Nonequilibrium heterogeneous catalysis in the long mean-free-path regime

It is shown that a standard principle of traditional catalysis-that a catalyst does not alter the final thermodynamic equilibrium of a reaction-can fail in low-pressure, heterogeneous gas-surface reactions. Kinetic theory for this epicatalysis is presented, and two well-documented experimental examples are detailed: surface ionized plasmas and hydrogen dissociation on refractory metals. This phenomenon should be observable over a wide range of temperatures and pressures, and for a broad spectrum of heterogeneous reactions. By transcending some constraints of equilibrium thermodynamics, epicatalysis might provide additional control parameters and synthetic routes for reactions, and enable product streams boosted in thermochemical energy or desirable species.