Limits of Predictions in Thermodynamic Systems: A Review

TL;DR

This review discusses the fundamental limits and recent advances in nonequilibrium thermodynamics, highlighting the constraints, uncertainties, and limitations of current theoretical tools in predicting thermodynamic behavior far from equilibrium.

Contribution

It provides a comprehensive overview of key theoretical results in nonequilibrium thermodynamics, analyzing their practical applicability and limitations in physical predictions.

Findings

Fluctuation theorems constrain system dynamics far from equilibrium.

Thermodynamic uncertainty relations bound dissipation and precision.

Limitations include sensitivity to rare trajectories and non-physical dual dynamics.

Abstract

The past twenty years have seen a resurgence of interest in nonequilibrium thermodynamics, thanks to advances in the theory of stochastic processes and in their thermodynamic interpretation. Fluctuation theorems provide fundamental constraints on the dynamics of systems arbitrarily far from thermal equilibrium. Thermodynamic uncertainty relations bound the dissipative cost of precision in a wide variety of processes. Concepts of excess work and excess heat provide the basis for a complete thermodynamics of nonequilibrium steady states, including generalized Clausius relations and thermodynamic potentials. But these general results carry their own limitations: fluctuation theorems involve exponential averages that can depend sensitively on unobservably rare trajectories; steady-state thermodynamics makes use of a dual dynamics that lacks any direct physical interpretation. This review aims to present these central results of contemporary nonequilibrium thermodynamics in such a way that the power of each claim for making physical predictions can be clearly assessed, using examples from current topics in soft matter and biophysics.