Sciencemadness Discussion Board - Drying ethanol via ester hydrolysis.

Drying ethanol via ester hydrolysis.

Al Koholic - 18-10-2004 at 10:14

When possible, it seems to be the case that using dry solvents for various procedures is generally more favorable that using water containing solvents.

Producing dry ethanol for the synthesis of sodium ethoxide for example, using sodium to dry diethyl ether or THF for use in grignard, etc, etc. There is undoubtably an important place for dry solvents in the laboratory.

Certainly some solvents are purified with more ease than others. If I'm not mistaken, methanol, acetone, toluene, etc don't have tendencies to form azeotropes with water making them easy to purifiy by distillation. For this reason I figured the most important solvent this topic should focus on will be ethanol, an omnipresent substance in the lab and one of the most difficult to *dry* without some more exotic methods. Who here is ready to perform an azeotropic distillation with benzene to get pure ethanol? I'm not...

Anyway, getting to the point now, I've been thinking about using esters to perform the drying. What if one were to mix with 95% ethanol, some ethyl acetate for example. Say enough to suck up all the water on hydrolysis. Could you simply reflux this solution, hydrolysing the ethyl acetate into ethanol and acetic acid, drying the solution out in the process? A simple protected (drying tube) distillation could then be carried out to isolate the ethanol in a pure state no?

[Edited on 18-10-2004 by Al Koholic]

[Edited on 19-10-2004 by Al Koholic]

JohnWW - 18-10-2004 at 12:22

You mention methanol, acetone, toluene, etc., as not forming azeotropes with water. Actually, water forms two-phase minimum-boiling-point binary azeotropes with toluene and benzene - see Perry chapter 13, and the International Critical Tables.

As for your proposal "What if one were to mix with 95% ethanol, some ethyl acetate for example. Say enough to suck up all the water on hydrolysis. Could you simply reflux this solution, hydrolysing the ethyl acetate into ethanol and acetic acid, drying the solution out in the process? ": Ethanol also forms a minimum-boiling-point azeotrope with ethyl acetate, with 46% ethanol and boiling at 71.8ºC. Besides, ethyl acetate does not hydrolyse so easily merely in the presence of water (present as the impurity) as you suggest, except with added strong alkali or acid, which could cause complications due to solubility in either of the products and formation of an alkali metal acetate. I also note that a ternary azeotropic mixture is formed by water, ethanol, and ethyl acetate together, with 12.4% ethanol, 60.1% ethyl acetate, 27.5% water, boiling point 70.3ºC.

mick - 18-10-2004 at 12:26

I can not see it working.
If the ethyl acetate picks up water then it will go to ethanol and acetic acid and acetic acid could catalysis the esterification. You could end up in a circle.
If you could extact the acetic acid?
mick

neutrino - 18-10-2004 at 14:29

Vogel's 3rd had a thorough discussion about this very thing. I would post the relevant pages, but I'm away from my normal computer right now. What I remember is that standard anhydrous salts can be used to break azeotropes and dehydrate pretty thoroughly (esp CaSO4

. Magnesium metal can be added to alcohols to dry them very thoroughly, as it forms Mg(OH)2 and H2. There was something about using esters in there, but I can’t remember it.

BromicAcid - 18-10-2004 at 14:35

There is always that great method using NaOH that Organikum mentioned in the thread he started on this subject.

Magpie - 18-10-2004 at 18:41

Molecular sieves have been noted in my organic lab text as drying agents for solvents. But I have no idea whether they would work for ethanol, or how expensive they are.

neutrino - 18-10-2004 at 18:56

They are usually pretty cheap and should work for anything (I think). As promised, here's the pertinent text from Vogel about dehydration.

Attachment: Drying.rtf (15kB)
This file has been downloaded 3120 times

Al Koholic - 18-10-2004 at 20:02

Excellent text...thanks for the attachment there neutrino.

Mentioning ethyl acetate in the opening post was just a suggestion for the overall concept here. So it seems with higher molecular weight esters and some Na, one can get very dry ethanol.

Anyone think that dried KOH or NaOH could substitute for the Na metal in this scheme? Since I imagine the sodium is there just to provide the basic conditions and alkali metal ions I would imagine NaOH might just work as well.

Organikum - 19-10-2004 at 00:01

You didnt read the post Bromic linked to, did you Al Koholic? It answers your questions completely.

Toluene as Xylene as Benzene as dried by simple boiling/distilling 10% of the volume away, they form heterogenous azeotropes with water. The resulting aromatic solvent is dry enough for virtually all purposes.

