Harmala freebase crystalisation

[Sakkadelic]

I've been getting these really cool looking harmala freebase crystals almost consistently but I haven't figured out exactly how. What is happening is that during basification with lye solution using a pipette, at some point the harmalas precipitate not in the typical dense milky large clouds, instead it forms little translucent blobs that simultaneously appear and grow. Then after leaving it for some hours I come back to find these freebase needles.
It seems factors are at play like volume, pH and concentration of harmalas.

The processing and cleaning to get them is rather simple and standard. Starting with cold or hot brewed rue, filtered with a cotton cloth, then basified with lye, decant, acidify, filter with coffee filter, basify with lye.

 

[blig-blug]

Do any crystals form after your first basification? I'm getting thicker, shorter crystals on the first one. They're brown but shiny.

 

[Sakkadelic]

Do any crystals form after your first basification? I'm getting thicker, shorter crystals on the first one. They're brown but shiny.

I haven't got shiny stuff on first basification, sometimes it's like a dust and a bit shiny. Here's how it looked on a first basification when harmala concentration was high.



The stuff in OP was the best I got so far, it was from simmering for 1 hour the rue leftover from an extraction, and the solution remained cloudy after reacidification and filtering, so it wasn't particularly clean. After basification the solution became crystal clear and it does seem more colored and not crystalline stuff also precipitated below the needles.

 

[Sakkadelic]

Yesterday when doing the basification I ran out of lye solution, it was just enough to precipitate the harmalas, and now I checked the decanted solution by rubbing a drop between my fingers and it did not feel slippery at all so it's not highly basic

 

[Transform]

Yesterday when doing the basification I ran out of lye solution, it was just enough to precipitate the harmalas, and now I checked the decanted solution by rubbing a drop between my fingers and it did not feel slippery at all so it's not highly basic

This leaves me wondering whether a diffusion technique might help crystal growth too, which entails carefully pipetting a layer of base solution either under or over the harmala salt solution, depending on their relative densities.

Of course, you've had great results without fiddling around like this

 

[Sakkadelic]

This leaves me wondering whether a diffusion technique might help crystal growth too, which entails carefully pipetting a layer of base solution either under or over the harmala salt solution, depending on their relative densities.

Of course, you've had great results without fiddling around like this

That would probably work quite well. Or maybe putting it in another closed container with ammonia, would that work?

Any thoughts on how/why the blobs would transform into crystals? Next time i'll make sure to take pictures of the blobs

 

[Transform]

putting it in another closed container with ammonia, would that work?

I've tried this, it works rather nicely. Continuous controlled admission of smaller amounts of ammonia could be even better, and shouldn't be more complicated than rigging up a dropping funnel. [By this, I mean that the ammonia solution drips into a container separate from the harmala solution, but obviously within the aforementioned shared, contained vapour space.]

Subsequent crystal formation from amorphous blobs isn't a particularly unusual phenomenon. It's probably favored here because of the energy released during the formation of intermolecular bonding in the crystal lattice, which is presumably sufficient to overcome entropy loss at that temperature.

 

[Sakkadelic]

I was drying the crystals and scraped them too early, I wasn't happy with the wet mess and also the brown stuff so I decided to reprocess it.
I dissolved it with distilled vinegar and not everything dissolved, filtered through a piece of cotton stuffed in a funnel, then added lye solution drop by drop while gently stirring until the harmalas precipitated and the yellow color disappeared, added a couple more drops to be sure.
Like before the blobs formed and slowly settled at the bottom, I left it covered overnight and cameback to these nice xtals.

Before crystalisation


After crystalisation



The xtals are very fluffy and give an impression of a lot of harmalas, but then they look much less when they're broken during water washes, I would be surprised if these are above 250 mg.

I think the key to getting harmala freebase crystals like this is a dilute solution, dilute in harmalas, impurities and base. I don't know how it works the transformation from blobs to xtals but it feels like the harmala freebase has to break apart into single molecules or maybe redissolve before forming into needle xtlas, I feel like a concentrated solution would prevent this.

 

[Sakkadelic]

This time I waited long for it to dry and it did look dry but as I scraped it it was still wet. I believe there was a bit of lye contamination keeping it hygroscopic because I only water washed it once since I was trying to keep the xtals looking nice. Here's how the corner of the dish looked like anw. Perhaps collecting it with a coffee filter would be better.


