工业催化原理 英文课件Chapter41.pptVIP

Chapter4 Heterogeneous catalyzed reaction kinetics A heterogeneous catalyzed reaction may be generally considered to involve following consecutive steps 1. diffusion of reactants to the surface of catalyst (external diffusion) 2. diffusion to the inner surface (internal diffusion) 3. adsorption of reactants 4. reaction on the surface 5. desorption of products 6. diffusion of products away from the surface § 4.1 special features of heterogeneous reaction kinetics reaction occurs in the monolayer adsorbed on the surface, the rate depends on the reactant coverage upon the surface. reaction rate depends on the rate determine step, the slowest step in the reaction sequence. reaction is strongly affected by mass and/or heat transfer. However, for convenient, we usually assume the mass transfer rate is much faster so that its influence to the overall reaction rate can be excluded. §4.2 Reaction kinetics in ideal adsorption The rate of heterogeneous catalyzed reaction is determined by the surface coverage of adsorbed reactants. However, so far the coverage can not be directly measured. A general method is using some kinds of isotherm to correlate the coverage to the bulk concentration which can be determined experimentally. §4.2.1 Surface mass action law For a surface reaction aA + bB ?? cC + dD r = k ?Aa ?Bb ?o?? ?? = c+d -a-b It denotes that the vacancy of surface is important when ?? is not equal to zero. Also we always take ?? equal to zero when ?? is negative. §4.2.1 Surface mass action law For example, 2A ?? B ?? = -1 r = k ?A2 A ??2B ?? = 1 r = k ?A?o §4.2.2 Establishment of kinetics equations Unimolecular surface reactions Case 1 surface reaction is rate determining step A + ? ?? A* A* ?? B* rds B* ?? B + ? here A* and B* mean the adsorbates for the fast equilibrium step, Langmuir isotherm can be applied Unimolecular surface reactions r = - dPA / dt = k ?A ?A