Target-guided separation of Bougainvillea glabra betacyanins by direct coupling of preparative ion-pair high-speed countercurrent chromatography and electrospray ionization mass-spectrometry.

PubMed

Jerz, Gerold; Wybraniec, Sławomir; Gebers, Nadine; Winterhalter, Peter

2010-07-02

In this study, preparative ion-pair high-speed countercurrent chromatography was directly coupled to an electrospray ionization mass-spectrometry device (IP-HSCCC/ESI-MS-MS) for target-guided fractionation of high molecular weight acyl-oligosaccharide linked betacyanins from purple bracts of Bougainvillea glabra (Nyctaginaceae). The direct identification of six principal acyl-oligosaccharide linked betacyanins in the mass range between m/z 859 and m/z 1359 was achieved by positive ESI-MS ionization and gave access to the genuine pigment profile already during the proceeding of the preparative separation. Inclusively, all MS/MS-fragmentation data were provided during the chromatographic run for a complete analysis of substitution pattern. On-line purity evaluation of the recovered fractions is of high value in target-guided screening procedures and for immediate decisions about suitable fractions used for further structural analysis. The applied preparative hyphenation was shown to be a versatile screening method for on-line monitoring of countercurrent chromatographic separations of polar crude pigment extracts and also traced some minor concentrated compounds. For the separation of 760mg crude pigment extract the biphasic solvent system tert.-butylmethylether/n-butanol/acetonitrile/water 2:2:1:5 (v/v/v/v) was used with addition of ion-pair forming reagent trifluoroacetic acid. The preparative HSCCC-eluate had to be modified by post-column addition of a make-up solvent stream containing formic acid to reduce ion-suppression caused by trifluoroacetic acid and later significantly maximized response of ESI-MS/MS detection of target substances. A variable low-pressure split-unit guided a micro-eluate to the ESI-MS-interface for sensitive and direct on-line detection, and the major volume of the effluent stream was directed to the fraction collector for preparative sample recovery. The applied make-up solvent mixture significantly improved smoothness of the continuously measured IP-HSCCC-ESI-MS base peak ion trace in the experimental range of m/z 50-2200 by masking stationary phase bleeding and generating a stable single solvent phase for ESI-MS/MS detection. Immediate structural data were retrieved throughout the countercurrent chromatography run containing complete MS/MS-fragmentation pattern of the separated acyl-substituted betanidin oligoglycosides. Single ion monitoring indicated clearly the base-line separation of higher concentrated acylated betacyanin components. Copyright 2010 Elsevier B.V. All rights reserved.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Reuse of organobentonites with a carbon dioxide responsive solvent.

PubMed

Luan, Ling-Yu; Zhang, Li; Wang, Li-Hong

2018-05-22

Synthesized organobentonite (SOB), montmorillonite (MMT), and commercial organobentonite (COB) were used as adsorbents for paraffin oil, a model pollutant in land-based oil spills and oil pipeline rupture. The characterization of clays was carried out with scanning electron microscopy (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). After adsorption, oil was separated from adsorbents with a carbon dioxide responsive solvent N,N-dimethylcyclohexylamine (DMCHA), and DMCHA was subsequently separated from paraffin oil upon CO 2 bubbling instead of distillation with high energy cost. The adsorption capacity of oil to SOB, MMT, and COB was 0.686, 1.124, and 1.239 g/g, respectively. It was found that the adsorption capacity and rinsed amount of the adsorbents depended on the d-spacing, which is related to surfactant content. Electrical conductivity and pH measurements suggested that the separation process occurred via two steps. Firstly, during the initial 35 min, carbonate ions coexisted with bicarbonate ions. Then, only bicarbonate ions existed after the introduction of CO 2 gas for 120 min. Thus, organobentonites were feasible for hydrocarbon adsorption and could be simply reused by an amine-based responsive solvent. This work provided a cost-effective and sustainable method of recycling of organobentonites and the responsive solvent, which can be used to deal with leaked oil and oil spills.

Identification of ion-pair structures in solution by vibrational stark effects

DOE PAGES

Hack, John; Mani, Tomoyasu; Grills, David C.; ...

2016-01-25

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Identification of ion-pair structures in solution by vibrational stark effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hack, John; Mani, Tomoyasu; Grills, David C.

Here, ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N)more » infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.« less

Batch extracting process using magnetic particle held solvents

DOEpatents

Nunez, L.; Vandergrift, G.F.

1995-11-21

A process is described for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents. 5 figs.

Exciplexes versus Loose Ion Pairs: How Does the Driving Force Impact the Initial Product Ratio of Photoinduced Charge Separation Reactions?

PubMed Central

2014-01-01

Many donor–acceptor systems can undergo a photoinduced charge separation reaction, yielding loose ion pairs (LIPs). LIPs can be formed either directly via (distant) electron transfer (ET) or indirectly via the dissociation of an initially formed exciplex or tight ion pair. Establishing the prevalence of one of the reaction pathways is challenging because differentiating initially formed exciplexes from LIPs is difficult due to similar spectroscopic footprints. Hence, no comprehensive reaction model has been established for moderately polar solvents. Here, we employ an approach based on the time-resolved magnetic field effect (MFE) of the delayed exciplex luminescence to distinguish the two reaction channels. We focus on the effects of the driving force of ET and the solvent permittivity. We show that, surprisingly, the exciplex channel is significant even for an exergonic ET system with a free energy of ET of −0.58 eV and for the most polar solutions studied (butyronitrile). Our findings demonstrate that exciplexes play a crucial role even in polar solvents and at moderate driving forces, contrary to what is usually assumed. PMID:25243054

Higher Americium Oxidation State Research Roadmap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mincher, Bruce J.; Law, Jack D.; Goff, George S.

2015-12-18

The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained undermore » the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non-solvent-extraction separations are also under investigation. The first would separate Am(VI) by co-crystallization with uranium and the other oxidizable actinides as their nitrate salts. This novel idea has been successful in lab scale testing, and merits further investigation. Similarly, success has been achieved in separations using inorganic or hybrid ion exchange materials to sorb the lanthanides and actinides, while allowing pentavalent americium to elute. This is the only technique currently investigating Am(V), despite the advantages of this oxidation state with regard to its higher stability. The ultimate destination for this roadmap is to develop an americium separation that can be applied under process conditions, preferably affording a co-separation of the actinyl (VI) ions. Toward that end, emphasis is given here to selection of a solvent extraction flowsheet for testing in the INL centrifugal contactor hot test bed during FY16. A solvent extraction process will be tested mainly because solvent extraction separations of Am(VI) are relatively mature and the test bed currently exists in a configuration to support them. Thus, a major goal of FY16 is to select the oxidant/ligand combination to run such a test using the contactors. The only ligands under consideration are DAAP and DEHBA. This is not to say that ion exchange and co-crystallization techniques are unimportant. They merit continued investigation, but are not mature enough for hot test bed testing at this time.« less

Does an electronic continuum correction improve effective short-range ion-ion interactions in aqueous solution?

NASA Astrophysics Data System (ADS)

Bruce, Ellen E.; van der Vegt, Nico F. A.

2018-06-01

Non-polarizable force fields for hydrated ions not always accurately describe short-range ion-ion interactions, frequently leading to artificial ion clustering in bulk aqueous solutions. This can be avoided by adjusting the nonbonded anion-cation or cation-water Lennard-Jones parameters. This approach has been successfully applied to different systems, but the parameterization is demanding owing to the necessity of separate investigations of each ion pair. Alternatively, polarization effects may effectively be accounted for using the electronic continuum correction (ECC) of Leontyev et al. [J. Chem. Phys. 119, 8024 (2003)], which involves scaling the ionic charges with the inverse square-root of the water high-frequency dielectric permittivity. ECC has proven to perform well for monovalent salts as well as for divalent salts in water. Its performance, however, for multivalent salts with higher valency remains unexplored. The present work illustrates the applicability of the ECC model to trivalent K3PO4 and divalent K2HPO4 in water. We demonstrate that the ECC models, without additional tuning of force field parameters, provide an accurate description of water-mediated interactions between salt ions. This results in predictions of the osmotic coefficients of aqueous K3PO4 and K2HPO4 solutions in good agreement with experimental data. Analysis of ion pairing thermodynamics in terms of contact ion pair (CIP), solvent-separated ion pair, and double solvent-separated ion pair contributions shows that potassium-phosphate CIP formation is stronger with trivalent than with divalent phosphate ions.

Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions

DOE PAGES

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet; ...

2016-07-01

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS.

PubMed

Zhang, Yanyan; Su, Mao; Yu, Xiaofei; Zhou, Yufan; Wang, Jungang; Cao, Ruiguo; Xu, Wu; Wang, Chongmin; Baer, Donald R; Borodin, Oleg; Xu, Kang; Wang, Yanting; Wang, Xue-Lin; Xu, Zhijie; Wang, Fuyi; Zhu, Zihua

2018-03-06

Ion-solvent interactions in nonaqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF 6 ) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC) and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li + by EC. Besides, from the negative spectra, we also found that PF 6 - forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. In both LiFSI in DME electrolytes, however, no evidence shows that FSI - is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF 6 in EC-DMC electrolyte, suggesting that a significant amount of Li + ions stay in the vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in nonaqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.

Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanyan; Su, Mao; Yu, Xiaofei

2018-02-06

Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC,more » which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.« less

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

DOE PAGES

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne

2015-11-24

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ionsmore » having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D 2-tagged GlyGlyH +·(H 2O) 1–4 are presented. As a result, they display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

Investigation of Ion–Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanyan; Su, Mao; Yu, Xiaofei

Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC,more » which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.« less

Method for separating mono- and di-octylphenyl phosphoric acid esters

DOEpatents

Arnold, Jr., Wesley D.

1977-01-01

A method for separating mono-octylphenyl phosphoric acid ester and di-octylphenyl phosphoric acid ester from a mixture thereof comprises reacting the ester mixture with a source of lithium or sodium ions to form a mixture of the phosphate salts; contacting the salt mixture with an organic solvent which causes the dioctylphenyl phosphate salt to be dissolved in the organic solvent phase and the mono-octylphenyl phosphate salt to exist in a solid phase; separating the phases; recovering the phosphate salts from their respective phases; and acidifying the recovered salts to form the original phosphoric acid esters.

Bimodal Exciplex Formation in Bimolecular Photoinduced Electron Transfer Revealed by Ultrafast Time-Resolved Infrared Absorption.

PubMed

Koch, Marius; Licari, Giuseppe; Vauthey, Eric

2015-09-03

The dynamics of a moderately exergonic photoinduced charge separation has been investigated by ultrafast time-resolved infrared absorption with the dimethylanthracene/phthalonitrile donor/acceptor pair in solvents covering a broad range of polarity. A distinct spectral signature of an exciplex could be identified in the -C≡N stretching region. On the basis of quantum chemistry calculations, the 4-5 times larger width of this band compared to those of the ions and of the locally excited donor bands is explained by a dynamic distribution of exciplex geometry with different mutual orientations and distances of the constituents and, thus, with varying charge-transfer character. Although spectrally similar, two types of exciplexes could be distinguished by their dynamics: short-lived, "tight", exciplexes generated upon static quenching and longer-lived, "loose", exciplexes formed upon dynamic quenching in parallel with ion pairs. Tight exciplexes were observed in all solvents, except in the least polar diethyl ether where quenching is slower than diffusion. The product distribution of the dynamic quenching depends strongly on the solvent polarity: whereas no significant loose exciplex population could be detected in acetonitrile, both exciplex and ion pair are generated in less polar solvents, with the relative population of exciplex increasing with decreasing solvent polarity. These results are compared with those reported previously with donor/acceptor pairs in different driving force regimes to obtain a comprehensive picture of the role of the exciplexes in bimolecular photoinduced charge separation.

Method of separating and recovering uranium and related cations from spent Purex-type systems

DOEpatents

Mailen, J.C.; Tallent, O.K.

1987-02-25

A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

Separation and characterisation of five polar herbicides using countercurrent chromatography with detection by negative ion electrospray ionisation mass spectrometry.

PubMed

Kidwell, H; Jones, J J; Games, D E

2001-01-01

Five polar herbicides were separated and characterised using high-speed analytical countercurrent chromatography (HSACCC) in conjunction with online electrospray mass spectrometry (ESI-MS). The countercurrent chromatography used a standard isocratic biphasic solvent system of hexane/ethyl acetate/methanol/water in reverse phase to effect the separation of these five environmentally important compounds. The chromatograph was coupled to a triple quadrupole mass spectrometer via a standard electrospray liquid chromatography interface that was able to give mass spectra in negative ion mode of each compound. Limits of detection are reported for this series of compounds along with representative negative ion ESI-MS data and calibrations for the separation. Copyright 2001 John Wiley & Sons, Ltd.

A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Jinhong; Song, Jongchan; Lee, Hongkyung

Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interfacemore » of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.« less

ACCELERATED SOLVENT EXTRACTION OF ARSENICALS FROM ENVIRONMENTAL MATRICES WITH ION CHROMATOGRAPHY SEPARATION AND ICP-MS DETECTION

EPA Science Inventory

The two major sources of arsenic exposure used in an arsenic risk assessment are water and diet. The extraction, separation and quantification of individual arsenic species from dietary sources is considered an area of uncertainty within the arsenic risk assessment. The uncertain...

Calculation of activities of ions in molten salts with potential application to the pyroprocessing of nuclear waste.

PubMed

Salanne, Mathieu; Simon, Christian; Turq, Pierre; Madden, Paul A

2008-01-31

The ability to separate fission products by electrodeposition from molten salts depends, in part, on differences between the interactions of the different fission product cations with the ions present in the molten salt "solvent". These differences may be expressed as ratios of activity coefficients, which depend on the identity of the solvent and other factors. Here, we demonstrate the ability to calculate these activity coefficient ratios using molecular dynamics simulations with sufficient precision to guide the choice of suitable solvent systems in practical applications. We use polarizable ion interaction potentials which have previously been shown to give excellent agreement with structural, transport, and spectroscopic information of the molten salts, and the activity coefficients calculated in this work agree well with experimental data. The activity coefficients are shown to vary systematically with cation size for a set of trivalent cations.

Novel Separation of Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mariella, R

The separation of actinides and other elements of interest for nuclear forensics and threat reduction is currently performed using decades-old chemistries and ion-exchange columns. We propose to determine the technical feasibility of a novel method for separating actinide ions in solution. This method is based upon isotachophoresis (ITP), which has been applied in the purification of pharmaceuticals and other biochemical applications. This technique has the potential to separate inorganic ions more effectively than existing methods, which is key to analyzing very small samples. We will perform a quantitative assessment of the effectiveness of specific isotachophoretic approaches including predicting the physicalmore » and chemical properties, such as ion mobility, of inorganic ions under specific solvent conditions using a combination of ab initio calculations and semi-empirical methods. We expect to obtain a thorough understanding of the analytical systems parameters under which ITP is most effective for the separation of inorganic samples, including the influence of the double layer surrounding actinide ions, the Debye length for different ions and ion complexes, and Debye-Hueckel limits. Inorganic separations are key to nuclear forensics for countering terrorism and nuclear proliferation. If found to be feasible and potentially superior to currently used separation approaches, ITP could provide the conceptual basis for an improved means to separate samples of nuclear explosion debris for nuclear forensic analysis, in support of the Laboratory's missions in homeland and national security.« less

Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution

NASA Astrophysics Data System (ADS)

Olsen, Jógvan Magnus Haugaard; Hedegård, Erik Donovan

The absorption spectrum of the MnO$_{4}$$^{-}$ ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO$_{4}$$^{-}$, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO$_{4}$$^{-}$ in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO$_{4}$$^{-}$ absorption spectrum, whose assignment has been elusive.

URANIUM SEPARATION PROCESS

DOEpatents

Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

1959-07-14

The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

SEPARATION OF URANIUM FROM ZIRCONIUM AND NIOBIUM BY SOLVENT EXTRACTION

DOEpatents

Voiland, E.E.

1958-05-01

A process for separation of the uranium from zirconium and/or niobium values contained in 3 to 7M aqueous nitric acid solutions is described. This is accomplished by adding phosphoric acid anions to the nitric acid solution containing the uranium, zirconium, and/or niobium in an amount sufficient to make the solution 0.05 to 0.2M in phosphate ion and contacting the solution with an organic water-immiscible solvent such as MEK, whereby the uranyl values are taken up by the extract phase while the zirconium and niobium preferentially remain in the aqueous raffinate.

Chemical speciation and recovery of gold(I, III) from wastewater and silver by liquid-liquid extraction with the ion-pair reagent amiloride mono hydrochloride and AAS determination.

PubMed

El-Shahawi, M S; Bashammakh, A S; Bahaffi, S O

2007-06-15

A novel and low cost liquid-liquid extraction procedure for the separation of gold(III) at trace level from aqueous medium of pH 5-9 has been developed. The method has been based upon the formation of a yellow colored ternary complex ion associate of tetrachloro gold(III) complex anion, AuCl(4)(-) with the ion-pair reagent 1-(3,5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride, DPG(+).Cl(-). The effect of various parameters, e.g. pH, organic solvent, shaking time, etc. on the preconcentration of gold(III) from the aqueous media by the DPG(+).Cl(-) reagent has been investigated. The colored gold species was quantitatively extracted into 4-methyl pentan-2-one. The chemical composition of the ion associate of DPG(+).Cl(-) with AuCl(4)(-) in the organic solvent has been determined by the Job's method. The molar absorptivity (2.19x10(4)Lmol(-1)cm(-1)) of the associate DPG(+).AuCl(4)(-) at 362nm enabled a convenient application of the developed extraction procedure for the separation and AAS determination of traces of aurate ions. Mono-valence gold ions after oxidation to gold(III) with bromine water in HCl (1.0molL(-1)) media have been also extracted quantitatively from the aqueous media by the developed procedure. The chemical speciation of mono- and/or tri-valence gold species spiked to fresh and industrial wastewater samples has been achieved. The method has been also applied successfully from the separation of gold(I) and gold(III) species from metallic ions and silver. The developed method has also the advantage of freedom from most diverse ions.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

The chapter summarizes the state of knowledge about a metal transport in two-phase system. The first part of this review focuses on the distribution law and main factors determination in classical solvent extraction (solubility and polarity of the solute, as well as inter- and intramolecules interaction. Next part of the chapter is devoted to the reactive solvent extraction and the molecular modeling requiring knowledge on type of extractants, complexation mechanisms, metals ions speciation and oxidation during complexes forming, and other parameters that enable to understand the extraction process. Also the kinetic data that is needed for proper modeling, simulation and design of processes needed for critical separations are discussed. Extraction at liquid-solid system using solvent impregnated resins is partially identical as in the case of the corresponding solvent extraction, therefore this subject was also presented in all aspects of separation process (equilibrium, mechanism, kinetics).

The nature of cation-pi binding: interactions between tetramethylammonium ion and benzene in aqueous solution.

PubMed Central

Gao, J; Chou, L W; Auerbach, A

1993-01-01

A combined quantum mechanical and molecular mechanical Monte Carlo simulation method was used to determine the free energy of binding between tetramethylammonium ion (TMA+) and benzene in water. The computed free energy as a function of distance (the potential of mean force) has two minima that represent contact and solvent-separated complexes. These species are separated by a broad barrier of about 3 kJ/mol. The results are in good accord with experimental data and suggest that TMA+ binds to benzene more favorably than to chloride ion, with an association constant of about 0.8 M-1. Images FIGURE 2 PMID:8369448

Ionic liquid/water mixtures: from hostility to conciliation.

PubMed

Kohno, Yuki; Ohno, Hiroyuki

2012-07-21

Water was originally inimical to ionic liquids (ILs) especially in the analysis of their detailed properties. Various data on the properties of ILs indicate that there are two ways to design functions of ionic liquids. The first is to change the structure of component ions, to provide "task-specific ILs". The second is to mix ILs with other components, such as other ILs, organic solvents or water. Mixing makes it easy to control the properties of the solution. In this strategy, water is now a very important partner. Below, we summarise our recent results on the properties of IL/water mixtures. Stable phase separation is an effective method in some separation processes. Conversely, a dynamic phase change between a homogeneous mixture and separation of phases is important in many fields. Analysis of the relation between phase behaviour and the hydration state of the component ions indicates that the pattern of phase separation is governed by the hydrophilicity of the ions. Sufficiently hydrophilic ions yielded ILs that are miscible with water, and hydrophobic ions gave stable phase separation with water. ILs composed of hydrophobic but hydrated ions undergo a dynamic phase change between a homogeneous mixture and separate phases according to temperature. ILs having more than seven water molecules per ion pair undergo this phase transition. These dynamic phase changes are considered, with some examples, and application is made to the separation of water-soluble proteins.

Synthesis, characterization and analytical application of hybrid; acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions.

PubMed

Nabi, Syed A; Shalla, Aabid H

2009-04-30

A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na(+) ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 degrees C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb(2+) ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb(2+) has been selectively removed from synthetic mixtures containing Mg(2+), Ca(2+), Sr(2+), Zn(2+) and Cu(2+), Al(3+), Ni(2+), Fe(3+). In order to demonstrate practical utility of the material quantitative separation of the Cu(2+) and Zn(2+) in brass sample has been achieved on its columns.

Greatly Increasing Trapped Ion Populations for Mobility Separations Using Traveling Waves in Structures for Lossless Ion Manipulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Liulin; Ibrahim, Yehia M.; Garimella, Sandilya V. B.

The initial use of traveling waves (TW) for ion mobility (IM) separations using a structures for lossless ion manipulations (SLIM) employed an ion funnel trap (IFT) to accumulate ions from a continuous electrospray ionization source, and limited to injected ion populations of ~106 charges due to the onset of space charge effects in the trapping region. Additional limitations arise due to the loss of resolution for the injection of ions over longer periods (e.g. in extended pulses). In this work a new SLIM ‘flat funnel’ (FF) module has been developed and demonstrated to enable the accumulation of much larger ionmore » populations and their injection for IM separations. Ion current measurements indicate a capacity of ~3.2×108 charges for the extended trapping volume, over an order of magnitude greater than the IFT. The orthogonal ion injection into a funnel shaped separation region can greatly reduce space charge effects during the initial IM separation stage, and the gradually reduced width of the path allows the ion packet to be increasingly compressed in the lateral dimension as the separation progresses, allowing e.g. efficient transmission through conductance limits or compatibility with subsequent ion manipulations. This work examined the TW, RF, and DC confining field SLIM parameters involved in ion accumulation, injection, transmission and separation in the FF IM module using both direct ion current and MS measurements. Wide m/z range ion transmission is demonstrated, along with significant increases in signal to noise (S/N) ratios due to the larger ion populations injected. Additionally, we observed a reduction in the chemical background, which was attributed to more efficient desolvation of solvent related clusters over the extended ion accumulation periods. The TW SLIM FF IM module is anticipated to be especially effective as a front end for long path SLIM IM separation modules.« less

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

Highly selective Ba2+ separations with acyclic, lipophilic di-[N-(X)sulfonyl carbamoyl] polyethers.

PubMed

Elshani, Sadik; Chun, Sangki; Amiri-Eliasi, Bijan; Bartsch, Richard A

2005-01-14

New lipophilic acyclic polyethers with two N-(X)sulfonyl carbamoyl groups of "tunable" acidity exhibit remarkable selectivity for Ba2+ over other alkaline earth metal ions in competitive solvent extraction and transport across polymer inclusion membranes.

