NurdRage - 2023-10-21
In this video i synthesize nitrosylsulfuric acid and isopropyl nitrite, and i tried to make sodium nitrite but i failed. My original goal was to make sodium nitrite. Sodium nitrite sets itself apart from the more common sodium nitrate by having one less oxygen atom, which makes it quite unstable under various conditions. This particular challenge intrigued me, and I thought I'd give it a try, even though I knew it's notoriously tricky for amateur chemists like me to produce. I wanted to develop a low-temperature method, which involved several chemical reactions. I began by crafting nitrosylsulfuric acid from fuming nitric acid and sulfur dioxide. Having successfully created nitrosylsulfuric acid, I moved on to the next stage: generating isopropyl nitrite. The idea was to eventually use this compound to produce sodium nitrite. The formation of isopropyl nitrite was quite intricate and required careful temperature control to keep the reagents and products stable. I attempted to break down isopropyl nitrite into sodium nitrite using sodium hydroxide and methanol but this failed. I ended up with the decomposition of isopropyl nitrite instead. But at least i found a way to make isopropyl nitrite without starting with nitrites. Donate to NurdRage! Through Patreon (preferred): https://www.patreon.com/NurdRage Through Youtube Memberships: https://www.youtube.com/channel/UCIgKGGJkt1MrNmhq3vRibYA/join Twitter: https://twitter.com/NurdRage Reddit: https://www.reddit.com/r/NurdRage/ Instagram: https://www.instagram.com/nurdrageyoutube/
While I don't think there's much if any use for isopropyl nitrite offhand, I really appreciate this failure video, because failure is the mother of learning, and it's always interesting as a layperson with an interest in science to see things like these and whether or not they pan out or not.
It's mostly used for rec-reational purposes
I commented a few years ago but wanted to give an update: I started watching your videos back in 2009/2010 when I was in 5th grade, Im currently in my second year of getting my PhD in physical chemistry and definitely wouldnt have done it without your content.
wow that's amazing! I'm also sorry for ruining your life ;)
@@NurdRage my life has only gotten better the more ive learned. But you sitll share that blame ;)
Glad you are posting these sorts of videos to show that research isn’t all success and the pathway to discovering things isn’t always linear!
Would really love a series from an actual tinkerer like Nurdrage who tries things out on a solid procedure for making sodium nitrite. Ever since that kid unalived himself and parents flipped out at lawmakers, it’s been impossible to get for anyone in the US.
"Research is what I'm doing when I don't know what I'm doing" - Dr. Werner von Braun. You're in excellent company. Keep it up.
i’m excited to watch this :) so happy you’re still posting videos!
More failure videos please. Everyone puts out successes and makes it look so easy, but it isn't. It is the dozens of failures which actually impart knowledge.
Great video as always! Love the lab notes videos! Even when it doesn't go as planned there is still a lot of lessons to be learned.
👍
Thank you for bringing us along on the success and the failures. I had/have a bit of a learning disability so chemistry was not an option in public school but you Cody's lab poor man's chemist and AvE have enriched my life so much thank you and I love you
Well I did not expect to see the synthesis of such a party chemical on your channel XD
I remember using similar nitrites for making diazonium salts in anhydrous conditions, it was a very special use case, but still worth to be known about.
As for the idea, it may be not as farfetched as you think, but you overshoot it probably XD I found that one of the papers mentioned the stability of nitrite during organic nitrite hydrolysis, and it seems buffer is needed, and a bit of acidic pH with halide nucleophile. But maybe I read the papers wrong.
References:
Nitrosation by alkyl nitrites. Part 5. Kinetics and mechanism of reactions in acetonitrile; Michael J. Crookes and D. Lyn H. Williams
Kinetics of the aminolysis and hydrolysis of alkyl nitrites: Evidence for an orbital controlled mechanism; P. García-Santos, E. Calle, S. González-Mancebo & J. Casado
Evidence for concerted acid hydrolysis of alkyl nitrites; Emilia Iglesias, Luis García-Río, J. Ramón Leis, M. Elena Peña and D. Lyn H. Williams
Kinetics and mechanism of the nitrosation of alcohols, carbohydrates, and a thiol; S. Elaine Aldred, D. Lyn H. Williams and Michael Garley
Hydrolysis, nitrosyl exchange, and synthesis of alkyl nitrites; Michael P. Doyle, Jan W. Terpstra, Ruth A. Pickering, and Diane M. LePoire
Great stuff! Failures are in some ways more useful than success.
