First batch

Topic created by Charlie
on Thu, 14 Oct 2021 at 01:59

Charlie said on Thu, 14 Oct 2021 at 01:59...

A little debrief after I finished my first homemade batch today, while still fresh in my head.

After I sorted out which stir bars to use for my stirrer, I felt that I was plugging along well. I found that I needed the cross stirbar to mix the NaNO2 with the water. I found that I needed a tiny 4x10mm stirbar for the actual dropping as all of the other stirbars I had on hand were creating vortices.

I found that ice blended from a Vitamix is probably too wet, so I was getting ice water too quickly and had to switch it out more than once. I think it may be wise to get a Ninja blender so that I get drier ice that doesn't melt so quickly. I found some stirring trouble when the beaker started to float.

While dropping one drop every 4-5 seconds, I was getting a temperature reading of -1C to -3C on the surface of the yield with an infrared thermometer. While I used ACS-quality NaNO2, I did get some white paste on the dropping tube that I needed to clear a couple times. Is this maybe impure NaNO2?

At the end of dropping, I had a light green yield and a royal blue waste phase. After stirring for 15 more minutes out of the ice bath and transferring to the separatory funnel, I was left with a light yellow yield and a medium blue waste phase. As this sat for 20 minutes, the blue phase effervesced, and a very small amount (maybe 1%) of this blue phase ended up on top of the yield. I was not expecting this. Normal or problem?

I ran into a problem with the neutralization step as I found the baking soda creates a very thick emulsion, which I had trouble getting to stir. After I got a medium stir and then let it settle, I ended up losing 25% of my yield because I did not have filter paper on hand. It's possible I was also not cold enough that the baking soda didn't clump very well. The yield is drying on sieves at the moment.

In the end, the questions I am left with are:
Should my mix, while stirring, have a surface temp colder than -1C to -3C?
Why did some of my blue waste phase effervesce on top of the yield in the separatory funnel and is it a problem?
Is it normal for the neutralization emulsion to be extremely thick, difficult to stir, and should I use 10-micron filter paper for this step?

The Professor said on Thu, 14 Oct 2021 at 17:46...

Congrats! it sounds like you survived unscathed ;-)

the colder the better; the reactants won't get down to -12C setpoint of the cooling bath, but they should get down to -9C or so. I don't know how long you pre-chill the reactants, or if you let the reactants get down to -12C before you start dropping, but both of those will help to get lower temps from salted ice. Some cover the reaction vessel with cling wrap (with a hole for the dropping tube). Some pre-chill the salt and water into ice cubes (slushy really, not solid); Some use dry ice; whatever gets you there.

If your waste phase was so energetic that gasses erupted to the yield layer, then you likely had too fast drop rate (or had a short term period of steady flow before you got it slowed down, the temp rose in the vesssel, and stayed there.

Just guessing, but if that was the case, if you ever have to stop a steady stream from the stopcock, let the reaction get down in temp again before resuming dropping.

The neutralizing step is hard on a magnetic stirrer; after a trip to hobby lobby for some neodymium magnets, I can spin at top speed during neutralization.

I found that filter paper is too thick, even when pulling the yield through it under vacuum (hand pump), but a little square of paper towel in the funnel works well; if you are cold enough, the baking soda will become a paste and liquid yield can be poured off directly without a filter.

You might want to clamp the reaction vessel in place, or remove water periodically so that the vessel doesn't float

Charlie said on Thu, 14 Oct 2021 at 18:41...

TY Prof. I owe my limited first-time success all to you, so thank you.

I believe part of my difficulty controlling the temp is that I didn't have experience with the dropper and that I was dilly-dallying getting the right stir bar, stir speed and dropping speed figured out. What I thought would take me a couple hours, ended up probably taking 5 or maybe even 6 hours total once I got going with cold reactants, to be honest.

The reactants were -12C when I started, but I am sure they didn't stay that low for very long as everything was taking much longer than expected. MUCH longer than expected. I learned so much that I am still processing. I was exhausted wearing a mask and babysitting the dropping. I felt that the 3M mask didn't completely work, but I had a good vent hood which helped.

I found that as the volume in the dropping funnel decreased, the drop rate slowed and required me to make minor adjustments. I assume this is to be expected? I will try wrapping the top of the vessel next time, sounds like a good idea.

It's interesting that you mentioned making slush. I tried this a couple weeks ago on my own wondering if it would work. However, I discounted the idea because it seemed unnecessary. I would think that the slush would make the beaker tend to float even more than Ninja blender snow ice and salt? Clamping the beaker sounds like a good solution in any case.

Yes, the waste phase seemed very energetic and I didn't know what to make of this. At times, it resembled a mini lava pool. I am stuck on what you wrote: "you likely had too fast drop rate (or had a short term period of steady flow before you got it slowed down, the temp rose in the vesssel, and stayed there." I believe you hit the nail on the head. The waste phase at the end of dropping was a deep royal blue.

The questions that I would love to really ask you are:

-Am I correct that you have said many times that waste phase perfection would be just pale blue? (My yield was a pale green so I thought that maybe I hit that mark, but the waste was deep royal blue. That combination had me puzzled.)

-If yes to perfection being just pale blue, is this only achieved by slowing the reaction down through speed and temperature adjustment?

-And by having a pale blue waste phase, it will be less energetic and less likely to effervesce to on top of the yield?

-Lastly, what is the purpose of allowing the waste and yield to warm up before separating?

The Professor said on Thu, 14 Oct 2021 at 19:42...

achieving a steady drip rate with an equalizing dropping funnel is easier, but won't drop beneath the surface, so yeah, the difference in gravity between the top of the liquid ijn the funnel and the bottom of the funnel is changing, and so does the stopcock setting required for such a slow drip rate.

It might help to mark a position on the lab stand for the beginning of dropping, then one about 1/4 inch or so above that. Once you get a good drip rate, the next time the drip rate slows down, try tapping the dropping funnel to agitate the stopcock; it's likely that will get the drops running again, for a bit, then repeat. At about halfway about, raise the dropping funnel that extra 1/4 inch, and it should be easier to set drip rate for the bottom half of the dropping.

Some people in our group used an arduino or raspberry pi to control peristaltic pumps instead of using a dropping funnel; that would be fun.

yes, perfection is when the yield phase JUST turns green at -12C and the waste phase is JUST slightly pale blue.

