Hydrazine

Qualitative & Quantitative Test for Hydrazine (Sulphate)?

Damn

test

from THE CONDENSED CHEMICAL DICTIONARY:
<b>copper dihydrazinium sulfate</b>
&nbsp;&nbsp;CuSO₄(N₂H₄₂.H₂SO₄
&nbsp;Properties: Bluish powder; mp above 300°C, starts
&nbsp;&nbsp;to decompose at 140°C; very slightly solouble in
&nbsp;&nbsp;watrer, 250 ppm @ 80°C.
&nbsp;Hazard: Moderately toxic by ingestion or inhalation.
&nbsp;&nbsp;Skin and eye irritant.
&nbsp;Use: Foliage fungicide.

addition of copper sulfate to hot HS soloution (HS is very solouble in hot water) should produce it. you can then weigh the precipitate ...

Hydrazine

Anhydrous Hydrazine synthesis, Unabridged for Newbies, Kewls and the other downtrodden misunderstoods...

Success with hydrazinium sulphate

I made some hydrazine sulphate according to my post in the hydrazine oxidiser thread.
Noteworthy observations:
-when mixing the ammonia with the NaOCl (both at 4 deg C), no bubbles form. However, slight heating to 40 deg or so produces lots of bubbles, that subside quickly.
-boiling it initially keeps the temp at around 75 deg, until after 1/4 or so are evaporated, then the temp rises to 95 deg.
-at 1/4 of the original volume, crystals appear, which were filtered off. I hypothesise this is NaCl or NH4Cl.
-Using EDTA, the solution is slightly yellowishh at that point, with 2 g pig skin gelatine the solution is thick and a nice chlorine grean (?!?)
-Addition of H2SO4 to the solution at 4 deg cause massive gas evolution, and at least in part contains chlorine (smell)
- Temperature heats up considerably, to 50 deg. This was cooled again, and more H2SO4 added. Preciptiation (fairly fluffy) finally ensued. pH at that poiint is well below 0. Gas continued to evolve, which was green (not much annymore thoug)
-This was spun down (centrifuge) and the chlorine-smelling pellet was redissolved in hot water, and recrystallised.
-Due to the extreemly low pH at even that point, the preciptant was suspended with 96% ethanol, filtered, and repeated. Final product is a white crystalline powder that is not much soluble in water.
-Gelatine did indeed a higher yield than EDTA, even though there wasn't much to start off with. Hell, got a few grams, not like kilgorams I dreamed of

Addition of that to CuSO4 did indeed yield a turquoise blue precipitate.

What I am wondering...Why does gas evolve once the solution is boiled (i.e. at 40 deg) - gelatine or EDTA should prevent the latter!
I used analytical reagents of course. Anyway, this definitlely decreases my yield!
Why is there gas evolution upon the addition of H2SO4? Especially chlorine??? This one eludes me. NH3 is in excess (big time), so all of the NaOCl should react....

A definite peculiarity...

More to the production of Hydrazine

First and foremost I found something odd in one recently aquired library book, it mentioned that the resulting mixture from the production of hydrazine can be distilled instead of being precipitated, it said, and I quote "Distilling the resulting dilute solution of hydrazine yeilds a 58.5% hydrazine - 41.5% water azetropic solution..." (Inorganic Chemistry of Nitrogen, Jolly, 1964) which of course can be concentrated by distillation over sodium hydroxide pellets. Sounded interesting to me but I would have to look up the azetrope distillation temp.

But secondly, there is a book, it's new, and someone out there in college might have it in their library: "Hydrazine and its Derivatives : Preparation, Properties, Applications" this book came out in 2001 for the second edition and it is 2232 pages! Anyways, I had the first editon at another local library and ordered it, but here is what caught my eye, over one hundred pages on the preparation of hydrazine using numerous methods (Im guessing some interesting curiosity methods) regardless, amazon has it, but it's $393.12, I mean, come on! I'm not made of money!

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!

WOW

Smaller scale first?

I made an attempt today.

