Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

doi:10.1016/0016-7037(92)90217-7

Geochimica et Cosmochimica Acta

Volume 56, Issue 4, April 1992, Pages 1471-1483

https://doi.org/10.1016/0016-7037(92)90217-7 Get rights and content

Abstract

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (V^IV) and vanadium[V] (V^V) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions.

Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of V^IV to V^III H₂S were studied. Although H₂S is predicted from thermodynamic data to be capable of reducing V^IV to V^III, this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45°C), pH (3.6–6.8), ionic strength (0.05–0.1 m), and V concentrations (9.8–240 μmolar) likely to be found in nature. Because the reaction is very slow, H₂S concentrations in excess of natural conditions were used (8.1 × 10⁻⁴ to 0.41 atm). The results show that V^IV is reduced to V^III under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species.

The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, V^III. Because of the insolubility of V^III oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H₂S during mineralization. The experiments described here show that H₂S could have reduced V^IV to V ^III, and thus led to the formation of these deposits.

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Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

Abstract

Chem. Geol.

Polyhedron

Inorg. Chim. Acta

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Geoderma

Geochim. Cosmochim. Acta

Inorg. Chim. Acta

J. Inorg. Nucl. Chem.

J. Inorg. Nucl. Chem.

Geochim. Cosmochim. Acta

Talanta

Chem. Geol.

The stability of metal halide complexes in aqueous solution IV. The fluoride and chloride complexes of the vanadyl ion, VO2+

Acta Chem. Scand.

The Hydrolysis of Cations

Heats of dilution and the thermodynamics of dissociation of uranyl and vanadyl sulfates

J. Phys. Chem.

The electronic structure of the vanadyl ion

Inorg. Chem.

The mobilization and fixation of molybdenum, vanadium, and uranium by decomposing plant matter

J. Soil Sci.

Termoquimica de reacciones de disolucion II.4 Hidrolisis del ion V3+ (25°C, KC1 3M)

Anales de Quimica

Elemental, isotopic, and mineralogic distributions within a tabular-type uranium-vanadium deposit, Henry Mountains mineral belt, Garfield County, Utah

The constitution of the pentavalent vanadium ion in acid solution

J. Amer. Chem. Soc.

Oxidation of aqueous sulfideby O2: 1. General characteristics and catalytic influences

Kinetics of oxidation of aqueous sulfide by O2

Environ. Sci. Tech.

Vanadium

The reduction potential of vanadic acid to vanadyl ion in hydrochloric acid solutions

J. Amer. Chem. Soc.

Contribution a l'etude des ions des valences quatre et cinq du vanadium

Ann. de Chim. 12th Series

Multicomponent polyanions. 40. A potentiometric and 51V NMR study of equilibria in the H+-H2VO4−-C2O42− system in 0.6 M Na(Cl) medium

Acta Chem. Scand.

Multicomponent polyanions. 43. A study of aqueous equilibria in the vanadocitrate system

Acta Chem. Scand.

The crystal structure of montroseite, a vanadium member of the diaspore group

Amer. Mineral.

A crystal chemical study of montroseite and paramontroseite

Amer. Mineral.

Some thermodynamic relations among the vanadium oxides, and their relation to the oxidation state of the uranium ores of the Colorado Plateaus

Amer. Mineral.

Solutions, Minerals, and Equilibria

Origin of coffinite in sedimentary rocks by a sequential adsorption-reduction mechanism

Bull. Minéral.

Genesis of the tabular-type vanadium-uranium deposits of the Henry basin, Utah—A reply

Econ. Geol.

Genetic implications of the geochemistry of vanadium-uranium deposits in the Colorado Plateau region (abs.)

Hydrolysis of the oxovanadium(IV) ion and the stability of its complexes with the 1,2-dihydroxybenzenato (2—) ion

J. Chem. Soc. Dalton Trans.

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Chem. Rev.

The stability of metal halide complexes in aqueous solution IV. The fluoride and chloride complexes of the vanadyl ion, VO²⁺

Termoquimica de reacciones de disolucion II.4 Hidrolisis del ion V³⁺ (25°C, KC1 3M)

Oxidation of aqueous sulfideby O₂: 1. General characteristics and catalytic influences

Kinetics of oxidation of aqueous sulfide by O₂

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