YOur condition indicates that you DID achieve nitrosation of the batch, but the deep royal blue indicates that your powder and HCL are high quality; you can use less HCL until the waste phase is weakly blue.

the consequence of this is that your yield will likely have an obnoxious aroma; obnoxious aromas can mean a lot of things, but a saturated yield with a heavy excess of nitrous acid waste indicates that NO (the active ingredient) is bristling out of solution, into oxygen and generating NO2 (NO2, if in high enough concentration, is a brown or orange gas, but in low concentrations, you'll probably not notice a color, and you';ll think that the batch is ruined.

If that is the case, just leave the yield in a flask in the fridge for a few days. I noticed this accidently, when I was making some runs and testing them periodically (years ago now, but that's when I noticed the ion recombination effects or this reversible reaction). I don['t remember how many days exactly, and it will depend on how much of a molar excess is in YOUR reaction, but my advice is to not throw away a batch that you think is ruined until a week or so has passed; a tentative snuff every X days will tell you when the nitrite has boiled off its excess NO.

You'll eventually arrive at stoichiometric ratios that arrive at a yield that doesn't need this treatment.

Some dwell time in the reaction vessel isn't so much to let reactants get warm; it allows dissolved water to settle out of the yield.

Charlie said on Thu, 14 Oct 2021 at 20:05...

TY Prof. This is great info to chew on as I have to take care of other business today. Definitely want to express my gratitude for all of this info.

A pressing question at the moment (while processing the above info) is if there is any way to tell the color of the waste phase while in the ice bath, without lifting it out?

Lastly, should I cease dropping HCL and discard excess once the waste phase is pale blue and the yield a pale green? (I believe that I achieved pale blue waste pretty early on, maybe after just half of the HCL water mix.)

The Professor said on Thu, 14 Oct 2021 at 20:48...

I suggest waiting until the end of the dropping to determine if you have excess nitrous acid or not.

these are exaggerated but if, for example, you drop twice as fast as optimal during the first half of the prep, then stop dropping, you'll have an excess of nitrous in the waste phase AT THAT MOMENT, but only because the reaction has built up blue nitrous acid because reaction speed was too high; if you stop dropping acid now, you'll end up with unreacted alcohol, and the yield won't saturate.

Charlie said on Fri, 15 Oct 2021 at 01:57...

TY Prof.

I believe that you hit the nail on the head again --- that I didn't have the timing correct and built up excess nitrous. Because I was fiddling with the stopcock every 5 seconds, the drip rate ranged from a low of one drop per 8 seconds to as fast as one drop per 1.5 seconds (using the lap feature on my phone's stopwatch). I had to stop and restart things too much to deal with issues that popped up, but all because of my inexperience. Hopefully, on the next batch, I will be able to nail down the timing much better and then get better end results.

I believed you before when you said that it would take a couple weeks to get the timing down, but still the learning curve is more significant than I was expecting, for someone like me who has no chemistry experience whatsoever! In fact, I think the only Univ science courses I took were maybe biology the first year?! Now, that I have the first batch under my belt, I feel better prepared to make another attempt - now that the initial anxiety is over.

Would you be so kind to provide the info for the Hobby Lobby magnets? I would like to compare them to what's in my stirrer. I definitely had some big problema stirring the emulsion...all my stir bars were getting thrown off no matter the speed.. Maybe it's time to upgrade the magnets. Ty.

The Professor said on Fri, 15 Oct 2021 at 19:46...

adjusting the stopcock can be frustrating; teflon valves seem to have smoother action than glass. The adjustment is usually a teflon bar that you twist between your fingers; I suggest applying torque ONLY at the outermost edges of the bar; this puts the force at the outermost edges of the bar, the further away from the center of the rod the better; some even extend that bar length to have finer control.

hobby lobby sells standard (soft dark brown metal) kitchen magnets, and high strength (silver, hard metal) neodymium magnets. Most stir bars come with two kitchen magnets; I pop them off the bar and glue in neodymium replacements. The flea will now be coupled to the bar's rotation much more strongly.

Another thing, during neutralization, you don't need to have chilling bath circulating underneath the vessel, so the bottom of the beaker can be right yup against the bottom of the stirrer.

First year Chem would have given you more practice with a stopcock, but it's something that comes with pracrice.

Charlie said on Sat, 16 Oct 2021 at 03:05...

TY Prof. for this great info. I never would have thought of modifying the stopcock bar in a million years. I think somehow extending the stopcock bar would help tremendously! I caught early on that just tapping the end of the bar was the best way to go. However, thd dropping speed was definitely still all over the place, mostly from inexperience. I will have to work on how to extend the bar...

In response to part of the thread earlier, I never once saw any brown gas during the entire process - until I dumped the waste into the sink and a big poof of brown gas seemed to fill the sink.

I just picked up the Ninja blender at Costco. $20 off currently... now $50 before tax. Should do better than the wet Vitamix ice...

Thank you for the tip for neutralization. For that step, I had removed the beaker from the ice bath and was attempting to stir with the beaker sitting directly on the stirrer. Interestingly, I never saw any fizzing whatsoever, even when I managed to get a little stir. I didn't know if that meant I didn't need to use so much baking soda and that my yield was not especially acidic?

Nitritespecialist said on Sat, 16 Oct 2021 at 13:01...

@Charlie....you didn't say what alcohol you used....or what the initial odor and effects were.

Be mindful that whatever techniques you use, you will NEVER know for sure what you are ending up with UNLESS you can analyze each brew. So it's all one big guessing game.

With LRM's pentyl nitrite.....which I washed two weeks ago in brine/baking soda and placed on Kcarb/MS4.....it's much much better odor and effects wise...BUT I don't know if it's because it's more pure or not. Nobody can determine purity via a whiff. That's why chemists use analyzers. If you cannot determine purity via a whiff, then how can you possibly troubleshoot reactions? It's all just wild guesses.

The Professor said on Sat, 16 Oct 2021 at 16:12...

Lack of brown gas; that's a good thing, and typical of you undertake the preparation at low temperatures.

No fixing during neutralization is troublesome; there should have been fixing that indicates acid being neutralized (there will be excess acid, even if it's just nitrous acid).

Once you get around to treating the yield, it'll be fairly obvious if it is still stuffed with acid; it'll cause sore throat, nasal congestion, coughing.

