化学学报 ›› 1965, Vol. 31 ›› Issue (6): 463-469. 上一篇    下一篇

锑(Ⅲ)-1,2-环己二氦四乙酸络合物的极谱研究

汪尔康, 尚正心   

  1. 中国科学院应用化学研究所
  • 投稿日期:1964-08-21 发布日期:2013-06-03

POLAROGRAPHIC STUDY OF ANTIMONY(Ⅲ) COMPLEX WITH 1,2-DIAMINOCYCLOHEXANE-TETRAACETIC ACID

WANG ER-KANG, SHANG ZHENG-XIN   

  1. Institute of Applied Chemistry, Academia Sinica
  • Received:1964-08-21 Published:2013-06-03

在含三价锑的酸性4M氯化钠溶液中,当加入适量的1,2-环己二氨四乙酸时,得到两个波,较正波随1,2-环己二氨四乙酸浓度和pH的增高而降低,但两波之和是不变的。由对极谱波的性能实验(如波的对数分析,波高-汞柱高度关系,波高-滴落时间关系,波高-温度关系,悬汞电极,Ⅰ-Ⅴ示波极谱实验等)证明较正波为可逆三电子反应的动力波,受锑(Ⅲ)-1,2-环己二氨四乙酸络合物SbZ的解离速率控制。用前文的方法处理动力波。由动力波的半波电位移动的方程求得络合物的稳定常数和焓、熵、自由能变化等热力学函数;由动力电流方程测定络合物离解速率常数和反应活化能,并探讨各电极过程的反应机理。

The polarographic study of the behaviour of antimony (Ⅲ) complex with 1,2-diamino-cyclohexane-tetraacetic acid (H4Z),including the calculation of its stability constant and thermodynamic functions and the mechanism of complex formation, has not yet becn made in detail. If to an acidic 4 M sodium chloride solution, a certain amount of 1,2-diamino-cyclohexane-tetraacetic acid is added, two waves corresponding to three electrons electrode reaction of antimony(Ⅲ) appear. An increase in pH of the supporting electrolyte or in concentration of 1,2-diaminocyclohexane-tetraacetic acid results in an increase of the second wave (at more negative potential) at the expense of the original one. The limiting current of the total wave remains constant and is independent of the concentration of 1,2-diaminocyclohexane-tetraacetic acid and the pH values.The first wave is reversible and kinetically controlled by the rate of chemical reartion, whereas the sum of both waves is diffusion controlled. This is proved by the dependence of the wave height on the height of the mercury reservoir, by the time beater(Fig. 1),by the temperature dependence, by the hanging mercury drop electrode and by the oscillographic polarograph (Fig. 2).