SWIM usually uses sodium carbonate at pH 9.5 when using a separatory funnel and gets really good yields with that. SWIM doesn't get better results at pH 13.5 using tons of sodium hydroxide. SWIM thinks that’s a waste of money. SWIM doesn't use sodium hydroxide anymore. However, SWIM doesn't have problems with emulsions much because he mastered the technique of using a separatory funnel.
But now SWIM uses a continuous liquid/liquid extractor instead of a separatory funnel for all liquid/liquid extractions. That never has emulsions and is much easier to use than a separatory funnel. When using a continuous liquid/liquid extractor, you can extract all the DMT into the non-polar solvent at pH 8.0 without any problems. It works better than a separatory funnel but takes longer. But because it’s automatic, you turn in on and it does the liquid/liquid extraction work for you. No more shaking, no more emulsions, just pour in the solvents, turn on the system and leave it and come back the next day and its done a better job than any human could ever do.
For the initial plant extraction SWIM uses a Soxhlet. Like the continuous liquid/liquid extractor, a Soxhlet is all automatic. It can extract all the DMT from a plant by letting it run without any human interaction.
If you really want the best yields possible you need a Soxhlet and a continuous liquid/liquid extractor. With such a setup, you don’t need a strong base, because even sodium bicarbonate (instead of sodium carbonate) will work. DMT has a pKa of 8.68. Even a pH of 7.0 works to freebase all of it if you use a continuous liquid/liquid extractor with water, DCM and a little sodium bicarbonate, you just let it run on its own a little longer. The higher the pH, the shorter the run-time. But once you get above pH 9.5, the run-time is about the same no matter how much higher the pH is. At least this is what SWIM has found.
According to "Casarett and Doull's Toxicology: The Basic Science of Poisons", page 110, the following pKa/pH rules apply to all organic bases:
ph=pKa-3 = 99.9% ionized
ph=pKa-2 = 99.0% ionized
ph=pKa-1 = 90.0% ionized
ph=pKa+0 = 50.0% ionized
ph=pKa+1 = 10.0% ionized
ph=pKa+2 = 01.0% ionized
ph=pKa+3 = 00.1% ionized
How does this apply do DMT where pKa=8.68? As follows
ph=03.68 = 99.999% ionized
ph=04.68 = 99.990% ionized
ph=05.68 = 99.900% ionized
ph=06.68 = 99.000% ionized
ph=07.68 = 90.000% ionized
ph=08.68 = 50.000% ionized
ph=09.68 = 10.000% ionized
ph=10.68 = 01.000% ionized
ph=11.68 = 00.100% ionized
ph=12.68 = 00.010% ionized
ph=13.68 = 00.001% ionized
Imagine if your plant contained 500 mg of DMT (the average for about 100 grams of mimosa), the difference between pH 9.98 and 13.68 would be 450 mg of DMT in freebase form at pH 9.98 and 499.995 mg in freebase form at pH 13.68. This sounds good in theory, but in reality, freebase DMT is somewhat water soluble, so even at pH 13.68, using a separatory funnel you still need at least 3 pulls with non-polar solvent to get most of the DMT. This is the same amount of pulls you need at pH 9.98. This is because of the octanol/water partition coefficient of DMT not being so great. Each time you extract with non-polar solvent you only get a percentage of the freebase DMT. DMT has a predicted XlogP of 2.0. That’s not that high. Heptane, which is insoluble in water, has an XlogP of 4.3. In order to get all the DMT in one extraction, you’d need it to have an XlogP of at least 4.3 or higher, no matter how high the pH is and that is simple impossible.
When extracting DMT from any plant, there are many forces at play. Other molecules are interfering with the extraction process. Some are sticking to DMT, others are forming emulsions, some are lowering or raising the polarity of the water as the pH changes, etc. So in reality the extraction efficiency is usually less than theoretically possible.
When using a continuous liquid/liquid extractor, these forces can be dealt with by simply letting the extractor run longer. Even if pH 4.68 in maintained, a liquid/liquid extractor can eventually extract all of the DMT if left to run for many months, but that would extract all sorts of junk out of the water along with it. To be practical, a pH of about 8 and up is really needed to extract freebase DMT from water into a non-polar solvent like DCM.
One rule for a continuous liquid/liquid extractor is: the shorter the run time, the more pure the extraction. So higher pH values generally produce more pure results because less run time is needed, but then again, higher pH values also destroy some compounds that you might not want destroyed. Another rule is: the shorter the run time, the smaller the yield. Another rule is: the longer the runtime, the more the compounds degrade. So it’s all a balance. If it’s run too long, you get too many impurities and compounds start to degrade, if it’s not run long enough you get poor yields.
You have similar same types of problems with separatory funnels. If you extract with too much non-polar solvent, you get higher yields and more impurities, if you don’t use enough you get poor yields. If you take too long to extract because of emulsions and other problem then compounds start to degrade. The main problems with separatory funnels are: A) emulsions tend to form (bad emulsions can sometimes take days to separate); B) lots of manual work is needed (rolling, shaking, waiting for the layers to separate, etc.) The only advantage a separatory funnel has is that it takes less time than a continuous liquid/liquid extractor, but at the cost of far more manual labor.