Removing ethyl acetate by room temp fractionation

[engunear]

Its a bit like Everest: "because its there". Or wasting a perfectly good walk chasing a white ball and hitting it with funny looking sticks.

There is a Zen joke. "People who eat fugu are stupid. People who do not eat fugu are stupid too."

[der wo]

I do not really understand the problem. Yes you don't.
The heads contain not only ethylacetate, but also methanol and other nasty ingredients, so removing the ethylacetate is solving only a (small) part of the problem. Yes it solves not all problems.
And more important: alcohol is, after water, the cheapest ingredient of a drink. It is easily made by fermenting sugar and the loss of ethanol is hardly a problem or a large cost. Ethanol is cheap, but purified not. Much more interesting is the production of volatiles that contribute to the taste of a spirit. And these can be found mostly further in the distillation process. We don't talk about whiskey or brandy here, but about neutral.
When you fear the loss of alcohol in the heads: just add sugar to the mash to compensate for this loss. I don't fear a loss, I only want a good neutral.

[der wo]

BTW, I recently heard from a german TV-documentary, that the german state owned distillery (the only what is allowed to produce and sell neutral alcohol) uses sodium hydroxide to treat the spirit before the final distillation.
Sodium hydroxide is a much stronger pH riser than sodium carb or bicarb and it is better soluble in water and ethanol. But the handling is more dangerous, you can rise the pH over 14!

[engunear]

A few months later and my jar of ethyl acetate heads and sodium carb still stinks. The qty is too small for my still but my dad has a small one I intend to borrow. Then a repeat expt with caustic soda. I believe this, have read the chemistry and don't know why it isn't working.

[Bagasso]

A few months later and my jar of ethyl acetate heads and sodium carb still stinks. The qty is too small for my still but my dad has a small one I intend to borrow. Then a repeat expt with caustic soda. I believe this, have read the chemistry and don't know why it isn't working.

It isn't just ethyl acetate or esters that makes heads stink so pH treating is not a cure all.

My take is that it makes for a more noticeable or sharper transition because you are taking out the solventy compound with a boiling point butted up against ethanols

[engunear]

Hmmm, I guess so. It makes it hard to test the hypothesis that the method works. Not doubting the theory, mind. So maybe some of the other results claimed in this thread are for different compounds as well.

With a 2m fractionating still column, removing ethyl acetate is not much of an issue even with the 1 degree difference.

[Bagasso]

So maybe some of the other results claimed in this thread are for different compounds as well.

This made me think back to the time when everything seemed to be blamed on methanol.

Even if it wasn't actually ethyl acetate it would still be the same treatment that is causing the difference.

With a 2m fractionating still column, removing ethyl acetate is not much of an issue even with the 1 degree difference.

I don't know, those azeotropes don't care how much coulmn you are packing.

ETA: it isn't just azeotropes either but I figured it be the best understood.

[Odin]

Ethyl acetate reacts with O2, so just introduce the air bubbler and you will be fine.

Odin.

[MDH]

Ethyl Acetate is not responsible for the harshness of spirits. That belongs squarely to compounds found in the heads.

[Bagasso]

Ethyl Acetate is not responsible for the harshness of spirits. That belongs squarely to compounds found in the heads.

Ethtl acetate is found in the heads and it is used as nail polish remover with a smell that is described as solventy.

Could it also be other things? Sure but not having ever tasted straight ethyl acetate and going by the description I've seen I would say it could very well be part of it.

[thecroweater]

Acetone is more the nail Polish remover and should not be in heads but in your fore shots unless you're smearing the dickens out of it

[Bagasso]

Acetone is more the nail Polish remover and should not be in heads but in your fore shots unless you're smearing the dickens out of it

Ethyl acetate is also used as nail polish remover. As an alternative to acetone.

[der wo]

Ethyl acetate is that with the glue smell. It has a boiling point only little under that of ethanol, it's found mainly in the fores and heads.

[Odin]

Ethyl acetate is that with the glue smell. It has a boiling point only little under that of ethanol, it's found mainly in the fores and heads.

Amen. And if you add a lot of oxygen to a drink that has (too) much ethyl acetate to it, it will compound into 1 esther and 1 ethanol molecule, if I remember correctly. More booz' and better taste!

