TEK Ethyl acetate approach [CIELO]

[Loveall]

Yeah the droplets at the bottom.

I get most of the solvent back. Loosing 50 to 100g total, no more. But after it becomes soft isn't should not be shaken.

I think you can recover solvent by adding Ca(OH)2. I tested this and some is released. It is white because over the lime, but after a few days it dries up.

I've added citric acid slowly and all at once. It always worked.

I would not use other solvents. I tried acetone and ethyl acetate always xtalizaed better.

This is what I suggest you do for the second pull salting.

Add CaCl2 pellets. After a few minutes, they will look wet and absorb water. Add enough so no loose water is moving around (you may need 5g or so, not sure, just add pellets slowly).
Give time to clear, and to the decanted dry solubion, add 1% of DI water by weight. Shake well and make sure water ris absorbed. Now add citric acid. Clouds form, and after a few hours xtals. I have repeated this several times.

Removing the water first in your case with CaCl2 pellets may also remove some water soluble stuff that survived the microwave and is interfering with xtalization.

If citric acid is added to a dry solution the clouds settle as a loose powder. Some water present before adding citric acid is needed to turn them into xtals.



Regarding the droplets. One thing to try is rinse them with fresh ethyl acetate (I image it is dry from the bottle). It may de-oil the drops and make the mescaline citrate show up. I don't know how you got this results, I have never encountered these droplets.

Edit: updated water recomendatiom

 

[Loveall]

Shroombee, I tried to figure out how to you got the oil.

So I decided to try no microwave at all. Also, no salt or NaCl. Essentially, max water to see if that brings oil with it during precipitation.

Looking back I don't think I had that simple combo, I was always adding NaCl or microwaving or such.

Surprisingly that is working for me too and I have xtals at the bottoms of the jar forming. It could not be easier:

- Start with 69ron paste. I mixed 25g of lime in 300g of water to make it milky and then mixed in 100g of cacti chips powdered.
- Added ethyl acetate. Turns very green quickly. pH paper showed it becomes basic very quickly. At first I thought it may be green from the chlorophyll, buy after acidifying in the next step I know it isn't. Did 3 quick pulls (like 10 minutes each), about 600ml total. Some solvent absorbed but not too bad. Only gentle stirring, probably would work with no stirring at all too.
- I took a small ammount (50ml) and added citric acid (30mg). Got cloudy. pH paper went from basic to slightly acidic. A few hours later it cleared up and there are xtals .

It is so simple this way. I may have made it too complicated earlier (sorry, I was trying to figure stuff out). No microwave and no CaCl2 or NaCl means less chances of things going wrong. I think this is the way. Started in the morning with raw cacti chips and I think I'm looking at mescaline citrate crystals before lunch. I hope you try this out too (you can scale it down to see what happens). Make sure your pickling lime is Ca(OH)2 only and your citric acid is only citric acid. You may have done this already, it's just that sometimes they add stuff to brand names. Best of luck

 

[shroombee]

I think you can recover solvent by adding Ca(OH)2. I tested this and some is released. It is white because over the lime, but after a few days it dries up.

Just to be sure - you're saying add more lime to release solvent?

I would not use other solvents. I tried acetone and ethyl acetate always xtalizaed better.

By pulling with IPA or acetone I meant pulling beforehand to clean up the plant matter before proceeding with the rest of the tek. The IPA/acetone is dumped - not used for pulling any goodies or precipitating xtals. This suggestion was inspired by you saying the green stuff interferes with xtal formation.

Add CaCl2 pellets. After a few minutes, they will look wet and absorb water. Add enough so no loose water is moving around (you may need 5g or so, not sure, just add pellets slowly).
Give time to clear, and to the decanted dry solubion, add 1% of DI water by weight. Shake well and make sure water ris absorbed. Now add citric acid. Clouds form, and after a few hours xtals. I have repeated this several times.

Pull #2 is in the freezer. I decanted pull #3 this morning. Recovered about 180 grams solvent. Dried by slowly adding about 3-4 grams CaCl2 and swirling the solvent around. Some of the CaCl2 melted into briny water with the rest of the pellets sitting at the bottom. Was I supposed to add enough CaCl2 to absorb this briny water? Never saw the solvent become unclear (so I only waited until it seemed no more pellets would melt). Decanted and added 1% purified water (not DI water). Added many little amounts of citric acid, waiting and checking pH between additions.

