Abstract

The effect of medium acidity on the rate constant (k) of the reactions of alkanes (AlkH), cycloalkanes (c-AlkH), and arenes (ArH) in sulfuric acid solutions with peroxy compounds (H₂O₂ or (NH₄)₂S₂O₈), complexes (Pd(II), Pt(III), Hg(II)), acids (H₂CrO₄, HNO₃, H₂SO₄, HVO₃), 1-adamantanol (AdOH), and formaldehyde (CH₂O) was analyzed using the equation log k = C₀ – m₀H₀, where Н₀ is the Hammett acidity function, C₀ is the intercept on the ordinate, and m₀ is the slope of the line in the coordinates log k – H₀. All the reactions can be divided into three groups depending on the slope value (1 ~ m₀ ≤ 3.4) in accordance with the degree of protonation of the main species: single protonation (H₂O₂ or (NH₄)₂S₂O₈, Pd(II), Pt(III)) (group 1); protonation followed by dehydration (AdOH, H₂CrO₄, HNO₃, H₂SO₄, as well as HVO₃, and CH₂O in reactions with ArH in 57–65% and 60–80% H₂SO₄, respectively) (group 2); and more profound double or triple protonation (Hg(II), HVO₃, and CH₂O in reactions with AlkH and c-AlkH in 84–90% and 88–93% H₂SO₄, respectively) (group 3). For the active oxidant species in the HVO₃–H₂SO₄ system and in H₂SO₄ itself, the thermochemical characteristics of their reactions with 2,3-dimethylbutane were evaluated using the DFT B3LYP/6-311G(d,p) quantum-chemical method, and the possibilities of alternative reaction mechanisms were analyzed.

中文翻译：

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中等酸度对硫酸溶液中烃类氧化功能化速率的影响

摘要

中等酸度对硫酸溶液中过氧化合物（H ₂ O ₂或（NH ₄）的烷烃（AlkH），环烷烃（c -AlkH）和芳烃（ArH）反应速率常数（k）的影响₂ S ₂ O ₈），络合物（Pd（II），Pt（III），Hg（II）），酸（H ₂ CrO ₄，HNO ₃，H ₂ SO ₄，HVO ₃），1-金刚烷醇（AdOH） ，并使用等式log k = C ₀ – m ₀分析甲醛（CH ₂ O） ħ ₀，其中Н ₀是哈米特酸度函数，Ç ₀是在纵坐标上的截距，和米₀是在坐标线的斜率日志 ķ - ħ ₀。所有的反应可以分为依赖于斜率值（1〜三组米₀按照主要种类的质子化的程度≤3.4）：单质子化（H ₂ ö ₂或（NH ₄）₂小号₂ ö ₈，Pd（II），Pt（III））（第1组）; 质子化然后脱水（AdOH，H ₂CrO ₄，HNO ₃，H ₂ SO ₄以及HVO ₃和CH ₂ O与ArH分别在57-65％和60-80％的H ₂ SO ₄中反应）（第2组）；以及更深的双重或三次质子化（Hg（II），HVO ₃和CH ₂ O与AlkH和c -AlkH在84-90％和88-93％H ₂ SO ₄中的反应）（第3组）。用于HVO ₃ –H ₂ SO ₄系统和H ₂ SO _4中的活性氧化剂本身，使用DFT B3LYP / 6-311G（d，p）量子化学方法评估了它们与2,3-二甲基丁烷反应的热化学特性，并分析了替代反应机理的可能性。