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White Yeti
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I did consider steric hindrance as a potential drawback, but all things considered, it might work equally well as a catalyst because it has a higher
boiling point and it is more soluble in nonpolar solvents, as opposed to tert-butOH which is rather soluble/miscible with water. The higher boiling
point would allow it to persist in solution for longer before boiling off, making it more available and decreasing reaction time, possibly improving
yield.
@tetrahedron: Terpineol could be worth a try, but the higher steric hinderance could bring some issues. Its lower price could make it a good catalyst
to try out though.
"Ja, Kalzium, das ist alles!" -Otto Loewi
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blogfast25
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WY:
alpha-Terpineol was tried by me and didn't work at all. Very disappointing...
Linalool is definitely worth a shot.
There's another longer chain t-alcohol that was tested by 'garage chemist' but it didn't work either.
Another one worth considering is tetrahydro myrcenol. Not easy to get though. I have dihydro myrcenol but haven't had time to test it.
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White Yeti
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I remember reading about alternate catalysts upthread, it's a shame most attempts did work. I think that experimenting with catalysts is more a matter
of academic curiosity than preparatory improvement at this point.
That being said, I remember seeing a mechanism for this reaction, but for some reason I can't find it. If I could find it, the following question
would perhaps be unnecessary.
I was wondering if tertiary thiols could catalyse this reaction, thioterpineol for example. Thioterpineol specifically might not work because of its
structural similarity to terpineol, which yielded poor results. Other tertiary thiols could potentially be used, as long as the smell doesn't become
overwhelming.
"Ja, Kalzium, das ist alles!" -Otto Loewi
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blogfast25
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Quote: Originally posted by White Yeti  | I remember reading about alternate catalysts upthread, it's a shame most attempts did work. I think that experimenting with catalysts is more a matter
of academic curiosity than preparatory improvement at this point.
That being said, I remember seeing a mechanism for this reaction, but for some reason I can't find it. If I could find it, the following question
would perhaps be unnecessary.
I was wondering if tertiary thiols could catalyse this reaction, thioterpineol for example. Thioterpineol specifically might not work because of its
structural similarity to terpineol, which yielded poor results. Other tertiary thiols could potentially be used, as long as the smell doesn't become
overwhelming.
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Tertiary thiols? 'Availability!' springs to mind... Really hard to obtain/synthesise.
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tetrahedron
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why fix a synth that isn't broken? is t-BuOH really so hard to get?
From Mercaptans and Derivative Chemistry:
| Quote: | | The bond strength between the hydrogen and the larger sulfur atom is weaker in the case of mercaptans (RSH) than is the oxygen-hydrogen bond strength
in alcohols (ROH). As a result, mercaptans are more reactive, more highly ionized (RSH H+RS-) and more acidic than alcohols. |
| Quote: | | A characteristic reaction of mercaptans is mercaptide formation. When methyl mercaptan is bubbled into 25% aqueous sodium hydroxide, the hydrated
sodium mercaptide, CH3SNa • 4.5H2O, precipitates out as crystalline needles. |
the way it's described, this reaction is more favorable than the corresponding alcoholate formation. i wonder how this added acidity would affect the
original mechanism:
if still interested: Sulfole® 120 t-dodecyl mercaptan (msds)
| Quote: | | Sulfole® 120 mercaptan is a mixture of tertiary mercaptans, predominantly tertiary dodecyl mercaptan (thus the source for its acronym TDM). This
product contains highly branched C12H25 alkyl mercaptan isomers, produced by the addition of hydrogen sulfide to propylene tetramer. It is used as a
chemical intermediate to introduce bulky C12H25 alkyl-thio substituents into chemical substances. Its major use is as a chain transfer agent to
control molecular weight of polymeric systems undergoing free-radical polymerization. |
[Edited on 3-12-2012 by tetrahedron]
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blogfast25
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@tetrahedron:
No, t-butanol isn't really hard to get (and 2-methyl butan-2-ol (or M2B2) works fine too).
