Extractions&Ire - 2018-03-11
We have another attempt at making methalyll chloride, this time by reacting chlorine and isobutene both as gases at room temperature. Will the water help scrub out the HCl byproduct? Will removing UV stop radicals ruining the reaction? We find out. J O H N B L A C K S U P E R C H E M I S T: https://www.youtube.com/channel/UCQwT7_Hd61jorj3f0cenZuA Subreddit: https://www.reddit.com/r/ExplosionsAndFire/ Music: AFX (Aphex Twin) - 3 gerald Remix
Honestly I get really excited when I see your videos.
I don't even know what he's on about most the time but I like watching him jamming in the lab.
Interesting to watch and I admire your perseverance.
I’ve often wondered how the early chemists were able to figure out definitively what they had created with crude instruments. An NMR would be great here but few of us amateurs have one.
Yes early chemists are certainly very impressive, working out the composition, structures of things, without any 'technology' at all! Thats always the thing keeping amaetur Chem going, the idea that people back then did it fine, therefore so should we
Tape some stiff wire such as a wire coat hanger to the teflon piping you can bend it and it stays in shape.
Looking fprward to settling down in front of this vid.
This is proving to be an intriguing (and original) series.
Live audio all the way through.... amazing!.... I never acquired that sort of skills, doing experiments plus talking are just too much work to be done at once.... btw is your tube doing ok after this, mines severely damaged after undergoing similar abuse
Aussie Chemist The tube is wrecked, lost all flexibility. Might be good for one more chlorine run. The isobutene tube is okay except for the end that was in the chlorine, I'll have to amputate that bit.
And practise man, far too much practise.... And heavy editing
Extractions&Ire I’ve been looking for the ultimate tube for all environments, but there seems to be none, tried silicon, ployethylene.... none of them were invulnerable, PTFE is good but not exactly flexible... any good suggestions?
Aussie Chemist The best tubing apparently is a thing called Viton. The inertness of Teflon but actually has flexibility. No always easy to find though and of course.... Expensive. It might be cheaper to keep replacing rubber tubing, rather than buying real good inert stuff
@Extractions&Ire awhile ago I wanted to get viton gloves for working with very concentrated acids and bases. They were just too damn expensive so I ended up settling for butyl rubber
Even with the failures this has been an interesting series to watch so far :)
Good luck!
Get a 10 liter glass jug (used for wine). They're inexpensive.
1:39 : Yay! I'm helpful! ^^
Let me try to be helpful this time too by pointing you again to an other bit of that same paper I showed you last time :
https://pubs.acs.org/doi/pdf/10.1021/ie50359a022
I quote: "It is obvious, however, that the presence of large amounts of water vapor, especially if some of it appears in the liquid phase, will result in formation of isobutene chlorohydrin by a reaction in which the water partakes. Chlorohydrination then occurs separately from and in competition with the chlorination"
So there's your problem. You probably made that isobutene chloronium intermediate, but instead of rearranging to methallyl chloride by eliminating a proton, you got a nucleophilic addition from water and likely ended up with (CH₃)₂(CCl)CH₂OH. Hence the high boiling point.
(Also, when they say "it is obvious", I think they mean "from the litterature they reviewed". Or at least I hope, because it really wasn't obvious to me...)
They should ban the phrase 'it's obvious' from papers. If it really is obvious, it doesn't need to be written, but its actually obscure information so it just makes the paper sound like a jerk.
I've done some research, and I think you're right, here are the boiling points of some of those compounds:
2-methyl-propan-1,2-diol: bp ~233 (all measurements done under vacuum, likely decomposes under atmospheric distillation) No melting point found
3-chloro-2-methylpropan-2-ol: bp ~100 (given values vary from 70 to 123) mp: -20C
2-chloro-2-methylpropan-1-ol bp ~125 mp: 28.5
So yeah a mixture of all three, plus a bit of other shit would probably act quite similar to what we have. Decomposes on strong heating, with a bit of stuff coming over at like 150 (azeotrope between them?)
The one bit that doesn't quite work is the water solubility of the di-ol. A small blob didn't dissolve in a whole bucket of water, but maybe the chloro- derivatives dissolve in it enough to drag it out of solution?? Now i'm stretching.
Its probably a mix of the two chloro-alcohols.
So water is the enemy. Hmmmmm
Thanks for the help as always!
