How can Stagg reach 147?

[Gillman]

Not to mention the fire hazard, Jimbo!

Your earlier analysis by the way seems right on.

Gary

[Gillman]

But Tim isn't the only (for our purposes) relevant comparison the one between the size of ethanol and water molecules?

Gary

[pepcycle]

I can see how the wood, with the varying composition of the cells could act as a selectively permeable membrane. The dryness, sap content and temperature on the outside of the barrel would drive the transport of solvents (alcohol, water etc) into and through the wood from the inside. Kind of like a chromatography. A sophisticated separation method. Depending on conditions, water, ethanol or other materials might permeate. I didn't go to the chemistry references cited previously. It'd be above my head anyway. Most transport processes in biological systems are driven by differences from equilibrium. Just my view. Size Yes, Polarity, Yes, Temperature, Yes......All variables.

[jimbo]

permeable membrane, Kind of like a chromatography, transport processes, differences from equilibrium

I would say that you had a good understanding of the possibilities.

Regards, jimbo

[jimbo]

Not to mention the fire hazard, Jimbo!

Back in my oil refinery days, we used to say, "If you have an explosive mixture, it will."

Regards, jimbo

[tdelling]

> But Tim isn't the only (for our purposes) relevant comparison the one between

> the size of ethanol and water molecules?

I would argue that chemical interactions are more important than 'size'.

As a comparable example, say... okay, take two automobile tires

and fill one with water and fill the other with gasoline. The water will

stay in there for a long time, but the gasoline will be drippin' out

pretty soon. Gasoline is a mixture of molecules that are all bigger

in 'size' than water, but they soak into the tire and out the other

side easily.

Ethanol and water going through wood are the same way. 'Size' doesn't

matter. It's all in the chemical interactions.

Tim Dellinger

[Barrel_Proof]

This thread has survived far too long under the mistaken impression that Stagg 2003 is 147 proof. It is not. HazMat was bottled at 142.7 proof.

[jimbo]

I would argue that chemical interactions are more important than 'size'.

As a comparable example, say... okay, take two automobile tires

and fill one with water and fill the other with gasoline. The water will

stay in there for a long time, but the gasoline will be drippin' out

pretty soon. Gasoline is a mixture of molecules that are all bigger

in 'size' than water, but they soak into the tire and out the other

side easily.

Ethanol and water going through wood are the same way. 'Size' doesn't

matter. It's all in the chemical interactions.

Tim Dellinger

Tim, that just isn't true. Many separation processes depend on molecule size, not chemical reaction. In fact distillation is a separation process that has nothing to do with chemical reactions. Permeable membranes and chromatography are other examples of separation processes that do not depend on chemical reactions.

I contend that if there is a process going on in a whiskey barrel that leads to an increase in percent alcohol over time, it some sort of separation process, not a chemical reaction. And that separation process is very likely to be dependent on molecule size.

Your gasoline/water in a tire analogy doesn't make any sense. Whiskey is a totally miscible mixture of water and alcohol, not two totally different substances as are water and gasoline.

Regards, jimbo

[tdelling]

Okay, just to make one thing absolutely clear:

I fully support the view that the wood is acting as a semi-permeable

membrane, and that the rate of water loss depends on the humidity around

the cask.

Now to address your points:

>Many separation processes depend on molecule size, not chemical reaction.

I'm not sure where you've getting the term "chemical reaction". Chemical

reactions break and re-form the bonds that exist between individual

atoms in a molecule. I have not, at any place in this thread, claimed

that this is happening.

>In fact distillation is a separation process that has nothing to do with

>chemical reactions.

Exactly. It has everything to do with chemical interactions. The attraction

between a water molecule and the other molecules in solution is

stronger than the attraction between an ethanol molecule and the other

molecules in solution. Thus the ethanol molecule enters the gas phase

more easily.

>Permeable membranes and chromatography are other examples

>of separation processes that do not depend on chemical reactions.

From the Wikipedia

( http://en.wikipedia.org/wiki/Chromatography ):

"In chemistry, chromatography is a process for the separation of mixtures.

