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S.C. Wack
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BTW none of that applies to Name Brand 7.5% hypochlorite.
Now 90% of all the bleach bottles in the store are "low splash" and/or scented. Perhaps the remainder on the bottom shelf are old stock which will be
replaced with the modern, advanced, state of the art (i.e. shit) merchandise that everyone is clamoring for (how many times a day do you hear people
complain about bleach not being syrupy).
"Cloromax technology" (no, really) results in the Mn not decolorizing or precipitating, a persistent haze, and a different precipitation of the
sulfate. Perhaps this bleach has the same additive as the "low splash" product, just less of it. When combined with Dr. Thönnessen's amounts above,
the yield is 61%, and the product is inferior to the cheap hypochlorite sulfate.
Repeating without any additive (other than Thönnessen's 50% excess of NaOH and whatever secret ingredient is in the bleach) gave a clear colorless
liquid in which the haze did not appear until at the neutral point. This time, the magnetic stirring was continued as the conc. portion of the acid
was slowly added dropwise. The resulting first crop sulfate was the dull uniform fine powder of earlier stirring trials, yet this material was of
quite good purity. Unfortunately, 22% of the total was in the second crop, which had much more Na (and no organic residue) in it. There was none of
the gas which always evolved from the sulfate in contact with the mother liquor when using Mn. 64.6%.
Sodium bisulfate would have been tested if I or the stores had the prill in stock.
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S.C. Wack
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Lobry de Bruyn wrote in 1895-6 of adding barium chloride to hydrazine sulfate to form the dihydrochloride (insoluble in methanol), which is heated to
form the monohydrochloride, which is dissolved in methanol and basified with sodium methoxide, or barium bromide is added to the sulfate, followed by
KOH with the KBr precipitating with alcohol, or the sulfate is basified with KOH or NaOH, and the alkali sulfate is precipitated with alcohol. (Adams
and Marvel write in 1921 that this last method gives 50% hydrate in 50-60% yield after vacuum distillation) He also makes anhydrous hydrazine from the
"hydrate" with BaO.
Given all of that, it's striking that the professor did not mention basifying in part with barium hydroxide and in part with NaOH, followed by
precipitation of sodium sulfate with alcohol.
Most posters here seem to prefer NaOH at both stages, with a lot of salt at the end. Going for less salt, I converted hydrazine sulfate to dihydrazine
sulfate by adding barium hydroxide (112% of the theoretical weight of freshly recrystallized, vacuum filtered, undried octahydrate) to a pH around
4.4, obviously in hot solution followed by some workup. An interesting optical phenomenon was noted during the magnetic stirring of barium sulfate in
dihydrazine sulfate (with fluorescent tube light): the center of the vortex was blue. The barium sulfate was washed more by decantation than
filtering.
Distillation of the water was stopped at the theoretical weight of 50% concentration, and 105% of the theoretical amount of 50% NaOH was added. Less
than 62% of the expected weight of sodium sulfate was collected by vacuum filtration. Instead of precipitating the rest with methanol, distilling it
off, and vacuum distilling the remaining volatiles, the filtrate was distilled with aspirator vacuum. This distillate was found to be 17.3% hydrazine
(27% hydrazine hydrate), in 81% yield, by titration with iodate.
This concentration could have been higher if the dihydrazine solution had been properly analyzed, because it could have been boiled down further with
less NaOH added. It's unclear at which stage the missing hydrazine was lost, due to this overall sloppiness. The last portion of hydrazine to come
over was of presumably high concentration (oily drops in the receiver), so it's not unlikely that some was lost in the apparatus and residual
hydroxide and sulfate.
So, the whole process has to be repeated with more care, and this is in progress. What I was really interested in was this last part: the distillate
was concentrated in a desiccator with lime. If the initial daily water loss held steady, it would be hydrazine hydrate at 15 days and anhydrous
hydrazine at 21 days, this was however not the case, and the loss slowed some, even with fresh lime. Titration today indicates exactly 25% hydrazine
w/v.
