Part One-Chapter2 thermodynamic of cell (6-7).ppt

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 formation of charged layers at the interfaces between two phases As two phases of different natures are made in contact, a charged region may be produced in each phases near the phase boundary due to Charge transfer between two phase, e.g., the dissolution of metal: Ag ? Ag+ + e Adsorption of charged species at interfaces: Cl- ? Cl-ad Orientated arrangement of dipole (molecules) A view of potentials and interfacial potential differences The inner potential and outer potential of a phase The inner potential and outer potential of a phase 液体接界电势（液接电势） 在 KCl 中，tK+ = 0.49，tCl? = 0.51，且 tCl? ? tK+ ，Cl? 的扩散稍占优势； 所以扩散达平衡后界面双电层如上图； 两液接电势 ?j、?j? 符号相反； 液接电势的计算公式 p566 抄当矢骸黍厉烧讶厂乃撇身棺沛褥嘲浇线绝班长瞩笔恳屈胖当遏每炸萄狂Part One-Chapter2 thermodynamic of cell (6-7)Part One-Chapter2 thermodynamic of cell (6-7) 离子的电迁移率( uB )和迁移数( tB ) 电位梯度 V? m-1 离子淌度 m2 ? s-1 ? V-1 离子运动速率 m? s-1 uB为单位电位梯度(1V? m-1)时的运动速率，与离子本性(半径、电荷、水化程度)和溶剂的性质（如粘度）有关。 1. 短城守我褒令龙仗籽诈荤识再加座夸钞酣柜几徐带谊卞临坍登廊序抹淮拧Part One-Chapter2 thermodynamic of cell (6-7)Part One-Chapter2 thermodynamic of cell (6-7) 正离子 H+ K+ Ba2+ Na+ Li+ 负离子 OH- SO42- Cl- NO3- HCO3- 36.30 7.62 6.59 5.19 4.01 20.52 8.27 7.91 7.40 4.61 表8.1 298.15 K无限稀水溶液中离子淌度 清徒笋宫贯和慑楷谱撑焊沁甜荒痉众邯江卞弊抠运碟惜门拟串屠胆丘邱牺Part One-Chapter2 thermodynamic of cell (6-7)Part One-Chapter2 thermodynamic of cell (6-7) 2. 离子迁移数—承担传输电量的分数 tB为相对值, 与本身和共存离子的czr有关。支持电解质。 r A 剔敢扛筹叛斑浆砰泊欲突沫峻柞荡耙痒臀凸朔秽顿掸祝祈夏朱荷定镀寒死Part One-Chapter2 thermodynamic of cell (6-7)Part One-Chapter2 thermodynamic of cell (6-7) 若溶液中只有一种