The Base in Your Product

[Norolinda]

You may indeed have NaOH in your final product! When mixing the “soup” (more properly called the aqueous solution/phase) and the nonpolar solvent, (called ‘organic solvent/phase’), inevitably some of the highly basic aqueous solution will suspend itself in the organic phase, and will remain even after separation of the two phases. This dangerous substance is easily removed by water washing the organic phase. This technique is standard lab procedure, and every chemist of every level should be in the habit of doing this.

After the extraction is done, heat the solvent to around 40 C on a hotplate, and prepare some (clean, preferably distilled) water of the same temperature. Cold washes can cause lost yield due to precipitation of DMT from the organic phase. Place the organic phase in a sealable vessel that is easily vented, such as a seperatory funnel, and add 20% of the volume of the organic solvent of water. Invert, don’t shake: flip the vessel end over end and in a figure 8 pattern, and after every few flips, carefully vent the funnel pointing it away from your face; shaking will only make separation more difficult. After a minute of inverting, let the phases separate, discard the aqueous phase, and repeat twice more. Then proceed to freeze precipitation to yield a clean final product.

 

[Transform]

Dissolved CO₂ can cause losses when using distilled water for the wash. While this may be less of a problem if using hand-hot water, adding a little sodium carbonate to the wash water does a whole lot more to ameliorate the issue.

discard the aqueous phase

It would be wise to reserve the wash water in case of unanticipated losses in yield.

It's also possible to achieve a reasonable cleanup by first transferring the naphtha pulls into a (pyrex) jug with a few tens of mL of sodium carbonate solution in the bottom. Squirting the naphtha through the SC solution with a pipette helps too. Allow this to stand for a while so that it can settle out, then transfer the naphtha to the freeze precipitation dish.

This works well enough for those without a sep funnel (or too lazy to get one out of the cupboard).

 

[Norolinda]

Dissolved CO₂ can cause losses when using distilled water for the wash. While this may be less of a problem if using hand-hot water, adding a little sodium carbonate to the wash water does a whole lot more to ameliorate the issue.


It would be wise to reserve the wash water in case of unanticipated losses in yield.

It's also possible to achieve a reasonable cleanup by first transferring the naphtha pulls into a (pyrex) jug with a few tens of mL of sodium carbonate solution in the bottom. Squirting the naphtha through the SC solution with a pipette helps too. Allow this to stand for a while so that it can settle out, then transfer the naphtha to the freeze precipitation dish.

This works well enough for those without a sep funnel (or too lazy to get one out of the cupboard).

Thank you for your reply, very insightful. I have a few questions

With the Na2CO3, you're making NaHCO3 to prevent the CO2 from making a carbonate salt? How much dissolved CO2 is in distilled water? Does this apply to freshly distilled, or even perhaps freshly boiled water? Does the sodium bicarbonate solution not suspend itself into the organic phase and end up in the final product without desiccation? How much Na2CO3 is being added?

> Squirting the naphtha through the SC solution with a pipette helps too.

Fascinating technique. I wonder what other kinds of purifications in chemistry, synthetic or otherwise, use this trick. is it increased surface area that makes this work better than inverting?

Very wise indeed to not discard the aqueous phases until one is sure the product has not been lost to it, good catch.

> This works well enough for those without a sep funnel

very true, but I do love my sep funnels. enough to have 5 of them (different sizes of course)

 

[Transform]

Thank you for your reply, very insightful. I have a few questions

With the Na2CO3, you're making NaHCO3 to prevent the CO2 from making a carbonate salt? How much dissolved CO2 is in distilled water? Does this apply to freshly distilled, or even perhaps freshly boiled water? Does the sodium bicarbonate solution not suspend itself into the organic phase and end up in the final product without desiccation? How much Na2CO3 is being added?

> Squirting the naphtha through the SC solution with a pipette helps too.

Fascinating technique. I wonder what other kinds of purifications in chemistry, synthetic or otherwise, use this trick. is it increased surface area that makes this work better than inverting?

Very wise indeed to not discard the aqueous phases until one is sure the product has not been lost to it, good catch.

> This works well enough for those without a sep funnel

very true, but I do love my sep funnels. enough to have 5 of them (different sizes of course)

All good points, and I love a nice sep funnel well-used as well

There was a discussion here very recently where @CokFLHX reported losing nearly 50% yield with a water wash, so either there product was heavily contaminated or RO water can get surprisingly acidic. That seems like a particularly extreme case, and I'd say there must be a few question marks hanging over that, what with the RO water being obtained from an energy facility. But all that aside, using freshly boiled water would go a long way towards keeping the pH a bit higher. I still wonder, now that atmospheric CO2 levels have definitively crossed the 400ppm boundary already for some years (compared to the 350ppm there was when I was a kid), how much this >12.5% increase will be affecting the pH of distilled water, when we compare it to the locally elevated CO2 levels from human respiration in indoor environments, plus the influence of various forms of combustion, particularly ICE vehicular traffic in urban areas.

