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Vapor diffusion = huge xtals?

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Fuego

Riggly Maynard Charlston Bentsworth |||
Growing Crystals the concept can be found here. essencially we need a high boiling point solvent that dmt is highly soluble in, and a low boiling point solvent that can mix well with the other solvent, but that dmt is not soluble in almost at all.

im wondering if this process will work at freezing temperatures? if this is so then we could get a saturated xylene mixture and cold naptha as the precipitant for an extremely slow freeze precip. does anyone know at which point the mixture of these two will cause the dmt to fall out?
 
I would say it is possible, but engineering the appropriate solvents sounds pain-staking. I wouldn't do this at cold temperatures unless you had a couple life-times or your low-boiling solvent is extremely volatile. Essentially this is a slow way to 'crash-out'. Slow in the case of gorgeous crystals is a good thing though. That's my ape level understanding of it at least(a physical chemist would scoff).

I would first try it at room temperature, after some time(a few weeks maybe) I would then try applying cold temperatures to induce crashing if it failed. This is because the low boiling solvent needs to be volatile for this 'migration' to occur.

The problem here is this in my opinion: picking the right solvents and not needing a chemical supply house to do so. A low boiling solvent dmt is poorly insoluble in is hard to find. Acetone, methanol, ethanol, DCM, Ether, Ethyl acetate, even light fraction petroleum ether, all solvate dmt pretty happily atleast at temperatures where they are volatile. While the higher boiling solvents such as toluene, xylene, d-limonene or what have you will still solvate dmt probably adequately so thats the easy part. If I think of something for the low boiling solvent I'll post back but it's not likely to happen, at least not easily.

A freeze precipitation works under different principles. Principles of solubility and a few other branches of the thermodynamics tree. As for crashing dmt out of xylene with naptha this is unlikely to occur unless as you said really cold temperatures are used. As I said above it would be painfully slow if it is even possible. At least that's how I envision it, experimentation is the only way to know for sure.
 
Bump. Just started researching this hours ago.

My understanding is:

As long as the solvent (xylene proposed) is saturated, it shouldn't matter if the more volatile solvent (naphtha) also dissolves DMT, as long as it dissolves less. The goal is to shift the saturation point of the composite solvent by decreasing overall solubility.

Ideally the shift in saturation point would happen more slowly than it does during slow evaporation or slow cooling, to get larger crystals.

Even if it works, I wonder if it would have any advantages over just controlling the evaporation rate. Maybe cleaner crystals since evaporation concentrates impurities.
 
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Even a small percentage of xylene completely inhibits DMT freeze precipitation. A similar situation arises with ethanol and water. The best short term result in the latter case was an oil that separated out at the lowest freezer setting, redissolving with even a slight increase in temperature. Solid material was only recovered after… slow evaporation of the solvent.

The process may work with a carefully selected pairing of solvents, although I can't off the top of my head think of a sufficiently volatile solvent in which DMT is insoluble.


There's another kind of diffusion process to play with too, which I've used to precipitate harmala freebase from a solution of the salts. Place a beaker of the (aqueous) solution of harmala salts and a beaker of ammonia solution side by side in a larger container and seal it tightly. The ammonia diffuses into the harmala solution, precipitating the freebase. Maybe this would work with a DMT salt too.
 
Put simply, DMT is so soluble in xylene that single figure percentages of xylene in naphtha will be sufficient to keep the DMT dissolved. Looking at it with a bit more detail, the Van der Waals forces between xylene molecules and DMT molecules that make xylene such a good solvent here may even act to solubilise DMT in the naphtha, since xylene is freely miscible with naphtha. I would speculate that this means a given amount of xylene will potentially have, in effect, an increased solvating power when diluted in naphtha, in a way acting as a 'bridge' between the DMT and the naphtha alkanes. I.e. there may be a nonlinearity at the lower end of the graph.

Good call on the idea of trying butanol and hexane, although I'd suggest pentane might be better, not only on account of hexane's neurotoxicity. You'd have to take into account miscibility of those solvents as well as the aforementioned possible 'solvation' effect.
 
