What are higher alcohols anyway? And methanol discussion

[Dokimos]

I've seen the phrase "higher alcohol" used incorrectly a lot and I'm a chemistry pedant who would like to set this straight. I'd also try to dispell the methanol myth that almost everyone, distiller or not, believes.

First off, what is a higher alcohol?
Alcohols (molecules with a R-C-O-H all in a row with R being the "Rest of the molecule", whatever it is, and the others being carbon, oxygen, and hydrogen) can have varying lengths of carbon chains. Chains with 1, 2, 3, and 4 carbon atoms in the "R" group are called methanol, ethanol, propanol, and butanol respectively. And the list goes on from there with larger alcohol molecules. But the term "higher alcohol" indicates an alcohol molecule with a higher number of carbon atoms in the chain. Since we focus on ethanol here, methanol is NOT a higher alcohol. It's a lower alcohol. Conversely, propanol and butanol (along with pentanol, hexanol, etc.) are higher alcohols. And these will indeed give you a headache, but will not make you go blind like methanol will.

And that brings me to methanol. Let me say this emphatically:

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

Methanol has a lower boiling point than ethanol, but it has a higher affinity for water than ethanol, so it stays in the boiler for a while and drags its feet about evaporating. So if anything, it comes through in the tails. And very little of it is produced normally during fermentation, especially with grain ferments. There is some methanol production in fruit ferments as a byproduct of pectin, but this will still not make you blind from drinking brandy tails. Ethanol is, as it turns out, an antidote to methanol poisoning anyway.

Before you throw stones, please at least watch the Still Behind the Bench YouTube video on methanol. You might find it enlightening.

And for what it's worth, I'm a chemist.

Let me know what you think.

Dokimos

[shadylane]

"Methanol has a lower boiling point than ethanol, but it has a higher affinity for water than ethanol, so it stays in the boiler for a while and drags its feet about evaporating."

Best and simplest explanation I've heard so far.

[NZChris]

The methanol myth was debunked here several years ago. viewtopic.php?t=40606

Higher alcohols may taste nasty in isolation, but are congeners that are desirable in whiskeys and rums.

[MooseMan]

Great explanation Dokimos thanks for taking the time.

The way I've always explained it to people when they raise the concern of methanol in distilled product is, that there's a higher level of methanol produced in fruit based alcohol fermentation, so how do winemakers get the methanol out of your wine before bottling it? They don't!

After a couple seconds of thought while it sinks in, I usually get a "Huh, oh yeah!"


Since you're a chemist and seem to be versed in our hobby too, (Which is pretty handy!) Would you give your thoughts on the effect of pH modification of low wines/feints before a spirit run?

It's well known that people add soduim to gain a little extra good product, but many don't understand why, what how or how much, that includes me.
A solid explanation of what the addition of sodium is doing would be really useful, and clarification of whether it's a pure and simple pH reaction or another, more complex chemical interaction could lead us all into a better way to do things, or at the very least a more precise addition of the correct chemical.

Maybe in another thread rather than confuse this one?

[Saltbush Bill]

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

No need to yell.............I don't know where you have been before joining here, but 99% of members would already be aware of that.

[shadylane]

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

No need to yell.............I don't know where you have been before joining here, but 99% of members would already be aware of that.

What's wrong Salty. Ya got a hang over.

[Yummyrum]

It's well known that people add soduim to gain a little extra good product, but many don't understand why, what how or how much, that includes me.
A solid explanation of what the addition of sodium is doing would be really useful

MooseMan
Addition of Sodium Hydrogen carbonate ( baking soda) or Sodium Carbonate ( washing soda ) to low wines to reduce esters is used but it is not the Sodium but rather the basic of the carbonate that is doing the trick to the low wines .

But yes , an explanation in another topic would be great if you can Dokimos

Personally , I don’t bother . I’m not that greedy that I need an extra jar out of 20 keepers.

If you are making a Neutral wash like Shadys Sugar shine for a Neutral , you won’t be making many esters anyway .

Not to mention , there won’t be SFA methanol produced either . …. To be back on topic

[Canuckwoods]

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

No need to yell.............I don't know where you have been before joining here, but 99% of members would already be aware of that.

Why do you have to jump all over the guy for being helpful with an excellent explanation?

[Kareltje]

Depends on what you call foreshots, but methanol does come through in the heads. At least in the research articles I have seen.

Oh and in the formula R-C-O-H methanol has an R with 0 C-atoms, but 3 H-atoms.

Apart from that: your explanation is sound and solid. To many of us a bit superfluous, but indeed still widely believed. Alas.

[Big_dog]

Interesting - what’s in heads that give that mouth tingling/numbing then? Just curious.

[LordL]

Interesting - what’s in heads that give that mouth tingling/numbing then? Just curious.

Probably acetaldehyde and ethyl acetate. Probably some ppm's of acetone on the tounge there as well!

[Dokimos]

MeOH doesn't concentrate into any particular fraction, which is why trying to separate it is not worth thinking about on the hobby scale.

I know there are a lot of people who know this about methanol but there are a LOT who don't, particularly beginners. And I think that misunderstanding does a lot of damage to the perception of home distilling among the uninitiated.

Thanks Moose, I should have mentioned the wine thing. It illustrates the point very well.

Thanks for catching my R group error, kareltje!

It's nothing in particular that causes the tounge burn, as LordL says. Check out the Still Behind the Bench video on why spirits burn. He is way smarter than me.

