Nitrite production methods

Topic created by Father
on Fri, 22 Jul 2022 at 15:20

Father said on Fri, 22 Jul 2022 at 15:20...

Producing/preparation/synthesis of alkyl nitrites

To 1 mole of isoamyl alcohol placed in the beaker, a solution of 1.1 mole of sodium nitrite in 140 ml of water is added and the contents of the beaker are cooled to 0° C (with a mixture of ice and table salt). Then, while stirring well, 90 ml of concentrated hydrochloric acid are slowly added dropwise, while the temperature during the addition should not exceed 5C. The mixture is transferred to a separating funnel with a capacity of 1 l and shake with 400 ml of water. After separating the water layer, the organic phase is washed with a dilute soda solution and then with water several times. The reaction product is dried with a little calcium chloride and distilled under reduced pressure using a receiver cooled to low temperatures.

by B. Bochwic

Method 1
A 1-liter three-necked flask is fitted with a mechanical stirrer, a separatory funnel with a stem extending to the bottom of the flask, and a thermometer. The flask is cooled in a mixture of ice and salt and a solution of 95 grams of sodium nitrite in 375 ml of water is placed. When the temperature has fallen to 0° C slowly from the separatory funnel a mixture of 25 ml of water, 34 ml (62.5 g) of concentrated sulfuric acid and 135 ml (110 g) of n-amyl alcohol are added, which has previously been cooled to 0° C. The addition takes 45-60 minutes and the rate of addition must be controlled so that the temperature is maintained at ± 1° C . When the sulfuric acid and n-amyl alcohol have been added the mixture is left to stand for 1.5 hours and filtered from the precipitated sodium sulfate. The upper yellow n-amyl nitrite layer is separated, washed with a solution containing 1 grams of sodium bicarbonate and 12.5 g of sodium chloride in 50 ml of water, and dried with anhydrous magnesium sulfate. The resulting crude n-amyl nitrite (107 g) is satisfactory for many purposes. Upon distillation, it passes over largely at 104° C with negligible decomposition. The boiling point under reduced pressure is 29°/40 mm. n-Amyl and other alkyl nitrites decompose slowly upon standing and should be kept in a cool place. They must be used within a few days or, at most within two weeks of their preparation. The decomposition products include water, oxides of nitrogen, the alcohol and polymerisation products of the aldehyde.

by A. I. Vogel

Method 1.1
By another method to the round bottom flask cooled with ice-water 50 g of amyl alcohol and 300 g of cold 20% sulfuric acid are placed. From the funnel, 60 g of sodium nitrite in small portions with constant stirring are added. During the formation of amyl nitrite, addition each fresh portion of sodium nitrite must be stopped until the reaction from the previous addition is ended and the yellowish-red vapors have disappeared from the flask. About 30 minutes is required for this operation, meanwhile, the reaction is complete after waiting an hour longer. The amyl nitrite is separated in a separatory funnel, washed twice with water without shaking and dried by standing overnight with lumps of fused calcium chloride. Amyl nitrite is very gently distilled yielding 60 grams of final product with boiling point 97° C.

by H. Biltz

Method 1.2
An alternative method of preparation consist of a concentrated aqueous solution of 35 g of sodium nitrite is treated with 44 g of amyl alcohol, and the mixture cooled to 0° C. With efficient stirring and cooling 43 ml of hydrochloric acid (d=1.19) are added, the temperature being maintained at 0° C. The oil is then separated, washed, dried and distilled, amyl nitrite passing over at 94-98° C yielding 53 g of final product.

by M. Barrowliff

Method 2
In a two-necked flask with a capacity of 250ml equipped with a stirrer and dropping funnel, add 30ml water, 110ml isopropanol and 45ml conc. sulfuric acid. Place the flask in ice water so that the temperature of the mixture is 0 °C. After the mixture has cooled down, place a solution of 114 g of sodium nitrate in 450 ml of water in a separating funnel.
Start adding the solution at a rate such that the total time is about 2 hours. It should be ensured that the temperature does not rise above 2 °C
After this time, transfer the mixture to a separating funnel, separate from the water layer, and then wash three times with 30 ml of 5% sodium bicarbonate solution and 100 ml of 22% sodium chloride solution.
Separate the oil from the water layer, add a few grams of anhydrous sodium sulphate and set aside in a cool place for about 0.5 h. After this time, drain off the drying agent. We get pure isopropyl nitrate.

by ..?

Method 3
https://patentimages.storage.googleapis.com/5f/8d/00/71e3760a752c55/US20030149292A1.pdf

Method 4
https://www.freepatentsonline.com/4980496.html

Method 5
In a 5-liter beaker, 1200 ml (972 g) of isoamyl alcohol are placed and 1000 g of pure sodium nitrite are added. The mixture is cooled to 10° C and while stirring 325 ml of concentrated sulfuric acid are dropwise added very slowly. During this procedure, the nitrite should be kept from settling to the bottom, a process which is easily accomplished by having the stirring so vigorous that a clear layer of alcohol is never visible above the nitrite. During this addition of sulfuric acid, the temperature is an important consideration and should be kept below 25° C. After all of the sulfuric acid has been added (30-60 minutes), the stirring is continued and water gradually added. The obtained solution is poured in a large separatory funnel where isoamyl nitrite rises to the surface. More water is then added to the salt mixture, stirred, allowed to settle, and the nitrite again poured off together with most of the water. The extraction is continued until no more isoamyl nitrite rises to the surface. It is not necessary to dissolve all of the salt but the small lumps must be broken up and the remaining salt should be perfectly white. The yield of crude material amounts to 1300-1350 ml. The isoamyl nitrite is washed once with clean water to remove any acid, dried for a few minutes over calcium chloride and distilled. The fraction which boils from 92-100° C is collected yielding 1250-1300 ml or 1100-1145 g of isoamyl nitrite.

by A. Roger

Nitritespecialist said on Fri, 22 Jul 2022 at 18:07...

Wow...so many methods, but which one works best over time and doesn't require distillation to be fit to inhale? The last method, adding all the undiluted conc. sulfuric to pure SN and alcohol seems like it would be impossible to stir and keep cool. Although 25C isn't that cool.

Nitritespecialist said on Fri, 22 Jul 2022 at 18:10...

The amounts in the last example, divided by 100 are 12mls amyl alcohol per 10 grams SN per 3.25 mls of 98% sulfuric.

The Professor said on Fri, 22 Jul 2022 at 18:12...

You found most of the usual suspect writeups, and a couple of patents thrown in.

to borrow from the pdf, Alkyl nitrite preparation is a very simple chemical reaction called an ion swap. Simple reactants are added to a reagent (water in thyis case),

The Professor said on Fri, 22 Jul 2022 at 18:21...

The reactants 'fall apart' into their respective ions.

H and CL from HCL
or
H2 and SO4 from sulfuric acid

Na and NO2 from NaNO2 powder

1 or more methyl groups from an aliphatic alcohol

The writeups you found ALL will produce an alkyl nitrite that suitable for MOST purposes, like diazotonation.

If the product is intended for HUMAN inhalation, then there are aspects of the prep that should address und-desired, unhealthy consequences.

Using sulfuric acid, for example, guarantees corrosive Lye in the product. It also guarantees saponification of the product, which will short term reduce potency and long term destroy the product)

HCL is a much cleaner prep, but sequestering degradation components sp they don't interfere with inhalation is still important.

The pdf lists the possible decomposition and degradation products, along with a few techniques to overcome nasty aroma buildup and preservation.

Father said on Sat, 23 Jul 2022 at 02:50...

These methods can be freely modified and combined with each other or add something from yourself
Other alcohols can be used in these methods In slightly modified proportions depending on what nitrite we want to get
Unfortunately, most methods require distillation to purify the product but instead of distillation, another method of purification can be used

Example

beaker Y - dissolve NaNO3
beaker X - pour isopropanol, then concentrated sulfuric acid H2SO4 cooled to 0 °C
both solutions are cooled to 0 °C
in a 3-necked flask equipped with an electronic or traditional thermometer (-60 to +30), standing in an ice / NaCl bath (3:1), place the X solution, and the Y solution in the dropping funnel
slowly drop the solution Y to X 1.5-2h and control the temperature in the range -3 °C to -0 °C
(HNO2 acid is formed and low temperature favors isopropyl nitrite instead of nitrogen oxides)
after adding all of the Y solution, mix for 15 minutes,
turn off the stirrer, leave it for 15-25 minutes in an ice bath
decant the upper organic phase,
clean the product by adding anhydrous sodium carbonate and put it in the freezer (with a small amount of sodium carbonate)

the estr is collected in the upper organic layer, the "gel" layer is the water phase (sodium carbonate was also added to it and a layer of about 2 mm of estrer was collected with a syringe)

Anhydrous sodium carbonate in the amount of about 35-40g (add until it stops foaming, neutralizing the residual sulfuric acid, then until it stops dissolving at room temperature)

(When sodium chloride reacts with sulfuric acid (VI) at lower temperatures, an acid salt of sodium sulphate (IV) (NaHSO4) is formed, only after heating it fully reacts to (Na2SO4)
If the reaction mixture is supercooled, the dropwise solution does not react completely and at some point when it heats up again as a result of the reaction, there is an excess of reagent and a sudden increase in temperature

im.ge/i/Fabyec
im.ge/i/FaYepa

Nitritespecialist said on Sat, 23 Jul 2022 at 14:17...

