Experimental determination of the hydrolysis constants of Pt sup 2+ and Pd sup 2+ at 25C from the solubility of Pt and PD in aqueous hydroxide solutions

Journal Article · Mon Jul 01 04:00:00 EDT 1991 · Geochimica et Cosmochimica Acta; (United States)

DOI:https://doi.org/10.1016/0016-7037(91)90021-V· OSTI ID:5862793

Wood, S A ^[1]

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1. McGill Univ., Montreal, Quebec (Canada)

The solubilities of Pt and Pd metal were measured at 25C in 10{sup {minus}4} to 10.0 molal NaOH solutions under a reduced oxygen atmosphere in order to determine the stoichiometry and stability constants for Pt and Pd hydroxide complexes. Equilibration times of over one year were employed. The Pd data are consistent with the existence of Pd(OH){sub 2}{sup 0}(aq) from pH 9 to 12 and Pd(OH){sub 3}{sup {minus}} from pH 12 to 15.5. No conclusive evidence for a Pd(OH){sub 4}{sup 2{minus}} complex was obtained, but the data do not preclude its existence at high pH. For Pt, the data are consistent with a single complex for pH = 9 to 15.5, i.e., Pt(OH){sub 2}{sup 0}(aq). A graphical treatment of the data yields the following cumulative stability constants: log {beta}{sub 2} = 18.9 {plus minus} 1.0 and log {beta}{sub 3} = 20.9 {plus minus} 1.0 for Pd and log {beta}{sub 2} = 29.9 {plus minus} 1.0 for Pt. The stepwise stability constant for Pd(OH){sub 3}{sup {minus}} log K{sub 3} = 2.0 is in relatively good agreement with that derived from data in the literature (log K{sub 3} = 1.8). However, the cumulative stability constants for Pd measured in this work are considerably smaller than those reported in the literature. The log{beta}{sub 2} = 29.9 {plus minus} 1.0 value measured for Pt compares relatively well with a theoretically estimated value of 28.3. The data suggest that the predominant inorganic form of Pt and Pd in freshwaters may be the neutral hydroxide species. In seawater, the hydroxide complex of Pt is also predicted to predominate over the chloride complex, but, in the case of Pd, the hydroxide complex appears to be less stable and it is presently not clear whether the chloride or the hydroxide complex will predominate. In fluids responsible for serpentinization, Pt and Pd may also be mobilized as hydroxide complexes.

• OSTI ID: 5862793
• Journal Information: Geochimica et Cosmochimica Acta; (United States), Journal Name: Geochimica et Cosmochimica Acta; (United States) Vol. 55:7; ISSN GCACA; ISSN 0016-7037
• Country of Publication: United States
• Language: English

Related Subjects

58 GEOSCIENCES
580000* -- Geosciences
ALKALI METAL COMPOUNDS
AQUEOUS SOLUTIONS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
DISPERSIONS
DISSOLUTION
ELEMENTS
EQUILIBRIUM
GEOCHEMISTRY
HYDROGEN COMPOUNDS
HYDROLYSIS
HYDROXIDES
IONIC COMPOSITION
LYSIS
METALS
MIXTURES
OXYGEN COMPOUNDS
PALLADIUM
PALLADIUM COMPOUNDS
PALLADIUM HYDROXIDES
PH VALUE
PHYSICAL PROPERTIES
PLATINUM
PLATINUM COMPOUNDS
PLATINUM HYDROXIDES
PLATINUM METALS
PRECIPITATION
SEPARATION PROCESSES
SODIUM COMPOUNDS
SODIUM HYDROXIDES
SOLUBILITY
SOLUTIONS
SOLVOLYSIS
STABILITY
STOICHIOMETRY
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS