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Author: Subject: Hydrazine
Rosco Bodine
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[*] posted on 28-3-2013 at 23:00
catalytic use for manganese sulfate


Several related threads are involved with these references I am adding lately.

Related thread easier methods for Biurea / Hydrazodicarbonamide

http://www.sciencemadness.org/talk/viewthread.php?tid=6729&a...

Related thread Azides

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

US2692281 Biurea from hydrazine sulfate and urea

US3227753 Biurea or Hydrazine from Hypochlorite and Urea

Attachment: US2692281 Hydrazodicarbonamide from Hydrazine sulfate and Urea.pdf (76kB)
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Attachment: US3227753 Biurea (Hydrazodicarbonamide).pdf (254kB)
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[Edited on 29-3-2013 by Rosco Bodine]
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plante1999
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[*] posted on 4-4-2013 at 11:42


Does anyone have some hydrazine salt/hydrazine to trade for something here? I simply don't have easy access to NaOH or ammonia, I got one to urea and hypochlorite, and the synth is not fun anyway.

Gallium
Hexachloroethane
cobalt oxide
sodium cyanide
lead metal
lead acetate
Lead IV oxide
Anhydrous aluminium chloride
Silicon tetrachloride
Anhydrous iron III chloride
nickel metal
silver nitrate

If yes I can be contacted by email at hclo3@hotmail.com or by U2Us.

Thanks!




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[*] posted on 4-4-2013 at 13:20


Quote: Originally posted by plante1999  
Does anyone have some hydrazine salt/hydrazine to trade for something here? I simply don't have easy access to NaOH or ammonia, I got one to urea and hypochlorite, and the synth is not fun anyway.

Gallium
Hexachloroethane
cobalt oxide
sodium cyanide
lead metal
lead acetate
Lead IV oxide
Anhydrous aluminium chloride
Silicon tetrachloride
Anhydrous iron III chloride
nickel metal
silver nitrate

If yes I can be contacted by email at hclo3@hotmail.com or by U2Us.

Thanks!

Are you sure you cannot get ammonia or NaOH anywhere? This is very strange given the fact that eBay and other places sell these things so readily... What kind of hardware stores do you have where you live? I'm not sure if hydrazine would be able to be sent through regular mail either ... :S
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[*] posted on 4-4-2013 at 13:51


Yes they do ship, but I would need like 5Kg to have a good ratio for the shipping, and my local hardware store don't carry NaOH (they carry CuSO4 tough). I will keep a 500g bottle of it for when I really need it.

Well, I guess it can be neutralised...





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[*] posted on 22-7-2013 at 15:36


While rummaging through some old Berichte der Deutsch Chem. Gesellschaft on line I came across this interesting little paper. Its in German so I have a done a quick translation of it. It basically concerns the preparation of hydrous hydrazine from hydrazine hydrate using calcium oxide. The paper also has references to a couple of other methods which I'll dig out if anyone is interested though they may already have been posted before.



Attachment: Berichte Stahler hydrazine 1909.rar (923kB)
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Attachment: Action of CaO on Hydrazine Hydrate Ber. D. Chem. A Stahler 1909.docx (17kB)
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I would add a few comments to this translation.
1-I would flush the equipment with an inert gas, in this case natural gas (methane) is probably the most convenient for most people.
2-Run the thermal decomposition under reduced pressure to reduce decomposition. (water pump pressure)
3-The quantity of calcium oxide seems excessive unless the hydrate is fairly dilute. With >85% hydrate 350g of good commercial 95% CaO should be sufficient.
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[*] posted on 17-11-2013 at 05:20


I have lots of Urea, and not much Ammonia. Do you think it would be easier for me to do the Hoffmann rearrangement instead of Nurdrage's method? PS. I have all of the chemicals and equipment needed for both methods. Also, I will use UC235's method if I go with the Hoffmann rearrangement.



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[*] posted on 25-12-2013 at 11:19


An initial search of this thread didn't show this site so thought I would throw it in here for Hydrazine

Hydrazine Production - Lookchem.com




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[*] posted on 19-7-2014 at 09:17


Quote: Originally posted by Vargouille  
Has anyone tried the Peroxide Process?