It appears that an integral part of the alkyl nitrite liquid phase prep theory is that HNO2(nitrous acid) reacts rather "slowly" with the alcohol, which is contrary to some literature that says it reacts "rapidly". Nitrous acid is unstable and breaks down into nitrogen gases, which according to the Professor, if this happens, the nitrogen is simply lost forever. Since nitrogen is part of the active ingredient, we don't want to lose it. Nitrous acid is temporarily stable in cold dilute water, so we can't merely heat up the reaction temperature to get the alcohol and nitrous acid to form ester faster, since we risk losing nitrogen when and if the nitrous acid decides to degrade first. We could mix the reactants faster and more thoroughly, but any formed ester may be degraded by additional acid, water and perhaps oxygen.

So....the adjusted theory is that blue nitrous acid reacts so slowly with the alcohol, that it takes a lot of patience and very slow addition of acid for the reaction to reach completion. The higher the concentration of nitrous acid, the darker blue it becomes, and the greater danger there is of degradation, which is why the temperature has to be kept cool and the rate of addition has to be controlled. Also, the mixing speed needs to be adjusted so as to maximum contact of nitrous acid with the alcohol, without churning formed nitrite into the bottom layers of water and acid.

Scaling up seems very difficult for this method, but it's probably sufficient for personal use.

The Professor said on Sat, 23 Jul 2022 at 15:10...

Most of the heat that is generated during the prep comes from the first step, creating a weak acid (HNO2), from a strong acid and a powder (HCL and NaNO2).

In the liquid phase batch process, most makers tend to prep two solutions and mix them together. As long as NaNO2 is in one solution and HCL in the other, most prep write-ups will work, and may require contending with various by-products from various mixing strategies.

At home makers are hobbled a bit, in that an 'instant' or extremely quick heat sink isn't available to us. continuous flow reactor would instantly sink heat, but we tend to use an ice bath.

Using an ice bath, going as cold as possible (-12C is about as low as you can go without having to use high pressure equipment), WILL slow the reaction down to the point that HCL isn't boiling away reactants, IF the drip rate isn't too fast.

Once the excess heat has been dealt with, you now have a very slow reaction. You can't speed it back up again, but what you CAN do (and it would require an entirely different apparatus and procedure), is to prep HNO2 first, at -12C, and make the Alkyl nitrite at a higher temp.

Of you want to see the HNO2 get sucked up by the alcohol faster, that will do it.

It's trading time for complexity though.

Just remember that increased temps also guarantee more un-reacted alcohol; the prep will always be more pure the colder you do.

Father said on Sat, 23 Jul 2022 at 21:20...

This chemical experiment was performed for research purposes only
The end product is not intended for use
It seems to me that both acids are good, it all depends on the method, reagents and equipment used
Thank you everyone for valuable tips

Nitritespecialist said on Wed, 27 Jul 2022 at 20:30...

After reading the Professor's 43 page link, what jumps out most is that the nitrite layer becomes transparent green while the bottom water layer stays transparent blue as the reaction proceeds. The Professor claims this is a sign that the sodium nitrite, which is apt to degrade, is pure enough.

When the top layer becomes cloudy yellow, the sodium nitrite is likely degraded.

It seems probable that this is the case as I've noticed a positive correlation with yield when the top layer is transparent, even effervescing, green. At present, my sodium nitrite will not do this regardless of ratios, mixing speeds and temps.

The Professor said on Thu, 28 Jul 2022 at 21:03...

I make no such claim

Nitritespecialist said on Sat, 30 Jul 2022 at 20:09...

