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A probabilistic rate theory connecting kinetics to thermodynamics

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  • Michel, Denis

Abstract

Kinetics and thermodynamics are largely disconnected in current theories because Arrhenius activation energies (Ea) have strictly no influence on equilibrium distributions. A first step towards the incorporation of rate theories in thermodynamics is the identification of the pre-exponential term of the Arrhenius equation as an entropic quantity. A second step examined here is the possible contribution of Ea in equilibrium landscapes. Interestingly, this possibility exists if envisioning the energetic exponential term of Arrhenius rate constants as the probability that the energy of the reactant is sufficient for the transition. This radically new approach encompasses Maxwell–Boltzmann distributions and solves inconsistencies in previous theories, in particular on the role of temperature in kinetics and thermodynamics. These probabilistic rate constants are then reintroduced in dynamic systems to provide them with the two distinct facets of time: the time step and the time arrow.

Suggested Citation

  • Michel, Denis, 2018. "A probabilistic rate theory connecting kinetics to thermodynamics," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 503(C), pages 26-44.
    • Handle: RePEc:eee:phsmap:v:503:y:2018:i:c:p:26-44
    DOI: 10.1016/j.physa.2018.02.188
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    References listed on IDEAS

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    1. Lebowitz, Joel L., 1993. "Macroscopic laws, microscopic dynamics, time's arrow and Boltzmann's entropy," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 194(1), pages 1-27.
    2. Yin, Cangtao & Du, Jiulin, 2014. "The power-law reaction rate coefficient for an elementary bimolecular reaction," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 395(C), pages 416-424.
    3. Michel, Denis, 2013. "Simply conceiving the Arrhenius law and absolute kinetic constants using the geometric distribution," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 392(19), pages 4258-4264.
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    Cited by:

    1. Michel, Denis, 2018. "Test of the formal basis of Arrhenius law with heat capacities," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 510(C), pages 188-199.

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