Speciation of aqueous palladium(II) chloride solutions using optical spectroscopies

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Scientific paper

Spectroscopic measurements of palladium(II) chloride solutions have been performed under ambient to elevated temperature conditions with systematic changes in pH and [Cl -1 ]. Spectral signatures from electronic absorption spectra (Uv/Vis) and Raman vibrational spectra were determined, and these were subsequently used to systematically map out species along several paths of the predominance diagram. The species PdCl x ( H 2 O ) 4- x 2- x ( x = 2, 3, or 4) and Pd(OH) 2 were observed, along with a precipitation product formed from > 10 M [Pd 2+ ]solutions under near-neutral conditions. The elemental composition of the precipitation product was examined with a scanning electron micrograph (SEM) and was found to contain chloride as well as palladium. While sub-stoichiometric amounts of available OH - ligand produced UV/ Vis solution spectra likely to be from mixed Pd-Cl-OH species, the pH field of these species would be vanishingly small at low, geologically relevant palladium ion concentrations where [OH - ]is no longer the limiting reagent in the transformation. In mildly acidic media, where chloropalladium(II) species predominate, elevated temperatures (up to 90°C) cause lower charged palladium-chloride species to be favored, consistent with the lowered dielectric constant of water at higher temperatures.

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