Removing ethyl acetate by room temp fractionation

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engunear
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Re: Removing ethyl acetate by room temp fractionation

Post by engunear »

Excellently put, thecroweater.
I wonder how many posters in this thread have actually had the opportunity to smell and or taste the normal components generally present in a distillation run
A great question. Its probably a separate thread, but a list of recipes and/or sources for the different compounds might be very helpful. e.g. a brand of nail polish dominated by ethyl a fits. Acetone is easy to get. But some of the others perhaps not so, I don't even know half their names. Yeah, you can buy them buy the litre from supply houses, but maybe there are simpler methods.

Because I came at this by reading this thread starting out suspicious, tried some of the things, had them not work, then work, then a period of confusion before separating the effects of ethyl acetate and something else ... and still don't know what.
Other people can talk about how to expand the destiny of mankind. I just want to talk about how to make whiskey. I think that what we have to say has more lasting value.

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Re: Removing ethyl acetate by room temp fractionation

Post by Bagasso »

thecroweater wrote:You are going to get these compounds from about 76'c onwards meaning they will be in every fraction except the first fore shots depending on wash size and how much it smears into heads and counted as fores.
The OP isn't about what happens in the boiler and what comes over during a run it is, basically, about airing out.

The logic is simple; anything that would get cut out by doing a proper heads cut should air out first as well, with the corresponding drop in ABV. Whether it is actually ethyl acetate or something else doesn't really matter in the practical sense.

ETA: Reading the OP over again, the OP actually says that airing out worked but that he didn't like the drop in ABV. His plan was to try to find a way to reflux the airstream. OP hasn't been back since 2015 so who knows if he got it to work, although I think not because I'm pretty sure temps much lower than room temp are needed.
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Re: Removing ethyl acetate by room temp fractionation

Post by engunear »

I'm sorry if I'm gonna be ever the nitpicker here. I'm a huge distruster of n=1 experiments. Also I'm not saying the premise is wrong, just that I don't think the experiment proves it.

Aside from the fractionation aspect, there are a bunch of aromatics that could benefit from airing out and they have quite different BPs. We don't know, when it "worked" what was present, even though the title of the thread assumes it to be ethyl a. My gut tells me that ethyl acetate, having a BP just 1C different to ethyl alcohol will not air out effectively, but I trust my gut as much as n=1 experiments. They are both pointers to "more work beneficial here".

But I have the tools and the time to put the precise premise to the test, as do probably a few of us. Who else is brave? Can we make it n=2 or 3?
Other people can talk about how to expand the destiny of mankind. I just want to talk about how to make whiskey. I think that what we have to say has more lasting value.

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Re: Removing ethyl acetate by room temp fractionation

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engunear wrote:Aside from the fractionation aspect, there are a bunch of aromatics that could benefit from airing out and they have quite different BPs. We don't know, when it "worked" what was present, even though the title of the thread assumes it to be ethyl a.
True, but it doesn't matter. The OP can be wrong about it being ethyl acetate but I think the basic premise is getting rid of whatever it is that makes heads headsy.
My gut tells me that ethyl acetate, having a BP just 1C different to ethyl alcohol will not air out effectively, but I trust my gut as much as n=1 experiments. They are both pointers to "more work beneficial here".
I think BPs are not very good indicators of volatility. According to this article, The Chemistry of Whisky, "The most abundant ester in the ‘heart’ is commonly ethyl hexanoate, which has an aroma described as apple-like.", which has a boiling point of 168°C.

Isoamyl acetate also comes over early in the run and it has a BP of 142°C.

Something else to take into account is quantity. If you have 1L of 30%ABV low wines with 125mg/L of ethyl acetate (based on photonic's lab results) and after airing out you have lost 5ml, the ethyl acetate would only need to account for 2.5% of those 5ml.

All the congeners tested in photonic's wash only make up 764mg/l. Anything more volatile than ethanol should, in theory, be aired out with those 5ml.

Even if the rest is made up of 3.236ml of pure ethanol and 1ml of water. (Numbers pulled straight out of my hindquarters, for illustrative purposes only)
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Re: Removing ethyl acetate by room temp fractionation

Post by engunear »

If we are ever going to find an answer to the question posed in this thread, its going to to be by taking apart what "headsy" means, and testing each component on its own. Divide and conquer, make it fail, change one thing at a time, keep an audit trail etc. Even if someone takes some headsy booze and airs it out and a year later deems it great, what does that prove? Is the headsy booze in my shed the same as that tested?

