07章_电解质溶液分析.ppt

* 德拜-休克尔极限定律 德拜-休克尔极限定律的常用表示式： 这个公式只适用于强电解质的稀溶液、离子可以作为点电荷处理的体系。式中 为离子平均活度系数，从这个公式得到的 为理论计算值。用电动势法可以测定 的实验值，用来检验理论计算值的适用范围。 * 德拜-休克尔极限定律 对于离子半径较大，不能作为点电荷处理的体系，德拜-休克尔极限定律公式修正为： 则 式中 为离子的平均有效直径，约为 ，是与温度、溶剂有关的常数，在298 K的水溶液中， * 德拜-休克尔-昂萨格电导理论 弛豫效应（relaxation effect） 由于每个离子周围都有一个离子氛，在外电场作用下，正负离子作逆向迁移，原来的离子氛要拆散，新离子氛需建立，这里有一个时间差，称为弛豫时间。 在弛豫时间里，离子氛会变得不对称，对中心离子的移动产生阻力，称为弛豫力。这力使离子迁移速率下降，从而使摩尔电导率降低。 * 德拜-休克尔-昂萨格电导理论 * 德拜-休克尔-昂萨格电导理论 电泳效应（electrophoretic effect） 在溶液中，离子总是溶剂化的。在外加电场作用下，溶剂化的中心离子与溶剂化的离子氛中的离子向相反方向移动，增加了粘滞力，阻碍了离子的运动，从而使离子的迁移速率和摩尔电导率下降，这种称为电泳效应。 * 考虑弛豫和电泳两种效应，推算出某一浓度时电解质的摩尔电导率与无限稀释时的摩尔电导率之间差值的定量计算公式，称为 电导公式： 德拜-休克尔-昂萨格电导理论 电导公式 式中 和 分别是电泳效应和弛豫效应引起的使 的降低值。这个理论很好地解释了克尔劳乌施的经验式： * MICHAEL FARADAY MICHAEL FARADAY (1791-1867) English chemist and physicist, was a completely selftaught man. In 1812, while still a bookbinder’s apprentice, Faraday was drawn to chemistry by attending Davy’s lectures at the Royal Institute. His life was changed by an accident when Davy was temporarily blinded by an explosion and took on Faraday as his secretary. * MICHAEL FARADAY Faraday presented Davy with the careful notes he had taken at his lectures, and Faraday became a laboratory assistant when his predecessor was fired for brawling. Faraday’s first experiment consisted in constructing a voltaic pile using copper halfpenny pieces and zinc discs separated by paper soaked in salt solution. * MICHAEL FARADAY He decomposed magnesium sulfate with the pile. He produced the first known chlorides of carbon, C2Cl6 and C2Cl4, in 1820, and discovered benzene in 1825.He investigated alloy steels and optical glass. During this latter work, he discovered the rotation of the plane of polarization of light in a magnetic field. He discovered diamagnetism and coined the words paramagnetic and diamagnetic. * FRIEDRICH WILHELM GEORG KOHLARUSCH FRIEDRICH WILHELM GEORG KOHLARUSCH (1840-1910), German chemist and physicist, is best known for his work on the electrical conduct