If it's VERY acidicic, it might even curl/ closer off your nose. The yield can be neutralized again if you think it needs to be.

I posted previously how to discern what the interjecting poster says it's impossible, of you can't find it I'll look for it again

Anonymous said on Mon, 18 Oct 2021 at 01:21...

NitriteSpecialist, I used n-buytl alcohol, with ACS-grade NaNO2 and HCL, all from smaller chemical suppliers. I do not know the original manufacturers and they would not tell me.

TY Prof. for the info. on the magnets and about the lack of fizzing during neutralization. I am going to dissect my stirrer this week and see what's inside.

Today was day #4 of drying, so I finally took the chance to try my first batch. The odor is interesting and I don't know that it is something that I have ever really smelled exactly before. I went back through my notes to see what I may be smelling, and I do catch hints of mint, like Prof. has mentioned before. The smell is actually quite nondescript and not repulsive at all.. It doesn't necessarily smell like the base alcohol, nor like commercial poppers that I have bought over the past 25 years. It's interesting and a little puzzling.

I used the poppers during sex today and my opinion is that there are no negative side effects. No nose burning, no coughing, no congestion, no headache, etc. They are not extremely potent, but I believe that may be because my reaction took way too much time with all my starts and stops during the reaction. I would describe them on the lowest-end of what I would like as far as potency. They worked and gave me a very nice feeling of a flushed face, warmth on the chest and definitely anal relaxing. However, I would like to try to make them more potent, and more of heady-high than just a body-high. They did the trick, but the feeling was fleeting.

Like the Prof. mentioned, I believe that I had to have had NO bursting out of the solution because at times the pot resembled a lava pool. I don't have enough experience to know exactly what I was seeing, but my gut tells me that my fits and starts led to a protracted reaction that allowed too much NO to leave the yield and then led to weak yield. Please tell me Prof. if this a logical conclusion for a beginner?

The batch is definitely not garbage, but not very potent either. Hopefully, next batch will be improved.

Prof., I know we've done this dance before and going based upon my notes, I am confused about what to do at day #4 and beyond. Here is what I have written down in my notes.

"1) Dry on MS3 for 4 days (96 hours).

2) Cure with 1% potassium carbonate (On 9/26/21 Prof. recommended 0.5-2%) & 10% activated alumina; (what does 10-22 mean?)

3) For self-care: Bottle with 1% potassium carbonate (0.6g for 30 ml) (On 9/26/21 Prof. recommended 0.5-2%) & 3-5 beads activated alumina (or ~1 tsp. for 30 ml); on 10/13/21, Prof. said “I only use it if I'm going to be at home and using vials (only opened for use) That way, the vials stay viable until opened (the k-carb acting like a pause button).”

4) For product to take care of itself or intermittent exposure to oxygen (in response to my question about storing in 4 oz bottles on 9/26/21): Bottle with 10% baking or washing soda and 10% activated alumina (or ~1 tsp. for 30 ml); the acid sink can be baking soda or Kcarb. On 10/13/21, Prof. said “If I'm going to be travelling, I usually fill 30ml 'night stand' sized bottles with 10% w/v washing soda instead of 1% k-carb. the washing soda (or any carbonate really) acting like acid scavengers and neutralizing acids as the bottle is opened.”"

Prof., I know there are multiple ways to cook an egg, but to dumb this down for a beginner: After day #4 of drying on molecular sieves, should I dump the sieves in the garbage and add between 0.5-2% potassium carbonate to the 125ml flask if I plan to keep it bulk and not bottle? Should I add the AA or more MSs (which)? tysm

Charlie said on Mon, 18 Oct 2021 at 01:22...

Woops, above was me Charlie, not Anonymous!

Always Poppers. Everything Poppers. said on Mon, 18 Oct 2021 at 01:23...

Honestly, I enjoy reading through some of the DIY community comments but this is what it basically looks like to me.

$#* D 9888 aaa and then you make sure to get the uptake right or you will >*&DD Iaaa eei@#!!*). Ha! Ha! I know right. I remember when I $#@>>>>>UYYEEWWW and I didn't even have to give it a salt bath. Ha! Ha! Just stay clear of the androsycolorominium nitrite drain through or you will %$#*!!FDSKL:: and then boom!!!

You guys should upload to one of the alternative video platforms. So we can all see what you are doing. It would be great.

The Professor said on Mon, 18 Oct 2021 at 17:36...

Glad to hear that the reaction not only had a towels, but the yield had effects!

It sounds like you are on your way to reaction control.

You've demonstrated that undergoing the preparation at low temperatures removes energy from the reaction, and that makes a huge difference in limiting possible side reactions.

Yes, the aroma should be very non description, almost absent.

Once the nitrite is dry, it should be ready for use, or further past processing if you decide to get into that.

After 4 days, the sieves should still be active and ready to adsorb additional water. If your sieves don't dust very much, or you don't mind the cloudiness, you can leave them in the bottle. I usually dump them and switch from MS to AA for long term storage, it's more of an aesthetic thing though.

10-22 I'm not sure the context, but my personal post processing lasts that many days; that might be

The Professor said on Mon, 18 Oct 2021 at 17:38...

Great results for a first try, once you get a 1 mol prep down to perhaps 90 minutes or so, I'm sure that there will be less yield loss, and higher potency.

Good luck!

Charlie said on Mon, 18 Oct 2021 at 18:07...

Thank you Prof. When I initially tried dosing the batch for the first time, I was using a small 10ml bottle filled just half-way because I had not received the sippy cup and the centrifuge tubes I ordered to make a dosing mechanism.

I tried the sock method last night and they hit hard. Whoa, I could hear my heart beating in my ears! They didn't last much longer than when I was dosing out of the 10ml bottle, but whoa they were much stronger! I have a feeling I was not getting enough "headroom" with the nitrite to really feel it, but the sock method worked.

I appreciate your suggestion to keep the MSs. I think that sounds like a good plan. The nitrite is a nice, clear, pale yellow liquid and I do not notice any clouding yet, but will keep an eye for this. Like I wrote before, I know "there are many ways to cook an egg," so I understand that a lot of this is trial and error to see what works best for me, but I appreciate your experience, which is very much appreciated.

Thank you again for your comments and I plan to give it another whirl this week after I dissect and modify the stirrer if I find the magnets to be weak.

