Update on 4th German NAN

Topic created by Nitritespecialist
on Fri, 18 Jun 2021 at 12:47

Nitritespecialist said on Fri, 18 Jun 2021 at 12:47...

It's been 5 days since I made my 4th German NAN. I have tested this brew every day.

Today it's very potent still. Odor is mild/nondescript still although I did add more Kcarb two days ago as I detected the sting of acid. It seems to have helped. I should note that I did NOT elect to rewash this brew after 24 hours, instead opting to add more Kcarb in the event acid developed.

Effects: the first whiff and you think....not gonna do anything cause the odor seems too mild to have any effect. BUT after 30 seconds, you feel it, the ass relaxes and your first erotic thought becomes amplified. More whiffs sustain the effects. It only takes a minute or two after the last whiff to regain total normalcy.

So....this is only my 4th German NAN, so it may be too early to call this method a win win, but it's looking very promising. It is my hope that others will try this method and report back their results.

Jacko said on Mon, 21 Jun 2021 at 00:40...

I'm giving this a crack today, albeit a variation combing n-butyl and mixed isomers pentyl alcohols. Will update once we've tried it out.

Jacko said on Mon, 21 Jun 2021 at 04:32...

Wow. Damn... this is some strong medicine!

Well done on adapting and publicizing the German method Nitritespecialist, I'm a convert. The product is great, but that aside I find that the prep method is better in a practical sense than acid/acid-alcohol addition, as for the first time ever no NO2 was produced and it was overall just a nice, easy to manage reaction.

Because of what I have on hand and my own penchant for tinkering, I didn't follow your described method to the letter, but am super happy with the results. Don't have kcarb handy so have just used baking soda and anhydrous mag sulfate, but these seem good enough!

The product is a lovely clear gold, sweet smelling, and very potent. The mix of n-butyl and amyl hits nicely and I'm looking forward to trying it out in the flesh (so to speak) soon!

justchem said on Mon, 21 Jun 2021 at 23:16...

I did exacly the same like @Jacko. Same results!
Not 100% potent BUT it stays potent and good smelling for much longer than other methods. Its a must for me because setting up the reaction every 2-3 weeks is not the best for me

Jacko said on Tue, 22 Jun 2021 at 08:42...

My thinking is that order of addition is fundamental to the result.

My observations from the method:

- Adding the nitrite salt solution dropwise to the acid/alcohol mixture forms no visible NO2, whereas this off-gassing is nearly unavoidable when the order of addition is reversed at the same temperature and stirring rate. With acid addition, this is partially mitigated by addition below the surface but I have never achieved no NO2 before trying this method.
- No NO2 formation means no obvious path for nitrogen loss from the mix (bar invisible N2 gas, which the reaction doesn't, to the best of my knowledge, support). No significant nitrogen loss means that it most likely goes into the ester, increasing nitrosation and thereby popper potency.
- Dripping the nitrite solution into the magnetic stirrer vortex enables very rapid and even dispersion of NAN into the mixture. I keep my stir rate medium/high, enough to form a vortex but not so much the stirrer is exposed. My concern is overstirring may force air into the mix and oxidize some nitrite to nitrate.
- With acid addition methods, solution pH is decreasing from a high towards a neutral value, whereas in the German method is is rising from very low pH towards neutral. My view is that these conditions may favor more stable or pure nitrite ester formation.

Thoughts and critique welcome. I know from experience that order of addition and direction of pH swing are essential to other precipitation reactions that I'm familiar with, so the above makes sense to me, but appreciate alternative views.

The Professor said on Wed, 23 Jun 2021 at 18:18...

@Justchem: @Nitritespecialist is not respecting the stoichiometry, as PopChef2 told him more than three years ago (when he was on another "Eureka" rant).

I think i posted the preferred ratios alc/acid/nitrite above, both for dropping acid preps and dropping nitrite preps.

Your prep, if you followed the OP, has quite a bit of unsatisfied alcohol. Get the stoichiometry right and you should be golden.

The Professor said on Wed, 23 Jun 2021 at 19:22...

@Jacko:

I'm glad you are having more success with the dropping nitrite preparation.

-NOx formation: dropping nitrite requires a stir rate fast enough to create a moderate vortex; the HNO2 has just been born of the HCL + NaNO2 when it is captured by the alcohol and forms a yield.

This method doesn't rely on a slow build-up of HNO2 (in an aerobic environment with a slow stir rate) as does the dropping acid approach, so it's a bit disingenuous to say that NOx liberation is greatly reduced; the two methods just have different preferred embodiments, and of course, if you charge the apparatus with one method in mind, and use the other, the outcome will no longer be preferred.

e.g.

A slow stir rate, and dropping acid at 0C or below at 3-4 seconds per drop will generate NO NOx. A fast stir rate, dropping nitrite at RT will also generate little/no NOx.

