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Raman spectral study of ‘neat’ formic acid and aqueous and organic solutions of formic acid

✍ Scribed by R. J. Bartholomew; D. E. Irish

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
158 KB
Volume
30
Category
Article
ISSN
0377-0486

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✦ Synopsis

The Raman spectra of 'neat' formic acid and formic acid in several solvents (water, acetonitrile, 1,4dioxane and dichloromethane) were measured. In aqueous solution a very clear non-coincidence effect (NCE) indicative of resonance energy transfer was observed. The size of the NCE (ca 64 cm -1 ) indicates that strong intermolecular forces exist between the formic acid molecules, no doubt augmented by hydrogen bonding. In acetonitrile and 1,4-dioxane, two bands (at 1735 and 1765 cm -1 ) develop with dilution. The 1735 cm -1 band was assigned to 'free' formic acid monomer and the band at 1765 cm -1 to formic acid 'complexed' to the solvent. Liquid formic acid is unlike acetic acid in that it does not arrange itself into discrete, longlived dimers or polymers. It is viewed as a collection of monomeric units which interact through hydrogen bonding, thereby imposing local, short-term order in the liquid. This allows the resonance energy transfer to occur and results in a large non-coincidence effect.

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