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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}
}
  • From extraction experiments and c-activity measurements, the exchange extraction constants corresponding to the general equilibrium M+ (aq) + NaL+ (nb) , ML+ (nb) + Na+ (aq) taking place in the two-phase water nitrobenzene system (M+ = Li+, H3O+, NH+4; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML+ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: zH3O+ < Li+ < NH+4.
  • The influence of the dielectric constant of an organic solvent on the extraction of sodium picrate by 15-crown-5 ether was studied using sodium-22. The logarithm of the extraction constants decrease linearly with increase in the reciprocal value of the dielectric constant of an organic solvent.
  • Synergistic extraction of trivalent lanthanides(Ln) was investigated using thenoyltrifluoroacetone(HTTA) and crown ether(CE). Characteristic ion-pair extraction of the lighter Ln(III) was observed with 1,2-dichloroethane containing HTTA and 18-crown-6 or dicyclohexano-18-crown-6, in which the cationic complex, Ln(TTA){sub 2}CE{sup +}, was formed and extracted. Remarkable increases of an extractability and a selectivity were attained in the synergistic ion-pair extraction of the lighter Ln ions, which could be elucidated on the basis of size-fitting effect in the complex formation of the lighter Ln ions with CE. 19 refs., 2 figs., 3 tabs.
  • Competitive solvent extraction of alkali-metal cations from aqueous solutions into chlororform by a series of lipophilic crown ether carboxylic acids with varying ring sizes is reported. Extraction selectivity for Li{sup +} is observed for lipophilic crown ether carboxylic acids with 12-15-membered polyether rings containing four oxygen atoms. For lipophilic 14-crown-4-carboxylic acids, very high Li{sup +}/Na{sup +} selectivity coefficients of 17-20 are observed with no detectable extraction of K{sup +}, Rb{sup +}, or Cs{sup +}. Lipophilic crown ether carboxylic acids which contain 15-crown-5, 18-crown-6, and 21-crown-7 rings exhibit good selectivities for Na{sup +}, K{sup +}, and Cs{sup +}, respectively. In contrast,more » poor extraction selectivity is observed for lipophilic crown ether carboxylic acids with 24-crown-8, 27-crown-9, and 30-crown-10 rings.« less
  • The extraction of alkali metal nitrate salts by 24-crown-8 ethers bearing multiple benzo substituents has been surveyed in 1,2-dichloroethane diluent at 25 {degrees}C. The results reveal that the addition of benzo-substituents onto the 24-crown-8 increases both the extraction efficiency and the selectivity for the larger cations. Substitution of branched alkyl groups onto the benzo rings of 24-crown-8 ethers has a relatively small influence on their extraction properties.