Spectroscopy of Carboxylic Acids and Nitriles

IR

The carboxyl group is associated with two characteristic infrared stretching absorptions which change markedly with hydrogen bonding. The spectrum of a CCl₄ solution of propionic acid (propanoic acid), shown below, is illustrative. Carboxylic acids exist predominantly as hydrogen bonded dimers in condensed phases. The O-H stretching absorption for such dimers is very strong and broad, extending from 2500 to 3300 cm^-1. This absorption overlaps the sharper C-H stretching peaks, which may be seen extending beyond the O-H envelope at 2990, 2950 and 2870 cm^-1. The smaller peaks protruding near 2655 and 2560 are characteristic of the dimer. In ether solvents a sharper hydrogen bonded monomer absorption near 3500 cm^-1 is observed, due to competition of the ether oxygen as a hydrogen bond acceptor. The carbonyl stretching frequency of the dimer is found near 1710 cm^-1, but is increased by 25 cm^-1 or more in the monomeric state. Other characteristic stretching and bending absorptions are marked in the spectrum.

Nitriles show a distinctive absorption for the C-N triple bond which appear near 2250 cm^-1

Figure IR17. IR spectrum of benzonitrile. Source: SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology of Japan, 14 July 2008)

Hydrogen environments adjacent to a carboxylic acid are shifted to the region of 2.5-3.0 ppm.Deshielding occurs due to the fact that the sp² hybridized carbon the the carboxylic acid is more electronegative than a sp3 hybridized carbon.