Pre-loading NPS water content with NaCl?

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Just throwing an idea out there, wondering if it makes sense.

If it's difficult to control how dry NPS is, I wonder if you could at least control what gets dissolved into the water that's in the NPS.

Boil NPS with salt water, stirring constantly. Separate NPS, let it cool.

The goal is for the water dissolved in the solvent to be salt water.

Then when the solvent is used to re-dissolve crude spice, perhaps it would dissolve less water-soluble impurities, since the fresh NPS is already pre-loaded with occupied water molecules.

Na+Cl seems like it could do the job; obviously don't want the salt to react with DMT.

Then the salt can be rinsed out with distilled water washes on the NPS after DMT is picked up, before proceeding with recrystallization or mini-a/b.

Thoughts?

 

[Transform]

Concentrated brine will largely dry out naphtha anyhow, and much of your naphtha will evaporate if it's sitting atop boiling brine as well - depending on its boiling range, of course.

Salt won't react with DMT, you don't have to worry about that.

 

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Would it be mostly pointless then?

I just imagine anhydrous solvent being not as good for re-x if the solvent is left thirsty for atmospheric moisture or picks up water from the spice.

If the solvent is pre-saturated with water that has its hands full with nacl, wouldn't that be better than anhydrous? The goal would be for the solvent to turn away free h2o molecules in humidity and polar impurities in the crude.

 

[Transform]

A brine wash can help to remove suspended aqueous droplets, like from the base soup.

 

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Should I be worried about CO2 dissolved in non-polar solvents? In water, I've read that it's more soluble in distilled water and cold water. But 2x as soluble in heptane. Also mentionable is 3x in ethanol, 10x in acetone.

In water, the effects of acidity caused by CO2 forming carbonic acid and dissociating into H+ and carbonate ions can be neutralized with base right? Though I'm a little fuzzy on how a carbonate salt like sodium carbonate reacts with it.

But in non polar solvents like heptane where the water content is low, there's still tons of CO2 molecules, which can't be neutralized because they're not forming carbonic acid right? In a sense, they're already neutral in absence of water. But as soon as H2O mixes in, particularly pure water vapor from the air, could we assume it's forming carbonic acid?

Consider the scenario when someone is evaporating their solvent for crystals, perhaps under a fan, wouldn't it be constantly picking up H2O from the air and forming carbonate ions and H+ ions? Could those react with DMT and would that reaction pull the DMT carbonate into the invisibly small % of water? As the NPS evaporates faster, how does that affect the saturated CO2 and saturated water+carbonic acid molecules, with their potentially saturated dmt carbonate? The reaction reagents would become more concentrated. Would the dissolved acid eventually become concentrated enough to crash out as a separate layer, ensuring the last drops are basically carbonate goo?

In absence of complete anhydrous solvent and controlled gas environment, should we be doing something about the CO2? I wonder if it could be washed out entirely, or if a % solution of aqueous OH- ions could buffer potential reactions?

Is there any other way CO2 could directly react with dissolved amines? Or indirectly in the full context of oxygen, light, hydrocarbons etc. also being in solution.

And one more question - would the amount of gas, like CO2, dissolved in NPS affect the solubility of DMT? I'd think less gas = more room for DMT molecules but maybe there's some kind of synergy? Oh, and would it not also affect water's solubility in NPS? Perhaps in totally de-gassed NPS, water would be totally insoluble since there's no CO2 to react with?

 

[Transform]

Should I be worried about CO2 dissolved in non-polar solvents? In water, I've read that it's more soluble in distilled water and cold water. But 2x as soluble in heptane. Also mentionable is 3x in ethanol, 10x in acetone.

In water, the effects of acidity caused by CO2 forming carbonic acid and dissociating into H+ and carbonate ions can be neutralized with base right? Though I'm a little fuzzy on how a carbonate salt like sodium carbonate reacts with it.

But in non polar solvents like heptane where the water content is low, there's still tons of CO2 molecules, which can't be neutralized because they're not forming carbonic acid right? In a sense, they're already neutral in absence of water. But as soon as H2O mixes in, particularly pure water vapor from the air, could we assume it's forming carbonic acid?

Consider the scenario when someone is evaporating their solvent for crystals, perhaps under a fan, wouldn't it be constantly picking up H2O from the air and forming carbonate ions and H+ ions? Could those react with DMT and would that reaction pull the DMT carbonate into the invisibly small % of water? As the NPS evaporates faster, how does that affect the dissolved CO2 and dissolved water molecules, with their potentially dissolved dmt carbonate? The reaction reagents would become more concentrated. Would the dissolved water (carbonic acid) eventually become concentrated enough to crash out as a separate layer, ensuring the last drops are basically carbonate goo?

