中文关键词:补偿效应 Arrhenius方程 动力学定律 能量分布 英文关键词:Compensation effect, Arrhenius equation, Kinetic law, Energy distribution 基金项目:国家自然科学基金项目

作者	单位	E-mail
郭汉贤	太原理工大学	ghx20055@163.com
樊惠玲	太原理工大学	fanhuiling@tyut.edu.cn

摘要点击次数:2896 全文下载次数:0 中文摘要: 补偿效应揭示了Arrhenius方程中反应速率常数k的指数项（-E/RgT）与指前因子（ko）项存在着相互补偿关系。不仅存在于催化与非催化，均相与非均相的反应体系及需要克服能垒的物理过程，而且也存在于生命与非生命、能源、环境与材料等许多领域。本文对补偿效应的定位、理论解释及适用范围进行了探讨。指出其在化学/化工动力学中占有重要位置，不仅是一条定律，而且是与质量作用定律、Arrhenius定律并列的又一条基本定律。从统计学角度对补偿效应进行了概率分析，试图对其给出更为广义的理论解释。指出，均相反应体系和非均相反应体系，本质上都是不均匀的。中间络合物生成具有耗散结构特征,在近平衡(准平衡)线性区进行，无序度减小伴随着能量及无序度的同向变化，这是补偿效应存在的根本原因。从而提出了反应速率常数中能量分布、无序度分布的概率因子。其对补偿效应的概率解释与能量指数分布说/焓熵补偿关系说是统一的而非对立的。作者进而还讨论了自然指数律/自然补偿律，指出补偿效应是自然界存在/运动所遵循的自然律在化学反应领域的具体体现 英文摘要: The compensation effect reveals the compensative relationship between the pre-exponential factor (k0) and the exponential factor (–E/RgT) in the Arrhenius equation, which relationship exists not only in the heterogeneous, homogeneous catalytic reaction systems but also in noncatalytic reaction systems whose occurrence needs to overcome energy barrier. The compensative influences, in broader ways, can also be found in life science, biology, energy, environment and material sciences. The effort of this work is to explain the compensation effect as one of the laws beside the mass interaction and the Arrhenius equation. The article attempts to explain the compensation effect based on the probability analysis, pointing out that the absolute ununiformity of the heterogeneous and homogeneous systems and the energy Bolzmann exponential distribution are the basis of the general compensation effect. This explanation also agrees with that in the theory of enthalpy-entropy compensation. Additional efforts are made to look at the compensation phenomena or natural exponential distribution phenomena in nature, trying to conclude that the compensation effect in chemical kinetics is the law that more phenomena in nature may follow. 查看全文查看/发表评论下载PDF阅读器 相关附件：版权转让声明书 -->