German method Plus is working well

Topic created by Nitritespecialist
on Mon, 24 May 2021 at 14:06

Nitritespecialist said on Mon, 24 May 2021 at 14:06...

7 weeks after starting the German method plus adding a secondary sodium carbonate wash 24 hours later, all brews have aged well with nondescript, noncaustic odors and potency is maintained, even when stored at RT for 7 weeks and exposed periodically to air. All brews have been stored on a layer of Kcarb and MS4 as well.

Nitritespecialist said on Mon, 24 May 2021 at 14:12...

The primary difference between this method and others is the sequence of addition....the sodium nitrite solution being added last, and the additional, secondary wash/rinse/dry cycle 24 hours after the initial preparation. There are many patents describing various methods for making alkyl nitrites. The German method is recent, dating to 2008. The chemists explain the advantages of their method.

Canuck SB said on Tue, 25 May 2021 at 00:47...

@Nitritespecialist Dude i love reading your posts,the information you take time to give us is just efn awesome thanks for taking to time sharing these techniques your much appreciated good sir!!!!

Nitritespecialist said on Tue, 25 May 2021 at 15:26...

@SB...you are welcome. Ultimately, I hope my posts help others to make good poppers that last.

P.S. I just tired the most recent NAN brew....now 8 days old, stored around 45F in the frig and used/tested a handful of times. It still is plenty potent with noncaustic, nondescript odor. It seems like the anal effects are even improved above where it started 8 days ago.

I do encourage any home brewers to try the German method PLUS. I cannot guarantee everyone will have the same results, given we are not likely to be using the exact same reagents, same lots for example. But there still might be noticeable improvement, especially in duration of potency and a low, noncaustic odor.

s0079376 said on Fri, 28 May 2021 at 15:27...

@nitritespecialist Thanks for all your info I really appreciate it. I am curious if you have done any research into the link between nitrites and hemolytic anemia. I know that when I use OTC poppers these days I often experience several days of extreme fatigue, muscle weakness, shortness of breath etc which all correspond to symptoms of anemia. Do you experience any of these with your home brews?

Roger said on Fri, 28 May 2021 at 18:05...

I'm not OP but this looks relevant to your question:

https://www.researchsquare.com/article/rs-42399/v1

Enthusiast said on Fri, 28 May 2021 at 21:17...

@nitritespecialist: got any advise how to refine the food grade sodium nitrite?

Nitritespecialist said on Mon, 31 May 2021 at 12:22...

@s0079376....I have had mild anemia as well. At first I attributed it all to popper use. But I am 61 now and am pretty sure I have polymyalgia which is a type of autoimmune disorder with mild anemia as one of the signs. Still, when I was making isobutyl and isopropyl nitrite, I was having much greater signs of anemia. With n-amyl nitrite, I am having no noticeable signs of anemia related fatigue or blood pressure disturbances. But my sessions are short....perhaps only 5 to 10 minutes long up to a couple times a day. But I do strongly suspect hemolytic anemia can be caused by nitrite ions. This means the blood cells are actually breaking apart within the vessels and becoming nonfunctional. It could also mean the red cells have become damaged enough that when they circulate through the spleen, they are then removed from the blood and recycled.

Nitritespecialist said on Mon, 31 May 2021 at 12:26...

I should add, that as a medical lab tech, I have been able to test my blood often. The fatigue I was feeling was directly related to the mild anemia my CBC revealed. Normal red counts are from 4.5 to 6.5 for men. Mine had fallen as low as 2.75. Fortunately, my hemoglobin was still fairly high, which kept me from feeling tired even at rest.

The Professor said on Sun, 6 Jun 2021 at 00:32...

@Nitritespecialist:

regarding patents; it pays to remember that there are several patents for perpetual motion/energy machines. Just because some patent officer was convinced doesn't make it true.

you mention above that

"the chemists explain the advantages of their method"

They do not; they make a claim. Printing something doesn't make it true.

Is there truly any advantage to, in a batch or automated batch method, dropping the NaNO2 over dropping the acid?

I went back to batch processing to examine this.

My $0.02

each method requires a slightly different technique with regard to stirring speed and drop rate. Once that is sorted, the outcome is identical, although quite different visually.

And, of course, the claim that this results in a more stable nitrite is absurd from the beginning; the NO bond strength is what it is, and manner of production won't change very low bond strength (BDE of the NO bond in an alkyl nitrite is average 40kcal/mol-1.)

Jacko said on Mon, 7 Jun 2021 at 16:01...

@Professor - given that the patent in question was filed by none other than BASF (world's #1 chemical company) and that they have maintained it to date, including an extension to 2024, I would expect there is a tangible commercial advantage to using the method described over more traditional pathways.