We need a list of compounds, a bank of recipes to make them (or people willing to buy), some well designed experiments, and people willing to do the work.

That doesn't answer the "fractionation" part of the question, but it would be a start.
Other people can talk about how to expand the destiny of mankind. I just want to talk about how to make whiskey. I think that what we have to say has more lasting value.

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Re: Removing ethyl acetate by room temp fractionation

Post by Bagasso »

engunear wrote:If we are ever going to find an answer to the question posed in this thread, its going to to be by taking apart what "headsy" means, and testing each component on its own. Divide and conquer, make it fail, change one thing at a time, keep an audit trail etc. Even if someone takes some headsy booze and airs it out and a year later deems it great, what does that prove? Is the headsy booze in my shed the same as that tested?
I guess but it would be no different than the vague, "make good cuts".
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Re: Removing ethyl acetate by room temp fractionation

Post by acfixer69 »

Hey folks this is Home Distiller not big pharma. We each have sensitivity, in taste, run the finger thru the stream and feel it, smell it, taste it, at that point it is what it is to you. Next home batch will be what it is too.

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Re: Removing ethyl acetate by room temp fractionation

Post by The Baker »

While I have no idea what the experts are talking about, I respect what they do.
That is how knowledge is increased and techniques improved.

I'll stick my finger in it and taste and hopefully improve what I do because I don't understand the science.

Both approaches are valid.

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Re: Removing ethyl acetate by room temp fractionation

Post by acfixer69 »

I would be a fool to say I understand any of that. Point was nobeey Ignore.
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Re: Removing ethyl acetate by room temp fractionation

Post by thecroweater »

The reason some fractions don't come over when the bp might indicate they would is due to mixing with other compounds greatly changing and in some cases lowering of those boil points.
Cuts like most variable methods are a skill or craft not a science (unless everything and I mean every little thing is repeatable) it only remains "vague" until it is a skill you have acquired as is the way with all crafts, you learn what works for you. I would trust that long before adding all sorts of chemicals. Certainly sectors of the industry do have additives to ameliorate given problems, they have the sordid topic of coin to consider that is not such an influencing factor for the home distiller.
Edit posted before seeing the above two posts
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Re: Removing ethyl acetate by room temp fractionation

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thecroweater wrote:The reason some fractions don't come over when the bp might indicate they would is due to mixing with other compounds greatly changing and in some cases lowering of those boil points.
Of course, but this is repeatable.
Cuts like most variable methods are a skill or craft not a science (unless everything and I mean every little thing is repeatable) it only remains "vague" until it is a skill you have acquired as is the way with all crafts, you learn what works for you.
By "vague" I meant the phrase doesn't describe something concise. Jim doesn't make cuts the same as Joe but that doesn't men that one makes good cuts and the other doesn't.
I would trust that long before adding all sorts of chemicals.
To each his own.
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Re: Removing ethyl acetate by room temp fractionation

Post by thecroweater »

Oh for sure each to his own, it is the same with cuts and why to skilled distillers might cut differently.
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Re: Removing ethyl acetate by room temp fractionation

Post by acfixer69 »

thecroweater wrote:Oh for sure each to his own, it is the same with cuts and why to skilled distillers might cut differently.
like that right there. might look like a sig
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Re: Removing ethyl acetate by room temp fractionation

Post by Bagasso »

thecroweater wrote:Oh for sure each to his own, it is the same with cuts and why to skilled distillers might cut differently.
Exactly my point, "good cuts" is as specific as "the best ice cream flavor". It describes something vague and subjective.

In regards to the OP, and the post I was replying to, if someone feels using an air pump cleaned their distillate then that is their call to make. Maybe it isn't ethyl acetate and if members of HD do the footwork and figure out what "headsy" means and what causes it that would be good but it really isn't going to change how most do their thing. I mean, our senses are all most have to work with.
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Re: Removing ethyl acetate by room temp fractionation

Post by Yummyrum »

Well he's some results of a test I ran in my breaks today .

Measured 10mls of each into an evaporation basin and when the lowest one still had a measurable amount , I measured then to see how much each had evaporated .

The first time I did it , I had them sitting in the Fume hood but not running .Unfortunately someone mentioned the smell so I had to turn it on but it very quickly evaporated them ...LOL...good to see it worked .

So I did it again later when no one was around so it would evaporate more naturally .
This could account for the variations between the two tests . I was going to run it a third time but ran out of time .

