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Author: Subject: Diethylether (sulfuric acid saving method)
bnull
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[*] posted on 7-6-2024 at 09:43


Quote: Originally posted by RU_KLO  
So its not an easy task.... (instead of the second H2SO4 washing flask, sodium ethoxide would be used...)

The first flask is to absorb unreacted ethanol and hydrogen chloride. The second is to absorb water. Without the second flask, the sodium ethoxide will decompose.

I bought some 20 years ago (I'm quite old, you see) a small bottle of ether:ethanol 50:50. It was sold to remove surgical tapes (because, if you try to remove them, depending on the way you pull them and where they are stuck, you take out a nice patch of skin still glued to the tape; not much fun and hurts like hell meanwhile and afterwards. And yes, that was the time when I set my hand on fire accidentally). It's possible you can find the same kind of solution in a drugstore, a pharmacy, a chemist's (English is a mess), or a supplier of surgical materials, only remaining the question of separation of ether and ethanol.




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[*] posted on 7-6-2024 at 11:03


As far as I know, Williamson’s ether synthesis has mediocre yields in the best cases.
(See anisole by ChemPlayer or NileRed)
Might be better with sodium ethoxide, which must be a stronger base than sodium phenoxide.
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RU_KLO
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[*] posted on 7-6-2024 at 13:48


Quote: Originally posted by Keras  
As far as I know, Williamson’s ether synthesis has mediocre yields in the best cases.


To help mitigate this issue microwave-enhanced technology is now being utilized to speed up the reaction times for reactions such as the Williamson ether synthesis. This technology has transformed reaction times that required reflux of at least 1.5 hours to a quick 10-minute microwave run at 130 °C and this has increased the yield of ether synthesized from a range of 6-29% to 20-55% (data was compiled from several different lab sections incorporating the technology in their syntheses)

Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher (2010). Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels−Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis. Journal of Chemical Education, 87(1), 84–86. doi:10.1021/ed800001x

as Keras said, 30% is not much for all the trouble...
Also putting flammable liquids into a microwave doesnt seem to safe...


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[*] posted on 8-6-2024 at 00:20


Quote: Originally posted by RU_KLO  
This technology has transformed reaction times that required reflux of at least 1.5 hours to a quick 10-minute microwave run at 130 °C and this has increased the yield of ether synthesized from a range of 6-29% to 20-55% (data was compiled from several different lab sections incorporating the technology in their syntheses)


Thanks for the pointer. The yield remains moderate at best and, above all, I don’t know about any commercial (kitchen) microwave oven that allows to precisely control the temperature of the heated compound inside – and I don’t think that the common way to regulate the average power, i.e. duty cycling, is really adapted vs. a continuous power-regulated microwave source.
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[*] posted on 10-6-2024 at 08:39


How much heat does solvation of ethanol achieve by itself, and at which concentration?
Water gives about 160 Celsius around 85 % sulphuric acid. Ethanol has a bigger molar heat capacity than water (if lower heat capacity by mass).
Also sulphuric acid/water solution reaches boiling point of about 165 Celsius, which is 65 degrees above pure water, at 70% by mass... which is about 2,3 moles of water per mole of sulphuric acid. At what concentration can ethanol/sulphuric acid solution be heated to 140 Celsius (62 degrees above pure ethanol) without boiling?

[Edited on 10-6-2024 by chornedsnorkack]
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[*] posted on 12-6-2024 at 05:25


Quote: Originally posted by chornedsnorkack  
How much heat does solvation of ethanol achieve by itself, and at which concentration?
Water gives about 160 Celsius around 85 % sulphuric acid. Ethanol has a bigger molar heat capacity than water (if lower heat capacity by mass).
Also sulphuric acid/water solution reaches boiling point of about 165 Celsius, which is 65 degrees above pure water, at 70% by mass... which is about 2,3 moles of water per mole of sulphuric acid. At what concentration can ethanol/sulphuric acid solution be heated to 140 Celsius (62 degrees above pure ethanol) without boiling?

[Edited on 10-6-2024 by chornedsnorkack]

I think is more complicated than that.

Found this, but under reduced pressure:

"For the sulfuric acid + water + ethanol system, the
boiling points increase with decreasing mole fractions of
ethanol in the solution at fixed ratios of sulfuric acid/water,
and they also increase as the ratio of sulfuric acid/water is
increased."