The downside there is that the prep will no longer be anaerobic, and Oxygen is more of a peril to the yield than NOx. NOx is a waste of Nitrite. Solution (if you are generating clouds of Nox) is to increase the stochiometry to account for your losses to NOx. Whereas, with the dropping nitrite prep, NOx is less of an issue, but the spinning walls of the vortex are introducing Oxygen into the preparation; right in the middle of it. and that's what I mean by shaping the prep to favor the desired outcome.

The most critical by-products and side reactions are:

considering isobutyl nitrite, for example:

1,1'-diisobutoxy-isobutane
2-methyl propanoic acid
butanoic acid
isobutyl acetate
isobutyl nitrate

The presence of some of these by-products is displacing the nitrite (the acetate and aldehyde of the alcohol, for example; it is no longer pure, so it will be weaker in effect. Other by-products, such as nitrate, actually increase the reactivity of the solution, but the physiological effects are harder to tolerate.

So, the dropping nitrite prep DOES manage Nox better than dropping acid at STP, but one can manipulate (PV)/t with the dropping acid aproach to minimize both NOx AND byproducts.

Take the analogy of trying to bowl a strike. You can do it with a wide open lane and open gutters: most balls will either be partial pins or gutter balls. You can also do it with a narrow lane and bumper guards, strike every time.

Considering pH: it's probably more valuable to think of the dropping nitrite approach as moving from low pH to undefined pH (rather than higher pH). I don't really care what happens in the effluent phase, but that's the phase that will have a meaningful measure, as it will contain water (the solvent in the entire prep). The yield phase (or emulsified phase) is slowly becoming anhydrous; pH is meaningless in anhydrous conditions; one would need to use Hydrogen probe to get readings that mean anything)

Why does this matter? for one; your observation that in precipitating preps your experience prefers a swing from low pH to high is constrained by the reactants in use; in organic chemistry, for example, DNA can tolerate low pH better than high. In general, the pH swing of a prep is determined by initial pH, temp and concentration.

This tells you that a nitrite dropping prep will start out low pH (due to the high concentration HCL) and become undefined (the yield contains no H2O). While a high pH condition may be repugnant to the nitrite, an undefined pH is its preferred state.

This also tells you that a dropping acid prep will start out relatively more basic (the pKa of nitrite is actually weakly acidic) and swing down to undefined)

None of this effects the BDE of the yield, or its purity IF either method is engaged in its preferred embodiment.

justchem said on Thu, 24 Jun 2021 at 14:25...

@The Professor : On another site PopChef2 said to me that he no longer following his posted stoichiometry.Aw he said it is a start up guide .
I told him that I use a ratio Alc/NAN/HCL :1/ 1.15 /1.1
So if like to share your ratios I will the grateful .
If you use more water for the reaction will it be still undefined pH at the end?
Is this the reason for using a little bit of NaCL salt on reaction ?(to keep water saturated and pH undefined ?)

Nitritespecialist said on Thu, 24 Jun 2021 at 15:23...

It's now 6-24-2021 and it's been 11 days since I made my German brew NAN. I elected not to do the second wash initially. Instead I merely added more Kcarb. But after about a week, I detected more of an acidic bite and harsher/slamming effects, so I did rewash in washing soda/baking soda/brine a few days ago and noticed an immediate improvement in both odor and effects. Today, I just sampled it and it's VERY VERY potent...increasing heart rate rapidly, relaxing ass and feeling pretty good. Has a more pungent odor....slightly sweet and somewhat akin to ether, but more mild and nondescript. I only added more anhydrous Kcarb after the second wash a week later. The MS4 doesn't seem to be necessary.

The ratios I am using for the German method are 12 mls amyl alcohol per 7-7.5 grams SN per 10 mls muriatic 31%. The SN concentration is 40%...roughly 4 parts SN to 6 parts water.

Nitritespecialist said on Thu, 24 Jun 2021 at 15:40...

Regarding sequence of addition: I have noticed a difference in product, both odor and effects, depending the sequence, even when the ratios/amounts are identical. The differences are fairly consistent, over the course of many preps. If the odor and effects vary with sequence, with no change of ratios/amounts, it's safe to say that the mixing sequence changes the product. It's also safe to assume that if a chemical product maintains its good odor and effects for a long time, with the use of known effective preservatives, such as anhydrous Kcarb or sodium carbonate, that the harvest was more pure than other brews that failed to preserve using the same post processing methods.

Nitritespecialist said on Thu, 24 Jun 2021 at 15:45...

@Jacko....When I perform the German method, I have only noticed orange nitrogen gas form during the beginning of addition. I use a glass flask surrounded by ice. Near the end of addition, I see a slight green cast, looking from above, indicative of blue nitrous formation, but this fades fairly quickly by harvest time. The harvest layer is typically hazy light yellow and the water layer is colorless/transparent to slightly hazy.

