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化学进展 2003, Vol. 15 Issue (02): 81-   后一篇

• 综述与评论 •

在非平衡态热力学的基础上探索建立催化理的新途径

吴越*;杨向光   

  1. (中国科学院长春应用化学研究所 长春 130022)
  • 收稿日期:2002-07-01 修回日期:2002-09-01 出版日期:2003-03-24 发布日期:2003-03-24
  • 通讯作者: 吴越
下载PDF ( 2247 ) 引用
导出 被引次数 ( 4 | 2 )

ploring New Route for Establishing the Theory of Catalysis on the Basis of Non-Equilibrium Thermodynamics

Wu Yue*;Yang Xiangguang   

  1. (Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China)
  • Received:2002-07-01 Revised:2002-09-01 Online:2003-03-24 Published:2003-03-24
  • Contact: Wu Yue
平衡态热力学一直被认作多相催化理论的基石之一。但是，它并不能概括工作中的催化剂的状态和行为，这主要是这里还发生一些非平衡过程。催化体系常常处于非平衡状态之下，而非平衡态条件下体系状态和行为，同时取决于体系的动力学和热力学。联系动力学和热力学最一般的关系式并非原来的De Donder不等式：Ar≥0，而是新的De Donde方程ln r^-/r^-=A/RT。同时发生的总反应之间的热力学耦合对总反应的作用只是形式上的，远不及催化反应链中各基元步骤之间在动力学上的耦合那么重要。通过在动力学方程中引入反应亲和力（热力学位）得到的动力学-热力学结合近似分析，可以用来分析非平衡态的催化反应和催化剂状态。非平衡态热力学在建立多相催化理论中，较之原来的平衡态热力学将能提供更能采纳的和更有意义的物理化学背景。
关键词： 催化, 非平衡态热力学, 耗散结构
Conventional equilibrium thermodynamics has long been recognized as one of the most important cornerstone of the theory of heterogeneous catalysis, but it is not suited quite well to generalize the state and behavior of operating catalysts. It is principally to see that there are non-equilibrium processes involved. The catalytic system exits always in thermodynamically non-equilibrium state under which the state and behavior of the system depend upon both kinetics and thermodynamics. It is argued that the most general useful relation, relating kinetics and thermodynamics, is not the De Bonder inequality Ar≥,but the new equation of De Donde In r/r =A/R7\ What matter is not so much for theformal thermodynamic coupling between simultaneous overall reactions, but the kinetic coupling between the elementary processes of a catalytic sequence . By introducing the notion of chemical potential into the analysis of dynamic chemical phenomena, a joint kinetic-thermodynanmic approach allows one to analysis both catalytic reaction and non-equilibrium state of catalyst. Perspectively, the role of non-equilibrium thermodynamics in creating physic-chemical background for heterogeneous catalysis is in fact much more embracing and interesting than that given by conventional equilibrium thermodynamics.
Key words: catalysis, non-equilibrium thermodynamics, dissipative structure

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