spice limonene update

[burnt]

A hypothetical friend of mine did some hypothetical experiments. A few mgs (10 or so) of spice was dissolved in a few mL d-limonene. to d-limonene a few drops of glacial acetic acid (pure acetic acid) was added. The droplets collected at the bottom forming a white cloudy solution. water was added to the mixture and two phases formed, the upper being limonene and the lower water + acetic acid + spice in salt form (most likely). the aqeuous phase was collected with a pasteur pipette and placed in a seperate glass vial. a few drops of ammonium hydroxide was added to the solution until a cloudy precipitant formed. although the cloudy precipitant is probaly freebased spice there is no simple way to recover it except by using a non-polar solvent again.

therefore i would speculate that the best way to recover freebased spice from a clean acidic water solution would be to add sodium bicarbonate and cook it out.

 

[Sinewave]

Crackin' it up with spice.

 

[SyZyGyPSy]

Awesome hypothetical work, my hypothetical friend of burnt's! Mucho appreciado!

That's good to know that the glacial acetate didn't cause any problems reacting with the limo!

So I guess this is a dumb question but I gotta ask it... what woulda happened if'n your imaginary friend woulda just imagined that he evaporated that cloudy ammonium hydroxidated aqueous solution? Wouldn't the freebase spice be left behind? Or would there be toxicness left over along with it, ammonium acetate or something?

Also, while I'm asking stupid questions, how would one go about doing the sodium bicarbonate thing?

Just hypothetically curious...

 

[acolon_5]

Awesome hypothetical work, my hypothetical friend of burnt's! Mucho appreciado!

That's good to know that the glacial acetate didn't cause any problems reacting with the limo!

So I guess this is a dumb question but I gotta ask it... what woulda happened if'n your imaginary friend woulda just imagined that he evaporated that cloudy ammonium hydroxidated aqueous solution? Wouldn't the freebase spice be left behind? Or would there be toxicness left over along with it, ammonium acetate or something?

Also, while I'm asking stupid questions, how would one go about doing the sodium bicarbonate thing?

Just hypothetically curious...

This may been a stupid question as well, but can you just use a very fine filter and filter out all the preciptate?

 

[burnt]

This may been a stupid question as well, but can you just use a very fine filter and filter out all the preciptate?

well its basically the same reason why you dont just filter your basic solutions when doing normal extractions.

So I guess this is a dumb question but I gotta ask it... what woulda happened if'n your imaginary friend woulda just imagined that he evaporated that cloudy ammonium hydroxidated aqueous solution? Wouldn't the freebase spice be left behind? Or would there be toxicness left over along with it, ammonium acetate or something?

well the ammonium should for the most part evaporate. however this would require higher temperatures to evaporate the water and when left with a more pure spice solution and high temperatures and oxygen i would be worried about oxidation. but then again that could happen with sodium bicarbonate method too. it may be feasable however its more common to go into organic solvent with this method.

That's good to know that the glacial acetate didn't cause any problems reacting with the limo!

it cannot be said for sure if problems would arise but if done at normal temperatures and in a reasonable amount of time it should be ok.

Also, while I'm asking stupid questions, how would one go about doing the sodium bicarbonate thing?

no questions are stupid questions hehe. but yea this would involve mixing in a proper ratio of sodium bicarbonate (2:1 in the case of certain other alkaloids) in the acidic water solution. and heating and again evaporating some of the solution until the spice coagulates to form crystal rock precipitates (which float to the top in some alkaloids). i cannot say for sure why such a thing does not happen when heating with ammonium hydroxide (maybe it could i do not know). it seems to work for other alkaloids however that does not mean it will work with this one but it certainly seems worth trying. both ways may or may not work its tough to say.

the main reason for extracting the freebase back into an organic solvent in a normal alkaloid isolation is to help remove potential impurities as well as organic solvents are simply easy to evaporate and you dont need to use high temperatures and risk degradation or artifact formation.

 

[SyZyGyPSy]

Ok thanks, I forwarded your comments to Swim and he sez he haz a much better picture of the whole thing now. :d

So given that it's not necessary to go back into an np, just "how it's usually done," Swim thinks he'll try those other methods now.

So just to make sure, if one had a hypothetical solution with excess acetic acid (say one had just done a vinegar pull on the limo and salted out the spice), and one adds some 10% ammonium hydroxide soln to the vinegar, then evaps sail soln, there won't be any ammonium acetate residue left behind, right?

