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Sauron
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COS = carbonyl sulfide, how to deal with that?
S.C.Wack used to provide a compendium of selected monographs from Inorg.Syn, I think on rapidshare, and perhaps on ftp #1 (Axehandle) but thus far I
he has resisted all blandishments to re-up this item, to FTP #2, or 4shared or something.
I dunno if this item is even among his handpicks.
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Eclectic
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You feed the COS with oxygen to your heated vanadium catalyst tube. 
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Mr. Wizard
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You can liquefy ammonia with simple steel and iron fittings. There used to be a lot of links when you search for Crosley IcyBall. There was even one
made with regular steel plumbing pipe and it worked. (Larry Hall Icyball) also see IcyBall Patent #1,740,737 and IcyBall Patent #1,811,523
I downloaded a copy of the sites main information. Try searching for it. Liquid ammonia is dangerous and attacks brass and copper. Liquid propane
tankers are sometimes used to haul liquid ammonia in the summer season, if they have the right fittings, that is stainless steel or steel valves.
Strong ammonia fumes will attack every moist, damp, or wet area on your body. It can render your eyes to trash in seconds and leave your crotch and
armpits a scalding wound. Emergency workers are known to spread generous amounts of petroleum jelly (Vaseline) on sensitive areas, before using a
self contained breathing apparatus to go in and stop a leak at a plant using ammonia. On the other hand a spray of water can absorb enormous amounts
of the gas. An ammonia leak is a real nasty item, for you and all your neighbors, and it goes on for hours and hours and hours. Liquid ammonia
refrigerates itself so well that it will take forever to evaporate. I've been told a glass of liquid ammonia, without any insulation will last over 24
hours.
I don't know how this will work using Urea, but to say it can't be done isn't true.
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Sauron
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The German patent (looks like Akso's chemists) for the two step process:
Enka Glanzstoff, DE 1 297 088, 1967 (H. Maegerlein, H. Rupp, G. Meyer).
One step process at 115 C and 5 bar, this one definitely Akso
Akzo, DE 3 508 404, 1986 (G. Meyer, G. Sudheimer, H. Zengel, H.
BTW ammonium thiocyanate and thiourea are isomeri just as urea and ammonium cyanate are. Heating ammonium thiocyanate gets you thiourea. But slowly
and incompletely. I wonder if this goes both ways? The answer is yes, it is an equilibrium but the two (thiourea and thiocyanate) are very hard to
seperate so this method is not employed preparatively and is only of historical interest.
EUREKA!
Org.Syn. to the rescue
Ammonium dithiocarbamate. Gaseous ammonia is passed into 250 ml. of 95% ethanol (Note 1) contained in a 1-l. Erlenmeyer flask immersed in an ice bath
until the gain in weight is 39 g. (2.3 moles). To this solution, still cooled by the ice bath, is added a well-cooled mixture of 76 g. (60 ml., 1
mole) of carbon disulfide and 200 ml. of ether. The flask is stoppered loosely (Note 2) and allowed to remain in the ice bath for 2–3 hours and then
at room temperature overnight (Note 3). The mixture is again cooled in an ice bath or refrigerator, and the crystals are collected by filtration
(hood), sucked dry, and washed on the filter with two 50-ml. portions of ether. Air is drawn through the crystals for 5 minutes (Note 4) to effect
removal of most of the ether. The product is used promptly without further treatment; the weight of the lemon-yellow solid varies between 80 and 90
g., depending principally on the completeness of the removal of the solvent.
Collective Volume 3, p.763
I will attach the entire prep, which is of Rhodanine, so you will have the references and the notes for Part A which is the ammonium dithiocarbamate.
No interface reactor, no activated charcoal, just ethanolic NH3 and CS2/Et2O and you have what you want to pyrolize at 95-100 C to NH4SCN.
So there IS a simple easy way to make ammonium thiocyanate after all.
[Edited on 15-9-2007 by Sauron]
Attachment: CV3P0763.pdf (120kB)
This file has been downloaded 1577 times
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Sauron
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PS
The attached is the JACS article on which the Org.Syn. prep of rhodanine was based, for comparison of their procedure for ammonium dithiocarbamate. I
suspect the Org.Syn. variation is a little more thoroughly described.
Sorry about the double post!
[Edited on 15-9-2007 by Sauron]
Attachment: ja01309a053.pdf (336kB)
This file has been downloaded 1043 times
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S.C. Wack
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Some corrections if I may digress from the point of this thread entirely.
I specified "easy convenient amateur-friendly method", which CS2 is not exactly, as much fun as it is to make or spend outrageously large sums of cash
on.
Axehandle has FTP#2. There is a thread with this title.