Hope to see you follow through and succeed in the synthesis!
Glad you're still active, been watching since I was 10!
🤯
the lab notes do offer invaluable insight from the perspective of a professional, and reminds me as a chem undergrad to never neglect my own lab notes in the first place. undergrad lab sessions do suck and i know it'll get better once i start my master's year because there's always room for errors at that point, unlike undergrad where you have everything breathing down your neck everywhere! i wonder how benchtop nmrs would sound (if it is within your budget) to look for binary indicators of product in the first place. as always, thank you! you are i believe the first to inspire me to undertake the path i'm on now and that was many years ago now...
I think the nitrosylsulfuric acid production is quite interesting just by itself. It is unfortunate that it needs RFNA, but the product can do some of what you would use the nitrite, like making organic nitrites, diazoniums, etc.
A formal procedure for isopropyl nitrite as well as isopropyl nitrate, along with an explanation on why the methods differ so much despite ending up with so (relatively) similar compounds would be interesting.
Interesting video as always! Failures are also knowledge, thanks for posting it. Nice intro xD
I don't think a proper video and procedure on how to make isopropyl nitrite is necessary, I don't really see a use for it and if someone really wanted to make it, this labnotes video is more than enough. The nitrosyl sulfuric acid part is very useful! I never needed it, but that's definitely a good thing to know.
really cool process to see.
The easiest way I found to make nitrites happened by accident and early on. I was a pyrotechnics nerd back in the day and I tried to eyeball firecrackers flashpowder, recognizing a gray powder. It never dawned on me that aluminum would find use in fireworks at that age, so I assumed the ratios I'd been told for "flash" black powder (6-1-1) were by volume, not by weight, so I did that, ending up with a gray powder--one that didn't burn that well and oddly seemed to leave these little puddles that would solidify as a cement that looked like dried toothpaste (white toothpaste) albeit with weird color patches in it. This turned out to be slightly decomposed KNO3 or NaNO3 (I was using fertilizer grade so it was likely NaNO3) and was a combination of assumed nitrate salt and nitrite salts. A simple test is to break a piece and drop it into HCl, noting the NO2. I found the most efficient way to get nitrites is 1/1 up to 2/1 nitrate to sulfur by volume. Mix to homogeneity, burn, collect cement that forms. It's effective for amateurs.
Fantastic work!!! Your videos never disappoint in any way but educate with great details.
Also do primary and tert alcohols work too with this method ?
Yep! It's a broadly applicable method
Love this channel.
He's like the grizzled adult version of NileRed.
Thanks for sharing
Both Nitrosylsulfuric acid as well as isopropyl (or many other alkyl) nitrites are absolutely useful chemicals that can be used for further synthesis. Alkyl nitrites are frequently used as mild nitrosating agents, e.g to make Nitrosoresorcinol, nitrosophenol etc from which you can make interesting dyes. So yes, please go ahead! :)
Very interesting! It's unfortunate the hydrolysis of isopropyl nitrite results in tar, otherwise it would be a useful route for purifying nitrite via thermolysis too. That's great way synthesising nitrosylsulfuric acid though!
Very cool !
@NurdRage I´ve seen good wields of sodium nitrite when it comes to reaction which involves heating a mixture of sodium hydroxide and sodium nitrate while slowly and carefully add bits of sulfur from time to time.
the OG of the youtube science community
Hey! I suppose that you needed to use a tertiary alcohol, not a secondary one to make the nitrite.
Tertiary carbocations are more stable and have a higher rate of success with nucleophilic substitution, if you can stabilize the leaving group properly. A basic pH and the size of the NO2- leaving group should be enough for it. This could work better than the Sn2 mechanism you were trying to go for.
Also the Sn1 reaction, that the tertiary carbocation nucleophilic substitution follows requires polar protic solvents, so you don't need to worry about anhydrous conditions. So for example you could start from t-butil-alcohol, make it into t-butil-nitrite and put it in a solution of NaOH or KOH. Just be aware of the flame danger.
Bubbling nitrogen oxides from dissolving copper in HNO3 through a NaCO3 solution works quite well and you can recover the HNO3 by decomposition of the copper nitrate.
