Abstract:

Thermodynamic equilibrium state has the lowest possible energy, any non-equilibrium state is approaching equilibrium state unless existing external interactions and unified state parameters can be assigned only to the equilibrium state. Electromagnetic field can effectively enhance the heat and mass transfer processes, and it also has obvious effects on the equilibrium and stability of dielectric system. Based on the first and the second law of thermodynamics, the electric field energy is introduced into the thermodynamic differential equation, from which a new entropy function of dielectric system with the influence of electric field is deduced. Then, the equilibrium conditions and the stable conditions of dielectric systems under the action of electrostatic field are derived from the entropy criterion. The new equilibrium conditions require that the temperature, effective pressure, effective chemical potential, and electric field are uniform through the whole system. The new stable conditions require that the electric charge on the metal plates is proportional to the electric potential. This effective pressure includes mechanical effect from polarization, and the mechanical equilibrium is determined by real pressure and the electric polarization force. The effective chemical potential includes the effect of polarization potential energy, and the phase equilibrium is determined by concentration and polarization potential energy. The thermodynamic conclusions are consistent with that of electrodynamics and statistical physics, which have been confirmed by experiments.

Key words: thermodynamics, entropy, phase equilibria, vapor liquid equilibria, stability

摘要：

热力学平衡态是系统能量最低状态，在没有外界作用的条件下任何非平衡态最终都会趋向平衡态，热力学系统只有在平衡态才能用统一的状态参量来描述。电磁场能够有效地强化传热传质过程，对电介质系统的平衡及其稳定性有明显的作用。利用热力学定律将电场能量引入热力学基本微分式，构建了电场作用下电介质系统的熵函数，利用平衡态及其稳定性的熵判据导出了静电场作用下电介质系统的平衡条件及稳定条件。相比没有电场作用，平衡条件要求系统各相的等效压强、等效化学势和平行极板间电场强度相等；稳定条件要求产生电场的电荷量与电势呈正比。电场作用下的等效压强包括了电场极化作用的力学效果，力学平衡由压强和电极化力共同决定；等效化学势包括了电场极化势能的效果，相平衡由浓度和电势能共同决定。热力学结论与电动力学及统计物理的结论一致，已被实验证实。

关键词: 热力学, 熵, 相平衡, 汽液平衡, 稳定性