites such as butyl or isopropylnitrites:

1. C4H9OH + HNO2 => C4H9NO2 + H2O
2. C4H9NO2 + N2H4 => C4H9N3 + 2H2O (in basic media this intermediate momentaly hydrolizes to azide).
3. C4H9N3 + KOH => C4H9OH + KN3.

Process is caried out by heating alcoholic alkali solution with butylnitrite ant hydrazine, since azide formed is insoluble in this media it separates as solid precipitate. I can give exact procedure for this method.

References:

1. Azide from butylnitrite (prep of butylnitrite also given):

Attachment: KN3 From Butylnitrite.pdf (494kB)
This file has been downloaded 2151 times

2. Silver azide from AgNO3, NaNO2 and hydrazine sulphate, NaN3 from AgN3 in second patent:

Attachment: GB128014 (Hodgison silver azide from hydrazine).pdf (184kB)
This file has been downloaded 1219 times

Attachment: GB129152 (Improvements relating to production of Azides).pdf (184kB)
This file has been downloaded 1090 times

3. Carbonylhydrazide and carbonylazide:

Attachment: Curtius - Hydrazine und Azide Organicher Sauren.pdf (372kB)
This file has been downloaded 1272 times

Attachment: Curtius - Stickstoffekohlenoxide.pdf (83kB)
This file has been downloaded 1064 times

Guanylazide and Carbonylazide (Beil).jpg - 412kB

4. Azides by oxidation of hydrazine.

Attachment: Azides by oxydation of hydrazine.pdf (604kB)
This file has been downloaded 1070 times


[Edited on 16-9-2010 by Engager]

Rosco Bodine - 16-9-2010 at 15:46

I was unable to confirm Hodgkinsons route to silver azide by my own experiments the reaction simply would not work for me. I did produce sodium azide by freebasing hydrazine into methanolic sodium hydroxide and nitrosating with several different organic nitrites. The semicarbazide route I did not try but it is interesting since semicarbazide can be gotten different ways, including reaction of hydrazine sulfate sodium carbonate and potassium cyanate. See attached article.
Semicarbazide also has interest as a perchlorate and as a possible nickel semicarbazide complex nitrate or perchlorate analogous with the better known nickel hydrazine complex.

Anyway, it may well be that the Hodgkinson synthetic route does indeed work for Silver Azide and I was simply never able to get the reaction to cooperate for not having the specific conditions of pH exactly right. It seems curious however that the route should only work for Silver Azide as the product, being peculiar in that specificity in the same way as fulminate formation is peculiar to only Silver and Mercury.

Do you know if the Hodgkinson route has been attempted via the reaction with Calcium Nitrite in some pH controlled reaction as I have speculated may be possible, finding that reaction fails ? My thinking was a hope the precipitation of the undesired byproduct Calcium Sulfate would tend to drive the reaction in the same direction as occurs for Silver Azide, only different in regards to the reversal of which product is precipitated and which product should remain in solution. In terms of the reaction kinetics it would seem like it should work.

Also do you know if anyone has tried to condense Curtius's "carbazide" with formaldehyde ?

Attachment: Semicarbazide via hydrazine sulfate and alkali cyanate gattermann.pdf (104kB)
This file has been downloaded 1072 times


[Edited on 17-9-2010 by Rosco Bodine]

of possible interest are Glauberite and Carbamoyl Azide

Rosco Bodine - 25-8-2011 at 19:06

@chemoleo & @Engager

With regards to the double decomposition of hydrazine sulfate and conversion to nitrate or other soluble hydrazine salt, and precipitation of sulfate as a calcium value, the
anhydrous double salt of calcium and sodium CaNa2(SO4)2
generically called Glauberite may have some interest. I can find no solubility data for the double salt, for comparison with
CaSO4 - 2H2O solubility, but would think by inference from the attached patent US1343443 that it would be less soluble than CaSO4 by virtue of the double salt's precipitation being driven by CaSO4 which would therefore logically seem to be more soluble. This would seem to indicate for example that
probably a remnant supernatant solution of 2 moles of hydrazine nitrate would form above a crystalline precipitate of Glauberite, resultant from a mixing in solution of 2 moles Hydrazine Sulfate, 2 moles Sodium Hydroxide (or 2 moles Sodium Bicarbonate, or 1 mole Sodium Carbonate possibly may work as well), and 1 mole Calcium Nitrate. Alternately the Calcium Nitrate could be derived in situ from substitution of a reaction mixture of 2 moles Ammonium Nitrate with 2 moles NaOH and 1 mole Ca(OH)2, 2 moles of byproduct ammonia being evolved for some collateral use if desired.

