Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

Abstract

Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands.more » Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [1];  [3];  [2];  [3]
+ Show Author Affiliations
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Univ. of North Carolina, Wilmington, NC (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1223648
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 119; Journal Issue: 8; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Citation Formats

Mehio, Nada, Lashely, Mark A., Nugent, Joseph W., Tucker, Lyndsay, Correia, Bruna, Do-Thanh, Chi-Linh, Dai, Sheng, Hancock, Robert D., and Bryantsev, Vyacheslav S. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study. United States: N. p., 2015. Web. doi:10.1021/jp512778x.
Copy to clipboard
Mehio, Nada, Lashely, Mark A., Nugent, Joseph W., Tucker, Lyndsay, Correia, Bruna, Do-Thanh, Chi-Linh, Dai, Sheng, Hancock, Robert D., & Bryantsev, Vyacheslav S. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study. United States. https://doi.org/10.1021/jp512778x
Copy to clipboard
Mehio, Nada, Lashely, Mark A., Nugent, Joseph W., Tucker, Lyndsay, Correia, Bruna, Do-Thanh, Chi-Linh, Dai, Sheng, Hancock, Robert D., and Bryantsev, Vyacheslav S. Mon . "Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study". United States. https://doi.org/10.1021/jp512778x. https://www.osti.gov/servlets/purl/1223648.
Copy to clipboard
@article{osti_1223648,
title = {Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study},
author = {Mehio, Nada and Lashely, Mark A. and Nugent, Joseph W. and Tucker, Lyndsay and Correia, Bruna and Do-Thanh, Chi-Linh and Dai, Sheng and Hancock, Robert D. and Bryantsev, Vyacheslav S.},
abstractNote = {Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.},
doi = {10.1021/jp512778x},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 8,
volume = 119,
place = {United States},
year = {Mon Jan 26 00:00:00 EST 2015},
month = {Mon Jan 26 00:00:00 EST 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jp512778x
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 51 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Extraction of Uranium from Sea Water
journal, September 1964

  • Davies, R. V.; Kennedy, J.; McILROY, R. W.
  • Nature, Vol. 203, Issue 4950
  • DOI: 10.1038/2031110a0

Chemical Forms of Uranium in Artificial Seawater
journal, February 1982

Soluble rare earth and actinide species in seawater
journal, December 1989

Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs
journal, January 2013

Development of Sorbers for the Recovery of Uranium from Seawater. 1. Assessment of Key Parameters and Screening Studies of Sorber Materials
journal, August 1982

  • Schenk, H. J.; Astheimer, L.; Witte, E. G.
  • Separation Science and Technology, Vol. 17, Issue 11
  • DOI: 10.1080/01496398208056103

Extraction of uranium from the concentrated brine rejected by integrated nuclear desalination plants
journal, January 2009

Comparison of Amidoxime Adsorbents Prepared by Cografting Methacrylic Acid and 2-Hydroxyethyl Methacrylate with Acrylonitrile onto Polyethylene
journal, August 2000

  • Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
  • Industrial & Engineering Chemistry Research, Vol. 39, Issue 8
  • DOI: 10.1021/ie990474a

Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition
journal, October 2000

  • Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
  • Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411
  • DOI: 10.1016/S0969-806X(00)00298-X

How Amidoximate Binds the Uranyl Cation
journal, February 2012

  • Vukovic, Sinisa; Watson, Lori A.; Kang, Sung Ok
  • Inorganic Chemistry, Vol. 51, Issue 6
  • DOI: 10.1021/ic300062s

On the Metal Ion Selectivity of Oxoacid Extractants
journal, January 2013

  • Hay, Benjamin P.; Chagnes, Alexandre; Cote, Gérard
  • Solvent Extraction and Ion Exchange, Vol. 31, Issue 1
  • DOI: 10.1080/07366299.2012.709452

Protonation Constants of Some N-Substituted Amidoximes in a 50% Ethanol-Water Mixture (v/v).
journal, January 2000

  • DÜRÜSt, Nedime; Abdülkadir AKAY, M.; DÜRÜSt, Yasar
  • Analytical Sciences, Vol. 16, Issue 8
  • DOI: 10.2116/analsci.16.825

Binding ability of acetamide oxime with proton, copper(II), and dioxouranium(VI) in aqueous solutions
journal, January 1986

  • Hirotsu, Takahiro; Katoh, Shunsaku; Sugasaka, Kazuhiko
  • Journal of the Chemical Society, Dalton Transactions, Issue 8
  • DOI: 10.1039/dt9860001609

Micellar effects upon dephosphorylation by amidoximes
journal, March 1982

  • Bunton, Clifford A.; Nelson, Susan E.; Quan, Clifford
  • The Journal of Organic Chemistry, Vol. 47, Issue 7
  • DOI: 10.1021/jo00346a002

Enhanced reactivity of nucleophiles: orbital symmetry and the so-called “α-effect”
journal, January 1970

Amidoximes as Effective Acceptors of Acyl Group
journal, September 2001

  • Simanenko, Yu. S.; Prokop'eva, T. M.; Belousova, I. A.
  • Theoretical and Experimental Chemistry, Vol. 37, Issue 5, p. 288-295
  • DOI: 10.1023/A:1013807032618

Inhomogeneous Electron Gas
journal, November 1964

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934

MP2 energy evaluation by direct methods
journal, December 1988

A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982

  • Purvis, George D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.443164

A fifth-order perturbation comparison of electron correlation theories
journal, May 1989

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Ruthenium-Catalyzed Rearrangement of Aldoximes to Primary Amides in Water
journal, August 2012

  • García-Álvarez, Rocío; Díaz-Álvarez, Alba E.; Borge, Javier
  • Organometallics, Vol. 31, Issue 17
  • DOI: 10.1021/om3006917

p K a Calculations of Aliphatic Amines, Diamines, and Aminoamides via Density Functional Theory with a Poisson−Boltzmann Continuum Solvent Model
journal, May 2007

  • Bryantsev, Vyacheslav S.; Diallo, Mamadou S.; Goddard, William A.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 20
  • DOI: 10.1021/jp071040t

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp063552y

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p)
journal, March 2005

  • Andersson, M. P.; Uvdal, P.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 12
  • DOI: 10.1021/jp045733a

The benzene–argon complex: A ground and excited state ab initio study
journal, February 1998

  • Koch, Henrik; Fernández, Berta; Christiansen, Ove
  • The Journal of Chemical Physics, Vol. 108, Issue 7
  • DOI: 10.1063/1.475669

A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics
journal, August 1997

  • Cancès, E.; Mennucci, B.; Tomasi, J.
  • The Journal of Chemical Physics, Vol. 107, Issue 8
  • DOI: 10.1063/1.474659

Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998

  • Barone, Vincenzo; Cossi, Maurizio
  • The Journal of Physical Chemistry A, Vol. 102, Issue 11
  • DOI: 10.1021/jp9716997

Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model
journal, April 2003

  • Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni
  • Journal of Computational Chemistry, Vol. 24, Issue 6
  • DOI: 10.1002/jcc.10189

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993

Charge penetration in dielectric models of solvation
journal, June 1997

  • Chipman, Daniel M.
  • The Journal of Chemical Physics, Vol. 106, Issue 24
  • DOI: 10.1063/1.474048

Volume polarization in reaction field theory
journal, January 1998

  • Zhan, Chang-Guo; Bentley, John; Chipman, Daniel M.
  • The Journal of Chemical Physics, Vol. 108, Issue 1
  • DOI: 10.1063/1.475371

New formulation and implementation for volume polarization in dielectric continuum theory
journal, June 2006

  • Chipman, Daniel M.
  • The Journal of Chemical Physics, Vol. 124, Issue 22
  • DOI: 10.1063/1.2203068

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

Proton Affinity Distributions of TiO2-SiO2 and ZrO2-SiO2 Mixed Oxides and Their Relationship to Catalyst Activities for 1-Butene Isomerization
journal, November 1995

  • Contescu, C.; Popa, V. T.; Miller, J. B.
  • Journal of Catalysis, Vol. 157, Issue 1
  • DOI: 10.1006/jcat.1995.1285

Molecular mechanics calculations and metal ion recognition
journal, August 1990

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Evaluation of B3LYP, X3LYP, and M06-Class Density Functionals for Predicting the Binding Energies of Neutral, Protonated, and Deprotonated Water Clusters
journal, March 2009

  • Bryantsev, Vyacheslav S.; Diallo, Mamadou S.; van Duin, Adri C. T.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 4
  • DOI: 10.1021/ct800549f

First Principles Calculations of Aqueous p K a Values for Organic and Inorganic Acids Using COSMO−RS Reveal an Inconsistency in the Slope of the p K a Scale
journal, November 2003

  • Klamt, Andreas; Eckert, Frank; Diedenhofen, Michael
  • The Journal of Physical Chemistry A, Vol. 107, Issue 44
  • DOI: 10.1021/jp034688o

Prediction of acidity in acetonitrile solution with COSMO-RS
journal, April 2009

  • Eckert, Frank; Leito, Ivo; Kaljurand, Ivari
  • Journal of Computational Chemistry, Vol. 30, Issue 5
  • DOI: 10.1002/jcc.21103

Accurate p K a Calculations for Carboxylic Acids Using Complete Basis Set and Gaussian-n Models Combined with CPCM Continuum Solvation Methods
journal, August 2001

  • Liptak, Matthew D.; Shields, George C.
  • Journal of the American Chemical Society, Vol. 123, Issue 30
  • DOI: 10.1021/ja010534f

Absolute p K a Determinations for Substituted Phenols
journal, June 2002

  • Liptak, Matthew D.; Gross, Kevin C.; Seybold, Paul G.
  • Journal of the American Chemical Society, Vol. 124, Issue 22
  • DOI: 10.1021/ja012474j

Computational Approaches for the Prediction of pKa Values
reference-book, January 2013

On the Effects of Changing Gaussian Program Version and SCRF Defining Parameters: Isopropylamine as a Case Study
journal, September 2012

  • Amado, Ana M.; Fiuza, Sónia M.; Batista de Carvalho, Luis A. E.
  • Bulletin of the Chemical Society of Japan, Vol. 85, Issue 9
  • DOI: 10.1246/bcsj.20120016

A new definition of cavities for the computation of solvation free energies by the polarizable continuum model
journal, August 1997

  • Barone, Vincenzo; Cossi, Maurizio; Tomasi, Jacopo
  • The Journal of Chemical Physics, Vol. 107, Issue 8
  • DOI: 10.1063/1.474671

Resolution of a Challenge for Solvation Modeling: Calculation of Dicarboxylic Acid Dissociation Constants Using Mixed Discrete–Continuum Solvation Models
journal, May 2012

  • Marenich, Aleksandr V.; Ding, Wendu; Cramer, Christopher J.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 11
  • DOI: 10.1021/jz300416r

The Cluster−Continuum Model for the Calculation of the Solvation Free Energy of Ionic Species
journal, August 2001

  • Pliego, Josefredo R.; Riveros, José M.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 30
  • DOI: 10.1021/jp004192w

Tuning Amidoximate to Enhance Uranyl Binding: A Density Functional Theory Study
journal, October 2013

  • Abney, Carter W.; Liu, Shubin; Lin, Wenbin
  • The Journal of Physical Chemistry A, Vol. 117, Issue 45
  • DOI: 10.1021/jp408460x
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Polyamidoxime chain length drives emergent metal-binding phenomena
    journal, January 2019

    • Earl, L. D.; Do, C.; Wang, Y.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 2
    • DOI: 10.1039/c8cp02198h

    Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage
    journal, December 2019

    Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature
    journal, November 2017

    • Ladshaw, Austin P.; Wiechert, Alexander I.; Das, Sadananda
    • Materials, Vol. 10, Issue 11
    • DOI: 10.3390/ma10111268

    Colorimetric and visual determination of ultratrace uranium concentrations based on the aggregation of amidoxime functionalized gold nanoparticles
    journal, February 2019

    Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste
    journal, April 2018

    Relative p K a of some anilinium derivatives in methanol, acetonitrile, and tetrahydrofurane solvents
    journal, September 2018

    • Ghalami-Choobar, Bahram; Ghiami-Shomami, Ali; Fereidoonzadeh, Masoomeh
    • Journal of the Chinese Chemical Society, Vol. 66, Issue 2
    • DOI: 10.1002/jccs.201800139

    Bio-inspired nano-traps for uranium extraction from seawater and recovery from nuclear waste
    journal, April 2018

    Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature
    journal, November 2017

    • Ladshaw, Austin P.; Wiechert, Alexander I.; Das, Sadananda
    • Materials, Vol. 10, Issue 11
    • DOI: 10.3390/ma10111268
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: