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A Study of the Kinetics and Mechanism of Oxidation of Fluorene by Alkaline Hexacyanoferrate(III)

机译:碱性六氰合铁酸盐(III)氧化芴的动力学及机理研究

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Kinetics of hexacyanoferrate (III) (HCF) oxidation of fluorene (Fl) in organic alkaline medium has been studied by spectrophotometric technique at a constant ionic strength of 0.15 mol dmsup-3/sup and at a temperature of 25°C. The reaction showed a first order kinetics with respect to [HCF] and fractional-first order dependences on both [Fl] and [OHsup-/sup]. The oxidation rate was increased with the increase in the ionic strength of the reaction medium. The oxidation mechanism was suggested which involves formation of a 1:1 intermediate complex between fluorene and HCF species in a pre-equilibrium step. The final oxidation product of fluorene was identified by spectroscopic and chemical tools as 9H-fluorenone. The appropriate rate law expression was deduced and the reaction constants involved in the mechanism were evaluated. The activation parameters of the rate constant of the slow step along with the thermodynamic quantities of the equilibrium constants were evaluated and discussed.
机译:通过分光光度法研究了在恒定的离子强度为0.15 mol dm -3 且温度为25°C的条件下,分光光度法研究了芴(Fl)在有机碱性介质中氧化六氰铁酸酯(III)(HCF)的动力学。 C。该反应显示出相对于[HCF]的一级动力学,以及对[F1]和[OH -]的分数一阶依赖性。氧化速率随反应介质离子强度的增加而增加。提出了氧化机理,该机理涉及在预平衡步骤中在芴和HCF物种之间形成1:1的中间配合物。芴的最终氧化产物通过光谱和化学工具鉴定为9H-芴酮。推导了适当的速率定律表达式,并评估了该机理涉及的反应常数。评估并讨论了慢步速率常数的激活参数以及平衡常数的热力学量。

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