authors |
Lito, PF; Magalhaes, AL; Gomes, JRB; Silva, CM |
nationality |
International |
journal |
JOURNAL OF CHROMATOGRAPHY A |
author keywords |
Diffusion coefficient; Modeling; Non-polar systems; Polar systems; Transport properties; Universal model |
keywords |
TAYLOR DISPERSION TECHNIQUE; HIGH-TEMPERATURE DIFFUSION; FLUID CHROMATOGRAPHY SFC; IMPULSE-RESPONSE METHOD; LENNARD-JONES FLUID; LIMITING INTERDIFFUSION COEFFICIENTS; SLIGHTLY SOLUBLE GASES; PARTIAL MOLAR VOLUMES; HARD-SPHERE THEORY; ALPHA-AMINO-ACIDS |
abstract |
In this work it is presented a new model for accurate calculation of binary diffusivities (D-12) 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 D-12 calculation is provided online for users in Supplementary Data. (C) 2013 Elsevier B.V. All rights reserved. |
publisher |
ELSEVIER SCIENCE BV |
issn |
0021-9673 |
year published |
2013 |
volume |
1290 |
beginning page |
1 |
ending page |
26 |
digital object identifier (doi) |
10.1016/j.chroma.2013.03.049 |
web of science category |
Biochemical Research Methods; Chemistry, Analytical |
subject category |
Biochemistry & Molecular Biology; Chemistry |
unique article identifier |
WOS:000318377600001
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