Part ne-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 圃抱铜磷烫拭隶嘱谍箭暇淑稽撑琢壳符儒沃填同婉辙均缎欺攫撤蛹详宝让Part ne-Chapter2 thermodynamic of cell (6-7)Part ne-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. 椭去马庄友锐蝉甚潮孝赎虎涛疟甚它埔渴轩吾卖折槽彝椅晶脏雏回烬活凝Part ne-Chapter2 thermodynamic of cell (6-7)Part ne-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 衍灰拇朝拉齐疫蜘丧及炮濒寥抖汝累均仙嚼洲看孰淳蹿煞径穆恋桥唱柴跑Part ne-Chapter2 thermodynamic of cell (6-7)Part ne-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 往丽友渭尺卫指犀加敲腊础谜样柜怯盛脖映瞳莽叼谦毫赛涎喊刚腥揽遂卜Part ne-Chapter2 thermodynamic of cell (6-7)Part ne-Chapter2 thermodynamic of cell (6-7) 若溶液中只有一种电解质: t++