Abstract
The possibilities of thiacrown compounds in liquid—liquid extraction were tested by using 1,4,8,11-tetrathiacyclotetradecane (TTCT). Class a metals were not extracted at all; of the class ab metals, only copper(II) was extracted. Class b metals were extracted but their extractabilities varied considerably. The relationship between the distribution ratio of the b metal and its softness is discussed. The extraction behavior of copper(I) with TTCT was studied in detail. The copper(I)—TTCT cation was completely extracted at pH > 4.0 as an ion-pair with perchlorate, picrate or tetraphenylborate. The extraction of copper(I) with TTCT and picrate into different solvents decreased in the order nitrobenzene >1,2-dichloroethane > chloroform > carbon tetrachloride. A study of the extraction equilibria for copper(I) with TTCT in the presence of the picrate (Pic −) showed that copper(I) and TTCT form a 1:1 cation complex [Cu(TTCT)] +, which reacts with picrate to form the 1:1 ion-pair [Cu(TTCT)] +Pic −. The extraction constants are log K ex = 7.3 ± 0.3 and 9.0 ± 0.2 for chloroform and 1,2-dichloroethane, respectively, as the organic solvent.
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