Questions on the salting: In trying to get the pH to be basic throughout the solvent, over the course of 3 hours I added 847 mg of citric acid. I know - sounds like way too much. First addition was 57 mg and clouds formed at the bottom of the jar, as expected. I wanted to follow your technique of slowly letting the acid diffuse so I didn't swirl or mix the solvent. To check pH, I used a pipette to pull a little solvent and add a drop to pH paper. If I pull solvent from the surface, it is basic. Solvent pulled from the cloud is acidic. Over 3 hours I added citric acid 10 times, waiting then measuring pH. The surface very gradually became less basic. I noticed the pH paper reads slightly more basic than the 4 indicator pH strip. After 3 hours, I figure the pH through the two types of indicators is pH ~5-6.

Anyhow, pull #3 is in the frig.

 

[shroombee]

Start with 69ron paste. I mixed 25g of lime in 300g of water to make it milky and then mixed in 100g of cacti chips powdered.

When making 69ron paste (heh), I've always combined the powdered cactus chips with the lime, then slowly add water. I'll try this milky water method. I'd assume the results would be the same.

Added ethyl acetate. Turns very green quickly.

After mixing the milky water and the cactus powder, how long did you wait for the lime to work on the cactus before adding ethyl acetate?

Did 3 quick pulls (like 10 minutes each), about 600ml total. Some solvent absorbed but not too bad. Only gentle stirring, probably would work with no stirring at all too.

After each addition of fresh ethyl acetate, how long did you stir, and how long did you let things settle before decanting?

I took a small ammount (50ml) and added citric acid (30mg). Got cloudy. pH paper went from basic to slightly acidic. A few hours later it cleared up and there are xtals

Related to my previous post, did you swirl or mix the citric acid into the solvent? How are you taking the pH measurement?

It is so simple this way. I may have made it too complicated earlier (sorry, I was trying to figure stuff out).

No worries. We're just experimenting and learning. Had it not been for my lack of success, you may not have been inspired to try this simpler process. In extractions, and in life, there are no mistakes, just unplanned variations. :thumb_up:

Started in the morning with raw cacti chips and I think I'm looking at mescaline citrate crystals before lunch.

That could be the tag line for the tek. :lol:

I hope you try this out too (you can scale it down to see what happens). Make sure your pickling lime is Ca(OH)2 only and your citric acid is only citric acid. You may have done this already, it's just that sometimes they add stuff to brand names.

I will definitely try it out, probably tomorrow! Reviewing my materials to ensure there isn't anything obviously amiss:

HPLC-UV Ethyl Acetate: https://www.pharmco.com/ethyl-acetate-hplc-4x1-gal-f-33000hplccsgf
Pickling lime: https://www.amazon.com/Mrs-Wages-Pickling-1-Pound-Resealable/dp/B0084LZU1Q/
Ca Chloride: https://www.amazon.com/gp/product/B00ZPVKG6C/ (I checked the website and this is supposed to be anhydrous)
Citric acid: https://www.amazon.com/gp/product/B00EYFKNL8/
pH paper: https://www.amazon.com/gp/product/B07H1RJSGJ/
pH strips: Amazon.com

 

[Loveall]

Just to be sure - you're saying add more lime to release solvent?

Yes, I have seen more lime release solvent. Will be milky but clears up over time (patience needed).

By pulling with IPA or acetone I meant pulling beforehand to clean up the plant matter before proceeding with the rest of the tek. The IPA/acetone is dumped - not used for pulling any goodies or precipitating xtals. This suggestion was inspired by you saying the green stuff interferes with xtal formation.

Ah, you mean an IPA/Acetone pre-wash before water/lime. I guess an ethyl acetate wash could be done too. I don't think it is needed. I did say that the green didn't give good xtalization, BUT back then I was not aware of other variables. 1) Water: some water is needed (~1% or more) and 2) excess citric acid helps. Since I was not controlling this before, now I'm worried that I mistakenly attributed the more difficult xtalization to the green incorrectly. I have repeated effects 1) and 2) and I have growing confidence in them. Based on my latest results after working with more green without NaCl (more water in the extract), xtalization can be ok. Even if the green slows it down a little, in practice when having full water in ethyl acetate (3.4% I believe) and having extra acid (about twice the ammount needed to neutralize) hat looks like good xtalization occurs.

