This book provides an introduction to the modern statistical theory of nonequilibrium thermodynamics, based on a synthesis of the statistical thermodynamics of Onsager and the kinetic molecular theory of Boltzmann. Topics featured in the initial chapters include an introduction to stochastic processes and Brownian motion, the linear statistical theory of irreversible process, fluctuations in chemical reactions, and the Boltzmann equation. Using the author's canonical representation for the rates of elementary processes, the book develops the statistical thermodynamics of molecular process in a form that is useful for systems close to or far from equilibrium. Molecular noise arising from chemical reactions, electrochemical process, ion channels in membranes, hydrodynamics, and molecular collisions are treated in a unified way. The final chapters focus on the way in which nonlinear molecular mechanisms give rise to steady states, critical points, oscillations, and chaos, including the thermodynamic theory of steady states and its relationship to molecular fluctuations and linear stability.Broadly applicable to dynamical problems in chemistry, physics, and biophysics, the book should be accessible to graduate students, faculty, and other researchers in the physical sciences and engineering.

The structure of the theory ofthermodynamics has changed enormously since its inception in the middle of the nineteenth century. Shortly after Thomson and Clausius enunciated their versions of the Second Law, Clausius, Maxwell, and Boltzmann began actively pursuing the molecular basis of thermo­ dynamics, work that culminated in the Boltzmann equation and the theory of transport processes in dilute gases. Much later, Onsager undertook the elucidation of the symmetry oftransport coefficients and, thereby, established himself as the father of the theory of nonequilibrium thermodynamics. Com­ bining the statistical ideas of Gibbs and Langevin with the phenomenological transport equations, Onsager and others went on to develop a consistent statistical theory of irreversible processes. The power of that theory is in its ability to relate measurable quantities, such as transport coefficients and thermodynamic derivatives, to the results of experimental measurements. As powerful as that theory is, it is linear and limited in validity to a neighborhood of equilibrium. In recent years it has been possible to extend the statistical theory of nonequilibrium processes to include nonlinear effects. The modern theory, as expounded in this book, is applicable to a wide variety of systems both close to and far from equilibrium. The theory is based on the notion of elementary molecular processes, which manifest themselves as random changes in the extensive variables characterizing a system. The theory has a hierarchical character and, thus, can be applied at various levels of molecular detail.

This book provides an introduction to the modern statistical theory of nonequilibrium thermodynamics, based on a synthesis of the statistical thermodynamics of Onsager and the kinetic molecular theory of Boltzmann. Topics featured in the initial chapters include an introduction to stochastic processes and Brownian motion, the linear statistical theory of irreversible process, fluctuations in chemical reactions, and the Boltzmann equation. Using the author's canonical representation for the rates of elementary processes, the book develops the statistical thermodynamics of molecular process in a form that is useful for systems close to or far from equilibrium. Molecular noise arising from chemical reactions, electrochemical process, ion channels in membranes, hydrodynamics, and molecular collisions are treated in a unified way. The final chapters focus on the way in which nonlinear molecular mechanisms give rise to steady states, critical points, oscillations, and chaos, including the thermodynamic theory of steady states and its relationship to molecular fluctuations and linear stability.Broadly applicable to dynamical problems in chemistry, physics, and biophysics, the book should be accessible to graduate students, faculty, and other researchers in the physical sciences and engineering.

The structure of the theory ofthermodynamics has changed enormously since its inception in the middle of the nineteenth century. Shortly after Thomson and Clausius enunciated their versions of the Second Law, Clausius, Maxwell, and Boltzmann began actively pursuing the molecular basis of thermo­ dynamics, work that culminated in the Boltzmann equation and the theory of transport processes in dilute gases. Much later, Onsager undertook the elucidation of the symmetry oftransport coefficients and, thereby, established himself as the father of the theory of nonequilibrium thermodynamics. Com­ bining the statistical ideas of Gibbs and Langevin with the phenomenological transport equations, Onsager and others went on to develop a consistent statistical theory of irreversible processes. The power of that theory is in its ability to relate measurable quantities, such as transport coefficients and thermodynamic derivatives, to the results of experimental measurements. As powerful as that theory is, it is linear and limited in validity to a neighborhood of equilibrium. In recent years it has been possible to extend the statistical theory of nonequilibrium processes to include nonlinear effects. The modern theory, as expounded in this book, is applicable to a wide variety of systems both close to and far from equilibrium. The theory is based on the notion of elementary molecular processes, which manifest themselves as random changes in the extensive variables characterizing a system. The theory has a hierarchical character and, thus, can be applied at various levels of molecular detail.