There were plans to take this further before posting, but I made the mistake of mentioning this in a thread where I argued with an admin, who just hours later totally by coincidence announces his intention to lock this thread, and immediately this thread magically became the frontrunner in voting to be the very first of all
threads locked. (a lot of people spent a lot of time writing posts in this thread, just for it to be locked and unstuck, and for their posts to be
reduced to a much more important "summary" written by someone else, if mentioned at all...so why bother writing anything in the first place?)
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artemov
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Tried the urea + bleach + MEK method on a half-molar scale with 750ml of 5% bleach ...
After the solution is cooled for an hour or so (it retains heat really really well!), MEK is added and stirred for about 3-4 hours.
Unlike what Doug's Lab said, my mixture didn't become cloudy, clear, then cloudy again (ketone -> hydrazone -> ketazine?); it stayed cloudy (and
warm!) throughout.
Organic layer on top is separated, and 36% sulfuric acid is added.
White flaky ppt is formed almost immediately. An organic layer (MEK+ketazine?) floats on top of the aqueous/sulfuric acid layer (red line) ...
Will continue tmr and do a decantation/filtration to get an initial batch of hydrazine sulfate, then do a distillation with the filtrate to remove the
MEK/water to get a second batch, fingers crossed.
What can I use to wash the hydrazine sulfate after filtration?
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Colleen Ortiz
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Hydrazine has the chemical formula N2H4 and is an inorganic substance. It is a colorless flammable liquid with an ammonia-like scent that is a simple
pnictogen hydride. Hydrazine is extremely hazardous unless it is handled in solution, such as hydrazine hydrate (NH2NH2 xH2O). The global hydrazine
hydrate market was worth $350 million in 2015. Hydrazine is primarily employed as a foaming agent in the preparation of polymer foams, but it is also
utilized as a precursor to polymerization catalysts, medicines, and agrochemicals, and as a long-term storable propellant for in-space spacecraft
propulsion. In 2015, around two million tonnes of hydrazine hydrate were used in foam blowing agents. In addition, hydrazine is employed in the
preparation of gas precursors used in airbags, as well as in other rocket fuels. Hydrazine is utilized as an oxygen scavenger in both nuclear and
conventional electrical power plant steam cycles to manage dissolved oxygen concentrations in an effort to minimize corrosion. Hydrazines are a type
of organic compounds formed by substituting an organic group with one or more hydrogen atoms in hydrazine.
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vano
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Nickel and cobalt hydrazine nitrates. Cobalt is a much better explosive material than nickel, but also unstable. two days later it became very weak
because of decomposition.
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Sir_Gawain
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I made hydrazinium hydrogensulfate using 250 ml of 12.5% pool shock(actually 10%). I mostly followed NileRed's procedure except I used HCl to
neutralize sodium carbonate. My final yield was 26g. I'm going to do a titration to make sure it's not half sodium sulfate.
[Edited on 16-10-2022 by Sir_Gawain]
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Keras
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Is there any reason why sulphuric acid is preferred over hydrochloric acid in the neutralisation of hydrated hydrazine? Couldn't both be used?
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Sir_Gawain
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Hydrazine hydrogenchloride is about 10 times more soluble than hydrazine hydrogensulfate. Hydrochloric acid is sometimes used to neutralize the sodium
hydroxide and carbonate, then sulfuric acid to precipitate hydrazine hydrogensulfate. Sulfuric acid can be used for both (as NileRed did), but sodium
sulfate has a low solubility at low temperatures and can precipitate out and contaminate your product.
[Edited on 16-10-2022 by Sir_Gawain]
[Edited on 17-10-2022 by Sir_Gawain]
[Edited on 17-10-2022 by Sir_Gawain]
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Keras
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Quote: Originally posted by Sir_Gawain  | Sulfuric acid can be used for both (as NileRed did), but sodium sulfate has a low solubility at low temperatures and can precipitate out and
contaminate your product.
