MECHANISM OF CHARACTERISTIC DECOMPOSITION OF Cu(PCD)_2 EXTRACTED FROM HYDROCHLORIC ACID: CONTRIBUTION OF REACTION BETWEEN Cu(PCD)_2 AND CuClx^(2-x)

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To study the decomposition mechanism of copper(2) pyrrolidinecarbodithioato chelate (Cu(PCD)_2) extracted into di-isobutylketone (DIBK) with 1-pyrrolidinecarbodithioate (APCD) from 0,01～8 M hydrochloric acid solution, the effect of the ligand concentration in organic phase on the decomposition of Cu(PCD)_2 has been studied. The concentration of the free ligand in the extract decreases with time; this decrease obeys good first-order kinetics, and depends on the acidity. On the other hand, the concentration of Cu(PCD)_2 is not seemingly altered as long as the free ligand is present in the extract; however, the copper chelate begins to react with hydrochloric acid as soon as the free reagent has run out due to its decomposition. Furthermore, the reaction of Cu(PCD)_2 with hydrochloric acid in IBMK solution has also been studied kinetically. To monitor the reaction, the molar absorption coefficients of some species [CuCl(PCD), CuCl_2, and CuCl^-_3], which are formed in the course of this reaction, at 350 - 500 nm are determined. It can be thought that the reaction consists of not only simple ligand substitution by Cl^- but also of the path which gives CuCl(PCD) by reaction between Cu(PCD)_2 and CuCl_2,, and the path can be regard as the practical motive force of the decomposition of Cu(PCD)_2 extracted from hydrochloric acid solution.
琉球大学理学部の論文