Thanks for explaining about protonated DMT. Does the same apply when adding freebase to orange juice? What you're drinking is not DMT-citrate, but DMT H+ and citric anions?


Why is volatility important? This is for the acid step prior basing, not back-salting. Would you suggest using vinegar over citric acid? I forget where but read somwhere about someone mentioning a complication using vinegar followed by sunflower oil after basing. Hoping this is not a problem.


Ok so Calcium Hydroxide works better than Sodium Carbonate. I never used it. It's very low soluble in water, is that a problem? Do I just add Calcium Hydroxide powder straight to the (cold) acidic bark solution? Would 50g Calcium Hydroxide for 50g bark in around 700ml total solution volume work?

Good to known about possible precipitating goodies in the fridge. Better to let settle at room temp then. I want to do boils and discard solids to limit veggie oil emulsions.


Thanks for sharing the limonene tip, but will first try pure oils as the goal is easily obtainable food products.


I guess I will do tests (without DMT) with several oil types to observe emulsion issues and if any soap is left post back-salt evaporation.

If anyone has veggie oil experience, please share.

Aye. And if you drink brine you actually consume a bunch of sodium and a bunch of chloride ions that are not in any reasonable proximity to each other.

But this is the case for water only. If you dissolve, say, dmt-citrate in ethanol, methanol, IPA, acetone etc there will not be dissociation and you will have a "true" solution of dmt citrate.

Water is the only solvent where salts dissociate. Such reaction, chemically speaking, involves reaction of the salt with water. No water = no dissociation.

All clear now, cheers

Yes - DMT H+ and citrate anions.


The more acid, the more complex the resulting basic solution - which may work in your favor or against you, depending on the particulars.
I've heard phosphoric acid (which is non-volatile) is good at extracting DMT salts, so that's another option to consider?


The poor solubility is not a problem per se, but it means your base won't contribute to ionic strength that much, so you may want to make up for that by adding more NaCl.
I've read that Ca(OH)2 is less likely to lead to saponification than NaOH.

Food grade phosphoric acid sounds like an interesting option.

So it's better to use Calcium Hydroxide instead of Lye, as Lye has a higher risk of forming soap with the veggie oil.

Regarding adding table salt I read this post and got a bit worried because I suspect I might have had the same complication.

Could I use use Sodium Carbonate instead of salt to combine with Calcium Hydroxide for more ionic strenght? Sodium Carbonate + Lye + veggie oil will form soap, right? But also with Calcium Hydroxide?


Closed bottled carbonated water heats, filtered solids, reduced volume in open pan. All carbonic acid will evaporate leaving nothing to work against you in terms of basic solution complexity (no risk). I've spoken about it enough, heck I'll just give it a try.

Heating a sealed, pressurised vessel is potentially dangerous. Think very carefully about this to ensure that it is FAIL SAFE! (i.e. if it fails, it does so safely. Incorporate a reliable pressure relief mechanism - and beware of foaming and clogging. Or maybe omit this pressurised heating step entirely.)


I respectfully disagree here. For example, sodium chloride dissolves in DMSO and this particular reagent is used in a reaction that relies on chloride ions for it to take place. The NaCl is most assuredly dissociated into its constituent ions. (The difference is the degree of solvation (the ions being surrounded by fairly orderly clusters of solvent molecules) is far greater in the case of water - and it is this lack of solvation which allows the aforementioned reaction to take place in DMSO when it doesn't work using water as the solvent.) And as another example, 18-crown-6 complexation of potassium salts allows them to become soluble in benzene! The potassium cation is held inside a cyclic polyether and the anion (usually something like t-butoxide) is obliged to make its own way with things.

Apologies for not entirely relevant chem waffle, but I hope you get my point!


(Edit: being on the subject of irrelevant things, this came up as post no. 4301 for me. This is nice because 4301 = 11*17*23 )

Definitely, verseing things for the laymen is one area where I could do with improvement

Your explanation certainly holds when considering why something like potassium hydroxide won't dissolve in naphtha.

downwardsfromzero I'd vent the pressure of course, but good that you give a formal warning.

As we're on the chemistry tour and it seems you can use some practice talking to layman (lol), would you be so kind to explain the following:

Calcium Hydroxide only dissolved 1.85 g/l in water. If I place 50g Calcium Hydroxide in 500ml water, 0.925g dissolves and 49.075g does not. How does the undissolved Calcium Hydroxide increase the pH of the solution and aid in converting the protonated DMT.H+ ions into freebase DMT? I would think that all base needs to be dissolved to be able to do this?

The solubility of an ionic solute is defined through its solubility product. This is the mathematical product of the concentration in solution of each of the ions of the substance in question. Addition or removal of any one of these ions affects whether more of the substance precipitates or dissolves. It is a type of equilibrium effect.

