Solvent washing - why product moves to water layer?

[blue.magic]

I am literally following the Washing Spice tek after every pull to remove any possible traces of base.

Today I found the water layer under heptane pull was suspiciously cloudy so instead of discarding the water, I put about 35 ml of fresh heptane into the sep. funnel and shook it.

The new heptane layer looked clear and the water still cloudy:

I put the heptane layer in a Pyrex dish and evaporated a bit - to my surprise, it turned cloudy!

Since the heptane was cloudy at about 20 ml, it indicates the basic water layer captured quite a bit of spice.

I was suspicious this washing tek may be a reason I am losing spice in every extraction, the water even smelled of freebase DMT and contained tiny white strands. But now it seems confirmed the washing tek indeed eats quite a bit of DMT.

I never though such minuscule amount of basic water (15 ml) can capture so much DMT. Or maybe it stayed in the sep funnel somehow in the residual heptane?

Or am I doing something wrong or is the washing tek really a "lossy" technique?

Maybe using ice cold water would help?

 

[Ulim]

How basic? Just Na2CO3?

 

[blue.magic]

How basic? Just Na2CO3?

Yes. Just a pinch of Na2CO3. I've added more this time, something like 50 mg in 20 ml water.

 

[Ulim]

Not nearly basic enough. The dmt will move to the water layer to a great extent.

 

[null24]

I've never tried this, from what I understand, it is a dated technique that has been superseded by more effective cleaning methods.

I've been hearing lots of feedback regarding dated material appearing in the wiki and faq etc as state of the art. I understand that the mods are busy with life etc, would it be helpful in any way to kind of go through and point out some of this stuff for consideration? I've talked to new extractors who are going out and buying a bunch of plastic because they got the DMT Handbook here that recommends it, among other things.

We're losing it...

 

[Orion]

It is an old technique which I find does reduce yield too much to be worthwhile.

To be honest I think it's time these pages had a bit of a wash themselves, handbook or not. The wiki could even lose a few pounds once it gets a bit of a scrub.

 

[blue.magic]

It seems the Wiki really needs some cleanup...

It even mentions to use just "a pinch" of sodium carbonate (like if using more is a problem), which is now confirmed being not nearly enough.

I found this washing method mentioned in one book as "STB purification" so I thought it is commonly used and tried method.

It seems the only viable purification methods are recrystallization, mini A/B (lossy) or chromatography.

 

[Infundibulum]

The new heptane layer looked clear and the water still cloudy:

A clear indication that the separation has not reached equilibrium; the opaqueness of the water means that there is still heptane present in it.

I put the heptane layer in a Pyrex dish and evaporated a bit - to my surprise, it turned cloudy!

Makes sense

But now it seems confirmed the washing tek indeed eats quite a bit of DMT.

The tek indeed sucks ass, for all sorts of reasons. What were exactly your intentions for usign that tek? What did you want to wash away and what problem did you want to solve?

I never though such minuscule amount of basic water (15 ml) can capture so much DMT. Or maybe it stayed in the sep funnel somehow in the residual heptane?

DMT, with a partition coefficient of 2.5 is quite insolube in water, or in other words the water cannot be eating away the DMT.

 

[Northerner]

I've been having trouble with oily acacia extracts Infudibulum, so have experimented with some mini a/b's recently. I have been basing the hell out of the solution and gently heating it for the pulls, 4:1 base solution:solvent.

Is there an ideal ph, ratio and temperature that we could be using for mini a/b teks?

Would salting be of any value at this stage either?

I felt this is on topic, as the OP may have been answered.

 

[blue.magic]

The new heptane layer looked clear and the water still cloudy:

A clear indication that the separation has not reached equilibrium; the opaqueness of the water means that there is still heptane present in it.

Okay this step of the Washing Tek confused me:

4. Remove and collect the top NPS layer promptly ...

I though letting the mix sit for too long would cause DMT to move to water layer and the reason for prompt separation is to avoid losing product.

I know it's insoluble in water but I believed the tek was written by someone more experienced in chemistry than me so I just followed...

But now it seems confirmed the washing tek indeed eats quite a bit of DMT.

The tek indeed sucks ass, for all sorts of reasons. What were exactly your intentions for usign that tek? What did you want to wash away and what problem did you want to solve?

The product is actually OK, I just wanted to make sure there aren't any possible traces of lye present.

