Metal complexes in acetic acid. I. Kinetics and mechanism of reactions of tetra-.MU.-acetato-dicopper(II) with lithium chloride and hydrogen chloride.
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Kinetics of reactions of tetra-μ-acetato-dicopper(II) (copper(II) acetate dimer: Cu<SUB>2</SUB>(OAc)<SUB>4</SUB>) with lithium chloride and hydrogen chloride (XCl where X denotes Li or H) in acetic acid have been studied spectrophotometrically by using a stopped-flow technique with a computer-assisted averaging device. The rate of decomposition of copper(II) acetate dimer to the monomeric chloro complex is expressed as −d[Cu<SUB>2</SUB>(OAc)<SUB>4</SUB>]/d<I>t</I>=<I>k</I><SUP>XCl</SUP>[Cu<SUB>2</SUB>(OAc)<SUB>4</SUB>][XCl]. At 25 °C <I>k</I><SUP>LiCl</SUP>=(3.5±0.6)×10<SUP>5</SUP> mol<SUP>−1</SUP> kg s<SUP>−1</SUP> (Δ<I>H</I><SUP>\neweq</SUP>=50±10 kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP>=30±20 J mol<SUP>−1</SUP> K<SUP>−1</SUP>) and <I>k</I><SUP>HCl</SUP>=(4.8±1.0)×10<SUP>5</SUP> mol<SUP>−1</SUP> kg s<SUP>−1</SUP> (Δ<I>H</I><SUP>\neweq</SUP>=23±10 kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP>=−60±20 J mol<SUP>−1</SUP> K<SUP>−1</SUP>). Mechanisms are proposed for the decomposition of copper(II) acetate dimer and some discussions are made on the difference in reactivities of LiCl and HCl.
- 公益社団法人 日本化学会の論文
著者
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Sawada Kiyoshi
Laboratory Of Analytical Chemistry Faculty Of Science Niigata University
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Funahashi Shigenobu
Laboratory Of Analytical Chemistry Department Of Chemistry Faculty Of Science Nagoya University
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Tanaka Motoharu
Laboratory of Analytical Chemistry Faculty of Science Nagoya University
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Nishimoto Tetsuo
Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University
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Banerjee Pradyot
Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University
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