Assuming that's the case, Swim thinks this is the way to go. He may also try letting the precipitate settle, and vaccum filtering it with some 102 lab paper (or would 103 be better)? This is what he does with his harmaloids, and it works quite well. That seems superior to filtering the original basified solution for obvious reasons, less residual gunk being the main one... also you're not filtering NaOH, which doesn't evap... you're filtering ammo, which does, and quite nicely I might add. So no base residue left that way either... I could go on.

Also the use of low heat to evap H2O doesn't seem like that big a deal IMO. Swim has a foaf who uses a crock pot on "high" to evap the leftover petroleum solvent residue from his final product, and it's always been top-notch.

This is awesome, Swim can't wait to give it a shot. He sez it'll take him a week or so to swim out to his magickal yacht in international waters, but once he tries it he'll report back on the results.

Dude, thank you so much! 8)

 

[burnt]

Assuming that's the case, SWIM thinks this is the way to go. He may also try letting the precipitate settle, and vaccum filtering it with some 102 lab paper (or would 103 be better)? This is what he does with his harmaloids, and it works quite well. That seems superior to filtering the original basified solution for obvious reasons, less residual gunk being the main one... also you're not filtering NaOH, which doesn't evap... you're filtering ammo, which does, and quite nicely I might add. So no base residue left that way either... I could go on.

makes sense for sure.

Also the use of low heat to evap H2O doesn't seem like that big a deal IMO. SWIM has a foaf who uses a crock pot on "high" to evap the leftover petroleum solvent residue from his final product, and it's always been top-notch.

if it works it works cool.

well i hope your friend in international waters gets it to work out! let us know. if any complications arise let me know and maybe we can do some more hypothetical work to figure it out.

 

[Entropymancer]

Bump.

Any updates, SyzyGypsy? The idea of cooking the freebase spice out of aqueous solution with baking soda is intriguing...

 

[69ron]

Ammonium acetate will not evaporate off. It's a white solid.

One way to get the spice out of the water quickly is to add high proof drinkable alcohol, and saturate it with sodium carbonate. Sodium carbonate is insoluble in alcohol and causes the alcohol to rise to the top of the water. The sodium carbonate will also freebase the spice making it more soluble in the alcohol layer. Mix it and the spice goes into the alcohol. Remove the top alcohol layer and evaporate it to get freebase spice.

SWIM knows this works with isopropyl alcohol, but never tried it with drinkable alcohol (ethanol), but assumes it will work.

 

[burnt]

so the sodium carbonate will change the ionic strength of the water enough to make the water and alcohol separate into separate phases? if so excellent idea.

 

[Entropymancer]

As far as I know, this only works with isopropyl alcohol. I was under than impression that ethanol was just polar enough to remain miscible with water, even at high concentrations of salts.... I can't find a reference on that though, so I could be wrong.

 

[burnt]

Regardless isopropyl alcohol is easy to obtain.

 

[Infundibulum]

Okey, I had to try this out myself and see if it really works:

A. 20ml 1M Na2CO3 (pH goes up to ~12.2) were mixed with equal volume (20ml) of either isopropanol or ethanol

Results:

1) The isopropanol solution separated in 2 clear phases; the lower aqueous (7.5ml) and the upper water-saturated isopropanol (32.5ml)

2) The ethanol solution also separated in 2 phases; the lower aqueous (5ml) and the upper water-saturated ethanol (35ml). The upper ethanolic fraction remained somewhat cloudy even after ~1.5 hours



B. Experiment repeated with 20ml 1M NaOH mixed with equal volumes of either isopropanol or ethanol

Results:

No separation whatsoever



C. Experiment repeated this time with 20ml of 1M NaOH AND 1M Na2CO3 mixed with equal volumes of either isopropanol or ethanol

Results:

1) The isopropanol solution separated in 2 clear phases; the lower aqueous (15ml) and the upper water-saturated isopropanol (25.0ml)

2) The ethanol solution also separated in 2 phases; the lower aqueous (6ml) and the upper water-saturated ethanol (34ml). The upper ethanolic fraction remained again somewhat cloudy even after ~1.5 hours



D. 1M Sodium bicarbonate (NaHCO3, aka baking soda) gave pH~8.2. Addition of equal volume of either isopropanol or ethanol just gave a cloudy salt precipitate and no separation of phases

So...