I know you keep coming back to that same paper but man... I mean they have water in their setup as like the HCl scrubber don't they? So I assumed it would be alright
"Chlorine and liquid isobutene in a mole ratio of about 1 to 1.5 were mixed in a jet and reacted in a free space; then the reaction products were passed into water"
So, the whole thing only comes into contact with water after all the Cl2 has been consumed and the chloronium intermediate has rearranged to methallyl chloride and HCl. (That all happens in the part labeled "reactor" in figure 1, which is upstream of the HCl scrubber.)
For that, the reaction is run in a continuous flow, which, as said before, is great for industrial setups, but clearly impractical for home chemistry.That's why I suggested you scrub the HCl in solution instead.
On second thought, depending on how much t-butanol and sulfuric acid you have access to, you could try the brute force way : just take a big flask, connect it to your isobutene generator, and make enough of the stuff to flush the air out. Then, add the chlorine.
Once the addition finished, let them react for an hour or so, and finally add the water to scrub the HCl (maybe with some bicarbonate to neutralize it?)
Alternatively, if you want to be more efficient on the isobutene, maybe you could use dry ice to condense it on the bottom of the flask, and then let it slowly warm up and boil, so the cold, dense isobutene gas will displace the air mostly without mixing. (I've done it to fill a bottle with oxygen in the past, it works rather well).
(Also, don't expect isobutene to follow closely the perfect gases law. It will likely be a little denser than predicted. Which is good though, since you want an excess of it.)
Could you demonstrate chlorination of paraffin?
One interesting use of chlorinated paraffin wax is in smoke screens.
12:24 I was tempted to get some teflon tubing, but after seeing your troubles with it (not just in this video, many others, understandably), I held back. I feel like there must be some way to make it easier to work with... Maybe use heat to preform pieces into specific shapes that can be joined together with joints or something like that.
I consulted the Google Gods and most agreed upon recommendations made it sound like working with it was similar to handling wild anaconda in the jungle... "First, mechanically wrestle the tubing into place; then tie it down using cable and C-clamps making sure to use enough".. lol. I was thinking "yep, that sounds about right".
You'd think there would be some tubing that was only coated on the inside with teflon and would be more flexible, but I didn't find much that seemed to be worth it or any better than full teflon tubing.
Love these videos! Excited to see how it turns out!
super cool. Didn’t work. But super cool. Thanks for the shout out. Thats awesome.
Keep it up. I learn a lot from your videos. And even more from the discussion after.
I'm late to the party here, but.... ~20 years ago in college, for a chemeng course, we were successful taking the pyridine route.
hi
views: 0
I think you’re making an addition of cl2 to a doble bond
I love these videos. Good job! One of these days you’re going to get the methallyl chloride thing. I had a chuckle at the mention of JOHN BLACK SUPER CHEMIST. That guy is great and I love that you put the super hero effect on when you said his name.
I love the interludes with the music a la chemplayer. I think they are great segues and they look great too 👍🏼
kjpmi glad you like those bits!
Really entertaning video and series. Dont loose your hope and keep trying :D
Good video man. :)
Very intriguing! (And entertaining!)
Elyjah Vasquez glad you think so!
very interesting
we have another language unfortunately.
create in writing,
the text of what you are doing under the video.
this could help a lot.
Thanks for watching!
I do talk very fast I am sorry, I will think about putting more text in the video so people can still understand what is happening if you can't understand a lot of the talking
much we understand - thanks.
there are only details (nuances) - it is not clear.
in general - your videos are informative.
look like it's for Chem Player https://www.youtube.com/channel/UCiU1dHvZObB2iP6xkJ__Icw - it's an example.
1. what substance.
2. how much substance.
3. The formula.
a short entry right in the video on the screen.
for some experiments it may take a little explanation - what am I doing? - I'm doing it.
in general - you are doing very well.
Thank you.
NOOOOOO
WE LOST JOHN BLACK SUPER CHEMIST
F IN THE CHAT
I have a basic grasp on these things but I love your videos
i have a new extraction idea: make H3PO4 from bones remained in the meat u eat
TM Fan ohh man, I'd have to eat a lot of meat :P
Phosphoric acid is annoying because it eats through glass sometimes... But I'll think about it!
Extractions&Ire u can probably eat more chicken wings, legs, beef/lamb ribs, meat which contain higher bone content?
also why phosphoric acid dissolve glass?
so where do you go from here? it's a shame to see hard work with no product. are there any patents for the production of 1-MCP?
There are some papers, but most of them are chemical engineering type stuff... so I think we are close but its just working through the issues.... we'll get there!
As I said on reddit, you can use TCCA instead of NCS for Wohl-Ziegler halogenation :)
I need a better username That does sound magical, I'm just struggling to find any references that says it'll work, do you have any?
