Abstract
In several places in this book we have encountered the notion of a nonequilibrium steady state. Because of statistical fluctuations a steady state, like an equilibrium state, should not be thought of as the state of a single system, but rather as the state of an ensemble. For example, in Section 4.7 we examined the coupled chemical reactions A + X → 2X and 2X → E. Using the canonical theory we discovered that, on the average, there are two densities of X which do not change as a function of time. One of these was ρx (1) = 0, which was found to be unstable to small perturbations, and the other was ρx (2) = k1/2k2, which is stable. The stable density is like an equilibrium density in that it supports a stationary probability distribution. In other words, associated with the time-independent average density ρ(2) x is a unique, stationary probability distribution that characterizes single-time averages in the steady-state ensemble. This situation turns out to be relatively common. Indeed, it has already arisen in our treatment of electrochemical reactions in Section 5.7, in our discussion of reaction-diffusion fluctuations in Section 6.6, and in the calculation of the light scattering spectrum from a temperature gradient in Section 6.8. In this chapter we consider the statistical thermodynamic description of stable nonequilibrium steady states in a more general setting. We begin in this section by characterizing the average statistical state
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Keizer, J. (1987). Nonequilibrium Steady States. In: Statistical Thermodynamics of Nonequilibrium Processes. Springer, New York, NY. https://doi.org/10.1007/978-1-4612-1054-2_7
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DOI: https://doi.org/10.1007/978-1-4612-1054-2_7
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