The main goal of looking for alternative catalysts is to speed up the reaction for sodium synthesis. One expected (but as yet totally unproven) route
is to use longer chain t-alcohols because they can be reasonably expected to have more soluble Na alkoxides.
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hames
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Has anyone who's tried this synthesis experienced what I'd call localised gas eruptions that are fairly loud hissing like water refuxing back into hot
oil,I used 250mesh magnesium powder,and a solvent called recosol D-60 b.p 195-205C and T-butanol,I let it go for a few hours and I never noticed any
potassium form,I suspect my KOH or would the hot solvent drive off any water.
[Edited on 4-12-2012 by hames]
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blogfast25
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| Quote: Originally posted by hames | Has anyone who's tried this synthesis experienced what I'd call localised gas eruptions that are fairly loud hissing like water refuxing back into hot
oil,I used 250mesh magnesium powder,and a solvent called recosol D-60 b.p 195-205C and T-butanol,I let it go for a few hours and I never noticed any
potassium form,I suspect my KOH or would the hot solvent drive off any water.
[Edited on 4-12-2012 by hames] |
Any water in the solvent and in the KOH (all grades of KOH contain approx. 10 % water) is supposed to be reacted away by Mg + 2 H2O === > Mg(OH)2 +
H2. This is the initial hydrogen evolution.
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Nicodem
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One expected problem with the longer chain t-alcohols is their poor phase transfer. It seems obvious that the only way for potassium
t-alkoxide to form is in that the t-alcohol first gets absorbed onto the KOH surface which is essentially a very polar hydrated
surface. In this regard, t-butanol and t-pentanol appear optimal for potassium synthesis as was also demonstrated experimentally.
Meanwhile, sodium synthesis (if truly possible at all) represents the other problem, the problem of phase transfer of the sodium t-alkoxide
from the hydroxide phase into the organic phase. Up to now the focus has been into using longer chain t-alcohols to solve this problem, but
due to the above mentioned issue, perhaps the solution is best found in changing the solvent.
…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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blogfast25
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@Nicodem:
To a somewhat more polar solvent? By blending solvents, a more polar solvent system could be envisaged. But higher polarity usually means introducing
exoatoms which the alkali metals tend to be reactive towards...
[Edited on 5-12-2012 by blogfast25]
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Nicodem
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The problem of solvent inertness is indeed an annoying one, but I remember someone managed to get the potassium process to work in tetraline which one
could also intuitively expect to be unsuitable. Did anybody tried tetraline, cymene, diphenylmethane or other easily available high boiling
alkylaromatic solvents for sodium production? This thread is too long and I don't have the motivation to look for such examples.
Also, other solvents that could be more polar and possibly inert to sodium are ethers. Though I'm not sure they would be inert above 180 °C needed
for the reaction. Diphenyl ether is the most common solvent used for such temperatures, but I'm afraid it is also the most easy to cleave by a SET
reduction (e.g., DOI: 10.1021/jo00143a014). Polyglymes tend to solvate alkali metals by dissociation into alkali cations and electrons, and are thus
probably unsuitable (or not?), but simple high boiling dialkyl ethers might do.
Another option is to use a mixture of lower and higher t-alcohols, for example t-butanol and a long chain t-alcohol. One
for the deprotonation process at the NaOH surface, the other for solubility.
…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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White Yeti
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To this I answer:
| Quote: | | Experimenting with catalysts is more a matter of academic curiosity than preparatory improvement at this point. |
The reason I said this is because it's obvious this method works if one doesn't try to pull it off with a cheapo solvent. It's more interesting to
experiment with catalysts, which give insight into the reaction mechanism, and hold potential for marginal procedural improvement. There's more to
talk about when it comes to catalysis.
As discussed above, one area that hasn't seen much improvement was the preparation of sodium via this method. But to be perfectly honest, I think the
electrolysis of sodium hydroxide is a more viable route to preparing sodium in large quantities.
"Ja, Kalzium, das ist alles!" -Otto Loewi
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elementcollector1
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I finally worked out a method to get good KOH from NaOH, KCl, and H2SO4. It also generates free hydrochloric acid, which I'm bubbling into distilled
water. If that t-butanol arrives, I might be well on my way to trying this experiment myself!
