Format

Send to

Choose Destination
J Phys Chem B. 2012 Jul 12;116(27):7858-65. doi: 10.1021/jp302088y. Epub 2012 Jun 29.

Proposed principles of maximum local entropy production.

Author information

1
Chemistry Department, Stanford University , Stanford, California, United States.

Abstract

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.

PMID:
22746154
DOI:
10.1021/jp302088y
[Indexed for MEDLINE]

Supplemental Content

Full text links

Icon for American Chemical Society
Loading ...
Support Center