No one has asked me for the Inorg Syn collection. [edit- I obviously do not recall such a request] The relevant preparation isn't in that djvu
anyways.
I uploaded everything I had of my own at the time to the newer FTP, and it was all erased.
I put all of my book scans on 4shared along with other useful pdfs for a total of 975 MB for many months, in fact I started the thread on 4shared if
you look, and the WWW button which is no longer at the bottom of my posts, but was for some time, took you directly to them. One can find amongst my
scans the preparation of ammonium thiocyanate from CS2 and ammonia.
The 4shared collection is no longer there because my last 3 uploads and the rest of the collection got a single download between them in the last 3
months, and that one only because Mephisto wanted to see it, from its mention in the book scanning thread.
On topic- "from urea?"
No. Stick with what has been tried and true for many years for ammonia generation or just about anything else and you'll get more done. OK that may be
construed as discouraging experimentation... Experiments have shown that it is often a more efficient use of time and money to let other people do the
major experimentation for you. One often has their hands full with just the little tweaks.
| Quote: | Originally posted by 12AX7
...And SO2, and H2S. Now there's a refrigerant that'll discourage tampering! |
I ran into a working SO2 fridge a couple years ago from what, the 40's? Still around. Wonder if they're worth anything.
[Edited on 15-9-2007 by S.C. Wack]
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Sauron
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Actually I asked you for the Inorg.Syn. files back in Dec or Jan and you gave me an unresponse. Axhandle isn't around any longer to answer requests
for admission to his FTP site. To the best of my knowledge your stuff is not on MadHatter, I have been all over that one and have not seen it. I still
would like to have it, but, whatever.
I think we have got ammonium dithiocarbamate pretty well covered, details of the conversion of that to the thiocyanate and purification of same would
be nice (for Eclectic). As for myself I will just buy the thiocyanate if I decide to try this. Fortunately this is still a free country and I can
pretty much buy what I like. That includes cylinders of NH3 should I so desire.
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Eclectic
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Ammonia based refrigeration is good in situations where you need cooling powered by a low grade heat source, or electricity is not available. Such a
RV camping, or remote locations off the power grid, or situations where you might need refrigeration even if the power goes off for a week.
S.C., I think the old G.E. SO2 refrigerators may be collector's items if they are in good shape and still working. Please post a link to the
Inorganic Synth. prep of Ammonium Thiocyanate in volume 3 if you have it? I don't understant kmno4's link: http://55158856/wasny ???
[Edited on 9-15-2007 by Eclectic]
OH! I see, it's an IQ test. I guess I passed.
[Edited on 9-15-2007 by Eclectic]
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DeAdFX
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Would the catalytic decomposition of urea via Urease be worth a try? A large amount of Ammonia/CO2 gas could be formed with little use of other
chemicals (just a little bit of phosphates for pH buffer). Sperating the two gases and maintaing optimal conditions for the enzyme are the only
things I can think of.
Or perhaps for the engineering type one could desgin a vessel in which urea + water react at high pressures/temperature?
Ammonia on demand
http://www.freepatentsonline.com/7008603.html
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Eclectic
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V2O5 (with or without tungstates) will catalyze urea hydrolysis at 100 C or so. You'd need a good condenser design to avoid blockage by solid
ammonium carbonate, then you still have to get rid of the CO2 and water, unless you want to just use ammonium carbonate as your ammonia source in your
reactions.
@Sauron
Check your 4share root folder.
[Edited on 9-15-2007 by Eclectic]
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DeAdFX
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| Quote: | Originally posted by Eclectic
V2O5 (with or without tungstates) will catalyze urea hydrolysis at 100 C or so. You'd need a good condenser design to avoid blockage by solid
ammonium carbonate, then you still have to get rid of the CO2 and water, unless you want to just use ammonium carbonate as your ammonia source in your
reactions.
@Sauron
Check your 4share root folder.
[Edited on 9-15-2007 by Eclectic] |
Sorry for a thread revival but...I was wondering if this could some how work out as a crude way to get mostly CO2 free ammonia...
The ammonium carbonate and water is mixed with 2 mols of an organic amine (high boiling point). The mixture is lightly heated and hopefully mostly
pure ammonia is collected in a container full of water.
The organic amine could then be regenerated by heat and or vacuum?
(NH4)2CO3 (aq) + NHxRx (aq) + heat ------> NH3 (g) + (NHxRx)2CO3
NH3 (g) + H2O ----> NH4OH(aq)
(NHxRx)2CO3 + heat/vacuum? --------> 2NHxRxOH + CO2(g)
or perhaps just using a diver's solution(ammonia/ammonium thiocyanate would be a better idea to seperate the two gases?
[Edited on 11-8-2008 by DeAdFX]
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