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Testing the theory of oxidation with Lagavulin

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Testing the theory of oxidation with Lagavulin

Postby Thesh » Fri Jan 12, 2007 10:35 pm

I have two bottles of Lagavulin 16, one that I have opened in 2005 and has been partially empty for at least the last year, at least half empty for the last 6 months, mostly empty for the last 3 months. The other bottle I got last week and have just opened today. I want to see if I am ruining my bottles by opening all of them at once.

Now I am not going to try to give tasting notes, as I have a hard time placing flavors. However, I do notice a distinct difference between these two bottles. The textures are identical, the taste is almost indistinguishable. I can notice a difference, although it is hard to figure what it is. The difference that I notice the most? The nose. The old Lagavulin has the nose that I remember, that blend of peat and sweetness that I have grown accustomed to. The new Lagavulin has something that I don't remember. This strong briny smell that sweeps over the peat.

What I will never know, however, is if this is a difference between the batches? Or a change in the whisky over the years? Am I going to see the same difference if I try this again in a few weeks?

That said, I can't see that I do not enjoy the old one because of this. They are both quite enjoyable.
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Postby peergynt323 » Fri Jan 12, 2007 10:46 pm

The problem is not so much opening them as leaving them almost empty for too long. It doesn't sound like your Lagavulin has experienced too much oxidation. I have ruined a few bottles, notably an Aberlour A'bunadh and a Balvenie 10yo FR.
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Postby vitara7 » Sat Jan 13, 2007 12:25 am

what i find in thatt senario, is move the alochol into a smaller sized bottle, more matched tot eh volume of the whisky.
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Postby Deactivated Member » Mon Jan 15, 2007 5:32 am

Excuse me if I sound too much like Mr Picky, but I have never been comfortable with the term "oxidation" for the phenomenon of a largely-empty bottle, open too long, going off. It implies a chemical change of a particular sort in the whisky in the bottle--a sort of rusting, if you will. The term is borrowed, if I am not mistaken, from the wine business, and I don't know if the process is exactly parallel or not. But I really think the problem in such cases is simply evaporation, of alcohol and perhaps also of other volatiles. Maybe it's the same in wine--I have no idea. I'm sure I'm not going to stop anyone using the word, but I wish there were a better one. I usually say "deterioration", which covers any possible undesirable change.
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Postby dram_time » Mon Jan 15, 2007 6:15 am

I think Mr T. is right here, if you leave a glass of the Laga out over night, just s small one mind, try it in the morning and all thats left is a pretty disgusting glasss of peaty water.

As for bottles I dont think its so much the length of time that they have been open for, but as above, the amount of air / whisky in the bottle, and may be even how many times the bottle is opened and exposed to new air for more alcohol to evaporate into.

I say this because even when i have got stuck into a bottle, and finnished it in under a week, the last 1/4 has still lost some of its 'punch and taste' just as if i had the bottle open for a month.

Dt.
[spelling, its early.]
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Postby Drammer » Tue Jan 16, 2007 12:12 am

I think the best way would be to buy identical bottles, by comparing lot/batch numbers etc, I know diageo laser-etches it on the bottom. Then opening one and leaving the other closed. After some time you try both.

If you want to get scientific about it you need several people testing it and also several whiskies because it can differ, maybe peatiness is the first thing to evaporate, maybe its sherriness or whatever.

Just thinking out loud here, but one thing is for sure: It's gonna be expensive :P
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Postby peergynt323 » Tue Jan 16, 2007 2:08 am

MrTattieHeid wrote:Excuse me if I sound too much like Mr Picky, but I have never been comfortable with the term "oxidation" for the phenomenon of a largely-empty bottle, open too long, going off. It implies a chemical change of a particular sort in the whisky in the bottle--a sort of rusting, if you will. The term is borrowed, if I am not mistaken, from the wine business, and I don't know if the process is exactly parallel or not.

I'm fairly certain that it's the same phenomenon. The effect is more pronounced in wine because of the lower alcohol content. Decanting a wine for a few hours will help it to "open up," but leaving a glass of it overnight will cause it to start its transformation into vinegar.


MrTattieHeid wrote:But I really think the problem in such cases is simply evaporation, of alcohol and perhaps also of other volatiles. Maybe it's the same in wine--I have no idea. I'm sure I'm not going to stop anyone using the word, but I wish there were a better one. I usually say "deterioration", which covers any possible undesirable change.

This is hard for me to believe because higher alcohol spirits fare better when it comes to oxidation. A reclosed wine bottle will be undrinkable after only a few days. Port will last a few weeks because of the higher alcohol content. Whisky opens up over a period of weeks and goes off after a year or so.

