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Author: Subject: Preparation of Hydrazine Sulfate (Hofmann Degradation)
PHILOU Zrealone
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[*] posted on 27-4-2015 at 04:42


Quote: Originally posted by Hawkguy  
Okay so after doing this a few times, I noticed that the yields are low, as warned. Is it possible to distill Hydrazine out of the solution (After boiling off water) after the neutralization with Hydrochloric Acid? Or will Hydrazine Hydrochlorides have been formed after the HCl addition, making it difficult to distill?

Hydrazine distillation is bad news...
-risk of fire (or explosion) due to the endothermic nature of N2H4
-corrosive to glass...will ruin your distillation setup

HCl addition will indeed form N2H4.HCl what is non volatile...and this might be good for concentration by evaporation.

Note that HCl will not displace the H2SO4 if you start from N2H4.H2SO4!




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[*] posted on 20-7-2015 at 11:00


I'm preparing to make some hydrazine sulfate.

To do this I bought a fresh gallon of 13.5% swimming pool grade aqueous NaOCl, "Hasachlor" brand. I bought this about 1 month ago. Knowing it can lose strength, especially in the summer heat, I titrated a sample with 3.96M sodium thiosulfate. I had made up this thio 7 years ago and stored it in an amber bottle with a ptfe seal (Qorpak, 125ml, wide-mouth). The NaOCl strength was found to be a disappointing 8.5%.

To check the concentration of my thio I titrated it against some 0.165M Cu(NO3)2 made with copper wire, also 7 years ago. The result indicated 0.169M Cu(NO3)2. This verified my thio. This amazed me.

[Edited on 20-7-2015 by Magpie]

[Edited on 20-7-2015 by Magpie]

[Edited on 20-7-2015 by Magpie]




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[*] posted on 23-7-2015 at 19:31


Here's pictures of the hydrazine sulfate I made yesterday. The pictures show the product before and after an all day air dry. The yield was 39.8g for a %yield of 55.6% based on NaOCl.

I made another batch today and still need to make one more. It was 90°F in the lab today and I'm worn out so will take tomorrow off.

HS batch 1 before drying.jpg - 85kB HS batch 1 after drying.jpg - 67kB




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[*] posted on 16-10-2015 at 16:10


Sorry to revive this old thread...

Could someone offer some advice on the disposal of hydrazine salt solutions? Would nitrous acid solve the problem by first forming hydrogen azide and then reacting with it?




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[*] posted on 17-10-2015 at 04:13


Quote: Originally posted by subsecret  
Sorry to revive this old thread...

Could someone offer some advice on the disposal of hydrazine salt solutions? Would nitrous acid solve the problem by first forming hydrogen azide and then reacting with it?


Make them alkaline to produce free hydrazine and add bleach. Nitrogen gas will form copiously.
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[*] posted on 18-12-2015 at 22:52


Well I just have to say thanks for posting a smaller scale procedure and your results of it. I have been wanting to perform this synthesis for a while now and after considering how expensive hydrazine sulfate is vs the cost of components to make it, I carried out this synthesis last night with pleasing results. Following this synthesis to a T except for having 12.5% pool hypochlorite and adjusting the other reagents accordingly got me a yield of 48.97g of crispy Snow White hydrazine sulfate crystals. The whole process went off without any problems at all and was well under control except briefly when my flask foamed up s little during the neutralisation with HCl. Otherwise perfect.

[Edited on 19-12-2015 by NeonPulse]

image.jpeg - 1.5MB




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[*] posted on 19-12-2015 at 09:37


That's a great yield - nice going.



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[*] posted on 6-1-2016 at 21:54


After seeing a patent advertizing a >80% yield earlier, i can just imagine the US patent show where they come up with this shit. "For my next trick, I will pull an entire patent for Hydrazine Sulfate.... Out of my ass."
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[*] posted on 23-4-2016 at 19:00


How does one test for hydrazine with out silver or much of any thing ells?
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[*] posted on 23-4-2016 at 20:40


hydrazine can make a copper mirror. I am yet to try it but it seems like as good a test as any.



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[*] posted on 23-4-2016 at 21:18


ya but I'd need a copper compound, less I can use bare copper! so far 10 grams did not fully dissolve fully in 100g of distilled water. very nice free flowing crystals.

Basically I wasn't planning to make any such thing, but got bored and you-tube inspired, so now just need to test it!