The Professor said on Thu, 24 Jun 2021 at 22:18...

@justchem: The preparation guides that PopChef2 has posted are intended to be a starting point, yes.

He no longer uses a batch or semi-automated batch procedure, also yes.

His guides have a section involving how to adapt the stoichiometry to both your embodiment, and the current state of your reactants.

If you are interested, bring it up to him; just ask for a new section in the prep guide to account for an embodiment that drops Nitrite instead of acid.

The post here that contains @Nitritespecialists 'recipe' is below 1:1:1 (the theoretical stoichiometry for perfect powder and stirring losses) which guarantees un-reacted alcohol, so it's guaranteed to NOT nitrosate the alcohol.

The Professor said on Thu, 24 Jun 2021 at 22:29...

@Justchem: asked

"If you use more water for the reaction will it be still undefined pH at the end?

Is this the reason for using a little bit of NaCL salt on reaction ?(to keep water saturated and pH undefined ?)"

Water is the solvent in the reaction; it's main purpose is to act as a heat sink via its mass. Ultimately, all the water ends up in the waste phase, as the yield is anhydrous (therefor having an undefined pH)

Salting out is another thing entirely, In a dropping acid embodiment, the reaction salts itself out with just a titch of excess HCL. In the dropping Nitrite embodiment the yield will still be slightly emulsified, and will separate by leaving it standing over the waste phase for about 15 minutes. Or, one could manually salt out the yield.

Nitritespecialist said on Fri, 25 Jun 2021 at 15:41...

My German NAN is now 12 days old...about 5 mls left in a 10ml bottle. Tested and it's VERY potent still with good odor....somewhat more pungent than first made...slight ether like odor. Does NOT sting the nostrils so assuming little acid in it. Stored at RT and only with a small layer of anhydrous Kcarb. Has had lots of air exposure and is still very potent. I even rewashed and redried it on day 7 and this did NOT kill it. It only made it better. It's safe to assume that this German method is producing a purer product and this is why potency and odor are maintained for much longer. I have used Kcarb, Sodium Carbonate, Activated alumina and MS4 almost always....but 99.9% of the time, I've been lucky to get 3 days tops in terms of potency and odor. So clearly the preservatives DO NOT work if the popper is not pure enough.

The Professor said on Fri, 25 Jun 2021 at 23:30...

@Nitriteaspecialist said:

"It's safe to assume that this German method is producing a purer product and this is why potency and odor are maintained for much longer. I have used Kcarb, Sodium Carbonate, Activated alumina and MS4 almost always....but 99.9% of the time, I've been lucky to get 3 days tops in terms of potency and odor. So clearly the preservatives DO NOT work if the popper is not pure enough."

It's not safe to assume that dropping nitrite results in a more pure yield. Before I moved to a vapor phase prep, I was using an acid dropping prep, and my yield was bristling with NO, potent as all get out, inflated the lung with each inhale, recovery was within a couple of minutes, and yield preserved for more than 3 months. It smelled slightly of ginger ale

The Professor said on Sat, 26 Jun 2021 at 00:02...

"Nitritespecialist said

"99.9% of the time, I've been lucky to get 3 days tops in terms of potency and odor. So clearly the preservatives DO NOT work if the popper is not pure enough.""

The only 'Clearly' is that clearly you can't produce a viable Alkyl NItrite via acid dropping. Those that CAN (at least in our corner of the interweb) get a mild and potent product that preserves for months.

This inverse prep method reminds me quite a bit of the (Adam's Family or Munsters) episode where the guy invents a new engine that gets outrageous MPG and produces no pollution, all in an engine the size of a suitcase.

Investors are lined up, until he brings out the muffler (a huge and heavy thing that negates all of the other benefits)

Case in Point.....have you bothered to measure the yield between each method?

I have.

In a preferred embodiment of the acid dropping method, I get an average yield of 135ml from a molar batch.

In a preferred embodiment of the dropping nitrite method, I get 105ml from a molar batch.

30% yield loss and identical product (for me, I don't really know why you fail so much)

As well as lysing yield, the constant re-introduction of the yield back into the reactant phase (via the slope of the vortex) is guaranteed to be producing acetate.

Jacko said on Sat, 26 Jun 2021 at 08:01...

@ The Professor, just curious, where does the acetate come from? I haven't heard of C5 (or other) alcohols breaking into smaller C-chains in aqueous acid reactiobs, but that said, this type of reaction is different to those I'm familiar with from work (dehydration, neutralization and metasthesis).

On yield, I'm fortunate enough to have a lot more reagents on hand than I really need (kilos and litres, respectively), so am less fussed with this if I have an easier prep method, but each to their own :-)

I will tweak stoichiometry next run and see if the product changes noticeably. Also noted about O2 in the vortex, any suggestions to counter this with bench scale kit?

