Fugacity

The question came up while discussing the grand canonical ensemble the other day of just where the word fugacity came from. Having a couple people in the room who received the “benefits of a classical education” (Gruber 1988), we guessed that the root was the Latin fugere, “to flee” — the same verb which appears in the saying tempus fugit. Turns out, the Oxford English Dictionary sides with us, stating that fugacity was formed from fugacious plus the common +ty suffix, and that fugacious (meaning “apt to flee away”) goes back to the Latin root we’d guessed.

Gilbert N. Lewis appears to have introduced the word in “The Law of Physico-Chemical Change”, which appeared in the Proceedings of the American Academy of Arts and Sciences 37 (received 6 April 1901).

If any phase containing a given molecular species is brought in contact with any other phase not containing that species, a certain quantity will pass from the first phase to the second. Every molecular species may be considered, therefore, to have a tendency to escape from the phase in which it is. In order to express this tendency quantitatively for any particular state, an infinite number of quantities could be used, such, for example, as the thermodynamic potential of the species, its vapor pressure, its solubility in water, etc. The quantity which we shall choose is one which seems at first sight more abstruse than any of these, but is in fact simpler, more general, and easier to manipulate. It will be called the fugacity, represented by the symbol [tex]\psi[/tex] and defined by the following conditions: —

1. The fugacity of a molecular species is the same in two phases when these phases are in equilibrium as regards the distribution of that species.

2. The fugacity of a gas approaches the gas pressure as a limiting value if the gas is infinitely rarefied. In other words, the escaping tendency of a perfect gas is equal to its gas pressure.