电化学的有关概念.pptVIP

电化学的有关概念： 电池、电极 双电层结构 液接电位、盐桥 传质过程：扩散、迁移、对流 极化：浓差极化、电化学极化 过电位 Applications Direct potentiometry Potentiometric Titrations Direct potentiometry Potentiometric Titrations Determination of acid with NaOH (pH) Determination of Cl– with AgNO3 (AgCl, Ag+ ISE) Determination of Al3+ with NaF (AlF63–, F– ISE) Determination of Fe2+ with K2Cr2O7 (Fe3+, Pt) What would E vs. Volume curves look like? 思考题 推导式子：Eb = c – 0.592pH 直接电位法的校正曲线法、标准加入法 为什么要使用总离子强度调节液 电位滴定法的滴定曲线及终点的确定 * Potentiometric Methods A.) Introduction: 1.) Potentiometric Methods: based on measurements of the potential of electrochemical cells in the absence of appreciable currents (i . 0) 2.) Basic Components: a) reference electrode: gives reference for potential measurement b) indicator electrode: where species of interest is measured c) potential measuring device B.) Reference Electrodes: 1.) Need one electrode of system to act as a reference against which potential measurements can be made ? relative comparison. Desired Characteristics: a) known or fixed potential b) constant response c) insensitive to composition of solution under study d) obeys Nernest Equation e) reversible. 2.) Common Reference Electrodes used in Potentiometry a) Calomel Electrode (Hg in contact with Hg2Cl2 KCl) i. Saturated Calomel Electrode (SCE) very widely used ? cell: Hg/Hg2Cl2 (satd), KCl (xM)|| ? reaction: Hg2Cl2 (s) + 2e- ? 2Hg+ + 2Cl- Note: response is dependent on [Cl-] b) Silver/Silver Chloride Electrode - most widely used reference electrode system - Ag electrode in KCl solution saturated with AgCl ? cell: Ag/AgCl (satd), KCl (xM)|| ? reaction: AgCl (s) + e- ? Ag(s) + Cl- Advantage – one advantage over SCE is that Ag/AgCl electrode can be used at temperatures 60oC Disadvantage – Ag reacts with more ions c) Precautions in the Use of Reference Electrodes - need to keep level of solution in reference electrode