In the case of calcium hydroxide neutralising protons on the DMT molecular ion, the proton reacts with a hydroxide ion to form a molecule of water. This means that another hydroxide ion can dissolve from the remaining solid calcium hydroxide to take its place. So, while there is solid Ca(OH)2 present in the reaction mixture, the hydroxide concentration is kept at a maximum as it is being replenished constantly.

If you were to use limewater, without the undissolved Ca(OH)2, this effect would not be able to take place so the hydroxide ions would decrease in concentration much more markedly, with a corresponding decrease in the pH of the solution.

One more thing about solubility product (Ksp) is that it is also determined by the stoichiometry of each respective ion. What this means is, in the case of something like Ca(OH)2, because the compound contains two equivalents of hydroxide for each equivalent of calcium the Ksp is calculated as the second power (square) of the concentration of the hydroxide ions:

Ksp (Ca(OH)2) = [Ca][OH]^2 (the square brackets are a formal notation meaning the concentration of the ion species in solution)
An upshot of this is that the increase in concentration of the calcium ions in solution has less effect on the solubility of the Ca(OH)2 than the removal of hydroxide.


So, to put it simply, the solid Ca(OH)2 helps keep the pH up because it can carry on dissolving while the dissolved part is being used up.

Great explanation, thanks for that!

So the amount of calcium hydroxide which is "used up" corresponds directly to the amount of DMT (and other plan compounds) present in solution converted to freebase. This means you'd probably need very little base. Maybe 10g or so for a 500ml solution with 50g MHRB? I guess adding too much is no issue because it would just stay undissolved.

As you advised me in an other post, I will start with a vinegar back-salt first as this is proven to work. The only thing I'd like to know is how much back-salting solution volume to use when back-salting (say) 1g DMT from veggie oil. Does 50ml vinegar @ pH 4 sound reasonable? The less the better as water takes a long time to evap. But I guess there is an efficiency limit regarding the absorption of spice due to saturation and I shouldn't go too low. Can't seem to find good info about this.

When the vinegar back-salt succeeds I will repeat using the same volume of the carb water to back-salt from the same batch of DMT containing veggie oil.

Well, you can use simple arithmetic to work out how much acetic acid will neutralise any given amount of base, then work out what volume of vinegar that corresponds to.

* convert weight of DMT into molar quantity by dividing by the molar mass, in this case 188g/mol in whole figures.

* check the molar ratio the neutralising acid requires. Acetic acid and DMT are both monobasic so they neutralise in a 1:1 ratio (fortunately!)

* apply the molar mass calculation in reverse using the molar mass of acetic acid, 60g/mol.

* divide this by the concentration of the vinegar (which should be a w/v - weight per volume - value) to find the volume of vinegar required.

* This all boils down to the following equation:

((1/188)*60)/(5/100) == (60/188)*(100/5) == 6000/940 == 300/47 mL

I'll leave the last step to you


You would need to know the concentration of carbonic acid in the fizzy water, or more specifically you'd need to calculate the hydrogen ion concentration - which is slightly more complicated. You'd be better off using a definite excess of carb water; considering the carbonic acid is entirely volatile there's no problem with slow evaporating residues as there would be with acetic acid.

But, all that being said, what you would learn by using the same volume as the calculated volume of vinegar is what the effective concentration of your carb water is (up to the maximum of 5% [expressed as monobasic H+.HCO3-]; once there is more than that amount all the DMT is neutralised anyhow.) This is something that would have practical value in future carb water backsaltings.

Don't think you win the verseing things to laymen 1st price. Just kidding, this type of raw data is exactly what I like to read, thanks again!

So: 300/47 == 6.4ml of a 5% vinegar solution "neutralizes" 1000mg freebase DMT
6.4ml of 5% solution contains 0.32g acetic acid (6.4/1000*50)
Meaning: 320mg acetic acid neutralizes 1000mg DMT

Carbonic acid has a molar mass of 62g⋅mol−1.
My carbonized mineral water has pH 3.8.
This means it's about 0.05 M == 3.1g per liter == 3.1% carbonated (62*0.05)

If carbonic acid has a molar mass of 62g⋅mol−1, neutralizes DMT at a 1:1 ration and the solution contains 3% carbonic acid,
then we can use the same formula as above to calculate how much volume of carbonic solution is needed to back-salt 1000mg DMT:

((1/188 )*62)/(3/100) == (62/188 )*(100/3) == 11ml

So: 11ml of a 3% carbonated solution neutralizes 1000mg DMT into DMT-carbonate
11 ml of 3% carbonic solution contains 0.33g carbonic acid (11/1000*30)
Meaning: 330mg carbonic acid neutralizes 1000mg DMT

As you mentioned I don't see an issue using factor 5x more carbonated water, as all carbonic acid will evaporate anyway leaving behind freebase DMT.

