Malic, Citric, Ascorbic Acids and Triethyl Citrate

[cammelspit]

Ok, guys, I have a few questions some of you smart people might be able to help me with. So, I decided to finally go and buy some souring agents. I bought some Malic, Citric and Ascorbic acids in powder form in relatively small amounts for very very cheap. My plan here is to try and test out using these in my DIY juices. I have been vaping my own DIY juice exclusively and haven't bought pre-made juice in about three years now.

I guess what I really need here is some advice on how to start. Here is my plan... I plan to mix approximately 1gram of each of these acids per 10ml of PG using 30ml bottles. I then plan to start with a 0.5%-1% concentration each in their own 30ml test batch using the same green apple flavoring I ADORE and have been using for a while. A sour apple flavor sounds too good not to make if I can nail it. I then plan on taking these mixes and further mixing them in a fourth 30ml bottle while keeping track of the ratio until I find a flavor balance I like. Does this sound like a reasonable method here? Does anyone have any specific information or personal experience with these additives and can help shed some light?

My biggest fear is that I have heard a large portion of Ascorbic acid oxidizes and you lose 50% of it or more in the vaping process. I mean, I actually use a pretty low wattage, typically around 35 watts, in my favorite RTA almost all of the time. These acids were really cheap anyway so if I end up not being able to use one or even all of them in my recipes it doesn't bother me as I can just make some sour gummy worms with my son anyway.

The other big thing is the Triethyl Citrate. I know it kills plastic clearos and such but all my stuff is glass. I also know it is very commonly used in commercial juices to make essential oil emulsify. Any recommendations on concentrations? My main reason for getting some was because I have one flavor that's is really good but it always separates out after an hour or so and increasing my typical 5% ethanol I always include for thinning to as high as 15% doesn't seem to help. My biggest concern here is there is essentially zero info out there on this stuff. I have read that it could even be used in place of PG because it doesn't have that throat hit, which I hate so this is enticing to some degree.

THoughts, comments, links, anecdotes, I will take all of it and anything else you feel is remotely relevant. I intend on experimenting here this weekend and was hoping for some advice and such regarding a starting point here.

Sorry for the wall, I tend to always ramble when I post online. Thanks in advance for any insight you may be able to provide!

 

[dannyv45]

It sounds to me like you have a very solid handle on what your mixing. Any crystal/solid (Menthol, Malto etc..) I've ever done was always a 10% concentration. Which would be basically what your doing (1ml crystal in 9ml solution (PG/alcohol) then just start adding that mixed concentrate at 1% to a mix and work up until you reach your desired strength. So I'm pretty sure this holds true for your sour materials as well. If your indoubt about the final strength (Maybe being to overpowering at 10%) start with 5% concentrated solution. I would mix the plastic killers in glass bottles for long term storage. Other then that it sounds like you have things under control but as with everything in the DIY community every days a new learning experience so don't be afraid to experiment.

Failure is nothing more then another learning opportunity.

 

[dc99]

Triethyl Citrate is an emulsifier and I have read a few times that it truly helps with flavors that dont blend well. I know some people use it to thin there mixes. The problem with malic and citrus acid is getting the sourness to transmit to vapor. Ive been chasing sour for a very long time. No matter how much I have tried (% wise) I have never got sour. A little tart but never sour. Unlike "sweet" when it is vaporized it seems to bypass your receptors and leave you with just a bit of tartness and nothing more. I wish you luck and if you do succeed please inform us.

 

[cammelspit]

Hey thanks, I was a little concerned honestly. Even though I have been mixing for years, I have never done anything like this before. I always stick to pre-made flavorings, PG and VG with a little vodka for thinning and that's it. If I do come across any insights though I will be sure to post about it.

 

[IDJoel]

I plan to mix approximately 1gram of each of these acids per 10ml of PG using 30ml bottles. I then plan to start with a 0.5%-1% concentration each in their own 30ml test batch using the same green apple flavoring I ADORE and have been using for a while. A sour apple flavor sounds too good not to make if I can nail it. I then plan on taking these mixes and further mixing them in a fourth 30ml bottle while keeping track of the ratio until I find a flavor balance I like. Does this sound like a reasonable method here?

Your plan sounds reasonable. I also agree with Danny's math of using a 1part+9parts=10parts ratio to achieve a 10% solution. As you wrote it, "1 gram in 10mL," will only produce a 9.091% solution.

My biggest fear is that I have heard a large portion of Ascorbic acid oxidizes and you lose 50% of it or more in the vaping process. I mean, I actually use a pretty low wattage, typically around 35 watts, in my favorite RTA almost all of the time.

I don't know what you have available in the way of hardware; but, perhaps, using a temperature controlled device might(?) be more informative/controlled. Wattage, in and of itself, is not particularly informative. Temperature will fluctuate based on resistance, mass, and duration when constant wattage is applied.

Temperature (I am guessing; I am no chemist/physicist) is one of the hurdles to getting "sour" from these acids. All three having boiling points higher than we (safely) vape at. What doesn't get boiled off; remains behind, and contributes to clogging wick & coil.

These acids were really cheap anyway so if I end up not being able to use one or even all of them in my recipes it doesn't bother me as I can just make some sour gummy worms with my son anyway.

Another use for your bulk acids, if you end up with a lifetime supply of gummy worms; is as a household cleaner. Citric acid (I haven't tried Ascorbic, or Malic) is great for removing hard water stains.

The other big thing is the Triethyl Citrate. I know it kills plastic clearos and such but all my stuff is glass. I also know it is very commonly used in commercial juices to make essential oil emulsify. Any recommendations on concentrations? My main reason for getting some was because I have one flavor that's is really good but it always separates out after an hour or so and increasing my typical 5% ethanol I always include for thinning to as high as 15% doesn't seem to help. My biggest concern here is there is essentially zero info out there on this stuff. I have read that it could even be used in place of PG because it doesn't have that throat hit, which I hate so this is enticing to some degree.

I also don't know anything about Triethyl Citrate. I would be most concerned about inhalation safety; and start my research there. Low percentage usage (as an adjunct) may be different than as a high(er) percentage carrier. I know some use PEG400 as a PG substitute. Perhaps that would be worthy of further research too (though I have know idea how it behaves as a solvent/carrier).

THoughts, comments, links, anecdotes, I will take all of it and anything else you feel is remotely relevant. I intend on experimenting here this weekend and was hoping for some advice and such regarding a starting point here.

The other question I have regarding obtaining "sour;" is does the presence (and the percentage of) nicotine affect the souring effect of these acids? It is fairly common to use Citric acid to balance pH and create nicotine salts by reacting with freebase nicotine. What I have never heard anyone discuss is if this reaction reduces the potential sour affect.

Perhaps, since you are willing to experiment; you might try a few side-by-side comparisons of "with nic" vs. "without nic," to see if/how much nicotine impacts the ability of the acids to provide sour.


And, as a final side note; I have just recently come across this article on acids and souring for food use:
http://www.bartek.ca/pdfs/BulletinsMalic/Improving the Flavor of Fruit Products with Acidulants.pdf
I found the sourness comparisons interesting. I have no idea if/how it might apply to vaping; but I still thought it worth a gander.

I am eager to see what comes from your experiments; thanks for taking the time to experiment and share!

 

[cammelspit]

Yeah, the only thing I am waiting on now is the 30ml bottles I got for the experiments. I only have 100ml bottles on hand right now since that is my preferred size for everyday carry. I would be more than happy to do some zero nic, low nic, high nic comparisons as well, seems like a good idea to me. Initially, I intended to do some PG only zero nic tests just for my own sanity as a baseline that is easier to get accurate than my typical 70/30 VG/PG mixes. Plus the fact that I am getting kinda low on VG and have been lazy about ordering more.

