Time reversal symmetry in thermodynamics

摘要

One of the most general laws of physics is the law of time reversal symmetry. The dynamic relationships of classical and quantum mechanics, electrodynamics and particle physics all are consistent with this law. But it is generally accepted that processes in macroscopic material systems represent exceptions: they do not show such symmetries. In this paper the answer to this old question is given based on a consequent rigorous thermodynamical ground. This paper consists of four parts. In the introductory part the concepts: absolute process rates, the time reverse processes and the principle of reversibility are introduced. The next section deals with the two general conditions of equilibrium: the balance of potentials (involving the Zeroth Law) and the law of Detailed Balance. In the third part a critical survey of the various formulations called Microscopic Reversibility is presented. The limitations of its validity and the relation of this law and the rate equations of the Mass Action type are discussed. In the last part an alternative type of rate relations is introduced, called Potential Action rate equations. Using a strictly exact treatment a law called the General Reversal Symmetry is derived. This law implies the extension of the validity of the time reversibility to macroscopic material systems. The result is: the number of the independent rate equations is reduced, and, on the other hand, numerical relations between their constant parameters are yielded.