Abstract
Photochemical redox reactions of Fe(III) complexes of polycarboxylates (e.g., citrate, malonate, oxalate) occur on time scales of minutes in sunlight and are potentially important sources of Fe(II), O2-/HO2, H2O2, and OH in atmospheric water drops and surface waters. Quantum yields for Fe(II) formation, determined from experiments and equilibrium speciation calculations, are (1) 0.28 for Fe(OH) (citrate)-at 436 nm, (2) 0.027 for Fe(malonate)2- at 366 nm, and (3) 1.0 for Fe(oxalate)3 at 436 nm. Competitive reactions of O2 and Fe(III) with the polycarboxylate radicals and/or the carbon-centered radicals derived from decarboxylation, as well as speciation of Fe(II) and Fe(III), affect the experimental quantum yields of Fe(I) formation.
Published Version
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