Non-equilibrium thermodynamics

About: Non-equilibrium thermodynamics is a research topic. Over the lifetime, 8987 publications have been published within this topic receiving 296048 citations.

Molecular dynamics with coupling to an external bath.

Abstract: In molecular dynamics (MD) simulations the need often arises to maintain such parameters as temperature or pressure rather than energy and volume, or to impose gradients for studying transport properties in nonequilibrium MD A method is described to realize coupling to an external bath with constant temperature or pressure with adjustable time constants for the coupling The method is easily extendable to other variables and to gradients, and can be applied also to polyatomic molecules involving internal constraints The influence of coupling time constants on dynamical variables is evaluated A leap‐frog algorithm is presented for the general case involving constraints with coupling to both a constant temperature and a constant pressure bath

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I

Abstract: A mechanism for electron transfer reactions is described, in which there is very little spatial overlap of the electronic orbitals of the two reacting molecules in the activated complex. Assuming such a mechanism, a quantitative theory of the rates of oxidation‐reduction reactions involving electron transfer in solution is presented. The assumption of "slight‐overlap" is shown to lead to a reaction path which involves an intermediate state X* in which the electrical polarization of the solvent does not have the usual value appropriate for the given ionic charges (i.e., it does not have an equilibrium value). Using an equation developed elsewhere for the electrostatic free energy of nonequilibrium states, the free energy of all possible intermediate states is calculated. The characteristics of the most probable state are then determined with the aid of the calculus of variations by minimizing its free energy subject to certain restraints. A simple expression for the electrostatic contribution to the free energy of formation of the intermediate state from the reactants, ΔF*, is thereby obtained in terms of known quantities, such as ionic radii, charges, and the standard free energy of reaction. This intermediate state X* can either disappear to reform the reactants, or by an electronic jump mechanism to form a state X in which the ions are characteristic of the products. When the latter process is more probable than the former, the over‐all reaction rate is shown to be simply the rate of formation of the intermediate state, namely the collision number in solution multiplied by exp(—ΔF*/kT). Evidence in favor of this is cited. In a detailed quantitative comparison, given elsewhere, with the kinetic data, no arbitrary parameters are needed to obtain reasonable agreement of calculated and experimental results.

Nonequilibrium Equality for Free Energy Differences

Abstract: An expression is derived for the equilibrium free energy difference between two configurations of a system, in terms of an ensemble of finite-time measurements of the work performed in parametrically switching from one configuration to the other. Two well-known identities emerge as limiting cases of this result.

Introduction to chemical engineering thermodynamics

Abstract: Preface 1 Introduction 2 The First Law and Other Basic Concepts 3 Volumetric Properties of Pure Fluids 4 Heat Effects 5 The Second Law of Thermodynamics 6 Thermodynamic Properties of Fluids 7 Applications of Thermodynamics to Flow Processes 8 Production of Power from Heat 9 Refrigeration and Liquefaction 10 Vapor/Liquid Equilbrium: Introduction 11 Solution Thermodynamics: Theory 12 Solution Thermodynamics: Applications 13 Chemical-Reaction Equilibria 14 Topics in Phase Equilibria 15 Thermodynamic Analysis of Processes 16 Introduciton to Molecular Thermodynamics Appendixes A Conversion Factors and Values of the Gas Constant B Properties of Pure Species C Heat Capacities and Property Changes of Formation D Representative Computer Programs E The Lee/Kesler Generalized-Correlation Tables F Steam Tables G Thermodynamic Diagrams H UNIFAC Method I Newton's Method Author Index Subject Index