The Description specifically refers to batch exotherm control (easy enough to manage with equipment), avoidance of unwanted side-products/better product purity, and better storage stability. All three are desirable, and the latter two especially are solid business reasons to patent a novel method and shell out many thousands of Euros over the patent life to maintain protection.

BASF has left the conditions in the claims as broad as possible, but it's not too hard to guess which ends of the respective ranges are more favourable. I absolutely need to try this out...

You have alluded to maximising nitrosation of the ester previously as a source of greater potency. Can you explain this a little more? Do you mean an excess of nitroso groups relative to mols alcohol? If so, any pointers on how this might be achieved as a (somewhat) stable product?

The Professor said on Mon, 7 Jun 2021 at 19:13...

@Jacko.
\
Yes, BASF must have a financial reason for the patent; It's a hard thing to discover, considering that most chemists I know produce their own Alkyl nitrite in situ and as needed; they don't go to a pharmacy and but it pre-made; and I doubt that the use a batch process unless they need small amounts.

Yes, they do mention thermochemistry, a bit, but there's is no explanation for any of their claims, aside from the mention of cooling equipment.

e.g. if they believe that their inverse drop method reduces by-products, as they've claimed, then there would be a 'method of operation' either through a theoretical prediction, or some sort of fragmentation analysis

Of the three qualities you mentioned

1. exothermic control: they don't bring anything new, just mention that existing techniques are adequate

2. Avoidance of unwanted by-products. Practically ALL of the many existing preparation techniques will provide a yield suitable for normal chemistry uses. One of the commercially used nitrite stabilizers actually smells like dead, rotten fish. The only use I can think of in which that would be a detriment is with inhalation by human; not considered a legitimate purpose at this time.

3. Better storage stability. They seem to believe that there is some inherent benefit, and mention the hydrolysis if left over the waste phase is reduced. There's no reason to leave the yield over the waste phase, so IF their method somehow magically prevents hydrolysis under those cxonditions, then its a solution to a problem that doesn't exist.

My experience; the traditional batch method is best with a very gentle agitation of the reaction chamber, with HCL dropping beneath the surface of the water. This creates a quasi-anerobic condition in the chamber. HCL drops into H2O/NaNO2 and creates HNO2 and NaCl.
HNO2 rises into the alcohol and nitrosates it to produce the yield RNO2.

Easy peasy, very little chance of by-products. Slight adjustments of dropping speed and temp sort it out nicely.

The inverse method starts by mixing the alcohol and HCL, and drops the H2O/NaNO2 into the HCL/R.

You won't see that puff of blue with each drop, since the HCL and alcohol molecules are so close together, the already short lived HNO2 has practically no chance to develop before it runs into an alcohol molecule.

Long story shortened; after sorting the optimum stirring speed and drop rate, instead of short bursts of royal blue and a SLOW build up of a yield layer, you get an almost instantly opaque, turbid liquid that quickly (at the end) separates into the yield and waste phases.

THis method would be very difficult to acheive with sulphuric acid, which would dessicate the co-located alcohol and produce side-reactions.

HCL is a cleaner prep reactant, and won't bother the alcohol.

It's a aix of one half, dozen the other situation; both methods yield good results if the method is adapted slightly for each.

The Professor said on Mon, 7 Jun 2021 at 22:10...

@Jacko

I guess what I'm getting at: this patent doesn't say anything new; other patents claim superior stability for various reasons, even the one that asks for a heavy excess of reactants way above the stoichiometry That patent also mentions superior stability, and claims that one can leave the yield over the waste for days without much hydrolysis. Also, the patent that calls for leaving the reactant chamber for X hours so that the somehow emulsified yield will have time to separate; it mentions a superior stability as well, and it is also incorrect.

If one's intent is to develop an Alkyl Nitrite preparation procedure that is suitable for inhalation, then a commercial patent isn't the place to go looking for some type of secret key to the bank.

@Nitritespecialist has been obsessed with patent searches, and 'a-ha' moments, to his self-identified failure, for years.

One would be better served by using critical thinking to understand the preparation process, the degradation process, and adapt a procedure that makes the desired reaction the preferred reaction, taking all the potential energy of the reactants and aligning the caloric gradient such that side-reactions are NOT available.

ANY preparation procedure will produce some type of yield, and NONE will be that secret key (A successful maker would consider their preparation technique to be proprietary, and wouldn't feel the need to patent their IP. Their IP would be in the proprietary cardon, so as not to reveal their advantage to competitors.

One's chemistry AND reasoning skills are involved.

Nitritespecialist said on Thu, 10 Jun 2021 at 09:44...

@Jacko.....nobody can look at these reactions and see exactly what's happening chemically. They can guess and speculate. And nobody can know exactly what they've ended up with without a chemical analysis.

