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Magpie
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I'm sorry I can't comment on the actual synthesis itself.
But I do have opinions on patents in general: I don't trust them. When attempting to make KOCN I had collected 4 or 5 patents, all claiming an
advantage over the current method. Sometimes they even conflicted with each other. None of them worked for me.
My success with very early (~1900) journal articles is not very good either (re: malonic acid).
[Edited on by Magpie]
[Edited on by Magpie]
The single most important condition for a successful synthesis is good mixing - Nicodem
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len1
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Yes thats what I thought, the H2 formed is meant to protect the metal, just as in the electrolytic method of K production from KOH. But in this case
the K is heavier than the bath, so as soon as the reaction starts subsiding you can turn the stirrer off and the K, if it actually existed, would sink
to the bottom. There would be no need for Ar at the end, if it wasnt required in the beginning.
These little details differentiate real work from fantasy. I noticed this oddity, but didnt put too much weight on it before I tried the experiment.
Now I see its true import.
I didnt know about the legal status of this patent. How does one check that? To be honest I feel emotionally gutted, having been taken for a ride
like that. I have been prepairing for this experiment for over a year.
I really dont believe anything can save this patent. Grignards are hard to start because of moisture and a protective MgO layer over the Mg. I
believe the ultrasound is used to form a breach in this layer and expose fresh Mg to the organic halide. This reaction IS meant to happen with water
present, the Mg acts as a dehydrating agent and supposedly violently. Well the Mg did react with water - it became a dull colour, there was no
problem with initiation. Its just that it didnt react with the KOH. i guess I should have known - try heating Mg with KOH powder to 200C - they
dont react. So stirred in a hydrocarbon its likely to be even more so. The fact that the supposedly measured quantities in the patent were actually
calculated, and the elementary error that the reaction goes to MgO resulting in an impossible 'measurement' of H2 released in the 100-130 C phase, the
lack of any K in my experiments, conducted exactly as in the patent, and the sluggish as one would expect, rather than 'violent' reaction of the Mg
with water solidifies my belief that its all rubbish. The guy never did the exp.
[Edited on 23-12-2007 by len1]
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not_important
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espacenet patent searches give an intro page with tabs for the full doc and legal status. This one ends with
| Quote: |
PRS Date : 2000/04/25
PRS Code : FP
Code Expl.: - EXPIRED DUE TO FAILURE TO PAY MAINTENANCE FEE
EFFECTIVE DATE: 20000216
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if it was practical I'd expect they'd keep it alive. Combine that with an absence of reviewed publication and you have to wonder.
http://v3.espacenet.com/legal?DB=EPODOC&IDX=US4725311&am...
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len1
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Thanks for that not important. I must say the owners look convincing, a german enterprise and several german scientists - you generally dont expect
that sort of thing from them. That the results regarding H2 evolution are 'cooked', is without doubt, but I guess out of respect for the type of
individuals involved, I will give one more chance to the process. Maybe it did work, but for one reason or another the did not measure the H2
evolved, but decided to cook it up for solidity.
I shall repeat the experiment, but will keep it going longer than their 4 hours, will use a hotter plate and more violent aggitation - although I dont
want to break the flask. I havent got a ready means of applying ultrasound inside a rb flux thats heated and stirred - but the addition of the
alcohol, I believe fulfills this roll - thats after all what the patent claims.
I will report the results shortly - but realistically I dont expect anything but confirmation of what Ive already written - and I will be able to
leave the topic with a clear conscience. Len
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len1
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This time I ran the experiment for 6 hours. Changes from the previous runs were as follows
1) The heat output was upped so the reagents were at a vigorous boil at 200C, to achieve this the RB flask was placed in a sand bath maintained at
240C.
2) Freshly cut Mg turnings, from a third source were used and thrown straight into the hot solution - there was no time for the Gringard stopping MgO
to form
3) The mixture was stirred very vigorously from a special fast overhead motor
4) As before I did not use my good ground-glass multi-necked flasks, KOH at high T etches glass, and I dont want them stained, especially on an
experiment that appears dodgy. I used a cheap flask with a rubber stopper - there was no perceptible leak or interaction with the rubber at 200C.
