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Title: Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF3SO3 Media to 250 °C

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4]
  1. Univ. of Illinois, Champaign, IL (United States). Illinois State Water Survey
  2. Univ. of South Bohemia, Ceske Budejovice (Czech Republic). Inst. of Physics and Biophysics
  3. Texas Tech Univ., Lubbock, TX (United States). Dept. of Geosciences
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
+ Show Author Affiliations

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb+ and Na+ reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1265536
Journal Information:
Journal of Physical Chemistry. C, Vol. 119, Issue 27; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (38)

Mineral-Aqueous Solution Interfaces and Their Impact on the Environment journal October 2012
Ligand properties of surface silanol groups. I. surface complex formation with Fe3+, Cu2+, Cd2+, and Pb2+ journal May 1976
Site-binding model of the electrical double layer at the oxide/water interface
  • Yates, David E.; Levine, Samuel; Healy, Thomas W.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 70, Issue 0 https://doi.org/10.1039/f19747001807
journal January 1974
Surface ionization and complexation at the oxide/water interface journal March 1978
A comparison of electrostatic models for the oxide/solution interface journal March 1980
"In situ" ATR-Fourier transform infrared studies of the goethite (α-FeOOH)-aqueous solution interface journal March 1986
In Situ X-ray Absorption Study of Surface Complexes: Selenium Oxyanions on agr-FeOOH journal November 1987
Molecular statics calculations for iron oxide and oxyhydroxide minerals: Toward a flexible model of the reactive mineral-water interface journal May 1996
Ewald methods for polarizable surfaces with application to hydroxylation and hydrogen bonding on the (012) and (001) surfaces of α-Fe2O3 journal August 1997
Anion Adsorption on Oxide Surfaces:  Inclusion of the Water Dipole in Modeling the Electrostatics of Ligand Exchange journal January 2006
Intrinsic Proton Affinity of Reactive Surface Groups of Metal (Hydr)oxides: The Bond Valence Principle journal December 1996
A Surface Structural Approach to Ion Adsorption: The Charge Distribution (CD) Model journal May 1996
On the relationship between charge distribution, surface hydration, and the structure of the interface of metal hydroxides journal September 2006
Inner-sphere complexation of cations at the rutile–water interface: A concise surface structural interpretation with the CD and MUSIC model journal April 2009
Electric Double Layer at the Rutile (110) Surface. 1. Structure of Surfaces and Interfacial Water from Molecular Dynamics by Use of ab Initio Potentials journal August 2004
Electric Double Layer at the Rutile (110) Surface. 2. Adsorption of Ions from Molecular Dynamics and X-ray Experiments journal August 2004
Comment on Parts 1 and 2 of the Series “Electric Double Layer at the Rutile (110) Surface” journal February 2007
Electric Double Layer at the Rutile (110) Surface. 4. Effect of Temperature and pH on the Adsorption and Dynamics of Ions journal October 2013
Molecular Dynamics Simulation of the Structural and Physical Properties of the Four Polymorphs of TiO 2 journal May 1991
Potentiometric Titrations of Rutile Suspensions to 250°C journal April 1998
Potentiometric studies of the rutile–water interface: hydrogen-electrode concentration-cell versus glass-electrode titrations journal May 2002
Ion Adsorption into the Hydrothermal Regime: Experimental and Modeling Approaches book January 2006
Ion Pair Formation and Primary Charging Behavior of Titanium Oxide (Anatase and Rutile) journal February 2001
Atomic-Scale Surface Roughness of Rutile and Implications for Organic Molecule Adsorption journal May 2013
Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework journal November 2008
Modeling Water Adsorption on Rutile (110) Using van der Waals Density Functional and DFT+U Methods journal October 2013
ReaxFF Reactive Force Field Study of the Dissociation of Water on Titania Surfaces journal May 2013
Water on Titanium Dioxide Surface: A Revisiting by Reactive Molecular Dynamics Simulations journal December 2014
Comparisons of Multilayer H 2 O Adsorption onto the (110) Surfaces of α-TiO 2 and SnO 2 as Calculated with Density Functional Theory journal September 2008
Structure of rutile TiO2 (110) in water and 1molal Rb+ at pH 12: Inter-relationship among surface charge, interfacial hydration structure, and substrate structural displacements journal February 2007
On the Temperature Dependence of Intrinsic Surface Protonation Equilibrium Constants: An Extension of the Revised MUSIC Model journal July 2001
Modeling the surface complexation of calcium at the rutile-water interface to 250°C journal January 2004
Molecular dynamics simulation study of ionic hydration and ion association in dilute and 1 molal aqueous sodium chloride solutions from ambient to supercritical conditions journal September 1998
Rubidium ion hydration in ambient and supercritical water journal August 1996
Rb + and Sr 2+ Adsorption at the TiO 2 (110)−Electrolyte Interface Observed with Resonant Anomalous X-ray Reflectivity journal September 2009
Dielectric Properties of Water at Rutile and Graphite Surfaces: Effect of Molecular Structure journal February 2014
The Variable Capacitance Model: A Strategy for Treating Contrasting Charge-Neutralizing Capabilities of Counterions at the Mineral/Water Interface journal February 2014
Fits to hypernetted chain calculations for electrostatic potential and ion concentrations for use in surface complexation book January 2006

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