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Fleaker
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@blogfast25:
2-methyl-2-butanol is seemingly more reactive than t-butyl alcohol. I don't think that discoloration is as readily seen with t-butanol; I've made
KtBuO before, and I don't remember seeing any color to it, but I made it from the metal and the alcohol. Truthfully, I don't remember their being a
yellow color to any simple alkoxide in my experience (i.e. NaOMe, NaOEt, NaOiPr) as long as air is kept from them. Of course, heating in the presence
of air probably leads to polymers and various degradation products. My base bath at work is KOH-saturated isopropanol and is a sullen gray.
@Len1 :
KOH and Mg producing K is well known; my erstwhile partner has had success with it in a nickel plated steel pipe still if I remember rightly. To be
candid, one thing I'm curious about is whether Mg can be substituted for calcium in reducing CsCl or RbCl.
I honestly hope Pok isn't faking as Wilco's results are encouraging.
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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Wilco and I really thought (not in jest, seriously) more of you than this classic
/quote
All the equations and numbers you are bringing with you do not do justice to Pok's work. /quote
All I can say is that if you dont uinderstand the equations, enjoy his work.
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MagicJigPipe
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| Quote: | | Pok, if you are truly genuine, you have the responsibility to stick with us all the way |
I must take issue with this. Pok doesn't have the responsibility to do shit but post his experiment in the best way that he could. And he didn't
even have to do that. I hope he isn't lying for two reasons now. The first is obvious but the second is so that I will stop seeing this bickering
(not referring to the above quote).
Time shall tell. Let us keep an open mind until more evidence has been collected contrary to Pok's "results".
I will be trying this as soon as I get back this weekend. Probably Sunday. It probably won't work and, if it doesn't, that will be one more nail in
the coffin. However, the coffin will not be completely closed until someone does his experiment exactly (which I will be unable to do due to my
inability to gain access to Shellsol D70).
By the way,
My message to Kremer Pigment's in the USA:
| Quote: | Hi, I noticed that, in Europe, a product can be had from your company called "Shellsol D70". I was wondering if I, in the United States, would be
able to order some from you?
Thank you for your prompt reply! |
Their reply:
| Quote: | Dear Customer,
This product can be ordered for you, but it would have to come in one of our HAZMAT shipments due to its flammability. Unfortunately, we only receive
these shipments three times a year, so there would be a wait time of approximately 3-4 months for this item. The only solvents we carry with
regularity are Shellsol T, ethyl alcohol, acetone, and ethyl acetate.
Best Regards,
Becca Pollak
Kremer Pigments Inc. NYC
Phone (212) 219-2394
Fax (212) 219-2395
1 (800) 995-5501
USA Store Location:
247 West 29th Street
New York, NY 10001
(Btw. 7th & 8th Aves.)
Open:
Monday - Saturday 11:00am - 6:30pm[ |
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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Sedit
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Quote: Originally posted by MagicJigPipe  | | I must take issue with this. Pok doesn't have the responsibility to do shit but post his experiment in the best way that he could.
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This is nonsense and I say this to all those making simular remarks. It is the scientist goal to prove the experiment at hand not the peer reviewers.
Yes the peer reviewers are there to ensure a non corrupt system but in the end its up to the "inventor" to justify his claims or take a hike.
PS: for instants would it kill the fellow to show it reacting in water? or even physically prove he even has access to t-BuOH? Yeh its all beating
around the bush type shit while countless efforts here and over at the german forum fail time and time again. It will never be up to poks standard in
the end and I have reached the conmclusion this issx just due to him making excuses for why there synthesis didn't work....... its over folks you have
been had. Prove me wrong and Ill eat my words.
I will leave this thread honestly unlike pok, and not return until someone I trust has big balls of K.
[Edited on 16-12-2010 by Sedit]
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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woelen
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My ShellSol D70 arrived yesterday. Next weekend I'll try the experiment, using the same amounts as Pok did. I will use a 100 ml erlenmeyer in a sand
bath, keeping temperatures between 200 and 240 C and I'll use a dripping funnel to insert the tert-butanol (dissolved in ShellSol D70) slowly over a
period of 30 minutes.
@Len1: What was irking me in your posts (assuming len2 is the same person as len1, correct me if I am wrong) is the anger which shines through them.
An experiment may fail and that may be frustrating, but it is not fair to put that anger on the person who made the write-up of the experiment. You
even may express your doubts (and to be honest, I also feel some doubts), but using words like 'trolling' and so on is not good manner.
Btw, generally I do appreciate your contributions very much, you have had beautiful results and you shared them with us. So, if you have the chemicals
exactly like Pok has and you have the apparatus, then why not give this thing a final shot even if this means risking 4 or 5 hours of your time and a
few bucks worth of chemicals? That's why I decided to purchase the ShellSol D70. I just want to settle this for myself and the only way I can do that
is by means of experiments. The more people try to replicate the experiment as close as possible to what Pok did, the better the arguments will be
either against or in favor of Pok's claims. Again I just want to say: let experimental outcome decide.
