伏安分析法-英文版-voltammetry2.pptVIP

●Advantages of single-sweep polarography Sensitivity: DL ~ 10-7mol.L-1, 2-3 magnitude order higher than classical polarography More precise, measuring peak height, but not wave height Simple, rapid Higher resolution, peak separation of 35 ~ 50mV resolved Little prewave interference, 5s interval time before scanning Little oxygen wave interference, in-reversible electrode reaction shows very weak or even no wave （沉积过程） （溶出过程） 根据溶出过程中阳极电流与离子浓度的线性关系进行定量 Electrodes in stripping voltammetry ●Hung mercury electrode ● glass carbon electrode mercury plating(镀汞膜的玻璃态石墨电极） Problems ■ Compared with other polarographic methods, how about the sensitivity of sripping voltammetry? ■ what advantages do hung mercury electrode and mercury membrane electrode have ? * Voltammetry §5-6 Polarographic Catalytic Wave Diffusion process Electrode reaction Chemical reaction Adsorption process Reactant product 如果化学反应与电极反应同时发生（平行），而且化学反应为定速步骤，则该极谱波称为极谱催化波 ， 例如， A + ne- → B (electrode reaction) B + X → A + Z (chemical reaction) k1 ? A is called catalyst ? polarographic current is called catalytic current, i1∝[A] ? chemical reaction is its velocity-determining step ? X must have high over-potential on the electrode to insure catalytic circle For example Total reaction: 2Fe2+ + H2O2 → 2OH- + 2Fe3+ Another one: MoO52- 2H+ + 2e → MoO42- + H2O MoO42- + H2O2 → MoO52- + H2O When no adsorption exists, catalytic wave and classical polarographic wave have same shape, catalytic current is expressed as follows: i1 = 0.51nF D 1/2 m 2/3 t 2/3 k 1/2 Cx1/2 CA Limiting catalytic current Concentration of X and A in solution Rate constant For polarographic catalytic wave, the current is independent on height of mercury column: i1 ∝ m 2/3t 2/3 ∝ h 2/3 h -2/3 ∝ 1 Difference between catalytic wave and diffusion wave: But for diffusion-controlled current id ∝ m 2/3t 1/6 ∝ h 2/3 h -1/6 ∝ h1/2 Temperature coefficients: 1% ~2% / ℃ for id 4% ~ 5% and more / ℃ i1 催化氢波（自学）