Gemmy crystals is my main motivation. I think it was @CaptainFuture that posted transparent diamonds so long ago and seem so elusive. I really like challenges tho so this has become an addiction of sorts. Sometimes I doubt those diamonds were even DMT; but the concept of purity still attracts me. And I like to know why things are the way they are -- it wouldn't be as satisfying if diamonds just happened accidentally.

I had a really bad chem teacher in school. I'm learning so much more now, from youtube mostly. But I'm taking shortcuts while searching for such specific solutions. I'm banging out 9h of organic chem reading / videos daily and my head literally feels like it's going to pop trying to connect all the dots. I need to take a few days off to catch up on sleep, but I wanted to decompress some more conjectures from where I'm at currently.


@Transform What was the hypothesis in the ethanol/water crystallization? Are there other freebase molecules that can be freeze precipitated in water-alcohol? Could the thing in common with ethanol and xylene precipitating goo's, be water? I read those both form azeotropes with water, not sure if that is even relevant, but something in common. I've been developing a superstition toward H2O over the past couple weeks.

I'm starting to get a loose understanding of what a surfactant is; basically, any molecule with a polar head and nonpolar body. Ethanol qualifies. Even though it's miscible; in general, surfactant molecules seem to flip their orientation, relative to the solvent, depending on whether the solvent is polar or non-polar. So in a solution of mostly polar molecules, I think surfactants like ethanol find the surfaces of a solution to be a favorable place, out of consideration for their non-polar bodies that want to be furthest out of a polar solution they can be. I picture this as a film of surfactant molecules at the boundary between the water-air and water-glass. And I guess any excess are "dissolved" as micelles.

Since DMT is insoluble in water, but soluble in ethanol, when mixed together in solution I picture a pressure pushing dissolved DMT molecules toward the surfaces of the polar solution. There they can hang out, outside the shell of oriented non-polar bodies of ethanol molecules that are providing a locally non-polar micro-environment. I'm guessing this has to be a factor in crystallization. On one hand, I might assume that coagulating DMT molecules at the boundary with glass seems like a great start for building crystals. But maybe the molecular pressure effectively creates a supersaturation at the surface, inhibiting nucleation. Or maybe it's like super-nucleation; only instead of crystals growing everywhere, you get individual molecules depositing amorphously. For whatever reason, they can't solidify, then pool into an oil. Maybe since ethanol is partially polar, when there's a lot of water crowding it, DMT prefers to stay dissolved in itself - even though it's below melting point? I wonder if a seed were introduced to the oil if it would grow?

Anyway I'm more hopeful for surfactants in a non-polar solution. n-butanol is technically also a surfactant, so once hexane diffuses into it there should be a layer of n-butanol at the surfaces of the solution with their polar heads sticking out. I'm not sure what to expect from it. I'm a little worried that it might hinder the vapor diffusion process, if gaseous hexane is repelled from the polar air-surface of a butanol-hexane solution. Maybe it would also slow down the evaporation of dissolved hexane from butanol-hexane solution, leading to a lower vapor pressure than you'd expect from just averaging the two. Not sure how it might affect DMT in solution. Might make it more difficult to nucleate by repelling DMT from surfaces. But then I picture a protective blanket over the growing crystal. Maybe it would limit interactions between dissolved DMT molecules and the crystal surface -- leading to a more gentle, controlled growth. Or influence the crystal shape somehow... perhaps it would encourage needles that reach into the solution.

Circling back to water, which may be a contaminant in non-polar solvent, I'm interested in drying methods. On my way to that I was researching CO2 as an inert gas to replace wet air. I know CO2 can dissolve in water and form carbonic acid, which might be a problem for aqueous solutions. But, I read something interesting about carbonic acid. Seems it's very weak, and in the presence of water, other water molecules pull H2O off CO2 in a continuous back and forth. To me, this suggests that if a water molecule can be isolated, it will stay locked to CO2. So I wonder if percolating CO2 through a non-polar solvent would eventually dry it out completely? I picture it grabbing H2O and escorting it to the surface, although I don't really know what would happen to carbonic acid in non-polar solvent. It would be magic if H2O just evaporated away once getting ejected to the surface. Or maybe another molecule could be made available to bind with any carbonic acid that forms.

I also wonder how CO2 + surfactants might work together to manipulate water. When I search CO2 drying on google it's all about supercritical CO2. Which would be nice, but hopefully not necessary.
 
