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@ARTICLE{Rennert:53450,
      author       = {Rennert, T. and Pohlmeier, A. and Mansfeld, T.},
      title        = {{O}xidation of {F}errocyanide by {B}irnessite},
      journal      = {Environmental Science $\&$ Technology},
      volume       = {39},
      issn         = {0013-936X},
      address      = {Columbus, Ohio},
      publisher    = {American Chemical Society},
      reportid     = {PreJuSER-53450},
      pages        = {821 - 825},
      year         = {2005},
      note         = {Record converted from VDB: 12.11.2012},
      abstract     = {The Fe-CN complexes ferrocyanide, [Fe-II(CN)(6)](4-), and
                      ferricyanide, [Fe-III(CN)(6)](3-), which are contaminants in
                      soil and groundwater, form a redox couple,
                      [Fe-II(CN)(6)](4-) reversible arrow [Fe-III(CN)(6)](3-) +
                      e(-), E-H = 356 mV. We studied the oxidation of
                      [Fe-II(CN)(6)](4-) by birnessite, delta-(MnO2)-O-IV, in
                      batch experiments as influenced by [Fe-II(CN)(6)](4-)
                      concentration, pH, and reaction time. Additionally,
                      stopped-flow experiments were carried out at five
                      temperatures (10-30 degreesC) and four pH values (pH
                      4.1-5.3). In the batch experiments, [Fe-II(CN)(6)](4-) was
                      completely oxidized to [Fe-III(CN)(6)](3-), and oxidation
                      did neither depend on time for t > 2 min, nor on
                      concentration (0.12-0.47 mM), nor on pH (pH 3.3-9.9).
                      Lasting adsorption of Fe-CN complexes on the birnessite
                      surface or precipitation of manganese ferricyanide were not
                      detected. Manganous ions resulting from the reductive
                      dissolution of birnessite did not precipitate as manganese
                      oxide because an identical decrease of Mn solution
                      concentrations was observed under air and under a N-2
                      atmosphere. Two processes were detected by the stopped-flow
                      experiments. The first rapid one with an activation energy
                      of approximately 60 kJ mol(-1) was attributed to short-term
                      adsorption and simultaneous oxidation of [Fe-II(CN)(6)](4-)
                      on the birnessite surface. The second slower process with an
                      activation energy of approximately 20 kJ mol(-1) was
                      attributed most probably to diffusion of the reaction
                      product Mn2+ into the interior of the birnessite, which
                      creates fresh reaction sites at the outer surface.},
      keywords     = {J (WoSType)},
      cin          = {ICG-IV},
      ddc          = {050},
      cid          = {I:(DE-Juel1)VDB50},
      pnm          = {Chemie und Dynamik der Geo-Biosphäre},
      pid          = {G:(DE-Juel1)FUEK257},
      shelfmark    = {Engineering, Environmental / Environmental Sciences},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000226712600030},
      doi          = {10.1021/es040069x},
      url          = {https://juser.fz-juelich.de/record/53450},
}