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The idea of microscopic reversibility was born together with physical kinetics. In 1872, Ludwig Boltzmann represented kinetics of gases as statistical ensemble of elementary collisions. [2] Equations of mechanics are reversible in time, hence, the reverse collisions obey the same laws.
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.
Statistical mechanics, also known as statistical thermodynamics, emerged with the development of atomic and molecular theories in the late 19th century and early 20th century, and supplemented classical thermodynamics with an interpretation of the microscopic interactions between individual particles or quantum-mechanical states.
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 ...
In physics, Loschmidt's paradox (named for J.J. Loschmidt), also known as the reversibility paradox, irreversibility paradox, or Umkehreinwand (from German 'reversal objection'), [1] is the objection that it should not be possible to deduce an irreversible process from time-symmetric dynamics.