Investigation of the Association of Alcohols and Phenols by the NMR Method

Abstract

A.I.Brodskii (deceased), V.D.Pokhodenko, and V.S.KutsThe review discusses and analyses the literature on the study of the association of alcohols and phenols by the NMR method. The methods for the determination of the equilibrium constants and heats and entropies of formation of the association complexes of the above substances in both inert and basic solvents are described for equilibria of different types. The polar and steric effects of the substituents in alcohols and phenols on the thermodynamic functions for the formation of self-association complexes and also of association complexes with polar molecules has been analysed. The bibliography comprises 151 references. CONTENTS

Dielectric studies of molecular association. Concentration dependence of dipole moment of 1-octanol in solution

“…For example, if we consider a monomer-dimer-trimer equilibrium, we may write 2(monomer) -* dimer 3 (monomer) -trimer with corresponding equilibrium constants, K2 and K3. From this may be developed3 µ 2 = ~[c^i2 + 2µ22 + 3µ32] (4) or µ* 2 = ~[c^i2 + 2K2c2g^iJ + 2K2Cy,g^2} (5) where subscripts 1, 2, and 3 refer to monomer, dimer, and trimer, respectively, c,• represents the concentration of these species, and c the total alcohol concentration. From the mass balance c = ct + 2cz + 3c3 = ct + 2K2c2 + SK2c2 (6) For any general model these equations have the form18 µ 2 = 7 ( )^ µ2 We may use eq 7 and 8 to obtain values for the K's and jit's by a least-squares method.…”