All I can say is I have tried the German method 3 times and all 3 times I have ended up with a product that last for weeks and now months stored at RT and exposed to air periodically. I adopted the extra wash/rinse cycle after 24 hours, which seemed to help longevity. Also, adding more anhydrous Kcarb later helps - if there is any degradation of odor/effects.

Nitritespecialist said on Thu, 10 Jun 2021 at 09:49...

@Jacko...and yes....I have tried a number of methods of addition, BUT this is the first time I added the 40% SN solution to the acid/alcohol mixture. And it's also the first time I've had poppers that lasted weeks and months at RT and exposed to air periodically while being used.

So.....best advice....try the various methods and see what works best for you.

Nitritespecialist said on Thu, 10 Jun 2021 at 20:53...

@Jacko...not seeing blue nitrous because it immediately reacts with the alcohol would seem like a benefit to me. Having it sit around risks losing it as nitrogen gases.

I have tried various ways of adding the reagents and I can detect differences in odor and effects with each method, so it's safe to assume the end product is not identical for each way.

The Professor said on Fri, 11 Jun 2021 at 18:59...

@nitritespecialist:

said "nobody can look at these reactions and see exactly what's happening chemically. They can guess and speculate. And nobody can know exactly what they've ended up with without a chemical analysis."

It's called the scientific method. I know from your posts that you prefer a "scattershot" wild guess method, and like to toggle back and forth between what you like and what you don't like. I know this is useless for you, but other more able to reason people may find it interesting and useful.

As a matter of fact, the makers in our little group are having great success stories ; you are somewhat of a legend in this circle (as a cautionary tale).

For those interested, what I mean by 'get to know the reaction' isn't some mystical thing; it's a methodical process.

Rather than a decade or more, it takes a few weeks to a month to lock this preparation down; The variances are in the range of 20% or so, and are not inscrutable to those prepared and ABLE to reason.

That;'s not you, by your own offered evidence, so please don't reply to my posts anymore; you are the prototypical 'unarmed man' when dealing with the ability to reason.

one short example; your assumption that "not seeing blue nitrous because it immediately reacts with the alcohol would seem like a benefit to me. Having it sit around risks losing it as nitrogen gases."

many things wrong with that idea.

1. The traditional alcohol and nitrite solution, with acid dropped and a slow stir rate creates anerobic conditions in the Rx chamber. That's a preferred condition, as OXYGEN exposure generates gaseous NO2 from HNO2 in solution.

2. the method of alcohol and acid, with NaNO2 dropped requires a faster stir rate for optimum results. This is constantly churning OXYGEN into the reaction chamber. that's NOT a preferred condition.

3. The esterification process occurs when the weak acid hno2 reacts with the alcohol. There's no need to have the alcohol in such direct contact with such a strong acid as HCL or Sulphuric. In the case of Sulphuric, you risk dessicating the alcohol (nasty), and in both cases you are offering up the alcohol to side-reactions, since the energy well is steeper.

4. you say "it's also the first time I've had poppers that lasted weeks and months at RT and exposed to air periodically while being used."

My response would be that you are using stabilizers, so whatever result you are getting will be more stable for longer than a perfect nitrite that isn't stabilized.

Stabilized nitrite will not change much for a few months, preparing the nitrite and stabilizing the nitrite are two different topics. you yourself have demonstrated that a middling product won't change much over months is it is stabilized.

I guess you haven't discovered yet, but the cycle you go though of "you can't recover a bad prep" to "I brought it back to life" and back is funny as hell. you make a product that has bitter aroma and nasty effects; store it for X time, then re-wash and dry and 'miracle' ? No, you've simple reduced the yield of a mediocre prep, this somewhat concentrates what remains, and you like the result.

You haven't cleaned out any impurities, you haven't circumvented distillation and you haven't increased the bond strength of the yield; you have simply taken a weak product and reduced its volume, like a reduction in cooking.

ANy of those things you do, ask yourself, is the result hissing with NO ? does every inhale feel like its expanding your lungs? If not, then you didn't learn anything in ten + yrs.

Nitritespecialist said on Sat, 12 Jun 2021 at 00:08...

OMG......somebody just had a mega....as in MEGA meltdown!!!! Some serious issues going on in that one.

A forum should be a place where people come to share ideas....get new ideas and try new things. It's not a place to come to force ONE's idea on everyone else as if it's the gospel truth, the one and only way....the best and the greatest.

Jacko said on Sat, 12 Jun 2021 at 09:17...

I find myself wondering if beer home brewing forums ever get this heated, though I've never been interested enough to look :-)

@Nitritespecialist and @The Professor, I appreciate both of your points of view and I've picked up useful suggestions posts both of you have made. @The Professor, the suggestion of avoiding oxidation while stirring is one I'll follow up - CO2 or N2 with parafilm OK?

