循环伏安法：Cyclic Voltammetry（循环伏安法）.ppt

* 1.3.1 Cyclic Voltammetry（循环伏安法） (R.S.Nicholson and I. Shain, Anal.Chem., 1964, 36, 706) Figure 1.8 Figure 1.9 Figure 1.10 Reversible system: The peak current for a reversible couple (at 250C) is given by Randles-Sevcik equation: Where n is the number of electrons, A is the electrode area (in cm2), C is the concentration (in mol/cm3), D is the diffusion coefficient (in cm2/s), and ? is the scan rate (in V/s). (1.6) (1.7) (1.8) Figure 1.11 Q. L. Echegoyen et al, J. Am. Chem. Soc. 1992,114,3978 Irreversible and Quasi-reversible Systems: (1.9) (1.10) Figure 1.12 不可逆过程电流和电势随扫描速度的变化 Study of Adsorption Processes (1.11) Figure 1.13 Figure 1.14 (1.12) Study of Reaction Mechanisms Quantitative Applications Polarography (极谱) and Voltammetry (伏安法)的区别？ polarography A classical electroanalytical technique discovered in 1922 by J. Heyrovsky, for which he was awarded the Nobel Prize for Chemistry in 1959. Essentially, it is linear-sweep voltammetry using a dropping-mercury electrode for working electrode and a large mercury pool as counter electrode. voltammetry An electrochemical measuring technique used for electrochemical analysis or for the determination of the kinetics and mechanism of electrode reactions. Voltammetry is a family of techniques with the common characteristics that the potential of the working electrode is controlled (typically with a potentiostat) and the current flowing through the electrode is measured. In one of the most common applications of the technique, the potential is scanned linearly in time; this is called the linear-sweep voltammetry, LSV, or LV. Cyclic voltammetry (CV) is a linear-sweep voltammetry with the scan continued in the reverse direction at the end of the first scan, this cycle can be repeated a number of times. 6.7 多电子转移的电极过程 对于两电子还原反应，一般的表达式为： A + e ? B B + e ? C Fig.6.7 两电子转移反应示意图 对于此过程， 可以分为三个极限情况进 行讨论： (1) 第二步在更负的电位下反应， 我们可以观察到两 个分开的波。即： kf,2 - kb,2 kd,B (2) 第一步是决速步骤，即： kf,2 - kb,2 ?? kd,B