This reaction has probably to do with what's known as oxidizing or over oxidizing spirits.

Odin.

[Bagasso]

Amen. And if you add a lot of oxygen to a drink that has (too) much ethyl acetate to it, it will compound into 1 esther and 1 ethanol molecule, if I remember correctly. More booz' and better taste!

Similar to adding an alkali. Splits the etho from the acid and binds to it forming a salt. Called ester hydrolysis.

[MDH]

Some of the smoothest spirits I have tasted were over sixty years old, all being Armagnacs. Highly aged spirits contain large amounts of ethyl acetate.

Nail polish remover made from ethyl acetate smells fruity - like artifical banana or peardrop. Not like harsh alcohol, which is what isopropyl alcohol or acetone would.

There is no evidence to me that ethyl acetate makes spirits harsh. It does add a character which some like and others don't, but if you are going to write off ethyl acetate as the big culprit, you might as well write off almost every aged spirit ever made.

[Bagasso]

It does add a character which some like and others don't, but if you are going to write off ethyl acetate as the big culprit, you might as well write off almost every aged spirit ever made.

I'm not writing anything off but I am including it in the list of possible causes and there it will stay until someone tells me that they have had a taste and there was nothing solventy about it and even then I will probably have to taste for myself.

[der wo]

Sure? I thought, after long aging all ethyl acetate has converted into esters. And they have the different fruity characters.

[Bagasso]

Sure? I thought, after long aging all ethyl acetate has converted into esters. And they have the different fruity characters.

Ethyl acetate is already an ester, just not one that everyone describes as fruity.

[der wo]

Ok. Sorry. You are right. I would delete my post if I could.

[engunear]

Hey, der wo, don't worry. I made mistake when I was in high school, so I know what it feels like. Actually, it was not a mistake, I just mis-spoke.

Seriously, there is an idea in How to Make Whiskey that ethyl acetate combines with phenols over time which is why all Scotch uses a bit of peated barley.

This seems to me to be going down a terminal rat hole. On one hand, we believe that bases will remove ethyl acetate, and when we have a stinky bottle that is not corrected by bases then we say the stink is acetone. This might all be true, but how would we know? And if the stink is not ethyl acetate, do we still care? A reason we might care is mentioned above: that acetone has a BP of 56, compared to 76 for ethyl acetate, so its easier to separate.

We could cook ethyl acetate with alcohol and vinegar, then distill, then try to flip back ...

[Bagasso]

On one hand, we believe that bases will remove ethyl acetate, and when we have a stinky bottle that is not corrected by bases then we say the stink is acetone. This might all be true, but how would we know? And if the stink is not ethyl acetate, do we still care?

Ester hydrolysis is proven chemistry. Will it get us what we want? To me that sounds like a "how long is a string?" type of question.

Also, why would you use bases on a bottle of whisky, it will hydrolize all the esters, including the ones that you want to keep.

[thecroweater]

MDH you are right on the money . It doesn't worry me if guys have there terms mixed up but it is better for the reader if the information accurately reflects what the reader will find in real would results

[engunear]

Ester hydrolysis is proven chemistry.

And I'm not doubting it. But what is the hypothesis that we are talking about here? I thought, between the lines people were saying:

1) Much white spirit we make is kind of messed up by ethyl acetate, which makes in stinky.
2) If we add calcium carbonate, a base, and warm it or leave it, it will be good and obedient and turn the ethyl acetate back to ethyl alcohol and acetic acid, and the acetic acid will react with the calcium carbonate.
3) We can do this between first and second distillation, so all the calcium carbonate gets left behind.
4) We will have sweet smelling spirit without the hassle of leaving a honking great fractionating column at a drop a second for 3 hours.

Every word of that is totally reasonable, and overall its a damn fine idea. So I tried to test this with starting spirit that was stinky enough that variations in my nose from day to day, and my shitty smell memory, did not interfere with the result. And so far, my result is that one of those four lines is broken.

Maybe the stink is acetone. Maybe my pH is not high enough, and I should use caustic soda. Maybe ... but until I can see a rock solid result its just a hypothesis.

