第2章均相反应动力学基础.ppt

第2章 均相反应动力学基础 纪红兵 中山大学化学与化学工程学院 Tel:jihb@mail.sysu.edu.cn 反应速率表示方法 The Rate Expressions The Rate Expressions Suppose a single-phase reaction A P The most useful measure of rate for A is then 均相反应速率定义：单位时间内，单位体积反应混合物中某一组分i的反应量（或生成量）。 Caution 1 2 (-rA) 为一整体符号，恒为正值 Suppose a single-phase reaction aA+bB pP+sS The rates of all materials are related by Caution 3 According to the rate equation Caution 4 Or For the ideal gases where Caution 5 The rate of reaction in its various forms is defined as follows Based on unit volume of reaction fluid Based on unit mass of solid in fluid-solid systems Based on unit volume of solid in gas-solid systems In homogenous systems, the volume of fluid in the reactor is often identical to the volume of reactor. In such case V and VR are identical and are used interchangeable. In heterogeneous systems all above definitions of reaction rate encountered, the definition used in any particular situation often being a matter of convenience. These intensive definitions of reaction rate are related by The conversion 转化率 Suppose that NA0 is initial amount of A in reactor at time t=0, and that NA the amount present at time t. then the conversion of A in the constant volume system is given by 微分上式 Kinetics of Homogeneous Reaction 均相反应：反应物系中，所有反应物及生成物（包括催化剂在内）都处于同一相中。 影响反应速率的参数：浓度、温度、催化剂等，因此，反应速率与上述这些参数成函数关系。 Suppose a homogeneous irreversible reaction n= α+β Where α,β are not necessarily related to the stoichiometric coefficients. We call the powers to which the concentrations are raised the order of the reaction. Thus, the reaction is αth order with respect to A βth order with respect to B nth order overall 速率常数 kRate Constant k When the rate expression for a homogenous chemical reaction is written in the form in book, the dimensions of the rate constant k for nth-order reaction are (time)-1(concentration)1-n which for a first-order reaction becomes simply