Prof., you mentioned clamping the beaker down in the ice bath and I have been searching for a way to do this (spent way more time than I would like to admit!). The top rim of the 600ml low form Pyrex beaker with airline tubing taped to the bottom sits just flush/level with the top rim of the 8C Pyrex. How would I go about "clamping" the beaker in the ice bath because both rims sit flush/level with each other? I thought about using the clamp below and just using the jaws to press down on the top rim edges of the beaker:
https://www.amazon.com/gp/product/B00VF0OMGM/ref=ox_sc_act_title_1?smid=ACTB8CBED46SR&psc=1

Do you have any other suggestions?

The Professor said on Mon, 18 Oct 2021 at 19:11...

"I thought about using the clamp below and just using the jaws to press down on the top rim edges of the beaker:"

That's what I did; only I went even more ad hoc; I used one of the ring clamps i'd bought in a set of three (and use one for holding my separatory funnel)

it doesn't need to be held firmly in place, just kept from floating

https://www.amazon.com/Laboratory-Support-Stand-Clamps-Retort/dp/B08N14D1VB/ref=sr_1_3?dchild=1&keywords=laboratory+ring+clamps&qid=1634584912&sr=8-3

The Professor said on Mon, 18 Oct 2021 at 19:12...

yes, some type of dosing device that let's vapor build in a volume is much preferred over trying to sniff the vapors out of a small bottle

Charlie said on Mon, 18 Oct 2021 at 19:30...

Prof., thank you for that link. I also looked at those and was pondering if they would work! I will have to give it a whirl.

I had an opportunity to disassemble my Labline stirrer (new, old stock) and found that it has a very interesting U-shaped magnet that looks to be one-piece custom milled magnet. It would not be so easy to just pop off the magnets and replace them. However, it seems that it is a very strong magnet. Anything close clings with force.

I took some measurements and found that the top edges of the magnet sat about 5mm below the stirrer base. It has some set screws that hold it to the motor's pin so I adjusted the screws to raise the magnet closer to the stirrer's base. I tested it with some water, baking soda and the Bel-Art cross stirbar and it seemed to stir better than before, but I know the real test will be nitrite and baking soda. (I theorize that the magnet was possibly sitting too low before.) If this doesn't work, I will have to investigate a different stirrer, maybe the Hanna that you have proven works.

The Professor said on Mon, 18 Oct 2021 at 20:05...

That height setting may have increased the field strength enough to stay coupled to the flea

Charlie said on Tue, 19 Oct 2021 at 04:54...

@Professor, you mentioned the use of a peristaltic pump to drop the acid, which has led me down a little bit of a rabbit hole of sorts. I have a feeling the dropping funnel, at least the one I have, with a 2mm bore, is too tedious to monitor with the pressure changes over the drop.

I'm not keen at the moment building my own dosing system for simplicity's sake, so I looked for some low flow all-in-one pumps. I would like something plug and play. Any thoughts about something like this, which says that it can go as low as 1 ml/min.? If I calculated it correctly, 91 ml of 37% hydrochloric acid & 20 ml of water in 90 minutes would be about 1.25 ml/min.

https://www.amazon.com/Intelligent-peristaltic-Adjustable-Kamoer-Laboratory/dp/B097MG39QD/

Charlie said on Tue, 19 Oct 2021 at 05:39...

The manufacturer actually shows that pump machine as a low of 1.2 ml/min, page 46:

http://kamoerpumps.com/uploads/kamoer.pdf

This would seem to fit within the wet method, right? I figure for $100, it would be easier than building something myself, if it works as it says. The company seems to make other popular dosing equipment.

The Professor said on Tue, 19 Oct 2021 at 16:56...

I have no personal experience, but it can and has been done. IIRC, the guy on our site that did it used custom coded Arduino processors to control peristaltic pumps. It sounds like a fun project. I'm not sure what type of rubbing he used, but I remember a few trials, I don't know what he settled on, but the rubbing had to be acid resistant and it has to stay flexible at cold temperatures

The Professor said on Tue, 19 Oct 2021 at 16:58...

Tubing

Charlie said on Tue, 19 Oct 2021 at 17:48...

Thank you Prof.

I had come across some info. that said I would probably need Saint-Gobain "BPT-chemical stable tubing" for hydrochloric acid.

Charlie said on Tue, 19 Oct 2021 at 19:35...

Upon further research, it looks like Tygon Lab/LFL/Food, Style 500 RF FFKM, Tygon Chemical, Viton and PTFE tubes are all compatible with HCL.

It is silicone, C-Flex and Tygon Fuel that are not, while Pharmamed BPT and Norprene show minor effect of slight corrosion or discoloration with HCL.

Charlie said on Tue, 19 Oct 2021 at 23:44...

Professor, I am really thinking of giving this a go with my next try. I just don't see how I could possibly replicate the consistency of a pump with the dropping funnel that I have. I think with experience that I could get better with the funnel, but it would probably still require me to monitor frequently, especially after recognizing how finicky the stopcock acted last time around. I began to think that I would upgrade to a dropping funnel with a PTFE stopcock like you recommended, but then I started to consider why spend the money on another dropping funnel when I could put that toward a pump setup that would not require as much babysitting. Kamoer just released a newer peristaltic pump for about the same money that is controllable via a WiFi app, but I think that's probably overkill and may not be supported in the future. By the way, I settled on Saint-Gobain Tygon A-60-G tubing to work with the HCL. I'll let you know how it goes.

The Professor said on Tue, 19 Oct 2021 at 23:51...

Sounds like fun, plug and play

Charlie said on Wed, 20 Oct 2021 at 04:15...

Professor, would it be crazy to think of replacing the ice bath completely with something different? I have one of those Dometic 43 quart 12v compressor freezers meant for traveling and it got me thinking to just stick everything inside rather than mess with the ice bath. I think it gets down to -8F/-22C. What would you think if I wrapped the stirrer in something to insulate it (I'm not certain of it's operating temperature)? The peristaltic pump machine can operate to -20C. I know I would have a few cords protruding from the top, but I think it could still keep it fairly cold. Crazy or sane?

Charlie said on Wed, 20 Oct 2021 at 04:22...

I.e. are fumes a concern and dangerous in a confined space even at low temps such as -12C?

The Professor said on Wed, 20 Oct 2021 at 18:14...

a maker on our group uses a powered cooler; it works, but i don't know how well.

