摘要
The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.
The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.