A pinch or two of sodium carbonate seems like the easiest way of eliminating that concern!

In essence, it's as much about absorbing stray protons as forming bicarbonate. When CO2 dissolves in water, there's an equilibrium between water plus carbon dioxide and carbonic acid, and carbonic acid and bicarbonate plus a hydrated proton, and bicarbonate and carbonate plus another hydrated proton, alongside the autoionisation of water. Adding more CO2 increases the concentration of protons, apparently sometimes sufficiently to cause protonation of DMT and its subsequent solubilisation. But the consequence of adding alkali carbonate is indeed driving the formation of HCO3-.

You're probably familiar with the equations:
CO2 + H2O <=> H2CO3
H2CO3 + H2O <=> HCO3- + H3O+ }
} = free protons, pH decrease
HCO3- + H2O <=> CO32- + H3O+ }
Shuffling all this around a bit, we get:
CO2 + H2O + CO32- -> 2HCO3- and no stray protons (N.B. - starts to reverse above 70°C)
Moreover, SC is, of course, alkaline in solution due to mopping up protons and increasing the relative concentration of hydroxide:
CO32- + H2O <=> HCO3- + OH-
the latter of which also recombines with solvated protons, raising the pH:
H3O+ + OH- <=> 2H2O

The squirting of the naphtha through the SC solution isn't necessarily "better" than a good wash using a sep funnel, but it's pretty straightforward if one happens to have a pipette full of naphtha anyhow. Again, it's a matter of kitchen/jam jar chemistry vs. other lab techniques - "horses for courses". Either way is aimed at interfacing the polar and non-polar phases.

 

[brokedownpalace10]

I usually just squirt the Napthe from the pipette into a large, tall shot container of distilled water. Stir, let separate, and pull again into the final container. Would this work well and would it work better if I put a little sodium carbonate into the water?

 

[Norolinda]

All good points, and I love a nice sep funnel well-used as well

There was a discussion here very recently where @CokFLHX reported losing nearly 50% yield with a water wash, so either there product was heavily contaminated or RO water can get surprisingly acidic. That seems like a particularly extreme case, and I'd say there must be a few question marks hanging over that, what with the RO water being obtained from an energy facility. But all that aside, using freshly boiled water would go a long way towards keeping the pH a bit higher. I still wonder, now that atmospheric CO2 levels have definitively crossed the 400ppm boundary already for some years (compared to the 350ppm there was when I was a kid), how much this >12.5% increase will be affecting the pH of distilled water, when we compare it to the locally elevated CO2 levels from human respiration in indoor environments, plus the influence of various forms of combustion, particularly ICE vehicular traffic in urban areas.

A pinch or two of sodium carbonate seems like the easiest way of eliminating that concern!

In essence, it's as much about absorbing stray protons as forming bicarbonate. When CO2 dissolves in water, there's an equilibrium between water plus carbon dioxide and carbonic acid, and carbonic acid and bicarbonate plus a hydrated proton, and bicarbonate and carbonate plus another hydrated proton, alongside the autoionisation of water. Adding more CO2 increases the concentration of protons, apparently sometimes sufficiently to cause protonation of DMT and its subsequent solubilisation. But the consequence of adding alkali carbonate is indeed driving the formation of HCO3-.

You're probably familiar with the equations:
CO2 + H2O <=> H2CO3
H2CO3 + H2O <=> HCO3- + H3O+ }
} = free protons, pH decrease
HCO3- + H2O <=> CO32- + H3O+ }
Shuffling all this around a bit, we get:
CO2 + H2O + CO32- -> 2HCO3- and no stray protons (N.B. - starts to reverse above 70°C)
Moreover, SC is, of course, alkaline in solution due to mopping up protons and increasing the relative concentration of hydroxide:
CO32- + H2O <=> HCO3- + OH-
the latter of which also recombines with solvated protons, raising the pH:
H3O+ + OH- <=> 2H2O

The squirting of the naphtha through the SC solution isn't necessarily "better" than a good wash using a sep funnel, but it's pretty straightforward if one happens to have a pipette full of naphtha anyhow. Again, it's a matter of kitchen/jam jar chemistry vs. other lab techniques - "horses for courses". Either way is aimed at interfacing the polar and non-polar phases.

I was reading over that post thread, and I see they used RO water, and you mentioned that too. I generally mean water distilled by steam distillation when I talk about distilled… but that’s easy to get where I live. RO water, to my knowledge, can contain more junk — such as dissolved CO2 — than steam distilled water. I should be careful in clarifying that in the future. There’s also deionized water (ACS or similar grade) that I often use, but that’s pricey, at least where I’m at. I tend to save that for more delicate and complex procedures and for pH probe calibration.

