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.

Chemical Urban Legends: pH

What does the p in pH stand for?

The term pH has been in use for more than a century. It is a logarithmic measure of the hydrogen ion concentration ([H+]): pH = -log10[H+]. (Technically, there aren't bare protons (H+) floating around in solutions, but that wasn’t known when pH was introduced!) The original symbol used by Sorensen was p_H⁺.

Theories vary as to the origin of the p - most agree it means power but whether in Latin, French or German, seems in dispute. Thinking it would be either French or Latin as the original paper was published in French, I was surprised to find that it's neither, though the legend is both old and persistent. By 1920, many authors were assuming that it meant “power”, but Jens Norby returned to the original sources and points out that it was the arbitrary choice of the letters p and q for two variables in the work-up of the experimental data. The variable p eventually ends up in the formula arrived at for the concentration of the hydrogen ion.

The modern form pH was introduced in 1920, "as a matter of typographical convenience".

For the full explanation, see Jens G. Norby, The origin and the meaning of the little p in pH, Trends in Biochemical Sciences 25, 36-37 (2000). The illustration is a selection from the original paper: Sorensen, Compt. redn. du Lab. de Carlsberg 8 1-168 (1909).

A rose by any other name is poison ivy

In 1865 John Maisch published a short paper "On the Active Principle of Rhus Toxicodendron". For the unsensitized, rhus toxicodendron is the botanical name for poison ivy. Maisch isolated a fraction he considered to be the "active principle" responsible for the misery that is poison ivy and dubbed it toxicodendric acid. Are you itchy yet? (I am and Maisch surely was, he and various visitors to his lab suffered with outbreaks of poison ivy.)

By 1897 Franz Pfaff of Harvard had weighed in. Toxicodendric acid extracted from poison ivy turned out to be acetic acid - yes, vinegar, by another name, CH₃COOH. He showed the itch was in the oil.

Ant-acids

I'm teaching general chemistry this semester. Acids and bases are currently on our agenda, in particular how to assess the strength of an acid based on its molecular structure. When dissolved in water, strong acids, such as hydrochloric acid (HCl) or sulfuric acid (H₂SO₄) always transfer their protons (H) to water. For example: HCl + H₂O → Cl^– + H₃O⁺. Weak acids result when only some acid molecules transfer their protons to water. Organic acids, containing only carbon, oxygen, hydrogen and nitrogen, are generally weak acids. The archetypical weak organic acid is acetic acid, better known as vinegar: CH₃COOH. It's not the simplest organic acid, that would be formic acid: HCOOH.

Formic acid was first characterized in the late 17th century. Naturalists had observed that the vapors emitted by ant hills were acidic (using the equivalent of litmus paper), and in 1671 John Ray extracted the pure acid by distilling the crushed remains of red ants. Formica is Latin for ant, hence the name translates pretty literally as "ant acid". Formic acid is at least partially responsible for the sting in bee stings, ant bites and stinging nettles.

Even though chemists call formic acid weak, a 0.10 M solution has a pH of 2.4 (for comparison's sake, the same concentration of HCl has a pH of 1.0).

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I remember find ants all over my Formica counter in my post-doc days. Does the ubiquitous counter-top material have any connection to ants? Apparently not. It was originally created as a substitute for mica insulators. For mica....