Several Small Extractions are Better than One Big One & Ratios

[DMTerrestrial]

As for now I'm restricted to posting in the Nursery. Hopefully this post will generate good information exchange. Also if there is a better place for this post, I'm asking The Traveler or any other site mods, to place in the best section possible.

The following is some literature I came across in the PDF file "Organic Chemistry Laboratory Survival Manual-Zubrick-2nd Ed" Yes this book/PDF is from the late 80's but the information still holds true for today. Thought I'd share it. Yes we know to pull until you can't pull anymore, but from what I'm gathering, the more small pulls you do gives you more final product using less solvent. Obviously you will still need to use enough solvent to make the process manageable. The following doesn't touch on size of starting material (100g vs 1kg), just the size of the pulls. So my question is...Do you also save solvent doing Smaller Starting Batches vs. Huge Ones.... with Several Small Pulls vs. Few Large Pulls? (100g vs 1kg)

Now onto ratios.
I've read that a good rule of thumb for ratios is for every gram of MHRB you will mix 1ml/1g/15ml (Naphtha/NaOH/H2O)
I also read that adding more NaHO helps the spice become more available for extraction, giving better yields with less solvent/pulls.
I read that using less H2O also helps with yields, allowing more of the spice to come in contact with the solvent.
Finally I read that heating your MHRB/NaHO/H2O/Solvent solution allows for the solvent to become super-saturated,increasing the solubility of spice in the same amount of solvent. (This also means that you will have more impurities in your final product, but all this can be cleaned up with your favorite purification procedures.)

So one must ask themselves... Will a heated solution with a ratio for every gram of MHRB to 0.5ml/2g/7.5ml (Naphtha/NaOH/H2O) with several small pulls be one of the best ways get maximum yield with minimal solvent? Now of course these are rough numbers just used for an example. If anyone has experience in this area let me know your finding please.

 

[DMTerrestrial]

24 Hours and no response =(

Somebody must have something to chime in about.

 

[OGB]

I dont think if doing more pulls will change something. In theory its true that changing the solvent more often in short time intervals favours the extraction process, but i think that in such small scale extractions the difference will be minimal.

The next time you do an extraction... just do it in different containers and compare the methods you stated above.

Also Im putting just 4g NaOH / 100ml H2O (for a STB) Its sufficient to make the solution pH 14... and for me it works just fine.

 

[endlessness]

DMTerrestrial, please be patient! Its only been 24 hours

I dont know if this is maybe a sign of a characteristic specially of new generations, but more and more we see people coming here and complaining or being dissapointed if within a few hours people dont answer. It's like a widespread immediatism, where everything has to come at the very instant or it's a problem. Maybe this is a social phenomenon that is reinforced by the speed of telecommunications and the gradual dissapearance of many long-term human endeavors, people from the day they are born nowadays are exposed to flashing fast-paced information and very little learning of patience and controlled development. (Not judging you, btw just making general observations)

Maybe people who are interested havent logged in during the hours after you posted and might in some more hours. Or maybe people just arent interested at all, and this is something we just have to accept, even us mods or senior members have made threads before with no responses... There is of course the chance people who might be interested didnt see, but give it a week, or two, and then maybe bump your thread once.. Imagine if every single person that didnt get an answer in some hours would bump their threads/posts, the forum would be a mess of content-less posts of attempts to get attention.

I hope you understand this is meant as a constructive criticism, and an opportunity I felt to comment on something i noticed recently, def not an attack to you.


Now after this long detour, back to the topic: You are very right and I have seen this in practice myself! In fact, this was in the FAQ. The more saturated a solvent is, the less a substance will move to it. Like if you try to get into an elevator packed with people, maybe the first person that went in could go in fast because there was plenty of space, but the more people, the harder it is for them to move into the elevator, even if there is still theoretically space inside. Or think of when washing clothes (the example given in the FAQ), or very dirty dishes, where one will do one wash to get rid of most stuff, but then rinse and wash it again (or the washing machine has many cycles instead of just one long one), because there is always some dirt left behind.

Its not for nothing that ALL teks in this forum talk about 3 (or sometimes more) pulls, it comes from practical experience of many many years and different people.

Thanks for the explanation, I have added a link to this thread in the mentioned FAQ entry

 

[damon]

200g NaOH in 750ml would be way more than needed. 100g is plenty. And 750mL is a good number too, it works for me every time. You can use plain old salt to mess with the polarity, it is cheaper and safer than NaOH, to achieve the same result because NaOH won't make the PH any higher than 14.

