Molecular sieves

Topic created by Charlie Chuckles
on Sun, 19 Sep 2021 at 21:40

Charlie Chuckles said on Sun, 19 Sep 2021 at 21:40...

I've been doing a little reading and want to confirm that I have this correct about MS use with alkyl nitrites? Am I correct that type 3A is the better choice over 4A because:

Water molecule has a diameter of 2.6Å (ångström)
Molecular sieve type 3A has a diameter of 3Å
n-Butyl alcohol (1-Butanol) has a diameter of 4.63Å
n-Propyl alcohol (1-Propanol) has a diameter" of 4.56Å
Isopropyl alcohol (2-Propanol) has a diameter of 4.9Å

So...while type 4A "should" work to absorb water and reject alcohol, 3A is the "safer" choice?

I had some difficulty finding molecular diameter of Isoamyl alcohol (2-Pentanol) and n-amyl alcohol (1-Pentanol).

Charlie Chuckles said on Sun, 19 Sep 2021 at 21:41...

absorb=adsorb

The Professor said on Sun, 19 Sep 2021 at 21:59...

right on charles;

Activated alumina (various pore sizes) adsorbs water, plus some of the things you don't want it to adsorb; a semi-suitable substitute

MS4 pore size is just a bit too large , but will adsorb water also (as well as some tert-nitrite if you are into using that alcohol.

MS3 is the preferred choice

Charlie Chuckles said on Sun, 19 Sep 2021 at 22:13...

@The Professor:

Thank you, as always - also for the "topping" of knowledge about using tert.

Are the MS3A by the "jug" from the jungle ok if one doesn't have a pharma grade supplier?

If so, the jug says to dry at 550C/1020F. I've also seen where a 250C oven at a couple hours is recommended. Any opinion about this?

The Professor said on Sun, 19 Sep 2021 at 22:54...

MS can be recycled, but I don't bother. I sure it in a mason jar, under vacuum from a food saver level vacuum pump (on the cheap), and it stores nicely.

I don't bother trying to dry out out again after use, but those instructions seem to be the usual

Nitritespecialist said on Mon, 20 Sep 2021 at 00:19...

Actually, the sieves are probably not as necessary as an acid sink preservative such as anhydrous sodium carbonate or potassium carbonate. I've already mentioned the 1958 patent that stated these substances made alkyl nitrites last 20 times longer.

The sieves mostly attract water. But so does anhydrous mag sulfate, a good initial drying agent. And the anhydrous Kcarb does two things....helps keep the popper dry while preventing acid build up, which acts as an auto catalyst for popper degradation. The sieves might be able to dry the popper to the nth degree, but in the short term, the mag sulfate and Kcarb should work. If I had to use one over the other, I would pick the Kcarb.

The Professor said on Mon, 20 Sep 2021 at 00:36...

Those same documents you mention describe the 'Purpose' of using metallic alkali carbonates. To stabilize a(prevent the generation of nitric oxide gas, which starts the degradation cascade) in SRALED containers (the glass ampules that amyl nitrite used to come in)

The metallic alkali salts are overcome by oxygen when opened, and at that point, a PRESERVATIVE of some sort of required to neutralize acids (which go on to produce nitRATes)

The neutralization process produces water, and sieves adsorb the water that would otherwise destroy the product through hydrolysis.

See what I mean again Charlie? Ken can't hold his tongue and isolate his attacks, he is attempting his own version of the filibuster, randomly showing nonsense.

I told you I'd muddle through, with you or anyone else here that's truly interested, and I will

The Professor said on Mon, 20 Sep 2021 at 00:45...

Magnesium sulfate is a quick and dirty go to for macro level drying. It doesn't dry enough to prevent hydrolysis of the very fragile alkyl nitrites.

Google the adverse effects with mag sulfate to alkyl nitrite absorption and you will see why I don't recommend it at all for drying nitrite

Nitritespecialist said on Mon, 20 Sep 2021 at 13:17...

There are many drying agents. They all have their pros and cons. Some work faster than others. Some cloud the organic fluid and must be filtered off. But the most common drying agents work FASTER than sieves. They suck up more water faster, which is what is needed initially. Sieves are for longer term drying....

Charlie Chuckles said on Mon, 20 Sep 2021 at 16:44...

@The Professor

When you write that you have stored your NaNO2 with layers of MS, how are you keeping distinct/"clean" layers of NaNO2 in the storage vessel, or am I making this way too complicated!? I've been trying to wrap my head around what this looks like for optimal storage.

And when you write that you use a Food Saver type of sealer, are you referring to a mason jar sealer accessory attachment, or something else? Always, much thanks.

The Professor said on Mon, 20 Sep 2021 at 17:00...

Can somebody please thropw ken a bonhe? he's hungry for chewing on something.

