CONCURRENT SOLUTION AND ADSORPTION PHENOMENA IN CHROMATOGRAPHY .3. MEASUREMENT OF FORMATION CONSTANTS OF H-BONDED COMPLEXES IN SOLUTION

A gas-liquid chromatographic method for the quantitative evaluation of the stoichiometric formation constants of H-bonded complexes in nonaqueous solution is described. Theory is developed for the situation where multiple sorption occurs and methods for correcting for surface effects are described. The theory is tested by study of systems involving individual C3-C5 alcohols and didecyl sebacate in squalane. It is established that 1:1 complexes only are formed and formation constants and associated thermodynamic parameters are presented. The data are shown to be self-consistent and to compare well with values for other systems studied spectroscopically. The results indicate a quantitative relationship between the activity coefficients of the alcohols in squalane and the corresponding formation constants. The advantages of the glpc technique are outlined.