Kinetics of the Temperature-Dependent eaq- and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

Conrad, Jacy K.; Lisouskaya, Aliaksandra; Mezyk, Stephen P.; Bartels, David M.

doi:10.1002/cphc.202300465

Kinetics of the Temperature-Dependent e_aq^- and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

Journal Article · Wed Oct 25 00:00:00 EDT 2023 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202300465· OSTI ID:2228293

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Idaho National Laboratory (INL), Idaho Falls, ID (United States)
University of Notre Dame, IN (United States). Notre Dame Radiation Laboratory (NDRL)
California State Univ. (CalState), Long Beach, CA (United States)

The reactivity of chromium(III) species with the major oxidizing and reducing radiolysis products of water was investigated in aqueous solutions at temperatures up to 150 °C. The reaction between the hydrated electron (e_aq^-) and Cr(III) species showed a positive temperature dependence over this temperature range. The reaction was also studied in pH 2.5 and 3.5 solutions for the first time. This work also studied the reaction between acidic Cr(III) species and the hydroxyl radical (·OH). It was found that Cr³⁺ did not react significantly with the ·OH radical, but the first hydrolysis species, Cr(OH)²⁺, did with a rate coefficient of k= (7.2±0.3)×10⁸ M^-1 s^-1 at 25 °C. The oxidation of Cr(OH)²⁺ by the ·OH radical formed an absorbing product species that ultimately oxidized to give Cr(VI). In conclusion, these newly measured reaction rates allow for the development of improved models of aqueous chromium speciation for the effective remediation of liquid high-level nuclear waste via vitrification processes.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States); University of Notre Dame, IN (United States). Notre Dame Radiation Laboratory (NDRL)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC07-05ID14517; FC02-04ER15533

OSTI ID:: 2228293

Alternate ID(s):: OSTI ID: 2234331

Report Number(s):: INL/JOU--23-72230-Rev001

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 24 Vol. 24; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

