Part One-Chapter5 -Double layer-Chen SL 14-15.ppt

Chapter 13 The properties and structures of the electric double layer at electrode/electrolyte interfaces The electrode / electrolyte interfaces It is essential to have an electrode/electrolyte interface for the electrochemical reactions to take place. Such an interface is established by direct contact of the electrode (electron conductors) with electrolyte (ion conductors). The electric double layer is the core of the electrode/electrolyte interface, which is formed by the charges reside in the interfacial region, and in which the interfacial potential difference is distributed. The strategies and techniques used in studying the properties and structures of the electrode/electrolyte interfaces The properties of the electrode/electrolyte interfaces Surface tension ( ? ); surface adsorption (?i ) Interfacial capacitances ( cd ) The Gibbs Adsorption Isotherm The Gibbs-Duham equation at interfaces The electro-capillary equation Experimental evaluation of surface excesses and electric parameters 毛细管静电计 电毛细曲线的测定 体系平衡时： ∴ 恒定一个电位 ，通过调节贮汞瓶高度使弯月面保持不变，从而求得 。 Experimental evaluation of surface excesses and electric parameters The Electrocapillary curves 在较正和较负的电势下，都有过剩电荷，电荷都相互排斥，与通常的表面收缩相反，因此表面张力降低。 汞电极在不同无机盐液中的电毛细曲线 The differential capacitance ( Cd ) of electrode/electrolyte interfaces 两种测量q的方法比较： interfacial excesses-表面离子剩余量 实际上，由于下述原因做不到?恒定： 两电极体系中，改变组分i的浓度，参比电极电位发生变化； 在电解质溶液中不可能单独只改变一种离子的浓度，往往改变的是电解质M?+A?-的浓度。 为使用方便，常采用下面的公式： Summary of the experimental results Models For Electric Double layer Structures at Electrode/electrolyte Interfaces How do the excess charges and potential distribute themselves at the interfaces? The Helmholtz Model-紧密层模型 The Gouy-Chapman Model-分散层模型 Stern’s modification-GCS 分散层模型 Specific Adsorption-特性吸附 Superequivalent adsorption of anions Summary on the double layer structure Potential of Zero Charge (PZC) Studies at solid electrodes Studies at solid electrodes Double layer effects on electrode processes (no spe