第三章库仑分析法.pptVIP

 3 Coulometry (库仑分析法) 3.1 Faraday’s Law The relationship between the electrochemical reaction and the coulometry of electricity in the circuit can be expressed as: The mass of the subject reacting on the electrode is in direct proportion to the amount of electricity consumed in the system. Consuming same amount of electricity, the mass of the subject reacting on the electrode is in direct proportion of it’s M/n Discussion of the Law Meaning of each item Application for analysisElectrogravimetry Coulometry Conditions for the Law 100% current efficiency (exhaustive electrolysis) 3.2 Controlled potential electrolysis (控制电位库仑分析法) Electrolysis Another sample：0.01mol/L Ag+, 1.00mol/L Cu2+ being electrolyzed Standard potential： cathode anode If Ag+=10-7mol/L，then Controlling method Why and How The relationship between the potential and the electrolysis Changing potential of the electrodes Adding the “reference electrode”, making three electrodes system Schematic diagram of controlled potential electrolysis Measuring the quantity of the electricity-------Coulometer Silver coulometer (银库仑计) Titration coulometer (滴定库仑计) Gas coulometer (气体库仑计) Electronic integrator (电流积分库仑计) Titration Coulometer 3.3 Coulometric Titrations (controlled-current coulometry) （库仑滴定, 恒电流库仑分析） 3.3.1 Example For the determination of [Fe2+] ， Anode: Fe2+→Fe3+ + e （ferrous to ferric ion ) As the reaction took place, [Fe2+]↓，the anode potential ↑, then 2H2O＝O2+4H++4e If adding large number of Ce3+， Anode: Ce3+= Ce4++e Solution: Fe2++Ce4+= Fe3++Ce3+ 3.3.2 Principle of Coulometry Titration Adding mediator The mediator was electrolyzed to produce titrant, which reacting with the analyte according to stoichiometric(化学计量） relationship. When the analyte was consumed by proper indicating method, stop the electrolyzing and calculating the amount of analyte through the Faraday’s Law. 3.3.3 Indicating of the end-point 3.3.6 Application 卡尔.费休（Karl Fisher）法测