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 »
- Authors:
-
- Univ. of Tennessee, Knoxville, TN (United States)
- Univ. of North Carolina, Wilmington, NC (United States)
- 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.
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
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.
@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}
}
Web of Science
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