Effect of halogen substitution on the enthalpies of solvation and hydrogen bonding of organic solutes in chlorobenzene and 1,2-dichlorobenzene derived using multi-parameter correlations

Abstract

© 2015 Elsevier B.V. Enthalpies of solution at infinite dilution at 298 K, Δ<inf>soln</inf>H^A/Solvent, have been measured by isothermal solution calorimetry for 43 and 72 organic solutes dissolved in chlorobenzene and 1,2-dichlorobenzene, respectively. The measured Δ<inf>soln</inf>H^A/Solvent data, along with published Δ<inf>soln</inf>H^A/Solvent values taken from the published literature for solutes dissolved in both chlorobenzene solvents, were converted to enthalpies of solvation, Δ<inf>solv</inf>H^A/Solvent, using standard thermodynamic equations. Abraham model correlations were developed from the experimental Δ<inf>solv</inf>H^A/Solvent data. The best derived correlations describe the experimental gas-to-chlorobenzene and gas-to-1,2-dichlorobenzene enthalpies of solvation to within standard deviations of 1.5 kJ mol^-1 and 1.9 kJ mol^-1, respectively. Enthalpies of X-H⋯π (X - O, N, and C) hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons, etc.) with chlorobenzene and 1,2-dichlorobenzene were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the results determined using conventional methods.