Principle of Detailed Balance and the Second Law of Thermodynamics in Chemical Kinetics

2013 ◽  
Vol 135 (4) ◽  
Author(s):  
Mohammad Janbozorgi ◽  
M. Reza H. Sheikhi ◽  
Hameed Metghalchi
Keyword(s):  
Equilibrium State ◽  
Chemical Equilibrium ◽  
Rate Constants ◽  
Detailed Balance ◽  
Second Law Of Thermodynamics ◽  
Second Law ◽  
Elementary Chemical Reaction ◽  
Source Sink ◽  
Elementary Chemical ◽  
Reaction Equilibrium

The principle of detailed balance is shown to be a sufficient condition for the second law of thermodynamics in thermally equilibrated elementary chemical reactions. For an elementary reaction, the principle of detailed balance relates the forward and the reverse rate constants through the reaction equilibrium constant. It is shown that, in addition to the long known thermodynamic inconsistency at chemical equilibrium state, departure from this principle introduces an extra source/sink of entropy in the entropy balance for an elementary chemical reaction. The departure results in the wrong final chemical equilibrium state and, depending on the choice of the reverse rate constants, may lead to negative entropy productions during kinetic transients.

scholarly journals Do Electromagnetic Waves Exist in a Short Cable at Low Frequencies? What Does Physics Say?

2014 ◽  
Vol 13 (02) ◽  
pp. 1450016 ◽  
Author(s):  
Hsien-Pu Chen ◽  
Laszlo B. Kish ◽  
Claes-Göran Granqvist ◽  
Gabor Schmera
Keyword(s):  
Electromagnetic Waves ◽  
Detailed Balance ◽  
Second Law Of Thermodynamics ◽  
Blackbody Radiation ◽  
Second Law ◽  
Johnson Noise ◽  
Low Frequencies ◽  
Equipartition Theorem ◽  
Energy Equipartition ◽  
Simulation Results

We refute a physical model, recently proposed by Gunn, Allison and Abbott (GAA) [ http://arxiv.org/pdf/1402.2709v2.pdf ], to utilize electromagnetic waves for eavesdropping on the Kirchhoff-law–Johnson-noise (KLJN) secure key distribution. Their model, and its theoretical underpinnings, is found to be fundamentally flawed because their assumption of electromagnetic waves violates not only the wave equation but also the second law of thermodynamics, the principle of detailed balance, Boltzmann's energy equipartition theorem, and Planck's formula by implying infinitely strong blackbody radiation. We deduce the correct mathematical model of the GAA scheme, which is based on impedances at the quasi-static limit. Mathematical analysis and simulation results confirm our approach and prove that GAA's experimental interpretation is incorrect too.

scholarly journals APPLICATION OF THE POSTULATE OF NONEQUILIBRIUM TO CALCULATE THE NONEQUILIBRIUM OF SYSTEMS OF DISSIMILAR GASES AND LIQUIDS

2020 ◽  
Vol 17 (34) ◽  
pp. 998-1011
Author(s):  
Vladimir V RYNDIN
Keyword(s):  
Equilibrium State ◽  
Quantitative Characteristic ◽  
Second Law Of Thermodynamics ◽  
Irreversible Processes ◽  
Second Law ◽  
Nonequilibrium Systems ◽  
Real Property ◽  
Pure Solvent ◽  
Classical Thermodynamics ◽  
Isothermal Mixing

