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NurdRage
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Video of heating step
Here it is:
http://www.youtube.com/watch?v=8azkO_7iBl4
The video starts right after i add the last shot of t-amyl alcohol. it then time lapses 4 hours into 2 minutes and you can see the conversion of
magnesium turnings into potassium balls. Finally i show the molten potassium ball after it fully coalesces.
The final crust was rock-hard.
The parameters are: 30mL paraffin oil (0.86g/mL density), 6g KOH, 2.2g Mg, 2mL t-amyl alcohol (i used excess because my first shot didn't work).
If you guys want me to post a version with a different time-lapse factor let me know.
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Quote: Originally posted by Sedit  |
The activity of the HCl washed Magnesium was roughtly 2x that of the fresh turning judging from the hydrogen production.
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Looks like we have our activation means, a hydrochloric acid wash.
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len2
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Nudrage do you shake your mixture - or you also let it be like Wilco? What size particles are your Mg?
[Edited on 23-12-2010 by len2]
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condennnsa
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Nurdrage , what was the paraffin oil you used? Is it the viscous, clear, odorless stuff sold in drugstores?
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Sedit
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Nurdrage I must stress that yes the HCl washing does indeed help but the Slag, Oh the slag.... that is so active it rivals Aluminum in HCl if you know
what I mean. I want to reproduce that in a controled fashion.
My guess is the crude, more then likely oxides of Mg and Fe, are not allowing the molten Mg to form a nice melt but instead a hard crusty slag. This
slag must contain very fine Mg with an activation level well beyond anything I have seen yet.
IF someone has pure sand please mix it in with a small amount of melted Mg till its a solid crust. Once broken compair that to the way that normal
magnesium shavings react. Its shocking.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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NurdRage
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@Len2
No shaking or stirring during the video.
I did some initial grinding when i mixed the reagents, then after the "dehydration" step i stuck my spatula in and ground it up some more since it
hardened to cement. I popped a shot of alcohol, replaced the condenser, and then just let it simmer on its own, no extra stirring.
@Condennsa
I used this oil: http://www.sigmaaldrich.com/catalog/ProductDetail.do?lang=en...
@Sedit
Sand and molten magnesium? Did you make magnesium silicide?
----> interesting implications
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len2
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It seems you can get coalescence w/o stirring because liquid potassium rises in paraffin - it doesnt in D70. The other question I have is what is you
hotplate temp?
Thanks Nurdrage. Well Id say then your paraffin oil method is superior, because it eliminates the 1hrs worth of purification and the dioxane. Ill try
it, I just hope I dont have to use the spectro grade - Ill use the stuff we have round for oil baths and see if it works.
[Edited on 23-12-2010 by len2]
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NurdRage
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@len2
Hot plate temp set to 300 celsius. but when i stuck a thermocouple directly into the oil it read 180 celsius.
The actual temperature of the crust bed is probably somewhere in between (probably to the lower end).
If you're going to go with the paraffin oil route to save on coalescence work-up, then i think an important feature is the density of the oil. Mine
was 0.86g which is more dense than the liquid density of K at 0.82g. A nice advantage is that when everything cools, solid K is denser and sinks to
the bottom, making it safer and less susceptible to air oxidation.
[Edited on 23-12-2010 by NurdRage]
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Sedit
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No nurdrage im just trying to think of an inert agent to suspend the very fine, and very active Mg particals that are forming simular to whats going
on with my slag as I melt down crappy magnesium from an old anode.
Perhaps MgO would be the best agent to use in this case I suppose. Carbon on the other hand keeps nagging at the back of my mind as a possible
solution.
The main goal is to turn the metal into a material that contains very high surface area simular to how many catalyst are precipitated onto things like
silica.
After many runs over and over the clean metal reacts with water and 5% AcOH very slowly where as the crap thats left over reacts vigorously with each
and in AcOH it appears like someone tossed Zinc into HCl. This showes me that the slag is WAY more reactive then the pure metal, and as an added bonus
its brittle meaning I could break it into finer pieces with realative ease.
I feel if I can figure out how to make this "slag" in a controlled fashion the reaction time will drop dramaticly and quite possibly so will the
activation temperature.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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NurdRage
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@Sedit
The highly active magnesium would be great.
I'm also interested in your attempts to reactivate "deactivated" magnesium. Being able to use a wide range of easily obtainable, cheap, low grade
magnesium would be just as useful, if not more so, than producing super-grade stuff. A little extra time is alright if it still works.
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woelen
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Thread Pruned
23-12-2010 at 01:50 |
woelen
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Removed some spam and an angry reaction.