And thanks Yummyrum, that's the way I understand the sodium bicarbonate/carbonate thing. Essentially you're taking an ester and turning it into a salt. And salts don't evaporate at still temperatures. I would guess you could do the same thing with organic acids in the low wines too. For example, neutralize acetic acid (vinegar) with bicarbonate to make sodium acetate, which is a salt and therefore much harder to evaporate than the organic acid. Basically anything with a positive or negative charge will not evaporate easily and will stay in the boiler. Beyond that, I'd have to do more research. Always more to learn

[still_stirrin]

Interesting - what’s in heads that give that mouth tingling/numbing then? Just curious.

Probably acetaldehyde and ethyl acetate. Probably some ppm's of acetone on the tounge there as well!

+1.

Plus, high proof alcohol.

Alcohols above 55% to 60%ABV will cause “numbness” (or that “tingling” sensation you’ve experienced) to the nerves in your mouth and throat. And be forewarned, it can and will also cause tissue damage.

So, sampling or drinking high proof alcohol is not advisable. In fact, I’d caution you against it.
ss

[Renhoekk]

MeOH doesn't concentrate into any particular fraction, which is why trying to separate it is not worth thinking about on the hobby scale.

I know there are a lot of people who know this about methanol but there are a LOT who don't, particularly beginners. And I think that misunderstanding does a lot of damage to the perception of home distilling among the uninitiated.

Yeah you're not wrong. There's plenty of advice on other distilling websites and YouTube channels about how "the methanol comes off first so chuck it away so you don't go blind/die".

And the first thing the uninitiated ask about home distilling is "oh my goodness what if you go blind".

[Garouda]

Depends on what you call fore shots, but methanol does come through in the heads. At least in the research articles I have seen.

Oh and in the formula R-C-O-H methanol has an R with 0 C-atoms, but 3 H-atoms.

Apart from that: your explanation is sound and solid. To many of us a bit superfluous, but indeed still widely believed. Alas.

You'll also find methanol in the tails because of the strong bond methanol/water... You will always have methanol in fruit brandies because if you make a neutral and clean up all the methanol you can, you'll also get rid of the fruit flavours you want in your final product. In the William pear brandy, it's about 1%. By the way, if you press a fresh orange juice and leave it in your fridge, you'll also get some methanol in it...

[Yummyrum]

. By the way, if you press a fresh orange juice and leave it in your fridge, you'll also get some methanol in it...

Apparently that is actually a thing .
But a google search would suggest it’s quite low . …. Like you’d need to drink about 70 glasses to start doing damage
.

Fortunately , I have a work-a-round for that dilemma .
I add Tequila and a splash of Grenadine

[Kareltje]

Depends on what you call fore shots, but methanol does come through in the heads. At least in the research articles I have seen.

Oh and in the formula R-C-O-H methanol has an R with 0 C-atoms, but 3 H-atoms.

Apart from that: your explanation is sound and solid. To many of us a bit superfluous, but indeed still widely believed. Alas.

You'll also find methanol in the tails because of the strong bond methanol/water... You will always have methanol in fruit brandies because if you make a neutral and clean up all the methanol you can, you'll also get rid of the fruit flavours you want in your final product. In the William pear brandy, it's about 1%. By the way, if you press a fresh orange juice and leave it in your fridge, you'll also get some methanol in it...

Yes, I know.
When you plot the amount of methanol against the amount of ethanol the graph even show a strong rising. Only when you plot against the volume of the sample, the graph is about flat.

About the orange juice: I hardly drink it and if I do, I tend to follow Yummyrums advice!

[Garouda]

Apparently that is actually a thing .
But a google search would suggest it’s quite low . …. Like you’d need to drink about 70 glasses to start doing damage
.

Who said the opposite? I also mentioned the famous German Williams pear brandy, I could have said wine.
Do you know the main difference between a Cognac and an Armagnac?
Cognac is distilled in a 'Charentes Alembic' in two runs with cuts, while Armagnac goes through a continuous still, no cuts... The raw material is similar, white wine from white grapes.
That methanol issue should be taken with a pinch of salt (like your Tequila ). In fact, if we only make a stuff based on grain, sugar, molasses, there's no problem. I do not say we do not need to make cuts, there are other unwanted products than methanol.
I recommend reading some topics on Quora, well really, no, just kidding, I don't, there's a bunch of ultracrepidarian experts there...

[Garouda]

quote=Dokimos post_id=7744543 time=1677562116 user_id=83078]
And that brings me to methanol. Let me say this emphatically:

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

[/quote]

Methanol appears in almost equal concentration in all fractions of distillation, but more in the last fractions.
Methanol is highly soluble in water, therefore, methanol will distill more at the end of distillations, when vapours are richer in water. That means that methanol will accumulate more in the tail fraction

Concentration of the main congeners

Distribution of main volatile compounds

Distillation Techniques in the Fruit Spirits Production
Nermina Spaho University of Sarajevo, Faculty of Agriculture and Food Sciences, Bosnia and Herzegovina

[Setsumi]

And that brings me to methanol. Let me say this emphatically:

METHANOL DOES NOT COME THROUGH IN THE FORESHOTS!

Methanol appears in almost equal concentration in all fractions of distillation, but more in the last fractions.
Methanol is highly soluble in water, therefore, methanol will distill more at the end of distillations, when vapours are richer in water. That means that methanol will accumulate more in the tail fraction
image.png
image.png
Distillation Techniques in the Fruit Spirits Production
Nermina Spaho University of Sarajevo, Faculty of Agriculture and Food Sciences, Bosnia and Herzegovina

And the same text says: is a low alcohol environment methanol will be affiliated with water or tails (potstill) but in a high alcohol environment like a column or plater methanol will affiliate with alcohol en have a larger presence in heads. BUT it will be present throughout the run regardless.

Yes, I am pedantic.