Complex Systems and Statistical Mechanics, Department of Physics and Materials Science, University of Luxembourg, L-1511 Luxembourg City, Luxembourg.
J Chem Phys. 2021 Mar 7;154(9):094114. doi: 10.1063/5.0041225.
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.
目前所有的非平衡态开放化学反应网络的热力学理论都依赖于非相互作用物种的假设。我们开发了一种一般理论，在平均场方法中使用活度系数来考虑化学物种之间的相互作用。热力学一致性要求速率方程不遵守标准的质量作用动力学，而是要考虑与浓度相关的动力学常数的相互作用。许多理想公式的特征都得到了恢复。关键是，确定了理想化学系统偏离平衡的热力学势和驱动力。我们的理论是通用的，适用于任何导致下边界自由能的平均场相互作用表达式。