This is achieved by passing a sample mixture (the "analyte") in a stream of

solvent (the "mobile phase") through some form of material (the "stationary

phase") that will provide resistance by virtue of chemical interactions (not

reactions) between the components of the sample and the material."

The key phrase here is "resistance by virtue of chemical interactions".

My claim is that chemical interactions are what govern the behavior of

molecules in a chromatographic separation, and that chemical interactions

are what govern the behavior of ethanol in wood and the behaviour of

water in wood. These interactions are different, and thus the behavior

of water in wood is different than the behaviour of ethanol in wood.

I will concede that for very large molecules such as polymers, proteins,

DNA fragments, etc., there are some types of chromatography that

separate mixtures based on size, e.g. gel permation chromatograpy,

and electrophoresis-based methods which use electric fields to pull

on charged molecules. There is absolutely no way that these methods

could ever separate ethanol from water. Their sizes are just too close

to each other.

I will also concede that molecular sieves can be used to extract

water from ethanol, based on the pore size of the sieves. In

this case, it is impossible for the ethanol to enter the pores.

This is in high contrast to wood, where ethanol can obviously

enter the pores. Ethanol is in no way being excluded as it

is in the case of molecular sieves.

>I contend that if there is a process going on in a whiskey barrel that leads

>to an increase in percent alcohol over time, it some sort of separation

>process, not a chemical reaction.

I can fully agree with that.

>And that separation process is very likely to be dependent on molecule size.

I find that to be absurd. I have provided examples of molecules that have

similar size, but behave completely differently when allowed to permeate

through wood. I have also pointed out that there exists no known separation

process that can separate water from ethanol based on size without completely

excluding the ethanol.

Tim Dellinger

[pepcycle]

Quick Point.

There are separation methods where small molcecules are trapped and large molecules pass through. (Solid phase separation). The pores in the solid phase slow the progress of the small molecules and the larger ones pass around the solid phase. If wood acts like this sometimes, (depending on conditions such as hydration) water would get trapped and ethanol pass and under other conditions, the opposite could be true.

Just another point of view.

Ed

[tdelling]

>There are separation methods where small molcecules are trapped and large

>molecules pass through. (Solid phase separation). The pores in the solid phase

>slow the progress of the small molecules and the larger ones pass around the

>solid phase.

This is the "gel permeation chromatography" that I mentioned in my post,

also known as "size exclusion chromatography". There's a dense and hard to

follow description at

http://en.wikipedia.org/wiki/Gel_permeation_chromatography

which doesn't come right out and say that GPC doesn't work

for small molecules, but I'll tell you now that it doesn't

work for small molecules.

>If wood acts like this sometimes, (depending on conditions such as hydration)

>water would get trapped and ethanol pass and under other conditions, the

>opposite could be true.

I hadn't thought of it that way. That's an interesting theory. Perhaps

humidity swells something in the outer layers of the wood which closes

certain pores to hinder the ethanol molecules. This theory makes certain

predictions about the rate of ethanol loss slowing down. It would have to

happen only on the outer part of the wood, since the interior part is

subjected to the same EtOH/water ratio regardless of exterior humidity.

I'll have to think about it, but my gut still says that size doesn't

have much to do with it.

Tim Dellinger

[dgonano]

A most interesting and enlightening thread.I compliment

all the posters for there time and knowledge.

Is Stagg the highest proof bottling to ever appear?

What is the highest proof whiskey ever discovered in one cask?

At what proof would whiskey become undrinkable?

Any thoughts?

[dhooch]

I worked in a pharmacy when I was a teenager and we had 195 proof methol alcohol. Believe me, it was drinkable. No taste, but, drinkable!

[OneCubeOnly]

I worked in a pharmacy when I was a teenager and we had 195 proof methol alcohol. Believe me, it was drinkable. No taste, but, drinkable!

I sincerely hope you mean ethyl alcohol and not methyl, or you really will fall off that chair!!

[dgonano]

Well forget drinkable, how about marketable.There

must be a proof reached where the alcohol overwhelms

the the flavors.

[bobbyc]

Buffalo Trace found a barrel that was laying in an odd place in the rickhouse that was over 160 proof.

[dhooch]

You are absolutely right!