Utilization of Methacrylates and Polymer Matrices for the Synthesis of Ion Specific Resins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Czerwinski, Kenneth

2013-10-29

Disposal, storage, and/or transmutation of actinides such as americium (Am) will require the development of specific separation schemes. Existing efforts focus on solvent extraction systems for achieving suitable separation of actinide from lanthanides. However, previous work has shown the feasibility of ion-imprinting polymer-based resins for use in ion-exchange-type separations with metal ion recognition. Phenolic-based resins have been shown to function well for Am-Eu separations, but these resins exhibited slow kinetics and difficulties in the imprinting process. This project addresses the need for new and innovative methods for the selective separation of actinides through novel ion-imprinted resins. The project team willmore » explore incorporation of metals into extended frameworks, including the possibility of 3D polymerized matrices that can serve as a solid-state template for specific resin preparation. For example, an anhydrous trivalent f-element chain can be formed directly from a metal carbonate, and methacrylic acid from water. From these simple coordination complexes, molecules of discrete size or shape can be formed via the utilization of coordinating ligands or by use of an anionic multi-ligand system incorporating methacrylate. Additionally, alkyl methyl methacrylates have been used successfully to create template nanospaces, which underscores their potential utility as 3D polymerized matrices. This evidence provides a unique route for the preparation of a specific metal ion template for the basis of ion-exchange separations. Such separations may prove to be excellent discriminators of metal ions, even between f-elements. Resins were prepared and evaluated for sorption behavior, column properties, and proton exchange capacity.« less

Microstructural Analysis of the Effects of Thermal Runaway on Li-Ion and Na-Ion Battery Electrodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finegan, Donal; Robinson, James B.; Heenan, Thomas M. M.

Thermal runaway is a phenomenon that occurs due to self-sustaining reactions within batteries at elevated temperatures resulting in catastrophic failure. Here, the thermal runaway process is studied for a Li-ion and Na-ion pouch cells of similar energy density (10.5 Wh, 12 Wh, respectively) using accelerating rate calorimetry (ARC). Both cells were constructed with a z-fold configuration, with a standard shutdown separator in the Li-ion and a low-cost polypropylene (PP) separator in the Na-ion. Even with the shutdown separator, it is shown that the self-heating rate and rate of thermal runaway in Na-ion cells is significantly slower than that observed inmore » Li-ion systems. The thermal runaway event initiates at a higher temperature in Na-ion cells. The effect of thermal runaway on the architecture of the cells is examined using X-ray microcomputed tomography, and scanning electron microscopy (SEM) is used to examine the failed electrodes of both cells. Finally, from examination of the respective electrodes, likely due to the carbonate solvent containing electrolyte, it is suggested that thermal runaway in Na-ion batteries (NIBs) occurs via a similar mechanism to that reported for Li-ion cells.« less

Development of Cellulose/PVDF-HFP Composite Membranes for Advanced Battery Separators

NASA Astrophysics Data System (ADS)

Castillo, Alejandro; Agubra, Victor; Alcoutlabi, Mataz; Mao, Yuanbing

Improvements in battery technology are necessary as Li-ion batteries transition from consumer electronic to vehicular and industrial uses. An important bottle-neck in battery efficiency and safety is the quality of the separators, which prevent electric short-circuits between cathode and anode, while allowing an easy flow of ions between them. In this study, cellulose acetate was dissolved in a mixed solvent with poly(vinylpyrrolidone) (PVP), and the mixture was forcespun in a peudo paper making process to yield nanofibrillated nonwoven mats. The mats were soaked in NaOH/Ethanol to strip PVP and regenerate cellulose from its acetate precursor. The cellulose mats were then dipped in poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) to yield the cellulose/PVDF-HFP composte membranes. These membranes were characterized chemically through FTIR spectroscopy and solvent-stability tests, thermally through DSC, physically by stress/strain measurements along with weight-based electrolyte uptake, and electrically by AC-impedance spectroscopy combined with capacitative cycling.

Development of a universal solvent for the decontamination of acidic liquid radioactive wastes

NASA Astrophysics Data System (ADS)

Todd, T. A.; Brewer, K. N.; Law, J. D.; Wood, D. J.; Herbest, R. S.; Romanovskiy, V. N.; Esimantovskiy, V. M.; Smirnov, I. V.; Babain, V. A.

1999-01-01

A teritiary solvent containing chlorinated cobalt dicarbollide, polyethylene glycol and diphenylcarbamoylmethylphosphine oxide was evaluated in different non-nitroaromatic diluents for the separation of cesium, strontium, actinides and rare earth elements from acidic liquid radioactive waste. Decontamination factors of >95% for Cs, 99.7% for Sr, and 99.99% for actinides were achieved in four successive batch contacts using actual radioactive waste. Pilot plant testing in centrifugal contactors using simulated wastes, has demonstrated removal of >99% of all targeted ions.

SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Clark, H.M.; Duffey, D.

1958-06-17

A process is described for extracting uranium from uranium ore, wherein the uranium is substantially free from molybdenum contamination. In a solvent extraction process for recovering uranium, uranium and molybdenum ions are extracted from the ore with ether under high acidity conditions. The ether phase is then stripped with water at a lower controiled acidity, resaturated with salting materials such as sodium nitrate, and reextracted with the separation of the molybdenum from the uranium without interference from other metals that have been previously extracted.

A calix[4]arene strapped calix[4]pyrrole: an ion-pair receptor displaying three different cesium cation recognition modes.

PubMed

Kim, Sung Kuk; Sessler, Jonathan L; Gross, Dustin E; Lee, Chang-Hee; Kim, Jong Seung; Lynch, Vincent M; Delmau, Laetitia H; Hay, Benjamin P

2010-04-28

An ion-pair receptor, the calix[4]pyrrole-calix[4]arene pseudodimer 2, bearing a strong anion-recognition site but not a weak cation-recognition site, has been synthesized and characterized by standard spectroscopic means and via single-crystal X-ray diffraction analysis. In 10% CD(3)OD in CDCl(3) (v/v), this new receptor binds neither the Cs(+) cation nor the F(-) anion when exposed to these species in the presence of other counterions; however, it forms a stable 1:1 solvent-separated CsF complex when exposed to these two ions in concert with one another in this same solvent mixture. In contrast to what is seen in the case of a previously reported crown ether "strapped" calixarene-calixpyrrole ion-pair receptor 1 (J. Am. Chem. Soc. 2008, 130, 13162-13166), where Cs(+) cation recognition takes place within the crown, in 2.CsF cation recognition takes place within the receptor cavity itself, as inferred from both single-crystal X-ray diffraction analyses and (1)H NMR spectroscopic studies. This binding mode is supported by calculations carried out using the MMFF94 force field model. In 10% CD(3)OD in CDCl(3) (v/v), receptor 2 shows selectivity for CsF over the Cs(+) salts of Cl(-), Br(-), and NO(3)(-) but will bind these other cesium salts in the absence of fluoride, both in solution and in the solid state. In the case of CsCl, an unprecedented 2:2 complex is observed in the solid state that is characterized by two different ion-pair binding modes. One of these consists of a contact ion pair with the cesium cation and chloride anion both being bound within the central binding pocket and in direct contact with one another. The other mode involves a chloride anion bound to the pyrrole NH protons of a calixpyrrole subunit and a cesium cation sandwiched between two cone shaped calix[4]pyrroles originating from separate receptor units. In contrast to what is seen for CsF and CsCl, single-crystal X-ray structural analyses and (1)H NMR spectroscopic studies reveal that receptor 2 forms a 1:1 complex with CsNO(3), with the ions bound in the form of a contact ion pair. Thus, depending on the counteranion, receptor 2 is able to stabilize three different ion-pair binding modes with Cs(+), namely solvent-bridged, contact, and host-separated.

Effect of injection matrix concentration on peak shape and separation efficiency in ion chromatography.

PubMed

Zhang, Ya; Lucy, Charles A

2014-12-05

In HPLC, injection of solvents that differ from the eluent can result in peak broadening due to solvent strength mismatch or viscous fingering. Broadened, distorted or even split analyte peaks may result. Past studies of this injection-induced peak distortion in reversed phase (RPLC) and hydrophilic interaction (HILIC) liquid chromatography have led to the conclusion that the sample should be injected in the eluent or a weaker solvent. However, there have been no studies of injection-induced peak distortion in ion chromatography (IC). To address this, injection-induced effects were studied for six inorganic anions (F-, Cl-, NO2-, Br-, NO3- and SO4(2-)) on a Dionex AS23 IC column using a HCO3-/CO3(2-) eluent. The VanMiddlesworth-Dorsey injection sensitivity parameter (s) showed that IC of anions has much greater tolerance to the injection matrix (HCO3-/CO3(2-) herein) mismatch than RPLC or HILIC. Even when the injection contained a ten-fold greater concentration of HCO3-/CO3(2-) than the eluent, the peak shapes and separation efficiencies of six analyte ions did not change significantly. At more than ten-fold greater matrix concentrations, analyte anions that elute near the system peak of the matrix were distorted, and in the extreme cases exhibited a small secondary peak on the analyte peak front. These studies better guide the degree of dilution needed prior to IC analysis of anions. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, Michael; Bates, John K.

1981-01-01

A system and method for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 Kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

The separation distance distribution in electron-donor-acceptor systems and the wavelength dependence of free ion yields

NASA Astrophysics Data System (ADS)

Zhou, Jinwei; Findley, Bret R.; Braun, Charles L.; Sutin, Norman

2001-06-01

We recently reported that free radical ion quantum yields for electron-donor-acceptor (EDA) systems of alkylbenzenes-tetracyanoethylene (TCNE) exhibit a remarkable wavelength dependence in dichloromethane, a medium polarity solvent. We proposed that weak absorption by long-distance, unassociated or "random" D⋯A pairs is mainly responsible for the free radical ion yield. Here a model for the wavelength dependence of the free ion yield is developed for four systems in which differing degrees of EDA complex formation are present: 1,3,5-tri-tert-butylbenzene-TCNE in which only random pairs exist due to the bulky groups on the electron donor, and toluene—TCNE, 1,3,5-triethylbenzene-TCNE and 1,3,5-trimethylbenzene-TCNE. Mulliken-Hush theory is used to determine the excitation distance distribution of unassociated, random pairs at different wavelengths. For each absorption distribution, free radical ion yields at different wavelengths are then calculated using Onsager's result for the ion separation probability. Encouraging agreement between the calculated yields and our experimental results is obtained. As far as we are aware, this is the first time that photoexcitation of unassociated donor/acceptor pairs has been invoked as the source of separated radical ion pairs.

Process for removal of hazardous air pollutants from coal

DOEpatents

Akers, David J.; Ekechukwu, Kenneth N.; Aluko, Mobolaji E.; Lebowitz, Howard E.

2000-01-01

An improved process for removing mercury and other trace elements from coal containing pyrite by forming a slurry of finely divided coal in a liquid solvent capable of forming ions or radicals having a tendency to react with constituents of pyrite or to attack the bond between pyrite and coal and/or to react with mercury to form mercury vapors, and heating the slurry in a closed container to a temperature of at least about 50.degree. C. to produce vapors of the solvent and withdrawing vapors including solvent and mercury-containing vapors from the closed container, then separating mercury from the vapors withdrawn.

Solvate Structures and Computational/Spectroscopic Characterization of LiPF6 Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Sang D.; Yun, Sung-Hyun; Borodin, Oleg

2015-04-23

Raman spectroscopy is a powerful method for identifying ion-ion interactions, but only if the vibrational band signature for the anion coordination modes can be accurately deciphered. The present study characterizes the PF6- anion P-F Raman symmetric stretching vibrational band for evaluating the PF6-...Li+ cation interactions within LiPF6 crystalline solvates to create a characterization tool for liquid electrolytes. To facilitate this, the crystal structures for two new solvates—(G3)1:LiPF6 and (DEC)2:LiPF6 with triglyme and diethyl carbonate, respectively—are reported. The information obtained from this analysis provides key guidance about the ionic association information which may be obtained from a Raman spectroscopic evaluation ofmore » electrolytes containing the LiPF6 salt and aprotic solvents. Of particular note is the overlap of the Raman bands for both solvent-separated ion pair (SSIP) and contact ion pair (CIP) coordination in which the PF6- anions are uncoordinated or coordinated to a single Li+ cation, respectively.« less

Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Xiangping; Chen, Yongbin; Zhou, Tao, E-mail: zhoutao@csu.edu.cn

2015-04-15

Highlights: • Selective precipitation and solvent extraction were adopted. • Nickel, cobalt and lithium were selectively precipitated. • Co-D2EHPA was employed as high-efficiency extraction reagent for manganese. • High recovery percentages could be achieved for all metal values. - Abstract: Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt andmore » lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe–Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC{sub 2}O{sub 4}⋅2H{sub 2}O and Li{sub 2}CO{sub 3} using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor.« less

Carbon ion pump for removal of carbon dioxide from combustion gas and other gas mixtures

DOEpatents

Aines, Roger D.; Bourcier, William L.

2014-08-19

A novel method and system of separating carbon dioxide from flue gas is introduced. Instead of relying on large temperature or pressure changes to remove carbon dioxide from a solvent used to absorb it from flue gas, the ion pump method, as disclosed herein, dramatically increases the concentration of dissolved carbonate ion in solution. This increases the overlying vapor pressure of carbon dioxide gas, permitting carbon dioxide to be removed from the downstream side of the ion pump as a pure gas. The ion pumping may be obtained from reverse osmosis, electrodialysis, thermal desalination methods, or an ion pump system having an oscillating flow in synchronization with an induced electric field.

Carbon ion pump for removal of carbon dioxide from combustion gas and other gas mixtures

DOEpatents

Aines, Roger D.; Bourcier, William L.

2010-11-09

A novel method and system of separating carbon dioxide from flue gas is introduced. Instead of relying on large temperature or pressure changes to remove carbon dioxide from a solvent used to absorb it from flue gas, the ion pump method, as disclosed herein, dramatically increases the concentration of dissolved carbonate ion in solution. This increases the overlying vapor pressure of carbon dioxide gas, permitting carbon dioxide to be removed from the downstream side of the ion pump as a pure gas. The ion pumping may be obtained from reverse osmosis, electrodialysis, thermal desalination methods, or an ion pump system having an oscillating flow in synchronization with an induced electric field.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards understanding the effects of van der Waals strengths on the electric double-layer structures and capacitive behaviors

NASA Astrophysics Data System (ADS)

Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa

2017-10-01

Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

Electrochemical Properties of LLTO/Fluoropolymer-Shell Cellulose-Core Fibrous Membrane for Separator of High Performance Lithium-Ion Battery

PubMed Central

Huang, Fenglin; Liu, Wenting; Li, Peiying; Ning, Jinxia; Wei, Qufu

2016-01-01

A superfine Li0.33La0.557TiO3 (LLTO, 69.4 nm) was successfully synthesized by a facile solvent-thermal method to enhance the electrochemical properties of the lithium-ion battery separator. Co-axial nanofiber of cellulose and Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was prepared by a co-axial electrospinning technique, in which the shell material was PVDF-HFP and the core was cellulose. LLTO superfine nanoparticles were incorporated into the shell of the PVDF-HFP. The core–shell composite nanofibrous membrane showed good wettability (16.5°, contact angle), high porosity (69.77%), and super electrolyte compatibility (497%, electrolyte uptake). It had a higher ionic conductivity (13.897 mS·cm−1) than those of pure polymer fibrous membrane and commercial separator. In addition, the rate capability (155.56 mAh·g−1) was also superior to the compared separator. These excellent performances endowed LLTO composite nanofibrous membrane as a promising separator for high-performance lithium-ion batteries. PMID:28787873

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, M.; Bates, J.K.

1980-05-09

A system and method are described for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

Effects of Solvent and Ion Source Pressure on the Analysis of Anabolic Steroids by Low Pressure Photoionization Mass Spectrometry.

PubMed

Liu, Chengyuan; Zhu, Yanan; Yang, Jiuzhong; Zhao, Wan; Lu, Deen; Pan, Yang

2017-04-01

Solvent and ion source pressure were two important factors relating to the photon induced ion-molecule reactions in low pressure photoionization (LPPI). In this work, four anabolic steroids were analyzed by LPPI mass spectrometry. Both the ion species present and their relative abundances could be controlled by switching the solvent and adjusting the ion source pressure. Whereas M •+ , MH + , [M - H 2 O] + , and solvent adducts were observed in positive LPPI, [M - H] - and various oxidation products were abundant in negative LPPI. Changing the solvent greatly affected formation of the ion species in both positive and negative ion modes. The ion intensities of the solvent adduct and oxygen adduct were selectively enhanced when the ion source pressure was elevated from 68 to 800 Pa. The limit of detection could be decreased by increasing the ion source pressure. Graphical Abstract ᅟ.

Effects of Solvent and Ion Source Pressure on the Analysis of Anabolic Steroids by Low Pressure Photoionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Liu, Chengyuan; Zhu, Yanan; Yang, Jiuzhong; Zhao, Wan; Lu, Deen; Pan, Yang

2017-04-01

Solvent and ion source pressure were two important factors relating to the photon induced ion-molecule reactions in low pressure photoionization (LPPI). In this work, four anabolic steroids were analyzed by LPPI mass spectrometry. Both the ion species present and their relative abundances could be controlled by switching the solvent and adjusting the ion source pressure. Whereas M•+, MH+, [M - H2O]+, and solvent adducts were observed in positive LPPI, [M - H]- and various oxidation products were abundant in negative LPPI. Changing the solvent greatly affected formation of the ion species in both positive and negative ion modes. The ion intensities of the solvent adduct and oxygen adduct were selectively enhanced when the ion source pressure was elevated from 68 to 800 Pa. The limit of detection could be decreased by increasing the ion source pressure.

Application of ion mobility-mass spectrometry to microRNA analysis.

PubMed

Takebayashi, Kosuke; Hirose, Kenji; Izumi, Yoshihiro; Bamba, Takeshi; Fukusaki, Eiichiro

2013-03-01

Liquid chromatography/mass spectrometry is widely used for studying sequence determination and modification analysis of small RNAs. However, the efficiency of liquid chromatography-based separation of intact small RNA species is insufficient, since the physiochemical properties among small RNAs are very similar. In this study, we focused on ion mobility-mass spectrometry (IM-MS), which is a gas-phase separation technique coupled with mass spectrometry; we have evaluated the utility of IM-MS for microRNA (miRNA) analysis. A multiply charged deprotonated ion derived from an 18-24-nt-long miRNA was formed by electrospray ionization, and then the time, called the "drift time", taken by each ion to migrate through a buffer gas was measured. Each multivalent ion was temporally separated on the basis of the charge state and structural formation; 3 types of unique mass-mobility correlation patterns (i.e., chainlike-form, hairpin-form, and dimer-form) were present on the two-dimensional mobility-mass spectrum. Moreover, we found that the ion size (sequence length) and the secondary structures of the small RNAs strongly contributed to the IM-MS-based separation, although solvent conditions such as pH had no effect. Therefore, sequence isomers could also be discerned by the selection of each specific charged ion, i.e., the 6(-) charged ion reflected a majority among chainlike-, hairpin-, and other structures. We concluded that the IM-MS provides additional capability for separation; thus, this analytical method will be a powerful tool for comprehensive small RNA analysis. Copyright © 2012. Published by Elsevier B.V.

Thermomechanical analysis and durability of commercial micro-porous polymer Li-ion battery separators

NASA Astrophysics Data System (ADS)

Love, Corey T.

2011-03-01

Static and dynamic thermomechanical analysis was performed with a dynamic mechanical analyzer (DMA) to identify thermal and mechanical transitions for commercially available polymer separators under mechanical loading. Clear transitions in deformation mode were observed at elevated temperatures. These transitions identified the onset of separator "shutdown" which occurred at temperatures below the polymer melting point. Mechanical loading direction was critical to the overall integrity of the separator. Anisotropic separators (Celgard 2320, 2400 and 2500) were mechanically limited when pulled in tensile in the transverse direction. The anisotropy of these separators is a result of the dry technique used to manufacture the micro-porous membranes. Separators prepared using the wet technique (Entek Gold LP) behaved more uniformly, or biaxially, where all mechanical properties were nearly identical within the separator plane. The information provided by the DMA can also be useful for predicting the long-term durability of polymer separators in lithium-ion batteries exposed to electrolyte (solvent and salt), thermal fluctuations and electrochemical cycling. Small losses in mechanical integrity were observed for separators exposed to the various immersion environments over the 4-week immersion time.

The solvation of ions in acetonitrile and acetone. II. Monte Carlo simulations using polarizable solvent models

NASA Astrophysics Data System (ADS)

Fischer, R.; Richardi, J.; Fries, P. H.; Krienke, H.

2002-11-01

Structural properties and energies of solvation are simulated for alkali and halide ions. The solvation structure is discussed in terms of various site-site distribution functions, of solvation numbers, and of orientational correlation functions of the solvent molecules around the ions. The solvent polarizability has notable effects which cannot be intuitively predicted. In particular, it is necessary to reproduce the experimental solvation numbers of small ions. The changes of solvation properties are investigated along the alkali and halide series. By comparing the solvation of ions in acetone to that in acetonitrile, it is shown that the spatial correlations among the solvent molecules around an ion result in a strong screening of the ion-solvent direct intermolecular potential and are essential to understand the changes in the solvation structures and energies between different solvents. The solvation properties derived from the simulations are compared to earlier predictions of the hypernetted chain (HNC) approximation of the molecular Ornstein-Zernike (MOZ) theory [J. Richardi, P. H. Fries, and H. Krienke, J. Chem. Phys. 108, 4079 (1998)]. The MOZ(HNC) formalism gives an overall qualitatively correct picture of the solvation and its various unexpected findings are corroborated. For the larger ions, its predictions become quantitative. The MOZ approach allows to calculate solvent-solvent and ion-solvent potentials of mean force, which shed light on the 3D labile molecular and ionic architectures in the solution. These potentials of mean force convey a unique information which is necessary to fully interpret the angle-averaged structural functions computed from the simulations. Finally, simulations of solutions at finite concentrations show that the solvent-solvent and ion-solvent spatial correlations at infinite dilution are marginally altered by the introduction of fair amounts of ions.

Ion Association in AlCl3 Aqueous Solutions from Constrained First-Principles Molecular Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cauet, Emilie L.; Bogatko, Stuart A.; Bylaska, Eric J.

2012-10-15

Ab initio molecular dynamics was used to investigate the ion pairing behavior between Cl- and the Al3+ ion in an aqueous AlCl3 solution containing 63 water molecules. A series of constrained simulations was carried out at 300 K for up to 16 ps each, by fixing the inter-nuclear separation (rAl-Cl) between the Al3+ ion and one of the Cl- ions. The calculated potential of mean force of the Al3+-Cl- ion pair shows a pronounced minimum at rAl-Cl = 2.3 Å corresponding to a contact ion pair (CIP). Two local minima assigned to solvent separated ion pairs (SSIP) are identified atmore » rAl-Cl= 4.4 and 6.0 Å. The positions of the free energy minima coincide with the hydration shell intervals of the Al3+ cation suggesting that the Cl- ion is inclined to reside in regions of low concentration of waters, i.e. between the 1st and 2nd shells of Al3+ and between the 2nd shell and bulk. A detailed analysis of solvent structure around the Al3+ and Cl- ions as a function of rAl-Cl is presented. The results are compared to structure data from X-ray measurements and unconstrained AIMD simulations of single ions Al3+ and Cl- and AlCl3 solutions. The dipole moment of the water molecules inside the 1st and 2nd hydration shells of Al3+ and in the bulk region and those of the Clion were calculated as a function of rAl-Cl. Major changes in the electronic structure of the system result from the removal of Cl- from the 1st hydration shell of the Al3+ cation. Finally, two unconstrained AIMD simulations of aqueous AlCl3 solutions corresponding to CIP and SSIP configurations were performed (17 ps, 300 K). Only minor structural changes are observed in these systems, confirming their stability.« less

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents

NASA Astrophysics Data System (ADS)

Mazzini, Virginia; Liu, Guangming; Craig, Vincent S. J.

