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Eclectic
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Same here. Now I'm REALLY determined to make terpin hydrate.
I'll tap a pine tree and use nitric acid if I have to.
Um....maybe there is a peroxide intermediate and air oxidation is part of the process?
[Edited on 4-19-2011 by Eclectic]
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blogfast25
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On the plus side my Kremer terpineol got here today. Will U2U U tomorrow.
It really smells a bt like my second attempt at synthesising it but more musky and less citrussy. Subjectively, of course...
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blogfast25
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I tested the Kremer terpineol with potassium dichromate today. Remember that dichromate is only supposed to oxidise primary and secondary alcohols,
not tertiary ones.
10 ml each of 0.1 M K2Cr2O7 in 0.1 M H2SO4 was added to 3 test tubes. To #1, 8 drops of methylated spirits (methanol denaturated ethanol) was then
addedand to #2, 8 drops of terpineol, to #3, 8 drops of 2-methyl butan-2-ol (t-amyl alcohol or 2M2B).
At RT there’s not much going on: #1 darkens slightly, in #2 the floating terpineol darkens quite quickly, #3 was unaffected.
Then they were kept on a steam bath for a while. #1 reacts way fastest and oxidation runs to completion (only green/blue Cr3+ to be seen).
#3 also runs to complete reduction of the Cr2O7(2-) but it takes a much longer time (about half an hour).
Surprisingly #2 started to darken in colour at 100 C too. But that took even longer and didn’t run to completion. But green/blue Cr3+ can be
noticed. Is this due to small quantities of primary/secondary alcohols accompanying the t-amyl alcohol? Not sure…
I noted also the #2 test behaved very much like the home made ‘hydrated turpentine’ described (and tested) above.
So although it seems the commercial terpineol does contain some dichromate oxidisable stuff it’s probably at a level that’s acceptable for a test
in making K with the terpineol as a catalyst under test… Time allowing I should be conducting such a test tomorrow.
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Lambda-Eyde
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Isn't it possible for dichromate to break the double bond under harsh conditions, thus giving a false positive for secondary/primary alcohol?
Potassium permanganate, a slightly more powerful oxidant, is used to cleave double bonds to give alcohols under basic conditions and carboxylic acids
under acidic conditions.
This just in: 95,5 % of the world population lives outside the USA
Please drop by our IRC channel: #sciencemadness @ irc.efnet.org
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blogfast25
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The thought has certainly occurred to me. But are the described conditions 'harsh'? I don't really know enough about organic to answer that.
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blogfast25
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Commercial terpineol tested negative as a catalyst for making potassium. No use testing it for sodium then.
http://www.sciencemadness.org/talk/viewthread.php?tid=14970&...
Another potential precursor for a t-alcohol (type “2-methyl-2-ol”) is OTC (but not cheap) Ibuprofen:
http://www.sciencemadness.org/talk/viewthread.php?tid=16085
Extract with hexane (I’m told), esterify to methyl ester and double Grignard with MeI. Simple really 
[Edited on 22-4-2011 by blogfast25]
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m1tanker78
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In the context of this thread and sodium, which is more problematic?
1. Lack of catalytic activity?
2. Low or no solubility of NaOH in the target alcohol?
My understanding of these reactions is very limited but aren't #1 and #2 basically the same in this context?
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blogfast25
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Tanker:
It probably helps to understand the latest proposal for a reaction mechanism for K reduction, you’ll find it here:
http://www.sciencemadness.org/talk/viewthread.php?tid=14970&... (scroll up to my post of 2:41)
It’s suspected that for Na the problem is poor solubility of the sodium alkoxide (NaOR) in the HC, hence the search for longer chain t-alcohols…
[Edited on 28-4-2011 by blogfast25]
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m1tanker78
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I see. I assume you're still using Shellsol for the reaction medium? Why not substitute (or augment) it with something like triethylene glycol
monobutyl ether? It's one of the only HC's that I know of which is miscible with both water and most other HC's. A quick look at the data sheet puts
the density at 0.984 g/ml, BP ~ 272C. I should mention that it's a major component in DOT3 brake fluid.
