Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

Peiming Wang; Leslie L. Wilson; David J. Wesolowski; Jörgen Rosenqvist; Andrzej Anderko

doi:10.1016/j.corsci.2010.01.032

Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

Peiming Wang
, Leslie L. Wilson
, David J. Wesolowski
, Jörgen Rosenqvist
, Andrzej Anderko

Nanofabrication Research Laboratory

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO₂ has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl²⁺) and hydrolyzed species (MoOH²⁺, Mo(OH)₂⁺, and Mo(OH)₃⁰) in addition to the Mo³⁺ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.

Original language	English
Pages (from-to)	1625-1634
Number of pages	10
Journal	Corrosion Science
Volume	52
Issue number	5
DOIs	https://doi.org/10.1016/j.corsci.2010.01.032
State	Published - May 2010

Funding

The financial support of this work from the Science & Technology Program of the Office of Science and Technology and International (OST&I), Office of Civilian Radioactive Waste Management (OCRWM), US Department of Energy (DOE) is gratefully acknowledged. The experimental work was conducted by LLW, DJW, and JR at Oak Ridge National Laboratory, which is managed and operated by UT Battelle, LLC, under contract DE-AC05-00OR22725 for the US Department of Energy. The interactions among investigators in the OST&I Materials Performance Thrust are appreciated and gratefully acknowledged.

Keywords

B. Electrochemical calculation
B. Modeling studies
C. Thermodynamic diagrams

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10.1016/j.corsci.2010.01.032

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title = "Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion",

abstract = "To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO2 has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl2+) and hydrolyzed species (MoOH2+, Mo(OH)2+, and Mo(OH)30) in addition to the Mo3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.",

keywords = "B. Electrochemical calculation, B. Modeling studies, C. Thermodynamic diagrams",

author = "Peiming Wang and Wilson, \{Leslie L.\} and Wesolowski, \{David J.\} and J{\"o}rgen Rosenqvist and Andrzej Anderko",

year = "2010",

month = may,

doi = "10.1016/j.corsci.2010.01.032",

language = "English",

volume = "52",

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TY - JOUR

T1 - Solution chemistry of Mo(III) and Mo(IV)

T2 - Thermodynamic foundation for modeling localized corrosion

AU - Wang, Peiming

AU - Wilson, Leslie L.

AU - Wesolowski, David J.

AU - Rosenqvist, Jörgen

AU - Anderko, Andrzej

PY - 2010/5

Y1 - 2010/5

N2 - To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO2 has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl2+) and hydrolyzed species (MoOH2+, Mo(OH)2+, and Mo(OH)30) in addition to the Mo3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.

AB - To investigate the behavior of molybdenum dissolution products in systems that approximate localized corrosion environments, solubility of Mo(III) in equilibrium with solid MoO2 has been determined at 80 °C as a function of solution acidity, chloride concentration and partial pressure of hydrogen. The measurements indicate a strong increase in solubility with acidity and chloride concentration and a weak effect of hydrogen partial pressure. The obtained results have been combined with literature data for systems containing Mo(III), Mo(IV), and Mo(VI) in solutions to develop a comprehensive thermodynamic model of aqueous molybdenum chemistry. The model is based on a previously developed framework for simulating the properties of electrolyte systems ranging from infinite dilution to solid saturation or fused salt limit. To reproduce the measurements, the model assumes the presence of a chloride complex of Mo(III) (i.e., MoCl2+) and hydrolyzed species (MoOH2+, Mo(OH)2+, and Mo(OH)30) in addition to the Mo3+ ion. The model generally reproduces the experimental data within experimental scattering and provides a tool for predicting the phase behavior and speciation in complex, concentrated aqueous solutions. Thus, it provides a foundation for simulating the behavior of molybdenum species in localized corrosion environments.

KW - B. Electrochemical calculation

KW - B. Modeling studies

KW - C. Thermodynamic diagrams

UR - https://www.scopus.com/pages/publications/77949310485

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DO - 10.1016/j.corsci.2010.01.032

M3 - Article

AN - SCOPUS:77949310485

SN - 0010-938X

VL - 52

SP - 1625

EP - 1634

JO - Corrosion Science

JF - Corrosion Science

IS - 5

ER -

Solution chemistry of Mo(III) and Mo(IV): Thermodynamic foundation for modeling localized corrosion

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