Thermochemistry of Oxygen-Containing Organosilane Radicals and Uncertainty Estimations of Organosilane Group-Additivity Values,The Journal of Physical Chemistry A

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Thermochemistry of Oxygen-Containing Organosilane Radicals and Uncertainty Estimations of Organosilane Group-Additivity Values
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2021-09-24 , DOI: 10.1021/acs.jpca.1c06941
Hossein Janbazi ₁ , Christof Schulz _{2,

3} , Irenäus Wlokas _{1,

3} , Sebastian Peukert _{2,

3}

Affiliation

Si–C–H–O-containing radicals are important intermediates during the combustion and pyrolysis of precursors applied for the gas-phase synthesis of silica nanoparticles. Despite the industrial importance of silica nanoparticles, a comprehensive thermodynamics database of organosilane species is still missing. This work presents thermochemical data of 91 Si–C–H–O radical species. Quantum-chemical calculations and isodesmic reaction schemes are used to determine the standard enthalpy of formation, entropy, and heat capacities covering the 298–2000 K temperature range. In addition, 90 group-additivity values (GAVs) are calculated, which cover all relevant group increments. A combinatorial approach is used to ensure that all possible group increments are considered. The theoretically calculated species are used as a training set to derive 90 GAVs of Si–C–H–O radical species for the first time. In addition, uncertainty contributions of GAVs were estimated. These uncertainty estimates also comprise GAVs that were previously derived to compute thermochemical data of stable Si–C–H species and radicals as well as stable Si–C–H–O compounds. Therefore, uncertainty contributions of GAVs for a whole set of 243 group increments used to predict thermochemical data of Si-organic species are reported.

中文翻译：

含氧有机硅烷自由基的热化学和有机硅烷基团可加性值的不确定性估计

在用于气相合成二氧化硅纳米粒子的前体燃烧和热解过程中，含 Si-C-H-O 的自由基是重要的中间体。尽管二氧化硅纳米粒子在工业上具有重要意义，但仍然缺少有机硅烷种类的综合热力学数据库。这项工作提供了 91 种 Si-C-H-O 自由基物种的热化学数据。量子化学计算和等密度反应方案用于确定 298-2000 K 温度范围内的标准生成焓、熵和热容。此外，还计算了 90 个组可加性值 (GAV)，涵盖所有相关组增量。组合方法用于确保考虑所有可能的组增量。理论计算的物种被用作训练集，首次获得 90 个 Si-C-H-O 自由基物种的 GAV。此外，还估计了 GAV 的不确定性贡献。这些不确定性估计还包括先前用于计算稳定 Si-C-H 物质和自由基以及稳定 Si-C-H-O 化合物的热化学数据的 GAV。因此，报告了用于预测硅有机物种热化学数据的一整套 243 个组增量的 GAV 的不确定性贡献。

更新日期：2021-10-07

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