He just REPEATED what i said (that mag sulfate is a quick (but not efficient) dryer, and that MS is slower but more capable.

yet he felt the NEED to argue, and ended up saying the same thing. Although, it wouldn't be a statement from Ken if it didn't have something ridiculous in it:

He knows (or should know) this, but look at the degradation results i posted with regard to hydrolysis it IS an issue, but it's NOT a catalytic issue (in that hydrolysis takes off with an exponential growth curve.)

TL;DR

A nitrite can survive for 4 days while the MS gets it dry to within 20 PPM, and it will store BETTER than a nitrite that has been quickly dried with magnesium sulfate.

The Professor said on Mon, 20 Sep 2021 at 17:23...

Charles:

There are pics that popchef and the prior moderator have put in the wiki; I haven't added them to the guide available here yet.

It looks like popchef was storing his NaNO2 i think) under vacuum in mason jars. The pics show a perhaps two inch layer of MS, then a similar layer of NaNO2, that repeats until the jar is full; to seal the jars he was using a 'food saver' vacuum pump, with the gadget that fits atop a mason jar lid.

Searching through his early posts, he mentions dumping it into a screening device to pan out the powder from the MS.

Personally, I think this is overkill; he might have been trying to prevent the possibility of even a TRACE of water from getting into the jar, but that is WAY too much MS.

Storing in a vacuum sealed mason jar is good practice, and keeping the powder dry is also advised, but i'd not use quite that much MS.

maybe he found a sale on it

here are some other pics that have yet to be included in the free wiki

reactant storage: https://imgur.com/a/wjAb5#smaOzUm

preparation pics: https://imgur.com/a/j6RbW#dHimtwK

more prep: https://imgur.com/a/JiMZa#wBeeAuX

one thing I shold meniton; the guide mentions that an optimal outcome is a JUST green yield layer and a JUST blue waste layer

The pics show an EMERALD green yield phase and a ROYAL blue waste phase.

mentioned in the text, this was to demonstrate two things

1. that the yield layer, when super-saturated with NO, will turn green at -12C (a handy visual indicator)

2. That the waste phase, which is providing nitrous acid (ROYAL blue indicates purity) to the alcohol, is making good nitrous.

If you try to inhale a product that you've made, and it looks like the pics, it will likely smell very bitter/acrid right away, and you'll think it is a failure.

Adjust YOUR stoichiometry to the condition of YOUR reactants, such that the result is an EXTREMELY pale blue on bottom and green on top, and you will have reached an optimum condition.

I'm not disagreeing with popchef, I'm trying to make the guide more complete.

Nitritespecialist said on Mon, 20 Sep 2021 at 17:39...

Hmmmmm.....kind of hard to disagree with oneself. That's madness for sure...having an argument with oneself.

Everyone on here knows Popchef/Professor/Wetcotton are the same person.

Nitritespecialist said on Mon, 20 Sep 2021 at 17:42...

Oh...and just send all of your newfound popper making disciples some of your tainted poppers. Let them be the judge of how crappy they are. The proof is in the pudding or shall I say, your turbid tainted poppers.

Nitritespecialist said on Mon, 20 Sep 2021 at 17:46...

Yes folks....I was privy to one of the Professor's deluxe samples and boy did I get a full dose of turbid toxic heaven. The odor alone of that thick milky junk made me vomit. I waited a few days to see if it got better, but it never did so I had to dump it. Most toxic, turbid shit I ever forced myself to try.

Nitritespecialist said on Mon, 20 Sep 2021 at 17:48...

And yes folks, I have had some brews I didn't like, but never...NEVER as bad as what the Professor had made.

Charlie Chuckles said on Mon, 20 Sep 2021 at 17:49...

@The Professor

All of this is immensely helpful. I'm a little speechless TBH, other than to say thank you for being so gracious to help others out. This is far and above any help that I could have imagined. The visuals are priceless.

Unfortunately, those jar sealers are incredibly difficult to come by now...something about the manufacturer not even sure about restocking, if or when. Last week, I tried to make my own by creating a cheap DIY jar chamber, but alas did not work as I had intended, not so easy to get a good vacuum. Maybe I will shell out the current extortion price. Had one a year+ ago and tossed it while thinking, "this has been in the drawer forever; when will I ever use this?" :face-palm:

The Professor said on Mon, 20 Sep 2021 at 18:03...

I AM getting a store ready ken, and it WILL provide samples to anybody that is interested.

YOu downplay another maker's product as turbid toxic nasty, etc.

you KNOW that you liked the vapor (ignoring for qa moment the turbidity) and were even somehow thinking of 'allowing' popchef to make for you.

You , at the time, had two complaints, that later became the mantra that you repeat over and over)

Turbidity: alkyl; nitrites over Molecular sieve tend to get murky because the sieves are a clay like substance, and some particles that don't stick to the substrate will be agitated into the liquid if you shake thebottle.

