All current formulations of nonequilibrium thermodynamics of open chemical reaction networks rely on the assumption of non-interacting species. We develop a general theory that accounts for interactions between chemical species within a mean-field approach using activity coefficients. Thermodynamic consistency requires that rate equations do not obey standard mass-action kinetics but account for the interactions with concentration dependent kinetic constants. Many features of the ideal formulations are recovered. Crucially, the thermodynamic potential and the forces driving non-ideal chemical systems out of equilibrium are identified. Our theory is general and holds for any mean-field expression of the interactions leading to lower bounded free energies.
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7 March 2021
Research Article|
March 02 2021
Nonequilibrium thermodynamics of non-ideal chemical reaction networks
Francesco Avanzini
;
Francesco Avanzini
a)
Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg
, L-1511 Luxembourg City, Luxembourg
a)Author to whom correspondence should be addressed: [email protected]
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Emanuele Penocchio
;
Emanuele Penocchio
b)
Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg
, L-1511 Luxembourg City, Luxembourg
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Gianmaria Falasco
;
Gianmaria Falasco
c)
Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg
, L-1511 Luxembourg City, Luxembourg
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Massimiliano Esposito
Massimiliano Esposito
d)
Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg
, L-1511 Luxembourg City, Luxembourg
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Francesco Avanzini
a)
Emanuele Penocchio
b)
Gianmaria Falasco
c)
Massimiliano Esposito
d)
Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg
, L-1511 Luxembourg City, Luxembourg
a)Author to whom correspondence should be addressed: [email protected]
b)
Electronic mail: [email protected]
c)
Electronic mail: [email protected]
d)
Electronic mail: [email protected]
J. Chem. Phys. 154, 094114 (2021)
Article history
Received:
December 21 2020
Accepted:
February 15 2021
Citation
Francesco Avanzini, Emanuele Penocchio, Gianmaria Falasco, Massimiliano Esposito; Nonequilibrium thermodynamics of non-ideal chemical reaction networks. J. Chem. Phys. 7 March 2021; 154 (9): 094114. https://doi.org/10.1063/5.0041225
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