I think I'll start with lye basing and naphtha pulls. Freeze precip 50% naphtha and back salt the other 50% with carb water. Then compare yield. If back salting yield is poor I can always freeze the remaining naphtha and nothing is wasted.
If the back-pull yield is successful, I will repeat with calcium hydroxide, veggie oil and back salt 50% NPS into vinegar. If that succeeds if will back-salt the remaining 50% in carb water. Again comparing yield. I will perform two carbonic 50ml 10min back-salts on the same batch one after the other and compare yield. All yield should be contained in the first.

Will be using 100g MHRB 3x 3hr vinegar boiled (pH 4), plant matter filtered, reduced volume, settled for a week, discarded solid residue. Solution color is transparent dark red. Plant matter absence should hopefully decrease veggie oil emulsions. Each of the 4 tests contain 25% of the 100g root = 25g root and should yield around 250-500mg DMT.

I will start with carbonated mineral water. If I only need 50ml water, it shouldn't result in significant amounts of minerals and other solid residues contaminating the yield. Upon success I could buy a water distillator and carbonizer.

Bump.

I edited the post above. Could someone check the math? I want to get the theory behind the amount of back-salt acid solution volume needed right. Seems that around 1/3 part acetic acid by weight neutralizes 1 part DMT by weight. Same with Fumaric for FASA. Coincidence, or can we use this as a general guide?

Coincidence, mere coincidence.

I do not see exactly where are you going with the calculations, sure it is good to have a grasp of the maths and chemistry involved in titrations....

...but unnecessary. The rule of thumb is use some acid (1-2%, regardless of what acid) and multiple saltings and you are good.



PS, your carbonic acid calculations are wrong because there is not such thing as carbonic acid. CO2 reacts with water as (simplified):

CO2 + H2O <-> H2CO3 <-> H+ + HCO3- <-> H+ + CO3=

Hard to predict what species you have and how your titration will go without knowing other paramenters e.g. temperature and pressure.

Ok. I am no chemistry expert, just a practical dude being creative trying to make stuff work. Glad you guys are helping out.

I guess using an excessive amount carbonated water and back-salt more times than needed should work. But I want to optimize (minimize) the amount of carb water to speed up evaporation. Was hoping to convert carb water pH to calculate the required carb water volume for a DMT amount (estimation) in NPS. But from what I understand this is not possible due to too many variables? What about for pure DMT in clean NPS at atmospheric pressure and room temp? Really no way to calculate using chemistry?

I'm in the process of doing the extraction test. Did 3 acid boils on 100g MHRB. Filtered all plant matter and let it sit for a week then filtered plant residue. Split the dark red MHRB solution in two equal parts. Saved one part for later (for the calcium hydroxide + sunflower oil test). Based the other with lye and pulled with naphtha. Split the DMT containing NPS (Naphtha) in two equal parts. Put one part in the freezer, should be ready tomorrow.

I will back-salt the other NPS part with carbonated water today or tomorrow. Goal is to observe how well the back-salt worked by comparing yield to freeze precip. Will use 25ml carb water to back-salt 250ml NPS containing around 250mg DMT (1% from 1/4 100g bark). I will back-salt for 15min and separate. Then add new carb water for 15min and separate. Evap the two separately to compare and freeze the NPS to see if any DMT is left.

Unfortunately it seems that there is no way of knowing by theory if 25ml pH 3.8 carbonated water is realistic to back-salt 250mg DMT from NPS. It can only be learned by experimentation.

Wish me luck. And as always I'm all ears for advise, tips and tricks.

Update

I took the NPS (around 150ml) out of the freezer and nothing precipitated. Expected 250mg yield. Evaporated volume down to 20% and tried again. This time crystals were present. Also oily stuff. Strange as this Naphtha should work well. Yield is now drying, didn't weight yet.

I played around with the Naphtha batch. Noticed that when first adding 0.5 acetone to 1.0 NPS by volume, then FASA, no fumaric acid crashes out. I've then done this to the reduced NPS which I took out of the freezer (after separation of crystals). It went cloudy. This morning needle xtals were present. Guess DMT-Fumerate, will test of fumaric acid residue by washing with fresh acetone. If successful, means you can do FASA on acetone diluted Naphtha to get the last goodies out after freeze precip and separation.

I added carbonated water to the other 50% of NPS which I saved for this goal. As soon as I did, the NPS went cloudy. The carb. water below stayed clear.

