CHAPTER 4 ELECTRODE KINETICS 4.1 （第四章电极动力学4.1）.pdfVIP

CHAPTER 4 ELECTRODE KINETICS 4.1 POTENTIOSTATIC METHOD (TAFEL PLOTS) The rate of each reaction is controlled in part by the rate of an electron transfer reaction and in part by the rate of transport of a solution species into the near vicinity of the electrode surface. In this section, only the case in which the electron-transfer step is much slower then the mass-transport step will be considered. Under this assumption, the solution is homogeneous and the surface concentration of electrocution species is equal to its concentration in the bulk solution. Consider an electron transfer process consisting of the single elementary step O +e- R (1) cathodic rate = k C (o,t) c O (2) anodic rate = k C (o,t) a R where k and k are heterogeneous rate constants with units m s-1. If the concentrations c a have units of mol m-3, then the rates have units of mol m-2 s-1, the same units as flux. The difference between the cathodic and anodic rates in the net flux of O and is proportional to the net current [ (0, ) (0, )] (3) i FA k C t −k C t c O a R The temperature dependence of the rate constants kc and ka from transition state theory are equal: