scholarly journals A Non-Equilibrium Thermodynamics-Based View of the Kinetics of Autocatalytic Reactions – a Simple Illustrative Example

2020 ◽  
Author(s):  
Miloslav Pekař
Keyword(s):  
Second Law Of Thermodynamics ◽  
Rate Equations ◽  
Second Law ◽  
Equilibrium Thermodynamics ◽  
Autocatalytic Reactions ◽  
Chemical Potentials ◽  
Entropic Inequality ◽  
Reaction Stoichiometry ◽  
Kinetics Of ◽  
Non Equilibrium

Autocatalytic reactions are in a certain contrast with the linear algebra of reaction stoichiometry, on whose basis rate equations respecting the permanence of atoms are constructed. These mathematical models of chemical reactions are termed conservative.Using a non-equilibrium thermodynamics-based theory of chemical kinetics, this paper demonstrates how to properly introduce an autocatalytic step into a (conservative) rate equation. Further, rate equations based on chemical potentials or affinities are derived, and conditions for the consistency of rate equations with entropic inequality (the second law of thermodynamics) are illustrated.<br><div><br></div>

scholarly journals A Non-Equilibrium Thermodynamics-Based View of the Kinetics of Autocatalytic Reactions – a Simple Illustrative Example

2020 ◽  
Author(s):  
Miloslav Pekař
Keyword(s):  
Second Law Of Thermodynamics ◽  
Rate Equations ◽  
Second Law ◽  
Equilibrium Thermodynamics ◽  
Autocatalytic Reactions ◽  
Chemical Potentials ◽  
Entropic Inequality ◽  
Reaction Stoichiometry ◽  
Kinetics Of ◽  
Non Equilibrium

Autocatalytic reactions are in a certain contrast with the linear algebra of reaction stoichiometry, on whose basis rate equations respecting the permanence of atoms are constructed. These mathematical models of chemical reactions are termed conservative.Using a non-equilibrium thermodynamics-based theory of chemical kinetics, this paper demonstrates how to properly introduce an autocatalytic step into a (conservative) rate equation. Further, rate equations based on chemical potentials or affinities are derived, and conditions for the consistency of rate equations with entropic inequality (the second law of thermodynamics) are illustrated.<br><div><br></div>

scholarly journals Non-Equilibrium Thermodynamics View on Kinetics of Autocatalytic Reactions—Two Illustrative Examples

Molecules ◽  
2021 ◽  
Vol 26 (3) ◽  
pp. 585
Author(s):  
Miloslav Pekař
Keyword(s):  
Second Law Of Thermodynamics ◽  
Mass Action ◽  
Rate Equations ◽  
Equilibrium Thermodynamics ◽  
Mass Action Kinetics ◽  
Autocatalytic Reactions ◽  
Chemical Potentials ◽  
Entropic Inequality ◽  
Reaction Stoichiometry ◽  
Non Equilibrium

Autocatalytic reactions are in certain contrast with the linear algebra of reaction stoichiometry, on which rate equations respecting the permanence of atoms are constructed. These mathematical models of chemical reactions are called conservative. Using a non-equilibrium thermodynamics-based theory of chemical kinetics, it is shown how to introduce autocatalytic step into such (conservative) rate equation properly. Further, rate equations based on chemical potentials or affinities are derived, and conditions for the consistency of rate equations with the entropic inequality (the second law of thermodynamics) are illustrated. The theory illustrated here can be viewed as a tool for verifying and generalizing traditional mass-action kinetics by means of modern non-equilibrium thermodynamics, which is able to deal also with such rather problematic cases.

Supradegeneracy and the Second Law of Thermodynamics

2020 ◽  
Vol 45 (2) ◽  
pp. 121-132
Author(s):  
Daniel P. Sheehan
Keyword(s):  
Steady State ◽  
Statistical Mechanics ◽  
Population Inversion ◽  
Laboratory Experiments ◽  
Second Law Of Thermodynamics ◽  
Second Law ◽  
Boltzmann Factor ◽  
Energy Currents ◽  
Non Equilibrium

AbstractCanonical statistical mechanics hinges on two quantities, i. e., state degeneracy and the Boltzmann factor, the latter of which usually dominates thermodynamic behaviors. A recently identified phenomenon (supradegeneracy) reverses this order of dominance and predicts effects for equilibrium that are normally associated with non-equilibrium, including population inversion and steady-state particle and energy currents. This study examines two thermodynamic paradoxes that arise from supradegeneracy and proposes laboratory experiments by which they might be resolved.

scholarly journals Entropy meters and the entropy of non-extensive systems

2014 ◽  
Vol 470 (2167) ◽  
pp. 20140192 ◽  
Author(s):  
Elliott H. Lieb ◽  
Jakob Yngvason
Keyword(s):  
Second Law Of Thermodynamics ◽  
Surface Effects ◽  
Equilibrium States ◽  
Second Law ◽  
Intrinsic Properties ◽  
Mesoscopic Systems ◽  
Entropy Functions ◽  
Non Equilibrium

In our derivation of the second law of thermodynamics from the relation of adiabatic accessibility of equilibrium states, we stressed the importance of being able to scale a system's size without changing its intrinsic properties. This leaves open the question of defining the entropy of macroscopic, but unscalable systems, such as gravitating bodies or systems where surface effects are important. We show here how the problem can be overcome, in principle, with the aid of an ‘entropy meter’. An entropy meter can also be used to determine entropy functions for non-equilibrium states and mesoscopic systems.

scholarly journals The Non-Equilibrium Thermodynamics and Kinetics of Focal Adhesion Dynamics

2010 ◽  
Vol 98 (3) ◽  
pp. 366a
Author(s):  
Krishnakumar Garikipati ◽  
Joseph E. Olberding ◽  
Michael Thouless ◽  
Ellen M. Arruda
Keyword(s):  
Focal Adhesion ◽  
Equilibrium Thermodynamics ◽  
Thermodynamics And Kinetics ◽  
Kinetics Of ◽  
Non Equilibrium

The trouble with entropy

1998 ◽  
Vol 59 (4) ◽  
pp. 619-627 ◽  
Author(s):  
M. de HAAN ◽  
C. D. GEORGE
Keyword(s):  
Symmetry Breaking ◽  
Second Law Of Thermodynamics ◽  
The State ◽  
Large System ◽  
Second Law ◽  
Dynamical Description ◽  
Non Equilibrium

An understanding of the mechanisms leading to the symmetry breaking of the dynamical description of a large system with respect to the direction of time is necessary, but not sufficient to ensure the finding of a functional of the state of the system that would satisfy the requirements placed by the Second Law of Thermodynamics upon the non-equilibrium entropy S.

Cosmology in scalar–tensor–vector theory via thermodynamics

2018 ◽  
Vol 33 (24) ◽  
pp. 1850137 ◽  
Author(s):  
Onur Siginc ◽  
Mustafa Salti ◽  
Hilmi Yanar ◽  
Oktay Aydogdu
Keyword(s):  
Apparent Horizon ◽  
Second Law Of Thermodynamics ◽  
Entropy Function ◽  
Second Law ◽  
Generalized Second Law ◽  
Vector Theory ◽  
Theory Of Gravity ◽  
The Universe ◽  
Non Equilibrium

Assuming the universe as a thermodynamical system, the second law of thermodynamics can be extended to another form including the sum of matter and horizon entropies, which is called the generalized second law of thermodynamics. The generalized form of the second law (GSL) is universal which means it holds both in non-equilibrium and equilibrium pictures of thermodynamics. Considering the universe is bounded by a dynamical apparent horizon, we investigate the nature of entropy function for the validity of GSL in the scalar–tensor–vector (STEVE) theory of gravity.

Tensorielle chemische Potentiale — eine notwendige Erweiterung der Gibbs'schen Thermodynamik / Tensorial Chemical Potentials — a Necessary Extension of Gibbs' Thermodynamics

1975 ◽  
Vol 30 (11) ◽  
pp. 1433-1440 ◽  
Author(s):  
B. Stuke
Keyword(s):  
Chemical Potential ◽  
Spherically Symmetric ◽  
Relaxation Phenomena ◽  
Pressure Tensor ◽  
Equilibrium Thermodynamics ◽  
Equilibrium Conditions ◽  
Chemical Potentials ◽  
Thermodynamic Pressure ◽  
Fundamental Equations ◽  
Non Equilibrium

In a system with a non spherically symmetric pressure tensor, the chemical potential of at least one substance in the system has to be a tensor of the same character as the pressure. The necessary generalization of Gibbs' fundamental equations of thermodynamics is presented. Being already of consequence for equilibrium, this extension is more important for non-equilibrium thermodynamics, in particular for the proper thermodynamic formulation of general relaxation phenomena. Reasons are given why the distinction between dynamic and thermodynamic pressure, originating from the incomplete formulation of customary thermodynamics, is erroneous. Finally a tensorial temperature is introduced which can exist under extreme non-equilibrium conditions, e.g. shock waves

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