Rh. Bisby et al., TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY OF THE CARBONATE RADICAL, Journal of the Chemical Society. Faraday transactions (Print), 94(15), 1998, pp. 2069-2072
Citations number
34
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
The literature contains conflicting evidence regarding the protonation
state of the carbonate radical, a species which now appears to be of
biological significance. The time-resolved resonance Raman spectrum of
CO3.- has been observed. The radical was produced by oxidation of bic
arbonate and carbonate using sulfate radicals at pH values from 7.5 to
12.3. The resonance Raman spectrum was found to be invariant with pH
and contains a strongly polarised and intense band at 1062 cm(-1). The
spectrum is consistent with the radical having C-2v symmetry, indicat
ing some distortion from the predicted D-3h structure. The data sugges
t that the carbonate radical (CO3.-) formed by one-electron oxidation
of bicarbonate and carbonate does not undergo protonation to the conju
gate acid, HCO3., as previously suggested with a pk(a) of 9.6. Some bi
ochemical consequences of this are discussed.