Abstract
We revisit the description of reaction–diffusion phenomena within nonequilibrium thermodynamics and investigate the role of a nonstandard splitting of the entropy balance into the entropy production and the divergence of entropy flux. As previously reported by Pavelka et al. (Int J Eng Sci 78:192-217, 2014), a new term is identified following from the kinetic energy of diffusion. This newly appearing term acts as a thermodynamic force driving the reaction kinetics. Using the standard constitutive relations within the linear nonequilibrium thermodynamics, the governing equations for a reaction–diffusion problem in a two-species system are derived. They turn out to be linked to Burgers’ equation. It is shown that the onset of stability is not altered, but a non-periodic pattern can emerge. The latter follows from the relation of the governing equation to Burger’s equation with a source term. Hence, transients formed by glued and merging parabolic profiles are expected to appear at least in certain parameter regimes. We explore the significance of this effect and observe that for a comparable magnitude of the diffusion and of the new term stemming from the kinetic energy of diffusion, the solution is expected to be linked to the saw-tooth like solution to Burger’s equation rather than to the eigenmodes of the Laplacian. We conclude that the reaction–diffusion model proposed by Turing is robust to the addition of this effect of the kinetic energy of diffusion, at least when this new term is sufficiently small. As the governing equations can be rewritten into the classical reaction–diffusion problem but with reaction kinetics outside of the classical law of mass action, the analysis presented in this study suggests that a yet richer behaviour of the classical reaction–diffusion problems can be expected, if nonstandard reaction kinetics are considered.






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All the computations and figures were generated using Wolfram Mathematica 12.1. The Mathematica notebook can be found at http://kmlinux.fjfi.cvut.cz/~klikavac/files/RD_n_KED.nb and shall be replaced by a permanent link to university repository if accepted.
Notes
Affinity of a reaction is a measure of its distance to equilibrium which corresponds to zero affinity. If affinity is positive (minding the sign in its definition and noting that \(\nu _{k\alpha }\) is negative for products and positive for reactants), the reaction runs spontaneously.
Again note the sign convention mentioned above, yielding higher extended affinity with higher kinetic energy of the reactants.
In particular, the thermodynamic flux \(J_i\) is not only proportional to the corresponding force \(X_i\), but also is linear in all the identified thermodynamic forces \(X_1,\ldots \), a situation which is referred to as coupling (of forces).
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Acknowledgements
V.K. would like to acknowledge the helpful discussions with Andrew Krause in particular those concerning numerics. V.K. is grateful for the support from the Czech Grant Agency, project number 20-22092S and European Regional Development Fund-Project ‘Center for Advanced Applied Science’ (no. CZ.02.1.01/0.0/0.0/16_019/0000778).
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Communicated by Michael Hinczewski.
Appendix A: Details of the numerical solution
Appendix A: Details of the numerical solution
We include particular details for the discussion of the seemingly stationary profile to the governing equation (16). The final profile shown in Fig. 1 satisfies well the governing equation everywhere with the exception of boundary points, see Fig. 6. As this error does not scale with mesh size, we conclude that it is not an admissible smooth solution to the problem at hand.
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Klika, V. Pattern formation revisited within nonequilibrium thermodynamics: Burgers’-type equation. Biol Cybern 116, 81–91 (2022). https://doi.org/10.1007/s00422-021-00908-3
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DOI: https://doi.org/10.1007/s00422-021-00908-3