Another alternative would be switching to a jacketed reaction vessel, and pumping a mixture of solvents through the jacket; some of the solvent mixtures get much colder than salted ice, but would require that the waste be disposed of, ($$) rather than dumped down the public sewer.

If you don't like a magnetic stirrer, there are overhead stirrers that have much more torque.

The most dangerous vapor that CAN evolve from the preparation is nitrogen dioxide (NO2). If the prep is happening anaerobically, there will be NO NO2 emitted, but when NO bubbles up and hits oxygen, it turns into NO2.

Safe Occupational exposure rates can be found elsewhere. I don't recommend hovering over the reaction vessel in an enclosed space. When I was making this way, i would set the stopcock, walk away for 15 minutes or so, then check back in. As you get better with setting the stopcock, you'll discover how to reduce your exposure time.

A setup with pumps would greatly reduce exposure tie if the stopcock is too troublesome

Charlie said on Wed, 20 Oct 2021 at 18:36...

Thank you Prof.

The portable freezer that I own is an older one and uses refrigerant lines embedded in the walls similar to a manual-defrost freezer (remember those!), so I theorize that maybe I could make sure that the vessel(s) are contacting the area of the refrigerant lines. I know from experience it gets especially cold. I also know the most newer portable compressor coolers use fans and I think those would probably be less effective since they cool the air.

Maybe I will have to give it a try! I was thinking it would save me the hassle of switching out ice baths and dealing with them in the first place. I'll let you know how this works once the pump and tubing arrive!

I was hovering over the vessel last time around as I was babysitting the stopcock and since I had NO bursting out, you can guess how I felt after a couple hours even though I was wearing a 3M vapor respirator. Don't want to do that again!

Charlie said on Wed, 20 Oct 2021 at 19:39...

The n-butyl nitrite smells very much like ginger-ale, if anything. I think you may have said this Prof. I was wrong about the mint smell (which I now realize you said is tert-butyl). I opened the bottle yesterday and was immediately reminded of a very slight ginger-ale smell! I was like "that's what it is!"

The Professor said on Wed, 20 Oct 2021 at 22:19...

that's what it most smells like to me; ginger ale. sometimes I think butterscotch, but mostly ginger ale.

Not really what you get from OTC, eh?

Charlie said on Thu, 21 Oct 2021 at 02:17...

Exactly Prof! I had a hard time wrapping my head around the scent because I haven't smelled anything like it before. I was left puzzled until I opened that bottle yesterday and ginger-ale was all I could think of.

Well, I just ordered another stirrer. I got so tired of trying to make the Labline work. The Labline was throwing my stir bars off again. There is absolutely no way it spins at 60 RPMs. More like 3-4x that, much like the 250 RPM+ digital stirrer. I'm sure it would be a great stirrer for some things, just not for this. I tried re-neutralizing the butyl nitrite again using the digital stirrer and it makes quick work with the emulsion without issue using the Bel-Art cross stirbar, and it was nice to see how the baking soda clumps when the nitrite is cold. Should have remembered I had the digital stirrer in the closet!

I could not find the Hanna stirrer available, except used and that would work but I am hesitant to buy something again that can't be returned. I just ordered an Apera Instruments AI2801 and looks like it should spin nice and slow after watching a YouTube video. Says it has a 2-year warranty. Although, reviews are all over the place...I am concerned it may not be able to get through the NaNO2 and alcohol, but the digital stirrer will work as a backup.

Charlie said on Thu, 21 Oct 2021 at 17:48...

Prof., for my next batch, I plan on placing everything in the portable freezer, ice bath included. My reasoning is that I won't need to change out the ice bath and I can use the peristaltic pump to draw from the entire flask of HCL as it will remain very cold (no recharging the dropping funnel). If the portable freezer works, maybe I would skip the ice bath for the next batch, depending on my success with freezer + ice bath.

The concern I have at this point with the peristaltic pump is that the tubing has a very small inside diameter of 1/16". I think this will clog in no time with white paste if this tube is placed directly in the reaction vessel. My idea is to use a 10mm OD boro glass straw suspended in the beaker below the water line with the 1.5mm ID dropping tube from the peristaltic pump suspended inside that tube, maybe a couple inches above the water line. This way the dropping tube is effectively 10mm OD. Does this sound like it may reasonably work without clogging too much?

The Professor said on Thu, 21 Oct 2021 at 18:29...

I sent some of the white paste in to be analyzed; it is primarily butyric acid. It doesn't evolve within the dropping tube, but is a side reaction from the reactants combining; it shouldn't have any bearing on diameter of the tubing, but your proposed mechanism sounds like it's suitable.

I've been thinking about your troubles with the dropping funnel. First, is it a dropping/addition funnel or a separatory funnel? You mentioned a pear shape, which is usually a separatory funnel. A separatory funnel is useful for dumping the waste phase from the yield, and it's stopcock is best used as an off-on switch. An addition or dropping funnel is intended for setting a specific drop rate, they usually have a teflon stopcock and small bore for fine adjustments.

Another thing to try; if each drop is too reactive (foaming/boiling) or a slow drip rate is hard to achieve, you might try further diluting the HCL to accomodate.

Charlie said on Thu, 21 Oct 2021 at 19:11...

TY Prof.

Thank you for the info about the white paste! How interesting. I found that it had clogged the tube on my dropping funnel and I had to actually use a toothpick to scrape it out and clear the tube to allow the HCL to drop freely again. One of my many fits and starts.

The funnel I purchased for dropping the acid says it is a dropping funnel, but I could have been fooled. I ordered the 250ml version:
https://www.ebay.com/itm/172630969920?

I used some Thomas stopcock grease on the glass stopcock.

Separately, I have a Kimax 500ml Squibb separatory funnel for the final stages of prep. It has a PTFE stopcock.

Thank you for the tips about adding more water. I was considering doing just that if the peristaltic pump were to drip too fast at its slowest setting and if I still getting NO bursting out, however, it may be less likely if I better control the reaction temp.?

Charlie said on Thu, 21 Oct 2021 at 20:00...

I believe the bore on the dropping funnel's stopcock is 2mm.