Gonna show this one to my organic chem wife later, she'll love it :D
Thank you
The problem may be hidden in the proton near OH. Isopropanol has always seemed to me as somewhat more reactive alcohol. Once I added a bit of 68% HNO3 to an isopropanol in a test tube and it went nuts a mad 30 seconds later. I would try distillation of the ester and hydrolysis in an aqueous solution to prevent a too basic environment from appearing. It's more painful to purify than just suction but maybe (I'm not about to guarantee it) will work.
wow this is amazing video one question though! how water should I add with sodium hydroxide to dissolve the flesh of an farm animal that is exactly 152pounds? 🤔🤔🤔
out of curiosity, what are some of the sites you got to (besides ebay) when looking to get labware (new or used) on a budget?
Great video as always
Nothing special I'm afraid, most eBay, Amazon and AliExpress
now this is a subject dear to my heart; one of the very first projects I tried was making inorganic nitrites, with very mixed success
the big drawback with high-temperature methods is the poor purity of the end product, not least because it's readily oxidised to nitrate in air at the temperatures the reaction is carried out at - an inert atmosphere is essential
for a while I've actually had half a mind to prepare inorganic nitrites this way, and I'm delighted to see it done in practise
here's an idea: would it be worth diluting it in conc. sulphuric acid before adding it (dropwise) to a cold sodium hydroxide solution?
I immediately knew the problem, when he got methanol and sodium hydroxide...I literally just said "idiot" over and over again 😂
Nice one NurdRage. The old book I read said that if you melt sodium or potassium nitrate in an open crucible, then drop in charcoal powder a bit at a time, which goes up in flames. You keep adding the charcoal till it no longer combusts. Then you wash out the remaining salt, filter and crystalise to purify. But actually, I'm not 100% sure the resulting salt is a Nitrite, as the book is old and different terms are used. It was an assumption on my part. Does anyone with experience know if this would result in a Nitrite? If not, what else might it be?
Potassium nitrite is much easier to make yust by heating a mixture of potassium nitrate and calcium formate until it starts to.react. After letting it cool down the mixture is suspended and the suspension filtrated: the nitrite is in the filtrate then and has to be boiled down until all impurities cristallize out. The decanted supernatent contents our desired pure nitrite and can be evaporated hot to dryness.
I made a video about this precudere on my channel.
So you did. Nice video and nice channel.
Interesting, I'll take a look
@@rodneyvinen1594Thanks.
@@NurdRageThanks.
If you want a very expensive way to get purify sodium nitrite, here's one way I did it.
No matter how you can the impure nitrite, you add calcium or magnesium nitrate to precipitate insoluble carbonates and hydroxides. Filter. Then add silver nitrate to the solution and it will selectively precipitate silver nitrite. Filter the silver nitrite. Add sodium chloride to the supernatent to precipitate silver chloride.
Dissolve the pure silver nitrite in water and add sodium chloride and boil it for a while. It will precipitate silver chloride and leave behind pure sodium nitrite solution. Evaporate the supernaturnt under vacuum for best purity sodium nitrite.
Recover all the silver chloride and decomposite it under heat to pure silver. If you're very efficient, I think you can recover almost all the silver and reuse many times. One ounce of silver will probably get you 15 grams of nitrite so it's extremely inefficient. The biggest loss is having to remake silver nitrate again.
thats a pretty good idea! i'll keep it mind for purification.
Would this work with copper nitrate?
@@LFTRnowI'm not sure how stable copper nitrite is. If you mean to use copper nitrite to displace carbonates and hydroxides, then yes it would work.
I think that sodium azide can be made by using isopropyl nitrite in reaction with hydrazine. Sodium azide is interesting and very useful chemical, so making a video about that will be nice.
I have always wondered how well the method of bubbling nitrous oxides through an hydroxide solution works. How easy is it to separate the nitrite from the nitrate? According to the literature is just about solubility, but what is the yield? And couldn't feeding the nitrate back into the reaction lead to a somewhat quantitative yield, step by step?
Could the isopropyl nitrite be decomposed with a strong, non-nucleophilic base like NaH or NaNH3? Elimination reaction to give propene and NaNO2, plus either H2 or NH3
So far the most convenient nitrite production I found is roasting metal or metal oxide with nitrate e.g. Cr2O3 with sodium nitrate (the side product is sodium chromate - also useful chemical).
Another option is heating nitrate in a metal pipe over fire with somewhat controlled temperature - then nitrate and nitrite are separated by means of solubility. More precise separation of nitrate and nitrite is possible but takes more steps - this is often not necessary (some nitrite will inevitably oxidize to nitrate anyway).