Diethylether is easily dried by NaOH or better KOH pellets. This takes some time, a week at least, but gives ether dry enough for any Grignard.

Al Koholic - 19-10-2004 at 08:32

No no, I did read it...as it was formed in fact. Perhaps I should have put some more consideration into the title of the topic as it seems to be generating some confusion. This was intended to focus on drying with esters but was open to any interesting side notes.

[Edited on 19-10-2004 by Al Koholic]

mick - 20-10-2004 at 08:41

Is the solvent dry?
This is how I try to check stuff I use.
A quick empirical test.
I add 1 ml or so of the solvent to bit of calcium hydride, calcium carbide should do, with a quick shake.
If nothing happens the solvent is very dry.
If it is slightly cloudy and gradually clears then it is dry for most stuff.
If is is slightly cloudy and does not clear then it is OK for gram scale reactions.
If it bubbles then it is wet.
mick

unionised - 23-10-2004 at 04:00

A fine method, save only that this thread is about alcohol.
CaH2 + 2 EtOH --> Ca(OEt)2 +H2

mick - 23-10-2004 at 07:45

It is only a quick small scale empirical test, the assumption being that CaH2 reacts faster with water than the average solvent and is not too violent. If it is cloudy on addition at room temp then I would assume there is water. If the CaH2 settles and starts reacting with the solvent that is the end of the test.
mick

The idea is that as powder not lumps, the hydrogen forms on the surface rapidly with water and the rate of settling is somehow related to the water content of the solvent. I have not tried it with calcium carbide but it could work.
mick

[Edited on 23-10-2004 by mick]

unionised - 24-10-2004 at 22:25

It's still off-topic and I wouldn't try it with halogenated solvents.

mick - 25-10-2004 at 08:45

I checked out ethanol (about 5 ml) and calcium hydride (only a bit). I could not easily tell the difference between absolute ethanol and stuff that had been over molecular sieve. Both went cloudy and most of the calcium hydride settled out but the cloudiness did not clear as fast as I thought. Added a drop of water and instant bubbles. Thanks, just thought, the calcium hydride is crap, contains too much hydroxide, so it is going to be cloudy.
mick

Nicodem - 24-8-2005 at 11:22

Quote:

Does anyone know if CaC2 reacts with absolute Ethanol?

Why would it not? Generally speaking, any base with pKa (of the conjugated acid) above 15 will react with ethanol. Given that the pKa of acetylene is 24 you can bet CaC2 reacts with water and ethanol. Just as you can be even surer that calcium hydride reacts with both and any other protic solvent as well since the estimated pKa of its conjugated “acid”, H2, is of about 40!

What is all this about drying ethanol?
What is wrong with the azeotropic drying with toluene. The boiling point of the ternary azeotrope of water-toluene-ethanol is slightly below the boiling point of dry ethanol so it can be used to dry it. Someone could even find out that this is one of the methods used industrially by searching the net before asking: http://mccoy123.com/qvf-ethanol.htm

garage chemist - 24-8-2005 at 11:29

I removed my posting from here and posted it somewhere else since I saw that it was the wrong topic for this. I'm sorry that I did this so late...

The problem with the azeotropical drying is that you need a column. I don't have one.

But the reaction of CaC2 with Ethanol should produce Calcium Ethoxide, which should in turn help to dehydrate the ethanol.
I'll see how this turns out.

To remove the acetylene, I'll reflux the ethanol while bubbling air through it. This should get rid of any dissolved gas.

Nicodem - 24-8-2005 at 12:11

Why would you need a column for the azeotropical drying?
All you have to do is calculate how much toluene you need to dry a certain amount of 96% ethanol (check the composition of the ternary azeotrope), add the calculated amount of toluene but with some excess and distill off some more than the theoretic amount off the azeotrope. What remains in the flask is almost absolute ethanol contaminated with a minimum amount of toluene.

If you filter of the precipitated Ca(OH)2 after leting CaC2 dissolve in 96% ethanol you will be left with a solution of acetylene and some Ca(OEt)2 in dry ethanol. That's true, but you can't get rid of the acetylene the way you proposed. Pasing (dry) air trough the refluxing solution will, besides being very hazardous, take away also the ethanol vapors. Strange enough, but ethanols partial pressure at its boiling point is 1atm, meaning that the air will take it away.
I would rather not heat a mixure of air, acetylene and ethanol gas, though.

Edit: I realized where you got the idea that a column is needed. From the link I provided above

. That is a design for a continuous flow proces where the tolune is being recycled. I would say that if one uses pure toluene in at least some excess no column is needed.

