The reactions of CO.3- radicals with NO(x) radicals were studied by pulse radiolysis of deoxygenated aqueous solutions containing carbonate and nitrate ions. The .OH radicals react with carbonate to yield CO.3- and the e(aq)- reacts with nitrate to yield NO.32-, which then converts into NO.2. This conversion has a rate constant of 4.6x104 s-1 in alkaline solutions but is catalyzed by HCO3- (k=2.8x107 L mol-1 s-1). The CO.3- radicals react rapidly with both NO.32- (k=1.0x109 L mol-1 s-1) and NO2. (k=4.6x108 L mol-1 s-1). The expected combination product was short lived and was not observed on the microsecond time scale and the possible peroxynitrite product was not detected following γ-radiolysis. A similar study with solutions containing carbonate and nitrite shows that NO.22- reacts with CO.3- faster than NO.32- and NO reacts with CO.3- faster than NO.2. Copyright (C) 1999.
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