I told you I was a teenager. What do teenages know!

Besides, that was about 35 years ago. My mind is going quickly....

[jeff]

Personally, I think the current release of Stagg is a wee be too strong for casual enjoyment. I like to add a little water to it to fit my taste. That said, I prefer Stagg '02 neat most of the time.

[boone]

We bottle "pure grain", Gem Clear. The proof is 190. The label has a "caution flamable" symbol on the front.

Pure grain has no smell. I've had a few of my, sugar baby, "fellow mechanic's", pour this into my Pespsi can. I unkowingly, picked the Pepsi up and took a big ole chug...It'll set you on fire ...Instead of swallowing it I "sprayed" spit everywhere ...

We laughed really hard It was funny as hell

Occasionally, I use Gem Clear, to clean the transfer roller's on the label machine. Excellent cleaning product

The funniest part , thier faces when I told em there would be some really good surprises in order for them

Dancin' in the moonlight

Bettye Jo

[pepcycle]

I'm reachin' back to my chemistry training. Strong alcohol will denature protein. That is too say, change its conformation by interfering with the intermolecular bonding. An example of this is cooking an egg white. Taste buds and epithelium are protein. Somewhere around 140 proof or 70% alchohol that denaturing process will destroy human tissue, in effect, neutralizing taste buds and killing the first layer of cells. Try dropping some raw egg white into solutions of alchohol and you can get a pretty good idea of denaturing protein. In addition, alchohol is a dehydrating solvent, effectively penetrating cell membranes and poisoning the cell's metabolism. (read as disinfectant property) The stuff they rub on your skin to kill germs is 70% isopropyl alchohol. (or less) None of these things are things you want to expose your normal functioning body cells to. My experience is that anything over 125 proof is numbing and quickly anesthetizes the inside of your mouth and taste buds.

BTW: I was once told by a fairly knowledgable alcoholic not to eat raw seafood with high proof cocktails, like martinis. The solution will denature the surface of the chunk of food (oyster, clam etc) and make it indigestible, resulting in what he called the "sneakers in the dryer effect" in your stomach.

Save your cells, add the branch.

[ikewillett1]

Mike, I am from Indianapolis but am headed down to Louisville this evening. Do you know of any retailers in the Louisville area that still have some Stagg on hand?

Ike

[AVB]

Nothing like reading old posts to gain a little insight.

Something I think needs to be mentioned in this thread that wasn't, or if it was I missed it, is that bourbon uses charred barrels and scotch usually doesn't. I would think that this fact would have allot to do with the absorbtion and permeability of water into and through the barrel.

[dgonano]

Well most of the barrels used in the aging of Scotch Whisky

come from the U.S.A. They were previously used to age Bourbon. So they must be charred.

To further this discussion, I have a bottle of Old Overholt from the 1930's labeled "exactly as it came from the original barrel at 113 proof". This was aged in Pennsylvania. Maryland Rye also came out of the barrel at a lower proof.

[Gillman]

Dave that's interesting for another reason, it shows barrel proof whiskey in the bottle did not begin with Booker's bourbon.

There is, truly, nothing new under the sun - which hardly diminishes the importance of your find.

Before your post I could not think of a single whiskey before Booker's that was advertised as bottled at barrel proof.

Gary

[AVB]

No Dave, that isn't true. Most scotch does not use 1st or 2nd fill bourbon barrels. Sherry is by far the most widely used with oak (new, 2nd or 3rd fill) after that. When bourbon is used it is stated on the label the vast majority of the time because it is still fairly unusual.

While I don't have any scotch that is over 125 proof I do have 4 over 120 proof with the oldest being 23 years old, a Glen Ord (Rare Malts Expression). Cask Strength Scotch is fairly popular and it isn't uncommon to find bottles over 100 proof, I've got 15 or 16 myself.

Well most of the barrels used in the aging of Scotch Whisky come from the U.S.A. They were previously used to age Bourbon. So they must be charred.

To further this discussion, I have a bottle of Old Overholt from the 1930's labeled "exactly as it came from the original barrel at 113 proof". This was aged in Pennsylvania. Maryland Rye also came out of the barrel at a lower proof.