热力学耦合的相位描述及其最小耗散原理

Phase Description of Thermodynamic Coupling & Minimum Dissipation Principle

对热力学耦合进行相位描述,并对线性非平衡态热力学的熵产率方程进行了相位拓展,建立了蕴含热力学耦合机制的全相位熵产率方程。广义力与广义流之间的相位关系,唯像地决定了热力学过程的性质。当广义力与广义流之间同相位时,为熵产率大于0的自发过程;当广义力与广义流反相位时,为熵产率小于0的非自发过程。孤立体系内负熵产率的过程可以在正熵产率过程的驱动下进行。而且当自发过程与非自发过程之间发生热力学耦合时,其交叉唯象系数小于0,两个过程的广义流之间的相位差半个周期,这时整个孤立体系的熵产率最小,即说明满足热力学耦合时体系的耗散率最小。

For the first time the phase description of thermodynamic coupling was discussed, the entropy production rate equation of linear non-equilibrium thermodynamics was phase-extended, and the all-phase entropy production rate equation which contained the thermodynamic coupling mechanism was established. The phase relationship between generalized force and generalized flow phenomenologically determined characteristics of the thermodynamic process. When generalized force and generalized flow had the same phase, the process was a spontaneous one with the entropy production rate greater than zero;when general- ized force and generalized flow had the opposite phase, the process was a non-spontaneous one with the en- tropy production rate less than zero. In the system the process of the negative entropy production rate was driven by that of the positive entropy production rate. When the thermodynamic coupling occurred between the spontaneous process and non-spontaneous process, the crossed phenomenologieal coefficient was less than zero,there was a phase difference of half a cycle between the generalized flows of the two processes, and the entropy production rate of the isolated system was minimum.