1. This is the apparatus prior to any heating or anything. The test tube has been charged with about 3 g of urea and 2 g of nickel in the form of filings and small pieces also a stir bar was thrown in. This was in an oil bath that also contained a stir bar to allow for evener heating. The thermometer is also placed in there. The exit gasses passed through a piece of flint glass and into a second test tube in an ice bath filled with 6M H2SO4. Immediately after this picture was taken heating was begun.
   
2. Close up on the contents of the test tube prior to heating.
   
3. The mixture melted at about 137 C and heating was slowed and it stayed relatively constant at this temp. I held it here for about 20 minutes with very very infrequent bubbles. No precipitate came in the sulfuric acid so heating was increased after this time period.
   
4. Over the course of one hour heating gradually increased. This picture was taken when the mixture had reached 200C. It was constantly bubbling and expanding from the frothing. At the lower part of the test tube there was condensation that hardened shortly above the oil line. Then there was a space with no condensation and right at the top it was foggy due to additional condensation. Probably just urea. Meanwhile in the other test tube there was no precipitate. However a crust would occasionally form right were the gasses exited into solution and would break off in a semi-circle and float to the top so the top looked like it was covered in a thin skin, hydrazine sulfate?
   
5. It was shortly after the last picture that heating was discontinued entirely. Notice the foggy condensation on the generation test tube. The second test tube is somewhat milky white. This occurred because it got so cold after the H2SO4 addition. It cleared up after I let it sit awhile. Although there was a crust on the top the picture that I took did not turn out.
   
6. For the test tube that collected the gasses I added copper sulfate as mentioned further up thread as a test for hydrazine. I got a weird thick skin on the top of the liquid after stirring that looked remarkably like ice. Other then that I had no additional tests. I took the other test tube that had generated the gasses and added water to put some of it into solution. It made a milky white precipitate filled liquid. Copper sulfate produced no effect.
   

To me it looks like it didn't work too well if at all. Gas evolution was only significant at about 160C below that bubbles were few and far between. The nickel came out blackened. A good sign that something was going on with it but other then that nothing else. I plan on running this again next weekend with iron in place of nickel. And if that even doesn't work one last time with 14/20 lab ware with about 20g of urea, seeing how sluggish the reaction was with nickel shavings and such I believe the next attempt will be completely nickel powder. But as it looks now I don't think barely any hydrazine was formed at all.

[Edit] One other thing, the molten urea turned green towards the end, is that normal? I thought that maybe some nickel carbonyl may have formed and by all accounts I would consider molten urea an organic solvent so it could have went into solution and caused the color change.

[Edited on 4/11/2004 by BromicAcid]

hydrazine reaction alternative chelator

Does this mean one can use the "slime" from those kiddie chem sets?

Also BromicAcid here is a hydrazine test kit. http://cgi.ebay.ca/ws/eBayISAPI.dll?ViewItem&category=20...

[Edited on 2-5-2004 by rogue chemist]

Hydrazine Regurgitation

Today is the day, I've completed a fair bit already and here is the step by step:

1. Placed 8 g of nickel oxylate dihydrate into a 50 ml glass volumetric and stoppered loosely with a 10/30 stopper. Also a very small amount of HgO (<.0005 g) was added, this has a catalytic effect of promoting nickel carbonyl formation.
   
2. Heated slowly on a hot plate, first lots of water came off, I took the stopper out to just let the water evaprate away then it started to turn black at the bottom so I re-stoppered it. It continued to release gas until the whole mass turned black. Upon swirling the hot flask the power was free flowing. I set aside and allowed to cool.
   
3. I esitimated that my reaction should have yeilded slightly over 2 g of nickel power so while it cooled a little bit I weighed out 6 g of urea and placed that along with a stir bar in a 100 ml 14/20 RB flask.
   
4. All parts were previously washed and washed again with distilled water. They were dried in an oven and the joints were wrapped with teflon tape.
   
5. I added the cooled nickel powder to the urea flask, it formed little needles on the stir bar. I quickly put the still head in place and the rest of the assembly, a gas entry tube was put into the thermometer hole on top.
   
6. H2S (which supposedly increases the activity of nickel toward forming the carbonyl) was slowly put into the system, a very small amount total.
   