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len2
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Another interesting aspect is that the KOH does not react with the glass surface - which remains crystal clear - so that good flasks can be used.
Without adding the magnesium, you can see a milk-like fluid - which the KOH becomes at 160C floating at the bottom, and above it clear D70. I presume
there is no etching because the surface tension is such that the D70 forms a light coat on the bottom of the glass preventing the KOH from touching
it.
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Pok
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@MagicJigPipe
| Quote: Originally posted by MagicJigPipe | | Also, Pok, I don't think the boiling point of the solvent is extremely critical as long as it is higher than ~200*C or so, right? If it is critical,
why? The only thing I can think of is agitation of the reaction mixture. |
I only used Shellsol
D70 and can't give you infos about other solvents. But I also think agitation is neccessary and 200-250°C boiling point will do this job. The patent says "yes, its
important" afaik. Aromatics could react with K. | Quote: Originally posted by MagicJigPipe | | I see we have some evidence that supports that hypothesis but we can't be quite certain yet. I suppose alkali metals are more likely to react with
aromatics... That makes sense then... Could it just reduce yield instead of somehow poisoning the reaction? |
I think it would be yield reduction and not poisoning the reaction, but remember: even a low % aromatics content in
the solvent could destroy a large amount of the K, because so much solvent is needed.
@len2
| Quote: Originally posted by len2 | | I cant unfortunately change - I have no edit privelages on what I posted ages ago. I would however like to apologize to Pok (but he should learn how
liquid density changes with T in almost all cases, esp far from melting point) |
It's ok. We
both were a bit nervous. I know about density change with T. But the MSDS said:
density increase from 15->20°C - I also was suprised, maybe a mistake in the MSDS.
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blogfast25
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Len:
Very interesting point about the dioxane: strange that the coalescence occurs when the K floats, I'd have expected quite the opposite... But
nurdrage's results confirm it too...
In my 'medium kerosene' the K doesn't float, must work only with a heavier grade.
Another scheme I dreamt up (w/o realistic prospects of testing) is centrifuging the solvent-molten K mixture to apply force on the K globules and
force them into each other...
[Edited on 23-12-2010 by blogfast25]
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Arthur Dent
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oxide-free magnesium
| Quote: Originally posted by Sedit | | ...im just trying to think of an inert agent to suspend the very fine, and very active Mg particals ... |
I thought of an idea last night.... what if we took a solid piece of magnesium and grinded it with a medium coarse file (as per Pok's technique) but
under the shellsol?
This way, the Mg couldn't react with the air because it would already be in the solvent as the fresh Mg particules would be exposed...
I can realise that filing metallic magnesium immersed in a flammable liquid is something to be done VERY carefully but I can imagine this would
provide "ideal" conditions where the magnesium would be mostly devoid of oxides and what not.
Just a thought. 
Robert
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blogfast25
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Probably Robert, but as established the Mg really isn't as critical as we once thought... Neither is probably the solvent, within reason...
[Edited on 23-12-2010 by blogfast25]
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blogfast25
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| Quote: Originally posted by NurdRage | Here it is:
http://www.youtube.com/watch?v=8azkO_7iBl4
The video starts right after i add the last shot of t-amyl alcohol. it then time lapses 4 hours into 2 minutes and you can see the conversion of
magnesium turnings into potassium balls. Finally i show the molten potassium ball after it fully coalesces.
The final crust was rock-hard.
The parameters are: 30mL paraffin oil (0.86g/mL density), 6g KOH, 2.2g Mg, 2mL t-amyl alcohol (i used excess because my first shot didn't work).
If you guys want me to post a version with a different time-lapse factor let me know.
=================================
| Quote: Originally posted by Sedit |
The activity of the HCl washed Magnesium was roughtly 2x that of the fresh turning judging from the hydrogen production.
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Looks like we have our activation means, a hydrochloric acid wash.
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Fantastic: now that's what I call coalescence!
Can you tell us again the grade of 0.86 d parrafin oil you used or where you got it?
Smart also to reduce the amount of solvent a little bit...
Edit: Oh, I see: IR grade. Wiki states: 'Liquid paraffin, or mineral oil, is a mixture of heavier alkanes, and has a number of names, including
nujol, adepsine oil, alboline, glymol, medicinal paraffin, or saxol. It has a density of around 0.8 g/cm3.[3] Liquid paraffin (medicinal) is used to
aid bowel movement in persons suffering chronic constipation; it passes through the gastrointestinal tract without itself being taken into the body,
but it limits the amount of water removed from the stool. In the food industry, where it may be called "wax"'
That might just about do for potassium at about 200C (d = 0.828 at MP)...
