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In this way, microscopic reversibility was used to prove macroscopic irreversibility and convergence of ensembles of molecules to their thermodynamic equilibria. Another macroscopic consequence of microscopic reversibility is the symmetry of kinetic coefficients, the so-called reciprocal relations.
A Markov process is called a reversible Markov process or reversible Markov chain if there exists a positive stationary distribution π that satisfies the detailed balance equations [13] =, where P ij is the Markov transition probability from state i to state j, i.e. P ij = P(X t = j | X t − 1 = i), and π i and π j are the equilibrium probabilities of being in states i and j, respectively ...
The conservation of mass is expressed locally by the fact that the flow of mass density satisfies the continuity equation: + =, where is the mass flux vector. The formulation of energy conservation is generally not in the form of a continuity equation because it includes contributions both from the macroscopic mechanical energy of the fluid flow and of the microscopic internal energy.
Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G (Gibbs free energy) or H . [1] The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy , and volume for a closed system in ...
Due to the time reversibility of microscopic dynamics (microscopic reversibility), the kinetic theory is also connected to the principle of detailed balance, in terms of the fluctuation-dissipation theorem (for Brownian motion) and the Onsager reciprocal relations.
At higher temperatures when microscopic reversal is easier, the more stable thermodynamic product is favored because these intermediates have time to rearrange. Whether run at high or low temperatures, the mixture of the kinetic and thermodynamic products eventually reach the same ratio, one in favor of the more stable thermodynamic product ...
The reversibility of thermodynamics must be statistical in nature; that is, it must be merely highly unlikely, but not impossible, that a system will lower in entropy. In other words, time reversibility is fulfilled if the process happens the same way if time were to flow in reverse or the order of states in the process is reversed (the last ...
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]