Result - some white percipitate, which would have to be Mg(OH)2 formed and Mg darkened from interaction with water. No K formed as evidenced by
throwing contents of flask into water. Zilch in the language of the patent inventors.
I am now very confiedent this patent is rubbish and am sorry I wasted time on it. Reasons are:
1) No K formed in any experiments despite following patent closely, three different sources of Mg, the last freshy cut
2) The patent clearly 'cooks' the amount of H2 evolved. In water Mg + 2H2O -> Mg(OH)2 + H2, not Mg + H2O -> MgO + H2. SO 278mmol H2O releases
139mmol H2 not the 278 that the patent quotes. The hydroxide doesnt dehydrate at 200C. The very accurate wrong 'measurement' is in exact accord with
the incorrect theoretical formula, which shows that it was never measured. The same goes for the H2 released subsequently - construed to add up
exactly to 1000mmol, the amount of pure KOH used. If they cooked one part of their patent, they are likely to have cooked the rest.
3) This type of reaction was not really expected. KOH and Mg dont react at 200C the KOH form only an emulsion in the hydrocarbon and as such its
interaction with the Mg in this medium is not expected to be better than in the solid state.
In short 'BUSTED'. I feel unclean for having participated in this rort. I look forward to doing something more interesting.
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Fleaker
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Pity. Len, I think you would have better luck distilling potassium from KCl using some of your Na to displace it. That's at least tried and true.
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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len1
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Thanks. The whole point in this for me was to witness what I thought was an amazing reaction. Until you look closely the patent seems really
genuine, at worst I thought Ill get a low yield. I am not sure what the patent authors wanted to achieve by faking somthing that is so easy to check.
Len
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BromicAcid
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When I made my run at this I didn't have any special preparation of my reagents. My kerosene was taken straight from the gas station, my isopropyl
alcohol from the drug store, and my Mg out of a plastic bag that it came in from the pyro people when I bought it. My KOH was in large prills and
taken straight from the container, it was originally sold for soap making. No clue why I got such glaringly different results.
I had a strong effervescence throughout the procedure and I ran it at notably lower temperatures. Granted there is the possibility of water
contamination but I would not think that it would be to such great extent as to dissolve as much Mg as dissolved.
Because I have not posted them elsewhere (or maybe I have) here are more pictures from my attempt.
http://www.destructve.com/sciencemadness/IMAGE011.JPG
http://www.destructve.com/sciencemadness/IMAGE016.JPG
http://www.destructve.com/sciencemadness/IMAGE018.JPG
http://www.destructve.com/sciencemadness/IMAGE021.JPG
They are in chronological order, with the first picture taken within 30 minutes of beginning the heating and the second was taken after 3 or 4 hours
IIRC. The third picture was taken after the mixture had been stoppered and allowed to sit approx. 15 hours and you can see the strange color change
that I attributed to any K working around in there chewing things up and reacting. The final picture is form when I filtered the mixture and decided
to dump some of the solid material into some water, you can still see bubbles from the somewhat vigorous effervescence along the rim of the water in
the container.
Again, I don't know what happened differently, maybe your reagents were a bit too pure or maybe t-butanol just works like crap. My main reason for
posting here though is just to show exactly what I observed. With the validity of this patent being called into question I wanted to show that the
results that I posted about were not exaggerations and were what I actually saw, no matter their origin or how much of a fluke they may have been.
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len1
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I dont think your results are different. A white precipitate is generated from the reaction of Mg with H2O, that would occur in pure hot water as
well. The reaction generates H2 although at half the rate to what the patent authors 'measured'. Thats the effervesence. But the point of the
patent is not to form magnesium hydroxide.
My request to you or anyone else who thinks this reaction works, is
please show the potassium.
Anything else is pure speculation. Len
[Edited on 27-12-2007 by len1]
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crazyboy
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OK so I just repeated BromicAcid's experiment detailed on page 3 except I only used half the hydroxide and magnesium and I substituted potassium
hydroxide for sodium hydroxide. I also used a bean can with a 1/4" hole drilled in the top; I inserted a short piece of copper pipe into this hole and
plugged it with steel wool. (I did this to limit oxygen to the reaction chamber without causing too much pressure to build up. then I heated the can
with a blowtorch after about 30 seconds smoke began to come out of the hole I continued heating for 20 or so more seconds until all smoke had stopped.