1. sodium carbonate actually aids the separation of alcohols from water.
2. isopropanol does much better than ethanol, even though both separate as water-saturated fractions
3. addition of NaOH helps better separation of isopropanol from NaCO3 solution, driving the phase ratio (alcohol / water) from 0.23 to 0.6. (ratio = 1 is the best separation)

 

[burnt]

excellent cool thanks for the data. any endearing SWIMMERs can now attempt the limonene tek all the kinks seem worked out.

 

[Infundibulum]

Re to my previous post, one can get easily (in theory at least, but I am going to try it myself) sodium carbonate from sodium bicarbonate (baking soda) just by cooking it in the oven for some time. According to wikipedia, (Sodium bicarbonate - Wikipedia)


Thermal decomposition

Above 60 °C, it [sodium bicarbonate] gradually decomposes into sodium carbonate, water and carbon dioxide. The conversion is fast at 200 °C:[citation needed]

2NaHCO3 → Na2CO3 + H2O + CO2


Which basically means that there is no more need to worry about NaOH/lye as long as one can buy baking soda, cook it to Na2CO3 and thus having a fairly decent base that can give you a pH of at least 12

 

[69ron]

This reminds me of that old saying, "where there's a will, there's a way!"

Also, "there's more than one way to skin a cat", which is actually quite a gross saying. Where did that come from?

Yeah...SWIM made sodium carbonate from sodium bicarbonate before just by baking it in an oven. It is very easy to do but causes CO2 gas to form which causes the sodium bicarbonate to jump around in the pan. Make sure you cover the pan with tin foil or your whole oven will be covered in pieces of sodium carbonate.

I really like the idea of using limonene as the NPS. I hope someday a very good easy to use kitchen tech is developed around limonene. Everyone loves the wonderful smell of limonene. Even if your final product is contaminated with a trace of limonene, it'll just make your product smell nice without adding any toxicity.

This sodium carbonate trick is a great trick for separating IPA from water. It works better than salt because salt is very slightly soluble in IPA but sodium carbonate is not. Another thing that helps is after the IPA is separated, add MgSO4 (dried Epsom salt) to the IPA to remove all possible water from it, and then filter it. This way there should be no sodium carbonate in it at all because dry IPA can't hold it, but wet IPA can.

Is there an acid you can add to water that will cause water to be insoluble in IPA?

 

[Infundibulum]

Good question 69ron. it is apparent that the presence of salt(s) like sodium carbonate reduce the solubility of IPA. It is also apparent that other salts like NaCl can do the same trick. A water solution of Na2CO3 is basic by virtue of the fact that it can be seen as the product of a strong base (NaOH) and a weak acid (H2CO3) so upon its solubility we have:

Ma2CO3 -> 2Na+ + CO3=

and then CO3= + 2H2O <-> H2CO3 + 2OH- (and the latter hydroxides give you the basic pH)


So....

What if you dissolve the salt that is the product of a weak base (NH3) and a strong acid (HCl) like ammonium cloride (NH4Cl)?

1) solution becomes acidic, NH4Cl ->NH4+ + Cl- , then NH4+ + H2O <-> NH3 + H3O+

2) IPA becomes insoluble to this ammonium cloride solution -> I'm going to try this tomorrow

In theory therefore yes, you can have an acid solution into which IPA is insoluble

 

[SyZyGyPSy]

Bump.

Any updates, SyzyGypsy? The idea of cooking the freebase spice out of aqueous solution with baking soda is intriguing...

Yes, actully... there have been amazing advances with the limo tek. Swim's been meaning to post a revised tek but he's been real busy/lazy... hang in there, it's coming.

Basically the gist of it is: take aqueous soln of spice acetate salts, freebase by adding saturated sodium carbonate soln. Add isopropanol. Swim does this in an eyedropper bottle, using the eyedropper to suck off the iso. Repeat 3-4x with iso pulls to get all the spice. Evap combined iso pulls revealing spice and sodium carbonate. Redissolve the spice in dry (100%) isopropanol and evap. Swim evaps it onto a leaf, usually red poppy flower. The results are AMAZING! In his last batch, swim used a 3:1 weight ratio of spice to leaf, and had a two-toke breakthru when he tested it out. And it's not like smoking petroleum spice either... swim never wants to smoke petro spice again now that he's experienced this! There's no comparison... you gotta try it for yourself and see!
Full-on revised limo tek coming soon!

 

[Jorkest]

where can you find limonene?

 

[SyZyGyPSy]

Um... what's the rules for mentioning specific sources on this forum? Too lazy to check forum rules rite now...
How bout a hint? What you're looking for is a GREEN TERPENE from a DOT COM site.