2018-06-01

We present an experimental investigation of specific-ion effects in non-aqueous solvents, with the aim of elucidating the role of the solvent in perturbing the fundamental ion-specific trend. The focus is on the anions: CH3COO->F->Cl->Br->I->ClO4 ->SCN- in the solvents water, methanol, formamide, dimethyl sulfoxide (DMSO), and propylene carbonate (PC). Two types of experiments are presented. The first experiment employs the technique of size exclusion chromatography to evaluate the elution times of electrolytes in the different solvents. We observe that the fundamental (Hofmeister) series is observed in water and methanol, whilst the series is reversed in DMSO and PC. No clear series is observed for formamide. The second experiment uses the quartz crystal microbalance technique to follow the ion-induced swelling and collapse of a polyelectrolyte brush. Here the fundamental series is observed in the protic solvents water, methanol, and formamide, and the series is once again reversed in DMSO and PC. These behaviours are not attributed to the protic/aprotic nature of the solvents, but rather to the polarisability of the solvents and are due to the competition between the interaction of ions with the solvent and the surface. A rule of thumb is proposed for ion specificity in non-aqueous solvents. In weakly polarisable solvents, the trends in specific-ion effects will follow those in water, whereas in strongly polarisable solvents the reverse trend will be observed. Solvents of intermediate polarisability will give weak specific-ion effects.

Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents.

PubMed

Mazzini, Virginia; Liu, Guangming; Craig, Vincent S J

2018-06-14

We present an experimental investigation of specific-ion effects in non-aqueous solvents, with the aim of elucidating the role of the solvent in perturbing the fundamental ion-specific trend. The focus is on the anions: CH 3 COO - >F - >Cl - >Br - >I - >ClO 4 - >SCN - in the solvents water, methanol, formamide, dimethyl sulfoxide (DMSO), and propylene carbonate (PC). Two types of experiments are presented. The first experiment employs the technique of size exclusion chromatography to evaluate the elution times of electrolytes in the different solvents. We observe that the fundamental (Hofmeister) series is observed in water and methanol, whilst the series is reversed in DMSO and PC. No clear series is observed for formamide. The second experiment uses the quartz crystal microbalance technique to follow the ion-induced swelling and collapse of a polyelectrolyte brush. Here the fundamental series is observed in the protic solvents water, methanol, and formamide, and the series is once again reversed in DMSO and PC. These behaviours are not attributed to the protic/aprotic nature of the solvents, but rather to the polarisability of the solvents and are due to the competition between the interaction of ions with the solvent and the surface. A rule of thumb is proposed for ion specificity in non-aqueous solvents. In weakly polarisable solvents, the trends in specific-ion effects will follow those in water, whereas in strongly polarisable solvents the reverse trend will be observed. Solvents of intermediate polarisability will give weak specific-ion effects.

Synthesis and characterization of zirconium titanium phosphate and its application in separation of metal ions.

PubMed

Thakkar, Rakesh; Chudasama, Uma

2009-12-15

An advanced inorganic ion exchanger, zirconium titanium phosphate (ZTP) of the class of tetravalent bimetallic acid (TBMA) salt has been synthesized by sol-gel route. ZTP has been characterized for ICP-AES, TGA, FTIR and XRD. Chemical stability of the material in various media-acids, bases and organic solvents has been assessed. Cation exchange capacity (CEC) and effect of calcination (100-500 degrees C) on CEC has also been studied. Distribution behaviour of metal ions Co2+, Ni2+, Cu2+, Zn2+ (d-block), Cd2+, Hg2+, Pb2+, Bi3+ (heavy) and La3+, Ce3+, Th4+, UO(2)2+ (f-block) towards ZTP has been studied and distribution coefficient (K(d)) determined in aqueous as well as various electrolyte media/concentrations. Based on the differential selectivity, breakthrough capacity (BTC) and elution behaviour of various metal ions towards ZTP, a few binary and ternary metal ion separations have been carried out.

Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes.

PubMed

Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Menzel, Jennifer; Wiemers-Meyer, Simon; Winter, Martin; Nowak, Sascha

2015-08-28

A two-dimensional ion chromatography (IC/IC) technique with heart-cutting mode for the separation of ionic organophosphates was developed. These analytes are generated during thermal degradation of three different commercially available Selectilyte™ lithium ion battery electrolytes. The composition of the investigated electrolytes is based on 1M lithium hexafluorophosphate (LiPF6) dissolved in ethylene carbonate/dimethyl carbonate (50:50wt%, LP30), ethylene carbonate/diethyl carbonate (50:50wt%, LP40) and ethylene carbonate/ethyl methyl carbonate (50:50wt%, LP50). The organophosphates were pre-separated from PF6(-) anion on the low capacity A Supp 4 column, which was eluted with a gradient step containing acetonitrile. The fraction containing analytes was retarded on a pre-concentration column and after that transferred to the high capacity columns, where the separation was performed isocratically. Different stationary phases and eluents were applied on the 2nd dimension for the investigation of retention times, whereas the highly promising results were obtained with a high capacitive A Supp 10 column. The organophosphates generated in LP30 and LP40 electrolytes could be separated by application of an aqueous NaOH eluent providing fast analysis time within 35min. For the separation of the organophosphates of LP50 electrolyte due to its complexity a NaOH eluent containing a mixture of methanol/H2O was necessary. In addition, the developed two dimensional IC method was hyphenated to an inductively coupled plasma mass spectrometer (ICP-MS) using aqueous NaOH without organic modifiers. This proof of principle measurement was carried out for future quantitative investigation regarding the concentration of the ionic organophosphates. Furthermore, the chemical stability of several ionic organophosphates in water and acetonitrile at room temperature over a period of 10h was investigated. In both solvents no decomposition of the investigated analytes was observed and therefore water as solvent for dilution of samples was proved as suitable. Copyright © 2015 Elsevier B.V. All rights reserved.

Thin layer chromatography-ion mobility spectrometry (TLC-IMS).

PubMed

Ilbeigi, Vahideh; Tabrizchi, Mahmoud

2015-01-06

Ion mobility spectrometry (IMS) is a fast and sensitive analytical method which operates at the atmospheric pressure. To enhance the capability of IMS for the analysis of mixtures, it is often used with preseparation techniques, such as GC or HPLC. Here, we report for the first time the coupling of the thin-layer chromatography and IMS. A variety of coupling schemes were tried that included direct electrospray from the TLC strip tip, indirect electrospray from a needle connected to the TLC strip, introducing the moving solvent into the injection port, and, the simplest way, offline introduction of scratched or cut pieces of strips into the IMS injection port. In this study a special solvent tank was designed and the TLC strip was mounted horizontally where the solvent would flow down. A very small funnel right below the TLC tip collected the solvent and transferred it to a needle via a capillary tubing. Using the TLC-ESI-IMS technique, acceptable separations were achieved for two component mixtures of morphine-papaverine and acridine-papaverine. A special injection port was designed to host the pieces cut off the TLC. The method was successfully used to identify each spot on the TLC by IMS in a few seconds.

How Much Do Ultrathin Polymers with Intrinsic Microporosity Swell in Liquids?

PubMed

Ogieglo, Wojciech; Ghanem, Bader; Ma, Xiaohua; Pinnau, Ingo; Wessling, Matthias

2016-10-06

As synthetic membrane materials, polymers with intrinsic microporosity (PIMs) have demonstrated unprecedented permeation and molecular-separation properties. Here, we report the swelling characteristics of submicron-thick supported films of spirobisindane-based PIMs, PIM-1 and PIM-6FDA-OH, for six organic solvents and water using in situ spectroscopic ellipsometry. Surprisingly, PIMs swell significantly in most organic solvents, with swelling factors (SF = h swollen /h dry ) as high as 2.5. This leads to the loss of the ultrarigid character of the polymer and produces equilibrated liquid-like swollen films. Filling of the excess frozen-in fractional free volume with liquid was discovered next to swelling-induced polymer matrix dilation. Water hardly swells the polymer matrix, but it penetrates into the intrinsic microporous structure. This study is the first to provide fundamental swelling data for PIMs, leading to better comprehension of their permeation properties. Such an understanding is indispensable for applications such as solvent filtration, natural-gas separation, and ion retention in flow batteries.

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

NASA Technical Reports Server (NTRS)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

Fundamental investigation of stress corrosion cracking

NASA Technical Reports Server (NTRS)

Beck, T. R.; Blackburn, M. J.; Smyrl, W. H.

1972-01-01

Two principle areas studied were stress corrosion crack growth rates of a titanium alloy in liquid environments containing halide ions and pitting corrosion of titanium in bromide solutions. Two initial assumptions were made, that the rate of propagation was controlled by a macroscopic solution parameter and that this parameter was viscosity. A series of solutions were prepared using lithium chloride as the solute and water, methanol, glycerin, formic acid, acetone, dimethyl sulphoxide, etc. As solvents, these solutions were prepared with a 5:1 solvent-solute ratio. Viscosity was varied by changing the temperature and it was found: (1) In all solvents the velocity of cracking was proportional to the reciprocal of the viscosity. (2) Each solvent gave a separate relationship, (3) The temperature dependence and numerical values for the apparent activation energy of cracking and viscosity were the same.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery.

PubMed

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-02-06

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

PubMed Central

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-01-01

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

Optimation and Determination of Fe-Oxinate Complex by Using High Performance Liquid Chromatography

NASA Astrophysics Data System (ADS)

Oktavia, B.; Nasra, E.; Sary, R. C.

2018-04-01

The need for iron will improve the industrial processes that require iron as its raw material. Control of industrial iron waste is very important to do. One method of iron analysis is to conduct indirect analysis of iron (III) ions by complexing with 8-Hydroxyquinoline or oxine. In this research, qualitative and quantitative tests of iron (III) ions in the form of complex with oxine. The analysis was performed using HPLC at a wavelength of 470 nm with an ODS C18 column. Three methods of analysis were performed: 1) Fe-oxinate complexes were prepared in an ethanol solvent so no need for separation anymore, (2) Fe-oxinate complexes were made in chloroform so that a solvent extraction was required before the complex was injected into the column while the third complex was formed in the column, wherein the eluent contains the oxide and the metal ions are then injected. The resulting chromatogram shows that the 3rd way provides a better chromatogram for iron analysis.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

PubMed

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordon, John Howard; Alvare, Javier

Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution andmore » may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong

2017-07-05

Oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type, andmore » electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

DOE PAGES

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong; ...

2017-07-05

Here, oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type,more » and electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

Trends in mica–mica adhesion reflect the influence of molecular details on long-range dispersion forces underlying aggregation and coalignment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dongsheng; Chun, Jaehun; Xiao, Dongdong

Oriented attachment of nanocrystalline subunits is recognized as a common crystallization pathway that is closely related to formation of nanoparticle superlattices, mesocrystals, and other kinetically stabilized structures. Approaching particles have been observed to rotate to achieve co-alignment while separated by nanometer-scale solvent layers. Little is known about the forces that drive co-alignment, particularly in this “solvent-separated” regime. To obtain a mechanistic understanding of this process, we used atomic force microscopy-based dynamic force spectroscopy with tips fabricated from oriented mica to measure the adhesion forces between mica (001) surfaces in electrolyte solutions as a function of orientation, temperature, electrolyte type, andmore » electrolyte concentration. The results reveal a ~60° periodicity as well as a complex dependence on electrolyte concentration and temperature. A continuum model that considers the competition between electrostatic repulsion and van der Waals attraction, augmented by microscopic details that include surface separation, water structure, ion hydration, and charge regulation at the interface, qualitatively reproduces the observed trends and implies that dispersion forces are responsible for establishing co-alignment in the solvent-separated state.« less

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

DOE PAGES

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.; ...

2016-12-01

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

The origin of facet selectivity and alignment in anatase TiO 2 nanoparticles in electrolyte solutions: implications for oriented attachment in metal oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sushko, M. L.; Rosso, K. M.

Atomic-to-mesoscale simulations were used to reveal the origin of oriented attachment between anatase TiO2 nanoparticles in aqueous HCl solutions. Analysis of the distance and pH dependence of interparticle interactions demonstrates that ion correlation forces are responsible for facet-specific attraction and rotation into lattice co-alignment at long-range. These forces give rise to a metastable solvent separated capture minimum on the disjoining pressure-distance curve, with the barrier to attachment largely due to steric hydration forces from structured intervening solvent.

Bitumen recovery from oil sands using deep eutectic solvent and its aqueous solutions

NASA Astrophysics Data System (ADS)

Pulati, Nuerxida

Oil sands compose a significant proportion of the world's known oil reserves. Oil sands are also known as tar sands and bituminous sands, are complex mixtures of sand, clays, water and bitumen, which is "heavy" and highly viscous oil. The extraction and separation of bitumen from oil sands requires significant amount of energy and large quantities of water and poses several environmental challenges. Bitumen can be successfully separated from oil sands using imidazolium based ionic liquids and nonpolar solvents, however, ionic liquids are expensive and toxic. In this thesis, the ionic liquid alternatives- deep eutectic solvent, were investigated. Oil sands separation can be successfully achieved by using deep eutectic solvents DES (choline chloride and urea) and nonpolar solvent naphtha in different types of oil sands, including Canadian ("water-wet"), Utah ("oil-wet") and low grade Kentucky oil sands. The separation quality depends on oil sands type, including bitumen and fine content, and separation condition, such as solvent ratio, temperature, mixing time and mechanical centrifuge. This separation claims to the DES ability to form ion /charge layering on mineral surface, which results in reduction of adhesion forces between bitumen and minerals and promote their separation. Addition of water to DES can reduce DES viscosity. DES water mixture as a media, oil sands separation can be achieved. However, concentration at about 50 % or higher might be required to obtain a clear separation. And the separation efficiency is oil sands sample dependent. The highest bitumen extraction yield happened at 75% DES-water solution for Utah oil sands samples, and at 50 60% DES-water solutions for Alberta oil sands samples. Force curves were measured using Atomic Force Microscopy new technique, PeakForce Tapping Quantitative Nanomechanical Mapping (PFTQNM). The results demonstrate that, by adding DES, the adhesion force between bitumen and silica and dissipation energy will decrease comparing to DI water. At higher concentration DES solution (>80%DES), the amount of decrease can be up to 80-90%. In lower concentration, at about 50% decrease was observed. The results provide fundamental insights into the mechanism of bitumen separation from oil sands. The reduction of adhesion force between bitumen and minerals (silica) in DES media is the main reason which facilitates the separation between them, which by means existence of DES will favor bitumen and minerals separation. Comparing to other techniques, DES based separation is environmentally compatible and economically viable. The separation can easily happen at room temperature. Choline chloride and urea are biodegradable, environmentally compatible, accessible in large scale and easily prepared by mixing and heating (<80 °C). Further improvement is needed regarding to separation quality and efficiency, either in the direction of developing better separation techniques or by looking for chemical additives which can improve separation and reduce environmental side-effects.

Recovery of cesium

DOEpatents

Izatt, Reed M.; Christensen, James J.; Hawkins, Richard T.

1984-01-01

A process of recovering cesium ions from mixtures of ions containing them and other ions, e.g., a solution of nuclear waste materials, which comprises establishing a separate source phase containing such a mixture of ions, establishing a separate recipient phase, establishing a liquid membrane phase in interfacial contact with said source and recipient phases, said membrane phase containing a ligand, preferably a selected calixarene as depicted in the drawing, maintaining said interfacial contact for a period of time long enough to transport by said ligand a substantial portion of the cesium ion from the source phase to the recipient phase, and recovering the cesium ion from the recipient phase. The separation of the source and recipient phases may be by the membrane phase only, e.g., where these aqueous phases are emulsified as dispersed phases in a continuous membrane phase, or may include a physical barrier as well, e.g., an open-top outer container with an inner open-ended container of smaller cross-section mounted in the outer container with its open bottom end spaced from and above the closed bottom of the outer container so that the membrane phase may fill the outer container to a level above the bottom of the inner container and have floating on its upper surface a source phase and a recipient phase separated by the wall of the inner container as a physical barrier. A preferred solvent for the ligand is a mixture of methylene chloride and carbon tetrachloride.

Cross-Linked Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-co-HFP) Gel Polymer Electrolyte for Flexible Li-Ion Battery Integrated with Organic Light Emitting Diode (OLED)

PubMed Central

Kim, Ilhwan; Kim, Bong Sung; Nam, Seunghoon; Lee, Hoo-Jeong; Chung, Ho Kyoon; Cho, Sung Min; Luu, Thi Hoai Thuong; Hyun, Seungmin; Kang, Chiwon

2018-01-01

Here, we fabricate poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-co-HFP) by electrospinning for a gel polymer electrolyte (GPE) for use in flexible Li-ion batteries (LIBs). As a solvent, we use N-methyl-2-pyrrolidone (NMP), which helps produce the cross-linked morphology of PVDF-co-HFP separator, owing to its low volatility. The cross-linked PVDF-co-HFP separator shows an uptake rate higher than that of a commercialized polypropylene (PP) separator. Moreover, the PVDF-co-HFP separator shows an ionic conductivity of 2.3 × 10−3 S/cm at room temperature, comparable with previously reported values. An LIB full-cell assembled with the PVDF-co-HFP-based GPE shows capacities higher than its counterpart with the commercialized PP separator, confirming that the cross-linked PVDF-co-HFP separator provides highly efficient ionic conducting pathways. In addition, we integrate a flexible LIB cell using the PVDF-co-HFP GPE with a flexible organic light emitting diode (OLED), demonstrating a fully flexible unit of LIB and OLED. PMID:29614800

Cross-Linked Poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-co-HFP) Gel Polymer Electrolyte for Flexible Li-Ion Battery Integrated with Organic Light Emitting Diode (OLED).

PubMed

Kim, Ilhwan; Kim, Bong Sung; Nam, Seunghoon; Lee, Hoo-Jeong; Chung, Ho Kyoon; Cho, Sung Min; Luu, Thi Hoai Thuong; Hyun, Seungmin; Kang, Chiwon

2018-04-02

Here, we fabricate poly(vinylidene fluoride- co -hexafluoropropene) (PVDF- co -HFP) by electrospinning for a gel polymer electrolyte (GPE) for use in flexible Li-ion batteries (LIBs). As a solvent, we use N -methyl-2-pyrrolidone (NMP), which helps produce the cross-linked morphology of PVDF- co -HFP separator, owing to its low volatility. The cross-linked PVDF- co -HFP separator shows an uptake rate higher than that of a commercialized polypropylene (PP) separator. Moreover, the PVDF- co -HFP separator shows an ionic conductivity of 2.3 × 10 -3 S/cm at room temperature, comparable with previously reported values. An LIB full-cell assembled with the PVDF- co -HFP-based GPE shows capacities higher than its counterpart with the commercialized PP separator, confirming that the cross-linked PVDF- co -HFP separator provides highly efficient ionic conducting pathways. In addition, we integrate a flexible LIB cell using the PVDF- co -HFP GPE with a flexible organic light emitting diode (OLED), demonstrating a fully flexible unit of LIB and OLED.

Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.

2012-04-01

Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein-protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent.

Investigations on the photoreactions of phenothiazine and phenoxazine in presence of 9-cyanoanthracene by using steady state and time resolved spectroscopic techniques.

PubMed

Bardhan, Munmun; Mandal, Paulami; Tzeng, Wen-Bih; Ganguly, Tapan

2010-09-01

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).

Process chemistry of americium-241

DOE Office of Scientific and Technical Information (OSTI.GOV)

Navratil, J.D.

1983-01-01

Americium-241, one of the most useful actinide isotopes, is produced as a by-product of plutonium scrap recovery operations. Rocky Flats has supplied high purity americium oxide to the US Department of Energy's Isotope Pool since 1962. Over the years, the evolving separation and purification processes have included such diverse operations as ion exchange, aqueous precipitation, and both molten-salt and organic-solvent extraction.

Displacement-dispersive liquid-liquid microextraction based on solidification of floating organic drop of trace amounts of palladium in water and road dust samples prior to graphite furnace atomic absorption spectrometry determination.

PubMed

Ghanbarian, Maryam; Afzali, Daryoush; Mostafavi, Ali; Fathirad, Fariba

2013-01-01

A new displacement-dispersive liquid-liquid microextraction method based on the solidification of floating organic drop was developed for separation and preconcentration of Pd(ll) in road dust and aqueous samples. This method involves two steps of dispersive liquid-liquid microextraction based on solidification. In Step 1, Cu ions react with diethyldithiocarbamate (DDTC) to form Cu-DDTC complex, which is extracted by dispersive liquid-liquid microextraction based on a solidification procedure using 1-undecanol (extraction solvent) and ethanol (dispersive solvent). In Step 2, the extracted complex is first dispersed using ethanol in a sample solution containing Pd ions, then a dispersive liquid-liquid microextraction based on a solidification procedure is performed creating an organic drop. In this step, Pd(ll) replaces Cu(ll) from the pre-extracted Cu-DDTC complex and goes into the extraction solvent phase. Finally, the Pd(ll)-containing drop is introduced into a graphite furnace using a microsyringe, and Pd(ll) is determined using atomic absorption spectrometry. Several factors that influence the extraction efficiency of Pd and its subsequent determination, such as extraction and dispersive solvent type and volume, pH of sample solution, centrifugation time, and concentration of DDTC, are optimized.

SEPARATION OF RADIOACTIVE COLUMBIUM TRACER

DOEpatents

Glendenin, L.E.; Gest, H.

1958-08-26

A process is presented for the recovery of radioactive columbium from solutions containing such columbium together with radioactive tellurium. The columbium and tellurium values are separated from such solutions by means of an inorganic oxide carrier precipitate, such as MnO/sub 2/. This oxide carrier precipitate and its associated columbium and telluriuan values are then dissolved in an aqueous acidic solution and nonradioactive tellurium, in an ionic form, is then introduced into such solution, for example in the form of H/sub 2/TeO/sub 3/. The tellurium present in the solution is then reduced to the elemental state and precipitates, and is then separated from the supernataat solution. A basic acetate precipitate is formed in the supernatant and carries the remaining columblum values therefrom. After separation, this basic ferric acetate precipitate is dissolved, and the ferric ions are removed by means of an organic solvent extraction process utilizing ether. The remaining solution contains carrier-free columbium as its only metal ion.

Structural dynamics of a noncovalent charge transfer complex from femtosecond stimulated Raman spectroscopy.

PubMed

Fujisawa, Tomotsumi; Creelman, Mark; Mathies, Richard A

2012-09-06

Femtosecond stimulated Raman spectroscopy is used to examine the structural dynamics of photoinduced charge transfer within a noncovalent electron acceptor/donor complex of pyromellitic dianhydride (PMDA, electron acceptor) and hexamethylbenzene (HMB, electron donor) in ethylacetate and acetonitrile. The evolution of the vibrational spectrum reveals the ultrafast structural changes that occur during the charge separation (Franck-Condon excited state complex → contact ion pair) and the subsequent charge recombination (contact ion pair → ground state complex). The Franck-Condon excited state is shown to have significant charge-separated character because its vibrational spectrum is similar to that of the ion pair. The charge separation rate (2.5 ps in ethylacetate and ∼0.5 ps in acetonitrile) is comparable to solvation dynamics and is unaffected by the perdeuteration of HMB, supporting the dominant role of solvent rearrangement in charge separation. On the other hand, the charge recombination slows by a factor of ∼1.4 when using perdeuterated HMB, indicating that methyl hydrogen motions of HMB mediate the charge recombination process. Resonance Raman enhancement of the HMB vibrations in the complex reveals that the ring stretches of HMB, and especially the C-CH(3) deformations are the primary acceptor modes promoting charge recombination.