Remember the LATER video, in which popchef posted himself holding a 10ml clear bottle of his 'irresistible bliss'; he used a different sieve, and the loiquid remained completely clear when shaken.

you KNOW this, but are apparently going to run it up the flagpole, again.

Noxious toxic garbage, yes, i've heard it before from you. If you talk to person X you talk about having to use reactants in excess, to PUSH the equilibrium to the yield.

If you're talking to popchef (who tried your idea, and provided you with a sampler that had excess butanol in it, to show you that it didn't really work, you mention an odor that you couldn't tolerate as proof that what he made was toxic.

If it's something HE's done, excess butanol is a slightly sweet aroma; if it's something someone ELSE tries (and is NOT used or suggested by me) then it's a wretched nauseating odor.

Different words for a different audience from the same guy; that's hypocracy

Charlie Chuckles said on Mon, 20 Sep 2021 at 18:21...

P.S. Never mind, the jar sealers are available. :face palm: I'm mixing up old information again. Thanks again for the pictures and details.

The Professor said on Mon, 20 Sep 2021 at 18:27...

no problem,
enjoy!

Charlie Chuckles said on Tue, 21 Sep 2021 at 16:57...

I was reading that "I believe" Sigma said that small quantities of their 3A MSs can be oven dried at 175-260C (350-500F), followed by slow cooling in a closed system, such as a desiccator. I am hoping this transfers to other non-Sigma MSs?

https://www.sigmaaldrich.com/US/en/technical-documents/technical-article/chemistry-and-synthesis/reaction-design-and-optimization/molecular-sieves

Interestingly, they describe the critical diameter of water to be 3.2Å. I don't know enough to understand what that means for desiccating alkyl nitrite using their 3A MSs.

For mid-grade MSs, has anyone washed theirs before oven drying and does it make any difference for short-term desiccation? I read some use acetone.

The Professor said on Tue, 21 Sep 2021 at 18:31...

you'll most often see 2.9 or so angstroms referenced as water molecule diamtere; MS3 is optimum for this.

take a few grains of your sieve, hold them in your hand (or gloved hand if you're cautious) add a few drops of water, and the beads should INSTANTLY Become too hot to hold. if they slowly get warm, they should be dried.

If your MS came in glass vacuum sealed containers, they will likely be active; if they came in a plastic jug, they may have become wet, and will need to be dried

Drying instructions are on the bottle. I've had succewss with a kiln and drying cylinder (in the lab), but not much from a household stove; YMMV.

the brand of sieve isn't as important as the way it is stored; they are all practically identical.

THe thing about drying sieve is that you need to FORCE water back out of the pores; this happens with heat; acetone may help superficially, but is unlikely to get down into the pores to evaporate the water.

Charlie Chuckles said on Tue, 21 Sep 2021 at 19:26...

Thank you.

For the acetone washing, I should have been written that I was wondering about washing the MSs to remove dust, then oven drying them to remove moisture, and if it's even necessary. I saw that some MSs can be dusty. I saw this technique on another forum.

On a separate note, I found a digital stirrer with minimum 250rpms was too much and creating a vortex and sucking in air. Could I get away with a 100rpm and up or do I need to get one that starts at 0rpm?

The Professor said on Tue, 21 Sep 2021 at 20:09...

they are usually variable speed; the vernier can be set to any speed between 0 and the max specified.

Charlie Chuckles said on Tue, 21 Sep 2021 at 20:49...

Thank you. Now you know I wasn't kidding when I said I am starting at a baseline of the most elementary knowledge...that I didn't even know before testing out the stirrer that 250 rpm would be too much.

Charlie Chuckles said on Wed, 22 Sep 2021 at 18:47...

Is it ok to rinse dusty sieves in just DW before drying or is there a better method to rinsing dust off?

The Professor said on Wed, 22 Sep 2021 at 19:25...

water is what they adsorb; if you try to wash dust from them with water, they will get extremely hot and lose some of their ability to adsorb water (they have already adsorbed a certain percentaqe of their capability (about 17% of their weight in water)..

The soft, clay like material will also become eroded if submerged in nitrite. The nitrite itself has a high pKa (acid dissociation constant).

i wouldn't bother , since they will dust AGAIN when they heat up from adsorbing water (thermal cycles break down the clay's adherence to the substrate.

Charlie Chuckles said on Wed, 22 Sep 2021 at 19:37...

@Professor,

Thank you. Makes sense. There are all kinds of things written on the internet.

Do MSs tend to cloud nitrite even if they are top-quality sieves or is this typically a result of only low quality sieves? (In other words, are expensive sieves worth the premium?)

Is the trick to disturb them as little as possible and pour off the yield carefully to minimize cloudiness?

Maxed out 3 questions :-)

The Professor said on Wed, 22 Sep 2021 at 19:53...