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Yeah, I saw that in hindsight, and came upon a recipe clearly stating that filtering hydrazine hydrosulphate should not be done below 25 °C to limit
sodium sulphate contamination.
That being said, is it possible to use sodium bisulphate instead of sulphuric acid?
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Sir_Gawain
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You could try it but I don't think that would work. Even if it would, it would add a massive amount of sodium sulfate that would likely precipitate
out with your hydrazine hydrogensulfate. To neutralize 32g hydrazine you would need 240g NaHSO4. 2NaHSO4 + N2H4 = Na2SO4 + N2H5(HSO4) This would
produce 140g of sodium sulfate and only 130g of hydrazine hydrogensulfate.
[Edited on 17-10-2022 by Sir_Gawain]
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Keras
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| Quote: Originally posted by Sir_Gawain | | You could try it but I don't think that would work. Even if it would, it would add a massive amount of sodium sulfate that would likely precipitate
out with your hydrazine hydrogensulfate. |
Solubility of sodium sulphate at 25 °C seems to be one order of magnitude higher than that of hydrazine sulphate.
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Sir_Gawain
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It might work if you use hydrochloric acid to neutralize the sodium carbonate, then sodium bisulfate to precipitate hydrazine hydrogensulfate. If you
use sodium bisulfate for both steps there would be too much sodium sulfate produced. Try it and report back. If it does work it would be great for
people who can't get sulfuric acid.
[Edited on 17-10-2022 by Sir_Gawain]
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Keras
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Will do.
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Cubane538
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I've 50% conc. Hydrogen peroxide, Acetone & Liquid ammonia and I want to make hydrazine hydrate using these raw material..
Please guide.
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B(a)P
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| Quote: Originally posted by Cubane538 | I've 50% conc. Hydrogen peroxide, Acetone & Liquid ammonia and I want to make hydrazine hydrate using these raw material..
Please guide. |
You have responded to a thread with 23 pages of posts about the synthesis of hydrazine, reading through these posts will give you a good start. Is
there a reason you want to use these specific reagents? What concentration is your ammonia? Do you have access to methyl ethyl ketone?
When reading up on various routes to hydrazine, make sure you take in the safety aspects of the synthesis, hydrazine is a compound to be taken
seriously.
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Cubane538
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| Quote: Originally posted by B(a)P | | Quote: Originally posted by Cubane538 | I've 50% conc. Hydrogen peroxide, Acetone & Liquid ammonia and I want to make hydrazine hydrate using these raw material..
Please guide. |
You have responded to a thread with 23 pages of posts about the synthesis of hydrazine, reading through these posts will give you a good start. Is
there a reason you want to use these specific reagents? What concentration is your ammonia? Do you have access to methyl ethyl ketone?
When reading up on various routes to hydrazine, make sure you take in the safety aspects of the synthesis, hydrazine is a compound to be taken
seriously. |
My ammonia is 30% concentrate and yes I've access of Methyl ethyl ketone.
I tried Hofmann degradation method 3 times in which I got some Hydrazine sulphate in first attempt and no precipitation in second and third attempt!!!
Then I came to know about Ketazine process.
Also I've enough amount of 50% Hydrogen peroxide
So, I thought Ketazine process would work..
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B(a)P
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| Quote: Originally posted by Cubane538 | | Quote: Originally posted by B(a)P | | Quote: Originally posted by Cubane538 | I've 50% conc. Hydrogen peroxide, Acetone & Liquid ammonia and I want to make hydrazine hydrate using these raw material..
Please guide. |
You have responded to a thread with 23 pages of posts about the synthesis of hydrazine, reading through these posts will give you a good start. Is
there a reason you want to use these specific reagents? What concentration is your ammonia? Do you have access to methyl ethyl ketone?
When reading up on various routes to hydrazine, make sure you take in the safety aspects of the synthesis, hydrazine is a compound to be taken
seriously. |
My ammonia is 30% concentrate and yes I've access of Methyl ethyl ketone.
