第五章伏金安法 幻片1.ppt

;;Polarography First voltammetric technique Differs form hydrodynamic ●unstirred (diffusion dominates) ●dropping Hg electrode (DME) is used as a working electrode Current varies as drop grows then falls off;;In polarographic analysis, supporting electrolyte is usually added to increase the current-conductivity and eliminate migration current. Usually relatively higher concentration of strong electrolytes (alkali metal salts) serves as supporting electrolyte;（活塞）;Advantages of DME (compared to planar electrode) ● clean surface generated ● rapid achievement of constant current during drop growth ● remixing of solution when drop falls to remove previous diffusion layer ● high Hg overvoltage means even metals with high –Ve E0 can be measured without H2 formation;Sample Cells;;;§5-2 Equation of diffusion current A basis of polarographically quantitative analysis;;When the applied voltage exceeds the decomposition voltage, diffusion-controlled current is expressed as:;In above equations, K is called Ilkovic constant, it is expressed as follows:;;;How it works? ▲ The applied voltage is gradually increased, typically by going to a more positive( more negative decomposing potential) ▲ A small residual current is observed. ▲ When the voltage becomes great enough, reduction occurs at the analytical electrode causing a current. ▲ The electrode is rapidly saturated so current production is limited – based on diffusion of the analyte to the small electrode.;How it works ? The reduced species alters the surface of the mercury electrode. To prevent problems, the mercury surface is renewed by “ knocking off ” a drop –providing a fresh surface. This results in an oscillation of the data as it is collected.;●Direct comparison method;Wave height of polarographic wave is determined easier than peak current, so following equation is in more common use ;●Calibration curve method;●Standard addition method;在进行定量测定时，通常只需测量所得极谱波的波高(以毫米或记录纸格数表示)，而不必测量扩散电流的绝对值。;Quantitative Analy