Reduction of Mercury(II) by the Carbon Dioxide Radical Anion: A Theoretical and Experimental Investigation

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Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 16, Sucursal 4, 1900 La Plata, Argentina, Centro de Química Inorgánica (CEQUINOR, CONICET/UNLP), Facultad de Ciencias Exactas, Universidad Nacional de la Plata, Casilla de Correo 962, B1900AVV La Plata, Argentina, and Dipartimento di Chimica, Università della Calabria, Via P. Bucci, Cubo 14 C, 87030 Arcavacata di Rende, Italy
* To whom correspondence should be addressed. Tel.: (+54) 221 424 0172 (R.P.D.); (+54) 221 4257430/7291 (D.O.M.). Fax: (+54) 221 424 0172 (R.P.D.); (+54) 221 4254642 (D.O.M.). E-mail: [email protected] (R.P.D.); [email protected] (D.O.M.).
†INIFTA, Universidad Nacional de la Plata.
‡CEQUINOR, CONICET/UNLP, Universidad Nacional de la Plata.
§Università della Calabria (Fax: (+39) 0984 493 390).
Cite this: J. Phys. Chem. A 2010, 114, 49, 12845–12850
Publication Date (Web):November 18, 2010
Copyright © 2010 American Chemical Society
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The laser flash photolysis technique (λexc = 266 nm) was used to investigate the mechanism of the HgCl2 reduction mediated by CO2·− radicals in the temperature range 291.7−308.0 K. For this purpose, the CO2·− radicals were generated by scavenging of sulfate radicals by formic acid. The absorbance of the reduced radical of methyl viologen, a competitive scavenger of CO2·−, was monitored at 390 nm. Moreover, theoretical calculations, including solvent effects, were also performed within the framework of the density functional theory for various chemical species of Hg(I) and Hg(II) to aid in the modeling of the reaction of reduction of HgCl2 by CO2·−.

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Tables showing physicochemical analysis of the drinking water employed in the experiments shown in the inset of Figure 4, geometrical parameters of some of the species studied in the present work and their comparison with data obtained from other sources, and standard Gibbs energies of formation for selected species studied in the present work and their comparison with experimental data. This material is available free of charge via the Internet at

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