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What was the hypothesis in the ethanol/water crystallization?
Aqueous ethanol can be used to recrystallise a wide variety of organic substances. Thinking about this again, this usually involves boiling the solvent and the solute then recrystallises on cooling. In that sense, I may have been barking down the wrong temperature gradient.

Future experiments should involve establishing a floor for the concentration of aqueous ethanol where DMT becomes reliably insoluble, wherein (if the lab gods smile upon us) heating and cooling should be sufficient to bring about a recrystallisation. So, thanks for the inspiring discussion!

Recrysallisation tends to perform poorly where the material is excessively soluble in the chosen solvent s the high concentration leads to chaotic precipitation of oily goo once it occurs. [Tryptamines are also prone to this on account of the flexible sidechain.] Naphtha, being a relatively poor solvent for DMT, demonstrates to an extent how crystallisation performs better from poorer solvents.

My working hypothesis regarding DMT and ethanol is that they form a eutectic mixture. Azeotropes are not directly relevant to this. And I think your conceptions about surfactant action are largely a red herring, while classifying ethanol as a surfactant is something of a stretch.

Solid drying agents tend to be rather more convenient than handling compress gas- which itself would have to be dry to be of much use. Carbon dioxide has been of use when separating primary and secondary amines, particularly NMT in the latter case, from tertiary amines like DMT through the formation of what can be called 'auto- (or ipso-)carbamates'.

Gas purging, using nitrogen, argon or helium, is more typically used for removing dissolved oxygen from solvents prior to their use with oxygen-sensitive reagents. It does set me thinking whether CO₂ would force DMT carbonate out of a sufficiently moist NPS, either in the form of crystals or as aqueous droplets. It would need to be a solvent with a higher water capacity than naphtha, and this separation was not observed in the NMT carbonation experiments. Mescaline, however, does form a sufficiently stable carbonate (or maybe a carbamate - I'm not certain the carbonate has been completely positively confirmed) by absorption of CO₂ directly from the atmosphere. If it's the carbonate that forms, this would entail the concurrent absorption of moisture/water vapour - something of a moot point if the mescaline freebase itself wasn't completely dry (and it has an appreciable solubility in water).
 
I watched a few animations of surfactants that were pretty convincing of their behavior. I'm still stuck on the image of ethanol as a surfactant.
Future experiments should involve establishing a floor for the concentration of aqueous ethanol where DMT becomes reliably insoluble
What if water makes dmt more soluble in ethanol? Dmt dissolved in ethanol alone would have a certain solubility. Then, I imagine as water is added, it could be said the water is dissolved in ethanol. But, ethanol would treat water differently than it treats dmt, facing it's polar head toward water. For a time, more water molecules in ethanol solution might not affect dmt solubility at all, since the ethanol is effectively insulating the dmt molecules from the water. In my image, the ethanol might even be considered more non-polar than it was without water distracting its polar end. Maybe that would increase dmt solubility.

As more water is added, once ethanol is the minority in aqueous solution, I picture it starting to coagulate at surfaces and forming micelles in water to protect its nonpolar body. Even with a majority of water, dmt would still have the same amount of non-polar ethanol bodies to be dissolved in, since they're within the ethanol micelles and surface film. Idk if any amount of water would lower the solubility. Your idea about eutectic mixture sounds plausible, too.

Edit:

Found a few sources explaining C1-4 alcohols aren't hydrophobic enough to form micelles, but they still form a monolayer at the solution surface. I still think aqueous ethanol solution will push DMT out to the surfaces as ethanol gets diluted. But since individual ethanol molecules could still move freely through water without having to form micelles, maybe you're right about dilution lowering the solubility of DMT eventually. Coagulating chains at the boundary and possibly getting ethanol tied up in the lattice sounds like a recipe for polymerization.
The paper mostly went over my head tho, you might get more out of it.

Oh, I also wonder if DMT dissolved in ethanol changes its behavior. The reason it can't form micelles is because the hydrocarbon chain isn't long enough. But if its hydrocarbon tail is 'connected' to a DMT molecule, might it be considered a longer non-polar molecule? Together, they might still assemble as micelles in aqueous solution?
 
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