NurdRage - 2010-11-12
In this video we make hydrazine sulfate by the hypochlorite ketazine process. Warning: The reaction produces toxic gases and products. It also uses corrosive chemicals, gloves must be worn. Hydrazine sulfate is a useful substitute for the more dangerous pure liquid hydrazine in chemical reactions. Simply adding in a stoichiometric amount of base will release the hydrazine in-site and allow for it to be use in for such purposes as reductions, azotizations and various other synthetic uses. The process to make hydrazine sulfate is extremely simple: 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. 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. The top layer is methyl ethyl ketazine. If after a few hours the solution is clear but there is no seperation, you may to perform an extraction with 100mL of toluene. 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. Another process to make hydrazine sulfate is the hoffman rearrangement, a good procedure can be found in this thread: http://www.sciencemadness.org/talk/viewthread.php?tid=757&* The complete discussion on hydrazine and how to make it can be found here: http://www.sciencemadness.org/talk/viewthread.php?tid=1128 The message board itself, Science madness: http://www.sciencemadness.org They are by far the best chemistry message board i have ever seen.
I have to thank you. I have impressed my chemistry teacher multiple times because of watching your videos.
Great video! And that's a very good thing to note about the excess of ammonia since it greatly reduces the chances of nitrogen trichloride/chloramines. Also just to note on that fact, is direct reaction with hypochlorites and urea almost directly forms NCl3.
Great video! I was wondering, could a glass stir rod be used instead of a magnetic stirrer? my hotplate does not have a magnetic stirrer on it, I could always buy a stirrer alone since they aren't as expensive as the hotplate combo but would glass rod hand stirring work or does it need to remain covered?
Hey, I'm pretty clueless about chemics and I can't repeat any of your experiments, but I still enjoy watching them! Thanks for educating people :D
I really enjoy this channel. The practical stuff about chemistry I love, i just absolutely suck at theoretical stuff.
These videos are incredibly fascinating, I just think it's funny that some of the chemicals used are almost impossible to obtain in a lot of places. For good reason :)
Excellent videos you make, thanks ! One question though: is this just proof of consept or what would you use Hydrazine Sulfate for in real life ?
I used your method of making hydrazine with 2 small alterations. I used <5% NaOCl. Because of this my 2-butanone azine did not want to phase separate out of solution. Since after adding the NaOCl the reactionmixture remained clear and did not phase separate. I added a xylene thinner 137C+ distillate and shaked. (very likely xylene isomers with little contamination) I hydrolysed the top layer (xylene, 2-butanone azine etc.) with 19% H2SO4 which produced a white precipitate at the phase boundary.
Outstanding video! Thanks for taking the time to make it.
Even though I'm much more interested in physics and feel myself a lot better around stuff involving physics, I find your videos interesting enough to keep watching them ... And damn, even though I don't understand everything, it's still awesome to see how stuff can be made with fairly accessible stuff. Thanks for that and keep it up :)
As a chemistry student, one learns this particular reaction (the Raschig process) in the rather early inorganic chemistry courses, as a part of chemistry of nitrogen and redox reactions/industrial chemistry if it is a more technical education. So basically, every undergraduate chemistry student should be able to understand it (and most do, at least the better ones) way before he/she makes the BSc.
keep making vids!! youre really good chemist and love watching your vids!
Useful video - thanks I suggest same (*2) molar quantity (50g) of NaHSo4 as acid rather than conc. sulfuric, being much safer to store and use.
nice vid. It would be nice to see future videos based on creation of hard to find chemicals or producing common chemicals for less than the store prices. That would give people another route so if a chemical is hard to find or very expensive they can create it themselves from the raw materials(if they have access to them). Chemistry is all around us you don't always have to buy every chemical used if you create it yourself.
Although there have been many other influences, your channel is has played its part in rekindling my interest in becoming a chemist. Videos like these helped me learn enough chemistry on my own to pass my CLEP test with a high score and receive college credit necessary for my associates degree. I believe that that test was very influential in helping me land a job as a laboratory technician a month ago. Sadly I was just laid off, but I walked away with $2K, some experience, and a good reference.
Thanks for all the great vids. I was wondering if there are any books you could recomend for an novice interested in chemistry? Once again...thanks.
Hello fellow nurd (?), we did this experiment in college obtaining acid hydrazine sulfate, but we didn't used MEK or acetone at all, the resulting substance was pure too but our yield was about 23%. Our procedure was almost exactly the same apart from the MEK, so my question is if our lower yield was because of the absecene of MEK or just experimental errors. Anyway great video!
I performed this synthesis. The yeilds of the Methyl Ethyl Ketazine were very low. Only 7grams. I suspect the ammonia I have is of lower concentration than I had originally believed. I ran the first step twice to obtain ~14grams of methyl ethyl ketazine and proceeded to the hydrolysis. I ran into an issue where the hydrazine sulfate would not crystalize out of solution even after a full 24 hours. I had to chill the solution in the freezer for about 30 min to finally obtain the hydrazine sulfate
@Nurdrage: What catalysts are needed for the process using H2O2 instead of bleach? I don't see why this reaction won't proceed without any catalysts? I prefer using 35% peroxide (of which I have a lot) to using 6% bleach. PS: Great video. I absolutely love these more advanced videos dealing with organic chemistry. Keep it up! PPS: Nice to see you on the Sciencemadness board. :)
I'm a member at SM and I still love your video's, and have performed tons of syntheses of yours. BTW like the new videos with balanced equations and for SURE the ingredient annotations as I don't have to rewind and pause 50,0000 times. And the wife wants to know,, do you use a voice synthesizer to hide identity?
the consensus is that my bleach had an unusualy high salt content and salted out more of the ketazine. Yields can be improved if an extraction with toluene is performed.
I wonder, are there any other stable salts of hydrazine? Could you substitute some other acid for the hydrolysis phase to get another type of salt?
That ketazine looks very interesting by itself. I wonder if it can form a cage-like estructure.
Instead of waiting for the layers to separate, could one use a centrifuge (normally used for DNA samples, but can accommodate a container)?
Thank you. And the last think: could be calcium hypochloride used instead of the sodium one? Perhaps calcium hydroxide, which is produced, wouldn't react with hydrazine so much and destroy it thus we would end up with better yield.
One could use EDTA instead of gelatine to mask the traces of heavy metal ions interfering with the selective oxidation of the imine.
the dedication you put in documenting your efforts are commendable, I do not believe the good folks @sciencemadness are "looking down on you" just the fact that you explained this complex process in a way that a layman like me "got it" is impressive, you should seriously consider teaching professionally ! also thanks for revealing the secret ingredient of name brand epoxy thinner, that probably saved me hours of research, and that's another shop cleaning product to add to my list
First of all, and foremost, I love your videos, both in content and presentation. And although this may sound critical (and definitely not intended) I still must ask why the anonymity?
You can boil the 10% ammonia and lead the gasses through washbottles into the 10% ammonia solution to concentrate it. You will have to look up the details on your own.
we appreciate all the hardwork you put into your videos nurd
I know that took a lot of work, thank you. And keep doing great videos.
Finally a new video. Why don't you do a bunch of those colorful ionic reactions with color changes. I don't think that you'll need much time to film those. One nice 6 minutes video can be made... Keep up the nerd work ;)
Could you please make a video in which you take the hydrazine sulfate and incorporate it into a simple fuel cell? that would be so cool!!! Thanks.
Well ... thanks. And another thing I'd like to ask: you have said it's possible to make hydrazine sulfate by using hydrogen peroxide instead of sodium hypochloride. You have also said this reaction needs a catalyst. What kind of catalyst is it exactly? I believe my hydrogen peroxide is much purer then sodium hypochloride is, which could make much purer hydrazine sulfate.
It is necessary to form the methyl ethyl ketazine (butanone azine), yes. As he mentions, acetone can be used instead but fractional distillation must be used as opposed to simple phase separation.
I’ve always wondered if you could use sodium hydrogensulfate instead of sulfuric acid, could you?
@NurdRage Thank you very much for the effort and resources put into it, and all your video's in general.
That method produces highly contaminated hydrazine, almost inseperable from the isocyanuric acid.
I have a video (actually 2 parts) up of a working Hofmann rearrangement for hydrazine sulfate. I borrowed a handy concept from this video which I would not have thought of without it. Thanks!
That was fun. I'm thinking about doing it again with calcium hydroxide and ammonium sulfate in lieu of ammonia (I have plenty of those), and calcium hypochlorite solution. I don't know if the sulfate ion will interfere with the ketazine reaction.
This must have taken a lot of work and research to make this video so i hope people appreciate that.
Hi. You mentioned at the end of video that there's Peroxide process. Is process the same with hydrogen peroxide? Or there must be some additional catalyst? Thx
Another excellent video, thanks for posting!
the methyl ethyl ketozine that comes in that tin can, i've actually seen it more often in thesmall hardware shops that we have around the area (upstate newyork) than in big retail stores like the home depot and lowes. they usually pander to the local contractors and we have a few proffesional painters around the area so it must be lucrative enough to have on hand for them.
I've always wondered, how does the little spinny thing, which mixes, work? I have never seen one in real life.
@NurdRage What software are you using to add the organic molecules to your titles?
How would you recommend making concentrated ammonia solution, NurdRage? Perhaps combining a hydroxide salt and an ammonium salt and bubbling the evolved NH3 into a chilled container of water?
Can the methyl ethyl keytone seperated from the final step be re-used to make more hydrazine sulphate?
@sparky100able Yep, it can be bought. I very recently ordered and received 16 oz. (.95L) of 35% H2O2 from a health food store. Cost was a bit high at US$22. Best online prices I've seen were in the neighborhood of $50 per gallon (3.79L). Shipping it is costly, though, so I didn't overpay by so much as it may seem. So, then: how to use it, NurdRage? You mention catalysts...
NurdRage - 2013-10-20
Bleach has always had sodium hydroxide, it's a side effect of the manufacturing process (membrane electrolysis). But sodium hydroxide actually helps this process of making hydrazine. There is no wider conspiracy to alter clorox to "keep people like (me) from making hydrazine", this process still works and will work for the foreseeable future. But go ahead and keep calling me a dumb ass/asshole or whatever. I'll keep doing and teaching actual chemistry.
All Love - 2019-07-25
Please do a Wolff-kishner!