Differences in Solvent‐Effects on the Association of Primary, Secondary, and Tertiary Alcohols

Different association-parameters of primary, secondary, and tertiary alcohols dissolved in CCl4 and C6H6 were compared with their values in cyclohexane. The parameters are the monomer-fraction α1, the fraction of the open entities relatively to the formal number of molecules σαn, o, the average degree of association of one molecule σnw, the fraction of the number of all the real entities relatively to the formal number of molecules σαn and the mean association-constants kM of a monomer to a given entity (monomer, dimer…). The experimental methods were the determination of the partition-coefficients of the alcohols between the organic solvent and water and the infra-red spectrometry. This study shows that the concurrence the solvents CCl4 and C6H5 oppose to the auto-association of the alcohols is not the same for all the alcohols. These differences in solvent-effects lead in some cases to an inversion in the sequence of the alcohols ordered after their association-parameters in benzene and in CCl4 relatively to this sequence in C6H12.