Nic Salts vs Freebase vs Hybrid

E-liquids General
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Hey ELR,

So up until now I was fully satisfied with Nic Salts as I was in an employment situation when I could vape whenever I felt the need. I’ve now moved on to shift work for a better pay rate and am finding myself getting massive cravings between breaks. I remember back when I was still on analogue and working shifts, a stinkie or two on break lasted long enough to keep me satisfied till the next break. I am wondering if anyone else can offer any insight in to what is better to get through the day with 2-3 hours between breaks. I’m always seeing Riot Squads Hybrid nic for sale online and am wondering whether that could be the key, getting the instant Nic Salt hit with the Nic Freebase in it being more slow release to get me through till the next break. It is quite important for me to solve this fast as there is only 1 other vaper on my shift and everyone else is still on analogue so I’m constantly around the smell on break and dont want to be tempted to go back to analogue to get through the day. Please help!!!

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It appears that - once the ~30 Minute (or so) delay of absorbing (base or salt) vaped Nic is taken into account, the (decreasing exponential) plasma-level curves are (otherwise) indistinguishable. Nic Salts merely allow for higher (vaped) doses to be tolerated by chemo-receptors (in mouth/throat/esophagus).

However, the “neuro-psycho-pharmacological” effects are likely less straightforward to predict (from systemic plasma-levels). In the 48 years that smoked ~30 cigs/day, I was desiring another dose by ~30 minutes following the most recent cigarette. Awake ~16 hrs/day, that comes out to ~30 cig/day, and the (non-accidental) quantity of ~200 (1 carton) per week. Something of a standard for industry marketeers.

Nicotyrine (which results from the oxidation of Nicotine) is thought to prolong the internal systemic metabolism of absorbed Nicotine - by acting to suppress metabolizing activity of (one of the) Intestine and Liver CYP enzymes that metabolize foreign molecules. Here is an interesting paper about that.

Mixing together fractions of Nicotine (a free-base with a salt-form) simply diminishes the “salt benefits”. I am able to tolerate 20 mg/mL (2%) free-base (NET juice (~20% NET flavoring in PG, 60/40 net PG/VG) when vaped at 5-6 Watts. Note that Nic only starts to appear in vapor droplets above ~170 *C (or so).

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I mix both sometimes using freebase and NicSalt. That is fine on short and midterm for me. Mostly I use a higher Nic percentage when I have longer periods where I can’t vape. That’s contributing more than mixing it according to my personal experience.

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@Raven-Knightly so although Nic Salts can deliver a higher dose faster, they will not oxidize into Nicotyrine, correct? This is definitely something to keep in mind towards the argument of Hybrid Nicotine, even keeping the Freebase concentration low around 1-3mg/mL in combination with a Nic Salt concentration of maybe 20-30mg/mL, just so the Nicotyrine forms in the e-juice allowing less frequent Nicotine cravings. I wonder if you can get Nicotyrine as an additive and if so how to work out a safe but effective amount to add directly to a Nic Salt e-juice. Definitely something I want to keep looking into.

Regarding mixing them as it diminishes the “Salt Benefits”, I have read of people mixing both to get the throat hit from the Freebase and the immediate hit from the Salt but there was nothing too scientific about it so I didnt think too much of it. But if they were using say, instead of a 50/50 mix, a 25mg/mL Nic Salt with 3mg Freebase for the throat hit it is possible that some of their Freebase would oxidize into Nicotyrine which would eventually make that e-juice more effective in sustaining satisfaction, with the only drawback of it being much less smooth. What’s your thoughts here? Really appreciate the response.

@SteveTC thanks for the reply Steve. Can I ask what strengths and ratios you have done mixing Hyrbid Nic? I’ve also just switched back from 25mg/mL to 50mg/mL, though may not be able to keep doing this till I get a more concentrated Nic Salt solution as this makes my mixes around 60-65% PG by the time I add the Nic and flavoring, not allowing much room for VG. This is the main reason I wanted to lower my Nic intake so I could get to 65% VG in my Nic Salt mixes. I’m probably gonna have to bit the bullet short term and have higher PG to keep the higher Nic content but would love to find that sweet spot where I can have higher VG as well as having that longer lasting satisfaction.