But for the same paper, it seems that Sulfuric acid could be recovered at lower temperature with butyl acetate (Acid + Water + Butyl Acetate + Ethanol Quaternary System

how difficult is to get/make Butyl acetate? From wikipedia: It is a component of fingernail polish.[8]
(I found ethyl acetate un fingernail polish, not butyk

the paper talks about models, but can someone "translate" this for non engineer people? in the sense, how do you apply it and what are the benefits.
Does the sulfuric acid destilates with the butyl acetate (and how to separate it) or the butyl acetates remains in the boiling flask with water?

Determination and Modeling of Vapor–Liquid Equilibria for the Sulfuric Acid + Water + Butyl Acetate + Ethanol System
Geng Li, Zhibao Li*, and Edouard Asselin

https://pubs.acs.org/doi/10.1021/ie303197a









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[*] posted on 13-6-2024 at 07:19


After experimenting with this procedure a little bit I would like to put something into text that is probably quite obvious - you can't just feed all of the distillate back into boiling flask and redistill to try enrich it in ether. You just end up fractionating the mixture. The matching of the addition rate and distillation rate is done because a high concentration of sulfuric acid raises the boiling point of the mixture (a likely requirement for a different catalyst in a simple distillation setup).

Unrelated, but has anybody else observed white smoke upon addition of ethanol to the boiling flask? Also, even though this contradicts the pdf posted on page 1 which casts doubt on alkylation agents as intermediates in this reaction, has anybody tried adding sodium sulfate to potential catalyse formation of sulfuric esters? (https://www.sciencemadness.org/talk/viewthread.php?tid=78772)

[Edited on 13-6-2024 by jackchem2001]
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[*] posted on 3-7-2024 at 01:04


Continuing from my last post suggesting the addition of sodium sulfate to catalyse the formation of sulfuric esters (allowing a lower temperature to be used to avoid tarring), in ethyl bromide procedures diethyl ether is observed as a major impurity. Evidently, ethanol does react with some alkylating agents at much lower temperatures to give diethyl ether.

As I hate the smell of ether so I likely won't do this procedure again, but if anybody happens to be doing a run then consider adding a small amount of sodium sulfate to the boiler and report the results :)
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[*] posted on 5-7-2024 at 00:06


I have attempted this reaction and noticed something strange. thermal runaways.

At first i thought some sort of hydrolysis was occuring which could explain things, since i was using 95% ethanol, but i see now that water simply cannot accumilate in this reaction, which increases the mystery.

What i observed was that at seemingly arbitrary temperatures between each runaway, my PID controller would suddenly find itself unable to heat the acid solution further. it would get stuck at say, 140C. no reflux or enough distillate was comming over to explain the heat loss, i also re-attempted without a fractionating column thinking it was trapping the water leading to exothermic splitting/reformation of ethyl sulfate <-> sulfuric acid + ethanol. energy is being applied but it is not being reflected in a change of temperature, nor, any notable distillate although the head temp would begin to increase, but only after the runaway began, not leading up to it.

Suddenly, the column head temperature would skyrocket from the boiling point of ether to the boiling point of a low-ethanol +water steam, and the distillate would reflect as much. the addition of more ethanol during this runaway would instantly and increase the temperature.

eventually my acid tarred up and became so thick it would foam so i had to stop, but this phenomena occured long before any viscosity changes or clarity occured.


During a runaway, over the course of a minute, regardless of if the PID was still applying power, the temperature would suddenly rise from wherever it began, in this case, 140C, and it would rise up to around 156C. this temperature change did not correspond to any thermal-momentum, the lag between heat being generated by the mantle, and then transferring to where the thermometer could read it. it also occured in a span that almost matched how quickly the temperature would rise with a manunally set 100% duty cycle. (also yes i did verify the PID wasnt simply defective and suddenly locking on 100%)

ethanol was pumped in consistently by peri pump, shutting off automatically when the temperature had risen above 60C as i was concerned that ethanol would simply boil on the surface of the acid without reacting.


Eventually the runaways would accompany foaming that caused the ejection of the black thick acid so i had to stop. there was a major viscosity change after i tried to vacuum concentrate the acid, but this phenomena was present prior to that, i had just assumed the acid had become too diluted with water or something, since runaways would end with noticeable amounts of water in the condenser.

Does anyone know what was happening?
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