Formation kinetics of peroxovanadium(V) complexes in strongly acidic media as studied by a high-pressure stopped-flow technique

Shigenobu Funahashi, Koji Ishihara, Masahiko Inamo, Motoharu Tanaka*

*この研究の対応する著者

研究成果: Article査読

16 被引用数 (Scopus)

抄録

A high-pressure stopped-flow vessel was made of acid-proof tantalum block which enabled us to follow reactions of vanadium(V) ion with hydrogen peroxide in strongly acidic media. The rate for the formation of the monoperoxo complex (VO(O2)+) is expressed as d [VO(O2)+]/dt = (k1[H+]-1 + k2 + k3 [H+])[VO2+]- [H2O2] where k1 (s-1) (25 °C)=60.2 [ΔH (kJ mol-1 = 21.1 ± 2.6, ΔS (J mol-1 K-1) = - 140 ± 9, ΔV (cm3 mol-1) = 9.9 ± 1.7], k2 (mo1-1 dm3 s-1) (25 °C) = 3.47 × 103 [ΔH = 46.5 ± 1.3, ΔS = -21 ±4, ΔV = 2.8 ± 1.0] and k3 (mol-2 dm6 s-1) (25 °C) = 1.63 × 103 [ΔH = 20.1 ± 4.7, Δ [tl]S = -116 ± 16, ΔV = 14.2 ± 3.2]. The rates of formation and dissociation of the diperoxo complex are described as d [VO(O2)2-]/dt = kf [VO(O2)+] [H2O2] and - d [VO(O2)2-]/dt = kd [VO(O2)2-] [H+]2, respectively, where kf (mol-1 dm3 s-1) (25 °C) = 3.49 × 103 [ΔH (kJ mol-1) = 40.2 ± 0.8, ΔS (J mol-1 K-1) = -42±3, ΔV (cm3 mol-1) =0.0±0.2]. and kd (mol-2 dm6 s-1) (25 °C) = 3.79 × 103 [ΔH = 45.7 ± 1.7, ΔS≠ = -23 ∓ 6]. Positive volumes of activation for the monoperoxo complex formation have been attributed to an expanded transition state with the distorted pentagonal-bipyramidal structure.

本文言語English
ページ(範囲)65-71
ページ数7
ジャーナルInorganica Chimica Acta
157
1
DOI
出版ステータスPublished - 1989 3月 1
外部発表はい

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 無機化学
  • 材料化学

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