I currently do an 8 hour shift, meant to be 3 breaks but sometimes ends up only 2 as I work different hours to the other people on the same shift, they start like 2 hrs after me and finish 3 hrs later but everyone goes on break around the same time which usually means I’m going on break when they’re starting then going on my next break when they go for their first, then going home when they go on their second. Ideally I’ll get this sorted out so I get a 3rd break consistently which means I’d be able to have a break every 2 hrs instead of closer to every 3 hrs, but until then I’m stuck praying I can find a way to get high enough Nic satisfaction to last. Even then, every 2 hours is still a long time when I’m used to every 20-30 mins vaping.

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I use RTA and RDA, so probably a total different class with doing 3mg freebase and 3mg NicSalt. When I started I was on 24 mg freebase on a MTL and it was so harsh, so you have to keep that in mind.
If you want a higher VG you can buy your Nic or NicSalt also in VG. For example at Nicotine River.
Maybe you should consider an other more powerful device where you can vape more liquid and don’t have to go up so high in Nicotine levels in your juice

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Oxidation of Nicotine (for any and all various possible reasons) will form (some fraction of) Nicotyrine.

Referenced Paper:
Nicotyrine is usually not detected in e-liquids or e-cig aerosols, but was reported in an early analysis by the FDA. We found that this nicotine oxidation product accumulates in e-liquids over time, but only after exposure to air.

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… the nicotyrine to nicotine ratio (NNR) in particle phase as a function of the duration of e-cig activation. An aging experiment determined the NNR in e-liquids and aerosols as a function of time since initial exposure to air and storage condition.

Results: Nicotine and nicotyrine were quantified in all 3 e-liquids and aerosols. Duration of e-cig activation was inversely related to NNR (NNR = 0.04 with 3-s activation, 0.26 with 0.5 s). Aging influenced both e-liquid NNR and aerosol NNR. On average, the e-liquid NNR increased from 0.03 at 11 days after opening to 0.08 after 60 days. For similar heating durations, aerosol NNR increased from 0.05 at 11 days to 0.23 after 60 days. Storage conditions had little effect on NNR.

Conclusions: E-cig aerosols have variable nicotyrine quantities. Aerosol NNR depends on vaping technique and time elapsed since the e-liquid was exposed to air.

Source:
“On-Line Chemical Composition Analysis of Refillable Electronic Cigarette Aerosol - Measurement of Nicotine and Nicotyrine”

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Various salts of Nicotine form different ratios (on a molar quantity level) of Nicotine and the particular Acid used. JUULs use Benzoic Acid (ratio is 1:1 in that case). One could use free-base Nicotine (added to a presumably “balanced” Nicotine Salt brew) for reasons of taste perceptions - but that seems a bit different from your initial concerns. The absorption characteristics (may) not differ much between the spectrum between 100% free-base-form and 100% salt-form. My impression is that the effects are (primarily) ones related to “taming” perceived chemo-receptor (mouth, throat, esophagus) “irritations”.

From what I have read, free-base Nicotine is generally somewhat better absorbed than Nic Salts.

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@SteveTC I will definitely give it a go, I started out on sub-ohm with 6mg/mL Freebase but once I tried Salts I never looked back. Also love how portable the small devices like Uwell Caliburns ect are.

@Raven-Knightly it was more in my line of thinking that since Salts are stable they wouldn’t oxidize into Nicotyrine, is this incorrect? If so then that is good and I wouldn’t worry about mixing Salts and Freebase to try get the Nicotyrine, but since Salts are stable I was under the impression that the change wouldn’t occur. That is assuming that my Nicotine Salts are already Salts and not Freebase + Benzoic that doesnt form salt till its heated up. I only have a slightly beyond basic understanding of Chemistry and the likes so you’re definitely more qualified to answer than myself.