So the interesting things to me are that just because boiling points are close , does not mean that evaporation rates are close . looking at the Ethyl acetate and Ethanol , it is apparant that the Ethyl acetate is evaporation at a quicker rate than the Ethanol despite the 1 degC difference in boil point.
Also notice that the Butal-1-ol has a boil point of 117 deg but evaporated more than the water . Butan-2-ol ( 2-Butanol) Boils at 1degC less than water but it is evaporating at a much quicker rate .

Acetone BP 56 degC
Methyl Acetate BP 57.1 degC
Methanol BP 64.7 degC
Ethyl Acetate BP 77.1 degC
Ethanol BP 78.3 degC
2-Propanol BP 82.6 degC
1-Propanol BP 97 degC
2-Butanol BP 99 degC
Water BP 100 degC
1-Butanol BP 117.7 dgC
Samples.jpg
Fume hood.jpg
The pencil graph is the first run , the red graphs was the second run
Results.jpg
Note that these are testing the evaporation of pure substances but how they evaporate when mixed together is another story I can imagine .

Anyway something to mull over . :thumbup:

Oh and by the way IMHO Aussie fingernail polish clearly smells like Ethyl Acetate , 1-Butanol smells very much like the concentrated Tails smell you get in the packing of a reflux still ...and Methanol has no smell that I can percieve . 2-Propanol smells like Isopropal or Rubbing alcohol . The others have unique smells but hard to explain .....I don't do well explaining that kind of stuff :thumbdown: .
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Re: Removing ethyl acetate by room temp fractionation

Post by thecroweater »

With nail polish it really matters what brand, its why I specified Cutex™ as that common brand has acetone as the active ingredient and does not have acetate. I would like to know the comparable evaporation rates between a few things perhaps in a stand alone thread particularly between methanol and ethanol as I would like to see some held beliefs that don't fit what most actually find debunked with more than anecdotal evidence :thumbup: .
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Re: Removing ethyl acetate by room temp fractionation

Post by Yummyrum »

thecroweater wrote:I would like to know the comparable evaporation rates between a few things perhaps in a stand alone thread particularly between methanol and ethanol as I would like to see some held beliefs that don't fit what most actually find debunked with more than anecdotal evidence :thumbup: .
Yeah thats been something I've been thinking about too :thumbup: .....just trying to think of a practical way to provide some useable info
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Re: Removing ethyl acetate by room temp fractionation

Post by BugHunter »

I wouldn't be surprised to find that the same brand of polish remover may have different formulations, depending on what country it's sold in, or maybe even what state.
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Re: Removing ethyl acetate by room temp fractionation

Post by engunear »

Looking at yummyrum's data ... velly interlesting ... and lining up the partial pressure at 25C of each of those ... (sorry, no pretty graph, and some of my numbers needed an eyeball interpolation so may be off a little.) These partial pressures were calculated the Antoine equation at http://ddbonline.ddbst.com/" onclick="window.open(this.href);return false;" rel="nofollow (don't you love 19thC science and 21st century internet)

Compound PP BP
Acetone 230 56
Methanol 130 64.7
Ethyl A 100 77.1
Ethanol 50 78.3
Water 25 100
1-Butanol 5 117.7

If you plotted BP against PP you would get a monotonic line. So you'd expect, based on Antoine's equation, that the measured evaporation rates would follow the BPs at least in the order. So I'm puzzled at the experimental results (I absolutely love that someone did this.)

Yeah, we are not big pharma. This is high school chemistry (I did physics). We are just a bunch of blokes who like an opportunity to like to explore the artistic and scientific sides of making great booze.
Other people can talk about how to expand the destiny of mankind. I just want to talk about how to make whiskey. I think that what we have to say has more lasting value.

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Re: Removing ethyl acetate by room temp fractionation

Post by Bagasso »

Yummyrum wrote:Yeah thats been something I've been thinking about too :thumbup: .....just trying to think of a practical way to provide some useable info
I just came across this information on the Vapor-Liquid Equilibrium Data of methanol/water and, if I'm reading this right, methanol acts like ethanol.

What I mean is that just like the Distillate Strength chart on the parent site, the upper left diagram, near the bottom of the linked page, shows that the boiling point of the mixture increases as the amount of methanol decreases. Between 0.1 and 0 the boiling point goes from around 84°C to around 97°C. No expert here and I know the mixtures in our pots are much more complex but it seems to me to be the usual range for a typical potstill run.
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