Hydrolysis of Metal Ions Brown, Paul L.; Ekberg, Christian https://doi.org/10.1002/9783527656189	book	March 2016
Chromium in Environment, Its Toxic Effect from Chromite-Mining and Ferrochrome Industries, and Its Possible Bioremediation Coetzee, Johan J.; Bansal, Neetu; Chirwa, Evans M. N. Exposure and Health, Vol. 12, Issue 1 https://doi.org/10.1007/s12403-018-0284-z	journal	July 2018
SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000°C Johnson, James W.; Oelkers, Eric H.; Helgeson, Harold C. Computers & Geosciences, Vol. 18, Issue 7 https://doi.org/10.1016/0098-3004(92)90029-Q	journal	August 1992
The oxidation of chromium(III) by hydroxyl radical in alkaline solution. A stopped-flow and pre-mix pulse radiolysis study Zhao, Zhongwei; Rush, James D.; Holcman, Jerzy Radiation Physics and Chemistry, Vol. 45, Issue 2 https://doi.org/10.1016/0969-806X(94)E0011-7	journal	February 1995
Multiple time scales in pulse radiolysis. Application to bromide solutions and dipeptides Hug, Gordon L.; Wang, Yicheng; Schöneich, Christian Radiation Physics and Chemistry, Vol. 54, Issue 6 https://doi.org/10.1016/S0969-806X(98)00303-X	journal	June 1999
Temperature dependence of hydroxyl radical reactions with chloramine species in aqueous solution Gleason, Jamie M.; McKay, Garrett; Ishida, Kenneth P. Chemosphere, Vol. 187 https://doi.org/10.1016/j.chemosphere.2017.08.053	journal	November 2017
Reaction rates of the hydrated electron with N2O in high temperature water and potential surface of the N2O− anion Takahashi, Kenji; Ohgami, Shintaro; Koyama, Yasushi Chemical Physics Letters, Vol. 383, Issue 5-6 https://doi.org/10.1016/j.cplett.2003.11.050	journal	January 2004
A laboratory study of the oxidation of non toxic Cr(III) to toxic Cr(VI) by OH• free radicals in simulated atmospheric water droplets conditions: Potential environmental impact Djouider, Fathi; Hussain, Ahmad Journal of Hazardous Materials, Vol. 276 https://doi.org/10.1016/j.jhazmat.2014.05.004	journal	July 2014
Low LET radiolysis escape yields for reducing radicals and H2 in pressurized high temperature water Sterniczuk, Marcin; Yakabuskie, Pamela A.; Wren, J. Clara Radiation Physics and Chemistry, Vol. 121 https://doi.org/10.1016/j.radphyschem.2015.12.007	journal	April 2016
Review of the Scientific Understanding of Radioactive Waste at the U.S. DOE Hanford Site Peterson, Reid A.; Buck, Edgar C.; Chun, Jaehun Environmental Science & Technology, Vol. 52, Issue 2 https://doi.org/10.1021/acs.est.7b04077	journal	January 2018
Source of Molecular Hydrogen in High-Temperature Water Radiolysis Sterniczuk, Marcin; Bartels, David M. The Journal of Physical Chemistry A, Vol. 120, Issue 2 https://doi.org/10.1021/acs.jpca.5b12281	journal	January 2016
Pulse Radiolysis and Transient Absorption of Aqueous Cr(VI) Solutions up to 325 °C Conrad, Jacy K.; Lisouskaya, Aliaksandra; Bartels, David M. ACS Omega, Vol. 7, Issue 43 https://doi.org/10.1021/acsomega.2c04807	journal	October 2022
Ferrate Treatment for Removing Chromium from High-Level Radioactive Tank Waste Sylvester, P.; Rutherford, L. A.; Gonzalez-Martin, A. Environmental Science & Technology, Vol. 35, Issue 1 https://doi.org/10.1021/es001340n	journal	January 2001
Early stages of the hydrolysis of chromium(III) in aqueous solution. 1. Characterization of a tetrameric species Stuenzi, Hans; Marty, Werner Inorganic Chemistry, Vol. 22, Issue 15 https://doi.org/10.1021/ic00157a012	journal	July 1983
Early stages of the hydrolysis of chromium(III) in aqueous solution. 2. Kinetics and mechanism of the interconversion between two tetrameric species Stunzi, Hans; Rotzinger, Francois P.; Marty, Werner Inorganic Chemistry, Vol. 23, Issue 14 https://doi.org/10.1021/ic00182a035	journal	July 1984
Early stages of the hydrolysis of chromium(III) in aqueous solution. 3. Kinetics of dimerization of the deprotonated aqua ion Rotzinger, Francois P.; Stuenzi, Hans; Marty, Werner Inorganic Chemistry, Vol. 25, Issue 4 https://doi.org/10.1021/ic00224a019	journal	February 1986
Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide Rai, Dhanpat; Sass, Bruce M.; Moore, Dean A. Inorganic Chemistry, Vol. 26, Issue 3 https://doi.org/10.1021/ic00250a002	journal	February 1987
Early stages of the hydrolysis of chromium(III) in aqueous solution. 4. The stability constants of the hydrolytic dimer, trimer, and tetramer at 25.degree.C and I = 1.0 M Stuenzi, Hans; Spiccia, Leone; Rotzinger, Francois P. Inorganic Chemistry, Vol. 28, Issue 1 https://doi.org/10.1021/ic00300a015	journal	January 1989
The Reactivity of Metal Ions and Some Oxy Anions toward Hydrated Electrons ¹ Anbar, M.; Hart, Edwin J. The Journal of Physical Chemistry, Vol. 69, Issue 3 https://doi.org/10.1021/j100887a048	journal	March 1965