A lower fill level is directly proportional to the rate of exposure to the air and an important factor in how long the beverage will last before going off.
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Postby Deactivated Member » Tue Jan 16, 2007 2:31 am

peergynt323 wrote:This is hard for me to believe because higher alcohol spirits fare better when it comes to oxidation. A reclosed wine bottle will be undrinkable after only a few days.


That's exactly what makes me think it's something else going on with wine--"transformation into vinegar" is not simply a matter of evaporating alcohol, I think. It's the lower alcohol level that more easily permits other types of spoilage. At least, that's my guess; I'm not a chemist, nor do I....

Leave a dram out overnight in a glass, pg, and see what you think of it in the morning. Or even try it over a few hours. I don't think you need too much evaporation to make your whisky go flat, and not much more than that to make it bloody awful. It hasn't had time or opportunity to "oxidize"; it has simply lost a good portion of its wholesome Scottish goodness.

(Some here have reported improvement in a particular dram left out for half an hour or so; my guess is that some of the edgier spirity content has evaporated.)
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Postby peergynt323 » Tue Jan 16, 2007 2:47 am

MrTattieHeid wrote: It hasn't had time or opportunity to "oxidize"; it has simply lost a good portion of its wholesome Scottish goodness.


This is a viable theory, but I would have to respectfully disagree. To add control to your experiment, set a glass of ethyl alcohol next to the dram and see how much of it evaporates overnight. Only the molecules that are in contact with air have the opportunity to evaporate, so it's a slow process, even with 100% alcohol. It's much slower with a 40-60% ABV beverage.

A dram definitely goes off overnight. This is due to
A) The volume. The molecules in a liquid are constantly moving around and will have more contact with the air than what is in your bottle.
B) The open exposure to air. Whatever chemical reactions do take place will release the inert chemicals up into the air to be replaced by more oxygen. When your spirit is in the bottle, the oxygen that reacts with your whisky is no longer around to do harm.

In support of my theory, I contend that pure ethyl alcohol is scentless and tasteless.

MrTattieHeid wrote:(Some here have reported improvement in a particular dram left out for half an hour or so; my guess is that some of the edgier spirity content has evaporated.)


My theory is that like a decanted wine, the tannins from the wood have "softened" and the fruit and other flavor compounds have "opened up" (I have no idea what the chemistry is behind it).
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Postby Deactivated Member » Tue Jan 16, 2007 4:19 am

If evaporation off the surface is slow, how is oxygenation into the liquid any faster? How does it even occur at all without any agitation?

I'd bet that, if you left a glass of ethyl alcohol out overnight, you'd lose a significant amount to evaporation. Seems to me we did this as an experiment in grade school. I don't think you'd have to lose all that much to muck up your dram.

peergynt323 wrote:Only the molecules that are in contact with air have the opportunity to evaporate, so it's a slow process, even with 100% alcohol....A dram definitely goes off overnight. This is due to
A) The volume. The molecules in a liquid are constantly moving around and will have more contact with the air than what is in your bottle.


Seems to me you contradict yourself there.

peergynt323 wrote:B) The open exposure to air. Whatever chemical reactions do take place will release the inert chemicals up into the air to be replaced by more oxygen. When your spirit is in the bottle, the oxygen that reacts with your whisky is no longer around to do harm.


Sounds like evaporation to me!

The finite volume of air in the bottle becomes saturated, after which no further evaporation can take place. The more air in the bottle, and the more it is circulated and replaced, the more evaporation can take place in the bottle.

peergynt323 wrote:In support of my theory, I contend that pure ethyl alcohol is scentless and tasteless.


Surely you don't contend that whisky, or any alcoholic beverage, will taste the same with the alcohol removed. If that were so, nonalcoholic beers and wines wouldn't be so bloody awful.

Well, never mind...I'm certainly not qualified to carry this discussion any further! Just speculation on my part.
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Postby peergynt323 » Tue Jan 16, 2007 4:45 am

I wish I could offer the science behind it. My guess is that the oxygen + spirit -> spirit oxide reaction is spontaneous. This can be seen easier with wine. Get a mouthful of a really young, tannic cabernet. How does it taste? Now slurp in some air to give a lot of oxygen exposure to the wine. How does it taste now? It takes a matter of seconds to oxidize a small amount of wine, whereas getting rid of the alcohol cannot be accomplished easily.

