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Author: Subject: Preparation of Hydrazine Sulfate Paper
Hexavalent
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[*] posted on 16-2-2012 at 08:21
Preparation of Hydrazine Sulfate Paper


Note from bfesser:
Credit where credit is due. This write-up is <del>plagiarized</del> based heavily on work by UnintentionalChaos, demonstrated in his YouTube videos (UC235):
<a href="http://www.youtube.com/watch?v=JCrDttuw5co" target="_blank">Synthesis of Hydrazine Sulfate: Part 1</a> <img src="../scipics/_yt.png" />
<a href="http://www.youtube.com/watch?v=URIAB32Q_JQ" target="_blank">Synthesis of Hydrazine Sulfate: Part 2</a> <img src="../scipics/_yt.png" />
Which, in turn, was based on <a href="viewthread.php?tid=15091">Preparation of Hydrazine Sulfate (Hofmann Degradation)</a> by Magpie, and so on.

<hr width="80%" />
Could everyone please have a look at this and tell me what you think?

-Thanks

Attachment: Synthesis of Hydrazine Sulfate via the Hoffmann Rearrangement Process.pdf (173kB)
This file has been downloaded 1295 times

<!-- bfesser_edit_tag -->[<a href="u2u.php?action=send&username=bfesser">bfesser</a>: added note]

[Edited on 2.11.13 by bfesser]




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[*] posted on 16-2-2012 at 08:37


How much gelatine did you add?
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UnintentionalChaos
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[*] posted on 16-2-2012 at 09:33
Seriously....


Soooooo.....

You wrote up my youtube video down to the gram amounts and put your name on it, with mine 3rd, no less?

I used 0.6g of gelatine powder, Sciencesquirrel.

The only discrepancies from my prep were that you added the NaOCl/NaOH solution at a much lower rate than I did. I ran it in as quickly as my addition funnel could, as slower addition reportedly messes up the yield. You also used way too little sulfuric acid unless you were expecting truly terrible yields (10ml=18.4g~184mmol). Dihydrazinium sulfate is quite soluble and an excess of acid is necessary to precipitate the poorly soluble "hydrazinium bisulfate" if you will. I used 40g of sulfuric acid. The sodium hypochlorite comprised 527mmol, putting a cap on the yield (other reagents were in excess). The 40g of sulfuric reflected an optimistic 75% yield maximum based on this hypochlorite- a known excess based on previous experiments.

Actual yield was 53% with freshly prepared sodium hypochlorite (with a bare mimimum of excess NaOH) and 47% after it had sat for a month or so and probably degraded a bit.

As for references, I more or less built off of previous experimenters....I looked at Rosco's and magpie's writeups and deliberately increased the urea excess. These are originally based on Merck patent GB392845. The isolation of the product is based on Nurdrage's video utilizing the ketazine process.

[Edited on 2-16-12 by UnintentionalChaos]




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[*] posted on 16-2-2012 at 09:34


You're thirteen?! Are you sure about that?

That's some very nice work you've done there, I have only a few minor remarks:

1. You don't actually give the references. Those are normally given in the end of the document, in a list.

2. Instead of "Here is the method that was used" you should simply have a heading that says "Experimental".

3. Also, listing the steps in the reaction (with numbering) isn't customary.

But, as I said, that's some mighty fine work. What software did you use for the pdf?




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[*] posted on 16-2-2012 at 10:00


Thanks a lot for the input. Yes, Lambda, I'm 13!:)

I will add references at the end, and change the sub-heading to 'Experimental'

Will also remove steps.

I actually prepared the document as a Word 2007 Document, and, when I'd finished, changed the saving options to save it as a PDF.

UC - I made my 12.5% NaClO using a different method to you and with a higher driprate I found that foam would start to flood the RBF and go up into the condenser, hence the slower driprate.

My apologies for the acid quantities, I ran a small scale batch first and copied that amount instead.

Additionally, the yield I stated was my own calculated yield, not yours.

As for 'copying' your YouTube video, you didn't invent the synthesis . . .surely you should take pride that people like the way you present your work and want to use and adapt it for their own purposes. If the quantities you state are the exact molar quantities needed, then why reinvent the wheel and try and do it for myself? Waste of time if you ask me:)




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[*] posted on 16-2-2012 at 10:18


Here is the edited version;



Attachment: Chem2.pdf (242kB)
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[*] posted on 16-2-2012 at 12:11


Very nice work. It would also be nice to include some pictures if you took any.



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[*] posted on 16-2-2012 at 12:13


I did hope to take some but my camera was being buggy . . .so you'll have to take my word for it. What are the chances of this getting into Member Publications?



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[*] posted on 16-2-2012 at 13:48


Nice writeup. Some suggested revisions before it goes to Member Publications:

In the introduction you state 42% yield; it would be nice if you restated the yield at the end of the experimental section in terms of grams. You also didn't say if the yield was based on hypochlorite or urea (I would guess hypochlorite, since urea is in excess). That also reminds me that molar equivalents would be nice.

In describing the urea solution preparation, you say "39g of recrystallized urea was then added to a 1L single-neck RBF with 600mg (0.6g) alongside 50ml of distilled water." I think that sentence is missing "gelatine" before "alongside."

Finally, if you prepared your own hypochlorite solution, and did it in a manner different from your references, that preparation deserves its own discussion. This is especially true as 12.5% hypochlorite solution is not so commonly OTC as weaker 3-6% material.




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[*] posted on 16-2-2012 at 14:20


Thanks Polverone.

I will include the yields at the end and will change the urea sentence.

OK, slip of words, I did not make the hypochlorite solution - I actually purchased 14-15% NaOCl;

http://www.ebay.co.uk/itm/Sodium-Hypochlorite-14-15-w-w-500m...

and let it degrade somewhat on purpose.




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[*] posted on 16-2-2012 at 15:03


Edited version with everyone's suggestions;



Attachment: Chem3.pdf (249kB)
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[*] posted on 16-2-2012 at 15:22


Frankly, I think that what we need for member publications is a review of the hydrazine thread (or at least the state of amateur hydrazine sulfate synthesis), not an isolated synthetic procedure. Ideally this should contain a reference rich introduction with discussion of all reasonable methods, especially the historically (and industrially?) important raschig process (procedure for lab scale here: http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv1...). The chlorourea method that seems to present difficulties can be mentioned.

Following that, one should discuss and provide procedure for the Mr. Anonymous (Rosco Bodine's) prep at full scale. Notes should include discussion that scale reduction, as noted by Rosco and elaborated on by others, including Magpie leads to reduced yield. Assuming we get his permission to do so, a written preparative procedure based on Nurdrage's ketazine process video should be next.

My hybrid preparation, being largely derivative of the previous two and not particularly out of the box, but still of possible utility, should be last. In my eyes, its merits are elimination of potential NaCl contamination and reduction in acid consumption. At no time is free hydrazine able to leave the apparatus if a ground glass apparatus is used. The volumes of concentrated ammonia needed for the ketazine process are eliminated and replaced by cheap urea. It's downsides are increased effort for a similar yield to a small scale Mr. A prep, and requirement for MEK (which may be hard for some to come by), though it can be partly recycled. A bare-bones take on it could be to extract the regular Mr A. reaction mix with MEK and boil the organic phase with aq. sulfuric acid, eliminating need for the fancy glassware (which exist largely to prevent exposure to hydrazine). While running it in glass apparatus, the batch size is also constained by the flask size. A 1L flask only gets about 0.25mol per run.

Are there any that I'm forgetting to mention? I seem to remember something about H2O2/NH3/MEK but I don't remember if sufficient experimental details were provided for any sort of write up.




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[*] posted on 16-2-2012 at 16:56


UnintentionalChaos, you are right that a comprehensive review of amateur-friendly hydrazine syntheses would be nice. I hope someone will make that wiki page when we have a forum-linked wiki. In the mean time, if you or anyone else wants to produce a standalone PDF file reviewing the topic, I would be glad to add it to the Member Publications section. I just don't have the time to make the review myself.



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[*] posted on 16-2-2012 at 17:06


Hexavalent, I have placed your writeup in Member Publications.



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[*] posted on 17-2-2012 at 03:39


Thanks Polverone. I assume to make pure liquid hydrazine you could mix the sulfate with a stoichiometric amount of base and distill of the hydrazine?




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[*] posted on 17-2-2012 at 06:45


Quote: Originally posted by Hexavalent  
Thanks Polverone. I assume to make pure liquid hydrazine you could mix the sulfate with a stoichiometric amount of base and distill of the hydrazine?

:o Let me get this straight, you've synthesized hydrazine sulfate, but you have no idea how to work with it? Maybe you should finish kiddie chemistry before graduating to the big kid stuff. In all seriousness, stick to experimental work that won't kill you or others until, your understanding has improved. However, it is not my intention to discourage you from pursuing chemistry.
---
Be careful not to plagiarize the work of others. It would be nice to see some more primary sources in your writeup--literature references, patents, etc. Wikipedia should </strong>never</strong> be listed as a reference. All Wikipedia articles have a list of references from which material and facts have been drawn.
---
Some other notes:
-Aside from the first letter of a sentence, you should not capitalize the first letter of compound or element names. e.g. sodium hydroxide; not Sodium Hydroxide
-If you're on a Windows machine, use the Character Map to insert a degree symbol in place of your asterisks. Meaning is important here. In MS Word '07, select Symbol from the Insert tab. If you're on Mac, use whatever the hell it is that they offer--probably spin the wheel to the left for 4 hours, then click the single center button. :P In HTML, it's <strong>&amp;deg;</strong>
-Quoted from Wikipedia: "The expansion is typically given at the first occurrence of the acronym within a given text, for the benefit of those readers who do not know what it stands for." This is a common rule for chemical publications. Introduce methyl ethyl ketone before referring to MEK.




