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Rosco Bodine
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Quote: Originally posted by len1  | | I actually did the experiment to see how it compared to my previous method. Got an explosion because my hypochlorite was 12%. hence the post
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Hmmm.....that is interesting .....but mostly because it is so highly unlikely
http://www.youtube.com/watch?v=i7RbZNT5A2A&fmt=18 Psychobabble
http://www.youtube.com/watch?v=NNiie_zmSr8&fmt=18 Eye In The Sky
[Edited on 19-8-2010 by Rosco Bodine]
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len1
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Ah yes. Well now you are doing exactly what you accused me of. Playing the man and not the ball.
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Rosco Bodine
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Hey I'm having a little fun with a situation where you just keep digging a deeper hole on some bad numbers, and uh oh .....you dug slam to china where
there
was a reported "explosion" which now makes the bad numbers good ? Gimme a break and just knock it off with the B.S. How about a detailed description
of the process gone awry, so we can all wrap our heads around the "12% anomaly"
which you are now "reporting?" Because it seems pretty far fetched to me and I can guarantee you I'm not alone.
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len1
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Just when it looked like you might be a reasonable guy, proof again that Im dealing with some nasty wacko. You are not alone, there are a number of
you like that here. A testament to who you are is served by the inconsistencies of your posts and the sum total of what you have achieved. I think Ill
pass on trying to explain anything to you, let your ignorance be your reward.
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Rosco Bodine
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Please do cite chapter and verse about whatever "inconsistencies" you allege exist about my posts. I will gladly correct or retract whatever error
needs that attention.
Why do you make unfounded criticisms of good work that is accurately reported and well done, and then venture to think it is a
"debate" that is occurring? I criticized your post which was inaccurate and misleading.
Your response is what is ignorant, not the person or the work you criticize incorrectly.
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len1
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Has there been perhaps two Rosco's? One on this page, one on the one before, and one Mr Anonymous?
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Rosco Bodine
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Just one Rosco. No inconsistency. Mr. Anonymous was an alias used for e-mailed postings which were made before I became a forum member. Rosco is
also an alias. Neither alias is a testament to who I am, neither is who I am relevant to the validity of information I have offered. Where are you
going with this, you can't find a problem with the information I have shared, so now you have a problem with my screen name? How does any of this
relate to your misplaced decimal and other problems with your own work in justifying incorrect criticisms
of mine ?
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teresap989
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I think urea dinitrate can be prepared in much the same way as urea nitrate, you just use twice as much nitric acid.
It's quite a straightforward procedure, essentially a formation of diuronium nitrate CO(NH3+)2(NO3)2
__________________
watch free movies online
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S.C. Wack
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You want more Rachig, I have more Rachig. Worth reading? Well...
Preparation of Hydrazine by Raschig's Method.
By REGINALD ARTHUR JOYNER.
J. Chem. Soc. 123, 1114 (1923)
"Estimation" rather than preparation would have been more precise, since none is isolated. The results reinforce why it is done the way it is.
Of all the books to be popular, Vorobyova? What you've discovered is another example of why it's pointless to post...people don't read.
Attachment: jcs_123_1114_1923.pdf (449kB)
This file has been downloaded 2221 times
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verode
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| Quote: Originally posted by chemoleo | by the way, I think I figured out why this green chlorine- like gas evolves once the solution is *strongly* acidified: NaOCl disproportionates to
NaClO3 (!!) and NaCl. As I didnt use freshly prepared NaOCl, I am sure the green gas was ClO2, which is liberated when HClO3 is formed....
Lovely 
Thank the gods of chemistry for a superb fume cupboard! |
The Hofmann degradation is a reaction between an amide and a mixture of bromine and sodium hydroxide solution. Heat is needed. You may use urea and
you get hydrazine
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verode
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The Hofmann degradation is a reaction between an amide and a mixture of bromine and sodium hydroxide solution. Heat is needed. You may use urea and
you get hydrazine
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NurdRage
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Ketazine Process to make Hydrazine
I've had success with the Ketazine process for making hydrazine:
http://www.youtube.com/watch?v=UB7vwIFCnR0
For those of you that don't want to watch a 10 minute video, here is the write-up:
------------------------------------------------------------
Fumehood required!
