Sharma Shrinjay, Sleijfer Josh J, Op de Beek Jeroen, van der Zeeuw Stach, Zorzos Daniil, Lasala Silvia, Rigutto Marcello S, Zuidema Erik, Agarwal Umang, Baur Richard, Calero Sofia, Dubbeldam David, Vlugt Thijs J H
Engineering Thermodynamics, Process & Energy Department, Faculty of Mechanical Engineering, Delft University of Technology, Leeghwaterstraat 39, 2628CB Delft, The Netherlands.
Delft Institute of Applied Mathematics, Faculty of Electrical Engineering, Mathematics and Computer Science, Delft University of Technology, Mekelweg 4, 2628CD Delft, The Netherlands.
J Phys Chem B. 2024 Oct 3;128(39):9619-9629. doi: 10.1021/acs.jpcb.4c05355. Epub 2024 Sep 22.
Linear regression (LR) is used to predict thermochemical properties of alkanes at temperatures (0-1000) K to study chemical reaction equilibria inside zeolites. The thermochemical properties of C until C isomers reported by Scott are used as training data sets in the LR model which is used to predict these properties for alkanes longer than C isomers. Second-order groups are used as independent variables which account for the interactions between the neighboring groups of atoms. This model accurately predicts Gibbs free energies, enthalpies, Gibbs free energies of formation, and enthalpies of formation for alkanes which exceeds the chemical accuracy of 1 kcal/mol and outperforms the group contribution methods developed by Benson et al., Joback and Reid, and Constantinou and Gani. Predictions from our model are used to compute the reaction equilibrium distribution of hydroisomerization of C and C isomers in MTW-type zeolite. Calculation of reaction equilibrium distribution inside zeolites also requires Henry coefficients of the isomers which can be computed using classical force field-based molecular simulations using the RASPA2 software for which we created an automated workflow. The reaction equilibrium distribution for C isomers obtained using the LR model and the training data set for this model are in very good agreement. The tools developed in this study will enable the computational study of hydroisomerization of long-chain alkanes (>C).
线性回归（LR）用于预测温度范围为（0 - 1000）K的烷烃的热化学性质，以研究沸石内部的化学反应平衡。斯科特报告的C直至C异构体的热化学性质被用作LR模型中的训练数据集，该模型用于预测比C异构体更长的烷烃的这些性质。二阶基团用作自变量，以说明相邻原子基团之间的相互作用。该模型能准确预测烷烃的吉布斯自由能、焓、生成吉布斯自由能和生成焓，其精度超过了1 kcal/mol的化学精度，并且优于本森等人、乔巴克和里德以及康斯坦丁努和加尼开发的基团贡献法。我们模型的预测结果用于计算MTW型沸石中C和C异构体加氢异构化的反应平衡分布。计算沸石内部的反应平衡分布还需要异构体的亨利系数，这可以使用基于经典力场的分子模拟通过RASPA2软件来计算，为此我们创建了一个自动化工作流程。使用LR模型获得的C异构体的反应平衡分布与该模型的训练数据集非常吻合。本研究中开发的工具将有助于对长链烷烃（>C）的加氢异构化进行计算研究。