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[*] posted on 17-2-2012 at 07:40


That seems rather rude to me. Telling me off instead of suggesting things politely like everybody else on this thread has.

Yes, I do know how to work with hydrazine sulfate and believed that it could be mixed with the base to create the liquid. I was merely confirming my knowledge. My understanding is sufficient, thankyou.

How many more sources are necessary? The ones stated were the only ones I used, alongside my own personal experience.

Sodium Hydroxide vs sodium hydroxide . . .grammar Nazi.

Sorry about the MEK, but I think most people reading the publication would be aware of what it means. I would have done the way you said if I were writing for a public paper, for example, where not everybody would know its definition.








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[*] posted on 17-2-2012 at 08:25


Quote:
I assume to make pure liquid hydrazine you could mix the sulfate with a stoichiometric amount of base and distill of the hydrazine?


Not something you want to try without remote controlled equipment, or a sacrificial hot plate and running like hell.
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[*] posted on 17-2-2012 at 08:44


Yeah, I value my limbs, head and other bodily extensions too much to even attempt to make hydrazine in its liquid form. Just a bit of chemical curiosity:)



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[*] posted on 17-2-2012 at 09:44


Quote: Originally posted by Hexavalent  
....I assume to make pure liquid hydrazine you could mix the sulfate with a stoichiometric amount of base and distill of the hydrazine?


You should check the forum library for the procedure for this...Brauer IIRC. There's a reason why a "silver or copper distilling flask" is specified.




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[*] posted on 20-2-2012 at 11:01


Quote: Originally posted by Hexavalent  
That seems rather rude to me. Telling me off instead of suggesting things politely like everybody else on this thread has.

First, let me congratulate for your success at such an early age. You did an excellent job. However, you should not interpret bfesser's rather direct, but totally benign words, in such an emotional way. I understand that teenagers live in their own fragile world, but sometimes it is worthwhile to listen the advices of elders with coldblooded rationality. You must understand that the synthesis you undertook is not appropriate for those who don't have years of experience in practical chemistry. Therefore, it is comprehensible that many will look at every word you say very critically, looking out for signs of kewlishness or irresponsible behavior. Bfesser gave you some good advices on how to write reports and his and the following warnings on safety are all valid. There are many other experiments and syntheses you can perform in order to improve your skills to prepare yourself for the more demanding ones. Killing and maiming yourself at an early age is certainly not the best way to become a (live) chemist. Listening to good advices is much better.

PS: The wrong structure of hydrazine sulfate on the first page of the article should be corrected. References to primary literature instead of the obsolete wikipedia link would also increase the value.
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[*] posted on 20-2-2012 at 12:08


Thankyou Nicodem. I appreciate what you, and bfesser, have said and I genuinely understand where you are coming from.

Is this a more correct way of displaying Hydrazine Sulfate, showing that the sulfuric acid has essentially protonated the hydrazine;

http://upload.wikimedia.org/wikipedia/commons/2/20/Hydrazine...

I have undergone many experiments previously and, TBH, this was what interested me next. I have done many Fischer Esterifications, have attempted the preparation of anhydrous AlCl3 and hope to do a Grignard next with the arrival of my magnesium powder.

Infact BTW, my hydrazine sulfate will only be used as a source of hydrazine to condense 3-nitrophthalic acid with hydrazine to generate 3-nitrophthalhydrazide.

Could you suggest any other medium organic chem or advanced inorganic chem experiments that I could try? I have looked at Woelen's site and done most of the experiments he shows that I have the materials for.

-Hexavalent




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[*] posted on 20-2-2012 at 12:13


Quote: Originally posted by Hexavalent  

Could you suggest any other medium organic chem or advanced inorganic chem experiments that I could try? I have looked at Woelen's site and done most of the experiments he shows that I have the materials for.

-Hexavalent


Do extractions. They are extremely fun and can often leave you with nice fragrant compounds. You could extract essential oils from certain plants (just look it up on the internet), and then purify the compound (becuase often it will have other plant 'gook' mixed in.). They can be very challenging, but very rewarding. Plus you could then even sell these compounds to someone you know that makes soaps or something like that.




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[*] posted on 20-2-2012 at 12:19


Good idea, I have only ever done the extraction of limonene via steam distillation and (mainly) trans-cinnamaldehyde via simple solvent dissolving.

I have but one gripe - I have no sep funnel!




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[*] posted on 20-2-2012 at 12:22


A sep funnel isn't 'necessary', it just makes things a lot easier. You can often just swirl in a beaker and then decant. Or you can make a sep funnel by gluing two normal funnels together (never tried this so I can't say how well it works.



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