Pull #2 is in the freezer. I decanted pull #3 this morning. Recovered about 180 grams solvent. Dried by slowly adding about 3-4 grams CaCl2 and swirling the solvent around. Some of the CaCl2 melted into briny water with the rest of the pellets sitting at the bottom. Was I supposed to add enough CaCl2 to absorb this briny water? Never saw the solvent become unclear (so I only waited until it seemed no more pellets would melt). Decanted and added 1% purified water (not DI water). Added many little amounts of citric acid, waiting and checking pH between additions.

Questions on the salting: In trying to get the pH to be basic throughout the solvent, over the course of 3 hours I added 847 mg of citric acid. I know - sounds like way too much. First addition was 57 mg and clouds formed at the bottom of the jar, as expected. I wanted to follow your technique of slowly letting the acid diffuse so I didn't swirl or mix the solvent. To check pH, I used a pipette to pull a little solvent and add a drop to pH paper. If I pull solvent from the surface, it is basic. Solvent pulled from the cloud is acidic. Over 3 hours I added citric acid 10 times, waiting then measuring pH. The surface very gradually became less basic. I noticed the pH paper reads slightly more basic than the 4 indicator pH strip. After 3 hours, I figure the pH through the two types of indicators is pH ~5-6.

Anyhow, pull #3 is in the frig.

I think all this is fine. When I dried with CaCl2, I added extra pellets to not have a water layer which I also saw. I think it will be OK to decant off the brine water, I don't see how a lot of FB mescaline could end up there.

I let it sit overnight when I let the acid diffuse. It takes a while.

I think the extra citric acid is perfectly fine. Actually, I know think it will help with xtalization.

After mixing the milky water and the cactus powder, how long did you wait for the lime to work on the cactus before adding ethyl acetate?

Not long, maybe 5 minutes? I spent more time mixing until the paste seemed clumpy and stable (about 10 minutes).

After each addition of fresh ethyl acetate, how long did you stir, and how long did you let things settle before decanting?

Not very long, 30 seconds with very gentle stirring. Then let it settle for 10 minutes. The pH paper indicates alkaloids get picked up very fast and efficiently. Color changes quickly too.

Related to my previous post, did you swirl or mix the citric acid into the solvent? How are you taking the pH measurement?

Usually I let it sit and measure pH 12 hours later. Sometimes I swirl and then check pH right away.

Also, I buddy checked your materials. Looks good. Your ethyl acetate is different than mine. I use the one at the hardware store and it costs about the same as acetone I believe. We are using the exact same citric acid by the way.

Edit: Wiki experimental TEK has been updated with the simple the no microwave, no NaCl/CaCl2, allow water in the solvent, add extra citric acid, approach

 

[shroombee]

Ah, you mean an IPA/Acetone pre-wash before water/lime. I guess an ethyl acetate wash could be done too. I don't think it is needed.

Assuming an ethyl acetate wash could improve yields or expedite crystal formation (future experiment), are we sure the natural form of mescaline (malate) is not soluble in ethyl acetate?

Even if the green slows it down a little, in practice when having full water in ethyl acetate (3.4% I believe) and having extra acid (about twice the ammount needed to neutralize) hat looks like good xtalization occurs.

Is full water in the ethyl acetate attained by absorbing water from the cactus during pulls?

When you check pH, do you dip the pH paper into the solvent? I've been pulling with a pipette and adding a drop of solvent to the paper.

Also, I buddy checked your materials. Looks good. Your ethyl acetate is different than mine. I use the one at the hardware store and it costs about the same as acetone I believe. We are using the exact same citric acid by the way.

Thanks for checking!

So pull #3 (dried with CaCl2 and 1% water added) went into the frig at ~1:00 pm yesterday and by 11:00 pm it was still opaque, but no crystals. I moved it to the freezer. As of 1:50 pm today it hasn't cleared, but no crystals yet.

For pull #1, the solvent that failed to xtalize and left the oil droplets in the dish, I'll decant the solvent (save solvent) and let the oil sit out to dry. Then evaluate based on what the oil turns into.

For pulls where solvent fails to xtalize (not leaving oil), what's the process to recover the mescaline? Pull 3x with water at ~50% by weight, then evaporate the water?

How do we clean the solvent if we want to reuse it, since it probably has excess citric acid dissolved in it?

BTW, I started another run where I'm using the latest "keep it simple" process. I added my notes to the wiki. This is a small test of 50 grams powdered chips. Four pulls combined and salted. It's in the frig as of 11:00 am.

 

[metta-morpheus]

Great work loveall!

I just read this whole thread. I’m glad I got to “binge read it”, and not have to wait on the season ending cliff hanger on what will the test results bring!

