Kinetic Studies of the Solvent Extraction of Metal Complexes. I. The Extraction of the Beryllium(II)-TTA Chelate from Aqueous Perchlorate Media into Carbon Tetrachloride and Methyl Isobutyl Ketone
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概要
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The rate of extraction of beryllium ions from aqueous 4.0M or 0.1M sodium perchlorate-chloride or -nitrate ionic media into carbon tetrachloride or MIBK (methyl isobutyl keton) as a chelate complex with TTA (thenoyltrifluoroacetone) has been determined at 25°C. The rate of extraction in the carbon tetrachloride system is first-order with respect both to the beryllium ion and the dissociated TTA anion in the aqueous phase. The rate constant for this reaction is about 2×10<SUP>4</SUP>M<SUP>2</SUP>min<SUP>−1</SUP>. The rates in these systems are not influenced by the replacement of perchlorate ions by nitrate or chloride ions in the ionic media when the ionic concentration is kept constant. On the other hand, it was found that three extraction reactions take place in the MIBK systems. The rate of these extractions is in all cases first-order with respect both to the beryllium ion and the dissociated TTA anion, but is zeroth-, first, or second-order with respect to the perchlorate ions in the aqueous phase. Because of this, the extraction is much faster when the perchlorate concentration is larger; for example, when the concentration of the TTA anion is kept constant, the extraction from a 4.0M sodium perchlorate solution is about 200 times faster than that from the 4.0M sodium chloride solution. From these experimental results, the following conclusions were reached. In the carbon tetrachloride system, the beryllium ion first forms the TTA chelate in the aqueous phase, and then the complex is extracted into the organic phase. The rate-determining step is the 1: 1 complex formation in the aqueous phase. In the MIBK system, on the other hand, the formation of the TTA complex in the aqueous phase, followed by its extraction into the organic phase (zeroth-order reaction with respect to the perchlorate ion), also occurs, but at the same time, the beryllium ion in the aqueous phase is first extracted into the organic phase as ion-pairs, such as BeCl(ClO<SUB>4</SUB>) or BeNO<SUB>3</SUB>(ClO<SUB>4</SUB>) and Be(ClO<SUB>4</SUB>)<SUB>2</SUB> (first- and second-order reactions with respect to the perchlorate ions respectively), and the ion-pairs then react with the TTA anions in the organic phase. The enhancement of the rate of extraction by the perchlorate ions in the MIBK system seems to be explained by the overall effect of these extraction mechanisms.
- 公益社団法人 日本化学会の論文
著者
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Sekine Tatsuya
Departemnt of Chemistry, Science University of Tokyo
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Komatsu Yu
Department of Chemistry, Science University of Tokyo
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Koike Yasuaki
Department of Chemistry, Science University of Tokyo
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