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Bezaleel
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| Quote: Originally posted by Nicodem | One expected problem with the longer chain t-alcohols is their poor phase transfer. It seems obvious that the only way for potassium
t-alkoxide to form is in that the t-alcohol first gets absorbed onto the KOH surface which is essentially a very polar hydrated
surface. In this regard, t-butanol and t-pentanol appear optimal for potassium synthesis as was also demonstrated experimentally.
Meanwhile, sodium synthesis (if truly possible at all) represents the other problem, the problem of phase transfer of the sodium t-alkoxide
from the hydroxide phase into the organic phase. Up to now the focus has been into using longer chain t-alcohols to solve this problem, but
due to the above mentioned issue, perhaps the solution is best found in changing the solvent. |
| Quote: Originally posted by White Yeti |
As discussed above, one area that hasn't seen much improvement was the preparation of sodium via this method. But to be perfectly honest, I think the
electrolysis of sodium hydroxide is a more viable route to preparing sodium in large quantities. |
So, have 2-methyl pentane-2-ol and 2-methyl hexane-2-ol been tested for potassium and sodium synthesis?
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Beldensb5
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For anyone looking for some tertiary butyl alcohol, I was looking through eBay recently for a couple of chemicals and noticed someone is selling about
250ml of the alcohol for about $30. Not that terrible of a price, especially since some people are having such a difficult time obtaining it...
Heres a link... http://www.ebay.com/itm/Tertiary-Butyl-Alcohol-250ml-/170974...
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Mailinmypocket
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As long as you are making K it isn't that bad for the small quantities required. If you need it as a reagent that is somewhat expensive. I got twice
that much for 5$ less from a chemical supplier!
[Edited on 17-1-2013 by Mailinmypocket]
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EdMeese
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I love to fix syntheses that aren't broken, so what about replacing the KOH with preformed KOR? When R is tAmyl it can be made anhydrously from KOH
and tAmyl alcohol with azeotropic distillation and a Dean-Stark trap. I've no confidence in the reported melting points of KOtBu and KOtAm though, but
I'd ideally go to a solventless system....
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blogfast25
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| Quote: Originally posted by EdMeese | I love to fix syntheses that aren't broken, so what about replacing the KOH with preformed KOR? When R is tAmyl it can be made anhydrously from KOH
and tAmyl alcohol with azeotropic distillation and a Dean-Stark trap. I've no confidence in the reported melting points of KOtBu and KOtAm though, but
I'd ideally go to a solventless system....
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Production of alkali metals by reduction of the t-butoxides with Mg is covered by the patent [see page 1] on which this thread is based. But for
hobbyists it's a little heavy on the t-butanol!
With KOH we use only 0.1 mol of t-BuOH per mol of KOH, with K t-BuO the ratio of K/t-ButOH becomes 1.
Reacting KOH with t-ButOH produces water of course, the enemy of this reduction reaction. So you'd need to obtain water free K t-ButO.
[Edited on 26-1-2013 by blogfast25]
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EdMeese
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making the dry KOtBu is quite a pain, that (and presumably a lower mp) was the main reason for thinking t-amyl alcohol was the way to go. But I don't
have a bucket of that yet either.
And thanks, I didn't do the homework it seems :-)
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blogfast25
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| Quote: Originally posted by EdMeese | making the dry KOtBu is quite a pain, that (and presumably a lower mp) was the main reason for thinking t-amyl alcohol was the way to go. But I don't
have a bucket of that yet either.
And thanks, I didn't do the homework it seems :-) |
What makes you think the K alkoxide of t-amyl alcohol (don't let me try and 'go IUPAC' on this!) is easier to obtain water free, compared to K
t-butoxide?
Ooops: I see, azeoptropic distillation of the excess t-amyl alcohol/water mixture. All this compilcates the procedure no end of course. But it makes
for interesting thoughts ;-)
[Edited on 26-1-2013 by blogfast25]
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elementcollector1
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About to try this at my school. Any advice?
