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Author: Subject: unconventional sodium
Magpie
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[*] posted on 22-12-2007 at 12:26


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]




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len1
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[*] posted on 22-12-2007 at 14:30


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]

reagents.JPG - 80kB
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not_important
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[*] posted on 22-12-2007 at 17:18


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

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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[*] posted on 22-12-2007 at 17:44


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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[*] posted on 23-12-2007 at 00:43


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.

apparatus.JPG - 29kB
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[*] posted on 27-12-2007 at 09:10


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.



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[*] posted on 27-12-2007 at 14:03


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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[*] posted on 27-12-2007 at 14:34


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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[*] posted on 27-12-2007 at 15:19


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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[*] posted on 18-2-2008 at 20:13


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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[*] posted on 18-3-2008 at 18:18


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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[*] posted on 19-3-2008 at 19:50


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]




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[*] posted on 19-3-2008 at 21:59


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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[*] posted on 20-3-2008 at 02:07


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]




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[*] posted on 7-4-2008 at 14:46


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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[*] posted on 16-11-2009 at 12:34


I probably don't understand something but had anyone tried electrolyzing a NaCl solution in glycerol?
what will happen?
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[*] posted on 16-11-2009 at 14:05


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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[*] posted on 17-2-2010 at 14:22


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




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[*] posted on 6-11-2010 at 20:17


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.




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[*] posted on 21-11-2010 at 19:44
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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[*] posted on 2-12-2010 at 13:14
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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[*] posted on 5-12-2011 at 19:17


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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[*] posted on 27-1-2012 at 06:45


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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[*] posted on 1-3-2012 at 00:08


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? :D
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[*] posted on 1-3-2012 at 04:06


Quote: Originally posted by Alastair  
dipping a strong magnet
What substance in the reaction mixture would respond to a magnetic field, and how would it respond?
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