Apparatus and method for removing solvent from carbon dioxide in resin recycling system

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two-step resin recycling system and method solvent that produces essentially contaminant-free synthetic resin material. The system and method includes one or more solvent wash vessels to expose resin particles to a solvent, the solvent contacting the resin particles in the one or more solvent wash vessels to substantially remove contaminants on the resin particles. A separator is provided to separate the solvent from the resin particles after removal from the one or more solvent wash vessels. The resin particles are next exposed to carbon dioxide in a closed loop carbon dioxide system. The closed loop system includes a carbon dioxide vessel where the carbon dioxide is exposed to the resin, substantially removing any residual solvent remaining on the resin particles after separation. A separation vessel is also provided to separate the solvent from the solvent laden carbon dioxide. Both the carbon dioxide and the solvent are reused after separation in the separation vessel.

Desalting by crystallization: detection of attomole biomolecules in picoliter buffers by mass spectrometry.

PubMed

Gong, Xiaoyun; Xiong, Xingchuang; Wang, Song; Li, Yanyan; Zhang, Sichun; Fang, Xiang; Zhang, Xinrong

2015-10-06

Sensitive detection of biomolecules in small-volume samples by mass spectrometry is, in many cases, challenging because of the use of buffers to maintain the biological activities of proteins and cells. Here, we report a highly effective desalting method for picoliter samples. It was based on the spontaneous separation of biomolecules from salts during crystallization of the salts. After desalting, the biomolecules were deposited in the tip of the quartz pipet because of the evaporation of the solvent. Subsequent detection of the separated biomolecules was achieved using solvent assisted electric field induced desorption/ionization (SAEFIDI) coupled with mass spectrometry. It allowed for direct desorption/ionization of the biomolecules in situ from the tip of the pipet. The organic component in the assistant solvent inhibited the desorption/ionization of salts, thus assured successful detection of biomolecules. Proteins and peptides down to 50 amol were successfully detected using our method even if there were 3 × 10(5) folds more amount of salts in the sample. The concentration and ion species of the salts had little influence on the detection results.

Focused analyte spray emission apparatus and process for mass spectrometric analysis

DOEpatents

Roach, Patrick J [Kennewick, WA; Laskin, Julia [Richland, WA; Laskin, Alexander [Richland, WA

2012-01-17

An apparatus and process are disclosed that deliver an analyte deposited on a substrate to a mass spectrometer that provides for trace analysis of complex organic analytes. Analytes are probed using a small droplet of solvent that is formed at the junction between two capillaries. A supply capillary maintains the droplet of solvent on the substrate; a collection capillary collects analyte desorbed from the surface and emits analyte ions as a focused spray to the inlet of a mass spectrometer for analysis. The invention enables efficient separation of desorption and ionization events, providing enhanced control over transport and ionization of the analyte.

Superbase-derived protic ionic liquid extractants for metal ion separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bell, Jason R.; Dai, Sheng; Luo, Huimin

2014-04-19

Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.

Solvent-Ion Interactions in Salt Water: A Simple Experiment.

ERIC Educational Resources Information Center

Willey, Joan D.

1984-01-01

Describes a procedurally quick, simple, and inexpensive experiment which illustrates the magnitude and some effects of solvent-ion interactions in aqueous solutions. Theoretical information, procedures, and examples of temperature, volume and hydration number calculations are provided. (JN)

Preferential Solvation of an Asymmetric Redox Molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ionmore » pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.« less

Differential geometry-based solvation and electrolyte transport models for biomolecular modeling: a review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Guowei; Baker, Nathan A.

2016-11-11

This chapter reviews the differential geometry-based solvation and electrolyte transport for biomolecular solvation that have been developed over the past decade. A key component of these methods is the differential geometry of surfaces theory, as applied to the solvent-solute boundary. In these approaches, the solvent-solute boundary is determined by a variational principle that determines the major physical observables of interest, for example, biomolecular surface area, enclosed volume, electrostatic potential, ion density, electron density, etc. Recently, differential geometry theory has been used to define the surfaces that separate the microscopic (solute) domains for biomolecules from the macroscopic (solvent) domains. In thesemore » approaches, the microscopic domains are modeled with atomistic or quantum mechanical descriptions, while continuum mechanics models (including fluid mechanics, elastic mechanics, and continuum electrostatics) are applied to the macroscopic domains. This multiphysics description is integrated through an energy functional formalism and the resulting Euler-Lagrange equation is employed to derive a variety of governing partial differential equations for different solvation and transport processes; e.g., the Laplace-Beltrami equation for the solvent-solute interface, Poisson or Poisson-Boltzmann equations for electrostatic potentials, the Nernst-Planck equation for ion densities, and the Kohn-Sham equation for solute electron density. Extensive validation of these models has been carried out over hundreds of molecules, including proteins and ion channels, and the experimental data have been compared in terms of solvation energies, voltage-current curves, and density distributions. We also propose a new quantum model for electrolyte transport.« less

Short communication: separation and quantification of caseins and casein macropeptide using ion-exchange chromatography.

PubMed

Holland, B; Rahimi Yazdi, S; Ion Titapiccolo, G; Corredig, M

2010-03-01

The aim of this work was to improve an existing method to separate and quantify the 4 major caseins from milk samples (i.e., containing whey proteins) using ion-exchange chromatography. The separation process was carried out using a mini-preparative cation exchange column (1 or 5mL of column volume), using urea acetate as elution buffer at pH 3.5 with a NaCl gradient. All 4 major caseins were separated, and the purity of each peak was assessed using sodium dodecyl sulfate-PAGE. Purified casein fractions were also added to raw milk to confirm their elution volumes. The quantification was carried out using purified caseins in buffer as well as added directly to fresh skim milk. This method can also be employed to determine the decrease in kappa-casein and the release of the casein-macropeptide during enzymatic hydrolysis using rennet. In this case, the main advantage of using this method is the lack of organic solvents compared with the conventional method for separation of macropeptide (using reversed phase HPLC).

Microphase Separation in Oil-Water Mixtures Containing Hydrophilic and Hydrophobic Ions

NASA Astrophysics Data System (ADS)

Tasios, Nikos; Samin, Sela; van Roij, René; Dijkstra, Marjolein

2017-11-01

We develop a lattice-based Monte Carlo simulation method for charged mixtures capable of treating dielectric heterogeneities. Using this method, we study oil-water mixtures containing an antagonistic salt, with hydrophilic cations and hydrophobic anions. Our simulations reveal several phases with a spatially modulated solvent composition, in which the ions partition between water-rich and water-poor regions according to their affinity. In addition to the recently observed lamellar phase, we find tubular and droplet phases, reminiscent of those found in block copolymers and surfactant systems. Interestingly, these structures stem from ion-mediated interactions, which allows for tuning of the phase behavior via the concentrations, the ionic properties, and the temperature.

Quantitative analysis of psilocybin and psilocin in psilocybe baeocystis (Singer and Smith) by high-performance liquid chromatography and by thin-layer chromatography.

PubMed

Beug, M W; Bigwood, J

1981-03-27

Rapid quantification of psilocybin and psilocin in extracts of wild mushrooms is accomplished by reversed-phase high-performance liquid chromatography with paired-ion reagents. Nine solvent systems and three solid supports are evaluated for their efficiency in separating psilocybin, psilocin and other components of crude mushroom extracts by thin-layer chromatography.

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

Theoretical study on the sound absorption of electrolytic solutions. I. Theoretical formulation.

PubMed

Yamaguchi, T; Matsuoka, T; Koda, S

2007-04-14

A theory is formulated that describes the sound absorption of electrolytic solutions due to the relative motion of ions, including the formation of ion pairs. The theory is based on the Kubo-Green formula for the bulk viscosity. The time correlation function of the pressure is projected onto the bilinear product of the density modes of ions. The time development of the product of density modes is described by the diffusive limit of the generalized Langevin equation, and approximate expressions for the three- and four-body correlation functions required are given with the hypernetted-chain integral equation theory. Calculations on the aqueous solutions of model electrolytes are performed. It is demonstrated that the theory describes both the activated barrier crossing between contact and solvent-separated ion pairs and the Coulombic correlation between ions.

Theoretical study on the sound absorption of electrolytic solutions. I. Theoretical formulation

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Matsuoka, T.; Koda, S.

2007-04-01

A theory is formulated that describes the sound absorption of electrolytic solutions due to the relative motion of ions, including the formation of ion pairs. The theory is based on the Kubo-Green formula for the bulk viscosity. The time correlation function of the pressure is projected onto the bilinear product of the density modes of ions. The time development of the product of density modes is described by the diffusive limit of the generalized Langevin equation, and approximate expressions for the three- and four-body correlation functions required are given with the hypernetted-chain integral equation theory. Calculations on the aqueous solutions of model electrolytes are performed. It is demonstrated that the theory describes both the activated barrier crossing between contact and solvent-separated ion pairs and the Coulombic correlation between ions.

Volumetric, rheological, and optical properties of hydroxylamine hydrochloride aqueous solutions containing NaCl, KCl, and NH4Cl at 30°C

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Puyad, A. L.; Shaikh, U. B.; Solanke, S. S.

2014-04-01

Densities, viscosities, and refractive indices of aqueous solutions of hydroxylamine hydrochloride containing 0.05, 0.10, and 0.15 mol/dm3 NaCl, KCl, and NH4Cl were measured at different concentrations of hydroxylamine hydrochloride at 30°C. Viscosity coefficients A and B representing ion-ion and ion-solvent interactions were determined from Jones-Dole equation. Experimental properties and viscosity coefficients have been interpreted in terms of ion-ion and ion-solvent interactions. Ion-solvent interactions were found to be dominating over the ion-ion interactions in studied systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, H.N.; Pal, H.; Sapre, A.V.

Photoexcitation of complexes between fullerence C[sub 60] and organic amines in benzene solutions is known to result in charge separation (CS) and subsequent charge recombination (CR) reactions, which lead to varying yields of fullerence triplet formation. Picosecond flash photolysis studies are carried out on C[sub 60]-diphenylamine (DPA), C[sub 60]-triethylamine (TEA), C[sub 60]-diazabicyclooctane (DABCO), and C[sub 60]-triphenylamine (TPA) systems to find out mechanistic details of the triplet formation on CR by inducing heavy atom and polarity effects by using suitable solvents. It is found that in the case of C[sub 60]-DPA, C[sub 60]-TEA, and C[sub 60]-DABCO systems proton transfer from themore » amine cation to the C[sub 60] anion in the ion pair state dominates, leading to poor triplet yields, which improve in heavy atom containing solvents. In TPA, proton transfer is not possible and hence fullerene triplet yields are high. Increase of solvent polarity for this system results in decreased C[sub 60] triplet yields with a consequent increase in the ion dissociation yield. A suitable reaction scheme is proposed to explain the results obtained. 34 refs., 5 figs., 2 tabs.« less

Photopolymer Electrolytes for Sustainable, Upscalable, Safe, and Ambient-Temperature Sodium-Ion Secondary Batteries.

PubMed

Bella, Federico; Colò, Francesca; Nair, Jijeesh R; Gerbaldi, Claudio

2015-11-01

The first example of a photopolymerized electrolyte for a sodium-ion battery is proposed herein. By means of a preparation process free of solvents, catalysts, purification steps, and separation steps, it is possible to obtain a three-dimensional polymeric network capable of efficient sodium-ion transport. The thermal properties of the resulting solid electrolyte separator, characterized by means of thermogravimetric and calorimetric techniques, are excellent for use in sustainable energy systems conceived for safe large-scale grid storage. The photopolymerized electrolyte shows a wide electrochemical stability window up to 4.8 V versus Na/Na(+) along with the highest ionic conductivity (5.1 mS cm(-1) at 20 °C) obtained in the field of Na-ion polymer batteries so far and stable long-term constant-current charge/discharge cycling. Moreover, the polymeric networks are also demonstrated for the in situ fabrication of electrode/electrolyte composites with excellent interfacial properties, which are ideal for all-solid-state, safe, and easily upscalable device assembly. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of high energy density electrical double layer capacitors

NASA Astrophysics Data System (ADS)

Devarajan, Thamarai selvi

Electrochemical Double Layer capacitors (EDLCs) have shown themselves as a viable energy storage alternative. EDLCs have high power density, faster charge/discharge, wide operating temperature and long cycle life compared to batteries since it stores charge by physical separation. Despites all their advantages, their low energy density stand as a bottleneck for capacitors. This research aims to increase the energy density of EDLC without compromising the power density. Energy is proportional to the square of cell voltage. Cell voltage is mainly dependent on electrolyte breakdown. Electrolytes also provide ions for charge separation and conduction. Therefore various electrolytes (Solutes and Solvents) which can give high concentration, solubility and decomposition potential were characterized in the first part of the research. In that study, a novel ionic liquid OPBF4 had higher capacitance and comparable voltage window compared to commercial TEABF4 in Acetonitrile. However, the increased polarity of the fixed ring O-atom and the ion-ion interaction in OPBF4 was responsible for lowering its conductivity. Oxygenated ionic compounds with alkyl groups had lower stability due to beta elimination between two electron withdrawing atoms. Volume based thermodynamics and quantum chemical calculations were used to calculate ion size, HOMO/LUMO energies, and free energy changes and establish relationship with capacitance, redox potential and melting points respectively. In addition free energy of fusion was used to predict the melting point. Ion size had correlation with capacitance due to compact double layer formation. Free energy changes did not explain the differences in melting point and predicted dielectric constant was inconsistent with the polarity. This is presumably due to using Van der Waals volume instead of crystal structure volume and insufficient incorporation of polarization term. The HOMO/LUMO energies gave direct relation between oxidation and reduction potential at 1mA/cm 2. A brief study on non-polar co-solvents for EDLC was studied. Among the solvents studied, fluorinated solvents had low melting point and viscosity due to incorporation of asymmetry. However, because of low dielectric constant, TEABF4 is insoluble and had to be mixed with other solvents. The mixed fluorinated solvents had slightly higher voltage window due to decreased donicity of lone pairs of electrons. The second approach to increasing energy density is to increase capacitance. Capacitance is mainly dependent on surface area and porosity of electrodes. Nanostructured materials which can offer multiple charge storage are currently of interest. Hence, novel NiSi nanotubes were studied as electrodes for supercapacitor applications. Silicon material has high capacity and these inert electrodes can enable higher capacitance by controlling the porosity and functional groups in specific electrolytes. The Silicon wafers were made porous by anodization using hydrofluoric acid. In order to improve the conductivity, the porous silicon was doped, then plated with Ni using electroless plating method and annealed to form nickel mono silicide. Gold was deposited on the back side of the electrode to enhance conductivity. Our porous NiSi electrodes gave capacitance of about 1185muF /cm2 in 0.5 M H 2SO4. Further investigation of oxide formation and modification of functional groups will help achieve higher capacitance.

Effects of liquid chromatography mobile phases and buffer salts on phosphorus inductively coupled plasma atomic emission and mass spectrometries utilizing ultrasonic nebulization and membrane desolvation.

PubMed

Carr, John E; Kwok, Kaho; Webster, Gregory K; Carnahan, Jon W

2006-01-23

Atomic spectrometry, specifically inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) show promise for heteroatom-based detection of pharmaceutical compounds. The combination of ultrasonic nebulization (USN) with membrane desolvation (MD) greatly enhances detection limits with these approaches. Because pharmaceutical analyses often incorporate liquid chromatography, the study herein was performed to examine the effects of solvent composition on the analytical behaviors of these approaches. The target analyte was phosphorus, introduced as phosphomycin. AES response was examined at the 253.7 nm atom line and mass 31 ions were monitored for the MS experiments. With pure aqueous solutions, detection limits of 5 ppb (0.5 ng in 0.1 mL injection volumes) were obtained with ICP-MS. The ICP-AES detection limit was 150 ppb. Solvent compositions were varied from 0 to 80% organic (acetonitrile and methanol) with nine buffers at concentrations typically used in liquid chromatography. In general, solvents and buffers had statistically significant, albeit small, effects on ICP-AES sensitivities. A few exceptions occurred in cases where typical liquid chromatography buffer concentrations produced higher mass loadings on the plasma. Indications are that isocratic separations can be reliably performed. Within reasonable accuracy tolerances, it appears that gradient chromatography can be performed without the need for signal response normalization. Organic solvent and buffer effects were more significant with ICP-MS. Sensitivities varied significantly with different buffers and organic solvent content. In these cases, gradient chromatography will require careful analytical calibration as solvent and buffer content is varied. However, for most buffer and solvent combinations, signal and detection limits are only moderately affected. Isocratic separations and detection are feasible.

PROJECT W-551 DETERMINATION DATA FOR EARLY LAW INTERIM PRETREATMENT SYSTEM SELECTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

TEDESCHI AR

This report provides the detailed assessment forms and data for selection of the solids separation and cesium separation technology for project W-551, Interim Pretreatment System. This project will provide early pretreated low activity waste feed to the Waste Treatment Plant to allow Waste Treatment Plan Low Activity Waste facility operation prior to construction completion of the Pretreatment and High Level Waste facilities. The candidate solids separations technologies are rotary microfiltration and crossflow filtration, and the candidate cesium separation technologies are fractional crystallization, caustic-side solvent extraction, and ion-exchange using spherical resorcinol-formaldehyde resin. This data was used to prepare a cross-cutting technologymore » summary, reported in RPP-RPT-37740.« less

Rate- and Temperature-Dependent Material Behavior of a Multilayer Polymer Battery Separator

NASA Astrophysics Data System (ADS)

Avdeev, Ilya; Martinsen, Michael; Francis, Alex

2014-01-01

Designing battery packs for safety in automotive applications requires multiscale modeling, as macroscopic deformations due to impact cause the mechanical failure of individual cells on a sub-millimeter level. The separator material plays a critical role in this process, as the thinning or perforating of the separator can lead to thermal runaway and catastrophic failure of an entire battery pack. The electrochemical properties of various polymer separators have been extensively investigated; however, the dependency of mechanical properties of these thin films on various factors, such as high temperature and strain rate, has not been sufficiently characterized. In this study, the macroscopic mechanical properties of a multilayer polymer thin film used as a battery separator are studied experimentally at various temperatures, strain rates, and solvent saturations. Due to the anisotropy of the material, material testing was conducted in two perpendicular directions (machine and transverse directions). Material samples were tested in both dry and saturated conditions at several temperatures, and it was found that temperature and strain rate have a nearly linear effect on the stress experienced by the material. Additionally, saturating the separator material in a common lithium-ion solvent had softened it and had a positive effect on its toughness. The experimental results obtained in this study can be used to develop mathematical constitutive models of the multilayer separator material for subsequent numerical simulations and design.

High Temperature Stable Separator for Lithium Batteries Based on SiO2 and Hydroxypropyl Guar Gum

PubMed Central

Carvalho, Diogo Vieira; Loeffler, Nicholas; Kim, Guk-Tae; Passerini, Stefano

2015-01-01

A novel membrane based on silicon dioxide (SiO2) and hydroxypropyl guar gum (HPG) as binder is presented and tested as a separator for lithium-ion batteries. The separator is made with renewable and low cost materials and an environmentally friendly manufacturing processing using only water as solvent. The separator offers superior wettability and high electrolyte uptake due to the optimized porosity and the good affinity of SiO2 and guar gum microstructure towards organic liquid electrolytes. Additionally, the separator shows high thermal stability and no dimensional-shrinkage at high temperatures due to the use of the ceramic filler and the thermally stable natural polymer. The electrochemical tests show the good electrochemical stability of the separator in a wide range of potential, as well as its outstanding cycle performance. PMID:26512701

Novel, Solvent-Free, Single Ion-Conducting Polymer Electrolytes

DTIC Science & Technology

2007-10-31

the selected polymer electrolyte membrane and a LiFePO4 -based composite cathode film. The latter was prepared by blending the LiFePO4 active...following: charge Li+ + FePO4 + e LiFePO4 [1] discharge to which is associate a maximum...as separator in a Li/ LiFePO4 battery. . 1.Experimental. Calixpyrrole (CP, provided by the University of Warsaw), LiBOB (Libby) and PEO

Biexponential photon antibunching: recombination kinetics within the Förster-cycle in DMSO.

PubMed

Vester, Michael; Grueter, Andreas; Finkler, Björn; Becker, Robert; Jung, Gregor

2016-04-21

Time-resolved experiments with pulsed-laser excitation are the standard approach to map the dynamic evolution of excited states, but ground-state kinetics remain hidden or require pump-dump-probe schemes. Here, we exploit the so-called photon antibunching, a purely quantum-optical effect related to single molecule detection to assess the rate constants for a chemical reaction in the electronic ground state. The measurement of the second-order correlation function g((2)), i.e. the evaluation of inter-photon arrival times, is applied to the reprotonation in a Förster-cycle. We find that the antibunching of three different photoacids in the aprotic solvent DMSO significantly differs from the behavior in water. The longer decay constant of the biexponential antibunching tl is linked to the bimolecular reprotonation kinetics of the fully separated ion-pair, independent of the acidic additives. The value of the corresponding bimolecular rate constant, kp = 4 × 10(9) M(-1) s(-1), indicates diffusion-controlled reprotonation. The analysis of tl also allows for the extraction of the separation yield of proton and the conjugated base after excitation and amounts to approximately 15%. The shorter time component ts is connected to the decay of the solvent-separated ion pair. The associated time constant for geminate reprotonation is approximately 3 ± 1 ns in agreement with independent tcspc experiments. These experiments verify that the transfer of quantum-optical experiments to problems in chemistry enables mechanistic conclusions which are hardly accessible by other methods.

SEPARATION OF INORGANIC SALTS FROM ORGANIC SOLUTIONS

DOEpatents

Katzin, L.I.; Sullivan, J.C.

1958-06-24

A process is described for recovering the nitrates of uranium and plutonium from solution in oxygen-containing organic solvents such as ketones or ethers. The solution of such salts dissolved in an oxygen-containing organic compound is contacted with an ion exchange resin whereby sorption of the entire salt on the resin takes place and then the salt-depleted liquid and the resin are separated from each other. The reaction seems to be based on an anion formation of the entire salt by complexing with the anion of the resin. Strong base or quaternary ammonium type resins can be used successfully in this process.

Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory.

PubMed

Daschakraborty, Snehasis; Biswas, Ranjit

2016-03-14

A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (x(IL)). At higher IL concentrations (x(IL) > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with x(IL), deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the x(IL) dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume (V(mol)(dip)) for the rotating dipolar moiety in the present theory and suggests that only a fraction of V(mol)(dip) is involved at high x(IL). Expectedly, nice agreement between theory and experiments appears when experimental estimates for the effective rotational volume (V(eff)(dip)) are used as inputs. The fraction, V(eff)(dip)/V(mol)(dip), sharply decreases from ∼1 at pure dipolar solvent to ∼0.01 at neat IL, reflecting a dramatic crossover from viscosity-coupled hydrodynamic angular diffusion at low IL mole fractions to orientational relaxation predominantly via large angle jumps at high x(IL). Similar results are obtained on applying the present theory to the aqueous solution of an electrolyte guanidinium chloride (GdmCl) having a permanent dipole moment associated with the cation, Gdm(+).

Solvent system selectivities in countercurrent chromatography using Salicornia gaudichaudiana metabolites as practical example with off-line electrospray mass-spectrometry injection profiling.

