Journal of Chemical Thermodynamics, Vol.33, No.5, 565-579, 2001
(Solid plus liquid) equilibria, i.r., and semi-empirical studies of carbazole with selected tertiary amides
(Carbazole+tert-amide) systems were investigated through measurement of (solid + liquid) equilibria (s.l.e.) i.r. study, and semi-empirical calculations. The s.l.e. studies included three systems, namely (carbazole + tetramethylurea, or N, N-diphenylacetamide, or N-acetylcarbazole). In spite of the identical tertiary N-atom, and C=O group occurring in each studied amide assumed to dominate molecular interactions, the liquidus curves have revealed the presence of a hydrogen-bond complex only in the first system. The remaining two are simple eutectic systems, probably owing to sterical hindrance exhibited by large substituents. Each system, as well as (carbazole + N,N-dimethylformamide) were studied using i.r. spectroscopy in 1,1,2,2-tetrachloroethene solutions. In contrast to s.l.e. data, hydrogen-bond formation manifested itself in each system studied by the i.r. method. The enthalpy of complex formation was determined from the spectroscopic data for each system except for (carbazole + N-acetylcarbazole). The i.r. studies were supported by semi-empirical calculations performed for the optimized hydrogen-bond geometries.