第五章伏安法 幻片1.ppt

●advantages ●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 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） §5-7 Single-sweep polarography(单扫描极谱法） (Oscillographic polarography，示波极谱法) Classical polarography: ■ Slow direct current voltage scanning rate: 0.2V/min, some 100 drops of mercury per scan ■ Big residual current Single-wseep polarography: ■ Rapid scanning rate: 0.25V/sec, one drop of mercury per scan ■ Little residual current ■ Oscillographic polarograph U DME R Pt SCE i ip Ep -U i ip and Ep are respectively peak current and peak voltage U is toothed wave voltage(锯齿波电压) For reversible electrode reaction, diffusion current equation of single-sweep polarography is expressed as follows ip = 2.69×105n3/2 D1/2 u 1/2 AC u is scan rate of voltage(V.s-1), A is electrode area (cm2) Relationship between potential at peak Ep and halfwave potential E1/2 Ep = E1/2 – 1.1 = E1/2 - RT nF 0.028 n (25℃) For reduction wave, Ep is -28/n mV more negative than corresponding E1/2, and for oxidative wave, 28/n mV more positive than E1/2 BACK 由于使用高输入阻抗的电位计，所以极谱电流