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

Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

doi:10.1021/jp512778x

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

Journal Article · Mon Jan 26 00:00:00 EST 2015 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/jp512778x· OSTI ID:1223648

Mehio, Nada ^[1]; Lashely, Mark A. ^[2]; Nugent, Joseph W. ^[2]; Tucker, Lyndsay ^[2]; Correia, Bruna ^[2]; Do-Thanh, Chi-Linh ^[1]; Dai, Sheng ^[3]; Hancock, Robert D. ^[2]; Bryantsev, Vyacheslav S. ^[3]

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)

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 pK_a values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pK_a values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pK_a values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pK_a 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 pK_a units and 0.35 pK_a units, respectively, and a root mean square deviation of 0.46 pK_a units and 0.45 pK_a units, respectively. Finally, we employ our two best methods to predict the pK_a 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1223648

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 119, Issue 8; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 51 works

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