[Edited on 24-8-2005 by Nicodem]

garage chemist - 24-8-2005 at 12:37

The air stream through the refluxing ethanol will NOT take away the ethanol, since the ethanol vapor- air mixture has to pass through the reflux condenser where the ethanol will condense. But the Acetylene won't condense there, no matter how much of it the air contains. This is the important thing here.
And the mixture won't get hotter than about 78°C, and there will be complete abscence of ignition sources. I wouldn't have any safety concerns about it.

The "Organikum 15. Auflage" says that a column is needed when one has to separate liquids whose boiling points are closer together than 80°C. This statement is where I got the idea that a column is needed.
The separating capability of a simple distillation is greatly overestimated very often.
In the organic laboratory, a column is used in almost every distillation. It's a fixed component of every distillation setup.

[Edited on 24-8-2005 by garage chemist]

Nicodem - 24-8-2005 at 13:34

Sorry, you are right about the refluxing ethanol.
I don't know how efficient this way of removing acetylene is though. Some ethanol (the partial pressure at the condenser temperature) would inevitably pass trough and if you would need huge amounts of air you might be left with considerably less than you expected. Also drying the air would be almost as annoying as using a more practical way to dry ethanol. How are you going to test the presence of acetylene in ethanol or outgoing air? Not with a lighter I hope.
You underestimate the explosivity of acetylene. It can explode even without an ignition source. Not likely but it is possible. It is not predictable like methane or other hydrocarbons.

Are not the vapors over a boiling mixture that can form an (lower boiling) azeotrope, going to have the composition of the azeotrope until one of the components is over (and the azeotrope composition breaks up)?
At least that is what I thought before, but perhaps I confused this with the theory of steam distillation.

garage chemist - 24-8-2005 at 14:57

Some preparation I remember (preparation of polyethylene without pressure, using a very special catalyst) calls for oxygen- free petroleum ether. By "oxygen- free", there was meant "free from dissolved gaseous oxygen".
It was accomplished by refluxing the pet. ether while slowly bubbling dried nitrogen through it.
Apparently this removes all of the dissolved atmospheric oxygen, if it's enough for this very delicate synthesis.
So the acetylene should be removed completely by the air stream.
To test for presence of acetylene, one could go after the rather strong phosphine smell of it (due to phosphide-containing carbide).

I'll remove the acetylene after distillation of the nearly absolute ethanol from the residual carbide/calcium hydroxide/ethoxide.
Otherwise traces of moisture in the used air would produe acetylene again, as would the slow reaction of the ethanol with the carbide.
My synthesis doesn't call for absolute ethanol btw, only 99% ethanol is needed (use of really anhydrous ethanol actually lowers the yield).
I understand that one will not be able to obtain absolute ethanol with CaC2, not even by dissolving lots of metallic sodium in 99% ethanol (the equilibrium hydroxide + ethanol <---> ethoxide + water lies too far on the right side for this).

REAL ABSOLUTE ETHANOL can only be prepared by ester hydrolysis of, for example, ethyl formate with sodium ethoxide. Go to Lambdasyn for a detailed procedure (or ask Mephisto, Lambdasyn is in german).
Another useful ester for this is diethyl phthalate, again this gets hydrolyzed by sodium ethoxide (procedure is in Organikum).
Those reactions bind even the slightest traces of water.
The ester must be easy to remove from the absolute ethanol by distillation, since a considerable portion of it will remain undecomposed.
Ethyl formate boils low enough to be easy to separate with a column, diethyl phthalate boils high enough for this.

To test for absoluteness, a drop of a solution of aluminium triethylate in benzene is added to the ethanol. If the ethanol contains more than 0,005% water, a voluminous white precipitate will occur. This test is incredibly sensitive. Any access of undried air will result in a positive reaction, especially since ethanol of more than 96% concentration is very hygroscopic.

The -undoubtably inferior, but much cheaper- method of azeotropic water removal can only work with an efficient column. Azeotropes of compounds behave no different from the vapors of pure compounds, that means you need a column if the boiling points are closer together than 80°C.