As a non-chemist but someone familiar with process scale-up in other contexts, I can say with certainly that scaling a continuous process down to small bench scale batches is bloody difficult to control at the best of times and prone to variability, even if you're careful and methodical. I for one am prone to impatience and tinkering, so shortcuts and variations happen. Nonetheless, the results are generally acceptable, sometimes wonderful, but always interesting.

Nitritespecialist said on Sat, 12 Jun 2021 at 18:41...

@Jacko....yesterday, 6-11-2021, I made a German NAN brew, but I made a mistake and only added half the water to the SN solution...so I ended up with a solution that was 75 - 80% concentration.

I noticed during the Rx that I saw constant orange gas, which puzzled me. Then when I tested my product, it wasn't very good. So I retraced my steps and realized my mistake. When I repeated the synthesis with proper ratios, I got a great product.. Goes to show how easy it is to ruin a batch.

The Professor said on Sat, 12 Jun 2021 at 19:52...

@Nitritespecialist

said "OMG......somebody just had a mega....as in MEGA meltdown!!!! Some serious issues going on in that one."

saying something doesn't make it true; there's no meltdown, just an accumulation of facts; facts that annoy you , certainly, but facts none the less.

"A forum should be a place where people come to share ideas....get new ideas and try new things. It's not a place to come to force ONE's idea on everyone else as if it's the gospel truth, the one and only way....the best and the greatest."

you miss the point, again, but that's okay; you are not the audience, the audience is an interested reader who might otherwise think that your madness has merit; I'm just saving other people the time. I'm not forcing a my way or the highway approach (as you have done on other forums) I'm simply relating facts; facts that contradict your crazy talk, yes, but that doesn't negate the truth.

Forums are for sharing ideas? How about the two forums that you have abandoned so far? Other members were having wild success, and you were bringing them down, so you packed up and split, after years of dead ends and either ignoring good advice or berating people.

I see that you're here now, doing the same thing.

The Professor said on Sat, 12 Jun 2021 at 20:22...

@Jacko,

I don't fully understand your question. If you are dropping acid into alcohol and nitrite, a very slow stir bar speed will provide a gentle agitation, but will not create a vortex that sucks oxygen under the surface.

I've tried a blanket of argon and a cling film cap; that does keep out O2 if you are using a fast spin rate, but a slow spin rate works just as well for suppressing side reactions.

Your observation on batch scaling is right on. The smallest batch I've ever made is a half mole reaction. IME a micro-reaction with 5-10ml yield or so is a waste of time; too much variance (the powder losses and stirring losses will be approximately the same, but slight errors in stir speed, drop rate and dwell time make a wildly varying difference in the outcome.

slight example, I've posted about the by-product butanoic acid previously. That by-product's aroma is all over the map, depending on concentration, it can smell like cheese, body odor, vomit. Add to that various possible acidic by-products and you get aromas like grapefruit mixed ion there.

The point being that controlling the reaction with such small quantities is not going to happen by hanging over the reaction with an eyedropper and guessing when to drop, or by scooping clumped nitrite out of a ziplock bag. One will get results all over the map, aromas all over the map and strengths all over the map. That might lead one to believe that the reaction is too fickle and unreliable to repeat results, but TIMING and consistency provides results that can be analyzed, result can then be data points for the next hypothesis.

At least that's what I did; I designed a set of experiments. Each set of runs designed to provide data to answer one particular question.

e.g. what are the powder losses? might be one question. A series of at least 10 reactions will give enough data to answer that question.

Personally, I arrived at 5% as a typical case. the german patent agrees with a near 1:1.05 molar ratio (alc to powder). Another set of experiments gave me a 1:1.05-1:10 ratio for alc to acid (1:10 in a dropped acid prep, 1.05 in a dropped nitrite prep)).

After that comes the fun part; post processing

justchem said on Thu, 24 Jun 2021 at 14:59...

@The Professor . Who are the other two forums ?

charliechuckle said on Wed, 8 Sep 2021 at 01:56...

@The Professor

Thank you for sharing your knowledge. I am learning here, but I have an elementary question, if you would be so kind to indulge me.

You wrote:
My experience; the traditional batch method is best with a very gentle agitation of the reaction chamber, with HCL dropping beneath the surface of the water.

What is the best method to get the drop below the surface of the water? Is this achieved by gravity, I assume? Is it by positioning the separatory funnel high enough that the drop falls into water layer?

charliechuckle said on Thu, 9 Sep 2021 at 20:07...

@The Professor

Please disregard my silly beginner question if you come across it. I now realize from reading more on this site that the delivery tube itself should be below the surface, if what I found is a reliable source and I have every reason to believe it is accurate. I am embarrassed for asking such a "newbie" question. Thank you for all of your contributions here. I sincerely appreciate learning from your posts.