I will also attempt to replicate this very soon. Those crystals looked so beautiful!

 

[shroombee]

Loveall, can you run these tests with your materials and let us know the result. I'm wondering if the difference between my HPLC-UV ethyl acetate and your hardware store ethyl acetate is contributing to a difference in our results.

pH Tests:
- Drop of ethyl acetate on pH paper: no color change;
- Drop of ethyl acetate with some lime mixed in: light green;
- Drop of ethyl acetate with lime and a few drops of water mixed in: light green;
- Drop of ethyl acetate with citric acid and 3% water added: medium orange;

To 27.5 grams of ethyl acetate, I added 13 mg of citric acid. There were no clouds and the citric acid does not dissolve. The granules of citric acid sit at the bottom of the beaker.

Adding 0.8 grams of purified water to the 27.5 grams of ethyl acetate, the citric acid immediately dissolves. There are small bubbles of water at the bottom of the beaker, indicating not all of the water mixed into the ethyl acetate (because I didn't shake the ethyl acetate to mix the water).

Edit: If I mix about 3% water by weight into the ethyl acetate by shaking, then I can get a lot of citric acid to dissolve. For example, 100 mg into ~23 grams ethyl acetate + 3% water mixture.

 

[Loveall]

Shroombee, I will do those tests and reply to your points tomorrow. Citric acid is reportedly soluble in ethyl acetate, it should dissolve for you.

I want to report 1.1% yield from the simple tek (see images below). I have never gotten this high yield or such apparent purity before. The amount of work was minimal and the process (cacti chips to crystals) was done in 36h.

Washing the filter with fresh ethyl acetate a few times wicked all the green color away to the edges. It was very simple to do.

 

[shroombee]

Loveall, what ethyl acetate product are you using, and what kind of water do you add to the cactus (tap, DI, distilled, etc?) I will try to acquire the same.

I am not yet getting your results even after following the tek exactly. I suspect some difference in the materials we're using.

The specs on my ethyl acetate: Not less than 99.5% purity, typically 99.98%. And not more than 0.2% water, typically 0.01% water:

https://greenfield.com/wp-content/uploads/2018/11/Spec-Sheet-Ethyl-Acetate-General-Use-HPLC.pdf

BTW, the ethyl acetate I am using is also food grade, for those who want this to be a food grade tek:

https://greenfield.com/wp-content/uploads/2018/11/Food-Grade-Statement-Ethyl-Acetate.pdf

So if the proper water content in the ethyl acetate is critical to getting xtals, perhaps with the quick pulls my ethyl acetate isn't picking up enough from the cactus? And maybe even with the long 12 hour pulls it wasn't picking up enough?

Maybe a test you could run is to weigh your fresh ethyl acetate out of the can before and after drying it to gauge how much water it contains.

 

[Loveall]

Loveall, what ethyl acetate product are you using, and what kind of water do you add to the cactus (tap, DI, distilled, etc?) I will try to acquire the same.

I am not yet getting your results even after following the tek exactly. I suspect some difference in the materials we're using.

The specs on my ethyl acetate: Not less than 99.5% purity, typically 99.98%. And not more than 0.2% water, typically 0.01% water:

https://greenfield.com/wp-content/uploads/2018/11/Spec-Sheet-Ethyl-Acetate-General-Use-HPLC.pdf

BTW, the ethyl acetate I am using is also food grade, for those who want this to be a food grade tek:

https://greenfield.com/wp-content/uploads/2018/11/Food-Grade-Statement-Ethyl-Acetate.pdf

So if the proper water content in the ethyl acetate is critical to getting xtals, perhaps with the quick pulls my ethyl acetate isn't picking up enough from the cactus? And maybe even with the long 12 hour pulls it wasn't picking up enough?

Maybe a test you could run is to weigh your fresh ethyl acetate out of the can before and after drying it to gauge how much water it contains.

I have tested these both of these with good results:

M.E.K. Substitute - Klean Strip

www.kleanstrip.com

Green Archives - Jasco Help

www.jasco-help.com

The SDS states "100.0%" ethyl acetate. Same as your product SDS.

However, if citric acid is not dissolving in your ethyl acetate I think that is a problem. It should dissolve easily.

Physical

Citric acid is at standard conditions a white hygroscopic crystalline powder. It exists either in an anhydrous (water-free) form or as a monohydrate. The monohydrate can be converted to the anhydrous form by heating above 78 °C. It is soluble in water, ethanol, diethyl ether, ethyl acetate, DMSO and insoluble in benzene, toluene, chloroform, carbon disulfide.