[Edited on 24-8-2005 by garage chemist]

unionised - 25-8-2005 at 12:11

Moonshine stills seem to work quite adequately without a column to speak of and that's certainly not a boiling point difference of 80 degrees.
Also, it's possible to get pure alcohol by distillation without adding drying agents or third solvents. Anyone care to guess how?

neutrino - 25-8-2005 at 12:25

Salt?

unionised - 27-8-2005 at 03:42

Which bit of "without adding drying agents" is giving you trouble?

neutrino - 27-8-2005 at 05:56

So, 'no drying agents' means 'no chemicals whatsoever'?

unionised - 27-8-2005 at 11:01

In this instance, yes.
edit
sorry the last post was a bit curt I'm blaming a bad hangover.

[Edited on 28-8-2005 by unionised]

protem - 20-6-2006 at 00:58

Interesting notion - apparently according to wikipedia (ethanol)

" At pressures less than atmospheric pressure, the composition of the ethanol-water azeotrope shifts to more ethanol-rich mixtures, and at pressures less than 70 torr (9.333 kPa) , there is no azeotrope, and it is possible to distill absolute ethanol from an ethanol-water mixture. While vacuum distillation of ethanol is not presently economical, pressure-swing distillation is a topic of current research. In this technique, a reduced-pressure distillation first yields an ethanol-water mixture of more than 96% ethanol. Then, fractional distillation of this mixture at atmospheric pressure distills off the 96% azeotrope, leaving anhydrous ethanol at the bottoms."

unionised - 20-6-2006 at 08:55

It seems to have taken a while but someone has finally spotted that you can separate alcohol from water by distillation without adding any chemicals whatsoever. Azeotropic composition is pressure dependent.

I thought the change was the other way round i.e. that increasing the pressure led to a higher alcohol content. Does anyone else have any data on this?

so thats whats happening

Panache - 18-10-2007 at 18:20

i buy cheapish barrels of wine from small wineries and vac distil off the ethanol and have always wondered why i can intially get an extremely dry ethanol (albeit contaminated with wine flavoinoids) cf/ running the distillation at atmoshperic.
shit now i better go and research this.
As an add on to the thread it makes seperation of closely boiling fractions simplier if you do the distillation under pressure, i clean the vac distilled ethanol up this way vs slow distillation up a large column. this increased pressure really contains impurities and the neat spirit i get out doesn't require filtration through carbon to dilute into an acceptable vodka.
you need to use all stainless over course, as pressure and glass don't really go well, although i imagine if one carefully fibreglassed ones glass setup it would allow for some pressure to be applied.
anyways i'll try to quantify the water/ethanol azetropic behaviour under diminished pressure and post my results.
All should be aware that pressure gradients through a vac distillation setup exsist and the reading on your manometer does not represent the pressure above the boiling liquid unless it is connected via a large bore (ie half of your condensor diameter) tube that feeds directly to above your boiling liquid. Likewise digital manometers, utilising the conductance of the atmosphere within the vacuum, are less usefull IMO than mercury based ones as they require claibrating against whatever you happen to be distilling and they hate water.
anyway blah blah, i'm bored, watching a distillation 5 days a week can do that to you, glad i just found this site it's all over the place and
ace

alchemist3096 - 19-10-2007 at 10:01

Quote:

Originally posted by Al Koholic
What if one were to mix with 95% ethanol, some ethyl acetate for example. Say enough to suck up all the water on hydrolysis. Could you simply reflux this solution, hydrolysing the ethyl acetate into ethanol and acetic acid, drying the solution out in the process?

Usually what I have seen used for a drying agent is anhydrous calcium chloride. If a moderate amount is added to the solvent/reagent and allowed to sit for a minimum of 24 hours, the salt can be either decanted or filtered off leaving dry solvent/reagent (e.g. for Grignard reaction). This would probably be less problematic than using something like ethyl acetate.

Klute - 19-10-2007 at 10:37

CaCl2 can't be used to dry short-chained alcohols as it reacts with them forming solid adducts.

I obtain my anhydrous ethanol from 96% industrial denaturated ethanol, which is cheap, by leaving 1L of it over ~50g NaOh overnight, then add ~150g of CaO ( unslacked lime) from a gardenig store, and reflux with CaCl2 guard for 12H. The denaturants self condense (everythign turns yellow/orange). Then the Ethanol is distilled in a dried, guarded simple distn setup, with molecular seives in the receptor, until only the Ca(OH)2 paste is left (don't distill to dryness!). About ~200mL of ethano; are lost to this paste, but it's cheap.

The ethanol is left in the receptor and protected from atmospheric moisture, I personnaly keep it under Argon after having degassed it (3X vacuum-argon cycles). Be carefull when handling it, it's very hygroscopic, ideally use glass syringes. Anhydrous CuSO4 stays white when added to it. Sufficiently dry for any conventional uses IMHO.