7. The gas entry tube was replaced with a stopper and the apparatus was lowered into an oil bath and heating begun.
   
8. The mixture liquified and the urea took on a blue tint, probably some nickel oxylate that didn't decompose.
   
9. The mixture is currently heating away as it has for almost an hour. It is being held at 150 - 160 C and urea is crystalizing on the inside of some the glassware near where the reaction flask is.
   

There is no distillate so far, but I will keep posted. If I get distillate I will attempt to dissolve sodium metal in it. If it is anything but liquid ammonia (impossible) or hydrazine it should react appreciably.

Edit: Ran the reaction for 1 hour 30 minutes, no distillate, tiny little hairs of urea condensed on the inside of the reaction flask though. Urea crystalized though 80% of the glassware, no liquid anywhere. Heavy ammonia smell even though exit gasses were being washed.

Then I turned up the heat to 200C for 15 minutes, urea decomposed more but no sign of a distillate.

I think I'm done trying this for a while until someone else shows some promising results. If freshly made nickel powder will not react with urea with every accomidation made for the formation of carbonyl, I give up.

[Edited on 9/27/2004 by BromicAcid]

Hydrazine can also be made by reducing nitramine. Nitramine is made by hydrolysis of dinitrourea, that being made by dehydration of urea dinitrate, that is made by reacting urea and nitric acid (ask your buddies at E&W ). The reducing agent could be sodium sulfide or something.

Yea I have been there for a few years . I read that whole thread again and still find no mention of urea DInitrate. Just urea nitrate, nitrourea and dinitrourea.
My goal IS dinitrourea as you can read in the "KETO-RDX and DIKETO-HMX" thread on the E&W forum where I have posted about a few experements.
So far I can only get to nitrourea and then it goes wrong for some reason. I am just looking for another way to achieve the dinitrourea synth.

I will be attempting to perform the hydrazine synth using the NaOCl, urea and NaOH method. I am told that regular 6.25 is great for this because the reaction proceeds and is not too violent. However, if this does not work, would Ca(OCl)2 work? I can't figure out the equation for it. I haven't taken chemistry yet, all i know is from reading so pardon my dumbass . Also, adding dilute h2so4 would form the sulphate without hazardous explosion hazards, yes? I will report fairly soon :p. Thanks.

Hydrazine KClO3

KClO3 ?

the distillation

NaOCl from NaCl!

My hydrazine attempt using Mr Anonymous' method

You had to be doing something differently from the way the writeup described , because a volume increase of triple is
about average , sometimes a bit more but
quadruple would be the maximum and very unusual .....never ten times , unless
a spill of hydrazine just has a way of looking like a lot bigger mess than it is

You got some NaN3 , but wouldn't you like to have more grams for your effort ?

More thoughts about the HS procedure .....

The formation of hydrazine from urea is
definitely not without an indication that
some small reaction is occurring
It is almost unbelievable until you see
it yourself isn't it , just how much foam
can be afoot quickly as if it were a stampeding hydrazine " moose "

The first time I made hydrazine by the urea - pool chlorinator method , I had an overflowing mess too , so I kept working at refining the method until I had it down to an art . It very likely will make a mess if you start the reaction without allowing
it plenty of " room to grow " , and even
CYA with some overflow and return path like a really large funnel fitted snugly
into the neck of the flask . But if you do follow the directions given at great length
in the " improved " synthesis writeup ,
good results and yields will be predictable . Once you see it does work
in the way described , it will be a breeze to make up HS , even in large batches .

I have kilos of hydrazine sulfate as the product of many experiments studying the reaction , and it really is a simple synthesis after learning how the reaction behaves and how essential it is to allow it plenty of space .

When I make the HS , I use a half gallon
of hypochlorite in a batch run in a 4 liter
Erlenmeyer with a like capacity overflow funnel . I have a 12 liter flat bottom Florence so I could probably run a batch
using a full gallon of hypochlorite at one time and keep everything tidy by fitting
a five gallon plastic bucket with a rubber bushing and using it atop the flask as an overflow and return , in case the foam became excessive . Not exactly microscale , but saves work over several smaller batches . However unless you have some insane need for huge quantities of HS , a 4 liter erlenmeyer batch size is plenty for most folks .
Even with your 2 liter erlenmeyer you can make whole lot more in a controlled fashion than 15 grams . You should have gotten at least 55 grams . Keep the batches small until you know the reaction well , and then you can maximize the yield later . The reaction is sensitive to small variables which you will see if you do the synthesis a few times .