Similar with decanting. It takes two hours to decant the wine, but all of the alcohol is still there.
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Postby Deactivated Member » Tue Jan 16, 2007 4:49 am

Have you tried slurping your whisky?
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Postby peergynt323 » Tue Jan 16, 2007 4:58 am

Kind of. I had heard that Glenfarclas 105 is particularly closed for a whisky when you first open it. I took a coffee straw and blew some air into it. It did taste more open afterwards.
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Postby Deactivated Member » Tue Jan 16, 2007 5:31 am

I think I would refer to this as oxygenating, that is, simply mixing air into the liquid, rather than oxidizing, which is a chemical process. Oh, I'm in too deep...I hope you are not taking this too seriously! Where's a bloody chemist when you need one?
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Postby Mr Fjeld » Tue Jan 16, 2007 6:48 am

Doesn't "oxydation" simply refer to "something" being exposed to air and triggering various chemical processes? I think I vaguely remember something like this from early days at school? Also, I remember seing the fresco paintings by Cimabue in Basilica di San Francesco in Assisi which have "oxidised" because of the use of silver in his paint.
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Postby peergynt323 » Tue Jan 16, 2007 7:05 am

Rust is ferrous oxide. Silver can turn to silver oxide. Tannins in whisky and wine tend to soften with exposure to oxygen, but I don't know if they actually turn into "tannin oxide." My guess is that lots of different stuff happens with air exposure.
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Postby Mr Fjeld » Tue Jan 16, 2007 7:14 am

I guess it's safe to say that "something" will be affected when exposed to air such as whisky, wine, food etc. There's a reason why the producers provide caps, vacuum packed food, stoppers etc.
Oxydation as a concept sounds fine by me.
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Postby irishwhiskeychaser » Tue Jan 16, 2007 1:03 pm

Yes I think there maybe a slight confusion between airiation(oxygenating) and oxidation here.

Airiation in wine terms is a positive thing as it developes the flavours of the wine which has been shut away in a sealed bottle for x amount of years. However this is not oxidisation(We do a similar thing with whiskey but it is only by the glass and by adding water to develope the flavours, but you can use the slurp method to release the flavours in whisky also.). As the full bottle of wine will be drank in a relatively short period there is no chance for oxidation. however wine will last only a couple of days after opening. Why is this .. well it could be down to low alcohol but it may also be down to the fact it is made from fruit which in it's nature goes off quickly. Barley has a much much longer shelf life in it's natural form. However I cannot correlate a direct link between the liquid product and the raw product but it is worth thinking about.

Oxidation does happen in wine and is refered to as corking or a corked bottle. This is where a bottle has a faulty cork and is allowing air to pass in and out of the cork therefore the wine has a continious contact with new(fresh) air and aftera time goes off.

This probably can also happen with a whiskey but it seems to take a long long time with a full sealed bottle of whiskey.

An old derelict shop was being renovated for a new McDonnells in Cork City in Southern Ireland in the Late eighties. A barrel/cask of Kilbeggan pure potstill whiskey was found underneath a floor. John Teeling who had just bought the Kilbeggan brand for his new cooley project was thrilled with the discovery and bought what they reckoned was a 60-80year old cask of old kilbeggan whiskey. It was transported to Killbeggan and stored. However when it was opened to be tasted they got a shock. It was absolutely ruined and could not even be described as bad whiskey and it tasted vile. The cask had dried out on top and years of massive amounts of air passing through the cask had totally killed the whiskey.

There are also a small amount of casks from the fifties still at kilbeggan and eventhough they still taste like whiskey they are below the 40% legal vol limit to be called whiskey.

From these 2 examples we can see that whiskey does go off and does deteriorate just not neccessarily the same way as wine.
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Postby Mr Fjeld » Tue Jan 16, 2007 1:16 pm

Port, Madeira and Sherry - especially vintage stuff - have been exposed to oxydation. With these fortified wines it's a natural and wanted process.

I still think it's a working concept for our use. I saw an episode of "Waking the Dead" yesterday and the forensic detective describes one of the forensic evidences as oxydised. I think the concept is used in the chemical sciences too.

Edit: I was about to ask someone to check it up but realised that this shouldn't be necessary because we use concepts differently. Whisky jargon is full of imprecise concepts such as peat etc. We often describe whisky as peaty although there is no such thing and should be called smoky instead. Whatever works, and I think oxydation is perfectly ok.
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Postby Deactivated Member » Tue Jan 16, 2007 2:16 pm

Interesting story,iwc--and to think that it happened in Cork! :shock:
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Postby irishwhiskeychaser » Tue Jan 16, 2007 4:06 pm

MrTattieHeid wrote:Interesting story,iwc--and to think that it happened in Cork! :shock:


Would you believe that I did not even notice that. That's gas ... When I say Cork in relation to the Irish City and cork in relation to a capping device on a bottle it does not actually register in my brain as the same word .... wierd :shock:
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Postby peergynt323 » Tue Jan 16, 2007 6:24 pm

The slurp method does more than just oxygenate though. People use it (as well as aerators) as a shortcut for decanting, which is obviously not oxygenation.