In absence of complete anhydrous solvent and controlled gas environment, should we be doing something about the CO2? I wonder if it could be washed out entirely, or if a % solution of aqueous OH- ions could buffer potential reactions?

Is there any other way CO2 could directly react with dissolved amines? Or indirectly in the full context of oxygen, light, hydrocarbons etc. also being in solution.

And one more question - would the amount of gas, like CO2, dissolved in NPS affect the solubility of DMT? I'd think less gas = more room for DMT molecules but maybe there's some kind of synergy?

This could be part of the problem with crystals liquefying in the when fresh from the freezer under humid conditions. Having your fresh viewpoint on this matter is remarkably helpful

I wonder if this is being compounded by the increasing CO₂ concentration in the atmosphere as well.

The relatively higher solubility of CO₂ in nonaqueous solvents isn't entirely relevant since we're dealing with an equilibrium involving partial pressures, although it becomes more relevant if the local atmospheric CO₂ concentration is particularly elevated for any reason.

CO₂ has been used in various methods for separating tertiary amines from primary and secondary ones, reacting with the latter two to form what I call their auto-carbamates, while leaving virtually all of the tertiary amine untouched. This is as their free bases, in a broadly anhydrous NPS. There were a few experiments here using this overall phenomenon to separate NMT from DMT and it was apparently successful - DMT was freed from NMT and there was no large loss of DMT noted. This appears to indicate that DMT in NPS is fairly tolerant of far higher concentrations of CO₂ than usual background levels, at least in the absence of condensing water vapour.

 

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The relatively higher solubility of CO₂ in nonaqueous solvents isn't entirely relevant since we're dealing with an equilibrium involving partial pressures

Can you explain this more please? I guess I was assuming the dissolved CO2 would be higher than atmosphere, but how should I consider the pressure and equilibrium?

I haven't checked recently but my space is frequently over 800 ppm for multiple reasons. I'm a CO2 exporter

Do you know of anything that could bind with a solution's CO2 content like you can do with MgSO4 for water content? I think I came across something recently while researching but apparently I lost track of that lead.

 

[Hailstorm]

NPS usually comes in contact with alkaline water. I would not worry about carbonic acid protonating DMT in that environment.

 

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NPS usually comes in contact with alkaline water. I would not worry about carbonic acid protonating DMT in that environment.

Hi Hailstorm - Nice to see you around! Your contributions have been a huge asset in my research

I'm only worried about trace quantities of water that might be contaminating the solvent. But you're right, if the last thing the NPS came in contact with was alkaline water, then whether there's an invisible emulsion or not, it shouldn't be enabling carbonic acid to form.

What about humidity though? (After separating the NPS from the alkaline solution) At the surface of the non-polar solvent, I imagine it's pretty effective at blocking polar molecules from entering. But if it sloshes around or gets H2O vapor stirred into it, and there's CO2 dissolved in the solvent already or introduced from the air, could that be creating carbonic acid and carbonates on a very small scale? Not enough to affect yields, but enough to affect its crystallinity maybe? If the insoluble carbonate molecule just plants itself on a crystal face. Or if enough coagulate, could that be a reason for goo / waxiness?

 

[Hailstorm]

Even in water most CO2 does not dissociate and stays as molecular CO2. In a non-polar solvent, nearly no CO2 dissociation takes place.

If the NPS is not dry, there are microscopic droplets of water where protonation could take place (unless the water is basic). However, a) CO2 won't dissolve in water as readily as it will in the NPS; b) DMT is poorly soluble in water so it will not partition into those droplets either; and c) CO2 will not dissociate in those water droplets much.

Small amounts of water in the NPS plus atmospheric CO2 should result in negligible DMT protonation. (NPS should still be dried for a whole host of other reasons.)

 

[Transform]

Can you explain this more please? I guess I was assuming the dissolved CO2 would be higher than atmosphere, but how should I consider the pressure and equilibrium?

The partial pressures thing is just referring to the relationship between the atmospheric CO₂ level and the proportion thereof that will dissolve into a given solvent. While acetone might be capable of dissolving CO₂ in relatively larger amounts, that doesn't mean it's particularly useful in selectively concentrating CO₂ from the atmosphere, for example.