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Rosco Bodine
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Has anyone tried making sodium potassium alloy from the mixed hydroxides NaOH and KOH ? It may be easier to completely dehydrate a melt of the mixed
hydroxides 50-50 mole %, mp 171C, by steam distilling away the water, before adding the Mg, to facilitate the start of the reaction, and the fluidity
of the resulting Na-K alloy would possibly make isolation of the product easier.
[Edited on 16-12-2010 by Rosco Bodine]
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NurdRage
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Woelen, when your run reacted with water, did it look something like this:
http://www.youtube.com/watch?v=NWbod97BjFc
The camera didn't render the lilac color as well as i'd like. i think also my KOH had significant sodium contamination. Nonetheless i'm going to
further explore this reaction.
My solvent in this particular run was white candle wax.
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woelen
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Yes, the flash of fire I had looked quite a lot like what you show in the video. A flash of pinkish light and a WHOOSH sound associated with it. The
first time, when I had my finger on the test tube there was a real bang and that was quite scary. The second time, when I swirled the test tube, there
was the flash and whoosh sound.
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NurdRage
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Yeah, I definitely heard that distinctive woosh sound.
good to know i'm on the right track. i'll see if i can get larger quantities.
The amount of grey gunk produced is staggering, i honestly wonder if its possible to get nice balls of potassium.
Thanks for your help.
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len1
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| Quote: |
A warning is not sufficient in such cases. Immediate banning is the only thing which works with trolls and this definitely is a troll
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Who wrote this?
[Edited on 16-12-2010 by len1]
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watson.fawkes
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dissolution of K in t-BuOH
In the original patent, tert-butanol is described as a "reaction promoter". I was chided that this is just a synonym for catalyst, but I'm not sure
the word "catalyst" applies here, because tert-butanol reacts with the intended product to form the alkoxide. That's not ordinary catalyst behavior.
In particular, alkoxide formation from the metal is a competing reaction.
K + t-BuOH --> t-BuOK + 1/2 H2
This reaction is on the wikipedia page for tert-butanol. There's commentary on this reaction by tracing references in that article. In this OrgSyn prep for β-carbethoxy-γ,γ-diphenylvinylacetic acid, tert-butanol is used to dispose of potassium crusts and unreacted
potassium. In this OrgSyn prep for ketene acetal, the first step is the preparation of the tert-butyl alkoxide of a mole of potassium. This reaction for 39 g of K
takes eight hours at reflux, not exactly a speedy reaction. The temperature of this reaction is at the boiling point of tert-butanol, much lower than
the Shellsol D70 boiling point.
The overall reaction for this process has been described as a displacement reaction from K to Mg. I now believe that this presentation of the process
inaccurately omits the effect of tert-butanol on the product. In particular, since the Mg alkoxide is also formed, we should probably consider the
total (unbalanced) reaction as follows. I've left off the alkane solvent, although I'm not fully convinced that it doesn't participate.
KOH + Mg + t-BuOH --> K + t-BuOK + Mg(OH)2 + MgO + (t-BuO)2Mg + H2O + H2
In particular, consider the effect of treating K tert-butoxide as an ordinary product. Here's a balanced idealization of the reaction:
( 2 + x ) KOH + Mg + ( x ) t-BuOH --> 2 K + Mg(OH)2 + ( x ) t-BuOK
The easiest consequence of this reaction is that if there's too much tert-butanol present, it's going to diminish yields. The patent already reports
that product alkoxides are a side product; see examples 1 and 6 in particular. On the other hand, this need not be a problem in practice. Leftover KOH
and t-BuOK can simply be used as reactants for a subsequent batch. Presumably it's readily easy to do a solvent separation of these from Mg(OH)2 and
MgO.
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watson.fawkes
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adsorption of K onto Mg surface
This morning, I had an insight about the possible significance of the phrase "particularly in the form of turnings" in the patent description. Let me
assume, for the sake of argument, that the final step in formation of K is the following reaction:
2 t-BuOK + Mg --> 2 K + (t-BuO)2Mg
My hypothesis is that this K product remains adsorbed onto the surface of the Mg. As more K is produced, it will agglomerate on the Mg, but the
globule so formed can't be much bigger than the Mg particle it's attached to. So the smaller the Mg particles, the smaller the K globules produced,
and thus also the harder for them to merge. One of the common assumptions about the form of Mg in this process is that increased surface area would
enhance reaction rates. That's likely true insofar as the chemical reaction goes. It seems to me that one of the tacit assumptions here has been that
this chemical reaction is the rate-limiting step.
