物理化学下册课件5.pptVIP

* 三. Neutralization reaction and precipitating reaction Anode: Cathode: Or Precipitating reaction Anode: Cathode: At equilibrium 例: 电池： Ag|AgCl(s)|KCl(aq)|Hg2Cl2(s)|Hg 25℃时，z =1的电池反应?rHm=5435J?mol-1，各物质的规定熵Sm/J?mol-1?K-1分别为：Ag(s):42.55, AgCl(s):96.2, Hg(l):77.4, Hg2Cl2(s):195.8l。 试计算25℃时的电池电动势和电动势的温度系数。 Anode: Cathode: Cell: 例:已知25oC时AgBr的溶度积Ksp=4.88?10-13, Eo(Ag+/Ag)=0.7994V, Eo{Br2(l)/Br-}=1.065V。试计算25oC时：AgBr(s)的标准生成吉布斯函数。 解: Anode: Cathode: Anode: Cathode: At equilibrim §7.10 Electrolysis and polarization effects 1mol?dm-3 HCl 一. Electrolytic voltage Cathode: Anode: Cell: At P41 表7.10.1 列出了几种电解质的分解电压 Discussions: (1)HNO3, H2SO4, NaOH的分解电压很接近? (2)为什么HCl, CdSO4, NiCl2的分解电压不同? (3)为什么实际分解电压一般小于理论分解电压? 二. 极化作用(Polarization effects) 1. 电极反应的过电位 (Overpotential of electrode reaction) Equilibrium Nonequilibrium Anodic polarization Cathodic polarization 2. Polarization effects (1) 欧姆(电阻)极化 (Ohmic polarization) 对于Galvanic cell: 对于Electrolytic cell: (2) Concentration polarization Cathode (-): Anode (+): (3) Electrochemical polarization Cathode: Anode: Galvanic cell Galvanic cell 3. Polarization curves Cathode: Anode: 在电化学动力学研究中,常研究单电极体系 “三电极”法 三. Electrode reactions during electrolysis Anode: R = O + ne e.g. OH- → O2, M → Mn+ Ea = Ea,e + ?a 优先进行的阳极反应(Preferential anodic reaction): Ea,min Cathode: O + ne = R e.g. H+ + e → H2; Mn+ + ne → M Ec = Ec,e - ?c Preferential cathodic reaction: Ec,max Electrolytic cell Vmin=Ea,min-Ec,max If V﹥(or ) Vmin, other electrode reactions could occur. e.g. “HCl + FeCl3” mixed solution is electrolyzed using Pt electrode. Preferential cathodic reaction: Fe3+ + e = Fe2+ Other possible cathodic reactions: Fe3+ + 3e =Fe Fe2+ + 2e =Fe 2H+ + 2e = H2 Cathodic electrochemical deposition of metals Mz+ + ze = M Ee = E°+ (RT/zF)lna(Mz+) In aqueous solution: 2H+ + 2e = H2 (pH7) 2H2O + 2e = H2 + 2OH- (pH7) (a)E°(Mz+/M)0[E°(H+/H2)], deposition occurs, Cu2+, Ag+. (b) ?