The reaction may possibly also proceed from simply digesting a mixture of 2 moles of Hydrazine Sulfate, 2 moles of Sodium Nitrate, and 1 mole of Calcium Hydroxide Ca(OH)2 at ordinary temperature with mixing for an extended time.

@chemoleo With regards to the reaction of nitrous acid with semicarbazide mentioned by Engager above, attached also is an article which may be informative, but is a German language article, which you should be better able to understand and possibly help with translation.

There is more discussion and references for the carbamoyl azide in the thread specific to Azides
http://www.sciencemadness.org/talk/viewthread.php?tid=1987&a...

Attachment: US1343443 Glauberite_CaSO4 - Na2SO4 double salt.pdf (103kB)
This file has been downloaded 1022 times

Attachment: Die Zersetaung dos Carbarninslureadds NH,CO. N8 fir sioh nnd in aromatisohen Kohlenwasserstoffen.pdf (958kB)
This file has been downloaded 1304 times

[Edited on 26-8-2011 by Rosco Bodine]

AndersHoveland - 26-5-2012 at 11:45

Quote: Originally posted by Engager  

Hydrazine dinitrate (N2H4*2HNO3): Solid which melts at 104 °C when fast heated. As dibasic salt it is much more unstable then mononitrate. Then heated slowly, approximately at 80 °C it begins to decompose without melt, forming hydrogen azide along with other products. Even in dessicator with H2SO4 drying is accompanied by formation of HN3, residue consists of hydrazine mononitrate and ammonium nitrate. Good soluble in water, but solutions containing more than 30% of salt decompose on heating. More powerful explosive then Tetryl but less powerful then PETN.


Hydrazinium di-nitrate has a detonation velocity only around 400-600 m/sec lower than the mono-nitrate. Hydrazine mono-salts are not very good bases, so the di-nitrate hydrolyses in water (the sulfate is only stable in water because of the very low solubility). To add the second nitrate ion, nitric acid dissolved in alcohol, without any water, needs to be used. Such a solution could be prepared by slowly dripping anhydrous nitric acid into a large excess of pure alcohol (if there is not enough alcohol, or the alcohol is added too fast, there could be a reaction with brown fumes).

Perhaps the di-nitrate off dimethylhydrazine could be made, to improve oxygen balance? It would probably be more energetic than mixtures of hydrazine nitrate with hydrazine.

hydrazinium nitrate NH2NH3[+] NO3[-]
detonation velocity: 8690m/s
density: 1.60g/cm3
melting point: 63 °C

hydrazinium dinitrate [+]NH3NH3[+] NO3[-] NO3[-]
The dinitrate of hydrazine, N2H6(NO3)2 , has an even higher melting point (80 °C) than the mononitrate, and is more easily detonated than is the mononitrate, although it has a slightly lower detonation velocity.
I actually read the exact detonation velocity many years ago in a publication, but unfortunately cannot now find the exact figure or any references.

More information about hydrazinium di-perchlorate:
Quote:

Not only is the monoperchlorate much less energetic as an oxidizer than the hydrazinium diperchlorate, but it is much more sensitive to detonation by shock than the diperchlorate.

Preparation of hydrazinium diperchlorate using sodium perchlorate and hydrazinium dichloride In a reaction vessel equipped with stirring means, a cooling device and inlets for supplying nitrogen and liquid hydrogen fluoride, the following reactants are added; a pulverized and intimately admixed mixture of 2.45 parts by weight of anhydrous sodium perchlorate and 1.05 parts by weight of hydrazinium. dichloride. The mixture is chilled to -80 °C., purged with a nitrogen atmosphere, evacuated and 9.88 parts by weight of anhydrous liquid hydrogen fluoride is added to the reaction mixture. The system is brought back to atmospheric pressure by reintroducing nitrogen to the system and the reaction is initiated by allowing the reaction mixture to warm to room temperature. The solvolysis of the hydrazinium dichloride to the fluoride salt is evidenced by the evolution of bubbles of hydrogen chloride gas. The hydrogen fluoride suspension is stirred vigorously for 5 hours and allowed to settle. The insoluble fraction is hydrazinium. diperchlorate and the soluble fraction is principally sodium fluoride, which has a solubility in hydrogen fluoride.