It's not true, though, about the physical transformation of small K globules into larger ones. In this case, it's the characteristic contiguous
surface area of the Mg that matters. A useful way to think about this is that contiguous Mg surface acts as a catalyst for the merging of K globules.
If you've got micron-sized Mg particles, I can easily see how its entire surface might become passivated by a layer of K that has not yet merged. On
the other hand, a chip or shaving has enough surface area that product K will bead up on the surface, not only increasing its characteristic globule
size, but also exposing new Mg surface. So perhaps the agglomeration of K is the rate limiting step.
Assuming this hypothesis is true, there should be threshold of some minimum effective contiguous Mg area. It's essentially a tradeoff between K-Mg
adhesion and K-K cohesion. Above a certain contiguous Mg surface area, the K will just bead up and extra contiguity won't be any faster. It also means
trying the reaction with ordinary Mg strip may be worth trying.
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Pok
potassium Prometheus
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@Sedit
| Quote: Originally posted by Sedit | It is the scientist goal to prove the experiment at hand not the peer reviewers.
its up to the "inventor" to justify his claims or take a hike. |
Ok. I'm trying to do this the whole time. And I'm planning do repeat the synthesis within the next time. Tell me what you want to see (photos, videos,
whatever) and I will remember this. But I think others will be faster here.
Correct me if I'm wrong - Do you want me to show the K reacting with water?: I did the experiments 1 year ago but made a video of a tiny amount of K
reacting with water. If this is required (and possible to add a video here) I can do it. I also can make a new video of some K I still have. But I
could have used bought K, so this wouldn't prove my claims.
I could give you a picture of the t-BuOH in the original container - its a crystalline solid at room temperature but very easily supercools (at least
in the purity I used) and can thus remain liquid. I also could send you an amount of 1 gram t-BuOH or so. Although this also wouldn't prove anything.
@ watson.fawkes
If my experiences are welcome (although considerred sceptically) I will give some comments about this - otherwise (e.g. not believing me) just ignore
me  .
| Quote: Originally posted by watson.fawkes | | If you've got micron-sized Mg particles, I can easily see how its entire surface might become passivated by a layer of K that has not yet merged. On
the other hand, a chip or shaving has enough surface area that product K will bead up on the surface, not only increasing its characteristic globule
size, but also exposing new Mg surface |
I don't know about micron-sized Mg as I didn't use it. I could imagine this. The point with Mg chips or shavings seems very probable to me: I don't
think that K builds a layer on the Mg (chips or shavings). After about 20 mins of t-BuOH addition the first K was visible in realy tiny beads. They
indeed were attached to the Mg shavings but didn't cover their entire surface. It looked like water drops on a leaf. K and Mg here seem to hehave like
a polar liquid attached to an unpolar solid. On becomming bigger (and due to turbulences by boiling) it will more likely coalesce to form bigger balls
(some with a surface coated with mg filings) than covering the Mg.
PS: for all wanting to try the synthesis. It might be that too high temperature favors production of tiny balls not wanting to coalesce. I remember
that in my "unsuccessful" procedures (with temperature control) I raised the temperature to 230°C or so. Although the patent says "up to the boiling
point" (you shouldn't be able to make it "too" warm) it might be the reason for tiny balls - but even here you should get max. 2-3mm K balls.
[Edited on 16-12-2010 by Pok]
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blogfast25
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| Quote: Originally posted by NurdRage | Yeah, I definitely heard that distinctive woosh sound.
good to know i'm on the right track. i'll see if i can get larger quantities.
The amount of grey gunk produced is staggering, i honestly wonder if its possible to get nice balls of potassium.
Thanks for your help. |
Can you please describe your experiment in much greater detail?
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woelen
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| Quote: Originally posted by len1 |
| Quote: |
A warning is not sufficient in such cases. Immediate banning is the only thing which works with trolls and this definitely is a troll
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Who wrote this?
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I fully stand behind these words, a real troll must be banned straight away and the guy from that old 2008 thread definitely was a troll. But who's
trolling now in this potassium-thread  ?
Instead of spending your time on searching and digging up old and off-topic info, you'd better spend your valuable time on replicating Pok's
experiment
[Edited on 16-12-10 by woelen]
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watson.fawkes
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| Quote: Originally posted by Pok | | The point with Mg chips or shavings seems very probable to me: I don't think that K builds a layer on the Mg (chips or shavings). After about 20 mins
of t-BuOH addition the first K was visible in realy tiny beads. They indeed were attached to the Mg shavings but didn't cover their entire surface. It
looked like water drops on a leaf. |
Thank you for this observation. It's exactly the sort of thing I'd expect
if we have this sequence: reaction -> adsorption -> agglomeration. My guess is that the characteristic minimum contiguous area I'm thinking
about is at about the diameter of these first beads you saw or a bit above that (say double). To your best estimate, what was the smallest diameter of
the beads of K that you saw? I would surmise that they were somewhere in the 0.1 - 1.0 mm range, but I'd prefer your first-hand account. Thanks in
advance.
