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Thermodynamic affinity in constrained free-energy systems

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Abstract

Affinity is the generic measure of the deviation of a state from stable equilibrium. Affinity, as introduced by de Donder, is a thermodynamic state property defined in terms of p, T, and system composition during the course of a chemical change. When incorporating reaction kinetic constraints to minimization of Gibbs energy of a multiphase system, affinity can be followed in terms of the extents of the constrained reactions. This property then becomes calculated in terms of the constraint potentials received as additional Lagrange multipliers in the minimization routine. Thus, received affinities are consistent with the respective values calculated from the chemical potentials of the reactants and products of the constrained reactions and their limiting behaviour corresponds to that defined for both stationary and stable equilibrium states. The intermediate affinities can be used in the respective reaction rate calculations, or as input parameters, to define the local chemical equilibrium set by known reaction kinetic constraints. Thus, they become a useful concept in modelling reactive processes.

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Notes

  1. For example, West et al. list 51 reactions including (i) thermal decomposition, which initiates the radical reaction chain; (ii) radical abstraction of Cl and disproportionation; (iii) oxidation; and (iv) dimerization forming a Ti2O x Cl y species.

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Acknowledgements

This work was supported by the Strategic Research Council at the Academy of Finland, project Closeloop (Grant Number 303543).

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Authors and Affiliations

  1. VTT Technical Research Centre of Finland Ltd, Espoo, Finland

    Pertti Koukkari, Risto Pajarre & Petteri Kangas

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  1. Pertti Koukkari
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  2. Risto Pajarre
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  3. Petteri Kangas
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Correspondence to Pertti Koukkari.

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Koukkari, P., Pajarre, R. & Kangas, P. Thermodynamic affinity in constrained free-energy systems. Monatsh Chem 149, 381–394 (2018). https://doi.org/10.1007/s00706-017-2095-5

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  • DOI: https://doi.org/10.1007/s00706-017-2095-5

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