I removed the copper pipe and began to use a can opener to remove the lid. When the lid was only partially off I could tell there was no fire in the
can when it was removed the contents lit with a bright yellow glow it wasn't as bright as magnesium and it went on for about 50 seconds. Then it died
down and I let it cool. I came back 5 minutes later and poured in some cold water the mass relit with brilliant yellow flame then was extinguished.
Did I produce pure sodium? Or was it just magnesium burning in the presence of a sodium salt with little oxygen that caused the slow yellow flame? I
plan on repeating this with more Mg and NaOH and pouring xylene in the can after it is cooled instead of opening it to the air does this sound like a
good idea?
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crazyboy
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Well I believe I just made impure elemental sodium metal. I heated 15g Mg and 33g NaOH in a sealed soup can in an argon atmosphere with a blowtorch
for about a minute or two. Then I let it cool and poured in xylene (kind of screwed everything up) the chunk was broken up with a screwdriver and the
chunks and soot where found to release hydrogen gas and combust when dropped into water.
The xylene screwed the whole thing up because it was oily and wouldn't get off the chunks so when they were tossed in they only liberated hydrogen and
only a few actually burst into flames. I know this was the xylenes fault because they burnt with a sooty flame and when they where heated with a
lighter they burned sootily but when the burnt piece was tossed back into the water it burned much better then the ones still coated with xylene.
Here is some short demos of my homemade sodium: http://s179.photobucket.com/albums/w318/crazyboy25/?action=v...
It might seem to burn with a oily flame not like that of sodium this is due to xylene not the sodium.
[Edited on 18-3-2008 by crazyboy]
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kilowatt
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Nice work. Next you could try distilling it under argon to see if you can get any pure sodium metal out. Sodium boils at 883°C. Make sure
everything is thoroughly purged of air of course. Be sure to allow venting, since if you got any sodium hydride that will want to decompose to sodium
and hydrogen. Maybe this process could even be coupled with just such a distillation, so it is a one step thing.
[Edited on 19-3-2008 by kilowatt]
The mind cannot decide the truth; it can only find the truth.
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crazyboy
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Thanks! How would you suggest doing that? I mean an all glass setup would corrode with the molten NaOH and if it didn't I would think the heat would
be too much for the glass. Perhaps a metal can with an all copper condenser? Perhaps even a feed of argon into the can at all times? I'm not trying to
shoot down your ideas i'm just looking for practical ideas.
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kilowatt
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I was thinking an iron reflux still made of threaded pipe fittings, with stainless steel scrubbers for column packing. The magnesium oxide smoke
would come right over with a simple retort. I would definitely keep argon flowing through it slowly. This will help the distillation along as well
as insuring there is no air inside.
[Edited on 20-3-2008 by kilowatt]
The mind cannot decide the truth; it can only find the truth.
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crazyboy
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Sorry guys I’m going to have to side with len1 on this I just retested the experiment with NaOH and aluminum results seemed positive gray solid
burns yellow reacts with water almost everything you would expect; almost. I noticed the "sodium" was very brittle previously I had just attributed
this to impurities but rethinking it this is what is probably happening:
The sodium hydroxide melts and forms a very intimate mixture with the aluminum. The gray stuff is just sodium hydroxide and aluminum fused together
when they are added to water the same reaction occurs as if you were adding aluminum foil to NaOH soln. hydrogen and heat are produced. But because
the mix is so intimate much hydrogen and heat is produced and sometimes that heat ignites the hydrogen.
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hashashan
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I probably don't understand something but had anyone tried electrolyzing a NaCl solution in glycerol?
what will happen?
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bbartlog
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Quote: Originally posted by hashashan  | I probably don't understand something but had anyone tried electrolyzing a NaCl solution in glycerol?
what will happen? |
I wouldn't know the specifics, but given that sodium glycerate is a known compound I think you can be fairly sure that you aren't going to end up with
elemental sodium. If you poke around in the scimadness library a while you may be able to find a reference in one of the older books on
electrochemistry; they record a lot of results for simple experiments such as the one you are describing.