Setup so far:
-Hotplate w/ stirrer, stir bar
-Mineral oil, 70 mL as solvent
-~1mL t-BuOH
-reflux condenser w/ rubber joint
-100mL Erlenmeyer flask
The mix will be lightly stirred to promote K production, but can I get away with heavier stirring?
Also, due to the length of the club, it would be wonderful to get this done in an hour, instead of the usual 3-4. Stirring greatly speeds up reaction
time, according to the Raging Nurd, but by how much?
If speeding up time really isn't an option, I could always set up the mix in the morning, and come back later as it's finishing. Possibly.
Any thoughts?
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blogfast25
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| Quote: Originally posted by elementcollector1 | About to try this at my school. Any advice?
Setup so far:
-Hotplate w/ stirrer, stir bar
-Mineral oil, 70 mL as solvent
-~1mL t-BuOH
-reflux condenser w/ rubber joint
-100mL Erlenmeyer flask
The mix will be lightly stirred to promote K production, but can I get away with heavier stirring?
Also, due to the length of the club, it would be wonderful to get this done in an hour, instead of the usual 3-4. Stirring greatly speeds up reaction
time, according to the Raging Nurd, but by how much?
If speeding up time really isn't an option, I could always set up the mix in the morning, and come back later as it's finishing. Possibly.
Any thoughts? |
The stirring bit is controversial and I'm not convinced faster stirring works, as Nurdrage claims.
You can split the experiment into two parts, though: 2 hours for actual reaction, then cool to RT and stopper properly.
Then, next session, dilute flask contents slightly with fresh solvent, add a few drops of isopropanol (99 %) or ethanol (99%), transfer to a clean
conical flask and heat to about 100 C (e.g. on steam bath). Swirling the flask regularly will make the droplets of K (assuming some formed in the
first session, of course!) coalesce into larger and larger ones. This too will take 1 - 2 hours...
[Edited on 25-2-2013 by blogfast25]
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elementcollector1
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Might be able to do that... Maybe. The 2-hr reaction will be the tricky part, because the time window is only an hour and 20 minutes long. Could set
up at lunch...
Or I could try to extend Science Club for the day to fit the time window. Unlikely, but possible.
Could make the lab into 2 days, but we do have other stuff to do.
I think that I'll give this a try at home this week, and then show it to the club next week. That way I might get 'familiar' with the experiment, and
might be able to do it faster.
Can you tell I'm nervous? ;D
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MrHomeScientist
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Definitely a good idea to familiarize yourself with an experiment before showing it off, especially if it involves explosive metals! I rarely record
my first attempt at an experiment for posting to YouTube - I almost always run into problems that would make a video presentation of it pretty boring
 I can't wait to try this one out myself - now that I have all the materials I
just need to work out the logistics and set aside some time one of these weekends.
That's great that you have a Science Club; I feel like most schools nowadays don't have anything like that. Do you focus on chemistry or is it more
broad?
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elementcollector1
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It's much more broad than chemistry, and more often focuses on physics (our coach was a physicist or something, he's retired now). We just went to the
Science Bowl, which we've been training for all year. It focuses on everything from Math to Energy to Earth and Space, with Chemistry, Physics and
others thrown in there as well. (We took fifth and fourth place with our two teams, too.  )
Anyway, enough OT bragging about our awesome club.
Unfortunately, can't actually try out stirring - so I guess it's the 4-hour long haul for me. If it works, I'll bring in a sample of K metal to the
meeting and compare results. If it doesn't... Ah well.
EDIT: I have 40 mesh Mg 'powder' as well as turnings, and the powder should speed up the rate of reaction significantly. Only problem is, I might not
recognize the potassium for the magnesium! 
Also, I'm attempting to make my 125 mL Erlenmeyer as dry as possible for the synth, because any water, no matter how small an amount, is going to
impact yield. Any suggestions for getting the glass super-dry?
[Edited on 25-2-2013 by elementcollector1]
Elements Collected:52/87
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