Shebang! 27 quid for 500 ml from the extortionists at Aldrich... 
[Edited on 23-12-2010 by blogfast25]
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condennnsa
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Well I finally found a source for t-butanol (Merck), at 25 euro/1L, but it'll be some 3-4 weeks till I get it. Also ordered 1 kg of 63 um magnesium
from czort. God I hate the holidays, I have to wait so much time to try this out.
Indeed nurdrage, the fact that you were able to coalesce all potassium in that huge ball is amazing. Your results make me believe that paraffin oil
might be a better solvent for this procedure than shellsol, and it's also completely odorless.
[Edited on 23-12-2010 by condennnsa]
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watson.fawkes
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CAS 8052-41-3 is also known as Stoddard solvent. There are two kinds of refinement used to get Shellsol D70 and its relatives:
fractional distillation with a relative narrow boiling point range and hydrogen treatment to remove aromatics and alkenes. Stoddard solvent is
refined only with the first of these, not the second. While the jury is out on the exact effect of aromatic and alkene impurities, it seems that they
don't poison the reaction unless the quantities are particularly high. They may (although this has not been verified in the present process) reduce
yields by reacting with metallic potassium.
I might point out that it's certainly not out of the question to do your own hydrogenation treatment, although the pressure vessel and other equipment
to do so isn't nearly as common or inexpensive as glassware.
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Eclectic
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K-1 water white kerosine made for unvented heaters and lamps should be fully hydrogenated. Aromatics cause smoke and odors, and would totally freak
out EPA and consumer protection agencies.
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Alchemist
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Other Alcohols
Hello again,
Has anyone as yet tried any other alcohols other than t-butanol or t-pentanol and not just tert alcohols. There must be more c3 to c8 carbon alcohols
that would work than just the above two!
Keep up the great work everyone, the Alchemist.....
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NurdRage
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It's amazing how we've all coalesced (pun very much intended) into an unofficial research team.
We're all exploring various aspects that we find interesting: I think Sedit is investigating magnesium quality and activation, Woelen and Len1/2 are
exploring mechanisms and coalescence methods, Blogfast25 seems to be looking at solvents and coalescence methods, and i'm exploring solvents and
activation conditions.
We need a theme song 
Anyway, as we compile more data i agree with Woelen that we should start assembling it together in a nice concise and comprehensive form.
@alchemist
I think someone tried isopropanol but that didn't work. t-butanol and t-pentanol (t-amyl alcohol) were explored first because those were readily
available and perhaps the easiest/cheapest to get for the amateur. They can even be made by a very motivated amateur. More exotic alcohols i think are
less accessible.
If you want to explore other alcohols go for it, or if you can propose an accessible synthesis for them using OTC materials i'd love to hear it. I might try them when i can find the time.
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watson.fawkes
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| Quote: Originally posted by NurdRage | | If you want to explore other alcohols go for it, or if you can propose an accessible synthesis for them using OTC materials i'd love to hear it. I might try them when i can find the time. |
Funny you mention this; I was just looking into this possibility this morning.
Amyl alcohols are found as a major component in fusel alcohols, ordinarily considered by-products of fermentation, rather than targets. There's an
interesting paper on the Wikipedia page for fusel alcohol that addresses their origin. The Ehrlich pathway for fusel alcohol production: a century of research on Saccharomyces cerevisiae metabolism; full text is available at
the link. Here's the central topic: | Quote: | | Fusel alcohols are derived from amino acid catabolism via a pathway that was first proposed a century ago by Ehrlich. |
I haven't dug into the paper very far, but it looks like leucine is a decent candidate for fermentation with some yield as the
primary alcohol isoamyl alcohol (3-methyl-1-butanol). Leucine is readily found in soy protein, available in powdered form at any health food store.
Now I don't know what the activity of a heavier, primary alcohol is going to be for making potassium, but the patent text hints that they might work.
(It might also be that they don't work well, but well enough to disclose in the patent so that they can claim them.) I also don't know what the yield
from soy protein is likely to be, but the Wikipedia page on leucine states that soy protein is about 5% leucine. It's unlikely to be worth doing if
all you want is this particular fraction, but it's certainly possible that the fusel oil from such a fermentation might mediate the Mg / KOH reaction
in relatively impure form.
So if someone else wants to brew up a really smelly wort and tell us all about it here, I'm all ears. I am not all noses, no no no.
[Edited on 24-12-2010 by watson.fawkes]
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Sedit
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My Mg is better then yours
LMAO seriously though when you first suggested about me looking for a super activated Magnesium I thought eh ok, cool. But then as I started to play
with some of the products of my Mg cleaning experiance I really think I may be on to something pretty big.