I believe some of my trouble with fine-tuning the stopcock may be attributed to pressure changes due to the decreasing volume in the funnel, as well as the build up of the paste changing the back pressure on the funnel. The inside diameter of the funnel tube is 5.5mm and much of that became clogged with white paste. At a couple points in the process, absolutely no drops would come out unless I lifted the whole funnel out and started again (more of my fits and starts!). This was toward the end and may be alleviated if I were to raise the funnel the 1/4" like you recommended for the last half of the HCL. Hopefully, the peristaltic pump, arriving shortly, will prevent these issues without causing new ones!

Charlie said on Thu, 21 Oct 2021 at 21:19...

My Kamoer F01A-STP arrived and I am impressed so far. From the instruction booklet, it is clearly made for aquarium dosing. However, I could see how this could be an energy hog for that use as an Amazon reviewer noted because the internal fan does not turn off as long as the unit is powered on.

After priming and calibrating, I found that it actually operates at a very-low flow in manual mode, maybe much lower than the specifications indicate of 1 ml/minute. I am testing and calibrating now to be able to drop 110ml in 90 minutes. It looks like it will handle this with remarkable accuracy.

The Professor said on Thu, 21 Oct 2021 at 21:35...

sounds great

Charlie said on Thu, 21 Oct 2021 at 22:14...

TY Prof. for the tip about the peristaltic pump...it's another thing I would have never thought of in a million years without your help. I was very easily able to dial in the Kamoer F01A-STP to give a drop rate of 110 ml in 90 minutes. It equates to about one drop every 2 seconds, but the 1.5mm ID tubing and the drops are teeny tiny. I am testing out a full 90 minute run at the moment rather than an extrapolation.

The F01A-STP's flow dial is a little finicky, but not too terrible to dial in and hoping it will stay where it's set. Keep in mind, I am testing with room temp distilled water and the included silicone tubing while I wait for the Tygon Chemical tubing to arrive. It will be interesting to see if cold HCL changes the flow at all in the Tygon Chemical tubing.

It is nice how the pump's display counts up the milliliters dispensed in 1/100ths of milliliters. I think it's a little off, but I believe probably accurate enough for this prep. The flow dial is set at about 1/3 of maximum, so this shows you that the pump machine can probably achieve a much slower flow rate than the specification of 1 ml/minute.

Charlie said on Fri, 22 Oct 2021 at 01:18...

An interesting note about the Kamoer F01A-STP. While it has some auto modes to dispense based on amount and time, the manual mode is the only mode that supports adjustment to the flow speed adjustment knob. I was able to adjust the flow speed to drop 110ml is 88 minutes.

The pump head components say they need replacement after running 1000 hours and the motor head has a lifespan of 5000 hours. For $100, I'm pretty happy. It seems to be built robustly, it's pretty intuitive and fairly accurate. I need to find out if there is a way to calibrate for longer than 60-seconds, but not that I really need the display to be accurate.

Charlie said on Fri, 22 Oct 2021 at 19:36...

More tinkering with the Kamoer peristaltic pump. I was wrong...the auto feature will operate at the flow rate set in manual mode. The manual is very basic and not clear. Auto modes will dispense based on either a set length of time or a set volume amount, as well as an interval mode.

However, in auto mode for example, if I were to set it to dispense 110 ml of liquid, it would determine the set volume amount from prior calibration. Yet, I know that the calibration is slightly off. I am using a Class A measuring cylinder and I believe that the calibration is off in the area of 10%. There is no way to calibrate the pump for more than 60 seconds, which is where to problem starts.

Consequently, I believe it will be better to know, for example, that I can drop 110 ml in 88 minutes. I'll use manual mode and set my own timer for 88 minutes. Despite this challenge with an inadequate calibration feature, I am extremely happy with the consistency of the pump and that will allow me to later make adjustments to the process with some reliability (i.e. if I need to speed up or slow down the flow).

Nitritespecialist said on Fri, 22 Oct 2021 at 19:58...

@Charlie.....I had some brews of isobutyl nitrite that smelled like ginger ale, but never the n-butyl. It will be interesting to see if you get a consistent odor over time....over the next 3 to 6 months for example. If you do, I would consider that some sort of success...although it doesn't prove purity. The n-butyl I bought from Sigma..smelled nothing like anything I ever made, but the distinct Locker Room scent was a huge clue that the odor is most likely indicative of n-butyl nitrite. The residual fluid in the bottle developed a very very sweet banana like odor.

The Professor said on Fri, 22 Oct 2021 at 21:02...

manual mode sounds like it will do the job just fine;

you SHOULDN'T be getting the traditional 'locker room' scent from this preparation that the intruding poster mentioned. That is an effect of butyric acid, which becomes solid at -5C or so.

That's the foamy paste that sticks to the dropping tube; if you let it sit and become reabsorbed into the yield, THEN your odor will start out a bit like a locker room (butyric acid has a wide range of odors, varying by concentration: cheese, butter, rancid butter, vomit, body odor etc.) but will progress to nastier aromas later on. By culling the solid from the reaction vessel, you are removing the butyric acid side reaction, the body odor aroma AND the more obnoxious aromas that would otherwise build up

The Professor said on Fri, 22 Oct 2021 at 21:18...

if you start to get a very sweet, banana like odor from any of the butyl isomers, that's butyl acetate, not butyl nitrite. It has no effects other than odor, but it exposes the presence of acetic acid in the mix.

Acetic acid is a possible side reaction at higher temps. In the presence of n-butyl alcohol, acetic acid becomes butyl acetate instead of butyl nitrite. If that wasn't bad enough, acetates combine with other decomp products to become nitrates. Both nitrates and acetates are stealing ions that otherwise would become nitrites; not good.

NitRATe has a much higher body load than nitRITe; instead of feeling energized, NitRATes will have an intoxicating effect; you will feel lethargic, nauseous and 'drugged' rather than energized, excited, and
euphoric, and recovery time will be protracted .

None of this happens if you remove the activation energy required; down at -12C you should not be having any of those problems

Charlie said on Fri, 22 Oct 2021 at 21:44...

Thank you for all the info.

I am very excited and anxious to give this another try as soon as my new equipment supplies arrive.

I'm thinking for the next batch that I will use a 500 ml Erlenmeyer flask with a drilled #7 stopper for the reaction vessel. I will place a 10mm Boro straw in the drilled stopper hole and suspend that just under the water line. I will suspend the Tygon chemical tube from the peristaltic pump inside of that. This should make cleaning off any paste on the Boro straw as easy as pulling the stopper out (thanks Prof. for explaining why the white paste needs to be removed as it builds up). I hope it will beat trying to clean the dropping tube out with a toothpick without spilling acid, like the balancing act I found myself in before!

