《新103第3章化学动力学基础》.ppt

* Effect of Catalyst on Reaction Rate 催化剂对反应速率的影响 Catalyst is a substance which can accelerate a chemical reaction greatly in spite of its small amount, and can not be consumed in the reaction. 催化剂: 存在少量就能显著加速反应，本身并无损耗的物质。 Heterogeneous catalyst 异相催化剂in hydrogenation and decomposition of H2O2: platinum black 铂黑、MnO2. Homogeneous catalyst均相催化剂: Co2(CO)8. Enzyme * Characteristics 主要特征 1. can accelerate a reaction. can not make an improbable reaction to happen in thermodynamics.催化剂只能对热力学上可能发生的反应起加速作用，而对热力学上不可能发生的反应并不起作用; 2. change the route of a reaction. 催化剂只能改变反应途径(或称机理)，不改变反应的始态和终态, 它同时加速正、逆反应速率，缩短平衡时间; 3. be selective. 催化剂有选择性，不同反应选择不同催化剂。 4. Be applicable under certain conditions. 每种催化剂只在特定条件下起作用，否则，将失效。 For example, * 速率理论与机理 Rate Theory and Mechanism * Collision Theory of Reaction Rate反应速率的碰撞理论 It assumes that the reacting molecules must collide in order to react. The theory supposes that the reaction rate depends on the number of collisions per unit time occurring with the correct geometry. 碰撞理论认为: 化学反应的先决条件是反应物分子间需互相碰撞。显然，反应速率与分子间的碰撞频率相关。 * Effective collision有效碰撞 From the kinetic theory of gases, the number of collisions that occurs between any two molecules under standard condition is evaluated as the value of 1032 L?1?s?1. 由气体分子动理论的计算表明: 在标准状态下，每秒、每升体积内，气态分子间的碰撞次数可达1032次，即，碰撞次数为1032 L?1?s?1。 分子间的碰撞次数= Not all collisions result in the reaction. Only effective collisions enable the reaction to occur. 因此，大多数碰撞并不导致反应。只有少数分子间的碰撞才能发生反应 * The theory believes that only the interaction between activated molecules can make the reaction happened. 所以，只有能量足够大的分子间发生的碰撞才能导致化学反应。这种能发生化学反应的碰撞称为有效碰撞(effective collision)，这些分子称为活化分子(activated molecules)。 Orientation of collision碰撞方向 另外，化学反应的本质是原子间的结合方式发生变化—反应物分子间的化学键破裂，生成物分子间形成新化学键。整个反应需足够的能量。 * N O O O O N O O O O N O O O O N O O O O N O N O O O O N O O O O N O O O O O O O 发生有效碰撞时，还需考虑分子的取向. For example, NO(g) + O3(g) == NO2(g) + O2(g) * 300 K 500 K Average energy Minimum energy Activation e