武汉大学电化学陈胜利chaperkineticsofinterfacialchargetransfer.pptxVIP

武汉大学电化学陈胜利Chaperkineticsofinterfacialchargetransfer会计学第1页/共29页Chapter 2Charge transfer kinetics at electrode/electrolyte interfaces查全性，电极过程动力学导论，科学出版社（第三版），2002年．第4章，p129-170.A. Ｊ．Bard, L. R. Faulkner 著，邵远华等译，电化学方法原理和应用，化学工业出版社，２００５年, 第3章，p61-95kfC +DA + BkbA brief review of the chemical reaction kinetics第2页/共29页Reaction rates and chemical equilibriumElementary reaction :v = vf – vb = kf cA cB - kb cC cDMass action law :Dynamic equilibrium ( v = 0) :第3页/共29页A brief review of the chemical reaction kineticsThe rate constant and the activation free energySimple representation of free energy changes during an elementary reactionLUMOLUMOHOMOHOMOOz + e Rz-1第4页/共29页A schematic view of electrode reaction at solid/solution interfacesPotential shifts negatively -? -?Rz-1Rz-1eEFErErEFOzOzEquilibriumThe electrode potential control the Feimi level of electrode, which determine the direction and the rate of charge transfer. How does the rate of an interfacial reaction vary with the electrode potential ?kfBA kb第5页/共29页Phenomenological description of the interfacial charge transfer kinetics—— Butler-Volmer modelv = vf – vb = kf cA - kb cB第6页/共29页Effects of potentials on the activation free energy of interfacial charge transfer reactions1 --- Free energy curve at j0 (initial potential)2 --- Free energy curve at j3 --- Distribution of potential change4 --- Free energy change of an electron curve 2 = curve 1 – curve 4O· · · eO + eRa, b --- transfer coefficientO + nekcRka第7页/共29页Effects of potentials on the reaction rate of interfacial charge transfer reactionskc0 --- rate constant of reduction reaction at ?0 ka0 --- rate constant of oxidation reaction at ?0 If We set ?0 = 0, then ? - ?0 = ?O + nekcRkalg i0第8页/共29页ic --- the current due to reduction ic --- the current due to oxidationic0 --- the reduction current at zero potentialia0 --- the oxidation current at zero potentialAs j = j平i0 ---- exchange current density第9页/共29页O + nekcRka第10页/共29页Thus, at standard equilibrium