[Edited on 22-4-2005 by Rosco Bodine]

For best results follow Mr. A's method *exactly*

Because that method has been carefully optimized already , and any thing you do to change things even in a small way will
cause a disproportionate negative effect .
Do the procedure the way it was described *first* to confirm it works , and then change things to prove the * small * changes adversely affect the reaction in much * larger * ways you wouldn't have expected Been there , done that .

You quickly pour in a steady stream the urea and gelatine into the well stirred cold basified hypochlorite . Just pour it in
quickly , " in a lump " as the expression
goes . You should have one to two minutes before the foaming begins ,
so you have plenty of time to mix the two liquids if you pour the urea-gelatine solution in without any delay , the idea being to get it all in and mixed before the
foaming will complicate adding anything .

You should really have a 3" stirbar , even in a two liter flask , the octagon sort 3" X 1/2" should do okay . And yes , at first you have to reduce the stirring speed to keep the shallow pool from splashing and just pull as good a " swirling " shallow vortex as can be managed . The speed can be increased later as the foam begins to rise so that the stirbar is actually churning through and tearing apart the foam and helping to break apart the bubbles so that it returns to a liquid state and very slowly settles out again as a lower layer , over the course of the reaction , which may take a half hour or more . Everything about what happens has been described in Mr. A's very detailed description . Trust the information as a lot of work and many experiments were done to pin down all those important details .

The sequence of preparation of the reagents is important , the temperatures
and how the prepared reagents are added together is also important .
The reaction * is * sensitive to small variables and they have all been covered
in the described procedure , so don't deviate one iota in the belief that it probably won't make any difference , because just the opposite is probably true instead

And please , for anybody who makes arbitrary changes in one of Mr. A's or
Rosco's described experiments and then gets a different result , understand that what detail was thought not to be consequential , was indeed consequential . For every process where it is described what works , there are unwritten volumes about variations on the method which don't work , and when something is changed about a procedure ,
it usually does matter , even if the reason is not obvious why that change should have any bearing on the outcome . The troubleshooting of the variables has usually already been done for those procedures where exacting methods have been detailed . So roll that ready made wheel first and see how it goes , before
reinventing it in any detail and then saying it isn't round

You are trying to apply linear two dimensional thinking to a much more complex scenario than lends itself to such analysis . You can trust me on that or you
can prove it for yourself with failed syntheses by testing your theories in
the flask . Lets not debate the theory .
Better to talk about the comparisons of
experimental results later , and what may be concluded from what actually occurs .
Anyone is welcome to make whatever improvements on the methods are valid ,
and describe their improved yields and
all of the details about how this was achieved . But that is for later , after the
proof is established by the results of their
experiments , not by estimates in advance
of what results are unknowns until such
experiments are completed .

rogue chemist :

Thanks for the confirmation .

I know my own work pretty well on procedures and methods that are
either completely my invention or
are variations and /or improvements
upon already known methods . And
I'm never afraid to say " I don't know "
but this isn't one of those times

[Edited on 23-4-2005 by Rosco Bodine]

You could probably put your smaller stirbar inside of a hollow poly tube like
an old marker pen or similar into which it would fit snugly , and provide a bit of extra diameter and length . Size does matter although you will have to watch the speed to keep it from uncoupling in
the mixture . There's nothing in this reaction which should terribly attack the
poly , although I haven't tried this to make certain . Just make sure you keep the stirring going throughout the reaction . You will see the spiraling bands
in the foam indicating that the entire mass of foam is actually moving , especially just before it begins to disintegrate of its own accord as you are
ramping up the heating .

Something you really should do is provide some expansion room and return path for any potential overflow . If you dont have
a large funnel handy , then cut the bottom
out of a 3 liter PET soda bottle and invert it and secure the open neck of the soda bottle in the open neck of the flask with
a sleeve bushing cut from a large diameter
hose , or perhaps simply duct tape the necks of the two vessels together . Whatever overflow occurs will rise up into
the soda pop bottle and then flow right back down into the flask as the foam disintegrates with passing time . Sit a small soup bowl or cereal bowl or saucer
in the opening where you have removed the bottom of the bottle , after you pour
the urea-gelatine down through the opening and into the flask . Just dump and cover . You should be able to scale up at least 50% from the 475 ml , and perhaps 75% more without any overflow .

