Enthalpies of hydrogen bond formation of 1-octanol with aprotic organic solvents. A comparison of the solvation enthalpy, pure base, and non-hydrogen-bonding baseline methods

Abstract

Enthalpies of solution (ΔHs) of 1-octanol and five model compounds (di-n-butyl ether, n-heptyl methyl ether, 1-fluoro-octane, 1-chlorooctane, and n-octane) have been determined in 13 solvents (heptane, cyclohexane, CCl4, 1,1,1-trichloro-ethane, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to calculate the enthalpy of hydrogen bond formation (ΔHh) of 1-octanol with each solvent, using the pure base (PB), solvation enthalpy (SE), and non-hydrogen-bonding baseline (NHBB) methods. Evidence is presented suggesting that (a) the SE method is susceptible to mismatches of the 1-octanol vs. model polar and dispersion interactions, (b) the PB method is sensitive to polar interaction mismatches, whereas (c) the NHBB method compensates for both polar and dispersion interactions mismatches. The (apparent) ΔHh values determined by the SE and PB methods may be as much as several kcal/mol (nearly 50%) too large, because of the inclusion of other polar and dispersion interactions. The NHBB method is therefore preferred for determining enthalpies of H-bond formation from calorimetric data. However, apparent ΔHh values from the SE and PB methods can be incorporated into total solvatochromic equations using Taft–Kamiet π*, β, and ξ parameters, to provide enthalpies of H-bond formation in good agreement with ΔHh (NHBB).