Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · ChemPhysChem
 [1];  [2];  [3];  [2]
  1. Idaho National Laboratory (INL), Idaho Falls, ID (United States)
  2. University of Notre Dame, IN (United States). Notre Dame Radiation Laboratory (NDRL)
  3. California State Univ. (CalState), Long Beach, CA (United States)
+ Show Author Affiliations
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 (eaq-) 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.
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; 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 book March 2016
Chromium in Environment, Its Toxic Effect from Chromite-Mining and Ferrochrome Industries, and Its Possible Bioremediation 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 journal August 1992
The oxidation of chromium(III) by hydroxyl radical in alkaline solution. A stopped-flow and pre-mix pulse radiolysis study journal February 1995
Multiple time scales in pulse radiolysis. Application to bromide solutions and dipeptides journal June 1999
Temperature dependence of hydroxyl radical reactions with chloramine species in aqueous solution journal November 2017
Reaction rates of the hydrated electron with N2O in high temperature water and potential surface of the N2O− anion 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 journal July 2014
Low LET radiolysis escape yields for reducing radicals and H2 in pressurized high temperature water journal April 2016
Review of the Scientific Understanding of Radioactive Waste at the U.S. DOE Hanford Site journal January 2018
Source of Molecular Hydrogen in High-Temperature Water Radiolysis journal January 2016
Pulse Radiolysis and Transient Absorption of Aqueous Cr(VI) Solutions up to 325 °C journal October 2022
Ferrate Treatment for Removing Chromium from High-Level Radioactive Tank Waste journal January 2001
Early stages of the hydrolysis of chromium(III) in aqueous solution. 1. Characterization of a tetrameric species 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 journal July 1984
Early stages of the hydrolysis of chromium(III) in aqueous solution. 3. Kinetics of dimerization of the deprotonated aqua ion journal February 1986
Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide 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 journal January 1989
The Reactivity of Metal Ions and Some Oxy Anions toward Hydrated Electrons 1 journal March 1965
Chromium(III) Sulfate in Acid Sulfate Solutions journal April 1962
Hydrolytic Polymerization in Boiled Chromic Solutions1 journal July 1959
Hydroxyl Radical Self-Recombination Reaction and Absorption Spectrum in Water Up to 350 °C journal March 2007
Solubility and Phase Behavior of Cr(III) Oxides in Alkaline Media at Elevated Temperatures journal January 1998
Forty years of durability assessment of nuclear waste glass by standard methods journal December 2021
One-electron redox kinetics of aqueous transition metal couples Zn 2+/+ , Co 2+/+ , and Ni 2+/+ using pulse radiolysis 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 journal January 1974
Oligomerization of chromium(iii) and its impact on the oxidation of chromium(iii) by hydrogen peroxide in alkaline solutions 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 journal January 1974
Re-evaluation of the thiocyanate dosimeter for pulse radiolysis 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 journal January 1996
55. Structure and reactivity of the oxyanions of transition metals. Part VIII. Acidities and spectra of protonated oxyanions journal January 1960
60Co ? radiolysis of potassium dichromate in acid solution journal January 1963
Vitesses d’oxydation d’ions minéraux par les radicaux OH journal January 1965
Design of an optical cell for pulse radiolysis of supercritical water 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 journal January 1999
Formation of Ion-pair Cr3+–SO42−in Aqueous Solution 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 journal July 2019

Similar Records

High-Temperature Reaction Kinetics of the eaq– and HO2• Radicals with Iron(II) Ions in Aqueous Solutions
Journal Article · Mon Jun 26 20:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1991955
High temperature gamma radiation-induced chromium redox chemistry via in situ spectroscopic measurements
Journal Article · Tue Nov 28 19:00:00 EST 2023 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:2228294

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
aqueous solutions
chromium(III) ions
elevated temperatures
hydrated electron
hydroxyl radical
pulsed electron radiolysis
reaction kinetics
water radiolysis