Department of Chemistry, Associate Laboratory CICECO, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal.
J Chromatogr A. 2013 May 17;1290:1-26. doi: 10.1016/j.chroma.2013.03.049. Epub 2013 Mar 27.
In this work it is presented a new model for accurate calculation of binary diffusivities (D12) of solutes infinitely diluted in gas, liquid and supercritical solvents. It is based on a Lennard-Jones (LJ) model, and contains two parameters: the molecular diameter of the solvent and a diffusion activation energy. The model is universal since it is applicable to polar, weakly polar, and non-polar solutes and/or solvents, over wide ranges of temperature and density. Its validation was accomplished with the largest database ever compiled, namely 487 systems with 8293 points totally, covering polar (180 systems/2335 points) and non-polar or weakly polar (307 systems/5958 points) mixtures, for which the average errors were 2.65% and 2.97%, respectively. With regard to the physical states of the systems, the average deviations achieved were 1.56% for gaseous (73 systems/1036 points), 2.90% for supercritical (173 systems/4398 points), and 2.92% for liquid (241 systems/2859 points). Furthermore, the model exhibited excellent prediction ability. Ten expressions from the literature were adopted for comparison, but provided worse results or were not applicable to polar systems. A spreadsheet for D12 calculation is provided online for users in Supplementary Data.
本文提出了一种新的模型，用于准确计算无限稀释于气体、液体和超临界溶剂中溶质的二元扩散系数（D12）。该模型基于 Lennard-Jones（LJ）模型，包含两个参数：溶剂的分子直径和扩散活化能。该模型具有通用性，因为它适用于极性、弱极性和非极性溶质和/或溶剂，适用于广泛的温度和密度范围。该模型通过最大的数据库进行了验证，共有 487 个系统，总计 8293 个点，涵盖了极性（180 个系统/2335 个点）和非极性或弱极性（307 个系统/5958 个点）混合物，平均误差分别为 2.65%和 2.97%。对于系统的物理状态，气态（73 个系统/1036 个点）的平均偏差为 1.56%，超临界（173 个系统/4398 个点）为 2.90%，液态（241 个系统/2859 个点）为 2.92%。此外，该模型还具有出色的预测能力。采用了文献中的 10 个表达式进行比较，但结果较差或不适用于极性系统。一个用于 D12 计算的电子表格已在补充数据中提供给用户。