When I dried the ethyl acetate after the pulls as best I could with Ca(OH)2 and K2CO3, FB mescaline stayed in solution (because it crashed later). When salting that with citric acid, clouds formed but only painfully slowly settled to a loose powder impossible to handle (anhydrous mescaline citrate?). Adding 1% water made the powder sticky as if it were absorbing some water (sticking to the wall, easier to handle). Adding another 1% water and excess citric acid (2% water total with a slight red appearing on the pH paper) gave very nice xtals, looking long and needle like (a mescaline citrate hydrate form?). They grow into these nice long needles in the cleaner microwaved extract, from the raw green cactus extract they still crash, but that was with no drying (assuming 3.4% water) and had extra citric acid to force the xtalization more.

I plan to do the tests today. I dunk the pH strip in the ethyl acetate instead of using drops. One question, when you mixed lime with ethyl acetate did it get milky and did you wait to clear before sapling the drop?

I also want to measure the solubility of citric acid in ethyl acetate. It should be high.

 

[Loveall]

Loveall, can you run these tests with your materials and let us know the result. I'm wondering if the difference between my HPLC-UV ethyl acetate and your hardware store ethyl acetate is contributing to a difference in our results.

pH Tests:
- Drop of ethyl acetate on pH paper: no color change;
- Drop of ethyl acetate with some lime mixed in: light green;
- Drop of ethyl acetate with lime and a few drops of water mixed in: light green;
- Drop of ethyl acetate with citric acid and 3% water added: medium orange;

To 27.5 grams of ethyl acetate, I added 13 mg of citric acid. There were no clouds and the citric acid does not dissolve. The granules of citric acid sit at the bottom of the beaker.

Adding 0.8 grams of purified water to the 27.5 grams of ethyl acetate, the citric acid immediately dissolves. There are small bubbles of water at the bottom of the beaker, indicating not all of the water mixed into the ethyl acetate (because I didn't shake the ethyl acetate to mix the water).

Edit: If I mix about 3% water by weight into the ethyl acetate by shaking, then I can get a lot of citric acid to dissolve. For example, 100 mg into ~23 grams ethyl acetate + 3% water mixture.

My pH paper results (using the same paper as you, the plain one with one color change)

- Plain ethyl acetate: no color change
- added Ca(OH)2: no color change. This is cloudy and settles clear over time (loose powder at the bottom).
- added Ca(OH)2 and drops of water: no color change. This time the lime settles to a sticky white layer at the bottom because if the water (instead of loose cloudy powder as before). The big difference vs no water drops added indicates to me that the ethyl acetate was relatively dry to begin with.
- added citric acid alone: dissolves well. Tested up to 250mg of citric acid (monohydrate) in in 50g of solvent (0.5% solubility at least) it all dissolved. pH paper turns red (see below, sorry for the bad focus). Result does not chance if adding drops of water.

So, our ethyl acetate sources are behaving differently. Ethyl acetate alone should dissolve citric acid, if yours is not doing that it seems to be having an issue.

You also asked how to reuse ethyl acetate. Haven't tried his yet, but I imagine a water wash should do the trick. Here a 5% washing soda wash is recommended, that should work well for us and neutralize excess citric acid so the solvent is neutral and ready to pull (I think we can skip the drying step since it is going into a wet paste anyway). We could also try to re use the ethyl acetate straight without any washes, the lime should neutralize excess citric acid (calcium citrate clouds may form while doing this).

If you can get the same ethyl acetate I have (should only be $25 a gallon or so at the local hardware store) you should get the same results I'm getting

 

[shroombee]

I have tested these both of these with good results:

http://www.kleanstrip.co...oduct/m.e.k.-substitute

http://www.jasco-help.co...jasco-m.e.k.-substitute

The SDS states "100.0%" ethyl acetate. Same as your product SDS.

The SDS of the Pharmco HPLC-UV product I'm using is also 100% ethyl acetate:

https://greenfield.com/wp-content/uploads/2019/08/Ethyl-Acetate.pdf

However, the spec sheet of this 100% ethyl acetate says it can have as much as 0.5% of impurities, including 0.2% water and still meet ACS specifications:

https://greenfield.com/wp-content/uploads/2018/11/Spec-Sheet-Ethyl-Acetate-General-Use-HPLC.pdf

I assume the hardware store ethyl acetate does not meet these purity standards, so what are the impurities (maybe just water)? And do the impurities facilitate xtal formation?

