Enthalpy of solvation correlations for organic solutes and gases dissolved in dichloromethane and 1,4-dioxane
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ORIGINAL RESEARCH
Enthalpy of solvation correlations for organic solutes and gases dissolved in dichloromethane and 1,4-dioxane Anastasia Wilson • Amy Tian • Nishu Dabadge • William E. Acree Jr. • Mikhail A. Varfolomeev • Ilnaz T. Rakipov • Svetlana M. Arkhipova • Michael H. Abraham
Received: 9 October 2012 / Accepted: 4 February 2013 Ó Springer Science+Business Media New York 2013
Abstract Enthalpies of solution at infinite dilution of 53 organic solutes in dichloromethane and 10 organic solutes in 1,4-dioxane were measured using semi-adiabatic solution calorimeter. Enthalpies of solvation for 103 organic vapors and gaseous solutes in dichloromethane and for 116 gaseous compounds in 1,4-dioxane were determined from the experimental and literature data. It is shown that an Abraham solvation equation with five descriptors can be used to correlate the experimental solvation enthalpies within standard deviations of 2.07 and 2.29 kJ mol-1 for dichloromethane and 1,4-dioxane, respectively. The derived correlations provide very accurate mathematical descriptions of the measured enthalpy of solvation data at 298 K, which in the case of 1,4-dioxane span a range of 121 kJ mol-1. Division of the experimental values into a training set and a test set shows that there is no bias in predictions, and that the predictive capability of the correlations is better than
This study is honoring Maria Victoria Roux in occasion of her retirement.
Electronic supplementary material The online version of this article (doi:10.1007/s11224-013-0233-1) contains supplementary material, which is available to authorized users. A. Wilson A. Tian N. Dabadge W. E. Acree Jr. (&) Department of Chemistry, University of North Texas, 1155 Union Circle # 305070, Denton, TX 76203-5017, USA e-mail: [email protected] M. A. Varfolomeev I. T. Rakipov S. M. Arkhipova Chemical Institute, Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia M. H. Abraham Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
3.5 kJ mol-1. Enthalpies of hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons, etc.) with 1,4-dioxane were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the available literature data. Keywords Enthalpy of solvation Enthalpy of solution Enthalpy of transfer Mathematical correlation Solvation parameter model Enthalpy of hydrogen bond
Introduction This study continues development of Abraham model correlations for describing enthalpies of solvation, Dsolv H , of organic vapors and gases into water and organic solvents [1–12]. The correlation equation for Dsolv H takes the mathematical form of [1–12]: Dsolv H ¼ cl þ el E þ sl S þ al A þ bl B þ ll L ð1Þ
Dsolv H ¼ cv þ ev E þ sv S þ av A þ bv B þ vv V ð2Þ Each term on the right-hand side of Eqs. (1) and (2) represents a different type of solute–solvent interaction contribution to the dissolution process. The upper case quantities d
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