As far as hardware is concerned, I do have a TC device so temp controls should be easy to manage with a quick coil job. I am only using my Kanthal right this second because I have a metric .... load of it sitting around. I have both titanium and stainless wire on hand so shouldn't be an issue since I am getting close to needing a new coil anyways.

Hopefully, my bottles come in before this weekend because I am kind of chomping at the bit to get started messing around with this here.

 

[cammelspit]

UPDATE: Just got my bottles in a few hours ago. Sadly, I don't think I will be able to get to my experiments in earnest today. I also found that some ejuice flavors that are tart use Tartaric acid in them. Tartaric acid is very readily available because it is used in winemaking to adjust PH levels. It is also rather cheap from what I have been able to find online. I wonder if I will be buying a fourth souring agent and further increasing my dataset. I should have some usable notes and such by next weekend as long as I don't increase the complexity of my tests too much. I just didn't want anyone curious about this stuff thinking I have abandoned you guys or anything, especially if it takes a while longer to get usable data.

 

[cammelspit]

Ok, guys, I have some VERY interesting findings to share. I went and decided on 1G each of the three acids Citric, Malic, and Ascorbic all being dissolved in 10ML of PG. Unfortunately, these acids are not very soluble in PG. Not one of these was able to fully dissolve into PG at these concentrations. I used hot water in a bowl to try and get them to dissolve more but unfortunately, they simply won't do it. All three acids are almost insoluble in VG entirely. Because I am a little crazy, I decided that I would taste the solution, this is after they have been allowed to sit and any undissolved acid has sunk to the bottom meaning they are absolutely at the tip top level possible in solution. Turns out, all three taste quite sour in their different yet similar ways. After this, I decided to up the crazy factor a bit and vape these juices that were fully saturated directly in a dripper and here is what I have found.

I used my old plume veil dripper with a brand new dual 8 wrap, 28guage, 3.5mmID, SS316l arrangement. I had my RX 2/3 set to the built-in SS mode, 200c, and 40w max output.

Ascorbic Acid
Mild Sour.
Least soluble in 100%PG.
A good half of what I put in there simply settled out at the bottom of the bottle.
Very noticeable as being sour for sure but even tasting this acid straight out of the package as the pure powder wasn't overwhelmingly sour and gave the taste of sourness without the lip-puckering effect.

Citric Acid
Reasonable sour.
Mediocre solubility in 100%PG.
Perhaps half the amount of this acid was left sitting at the bottom of the bottle compared to Ascorbic acid.
has a very strong sour flavor both in raw pure powder form and when dissolved at this concentration in this juice when tasted directly on the tongue. When vaped, this gives me the distinct impression I am tasting but a bland lemon. This is the best overall performer in the amount of sour that makes it into your mouth when vaped.

Malic Acid
Essentially no sour at all.
Most soluble in 100%PG.
Malic acid, when tasted orally and directly, has a very different kind of sour taste. I now know what people will call citric acid "sour" and Malic acid "tart" but it is hard to put into words. With this acid very little was left in the bottle to settle out but there was still some there. When vaped, there was almost no sour at all and if you had asked me on a scale of one to ten how sour this was, I would say 1 for almost undetectable sourness. Oddly, on a whim, I decided to pair this drop for drop with my much-loved apple flavor juice and the whole experience changed. It made the apple flavor taste more like a REAL apple. It was as if I bit right into a real granny smith apple right there. So this is certainly doing something to the flavoring here but I can't be sure exactly what yet.

So, I then got kind of disappointed with these results and decided to go on a research kick and see if there was anything I could find at all about what was going on here. I have a hypothesis that will need much greater testing here to confirm. I think it's all about solubility. The one acid I expected to perform the worst is the Ascorbic acid but in reality, it was totally there in the final flavor just a tad subdued. Seeing as Ascorbic acid is the least soluble in PG, the actual fully saturated solution has less than 5% by weight, probably closer to 3% or 4% max or by volume this equates to MUCH less than even that. I just don't think enough can be dissolved into the solution to give a good sour taste while vaping. Remember, when we vape something it is atomized very well and the actual amount of liquid that would come into contact with our tongues is extremely low overall. So the question here is how EXACTLY to we get more to dissolve into solution?