The postulate of nonequilibrium is at the heart of the second law of thermodynamics. According to this postulate, there is a real property of matter – “nonequilibrium,” which characterizes the uneven distribution of matter and motion in space. All processes (reversible and irreversible) can occur only in nonequilibrium systems. As a quantitative characteristic of the nonequilibrium of the system, the maximum work that can be performed during the transition of the nonequilibrium system to the equilibrium state is considered. The only formulation of the second law is given. When real (irreversible) processes occur, the nonequilibrium of the isolated system decreases, and in reversible processes, the nonequilibrium in the system of locally equilibrium subsystems does not change (the increment of one kind of the nonequilibrium entirely compensated by a decrease in the disequilibrium of some other kind). When the system reaches an equilibrium state, the disequilibrium disappears, and all processes cease. The article provides a calculated confirmation of the theoretical provisions of the concept of nonequilibrium and its mathematical apparatus by examples of determining the loss of the nonequilibrium of system when an isothermal mixing of dissimilar gases, and changes of nonequilibrium of system "pure solvent – solution" in the transition of part of the solvent in the solution. The mixing of the same gases leads to the Gibbs paradox, which is also considered in this paper. The concept of nonequilibrium was developed and the quantitative characteristics (measures) of nonequilibrium of the system were introduced allow to study nonequilibrium systems consisting of locally equilibrium subsystems in the sections of classical thermodynamics as simply as individual equilibrium systems.

Irreversibility and Limiting Possibilities of Macrocontrolled Systems I: Thermodynamics

2001 ◽  
Vol 08 (04) ◽  
pp. 315-328 ◽  
Author(s):  
A. M. Tsirlin ◽  
V. Kazakov ◽  
N. A. Kolinko
Keyword(s):  
Equilibrium State ◽  
Second Law Of Thermodynamics ◽  
Perfect Competition ◽  
Second Law ◽  
Extremal Principle ◽  
Maximal Power ◽  
Resource Exchange ◽  
Arbitrary Structure ◽  
Heat Engines ◽  
Maximal Profit

In this paper, two types of systems — thermodynamic and economic — are considered, which include a large number of micro subsystems and are controlled on the macro level (macrocontrolled systems). The analogy between the maximal work problem in thermodynamics and the maximal profit problem in a microeconomic system is investigated. The notion of exergy is generalized for the systems which do not contain reservoirs, and the conditions of maximal power of heat engines are generalized for systems with arbitrary structure. The notion of system profitability and the measure of irreversibility of an microeconomic processes are introduced. The extremal principle which determines an equilibrium state of open microeconomic system, is formulated. The conditions of optimality of resource trading and the expression for profitability of resource exchange are formulated for systems which include market with perfect competition, and for systems which do not include it. Economic analogues of the second law of thermodynamics are formulated using introduced concepts. The first part of the paper is devoted to thermodynamic systems and the second to microeconomic systems.

scholarly journals Fermi’s Golden Rule and the Second Law of Thermodynamics

2020 ◽  
Vol 50 (11) ◽  
pp. 1509-1540
Author(s):  
D. Braak ◽  
J. Mannhart
Keyword(s):  
Quantum Dynamics ◽  
Transition Probabilities ◽  
Detailed Balance ◽  
Golden Rule ◽  
Second Law Of Thermodynamics ◽  
Optical Systems ◽  
Quantum Mechanical ◽  
Second Law ◽  
Fermi's Golden Rule ◽  
Fermi’S Golden Rule

AbstractWe present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi’s “golden rule”. This Gedankenexperiment introduces a collection of two-level systems that absorb and emit radiation randomly through non-reciprocal coupling to a waveguide, as realized in specific chiral quantum optical systems. The non-reciprocal coupling is modeled by a hermitean Hamiltonian and is compatible with the time-reversal invariance of unitary quantum dynamics. Surprisingly, the combination of non-reciprocity with probabilistic radiation processes entails negative entropy production. Although the considered system appears to fulfill all conditions for Markovian stochastic dynamics, such a dynamics violates the Clausius inequality, a formulation of the second law of thermodynamics. Several implications concerning the interpretation of the quantum mechanical formalism are discussed.

