Re-basefying vinegar - gone wrong?

[dooby]

Hello,

I had somewhere between 150-200 ml of vinegar from salting my naphtha pulls...

I added 4 gr of NaOH to 100 ml of water and poured this into the vinegar...

I am definitely pulling something (using naphtha again) but it doesn't seem like a lot...

Could I have under-basefied?

Any thoughts, please?

PLUR

 

[ymer]

If you don't have a way to test PH you can simply add 5-10 more grams of naoh to make sure your ph is high enough.

 

[dooby]

I added 4 gr of NaOH and pulled again with the same naphtha I used on my first attempt...

Warm/hot naphtha did not cloud up upon cooling...

I'll try adding 2 gr of NaOH and 10 gr of NaCl (hopefully raising the ionic strength of the basic solution) and pull again with fresh naphtha...

If this doesn't work, perhaps the bark was not depleted in which case I'll try to find some toluene to do more pulls (so glad to have not discarded my "starting" material)...

It's quite difficult to imagine what could have gone wrong - hopefully something will come out of this in the end, both yield-wise and educationally

PLUR

 

[dooby]

If I calculate the amount of spice that should be somewhere (amount of mhrb x average alkaloid content)...200 gr x 0.5-2% = 1-4 gr
And if I subtract the amount of spice that was already precipitated in the fridge...700 mg
And if I assume that all steps were done correctly...using Cybs hybrid A/B salt tek + back-salting of naphtha pulls with vinegar, evap partially, STB with NaOH, naphtha pulls
There should be anywhere between 0.3 and 3.3 gr of spice sitting in 200 ml of naphtha (pulls were done with warm solution and naphtha)...

Yet there is no clouding of my naphtha whatsoever even after sitting in the fridge for a while...

Possible causes?

-Not enough pulls? (total of 700-800 ml of naphtha was used in total, pulls were done warm/hot)

-Inadequate salting of pulls with vinegar?

-Inadequate re-basing of vinegar (added 8 gr NaOH to about 150-200 ml of 7% white vinegar and 150-200 ml of water so far)

What would be the best place to start trying to correct whatever mistake(s) I may have made?

Thank you

PLUR

 

[Infundibulum]

What was the reasoning behind salting the naphtha pulls? Wouldn't that be better to freeze-precipitate it? Unless of course you have no freezer at your disposal...

But anyway, 200ml of 7% vinegar (as you describe) need around ~11g of NaOH to fully neutralise (that is, pH=7). A bit less will be necessary since a portion of the acetic acid has been neutralised by dmt, but most certainly nowhere as little as 8g of NaOH.

Try at least 20g of NaOH and then pull again with naphtha.

Sidenote: a nice thing with acids other than acetic is that upon basification the freebase dmt crashes out and will crystallise out of the basified water. This definitely happens when dmt fumarate is used (with either sodium carbonate or NaOH as the base) but not always when dmt acetate is involved (at least not when sodium carbonate is used to base it, but may work with NaOH?). When dmt crashes out the aqueous basified solution, the solution gets very cloudy almost immediately (and you also know that you based enough) and crystals form if left for a couple of days.

 

[dooby]

Thanks a million!

I'll add 12 gr of NaOH to my solution...

I'll let you know if the solution clouds up or not

If this doesn't work out I'll try doing additional pulls on my mhrb/base mix...

PLUR

Edit - Indeed I do not own a freezer so the vinegar was used so I would end up with a lot less solvent to evaporate (I saved at least 600 ml)

 

[dooby]

Wow! (and I do mean Wow!)
Upon adding the first +/- 3 gr of NaOH it didn't just cloud up, it turned into milk, same color, same lack of transparency...I saw "lightning bolts" of whiteness appear very rapidly just before I started swirling the bottle to mix...

I'll leave it be for a while to see if something separates/crystallizes...

Nearly had a heart attack because of the speed and severity of the reaction

 

[dooby]

The events described in my previous post appear to be quite normal, it's just something I hadn't ever witnessed before and that I certainly wasn't expecting...the trials and tribulations of a neophyte

Anyway, the solution has become a bit more transparent, with a (thick) layer of (presumably) alkaloids on the bottom and the top... Some are still suspended somewhere in between, as if they can't decide whether to float or sink...

Pulls with warm/hot naphtha are on the way...

