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首页> 外文会议>Fifth International Manuel M.Baizer Symposium in Honor of Professor Jean Michel Saveant at the 201st Meeting of the Electrochemical Society Centennial Meeting May 12-17, 2002 Philadelphia, PA, USA >POLAROGRAPHIC STUDY OF THE KINETICS AND EQUILIBRIA OF THE REACTION OF BENZALDEHVDES WITH HYDRAZINE
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POLAROGRAPHIC STUDY OF THE KINETICS AND EQUILIBRIA OF THE REACTION OF BENZALDEHVDES WITH HYDRAZINE

机译：苯并乙醛与肼反应的动力学和平衡的极谱研究

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摘要

Whereas kinetics and mechanism of reactions of semicarbazide and hydroxylamine with carbonyl compounds has been studied in considerable detail, relatively little attention has been paid to equilibria involved, as well as to reactions with unsubstituted hydrazine. Polarographic current-voltage curves enable simultaneous determination of the aldehyde and hydrazone. Anodic oxidation waves are used to prove absence of azine formation, variations in concentration of the intermediate carbinolamine can be determined. Preliminary investigation of the kinetics of the reaction of benzaldehyde with hydrazine indicated a decrease in the rate of establishment of the equilibrium with pH increasing from 2 to 6. The equilibrium constant increases in this pH-range. The shape of the dependence of K= [ArCH=NNH_2] / [ArCHO][NH_2NH_3~+] on pH indicates the presence of a rapidly established acid-base equilibrium, preceding the dehydration of carbinolamine, which is the rate determining step. Investigation of kinetics and substituent effects is in progress.
机译：尽管已经对氨基脲与羟胺与羰基化合物反应的动力学和反应机理进行了详细的研究，但对平衡的关注以及与未取代肼的反应的关注相对较少。极谱电流-电压曲线能够同时测定醛和。阳极氧化波用于证明没有形成嗪，可以确定中间体甲醇胺浓度的变化。对苯甲醛与肼的反应动力学的初步研究表明，随着pH从2增加到6，平衡建立的速率降低。在此pH范围内，平衡常数增加。 K = [ArCH = NNH_2] / [ArCHO] [NH_2NH_3〜+]对pH的依赖性形状表明，在甲醇胺脱水之前，存在一个快速建立的酸碱平衡，这是速率确定的步骤。动力学和取代基作用的研究正在进行中。

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