Start with 250mL of ammonia and add to it 100mL of methyl ethyl ketone. Stir and then slowly add 1/4 mole equivalent of sodium hypochlorite based
bleach. if using 10% bleach then about 186g is needed. If using 6% household bleach about 310g is needed.
As the bleach is added the reaction will heat up and bubble vigorously, slow down the addition if it's bubbling too much. Chilling with an icebath is
helpful to keep the reaction under control. After all the bleach is added, keep stirring until the mixture stops bubbling. Then stop stirring and
allow it to stand for a few hours or so until it separates into two clear layers. if an icebath was used it will take overnight.
The top layer is methyl ethyl ketazine. Separate it using a seperatory funnel or by careful decantation.
In a separate container, add 20mL of concentrated sulfuric acid to 100mL of water and stir. Then add the hot solution directly to the ketazine and
keep stirring. The hydrolysis will generate crystals of hydrazine sulfate. Let solution cool to room temperature on its own and then filter off the
crystals of hydrazine sulfate.
Acetone can be used in place of MEK, but you'll need to distill it off (use 50mL acetone in the reaction and distill 150mL of liquid) or extract it
out with toluene into the acid solution.
----------------------------------------------------
The yield is around 30-60% depending on how slow and careful you are. It's not as good or as easy as the hoffman degradation method already posted in
this thread. But i like the ketazine approach since its pretty robust and very forgiving if you mess up the concentrations or use alternative
equipment or glassware. Purity is excellent, titration (with iodine) shows it to be 95%+ pure.
Maybe the hoffman degradation yield/purity can be improved by using a ketazine extraction step instead of treating with hydrochloric acid and sulfuric
acids. I have not been able to test this myself since i'll be honest; i could never get the hoffman degradation to work reliably for me.
[Edited on 13-12-2010 by NurdRage]
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BromicAcid
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Great video, and I've always been interested in the ketazine process, nice to see it at work. Any clue if you have significant chloroform
contamination in your organic phase considering you're adding hypochlorite to a methyl ketone?
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NurdRage
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To be honest i never actually measured that. I don't think it's an issue since the chloroform doesn't crystallize out with the hydrazine sulfate.
The side reaction might be responsible for the lower yields, but i never figured out how to inhibit it.
If you're looking for pure methyl ethyl ketazine then i suppose it would be an issue. in that case it can be remade from the pure recrystallized
hydrazine sulfate by simply mixing it with aqueous excess sodium hydroxide and MEK.
[Edited on 14-12-2010 by NurdRage]
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woelen
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Thread Pruned
23-12-2010 at 02:38 |
xxx
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in patent 3869541 ketazine
why he used salt catalyst?
if anyone know?
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UnintentionalChaos
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I recently ran a hybrid hydrazine synthesis, combining the ketazine process and the Hoffman. I did a scaled-down Hoffman with a little excess urea and
fresh 12.5% NaOCl. At the end, in lieu of acid neutralization, I added butanone and stirred for a while, then seperated off the organic phase. this
was mixed with aqueous sulfuric acid and stirred. Heating was then applied and the butanone distilled off as it's azeotrope with water. The resulting
solution was cooled and the product filtered and washed to give 52.5% yield of putative hydrazine sulfate. After drying, 77% of the butanone was
recovered.
My question concerns the slight excess of urea. Does urea react with hydrazine to give aminoguanidine? Even if the reaction is slower, the hydrazine
seems to very readily react with ketones and I'm worried that I may have quite some impurity in my final product. I could do an iodine titration or
take a m.p. but I'd like to hear if my concerns have any basis first.
[Edited on 1-2-11 by UnintentionalChaos]
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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lucky123
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hydrazine sulfate...
I was just curious what can be made with this hydrazine sulfate? Primaries and secondaries or is it explosive by itself?