I found a US patent claiming a 86.74% yield with proportions of H2O2:MEK:NH3 of 1:2:3.43, with a "working solution" comprised of three parts acetamide, 1.8 parts ammonium acetate, 0.033 g Na2HPO4, and 1.77 g EDTA, disodium salt (1 part representing 0.35 moles in the example given). It may be significant that the ammonia was gaseous, and H2O2 was 69.27%, although it says that aqueous ammonia and 30% H2O2 are acceptable. Ullmann's says that some sort of catalyst is required, though, or else the reaction will be too slow.


I recently read a patent (see http://www.google.com/patents/WO2003068369A1?cl=en ) that used singlet oxygen (formed from exposing O2 to an electrically formed corona, and for more details on singlet oxygen, please see my recent thread at http://www.sciencemadness.org/talk/viewthread.php?tid=31729#... ) as a means to process polluting exhaust gases. Apparently, SO2 in water vapor is converted to H2SO4, which is then scrubbed with Ca(OH)2 to CaSO4. HCN is broken down into less toxic gases, H2S and water to H2SO4 as well, but interestingly, no mention of the action of singlet oxygen on ammonia. I suspect, in the presence of excess NH3, a possible reaction product with singlet oxygen to be:

4 NH3 + O2* --?--) 2 N2H4 + 2 H2O

which would not be desirable for an invention that reputedly controls toxic emmissions, but in line with the Peroxide process cited above by Vargouille.

Note, water is to be avoided (so no aqueous ammonia) as it is a quenching agent for singlet oxygen (forming H2O2, and with water vapor, more likely, very concentrated H2O2, paralleling the preparation cited above). Also interestingly, the Peroxide Process mentions the employment of Ammonium acetate, which per my research, is cited as a H+ absorbent allowing the formation of singlet oxygen with non-basic H2O2. As such, when I attempt the above reaction, I will perform a run with ammonium acetate as well.
--------------------------------------------

For those looking to a simple, but still speculative, small scale synthesis of N2H4, here is possibly something of note. First, it is known that the photolysis of solid (cold) ammonia proceeds (see for example a recent article in "THE JOURNAL OF CHEMICAL PHYSICS ", 133,214506(2010), "Photolysis of solid NH3 and NH3–H2O mixtures at 193nm", by M.J.Loeffler and R.A. Baragiol, link: http://gsfcir.gsfc.nasa.gov/authors/publication/17876/ ), with the formation of radical (X) species:

NH3 + uv ----) NH2(X) + H (X)
NH2(X) + NH2(X) ---) N2H4

which is not practical for the most part (frozen NH3). However, one can absorb NH3 on MgCl2 forming MgCl2(NH3)6. Place the latter in a transparent sealed tube, permitting uv treatment, and a little heat to expell the now highly pressurized ammonia while applying uv light. In essence, simulating the action of uv light on condensed ammonia.

Also, there is another possible path to N2H4 with ammonia in the presence of water vapor that has been fragmented by uv radiation (see, for example, "Ammonia Photolysis and the Greenhouse Effect in the Primordial Atmosphere of the Earth", by W. R. KUHN AND S. K. ATREYA, link: https://www.google.com/url?sa=t&source=web&rct=j&... ):

NH3 + OH(X) ---) NH2(X) + H2O
NH2(X) + NH2(X) ---) N2H4

Note, per this article, "Effect of Nonequilibrium Excitation on the Ignition of Combustible Mixtures", by N.A. Popov at Skobel’tsyn Institute of Nuclear Physics, Moscow State University, link: http://www.researchgate.net/publication/257390643_Effect_of_... to quote from page 4:

"Indeed, NH2 radicals formed as a result of UV photolysis of ammonia hardly react with O2 and H2 molecules. However, a fairly fast reaction of NH2 with O(3P) atoms may occur, which causes the emergence of additional channels of production of hydrogen radicals H and OH, as well as nitrogen oxides [26],
NH2 + O → NH + OH; NH2 + O → HNO + H;
NH + O2 → NO + OH; NH + O2 → NO2 + H. "

where the author notes on page 2, with respect to the creation of O(3P), to quote:

"The absorption of radiation by oxygen molecules in the Schumann-Runge continuum region is accompanied by O2 dissociation and excited O(1D) atoms production [22],

O2(X3Σ−g) + h ω → O(3P) + O(1D) "

As such, it is probably best to remove all O2 by flooding with NH3.

I do expect some interesting experiments.