@ Nitritespecialist, interesting that you still get NO2, I saw and smelled none in my last batch but will keep an eye out. This was what surprised me the most about the German method, though the explanation further up thread covers why. Did notice some blue flickers in the mix briefly when drops were added faster (manual teat pipette) but these vanished very fast.

Jacko said on Sat, 26 Jun 2021 at 09:33...

Further on equipment, a general question, can anyone suggest a piece of bench-scale glassware that has a port (or two) for addition of reagents but also a sealed lid to allow inert gas blanketing?

These are easy enough to find as 1L plus pilot scale reactors (though $$$), but I'd imagine a dmaller volume bench equivalent must exist?

Separately but related, would CO2 be an inert gas for the purposes of this reaction, or could carbonation have untoward effects? I'm just pondering the potential of dry ice as a cooling and gas source. If this is a terrible idea, let me know!

Nitritespecialist said on Sat, 26 Jun 2021 at 12:09...

@Jacko....I also some some blue "flickers" as you describe that quickly dispersed. I read once, in a drug journal, that adding CO2 to alkyl nitrites helped protect against unwanted side effects. You could probably use argon too...since it's heavier than air and might be more apt to create a blanket of inert gas over the reaction. Right now, my brews are lasting for so long, that I don't need to try something different.

The Professor said on Sat, 26 Jun 2021 at 17:17...

@Jacko:. High concentration HCL is just begging to react out almost completely dissociates in water... Lots of H ions floating around. Add atmospheric oxygen and yield hydrolyzing from sliding back down onto the vortex and voila, acetic acid. Acetic acid and butyl alcohol = butyl acetate.

By easier prep method, I'm not understanding what makes the acid drop and ice bath method more difficult?

IMO, the best way to minimize regurgitating yield back into the reaction, and to minimize side-reactions is too use a barely spinning stir bar, and drop nitrite instead of acid.

You could try covering the chamber with a cap of some sort, or a layer of argon, but you'll still be creating a sloping vortex that reintroduces yield (now mixed with argon). Argon is mostly insert, but my point is that I don't see a gaseous covering doing much in a dynamic system.

Sure, a 30% yield loss isn't much to an individual. My point there is, of current manufacturers don't even waste the raw yield it takes to properly neutralize the product, why would they invite even more yield loss? For them it's just a numbers game, minimize cost, maximize profit.

I'm not familiar with any glassware of the shelf for those requirements, sorry. There is a maker in our group that has started using dry ice for the bath, and is having good outcomes at -15C or so, but using a drop acid method.

The Professor said on Sat, 26 Jun 2021 at 17:37...

@Jacko: I gobbled that a bit.

By easier prep method, I'm not understanding what makes the acid drop and ice bath method more difficult?

IMO, the best way to minimize regurgitating yield back into the reaction, and to minimize side-reactions is too use a barely spinning stir bar, and drop ACID instead of NITRITE.

Jacko said on Sun, 27 Jun 2021 at 18:40...

@The Professor, due to the kit I have, I find measuring and dropping the acid multiple times a lot more fiddly, not to mention potential for spills. I'm using a glass 10ml bulb pipette and 3ml disposable pipette. Really need to upgrade to a proper burette on a clamp stand...

With the nitrite dropping method, I can measure, make up and freeze the acid/alcohol mix in a single batch and be done with it. Also, not making the NO2 is a plus.

The Professor said on Sun, 27 Jun 2021 at 23:25...

@Jacko; you might find a dropping funnel more useful than a buret; just charge it and let it drop.

NO2 will not evolve if the reaction is kept under 0C, and the acid is dropped under the surface (through the alcohol layer and into the water later).

Nitritespecialist said on Tue, 29 Jun 2021 at 15:27...

@Jacko....the most important thing is what are the traits of your finished popper using the various mixing strategies? That should point the way to the most preferred method. I encourage everyone to try the various ways and then decide based on the quality of the product alone. For me, adding 40% SN solution to the acid/alcohol seems to work much better in terms of product quality. I don't know why and I have not done it long enough to say it will work better using all brands and sources of reagents.

Jacko said on Thu, 1 Jul 2021 at 08:56...

@The Professor, thanks for the tip, I'll look into one of these. I'm guessing you can regulate drop rate by a tap or valve? This could actually be handy for some other things I'm working on as well.

@Nitritespecialist, so far I have found the nitrite dropping method is giving me a smoother product that is noticeably stronger when freshly made. Haven't had long enough to compare effects over time, though.

That said, from recent advice my acid dropping method wad a bit off track and could likely be improved! As to reagents, the area I could look at sometime soon is upgrading my SN if I can find a quality reagent grade at an acceptable price.