I have some ideas. First off, it seems that water, plain old water is the BEST thing you can use to dissolve these acids but they also become rather unstable when you do so. Alcohol apparently can be used to dissolve much more than PG based on a few research papers I found. I mean, the math and all was WAY above my pay grade but the general conclusions here lead me to that conclusion. Apparently, Ascorbic acid, in particular, has had the most solubility research done one it, I mean, it is vitamin C after all and is super common to see added to all sorts of things. The paper I read mentioned that water can be present at up to 12% by weight without the acid becoming unstable and breaking down over time too quickly. PG is apparently incredibly stable but can't carry much in it. Pure 100% ethanol has none of the issues water solutions have but doesn't really resolve the problem that PG has but it does to a much better job at it. These same conclusions all seem to have been arrived at with all other information I was able to glean with regards to both citric and Malic acids as well, obviously with differing percentages and such but still, pretty darn close.

So, here is my new plan! I am going to attempt an aqueous solution of approximately 10% by weight of distilled water, approximately 40% pure grain alcohol such as everclear, and the rest being PG. I will then try adding tiny amounts of each acid in as small a quantity I can until I find they are in a fully saturated state. From there, hopefully, I should be able to about quadruple the solubility of the acids based on my layman's understanding of what little information I could get. If I can get to that concentration we should be great with a much much more sour concoction. The only issue I see is diluting it further with a PG/VG mix will surely leave it less sour so I may end up having to use this solution be entirely the replacement for PG in my final mix.

The way I see it, I don't need to have warhead sour or even lemon head level sour for that matter, I only need a reasonably capable sour note because it's not like I am going to make a sour only recipe in the same way I would for a menthol one.

Any thoughts or suggestions you guys can come up with? I spent a good two hours today painstakingly measuring the weighing the powders and PG just to come up more or less empty-handed and if anyone can think of anything here I am all ears.

Again, sorry for the wall.

 

[IDJoel]

Any thoughts or suggestions you guys can come up with? I spent a good two hours today painstakingly measuring the weighing the powders and PG just to come up more or less empty-handed and if anyone can think of anything here I am all ears.

That sounds like a lot of work! Thanks for reporting you initial results. I am going to need to reread it a few more times before I can even think if I have anything pertinent to say.

I did want to get this out quick, hopefully before your next round:

1.) Watch your simple math; I think(?) you are still calculating wrong. 1 gram acid, plus 10mL PG (10.38 grams) is providing a total of 11.38 grams. 1 divided by 11.38 equals 0.08787335... or 8.787%. That is an unusual target. I am guessing you were trying for 10%. I realize it doesn't matter in this instance because none of your three trials fully dissolved. But, if it had... and you reported findings for a "10% solution", that would have been erroneous.

2.) Try powdering your acid crystals. I have only very limited experience trying to use Citric Acid; but I found if I put the CA crystals in a zip-lock bag, and then rolled them (rather aggressively) with the kitchen rolling pin; I could reduce them to a very fine powder... almost like powdered sugar. This powder seemed to dissolve much better/faster in the warm PG than the larger crystals did.

3.) How long did you wait before pronouncing them supersaturated? I fiddled around with my sorry CA attempt, for about a week, before I threw in the towel (I couldn't get it to dissolve either). But, I didn't toss the solution, and it remained on my desk. A couple of weeks later, I happened to look at it, and all visible CA was gone! It just t o o k a r e a l l y l o n g t i m e.

So, if you still have those first testing samples, you might want to park them for at least a month, just to see what (if anything) more, will dissolve.

Good luck with round two; and thanks again for sharing your findings.

