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在纳米浓度范围内使用氯配合的三价铑作为均相催化剂,通过碱性介质中与联吡啶络合的铜(II)络合物氧化乳糖的动力学:分光光度研究。

Kinetics of the oxidation of lactose by copper(II) complexed with bipyridyl in alkaline medium using chloro-complex of rhodium(III) in its nano-concentration range as homogeneous catalyst: a spectrophotometric study.

机构信息

Department of Chemistry, University of Allahabad, Allahabad 211 002, India.

出版信息

Carbohydr Res. 2012 Jun 1;354:94-101. doi: 10.1016/j.carres.2012.03.035. Epub 2012 Apr 10.

Abstract

Kinetics of the oxidation of lactose by Cu(II) complexed with bipyridyl have been investigated at 40 °C for the first time spectrophotometrically using Rh(III) chloride as homogeneous catalyst in aqueous alkaline medium in its nano-concentration range. The order of reaction was found to be fractional positive-order, when the concentration of Rh(III) chloride was varied from 0.30×10(-9) M to 6.00×10(-9) M. The reaction shows fractional positive-order kinetics with respect to [lactose] and [OH(-)] and zeroth-order kinetics with respect to [Cu(II)]. The reaction also shows slight increase in the rate by decreasing dielectric constant of the medium and remains unaffected by the change in ionic strength of the medium. The reaction was carried out at four different temperatures and observed values of rate constants were utilized to calculate various activation parameters specially the entropy of activation (ΔS(#)). The species, RhCl(3)(H(2)O)(2)OH, was postulated as the main reactive species of Rh(III) chloride for the oxidation of lactose by Cu(II) in alkaline medium. On the basis of kinetic and equivalence studies together with spectrophotometric information for the formation of a complex, [formula see text] the most appropriate mechanism for the aforesaid reaction has been proposed. Support to the proposed mechanism was also given by the observed activation parameters and multiple regression analysis. Sodium salts of formic acid, arabinonic acid and lyxonic acid were identified as the main oxidation products of the reaction under investigation.

摘要

首次在 40°C 下使用 Rh(III) 氯化物作为均相催化剂,在纳米浓度范围内,通过分光光度法研究了与联吡啶络合的 Cu(II) 氧化乳糖的动力学。当 Rh(III) 氯化物的浓度从 0.30×10(-9) M 变化到 6.00×10(-9) M 时,发现反应的反应级数为分数正序。该反应对[lactose]和[OH(-)]呈分数正序动力学,对[Cu(II)]呈零级动力学。该反应还显示出通过降低介质介电常数略微增加速率,并且不受介质离子强度变化的影响。在四个不同温度下进行了反应,并利用观察到的速率常数值计算了各种活化参数,特别是活化熵(ΔS(#))。假定RhCl(3)(H(2)O)(2)OH是 Rh(III) 氯化物氧化乳糖在碱性介质中的主要反应性物种。基于动力学和等价研究以及形成络合物的分光光度信息,[公式见正文]提出了上述反应最合适的机制。观察到的活化参数和多元回归分析也为所提出的机制提供了支持。在所研究的反应中,甲酸、阿拉伯酸和木糖醇酸钠被确定为主要氧化产物。

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