§121 碰撞理论.pdf

Physical Chemistry II Chapter 12 Rate Theories of elementary reaction §12.1 碰撞理论 Simple Collision Theory (SCT) for Bimolecular Reactions Interaction between A and B They come within a certain distance They collide with each other d B d A 分子碰撞 /有效碰撞 Not all the collision is effective The collision can be either reactive collision or elastic collision reactive collision elastic collision Only the A reaction can reactants collide take place collision To predicte the rate frequency constant 1 The fundament of SCT 碰撞理论基本点 基本假设For gaseous bimolecular reaction 1) 反应物的碰撞是反应的前提条件 反应速率与碰撞频率(Z) 成正比 2) 能量超过某临界值(E ) 的分子的碰撞为反应 c 碰撞（有效碰撞） 3) 反应速率/ r Z AB q r: 单位时间，单位体积内发生的有效碰撞次数 反应速率/ r ZAB q ZAB : the collision frequence of A with B per unit cubic meter per second q: the portion of effective collision. r: 单位时间，单位体积内发生的有效碰撞次数 Theoretical work aims to calculate Z and q. AB 2 Calculation of ZAB by kinetic theory of gases 硬球模型——3 点假设 1) the molecules can be taken as rigid ball without inner structure 刚性无内部结构的硬球 CH4 CHCl3 dA dB d and d are the diameter of A and B molecule， A B respectively 2) 分子除了瞬间碰撞外没有其它作用 3) 在碰撞瞬间，两个分子