Kinetics and mechanism of complex formation of nickel(II) with 1-(2-pyridylazo)-2-naphthol in acetic acid.
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概要
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The complex formation reactions of nickel(II) nitrate, nickel(II) acetate, and nickel(II) chloride with 1-(2-pyridylazo)-2-naphthol (PAN) in acetic acid (HOAc) to form the 1:1 nickel(II)–PAN complex have been studied kinetically by using a stopped-flow technique. The second-order rate constants and activation parameters at 25 °C are <I>k</I>=(1.4±0.1)×10<SUP>4</SUP> mol<SUP>−1</SUP> kg s<SUP>−1</SUP>, Δ<I>H</I><SUP>\neweq</SUP>=51.2±1 kJ mol<SUP>−1</SUP>, Δ<I>S</I><SUP>\neweq</SUP>=6.4±4 J mol<SUP>−1</SUP> K<SUP>−1</SUP>, and Δ<I>V</I><SUP>\neweq</SUP>=23.4±2.4 cm<SUP>3</SUP> mol<SUP>−1</SUP> for Ni(NO<SUB>3</SUB>)<SUB>2</SUB>, <I>k</I>=(1.1±0.1)×10<SUP>4</SUP> mol<SUP>−1</SUP> kg s,<SUP>−1</SUP>, Δ<I>H</I><SUP>\neweq</SUP>=49.5±1 kJ mol<SUP>−1</SUP>, Δ<I>S</I><SUP>\neweq</SUP>=−1.3±4 J mol<SUP>−1</SUP> K<SUP>−1</SUP>, and Δ<I>V</I><SUP>\neweq</SUP>=15.5±2.6 cm<SUP>3</SUP> mol<SUP>−1</SUP> for Ni(OAc)<SUB>2</SUB>, and <I>k</I>=(4.8±0.1)×10<SUP>4</SUP> mol<SUP>−1</SUP> kg s<SUP>−1</SUP>, Δ<I>H</I><SUP>\neweq</SUP>=51.4±1 kJ mol<SUP>−1</SUP>, Δ<I>S</I><SUP>\neweq</SUP>=17.0±4 J mol<SUP>−1</SUP> K<SUP>−1</SUP>, and Δ<I>V</I><SUP>\neweq</SUP>=35.4±5.5 cm<SUP>3</SUP> mol<SUP>−1</SUP> for NiCl<SUB>2</SUB>. The positive value of Δ<I>V</I><SUP>\neweq</SUP> strongly suggests a dissociative mode of activation.
- 公益社団法人 日本化学会の論文
著者
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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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Hioki Akiharu
Laboratory of Analytical 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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