均相单一化学反应的不可逆过程热力学

根据质量守恒方程,基于不可逆过程热力学中通量和力之间的关系,将不可逆过程热力学线性理论推广应用于既远离平衡又没有产生耗散结构的均相存在单一化学反应的体系,建立了远离平衡的化学反应动力学方程及其对于理想气体体系的表达式,沟通了热力学和动力学之间的联系·将动力学方程应用于水煤气反应,得到了和实测数据吻合的五次关系式·结果说明考虑了高次项后,可将不可逆过程热力学应用于远离平衡体系,并为化学动力学的研究提供了一种新的手段·

Thermodynamics of Irreversible Process in Homogeneous Single Chemical Reaction

The prevalent linear thermodynamic expressions of irreversible process are just available to those physicochemical changes which are close to equilibrium. On the other hand, the studies on the physicochemical changes far from equilibrium are mainly focusing on dissipative structures. A nonlinear dynamic equation is therefore set up for the chemical reactions far from equilibrium by way of extending the linear expressions to the homogeneous single chemical reaction systems far from equilibrium with no dissipative structure involved. The equation has been applied to water-gas reaction with a quintic expression obtained in high conformity to measured data with a maximum error of 8%. The result reveals that in such a way the thermodynamics of irreversible process can be applied to homogeneous single chemical reaction systems far from equilibrium.