Solution enthalpies of 1,4-dioxane: Study of solvent effects through quantitative structure–property relationships

Abstract

Solution enthalpies of 1,4-dioxane have been obtained in 15 protic and aprotic solvents at 298.15 K. Breaking the overall process through the use of Solomonov's methodology the cavity term was calculated and interaction enthalpies (Delta H-int) were determined. Main factors involved in the interaction enthalpy have been identified and quantified using a QSPR approach based on the TAKA model equation. The relevant descriptors were found to be pi* and beta, which showed, respectively, exothermic and endothermic contributions. The magnitude of pi* coefficient points toward non-specific solute-solvent interactions playing a major role in the solution process. The positive value of the beta coefficient reflects the endothermic character of the solvents' hydrogen bond acceptor (HBA) basicity contribution, indicating that solvent molecules engaged in hydrogen bonding preferentially interact with each other rather than with 1,4-dioxane. (C) 2013 Elsevier B.V. All rights reserved.

Use of quantitative structure–property relationships to study the solvation process of 18-crown-6

“…A set of 14 different solvents was chosen based on their chemical representativeness and descriptors availability, guaranteeing at the same time the absence of any intercorrelation among the above referred solvent scales, namely a, b and p* scales [8,16].…”

“…Solution enthalpies were measured at 298.15 AE 0.01 K using a Thermometric 2225 precision solution calorimeter which has been fully described elsewhere [8,[17][18][19]. All measurements were done at an average pressure of 1015.2 AE 0.2 h Pa.…”

“…These compounds are also part of a much broader class of molecules, that of cyclic ethers. In a previous paper we have discussed the solution enthalpies of one such compounds, viz., 1,4-dioxane [8]. In that work, quantitative structure-property relationships (QSPR) were used to analyze the type and magnitude of solvent effects, thus allowing a deeper and more systematic understanding of the solution process of 1,4-dioxane.…”

“…A quantitative structure-property relationship (QSPR) approach to solution enthalpies has already been thoroughly applied and discussed by us in previous works [8][9][10][11]. In all these studies the Taft-Abboud-Kamlet-Abraham -(TAKA) model equation (Eq.…”

Effect of base–acid properties of the mixtures of water with methanol on the solution enthalpy of selected cyclic ethers in this mixture at 298.15 K

“…The effects of solvent energetic and structural properties [18][19][20], solvation capabilities [21][22][23][24][25][26][27], and acid-base properties of pure and mixed solvents on chemical changes have been reported [28][29][30][31]. One of the methods in the investigation of the solvation is the study of the enthalpy of dissolution of the solute.…”