Hydrazine sulfate.jpg - 132kB

[Edited on 24-4-2016 by XeonTheMGPony]
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[*] posted on 24-4-2016 at 00:10


Copper sulfate would be the go-to for this one. But I think any Cu(II) salt would do. Copper wire and nitric acid or even vinegar will get you on your way.

That said, I am, to quote chemplayer, a hydrazine virgin. There are others around whose advice is likely to be a lot better than mine.




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[*] posted on 24-4-2016 at 04:11


Quote: Originally posted by XeonTheMGPony  
ya but I'd need a copper compound, less I can use bare copper! so far 10 grams did not fully dissolve fully in 100g of distilled water. very nice free flowing crystals.

Basically I wasn't planning to make any such thing, but got bored and you-tube inspired, so now just need to test it!



[Edited on 24-4-2016 by XeonTheMGPony]

Take an aliquot (20 mg or so) of your batch of N2H6SO4 in a test tube, dissolve into 1ml of demineralized water, add some soluble copper (II) salt (also about 20 mg) dissolved into demin water too...allow it to fall drop by drop into the test tube.
Blue CuSO4, blue Cu(NO3)2 or green CuCl2 will expell N2 bubbles, the solution will turn black, brown with a spongy precipitate of solid Cu or Cu2O.

Ammonium salts (sulfate, nitrate or chloride) will not give any precipitate nor bubbling.

Do it on an aliquot of your batch and not on all your batch since Cu(2+) and other metals do have a catalytic effect on the decomposition of hydrazine...so a minute amount may ruin a big deal of your batch gained after some intensive labour.

I would test it on a smarter way via mild basification with NaOH or Ca(OH)2 saturated solution (the later will precipitate some CaSO4 so filtrate).
N2H6SO4 + NaOH --> N2H4 + NaHSO4 + H2O
N2H6SO4 + 2NaOH --> N2H4 + Na2SO4 + 2H2O
N2H6SO4 + Ca(OH)2 --> N2H4 + CaSO4(s) + 2H2O

Then introduction drop by drop of green solution of Ni(NO3)2 or of red solution of Co(NO3)2.
The first will give a blue colored precipitate that upon agitation turns pink lilac; the second one will give a peach-light brown precipitate.
Ni(NO3)2 + 3 N2H4 --> Ni(N2H4)3(NO3)2 (pink clay like precipitate)
Co(NO3)2 + 3 N2H4 --> Co(N2H4)3(NO3)2 (light peach-brown clay like precipitate)
Both precipitate are safe energetic materials...once dry they burn when exposed to a naked flame like black powder in the open, but detonate when in large quantity (self confinement) or in minute quantity when confined into aluminium wrapping foil.

Beware 50 mg wrapped into several layers of Al foil and trown in a camp fire will make after a few seconds delay a 20-40 cm diameter fireball with a loud report and will spray burning wood/charcoal meters away!

[Edited on 24-4-2016 by PHILOU Zrealone]




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[*] posted on 24-4-2016 at 06:25


That's what I figured, need to go and pick up some copper sulfate. I was planing to stock up on that sort of stuff befor making it but like I say sever boredom (Crappy weather) + you tube and I happened to have the supplies for the synth, must say it went flawlessly.

I used chem players vid, divided the measures in half, Kept every thing well chilled during the mixing stages.

once the first half of the reaction was don I proceeded to the hot stage. putting the 500Ml beaker into a large water bath that was prewarmed, I slowly nudged it to 85c, once it hit 80c I started the count down to 5 minutes.

After as per instructions I set it aside to cool slowly, once just warm to the touch I put it in the fridge till cold (At this point my 50/50 water to sulfuric acid had been in the freezer for an hour.

I put the 500Ml beaker into an ice bath and started the finale stage of adding in the dilute acid to the mother liqueur to precipitate out the hydrozine.

Once the neutralization had finished for the basses the Hydrozine sulfate immediately started to fall out as sulfate with each drop! Was perfect run.

[Edited on 24-4-2016 by XeonTheMGPony]
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[*] posted on 25-4-2016 at 20:44


Well they only sell copper sulfate by the 20 pound pail here so I made some, and after that was don I tested it, and I do indeed have Hydrazine sulfate! Copper precipitated out second the drop mixed!

I am still drying the crystals so not sure of exact yield will report weight once fully dried

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