Java kindly supplied some references for me that you can find in the request threed now. They where on the topic of salting out AcOH from an aq solution. Our member Jon mentioned to me a process he used to obtain his "GAA" which worked by boiling salt and vineger until you had the solution super saturated with NaCl and adding Isopropyl alcohol. This seperates into two layer and you abstract the upper phase and distill the IPA to retrieve your pretty dry AcOH.

I attempted this on a small scale using 5% distilled Vineger solution and it showed me quickly that the shear mass was going to prohibit me from doing it this way on anything other then very small scale.Since the papers java provided mentioned using sodium sulfate as the salt as well I decided to add Sodium Acetate and Sodium Bisulfate with just enough water to get them to react. This was all not completely thought thru and I just did a dash of this and a dash of that. The smell of AcOH was strong as can be as to be expected. I added 70% IPA and very quickly the upper phase came into play with a little shaking. The salt needed was created insitu from the reaction of the bisulfate with the acetate supersaturating it with ease. I added a bit of NaCl just to make sure(wish I didn't because I dont think it was needed) and this was shaken every few hours and left over night.

The top layer was extracted and a small eye dropper full was taken out to allow the IPA to evaporate and to my suprise there was much more AcOH then I expected left behind. I then added MgSO4 to dry the upper phase and this proved that Jons AcOH was indeed a tad bit wet because all of the MgSO4 had caked after about an hour. More MgSO4 was added and I am giving it time right now to react before moving on. Once alls said and done I am very confident that I will have a decent amount of GAA to work with in good purity not to mention very dry. Next time I would most definitly reflux the mixture before extracting the upper phase though even if only for 20 minutes or so just to be sure of full reaction and super satuation.

It is more cost effective then using vineger and better then using NaOAc+H2SO4.
No high heats are needed as with normal NaOAc + Bisulfate.
No SO2 in the product that you get from over heating either.
IPA is reusable so that cost is dead.
Muratic acid can be used as well just with a bit more bulk to fully ensure this is a cheep proccess.
No hazard shipping fees because your ordering NaOAc instead of concentrated acid.

I will perform this again and figure up my stochiometry next time and do it right before I send this out as a full write up. Just thought I would post this here for now incase anyone wants to perform this as well.

Well more to come I want to distill it tonight but I may not have the time since I still got baths to give and homework to do(yeh Im getting more homework then them!!! ) but I will not have them this weekend there mom will so I hope to accomplish alot which is another story all together that you all will see hopefully soon enough.

Peace
~Sedit

Jon's actually could have produced dry.  Isopropyl alcohol forms an azetrope of 88% IpOH and 12% water which boils at ~80C.  I dunno how much IpOH you added, or how much water was present, I'm just reminding you of azeotropes.

Good work though, I knew salting out AcOH was possible, but I didn't think about NaHSO4 + NaOAc.  Two thumbs up for sedit, hahaha.

Im distilling 130..ish... ml of IpOH/AcOH mix so if all goes well Ill let everyone know the concentration extracted and possibly after a few runs build a graph of concentration extracted. H2O does come along in a decent amount but it should be ok. I still have to make sure IpOH and AcOH do not form an azeotrope. If it does its not a huge problem because the IpOH will be used for the same thing over and over again but I want to know.

Im gonna scale up my next batch but I wanted to run a quick and dirty to make sure Im not wasting the larger mass of my reagents.

There was something else I wanted to ask you folks when I started posting this.... but I can't remember.... That has been an all to common thing for me latly and its starting to worry me just a little bit, but what can you do.... maybe im just getting old who knows.

Ok lemme jot down some notes real quick because I have a habit of losing my paper ones. Im doing this on a 1 mol scale now and here are the temperatures of my last run.

Oil bath temperatures in Fahrenheit

239.0 Mixture started to boil with faint fine bubbles.
248.5 temperature stabilized as the IpOH began to distill over.
265  trace AcOH started to distill over and distillation was ceased.



New Run

Molar weights

120.06 grams a mol NaHSO4
136.08 grams a mol NaOAc*(H₂O)₃

73.20% of weight in AcOH is generated from 1 mol of NaOAc

60.04596 grams of AcOH * density of 1.049 = 62.98 ml Theoretical yeilds of AcOH.

Materials where all mixed and 75ml of H2O was added to dissolve. 6.5 grams extra Bisulfate was added to ensure conversion. There is now a thick mush with the strong overwhelming smell of Acetic acid. This was then heated on an oil bath which is in the middle of working at the moment. More water may be added to ensure completetion.


[EDIT]

OK well the mixture was refluxed for 1-2 hours or so. I personaly think I should use more H2O as it took sometime before the Sodium Bisulfate dissolved. Perhaps using a saturated solution of H2O/Bisulfate would work better since I fear I will have some left over Unreacted acetate. Im going to test that theory when alls said and done by drying some of the Sodium Sulfate and adding a bit of acid to see if the smell of AcOH presents itself. I can even envision a few other workups of this such as distilling the mixture after the reflux and salting out the distillate. All in all im kind of annoyed that I was unable to completely liquify the reaction soup but atlest this makes sure my solution is saturated. I will now add 100ml of anhy IpOH and hopefully find the time to finish up tonight.

