Unbending the bends

Sometime before dawn this morning, we took our oldest son to the airport. He's bound for the Caribbean for a pre-orientation trip for college (learning to sail with a team of other freshmen). They will get the chance to do a little snorkeling, but when his dad asked him about whether or not they'd be doing any scuba diving, he replied enigmatically,"There is no hyperbaric chamber in the Virgin Islands. They'd have to fly you to Puerto Rico, I guess."

My first response was to wonder how they would do that, given that most aircraft are pressurized to something around 10,000 to 15,000 feet, which would certainly exacerbate the bends - the outgassing of nitrogen from the blood, which can cause embolisms (blockages) in your blood vessels and painful swelling in your joints.

Henry's law governs the amount of gas dissolved in a liquid: the amount of dissolved gas depends on the external pressure of the gas. For example as the pressure of carbon dixoide increases, so does the amount of dissolved carbon dioxide. Some portion of that dissolved CO₂ turns into carbonic acid (H₂CO₃), and lowers the pH, which gives soda water it's characteristic bite. It also means that acidification of the ocean is a risk of fossil fuel burning, and the resultant carbon dioxide in the atmosphere. Climate deniers will say that there is no data linking CO₂ levels with changes in the ocean pH, suggesting it's because the oceans aren't plain water, and that this will complicate the chemistry. True. But your blood is pretty chemically complicated, and this is essentially the system that is used to control your blood's pH.

So why would flying make the bends worse? As the external pressure of nitrogen falls with altitude, more nitrogren comes out of solution in your blood stream and joints. Neither are places where you want more bubbles. If possible, victims of the bends are evacuated on planes that can be pressurized to lower altitudes (an expensive proposition, and one often not covered by travel insurance).

Bariatric chambers allow the external pressure to be increased, and then slowly decreased to prevent the formation of large bubbles. It can take several "dives" to assuage the symptoms. I sat with my mother while she underwent treatment in a hyperbaric chamber, it's not for those with claustrophobia is all I will say.

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Photo is from Wikimedia.

Red Dwarfs

A version of this was written as a guest post for an artist friend's blog.

If you see a colored compound in chemistry, you can almost bet that it will contain a transition metal. Though we think of metals as being a shiny grey hue (with a few exceptions, gold being one), metals are key elements in producing colors for artist. The visible frequencies of light are relatively low in energy, and conveniently correspond to the small gaps in energy that electrons can leap in metals (what chemists call d to d transitions). Cobalt blue, one of my favorite hues, is (as its name suggests) a cobalt salt: CoAl₂O₄. To get different colors, you have to use different metal salts. You can get a brilliant, though not long-lasting, yellow pigment using lead chromate, the same chrome yellow that Vincent Van Gogh made famous. Tweaking colors to get slightly different hues requires either mixing materials or finding a different salt altogether, the gaps that the electrons leap over when they absorb light aren't adjustable.

But there are other ways to capitalize on the properties of metals to create color. Red stained glass has been made for centuries by adding gold to molten glass and carefully controlling the temperature. The gold clusters together in small particles which then become evenly distributed and suspended in the glass.

These tiny clusters are called nanoparticles, because they are 100 nanometers or less in size. One nanometer is 1 billionth of a meter, the period in this sentence is about a million nanometers across, the little gold balls in red glass are about 25 nanometers in diameter. (The prefix nano, comes from the Greek word for "dwarf," hence the title of this post.)

The gold nanoparticles are not dissolved in the glass, but form a colloid. And one property of colloids is that they scatter light. Different frequencies of light scatter differently, which is why the sky is blue, though the scattering of light by a colloid is a slightly different process. (Scattering isn't the only process involved in the color, but unless you really want to fly off the math cliff with me, let's leave talk of quantum dots and wavefunctions to another day.)

The color of light that a colloid scatters depends on the size and shapes of the particles dispersed. It turns out just by varying the size and shape of the particles involved you can tune your gold nanoparticles to be red, red-violet or even green and many colors in between!

If you are interested in knowing more about the history and chemistry of color, Bright Earth: Art and the Invention of Color by Philip Ball is a terrific introduction. He has a recent blog post about color here. For a readable introduction to nanoparticles, quantum dots and color, try this article in the NY Times.