And then 50mL seems like too little. If you don't mind evaporating some solvent, it doesn't hurt to use more. I might use 50mL for one pull, but I tend to use too much, I just want to make sure I get it all. I might use as much as 200mL, over 4 pulls, but 3 is usually enough. For a really big batch, you can use small amounts over 5 or 6 pulls. I haven't found the volume of solvent to be that important, you just need to use enough of it to get all the spice out. I also prefer to use FASA or FASW on limo over freezing naptha, so the volume doesn't matter as much. The amount of agitation matters too, I don't like to agitate too much because with lower volumes of water it will be sludgy and it will trap solvent. You would ideally roll the container around, not shake it.

 

[DMTerrestrial]

I dont think if doing more pulls will change something. In theory its true that changing the solvent more often in short time intervals favours the extraction process, but i think that in such small scale extractions the difference will be minimal.

The next time you do an extraction... just do it in different containers and compare the methods you stated above.

Also Im putting just 4g NaOH / 100ml H2O (for a STB) Its sufficient to make the solution pH 14... and for me it works just fine.

For how much MHRB?

You make a very valid point Endlessness, and I'm happy you have made me aware of the situation, no hard feeling. Thank you for pointing me to the FAQ, it's been months since I signed up and just now began posting. FAQ slipped my mind, this will help me from posting redundant topics, which I believe was mentioned in the rules. So my apologies. Also thank you for siting this page in the FAQ, it makes me as if feel I have helped add to the community.

Any thoughts on heating the solution to get the solvent super saturated. In theory it seems to be a good idea, but is it recommended?

Thank you fellow Terrestrial.

 

[billydgator]

Several smaller extractions? like... If i extracted 1kg at once i would get 14g of spice, but if i split it into 4 250g extractions i could get more than 14g? What about a 10kg extraction compared to 4 2.5 kg extractions?
I dont think it makes a difference if you use the right technique when doings your pulls. 4 masses have more surface area than 1 so when your solvent contacts the mixture it may saturate quicker, resulting in more yeild in your intial pulls. As far as how much solvent to use, id say it could differ with each pull. if your solvent wasnt as saturated as previous pulls with the same mixing technique and temperature, you may not need as much on the next one.

 

[endlessness]

No no, more like: Several pulls (and/or several acidic boils in plant material for those doing A/Bs) instead of just one

 

[Eaglepath]

DMTerrestrial, please be patient! Its only been 24 hours

I dont know if this is maybe a sign of a characteristic specially of new generations, but more and more we see people coming here and complaining or being dissapointed if within a few hours people dont answer. It's like a widespread immediatism, where everything has to come at the very instant or it's a problem. Maybe this is a social phenomenon that is reinforced by the speed of telecommunications and the gradual dissapearance of many long-term human endeavors, people from the day they are born nowadays are exposed to flashing fast-paced information and very little learning of patience and controlled development. (Not judging you, btw just making general observations)

Maybe people who are interested havent logged in during the hours after you posted and might in some more hours. Or maybe people just arent interested at all, and this is something we just have to accept, even us mods or senior members have made threads before with no responses... There is of course the chance people who might be interested didnt see, but give it a week, or two, and then maybe bump your thread once.. Imagine if every single person that didnt get an answer in some hours would bump their threads/posts, the forum would be a mess of content-less posts of attempts to get attention.

I hope you understand this is meant as a constructive criticism, and an opportunity I felt to comment on something i noticed recently, def not an attack to you.


Now after this long detour, back to the topic: You are very right and I have seen this in practice myself! In fact, this was in the FAQ. The more saturated a solvent is, the less a substance will move to it. Like if you try to get into an elevator packed with people, maybe the first person that went in could go in fast because there was plenty of space, but the more people, the harder it is for them to move into the elevator, even if there is still theoretically space inside. Or think of when washing clothes (the example given in the FAQ), or very dirty dishes, where one will do one wash to get rid of most stuff, but then rinse and wash it again (or the washing machine has many cycles instead of just one long one), because there is always some dirt left behind.

Its not for nothing that ALL teks in this forum talk about 3 (or sometimes more) pulls, it comes from practical experience of many many years and different people.