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Ephoton
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think I found a new one. it uses amalgumated copper electrodes and a salt solution.
it works for gallium as well 
http://www.patentstorm.us/patents/4012298/description.html
e3500 console login: root
bash-2.05#
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madscientist
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ordenblitz, if you're still around, I'd be interested to hear what the results would be with an attempt to prepare NaAlH4 in an manner analogous to
your NaBH4 preparation:
6NaOH + 4Al ----> NaAlH4 + 2NaH + 3NaAlO2
Reading this thread I can't help but think the most useful application of this thermite reaction is not to be found in the alkali metals, but rather a
handful of powerful reducers and bases that are otherwise unavailable to the amateur - aluminum hydrides in particular.
I weep at the sight of flaming acetic anhydride.
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symboom
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production of sodium metal
i have made sodium metal from sodium hydroxide with great success using a wide iron container with the cathode patuding from the bottom of the
container then putting iron screen would have been more pure if i used argon gas
potassium metal however from potassium hydroxide i am going to have to use argon
i read that molten fused sodium cyanide electrolysis but cyanide compounds are toxic and a problem and correct me if i am wrong but the products
formed are cyanogen a toxic and flammable gas and sodium metal
does anyone what is the electrolysis of molten sodium cyanate products
[Edited on 22-11-2010 by symboom]
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chedo
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Potassium made in Germany
| Quote: Originally posted by len1 | I dont think your results are different. A white precipitate is generated from the reaction of Mg with H2O, that would occur in pure hot water as
well. The reaction generates H2 although at half the rate to what the patent authors 'measured'. Thats the effervesence. But the point of the
patent is not to form magnesium hydroxide.
My request to you or anyone else who thinks this reaction works, is
please show the potassium.
Anything else is pure speculation. Len
[Edited on 27-12-2007 by len1] |
Look here:
http://www.versuchschemie.de/topic,14677,-Synthese+von+Kaliu...
| Quote: | Abstract not available for EP0244894
Abstract of corresponding document: US4725311
A process of producing alkali metal by a reduction of alkali metal compounds with metallic reducing agents, which is simplified and avoids corrosion
of the reaction vessel and part thereof in that the reduction is effected with particulate magnesium in an organic solvent which under the conditions
of the process is inert to the alkali metal to be produced. The reaction is effected at temperatures from 100 DEG to 300 DEG C. In an embodiment of
the process the reduction is effected in the presence of an alcohol used as a reaction accelerator. |
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runninfarmer
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I've seen a lot of people make sodium metal from NaOH using Mg as a reducer. I've also read the two large threads about it on here.
But I can't see where anyone used NaCl alone with Mg to produce Na metal. Does it not work? Do you have to use NaOH to get the reduction to work?
Thanks for the help
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zuluwhiskey
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I've been scouring the internet on making sodium and here's what I found:
http://en.m.wikipedia.org/wiki/Sodium_amalgam
If you look at the "uses" section, you'll find:
| Quote: | | Sodium amalgam is a by-product of chlorine manufactured by mercury cell electrolysis. In this cell, brine (concentrated sodium chloride solution) is
electrolysed between a liquid mercury cathode and a titanium or graphite anode. Chlorine is formed at the anode, while sodium formed at the cathode
dissolves into the mercury, making sodium amalgam. Normally this sodium amalgam is drawn off and reacted with water in a "decomposer cell" to produce
hydrogen gas, concentrated sodium hydroxide solution, and mercury to be recycled through the process. |
Just distill of the mercury in an inert atmosphere?...
Sodium amalgam in action
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Alastair
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len1 and everybody else, i understand that skimming sodium off a solvent is perfect and you get it nearly clean.
however, has nobody thought of dipping a strong magnet into any nps and thus recovering sodium from MgO or Al2O3 or whatever acids and salts?
Or am i just clumsy? 
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watson.fawkes
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What substance in the reaction mixture would respond to a magnetic field, and how
would it respond?
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