Theoretical Kinetic Study of SF6 Decomposition via Reactions With H and OH Radicals

IF 4.3 3区 工程技术 Q2 ENERGY & FUELS
Naeun Kim, Min Jung Lee, Hyunguk Kwon
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Abstract

A comprehensive kinetic model for SF6 decomposition in combustion environments has been hindered by the lack of accurate thermodynamic and kinetic data, particularly for radical-driven high-temperature chemistry. This study provides ab initio thermodynamic and kinetic data for SF6 decomposition via reactions with H and OH radicals, key species in combustion chemistry. The thermodynamic properties of various fluorinated species are provided in NASA polynomial format, allowing direct integration into kinetic simulation packages. Three major reaction pathways are examined using density functional theory (DFT) calculations are as follows: (1) SFn + H → SFn − 1 + HF, (2) SFn + OH → SOFn − 1 + HF, and (3) SOFn + OH → SO2Fn − 1 + HF. These reactions are key steps in forming major products, such as SO2 and SO2F2. Temperature-dependent rate constants are computed, and the corresponding Arrhenius parameters are determined. The decomposition of SFn species is more strongly promoted by OH radicals than by H radicals. SOFn species, formed from SFn and OH radicals, subsequently react with OH radicals to generate SO2 and SO2F2. These findings provide a valuable thermodynamic and kinetic dataset that can be integrated into combustion or pyrolysis kinetic models to develop a detailed SF6 decomposition model.

Abstract Image

SF6与H、OH自由基反应分解的理论动力学研究
由于缺乏准确的热力学和动力学数据,特别是自由基驱动的高温化学,SF6在燃烧环境下分解的综合动力学模型一直受到阻碍。该研究为SF6与H和OH自由基(燃烧化学中的关键物质)的分解提供了从头计算的热力学和动力学数据。各种氟化物质的热力学性质以NASA多项式格式提供,允许直接集成到动力学模拟包中。利用密度泛函数理论(DFT)计算考察了三种主要的反应途径:(1)SFn + H→SFn−1 + HF, (2) SFn + OH→SOFn−1 + HF, (3) SOFn + OH→SO2Fn−1 + HF。这些反应是形成SO2和SO2F2等主要产物的关键步骤。计算了温度相关的速率常数,并确定了相应的Arrhenius参数。OH自由基比H自由基更能促进SFn的分解。SOFn由SFn和OH自由基形成,随后与OH自由基反应生成SO2和SO2F2。这些发现提供了一个有价值的热力学和动力学数据集,可以集成到燃烧或热解动力学模型中,以开发详细的SF6分解模型。
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来源期刊
International Journal of Energy Research
International Journal of Energy Research 工程技术-核科学技术
CiteScore
9.80
自引率
8.70%
发文量
1170
审稿时长
3.1 months
期刊介绍: The International Journal of Energy Research (IJER) is dedicated to providing a multidisciplinary, unique platform for researchers, scientists, engineers, technology developers, planners, and policy makers to present their research results and findings in a compelling manner on novel energy systems and applications. IJER covers the entire spectrum of energy from production to conversion, conservation, management, systems, technologies, etc. We encourage papers submissions aiming at better efficiency, cost improvements, more effective resource use, improved design and analysis, reduced environmental impact, and hence leading to better sustainability. IJER is concerned with the development and exploitation of both advanced traditional and new energy sources, systems, technologies and applications. Interdisciplinary subjects in the area of novel energy systems and applications are also encouraged. High-quality research papers are solicited in, but are not limited to, the following areas with innovative and novel contents: -Biofuels and alternatives -Carbon capturing and storage technologies -Clean coal technologies -Energy conversion, conservation and management -Energy storage -Energy systems -Hybrid/combined/integrated energy systems for multi-generation -Hydrogen energy and fuel cells -Hydrogen production technologies -Micro- and nano-energy systems and technologies -Nuclear energy -Renewable energies (e.g. geothermal, solar, wind, hydro, tidal, wave, biomass) -Smart energy system
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