Thanks for the explanation, I have added a link to this thread in the mentioned FAQ entry

The monkeys are getting crazier and crazier before they explode and transcend... Haven´t you read Mckenna and novelty theory... Soon 24 hours will be a lifetime!

 

[Rsdz]

I'm super new to all of this. Could someone with a bit of wisdom explain what is meant by several acid baths? Is this speaking of doing an acid bath, removing the matter and repeating? In sorry if this is a stupid question or in the wrong place. I'll move it or delete it if told to do so or where to place it. Thank you in advance. :?

 

[Loveall]

I'm super new to all of this. Could someone with a bit of wisdom explain what is meant by several acid baths? Is this speaking of doing an acid bath, removing the matter and repeating? In sorry if this is a stupid question or in the wrong place. I'll move it or delete it if told to do so or where to place it. Thank you in advance. :?

Yes, that's it. The acidic baths are then typically combined and reduced in volume before the next step(s).

 

[Loveall]

With a little math we can quantify this.

The key concept is the partition coefficient (p). It is the ratio of concentrations at equilibrium of "where you are moving the product" to "where the product comes from". The partition coefficient is a constant for the solvent, temperature, ionic strength, pH, that one chooses, but once those are set, the partition coefficient is constant between pulls (to first order). It can be shown that during the first pull using volume V, the yield is,

y1(V) = 1- a/(V+a)

Where a is constant related to the volume of the source (S) and the partition coefficient,

a = S/p

It has units of volume and can be though of the as the "effective volume" of the source that is holding on to product (because its volume is normalized by the partition coefficient). The larger the partition coefficient, the more difficulty the source has holding on to the product and the smaller it appears to the pulling agent (and vice versa).

We can now say that if we use twice the volume in the first pull, yield goes up to,

y1(2V) = 1 - a/(2V+a)

If two pulls are done back to back it can be shown that the yield is,

y1(V) + y2(V) = 1 - [a/(V+a)]^2

As an example, let's take a = V which is realistic situation.

A single pull with twice the volume, yields:

y1(2V) = 1 - 1/3 ~ 67%

Two pulls will yield,

y1(V) + y2(V) = 1 - (1/2)^2 = 75%

Which is a nice yield boost. To get above 95% it is not practical to increase the volume, instead multiple pulls are the way to get there.

In general we can also define the dimensionless quantity a,

𝛼 = pV/S

Which can be thought of as the ratio of 'effective" volumes. One large pull of n volumes yields,

y1(nV) = 1 - 1/(1+n𝛼)

Where as multiple pulls each of volume V yield,

y1(V)+y2(V)+...+yn(V) = 1 - [1/(1+𝛼)]^n

The differences are substantial with multiple pulls. For example using 𝛼=1 and n=5,

y1(5V) = 1 - 1/6 ~ 83%
y1(V)+y2(V)+...+y5(V) = 1 - (1/2)^5 ~ 97%

So the product loss is over 5x higher on the single pull (3% loss) vs multiple pulls (17% loss). This ratio of product left behind (w) for a single pull of volume nV compared to n pulls of volume V is,

w = (1+𝛼)^n/(1+n𝛼)

Whish grows almost exponentially with n (!). For a typical case where 𝛼 = 1, w = 2^n/(1+n).

PS: These formulas have not been verified, but they are correct to the best of my knowledge. Apologies if there is a mistake. They are also only first order approximations.

 

[Loveall]

One more thing to mention, the discussion above is for unsaturated pulls. If the pulls are saturated, the partition coefficient equilibrium will not be reached, and it is more practical to increase the volume up to the saturation point instead of doing multiple pulls. Important to mention this, as it is one situation that could be encountered (e.g. when too little napthata is used to pull from alkaline water rich DMT).

However, in proper extractions (with pulls at or above the saturation point), multiple pulls are beneficial.

Assuming saturation is not an issue, the plot below quantifies the yield for 5 pulls of a single volume vs. single pull of 5 volumes (n = 5 is fixed for illustration purposes). Depending on the tek, typically 𝛼 ~ 1 or less for Mescaline (in this example it was 0.7) and 𝛼 ~ 1.5 or more for DMT.

