Abstract
The electrochemical reduction of anhydrous alkali-metal perchlorates and of their complexes with 1,4,7,10- tetraoxacyclododecane (12-crown-4) has been investigated in propylene carbonate by normal polarography and potentiometry using a dilute amalgam pool electrode. Stability constants and stoicheiometries derived from partially irreversible polarographic waves corrected according to Gellings have been compared with potentiometric data. The ligand 12-crown-4 exhibits a high selectivity for Na+ which forms 1 : 2 complexes (log β1= 3.5 ± 0.2, log β2= 6.31 ± 0.04). The stability constants of the 1 : 1 adducts with Li+(log β1= 2.93 ± 0.05), K+(2.15 ± 0.05), Rb+(1.69 ± 0.04), and Cs+(1.43 ± 0.05) decrease with increasing ionic radius of the encapsulated ion.
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