scholarly journals STATEMENT OF THE SECOND LAW OF THERMODYNAMICS ON THE BASIS OF THE POSTULATE OF NONEQUILIBRIUM

2019 ◽  
Vol 16 (32) ◽  
pp. 698-712
Author(s):  
Vladimir V. RYNDIN
Keyword(s):  
Equilibrium State ◽  
Quantitative Measure ◽  
Second Law Of Thermodynamics ◽  
Irreversible Processes ◽  
Second Law ◽  
Unequal Distribution ◽  
Maximum Work ◽  
Reversible Processes ◽  
Objective Property ◽  
Physical Laws

Most physical laws are quantitative expressions of the philosophical laws of the conservation of matter and its properties of motion. The first law of thermodynamics (FLT) is an analytical expression of the law of conservation of motion when its shape changes. As for the second law of thermodynamics (SLT), it has not yet been clarified which property of matter does not change during the course of reversible processes and changes during the course of irreversible processes in an isolated system (IS). Hence, a large number of the SLT statements and an abundance of material to clarify these formulations. The author of the SLT is based on the “postulate of nonequilibrium”, according to which there is an objective property of matter - “nonequilibrium”, which characterizes the unequal distribution of matter and movement in space. All processes (reversible and irreversible) can proceed only in nonequilibrium systems. This leads to the only formulation of the second law of thermodynamics: when the reversible (ideal) processes occur in an isolated system, the nonequilibrium is preserved, and with the occurrence of irreversible (real) processes – decreases. When the system reaches an equilibrium state, the nonequilibrium disappears, and all processes cease. As a quantitative measure of the nonequilibrium of the system, we consider the maximum work that can be done when a nonequilibrium system transitions to an equilibrium state. The following quantities are used to calculate this work: “potential difference”, “entropy difference”, change in exergy. All these values decrease in the course of real (irreversible) processes in the isolated system and do not change in the course of reversible processes. As a result, a generalized expression of the SLT through the quantitative characteristics of the nonequilibrium of the system in the form of an inequality, which includes R. Claudius’s inequality for changing the entropy of an isolated system, is obtained.

First and second laws of thermodynamics: relationship, “inconsistency”, hidden effects

2020 ◽  
pp. 63-73
Author(s):  
A. M. Savchenko ◽  
Yu. V. Konovalov ◽  
A. V. Laushkin
Keyword(s):  
Free Energy ◽  
Internal Energy ◽  
Second Law Of Thermodynamics ◽  
Second Law ◽  
Entropy Of Mixing ◽  
Ideal Mixing ◽  
Laws Of Thermodynamics ◽  
Relationship Of ◽  
The Relationship

The relationship of the first and second laws of thermodynamics based on their energy nature is considered. It is noted that the processes described by the second law of thermodynamics often take place hidden within the system, which makes it difficult to detect them. Nevertheless, even with ideal mixing, an increase in the internal energy of the system occurs, numerically equal to an increase in free energy. The largest contribution to the change in the value of free energy is made by the entropy of mixing, which has energy significance. The entropy of mixing can do the job, which is confirmed in particular by osmotic processes.

The Analogical Turn (1884–1887)

2018 ◽  
Author(s):  
Olivier Darrigol
Keyword(s):  
Boltzmann Equation ◽  
Statistical Mechanics ◽  
Mechanical System ◽  
Thermal Equilibrium ◽  
Special Kind ◽  
Second Law Of Thermodynamics ◽  
Second Law ◽  
Equipartition Theorem ◽  
Royal Road ◽  
H Theorem

This chapter recounts how Boltzmann reacted to Hermann Helmholtz’s analogy between thermodynamic systems and a special kind of mechanical system (the “monocyclic systems”) by grouping all attempts to relate thermodynamics to mechanics, including the kinetic-molecular analogy, into a family of partial analogies all derivable from what we would now call a microcanonical ensemble. At that time, Boltzmann regarded ensemble-based statistical mechanics as the royal road to the laws of thermal equilibrium (as we now do). In the same period, he returned to the Boltzmann equation and the H theorem in reply to Peter Guthrie Tait’s attack on the equipartition theorem. He also made a non-technical survey of the second law of thermodynamics seen as a law of probability increase.

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