Nitrosation Reactions and the Chemistry of Nitric Oxide

Topic created by Anonymous
on Thu, 9 Jun 2022 at 11:15

Anonymous said on Thu, 9 Jun 2022 at 11:15...

is a Google Book written by D.L.H. Williams, Professor of Chemistry, University of Durham, UK. It was published in 2004.

In it, he states alkyl nitrites are prepared by using a large excess of alcohol, which moves the reaction to the right and is then distilled off to separate the product from the alcohol.

The person who wrote the WikiLink clearly states that there are various ways to make alkyl nitrites. The question is.....which is best for making a high quality, consistent popper worthy of sniffing straight from the bottle.

Hopefully, someone interested in selling poppers commercially will discover and use the best method. It matters not to me how people make poppers at home.

Anonymous said on Thu, 9 Jun 2022 at 11:37...

0 (1 ) 2NO + 02 - 2N02
(2) N02 + NO N2O3
(3) ROH + N203 - RONO + HONO
(4) ROH + HONO - RONO + H20
(5) N2O3 + H20 - 2HONO
25 (6) 2N02 5= N20*
(7) ROH + N2O4 - RONO + HNO3
(8) N20<l + H20 - HONO + HNO3
wherein R represents a methyl or ethyl group.
30 The desired reaction sequence for the formation of alkyl nitrite occurs via Reactions (1)-<4). The sum of
these reactions yields as the overall process reaction: (1) 2ROH + 2NO + 1 202 — 2RONO + H20
Reaction (5) takes place because the water formed in Reaction (4) can react with dinitrogen trioxide
35 (N203). Reaction (5) can be tolerated provided enough alcohol is supplied to react with substantially all of
the nitrous acid formed in Reaction (5) according to Reaction (4) yielding alkyl nitrite and additional water.
Reactions (6) through (8) are undesired since they lead to the formation of nitric acid, a compound
which subsequently must be separated from product alkyl nitrite. Further, these reactions consume nitric
oxide in forming undesired nitric acid.

The preceding chemical info was taken from a patent and used in the WikiLink description of how to make poppers at home. It shows the basic steps of alkyl nitrite formation. Applicant: UNION CARBIDE CORPORATION
39 Old Ridgebury Road

In the patent, they are using a vapor phase method of making alkyl nitrites, but the chemistry is virtually the same. The alcohol component has to be present to react with the NO2 molecule. If it's not present, you get all sorts of side reactions and nitric acid.
© Date of publication of application: Danbury Connecticut 06817(US)

Anonymous said on Thu, 9 Jun 2022 at 14:13...

I did make 30mls of n-butyl nitrite based on the excess alcohol theory. I used a very cold ice bath. I poured 30 mls of cold butanol into a flask, hit the stir button and slowly dripped in 28 mls of cold 31.45% HCl. I poured 22 grams of SN into 40 mls of DW, chilled and slowly added this to the acid/alcohol mixture. I saw tame bubbles form, specs of blue that quickly disappeared and very little brown gas. Yield was transparent light yellow and about 80%. Washed with baking soda rinse solution and then used brine to clear and dry the nitrite.

Odor sweet, similar to the alcohol as expected. No trace of bitterness.

Effects: much improved over the excess acid method. Very sustainable and mildly pleasant prostate effects. Mild sense of euphoria. No weird effects of any sort. No racing heart beat.

So....the residual alcohol so far hasn't caused worse effects and in fact the nitrite has improved effects and odor compared to the excess acid method.

It's important to note that this method is based on the knowledge that the goal is generating nitrous acid that will rapidly, instantly combine with the alcohol. Nitrous acid is unstable and will quickly degrade into nitrogen gases. It is most stable at 0C temperature in a dilute solution. If the concentration is too great, it degrades. Therefore, it's imperative to have ample alcohol always present to capture the nitrogen ASAP.

Moreover, due to the fact perfectly balanced ratios of reagents will eventually reach a point of reversible equilibrium, whereby not all reactants are used up to form product, it is necessary to add an excess of alcohol to force the reaction to completion. If either excess acid or SN is used instead, the risk is two fold.....acid degradation of forming nitrite, and excess nitrous acid forming that subsequently forms nitric acid and other undesirable nitrogen compounds. There should NOT be any visible nitrous acid hanging around in the pot because this means it could easily degrade before combining with any alcohol that might be present.

The Professor said on Thu, 9 Jun 2022 at 16:17...

