HR: 08:30h
AN: U51C-02    [Abstracts]
TI: Kinetics of Reductive Dissolution: Influence of Nanoparticle Size and Aluminum Doping on Ferrihydrite Reactivity
AU: * Penn, R L
EM: penn@chem.umn.edu
AF: University of Minnesota, Department of Chemistry, 207 Pleasant St. SE, Minneapolis, MN 55455, United States
AU: Erbs, J J
EM: erbs@chem.umn.edu
AF: University of Minnesota, Department of Chemistry, 207 Pleasant St. SE, Minneapolis, MN 55455, United States
AU: Jentzsch, T L
EM: jentzsch@chem.umn.edu
AF: University of Minnesota, Department of Chemistry, 207 Pleasant St. SE, Minneapolis, MN 55455, United States
AB: The composition and size of iron oxide nanoparticles in natural systems varies considerably. Here, we present results examining the influence of size, and aluminum and arsenic doping on the redox reactivity of iron oxide (ferrihydrite and magnetite) nanoparticles as determined from kinetic studies using either hydroquinone as a reductant or benzoquinone as an oxidant. Variable-temperature experiments are used to determine activation energies and frequency factors so as to quantitatively compare reactivities of the nanoparticles as a function of varying composition and size. Results show that surface-area normalized rate constants for reductive dissolution of ferrihydrite and for oxidation of magnetite decrease with increasing size. Interestingly, aluminum doping results in increased reactivity in the ferrihydrite system whereas aluminum doping in the magnetite system results in substantially depressed reactivity. Finally, variations in reactivity as a result of arsenic doping are strongly dependent upon the preparation method. Ferrihydrite prepared by coprecipitation with arsenate exhibit enhanced reactivity, while particles equilibrated with solutions containing arsenate exhibit decreased reactivity. The impact of small changes in synthetic and storage procedures will also be specifically addressed.
DE: 1030 Geochemical cycles (0330)
DE: 1042 Mineral and crystal chemistry (3620)
SC: Union [U]
MN: 2007 Joint Assembly