I'm still trying to figure out in my head how I will set this all up in the portable freezer. For example, will I keep the pump itself outside the freezer, while keeping the acid vessel and tubing in the freezer. The pump.says it can operate in -20C, but maybe I don't want to stress the electronics (it's possible to peek at the circuit boards in the pump through the vent holes and it's not an uncomplicated piece of tech).

I'm hopeful that by using a freezer that I won't have to change ice baths, just maybe stop the pump and clear the butyric acid once or twice. If it works (fingers crossed), I'm an curious if the cooling capacity of the freezer would allow me to forgo an ice bath completely in the future. That would definitely simplify the equipment and process.

Charlie said on Sat, 23 Oct 2021 at 00:15...

My portable freezer has a turbo blast mode. I'll have to test what happens if I use that feature during the reaction. Prof., if I set the freezer to -22C/-8F (the lowest setting), I know the reaction vessel, even if also inside a salted ice bath, probably won't reach that low.

However, if it were to get colder than -12C, are there additional concerns to consider? I know you mentioned someone else was using dry ice to get to -15C, but I cannot recall if there are any other considerations except for white paste buildup at temps that low...or lower?

Nitritespecialist said on Sat, 23 Oct 2021 at 15:34...

I am only the messenger. I have described 95% Sigma Aldrich's n-butyl nitrite as best I could. If someone doesn't think it's a worthy enough "standard", then just state it. YOUR "standard" is better.

By Locker Room scent, I did NOT mean nasty body odor. I have described this odor previously as being a newly cleaned and deodorized locker room. It is NOT a BAD odor. There were ZERO bad odors in Sigma's n-butyl nitrite.

Nitritespecialist said on Sat, 23 Oct 2021 at 15:37...

And really...when did this public forum become a private forum, forbidden to "intruders"?

Nitritespecialist said on Sat, 23 Oct 2021 at 15:43...

@Charlie.....it's obvious that what you have been encountering with your attempts with making poppers has been far move involved....not simple in the least. I hope you find lasting success, but the proof will be in the pudding after many months of trial and error. Whether you will be able to make consistently good poppers, with similar odors, effects and lasting potency, over months is the million dollar question.

It's always good to have a known "standard" by which to judge brews. Ideally, that's where one would start.

The Professor said on Sat, 23 Oct 2021 at 18:39...

Going below -12C or so will have challenges, but you seem to be up to the task. E. G. The maker on our forum that uses dry ice dilutes in water, if not the temp is way too low and freezes the liquid.

That's probably why your dropping funnel (with a very thin walled small diameter down tube) freezes up, and the extension I was using, with about 3/4 inch diameter, didn't.

I'm looking forward to your results with the pump. I think it has great potential

Charlie said on Sat, 23 Oct 2021 at 20:28...

Ty Prof.

Earlier you mentioned an overhead stirrer. I believe that I could really ditch the ice bath if I could place the reaction vessel directly on the floor of the portable freezer, and use turbo blast mode, since it has refrigerant coils in the floor and walls. This would mean I would need an overhead stirrer in lieu of the magnetic stirrer. The lab-grade overhead stirrers are pricey and large. I see there are some cheaper ones. I wonder if something like this would work? Any experience or thoughts?

https://youtu.be/hgKE4XXXc6U

The Professor said on Sat, 23 Oct 2021 at 20:53...

I have one, for other purposes, but you don't have to pay $$$; a $$ model should work just fine, ebay usually has used ones for sale. you aren't mixing viscous fluids or solids, so you don't need a particularly strong one. In a pinch, a drill press, or even a hand held drill with a paddle biut would work.

I've been thinking about keeping the tubing from freezing up; what about using a test tube, inverted, to clamp onto the lab stand, cutting a hole in the bottom of the tube, and epoxying the pump tube into the bottom (the top now, since its inverted) and the opening of the tube goes into the reaction vessel, below the surface, and into the water/NaNO2 phase; the tube will provide a column of air within which to pump HCL into the bottom of the test tube (now the top) each drop will fall under the surface, and enter the reaction vessel through the test tube opening; the wider diameter and air gap will prevent the tubing from freezing.

might be worth a try

The Professor said on Sat, 23 Oct 2021 at 20:54...

hand held drill or electric scre2wdriver, slow spin rate

The Professor said on Sat, 23 Oct 2021 at 21:16...

ken said "I am only the messenger. I have described 95% Sigma Aldrich's n-butyl nitrite as best I could. If someone doesn't think it's a worthy enough "standard", then just state it. YOUR "standard" is better."

I call BS on this one, no surprise.

You've been called out repeatedly that your choice of a standard is unsuitable, yet you still cling to it when it is a handy bludgeon.

When posting to others, you are aware that the products sold as solvent by sigma aldrich and others is unsuitable for a 'poppers' standard.; The solvents aren't produced with inhalation in mind, are often acidic and stabilized with chemicals that are repugnant to the human airway.

When arguing with ME, you always fall back on 'well the sigma standard that I bought wasn't like that at all'.

It seems that this forum has had enough of you, and being the attention seeker you are, you resort to imposing yourself into other people's conversations with nuisance lies and obstruction

Charlie said on Sat, 23 Oct 2021 at 21:52...

Thank you Prof. for the idea about the inverted test tube! That sounds very viable.

Thank you for the idea for the overhead stirrer. Yesterday, I had actually just pulled out my KitchenAid hand blender fitted with an emulsion rod to see if it would work! However, it was creating a vortex even on the lowest speed.

I just received the Apera stirrer and it stirs magnitudes slower than the Labline that I had been struggling with. What a difference, OMG! I think the Labline was a dud and didn't match the specifications of 60 RPM low - not even close. It wasn't going to work no matter which stir bar I used, how much I tried and how much patience I expended.

I'm first going to give the peristaltic pump a try with the 10mm boro glass straw in a #7 drilled stopper fitted onto a 500ml Erlenmeyer flask placed in an ice bath. I was hoping that this would simulate a dropping funnel's tube. I am considering I may encounter different pressure issues than before. However, I will definitely readjust and give the inverted test tube idea a go if I find this initial idea doesn't work out. I first wanted to give my initial idea a go because it would mean that I wouldn't have to try to fit a lab stand in the freezer, and I already have the supplies coming.