[der wo]

The rock solid results are here I think:
http://homedistiller.org/forum/viewtopic.php?f=1&t=6749
https://www.stilldragon.org/discussion/ ... sis-thread" onclick="window.open(this.href);return false;" rel="nofollow

[Bagasso]

Ester hydrolysis is proven chemistry.

And I'm not doubting it. But what is the hypothesis that we are talking about here?

Yeah I think everyone needs to be on the same page.

I thought, between the lines people were saying:

1) Much white spirit we make is kind of messed up by ethyl acetate, which makes in stinky.

Not exactly. It's kind of messed up by a few things. One of them might be ethyl acetate.

2) If we add calcium carbonate, a base, and warm it or leave it, it will be good and obedient and turn the ethyl acetate back to ethyl alcohol and acetic acid, and the acetic acid will react with the calcium carbonate.

True but so will every other ester. Some ketones will also react.

3) We can do this between first and second distillation, so all the calcium carbonate gets left behind.

Yes we end up with calcium acetate which would stay behind.

4) We will have sweet smelling spirit without the hassle of leaving a honking great fractionating column at a drop a second for 3 hours.

No because ethyl acetate is only one of many variables.

Every word of that is totally reasonable, and overall its a damn fine idea. So I tried to test this with starting spirit that was stinky enough that variations in my nose from day to day, and my shitty smell memory, did not interfere with the result. And so far, my result is that one of those four lines is broken.

Maybe the stink is acetone. Maybe my pH is not high enough, and I should use caustic soda. Maybe ... but until I can see a rock solid result its just a hypothesis.

What does rock solid mean to you? Reminds me of activated carbon. Take a stripped wash and run it through activated carbon and you will get rock solid results without getting sweet smelling spirits. Of course by rock solid I mean that you will notice a definite change but it will not clean everything up.

In my experience I've had a problem for a while with something in my spirits that I just can't get rid of. After trying every bit of advice on here I still never got more than a sliver of nice smelling hearts and even those didn't taste all that great. That is probably why I ended up trying the not so popular things like AC, pH treating and others. Last batch has me thinking it was the plant food I was using as nutrients.

So all the other stuff HD approved or not never gave me sweet spirits but I wouldn't say that they did not do what they were supposed to.

[engunear]

Der wo's link is rock solid. Short of using a gas chromatograph, I can't imagine a better experiment.

So my stinky bottle needs to be re-distilled, and if it comes out clean, then I'll know the stink was ethyl a., and if not, the "complex mix" hypothesis rules.

Interesting, with Grim, after heating and leaving overnight then the hydrolysis had not gone through, and even when he distilled he still had some esters in his heads (do I read that right?). This is reminiscent of the Arroyo method of accelerating ethyl lactate production by running a stripping still on full reflux for an hour.

[Bagasso]

Der wo's link is rock solid. Short of using a gas chromatograph, I can't imagine a better experiment.

I linked to that thread in the previous page.

Interesting, with Grim, after heating and leaving overnight then the hydrolysis had not gone through, and even when he distilled he still had some esters in his heads (do I read that right?).

Do we know that they are in fact esters?

[engunear]

Sorry I missed it, Bagasso. Good link. Also would have saved me some un-necessary posting.

He has added only acids, and it is basic chemistry that acid + alcohol -> ester + water. So I believe Grim has only esters.

As for the stinkiness in my bottle, it seems reasonable to say that what survives after re-distillation is not ester. Maybe thats what you meant.

[Bagasso]

He has added only acids, and it is basic chemistry that acid + alcohol -> ester + water. So I believe Grim has only esters.

Yeah but is his alcohol just ethanol? He said "300ml tails, 200ml hearts" so I'm going to have to go with no, it isn't just acid and ethanol.

Also, from further reading after my last post I came across a claim that some esters are harder to crack than others.

As for the stinkiness in my bottle, it seems reasonable to say that what survives after re-distillation is not ester. Maybe thats what you meant.

Right. There are a lot of different things in distillate. Looking at these Azeotrope tables from wiki there are a bunch of compunds forming bonds with both ethanol and water.

Not sure what you meant by "complex mix hypothesis" but I get the feeling that that might be a part of it.