中山大学 第2章 均相反应动力学基础.pptx

第2章 均相反应动力学基础;均相反应的基本概念（1）;反应速率表示方法 The Rate Expressions ;The minus sign means disappearing;例如，有一简单反应 A 　P;Caution 1 2;Caution 3;Caution 4;Caution 5;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;微分上式;Kinetics of Homogeneous Reaction;Suppose a homogeneous irreversible reaction ; n= α+β（n为总反应级数） 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;反应的级数：动力学方程中浓度项的幂数，（如?，?），由实验确定的常数。 基元反应级数?，?等于计量系数值， ?=a， ?=b 非基元反应，应通过实验来确定 级数的大小反映了该物料浓度对反应速率影响的程度。级数越高，表明该物料浓度的变化对反应速率的影响越显著，如是负值，表明抑制反应，使反应速率下降。;反应速率常数 kRate Constant k;反应速率常数值的大小决定了反应速率的高低和反应进行的难易程度 不同反应有不同的速率常数， 对于同一反应，k随温度、浓度和催化剂的变化而变化。其中，温度是影响反应速率的主要因素之一。;Arrhenius’ Law;For such reaction the temperature-dependent term, the reaction rate constant, has been found in practically all cases to be well represented by Arrhenius’ Law: k=k0e-E/RT Where: k0 frequency or pre-exponential factor E Activation energy At two different temperatures, Arrhenius’ Law indicates that ;Activation energy and temperature dependency;等温恒容过程;单一反应 The Single Reactions 一级反应(不可逆单分子一级反应） Irreversible Unimolecular-Type First-Order Reaction;A plot of ln(1/1-XA) or ln(CA0/CA) vs. t, as shown on the right, gives a straight line through the origin for this form of rate of equation. ;二级反应 Irreversible Bimolecular-Type Second-Order