Now, I am going to test that the stirrer will operate consistently at -22C. ;-)

The Professor said on Sat, 23 Oct 2021 at 22:19...

i forgot about your idea with the 10mm tubing; that would likely be more compact

Charlie said on Sat, 23 Oct 2021 at 22:20...

P.S. Thank you for getting me to consider that I need a column of air in the dropping tube to get the drops below the surface of the water. I am going to seal the top of the Boro straw and peristaltic pump tube with some modeling clay. Same overall idea as yours but using the Boro straw and modeling clay vs. test tube and epoxy.

Charlie said on Sat, 23 Oct 2021 at 22:29...

I will have to think more about how to join the pump tube and the glass straw together more permanently if it works temporarily. Maybe some epoxy like you mentioned.

Charlie said on Sun, 24 Oct 2021 at 19:45...

A little update on testing the modified apparatus.

I decided to freeze overnight a 500ml flask with isopropyl alcohol in an 8C Pyrex filled 2/3 full with regular tap water. The "ice bath" now a giant ice cube, got to -24C and the alcohol reached -22C. I ran the stirrer with the flask of alcohol sitting atop a piece of Styrofoam in the freezer for 2 hours and it chugged away nice and slow with no problem. It may be a little tricky to remove the yield in the end if the flask is frozen in a giant ice cube depending how frozen the ice bath remains. I plan to next test the full apparatus with the peristaltic pump and some alcohol for 90 min.

Prof., I have a question about step 16 and 17, where it says these steps should be done removed from the ice bath. Would you be so kind to explain the rationale behind doing these steps outside of the ice bath? Step 18 and 19, I remember you mentioned earlier was to allow dissolved water to settle out of the yield.

The Professor said on Sun, 24 Oct 2021 at 20:21...

Sounds like you're on the road to success with the freezer; good luck!

19 is giving the yield some time to let the water precipitate out of solution

16+17 seem to be giving the reactants a bit of extra time to find each other in the solvent.

It won't be much of an issue with 1 or 2 mole reactions, but if you are making liters at a time you're going to have quite a large reaction vessel (with this process), and there will be unreacted components, still floating in the solvent, waiting to find each other.

Charlie said on Sun, 24 Oct 2021 at 20:44...

TY Prof. Ok, that makes sense. I don't ever plan to do more than 1 mol so I'll have to see if there's any difference between doing 16 & 17 outside of the ice bath once I get the other processes ironed out.

The Professor said on Mon, 25 Oct 2021 at 13:59...

There might be some ironing left to do.

This is probably a 'silver lining' situation, in that had I known the style of dropping funnel you purchased (long thin stem) I'd have suggested otherwise (a thick glass extension).

The thin walled down-tube of your funnel isn't suitable for low temperatures; it's a balancing act trying to figure how much detail to include in a guide, and the guide failed you in this case (costing you more money).

On the bright side, the peristaltic pump will be much more repeatable than a dropping funnel, and I believe will be superior once you get the apparatus running smoothly.

Charlie said on Mon, 25 Oct 2021 at 16:22...

TY Prof.

Oh, gosh no, I don't think the guide failed me in the least. If anything, the guide saved me so much money. I would have been lost in the dark without it. You showed me exactly the dropping funnel that I should have purchased and it was in at least one of the guide photos as well! It was my fault for not sticking to the tried and true and thinking that I could order one from overseas and save some money. I believe in learning experiences. I did not even know what a dropping funnel was 2 months ago!

I agree that I think this was a silver lining instance. I love repeatability and I think the peristaltic pump will fill this need nicely. By buying the wrong funnel, it also forced me to examine my cooling apparatus and led me to trying some different methods for that.

I am very excited to give this another try. Of course, I'm waiting on chemical tubing and it's the one thing that seems delayed...

Charlie said on Mon, 25 Oct 2021 at 16:39...

Prof., last evening, you also got me thinking that I need to use a larger diameter tube. I started looking for something that would work and found some larger 14mm borosilicate tunes that are meant for drinking Boba tea. I may give them a try if I find the 10mm are clogging.

Charlie said on Tue, 26 Oct 2021 at 16:39...

Prof., I noticed that the nitrite started to eat away at the black neoprene stopper on the flask after about 2 weeks. Should I have used a cork stopper instead of black neoprene? ty

The Professor said on Tue, 26 Oct 2021 at 18:15...

Look for glass on glass joint. Strippers are available separately if you know your joint size, e.g https://www.ctechglass.com/ctech-1420-joint-solid-pennyhead-glass-stopper-laboratory-glass-p-97.html?gclid=CjwKCAjwzt6LBhBeEiwAbPGOgfKKTNCEozg012MKngDkJ8xCpLtbi6xAh5Ik5mTJSX91ktG6_Ywr3hoCdtMQAvD_BwE

Charlie said on Tue, 26 Oct 2021 at 19:10...

TY Prof.! Makes sense to use glass stopper. What was I thinking using rubber...

The Professor said on Tue, 26 Oct 2021 at 20:13...

https://youtu.be/Eau5LvPwJSY

Charlie said on Tue, 26 Oct 2021 at 21:32...

TY Prof.! Now I can put that large tube of Thomas stopcock grease to good use! I thought it was going to be useless now that I am using a peristaltic pump.

Charlie said on Wed, 27 Oct 2021 at 02:09...

Prof., you may not know how grateful I am that you check these threads on the chance that I post a call for help. Like I mentioned before, you saved me from making countless mistakes.

Before I go and make more novice mistakes, I figure why not post my ridiculous question here to save myself some possible grief and so that others can learn along with me!

Is there any problem with freezing the reagent mixes overnight rather than the ~2 hours? I.e. the NaNO2/water/alcohol and the HCL/water.

P.S. I will start a new thread after I get my 2nd batch under my belt.

The Professor said on Wed, 27 Oct 2021 at 17:54...

pre-chilling overnight is no problem; neither of the mixes should freeze over in a standard household freezer, and as long as they are stoppered, there shouldn't be evaporation.

this topic is getting long; it would probably be appropriate to start another one with your next batch.

no question is too silly to ask, and may help anyone following along, and myself in making the guide better