But I have to be practical and realize, while you and I are careful about the quality of the water we use — it’s a reagent after all! — not everyone here will be. I know from experience as a mod on DMT forums on Reddit that people absolutely use tap/suspect water despite my best efforts to convince people otherwise.

My concern is, without desiccation with some MgSO4 or the like, you’ll end up with at least some (slightly) basic compound in your final product simply from the aq phase getting suspended in the organic phase. As much as I’ve tried to convince people to desiccate the organic phase post wash as is standard, it simply doesn’t happen.

This conversation has reminded me I have more to think about inasmuch as how real-world chemistry is different than book chemistry. Much as physicists do equations ignoring air resistance and the like, so too do chemists like me sometimes forget there are IRL things to consider. Also, it’s so nice to talk to a(nother) real chemist about these issues. Too often do I end up stabbing in the dark without guidance from wiser ones.

 

[Transform]

I usually just squirt the Napthe from the pipette into a large, tall shot container of distilled water. Stir, let separate, and pull again into the final container. Would this work well and would it work better if I put a little sodium carbonate into the water?

I'm fairly confident that a pinch or two of SC wouldn't do any harm and might even help.

 

[Transform]

I was reading over that post thread, and I see they used RO water, and you mentioned that too. I generally mean water distilled by steam distillation when I talk about distilled… but that’s easy to get where I live. RO water, to my knowledge, can contain more junk — such as dissolved CO2 — than steam distilled water. I should be careful in clarifying that in the future. There’s also deionized water (ACS or similar grade) that I often use, but that’s pricey, at least where I’m at. I tend to save that for more delicate and complex procedures and for pH probe calibration.

But I have to be practical and realize, while you and I are careful about the quality of the water we use — it’s a reagent after all! — not everyone here will be. I know from experience as a mod on DMT forums on Reddit that people absolutely use tap/suspect water despite my best efforts to convince people otherwise.

My concern is, without desiccation with some MgSO4 or the like, you’ll end up with at least some (slightly) basic compound in your final product simply from the aq phase getting suspended in the organic phase. As much as I’ve tried to convince people to desiccate the organic phase post wash as is standard, it simply doesn’t happen.

This conversation has reminded me I have more to think about inasmuch as how real-world chemistry is different than book chemistry. Much as physicists do equations ignoring air resistance and the like, so too do chemists like me sometimes forget there are IRL things to consider. Also, it’s so nice to talk to a(nother) real chemist about these issues. Too often do I end up stabbing in the dark without guidance from wiser ones.

Saturated brine is another way of pulling out a certain amount of trapped water from NPS.

 

[Norolinda]

Saturated brine is another way of pulling out a certain amount of trapped water from NPS.

I have also mentioned this to people; similarly, it falls on deaf ears. But I agree a few hundred milligrams of SC couldn’t be that bad.

 

[Sakkadelic]

This technique is standard lab procedure, and every chemist of every level should be in the habit of doing this.

I don't see why it shouldn't be part of every dmt extraction tek. It's simple and really not a lot that can go wrong (except spilling :b). I find that it makes the extraction easier and less stressfull.

I do similar to what Trasform and Brokedownpalace10 mentioned, a kitchen chemistry verison. I don't add SC bcz I assume that the tiny bit of base soup that comes along will be enough since I don't use a lot of water. I pull carefully but I don't stress if a bit of the base comes along. But yeah i don't see why not add SC so I will do it next time.

I also do that to work around emulsions. I just pull it along the NPS into water and pull again. Somehow when you try pulling the emulsion it dissipates. And once you have one it's likely to happen again at every pull/mixing. But no worries, just pull into water first!

Pro tip :b : have 2 glass pipettes 1 "dirty" and one "clean".
Or at least make sure to thoroughly wash it and dry it before the final pull.

 

[brokedownpalace10]

I also do that to work around emulsions. I just pull it along the NPS into water and pull again. Somehow when you try pulling the emulsion it dissipates. And once you have one it's likely to happen again at every pull/mixing. But no worries, just pull into water first!

Exactly what I do. Except I just work around the emulsion, letting it be there, until I get near the end of my pulls. Then, I get a bigger container of water and squirt that last pull emulsion and all into it and pull from there. I even shake the mixture early on, not sweating an emulsion. I can fix that later.

 

[CokFLHX]

All good points, and I love a nice sep funnel well-used as well

There was a discussion here very recently where @CokFLHX reported losing nearly 50% yield with a water wash, so either there product was heavily contaminated or RO water can get surprisingly acidic. That seems like a particularly extreme case, and I'd say there must be a few question marks hanging over that, what with the RO water being obtained from an energy facility. But all that aside, using freshly boiled water would go a long way towards keeping the pH a bit higher. I still wonder, now that atmospheric CO2 levels have definitively crossed the 400ppm boundary already for some years (compared to the 350ppm there was when I was a kid), how much this >12.5% increase will be affecting the pH of distilled water, when we compare it to the locally elevated CO2 levels from human respiration in indoor environments, plus the influence of various forms of combustion, particularly ICE vehicular traffic in urban areas.