Sieves at any price tag will cloud alkyl nitrites; it has absolutely NO bearing on the vapor quality or side-reaction by products; clay is essentially inert, with almost NO vapor pressure.

If you are intending to produce for your own use, and want the liquid to remain transparent, i suggest drying over MS3 for 4 days, doing whatever else you might want to do for post processing, curing, etc.

When you are ready to bottle, decide if you are going to take care of your nitrite (store in a low headspace container (like a vial) and dose from a high headspace container (like a sippy cup)

If are are going to care for the nitrite, I suggest bottling with 1% w/v potassium carbonate (metallic alkali carbonates prevent nitrite from generating gas in a sealed bottle), and about 3-5 beads of activated alumina (also an adsorbant, but it won't dust). Open the bottle ONLY to fill your dosing device, and it will stay pristine.

If you want the nitrite to take care of itself, I suggest 10% baking or washing soda, and 10% Activated alumina. IIRC, this is about 1 tsp for a 30ml bottle.

As you repeatedly open and close the bottle, the soda will neutralize any acids, leaving behind a salt and water.

The salts build up, and eventually congests the soda (turning it pinkish; it should take about 3 months for things to degrade that far though)
The water needs to be adsorbed, thus the tsp of activated alumina.

your choice; but i guess the TL;DR is to DRY (a production step) with MS3 (for 4 days) and STORE with AA

Charlie Chuckles said on Wed, 22 Sep 2021 at 20:03...

@Professor

Thank you, you also answered the unspoken questions simmering, namely if the cloudiness has any negative bearing on the nitrite. I'm not going to worry about it then. Will heed the advice for caring for it.

The Professor said on Fri, 24 Sep 2021 at 00:23...

If you buy 10lbs of sieve for $50, it will likely come in a 0plaswtic jug, and will need to be activated

If you buy 500 grams for $120, it will likely come in a vacuum sealed glass bottle, and will be pre-activated.

IF you have a glass blowing furnace lying around, the cheaper, bulk stuff might be worth it (If you are making hundreds of gallons of nitrite)

The company I used to buy them from is no longer in business; they used to sell pre3-activated MS 1t $80 for 1000 grams.

The closest I'm finding now is cole parmer, $115 for 500 grams. 4 teaspoons will treat 120 ml.

https://www.coleparmer.com/i/spectrum-chemical-molecular-sieve-activated-type-5a-8-12-mesh-500-g/8012775?PubID=UX&persist=true&ip=no&gclid=CjwKCAjwy7CKBhBMEiwA0Eb7alOt-KFItio5Oqc0ty-WTmpqtrjnGLZy_2jA24X1AWDv4wk0lNsyThoCAhIQAvD_BwE

Charlie Chuckles said on Mon, 27 Sep 2021 at 20:57...

I was reading a recent review of the 3A 7# jug @ the jungle and a reviewer said they sucked up as much alcohol as water...

"Mixed these in with 1.75L of 190 proof ethanol and while what came out was 200%, the total volume was only 700 ml after I added enough pellets to fully dry it. This stuff soaked up 875ml of ethanol. The other issue was that the dust it let loose was so fine that my Buchner filter couldn’t get it clear so I had to centrifuge it clear. This stuff is worse than useless."

Professor, I've been looking at Sigma's 3A 8-12 mesh. I would assume Sigma's are pre-activated, right? They come in a poly bottle.

Charlie Chuckles said on Tue, 28 Sep 2021 at 04:33...

P.S. The Sigma website doesn't mention anything about them being activated. For the price, I would hope they are???

The Professor said on Tue, 28 Sep 2021 at 19:23...

diameter of an ethanol molecule is 4.4 angstrom (and won't fit in an MS3a pore); the reviewer or the product was faulty

I'd ask before purchasing; at sigma prices the SHOULD be pre-activated, but it wouldn't hurt to confirm

Charlie Chuckles said on Tue, 28 Sep 2021 at 20:07...

Thank you Professor.

What size spin bar did you use when you were doing the method in the guide? For 1 mol or 1/2 mol synthesis? I have a feeling the 1" is too much and need to size down. That was probably part of my problem with the stirrer I was using, although I now ordered a good one that starts at 60 RPMs.

The Professor said on Tue, 28 Sep 2021 at 22:15...

i use this one: i use them for other preps aside from alkyl nitrites; they work well at slow stir speeds

https://www.amazon.com/gp/product/B002VBW6YE/ref=ppx_yo_dt_b_search_asin_title?ie=UTF8&psc=1

Charlie Chuckles said on Wed, 29 Sep 2021 at 12:33...

Thank you Professor. I will give it a try.

When I was looking at the photos in the guide, I wasn't sure if I was seeing a cross-shaped spinbar or just a regular spinbar spinning. Thanks for the info!