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The contents and chemical characteristics of e-juices are complicated by their various ingredients present. (In general), making (loosely-bound) “salts” of Alkaline molecules in solution with Acidic components can potentially “stabilize” the Alkaline molecule of interest - including reducing the rate of Oxidation. Chemistry in practice is a (very highly) empirical science built upon valid prior observations under certain specific conditions. (Probably), too complex to make reasonable speculations about. A (loosely-bound) “salt” in solution (at a given Temperature and Pressure) has certain characteristics. At some (higher than room/atmospheric) temperature and pressure, thermal decomposition begins (and will be different, depending on the sum of all included components). Very hard to generalize about these complicated solutions with any confidence. Probably best to slowly change (just) one variable at a time.

Nic Salts (by design) have to operate from (room to hundreds of degrees) Temps. They remain “salts”.

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Disclaimer: I am by no means a “chemist” (my background is more one regarding electronic design).

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Another paper reporting measured Nicotine and Nicotyrine components (in e-juice and vapors):

“Evaluation of E-Vapor Nicotine and Nicotyrine Concentrations
under Various E-Liquid Compositions, Device Settings, and Vaping Topographies”

Factors Affecting E-Vapor Nicotine and Nicotyrine Levels

VG-based e-liquids emitted 8.0- and 10-fold more nicotine and nicotyrine, respectively, than PG based e-liquids. In general, the amount of nicotine in e-vapor was proportional to the e-liquid nicotine concentration. e-liquids containing 12 mg/mL nicotine generated a significantly higher amount of nicotyrine than e-liquids containing 3.0 mg/mL nicotine (p < 0.001), while e-liquids with 12, 24, and 36 mg/mL nicotine showed similar nicotyrine production. On average, the nicotyrine/nicotine ratio for e-vapor was 5.7-fold higher than that for the corresponding e-liquid. …

… A longer puff duration increased e-vapor nicotine and nicotyrine levels. A 3.8 s puff generated 3.3 to 6.9-fold higher nicotine and 9.6 to 12-fold higher nicotyrine concentrations than a 2 s puff (p < 0.001).

… Nicotyrine can be formed during e-liquid preparation through the reaction between nicotine and air. In our study, we found that the nicotyrine/nicotine ratio of high-purity nicotine solution was <0.01, and the nicotyrine/nicotine ratio was 0.01–0.02 for freshly made e-liquids in our lab. Another study indicated that exposing e-liquids (PG:VG mixture with 18 mg/ mL nicotine with tobacco flavor) to air increased nicotyrine/ nicotine ratio from 0.03 to 0.04 to 0.08–0.09 after 65 days. The air flowing through the sample filters facilitated nicotyrine formation, and we observed a linear relationship (r2 = 0.802) between the nicotyrine formation and the volume of air introduced. …

… nicotine and nicotyrine concentrations in the e-vapor were determined by e-liquid base materials and nicotine levels in e-liquid. … VG and PG and VG-based e-liquids generated significantly higher amounts of nicotine and nicotyrine than PG-based e-liquid. … Larger puff volumes increased e-vapor nicotine and nicotyrine concentrations. More air flowing through e-cigarette coils facilitates the evaporation of e-liquids. In contrast, we observed that lower puff volumes facilitated nicotyrine formation by changing the retention time within the cartomizer. Increasing retention time provides a longer reaction time between nicotine and the air around the cartomizer, leading to higher levels of nicotyrine formation. … The thermal decomposition of nicotine to nicotyrine is temperature dependent. Between 200 and 400 °C, the nicotine to nicotyrine conversion efficiency is proportional to temperature increase. However, above 400 °C, the nicotyrine yield is significantly decreased with increasing temperature. …

… The pH value is a critical factor that changes gas/particle partitioning of nicotine and its absorption. The measured e-vapor pH values were between 8.09 and 9.52. This coincides with reported pH values that ranged from 7.3 to 9.3 for e-liquids containing 6.0–24 mg/mL nicotine and other flavors, while e-liquids without nicotine showed much lower pH values (5.1–6.4). At basic conditions (pH ≥ 8), nicotine (p K a = 8.02) is predominantly present in its unprotonated form (Nic), which facilitates the absorption of nicotine through biological membranes In addition, only unprotonated nicotine can be vaporized into the gas phase, which increases deep lung deposition. …

Note: The formation of “Nicotine Salts” lowers the pH of the e-liquid solution (relative to free-base).