Chromium(III) Sulfate in Acid Sulfate Solutions Fogel, Norman.; Tai, Julia Ming Jen.; Yarborough, Jean. Journal of the American Chemical Society, Vol. 84, Issue 7 https://doi.org/10.1021/ja00866a017	journal	April 1962
Hydrolytic Polymerization in Boiled Chromic Solutions¹ Laswick, John A.; Plane, Robert A. Journal of the American Chemical Society, Vol. 81, Issue 14 https://doi.org/10.1021/ja01523a020	journal	July 1959
Hydroxyl Radical Self-Recombination Reaction and Absorption Spectrum in Water Up to 350 °C Janik, Ireneusz; Bartels, David M.; Jonah, Charles D. The Journal of Physical Chemistry A, Vol. 111, Issue 10 https://doi.org/10.1021/jp065992v	journal	March 2007
Solubility and Phase Behavior of Cr(III) Oxides in Alkaline Media at Elevated Temperatures Ziemniak, S. E.; Jones, M. E.; Combs, K. E. S. Journal of Solution Chemistry, Vol. 27, Issue 1, p. 33-66 https://doi.org/10.1023/A:1022688528380	journal	January 1998
Forty years of durability assessment of nuclear waste glass by standard methods Thorpe, Clare L.; Neeway, James J.; Pearce, Carolyn I. npj Materials Degradation, Vol. 5, Issue 1 https://doi.org/10.1038/s41529-021-00210-4	journal	December 2021
One-electron redox kinetics of aqueous transition metal couples Zn ^2+/+ , Co ^2+/+ , and Ni ^2+/+ using pulse radiolysis Lisovskaya, Alexandra; Kanjana, Kotchaphan; Bartels, David M. Physical Chemistry Chemical Physics, Vol. 22, Issue 34 https://doi.org/10.1039/D0CP03214J	journal	January 2020
Ultraviolet–visible spectrum, and kinetics of formation and decomposition, of penta-aquahydridochromium(III) and chromium(I) in aqueous perchlorate solutions: a pulse-radiolysis study Cohen, Haim; Meyerstein, Dan J. Chem. Soc., Dalton Trans., Issue 23 https://doi.org/10.1039/DT9740002559	journal	January 1974
Oligomerization of chromium(iii) and its impact on the oxidation of chromium(iii) by hydrogen peroxide in alkaline solutions Rao, Linfeng; Zhang, Zhicheng; Friese, Judah I. Journal of the Chemical Society, Dalton Transactions, Issue 2 https://doi.org/10.1039/b104154c	journal	January 2002
Ultraviolet–visible spectrum, and kinetics of formation and decomposition, of penta-aquahydridochromium(III) and chromium(I) in aqueous perchlorate solutions: a pulse-radiolysis study Cohen, Haim; Meyerstein, Dan J. Chem. Soc., Dalton Trans., Issue 23 https://doi.org/10.1039/dt9740002559	journal	January 1974
Re-evaluation of the thiocyanate dosimeter for pulse radiolysis Buxton, George V.; Stuart, Craig R. Journal of the Chemical Society, Faraday Transactions, Vol. 91, Issue 2 https://doi.org/10.1039/ft9959100279	journal	January 1995
Disproportionation of Cr V generated by the radiation-induced reduction of Cr VI in aqueous solution containing formate: a pulse radiolysis study Buxton, George V.; Djouider, Fathi Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 21 https://doi.org/10.1039/ft9969204173	journal	January 1996
55. Structure and reactivity of the oxyanions of transition metals. Part VIII. Acidities and spectra of protonated oxyanions Bailey, N.; Carrington, A.; Lott, K. A. K. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9600000290	journal	January 1960
60Co ? radiolysis of potassium dichromate in acid solution Anderson, A. R. Transactions of the Faraday Society, Vol. 59 https://doi.org/10.1039/tf9635901299	journal	January 1963
Vitesses d’oxydation d’ions minéraux par les radicaux OH Muller, Jean-Claude; Ferradini, Christiane Journal de Chimie Physique, Vol. 62 https://doi.org/10.1051/jcp/1965620654	journal	January 1965
Design of an optical cell for pulse radiolysis of supercritical water Takahashi, Kenji; Cline, Jason A.; Bartels, David M. Review of Scientific Instruments, Vol. 71, Issue 9 https://doi.org/10.1063/1.1288258	journal	September 2000
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
Removal of Chromium from Hanford tank Sludges Lumetta, G. J.; Rapko, B. M. Separation Science and Technology, Vol. 34, Issue 6-7 https://doi.org/10.1080/01496399908951105	journal	January 1999
Formation of Ion-pair Cr³⁺–SO₄²⁻in Aqueous Solution Tsuchiya, Ryokichi; Umayahara, Akira Bulletin of the Chemical Society of Japan, Vol. 36, Issue 5 https://doi.org/10.1246/bcsj.36.554	journal	May 1963
Kinetics and mechanism of the advanced oxidation process of Cr(III) to Cr(VI) by SO₄ ⁻˙ free radicals in slightly acidic simulated atmospheric water Djouider, Fathi Radiochimica Acta, Vol. 108, Issue 2 https://doi.org/10.1515/ract-2019-3134	journal	July 2019

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Kinetics of the Temperature-Dependent eaq- and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

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Kinetics of the Temperature-Dependent e_aq^- and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions