化学学报 ›› 1982, Vol. 40 ›› Issue (7): 611-620. 上一篇    下一篇

论文

稀土元素的电分析化学研究——Ⅱ.钪-氯化铵-铜铁试剂-二苯胍体系的络合吸附波机理的研究

高小霞, 焦奎   

  1. 北京大学化学系
  • 投稿日期:1980-11-10 发布日期:2013-06-03
  • 通讯作者: 高小霞

STUDIES ON THE ELECTROANALYTICAL CHEMISTRY OF RARE EARTHS Ⅱ. ON THE MECHANISM OF THE ADSORPTIVECOMPLEX WAVE OF Sc3+-NH4Cl-CUPFERRONDIPHENYLGUANIDINE SYSTEM

GAO XIAO-XIA, JIAO KUI   

  1. Chemistry Department, Peking University
  • Received:1980-11-10 Published:2013-06-03

在示波极谱上,在氯化铵底液中,pH4~7时,Sc3+-铜铁试剂(Cup)-二苯胍(DPG)体系产生一个较大的催化波,在1×l0-7~1×l0-6M Sc3+浓度内与波高有线性关系,而在dc极谱上不产生催化波.此波为络合吸附波,络合物在电极上的吸附平衡不能瞬时达到.络合物组成为:Sc3+:Cup:DPG:CL-=1:1:1:2,它具有八面体构型.在实验条件下,条件稳定常数β=1.22×107.四元络合离子吸附于电极表面,络合物中的Cup以酸形式在电极上还原,产物为苯肼;释出的Sc3+可以再络合、吸附,产生催化电流.

The catalytic system Sc3+-NH4Cl-Cupferron (Cup)-diphenylguanidime (DPG) suggested by Yao et al gives a sensitive derivative wave in single sweep polarograph.The linear relationship between the wave bights Hw and the concentration of SC3+ in the range of 10-7~10-6 M has been used successfully in the ores analysis for Sc, We compared the waves in single sweep polarograph with that in the do polarograph and applied several electrochemical methods to investigate the mechanism of this wave, The experiments of electrocapillary curves, variation of the height of the mercury column and the time of the rest period befere scanning, the temperature coetlicent, cyclic voltammetry etc, indicated that the wave is adsorptive complex in nature and the ligand-Cupferron in the complex is catalytically reduced but not the canon Sc3+ therefore we call such catalytic wave as "adsorptive-complex wave".