… It is likely that e-cigarette vaping could deliver a significantly higher amount of nicotyrine than conventional cigarette smoking. Previous studies reported that experienced e-cigarette users change their vaping patterns (e.g., number of puffs, e-liquid nicotine concentration, device power output, and vaping topography) to achieve similar levels of plasma nicotine as conventional cigarette smokers. Given the same nicotine intake, e-cigarette users can be exposed to 2–63 times more nicotyrine than conventional cigarette smokers because the nicotyrine/nicotine ratio for e-vapor and the combustion tobacco smoke ranged from 0.025 to 0.202 and from 0.003 to 0.013, respectively.

Nicotyrine in e-vapor might indirectly help e-cigarette users to take fewer puffs to satisfy their nicotine craving, leading them to inhale fewer potentially harmful chemicals emitted from e-cigarettes. Nicotyrine inhibits human cytochrome P450 isoforms (i.e, CYP2A13 and CYP2A6) slowing serum nicotine metabolism, thus increasing nicotine’s biological half-life. …

… Measured nicotyrine concentrations in our study were shown to be 5–40 times lower than that of nicotine. … it is not currently possible to determine whether the measured nicotyrine concentrations in e-vapor are sufficient to inhibit nicotine metabolism because, to the best of our knowledge, there are no studies on nicotyrine absorption and distribution through the human airway. …

… this study measured nicotine and nicotyrine concentrations in e-vapor under real-world vaping patterns. Higher e-liquid nicotine levels, higher device power settings, and larger puff volumes contributed to higher amounts of nicotine and nicotyrine emissions. Nicotine levels in e-vapor observed in our study were lower than or comparable to nicotine levels in cigarette smoke, while the observed nicotyrine concentrations per unit amount of nicotine emission were significantly greater than that of cigarette smoke.

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The Difference

As you probably know by now, nicotine salts are essentially nicotine compounds in their purest forms. While freebase nicotine goes through a process of chemical modification, nicotine salts are extracted straight from the tobacco plant and combined with benzoic acid. This combination allows the e-liquid to vape at low temperatures and not give users that unpleasant harshness that can ruin a vaping session. Therefore, these two types of nicotine are very different in terms of their molecular compositions. And, it’s known that salt-based nicotine is far more stable than its freebase counterpart, which is why many users find that pod-vaping is generally more consistently enjoyable than sub-ohm vaping.

When You’ve Left E-Liquid to Sit

Interestingly, salt nic e-liquids oxidize at a slower rate than freebase nic e-liquids. That’s because nicotine salts are more stable, meaning they don’t break down as quickly. In other words, your salt nic vape juice won’t evaporate as quickly as your vape juice that’s made with freebase nicotine.

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Freebase nicotine is pretty basic, says Thomas Eissenberg, a health psychologist at Virginia Commonwealth University - as in, it has a pH much higher than 7. Regardless of whether a substance is acidic or basic, the farther away from 7 it is, the more corrosive it’ll be; freebase nicotine has a pH of around 9, and household bleach has a pH of about 12.5. While our lungs can take in some freebase nicotine, after a while they need a break. So the tobacco industry found another way to make nicotine easier to take in: turning it into a salt.

Salts, chemically speaking, are made of two components with positive and negative charges - opposites that attract, keeping them stuck together. In the case of nicotine salts, the nicotine molecule has an extra positively-charged hydrogen ion (or proton) tacked on, giving it a pH closer to neutral 7. This protonated nicotine, used in most cigarettes, will still make you cough, but it goes down smoother.

The first e-cigarettes that hit the market in the mid 2000s contained freebase nicotine - the same harsh substance commonly used in cigars and pipe tobacco. But soon, vape manufacturers started capitalizing on the smoother nicotine salts.

Juul was one of the first companies to get on board. As the Verge reported back in 2018, Juul founders caught wind of the nicotine salt trick as early as 2013 - two years before they started selling their e-cigarettes (technically, the first company to use nicotine salts was British American Tobacco, whose vapes are known as Vuse). The startup patented a way to make protonated nicotine with any of a number of carboxylic acids. On its pod ingredient list, Juul states that it uses one called benzoic acid.

Source: https://qz.com/1723861/changing-the-nicotine-in-e-juice-could-curb-teen-vaping

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