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  2. Microscopic reversibility - Wikipedia

    en.wikipedia.org/wiki/Microscopic_reversibility

    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.

  3. Reversible process (thermodynamics) - Wikipedia

    en.wikipedia.org/wiki/Reversible_process...

    The dependence of work on the path of the thermodynamic process is also unrelated to reversibility, since expansion work, which can be visualized on a pressure–volume diagram as the area beneath the equilibrium curve, is different for different reversible expansion processes (e.g. adiabatic, then isothermal; vs. isothermal, then adiabatic ...

  4. Detailed balance - Wikipedia

    en.wikipedia.org/wiki/Detailed_balance

    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 ...

  5. Crooks fluctuation theorem - Wikipedia

    en.wikipedia.org/wiki/Crooks_fluctuation_theorem

    The Crooks fluctuation theorem (CFT), sometimes known as the Crooks equation, [1] is an equation in statistical mechanics that relates the work done on a system during a non-equilibrium transformation to the free energy difference between the final and the initial state of the transformation.

  6. Onsager reciprocal relations - Wikipedia

    en.wikipedia.org/wiki/Onsager_reciprocal_relations

    The basic thermodynamic potential is internal energy.In a simple fluid system, neglecting the effects of viscosity, the fundamental thermodynamic equation is written: = + where U is the internal energy, T is temperature, S is entropy, P is the hydrostatic pressure, V is the volume, is the chemical potential, and M mass.

  7. Fundamental thermodynamic relation - Wikipedia

    en.wikipedia.org/wiki/Fundamental_thermodynamic...

    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 ...

  8. Hammond's postulate - Wikipedia

    en.wikipedia.org/wiki/Hammond's_postulate

    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 ...

  9. Kinetic theory of gases - Wikipedia

    en.wikipedia.org/wiki/Kinetic_theory_of_gases

    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.