Using damn near freezing cold water(have you been outside lately ) I added a
couple chunks of Mg from an ingot I made. Then I added a few chunks of the stuff I removed from the dirty Magnesium. The results are amazing to me.
The clean Mg did almost nothing for atlest 5-10 minutes or so, I dunno my perception of time is messed up when im playing, Yet the instant the other
material which is like a sponge almost hit the water a rapid steady stream of bubbles came off. It took over 20 minutes I believe before the normal Mg
was even producing half of the bubbles as this other material.
I believe there will be a level point somewhere in between as the clean magnesium gets going and the old starts to level out but I may very well be
wrong.
I plan on setting up two inverted test tubes filled with distilled water and a sample of magnesium fillings under one and my material under the other.
Judging from the rate if it stays steady I would expect my material to fill the tube in well under one tenth the time if that but only experiment will
tell.
I have a theory and it may not help this potassium synthesis if its how its working. I feel the oxidation that is contained in the slag is some water
soluble material that is giving a huge surface area to the active amount of Magnesium.
In the case of the current potassium experiment I would suggest that someone take magnesium pieces and ball mill them with wax and something to grind
them like stainless steel shot. The resulting material should be very active once the wax melts under the current reaction conditions and provide a
great surface area causing the reaction to run exponetialy faster as does the hydrogen production in my water based experiments.
Hey, can I patent this
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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blogfast25
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@Nurdrage:
Well, my ‘Coalescence Department’ is now closed of course, with your ‘floating coalescence’ method putting it firmly out of business! Thanks
for nothing!
But thankfully there remains much to researched, IMHO:
• Type of alcohol
• Quantity of alcohol
• KOH/Mg ratios
• Reagents/solvent ratios
• Magnesium
WE may want to develop a test tube procedure for the evaluation of different treatments all at once, in order speed up testing and increase
resolution…
But first I need to get my hands on a suitably heavy mineral oil… Yesterday I found an ‘outdoor lamp oil’ that’s clearly heavier than the
kerosene I’ve got but it contains Citronella oil (which itself is made up mainly of Citronellal [an aldehyde], Citronellol [a primary alcohol] and
Geraniol [another primary alcohol]) so maybe I’ll be making ‘citrus flavoured’ potassium, definitely patentable, that one!
Today I’m gonna see if the pharmacy has got anything…
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Nicodem
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I think it would be more interesting to do a scientific research on this reaction to figure out the mechanism of the reaction. Perhaps science is not
as popular as madness, but I still think this is a great opportunity for this forum to contribute to science, given the complete obscurity of this
reaction in the scientific literature (BTW, did anybody actually made a thorough literature search?).
I could contribute by doing the basic experiment, thus testing the reaction of t-BuOK with Mg to figure out if the currently proposed mechanism has
any validity. If the equilibrium of t-BuOK + Mg <=> t-(BuO)2Mg + K is truly directed toward the left side, then there should be no formation of
potassium until a pellet of KOH is added (this addition representing a crude validation test, since the actual absence of a reaction would mean
nothing given the stochastic nature of the Mg surface activation process). Unfortunately I have no shellsol or undecane. Perhaps after my vacations
are over I will give this a try with paraffin wax. Even though a negative reaction outcome would not give any totally conclusive answers, a positive
outcome would. It would tell us the equilibrium direction of the reaction and disprove the hypothesis about the driving force of the overall KOH + Mg
reaction.
Using a longer chain t-alcohol as catalyst might prove useful in the synthesis of sodium where t-BuOH is unlikely to work given the practical
insolubility of t-BuONa in alkanes. A crude way to "fatty t-alcohols" can be the reaction of a large excess of MeMgI or EtMgI(Br) with pure margarine
in refluxing THF or other ethers. The preparation of grignard reagents require Mg and dry solvents. Purifying the products would require some
knowledge of organic chemistry, but already with extractions it might be possible to get them pure enough for this reaction. I doubt it requires a
very pure catalyst, as all the impurities would be destroyed by the reaction conditions (hot KOH!).
PS: It would be nice if one of the members with experience about this reaction writes a general warning and an explanation about the hazards involved.
For example, what to do if the flask containing potassium balls heated at 200 °C suddenly breaks and the metal and oil catch fire? I think there will
be many who will now try to reproduce the experiment, and many probably don't have a clue of the possible consequences if things go bad. Personally,
heating alkali metals scares me terribly. Glassware is not immune to heat shocks! My memories of burning sodium metal are not pleasant and somehow to
me potassium sounds worse. After a consensus is reached about the best warning disclaimer and instructions on how to extinguish the fire, we could
then link to it from the first post in the thread.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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