Vogel also mentions nitrate reduction with zinc in alkaline environment but I haven't tried yet.
"separated by means of solubility" could you expand on that? From what I saw is that nitrate and nitrite solubility are almost the same in various solvents
@@user-py9cy1sy9u "separated by means of solubility" means you shall regret the whole procedure you're trying to do
@@user-py9cy1sy9u Sorry I wasn't concrete enough. Both salts are generally soluble but potassium nitrate is considerably less soluble than nitrite and might be removed by fractional crystallization (it should precipitate preferentially - but I haven't tried). The solubility can be decreased by common ion effect. Barium nitrate is even less soluble compared to corresponding nitrite but it can be removed more completely by just heating the solution (it will decompose). If lead was used for nitrate reduction, then residual lead nitrate can be decomposed by boiling in anhydrous methanol. Both barium and lead are toxic but can be removed by bubbling carbon dioxide through solution (in case of lead, dissolve it first in alkali as plumbate, then add CO2). If you already have a mixture of sodium salts, I think one possible separation is with calcium hydroxide - this will precipitate double salt of calcium nitrite-calcium hydroxide that will redissolve in more water. Conversion to sodium nitrite can then be done by double displacement and removal of insoluble calcium salt by filtration. Some separations are possible in form of other double salts and mixed crystals, but there are various eutectic mixtures. See e.g. "Ullmann's Encyclopedia of Industrial Chemistry - Nitrates and Nitrites"
Can someone please help explain why the reaction didn't work?
I am just an amateur but my guess is in the reaction the the methanol competed for the NaOH and form sodium methoxide and other side products.
Have you tried the NO2 + NO gas into NaOH method for sodium nitrite yet? It seems to be a promising route.
Have you tried the sodium nitrate/calcium sulfite method? You said you didn't want to use a high temperature method, but it only requires 300C.
Great
Would electrolysis of sodium nitrate with silver electrodes or platinum work in driving off some oxygen from the nitrate ?
@NurdRage So I am new to the home chem realm and am accumulating the labware needed.. How many cheap amazon vacuum pumps should i expect to go through in the first year or so? I imagine things like nitric acid or very basic solutions will be hard on the pump and tubing.. figure ill just buy 2 or 3 so im not out of one when i need it, but i didnt know what to expect and that you might have some words of wisdom lol
oh my, you shouldn't be destroying vacuum pumps! The "Rotary vane" or "reciprocating" vacuum pumps you see on amazon SHOULD NOT be used for hard chemistry! They'll get destroyed. Something better for chemistry is the "water circulating vacuum pump". You need to fill them with water first, but they are much more resistant to chemicals. You still have to maintain them and change the water often, especially after a heavy experiment. But they are great and robust compared to rotary vane pumps.
Never suck actual liquid into a vacuum pump no matter what type it is. Vacuum pumps are for gas, liquid pumps are for liquids.
The vane pumps on amazon are good for refrigerator repair and degassing, they're designed for safe gases like air. But anything even slightly corrosive destroys them.
you should recreate the nitrosylsulfuric acid and then use it to prepare a few azo dyes!
Nice! Wouldn't sodium nitrate thermally decompose into nitrite? I remember from Wikipedia that it happens with potassium nitrate and quick google search suggests that it should work with sodium nitrate too.
I’m working with NHO3 and Hg, are laytex gloves alright because it’s what I have been using….I’d rather avoid a horrible death from Mercury poisoning…
@NurdRage - 2023-10-21
Do you guys want me to make a proper isopropyl nitrite video from this?
@Hippucytees - 2023-10-21
Usually, its best to operate on principal to see something the whole way through. You started, so you'll finish. Knowing you, you won't be happy with failure, so the only reason you asked this is because you must be busting to get at some other project your excited about. Otherwise, if youre gonna do something, do it right..
@valsodar6723 - 2023-10-21
Evan faillure can teach U how to NOT DO That ;)
@ProfaneGod - 2023-10-21
Yes
@lespycrab8265 - 2023-10-21
Yes
@haxmoasta5054 - 2023-10-21
There is very little content on YouTube covering successful nitrite synthesis, so I guess we would all be interested in more videos about this topic. Maybe the alkyl nitrate can be converted to sodium nitrite in less harsh conditions, would appreciate if you invested in another attempt