应用电化学第一章电化学基础详解.pptVIP

1.4.2 Butler-Volmer equation when E=Ee, no net current flows, there is a dynamic equilibrium at the electrode surface electrode reaction By convention, anodic currents are taken as positive. Io is known as the exchange current density. The experimental current (or net current, or polarized current) 提示：see p9 fig.1.3 The relationship between I and E? Butler –Volmer equation (basic equation of electrochemical polarization) The equilibrium potential Ee and the exchange current density Io together totally characterize the equilibrium situation at an electrode. 如何理解？ where n is the number of electrons, αA, αC are the anodic transfer coefficient and cathodic transfer coefficient respectively. 拓展阅读： B-V方程推导过程: see pp10-11 B-V equation is a very useful equation in experimental and applied electrochemistry and shows that the measured current is a function of (a)? overpotential (b)??exchange current (c)? the transfer coefficients Discussion The transfer coefficients are, at least for simple electron transfer processes, not independent variables. In general αA + αC =1 Overpotential η at η=0 I=0 η↑, I↑ so, we said that the overpotential is the drive force of electrode processes. Simplification of B-V equation A) High overpotential region （ Tafel region） 120mV(52mV) The limiting forms of B-V equation ----Tafel law η=a+blogI 拓展： B-V方程简化得到Tafel 方程 the cathodic Tafel law b=2.3RT/αCnF, a=-blogIo the anodic Tafel law b=2.3RT/αAnF, a=-blogIo B) Low overpotential region (linearly polarized region) 10mV WhenαA =αC =0.5 I=Io(nF/RT)η η=KI K=RT/nFIo (4) Polarization curve Tafel laws are the basis of a simple experimental procedure for determining I0, αA, αC. 1.4.3 Basic kinetic parameters of electrochemical polarization (1)??? Exchange