Ken you are using up bandwidth on this forum on order to try to discredit me. You ALWAYS are worker outright lying or you misunderstand what you have ready.

This is the THIRD time you are trying to hoodwink people worth the same bit of reading.

A normally intelligent human can easily understand your motive now is not too understand the process, it is to argue with whomever really understands the process.

Claiming that the process is the same with different methods of preparation is entirely untrue, and anyone who you might be trying to convince otherwise already had your number, you SHOUT it
out proudly.

Cut-and-paste reports of your peeps doesn't gain you any credibility; they reveal your persistent willful ignorance in the face of facts, and your inability to understand the simplest scientific principles.

Your 'moreovers', 'furthermore' and'therefore' are all incorrect conclusions that are going to get anyone else following them into harms way.

The Professor said on Thu, 9 Jun 2022 at 16:25...

Btw Ken, doesn't an excess of alcohol sound familiar? Don't you remember that we all tried it at poppersplace?

How is it that when you do it, you can report after ONE day that is improved over your other methods ) which you ALSO fought to the ground as a great improvement?

Also, how is it that when we do our, your opinion is that the product "reeks of butanol" and when you do it the product "has improved affects"?

Oh yeah, you're a proven liar with a diseased Spleen.

The Professor said on Thu, 9 Jun 2022 at 16:29...

And still no acknowledgment of want of your attempts to try to embed your lies into a quote from the book? That was one of your most transparent lies, yet you sheriff it off. (Lying to your audience is not cool, but ignoring a lie you've been called out on is finky.

Anonymous said on Thu, 9 Jun 2022 at 17:30...

Nitrosation Reactions and the Chemistry of Nitric Oxide, 2004, by Williams.

Chapter 6, page 105.

6.1 Nitrosation of alcohols

........."the reaction sets up an equilibrium which can be driven to the right by a large excess of alcohol, or by removal of the alkyl nitrite by distillation."

Anonymous said on Thu, 9 Jun 2022 at 17:39...

The quote from Professor Williams book speaks for itself. He gives two options to make the alkyl nitrite reaction proceed to completion, which drive it to the right, ADD a lot of EXCESS alcohol

OR remove the forming product via distillation, which will do the same thing, drive the reaction toward product. Just letting the reactants sit in the pot forever at -12C is not going to achieve the same thing.

The Professor said on Thu, 9 Jun 2022 at 19:14...

Again you misinterpret what you have read. Previous postings here describe the extent to which Lee Chattelier's principle can make adjustments (it's called kinetic reaction control, and is similar to counter steering during a skid in order to persuade the vehicle NOT to spin off the road).

That is a narrow window of opportunity and ability to control a skid; counter steering only does so much.

The other type of reaction control, thermodynamic control, is used in COMBINATION with kinetic controls, and is akin to slowing the vehicle speed; stopping the skid in its tracks.

THAT involves prepping at as cold as possible and with as high pressure was possible.

THAT will be making the product in an environment which strongly favors the forward reaction.

You get more product, less ingredients, less poisonous side reactions from doing it properly, and what you've been doing has always been junkie level.

You've been on a roll again lately! The three of the top posts are your relentless attack against reality.

Unfortunately, they all say the same thing, and it's completely wrong, so thanks for driving more people to the truth, and enriching their lives by NOT choosing your nonsense.

Anonymous said on Thu, 9 Jun 2022 at 23:14...

"There are several ways to prepare Alkyl nitrites; this guide’s primary focus is on the liquid batch process, since it will be
the easiest preparation for a non chemist. There is a short section describing a more expensive, but more accurate procedure."

The above is a quote from the WikiLink document on how to make poppers.

It clearly states there are multiple ways to make alkyl nitrites. Surprisingly, it doesn't even state that the one described is the BEST. It actually implies by the next sentence that there is a better, more accurate method, but it's too expensive.

What I have done is show and test other methods. But not method can be proven to be optimal without constant testing of each product via an analyzer. This is how professional chemists do it in professional labs.

Anonymous said on Thu, 9 Jun 2022 at 23:18...

I have little doubt that the optimal popper for sniffing would have been subjected to fractional distillation. It's the best way to increase purity and then if any additives are added to extend shelve life, change the odor, or in some way decrease volatility, there is a better chance the shelf life will consistent.

The Professor said on Thu, 9 Jun 2022 at 23:55...

I'm not sure where you are getting your information from, but constant testing is NOT some in any manufacturing discipline.

