自动控制阴极电位电解分析试验装置示意图three-electrodesystem.PPTVIP

Chapter 8 Bulk Electrolysis: Electrogravimetry and Coulometry 8A Electrolytical Analysis Controlled-current electrolytical analysis Controlled-potential electrolytical analysis 8B Electrogravimetric Methods  8B-1Controlled-Current Electrolytical Analysis three-electrode system 8C Coulometry Determination of charge 8C-2 Coulometric Titration 8D Other Coulometric Methods 8A Electrolytical Analysis 8B Electrogravimetric Methods 8C Coulometry 8D Other Coulometric Methods What are electrolytical analysis and coulometry? André Marie Ampère (1775-1863) Pt Pt + - Cu2+ H+ SO42- OH- R A Figure 8A-1 Apparatus for electrolysis Analysis IUPAC Anode: Oxidation reactions Cathode: Cu2++2e- Cu Anode: 2H2O 4H++O2+4e- Cathode: Reduction reaction So, in CuSO4 solution Electrolytical cell Battery Positive Negative Ecell=E正-E负 = 0.31-1.22 = 0.91V 实际分解电压Eapplied Overpotential: ? 理论分解电压Ecell Eapplied= E+- E- + iR =(E+ +?+) - (E--?-)+iR = (E+ - E-) + (?++?-)+ iR = Ecell+ ? + iR Ohmic Potential; IR Drop Polarization Effects 8A-2 Ag Cd 0.00mR - 0.734 V + - - [Cd2+] = 0.00500 M [Cl-] = 0.200 M 2.00mR - 0.764V + - - Ag Cd R=15.0Ω I Fig. 8-3 An electrolytic cell for determination Cd2+ Ecell = Eright – Eleft = - 0.734V Eapplied = Ecell – IR = - 0.764V An example for overpotential The metal is deposited on a weighed platinum or other metal cathode, and the increase in mass is determined. Figure 8B-1 Apparatus for electrodeposition of metals without cathode-potential control. A two-electrode eletrolytical cell WE: large-surface-area platinum gauze CE: plane Pt Low selectivity Constant current 自动控制阴极电位电解分析实验装置示意图 three-electrode system 自动调节E外 constant negative potential 控制阴极电位 Instrument 8B-2 Controlled-Potential Electrolytical Analysis Figure 8B-2 Curve i-E of separation ion A and ion B. 8B-3 Choice of Negative Potential a: EA c: EC To separate A and B ,