title: Kinetic isotope effects in complex reaction networks: formic acid electro-oxidation.
abstract: The determination of kinetic isotope effects (KIEs) for different reaction pathways and steps in a complex reaction network, where KIEs may affect the overall reaction in various different ways including dominant and minority pathways or the buildup of a reaction-inhibiting adlayer, is demonstrated for formic acid electrooxidation on a Pt film electrode by quantitative electrochemical in situ IR spectroscopic measurements under controlled mass-transport conditions. The ability to separate effects resulting from different contributions--which is not possible using purely electrochemical kinetic measurements--allows conclusions on the nature of the rate-limiting steps and their transition state in the individual reaction pathways. The potential-independent values of approximately 1.9 for the KIE of formic acid dehydration (CO(ad) formation) in the indirect pathway and approximately 3 for the CO(ad) coverage-normalized KIE of formic acid oxidation to CO2 (direct pathway) indicate that 1) C-H bond breaking is rate-limiting in both reaction steps, 2) the transition states for these reactions are different, and 3) the configurations of the transition states involve rather strong bonds to the transferred D/H species, either in the initial or in the final state, for the direct pathway and--even more pronounced--for formic acid dehydration (CO(ad) formation).
authors.affiliation: Department of Surface Chemistry and Catalysis, University of Ulm, 89069 Ulm, Germany. yachen@ustc.edu.cn
authors.forename: Yan-Xia
authors.initials: YX
authors.lastname: Chen
authors.forename: Martin
authors.initials: M
authors.lastname: Heinen
authors.forename: Zenonas
authors.initials: Z
authors.lastname: Jusys
authors.forename: Rolf Jürgen
authors.initials: RJ
authors.lastname: Behm