Inductive Effect Of Polar Groups On C-H And C-F Stretching Vibrations Of Alkyl And Perfluoroalkyl Groups And Its Relation To Adsorption

In a previous article1 the methyl stretching vibrations for a series of xanthates and amines were reported, and the frequency of the methyl stretching vibrations in a homologous series of the alkyl compounds were shown to decrease exponentially with chain length and approach a limiting value corresponding to that of saturated hydrocarbon beyond six or seven carbons. These observations were explained quantitatively by the theory of Goto and Takenaka2 who proposed an equation relating the frequency shifts to the inductive effect of polar groups. As a result, the alkyl groups in the shorter chain heteropolar compounds were interpreted as becoming somewhat polar, and a good correlation was observed between the CH3-stretching frequencies and such surface chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration" The substitution of fluorine atoms, the most electronegative of all atoms, for the hydrogen atoms in alkyl groups was expected to reverse the direction of the inductive effect within a heteropolar molecule, and its effect on the C-F stretching frequency shifts and on some surface chemical properties became of interest. In a recent study the C-F stretching frequencies of a series of normal perfluorocarboxylic acids and a few 1,1' -dihydroperfluoro alcohols were determined as a function of chain length and the results were compared with the corresponding hydrocarbon analogs. Furthermore, the nature of the induced polarity in the hydrocarbon and fluorocarbon groups was investigated through surface potential measurements at the interfaces of air-aqueous solutions of normal butyl alcohol and of l,l'-dihydroperfluorobutyl alcohol and through differential capacity and electrocapillary measurements at the interfaces of mercury-aqueous solutions containing the above two alcohols. Experimental Normal perfluorocarboxylic acids and 1,1' -dihydroperfluoro alcohols were provided through the courtesy of the 3M Company, St. Paul, Minnesota. Normal butyl alcohol was purchased from Distillation Product Industries, Rochester, New York. A Perkin-Elmer Model 621 infrared spectrophotometer was used to investigate the spectra in the frequency region of 1200 to 1270 cm-l with frequency scale