For those of you who can't be bothered to read the entire thread and are wondering why I've gone through the process of back-salting my naphtha pulls with vinegar: I do not own a freezer nor fumaric acid and thanks to vinegar I was able to save 600 ml of solvent from having to be evaporated...

PLUR

 

[dooby]

So I used a total of 200 ml of naphtha to pull from the solution and had it in the fridge overnight...
Crystals had formed and the basic solution had separated into a clear liquid with a bottom layer of alkaloids in it...
Naphtha from the fridge was decanted from the crystals and re-heated for additional pulls...
After a while, pulls didn't turn cloudy anymore upon release in the vessel containing the already-formed crystals but the basic solution was still very cloudy...
Having used the 200 ml I wanted to use for these final pulls (maximum amount I am prepared to let evaporate) I put the collection vessel back in the fridge...
I'll leave the basic solution as-is to see if more alks precipitate and try to pull again tomorrow...
Should this not change the solution's cloudiness I'll add a gram or so of NaOH and pull again...
I am glad I'm pulling from a clear solution (at least it should be clear when left undisturbed for a while, except a possible layer of precipitated alkaloids) because it allows me to see exactly how much stuff is still left in there
But the fact that after a number of pulls, additional pulls didn't have any effect anymore on the solutions cloudiness makes me wonder if there's some law of chemistry, physics or other that prevents 100% removal of the alks from basic solution through pulling with nps...

PLUR

 

[Mindlusion]

So I used a total of 200 ml of naphtha to pull from the solution and had it in the fridge overnight...
Crystals had formed and the basic solution had separated into a clear liquid with a bottom layer of alkaloids in it...
Naphtha from the fridge was decanted from the crystals and re-heated for additional pulls...
After a while, pulls didn't turn cloudy anymore upon release in the vessel containing the already-formed crystals but the basic solution was still very cloudy...
Having used the 200 ml I wanted to use for these final pulls (maximum amount I am prepared to let evaporate) I put the collection vessel back in the fridge...
I'll leave the basic solution as-is to see if more alks precipitate and try to pull again tomorrow...
Should this not change the solution's cloudiness I'll add a gram or so of NaOH and pull again...
I am glad I'm pulling from a clear solution (at least it should be clear when left undisturbed for a while, except a possible layer of precipitated alkaloids) because it allows me to see exactly how much stuff is still left in there
But the fact that after a number of pulls, additional pulls didn't have any effect anymore on the solutions cloudiness makes me wonder if there's some law of chemistry, physics or other that prevents 100% removal of the alks from basic solution through pulling with nps...

PLUR

Glad it worked out!

to answer your question, (I bolded it) You will never be able to 100% recover anything from a chemical system.

The law of chemistry/physics behind this is the law of chemical equilibrium.

For example, your acidic DMT solution is resting at an equilbrium that allows all the DMT to remain in solution.

When you add the base to raise the pH, your pushing the equilibrium far to the right, forcing the DMT to precipitate out of solution.

BUT, no matter how much base you add, when the system reaches equilibrium there will always be a small amount of DMT still in solution. You never reach 0. ( kind of like, 1, 0.1 0.01 0.001 0.00001 0.0000000001 etc.)

This same concept of equilibrium also occurs in the NPS extraction. The equilibrium in the basic rootbark solution, you will never be able to recover 100% of the DMT. If you keep adding fresh solvent, it stresses the equilibrium more and more forcing more DMT out of the solution. ( This is why we do more then 1 pull)

It also occurs with your solvent, It will be partially dissolved in your basic solution, but again, only a very small amount.

I hope I made some sense.

By the way, you can use this to your advantage. It looks like you used 350ml or so of water in your solution.

You can stress the equilibrium more by using less water! (Less room for the DMT) I typically use only 50mls of vinegar, and then add the saturated base solution until I get precipitate.

 

[dooby]

Thanks, that makes total sense...

One more attempt will be made though to pull more alks out of solution, there's just too many still in there... If this fails, I'll save this solution so I can combine it with future batches...

Would it be worth a try to put the solution in the fridge for a while, thus allowing the alks to settle at the bottom of the jar, then pour off some of the solution before pulling again? Or maybe pour all of it through a coffee filter and rinse with cold water?

Thanks again for the explanation...

PLUR

 

[Mindlusion]

Thanks, glad you gained something.

