Preparing syrian rue extract, does your base matters?

[Jees]

There's something special about using ammonia and basing harmalas. One can see it in situ under microscope, and results on large batches confirm a different kind of crystallization process going on. Observed differences:

Ammonia:
1) makes a transparent initial milk, never becomes really white-ish
2) settling happens fully in 30 mins
3) filtrate looks a tad darker

Lye:
1) makes a very white-ish milk color that remains very long like that
2) settling takes a lot of hours
3) filtrate looks a tad lighter


Ammonia vs NaOH: seems to affect crystal growth, especially crystal growth speed, and likely final crystal size. When you initially base the acidic tea then extreme small crystals like dust forms, that is the 'milk'. If you filter rapidly then a lot of that milk will eventually go trough the coffee filter, this does not happen when you let it stand overnight. So there is a process that the milk undergoes, the dust becomes bigger crystals and the white color fades. After overnight settling you can filter trough a coffee filter, nothing will fall trough. It is exactly this process that is incredibly speed up with ammonia. A drop in situ under microscope takes like 5 minutes for the 'dust milk' to become recognizable visible crystals with ammonia. Using lye the milk/dust simply refuses to do that so fast and you might suffer from drop evaporation.

Back to those pots in the picture: basing with ammonia the milk is semi transparent because the immediate crystals forming process eats the fine 'dust' rapidly into crystals that are less a white effect in the pot. With lye this goes very much slower making the milk appear ultra white in comparison and staying longer like that.
The immediate build bigger crystals under ammonia sink a ton faster that the fine 'dust'.

About filtrate color, this is a bit unclear at the moment. The lighter tan in the lye pot filtrate suggest more material has crystallized? Though both pots where topped at same 12.5 pH. I hardly imagine that the ammonia pot missed out on precipitating harmalas at that pH level, and I wager to think less plant dirt was able to attach itself to the crystals in the case of ammonia. If that is so this would be an extra advantage for ammonia.

Rest to note that in the VDS thread it was already mentioned that I could not perceive pH depression effects from lye, unlike ammonia and calcium carbonate. The weak base effect seem to be responsible. So when I based that pot with ammonia I carefully tried to observe any indication for a pH depression, but no. To no surprise because the needed concentration for pH depressions to occur are not met. So in this stage it was not possible to separate harmine using VDS's pH depression method.

To meet same end pH, the ammonia pot got topped up with NaOH til 12.5 and this was done immediately after ammonia got it til 9.5

 

[Sabnock1990]

I use Sodium Carbonate (washing soda).

 

[Jees]

I use Sodium Carbonate (washing soda).

That also enables pH depression precipitation in the right conditions, a weak base, which sets in in same the category as ammonia when it comes to crystal growth mechanism :thumb_up:

Don't be afraid to top off with some lye to get high enough to retrieve the last traces of harmaline. I have (only) indications that the more dilute the alkaloids get (in their salted state) the higher they need a pH to finally precipitate. This means the last amounts fall out under a higher pH than the first for a given alkaloid.
The route of certain fixed pH for certain alkaloids to precipitate has been debunked, it's a system with a lot of variables playing role, a 'living' system one could say. Even salt content has seen to play a huge role when working with pH depression system if one is into that practice.

 

[Jees]

Both based pots went trough a separate coffee filter, and now their filtrates look identically, so no differences how the different bases take out on plant 'dirt'. In OP it looked like there was a slight difference, but not here.
The drip trough speed was also strict identical, about 1 hour.

In attachment a little movie how I clean those coffee filters from their caught freebase alks, I don't like to scrape that mud it's a big mess. Just rip the filter open and place in a pot (or on a plastic cutting board surface) and flush the freebase off, fast clean and easy.
:thumb_up:

PS:
1) I posted such a movie before somewhere but this is a better footage;
2) I'm still fiddling with movie formats to make good quality and still small size for forum use. Too bad nexus wont upload mp4 so I made an mp4 and renamed it as a mpg for the upload. Normally this should be no problem but if someone encounters problems playing it please come back with feedback, pm is OK, thank you.
(a real mpg is 1MB larger than mp4 for this small movie, and at a much lesser quality with equal settings)

 

[Jees]

Opening that coffee filter and plastering it on the inner side of a pot can be somewhat fiddling, especially if there are a loot of alks caught. An even easier variation is to rip the coffee filter open on a horizontal flat dining plate, then tilt the plate over the pot and flush it clean. One can try to support the plate as in pic, but it can be done with plate in one hand and other hand squeezing the water flushing bottle. :thumb_up:

Personally I find the 'lower knowledge' of huge importance when really executing the principle 'higher knowledge'. Thing become fun instead of draggy when it's fast, clean and easy to perform.

