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Proposed principles of maximum local entropy production.
John Ross,
Alexandru Dan Corlan,
Stefan C Müller,
J Phys Chem B. 116(27):7858-7865, 2012
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.
[Medline]