Yeah, time is essential. Leave it in the fridge for a couple days for the freebase DMT to crystalize.

Although, you can be pretty sure that you got 99.9% of the DMT, there is no sense in contaminating future batches for the sake of a few micrograms.

When the solution has turned from milky white to colourless clear. It safe to dump it. (typically 2-3 days)

Definitely pour it through a filter and rinse with cold water. Great idea. Although DMT can stick to paper, My best tool is a fine mesh sieve, these things are awesome!

NOTE: only use these 2-3 days since if rushed too early the crystals will be too small and fall through the sieve. But you know this, milky white solution means, DMT is still in it.

 

[dooby]

Cool, I was wondering if those steel mesh sieves could be of any use to me...thanks for confirming

It's been sitting in the fridge for 36 hours now... Solution is getting increasingly clearer with a quarter inch thick layer going around the sides of the jar (it has a slightly convex bottom)... Can't wait to see it on my scale as I'm too new at this to be guesstimating quantities...

PLUR

 

[dooby]

I bought a stainless steel tea filter because it has a finer mesh than the other sieves...

However, my attempt to filter the alks out of solution has failed...Upon moving the jar from the fridge to my workspace they had already gone back into solution making it cloudy again...

I shall pull with naphtha then...

 

[dooby]

I also figured out why pulling from the re-basefied vinegar is proving to be such a tedious process...

When doing my initial pulls my basic solution was warm/hot and my nps (which I thought to be pre-heated as well) had ample time to reach temperature equilibrium so the pulls were in effect warm/hot...

Now I want to pull from a cold/room-temperature solution and there is little decrease in cloudiness of the solution after each pull...

I figured out that the insulation provided by the jar/beaker my naphtha is taking its baths in is too high (jar is thick normal glass, beaker is thin borosilicate) so I am not sufficiently pre-heating my naphtha...

I do not have a thermometer so I would like some input from my fellow Nexians: how long should it take for 75 ml of r/t naphtha in a near-noiling water bath to be hot?

The borosilicate beaker can get to a point where the outside is almost too hot to touch, at this point its inside is still quite cool...

Any info would be greatly appreciated...

 

[Mindlusion]

Naphtha has a much lower specific heat density then water, so it should heat up to near boiling quite quickly, less then a minute.

I'm confused to why are you are doing this though, surely it will give you a better product.

When precipitating out of the basic water, the akaloids can be oily, and crystals quite small. but I was able to filter them even after only 4 or 5 hours. :?
The solution of course was still milky white, but I was able to recover most of the alks.

3 days later, the solution is clear I was able to recover the rest, and crystals were much larger.


Ive never had them go back into the solution, They just aren't soluble.

It could be due to impurities, or solvent. I used xylene last time.

You could try the precip again, maybe give it <48 hours this time.

 

[dooby]

I should have chosen my words more carefully, it didn't go back into solution, it went back into suspension...

That being said, I admit that I should have waited longer before attempting to filter out the alks...

I'm doing naphtha pulls right now so I can skip the re-x (if the crystals turn out to be nice and white) - if they don't I might go for an actived carbon cleaning...

I've seen some video about filtering through activated carbon and they put some diatomaceous earth on top of the layer of carbon then filtered through both... Does anyone have any experience with spice + diatomaceous earth? Any contra-indications?

 

[dooby]

Again, pulling doesn't seem to remove much of what I up to this point believed to be alkaloids...

Possible causes?
- something is wrong with my naphtha
- something has precipitated as a result of a side-reaction and it's insoluble in naphtha
- insufficient ionic strangth of the solution

Possible solutions?
- pulling with fresh naphtha
- adding NaCl to improve ioninc strength
- leave solution to settle, pipette off some of the top basic layer, then try pulling

All my initial pulls were also done with this naphtha, only much warmer/hotter than the pulls I'm doing now... Could this be related to my problem? Maybe I should try heating not only the naphtha but the basic solution as well...

PLUR

 

[downwardsfromzero]

The cloudiness might be from the vinegar/NaOH itself??

 

[dooby]

I have no idea yet, when left alone for a while, the solution turns clear and the cloudiness forms a white crystalline layer...

Whatever it is, it shouldn't be sodium acetate as this is colourless... Also the amount of sodium acetate that is soluble in water is bigger than the total amount of acetic acid and sodium hydroxide I used...hence it must be alkaloids