Brake fluid by itself (although hygroscopic) seems like it can serve as the reaction medium AND produce clean, floating potassium (maybe even sodium)
- eliminating the need for the additional and expensive step of heating the K (or Na) in i.e. dioxane to clean and coalesce. It isn't terribly viscous
either.
I did a quick experiment last night which was nothing more than heating some sodium ore in brake fluid. Unfortunately, I don't have the proper
equipment for reflux. I was delighted when I saw CLEAN sodium spherelets as well as some larger globules rise to the surface, leaving the block
residue at the bottom. Of course, the hot sodium quickly oxidized at the surface so I didn't have a chance to test the ease of coalescence. Based on
what I witnessed, either Na or K should coalesce just fine if protected from air and moisture.
The figures for the particular BF I used are: BP ~ 232C; Specific Gravity ~ 1.05; Viscosity = 'Not Determined' but subjectively very low.
BTW BlogFast, your reaction writeup was very helpful. The K thread is so long that I completely forgot about it by the time I got to the last page.
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m1tanker78
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Hmmm well, I was unable to reproduce the favorable conditions I outlined in my previous post. The sodium readily popped up to the surface but came up
white and oxidized away fairly quickly. The only real change I made was to mostly drain the mineral oil from the ore before I added it to the hot BF.
I also pre-heated the BF some in an attempt to drive off moisture. This leads me to believe that on the first experiment, there was probably an ideal
blend of BF/MO which balanced the rate of oxidation and the overall density. I suppose the -O- bonds are what give BF a favorable specific gravity.
It's hard to tell if moisture is the culprit or if the hot sodium is breaking down the ether by stripping the bonding -O-. At RT, Na remains clean and
shiny in a BF/MO blend. I wish I could test this in an inert environment with proper reflux.
BF isn't off the bench just yet. I'm going to attempt to blend it with a HC to increase the overall SG and reduce the metal interaction with the
glycol ether.
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blogfast25
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Triglycol Monobutyl Ether hardly qualifies as a hydrocarbon in my book: it has four oxygen hetero atoms in it, one of them present as a primary
alcohol function!
The latter function alone would disqualify it both as a reaction medium and as a coalescing medium. The oxidation you observed may well be
nothing more than the reaction of the primary alcohol group with the sodium, forming an alcoholate (alkoxide). Certainly at reaction temperatures that
is precisely what would happen.
Still, I’m glad you brought up this material because it’s fairly OTC and if esterified, e.g. to its ethyl ester, it might be much more suitable as
a coalescing liquid. The many oxygen atoms in it would make it less suitable as a reaction medium because of potassium’s affinity for oxygen.
And it does have a high density and may have high surface tension due to some polarity.
A whole range of solvents have been tested for K by several experimenters, including me. Currently I use a medium-heavy kerosene (lamp oil, in plain
English) because it’s cheap and works well. Shellsol D is quite expensive by comparison and offers no great advantages. Basically anything that’s
inert to potassium and has a boiling point of no less than 180 C is suitable.
[Edited on 29-4-2011 by blogfast25]
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m1tanker78
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BlogFast: Point taken about it not being a HC and about the unsuitability at higher temps.
As far as BF being a potential coalescing fluid..... I leave you with this video. They are sodium spherelets in a BF/HC blend - enough BF to where
they just barely float to the surface at BP. If I can eliminate all the 'x-factors' to make it reliable, this will drastically improve the way I do my
post processing! I don't want to get my hopes up too high yet.....
<iframe sandbox width="640" height="510" src="http://www.youtube.com/embed/mw-lhQiO2WY?rel=0" frameborder="0" allowfullscreen></iframe>
Tank
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blogfast25
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Okay, the video is a bit inconclusive but I was thinking last night that it would be worth trying DOT 3 anyway. I should be able to get some today.
Thanks for the information!
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m1tanker78
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Sorry about that. T'was late and I got caught up in the half-asleep excitement. 
Sadly, I wind up throwing away a good portion of Na because it takes more time to refine than it takes to make a little more. The hard-to-refine stuff
sort of piles up in a can with oil until I get fed up and just toss it (after incinerating). It's hard to explain but I'll leave that for another
thread.
