Non-equilibrium thermodynamics

Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions.

Almost all systems found in nature are not in thermodynamic equilibrium, for they are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems and to chemical reactions. Many systems and processes can, however, be considered to be in equilibrium locally, thus allowing description by currently known equilibrium thermodynamics.[1] Nevertheless, some natural systems and processes remain beyond the scope of equilibrium thermodynamic methods due to the existence of non variational dynamics, where the concept of free energy is lost.[2]

The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by equilibrium thermodynamics.[3] One fundamental difference between equilibrium thermodynamics and non-equilibrium thermodynamics lies in the behaviour of inhomogeneous systems, which require for their study knowledge of rates of reaction which are not considered in equilibrium thermodynamics of homogeneous systems. This is discussed below. Another fundamental and very important difference is the difficulty, in defining entropy at an instant of time in macroscopic terms for systems not in thermodynamic equilibrium. However, it can be done locally, and the macroscopic entropy will then be given by the integral of the locally defined entropy density. It has been found that many systems far outside global equilibrium still obey the concept of local equilibrium.[4]

  1. ^ Kjelstrup, S; Bedeaux, D; Johannessen, E; Gross, J (June 2010). Non-Equilibrium Thermodynamics for Engineers. WORLD SCIENTIFIC. doi:10.1142/7869. ISBN 978-981-4322-15-7.
  2. ^ Bodenschatz, Eberhard; Cannell, David S.; de Bruyn, John R.; Ecke, Robert; Hu, Yu-Chou; Lerman, Kristina; Ahlers, Guenter (December 1992). "Experiments on three systems with non-variational aspects". Physica D: Nonlinear Phenomena. 61 (1–4): 77–93. Bibcode:1992PhyD...61...77B. doi:10.1016/0167-2789(92)90150-L.
  3. ^ Pokrovskii, Vladimir (2020). Thermodynamics of Complex Systems: Principles and applications. IOP Publishing, Bristol, UK. Bibcode:2020tcsp.book.....P.
  4. ^ Groot, Sybren Ruurds de; Mazur, Peter (1984). Non-equilibrium thermodynamics. Dover books on physics (Dover ed., 1. publ., unabridged, corr. republ ed.). New York, NY: Dover Publ. ISBN 978-0-486-64741-8.