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condennnsa
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| Quote: Originally posted by NurdRage |
My solvent in this particular run was white candle wax.
Yeah, I definitely heard that distinctive woosh sound.
good to know i'm on the right track. i'll see if i can get larger quantities.
The amount of grey gunk produced is staggering, i honestly wonder if its possible to get nice balls of potassium.
Thanks for your help.
|
Nurdrage, was the potassium in the video produced by this process? If so, it's great work!! Please share some details of your setup!
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NurdRage
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25mL of white candle wax (essentially high boiling paraffin) was melted into a 100mL round bottom flask. 5.6g of tech grade KOH (85%) was added along
with 3g of magnesium powder (99%). The flask was fitted with a liebig condensor and a bubbler to prevent air backflow. The flask was heated on an oil
bath. Evolution of a non-condensing gas (presumably hydrogen) was observed when the oil bath reached 110 celsius. When the oil bath reached 150
celsius 1mL of t-butanol (99% anhydrous sigma aldrich) was injected into the top of the liebig condensor after carefully removing the bubbler. Before
the liquid could reach the flask the bubbler was replaced. Vigrous refluxing occured as the t-butanol hit the reaction mixture. A very small, but
constant, evolution of gas was noticed in the bubbler. Oil bath temperature was maintained at 220 celsius for 2 hours. It was noticed at several
intervals that the t-butanol had solidified in the condensor. cooling water was shut-off to allow the t-butanol to melt and return to the reaction.
Water circulation was restored after all the t-butanol melted.
After 2 hours heating was discontinued and the bath was allowed to cool to 130 celsius. The round bottom flask was disconnected from the condensor and
its grey-pasty contents was dumped directly into 10mL of water in a beaker. Beaker was heated on the hotplate to remelt all paraffins. a stir bar was
added to aid in mixing.
Video in the link before.
A lot of unreacted magnesium powder was directly observed in the bottom of the beaker when stirring was shut off.
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NurdRage
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In hindsight, i should have added the stirbar first and stirred the mixture while it was heating. candle wax doesn't boil at 220 celsius so there was
no self-stirring.
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Pok
potassium Prometheus
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| Quote: Originally posted by watson.fawkes | | To your best estimate, what was the smallest diameter of the beads of K that you saw? I would surmise that they were somewhere in the 0.1 - 1.0 mm
range, but I'd prefer your first-hand account. Thanks in advance. |
They were so tiny that I hardly could distinguish between twingling Mg shavings and shiny K beads (I already mentioned on versuchschemie.de that you
may mistake Mg with K at the beginning because both are so shiny). I can only say for sure: < or = 0.5mm. But I can't exlude that the smallest ones
were about 0.01mm (??) or even smaller (??). I looked at the mix for the hole time (from beginning of tert.BuOH) but only the 0.5mm DEFINITLY was K.
Maybe this just was the limit for my eyes. Much less than 0.5mm would be difficult to see even without twingling of the Mg.
[Edited on 16-12-2010 by Pok]
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blogfast25
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@Nurdrage:
The 'explosions' (small and larger) to be seen in the video of your gunk are of course quite, shall we say, 'titillating'? Something happened in your
reaction mix that's not easily explained or explained away...
Could be microdrops of K reaching oxygen, could be something else causing some lilac (with all that KOH around)...
Quite intrigueing... thanks also for the write up. You might want to repeat all with a less viscous 'solvent': higher viscosity impedes metal
coalescence, assuming K metal did form...
[Edited on 16-12-2010 by blogfast25]
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blogfast25
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| Quote: Originally posted by NurdRage | | In hindsight, i should have added the stirbar first and stirred the mixture while it was heating. candle wax doesn't boil at 220 celsius so there was
no self-stirring. |
If you've followed the discussion, then beware (maybe!) of too vigorous stirring but a simmering boil is probably to be preferred.
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NurdRage
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I've been following.
Which is why i didn't do any stirring at first. But i failed to take into account that candle wax doesn't boil near the temperatures we want. Without
that self-agitation i'll need to put in some external agitation.
Anyway, i'm looking into various solvents. While i can order anything, i want to stick to the solvents most amateurs have easiest access to. Candle
wax is probably the easiest highest boiling solvent, although very far from ideal.
i'm working on it
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blogfast25
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Sure. We need quite few taking part in this: if one can replicate it then we'e essentially done here. If not, it's tar and feathers for our German
friend...
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Eclectic
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K-1 kerosene or low sulfur diesel fuel with the volatiles fractionated off would be the most available for anyone with distillation equipment. It's
just a broader boiling range cut of basically the same stuff as shellsol or varsol.
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