Chemistry Department, Stanford University , Stanford, California, United States.
J Phys Chem B. 2012 Jul 12;116(27):7858-65. doi: 10.1021/jp302088y. Epub 2012 Jun 29.
Articles have appeared that rely on the application of some form of "maximum local entropy production principle" (MEPP). This is usually an optimization principle that is supposed to compensate for the lack of structural information and measurements about complex systems, even systems as complex and as little characterized as the whole biosphere or the atmosphere of the Earth or even of less known bodies in the solar system. We select a number of claims from a few well-known papers that advocate this principle and we show that they are in error with the help of simple examples of well-known chemical and physical systems. These erroneous interpretations can be attributed to ignoring well-established and verified theoretical results such as (1) entropy does not necessarily increase in nonisolated systems, such as "local" subsystems; (2) macroscopic systems, as described by classical physics, are in general intrinsically deterministic-there are no "choices" in their evolution to be selected by using supplementary principles; (3) macroscopic deterministic systems are predictable to the extent to which their state and structure is sufficiently well-known; usually they are not sufficiently known, and probabilistic methods need to be employed for their prediction; and (4) there is no causal relationship between the thermodynamic constraints and the kinetics of reaction systems. In conclusion, any predictions based on MEPP-like principles should not be considered scientifically founded.
已经出现了一些依赖于某种形式的“最大局部熵产生原理”(MEPP)应用的文章。这通常是一个优化原理,旨在弥补复杂系统缺乏结构信息和测量的不足,即使是像整个生物圈、地球的大气甚至太阳系中不太为人知的天体这样复杂和特征不明显的系统。我们从一些著名的论文中选择了一些支持这一原理的观点,并通过一些众所周知的化学和物理系统的简单例子来证明它们是错误的。这些错误的解释可以归因于忽略了一些经过充分验证的理论结果,例如:(1)非孤立系统(如“局部”子系统)中的熵不一定会增加;(2)经典物理学所描述的宏观系统通常是内在确定论的,其演化过程中没有可以通过补充原理来选择的“选择”;(3)宏观确定性系统可以在其状态和结构足够已知的程度上进行预测;通常情况下,它们并不是足够已知的,需要采用概率方法进行预测;(4)热力学约束与反应系统动力学之间没有因果关系。总之,任何基于 MEPP 类原理的预测都不应被视为有科学依据。