Oh, now that I checked, chlorine is just too reactive for Wohl-Ziegler reaction. (but it would work with tribromoisocyanuric acid, the mechanism is the same as with NBS)
The double bond is annoying, it would be nicer to not have it, do a chlorination and then introduce it later, but oh well, the literature says this should work and I feel we're closeee
Yeah, that's what my previous procedure did but these bromoisobutene isomers are a pain to separate.
But tribromoisocyanuric acid should be easy to make:
1. Make dilute hydrobromic acid like nurdrage
2. Slowly, with cooling add dilute hydrogen peroxide to make a mixture of bromine and water
3. Drip in trisodium cyanurate, tribromoisocyanuric acid will precipitate:
Na3C3N3O3 + 3 Br2 = C3Br3N3O3 + 3 NaBr
Use NaOH to make sodium cyanurate, NaHCO3 is not basic enough. You can do Wohl-Ziegler reaction in chloroform or DCM.
Awesome shout out to John Black Super Chemist. That guy is great.
video stabilization please very shakey
I would run a NMR for you. I just don't know how much shipping is from Australia to Germany and how long it would take. But as long as you can seal it well enough so it doesn't smell it shouldn't be a problem. Greetings
Are we 100% sure this channel isn't run by Matt Parker?
I know this vid is like 2 years old, but I wanted to point out that just maybe using a strong Arrhenius base like NaOH would pretty much fuck up your whole chlorine as it readily disproportionates
It's create sodium chloride and acetic acid, pity chips weren't also a by-product, lol.
At what point would it be the smart thing to do to try and obtain the pre-made chemical?
Depends on cost, availability, and regulatory hoops. My rule of thumb: if it costs more than a dollar per gram, either try to make it yourself, or find another way.
200L trash bag may be usefull for measuring volume.Bottles are not good, you have to get rid of air with vacuum
I know this is unrelated to the video but... what was the name of the explosive made from Methyl ethyl ketone?
HV Lab methy ethyl keytone peroxide
Thanks, maybe I will try to make some of that.
HV Lab I highly suggest against it. I've made the compound and it is amazing unstable, even by organic peroxides measures. Would suggest if you're interested in explosives to start off with another one. If you're interested HMU on instagram @science_and_anonymous
Isn't methyl acetylene straight?
BP 71c
be careful when storing sensitive compounds over molecular sieves, they can sometimes catalyze the degradation of your product, for example if you leave a bunch of acetone over sieves for a week, it will have all sorts of crap in it, because the acetone started to polymerize via aldol condensation
Why you don’t use a canister R600a as your source of iso-Butane? Seems much easier to me
(There are also some camping gas cans that contain pure isobutane - I think Coleman does sell them)
We need isobutene for this, which has a double bond in the structure. Isobutane doesn't have that double bond so can't react with the chlorine :(
Extractions&Ire f**k - That’s why my chemistry sucks - just one letter make it or brake it 🤣
It's still sickening to watch, but it's because I can smell it through my screen.
Captain hindsight here. I probably would have used more dry ice, but just on the receiving flask and tubed the vapors into it. A tiny bit of antimony trichloride as a chlorination catalyst and simultaneously piped in the chlorine. I dont think the methallyl chloride will care about the HCl, in fact starting with a few drops of conc. HCl to make sure you don't end up with a basic environment.
pv-nRT Nernst equation...
Ah, yes. My favourite.
??? He says ideal gas law wtf u mean
I got no evidence to support this, just a random guess: Might the water be interfering with the reaction?
(Actually, some evidence, but only remotely related): When I chlorinated toluene under UV light, water was something that needed to be excluded, since it reacts with benzyl chloride to form benzyl alcohol and hydrochloric acid, which is why it works as a lachrymator. I wouldn't be surprised if the methallyl chloride would react with it too. Methallyl alcohol (the hydrolysis product I'd guess) has a boiling point of 115C though, so it's quite a bit off. Still leaves possibility for an azeotrope of methallyl chloride with the alcohol, or the alcohol with some overchlorinated products, lots of possibilities there.
I gotta say though, it's nice that you keep us up to date and also show us some failures. Keep up the good work!
I'll bet that's what it is, the allyl group has resonance so the methyl on the allyl group behaves like a benzylic carbon hence why methallyl chloride is a lachramator
Yes I think I agree, water is probably the enemy (now that we can basically exclude UV as an issue). Water is the only thing that is there enough to completely mess up the reaction enough, that there's not even a little bit of a product in there. Not sure exactly what the water is doing, but its probably the water
William Ford - 2019-08-14
Me: [sees that you drew methyl acetylene with an angled triple bond] *TRIGGERED*