Proposed Principles of Maximum Local Entropy Production

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• 作者：John Ross ; Alexandru D. Corlan ; Stefan C. M眉ller
• 刊名：The Journal of Physical Chemistry B
• 出版年：2012
• 出版时间：July 12, 2012
• 年：2012
• 卷：116
• 期：27
• 页码：7858-7865
• 全文大小：338K
• 年卷期：v.116,no.27(July 12, 2012)
• ISSN：1520-5207

文摘

Articles have appeared that rely on the application of some form of 鈥渕aximum local entropy production principle鈥?(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 鈥渓ocal鈥?subsystems; (2) macroscopic systems, as described by classical physics, are in general intrinsically deterministic鈥攖here are no 鈥渃hoices鈥?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.