[Edited on 20-7-2014 by AJKOER]
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[*] posted on 7-8-2014 at 14:52


Is it possible to make Sodium/Lead Azide with Hydrazine sulfate? I don't want to work with hydrazine hydrate and would largely prefer to work with the sulfate salt.
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[*] posted on 29-12-2014 at 18:40


So I have a free-basing question.

I'm trying to make NHN (well the cobalt analogue) so I can't freebase the hydrazine from the sulfate with sodium hydroxide, as despite my best efforts some sodium hydroxide ends up in the solution, dropping Cobalt Hydroxide instead of the wanted CoHN complex.

I've seen vague murmurs of using calcium hydroxide to freebase in the 'Exotic Primaries' thread but how does this work? Calcium sulfate has a lower solubility in both alcohol and water, so how does that precipitation reaction work (assuming it's driven by drop in solubility of the products?)

CaOH + N2H4.SO4 --> N2H4.OH + CaSO4 ??

If not, how do I freebase without precipitating metal hydroxides later on in hydrazine complex salt synths?

Thanks

Edit: Or does this proceed more as an acid/base reaction, in which case the solubilities don't matter?

[Edited on 30-12-2014 by Tdep]
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thumbup.gif posted on 12-1-2015 at 19:19


Hydrazine... Dealt with that when I worked at a generating plant. Smelled awful... Like ammonia.
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[*] posted on 12-1-2015 at 20:17


Quote: Originally posted by Kavion123  
Hydrazine... Dealt with that when I worked at a generating plant. Smelled awful... Like ammonia.


Dude thats not really diddly doodly dandy, the stuff is pretty damn bad. Were you wearing protection?
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[*] posted on 12-1-2015 at 20:34


Quote: Originally posted by Hawkguy  

Dude thats not really diddly doodly dandy, the stuff is pretty damn bad. Were you wearing protection?


Just goggles and gloves. I only worked there for a few months before being hired by Bayer CropScience. I got to inhale a bunch of pesticides, herbicides, and fungicides there!
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[*] posted on 14-5-2015 at 20:56


How can I test for Hydrazine Hydrate in solution, without Silver Nitrate? I just distilled some stuff at just over a hundred degrees and it has a particular smell. Wanna see if its the stuff, because the Hydrazine Sulfate I started with was collected after a messy explosion...
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[*] posted on 7-7-2015 at 10:25


COPPER IS EVIL! Cu2+

Just for your info:

I redid this experiment --- the Nurdrage method : mix 2-butanone and ammonia solution. Then drip NaClO slowly.
The glassware in which I had my NaClO was contaminated by a copper compound.

My yield was 0%.
Definitely, the presents of Cu2+ messes it up.
------------------------
From
http://www.lookchem.com/Chempedia/Chemical-Technology/Inorga...

2 NH2Cl + N2H4 → N2 + 2 NH4Cl
This reaction is particularly catalyzed by copper. A large excess of ammonia and the addition of complexing agents such as ethylenediaminetetra-acetic acid (EDTA) are used as countermeasures.





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[*] posted on 27-7-2015 at 04:30


Quote: Originally posted by chemoleo  
Yes, and when I added H2SO4, besides all the gases it produced, the smell it produced didnt seem healthy, thats why I kept it under the fume cupboard at all times. the smell was rather asphyxicating that is. Kind of not painful, but pleasant either.
[Edited on 3-12-2003 by chemoleo]



Please tell me if I am mistaken, but I thought reacting NaOCl and NH3 would produce chloramine, a pungent white/greenish gas,( is that the purpose adding of glue/gelatin/EDTA so ammonia re-reacts with chloramines)?. The description appears to describe the properties of this gas or other by-products. What is the best agent to use to increase surface tension(could the reaction be taken out in a sealed container). Is an excess of ammonia is required to produce hydrazine ?

Thank you. :)


[Edited on 27-7-2015 by AWLB]
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[*] posted on 27-7-2015 at 08:54


I have used the chloramine process and the Hofmann degradation process to produce hydrazine. This is then converted to the hydrazine sulfate (HS) for convenient storage as a crystalline solid.

I prefer the Hofmann degradation process. I provided a procedure for same in the Prepublication section of this forum. The gelatine (or EDTA) is used to complex heavy metals such as Cu++ as they catalyze decomposition of hydrazine.

I just finished making 3 batches of HS. The first two gave 56% yield and the last, 48%. The yield is very sensitive to temperature control thoughout the multi-step procedure.