This "purity of ethyl acetate" reasoning might be a red herring and the assumed impurities in the hardware ethyl acetate might not be significant. I don't know. It just seems to be one of the obvious differences between our processes.

As you can see from my latest experiment log and the quality of my materials, I believe I've followed everything exactly as it's supposed to be. And I haven't yet produced the desired results.

BTW, the extraction I ran yesterday (experiment #2 in the log) using the updated simple tek is still in the frig with no xtals after 24 hours. The solvent has not cleared yet. How long do you wait to start seeing xtals?

from the raw green cactus extract they still crash, but that was with no drying (assuming 3.4% water) and had extra citric acid to force the xtalization more.

Are you assuming the 3.4% water was absorbed from the cactus during the pulls? Or (conjecturing here) does the water come as an impurity straight from the hardware ethyl acetate?

If I add water to the ACS grade ethyl acetate, it does not readily mix into the solvent. Rather, the water droplets sit at the bottom of the beaker. I have to shake the solvent + water to get it to combine. Does that imply ethyl acetate does not pick up much (if any) water during the 10 minute cactus pulls and I am salting with nearly anhydrous ethyl acetate?

One question, when you mixed lime with ethyl acetate did it get milky and did you wait to clear before sapling the drop?

It got milky. I did not wait for it to clear. The original purpose of the pH paper tests was to generally familiarize myself with how the pH paper reacts to ethyl acetate. They were admittedly clumsy tests. :roll:

I also want to measure the solubility of citric acid in ethyl acetate. It should be high.

I will also run more solubility tests. Maybe you can test straight from the container versus dried ethyl acetate. In researching, I see it stated that citric acid is soluble in ethyl acetate, although not specifically "high solubility". However, I can't find the solubility metric anywhere. The solubility of citric acid monohydrate in ethyl acetate is 5.28g / 100g:

Citric Acid Monohydrate, Honeywell Fluka, Quantity: 1 kg | Fisher Scientific

www.fishersci.com

We are using the same brand citric acid and it's anhydrous, not the monohydrate.

 

[Loveall]

It only takes a few hours to xtalize. I have been stuck before with a cloudy solution that was stubborn and didn't Xtalize, and I think that was because it was not wet and acidic enough. Are you seeing anything at the bottom (e.g loose powder)?

What helps is adding more citric acid and more water (but avoid water layers forming or citric acid not dissolving so add small amounts). That may help with crashing. Try adding a little of each in increments. What happens first is a loose powder settles. Then it becomes sticky (~1% water) and clings to the jar. Then as more water/citric acid is added (~2% water, red pH paper) it turns into beautiful xtals after shaking or scraping to knock loose the sticky stuff.

Just did a test with plain ethyl acetate and water. 30s of gentle stirring and 10 minutes of settling absorbs water. I think the ethyl acetate that I'm using absorbs water from the paste because of this. At equilibrium with plain water, ethyl acetate is supposed to be 3.4% water, but it is likely less because of the lime making the water basic.

The different grades of ethyl acetate may be absorbing water differently. CaCl2 will say if there is water in the ethyl acetate as you have seen before.

Another thing is that I have not been the best at is keeping my citric acid sealed and I've been using it for cooking for a long time. I may have inadvertently hydrated it a bit. Are you sure the millard citric acid comes as the anhydrous form? If it is, the issue could be that I'm inadvertently using monohydrate citric acid while you are using the proper anhydrous citric acid, but I would imagine that by adding water later it should all work. Maybe you are really close to forcing xtalization and just need a little more citric acid and water

Edit: If you add too much water and get layers while trying to force xtalization, you should be able to revert this by adding fresh ethyl acetate. Excess citric acid helps with xtalization a bunch. Best results I get is when the pH paper has some red coloring.
Edit2: It would be really cool if we can explain our different results because of the difference in hydrated and anhydrous citric acid. We can make the tek more robust by hydrating citric acid. Maybe it is better to add citric acid saturated water (CASW) instead of citric acid powder with variable hydration depending on storage.
Edit3: We could be witnessing mini manske like effect, water and excess citric acid ions force mescaline citrate to crash as xtals.

 

[shroombee]

This is cool that we might be working towards an understanding of the edge cases in this tek.