So I gave it another A/B cycle without filtering. This time I wanted to try and not get xtals so I kept the acid volume minimal so as to keep the concentration high. once I added enough lye, the whole solution turned milky and fine powdery harmalas strated settling as apposed to the previously observed numerous but seperate blob formations. I topped it with water and after a few hours it didn't seem like any xtals were forming. I water washed it 3 times and dried it in a dish and got 150 mg.
Here's how the dish looked like (yes that's only 150 mg)


And here's a picture showing the freebase from 2 A/B cycles vs freebase from 4 A/B cycles (including 2 crystalistions).


This is one of the cleanest looking freebase I ever got without manske.

One thing to note is that when freebase harmala is crystalised brown stuff seem to seperate and coagulate and settle below the xtlas, and upon acidification they don't dissolve. But when precipitated in the typical way (and as I mentioned I did not filter the reacidified xtals + small amount of brown stuff), the brown stuff is mixed and maybe integrated in the freebase, while some of it does not dissolve upon acidification and can be removed with filtration, some does seem to pass through giving the freebase a tan color. So if one is able to seperate the freebase xtals from the brown stuff below (separatory funnel?) this I believe would be a great way to clean harmalas.

About the brown impurities, it seems like when they are acidified in solution they can become very finely dispersed making the solution look cloudy and filtering with a coffee filter or cotton does not fully remove them. However, when dried and acidified from powder they stay in bigger particles making them easier to filter.

 

[awalmartbag]

I got some shorter crystals today while basifying. Probably still too much other crap in this solution. Maybe I will do another A/B cycle and see if I can get them more needle-like and pure white like yours

 

[Sakkadelic]

I got some shorter crystals today while basifying. Probably still too much other crap in this solution. Maybe I will do another A/B cycle and see if I can get them more needle-like and pure white like yours

View attachment 109265

What was your basification process to get these xtals? It would be nice to pinpoint the factors leading to xtals rather than fine particles.

More important than A/B cycles is water washes, use slightly basic water and wash a few times until the liquid is nearly colorless. You can collect all the water and let settle to recover any lost harmalas. Keep things covered to minimize CO2 from the air dissolving into solution.

 

[awalmartbag]

I poured strong NaOH solution (5g in 50mL d-H2O) into clear acidic harmala solution (5g citric acid in 500mL d-H2O), which was the result of 2 A/B cycles and had been rinsed with ~500mL weakly basic solution prior to acidification. The amount of seeds originally used was ~400g, but these were 3 different batches/experiments, some with bad yields. Maybe equivalent to 200g when everything is done properly.

The crystals formed pretty much instantly as the solution was basified (I guess that's why they are smaller). I'm now waiting for it to cool in the fridge - maybe they'll grow a bit more.

Then I'm going to try washing these like you suggested and re-x.

 

[awalmartbag]

Nothing much happened as it cooled, the crystals just settled. I filtered and washed them with 2L basic water, but it did not do much to help the color.

 

[Sakkadelic]

I poured strong NaOH solution (5g in 50mL d-H2O) into clear acidic harmala solution (5g citric acid in 500mL d-H2O), which was the result of 2 A/B cycles and had been rinsed with ~500mL weakly basic solution prior to acidification. The amount of seeds originally used was ~400g, but these were 3 different batches/experiments, some with bad yields. Maybe equivalent to 200g when everything is done properly.

The crystals formed pretty much instantly as the solution was basified (I guess that's why they are smaller). I'm now waiting for it to cool in the fridge - maybe they'll grow a bit more.

Then I'm going to try washing these like you suggested and re-x.

That is curious as my trials made me suspect that low concentrations and slow basification led to xtals. Also for your case the xtals formed instantly while mine took hours to transform from blobs into xtals.

Nothing much happened as it cooled, the crystals just settled. I filtered and washed them with 2L basic water, but it did not do much to help the color.

Did you filter the whole liquid or just the portion with xtals? I wonder if impurities get trapped by the filter and get recovered with the freebase. Bcz I expect the color to get diluted if nothing is redissolving back into solution.

 

[awalmartbag]

I just tried to replicate the quick crystallization and ended up getting blobs, much like your pic above.

I filtered everything. I think you're probably right about the impurities, so for this cycle, I decanted instead of filtering (the blobs settled quite quickly) and my liquid has lost a fair amount of color.

So now I'm going to top it up to 1L and try to do another re-x.

I had this idea of slow basification too, and a few days ago tried dripping ~0.5M NaOH sln at <1mL/min into the acidic harmala brew over several hours. It did not work BUT I may have attempted this too soon - it was at a stage where the solution was still a deep red color, with many impurities. It's possible that it would work better now...

 

[Transform]

I had this idea of slow basification too

I've tried this with an ammonia diffusion method. Alas, it did not result in huge crystals.