The following are quotes from the Wiki.pdf file produced by the Professor. Interrupt it as you will. I strongly theorized 10 years ago that the sodium nitrite must in fact oxidize quickly enough to impact the quality of brews just over a few weeks time and certainly over several months time. Here the Professor has done nothing but back up those theories. In a basement home lab, with no access to chemical analyzers, it is virtually impossible to know the purity of the starting reagents and the products produced. Without knowledge of the purity as well as any impurities present, no real knowledge can be gained. And yes.....impurities, such as water and acid will definitely increase the degradation of even highly pure popper. Impurities are NOT a factor ONLY if they are inert, BUT without knowing what all the impurities are in each given sample, it's all just a big guessing game.

Oxidation losses:. As your sodium nitrite oxidizes into sodium nitrate, less and less nitrous acid will be produced. In
order to satisfy the alcohol, more and more NaNO2 will be required. Eventually, the nitrate level contaminating the
nitrite will be high enough to cause problems with the yield, and the NaNO2 should be replaced.My data suggests a
starting ratio of 1.00:1.15:1.10 (alcohol to Acid to Sodium Nitrite).
The preferred rations for YOUR reactant quality and reaction speed (too fast and you waste reactants on NO2) will be
found empirically during the data logging step.
If you have already proven, for example, that your NaNO2 is still viable, you can dial down the excess NaNO2 to the
point where the waste phase is just BARELY tinted by the royal blue of HNO2.
Some of the pics shown here depict a vibrant blue bottom layer, and a brilliant green yield layer. I purposely exceeded
the stoichiometry to show what good NaNO2 powder looks like when it has made HNO2
At -12C, and when super-saturated with NO, the top phase (yield) will turn a brilliant green; perfection is the yield JUST
starts to turn green. The bottom layer will become a shade of royal blue. Perfection is the waste JUST has a tint of blue.

Nitritespecialist said on Sun, 31 Jul 2022 at 14:15...

The problem with getting ACS grade Sodium Nitrite is that it's expensive, especially considering the Hazmat shipping charges the big outfits charge. Sigma offers anhydrous sodium nitrite, but it's very expensive with shipping charges.

So....taking a chance on buying from a second hand dealer means the quality of the SN is not known with any high degree of assurance. So...when making brews starting with such uncertainty, one can never know what will come out of the pot. One risks wasting a lot of reagents, tossing money down the drain literally. And even if the reagents are good enough from the start, one has to know for certain that any post processing steps used are sufficient to give batches a few months of shelf life, lest you just toss money down the drain again. Making great poppers that can be sold on shelves is NO EASY TASK. Everyone keeps asking who does sell great, consistently good poppers and all I keep reading is "I dunno", but sometimes so and so has a good one....hit and miss...hit and miss....every single time.

The Professor said on Sun, 31 Jul 2022 at 16:55...

I don't 'back up' any of your theories regarding anything.

It seems that you can't understand English sentences anymore, and are looking for validation wherever you can find it.

First paragraph, worded as if you know what you are talking about (you don't). You show your ignorance by demanding that any impurities will accelerate decomposition. They don't

You persist with this fantasy, even when it has been disproven. There are NO catalyzing imurities, it's all a linear process.

It doesn't matter that you deny it, to me, or anyone that cares about the integrity of their product. It only matters that it's true, and until it's addressed as the truth, you'll not be able to understand and cope with it.

It might be a guessing game for Ken, but actual scientists have identified the degradation components, and they are mentioned in the pdf.

I'll leave my comments on paragraph 1 if you're tirade at that. You think I'm confirming something that you have experienced, but YOU we're account clumpy powder from a plastic bag, and I've been first refining my powder, and then storing it under vacuum, and my powder stays viable for the duration, and yours turns to junk in weeks.
The remainder of your first part is the text from the wiki that you are bending to your will and claiming that emerald green is an indicator of viable powder.

The text you wrote, and elsewhere, clearly states that the emerald green color is due to the yield becoming super-saturated with nitric oxide.

Super-saturation is a function of prep environment and procedure.

The royal blue blooming from each drop of HCL, however, is and indicator of powder quality.

This sentence was added because makers viewing the pictures might otherwise misunderstand the pictures, and think that a preferred end point of the prep leaves a deep royal blue waste phase.

It's funny to me that you are misunderstanding explanatory text.

Your second postt is another disproven and old complaint, and it starts with fallacy (of course)

You're trying to persuade, and begin with an 'if then' statement that says 'there's a problem with ACS grade powder, and it's due to high shipping costs. There's absolutely no forensic investigation of anything, just two unrelated concepts, worded so that one is supporting the other, when in fact neither do.