It only takes a few hours to xtalize. I have been stuck before with a cloudy solution that was stubborn and didn't Xtalize, and I think that was because it was not wet and acidic enough. Are you seeing anything at the bottom (e.g loose powder)?

I am not seeing anything at the bottom. The only thing I've ever gotten visible at the bottom was the first pull on experiment #1 where I have the oil.

Then as more water/citric acid is added (~2% water, red pH paper) it turns into beautiful xtals after shaking or scraping to knock loose the sticky stuff.

I added the amount of citric acid called for in the updated simple tek, and the pH paper shows no color change (it is the same color as the raw paper). It is not red. Before adding citric acid the pH paper is green, as expected from the combined raw pulls.

Are you sure the millard citric acid comes as the anhydrous form?

Yes, it says so on the front of the package: "Pure, fine grain, anhydrous".

https://www.amazon.com/gp/product/B00EYFKNL8/

Some solubility tests I just ran using anhydrous ethyl acetate and anhydrous citric acid:

1) Dropping a single grain of citric acid into 30 grams ethyl acetate. I watched this grain for 10 minutes and it did not dissolve. After 10 minutes I pressed at it with a fork and it was still a firm solid. With a little effort I was able to break it up. I don't really know if it dissolved or whether there are solid pieces that are too small to see.

2) Added about 1% by weight purified water to the ethyl acetate. Shook moderately to get the ethyl acetate to absorb the water (perhaps I could have waited 10 minutes). I dropped a single grain of citric acid into this solution and it half dissolved over 10 minutes.

3) Dropped another grain of citric acid into the 1% water solution and stirred for 3 minutes. The grain did not dissolve, but light pressure crushed the grain.

4) Dropped a grain of citric acid into purified water. Grain dissolves in 30 seconds with no agitation required. A grain will dissolve in 10 seconds with light agitation.

5) I will do a solubility test of citric acid in 3% water + ethyl acetate. I've mixed the solution (moderate shaking) and the solution is cloudy. I am waiting for it to clear before dropping a grain.

6) Lime added to ethyl acetate. Cloudy and settles over time. No change with pH paper. Same result as your test, which is different from my first test where I didn't let the lime settle.


So it appears that anhydrous ethyl acetate would not effectively wash away excess anhydrous citric acid from an end product. Citric acid monohydrate may be different. I'll make some by dissolving anhydrous in cold water and evaporating. Then will run these tests again. These tests may lead to a step in the tek for a method to ensure excess citric acid is washed away (or might not be needed).

If you add too much water and get layers while trying to force xtalization, you should be able to revert this by adding fresh ethyl acetate. Excess citric acid helps with xtalization a bunch. Best results I get is when the pH paper has some red coloring.

Okay I'm going to take the extract from yesterday's experiment and add water and citric acid.

 

[Loveall]

Sounds good. I suggest to add citric acid first to experiment #2. You can shake it. You want some red on the pH paper. It should Xtalize then I believe. It could happen quickly too.

 

[Loveall]

I repeated the simple tek. Same as before four pulls seem like plenty (see first image). This time I added 1g of citric acid (even more than before). Clouds are settling to crystals again, fast and efficiently starting to stick to the jar walls very quickly.

Shroombee, I hope it works for you. Let us know how adding more citric acid goes. I think excess citric helps Xtalize the mescaline citrate clouds. You want red on the pH paper. See second image below (pre and post adding the citric acid).

 

[shroombee]

Loveall, have you run the simple tek and salted the pulls separately? Curious if there would be any differences based on the concentration of freebase in the solvent.

I have a pull in the frig now where I added citric acid to water to make CASW, then added the CASW to the pull and mixed with the magnetic stirrer. pH paper is red as in your photo. The amount of water I added would bring the water percentage up to around 2% in the extract (4 grams water into 195 grams ethyl acetate). It's interesting that the water appears to be totally mixed into the solvent (no droplets at the bottom). Meaning at most there was 1.0-1.3% water in the pull to begin with. This is assuming max water percentage is 3.3% and the other compounds dissolved in the solvent don't help to increase solubility of water in the ethyl acetate. The pull is the 4th from my first run that I hadn't salted yet. Even if I get xtals, yield may be low. We'll see.

I may have time to do another run tomorrow and I will experiment with different salting methods, such as adding water first then citric acid, adding CASW, adding citric acid monohydrate, et cetera. Probably will combine the four pulls, then split the extract into four jars to run these separate experiments.

 

[Loveall]

Loveall, have you run the simple tek and salted the pulls separately? Curious if there would be any differences based on the concentration of freebase in the solvent.

