A Case of Irrationality?*

As soon as Maxwell published his first paper on the kinetic theory of gases in 1860, he noted that a major consequence of its principles, namely the equipartition theorem, conflicted with known empirical data about the specific heats of poly-atomic gases. According to the equipartition theorem, the total kinetic energy of an isolated system of particles at equilibrium is equally distributed among the particles’ degrees of freedom. The equipartition theorem implies that the calculated values of γ, the ratio between the specific heat of a substance at constant pressure and its specific heat at constant volume, disagree with the measured ones, except for monoatomic gases. The calculated values of γ are too small compared to the measured ones (see table 1). This is called the “specific heats problem”. It originates in the