The point of the video was to show that:
1. A BF/HC blend can float Na (and hence, K) at elevated temps with minimum oxidation. The soda can was used to prolong the blend since the BF
volatilizes at that temp.
2. The same can coalesce Na (assume K). In the video clip, some coalescence had already taken place.
3. The Na that came up from 2 teaspoons worth of [otherwise] garbage is virtually free of crusty impurities.
BlogFast, I brought this up with the hope that it will be of good use for the people who are now making K. I'm eager to see your results and help out
in any way I can (with my limited resources). Something tells me the blend might work OK as the reaction medium (to float ALL the K and thus, increase
yield). I'll leave that up to you guys...
Tom
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blogfast25
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Thanks Tom, the result of a simple test with K, using DOT 4, are reported in the K thread. The test wasn't positive but the K did float (but it also
reacted briskly with the brake fluid, Na has lower reactivity and may be much more suitable...)
In your video, I seem to see Na globules bobbing up and then down again: that's often a sign that H2 is being generated; they pick up hydrogen, come
to float, then 'offload' the hydrogen and nosedive again...
[Edited on 30-4-2011 by blogfast25]
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m1tanker78
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Quote: Originally posted by blogfast25  |
In your video, I seem to see Na globules bobbing up and then down again: that's often a sign that H2 is being generated[...] |
Blog, the globules are bobbing up and over because of the gentle boiling of the blend. This isn't possible with Na in straight mineral oil. The higher
SG of the blend permits them to 'ride the currents'.
Tom
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blogfast25
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You got that stuff to boil? At about 232 C, no wonder it's fuming!  Hmm. Try
coalescing at much lower temps. Just an idea...
[Edited on 30-4-2011 by blogfast25]
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m1tanker78
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Blog, I coalesce Na slightly beyond the MP. After coalescence, it's good practice to ramp up the oil temp to boiling, if possible. Doing so promotes
the separation of surface contaminants.
I was concerned more with the SG than with coalescence in the vid. I found it interesting that they coalesced at all at such a high temp. Then again,
the blend's viscosity at BP is similar to water (subjectively).
Tom
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blogfast25
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And you don't lose much Na to Na alcoholate? That must be good progress to recover bits and pieces from 'dirty' sodium, right?
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m1tanker78
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You got that right! Last night, I took the same batch from the video and heated it up to just under boiling and kept it that way for ~ 90 minutes.
Throughout the first 5 or 10 minutes, I added BF drop by drop until the Na bits began to surface with the circulating effect (similar to the video but
with a little less buoyancy). I replenished BF as necessary. I couldn't observe any appreciable loss. The bits remained shiny (not white). A little
further coalescence may have taken place but I wasn't really paying attention to that aspect. It goes without saying, all of this is strictly
subjective observation at this point. After a total of ~ 2 or 3 hours @ BP, there SHOULDN'T be any nascent Na left.
This is [potentially] a large leap for me to increase Na recovery and, thus, total yield. This may also prove to be VERY useful for the
'sodium-by-thermite' crew. If/when the K process is successfully implemented to make Na, there should be some good use in wringing out the fine Na
from the junk. Still speculation at this point for all of the above.
The esterification process you propose sounds very interesting indeed. Not easy but not impossible.
Tom
[Edited on 5-1-2011 by m1tanker78]
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blogfast25
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Yes, for those who wish to recover their relatively meager yields from magnesiothermic or aluminothermic sodium this should be very useful. Ping
Nurdrage, he should be interested...
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NurdRage
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no need to, i already came across using brake fluid a couple of months ago.
i'll share my findings in a video after i've perfected the process.
[Edited on 2-5-2011 by NurdRage]
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blogfast25
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Look forward to watching that.
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m1tanker78
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| Quote: Originally posted by NurdRage | no need to, i already came across using brake fluid a couple of months ago.
i'll share my findings in a video after i've perfected the process.
[Edited on 2-5-2011 by NurdRage] |
Hehehe....
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NurdRage
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?????
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