I have a pull in the frig now where I added citric acid to water to make CASW, then added the CASW to the pull and mixed with the magnetic stirrer. pH paper is red as in your photo. The amount of water I added would bring the water percentage up to around 2% in the extract (4 grams water into 195 grams ethyl acetate). It's interesting that the water appears to be totally mixed into the solvent (no droplets at the bottom). Meaning at most there was 1.0-1.3% water in the pull to begin with. This is assuming max water percentage is 3.3% and the other compounds dissolved in the solvent don't help to increase solubility of water in the ethyl acetate. The pull is the 4th from my first run that I hadn't salted yet. Even if I get xtals, yield may be low. We'll see.

I may have time to do another run tomorrow and I will experiment with different salting methods, such as adding water first then citric acid, adding CASW, adding citric acid monohydrate, et cetera. Probably will combine the four pulls, then split the extract into four jars to run these separate experiments.

Ok, 4th pull may not have much. Any xtals there? Did it cloud up?

How about for experiment #2 combined pulls? Have you tried simply adding more citric to that? Last I heard it was cloudy after salting, but the clouds were not crashing. I think excess citric acid could help force the issue for those clouds (which I think may be mescaline citrate clouds).

The water being alkaline could be making the ethyl acetate dryer compared to it's equilibrium with plain water.

 

[shroombee]

Ok, 4th pull may not have much. Any xtals there? Did it cloud up?

Experiment #1, 4th pull clouded but no xtals 12 hours after going into the frig. Still cloudy. Transferred to the freezer this morning. Nothing after 4 hours.

Edit: X1, P4 now showing ice/crystals about 5 hours after hitting the freezer. There is approximately 4 mg citric per gram of solvent in this pull.

How about for experiment #2 combined pulls? Have you tried simply adding more citric to that? Last I heard it was cloudy after salting, but the clouds were not crashing. I think excess citric acid could help force the issue for those clouds (which I think may be mescaline citrate clouds).

Experiment #2: I'll put all the details into the tek log, but here's a summary:

After 26 hours in the frig there were no xtals. Solvent is not "cloudy" but definitely opaque, unlike when first pulled and it's an emerald green and we can see through it. There was around 0.5-1.0 ml of thin oil sliding around at the bottom of the jar. Transferred everything to a beaker. I added 2 grams of water to 417.1 grams solvent (this is combined pulls #1-4). Added water before I saw you recommend just trying citric acid first. Stirred for 3 minutes with the magnetic stirrer. Oil did not mix back into the solvent. Decanted the solvent away from the oil. Added a total of 300 mg citric acid (now a total of 550 mg in 417.1 grams solvent).

I split the solvent into two jars: (A) is 75% of the original and (B) is 25%. To (B) I added 200 mg citric, so now it contains 3.375 mg citric per gram of solvent (a lot!) Placed (A) and (B) in the frig. No xtals after 16 hours, so transferred both to the freezer.

Checked 4 hours later (as I'm writing this) and (A) has ice(?) formations at the bottom and some floating in the solvent. Maybe it's mescaline xtals. It might be water ice. I don't want to disturb it too much and it's difficult to see through the frost on the outside of the jar, even with a flashlight.

(B) is starting to show ice/xtals, 30-60 minutes behind (A) in timing. So both are promising. Interesting that (A) and (B) are the same except (B) has much higher acid and (B) is lagging slightly behind (A). Might be a data point to keep in mind.

Regarding the oil, I ended up having two 1,000 ml beakers with oil droplets at the bottom. I let the ethyl acetate evaporate off and there isn't that much oil. I'm thinking use 190 proof ethanol to get the oil out of the beakers and onto an evaporation plate so I can try to weigh it. Then see if it's worth investigating further. It might just be plant oils that somehow dropped out of the solvent. They have a familiar smell like the 69ron acetate evaporations where there is usually some oil present on the evaporation plate. Taste is bitter.

I also made some citric acid monohydrate by dissolving anhydrous citric acid in water and evaporating at 95 degrees in the dehydrator. It scrapes up to a fine hydrated powder that sticks to itself. I expect it will dissolve easily in anhydrous ethyl acetate, unlike the hard grains of anhydrous citric acid. Will report on this later.

BTW, I'm unlikely to obtain those hardware store ethyl acetate "MEK Substitute" products in my location. It's best for me to use food grade materials anyhow, for personal reasons.

Happy Sunday! :d