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The Rate-Controlled Constrained-Equilibrium Approach to Far-From-Local-Equilibrium Thermodynamics

机译:远离局部平衡热力学的速率控制约束平衡方法

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The Rate-Controlled Constrained-Equilibrium (RCCE) method for the description of the time-dependent behavior of dynamical systems in non-equilibrium states is a general, effective, physically based method for model order reduction that was originally developed in the framework of thermodynamics and chemical kinetics. A generalized mathematical formulation is presented here that allows including nonlinear constraints in non-local equilibrium systems characterized by the existence of a non-increasing Lyapunov functional under the system’s internal dynamics. The generalized formulation of RCCE enables to clarify the essentials of the method and the built-in general feature of thermodynamic consistency in the chemical kinetics context. In this paper, we work out the details of the method in a generalized mathematical-physics framework, but for definiteness we detail its well-known implementation in the traditional chemical kinetics framework. We detail proofs and spell out explicit functional dependences so as to bring out and clarify each underlying assumption of the method. In the standard context of chemical kinetics of ideal gas mixtures, we discuss the relations between the validity of the detailed balance condition off-equilibrium and the thermodynamic consistency of the method. We also discuss two examples of RCCE gas-phase combustion calculations to emphasize the constraint-dependent performance of the RCCE method.
机译:描述非平衡状态下动力系统时间相关行为的速率控制约束平衡(RCCE)方法是一种通用的,有效的,基于物理的模型降阶方法,最初是在热力学框架内开发的和化学动力学。本文介绍了一种广义的数学公式,该公式允许在非局部平衡系统中包括非线性约束,其特征是在系统内部动力学下存在不增加的Lyapunov函数。 RCCE的通用公式可以阐明该方法的本质以及化学动力学上下文中热力学一致性的内置一般特征。在本文中,我们在广义的数学物理框架中研究了该方法的细节,但是为了明确起见,我们在传统的化学动力学框架中详细描述了该方法的著名实现。我们将详细说明证明并阐明明确的功能依赖性,以便找出并阐明该方法的每个基本假设。在理想气体混合物化学动力学的标准上下文中,我们讨论了详细平衡条件不平衡的有效性与该方法的热力学一致性之间的关系。我们还将讨论RCCE气相燃烧计算的两个示例,以强调RCCE方法的约束相关性能。

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