Alcohol

Forget the caffe latte, screw the raspberry iced tea
A Malibu and Coke for you, a G&T for me
Alcohol, Your songs resolve like
my life never will
When someone else is picking up the bill
I love you more than I did the week before
I discovered alcohol
O Alcohol, would you please forgive me?
For while I cannot love myself
I’ll use something else
–”Alcohol,” Barenaked Ladies

If you take a molecule of the simplest hydrocarbon, methane, remove one of its four hydrogen atoms and replace it with a hydroxyl group (-OH), you get methanol, the simplest alcohol. The hydrogen at the end of the hydroxyl is more “labile” than the others, so it’s relatively easy for methanol to lose it. That leaves the oxygen with a very friendly bond dangling, and it likes to hook up with its nearby carbon buddy, to form what is called the carbonyl bond. Since carbon is pretty firmly quadrigamous, it has to give up something, and since the carbon already has three hydrogens, one of them just has to go. Essentially, the methanol gives up two hydrogens, enough for a hydrogen molecule. In smog photochemistry, the hydrogens go one at a time, as part of a process involving “hydrogen centered radicals.”

This result of dehydrogenating methanol yields formaldehyde, the simplest aldehyde. “Aldehyde” is, in fact, a contraction of “alcohol de-hydrogenated.” Rounding out the “simplest of its kind” bestiary, is formic acid, the simplest carboxylic acid. It has an alcohol group (-OH), and a carbonyl group (C=O), and a single, lonely hydrogen remaining with the carbon, though it has another hydrogen in the hydroxyl group, which it easily loses in solution, giving formic acid its acidic character.

Formic acid is pretty nasty stuff; ants make it and it’s what they use to sting you with. In fact, formic acid was first isolated by distilling dead ants. Formic acid is specifically toxic to the optic nerve, so the ingestion of formic acid, or a formic acid precursor, can cause blindness.

Methanol is a formic acid precursor, biologically, so formic acid is responsible for most of methanol’s bad effects when ingested. The enzymes that turn methanol into formic acid are cross-potentiated by ethanol, so ethanol is an antidote to methanol poisoning. The metabolization of ethanol substitutes for the metabolization of methanol, giving time for the methanol to be excreted via lungs or urine.

Ethanol is our old friend grain alcohol, the active ingredient in the demon rum. Bootleg ethanol during Prohibition and at other times was sometimes cut with methanol, to give it “more kick” or simply because denatured alcohol is cheap. “Denatured alcohol” is usually made unsafe for consumption by the addition of methanol. There’s an urban legend that says you can make denatured alcohol fit for drinking by filtering it through pumpernickel. It’s not an urban legend that people have tried this, of course; clearly people have tried it. The question is whether or not it does any good.

Ethanol has two carbons to methanol’s one; a way of looking at the setup is that if you replace one of methanol’s hyrdrogens with a methyl group (-CH3), you get ethanol. The same thing happens for formaldehyde/acetaldehyde and formic/acetic acid. However, acetaldehyde and acetic acid (vinegar) are much more biologically benign. Acetaldehyde forms a trimer in the presence of acid catalysts such as sulphuric or phosphoric acid, to make paraldehyde, a pharmacological sedative.

But it is ethanol, not paraldehyde that most people are familiar with. Simply stated, ethanol ingestion gets you drunk. It gets you blotto, looped, lit, loaded, hammered, wasted, pickled, pissed, polluted and plastered. It intoxicates, inebriates, befuddles, besots, bewilders, and stews. It makes you three sheets to the wind, and either more or less interesting than you are when sober. Whatever it does, a lot of people want it done to them, at least from time to time, so ethanol technology has an ancient history.

Many of the most basic tricks of the chemical laboratory were first used to do something interesting to ethanol, especially to concentrate it into hard liquor. Distillation is the best known, and can be used to concentrate alcohol to 96% purity, the rest being water. Ethanol and water at the 96/4 proportions form an azeotrope, which is a mixture of stuff that boils in the same proportions as it is in liquid form. You have to work hard to break up the ethanol and water azeotrope, and if you do, you’ve probably wasted your time, because exposure to air will allow the ethanol to absorb enough water to form the azeotrope again. Besides, for most people, 192 proof is quite enough.

When I lived in upstate New York we’d drive out into the country (which was a short drive) every fall and buy fresh apple cider in big plastic jugs. Sometimes we couldn’t finish a jug before it went hard; sometimes we’d just let it sit on the back porch until it went hard. Then we’d make applejack, a traditional New England drink.

The principle of applejack is pretty simple: water freezes at a higher temperature than alcohol, and when you cool a water alcohol mixture, water freezes out. Here’s a list of the volume of ethanol in a water/alcohol mix, and the freezing point of the water in that mixture (in degrees F and C):

[0:32,0], [10:25,-4], [20:15,-9], [30:5,-15], [40:-10,-23], [50:-25,-32], [60:-35,-37], [70:-55,-48], [80:-75,-59], [90:-110,-73], [100:-175,-114],

Put it another way, if you have some dilute ethanol mixture, and you cool it to the requisite temperature, the water will freeze out until you get the water/ethanol mixture above. So if you start with a 14% mix of ethanol and water (the highest alcohol you can get from fermentation alone), the water will begin freezing at somewhere near 20 degrees F. Most freezers are around 0 degrees F, so you can boost your ethanol concentration to around 35%. In applejack there is additional freezing point depression caused by the sugar, so your actually wind up with more like a 30% concentration of ethanol, but that’s 60 proof, and that ain’t bad. If you happen to have a real cold snap (the coldest it got while I was at RPI was -28 F), you can get upwards of 80 proof.

Those old New Englanders knew their stuff.

The theater group at RPI had a traditional beverage they called “Players’ Punch,” or alternately, “blog” (no relation to weblogs, of course; it was probably a backformation of “grog” and possibly “blotto”). It consisted of various fruit juices and sodas, plus laboratory ethanol (the commercial equivalent is Everclear), or, failing that, whatever liquor was available, usually vodka or rum. To this was added dry ice, which chilled it mightily, and froze out some of the water. Potent stuff, and pretty dangerous, because the perception of alcohol content involves smelling the alcohol vapors, and if you get the drink cold enough, it deceives. Also, the dry ice added some carbonation, and carbonation enhances alcohol absorption by the digestive tract.

A high school friend of mine who went to Vanderbilt University, told me of a concoction called the “Funderburg,” no doubt named for its creator. It was a blender drink; I think it used frozen concentrated grape juice. I decided to make blender daiquiris by a similar method. That was the year I ran a lab course for undergraduates, which meant that I had access to the fabled laboratory ethanol.

The drink was simplicity itself: one 6 oz. can of frozen limeade concentrate, then the same can filled with 95% ethanol. To that was added a tray of ice. Then hit the max button on the blender. The final result looked a bit like a slushy, and was very cold. The liquid itself was somewhere around 80 proof, by my estimate, but because of the cold, it tasted about as alcoholic as wine. Very dangerous stuff.

Whenever I think about this particular concoction, I’m bound to remember one particular night in 1972 involving the blender daiquiris plus the Quicksilver Messenger Service’s extended version of “Who Do You Love?” by Bo Diddley. Modesty and discretion compel me to refrain from giving specifics. I will note, however, that the effects of ethanol are such that, while one may still remember that actions have consequences, the relative values placed on the actions vs. consequences may change substantially. Suffice it to say that it all Seemed Like a Good Idea at the Time.