Hmmm, filtering might be a problem if there are two phases... I know filters can be used as makeshift separatory funnels if the filter is wet with the solvent you want to pass through.

OK I have some notes to mention. It appears that all the shit there and floating around and dissolved in there without NaCl the IpOH WILL NOT SALT OUT. I added what I decanted from the reaction mixture into the last bottle I used for the first synthesis. There was a thin layer of IpOH on top left over but after adding the new work it immediately went away. After shaking to push the NaCl that was there into the new solution the layer came back in a big way. This proved to me that Sodium sulfate will not do it. OH well that just means that NaCl will have to be added next time before the reflux.


I have another issue that is a more pressing matter at hand. The old layer which has been sitting in the bottle from a couple days ago had a funny smell.... I anticipated this a while ago but never thought it would be a problem. A quick whiff showed a fruity acetone smell simular to ethylacetate or nailpolish remover. I am almost certine that what Im smelling is Isopropyl acetate. The esterfication is catalysed by acids IIRC and that kind of fucks up the thought of using HCl or H2SO4 with the reflux like I wanted to. NaHSO4 could do so as well but its not as strong an acid so I think when alls said and done distillation of the mixture will be needed before refluxing with NaCl.

I thought about increasing temperature like you said but it just seems very impractical.

 I did note something interesting though. After seperation of the layers I tryed to add anhydrous MgSO4 to dry it but instead I once again ended up with a duel phase mixture. Kind of makes me think MgSO4 is much better then NaCl by far. More test should be in order but at the moment my main goal is to just get dry AcOH as its needed very much at the moment since I know of no other solvent I could perform Alkene bromination in. Not to go to far off topic but I have heard some say to use DMSO and others that say it forms a complex when attempting bromination in it. I am leaning towards complex but am unsure. Any thoughts?


PS:Plus next time I think I am just going to do this GAA shit using Dichloromethane instead of fucking with IpOH. DCM distills quickly and seperates layers with ease. No real need to go thru the BS Im dealing with right now since DCM would shorten this whole process 5 fold or so.

I actually wouldn't trust a dichromate to oxidise ethanol.  KMnO4 would take it right to AcOH without much fuss though (just watch the temp)

I know KMnO4 in an alkaline enviroment would work but I don't have any. I have been reading discussions of Mn+ Ions in electrochemical cells to produce acetic acid so I may have just found some use for my shit MnSO4 oxidiser that was taking everything to carboxylic acids and junk anyway. Still trucking thru Science Madness at the moment to see how many ways I can pull up. Its funny that I have yet to come across this salting out process and everyone is concerning themselfs with the existance phantom azeotrops with H2O and AcOH. I will have to share with them as well when I get everything down packed and it seems to me like DCM is the way to go. Im going to distill some later and try to use that since it will be much dryer... and easyer to seperate from the AcOH. Plus no Ester formation with IpOH either.

Seems as simple as adding Ethanol to the mixture before the power is turned on and letting it work with the ethanol in solution. Distill to yeild a high concentration of AcOH and then salt it out. Since all the fiddling with the MnSO4 sulfate cell is to prevent oxidation to the carboxylate should be an easy high yeilding (CHEEP) synthesis for glacial acetic acid.

Still any other suggestions on way to perform the oxidation would be appreciated.



PS:Vesp I think Im just gonna take the lose and not toy with it anylonger. I think its just time to fool with the E-cell again.

OK all finished(about time). I was left with 40ml of a slightly milky liquid. Experiance tells me that this will clear up in a day or so. Still not sure what causes it but it goes away in time.

The distillation of the crude mixture was pretty uneventful. Left over IpOH and the ester came over first and after a few ml you could see the change take place in the condenser because as the alcohol comes over it produces no beading up as it condenses and just flows out of it where as soon as the AcOH started to come over the surface tension allowed droplets to form in the condenser and I knew it was time to switch flask.

What kind of bugs me a bit was the fact that in a pathetic attempt to check the purity I weighed it and measured it. Weight was 38.8 grams and it was about 40ml.

This adds up to a density 1.03 roughly. Given that im shooting for 1.049 I guess this isn't to bad considering that if I undershot the amount by .5 ml it would put me almost right where I want it. The yeilds are not exactly what I want them to be but The remaining IpOH was added back to the flask that I started with and I will attempt to extract again since there is still strong AcOH smell left.

I am trying to take pictures but I can not find the cable to my camera to get them on the computer. Nothing really special just a picture of the distillate and a picture of the duel phase mixture. Pretty uneventful but Im a big fan of graphical illustrations. As soon as I get them done I will send a writeup to the General chemistry section followed with another attempt using HCl and DCM which I feel shows more potential because the DCM will seperate easyer and cleaner and the HCl will make sure all the NaOAc was acidifyed and also form NaCl which workes well for salting out AcOH. There is also a paper I am waiting on that talks about using Pottasium carbonate as a salt so I wounder if Sodium carbonate will work as well.