1st back-salt: 75ml carb. water pH 4.25 prior, 15min wait, pH 5.25 after separation
2nd back-salt: 100ml carb. water pH 4.25 prior, 15min wait, pH 4.75 after separation
3th back-salt: 25ml H2O with 25ml vinegar pH 2.75 prior, 15min wait
4th back-salt: 50ml vinegar (think 5%) let it wait 24 hrs

Results

1st back-salt:
very thin layer of transparent oily residue. Couldn't scape. When I tried yellowish residue on knife blade. Smelled dirty oily. Dissolved everything in Acetone. Added FASA. Went cloudly. Is still cloudy 1.5 day later.

2nd back-salt:
Same result like 1st, but less amount. Also couldn't scrape

3th back-salt:
During back-salting the vinegar stayed just as transparent as the carb water prior. Thicker white residue. Also couldn't scrape. I tasted it, it burned like DMT would. I did a comparison by evaporating 25ml vinegar on its own on a separate plate. It also had a white residue (acetic acid). Only tasted acidic. The back-salted vinegar residue did seem like more.

4th back-salt:
Towards the end of the day the cloudy NPS finally became transparent. The vinegar below went yellow. The NPS had a white layer floating on the bottom. The vinegar was separated and is drying now.

Conclusion

Difficult to say. The carb water didn't pull enough. However neither did the vinegar. I suspect something to be wrong with the NPS maybe, as it didn't freeze precipitate without reduction. Maybe spreading a 250mg theoretical yield over 4 large plates was too much surface area. Or maybe it just didn't pull out of the naphtha. Too bad the naphtha went cloudy after adding carb. water. Don't get why. But it seems the carb water did pull something.

Next

Next is adding the DMT which I just extracted straight to some sunflower oil. Then back-salt with carb water. See what that does. If it works I will continue to base the remaining MHRB solution with calcium hydroxide, pull with sunflower oil, back salt with carb. water and end by backsalting with vinegar to see if anything remains.

It seems you were using carbonated mineral water, which contains dissolved solids.

You'll likely get better results (in terms of salt contamination) by using carbonated distilled/de-ionised/RO water.


As Infundibulum explained above, there's an equilibrium between the various ionisation states of carbonic acid in carbonated water. This limits the amount of H+ ions available at any one time so using a large excess of CO2 would make the process more effective. In order to minimise the amount of water that needs to be evaporated it would be worth allowing longer extraction times. This would give the equilibrium reaction more time to replenish the H+ ions that have been taken up by the DMT base.

The most important equilibrium reaction to be considered is:
DMT + H2CO3 <-> DMT.H+ + HCO3-

It's possible to put figures to this (but not by me, on a Sunday afternoon )
If you really get into the details, you'd be looking at the solubility of CO2 in naphtha and maybe finding out why the naphtha went cloudy.

I can add clean carb water to clean naphtha to observe what will happen. By bet is that it won't go cloudy and that what did was caused by the plant material in the naphtha.

The only reason I used naphtha was to do a 1:1 comparison between freeze precip and back-salting. I eventually got 220mg out of freeze precip by reducing NPS volume and freezing again. But the back-salt failed. I think I did manage to pull everything from the NPS after backsalting in 5% vinegar for 24 hours. I evaporated the water, leaving a oily yellow yield and the naphtha was clear.

For the next step I will dissolve 220mg DMT into 100ml sunflower oil and backsalt in 100ml carb waterand leave it for 1 hours. Separate and add 100ml carb water for 3 hours. Last time 100ml for 6 hours.

pH 4.65 is the lowest I can go using a carbonizing machine. The mineral water used previously has a pH is 4.25 (it has more gas). Again, no idea if 100ml carb water pulls 220mg DMT, will see.

Small update:

I dissolved 150mg freebase DMT in 40ml sunflower oil. Heated it in a warm water bath to aid dissolving. Added the oil to 100ml carbonated water (pH 4.65). Left it 12 hrs. Separated the water from the oil. The water measured pH 5.3. The pH went higher from the initial pH because too much air in bottle I think, making the gass escape the water. Will use smaller bottle next time and fill to top. Water smelled and tasted very DMT-ish. Evaporated water on a dish. Left an off-white hard oily residue. Smelled like honey. Experiment seemed to work. Couldn't scrape from the steel plate with a razor because the plate material scratched. Should have tested prior. Will dissolve yield in ethanol and re-evaporate on a glass plate. I can't weight the yield yet so can't comment on efficiency, but all in all the tek seems to work.

Good to hear of your experiments! Do you have any further updates?

Those dedicated to getting to the bottom of this particular investigation would do well to consider getting a beverage carbonation device (i.e. soda stream) to maximise the CO2 concentration during the process. I keep thinking about doing so myself.

This would be used for making charcoal

I would plan to carbonate the oil and distilled water directly, rather than preparing soda water and adding it to the oil.