Whatever the scale you use , keep to exactly the described relative proportions
on every ingredient . The amount of gelatine will have significant bearing on
the reaction so weigh it carefully and make sure your glassware is very clean
and definitely use only distilled water .
Metal ions poison the reaction .

[Edited on 23-4-2005 by Rosco Bodine]

Well shit, I may have hydrazine poisoning. I have had a headace and had some nausea today, symptoms of hydrazine poisoning. As well I have felt weird today, not a way I have felt before. I wore a respirator the entire synthesis, except during filtration.

It could just be that I'm a bit of a hypochondriac, and this is just a placebo type effect. But I am still worried.

Studying the tradeoffs involving volatility scenarios from transesterfication , solubilities for the reactants , ect . ....

The best method in my mind for simplifying
the apparatus requirements , while still
having a good product yield from a given volume of reaction mixture , would be to
use a methanol free denatured ethanol
for freebasing the hydrazine . And then
to either use isopropyl nitrite obtained by
either microteks method , or the more usual method using nitrite and HCl , to
nitrosate the basified hydrazine extract
in ethanol , with the reaction done in a
salted ice bath . Alternately , simply bubbling N2O3 into the basified ethanolic
extract of hydrazine , cooled in a salted ice bath might work . Using ethanol should be the compromise which is easier for the extraction not being as picky about the moisture , while providing better solubility and a more concentrated reaction mixture , and yet still having a not too low of a boiling point for the transesterfication product which would be ethyl nitrite , which boils at 17 C . Salted ice would keep the reaction cold enough if it was done slowly , to keep the nitrite in the reaction .

Methyl nitrite on the other hand , boils away at - 12 C , so it tries to escape even at very cold temperatures unless a bit of pressure is used to contain it , the loss of nitrite is probably 50% , which is unacceptable .

So a variation on microteks method , but using ethanol for the extraction could prove useful , but only for denatured alcohols where methanol is not the
denaturant . It is possible that some
other denaturants might be problematic ,
and this would have to be examined .
It is also possible that a methanol denatured ethanol could be stripped of its methanol in advance by bubbling through
it sufficient N2O3 to esterfy and volatilize
any methanol . Warming the alcohol would drive out any residual methyl nitrite
leaving essentially pure ethanol . This same methanol removal method could be useful for purifying methanol denatured alcohol for use in fulminate synthesis , or other uses where the methanol denaturant is undesirable , and ethanol
alone is what is required . Hmmmm , the
revenue folks are sure to love this news Transesterfication purified moonshine anybody ? Pass me the jug

Your two year old NaOCl is not NaOCl anymore . The storage life for the 10% is only a matter of weeks at cool temperatures . At subfreezing temps it
could be stored longer , but normal shelf life at ordinary temperature is very short .

[Edited on 24-4-2005 by Rosco Bodine]

Keep to the stated proportions regardless
of the physical observations . There is some overlap for the -Cl and -SO4 neutralizations so that the CO2 evolution is not a precise indication of where the neutralization actually is in its progress .
I also believe the hydrazine is already largely tied up as a carbonate in the mixture , or as a complex with other carbonates . So you will get some CO2 evolution beyond the point where you would expect it to stop , even into the addition of the H2SO4 . But the ratios
have been worked out to be optimum for
the precipitation of the HS at the end ,
in pure form . So use the quantities given .

