六氰合铁(III)催化银(I)氧化对氯苯酚的实验和计算动力学评估:机理途径探索

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL
Asha Rolaniya, Akta Yadav, Priyanka Jain and Riya Sailani
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引用次数: 0

摘要

本研究深入探讨了对氯苯酚(p-CP)与六氰基铁酸盐(III)[HCF (III)]之间的氧化还原反应,该反应由 Ag (I) 在碱性环境中催化。研究结果表明,对氯苯酚和氧化剂都有一阶依赖性,反应速率也显示出对 Ag (I) 的一阶依赖性,根据方程式 kobs = a + b [OH-],介质进一步放大了反应速率。有趣的是,离子强度在整个反应过程中保持不变,对反应速率没有明显影响。活化和热力学参数的评估采用阿伦尼乌斯方程和艾林方程。光谱分析确定对苯二酚的氧化产物为对苯二酚。研究还扩展到了各种有机溶剂,并通过 Taft 和 Swain 的多参数方程仔细研究了它们的影响。值得注意的是,速率常数与 Kamlet-Taft 的溶解变色参数(α、β、π*)的相关性令人满意。在动力学研究结果的基础上,提出了一个合理的反应机制。通过在 b3lyp/6-311*g (d,p) 水平上进行密度泛函理论(DFT)计算得出的额外证据大大加强了这一观点。这些计算揭示了与动力学实验中观察到的反应趋势相一致的活化能势垒,从而为所提出的机理提供了坚实的支持。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Experimental and computational kinetic evaluations of silver(i)-catalyzed oxidation of p-chlorophenol by hexacyanoferrate(iii): exploring the mechanistic pathway

Experimental and computational kinetic evaluations of silver(i)-catalyzed oxidation of p-chlorophenol by hexacyanoferrate(iii): exploring the mechanistic pathway

The present investigation delves into the redox reaction between p-chlorophenol (p-CP) and hexacyanoferrate(III) [HCF(III)], catalyzed by Ag(I) in an alkaline environment. Findings reveal a first-order dependence on both p-CP and the oxidant, and the reaction rate showcased a first-order reaction towards Ag(I), which was further amplified by the medium as per the equation kobs = a + b[OH]. Interestingly, the ionic strength remained unchanged throughout the reaction, exerting no discernible effect on the reaction rate. For the evaluation of activation and thermodynamic parameters, Arrhenius and Eyring equations were utilized. Spectral analysis identified the oxidation product of p-CP as hydroquinone. The exploration was further extended to various organic solvents, with their effects scrutinized through Taft's and Swain's multiparametric equations. Notably, the rate constants failed to correlate satisfactorily with Kamlet–Taft's solvatochromic parameters (α, β, π*). Based on the kinetic findings, a plausible reaction mechanism was proposed, which was further supported by the density functional theory (DFT) calculations performed at the b3lyp/6-311*g (d,p) level. The activation energy values obtained from the DFT results were consistent with the reactivity trends observed in the experimental data, thereby validating the proposed mechanism.

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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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