I haven't checked recently but my space is frequently over 800 ppm for multiple reasons. I'm a CO2 exporter

Even this 800ppm is unlikely to have that significant an impact on your experiments. Calculating the likely concentration of CO₂ in your solvents relative to its atmospheric concentration can be a fun homework exercise which I'll leave up to you, since I'm a massive shirker in that particular department.

Do you know of anything that could bind with a solution's CO2 content like you can do with MgSO4 for water content? I think I came across something recently while researching but apparently I lost track of that lead.

@Hailstorm rightly points out that contact with alkaline solutions will take care of this to all practical intents and purposes, as well as clearing up the most salient points of your concerns (thanks, HS!)

Barium hydroxide springs to mind as a highly effective means of removing limited amounts of CO₂ from a system, but I think that's unnecessary unless you have a very good reason for doing so.

Are you really planning to work in controlled atmospheres or with sealed apparatus? It would, of course, make for an useful research project - I'm rather interested in how DMT might behave under high atmospheric concentrations of CO₂ as much as whether minimising its level has any noticeable effects on DMT's behaviour.

Extant research into the use of amines for carbon capture and storage can provide some level of insight into the questions here, only it tends to focus on liquid amines, making DMT a special case relative to that.

 

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Are you really planning to work in controlled atmospheres or with sealed apparatus? It would, of course, make for an useful research project - I'm rather interested in how DMT might behave under high atmospheric concentrations of CO₂ as much as whether minimising its level has any noticeable effects on DMT's behaviour.

Hailstorm has alleviated my concerns I think, but I could still arrange an experiment like that. I have two CO2 tanks and two meters, one for low PPM and one going all the way to 100%. I got the sensors for a cannabis quarantine experiment where I kept clones in a 100% CO2 chamber to kill any mites. The clones all experienced a kind of wilting I'd never seen before. At the time I wasn't privy to CO2 creating carbonic acid in the water that the cuttings sat in. That experience is probably what spooked me on dissolved CO2. What makes you curious about it?

 

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Hailstorm has alleviated my concerns I think, but I could still arrange an experiment like that. I have two CO2 tanks and two meters, one for low PPM and one going all the way to 100%. I got the sensors for a cannabis quarantine experiment where I kept clones in a 100% CO2 chamber to kill any mites. The clones all experienced a kind of wilting I'd never seen before. At the time I wasn't privy to CO2 creating carbonic acid in the water that the cuttings sat in.

Yes, I'm glad HS has cleared that up nicely. It's always worth remembering the magnitudes of difference between 800ppm and 100%, too.

That experience is probably what spooked me on dissolved CO2. What makes you curious about it?

I'm principally concerned with understanding the behaviour of DMT in relationship with dissolved CO₂ and associated species with a view to harnessing this for low hazard/food safe extraction and purification methods, as well as in order to gain insight into the "crystals dissolving into goo" phenomenon sometimes reported under circumstances of high relative humidity.

 

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I remembered a video I wanted some opinion on.
View attachment Swirling.mp4
This was hours after dropping dry ice in hexane-dmt freebase solution. The convection was more visible than usual. I wondered if this is the dissolved CO2 that I'm seeing or if lots of dissolved gas makes the normal convection more visible?

Aside from CO2 byproducts, which I'm no longer concerned about, how might molecular CO2 muck up a crystal? I'm picturing a bunch of straight-chain alkane molecules sliding past each other and vibrating around, and DMT molecules getting shuffled in that simple solvent. But say for example the solvent is saturated with CO2 molecules. Would that change properties, like DMT's solubility? Could you precipitate DMT out by pushing CO2 in? Or just get a bigger pull from degassing a solvent first? And maybe the DMT molecules would have an easier time shuffling into their crystal positions with different levels of dissolved gases? Or maybe the small molecules bouncing around would be the equivalent of a messy workspace, preventing the lattice from growing properly? Perhaps even change its habit or polymorph?

And I think a lot about the moments between freebasing a salt solution and adding non polar solvent... When the freebase molecules pool into an oil layer above the water. Is DMT essentially a non-polar solvent during this time? Dissolving other non-polar molecules, like CO2? Idk what harm that could do, but it's fascinating to imagine. Or molecular oxygen, also non-polar. Nothing to worry about?

Or this video, of DMT crystallizing out of a melt between two slides and secreting a gas (I think?). It seems to come out of the melt, as if it was dissolved, but rejected by the crystals. The bubbles of gas get trapped between crystals, and really strange things happen at the interface and within these gas pockets.