A pinch or two of sodium carbonate seems like the easiest way of eliminating that concern!

In essence, it's as much about absorbing stray protons as forming bicarbonate. When CO2 dissolves in water, there's an equilibrium between water plus carbon dioxide and carbonic acid, and carbonic acid and bicarbonate plus a hydrated proton, and bicarbonate and carbonate plus another hydrated proton, alongside the autoionisation of water. Adding more CO2 increases the concentration of protons, apparently sometimes sufficiently to cause protonation of DMT and its subsequent solubilisation. But the consequence of adding alkali carbonate is indeed driving the formation of HCO3-.

You're probably familiar with the equations:
CO2 + H2O <=> H2CO3
H2CO3 + H2O <=> HCO3- + H3O+ }
} = free protons, pH decrease
HCO3- + H2O <=> CO32- + H3O+ }
Shuffling all this around a bit, we get:
CO2 + H2O + CO32- -> 2HCO3- and no stray protons (N.B. - starts to reverse above 70°C)
Moreover, SC is, of course, alkaline in solution due to mopping up protons and increasing the relative concentration of hydroxide:
CO32- + H2O <=> HCO3- + OH-
the latter of which also recombines with solvated protons, raising the pH:
H3O+ + OH- <=> 2H2O

The squirting of the naphtha through the SC solution isn't necessarily "better" than a good wash using a sep funnel, but it's pretty straightforward if one happens to have a pipette full of naphtha anyhow. Again, it's a matter of kitchen/jam jar chemistry vs. other lab techniques - "horses for courses". Either way is aimed at interfacing the polar and non-polar phases.

I wanted to jump on here and share my experience. I had a small amount I water washed, and had the same result. Lost over 50%. I had the water good and hot as well as the solvent. Not sure what im
Doing wrong.
I’ve successfully completed a water wash before using the same water I always use and it was fine.
I’ve also washed in water in the same step as the pull. Just instead of siphoning directly to the glass dish, I squirted it into a small jar of hot water, mixed, and siphoned into a second water cup once it separated, then into the dish and the yield was expected.

So I don’t think the water used has some property that is causing it. They guys in waste water have assured me that the water from the RO is 99% pure water. I’ve tested the pH and it tests neutral. I dunno.

I won’t be doing it again though. I would rather have yellow crystals than no crystals

 

[Advocate4TheMT]

I wanted to jump on here and share my experience. I had a small amount I water washed, and had the same result. Lost over 50%. I had the water good and hot as well as the solvent. Not sure what im
Doing wrong.
I’ve successfully completed a water wash before using the same water I always use and it was fine.
I’ve also washed in water in the same step as the pull. Just instead of siphoning directly to the glass dish, I squirted it into a small jar of hot water, mixed, and siphoned into a second water cup once it separated, then into the dish and the yield was expected.

So I don’t think the water used has some property that is causing it. They guys in waste water have assured me that the water from the RO is 99% pure water. I’ve tested the pH and it tests neutral. I dunno.

I won’t be doing it again though. I would rather have yellow crystals than no crystals

How are you my friend? Just chiming in. Obviously the cleaner the water the better. R/O is great. But what you really need if you're taking that step, is RO/DI water. Which requires one more filter on the Reverse osmosis kit for the final step to deionize the water after the R/O process bringing it to 0 PPM's.

 

[premeditated]

So how important is the water wash

 

[Ernestine]

It's optional.

 

[premeditated]

Dissolved CO₂ can cause losses when using distilled water for the wash. While this may be less of a problem if using hand-hot water, adding a little sodium carbonate to the wash water does a whole lot more to ameliorate the issue.


It would be wise to reserve the wash water in case of unanticipated losses in yield.

It's also possible to achieve a reasonable cleanup by first transferring the naphtha pulls into a (pyrex) jug with a few tens of mL of sodium carbonate solution in the bottom. Squirting the naphtha through the SC solution with a pipette helps too. Allow this to stand for a while so that it can settle out, then transfer the naphtha to the freeze precipitation dish.

This works well enough for those without a sep funnel (or too lazy to get one out of the cupboard).

How many mg of sodium carbonate

 

[Sakkadelic]

How many mg of sodium carbonate

The main purpose is to neutralize any acidity in the water, a pinch is enough if working with distilled water which is expected to be neutral but can be slightly acidic due to dissolved CO2 as Transform mentioned. Adding extra won't hurt, it's not really critical.