Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?

Meichtry, Jorge M.; Slodowicz, Mariel; Cancelada, Lucía; Destaillats, Hugo; Litter, Marta I.

doi:10.1016/j.ultsonch.2018.05.014

Title: Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?

Abstract

In this research, the sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformationmore »« less

Authors:

Meichtry, Jorge M. ^[1]; Slodowicz, Mariel ^[1]; Cancelada, Lucía ^[2]; Destaillats, Hugo ^[3]; Litter, Marta I. ^[4]

National Atomic Energy Commission (CNEA), Buenos Aires (Argentina); National Scientific and Technical Research Council of Argentina (CONICET)
National Atomic Energy Commission (CNEA), Buenos Aires (Argentina)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
National Atomic Energy Commission (CNEA), Buenos Aires (Argentina); National Scientific and Technical Research Council of Argentina (CONICET); Univ. Nacional de General San Martin, Buenos Aires (Argentina)

Publication Date:: Fri May 18 00:00:00 EDT 2018

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); Agencia Nacional de Promoción Científica y Tecnológica (Argentina)

OSTI Identifier:: 1637284

Grant/Contract Number:: AC02-05CH11231; PICT2011-0463; 2015-208; PICT-3640

Resource Type:: Accepted Manuscript

Journal Name:: Ultrasonics Sonochemistry

Additional Journal Information:: Journal Volume: 48; Journal ID: ISSN 1350-4177

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cr(VI); sonochemical reduction; organic additives

Citation Formats


                    Meichtry, Jorge M., Slodowicz, Mariel, Cancelada, Lucía, Destaillats, Hugo, and Litter, Marta I. Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?.  United States: N. p., 2018. 
Web.  doi:10.1016/j.ultsonch.2018.05.014.

Copy to clipboard


                    Meichtry, Jorge M., Slodowicz, Mariel, Cancelada, Lucía, Destaillats, Hugo, & Litter, Marta I. Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?.  United States.  https://doi.org/10.1016/j.ultsonch.2018.05.014

Copy to clipboard


                    Meichtry, Jorge M., Slodowicz, Mariel, Cancelada, Lucía, Destaillats, Hugo, and Litter, Marta I. Fri .  
"Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?".  United States.  https://doi.org/10.1016/j.ultsonch.2018.05.014.  https://www.osti.gov/servlets/purl/1637284.

Copy to clipboard


                    
@article{osti_1637284,

  title        = {Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?},

  author       = {Meichtry, Jorge M. and Slodowicz, Mariel and Cancelada, Lucía and Destaillats, Hugo and Litter, Marta I.},

  abstractNote = {In this research, the sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformation into different Cr(III) species is considered a major factor in the acceleration of Cr(VI) reduction processes. Mechanistic pathways are proposed.},

  doi          = {10.1016/j.ultsonch.2018.05.014},

  journal      = {Ultrasonics Sonochemistry},

  number       = ,

  volume       = 48,

  place        = {United States},

  year         = {Fri May 18 00:00:00 EDT 2018},

  month        = {Fri May 18 00:00:00 EDT 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.ultsonch.2018.05.014

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 10 works

Citation information provided by
Web of Science

Figures / Tables:

Fig. 1: Temporal profile of normalized Cr(VI) concentration ([Cr(VI)]/ ([Cr (VI)]₀) during the sonochemical experiments of Cr(VI) in the presence of different additives: (a) with EDTA, Cit, FA, SLS, PhOH and t-BuOH; (b) with MeOH, EtOH and 2-PrOH. Conditions: [Cr(VI)]₀ = 0.30 mM, pH 2 (HClO₄), T = 30 °C,more »

All figures and tables (5 total)

Save / Share:

Export Metadata

Save to My Library

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction

Journal Article Groenewold, Gary S ; Van Stipdonk, Michael J ; de Jong, Wibe A ; ... - ChemPhysChem

UO2+-solvent complexes having the general formula [UO2(ROH)]+ (R = H, CH3, C2H5, and n-C3H7) were formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they were isolated by mass-to-charge ratio, and then photofragmented using a free electron laser scanning through the 10 ?m region of the infrared spectrum. Antisymmetric O=U=O stretching frequencies (?3) were measured for all four complexes, which ranged from ~ 953 cm-1 for H2O to ~ 944 cm-1 for n-PrOH, with the value for the EtOH-containing complex intermediate, systematically decreasing with increasing nucleophilicity of the solvent. The value for themore »« less
https://doi.org/10.1002/cphc.200800034
Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction

Journal Article Groenewold, G S ; Van Stipdonk, Michael J ; De Jong, Wibe A ; ... - Chemphyschem, 9(9):1278-1285

UO2+-solvent complexes having the general formula [UO₂ (ROH)]+ (R = H, CH₃, C₂H₅, and n-C₃H₇) were formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they were isolated by mass-to-charge ratio, and then photofragmented using a free electron laser scanning through the 10 μm region of the infrared spectrum. Antisymmetric O=U=O stretching frequencies (ν3) were measured for all four complexes, which ranged from ~ 953 cm¯¹ for H₂O to ~ 944 cm¯¹ for n- PrOH, with the value for the EtOH-containing complex intermediate, systematically decreasing with increasing nucleophilicity of the solvent. The valuemore »« less
https://doi.org/10.1002/cphc.200800034
Solvent effects in the reactions of peroxyl radicals with organic reductants. Evidence for proton-transfer-mediated electron transfer

Journal Article Neta, P ; Huie, R E ; Maruthamuthu, P ; ... - Journal of Physical Chemistry; (USA)

Absolute rate constants for the reactions of substituted methylperoxyl radicals with ascorbate, urate, trolox (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid), and TMPD (N,N,N{prime},N{prime}-tetramethyl-p-phenylenediamine) have been determined by pulse radiolysis is different solvents. In water-alcohol or water-dioxane solutions, the rate constants for trihalomethylperoxyl radicals generally increase with increasing water content. The rate constant for reaction of CCl{sub 3}O{sub 2}{center dot} radicals with trolox was measured in water, MeOH, i-PrOH, t-BuOH, ethylene glycol, diethyl ether, dioxane, acetone, acetonitrile, formamide, dimethylformamide, pyridine, and CCl{sub 4}. The rate constants were found to correlate well with a two-parameter equation that includes the dielectric constant of the solvent and themore »« less
https://doi.org/10.1021/j100359a025
THE DETECTION OF RADIOISOTOPES IN URINE. PART II (in German)

Journal Article Schulte, K E ; Henke, G - Pharmazie (West Germany)

A review of methods for identification and separation of radioisotopes is presented. The characterization of radionuclides of a urine sample by desermination of the type and energy of the radiation is discussed. Separation of radioactive cations of urine is reviewed, with particular attention to qualitative separation of isotope mixtures, preparation of the sample for cation separation, and separation of radioactive cations of urine by precipitation of groups. Analysis of the cations in a model sample of urine is tabulated. Great emphasis is placed on the use of paper chromatography of inorganic ions; a general review is given of this topicmore »« less

Similar Records