极谱与伏安法英文版PolarographandVolatmmetry分析.pptVIP

4 Polarography and Voltammetry (极谱分析与伏安分析法) 4.1 Apparatus and Principle of Polarography 4.1.1. Terminology Voltammetry：Measurement of a current at a microelectrode as a function of the potential( versus a reference electrode) of the microelectode. Polarography: A branch of voltammetry in which working electrode consists of dropping-mercury electrode (DME) (滴汞电极)  4.1.2. Apparatus of Polarography 4.1.3. Polarographic wave (极谱波) Shape of the i-e curve of polarography （2）Formation of the polarographic wave -② Residual current (残余电流): ir ② Decomposition potential: where Cd2+ could be reduced on the DME On the DME: Cd2++2e+Hg== Cd(Hg) Edme=E0+RT/nFln[CCd2+/CCd(Hg)] On the SCE: 2Hg-2e+2Cl-==Hg2Cl2 Half Wave Potential (半波电位）: E1/2 The Diffusion Plateau (极限扩散区)： 4.1.4. Other terminology and related  conception Polarization (极化) Concentration polarization Small A of the electrode or high current Low concentration Static solution Polarized electrode and Depolarized electrode (极化电极与去极化电极) Small area for the concentration-polarization Each fresh drop exposes a new Hg surface to the solution, making a more reproducible behavior of the electrode. There is high overpotential for H+ ion reduction at the mercury, making the possibility of analyzing metal ions in high H+ solution. The reduced metals to their mercury amalgam（汞齐） decrease the E, making the analysis of alkali metal(碱金属) or alkaline-earth metal (碱土金属) being possible. 4.2. Quantitative and qualitative  analysis of Polarography 4.2.1. Quantitative analysis (1) limiting current equation (扩散电流方程)（Ilkovic Equation 尤考维奇） id= kC0 k=607nD 1/2 m 2/3 t 1/6 id= 607nD 1/2 m 2/3 t 1/6 C0 id= 607nD 1/2 m 2/3 t 1/6 C0 D Depends on the character of the solution and T m，t Depend on the character of the capillary, such as the inner diameter, the height of the mercury reservoir and so on. When the T, the supporting electrolyte and the capillary were fixed, the limiting curre