New approach to IR study of monomer-dimer self-association: 2,2-dimethyl-3-ethyl-3-pentanol in tetrachloroethylene as an example

Abstract

The dimerization of 2,2-dimethyl-3-ethyl-3-pentanol in tetrachloroethylene in the diluted region has been studied at four temperatures by IR spectroscopy. The aforementioned solute compound is chosen because self-association beyond dimerization is hampered by the steric hindrance generated by the bulky sidechains. The integrated absorbances of the monomer bands were treated based on Eq. (9) to obtain its molar absorptivity and dimerization constant. The same dimerization constant as well as the molar absorptivity of dimer band can be obtained based on Eq. (13) from the data treatment of the integrated absorbances of the dimer band. The disparity between two values of dimerization constant determined by two independent sources offers an opportunity to check the consistency of the determination. The standard enthalpy and entropy of dimerization have also been calculated by means of van't Hoff plot, respectively, from the data of temperature-dependent dimerization constants obtained from the monomer bands and dimer bands. (C) 2003 Elsevier B.V. All rights reserved.