Len1 (Leonid Lerner) gives a thorough description of the Hofmann degradation process in his book. He claims to get a 62% yield but his batch is about 2X that of mine (38g). Rosco claims about 60% making a large batch, IIRC.

I have a good fume hood so don't get exposed to the hydrazine fumes. Occaisionally I will accidently get a small whiff before turning on the fan. It has an unpleasant, but not strong, amine (rotten fish) smell.

Hope this helps.

[Edited on 27-7-2015 by Magpie]




The single most important condition for a successful synthesis is good mixing - Nicodem
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[*] posted on 3-8-2015 at 21:07


Quote: Originally posted by AWLB  
What is the best agent to use to increase surface tension(could the reaction be taken out in a sealed container)

If you are talking about increasing the surface tension to reduce the prodigous foaming of the reaction, silicon oil has been suggested in the past as an agent to reduce foaming. I have no idea if that is effective, but in either case you are probably just better off attaching an enormous funnel to the top of your reaction flask to contain the excess foam.
With regards to conducting the reaction in a sealed container, the answer is basically no. The gas produced is nitrogen formed from the decomposition of hydrazine, and would rapidly build up pressure and rupture all but the strongest of vessels.
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[*] posted on 4-8-2015 at 08:26


Using the Hofmann degradation process at the 36g batch size I have no foaming problem. I use a 1L suction flask and the foam came up to the following marks for the last 3 batches: 900ml, 900ml, and 1000ml. Therefore, the funnel I had in place was not even needed.

I use gelatine, which is easy and cheap to get at the grocery store. I understand that the viscosity it builds helps reduce the amount of foam produced as well as sequestering the heavy metals.




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sad.gif posted on 15-8-2015 at 04:46
Methyl Isobutyl Ketone


I've tried making Hydrazine Sulfate using Methyl Isobutyl Ketone with freshly prepared concentrated ammonia solution made with ammonium bicarbonate and gelatin, i either used 6% hypochlorite solution or 6% hydrogen peroxide solution (in different experiements) but i couldn't get a sufficient amount to crystalize.
Does anyone know how i can improve the yield?

I've even tried heating it up to 85C for about an hour refluxing but i still barely get any crystals to come out of the solution even when i put it for hours in the freezer :(
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[*] posted on 17-8-2015 at 07:28


Hi,
I tried Hofmann degradation with MEK, but I think I screwed up, I added the MEK too early and left it overnight. It separated, I added H2SO4 to the organic layer and distilled off the MEK azeotrope (it came through at 72-75*C). BUT the aqueous layer got dark red/brown, and the organic layer got that color when I started distilling. Of course no HS precipitated. Now for the most important question- how can I safely neutralize it and dispose it? I think there have been some aldol condensation, and I hope there wasn't any halohydrin produced from the aldol... I was working in fume hood (and I used gas mask when needed)
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[*] posted on 18-8-2015 at 20:58


Can the version with MEK, bleach, and ammonia be done with ammonia that just has surfactants? I've been looking for some without for months, and am just about ready to buy some online, but I wanted to check here first.
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[*] posted on 18-8-2015 at 22:53


Quote: Originally posted by DFliyerz  
Can the version with MEK, bleach, and ammonia be done with ammonia that just has surfactants? I've been looking for some without for months, and am just about ready to buy some online, but I wanted to check here first.

The reaction foams quite a lot even without surfactants. Don't be surprised if you end up with an enormous and unmanageable quantity of foam.
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[*] posted on 19-8-2015 at 02:26


Quote: Originally posted by Oscilllator  

The reaction foams quite a lot even without surfactants. Don't be surprised if you end up with an enormous and unmanageable quantity of foam.


I once tried to do a hypochlorite/urea run on a 6L scale with household bleach (read- surfacants). Pretty sure a horror movie could be made about the 20L or so of foam that seeked to swallow me whole before I shut it off. Give it a shot, but try to find a method of stirring that will keep the foam down, and not encourage it
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[*] posted on 30-8-2015 at 05:12


Hi,
Have anyone tried using acetone to get hydrazine and know what we are aiming to, azine OR hydrazone? I have a recipe in a book where they are using acetone and they say you get hydrazone of acetone, and they are retrieving it as fraction distilling at 93-107 *C. How good would extraction with toluene be? How big should be portions of toluene for a run at about 0.5 mole of reagents? Would 5-6 extractions with 15-20 cm^3 of toluene be enough?
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