PubMed

Costa, Fernanda das Neves; Jerz, Gerold; Figueiredo, Fabiana de Souza; Winterhalter, Peter; Leitão, Gilda Guimarães

2015-03-13

For the development of an efficient two-stage isolation process for high-speed countercurrent chromatography (HSCCC) with focus on principal metabolites from the ethyl acetate extract of the halophyte plant Salicornia gaudichaudiana, separation selectivities of two different biphasic solvent systems with similar polarities were evaluated using the elution and extrusion approach. Efficiency in isolation of target compounds is determined by the solvent system selectivity and their chronological use in multiple separation steps. The system n-hexane-ethyl acetate-methanol-water (0.5:6:0.5:6, v/v/v/v) resulted in a comprehensive separation of polyphenolic glycosides. The system n-hexane-n-butanol-water (1:1:2, v/v/v) was less universal but was highly efficient in the fractionation of positional isomers such as di-substituted cinnamic acid quinic acid derivatives. Multiple metabolite detection performed on recovered HSCCC tube fractions was done with rapid mass-spectrometry profiling by sequential off-line injections to electrospray mass-spectrometry (ESI-MS/MS). Selective ion traces of metabolites delivered reconstituted preparative HSCCC runs. Molecular weight distribution of target compounds in single HSCCC tube fractions and MS/MS fragment data were available. Chromatographic areas with strong co-elution effects and fractions of pure recoverable compounds were visualized. In total 11 metabolites have been identified and monitored. Result of this approach was a fast isolation protocol for S. gaudichaudiana metabolites using two solvent systems in a strategic sequence. The process could easily be scaled-up to larger lab-scale or industrial recovery. Copyright © 2015 Elsevier B.V. All rights reserved.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

PubMed Central

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.

PubMed

Mazzini, Virginia; Craig, Vincent S J

2017-10-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Rectification of nanopores in aprotic solvents - transport properties of nanopores with surface dipoles

NASA Astrophysics Data System (ADS)

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A.; Siwy, Zuzanna S.

2015-11-01

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06340j

Method for low temperature preparation of a noble metal alloy

DOEpatents

Even, Jr., William R.

2002-01-01

A method for producing fine, essentially contamination free, noble metal alloys is disclosed. The alloys comprise particles in a size range of 5 to 500 nm. The method comprises 1. A method for preparing a noble metal alloy at low temperature, the method comprising the steps of forming solution of organometallic compounds by dissolving the compounds into a quantity of a compatible solvent medium capable of solvating the organometallic, mixing a portion of each solution to provide a desired molarity ratio of ions in the mixed solution, adding a support material, rapidly quenching droplets of the mixed solution to initiate a solute-solvent phase separation as the solvent freezes, removing said liquid cryogen, collecting and freezing drying the frozen droplets to produce a dry powder, and finally reducing the powder to a metal by flowing dry hydrogen over the powder while warming the powder to a temperature of about 150.degree. C.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Two tools for applying chromatographic retention data to the mass-based identification of peptides during hydrogen/deuterium exchange experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gershon, P D

2010-12-15

Two tools are described for integrating LC elution position with mass-based data in hydrogen-deuterium exchange (HDX) experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry (nanoLC/MALDI-MS, a novel approach to HDX-MS). The first of these, 'TOF2H-Z Comparator', highlights peptides in HDX experiments that are potentially misidentified on the basis of mass alone. The program first calculates normalized values for the organic solvent concentration responsible for the elution of ions in nanoLC/MALDI HDX experiments. It then allows the solvent gradients for the multiple experiments contributing to an MS/MS-confirmed peptic peptide library to be brought into mutual alignment by iteratively re-modeling variables among LC parameters such as gradient shape, solvent species, fraction duration and LC dead time. Finally, using the program, high-probability chromatographic outliers can be flagged within HDX experimental data. The role of the second tool, 'TOF2H-XIC Comparator', is to normalize the LC chromatograms corresponding to all deuteration timepoints of all HDX experiments of a project, to a common reference. Accurate normalization facilitates the verification of chromatographic consistency between all ions whose spectral segments contribute to particular deuterium uptake plots. Gradient normalization in this manner revealed chromatographic inconsistencies between ions whose masses were either indistinguishable or separated by precise isotopic increments. Copyright © 2010 John Wiley & Sons, Ltd.

Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

PubMed

Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap

2015-08-26

We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.

Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

PubMed

Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

2016-04-29

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

2014-06-10

A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

A critical overview of non-aqueous capillary electrophoresis. Part I: mobility and separation selectivity.

PubMed

Kenndler, Ernst

2014-03-28

This two-part review critically gives an overview on the theoretical and practical advances in non-aqueous capillary electrophoresis (NACE) achieved over the recent five years. Part I starts out by reviewing the aspects relevant to electromigration in organic solvents and evaluates potential advantages of the latter in comparison to aqueous solvent systems. The crucial role of solubility for the species involved in CE - analytes and back ground electrolyte constituents - is discussed both for ionic and neutral compounds. The impact of organic solvents on the electrophoretic and electroosmotic mobility and on the ionization (pKa values) of weak acids and bases is highlighted. Special emphasis is placed on methanol, acetonitrile and mixtures of these solvents, being the most frequent employed media for NACE applications. In addition, also solvents less commonly used in NACE will be covered, including other alcohols, amides (formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide), propylene carbonate, dimethylsulphoxide, and nitromethane. The discussions address the consequences of dramatic pKa shifts frequently seen for weak acids and bases, and the important contributions of medium-specific electroosmotic flow (EOF) to electromigration in nonaqueous media. Important for NACE, the role of the water content on pKa and mobility is analyzed. Finally, association phenomena rather specific to nonaqueous solvents (ion pairing, homo- and heteroconjugation) will be addressed, along with their potential advantages for the development of NACE separation protocols. It is pointed out that this review is not intended as a listing of all papers that have been published on NACE in the period mentioned above. It rather deals with general aspects of migration and selectivity in organic solvent systems, and discusses - critically - examples from the literature with particular interest to the topic. An analog discussion about the role of the solvent on efficiency will be presented in Part II. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of deep eutectic solvents applied in extraction and separation.

PubMed

Li, Xiaoxia; Row, Kyung Ho

2016-09-01

Deep eutectic solvents, as an alternative to ionic liquids, have greener credentials than ionic liquids, and have attracted considerable attention in related chemical research. Deep eutectic solvents have attracted increasing attention in chemistry for the extraction and separation of various target compounds from natural products. This review highlights the preparation of deep eutectic solvents, unique properties of deep eutectic solvents, and synthesis of deep-eutectic-solvent-based materials. On the other hand, application in the extraction and separation of deep eutectic solvents is also included in this report. In this paper, the available data and references in this field are reviewed to summarize the applications and developments of deep eutectic solvents. Based on the development of deep eutectic solvents, an exploitation of new deep eutectic solvents and deep eutectic solvents-based materials is expected to diversify into extraction and separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous countercurrent membrane column for the separation of solute/solvent and solvent/solvent systems

DOEpatents

Nerad, Bruce A.; Krantz, William B.

1988-01-01

A reverse osmosis membrane process or hybrid membrane - complementary separator process for producing enriched product or waste streams from concentrated and dilute feed streams for both solvent/solvent and solute/solvent systems is described.

Structure and Li+ ion transport in a mixed carbonate/LiPF6 electrolyte near graphite electrode surfaces: a molecular dynamics study.

PubMed

Boyer, Mathew J; Vilčiauskas, Linas; Hwang, Gyeong S

2016-10-12

Electrolyte and electrode materials used in lithium-ion batteries have been studied separately to a great extent, however the structural and dynamical properties of the electrolyte-electrode interface still remain largely unexplored despite its critical role in governing battery performance. Using molecular dynamics simulations, we examine the structural reorganization of solvent molecules (cyclic ethylene carbonate : linear dimethyl carbonate 1 : 1 molar ratio doped with 1 M LiPF 6 ) in the vicinity of graphite electrodes with varying surface charge densities (σ). The interfacial structure is found to be sensitive to the molecular geometry and polarity of each solvent molecule as well as the surface structure and charge distribution of the negative electrode. We also evaluated the potential difference across the electrolyte-electrode interface, which exhibits a nearly linear variation with respect to σ up until the onset of Li + ion accumulation onto the graphite edges from the electrolyte. In addition, well-tempered metadynamics simulations are employed to predict the free-energy barriers to Li + ion transport through the relatively dense interfacial layer, along with analysis of the Li + solvation sheath structure. Quantitative analysis of the molecular arrangements at the electrolyte-electrode interface will help better understand and describe electrolyte decomposition, especially in the early stages of solid-electrolyte-interphase (SEI) formation. Moreover, the computational framework presented in this work offers a means to explore the effects of solvent composition, electrode surface modification, and operating temperature on the interfacial structure and properties, which may further assist in efforts to engineer the electrolyte-electrode interface leading to a SEI layer that optimizes battery performance.

Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries.

PubMed

Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun

2015-04-01

Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe-Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC2O4 ⋅ 2H2O and Li2CO3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor. Copyright © 2015 Elsevier Ltd. All rights reserved.

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Single column comprehensive analysis of pharmaceutical preparations using dual-injection mixed-mode (ion-exchange and reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Taylor, Mark R; Haddad, Paul R; Nesterenko, Pavel N; Paull, Brett

2013-12-01

The comprehensive separation and detection of hydrophobic and hydrophilic active pharmaceutical ingredients (APIs), their counter-ions (organic, inorganic) and excipients, using a single mixed-mode chromatographic column, and a dual injection approach is presented. Using a mixed-mode Thermo Fisher Acclaim Trinity P1 column, APIs, their counter-ions and possible degradants were first separated using a combination of anion-exchange, cation-exchange and hydrophobic interactions, using a mobile phase consisting of a dual organic modifier/salt concentration gradient. A complementary method was also developed using the same column for the separation of hydrophilic bulk excipients, using hydrophilic interaction liquid chromatography (HILIC) under high organic solvent mobile phase conditions. These two methods were then combined within a single gradient run using dual sample injection, with the first injection at the start of the applied gradient (mixed-mode retention of solutes), followed by a second sample injection at the end of the gradient (HILIC retention of solutes). Detection using both ultraviolet absorbance and refractive index enabled the sensitive detection of APIs and UV-absorbing counter-ions, together with quantitative determination of bulk excipients. The developed approach was applied successfully to the analysis of a dry powder inhalers (Flixotide(®), Spiriva(®)), enabling comprehensive quantification of all APIs and excipients in the sample. Copyright © 2013 Elsevier B.V. All rights reserved.

Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva P. (Inventor)

1996-01-01

Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

Molecular mechanisms of decomposition of hydrated Na+Cl- ion pairs under planar nanopore conditions

NASA Astrophysics Data System (ADS)

Shevkunov, S. V.

2017-02-01

The decomposition of Na+Cl- ion pairs under the conditions of a nanoscopic planar pore with structureless walls in a material contact with water vapor at 298 K is simulated by Monte Carlo method. The transition from the state of a contact ion pair (CIP) to the state of solvent-separated ion pair (SSIP) is shown to occur as a result of an increase in the vapor pressure over a pore after exceeding the threshold number of molecules in a hydrate shell. It is found that the planar form of a molecular cluster under the conditions of a narrow pore does not level an abrupt structural transition and the formation of hydrogen bonds in the hydrate shell starts after three molecules are added. The hydrogen bond length under pore conditions is found to be resistant to variations in the hydrate shell size and coincides with that in water under normal conditions.

Method of making formulated plastic separators for soluble electrode cells

NASA Technical Reports Server (NTRS)

Sheibley, D. W. (Inventor)

1982-01-01

A method making a membrane comprised of a hydrochloric acid-insoluble sheet of a mixture of a rubber and a powdered ion transport material is disclosed. The sheet can be present as a coating upon a flexible and porous substrate. These membranes can be used in oxidation-reduction electrical accumulator cells wherein the reduction of one member of a couple is accompained by the oxidation of the other member of the couple on the other side of the cell and this must be accompained by a change in chloride ion concentration in both sides. The method comprises preparing a mixture of fine rubber particles, a solvent for the rubber and a powdered ion transport material. The mixture is formed into a sheet and dried to produce a microporous sheet. The ion transport material includes particles ranging from about 0.01 to 10 microns in size and comprises from 20 to 50 volume percent of the microporous sheet.

Detection of chlorinated and brominated byproducts of drinking water disinfection using electrospray ionization-high-field asymmetric waveform ion mobility spectrometry-mass spectrometry.

PubMed

Ells, B; Barnett, D A; Froese, K; Purves, R W; Hrudey, S; Guevremont, R

1999-10-15

The lower limit of detection for low molecular weight polar and ionic analytes using electrospray ionization-mass spectrometry (ESI-MS) is often severely compromised by an intense background that obscures ions of trace components in solution. Recently, a new technique, referred to as high-field asymmetric waveform ion mobility spectrometry (FAIMS), has been shown to separate gas-phase ions at atmospheric pressure and room temperature. A FAIMS instrument is an ion filter that may be tuned, by control of electrical voltages, to continuously transmit selected ions from a complex mixture. This capability offers significant advantages when FAIMS is coupled with ESI, a source that generates a wide variety of ions, including solvent clusters and salt adducts. In this report, the tandem arrangement of ESI-FAIMS-MS is used for the analysis of haloacetic acids, a class of disinfection byproducts regulated by the US EPA. FAIMS is shown to effectively discriminate against background ions resulting from the electrospray of tap water solutions containing the haloacetic acids. Consequently, mass spectra are simplified, the selectivity of the method is improved, and the limits of detection are lowered compared with conventional ESI-MS. The detection limits of ESI-FAIMS-MS for six haloacetic acids ranged between 0.5 and 4 ng/mL in 9:1 methanol/tap water (5 and 40 ng/mL in the original tap water samples) with no preconcentration, derivatization, or chromatographic separation prior to analysis.

Chemical isolation of .sup.82 Sr from proton-irradiated Mo targets

DOEpatents

Grant, Patrick M.; Kahn, Milton; O'Brien, Jr., Harold A.

1976-01-01

Spallation reactions are induced in Mo targets with 200-800 MeV protons to produce microcurie to millicurie amounts of a variety of radionuclides. A six-step radiochemical procedure, incorporating precipitation, solvent extractions, and ion exchange techniques, has been developed for the separation and purification of Sr radioactivities from other spallation products and the bulk target material. Radiostrontium can be quantitatively recovered in a sufficiently decontaminated state for use in biomedical generator development.

Production and recovery of Americium-241

DOE Office of Scientific and Technical Information (OSTI.GOV)

Navratil, J.D.

1984-01-01

Americium-241, one of the most useful actinide isotopes, is produced as a by-product of plutonium scrap recovery operations. Rocky Flats (RF) has supplied high-purity americium oxide to the US Department of Energy's Isotope Pool since 1962. Over the years, the evolving separation and purification processes have included such diverse operations as aqueous precipitation, ion exchange, and both molten-salt and organic-solvent extraction. A review is presented of the production and recovery processes of americium-241. 5 references.

Ion conducting fluoropolymer carbonates for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

2017-09-05

Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

Separation of amaranthine-type betacyanins by ion-pair high-speed countercurrent chromatography.

PubMed

Jerz, Gerold; Gebers, Nadine; Szot, Dominika; Szaleniec, Maciej; Winterhalter, Peter; Wybraniec, Slawomir

2014-05-30

Betacyanins, red-violet plant pigments, were fractionated by ion-pair high-speed countercurrent chromatography (IP-HSCCC) from leaves extract of Iresine lindenii Van Houtte, an ornamental plant of the family Amaranthaceae. An HSCCC solvent system consisting of TBME-1-BuOH-ACN-H2O (1:3:1:5, v/v/v/v) was applied using ion-pair forming heptafluorobutyric acid (HFBA). Significantly different elution profiles of betacyanin diastereomeric pairs (derivatives based on betanidin and isobetanidin) observed in the HSCCC in comparison to HPLC systems indicate a complementarity of both techniques' fractionation capabilities. The numerous diastereomeric pairs can be selectively separated from each other using the HSCCC system simplifying the pigment purification process. Apart from the three well known highly abundant pigments (amaranthine, betanin and iresinin I) together with their isoforms, three new acylated (feruloylated and sinapoylated) betacyanins as well as known pigment hylocerenin (previously isolated from cacti fruits) were characterized in the plant for the first time and they are new for the whole Amaranthaceae family. Copyright © 2014 Elsevier B.V. All rights reserved.

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

PubMed Central

Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

2015-01-01

The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

The Ionic Atmosphere around A-RNA: Poisson-Boltzmann and Molecular Dynamics Simulations

PubMed Central

Kirmizialtin, Serdal; Silalahi, Alexander R.J.; Elber, Ron; Fenley, Marcia O.

2012-01-01

The distributions of different cations around A-RNA are computed by Poisson-Boltzmann (PB) equation and replica exchange molecular dynamics (MD). Both the nonlinear PB and size-modified PB theories are considered. The number of ions bound to A-RNA, which can be measured experimentally, is well reproduced in all methods. On the other hand, the radial ion distribution profiles show differences between MD and PB. We showed that PB results are sensitive to ion size and functional form of the solvent dielectric region but not the solvent dielectric boundary definition. Size-modified PB agrees with replica exchange molecular dynamics much better than nonlinear PB when the ion sizes are chosen from atomistic simulations. The distribution of ions 14 Å away from the RNA central axis are reasonably well reproduced by size-modified PB for all ion types with a uniform solvent dielectric model and a sharp dielectric boundary between solvent and RNA. However, this model does not agree with MD for shorter distances from the A-RNA. A distance-dependent solvent dielectric function proposed by another research group improves the agreement for sodium and strontium ions, even for shorter distances from the A-RNA. However, Mg2+ distributions are still at significant variances for shorter distances. PMID:22385854

Evaluation of Production Version of the NASA Improved Inorganic-Organic Separator

NASA Technical Reports Server (NTRS)

Sheibley, D.

1983-01-01

The technology of an inorganic-organic (I/O) separator, which demonstrated improved flexibility, reduced cost, production feasibility and improved cycle life was developed. Substrates to replace asbestos and waterbased separator coatings to replace the solvent based coatings were investigated. An improved fuel cell grade asbestos sheet was developed and a large scale production capability for the solvent based I/O separator was demonstrated. A cellulose based substrate and a nonwoven polypropylene fiber substrate were evaluated as replacements for the asbestos. Both the cellulose and polypropylene substrates were coated with solvent based and water based coatings to produce a modified I/O separator. The solvent based coatings were modified to produce aqueous separator coatings with acceptable separator properties. A single ply fuel cell grade asbestos with a binder (BTA) was produced. It has shown to be an acceptable substrate for the solvent and water based separator coatings, an acceptable absorber for alkaline cells, and an acceptable matrix for alkaline fuel cells. The original solvent based separator (K19W1), using asbestos as a substrate, was prepared.

Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II) Ions and Histidine-Containing Peptides.

PubMed

Li, Hsin-Yi; Chen, Chien-Yuan; Cheng, Hui-Ting; Chu, Yen-Ho

2016-10-13

Based on a common structural core of 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5- a ]pyridine, a number of bicyclic triazolium ionic liquids 1 - 3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1 , 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II) ions and, for the first time, histidine-containing peptides.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri

1997-01-01

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

DOEpatents

Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.

1997-09-09

Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Bruce A.

The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to researchmore » advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a noncomplexing aqueous solution and submission of this scientific breakthrough as a paper in Science; The first-ever co-crystallization of Am(VI) with UO 2(NO 3) 2 ∙ 6H 2O, opening the door to a new approach for separating hexavalent actinides as a group; Results showing that three potentially problematic metals will not present risk in ALSEP; Improvement in ALSEP contactor stripping kinetics to acceptable performance; A comparison of centrifugal contactors vs mixer-settlers showing the former performs better in ALSEP stripping; Synthesis of new mixed N,O-donor extractants with enhanced solubility and strength for selective trivalent actinide extraction; Development of computational methods showing promise in prediction of the selectivity of new extractants for trivalent actinides vs lanthanides; An order-of-magnitude improvement in aqueous Am/Eu complexation selectivity of an alternative macrocyclic stripping agent for ALSEP, potentially enabling an option for an Am product stream free from both Ln and Cm. An alternative aqueous combination of dipicolinate complexant and malonate buffer that may present options for ALSEP and TALSPEAK (Trivalent Actinide-Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) type separations. The ALSEP concept is advancing toward a benchtop flowsheet demonstration planned for FY 2016, and a bench-scale test bed at Idaho National Laboratory (INL) will be employed to demonstrate at least one tandem Am oxidation and separation concept. This report outlines the goals of the STAAR, significance of achieving these goals, STAAR organization around the above aims and questions, recent highlights, and future directions. The report also includes a listing of publications, reports, patents, and dissertations.« less

Solvation behavior of carbonate-based electrolytes in sodium ion batteries.

PubMed

Cresce, Arthur V; Russell, Selena M; Borodin, Oleg; Allen, Joshua A; Schroeder, Marshall A; Dai, Michael; Peng, Jing; Gobet, Mallory P; Greenbaum, Steven G; Rogers, Reginald E; Xu, Kang

2016-12-21

Sodium ion batteries are on the cusp of being a commercially available technology. Compared to lithium ion batteries, sodium ion batteries can potentially offer an attractive dollar-per-kilowatt-hour value, though at the penalty of reduced energy density. As a materials system, sodium ion batteries present a unique opportunity to apply lessons learned in the study of electrolytes for lithium ion batteries; specifically, the behavior of the sodium ion in an organic carbonate solution and the relationship of ion solvation with electrode surface passivation. In this work the Li + and Na + -based solvates were characterized using electrospray mass spectrometry, infrared and Raman spectroscopy, 17 O, 23 Na and pulse field gradient double-stimulated-echo pulse sequence nuclear magnetic resonance (NMR), and conductivity measurements. Spectroscopic evidence demonstrate that the Li + and Na + cations share a number of similar ion-solvent interaction trends, such as a preference in the gas and liquid phase for a solvation shell rich in cyclic carbonates over linear carbonates and fluorinated carbonates. However, quite different IR spectra due to the PF 6 - anion interactions with the Na + and Li + cations were observed and were rationalized with the help of density functional theory (DFT) calculations that were also used to examine the relative free energies of solvates using cluster - continuum models. Ion-solvent distances for Na + were longer than Li + , and Na + had a greater tendency towards forming contact pairs compared to Li + in linear carbonate solvents. In tests of hard carbon Na-ion batteries, performance was not well correlated to Na + solvent preference, leading to the possibility that Na + solvent preference may play a reduced role in the passivation of anode surfaces and overall Na-ion battery performance.

Microfluidic thread based electroanalytical system for green chromatographic separations.

PubMed

Agustini, Deonir; Fedalto, Lucas; Bergamini, Márcio F; Marcolino-Junior, Luiz Humberto

2018-02-13

The use of miniaturized chromatographic systems is an important strategy for reducing the consumption of supplies related to separations, allowing the development of more sustainable analytical methodologies. However, the high cost and complexity in the production of these systems combined with the operational difficulties and the need for the use of solvent and sample pretreatment are challenges to be overcome in order to make the chromatographic methods greener. Here, we report the construction and development of a low cost microfluidic system for green and solvent-free chromatographic separations with electrochemical detection integrated into cotton threads without the use of any mechanical pumping to transport the solutions. The manufacture of the proposed system was performed by simple assembly of the components, with the separation of the species based on an ion exchange mechanism and detection using gold electrodes manufactured directly on the cotton threads. A linear range of 0.025-5.0 mM was obtained for the effective separation of ascorbic acid (AA) and dopamine (DA) with detection limits of 2.89 μM (for AA) and 4.41 μM (for DA). Each analysis was performed at a low cost (less than 0.01 dollars), and with a small volume of waste generated (107.1 μL). So, the proposed system was successfully employed to determine the levels of AA and DA present in the tears of healthy volunteers without sample pretreatment, indicating the good analytical performance of the system and the possibility of performing greener chromatographic separations.

