Infrared Study of Solute/Solvent Interactions between Separate Chloroform Solutions of Alkanes,Cycloalkanes,Alkenes,Cycloalkenes,Cyclohexadienes,Benzene,and Carbon Tetrachloride

Abstract

The intermolecular deuteron bonds formed between Cl₃CD and ClCCl₃, are stronger than between Cl₃CD and ClCCl₂D, since the Cl atoms of CCl₄, are more basic than Cl atoms for CDCl₃. The n-alkanes act as a diluent for CDCl₃ molecules, and the strength of the intermolecular proton bond in (Cl₃CD:ClCCl₂D) _n complexes increases as n becomes larger. Solvent density also plays an important role in solute/solvent interaction. Increased solvent density causes the CD:Cl or CD:π (of C=C group) intermolecular bond distance to decrease, causing the bond to be stronger. A repulsion exists between the intermolecular π electron system of benzene, 1,3-cyclohexadiene, or 1,4-cyclohexadiene and the chlorine atom δ electrons of CDCl₃, and this repulsive effect is a factor in establishing the equilibrium intermolecular bond distance formed between the CD:π bonds of benzene (or cyclohexadienes) and the proton of CDCl₃. These conclusions are based on the study of the _v CD, _v C=C, and _v (C=C)₂ frequencies vs. mole % CDCl₃ (or CHCl₃)/solvent system.