三氟甲基磺酰氟的过热分解产物规律与成因分析

doi:10.19595/j.cnki.1000-6753.tces.251460

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摘要 SF₆替代气体的化学稳定性及其分解特性直接关系到环保气体绝缘电气设备的绝缘强度与运维安全。为探究三氟甲基磺酰氟（CF₃SO₂F）气体在局部过热条件下的分解特性及产物形成原因,该文开展了局部过热缺陷模拟实验,利用气相色谱-质谱联用（GC-MS）技术,分析了不同温度下CF₃SO₂F气体的分解产物种类及其含量变化趋势。结合量子化学计算得到CF₃SO₂F的分解路径及主要产物合成路径的焓变、自由能变等结果,揭示了过热分解产物的热力学生成机制。实验结果表明,CF₃SO₂F气体约在250℃时开始逐步分解,400℃时基本分解完全,主要生成CF₄, C₂F₆, C₃F₈, SO₂, SO₂F₂和SOF₂等产物。热力学分析显示,CF₃SO₂F分子中C-S键断裂路径的能垒最低,全氟烷烃的合成难度依次为CF₄<C₂F₆<C₃F₈。研究结果可为CF₃SO₂F气体的实用化和工程化应用提供理论与实验依据。

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	申偲杰
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关键词 ：三氟甲基磺酰氟, 局部过热, 气相色谱-质谱联用技术, 分解特性, 量子化学计算

Abstract：The chemical stability and decomposition characteristics of SF₆ alternative gases play a crucial role in determining the insulation performance and operational safety of environmentally friendly gas-insulated electrical equipment. Among the potential substitutes, trifluoromethanesulfonyl fluoride (CF₃SO₂F) has attracted increasing attention due to its excellent dielectric properties and low global warming potential (GWP). However, its thermal stability under overheating conditions has not been systematically studied, and a clear understanding of its decomposition behavior is essential for its reliable application in power equipment.
To clarify its decomposition mechanism and major gaseous products, a series of overheating defect simulation experiments were conducted under controlled temperature conditions. The chamber was cleaned and evacuated to remove residual moisture and oxygen, then charged with CF₃SO₂F at a preset pressure and heated stepwise from 120℃ to 400℃ to simulate localized overheating. The decomposition products were identified and quantified using gas chromatography-mass spectrometry (GC-MS), and their temperature-dependent concentration trends were analyzed, providing key insights into the decomposition pathways of CF₃SO₂F.
Experimental results show that CF₃SO₂F remains thermally stable below approximately 250℃ but begins to gradually decompose as the temperature increases beyond this threshold. At 400°C, CF₃SO₂F is almost completely decomposed, and the dominant products are CF₄, C₂F₆, C₃F₈, SO₂, SO₂F₂, and SOF₂. Among these species, fluorocarbon products (CF₄, C₂F₆, and C₃F₈) are indicative of the cleavage and recombination of C-F fragments, while sulfur-oxygen products (SO₂, SO₂F₂, and SOF₂) reflect the oxidation and rearrangement processes of the sulfonyl group under high-temperature conditions. The formation of such products suggests that multiple parallel and consecutive reactions occur during CF₃SO₂F decomposition, governed by both thermal activation and radical recombination mechanisms.
To further elucidate the molecular-level mechanisms, comprehensive quantum chemical calculations were performed at the M06-2X/aug-cc-pVTZ level combined with single-point energy refinement at the CBS-QB3 level for improved energetic accuracy. Several plausible decomposition and product formation pathways were proposed and characterized by geometry optimization, transition state search, and intrinsic reaction coordinate (IRC) analysis. The computed thermodynamic parameters, including enthalpy (ΔH) and Gibbs free energy changes (ΔG), were used to assess the feasibility and spontaneity of each pathway. Results show that the C-S bond cleavage pathway possesses the lowest energy barrier, confirming it as the primary decomposition route of CF₃SO₂F. Subsequent radical recombination reactions lead to the generation of CF? and longer-chain perfluorocarbons (C₂F₆ and C₃F₈), with increasing synthetic difficulty following the order CF₄<C₂F₆<C₃F₈. Meanwhile, the formation of sulfur-oxygen species is mainly attributed to rearrangement and oxidation reactions involving SO₂F and SOF intermediates under elevated temperature conditions.
Overall, the combination of experimental and theoretical results provides a comprehensive understanding of the thermal decomposition mechanism of CF₃SO₂F. The findings indicate that although CF₃SO₂F exhibits good thermal stability under moderate conditions, it undergoes significant decomposition under severe overheating, producing fluorocarbons and sulfur oxides that may influence insulation performance and environmental safety. The established decomposition pathways and thermodynamic data offer valuable theoretical and experimental guidance for assessing the stability, safety, and engineering applicability of CF₃SO₂F as a potential alternative to SF₆ in gas-insulated electrical equipment.

Key words： Trifluoromethanesulfonyl fluoride overheating gas chromatography-mass spectrometry decomposition characteristics quantum chemistry calculation

收稿日期: 2025-08-21

PACS:

TM85

基金资助:国家重点研发计划（2021YFB2401400）和怀柔科学城成果落地项目（Z221100005822004）资助

通讯作者: 韩冬女,1975年生,博士,副研究员,研究方向为SF6气体及其替代技术、电力设备故障检测等。E-mail：donghan@mail.iee.ac.cn

作者简介: 申偲杰女,2001年生,硕士研究生,研究方向为SF6气体及其替代技术、电力设备故障检测等。E-mail：shensijie@mail.iee.ac.cn

引用本文:

申偲杰, 高克利, 颜湘莲, 段竣然, 张国强, 韩冬. 三氟甲基磺酰氟的过热分解产物规律与成因分析[J]. 电工技术学报, 2026, 41(15): 5285-5295. Shen Sijie, Gao Keli, Yan Xianglian, Duan Junran, Zhang Guoqiang, Han Dong. Thermal Decomposition Behavior and By-Product Formation Mechanism of Trifluoromethanesulfonyl Fluoride. Transactions of China Electrotechnical Society, 2026, 41(15): 5285-5295.

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