Lithium-Ion Electrolytes with Fluoroester Co-Solvents

NASA Technical Reports Server (NTRS)

Smart, Marshall C. (Inventor); Smith, Kiah (Inventor); Bhalla, Pooja (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, G. K. Surya (Inventor)

2014-01-01

An embodiment lithium-ion battery comprising a lithium-ion electrolyte of ethylene carbonate; ethyl methyl carbonate; and at least one solvent selected from the group consisting of trifluoroethyl butyrate, ethyl trifluoroacetate, trifluoroethyl acetate, methyl pentafluoropropionate, and 2,2,2-trifluoroethyl propionate. Other embodiments are described and claimed.

Selective and sensitized spectrophotometric determination of trace amounts of Ni(II) ion using α-benzyl dioxime in surfactant media

NASA Astrophysics Data System (ADS)

Ghaedi, Mehrorang

2007-02-01

Highly sensitive and interference-free sensitized spectrophotometric method for the determination of Ni(II) ions is described. The method is based on the reaction between Ni(II) ion and benzyl dioxime in micellar media in the presence of sodium dodecyl sulfate (SDS). The absorbance is linear from 0.1 up to 25.0 μg mL -1 in aqueous solution with repeatability (RSD) of 1.0% at a concentration of 1 μg mL -1 and a detection limit of 0.12 ng mL -1 and molar absorption coefficient of 68,600 L mol -1 cm -1. The influence of reaction variables including type and amount of surfactant, pH, and amount of ligand and complexation time and the effect of interfering ions are investigated. The proposed procedure was applied to the determination of trace amounts of Ni(II) ion in tap water, river water, chocolate and vegetable without separation or organic solvent extraction.

Effects of dilute aqueous NaCl solution on caffeine aggregation

NASA Astrophysics Data System (ADS)

Sharma, Bhanita; Paul, Sandip

2013-11-01

The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.

Electric Double Layer Composed of an Antagonistic Salt in an Aqueous Mixture: Local Charge Separation and Surface Phase Transition

NASA Astrophysics Data System (ADS)

Yabunaka, Shunsuke; Onuki, Akira

2017-09-01

We examine an electric double layer containing an antagonistic salt in an aqueous mixture, where the cations are small and hydrophilic but the anions are large and hydrophobic. In this situation, a strong coupling arises between the charge density and the solvent composition. As a result, the anions are trapped in an oil-rich adsorption layer on a hydrophobic wall. We then vary the surface charge density σ on the wall. For σ >0 the anions remain accumulated, but for σ <0 the cations are attracted to the wall with increasing |σ |. Furthermore, the electric potential drop Ψ (σ ) is nonmonotonic when the solvent interaction parameter χ (T ) exceeds a critical value χc determined by the composition and the ion density in the bulk. This leads to a first-order phase transition between two kinds of electric double layers with different σ and common Ψ . In equilibrium such two-layer regions can coexist. The steric effect due to finite ion sizes is crucial in these phenomena.

Effects of dilute aqueous NaCl solution on caffeine aggregation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Bhanita; Paul, Sandip, E-mail: sandipp@iitg.ernet.in

The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogenmore » bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.« less

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions using Aliquat 336.

PubMed

Nayl, A A

2010-01-15

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions by solvent extraction technique were studied using different forms of Aliquat 336 diluted with kerosene. The extraction percent of each metal ion was found to increase with increasing pH and extractant concentration. Co(II) was preferentially extracted by different forms of Aliquat 336 over Ni(II) under the same extraction conditions. From analysis of the experimental results, the extraction mechanism of R(4)N-forms was proposed with Co(II). It was found that the highest separation factor (S(Co/Ni)) value of 606.7 was obtained with 0.36 M R(4)N-SCN in kerosene from 2.0M H(2)SO(4) solution at pH 4.8 and shaking time of 20 min. Stripping of the two metal ions from the organic phase was also investigated. Based on the experimental results, a separation method was developed and tested to separate high purity Co(II), Ni(II) and Ln(III) from Ni-MH batteries leached by 2.0M H(2)SO(4). Based on the experimental results, a flow sheet was developed and tested and 0.34 g Co, 1.39 g Ln and 5.2g Ni were obtained from the leaching process.

Qualitative Investigation of the Decomposition of Organic Solvent Based Lithium Ion Battery Electrolytes with LC-IT-TOF-MS.

PubMed

Schultz, Carola; Vedder, Sven; Winter, Martin; Nowak, Sascha

2016-11-15

The development of a novel high performance liquid chromatography (HPLC) method hyphenated to an ion-trap time-of-flight mass spectrometer (IT-TOF-MS) for the separation and identification of constituents from common organic carbonate solvent-based electrolyte systems in lithium ion batteries (LIBs) is presented in this work. The method development was conducted for the qualitative structural elucidation of electrolyte main constituents with a special focus on the aging products of these components. The determination of their limits of detection was performed as well. Four different LiPF 6 -based LIB electrolytes were investigated in this study. The selected aging procedures for the electrolytes were thermal aging (storage at 60 °C for 2 weeks, storage at 60 °C in the presence of 2 vol % water contamination for 2 weeks) and electrochemical aging for 100 cycles at 2C. After thermal aging, several aging products were identified. The formation of organic phosphate aging products and several organofluorophosphates aging products was observed after thermal aging with water. Additionally, the content of carbonate aging products increased. After electrochemical aging, several carbonate aging products were detected. Electrochemical aging at 60 °C leads to the additional generation of organofluorophosphate aging products.

Apparatus and method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.; Coops, M.S.

1982-01-19

A method and apparatus for separating and reprocessing spent nuclear fuels includes a separation vessel housing a molten metal solvent in a reaction region, a reflux region positioned above and adjacent to the reaction region, and a porous filter member defining the bottom of the separation vessel in a supporting relationship with the metal solvent. Spent fuels are added to the metal solvent. A nonoxidizing nitrogen-containing gas is introduced into the separation vessel, forming solid actinide nitrides in the metal solvent from actinide fuels, while leaving other fission products in solution. A pressure of about 1.1 to 1.2 atm is applied in the reflux region, forcing the molten metal solvent and soluble fission products out of the vessel, while leaving the solid actinide nitrides in the separation vessel.

Rectification of nanopores in aprotic solvents--transport properties of nanopores with surface dipoles.

PubMed

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A; Siwy, Zuzanna S

2015-12-07

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li(+) ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.

System for removing contaminants from plastic resin

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2010-11-23

A resin recycling system that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The system includes receiving the resin in container form. A grinder grinds the containers into resin particles. The particles are exposed to a solvent in one or more solvent wash vessels, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. A separator is used to separate the resin particles and the solvent. The resin particles are then placed in solvent removing element where they are exposed to a solvent removing agent which removes any residual solvent remaining on the resin particles after separation.

Separation properties of aluminium-plastic laminates in post-consumer Tetra Pak with mixed organic solvent.

PubMed

Zhang, S F; Zhang, L L; Luo, K; Sun, Z X; Mei, X X

2014-04-01

The separation properties of the aluminium-plastic laminates in postconsumer Tetra Pak structure were studied in this present work. The organic solvent blend of benzene-ethyl alcohol-water was used as the separation reagent. Then triangle coordinate figure analysis was taken to optimize the volume proportion of various components in the separating agent and separation process. And the separation temperature of aluminium-plastic laminates was determined by the separation time, efficiency, and total mass loss of products. The results show that cost-efficient separations perform best with low usage of solvents at certain temperatures, for certain times, and within a certain range of volume proportions of the three components in the solvent agent. It is also found that similar solubility parameters of solvents and polyethylene adhesives (range 26.06-34.85) are a key factor for the separation of the aluminium-plastic laminates. Such multisolvent processes based on the combined-system concept will be vital to applications in the recycling industry.

Simultaneous determination of inorganic anions and cations by supercritical fluid chromatography using evaporative light scattering detection.

PubMed

Foulon, Catherine; Di Giulio, Pauline; Lecoeur, Marie

2018-01-26

Supercritical fluid chromatography (SFC) is commonly used for the analysis of non-polar compounds, but remains poorly explored for the separation of polar and ionized molecules. In this paper, SFC has been investigated for the separation of 14 inorganic ions sampled in aqueous solutions. Four polar stationary phases were first screened using CO 2 -methanol-based mobile phases containing water or different acidic or basic additives, in order to select the most efficient conditions for the simultaneous retention of inorganic cations and anions and to favor their detection using evaporative light scattering detector (ELSD). Orthogonal selectivity was obtained depending on the stationary phase used: whereas anions are less retained on HILIC stationary phase, 2-ethylpyridine (2-EP) stationary phase exhibits strong interaction for anions. Best results were obtained under gradient elution mode using a 2-EP stationary phase and by adding 0.2% triethylamine in the CO 2 -methanol-based mobile phase. The composition of the injection solvent was also investigated. The results showed that a methanolic sample containing a percentage of water not exceeding 20% does not affect the analytical performances obtained on 2-EP. Moreover, the presence of triethylamine in the injection solvent contributes to eliminate peaks shoulders. Among the 14 inorganic ions tested, three cations (Li + , Ca 2+ and Mg 2+ ) and five anions (Cl - , Br - , NO 3 - , I - , SCN - ) were totally resolved in 15 min. NO 3 - and NO 2 - still coeluted in the final optimized conditions. The other investigated ions were either strongly retained on the stationary phase or not detected by the ELSD. Copyright © 2017 Elsevier B.V. All rights reserved.

PREPARATION OF HIGH PURITY UF$sub 4$

DOEpatents

Magner, J.E.; Long, R.S.; Ellis, D.A.; Grinstead, R.R.

1962-04-17

S>A process for preparing very highly pure uranous tetrafluoride from impure uranium laden solvent extraction strip solutions, ion exchange process and resin-inpulp process eluate solutions which are at least 8M in hydrochloric acid is described. The process first comprises treating any of the above-mentioned solutions with a reducing agent to reduce the uranium to the + 4 oxidation state, and then contacting the reduced solution with an extractant phase comprising about 10 to 70% of tri-butyl phosphate in an organic solvent-diluent selected from benzene, ethyl-benzene, chlorobenzene, xylene, kerosene, or the like. The uranium is extracted into the extractant phase and is subsequently precipitated by treating the extractant with an aqueous fluoride solution. The highly pure uranous tetrafluoride precipitate is separated from the phases and recovered for subsequent utilization. (AEC)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, K.S.; Freilich, S.C.; Schaeffer, C.G.

Studies were initiated utilizing picosecond (ps) absorption spectroscopy, to directly monitor the dynamics of electron transfer from 1,4-diazabicyclo(2.2.2)octane (Dabco) to the excited states of benzophenone and fluorenone. These two systems were chosen because of their contrasting photochemistry. The quantum yield for photoreduction of benzophenone in polar solvents is generally greater than 0.1, while that of fluorenone is zero. In polar solvents, the proposed mechanism dictates that an electron is transferred to the excited singlet state fluorenone, which then back-transfers the electron, regenerating ground-state fluorenone and amine. Photolysis of benzophenone in the presence of an amine transfers an electron to anmore » excited triplet state, forming an ion pair that is stable relative to diffusional separation. The results of this study verify this proposal.« less

Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous sample-rotated small angle x-ray scattering and electrochemical methods approach [Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous grazing transmission small angle x-ray scattering and electrochemical methods approach

DOE PAGES

Hammons, Joshua A.; Ilavsky, Jan

2017-01-18

Nanoparticle electrodeposition is a simple and scalable approach to synthesizing supported nanoparticles. Used with a deep eutectic solvent (DES), surface nanoparticles can be assembled and exhibit unique surface charge separation when the DES is adsorbed on the nanoparticle surface. Key to understanding and controlling the assembly and the capacitance is a thorough understanding of surface particle mobility and charge screening, which requires an in-situ approach. In this study, Pb particle formation, size, shape and capacitance are resolved in a 1:2 choline Cl –: urea deep eutectic solvent whilst sweeping the cell potential in the range: 0.2 V to –1.2 Vmore » (vs. Ag/AgCl). These system parameters were resolved using a complementary suite of sample-rotated small angle X-ray scattering (SR-SAXS) and electrochemical impedance spectroscopy (EIS), which are presented and discussed in detail. This approach is able to show that both particle and ion transport are impeded in the DES, as aggregation occurs over the course of 6 minutes, and dissolved Pb ions accumulate and remain near the surface after a nucleation pulse is applied. The DES-Pb interactions strongly depend on the cell potential as evidenced by the specific differential capacitance of the Pb deposit, which has a maximum value of 2.5 +/– 0.5 F g –1 at –1.0 V vs. Ag/AgCl. Together, the SR-SAXS-EIS approach is able to characterize the unique nanoparticle capacitance, mobility and ion mobility in a DES and can be used to study a wide range of nanoparticle deposition systems in-situ.« less

Life of superoxide in aprotic Li-O₂ battery electrolytes: simulated solvent and counter-ion effects.

PubMed

Scheers, J; Lidberg, D; Sodeyama, K; Futera, Z; Tateyama, Y

2016-04-21

Li-air batteries ideally make use of oxygen from the atmosphere and metallic lithium to reversibly drive the reaction 2Li + O2↔ Li2O2. Conceptually, energy throughput is high and material use is efficient, but practically many material challenges still remain. It is of particular interest to control the electrolyte environment of superoxide (O2*(-)) to promote or hinder specific reaction mechanisms. By combining density functional theory based molecular dynamics (DFT-MD) and DFT simulations we probe the bond length and the electronic properties of O2*(-) in three aprotic solvents - in the presence of Li(+) or the much larger cation alternative tetrabutylammonium (TBA(+)). Contact ion pairs, LiO2*, are favoured over solvent-separated ion pairs in all solvents, but particularly in low permittivity dimethoxyethane (DME), which makes O2*(-) more prone to further reduction. The Li(+)-O2*(-) interactions are dampened in dimethyl sulfoxide (DMSO), in relation to those in DME and propylene carbonate (PC), which is reflected by smaller changes in the electronic properties of O2*(-) in DMSO. The additive TBA(+) offers an alternative, more weakly interacting partner to O2*(-), which makes it easier to remove the unpaired electron and oxidation more feasible. In DMSO, TBA(+) has close to no effect on O2*(-), which behaves as if no cation is present. This is contrasted by a much stronger influence of TBA(+) on O2*(-) in DME - comparable to that of Li(+) in DMSO. An important future goal is to compare and rank the effects of different additives beyond TBA(+). Here, the results of DFT calculations for small-sized cluster models are in qualitative agreement with those of the DFT-MD simulations, which suggests the cluster approach to be a cost-effective alternative to the DFT-MD simulations for a more extensive comparison of additive effects in future studies.

Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous sample-rotated small angle x-ray scattering and electrochemical methods approach [Surface Pb nanoparticle aggregation, coalescence and differential capacitance in a deep eutectic solvent using a simultaneous grazing transmission small angle x-ray scattering and electrochemical methods approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammons, Joshua A.; Ilavsky, Jan

Nanoparticle electrodeposition is a simple and scalable approach to synthesizing supported nanoparticles. Used with a deep eutectic solvent (DES), surface nanoparticles can be assembled and exhibit unique surface charge separation when the DES is adsorbed on the nanoparticle surface. Key to understanding and controlling the assembly and the capacitance is a thorough understanding of surface particle mobility and charge screening, which requires an in-situ approach. In this study, Pb particle formation, size, shape and capacitance are resolved in a 1:2 choline Cl –: urea deep eutectic solvent whilst sweeping the cell potential in the range: 0.2 V to –1.2 Vmore » (vs. Ag/AgCl). These system parameters were resolved using a complementary suite of sample-rotated small angle X-ray scattering (SR-SAXS) and electrochemical impedance spectroscopy (EIS), which are presented and discussed in detail. This approach is able to show that both particle and ion transport are impeded in the DES, as aggregation occurs over the course of 6 minutes, and dissolved Pb ions accumulate and remain near the surface after a nucleation pulse is applied. The DES-Pb interactions strongly depend on the cell potential as evidenced by the specific differential capacitance of the Pb deposit, which has a maximum value of 2.5 +/– 0.5 F g –1 at –1.0 V vs. Ag/AgCl. Together, the SR-SAXS-EIS approach is able to characterize the unique nanoparticle capacitance, mobility and ion mobility in a DES and can be used to study a wide range of nanoparticle deposition systems in-situ.« less

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Separation of heavy metals: Removal from industrial wastewaters and contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, R.W.; Shem, L.

1993-01-01

This paper reviews the applicable separation technologies relating to removal of heavy metals from solution and from soils in order to present the state-of-the-art in the field. Each technology is briefly described and typical operating conditions and technology performance are presented. Technologies described include chemical precipitation (including hydroxide, carbonate, or sulfide reagents), coagulation/flocculation, ion exchange, solvent extraction, extraction with chelating agents, complexation, electrochemical operation, cementation, membrane operations, evaporation, adsorption, solidification/stabilization, and vitrification. Several case histories are described, with a focus on waste reduction techniques and remediation of lead-contaminated soils. The paper concludes with a short discussion of important research needsmore » in the field.« less

Separation of heavy metals: Removal from industrial wastewaters and contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, R.W.; Shem, L.

1993-03-01

This paper reviews the applicable separation technologies relating to removal of heavy metals from solution and from soils in order to present the state-of-the-art in the field. Each technology is briefly described and typical operating conditions and technology performance are presented. Technologies described include chemical precipitation (including hydroxide, carbonate, or sulfide reagents), coagulation/flocculation, ion exchange, solvent extraction, extraction with chelating agents, complexation, electrochemical operation, cementation, membrane operations, evaporation, adsorption, solidification/stabilization, and vitrification. Several case histories are described, with a focus on waste reduction techniques and remediation of lead-contaminated soils. The paper concludes with a short discussion of important research needsmore » in the field.« less

Functional membranes. Present and future

NASA Technical Reports Server (NTRS)

Kunitake, T.

1982-01-01

The present situation and the future development of the functional membrane are discussed. It is expected that functional membranes will play increasingly greater roles in the chemical industry of the coming decade. These membranes are formed from polymer films, liquid membranes or bilayer membranes. The two most important technologies based on the polymeric membrane are reverse osmosis and ion exchange. The liquid membrane is used for separation of ionic species; an extension of the solvent extraction process. By using appropriate ligands and ionophores, highly selective separations are realized. The active transport is made possible if the physical and chemical potentials are applied to the transport process. More advanced functional membranes may be designed on the basis of the synthetic bilayer membrane.

Co-solvents with high coulombic efficiency in propylene carbonate based electrolytes

DOEpatents

Liu, Gao; Zhao, Hui; Park, Sang-Jae

2017-06-27

A homologous series of cyclic carbonate or propylene carbonate (PC) analogue solvents with increasing length of linear alkyl substitutes were synthesized and used as co-solvents with PC for graphite based lithium ion half cells. A graphite anode reaches a capacity around 310 mAh/g in PC and its analogue co-solvents with 99.95% Coulombic efficiency. Cyclic carbonate co-solvents with longer alkyl chains are able to prevent exfoliation of graphite when used as co-solvents with PC. The cyclic carbonate co-solvents of PC compete for solvation of Li ion with PC solvent, delaying PC co-intercalation. Reduction products of PC on graphite surfaces via single-electron path form a stable Solid Electrolyte Interphase (SEI), which allows the reversible cycling of graphite.

Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

2016-09-01

Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

NASA Astrophysics Data System (ADS)

Gill, Dip Singh; Rana, Dilbag

2009-04-01

Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

What is the minimum number of water molecules required to dissolve a potassium chloride molecule?

PubMed

Sen, Anik; Ganguly, Bishwajit

2010-12-01

This work answers an unsolved question that consists of determining the least number of water molecules necessary to separate a potassium chloride molecule. The answer based on accurate quantum chemical calculations suggests that tetramers are the smallest clusters necessary to dissociate KCl molecules. The study was made with Møller-Plesset second-order perturbation theory modified with the cluster theory having single, double, and perturbative triple excitations. With this extensive study, the dissociation of KCl molecule in different water clusters was evaluated. The calculated results show that four water molecules stabilize a solvent separated K(+)/Cl(-) ion-pair in prismatic structure and with six water molecules further dissociation was observed. Attenuated total reflection infrared spectroscopy of KCl dissolved in water establishes that clusters are made of closely bound ions with a mean of five water molecules per ion-pair [K(+)(H(2)O)(5)Cl(-)]. (Max and Chapados, Appl Spectrosc 1999, 53, 1601; Max and Chapados, J Chem Phys 2001, 115, 2664.) The calculated results tend to support that five water molecules leads toward the formation of contact ion-pair. The structures, energies, and infrared spectra of KCl molecules in different water clusters are also discussed. © 2010 Wiley Periodicals, Inc.

Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometrymore » of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.« less

Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schroeder, D.J.; Hubaud, A.A.; Vaughey, J.T., E-mail: vaughey@anl.gov

2014-01-01

Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stabilitymore » of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.« less

Methods for recovering a polar solvent from a fluid stream contaminated with at least one polar impurity

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.

2012-11-13

A method of removing a polar solvent from a fluid volume contaminated with at least one polar impurity, such as a free fatty acid, is provided. The method comprises providing a fluid volume that includes at least one polar impurity dissolved in at least one solvent. The fluid volume is contacted with an expanding gas to remove the at least one solvent. The expanding gas may be dissolved into the at least one solvent in the fluid volume to form a gas-expanded solvent. The immiscibility of the polar impurities in the gas-expanded solvent enables separation of the polar impurities from the gas-expanded solvent. After separation of the polar impurities, at least one of the temperature and pressure may be reduced to separate the solvent from the expanding gas such that the clean solvent may be reused.

The development of novel Nexar block copolymer/Ultem composite membranes for C2-C4 alcohols dehydration via pervaporation.

PubMed

Zuo, Jian; Shi, Gui Min; Wei, Shawn; Chung, Tai-Shung

2014-08-27

Novel composite membranes comprising sulfonated styrenic Nexar pentablock copolymers were developed by dip-coating on poly(ether imide) hollow fibers for pervaporation dehydration of C2-C4 alcohols. The advantages of using block copolymers as the selective layer are (1) their effectiveness to synergize the physicochemical properties of different chemical and structural moieties and (2) tunable nanoscale morphology and nanostructure via molecular engineering. To achieve high-performance composite membranes, the effects of coating time, ion exchange capacity (IEC) of the copolymer, and solvent systems for coating were investigated. It is revealed that a minimum coating time of 30 s is needed for the formation of a continuous and less-defective top layer. A higher IEC value results in a membrane with a higher flux and lower separation factor because of enhanced hydrophilicity and stretched chain conformation. Moreover, the composite membranes prepared from hexane/ethanol mixtures show higher separation factors and lower fluxes than those from the hexane solvent owing to microdomain segregation induced by ethanol and a smooth and dense top selective layer. These hypotheses were verified by atomic force microscopy and positron annihilation spectroscopy. The newly developed composite membranes demonstrate impressive separation performance with fluxes exceeding 2 kg/m(2) h and separation factors more than 200 for isopropyl alcohol and n-butanol dehydration from 85/15 wt % alcohol/water feed mixtures at 50 °C.

