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The principle of microscopic reversibility in physics and chemistry is twofold: First, it states that the microscopic detailed dynamics of particles and fields is time-reversible because the microscopic equations of motion are symmetric with respect to inversion in time ( T-symmetry );
The principle of detailed balance was explicitly introduced for collisions by Ludwig Boltzmann.In 1872, he proved his H-theorem using this principle. [1] The arguments in favor of this property are founded upon microscopic reversibility.
In physical and chemical kinetics, T-symmetry of the mechanical microscopic equations implies two important laws: the principle of detailed balance and the Onsager reciprocal relations. T-symmetry of the microscopic description together with its kinetic consequences are called microscopic reversibility.
The theory developed by Onsager is much more general than this example and capable of treating more than two thermodynamic forces at once, with the limitation that "the principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present", in which case "the reciprocal relations break down". [1]
These relations are derived from statistical mechanics under the principle of microscopic reversibility (in the absence of external magnetic fields). Given a set of extensive parameters X i (energy, mass, entropy, number of particles and so on) and thermodynamic forces F i (related to their related intrinsic parameters, such as temperature and ...
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This equality was shown to be necessary by Lars Onsager using statistical mechanics as a consequence of the time reversibility of microscopic dynamics. The theory developed by Onsager is much more general than this example and capable of treating more than two thermodynamic forces at once. [10]