Journal of Physical Chemistry B, Vol.105, No.2, 520-526, 2001
Cavity formation and dipolar contribution to the gauche-trans isomerization of 1-chloropropane and 1,2-dichloroethane
The effects of pressure and temperature on the gauche-trans conformational equilibrium of 1-chloropropane and 1,2-dichloroethane dissolved in diethyl ether (ethoxyethane) are measured using Raman spectroscopy and analyzed using thermodynamic perturbation theory. The effects of solvation on the isomerization equilibrium, monitored using the C-Cl stretch band intensities of the two conformers, are interpreted as a sum of intermolecular attractive and repulsive solute-solvent interactions. A perturbative analysis of the isomerization enthalpy, DeltaH, and volume, DeltaV, is used to extract repulsive cavity formation and attractive mean field solvation contributions to the conformational equilibrium. Comparison of the thermodynamics of the two solutes with each other, and with previous gas phase and solution results, are used to confirm the self-consistency of the perturbative modeling strategy and to quantify dipolar contributions to the gauche-trans isomerization process.