Dissecting steric and polar substituent effects in linear free energy Relationships: Re-Assessment of the Taft equation with Temperature-Dependent kinetic modeling

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science Pub Date : 2025-09-26 DOI:10.1016/j.ces.2025.122700

Sindi Baco , Mélanie Mignot , Christoph Held , Julien Legros , Sébastien Leveneur

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Abstract

Kinetic models are vital for developing process flow diagrams that support cost, risk, and environmental assessments, but constructing them is time-consuming, particularly when screening multiple substituents or solvents. Linear Free Energy Relationships (LFERs) can reduce experimental effort, yet most existing formulations neglect temperature effects. In this work, we quantify the temperature dependence (20–50 °C) of Taft’s polar (σ*) and steric (Es) substituent parameters for methyl, ethyl, n-propyl, and 2-chloroethyl groups using kinetic data from esterification and saponification of levulinate derivatives in aqueous media. Both σ* and Es varied linearly with temperature, with the strongest sensitivity observed for 2-chloroethyl (–0.007 °C⁻¹ for σ*, 0.008 °C⁻¹ for Es). Incorporating these temperature coefficients into LFER-based kinetic models enhances their predictive accuracy for reaction rates, enabling more efficient process design in biomass valorization and related chemical systems.

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线性自由能关系中的立体和极性取代效应解析：用温度相关动力学模型重新评价塔夫脱方程

动力学模型对于开发支持成本、风险和环境评估的工艺流程图至关重要，但是构建它们非常耗时，特别是在筛选多个取代基或溶剂时。线性自由能关系（LFERs）可以减少实验的工作量，但大多数现有的公式忽略了温度的影响。在这项工作中，我们量化了Taft的极性（σ*）和空间（Es）取代基参数对甲基、乙基、正丙基和2-氯乙基的温度依赖性（20-50 °C），使用了乙酰丙酸衍生物在水介质中的酯化和皂化的动力学数据。σ*和Es随温度呈线性变化，2-氯乙基的灵敏度最高（σ*为-0.007 °C−1，Es为0.008 °C−1）。将这些温度系数整合到基于lfe的动力学模型中，可以提高其对反应速率的预测精度，从而在生物质增值和相关化学系统中实现更有效的过程设计。

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来源期刊

Chemical Engineering Science 工程技术-工程：化工

CiteScore

7.50

自引率

8.50%

发文量

1025

审稿时长

50 days

期刊介绍： Chemical engineering enables the transformation of natural resources and energy into useful products for society. It draws on and applies natural sciences, mathematics and economics, and has developed fundamental engineering science that underpins the discipline. Chemical Engineering Science (CES) has been publishing papers on the fundamentals of chemical engineering since 1951. CES is the platform where the most significant advances in the discipline have ever since been published. Chemical Engineering Science has accompanied and sustained chemical engineering through its development into the vibrant and broad scientific discipline it is today.