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Kinetics and Mechanism of Oxidation of Carbenicillin by Copper (III) Periodate Complex in Aqueous Alkaline Medium
Journal of Chemistry ( IF 2.8 ) Pub Date : 2020-06-06 , DOI: 10.1155/2020/4060984
Yuv Raj Sahu 1 , Parashuram Mishra 1
Affiliation  

Kinetics and mechanism of oxidation of carbenicillin by diperiodatocuprate [DPC-III] in aqueous alkaline medium were studied spectrophotometrically at 298 K and an ionic strength of 0.10 mol·dm−3. The reaction between DPC (III) and carbenicillin in the alkaline medium showed (CRBC : DPC-III) 1 : 4 stoichiometry. The reaction products were identified by the CHNS test, FT-IR, and LC-MS spectral reports. The reaction was of pseudo-first order with respect to DPC (III) and fractional order with respect to carbenicillin as well as alkali but retarding effect with respect to periodate. Monoperiodatocuprate (MPC-III) was found to be the main active species in the alkaline medium in the form of [Cu (H2IO6) (H2O)2]. Activation and thermodynamic parameters with respect to uncatalyzed rate constants (ku) and slow step rate constant (k) as well as equilibrium constants were determined. The plausible mechanism consistent with experimental results was proposed and discussed in detail.

中文翻译:

高碘酸铜(III)配合物在碱性水溶液中氧化羧苄青霉素的动力学和机理

用分光光度法在298 K和0.10 mol·dm-3的离子强度下研究了双高碘铜酸盐[DPC-III]在碱性水溶液中氧化羧苄青霉素的动力学和机理。DPC(III)和羧苄青霉素在碱性介质中的反应显示(CRBC:DPC-III)1:4化学计量。反应产物通过 CHNS 测试、FT-IR 和 LC-MS 光谱报告进行鉴定。该反应对于 DPC (III) 是准一级反应,对于羧苄青霉素以及碱反应是假一级反应,而对于高碘酸盐有阻滞作用。发现单高碘铜酸盐 (MPC-III) 是碱性介质中以 [Cu (H2IO6) (H2O)2] 形式存在的主要活性物质。确定了与未催化速率常数 (ku) 和慢步速率常数 (k) 以及平衡常数有关的活化和热力学参数。提出并详细讨论了与实验结果一致的合理机制。
更新日期:2020-06-06
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