Thermodynamics of adsorption in porous materials

Thermodynamic equations are developed for adsorption of multicomponent gas mixtures in microporous adsorbents based on the principles of solution thermodynamics. The conventional spreading pressure and surface area variables, which describe 2-D films, must be abandoned for adsorption in micropores, in which spreading pressure cannot be measured experimentally or calculated from intermolecular forces. Adsorption is divided into two steps: (1) isothermal compression of the gas, (2) isothermal immersion of clean adsorbent in the compressed gas. Thermodynamic functions (Gibbs free energy, enthalpy; and entropy) from solution thermodynamics provide a complete thermodynamic description of the system. Applications are described for characterization of adsorbents, gas storage at high pressure, mixture adsorption, enthalpy, balances, molecular simulation, adsorption calorimetry; and shape selectivity in catalysis.