H_2O_2分解反应的不可逆过程热力学

Thermodynamics of Irreversible Processes in Reaction of Hydrogen Peroxide

扩展现行的线性不可逆过程热力学理论到远离平衡又没有产生耗散结构的体系,建立非均相体系只存在一个化学反应的反应速率通用方程,并将此反应速率方程应用于H2O2催化分解反应这个经典的动力学问题,分别得到了298K及308K条件下和实测数据吻合的四次关系式·结果表明考虑了高次项后,不可逆过程热力学可以用于远离平衡体系的化学反应·高次近似时,取多少次方对不同的化学反应条件是不同的,这决定于其远离平衡的程度,并且通过对线性不可逆过程热力学扩展的应用为远离平衡的化学反应的研究提供了一种新的方法·

Thermodynamics of irreversible process offers linear expressions among different physical quantities when there are physical-chemistry changes in the systems close to equilibrium. Extending such existing linear expressions to those systems which are not only far from equilibrium but without dissipative structure formed, a general nonlinear equation is given to express the chemical reaction rate that is the only one in a heterogeneous system. The equation is applied to the catalytic reaction of hydrogen peroxide, i.e., a classical thermodynamic problem, some quartic expressions are obtained in conformity to the experiment data at 298K and 308K correspondingly. It shows that the thermodynamics of irreversible process can be applied to those chemical reacting systems which are far from equilibrium if taking the higher terms into consideration. In the higher degree approximation process, however, the different degrees of higher terms require different reactive conditions depending on how far away they are from equilibrium. The extensional application of linear thermodynamic expressions thus provides a new approach to the study on the chemical reactions far from equilibrium.