I tried Hofmann degradation method 3 times in which I got some Hydrazine sulphate in first attempt and no precipitation in second and third attempt!!!
Then I came to know about Ketazine process.
Also I've enough amount of 50% Hydrogen peroxide
So, I thought Ketazine process would work.. |
There are plenty of posts here on the ketazine process. Nurdrage also posted a pretty detailed video on this process. What were you going to use the
hydrogen peroxide for? Are you proposing the peroxide ketazine process? I think this requires a catalyst, hypochlorite is a lot easier. If you look
through this thread you will also find a method that was trialed fairly successfully using chloroacetone. You will get more help if you pick an
approach, research it, then come back with more targeted questions.
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Cubane538
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Yes, I'm talking about peroxide ketazine process. And I want to use Hydrogen peroxide as oxidising agent.
I know about hypochlorite ketazine process, but I don't know how much concentration of hypochlorite is best for good yield. Also I don't have much
hypochlorite.
Can you tell me which process yields better,
Peroxide ketazine process or Hofmann degradation?
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ManyInterests
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I have a question: This is concerning saving my sanity when it comes to making hydrazine sulfate, and I will need to make a lot more very soon. Also
entirely about the Hoffman rearrangement of urea.
When adding the sodium hydroxide to the bleach solution (while cool and maintaining a temperature below 15C). Is it possible to store the solution for
later before adding the gelatine/urea mix to the whole thing and heating? I'm asking this because it often takes me a long time to add the sodium
hydroxide solution and keep it all cool. If I could do this step and complete the others in another day it would make my life a lot easier.
Would there be any degradation of the material if it happens?
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Sir_Gawain
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It’s perfectly fine to store the bleach/lye solution. If anything, it should slow degradation.
“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
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ManyInterests
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Good, making hydrazine sulfate is a lengthy and fairly stressful process for me. Doing this allows me to spread a synthesis over a few days when
needed (adding the sodium hydroxide to the bleach, then doing the urea/gelatine addition with heating later and then after cooling I can add the
muriatic acid + sulfuric acid to get the sulfate to crash and allow it to cool to ambient temperature of 10-15C overnight to maximize yield).
That'll make things easier.
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fx-991ex
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Do you think using drain opener will work for hydrazine sulfate? i think i saw some video where people did it and it worked but am not sure if my
memory is correct on this.
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dettoo456
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Drain opener as H2SO4 for the neutralization or NaOH as the base in the Hoffmann rearrangement?
Dilute concentrations of H2SO4 (50% or higher) will be fine for neutralization and NaOH in crystal form or highly concentrated ‘gel’ should be
fine for the Hoffmann step as well.
The preparation in general can tolerate H2O in excess, and only a slight yield drop would be noticed since N2H5HSO4 decently insoluble.
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Sir_Gawain
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| Quote: Originally posted by fx-991ex | | Do you think using drain opener will work for hydrazine sulfate? i think i saw some video where people did it and it worked but am not sure if my
memory is correct on this. |
I use 93% sulfuric acid drain opener. It’s pretty pure and I’ve gotten over 60% yields using it.
“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
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ManyInterests
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I got one question about freebasing. This is because I am sure my NHN (Nickel-hyrazine-nitrate) synthesis failed due to improperly freebased
hydrazine.
In the past the ingredients were at room temperature and mixed in an ice bath (50% of the sodium hydroxide solution put in at first with the other
half later) and mixed with 95+% ethanol.
I guess the last times I did it, I made a huge mistake of putting them in the fridge for 24h (all ingredients. the hydrazine sulfate, the sodium
hydroxide, and the ethanol) and I was informed that the temperature was far too low for a proper hydrazine freebasing to occur. I suppose if I took
the mixture outside of the additional ice bath and let the temperature rise for an additional 15 or 20 minutes I would have had the proper freebasing.
I never took a temperature reading while freebasing before. When I filtered out the stuff I failed at it was at 9C. Was that too low a temperature?
What is a decent range to free base it?
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