 

[stols001]

Thanks for your update (including tasting it) very interesting findings. I don't think you are the first to have trouble dissolving these concentrates into a solution, I know (at least with citric acid) some folks use a bit of heat (judiciously, you don't want to overdo it) although it sounds as if, from IDJoel's thoughts ,that time may work just as well (without worry of degradation of the contents) like many things in DIY.

I hope you're able to fine tune the process for yourself, but really interesting findings, thank you

Anna

 

[madstabber]

You may need to give them more time to dissolve. I use ethyl maltol(crystals)in my mixes and it usually takes a week or so for them to dissolve. I don’t use heat I just shake occasionally but within a week I usually don’t see any crystals left. Good luck with your experiments and thank you for sharing what you’ve learned.

 

[cammelspit]

1.) Watch your simple math; I think(?) you are still calculating wrong. 1 gram acid, plus 10mL PG (10.38 grams) is providing a total of 11.38 grams. 1 divided by 11.38 equals 0.08787335... or 8.787%. That is an unusual target. I am guessing you were trying for 10%. I realize it doesn't matter in this instance because none of your three trials fully dissolved. But, if it had... and you reported findings for a "10% solution", that would have been erroneous.

Believe it or not, I did this entirely intentionally so I will try to explain my reasoning. Firstly, I needed to start with a simple and reproducible amount. The decision I had to make was to go 10% by weight or by volume and I chose weight. But if I measured the PG by weight then I would be overflowing a 10ML bottle because of course, I didn't think it through well enough beforehand. SO I figured if anyone else wanted to reproduce this, they could just put one even gram of powder and top off a 10ML bottle. It was more of an ease of replication thing.

2.) Try powdering your acid crystals. I have only very limited experience trying to use Citric Acid; but I found if I put the CA crystals in a zip-lock bag, and then rolled them (rather aggressively) with the kitchen rolling pin; I could reduce them to a very fine powder... almost like powdered sugar. This powder seemed to dissolve much better/faster in the warm PG than the larger crystals did.

I can try powering them a lot farther. I actually have more than one coffee grinder so it might be worth it to just run it through that for a minute or so to really powderize it. I considered this as an option right off the bat but decided it wasn't worth it to have to clean the grinder really well four times in a row. Besides, the stuff i got is very fine grained and not very crystal-like. I can maybe try it out though because anything that can help is a good thing in my book.

3.) How long did you wait before pronouncing them supersaturated? I fiddled around with my sorry CA attempt, for about a week, before I threw in the towel (I couldn't get it to dissolve either). But, I didn't toss the solution, and it remained on my desk. A couple of weeks later, I happened to look at it, and all visible CA was gone! It just t o o k a r e a l l y l o n g t i m e.

So, if you still have those first testing samples, you might want to park them for at least a month, just to see what (if anything) more, will dissolve.

Good luck with round two; and thanks again for sharing your findings.

Ok, so this one surprises me a lot here. I waited a good two hours with shaking every five minutes or so for all three tests. A whole week? I haven't thrown them out and have no intention of ever doing so until I am 100% sure I am never going to try this again. I have let experiments in the past sit for several months before I finally needed the bottle back, hoping that somehow the extra steeping time would mellow out a flavor I didn't like or change it somehow for the better. Bottom line, even zero nic with just PG, of which I have almost a gallon still left, I just don't have the heart to toss anything out unless I absolutely have to.

At least I know these will be somewhat useful even if I can't get that decent sour taste I am searching for. Especially the Malic acid gave a completely different flavor profile to a flavor I am very familiar with. Ascorbic is supposed to be good as an antioxidant so that could help keep flavors more shelf stable for longer-term storage, especially those that use natural flavorings instead of artificial flavoring.

I won't be defeated this easily for sure, I just didn't realize this was going to be more of a battle. Now that I spent the few bucks on the acids and I have a better idea of what I need to achieve, I am more motivated to find something that will work well enough.

I will keep you guys posted on any developments as they happen. Thanks!