Publications [#232381] of Alvin L. Crumbliss

Journal Articles

  1. Crumbliss, AL; Lugg, PS; Childers, JW; Palmer, RA, "Fourier transform infrared photothermal spectroscopic characterization of Prussian blue surface modified electrodes. Countercation effects", The Journal of Physical ChemistryJanuary,, 1985, 89(3), 482-488, American Chemical Society (ACS) [doi].
    (last updated on 2023/06/01)

    Abstract:
    Fourier transform infrared photothermal spectroscopy was used in conjunction with cyclic voltammetry to characterize graphite electrodes which were surface modified by the deposition of an iron-containing plasma polymer or iron-containing plasma deposit followed by the electrochemical deposition of iron hexacyanoferrate. These results support the formation of surface-bound Prussian brown, Berlin green, Prussian blue, and Everitt's salt depending on the potential of the electrode and the identity of the cation of the bulk electrolyte. The electrode-surface-bound iron hexacyanoferrate acts as a zeolite in which hydrated K+ and Na+ may enter into the lattice. Hydrated Li+, which possesses a larger hydration shell, cannot enter the countercation sites associated with the low-spin iron redox couple and, having entered those sites associated with the high-spin iron redox couple, is unable to exit. The naked or unsolvated cations K+, Na+, or Li+ can enter these countercation lattice sites when the solvent is propylene carbonate. Results presented here suggest that the countercation lattice sites associated with the high-spin Fe(3+/2+) redox couple are distinguishable from the countercation cavities associated with the low-spin Fe(III/II) redox couple. © 1985 American Chemical Society.