Finish out all of with a shrug of the shoulders? How about back a few months ago (before your silly brewmeister escapade) when you were over-the-moon about locker room products, vouching for them all over and repeatedly? That contradicts the lie above, if you care.

You have once again demonstrated your ease and comfort with lying, your inability to understand simple concepts and your repetitive claims that aren't valid.

I've been making product with consistent purity and effects for a few weeks after a started. I started making with food grade reactants and Wal-Mart reagent. I started making 1 mol batches, and wouldn't consider any result I've had to be a 'waste of money'

By comparison, ken is still confused about the process and had wasted gallons of reactant, a few milliliters at a time.

Nitritespecialist said on Mon, 1 Aug 2022 at 15:04...

wow...what a garbled chunk of BS!!! I don't think any honest "scientist" would jibber jabber with such angry intent as that.

Nitritespecialist said on Mon, 1 Aug 2022 at 15:05...

Water is an impurity. Acid is an impurity. They both hasten degradation. Not very hard to understand.

PopperExpert said on Mon, 1 Aug 2022 at 15:07...

Oh yeah.....the Professor deliberately chooses to ignore the most obvious conclusions...that without chemical analyzers, no real, conclusive knowledge can be gained from making poppers at home. Just someone's opinion as to what they've ended up with. Obviously the Professor thinks his crap is to die for, but what garbage is in it...is the million dollar question.

Popperasswipe said on Mon, 1 Aug 2022 at 15:11...

I've decided to just buy factory made isobutyl nitrite and clean it up a bit. At least I'll have some certainty as to what I'm starting with.

The Professor said on Mon, 1 Aug 2022 at 17:06...

Out only costs a couple of hundred dollars to have your product tested. Much cheaper than psychotherapy.

The Professor said on Mon, 1 Aug 2022 at 17:13...

Acid and water and heat and light ALL facilitate decomposition, but that's NOT what you said, you said that they ACCELERATE decomposition.

Look at the graphs in the pdf that shows decomposition and they are straight or nearly straight lines.

IF a decomposition avenue were also a decomposition accelerant the graphs would be curved upwards towards an exponential response.

If you call that a 'garbled chunk of BS', that seems like a perfect demonstration of how shallow a mind can be?

The Professor said on Mon, 1 Aug 2022 at 19:28...

poPPERASSWIPE,

You don't have to live inside Ken's head you know; you CAN escape from his malfunction and be your own individual.

Anonymous said on Fri, 2 Sep 2022 at 05:24...

I think we are making things way too hard. My method is very similar to method 5 above. I made two batches that came out good without too much effort. I made two batches and the first batch was good. The second was very good.

1. I start off with a mixture of 92 ml of Isobutyl and 82,8 g of NaO2. I start up the mixer and let it work. It won't pull all the NaO2 into the alcohol but don't worry about that now. Just turn the mixer up all the way while it is sitting in an ice bath.

2. I start with 58 ml of battery acid and drop it into the vortex of the mixer fairly quickly. I don't have proof but I think dropping it into the vortex spreads the acid quicker. Burning the alcohol I believe is a lot about poor mixing as temperate. I empty the acid into the vortex in like 10 minutes without any nitric gas whatsoever. As more acid is added, more of the NaSO2 that didn't get mixed well gets pulled into solution.

3. This is carry over from the wine industry which deals with product that is various tremendously from season to season. I had 10-20 ml more of acid to make the solution acidic. I then take a few spoon fulls of NaO2 and start sprinkling it into the solution, which is acidic. Initially, dropping NaO2 produces bubbles. After sprinkling enough, the bubbles stop because there is very little acid left for the NaO2 to react with. I start sprinkling NaO2 into it and smelling the solution. There will be a point where is goes from a strong acidic smell to smelling neutral. When that happens, stop. There is very little acid left. I strongly question why we are washing the poppers with baking soda rather than just adding NaO2 to neutralize the acid and at the same time produce nitric gas that will react with any remaining alcohol. I think this is how it should be done because the quality of the NaO2 and acid very a lot and this method introduces less water into the solution. You basically ballparking the solution and then initially making it acidic because acid is very easy to smell and then pulling it back to neutral.

4. I added dried epsom salt and MS3 and I have something that is totally neutral smelling. I added a little baking soda and decanted it but I don't think that was even necessary.

Pete said on Mon, 3 Oct 2022 at 23:21...

professor u really are a complete dick

Pete said on Mon, 17 Oct 2022 at 00:05...

i take that back i am a total tard lol