I think we can all agree that whisky and wine both "open up" with a little exposure to air and "go off" with prolonged exposure.
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Postby Ize » Thu Jan 18, 2007 1:35 pm

What I have gone through in my little brains is that this "oxidation" does not happen with spirit but with long ester chains. Oxigen in air (or the moisture/water in the air) splits, like water, ester chains in smaller chains which evaporate(?) more easily and aromas of the whisky are gone. I have made somekind of test with whisky in so that I have left whisky into two glasses for overnight, to one glass I added water and another was straight. The one with water was not that good in the morning (increase of ester chain splitting due to water?) but the straight one was still quite enjoyable.
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Postby Deactivated Member » Thu Jan 18, 2007 3:27 pm

An interesting thought. I usually mention "other volatiles" when discussing evaporation of this sort, but it's just conjecture on my part--chemistry is not my best subject. But I do think there's something else being lost besides alcohol, and you may have put your finger on it. Or not!
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Postby irishwhiskeychaser » Thu Jan 18, 2007 3:40 pm

MrTattieHeid wrote:An interesting thought. I usually mention "other volatiles" when discussing evaporation of this sort, but it's just conjecture on my part--chemistry is not my best subject. But I do think there's something else being lost besides alcohol, and you may have put your finger on it. Or not!



Is that congerners you are talking about. It seems that congerners have a big input into the taste.

Congerners

Chemical compounds found whithin whisky and formulated during fermentation, distillation and maturation carrying properties that have direct relevance to the taste and smell of the sprite. Some of the more delicate congerners can be lost during chill filtration.

Logical that you would lose some through evapouration also.
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Postby Deactivated Member » Thu Jan 18, 2007 3:50 pm

I suppose--I always thought of congeners as being heavy greasy things, less subject to evaporation. But honestly I have no clue.
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Postby irishwhiskeychaser » Thu Jan 18, 2007 4:23 pm

MrTattieHeid wrote:I suppose--I always thought of congeners as being heavy greasy things, less subject to evaporation. But honestly I have no clue.


Your probably right as I have no clue either :roll:
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Postby peergynt323 » Thu Jan 18, 2007 7:18 pm

http://www.wineint.com/story.asp?storyCode=1810

This article should clear up the confusion.

The particles removed in chill-filtration probably wouldn't evaporate. Chilling causes them to solidify at a higher temperature than alcohol or water, so they should evaporate at a higher temperature as well.
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Postby Deactivated Member » Thu Jan 18, 2007 8:03 pm

The High Molecular Esters would be a cool name for a band.

I wonder if perhaps unchillfiltered whiskies are less susceptible to the type of deterioration we are discussing? Just a wild random thought. Will keep this in mind as I read reports of spoilage in the future.
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Postby DramMeister » Thu Jan 18, 2007 9:41 pm

With regards to wine:
Ethanol (commonal garden alcohol) isn't easily oxidised by molecular oxygen in the air. Oxygen reacts with phenolics in the wine which then produce hydrogen peroxide which is a strong oxidising agent. This goes on to oxidise the ethanol.
High concentrations of tannins or other phenolics mop up some of the hydrogen peroxide and thus give some protection against oxidation.

I'll try to find out why higher alcohol content drinks take longer to oxidise.
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Postby TheLaddie » Fri Jan 19, 2007 3:04 am

MrTattieHeid wrote:The High Molecular Esters would be a cool name for a band.


Mr T's Rock Festival:

Death's Bony Arse
The High Molecular Esters

Any other cool names for bands Mr T?
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Postby Deactivated Member » Fri Jan 19, 2007 3:32 am

The Lower Volatile Parts? The :shock: More Pronounced Lower Volatile Parts?

Damn, should have kept a list--there have been a few in the past two years.
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Postby Muskrat Portage » Fri Jan 19, 2007 9:36 pm

DramMeister wrote:With regards to wine: ...I'll try to find out why higher alcohol content drinks take longer to oxidise.

DramMeister:
This is just conjecture on my part, but would higher alcohol content take longer to oxidise, due to it's having a greater affinity to the water in the air? This being why alcohol doesn't exist at 200 proof outside the laboratory setting.
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Postby peergynt323 » Fri Jan 19, 2007 9:59 pm

It may just be that water facilitates the spoiling reaction and with a higher ABV you have less water. Think dried fruits, powdered milk, etc.

Just think...we could make some powdered whisky essence!
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Whisky spoilage by oxidation

Postby Muskrat Portage » Sat Jan 20, 2007 2:05 am

peergynt323 wrote:It may just be that water facilitates the spoiling reaction and with a higher ABV you have less water. Think dried fruits, powdered milk, etc....

So as the water is absorbed, the spoilage continues apace. Makes sense.
peergynt323 wrote:...Just think...we could make some powdered whisky essence!

Now, what would we mix it into? Alcool?
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