第一部分 电分析化学研究方法.ppt

图5.10(5.8)Variationofconcentrationwithdistanceataplanarelectrodeforvariousvaluesoftaftertheapplicationofapotentialstep.图5.11(5.9)图5.12恒电流法的电流控制信号(a)电势响应信号(b)Sand方程：i?1/2/coxb=0.5nFA(?D)1/2=85.5nA(D)1/2图5.13(5.10)图5.14(5.11)(5.12)AqueousPhaseOrganicPhaseAqueousPhaseOrganicPhaseAsymmetricDiffusionField图5.15电荷在支撑在微、纳米玻璃管上的液/液界面的扩散模式 ChapterSix（第六章） KineticsandTransportinElectrode Reactions 电极反应的动力学和传质过程6.1 Introduction6.2 Theglobalelectrodeprocess:kineticsandtransport6.3 Reversiblereactions6.4 Irreversiblereactions6.5 Thegeneralcase6.6 Theeffectoftheelectrolytedoublelayeronelectrodekinetics6.7 Electrodeprocessesinvolvingmultipleelectrontransfer6.8 Electrodeprocessesinvolvingcoupledhomogenousreactions6.1 导言前面两章分别介绍了电极过程动力学和电极附近的物质传递过程，本章是两者的结合。6.2 通用的电极过程：动力学和传质Ox + ne = Rd物质传递系数(kd):描述在扩散层内的扩散速率（kd=D/?=D/d）(6.1)Figure6.1.Simplifiedschemeforanoxidation-reductionreactiononanelectrodesurfacekf=k0exp[-?nf(E-E0)]kb=k0exp[(1-?)nf(E-E0)]kd=D/?=D/d对于稳态，即，?c/?t=0电活性物质的流量J=-kf[O]S+kb[R]S =kd,O([O]S-[O]b)=kd,R([R]b-[R]S)扩散控制的极限阴极(阳极)电流密度jL,c(jL,a):jL,c/nF=-kd,o[O]b;jL,a/nF=kd,R[R]b(6.2)(6.3)假设p=kd,o/kd,R=(DO/DR)S这里s=1/2(droppingorstationaryelectrode);s=2/3(hydrodynamicelectrodes);s=1(microelectrodes)j=(kfjL,c+pkbjL,a)/(kd,O+kf+pkb)我们这里考虑两种极限情况：(1)在溶液中仅有O-1/j=1/(nFkf[O]b)+1/(nFkd,O[O]b) Kinetics Transport (6.4)(6.5)(6.6)k0kdreversiblesystem(可逆体系)k0kdirreversiblesystem(不可逆体系)(2)在溶液中仅有R1/j=1/(nFkf[R]b)+1/(nFkd,O[R]b) Kinetics Transport(6.7)6.3 可逆反应(reversiblereactions)k0kdE=Eo+RT/(nF)ln[O]S/[R]S假设电极是uniformlyaccessibleelectrode(I=Aj=nFAJ)E=Eo+RT/(nF)ln{(IL,c-I)kd,R/[(I-IL,a)kd,R]}=E1/2+RT/(nF)ln(IL,c-I)/(I-IL,a)这里 E1/2=Eo+RT/(nF)lnkd,R/kd,RE1/2称半波电势(half-wavepotential),