 

[Ulim]

Yeah you can expect them to behave differently.
Afterall Lye solutions are very dense and Ammonia solutions less dense.
So if he harmalas will sink in both it will ofc sink faster in the one with higher difference in density.

I bet after putting enough lye (maybe mix in KOH too) in the harmalas will float to the top instead of falling down. :roll:

 

[Jees]

^^ Super remark I missed out on so far but it is actually very obvious now that you mention it. I know there is crystal growth difference but maybe that is not the main effect after all. Thanks for the headsup :thumb_up:

 

[Ulim]

You could try really buffing up the weight of the solution by adding heavy foodsave salts.

Like for example potassium citrate. Or rochelle salt. Then look at the crystal growth

 

[Jees]

When doing the VDS approach, I certainly noted the enormous impact of salt on the pH where crystals formed, like harmine I could get it precipitating at pH 6 (instead of 7 - 7.5 as usual) just by lowering the salt content. I like your adds Ulim
[The salt comes from basing an acid]

-

Another practical tweak for evaporating something really fast:
a few$ radial fan on a few$ mains adapter.
This is a manske filtrate on a stove. If one bases that one gets slime for the remaining harmalas, not so practical. I was wondering to evap it to half volume, so doubling salt (it was 20gr/100ml at the beginning, so it will go slightly beyond full saturation) and doubling remaining potential harmala-concentrate, then cooling it again to see if there are going to be any needles forming. I don't expect much of it, just an experiment.

 

[Jees]

Ulim I have now more info about the base density difference being yes/no responsible for the drastic differences in settling time. It was a good call intuitively as lye-water becomes noticeably more viscous with rising concentration, while ammonia does not so. Yet with more study done this route should be left.

.

1) About how much of lye concentration are we talking about, is it any relevant?

Basing syrian rue tea is nothing like basing bark soup for making pulls.
For working on extracts of 260gr SR seeds in a 1.15 liter liquid, which was first made pH 2.75 with phosphoric acid, then basing this with 50ml of 8mol/liter NaOh, made it pH 12.5.
So we used a frail 16 gr worth of corresponding dry lye in this {1.15 liter + crystals} to get to pH 12.5

* Any visual clue of viscosity rise fails, e.g. dripping it of a spoon.
* At exact same 23degC room temperature at initial pH 2.75 the density was 1.008 while at lye-ed status pH 12.5 the density was 1.015. That is a 0.7% rise in density only, no wonder we could not observe difference eye wise.

2) We have strong new indications that another factor is key:

Any of the observations made about the huge settling speed differences in the previous posts, concern syrian rue extract before a manske was made.
Once 1 manske is done the situation suddenly changes and there is in practical terms no difference in settling speed anymore albeit one uses ammonia or lye. So much for density difference between ammonia and lye as a used base.

Why does that 1 manske plays such a role? Intuitively it would not make much sense.
I think to have incidentally an augmented case here where that difference got really pumped up to extremes. When basing my manske filtrate (out of curiosity) I got an amazing ton of slime as never seen before, see pic on the left. Under microscope there is not one single crystal, it is all a blubber very hard to filter.
My first thought was that diluted harmalas might suffer crystal forming and produce that slime, but I concentrated the slime-component high enough to abandon this possibility.

It seems ammonia or lye have a different effect on the slime component within the rue extract before manske, resulting in a huge settling speed difference.

.

The out of manske obtained rueHCL crystals got filtered + redissolved to pH 2.75 and re-based with lye to 12.5 and fairly fast settling occurred with only crystals to notice under microscope, no blubber. See picture on the right.

.

This re-opens for me the case: what the hell is this blubber?
It's said before and tested to be harmalas but why does it behave so darn differently on many aspects? As to why I got so much of it this time: maybe because I used a pressure pot (at highest setting, it has 2) and a lot of washes, I didn't count but proceeded as long as I got precipitations on basing, estimated 8 - 9 washes or so. It did occur to me that the very last wash, once based it did indeed started to look more like a slime than crystals, and that was before a manske!!
- Did the overkill on pressurized washes give me more of that slime?
- Did the phosphoric acid I used on the washes promote the slime component?

If I can get it filtered somehow (that's gonna be hard) I would like to have the slime analyzed. The above-slime liquid color indicate there are at least traces of harmalas though.

Conclusion so far:

is cases where not so much of that slime-component was derived from the seeds, there will probably be less a difference in settling speed between using ammonia or lye as a base. Still referring to before the very first manske status! Yet if you have a free choice then ammonia does a quicker job. After a manske there's no real difference whatever base you use.

 

[exquisitus]

yeah, been there. i too keep seeing the same "blubber"...
perhaps due to salt/harmalas ratio too high, being over a certain threshold?

 

[Jees]

Salt changing harmalas properties, hmmm, that very last wash I made was already showing slime tendencies in the base precipitant instead of hard crystals a la first washes. At that stage there was no salt added to do anything with the harmalas. There are also other stuffs in the seeds no doubt.

It certainly gets back to liquid when downing Ph, and back to slime when upping pH. But never crystals. Poly-morphed harmalas, is that ever possible?

 

[Jees]

When the FB is dried that will give a clue yield-wise if I had lost a lot of harmalas to the slime or not.

 

[ijahdan]

I never had this slime, but always used just vinegar as my acid, so could it be something to do with phosphoric acid? Ive based with NaOH, NaCO2 and ammonia, but now stick to ammonia as it seems to work quickly and can be cleanly evaporated at the end.

Reading through your posts,Jees, I now realise one reason Ive been getting low yields od harmaline doing the pH depression separation, that is, only basing just past the end of the second depression. Probably there was still harmaline left in solution but less concentrated and thus needing a higher pH.

Good thing syrian rue is so plentiful, allowing this kind of experimentation.

Edit: Just been reading up on sodium phosphates, which may be forming when basing phosphoric acid with sodium hydroxide, and it seems that they are used in the food industry to improve the water retaining properties of meats and for making processed cheese. Also used as laxatives. Maybe this slime could be due to a reaction between phosphates and proteins in rue?

 

[Jees]

^^ yes and that second depression is quite shallow, sometimes a small plateau.
After the first it is mandatory not to overshoot into harmaline, but for the second depression there is no fear for overshooting, you can keep basing :thumb_up:
According to freebase calculator: pH 10 still 39% of your harmaline could be liquid :shock:
11 --> 94% solid
11.5 --> 98% solid
12 --> 99.4%
So when goto 12.5 it incorporates all possible variables of metering errors and calculation uncertainties, and also my suspicion that the more dilute needs higher pH.
You can goto 9.5 with ammonia easily to get nice clean crystals and top up with a dash of NaOH to get high enough. Just my workflow, for now

 

[ijahdan]

Damn, I stopped at about pH 9 and threw the liquid away! Live and learn. Got plenty of harmine as a consolation prize anyway.

 

[exquisitus]

I never had this slime, but always used just vinegar as my acid, so could it be something to do with phosphoric acid?

always getting it. always vinegar.

 

[Jees]

Damn, I stopped at about pH 9 and threw the liquid away! Live and learn. Got plenty of harmine as a consolation prize anyway.

If that was basing your washes then it might mean a loss yes, because then the mechanics of pH depressions do not occur, the required conditions are not met. But once in the conditions where the depressions do occur, VDS showed good harmaline recovery at 9. Of course you can only recover what was put in.

Exquisitus, when do you meet slime? Basing manske filtrates? Or also when basing your washes?

 

[exquisitus]

Exquisitus, when do you meet slime? Basing manske filtrates? Or also when basing your washes?

strictly speaking always, inversely depending on harmala concentration. in the second case most visible when harmalas concentration is wayyy too low. so in practice i ignore the second case, nothing to see there. first case is just too pronounced not to notice.

 

[Jees]

Thanks for the reply E.

...most visible when harmalas concentration is wayyy too low...

idem ditto, the more washes done it becomes more visible.