PS: Link to plot source (formula is editable) Plot [100(1-1/(1+5x)), 100(1-1/(1+x)^5), {x,0, 3}] - Wolfram|Alpha

 

[Loveall]

There is a more convenient extraction parameter to make the plot. It was discussed in this post. It can be estimated by measuring the product of two consecutive pulls (M1 for the first and M2 for the second), as long as saturation is not an issue,

p = 1-M2/M1​

This parameter has the convenience that it only varies from 0 (not making progress to complete the extraction) to 1 (ideal conditions where everything is pulled immediately). p and 𝛼 are related by 𝛼 = p/(1-p). 𝛼 has a clear physical interpretation (ratio of effective volumes) but the plot is not as convenient since 𝛼 can go from 0 to infinity.

Elrik measured p ~ 0.4 for his mescaline extraction (𝛼 ~ 0.7).

The plot above comparing "a single pull of 5 volumes" vs "5 pulls of a single volume" can be redone for yield vs p (instead of yield vs 𝛼). It is a compact plot as p's domain is 0 to 1. For very bad extractions, the boost from multiple pulls is not as impressive (yield collapses to 0% if p = 0). For very efficient extractions, the difference also becomes smaller (both yields converge to 100%). It is in the intermediate case (which is what we usually encounter) that multiple pulls really shine compared to a single large volume pull (again, this applies when working in the non-saturated regime which is where we should set up the extraction volume).

If anyone measures p for their extraction/tek I'd be interested in the data. Cheers.

 

[doubledog]

Ime, p parameter in extraction is dependent also on presence of the soluble plant material in water. Most prominent is this effect in cactus extraction.

Extraction from reduced cactus tea with high amount of cactus pectin has lower p (more pulls are needed) than extraction from water, which does not contain lot of pectin (like when you acidify alkaline alcohol extract or decrease the amount of pectin some other way).

Ime p parameter is 0.4-0.7 in case of cactus, depending on exact extraction procedure.
For DMT, p is higher, I would say 0.6-0.8, most likely solubility of desired freebase substance in water is the difference.

In STB, first pull yield could be even lower than second one, if basing is not finished and first pull is done too quickly.

 

[Loveall]

Ime, p parameter in extraction is dependent also on presence of the soluble plant material in water. Most prominent is this effect in cactus extraction.

Extraction from reduced cactus tea with high amount of cactus pectin has lower p (more pulls are needed) than extraction from water, which does not contain lot of pectin (like when you acidify alkaline alcohol extract or decrease the amount of pectin some other way).

Ime p parameter is 0.4-0.7 in case of cactus, depending on exact extraction procedure.
For DMT, p is higher, I would say 0.6-0.8, most likely solubility of desired freebase substance in water is the difference.

In STB, first pull yield could be even lower than second one, if basing is not finished and first pull is done too quickly.

Thanks, good points. I have also seen that p is higher for DMT and of that order (0.6-0.8 ). I had an issue where the first pull was saturated, resulting in a small p, but that was addressed by increasing the pull volume.

I also had another issue where p jumped by a lot for later pulls. That was because I was leaving some DMT in the naphtha during freeze precipitation. It was a fixed ammount, and started to affect the ratios when the pulls carried less DMT.

I think there can be some value in tracking p to troubleshoot/optimize, especially when trying out new extractions.

 

[doubledog]

How do you know that saturation was an issue?

 

[Loveall]

How do you know that saturation was an issue?

When there is little drop between M1 and M2 it indicates that M1 was saturated. In the extreme case where both pulls are saturated, there is no chance to get to the partition equilibrium and M1 = M2 (which gives a false measurement of p = 0). The pull solvent simply cannot hold all the product the water wants to give. It can happen if the solvent volume is too small and the actual p is large. It's happened to me with DMT but never with Mescaline. Besides M1~M2 (and small p), another sign is naphtha clouding right away.

Small p could be caused by other issues and not saturation itself, like the bark not being done breaking down as you mentioned. Small p, does indicate something is wrong.

Anyway, unusal p values could hint at extraction issues (or success of p is in the expected region) in general. As I said before, a very large p in later pulls (>0.9) could mean stuff is being left in the naphtha freeze step.

 

[doubledog]

Thank you for the answer, Loveall.
Seems that low saturation point of naphtha is quite impractical, at least for the initial extraction.

 

[Loveall]

Thank you for the answer, Loveall.
Seems that low saturation point of naphtha is quite impractical, at least for the initial extraction.

Yep, it was for me. I learned to increase the naphtha volume to avoid saturation and unnecessary extra pulls. However, after saturation is avoided, increasing the volume doesn't help anymore and breaking up the solvent into multiple pulls is the way to go.