Thermochimica Acta, Vol.617, 8-20, 2015
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
Enthalpies of solution at infinite dilution at 298 K, Delta H-soln(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 Delta H-soln(A/Solvent) data, along with published Delta H-soln(A/solvent) values taken from the published literature for solutes dissolved in both chlorobenzene solvents, were converted to enthalpies of solvation, Delta H-solv(A/Solvent), using standard thermodynamic equations. Abraham model correlations were developed from the experimental Delta H-solv(A/Solvent) data. The best derived correlations describe the experimental gas-to-chlorobenzene and gas-to-1,2-dichlorobenzene enthalpies of salvation to within standard deviations of 1.5 kJ mol(-1) and 1.9 kJ mol(-1), respectively. Enthalpies of (X-H...pi(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 salvation equation. Obtained values are in good agreement with the results determined using conventional methods. (C) 2015 Elsevier B.V. All rights reserved.
Keywords:Enthalpy of solution;Enthalpy of solvation;Chlorobenzene;1,2-Dichlorobenzene;Molecular interactions;Hydrogen bonding