Non-equilibrium Thermodynamics

Explore non-equilibrium thermodynamics, covering key concepts, irreversible processes, transport phenomena, and real-world applications in engineering, biology, and environmental science.

 

Introduction

Non-equilibrium thermodynamics is a branch of thermodynamics that studies systems not in thermodynamic equilibrium. Unlike classical thermodynamics, which deals with systems in a state of balance where macroscopic properties are constant in time, non-equilibrium thermodynamics focuses on systems where gradients (such as temperature, pressure, or chemical potential) drive the processes. This field is essential for understanding natural phenomena and technological processes where equilibrium is not achieved, such as biological systems, chemical reactions, and transport processes.

Basic Concepts

Irreversible Processes:

    • In non-equilibrium thermodynamics, irreversible processes play a central role. These processes involve the production of entropy and cannot be reversed without leaving changes in the system or its surroundings. Examples include heat conduction, diffusion, and viscous flow.

Thermodynamic Forces and Fluxes:

    • Non-equilibrium thermodynamics often uses the concept of thermodynamic forces and fluxes. Thermodynamic forces (or affinities) drive the fluxes of physical quantities. For example, a temperature gradient (force) drives heat flow (flux), and a concentration gradient drives mass diffusion.
    • The linear relationship between forces and fluxes in near-equilibrium conditions is given by Onsager’s reciprocal relations, which state that the matrix of coefficients relating forces and fluxes is symmetric.

Entropy Production:

    • A key concept in non-equilibrium thermodynamics is entropy production. In an isolated system, entropy can never decrease, and non-equilibrium processes contribute to the overall increase in entropy. The rate of entropy production provides insights into the irreversibility and efficiency of processes.

Phenomena in Non-equilibrium Thermodynamics

Transport Phenomena:

    • Non-equilibrium thermodynamics provides a framework for understanding transport phenomena, such as heat conduction, mass diffusion, and momentum transfer (viscosity). These processes are described by laws such as Fourier’s law for heat conduction, Fick’s laws for diffusion, and Newton’s law of viscosity.

Chemical Reactions:

    • The study of chemical reactions far from equilibrium involves understanding how reaction rates are influenced by concentration gradients and how these reactions contribute to entropy production. Non-equilibrium thermodynamics can describe complex reaction networks and their dynamics.

Biological Systems:

    • Biological systems are prime examples of non-equilibrium systems. Processes such as cellular metabolism, signal transduction, and muscle contraction involve continuous energy and matter exchange with the environment, keeping these systems far from equilibrium.

Pattern Formation:

    • Non-equilibrium conditions can lead to the formation of complex spatial and temporal patterns. Examples include the Belousov-Zhabotinsky reaction (a type of chemical oscillation) and Rayleigh-Bénard convection (pattern formation in fluid layers heated from below).

Applications of Non-equilibrium Thermodynamics

Engineering and Technology:

    • Non-equilibrium thermodynamics is crucial in designing and optimizing engineering systems where heat, mass, and momentum transfer are important. Examples include heat exchangers, chemical reactors, and semiconductor devices.

Environmental Science:

    • Understanding the transport of pollutants, heat, and moisture in the environment relies on non-equilibrium thermodynamics. Models of atmospheric and oceanic circulation, climate change, and ecological systems all benefit from this field.

Materials Science:

    • The development and processing of new materials, especially those with nano-scale structures, often require non-equilibrium thermodynamics to understand phase transitions, diffusion processes, and mechanical properties.

Astrophysics and Geophysics:

    • Non-equilibrium thermodynamics helps explain processes in astrophysical and geophysical contexts, such as the behavior of stellar interiors, planetary atmospheres, and the dynamics of the Earth’s mantle and core.

Conclusion

Non-equilibrium thermodynamics is a vital and expanding field that provides essential insights into the behavior of systems far from equilibrium. Its principles are applicable across various scientific and engineering disciplines, enabling the analysis and optimization of processes involving heat, mass, and momentum transfer. As our understanding and computational capabilities continue to grow, non-equilibrium thermodynamics will play an increasingly important role in advancing technology and science.