Preparation of hydrazinium diperchlorate using potassium perchlorate and hydrazinium dibromide as reactants. In this example the same equipment and procedure is followed as described in before, except that 2.77 parts by weight of anhydrous potassium perchlorate, 1.94 parts by weight of hydrazinium dibromide and 10.65 parts by weight of anhydrous liquid hydrogen fluoride are used as reactants.

US 317459210 (1973)



As a side point of interest, hydrazine can also exist as a anion, in addition to its normal salts.
Quote:

Sodium hydrazide
Sodium hydrazide NaN2H3 is a pale yellow crystalline compound which is pyrophoric and can explode on exposure to air, and explodes violently when heated above 100 °C. It can be produced by gradually addition of drops of hydrazine hydrate into a suspension of sodium in ether, then heating in the absence of oxygen. Otherwise hydrazine reacts very vigorously with sodium metal, producing only hydrogen and ammonia. For the reaction between sodium amide and anhydrous hydrazine, it was found necessary to use the sodium amide in finely divided form, as otherwise it will react only very slowly with the hydrazine because a protective coating of the sodium hydrazide forms on the surface.


hydroxylammonium nitrate melts at 48 °C, and has been investigated as an alternative oxidizer for solid rocket propellents, although its performance is lower.
HONH3[+] NO3[-]

hydroxylamine perchlorate, hygroscopic solid
melting point between 87.5 and 89 °C. Decomposes at 120 °C.
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.

[Edited on 26-5-2012 by AndersHoveland]

Ral123 - 20-7-2012 at 20:18

Sorry for kicking that topic but I can't find information. Is hydrazine detonatable. H2O2 certainly is and hydrazine is more energetic. I'm almost sure it is, but with what critical diameter? And how about the methyl hydrazines?

Kalium - 20-7-2012 at 23:38

Quote: Originally posted by Ral123  
Sorry for kicking that topic but I can't find information. Is hydrazine detonatable. H2O2 certainly is and hydrazine is more energetic. I'm almost sure it is, but with what critical diameter? And how about the methyl hydrazines?

I found a paper titled "Combustion and detonation characteristics of hydrazine and its methyl derivatives". Sounds about right. :cool: I had to use my university's database to access it because the website wants people to buy it for 35 Euro. I tried copying some of it here but Adobe Acrobat did a shitty job OCR job so the pasted stuff was almost unreadable.

Attachment: Combustion and detonation characteristics of hydrazine and its methyl derivatives.pdf (1.2MB)
This file has been downloaded 1105 times

Ral123 - 30-4-2013 at 22:58

I have some hydrazine hydrate. Can you recommend a convenient process to make nitrate. I have high purity AN and HNO3. If it can't be anhydrous, I should know how much water's in it, so I declare it. I'm going to a remote place, where the toxicity won't be such a hazard. If I succeed, I'll post a sweet detonation test.

VladimirLem - 1-11-2013 at 10:16

Hi

im very interested in hydrazin nitrate and searched the shit out of google, does anyone have a synthesis of it?
just pooring some hydrazine into ?-% HNO3 or is it more difficult^^

btw: is there a way, that im not getting Di-nitrate "impurities"?....the Di-nitrate seems much more risky than the mono nitrate :(



Dany - 1-11-2013 at 10:43

Here's an article which explain the method for the formation of the mono and dinitrate salts of hydrazine. (the mono-nitrate hydrazine is called Astrolite A). Actually This article is on thermal decomposition of hydrazinium nitrate salts.

Dany.

Attachment: Vacuum Thermal Decompositions of the Nitrate Salts of Hydrazine.pdf (203kB)
This file has been downloaded 1325 times