Kinetic Studies of the Solvent Extraction of Metal Complexes. II. The Rate of the Extraction of Iron(III) with Thenoyltrifluoroacetone into Carbon Tetrachloride
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概要
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The rate of the solvent extraction of iron(III) in 4.0 M perchlorate ionic media with 2-thenoyltrifluoroacetone (TTA) into carbon tetrachloride has been measured under various conditions. The rate was found to be first order with respect to the concentration of iron(III) in the aqueous phase, first-order with respect to TTA in the organic phase, but independent and inversely first-order with respect to the hydrogen-ion concentration. From these results, it was concluded that the rate-determining step in this extraction is the formation of the first complex between the undissociated form, TTA(HA), and Fe<SUP>3+</SUP> in the higher acid concentration range, but that the reaction between the anionic form, TTA(A<SUP>−</SUP>), and Fe<SUP>3+</SUP> also becomes a rate-determining step as the acid concentration decreases. It was also found that chloride ions accelerate the extraction; this was interpreted by more rapid reactions between TTA (in the both forms, HA and A<SUP>−</SUP>) and an iron(III) chloride complex. From these results, the rate constants for the rate-determining reactions were calculated to be <I>K</I><SUB>HA</SUB>=10<SUP>0.57</SUP> M<SUP>−1</SUP> min<SUP>−1</SUP> and <I>K</I><SUB>A</SUB>=10<SUP>6.84</SUP> M<SUP>−1</SUP> min<SUP>−1</SUP> in 4.0 M(H, Na)ClO<SUB>4</SUB> at 25 °C by means of these equations: −d[Fe<SUP>3+</SUP>]⁄d<I>t</I>=<I>K</I><SUB>HA</SUB>[Fe<SUP>3+</SUP>][HA] (where [HA] is the total concentration of both enol and keto forms of uncharged TTA in the aqueous phase) and −d[Fe<SUP>3+</SUP>]⁄d<I>t</I>=<I>K</I><SUB>A</SUB>[Fe<SUP>3+</SUP>]·[A<SUP>−</SUP>]. The FeCl<SUP>2+</SUP> species reacts with both HA and A<SUP>−</SUP> more rapidly than does the Fe<SUP>3+</SUP> species, and the rate constants of the reactions of the former are in both cases higher than those of the latter by a factor of 28.
- 公益社団法人 日本化学会の論文
著者
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Komatsu Yu
Department Of Environmental Chemistry College Of Environmental Engineering And Architecture Kanazawa
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Sekine Tatsuya
Departemnt of Chemistry, Science University of Tokyo
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Yumikura Jun-ichi
Department of Chemistry, Science University of Tokyo
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Komatsu Yu
Department of Chemistry, Science University of Tokyo
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