Chloride leaching and solvent extraction of cadmium, cobalt and nickel from spent nickel-cadmium, batteries using Cyanex 923 and 272

NASA Astrophysics Data System (ADS)

Reddy, B. Ramachandra; Priya, D. Neela

Studies are conducted on the leaching and solvent extraction separation of metals from chloride leach liquor of spent nickel-cadmium batteries with Cyanex 923 and 272 diluted in kerosene as the extractants. Dissolution of the metals increases with increase in acid concentration and time but decreases with the solids-to-liquid ratio. Complete dissolution of Cd, Co and Ni can be achieved with 1.5 M HCl at 85 °C for 8 h and a solids-to-liquid ratio of 4. Treatment of leach liquor for the separation of metals with Cyanex 923 shows that increase of extractant and chloride ion concentration increases the percentage extraction of cadmium. The plot of log[distribution coefficient] versus log[extractant]/[Cl -] is linear with a slope of 2, which indicates that the extraction follows a solvation mechanism with the extracted species as CdCl 2·2S (S, Cyanex 923). Moreover, Cyanex 923 enables a clear separation of Cd from Co and Ni. Extraction of cobalt with Cyanex 272 involves a cation-exchange mechanism with the formation of a 1:2 metal-to-ligand complex in the organic phase. Based on the distribution data, extractant concentration and equilibrium pH of the aqueous phase, a possible separation process is proposed for the recovery of cadmium, cobalt and nickel with >99% efficiency.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02691a Click here for additional data file.

PubMed Central

Mazzini, Virginia

2017-01-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity. PMID:29147533

Solvent recovery opportunities in the pharmaceutical industry.

PubMed

Barton, P I

2000-11-01

Opportunities for recovering and recycling waste solvent streams in the pharmaceutical industry are reviewed. A major obstacle to solvent recovery and recycling is the existence of azeotropic compositions, and thus separation barriers, in the mixtures in question. Advances in the understanding of these complex separation problems are discussed. Recent progress on novel designs for small-scale, flexible azeotropic separation processes is reviewed. Also considered is the alternative and complementary approach of integrating solvent use within a batch process so that the formation of hard-to-separate azeotropic compositions is prevented.

Quantifying the loss of methane through secondary gas mass transport (or 'slip') from a micro-porous membrane contactor applied to biogas upgrading.

PubMed

McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

2013-07-01

Secondary gas transport during the separation of a binary gas with a micro-porous hollow fibre membrane contactor (HMFC) has been studied for biogas upgrading. In this application, the loss or 'slip' of the secondary gas (methane) during separation is a known concern, specifically since methane possesses the intrinsic calorific value. Deionised (DI) water was initially used as the physical solvent. Under these conditions, carbon dioxide (CO2) and methane (CH4) absorption were dependent upon liquid velocity (V(L)). Whilst the highest CO2 flux was recorded at high V(L), selectivity towards CO2 declined due to low residence times and a diminished gas-side partial pressure, and resulted in slip of approximately 5.2% of the inlet methane. Sodium hydroxide was subsequently used as a comparative chemical absorption solvent. Under these conditions, CO2 mass transfer increased by increasing gas velocity (VG) which is attributed to the excess of reactive hydroxide ions present in the solvent, and the fast conversion of dissolved CO2 to carbonate species reinitiating the concentration gradient at the gas-liquid interface. At high gas velocities, CH4 slip was reduced to 0.1% under chemical conditions. Methane slip is therefore dependent upon whether the process is gas phase or liquid phase controlled, since methane mass transport can be adequately described by Henry's law within both physical and chemical solvents. The addition of an electrolyte was found to further retard CH4 absorption via the salting out effect. However, their applicability to physical solvents is limited since electrolytic concentration similarly impinges upon the solvents' capacity for CO2. This study illustrates the significance of secondary gas mass transport, and furthermore demonstrates that gas-phase controlled systems are recommended where greater selectivity is required. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ionic association of lithium salts in propylene carbonate/ 1,2-dimethoxyethane mixed systems for lithium batteries

NASA Astrophysics Data System (ADS)

Ishikawa, Masashi; Wen, Shi-Qui; Matsuda, Yoshiharu

1993-06-01

The ionic association constants of lithium perchlorate, lithium trifluoremethylsulfate, lithium hexafluorophosphate, and lithium tetrafluoroborate have been determined experimentally (by Shedlovsky's method) in various mixtures of propylene carbonate and 1,2-dimethoxyethane as typical electrolyte systems for rechargeable lithium batteries. The association constants vary extensively for different mixing ratios of propylene to 1,2-dimethoxyethane and for different species of salts. These values are compared with the theoretical values as predicted by the Fuoss and Bjerrum equations. On the basis of this comparison and some physical properties of the solution, the variation in the ionic association constants may be ascribed to the charge of ionic association species, i.e., a contact ion-pair and a solvent-separated ion-pair.

The influence of self-assembling supramolecular structures on the passive membrane transport of ion-paired molecules.

PubMed

Benaouda, F; Brown, M B; Shah, B; Martin, G P; Jones, S A

2012-12-15

Weak ion-ion interactions, such as those associated with ion-pair formation, are difficult to isolate and characterise in the liquid state, but they have the potential to alter significantly the physicochemical behaviour of molecules in solution. The aim of this work was to gain a better understanding of how ion-ion interactions influenced passive membrane transport. The test system was composed of propylene (PG) glycol, water and diclofenac diethylamine (DDEA). Infrared spectroscopy was employed to determine the nature of the DDEA ion-pair interactions and the drug-vehicle association. Passive transport was assessed using homogeneous synthetic membranes. Solution-state analysis demonstrated that the ion-pair was unperturbed by vehicle composition changes, but the solvent-DDEA interactions were modified. DDEA-PG/water hydrogen bonding influenced the ion-pair solubility (X(dev)) and the solvent interactions slowed transport rate in PG-rich vehicles (0.84±0.05 μg cm(-2) h(-1), at ln(X(dev))=0.57). In water-rich co-solvents, the presence of strong water structuring facilitated a significant increase (p<0.05) in transmembrane penetration rate (e.g. 4.33±0.92 μg cm(-2) h(-1), at ln(X(dev))=-0.13). The data demonstrates that weak ion-ion interactions can result in the embedding of polar entities within a stable solvent complex and spontaneous supramolecular assembly should be considered when interpreting transmembrane transport processes of ionic molecules. Copyright © 2012 Elsevier B.V. All rights reserved.

Comparison of single-ion molecular dynamics in common solvents

NASA Astrophysics Data System (ADS)

Muralidharan, A.; Pratt, L. R.; Chaudhari, M. I.; Rempe, S. B.

2018-06-01

Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li+ and PF6- ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. We provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF6-), velocity relaxations are all similar: negative tail relaxations for the VACF and a clear second relaxation for γ (t ), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li+ ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ (t ). But the corresponding analysis of the solventberg Li+(H2O)4 does conform to the standard picture set by all the PF6- results.

A Grand Canonical Monte Carlo simulation program for computing ion distributions around biomolecules in hard sphere solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

The GIBS software program is a Grand Canonical Monte Carlo (GCMC) simulation program (written in C++) that can be used for 1) computing the excess chemical potential of ions and the mean activity coefficients of salts in homogeneous electrolyte solutions; and, 2) for computing the distribution of ions around fixed macromolecules such as, nucleic acids and proteins. The solvent can be represented as neutral hard spheres or as a dielectric continuum. The ions are represented as charged hard spheres that can interact via Coulomb, hard-sphere, or Lennard-Jones potentials. In addition to hard-sphere repulsions, the ions can also be made tomore » interact with the solvent hard spheres via short-ranged attractive square-well potentials.« less

RECOVERY OF PROTACTINIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Elson, R.E.

1959-07-14

The recovery of fluoride complexed protactinium from aqueous acidic solutions by solvent extraction is described. Generally the prccess of the invention com rises mixing an aqueous solution containing protactinium in a complexed form with an organic solvent which is specific for protactinium, such as diisopropyl carbinol, then decomposing the protactinium complex by adjusting the acidity of the aqueous solution to between 0-3 to 0-9 M in hydrogen ion concentration, and introducing a source of aluminum ions in sufficient quantity to establish a concentration of 0.5 to 1.2 M aluminum ion, whereupon decomposition of the protactinium fluoride complex takes place and the protactinium ion is taken up by the organic solvent phase.

Gas separation by composite solvent-swollen membranes

DOEpatents

Matson, S.L.; Lee, E.K.L.; Friesen, D.T.; Kelly, D.J.

1989-04-25

There is disclosed a composite immobilized liquid membrane of a solvent-swollen polymer and a microporous organic or inorganic support, the solvent being at least one highly polar solvent containing at least one nitrogen, oxygen, phosphorus or sulfur atom, and having a boiling point of at least 100 C and a specified solubility parameter. The solvent or solvent mixture is homogeneously distributed through the solvent-swollen polymer from 20% to 95% by weight. The membrane is suitable for acid gas scrubbing and oxygen/nitrogen separation. 3 figs.

Gas separation by composite solvent-swollen membranes

DOEpatents

Matson, Stephen L.; Lee, Eric K. L.; Friesen, Dwayne T.; Kelly, Donald J.

1989-01-01

There is disclosed a composite immobulized liquid membrane of a solvent-swollen polymer and a microporous organic or inorganic support, the solvent being at least one highly polar solvent containing at least one nitrogen, oxygen, phosphorous or sulfur atom, and having a boiling point of at least 100.degree. C. and a specified solubility parameter. The solvent or solvent mixture is homogeneously distributed through the solvent-swollen polymer from 20% to 95% by weight. The membrane is suitable for acid gas scrubbing and oxygen/nitrogen separation.

Separation of Gadolinium (Gd) using Synergic Solvent Mixed Topo-D2EHPA with Extraction Method.

NASA Astrophysics Data System (ADS)

Effendy, N.; Basuki, K. T.; Biyantoro, D.; Perwira, N. K.

2018-04-01

The main problem to obtain Gd with high purity is the similarity of chemical properties and physical properties with the other rare earth elements (REE) such as Y and Dy, it is necessary to do separation by the extraction process. The purpose of this research to determine the best solvent type, amount of solvent, feed and solvent ratio in the Gd extraction process, to determine the rate order and the value of the rate constant of Gd concentration based on experimental data of aqueous phase concentration as a function of time and to know the effect of temperature on the reaction speed constant. This research was conducted on variation of solvent, amount of solvent, feed and solvent ratio in the extraction process of Gd separation, extraction time to determine the order value and the rate constant of Gd concentration in extraction process based on the aqueous phase concentration data as a function of time, to the rate constant of decreasing concentration of Gd. Based on the calculation results, the solvent composition was obtained with the best feed to separate the rare earth elements Gd in the extraction process is 1 : 4 with 15% concentration of TOPO and 10% concentration of D2EHPA. The separation process of Gd using extraction method by solvent TOPO-D2EHPA 2 : 1 comparison is better than single solvent D2EHPA / TOPO because of the synergistic effect. The rate order of separation process of Gd follows order 1. The Arrhenius Gd equation becomes k = 1.46 x 10-7 exp (-6.96 kcal / mol / RT).

Underscreening in concentrated electrolytes.

PubMed

Lee, Alpha A; Perez-Martinez, Carla S; Smith, Alexander M; Perkin, Susan

2017-07-01

Screening of a surface charge by an electrolyte and the resulting interaction energy between charged objects is of fundamental importance in scenarios from bio-molecular interactions to energy storage. The conventional wisdom is that the interaction energy decays exponentially with object separation and the decay length is a decreasing function of ion concentration; the interaction is thus negligible in a concentrated electrolyte. Contrary to this conventional wisdom, we have shown by surface force measurements that the decay length is an increasing function of ion concentration and Bjerrum length for concentrated electrolytes. In this paper we report surface force measurements to test directly the scaling of the screening length with Bjerrum length. Furthermore, we identify a relationship between the concentration dependence of this screening length and empirical measurements of activity coefficient and differential capacitance. The dependence of the screening length on the ion concentration and the Bjerrum length can be explained by a simple scaling conjecture based on the physical intuition that solvent molecules, rather than ions, are charge carriers in a concentrated electrolyte.

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca-Cl and NH4-Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, D.; Ladipo, F.T.; Braddock-Wilking, J.

Low temperature crystal structures of (DABCO)H{sup +}Co(CO){sub 4}{sup -} (1) and (DABCO)H{sup +}Co(CO){sub 3}PPh{sub 3}{sup -} (2) (DABCO = 1,4-diazabicyclooctane) indicate that both salts exhibit N-H...Co hydrogen bonding. IR and NMR data indicate that these hydrogen bonded species persist in nonpolar solvents such as toluene, but exist as solvent separated ions in more polar solvents. Replacement of the axial CO ligand by PPh{sub 3} leads to a shortening of the N...Co separation in the solid state from 3.437(3) to 3.294(6) A. This change is accompanied by an increase in the angle between the equatorial carbonyl ligands. Thus, the crystallographic resultsmore » suggest a strengthening of the N-H...Co hydrogen bond upon increasing the basicity of the metal center, the first observation of this type in the solid state. This assertion is supported by variable-temperature {sup 1}H and {sup 13}C NMR data in toluene-d{sub 8} solution which, discussed in the light of ab initio calculations, indicate that the barrier to a fluxional process involving cleavage of the N-H...Co hydrogen bond is greater in 2 than in 1. The crystal structures of 1 and 2 have been determined by X-ray diffraction at 135(5) and 123(5) K, respectively. 19 refs., 2 figs., 5 tabs.« less

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

PubMed

Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R

2017-08-10

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

Apparatus and method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.

1982-01-19

Spent nuclear fuels, including actinide fuels, volatile and non-volatile fission products, are reprocessed and separated in a molten metal solvent housed in the reaction region of a separation vessel which includes a reflux region positioned above the molten tin solvent. The reflux region minimizes loss of evaporated solvent during the separation of the actinide fuels from the volatile fission products. Additionally, inclusion of the reflux region permits the separation of the more volatile fission products (noncondensable) from the less volatile ones (condensable).

Application of phase-trafficking methods to natural products research.

PubMed

Araya, Juan J; Montenegro, Gloria; Mitscher, Lester A; Timmermann, Barbara N

2010-09-24

A novel simultaneous phase-trafficking approach using spatially separated solid-supported reagents for rapid separation of neutral, basic, and acidic compounds from organic plant extracts with minimum labor is reported. Acidic and basic ion-exchange resins were physically separated into individual sacks ("tea bags") for trapping basic and acidic compounds, respectively, leaving behind in solution neutral components of the natural mixtures. Trapped compounds were then recovered from solid phase by appropriate suspension in acidic or basic solutions. The feasibility of the proposed separation protocol was demonstrated and optimized with an "artificial mixture" of model compounds. In addition, the utility of this methodology was illustrated with the successful separation of the alkaloid skytanthine from Skytanthus acutus Meyen and the main catechins and caffeine from Camellia sinensis L. (Kuntze). This novel approach offers multiple advantages over traditional extraction methods, as it is not labor intensive, makes use of only small quantities of solvents, produces fractions in adequate quantities for biological assays, and can be easily adapted to field conditions for bioprospecting activities.

Application of Phase-Trafficking Methods to Natural Products Research

PubMed Central

Araya, Juan J.; Montenegro, Gloria; Mitscher, Lester A.; Timmermann, Barbara N.

2010-01-01

A novel simultaneous phase-trafficking approach using spatially separated solid-supported reagents (SSR) for rapid separation of neutral, basic, and acidic compounds from organic plant extracts with minimum labor is reported. Acidic and basic ion exchange resins were physically separated into individual sacks (“teabags”) for trapping basic and acidic compounds respectively, leaving behind in solution neutral components of the natural mixtures. Trapped compounds were then recovered from solid phase by appropriate suspension in acidic or basic solutions. The feasibility of the proposed separation protocol was demonstrated and optimized with an “artificial mixture” of model compounds. In addition, the utility of this methodology was illustrated with the successful separation of the alkaloid skytanthine from Skytanthus acutus Meyen and the main catechins and caffeine from Camellia sinensis L. (Kuntze). This novel approach offers multiple advantages over traditional extraction methods, as it is not labor intensive, makes use of only small quantities of solvents, produces fractions in adequate quantities for biological assays, and can be easily adapted to field conditions for bioprospecting activities. PMID:20704309

Membrane formation in liquids by adding an antagonistic salt

NASA Astrophysics Data System (ADS)

Sadakane, Koichiro; Seto, Hideki

2018-03-01

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Exceptional ion rejection ability of directional solvent for non-membrane desalination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rish, Daniel; Department of Civil Engineering, University of Notre Dame, Notre Dame, Indiana 46556; Luo, Shirui

2014-01-13

The recently demonstrated directional solvent extraction (DSE) is promising for very low temperature, membrane-free water desalination. In this paper, we combine atomistic simulations and experimental validation to demonstrate that the currently used directional solvent, decanoic acid, can reject all major salt ions in seawater, with very high rejection rates. The salinities of the DSE recovered water show that ion rejection rates are ∼98%–99%—similar to those of the best reverse osmosis membranes. Our test also shows that the DSE process can desalt seawater to produce fresh water that meets drinking water standards.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

PubMed

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

PubMed

Ong, Mitchell T; Verners, Osvalds; Draeger, Erik W; van Duin, Adri C T; Lordi, Vincenzo; Pask, John E

2015-01-29

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.

Solvent annealing induced phase separation and dewetting in PMMA∕SAN blend film: film thickness and solvent dependence.

PubMed

You, Jichun; Zhang, Shuangshuang; Huang, Gang; Shi, Tongfei; Li, Yongjin

2013-06-28

The competition between "dewetting" and "phase separation" behaviors in polymer blend films attracts significant attention in the last decade. The simultaneous phase separation and dewetting in PMMA∕SAN [poly(methyl methacrylate) and poly(styrene-ran-acrylonitrile)] blend ultrathin films upon solvent annealing have been observed for the first time in our previous work. In this work, film thickness and annealing solvent dependence of phase behaviors in this system has been investigated using atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS). On one hand, both vertical phase separation and dewetting take place upon selective solvent vapor annealing, leading to the formation of droplet∕mimic-film structures with various sizes (depending on original film thickness). On the other hand, the whole blend film dewets the substrate and produces dispersed droplets on the silicon oxide upon common solvent annealing. GISAXS results demonstrate the phase separation in the big dewetted droplets resulted from the thicker film (39.8 nm). In contrast, no period structure is detected in small droplets from the thinner film (5.1 nm and 9.7 nm). This investigation indicates that dewetting and phase separation in PMMA∕SAN blend film upon solvent annealing depend crucially on the film thickness and the atmosphere during annealing.

[Supercritical and near-critical fluid solvents assisted reaction and separation processes].

PubMed

Song, R; Zeng, J; Zhong, B

2001-11-01

The tunability of supercritical and near-critical fluid (S/NCF) solvents offers environmental improvements and economic advantages from improved performances and flexibility for separation and reaction processes through density changes or cosolvents. The paper reviews the sustainable reaction and separation processes in S/NCF solvents such as supercritical carbon dioxide and near-critical water.

A new supramolecular based liquid solid microextraction method for preconcentration and determination of trace bismuth in human blood serum and hair samples by electrothermal atomic absorption spectrometry.

PubMed

Kahe, Hadi; Chamsaz, Mahmoud

2016-11-01

A simple and reliable supramolecule-aggregated liquid solid microextraction method is described for preconcentration and determination of trace amounts of bismuth in water as well as human blood serum and hair samples. Catanionic microstructures of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) surfactants, dissolved in deionized water/propanol, are used as a green solvent to extract bismuth (III)-diethyldithiocarbamate complexes by dispersive microextraction methodology. The extracted solid phase is easily removed and dissolved in 50 μL propanol for subsequent measurement by electrothermal atomic absorption spectrometry (ET-AAS). The procedure benefits the merits of supramolecule aggregates' properties and dispersive microextraction technique using water as the main component of disperser solvent, leading to direct interaction with analyte. Phase separation behavior of extraction solvent and different parameters influencing the extraction efficiency of bismuth ion such as salt concentration, pH, centrifugation time, amount of chelating agent, SDS:CTAB mole ratio, and solvent amounts were thoroughly optimized. Under the optimal experimental conditions, the calibration curve was linear in the range of 0.3-6 μg L -1 Bi (III) with a limit of detection (LOD) of 0.16 μg L -1 (S/N = 3). The relative standard deviations (RSD) of determination were obtained to be 5.1 and 6.2 % for 1 and 3 μg L -1 of Bi (III), respectively. The developed method was successfully applied as a sensitive and accurate technique for determination of bismuth ion in human blood serum, hair samples, and a certified reference material.

The study of membrane formation via phase inversion method by cloud point and light scattering experiment

NASA Astrophysics Data System (ADS)

Arahman, Nasrul; Maimun, Teuku; Mukramah, Syawaliah

2017-01-01

The composition of polymer solution and the methods of membrane preparation determine the solidification process of membrane. The formation of membrane structure prepared via non-solvent induced phase separation (NIPS) method is mostly determined by phase separation process between polymer, solvent, and non-solvent. This paper discusses the phase separation process of polymer solution containing Polyethersulfone (PES), N-methylpirrolidone (NMP), and surfactant Tetronic 1307 (Tet). Cloud point experiment is conducted to determine the amount of non-solvent needed on induced phase separation. Amount of water required as a non-solvent decreases by the addition of surfactant Tet. Kinetics of phase separation for such system is studied by the light scattering measurement. With the addition of Tet., the delayed phase separation is observed and the structure growth rate decreases. Moreover, the morphology of fabricated membrane from those polymer systems is analyzed by scanning electron microscopy (SEM). The images of both systems show the formation of finger-like macrovoids through the cross-section.

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

Microhydration of LiOH: Insight from electronic decays of core-ionized states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kryzhevoi, Nikolai V., E-mail: nikolai.kryzhevoi@pci.uni-heidelberg.de

2016-06-28

We compute and compare the autoionization spectra of a core-ionized LiOH molecule both in its isolated and microhydrated states. Stepwise microhydration of LiOH leads to gradual elongation of the Li–OH bond length and finally to molecular dissociation. The accompanying changes in the local environment of the OH{sup −} and Li{sup +} counterions are reflected in the computed O 1s and Li 1s spectra. The role of solvent water molecules and the counterion in the spectral shape formation is assessed. Electronic decays of the microhydrated LiOH are found to be mostly intermolecular since the majority of the populated final states havemore » at least one outer-valence vacancy outside the initially core-ionized ion, mainly on a neighboring water molecule. The charge delocalization occurs through the intermolecular Coulombic and electron transfer mediated decays. Both mechanisms are highly efficient that is partly attributed to hybridization of molecular orbitals. The computed spectral shapes are sensitive to the counterion separation as well as to the number and arrangement of solvent molecules. These sensitivities can be used for studying the local hydration structure of solvated ions in aqueous solutions.« less

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

PubMed

Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

2015-05-13

Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale.

PubMed

Carvalho, Nathalia F; Pliego, Josefredo R

2015-10-28

Absolute single-ion solvation free energy is a very useful property for understanding solution phase chemistry. The real solvation free energy of an ion depends on its interaction with the solvent molecules and on the net potential inside the solute cavity. The tetraphenyl arsonium-tetraphenyl borate (TATB) assumption as well as the cluster-continuum quasichemical theory (CC-QCT) approach for Li(+) solvation allows access to a solvation scale excluding the net potential. We have determined this free energy scale investigating the solvation of the lithium ion in water (H2O), acetonitrile (CH3CN) and dimethyl sulfoxide (DMSO) solvents via the CC-QCT approach. Our calculations at the MP2 and MP4 levels with basis sets up to the QZVPP+diff quality, and including solvation of the clusters and solvent molecules by the dielectric continuum SMD method, predict the solvation free energy of Li(+) as -116.1, -120.6 and -123.6 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively (1 mol L(-1) standard state). These values are compatible with the solvation free energy of the proton of -253.4, -253.2 and -261.1 kcal mol(-1) in H2O, CH3CN and DMSO solvents, respectively. Deviations from the experimental TATB scale are only 1.3 kcal mol(-1) in H2O and 1.8 kcal mol(-1) in DMSO solvents. However, in the case of CH3CN, the deviation reaches a value of 9.2 kcal mol(-1). The present study suggests that the experimental TATB scale is inconsistent for CH3CN. A total of 125 values of the solvation free energy of ions in these three solvents were obtained. These new data should be useful for the development of theoretical solvation models.