Doing different extractions and learning chemistry by practice, I learn nothing is 100% and even insoluble compounds can be dissolved (though to a tiny extent - but active amount of DMT is tiny, right?). With lye, I heard even tiniest amount of it can make the smoke harsh so this led me to adding this washing step as a king of "quality assurance". I encountered harsh smoke but this was before I used GVG so maybe it was just me burning the spice, not a presence of lye.

 

[blue.magic]

Another reason I have for washing are micro emulsions.

I imagined there are tiny (invisible) droplets of lye water floating in the NPS layer, that will prevent making crystals in the best case and make the smoke harsh and unhealthy in the worst case.

Even though I use fine pipette to separate organic layer from basic tea, sometimes very tiny droplets of it end inside the pipette. I use intermediate tall beaker to decant NPS from these droplets (they will fuse at the bottom of the beaker so decanting is easy). But still I thought some tiny amounts of water soluble stuff can contaminate the naphtha...

 

[Infundibulum]

Doing different extractions and learning chemistry by practice, I learn nothing is 100% and even insoluble compounds can be dissolved (though to a tiny extent - but active amount of DMT is tiny, right?). With lye, I heard even tiniest amount of it can make the smoke harsh so this led me to adding this washing step as a king of "quality assurance". I encountered harsh smoke but this was before I used GVG so maybe it was just me burning the spice, not a presence of lye.

That is true; nothing is 100% insoluble in that or the other solvent. But you can sort-or calculate (if so you are inclined!) how much dmt will be dissolved in the water if you know the partition coefficient of dmt. That is logP (experimentally determined values) but also comes with other names as XlogP and XlogP3 (modelled values). DMT-wiki has a fair amount of logP values for most of alkaloids of interest.

For DMT the partition coefficient is 2.5, which roughly means that in a mixture of 50% water and 50% octane, for 10^2.5 or roughly 300 parts of DMT dissolved in octane, 1 part of DMT will dissolve in the water layer.

In your case you have heptane, i.e. a fair approximation to octane and you use less water per non-polar solvent, so with everything done right you should not be losing more than 1 mg of DMT per 300 mg washed. In in practice however things will deviate for all sorts of reasons. As you discovered, a second (or even third) pull with fresh heptane will be able to salvage all that dmt that dared to defect to the water phase.

 

[blue.magic]

Doing different extractions and learning chemistry by practice, I learn nothing is 100% and even insoluble compounds can be dissolved (though to a tiny extent - but active amount of DMT is tiny, right?). With lye, I heard even tiniest amount of it can make the smoke harsh so this led me to adding this washing step as a king of "quality assurance". I encountered harsh smoke but this was before I used GVG so maybe it was just me burning the spice, not a presence of lye.

That is true; nothing is 100% insoluble in that or the other solvent. But you can sort-or calculate (if so you are inclined!) how much dmt will be dissolved in the water if you know the partition coefficient of dmt. That is logP (experimentally determined values) but also comes with other names as XlogP and XlogP3 (modelled values). DMT-wiki has a fair amount of logP values for most of alkaloids of interest.

For DMT the partition coefficient is 2.5, which roughly means that in a mixture of 50% water and 50% octane, for 10^2.5 or roughly 300 parts of DMT dissolved in octane, 1 part of DMT will dissolve in the water layer.

In your case you have heptane, i.e. a fair approximation to octane and you use less water per non-polar solvent, so with everything done right you should not be losing more than 1 mg of DMT per 300 mg washed. In in practice however things will deviate for all sorts of reasons. As you discovered, a second (or even third) pull with fresh heptane will be able to salvage all that dmt that dared to defect to the water phase.

Thanks. I should learn these values as well as molar counts - I am really lacking in that part.

So the lesson is to make the washing water more basic, wait until the liquid-liquid mixture fully resolves and do three pulls. Maybe washing the glassware 2-3 times with fresh solvent will help as well. It's tedious, but I always think medicine-making requires patience and focus.

 

[downwardsfromzero]

For DMT the partition coefficient is 2.5, which roughly means that in a mixture of 50% water and 50% octane, for 10^2.5 or roughly 300 parts of DMT dissolved in octane, 1 part of DMT will dissolve in the water layer.

Surely you mean octanol? The XlogP partition coefficient is typically measured between octanol (C8H17OH) and water, rather than octane. So for DMT the partition coefficient with an n-alkane likely (but not necessarily) would be even greater.

https://www.researchgate.net/public...s_by_Guiding_an_Additive_Model_with_Knowledge (Explains XlogP3)