Unveiling the Cerium(III)/(IV) Structures and Charge-Transfer Mechanism in Sulfuric Acid
Cailin Buchanan, Dylan Herrera, Mahalingam Balasubramanian, Bryan R. Goldsmith, Nirala Singh
Abstract
CT and the observed shift in the redox potential with acid is explained by the addition of the chemical step in the CT mechanism. The fitted parameters from this rate law qualitatively agree with DFT-predicted free energies and the reorganization energy. The combination of a two-step mechanism with MT should be considered for other metal ion CT reactions whose kinetics have not been appropriately described.
Topics & Concepts
ChemistryRedoxCeriumInner sphere electron transferExtended X-ray absorption fine structureSulfuric acidElectron transferDensity functional theoryOuter sphere electron transferElectrolyteReaction mechanismInorganic chemistryPhysical chemistryComputational chemistryAbsorption spectroscopyIonElectrodeCatalysisOrganic chemistryQuantum mechanicsPhysicsElectrochemical Analysis and ApplicationsChemical and Physical Properties in Aqueous SolutionsIonic liquids properties and applications