7 research outputs found
Entropy: The Markov Ordering Approach
The focus of this article is on entropy and Markov processes. We study the
properties of functionals which are invariant with respect to monotonic
transformations and analyze two invariant "additivity" properties: (i)
existence of a monotonic transformation which makes the functional additive
with respect to the joining of independent systems and (ii) existence of a
monotonic transformation which makes the functional additive with respect to
the partitioning of the space of states. All Lyapunov functionals for Markov
chains which have properties (i) and (ii) are derived. We describe the most
general ordering of the distribution space, with respect to which all
continuous-time Markov processes are monotonic (the {\em Markov order}). The
solution differs significantly from the ordering given by the inequality of
entropy growth. For inference, this approach results in a convex compact set of
conditionally "most random" distributions.Comment: 50 pages, 4 figures, Postprint version. More detailed discussion of
the various entropy additivity properties and separation of variables for
independent subsystems in MaxEnt problem is added in Section 4.2.
Bibliography is extende
The Michaelis-Menten-Stueckelberg Theorem
We study chemical reactions with complex mechanisms under two assumptions:
(i) intermediates are present in small amounts (this is the quasi-steady-state
hypothesis or QSS) and (ii) they are in equilibrium relations with substrates
(this is the quasiequilibrium hypothesis or QE). Under these assumptions, we
prove the generalized mass action law together with the basic relations between
kinetic factors, which are sufficient for the positivity of the entropy
production but hold even without microreversibility, when the detailed balance
is not applicable. Even though QE and QSS produce useful approximations by
themselves, only the combination of these assumptions can render the
possibility beyond the "rarefied gas" limit or the "molecular chaos"
hypotheses. We do not use any a priori form of the kinetic law for the chemical
reactions and describe their equilibria by thermodynamic relations. The
transformations of the intermediate compounds can be described by the Markov
kinetics because of their low density ({\em low density of elementary events}).
This combination of assumptions was introduced by Michaelis and Menten in 1913.
In 1952, Stueckelberg used the same assumptions for the gas kinetics and
produced the remarkable semi-detailed balance relations between collision rates
in the Boltzmann equation that are weaker than the detailed balance conditions
but are still sufficient for the Boltzmann -theorem to be valid. Our results
are obtained within the Michaelis-Menten-Stueckelbeg conceptual framework.Comment: 54 pages, the final version; correction of a misprint in Attachment
Engineering model reduction and entropy-based Lyapunov functions in chemical reaction kinetics
In this paper, the structural properties of chemical reaction systems obeying the mass action law are investigated and related to the physical and chemical properties of the system. An entropy-based Lyapunov function candidate serves as a tool for proving structural stability, the existence of which is guaranteed by the second law of thermodynamics. The commonly used engineering model reduction methods, the so-called quasi equilibrium and quasi steady state assumption based reductions, together with the variable lumping are formally defined as model transformations acting on the reaction graph. These model reduction transformations are analysed to find conditions when (a) the reduced model remains in the same reaction kinetic system class, (b) the reduced model retains the most important properties of the original one including structural stability. It is shown that both variable lumping and quasi equilibrium based reduction preserve both the reaction kinetic form and the structural stability of reaction kinetic models of closed systems with mass action law kinetics, but this is not always the case for the reduction based on quasi steady state assumption
Engineering Model Reduction and Entropy-based Lyapunov Functions in Chemical Reaction Kinetics
In this paper, the structural properties of chemical reaction systems obeying the mass action law are investigated and related to the physical and chemical properties of the system. An entropy-based Lyapunov function candidate serves as a tool for proving structural stability, the existence of which is guaranteed by the second law of thermodynamics. The commonly used engineering model reduction methods, the so-called quasi equilibrium and quasi steady state assumption based reductions, together with the variable lumping are formally defined as model transformations acting on the reaction graph. These model reduction transformations are analysed to find conditions when (a) the reduced model remains in the same reaction kinetic system class, (b) the reduced model retains the most important properties of the original one including structural stability. It is shown that both variable lumping and quasi equilibrium based reduction preserve both the reaction kinetic form and the structural stability of reaction kinetic models of closed systems with mass action law kinetics, but this is not always the case for the reduction based on quasi steady state assumption