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Title: Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

Abstract

A comparative quantitative analysis of the effect of solvent modifiers on an ion-pair extraction of an inorganic salt by a crown ether was conducted. Two classes of the solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenyl acetamide—the enhancement of the NaNO3 extraction by 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier quantified by the b solvatochromic parameter. Application of the solvent EPD modifier improved solvation of the sodium ion, lowering the large energy barrier of Na+ partitioning into the extraction phase. A HBD modifier 3,5-di-t-butylphenol 8 that forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO3 extraction by 1. The determined extraction constants were correlated with the b or a solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between 3,5-di-t-butylphenol 8 and nitrate anion in the presence ofmore » the sodium-loaded crown ether in the extraction phases was studied by vibrational spectroscopy. Formation of the simple 1:1 adduct was demonstrated.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
876899
Report Number(s):
PNNL-SA-44252
Journal ID: ISSN 0095-9782; JSLCAG; KP1302000; TRN: US200608%%282
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solution Chemistry, 34(10):1145-1166; Journal Volume: 34; Journal Issue: 10
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ADDUCTS; ANIONS; COMPUTERS; CROWN ETHERS; HYDROGEN; MODIFICATIONS; NITRATES; NITROBENZENE; SODIUM IONS; SODIUM NITRATES; SOLVATION; SOLVENTS; SPECTROSCOPY; TRANSPORT

Citation Formats

Levitskaia, Tatiana G., and Lumetta, Gregg J. Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether. United States: N. p., 2005. Web. doi:10.1007/s10953-005-7693-x.
Levitskaia, Tatiana G., & Lumetta, Gregg J. Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether. United States. doi:10.1007/s10953-005-7693-x.
Levitskaia, Tatiana G., and Lumetta, Gregg J. Mon . "Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether". United States. doi:10.1007/s10953-005-7693-x.
@article{osti_876899,
title = {Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether},
author = {Levitskaia, Tatiana G. and Lumetta, Gregg J.},
abstractNote = {A comparative quantitative analysis of the effect of solvent modifiers on an ion-pair extraction of an inorganic salt by a crown ether was conducted. Two classes of the solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenyl acetamide—the enhancement of the NaNO3 extraction by 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier quantified by the b solvatochromic parameter. Application of the solvent EPD modifier improved solvation of the sodium ion, lowering the large energy barrier of Na+ partitioning into the extraction phase. A HBD modifier 3,5-di-t-butylphenol 8 that forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO3 extraction by 1. The determined extraction constants were correlated with the b or a solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between 3,5-di-t-butylphenol 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phases was studied by vibrational spectroscopy. Formation of the simple 1:1 adduct was demonstrated.},
doi = {10.1007/s10953-005-7693-x},
journal = {Journal of Solution Chemistry, 34(10):1145-1166},
number = 10,
volume = 34,
place = {United States},
year = {Mon Oct 31 00:00:00 EST 2005},
month = {Mon Oct 31 00:00:00 EST 2005}
}