ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO3·-, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of FeII, MoIV, and WIV, the simple inorganic anions SO32-, ClO2-, NO2-, I-, and SCN-, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 105 to 3 × 109 M-1 s-1, the activation energies ranged from -11.4 to 18.8 kJ mol-1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550230606
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