Hydration and Aggregation of Monofunctional Sulfoxide and Other Neutral Oxygen-Donor Extractants: The Di(2-Ethylhexyl) Sulfoxide, Dodecane, Water System

Bruce A. Moyer; Catherine E. Caley; C. F. Baes

doi:10.1080/07366298808917966

Hydration and Aggregation of Monofunctional Sulfoxide and Other Neutral Oxygen-Donor Extractants: The Di(2-Ethylhexyl) Sulfoxide, Dodecane, Water System

Bruce A. Moyer, Catherine E. Caley, C. F. Baes

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

The nature of the hydration and aggregation of di(2-ethyl hexyl) sulfoxide (DEHSO) dissolved in wet dodecane at 25 °C has been characterized using Fourier transform infrared (FTIR) spectrophotometry, Karl Fischer titrations, and tritium-tracer equilibrium measurements. Least-squares computer modeling of the water content of 0.01-to-0.4 M DEHSO solutions equilibrated with water (optionally containing nonextractable CaCl₂to adjust the water activity a_win the range 0.28 to 1.0) indicates that the expected 1:1 species DEHSO•H₂O predominates at low DEHSO concentration (K₁₁= [DEHSO• H₂O]/([DEHSO]a_W) = 0.12 ± 0.01) with additional formation of hydrated dimeric species at the higher DEHSO concentrations. Analysis of the water vibrational bands in the FTIR spectra of 0.01-to-0.4 M DEHSO solutions in equilibrium with pure water supports the formation of both the 1:1 species and a dimer, identified by its spectral characteristics as the 2:1 dimer monohydrate. By reference to the available literature on the hydration of weak bases, the results suggest that at least part of the “nonideality” of solutions of weak-base extractants in wet nonpolar diluents may be explained by formation of the discrete 1:1 and 2:1 monohydrate species.

Original language	English
Pages (from-to)	785-817
Number of pages	33
Journal	Solvent Extraction and Ion Exchange
Volume	6
Issue number	5
DOIs	https://doi.org/10.1080/07366298808917966
State	Published - Jan 1988

Funding

Undergraduate research participant i n the Oak Ridge Science Semester Program sponsored by ORNL under subcontract with the Great Lakes Colleges Association/Associated Colleges of the Midwest. The authors gratefully acknowledge the support of the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department o f Energy under contract DE-AC05-840R21400 with Martin Marietta Energy Systems, Inc. The Oak Ridge Science Semester Program (C. E. Caley) was sponsored by ORNL under subcon-contract 19X-03487s with the Great Lakes Colleges Association/ Associated Colleges of the Midwest. Special thanks for technical assistance and/or guidance are extended t o G. M. Begun, G. N. Case, C. F. Coleman, W. J. McDowell, R. R. Shoun, and J. W. Roddy.

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title = "Hydration and Aggregation of Monofunctional Sulfoxide and Other Neutral Oxygen-Donor Extractants: The Di(2-Ethylhexyl) Sulfoxide, Dodecane, Water System",

abstract = "The nature of the hydration and aggregation of di(2-ethyl hexyl) sulfoxide (DEHSO) dissolved in wet dodecane at 25 °C has been characterized using Fourier transform infrared (FTIR) spectrophotometry, Karl Fischer titrations, and tritium-tracer equilibrium measurements. Least-squares computer modeling of the water content of 0.01-to-0.4 M DEHSO solutions equilibrated with water (optionally containing nonextractable CaCl2to adjust the water activity awin the range 0.28 to 1.0) indicates that the expected 1:1 species DEHSO•H2O predominates at low DEHSO concentration (K11= [DEHSO• H2O]/([DEHSO]aW) = 0.12 ± 0.01) with additional formation of hydrated dimeric species at the higher DEHSO concentrations. Analysis of the water vibrational bands in the FTIR spectra of 0.01-to-0.4 M DEHSO solutions in equilibrium with pure water supports the formation of both the 1:1 species and a dimer, identified by its spectral characteristics as the 2:1 dimer monohydrate. By reference to the available literature on the hydration of weak bases, the results suggest that at least part of the “nonideality” of solutions of weak-base extractants in wet nonpolar diluents may be explained by formation of the discrete 1:1 and 2:1 monohydrate species.",

author = "Moyer, \{Bruce A.\} and Caley, \{Catherine E.\} and Baes, \{C. F.\}",

year = "1988",

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doi = "10.1080/07366298808917966",

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T2 - The Di(2-Ethylhexyl) Sulfoxide, Dodecane, Water System

AU - Moyer, Bruce A.

AU - Caley, Catherine E.

AU - Baes, C. F.

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N2 - The nature of the hydration and aggregation of di(2-ethyl hexyl) sulfoxide (DEHSO) dissolved in wet dodecane at 25 °C has been characterized using Fourier transform infrared (FTIR) spectrophotometry, Karl Fischer titrations, and tritium-tracer equilibrium measurements. Least-squares computer modeling of the water content of 0.01-to-0.4 M DEHSO solutions equilibrated with water (optionally containing nonextractable CaCl2to adjust the water activity awin the range 0.28 to 1.0) indicates that the expected 1:1 species DEHSO•H2O predominates at low DEHSO concentration (K11= [DEHSO• H2O]/([DEHSO]aW) = 0.12 ± 0.01) with additional formation of hydrated dimeric species at the higher DEHSO concentrations. Analysis of the water vibrational bands in the FTIR spectra of 0.01-to-0.4 M DEHSO solutions in equilibrium with pure water supports the formation of both the 1:1 species and a dimer, identified by its spectral characteristics as the 2:1 dimer monohydrate. By reference to the available literature on the hydration of weak bases, the results suggest that at least part of the “nonideality” of solutions of weak-base extractants in wet nonpolar diluents may be explained by formation of the discrete 1:1 and 2:1 monohydrate species.

AB - The nature of the hydration and aggregation of di(2-ethyl hexyl) sulfoxide (DEHSO) dissolved in wet dodecane at 25 °C has been characterized using Fourier transform infrared (FTIR) spectrophotometry, Karl Fischer titrations, and tritium-tracer equilibrium measurements. Least-squares computer modeling of the water content of 0.01-to-0.4 M DEHSO solutions equilibrated with water (optionally containing nonextractable CaCl2to adjust the water activity awin the range 0.28 to 1.0) indicates that the expected 1:1 species DEHSO•H2O predominates at low DEHSO concentration (K11= [DEHSO• H2O]/([DEHSO]aW) = 0.12 ± 0.01) with additional formation of hydrated dimeric species at the higher DEHSO concentrations. Analysis of the water vibrational bands in the FTIR spectra of 0.01-to-0.4 M DEHSO solutions in equilibrium with pure water supports the formation of both the 1:1 species and a dimer, identified by its spectral characteristics as the 2:1 dimer monohydrate. By reference to the available literature on the hydration of weak bases, the results suggest that at least part of the “nonideality” of solutions of weak-base extractants in wet nonpolar diluents may be explained by formation of the discrete 1:1 and 2:1 monohydrate species.

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DO - 10.1080/07366298808917966

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ER -

Hydration and Aggregation of Monofunctional Sulfoxide and Other Neutral Oxygen-Donor Extractants: The Di(2-Ethylhexyl) Sulfoxide, Dodecane, Water System

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