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タイトル: | Kinetic study of the intermediate in the reaction between picryl chloride and sodium sulphite in aqueous solution |
著者: | Sasaki, Muneo |
著者名の別形: | ササキ, ムネオ |
発行日: | 20-Nov-1975 |
出版者: | The Physico-Chemical Society of Japan |
誌名: | The Review of Physical Chemistry of Japan |
巻: | 45 |
号: | 1 |
開始ページ: | 45 |
終了ページ: | 52 |
抄録: | The reaction between picryl chloride and sulphite ion in aqueous solution takes place rapidly to give an intense color which is attributed to a 1, 3-σ-complex formed by the reversible attack of a sulphite ion on the C_3-position of picryl chloride. The color slowly fades because picryl chloride present at equilibrium is attacked by sulphite ion to give 1, 1-σ-complex which rapidly loses chloride ion to form picryl sulphonate ion finally. The 1, 3-σ-complex dissociates to maintain equilibrium. The rates of appearance and disappearance of the transient colored species were measured in the range of 15-35℃ by the stopped-flow method. The rate constants at 25℃, activation enthalpies and activation entropies an each process are shown in Table 2 in the text. The 1, 3-σ-complex was verified by NMR spectrum in DMSO-H_2O solution. The formation of the 1, 1-σ-complex was inferred from the nature of the final products. It may be concluded that the sulphite attacks on C_1-position and C_3-position take place concurrently and the former may be accompanied with higher energy barrier. |
URI: | http://hdl.handle.net/2433/47012 |
出現コレクション: | Vol.45 No.1 |
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