Handheld chemistry

There was a time when chemists regularly reported the taste of newly synthesized compounds as well as other physical data (density, color, etc.). There was also a time when chemistry kits suggested doing chemistry in your hand, for fun. For a piece I wrote for Nature Chemistry (Homemade chemists) I found these instructions in a 1937 manual for a Chemcraft chemistry kit:

I'm a little cautious about using calcium oxide (CaO) as the reaction when it comes in contact with water is famously exothermic (you can cook an egg with it, see the video, and back in the day transporting CaO, or quicklime, by wooden ship, was hazardous duty). I wondered how exothermic was this reaction, and how much ammonia did it make relative to what you might encounter in a barn (the breakdown of urine yield ammonia) or your cat's litter box.

I'll admit to using Hess' law for fun. For those who have not enjoyed (endured?) an introductory chemistry class, Hess' law makes use of the fact that the energy content (heat of formation) of a molecule is a state function. Like altitude, it doesn't matter how you get to the top of the mountain from the valley, climbing straight up the side or meandering up a series of switchbacks, the change in altitude remains the same. So if I know where I am starting (the reactants, in this case calcium oxide (CaO) and ammonium chloride (NH₄Cl)) and where I end (the products, calcium chloride (CaCl₂, ammonia and water), I can figure out how much energy is used up (endothermic) or given off (exothermic).

The handheld reaction is 2 NH₄Cl(s) + CaO(s) → 2 NH₃(g) + H₂O + CaCl₂(s). I looked up the heats of formation in a handy table. To get a sense of magnitude, for 60 grams of CaO, which is about a tablespoon of material, the heat of formation is -635 kJ...or about the same amount of energy you can get from eating 3 Oreos. Overall, this reaction needs about 100 kJ to use up those 60 grams of CaO, in this case the energy comes from your warm hand. [Ed. note: While handheld chemical synthesis is an interesting way to "burn" calories, this is not a recommended weight loss technique!]

So your hand won't melt. Good to know. But if it were me, I'd do this in a test tube and warm it with my hand!

What the reaction does produce a surprising amount of ammonia. If you let the reaction go to completion (and since I don't know how fast the reaction proceeds, I can't tell you how long that will take), using about a 1.5 grams of ammonium chloride, and all the ammonia stays in a 1 cubic meter area around your hand, the concentration would be about 450 ppm. Since the CDC considers the IDLH (immediate danger to life and help) for ammonia to be 300 ppm, this would not be a great experiment to try in the tiny basement bathroom I used as a lab when I was a kid. Still, if you did this just until you could smell the ammonia, for most people that is about 50 ppm, a level considered reasonable for a brief (less than 5 minute) exposure. Levels inside a barn might be around 120 ppm.

Wash those hands.

Chemistry by accident

I just finished another Thesis column for Nature Chemistry, this one on the notion that chemistry sets are an essential part of turning kids into chemists — more particularly, what I called the Uncle Tungsten trope: risky chemistry is more fun and makes better chemists. As part of the article, I wondered how many accidents there are in home labs (not counting home meth labs). It turns out that in the US, the Agency for Toxic Substances and Disease Registry (ATSDR) keeps track of hazardous substance events. The data suggests there are around 1000 chemical incidents in private homes each year, and the vast majority involve carbon monoxide (nearly all the fatalities are caused by CO) or inappropriate mixing of common household chemicals (usually of bleach and something else: ammonia, pool acid, pesticides). As far as I can tell, none of the accidents were part of amateur chemistry gone awry.

There are no narratives linked to the data, but a chemist can read between the lines. When the primary chemical listed in a chemical accident is sucrose — table sugar — (a) what is the secondary chemical likely to be? (b) What was the intended goal of the experiment?

Answers: (a) potassium nitrate (or potassium chlorate) and (b) solid rocket fuel (or sparklers or smoke bombs or...). Sucrose oxidizes readily (toasted marshmallows, anyone?), and potassium salts (KNO₃, KClO₃) are good oxidizing agents.

It should go without saying, but do not try this at home. Especially do not try mixing bleach with anything. It will not make a stronger cleaner, bug killer, or weed killer. But it might kill you.