Typically, a preparation will start in a lab. A chemist will do his job developing a preparation procedure. Then, a process engineer will modify that process for manufacturing. Then the process will be verified by some chosen quality assurance procedures.

Process verification does include testing to verify the apparatus, and after monitoring the process output, a calibration interval is assigned.

The process is re-certified each interval, the intervals for a continuous flow process are typically a year.

Between calibrations, random testing will be done, but it's NOT continuous.

An example would be a process with a one year interval that is designed for at least x% accuracy. To guarantee x%, the standard deviation of the process is identified, and random QA Testing is done at those intervals, NOT continuously.

The Professor said on Fri, 10 Jun 2022 at 00:06...

Fractional distillation is one way to purify crude yield.

Another, less dangerous, method is hyperbaric, cryogenic simultaneous preparation and distillation.

That's what I do in the lab work NUBLU, in the vapor phase.

At home, I don't have a pressure chamber, so I make due with liquid batch process.

At -12C, there is no free energy available to allow side reactions. The only energy available is generated with each drop off acid into the chamber.

I use 37% HCL, as required by the sticker, and I dilute it until there is no generation of NO2, no bubbles or foaming and no temperature creep.

Then entire apparatus is insulated and void of oxygen.

There are no side reactions possible with this setup, and the results are extraordinary.

Can they be better? Well, sure, but 99.9% purity and 0.26% un-reacted alcohol is more than suitable for my post processing.

Charlie said on Fri, 10 Jun 2022 at 07:25...

"I use 37% HCL, as required by the sticker, and I dilute it until there is no generation of NO2, no bubbles or foaming and no temperature creep."

Prof, when you say no bubbles, do you mean absolutely no bubbles at all, even the little, tiny ones that look a little like bubbles when soda fizzes?

The Professor said on Fri, 10 Jun 2022 at 15:58...

I do; 'regular' sized bubbles are usually environmental atmosphere, and the tiny bubbles are usually nitric oxide.

When solutes fall out of a solution, they either evaporate or precipitate. Bubbles are evaporating out of solution, so they are quite energetic, despite a very cold ice bath, that indicates the reactants are boiling away and being wasted.

A slower drip rate will stop that; you are already, IIRC, using a slight molar excess of reactants

Charlie said on Fri, 10 Jun 2022 at 18:39...

Thanks Prof. Yes, a slight molar excess. Since I have already slowed down the drip rate, maybe I need to dilute my acid a little more because I am getting some teeny-tiny bubbles? :face palm: OK, back to the drawing board! ;-)

The Professor said on Fri, 10 Jun 2022 at 19:22...

from what you have been posting on PopperMakers, your product VISUALLY appears to be very fine.

A slight amount of tiny bubbles isn't going to change the world; that's what the slight excess is for.

A very slight additional dilution would stop those bubbles, but I doubt that the product outcome would be very discernable from what you are already doing.

IOW, there's also a window of cost v return; it sounds crazy from someone who chased purity into the vapor phase, but I mostly did that because I am curious, NOT because i could tell the difference between 98% purity and 99.9% purity

Charlie said on Fri, 10 Jun 2022 at 19:55...

Thank you Prof. I am not getting a large amount of bubbles, but I am getting some. At times, the prep is placid. Other times, small bubbles... The "tinkering/perfectionist" side of my personality is always searching for improvement. At least, I have a new goal is chase! I will try adding a few extra mL's of water to the acid to see what happens... Thank you again.

The Professor said on Sat, 11 Jun 2022 at 00:26...

good luck with your explorations. Yeah, I get it (the chase)

The Professor said on Mon, 20 Jun 2022 at 16:29...

readers that are new to this forum probably haven't experienced the lying, deceitful, willful ignorance that is Ken (aka anonymous, aka popperass, aka madeplentypoppers, aka NitriteSpecialist aka PopperExpert, aka PopperMaker, aka kenjoneslee, aka John Mulligan, etc.

He'll fight his wrong ideas to the ground, hasn't attained control of this reaction 13 years, and is wasting everyone's time.

another big yawn with no new content, a dollop of lies, with a dash of baloney

Those interested in the REAL science can always refer to the wiki, and join PopperMakers (a subreddit) if you need support for it.)

wiki:
https://nublu.maitriworks.org/files/Alky%20Nitrite%20Preparation%20wiki.pdf

Maker's forum:
https://www.reddit.com/r/PopperMakers/