Electrochemistry-3.ppt

Electrochemistry(3) Xuan Cheng Xiamen University Electrolytic Conductivity Electrolytic Conductivity Molar Conductivity 摩尔电导率与浓度的关系 强电解质的Lm与c的关系 强电解质的Lm与c的关系 离子独立移动定律 迁移数的测定方法 2.界面移动法 2.界面移动法 Molar conductivities of ions Molar conductivities of ions Applications of conductivity Applications of conductivity Applications of conductivity * * Physical Chemistry Physical Chemistry Electrochemistry The electric current I (16.46)* (16.47)* The electric current density j The conductivity ? The reciprocal of conductivity (resistivity) ? (16.50)* (16.49)* Physical Chemistry The resistance R (16.46)* (16.54) The conductance G 1 S=1 ?-1 Siemens ? ohm ?-1 mho Electrochemistry Physical Chemistry The conductivity of a solution depends on the number of ions present The molar conductivity ?m Electrochemistry (16.58)* The electrolyte’s stoichiometric molar concentration Physical Chemistry H2SO4 KOH KCl MgSO4 CH3COOH 0 15 5 10 c/(mol?dm-3) 20 40 60 80 Conductivity vs. concentration k/(S?m-1) 0 ? vs. c Strong electrolytes Fully ionized in solution: ionic solids, strong acids and bases The concentration of ions is proportional to the concentration of electrolyte added Weak electrolytes MgSO4 CH3COOH Neutral electrolytes KCl H2SO4 KOH Molar Conductivity Electrochemistry (16.58)* 演示 400 300 200 100 ?m/(S?cm2 ?mol-1) HCl NaOH AgNO3 CH3COOH 0 0.5 1.0 1.5 In an extensive series of measurements during 19th century, Friedrich Kohlrausch At low concentrations The infinite-dilute molar conductivity The infinite-dilute molar conductivity of the cations and anions Law of the independent migration of ions Molar Conductivity Physical Chemistry The limiting molar conductivity Electrochemistry 演示 由于溶液中导电物质的量已给定，都为1mol，所以，当浓度降低时，粒子之间相互作用减弱，正、负离子迁移速率加快，溶液的摩尔电导率必定升高。但不同的电解质，摩尔电导率随浓度降低而升高的程度也大不相同。 Electrochemistry 随着浓度下降， 升高，通常当浓度降至 以下时， 与 之间呈线性关系。德国科学家Kohlrausch总结的经验式为： 是与电解质性质有关的常数。将直线外推至 ，得到无限稀释摩尔电导率 。 Kohlrausch 随着浓度下降， 也缓慢升高，但变化不大。当溶液很