New empirical correlations for the prediction of critical properties and acentric factor of S-containing compounds

In the present study, simple empirical correlations have been developed to estimate the critical properties (<i>i.e.</i> T_C, P_C, and V_C) and acentric factor (ω) of S-containing compounds. The variables of correlations are a set of simple parameters, including normal boiling point temperature (T_b), molecular weight (MW), and the number of atoms and bonds. A comprehensive dataset containing more than 130 S-containing compounds, including thiophenes, sulfides, mercaptans, siloxanes, and others, has been used for the model development. The parameter selection of the models has been carried out using the Enhanced Replacement Method. Two specific linear and non-linear models have been separately developed for each critical property and ω. The genetic programming method was applied for the development of the non-linear model. Statistical evaluation of the developed models confirmed the satisfactory capability of the models to predict the critical properties and ω of new compounds. Indeed, the values of the coefficient of determination (R²) of the non-linear models for T_C, P_C, V_C, and ω were 0.9690, 0.9076, 0.9890, and 0.9467, respectively. In addition, the values of the average absolute relative deviation (AARD%) of the non-linear models for T_C, P_C, V_C, and ω were 2.1677, 7.8375, 3.8919, and 9.9344, respectively.

本研究针对含硫化合物开发了简易经验关联式，用以估算其临界性质（critical properties，即临界温度Tc、临界压力Pc与临界体积Vc）以及偏心因子（acentric factor，ω）。关联式的输入变量为一组简易参数，包括正常沸点温度（normal boiling point temperature，Tb）、分子量（molecular weight，MW）以及原子数与键数。模型构建所采用的综合数据集涵盖130余种含硫化合物，包含噻吩类、硫化物、硫醇类、硅氧烷类及其他类型含硫化合物。模型的参数筛选环节采用增强替换法（Enhanced Replacement Method）完成。针对每一项临界性质与偏心因子，分别构建了特定的线性与非线性模型；其中非线性模型的构建借助遗传编程（genetic programming）方法实现。对所构建模型的统计评估结果证实，上述模型对新化合物的临界性质与偏心因子具备良好的预测能力。具体而言，针对临界温度、临界压力、临界体积及偏心因子的非线性模型，其决定系数（coefficient of determination，R²）分别为0.9690、0.9076、0.9890与0.9467。此外，该类非线性模型的平均绝对相对偏差（average absolute relative deviation，AARD%）分别为2.1677%、7.8375%、3.8919%与9.9344%。