Do a molar quantities analysis , neutralization equivalents and some extra
for operating margins , and you will see the arithmetic is already worked out correctly . Quantity variations were tried for experimental confirmation that the math was applicable , which it was confirmed to be . I covered all the bases
on this HS synthesis . You can confirm that easily enough . It's like you are asking " are you sure " ....yeah I'm sure

There is an " extra strength " household
bleach usually labeled as " Ultra " bleach
and it is about 6 % while the regular bleach is usually 5.25 % NaOCl . The reaction for hydrazine should still work to some extent and you can experiment to see what sort of adjustments may benefit the reaction with the lower concentration bleach . The disadvantage will be the lower amount of hydrazine sulfate which is possible to get from a given volume of the reaction mixture . If the yields are similar percentages on a molar basis , then the economy of the reaction will be
unaffected , except for the increased labor and need for larger reaction vessels . Of course , if the foaming problem is gone then the volume requirement for the reaction vessels will
not be reduced because of the larger volume required for the more dilute solutions for a similar batch size . And after the neutralizing acids are taken into account , the volume efficency will be reduced . But if the process is still workable even with ordinary bleach , that is certainly a valuable development for
being able to substitute a more readily available form of NaOCl .

It may be possible to make NaOCl of high concentration by reacting calcium hypochlorite pool shock with sodium carbonate washing soda , filtering out the precipitated calcium carbonate from the calcium compounds , leaving a solution of NaOCl . It may be possible to boost the NaOCl content of ordinary bleach by this method . One would need to do a weight loss on heating test for the washing soda to determine its state of hydration . The
Arm and Hammer brand which I tested is typically 83.4 % Na2CO3 and the remaining weight is water of crystallization
in the form it is found straight from the box . Other brands or lots may vary .

So this is a possible adjustment method which may be useful if it is needed .
However , if useful yields are still obtainable from ordinary strength household bleach , then it probably easier to just work with what is available and
simply use larger batches since the process is very scalable up or down .

I have tossed around the idea that in an insulated container such as a large plastic lined picnic cooler , that a certain volume
and geometry reaction mass could probably achieve the conservation of its own heat of reaction sufficiently for the
exotherm to be sufficient alone to carry the reaction through to completion without any supplemental heating being required . If this is true , it may be easier
to make HS in kilogram quantities in one batch , using several gallons of bleach at
one time in a large enough scale batch to
achieve that conservation of the exotherm . All that would be required then is to let the reaction run on its own exotherm to completion , and then neutralize the mixture . On an industrial scale there seems no reason why this would not work , and down to a certain
limiting scale of perhaps three to five gallons of mixture , the same method may be adaptable to " small scale " method which is possible in " picnicware " sized
insulated containers

I would bet you would have the hydrazine hydrate in the isopropanol BUT they do use alkali to dehydrate hydrazine hydrate. Most reactions would not require anhydrous hydrazine anyway so if you wanted the hydrate I guess adding a little water to the extract and removing an isopropanol azeotrope under reduced pressure would be satisfactory.


P.S was not aware soonish was a word. I like it!

[Edited on 4/27/2005 by chloric1]

usual behavior of hydrated salt does not apply

Stoichiometry gives me a headache

Sometimes a bit of background music helps .

Anyway , if you simply must resort to chlorination , it would probably be easier
to use regular bleach as the starting point , chill it feezing cold and go ahead and add NaOH in the quantity needed
for the added NaOCl , plus whatever extra
NaOH is to be added for the extra needed in the hydrazine synthesis . Rechill the solution , and chlorinate it with the vessel
sitting upon a scale until it has absorbed the necessary weight gain . The strongly
basified mixture will chlorinate more easily
and you will have one less step to do afterwards , plus the product will be more stable .

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I can as well start from plain NaOH solution than from the really weak NaOCl bleach.

What I don't understand is why you have to monitor the weight gain of the NaOH during chlorination! Why don't just bubble in chlorine until no more is absorbed?
EDIT: sorry, I missed the part where you said that the extra NaOH is used in the hydrazine synthesis. Then chlorination would have to be stopped at the right point.
But even weak NaOH vigorously absorbs chlorine, you can be sure that there will be no problems with unreacted chlorine even when you chlorinate until all NaOH has been converted.
My scale only goes up to 500g, so I can't make a kilo of NaOCl with weight monitoring.
Perhaps add some extra NaOH after chlorination to bind the free chlorine, which would otherwise decrease the pH and destabilize the NaOCl.

I can get TCCA cheap and in large amounts, so I can make all the chlorine I'd ever need.
Calcium hypochlorit isn't available, though.

BTW nice background music!

[Edited on 28-4-2005 by garage chemist]