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Random
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Can I precipitate hydrazine with something other than sulfuric acid? Maybe hydrazine can be precipitated using potassium metabisulfite?
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woelen
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No, don't use potassium metabisulfite. What can be used though is NaHSO4 (pH minus for swimming pools). Dissolve this in water and add to the
hydrazine solution. Your product, however, will be somewhat contaminated with Na2SO4 and/or NaHSO4. For most practical purposes, this is not a real
problem.
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Random
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I thought about it as potassium metabisulfite should decompose to so2 and khso3 which would be oxidized by oxygen to KHSO4. Or maybe something like
Na2SO4 would also work?
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NurdRage
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are you using the ketazine process or the hoffman degradation method?
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Random
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Ketazine process, it seems easier. Just I need a way to isolate hydrazine without sulfuric acid, though I can make above compounds if that would work.
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UnintentionalChaos
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| Quote: Originally posted by Random | | Ketazine process, it seems easier. Just I need a way to isolate hydrazine without sulfuric acid, though I can make above compounds if that would work.
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So you have butanone azine isolated? To hydrolyze that, you need a strong acid; bisulfate will probably not cut it. HCl would probably be fine, but
you'll want to precipitate hydrazine sulfate afterwards with a bisulfate salt. The hydrochloride is quite soluble, IIRC
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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Random
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Well, I am going to make methyl ethyl ketazine, just I wanted to be sure that I will be able to isolate hydrazine from that so it wont be waste of
chemicals.
Now, I would then do that:
Isolate Ketazine layer, add HCl to hydrolize that (hydrazine hydrochloride in solution).
Mix potassium metabisilfite (decomposes to KHSO3 and SO2 in solution). Leave it in air to oxidize to KHSO4.
Add KHSO4 and SO2 solution to hydrazine hydrochloride and methyl ethyl ketone solution.
Hydrazine Sulphate should precipitatate. Now I need to filter it and the reaction is finished.
Now, is this right and would that work? By the way, what is the solubility of hydrazine sulfite, is it soluble or insoluble? Because I don't want to
make mess because of SO2. Or maybe hydrazine sulfite is insoluble too. I know MEK bisulfite adduct is almost insoluble too.
If someone wants to know source of MEK, you can get it from some nail polish removers mixed with isopropanol, it shouldn't make any trouble in the
reaction though, maybe somemore bleach should be used due to haloform reaction competing with isopropanol.
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UnintentionalChaos
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| Quote: Originally posted by Random | Well, I am going to make methyl ethyl ketazine, just I wanted to be sure that I will be able to isolate hydrazine from that so it wont be waste of
chemicals.
Now, I would then do that:
Isolate Ketazine layer, add HCl to hydrolize that (hydrazine hydrochloride in solution).
Mix potassium metabisilfite (decomposes to KHSO3 and SO2 in solution). Leave it in air to oxidize to KHSO4.
Add KHSO4 and SO2 solution to hydrazine hydrochloride and methyl ethyl ketone solution.
Hydrazine Sulphate should precipitatate. Now I need to filter it and the reaction is finished.
Now, is this right and would that work? By the way, what is the solubility of hydrazine sulfite, is it soluble or insoluble? Because I don't want to
make mess because of SO2. Or maybe hydrazine sulfite is insoluble too. I know MEK bisulfite adduct is almost insoluble too.
If someone wants to know source of MEK, you can get it from some nail polish removers mixed with isopropanol, it shouldn't make any trouble in the
reaction though, maybe somemore bleach should be used due to haloform reaction competing with isopropanol. |
Metabisulfite hardly oxidizes with any rapidity. That won't work. Sodium bisulfate is extremely cheap as pool pH down. In addition, bisulfite forms an
addition product with MEK. if hydrazine sulfite is insoluble, it will be heavily contaminated with MEK bisulfite adduct. Isopropanol will be oxidized
to acetone by hypochlorite (thereby lowering the yield of hydrazine), plus then some acetone azine can form (which is water miscible and will waste
even more of your product.
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
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