电极反应动力学 燃料电池课件.pptVIP

2011 SpringFuel Cell and Electrochemistry Lecture 9 Kinetics of electrode reactions Dynamic Equilibrium Dynamic Equilibrium The kinetic theory therefore predicts a constant concentration ratio at equilibrium, just as thermodynamics does; Kinetics describe the evolution of mass flow throughout the system, including both the approach to equilibrium and the dynamic maintenance of that state. Thermodynamics describe only equilibrium. Exchange velocity: equilibrium features nonzero rates of conversion of A to В (and vice versa), but those rates are equal. v0 The Arrhenius Equation and Potential Energy Surfaces Transition State Theory we focus on the special condition in which the entire system—A, B, and all other configurations—is at thermal equilibrium Essentials of electrode reactions we always saw that current is often limited wholly or partially by the rate at which the electroreactants are transported to the electrode surface. This kind of limitation does not concern a theory of interfacial kinetics. More to the point is the case of low current and efficient stirring, in which mass transport is not a factor determining the current. Instead, it is controlled by interfacial dynamics. Tafel equation Butler-volmer model of electrode kinetics Where α, the transfer coefficient Standard Rate Constant It simply is a measure of the kinetic facility of a redox couple. A system with a large k0 will achieve equilibrium on a short time scale, but a system with small k0 will be sluggish. The largest measured standard rate constants are in the range of 1 to 10 cm/s, and are associated with particularly simple electron-transfer processes. Molecular rearrangement upon electron transfer or multistep process can be very sluggish The Transfer Coefficient The transfer coefficient a should generally be a potential-dependent factor; In a typical chemical system, the free energies of activation are in the range of a few electron volts, but the full range of measurable kinetics usu