A fluorescent paramagnetic Mn metal–organic framework based on semi-rigid pyrene tetra­carboxylic acid: sensing of solvent polarity and explosive nitroaromatics

PubMed Central

Bajpai, Alankriti; Mukhopadhyay, Arindam; Krishna, Manchugondanahalli Shivakumar; Govardhan, Savitha; Moorthy, Jarugu Narasimha

2015-01-01

An Mn metal–organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H4 L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-L MOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt’s solvent polarity parameter (E T N). Further, the applicability of Mn-L to the sensing of nitroaromatics via fluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF. PMID:26306197

A fluorescent paramagnetic Mn metal-organic framework based on semi-rigid pyrene tetra-carboxylic acid: sensing of solvent polarity and explosive nitroaromatics.

PubMed

Bajpai, Alankriti; Mukhopadhyay, Arindam; Krishna, Manchugondanahalli Shivakumar; Govardhan, Savitha; Moorthy, Jarugu Narasimha

2015-09-01

An Mn metal-organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H4 L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-L MOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt's solvent polarity parameter (E T (N)). Further, the applicability of Mn-L to the sensing of nitroaromatics via fluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF.

Trace analysis of nitrite ions in environmental samples by using in-situ synthesized Zein biopolymeric nanoparticles as the novel green solid phase extractor.

PubMed

Hatamie, Amir; Nassiri, Mahmoud; Alivand, Meghdad Doust; Bhatnagar, Amit

2018-01-01

For the first time, a novel green method using Zein biopolymeric nanoparticles as a green dispersive solid-phase extractor is reported for the separation and preconcentration of trace amount of nitrite (NO 2 - ) ions in ppb levels. The Zein protein is a biodegradable hydrophobic plant protein that is obtained from corn and is composed of a number of hydrophobic amino acids. Zein bionanoparticles were synthesized in an anti-solvent process and used as a new biosorbent in the extraction technique. In the proposed technique, by using a standard method at first, a mixture of 1-naphthylamine and sulphanilic acid as selective regents was added to the samples, and in the presence of the nitrite ion, a red azo product was formed. After that, the ethanolic Zein solution (equal to 15mg) was injected rapidly into the sample, based on the anti-solvent process. Zein bionanoparticles (BNPs) were produced, the adsorbed colour product was separated by centrifugation, and finally samples were analysed with the spectrophotometric method. The influence of different variables such as pH, buffer and amount of buffer, amount of adsorbent and effect of time on extraction were investigated and Zein BNPs were characterized by TEM, SEM, and FT-IR techniques. The main advantages of Zein as a new solid-phase extractor are that this biopolymer is non-toxic, stable, widely available, biodegradable, very hydrophobic, and can be fabricated easily. Under optimal experimental conditions, the linear correlation coefficient (r 2 ) was found to be 0.9972 at the concentration range of 5.0-1000ngmL -1 . The limit of detection was 2.3ngmL -1 (0.05μM). This method was applied successfully for the analysis of sea and river waters as well as industrial wastewater samples. Finally, this method follows the US EPA (US Environmental Protection Agency) and WHO (World Health Organization) international standards for nitrite analysis. In addition, it has several advantages to warrant its applicability in the near future in separation science as a green biosorbent in both dispersive and normal solid-phase extraction. Copyright © 2017. Published by Elsevier B.V.

Exploring Solvent Shape and Function Using - and Isomer-Selective Vibrational Spectroscopy

NASA Astrophysics Data System (ADS)

Johnson, Mark

2010-06-01

We illustrate the new types of information than can be obtained through isomer-selective ``hole-burning'' spectroscopy carried out in the vibrational manifolds of Ar-tagged cluster ions. Three examples of increasing complexity will be presented where the changes in a solute ion are correlated with different morphologies of a surrounding solvent cage. In the first, we discuss the weak coupling limit where different hydration morphologies lead to small distortions of a covalent ion. We then introduce the more interesting case of the hydrated electron, where different shapes of the water network lead to dramatic changes in the extent of delocalization in the diffuse excess electron cloud. We then turn to the most complex case involving hydration of the nitrosonium ion, where different arrangements of the same number of water molecules span the range in behavior from simple solvation to actively causing a chemical reaction. The latter results are particularly interesting as they provide a microscopic, molecular-level picture of the ``solvent coordinate'' commonly used to describe solvent mediated processes.

Ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 2. Photoinduced electron transfer to counterions in solution.

PubMed

Bragg, Arthur E; Schwartz, Benjamin J

2008-04-24

The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by other factors that alter the solution environment local to the CTTS anion, including the presence of cosolutes, cosolvents, and other ions. In this paper, we examine the ultrafast CTTS dynamics of iodide in liquid tetrahydrofuran (THF) with a particular focus on how the solvent dynamics and the CTTS electron-ejection process are altered in the presence of various counterions. In weakly polar solvents such as THF, iodide salts can be strongly ion-paired in solution; the steady-state UV-visible absorption spectroscopy of various iodide salts in liquid THF indicates that the degree of ion-pairing changes from strong to weak to none as the counterion is switched from Na+ to tetrabutylammonium (t-BA+) to crown-ether-complexed Na+, respectively. In our ultrafast experiments, we have excited the I- CTTS transition of these various iodide salts at 263 nm and probed the dynamics of the CTTS-detached electrons throughout the visible and near-IR. In the previous paper of this series (Bragg, A. E.; Schwartz, B. J. J. Phys. Chem. B 2008, 112, 483-494), we found that for "counterion-free" I- (obtained by complexing Na+ with a crown ether) the CTTS electrons were ejected approximately 6 nm from their partner iodine atoms, the result of significant nonadiabatic coupling between the CTTS excited state and extended electronic states supported by the naturally existing solvent cavities in liquid THF, which also serve as pre-existing electron traps. In contrast, for the highly ion-paired NaI/THF system, we find that approximately 90% of the CTTS electrons are "captured" by a nearby Na+ to form (Na+, e-)THF "tight-contact pairs" (TCPs), which are chemically and spectroscopically distinct from both solvated neutral sodium atoms and free solvated electrons. A simple kinetic model is able to reproduce the details of the electron capture process, with 63% of the electrons captured quickly in approximately 2.3 ps, 26% captured diffusively in approximately 63 ps, and the remaining 11% escaping out into the solution on subnanosecond time scales. We also find that the majority of the CTTS electrons are ejected to within 1 or 2 nm of the Na+. This demonstrates that the presence of the nearby cation biases the relocalization of CTTS-generated electrons from I- in THF, changing the nonadiabatic coupling to the extended, cavity-supported electronic states in THF to produce a much tighter distribution of electron-ejection distances. In the case of the more loosely ion-paired t-BA+-I-/THF system, we find that only 10-15% of the CTTS-ejected electrons associate with t-BA+ to form "loose-contact pairs" (LCPs), which are characterized by a much weaker interaction between the electron and cation than occurs in TCPs. The formation of (t-BA+, e-)THF LCPs is characterized by a Coulombically induced blue shift of the free eTHF- spectrum on a approximately 5-ps time scale. We argue that the weaker interaction between t-BA+ and the parent I- results in little change to the CTTS-ejection process, so that only those electrons that happen to localize in the vicinity of t-BA+ are captured to form LCPs. Finally, we interpret the correlation between electron capture yield and counterion-induced perturbation of the I- CTTS transition as arising from changes in the distribution of ion-pair separations with cation identity, and we discuss our results in the context of relevant solution conductivity measurements.

U-EXTRACTION--IMPROVEMENTS IN ELIMINATION OF Mo BY USE OF FERRIC ION

DOEpatents

Clark, H.M.; Duffey, D.

1958-06-10

An improved solvent extraction process is described whereby U may be extracted by a water immiscible organic solvent from an aqueous solution of uranyl nitrate. It has been found that Mo in the presence of phosphate ions appears to form a complex with the phosphate which extracts along with the U. This extraction of Mo may be suppressed by providing ferric ion in the solution prior to the extraction step. The ferric ion is preferably provided in the form of ferric nitrate.

"Solvent-in-salt" systems for design of new materials in chemistry, biology and energy research.

PubMed

Azov, Vladimir A; Egorova, Ksenia S; Seitkalieva, Marina M; Kashin, Alexey S; Ananikov, Valentine P

2018-02-21

Inorganic and organic "solvent-in-salt" (SIS) systems have been known for decades but have attracted significant attention only recently. Molten salt hydrates/solvates have been successfully employed as non-flammable, benign electrolytes in rechargeable lithium-ion batteries leading to a revolution in battery development and design. SIS with organic components (for example, ionic liquids containing small amounts of water) demonstrate remarkable thermal stability and tunability, and present a class of admittedly safer electrolytes, in comparison with traditional organic solvents. Water molecules tend to form nano- and microstructures (droplets and channel networks) in ionic media impacting their heterogeneity. Such microscale domains can be employed as microreactors for chemical and enzymatic synthesis. In this review, we address known SIS systems and discuss their composition, structure, properties and dynamics. Special attention is paid to the current and potential applications of inorganic and organic SIS systems in energy research, chemistry and biochemistry. A separate section of this review is dedicated to experimental methods of SIS investigation, which is crucial for the development of this field.

Ionic liquids in lithium battery electrolytes: Composition versus safety and physical properties

NASA Astrophysics Data System (ADS)

Wilken, Susanne; Xiong, Shizhao; Scheers, Johan; Jacobsson, Per; Johansson, Patrik

2015-02-01

Ionic liquids have been highlighted as non-flammable, environmentally friendly, and suggested as possible solvents in lithium ion battery electrolytes. Here, the application of two ionic liquids from the EMIm-family in a state-of-the-art carbonate solvent based electrolyte is studied with a focus on safety improvement. The impact of the composition on physical and safety related properties is investigated for IL concentrations of additive (∼5 wt%) up to co-solvent concentrations (∼60 wt%). Furthermore, the role of the lithium salt concentration is separately addressed by studying a set of electrolytes at 0.5 M, 1 M, and 2 M LiPF6 concentrations. A large impact on the electrolyte properties is found for the electrolytes containing EMImTFSI and high salt concentrations. The composition 2 M LiPF6 EC:DEC:IL (1:1:3 wt%) is found non-flammable for both choices of ILs added. The macroscopic observations are complemented by a Raman spectroscopy analysis whereby a change in the Li+ solvation is detected for IL concentrations >4.5 mol%.

Dielectric relaxation of ethylene carbonate and propylene carbonate from molecular dynamics simulations

DOE PAGES

Chaudhari, Mangesh I.; You, Xinli; Pratt, Lawrence R.; ...

2015-11-24

Ethylene carbonate (EC) and propylene carbonate (PC) are widely used solvents in lithium (Li)-ion batteries and supercapacitors. Ion dissolution and diffusion in those media are correlated with solvent dielectric responses. Here, we use all-atom molecular dynamics simulations of the pure solvents to calculate dielectric constants and relaxation times, and molecular mobilities. The computed results are compared with limited available experiments to assist more exhaustive studies of these important characteristics. As a result, the observed agreement is encouraging and provides guidance for further validation of force-field simulation models for EC and PC solvents.

Effect of Branching on Rod-coil Polyimides as Membrane Materials for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Cubon, Valerie A.; Scheiman, Daniel A.; Bennett, William R.

2003-01-01

This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.

Hexavalent Americium recovery using Copper(III) periodate

DOE PAGES

McCann, Kevin; Brigham, Derek M.; Morrison, Samuel; ...

2016-10-31

Separation of americium from the lanthanides is considered one of the most difficult separation steps in closing the nuclear fuel cycle. One approach to this separation could involve oxidizing americium to the hexavalent state to form a linear dioxo cation while the lanthanides remain as trivalent ions. This work considers aqueous soluble Cu 3+ periodate as an oxidant under molar nitric acid conditions to separate hexavalent Am with diamyl amylphosphonate (DAAP) in n-dodecane. Initial studies assessed the kinetics of Cu 3+ periodate autoreduction in acidic media to aid in development of the solvent extraction system. Following characterization of the Cumore » 3+ periodate oxidant, solvent extraction studies optimized the recovery of Am from varied nitric acid media and in the presence of other fission product, or fission product surrogate, species. Short aqueous/organic contact times encouraged successful recovery of Am (distribution values as high as 2) from nitric acid media in the absence of redox active fission products. In the presence of a post-plutonium uranium redox extraction (post-PUREX) simulant aqueous feed, precipitation of tetravalent species (Ce, Ru, Zr) occurred and the distribution values of 241Am were suppressed, suggesting some oxidizing capacity of the Cu 3+ periodate is significantly consumed by other redox active metals in the simulant. Furthermore, the manuscript demonstrates Cu 3+ periodate as a potentially viable oxidant for Am oxidation and recovery and notes the consumption of oxidizing capacity observed in the presence of the post-PUREX simulant feed will need to be addressed for any approach seeking to oxidize Am for separations relevant to the nuclear fuel cycle.« less

Hexavalent Americium Recovery Using Copper(III) Periodate

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Brigham, Derek M.; Morrison, Samuel

2016-11-21

Separation of americium from the lanthanides is considered one of the most difficult separation steps in closing the nuclear fuel cycle. One approach to this separation could involve oxidizing americium to the hexavalent state to form a linear dioxo cation while the lanthanides remain as trivalent ions. This work considers aqueous soluble Cu3+ periodate as an oxidant under molar nitric acid conditions to separate hexavalent Am with diamyl amylphosphonate (DAAP) in n-dodecane. Initial studies assessed the kinetics of Cu3+ periodate auto-reduction in acidic media to aid in development of the solvent extraction system. Following characterization of the Cu3+ periodate oxidant,more » solvent extraction studies optimized the recovery of Am from varied nitric acid media and in the presence of other fission product, or fission product surrogate, species. Short aqueous/organic contact times encouraged successful recovery of Am (distribution values as high as 2) from nitric acid media in the absence of redox active fission products. In the presence of a post-PUREX simulant aqueous feed, precipitation of tetravalent species (Ce, Ru, Zr) occurred and the distribution values of 241Am were suppressed, suggesting some oxidizing capacity of the Cu3+ periodate is significantly consumed by other redox active metals in the simulant. The manuscript demonstrates Cu3+ periodate as a potentially viable oxidant for Am oxidation and recovery and notes the consumption of oxidizing capacity observed in the presence of the post-PUREX simulant feed will need to be addressed for any approach seeking to oxidize Am for separations relevant to the nuclear fuel cycle.« less

Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium-Oxygen Battery Electrolytes.

PubMed

Smirnov, Vladimir S; Kislenko, Sergey A

2018-01-05

The molecular life of intermediates, namely, O 2 - and Li + , produced during the discharge of aprotic Li-O 2 batteries was investigated by molecular dynamics simulation. This work is of potential interest in the development of new electrolytes for Li-air batteries. We present the results on the structure and stability of the Li + and O 2 - solvation shells and the thermodynamics and kinetics of the ion-association reaction in solvents such as dimethyl sulfoxide (DMSO), dimethoxyethane (DME), and acetonitrile (ACN). The residence time of solvent molecules in the Li + solvation shell increases with the solvent donor number and is 100 times larger in DMSO than in ACN. In DMSO and DME, the Li + ion diffuses with its solvation shell as a whole. On the contrary, in ACN it diffuses as a "bare" ion because of weak solvation. The rate constant for the association of the lithium ion with the superoxide anion in DMSO is two orders of magnitude slower than that in ACN due to fact that the free-energy barrier is 2.5 times larger in DMSO than in ACN. In addition, we show that despite the strong dependence of the Li + shell stability on donor number, the rate of association does not necessarily correlate with this solvent property. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced ion signals in desorption electrospray ionization using surfactant spray solutions.

PubMed

Badu-Tawiah, Abraham; Cooks, R Graham

2010-08-01

Solvent optimization is an important procedure in desorption electrospray ionization (DESI) and in this study the effects of solvent surface tension are explored. Data are presented for methanol/water/surfactant solvent systems, which show increases in ion signals of more than an order of magnitude when low concentrations of surfactants are added to the standard methanol/water (1:1) spray solvent. Examples of analytes tested include food chemicals, peptides, pharmaceuticals, and drugs of abuse. The improvement in ion intensity is mainly attributed to the effect of surface tension in producing smaller spray droplets, which are shown to cover a larger surface area. Surfactant-containing spray solutions allowed extension of DESI-MS analysis to previously intractable analytes like melamine and highly hydrophobic compounds like the sudan dyes. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Selective separation of copper over solder alloy from waste printed circuit boards leach solution.

PubMed

Kavousi, Maryam; Sattari, Anahita; Alamdari, Eskandar Keshavarz; Firozi, Sadegh

2017-02-01

The printed circuit boards (PCBs) from electronic waste are important resource, since the PCBs contain precious metals such as gold, copper, tin, silver, platinum and so forth. In addition to the economic point of view, the presence of lead turns this scrap into dangerous to environment. This study was conducted as part of the development of a novel process for selective recovery of copper over tin and lead from printed circuit boards by HBF 4 leaching. In previous study, Copper with solder alloy was associated, simultaneously were leached in HBF 4 solution using hydrogen peroxide as an oxidant at room temperature. The objective of this study is the separation of copper from tin and lead from Fluoroborate media using CP-150 as an extractant. The influence of organic solvent's concentration, pH, temperature and A/O phase ratio was investigated. The possible extraction mechanism and the composition of the extracted species have been determined. The separation factors for these metals using this agent are reported, while efficient methods for separation of Cu (II) from other metal ions are proposed. The treatment of leach liquor for solvent extraction of copper with CP-150 revealed that 20% CP-150 in kerosene, a 30min period of contact time, and a pH of 3 were sufficient for the extraction of Cu(II) and 99.99% copper was recovered from the leached solution. Copyright © 2016. Published by Elsevier Ltd.

Raman and Brillouin scattering of LiClO4 complexed in poly(propylene-glycol)

NASA Astrophysics Data System (ADS)

Schantz, S.; Torell, L. M.; Stevens, J. R.

1988-08-01

Raman spectra of LiClO4 complexed in poly(propylene-glycol) (PPG) have been obtained for concentrations of the monomer to salt ratio (ether oxygen):Li in the range 30:1-5:1. Splitting of the symmetric stretching mode of the ClO4- anion was observed with an intensity profile that varied with salt concentration. This phenomenon indicates a changing environment about the anion. A two-component band analysis leads to the identification of dissociated ions on one hand and solvent-separated ion pairs on the other. The concentration of ion pairs is relatively low compared to that of the dissociated ions, which are predominant for all concentrations. Despite the observed increase in the absolute number of dissociated ions at higher salt concentration, the electrical conductivity is reported to decrease in the same range. This indicates that the number of ``free'' charge carriers is of less importance for the conductivity than the mobility, which is damped in this concentration range. Frequency shifts of the disordered longitudinal-acoustic mode and increased hypersonic velocities, measured with Raman and Brillouin scattering techniques, respectively, indicate increased stiffness of the polymer matrix for increasing salt concentration, which probably results in decreased ion mobility.

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

DOE PAGES

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; ...

2014-12-19

We report that lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF more » $$\\bar{6}$$ anion. Li + prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li + solvation. Corresponding analysis for the PF $$\\bar{6}$$ anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. In conclusion, these results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.« less

Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

PubMed

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile

NASA Astrophysics Data System (ADS)

Dang, Liem X.; Chang, Tsun-Mei

2016-09-01

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li+ and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li+ in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li+-[BF4] and Li+-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li+. We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li+-[BF4] and Li+-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Quantum dynamics in continuum for proton transport II: Variational solvent-solute interface.

PubMed

Chen, Duan; Chen, Zhan; Wei, Guo-Wei

2012-01-01

Proton transport plays an important role in biological energy transduction and sensory systems. Therefore, it has attracted much attention in biological science and biomedical engineering in the past few decades. The present work proposes a multiscale/multiphysics model for the understanding of the molecular mechanism of proton transport in transmembrane proteins involving continuum, atomic, and quantum descriptions, assisted with the evolution, formation, and visualization of membrane channel surfaces. We describe proton dynamics quantum mechanically via a new density functional theory based on the Boltzmann statistics, while implicitly model numerous solvent molecules as a dielectric continuum to reduce the number of degrees of freedom. The density of all other ions in the solvent is assumed to obey the Boltzmann distribution in a dynamic manner. The impact of protein molecular structure and its charge polarization on the proton transport is considered explicitly at the atomic scale. A variational solute-solvent interface is designed to separate the explicit molecule and implicit solvent regions. We formulate a total free-energy functional to put proton kinetic and potential energies, the free energy of all other ions, and the polar and nonpolar energies of the whole system on an equal footing. The variational principle is employed to derive coupled governing equations for the proton transport system. Generalized Laplace-Beltrami equation, generalized Poisson-Boltzmann equation, and generalized Kohn-Sham equation are obtained from the present variational framework. The variational solvent-solute interface is generated and visualized to facilitate the multiscale discrete/continuum/quantum descriptions. Theoretical formulations for the proton density and conductance are constructed based on fundamental laws of physics. A number of mathematical algorithms, including the Dirichlet-to-Neumann mapping, matched interface and boundary method, Gummel iteration, and Krylov space techniques are utilized to implement the proposed model in a computationally efficient manner. The gramicidin A channel is used to validate the performance of the proposed proton transport model and demonstrate the efficiency of the proposed mathematical algorithms. The proton channel conductances are studied over a number of applied voltages and reference concentrations. A comparison with experimental data verifies the present model predictions and confirms the proposed model. Copyright © 2011 John Wiley & Sons, Ltd.

Controlling the intermediate structure of an ionic liquid for f-block element separations

DOE PAGES

Abney, Carter W.; Do, Changwoo; Luo, Huimin; ...

2017-04-19

Recent research has revealed molecular structure beyond the inner coordination sphere is essential in defining the performance of separations processes, but nevertheless remains largely unexplored. Here we apply small angle neutron scattering (SANS) and x-ray absorption fine structure (XAFS) spectroscopy to investigate the structure of an ionic liquid system studied for f-block element separations. SANS data reveal dramatic changes in the ionic liquid microstructure (~150 Å) which we demonstrate can be controlled by judicious selection of counter ion. Mesoscale structural features (> 500 Å) are also observed as a function of metal concentration. XAFS analysis supports formation of extended aggregatemore » structures, similar to those observed in traditional solvent extraction processes, and suggest additional parallels may be drawn from further study. As a result, achieving precise tunability over the intermediate features is an important development in controlling mesoscale structure and realizing advanced new forms of soft matter.« less

Time-resolved fluorescence study of exciplex formation in diastereomeric naproxen-pyrrolidine dyads.

PubMed

Khramtsova, Ekaterina A; Plyusnin, Viktor F; Magin, Ilya M; Kruppa, Alexander I; Polyakov, Nikolay E; Leshina, Tatyana V; Nuin, Edurne; Marin, M Luisa; Miranda, Miguel A

2013-12-19

The influence of chirality on the elementary processes triggered by excitation of the (S,S)- and (R,S)- diastereoisomers of naproxen-pyrrolidine (NPX-Pyr) dyads has been studied by time-resolved fluorescence in acetonitrile-benzene mixtures. In these systems, the quenching of the (1)NPX*-Pyr singlet excited state occurs through electron transfer and exciplex formation. Fluorescence lifetimes and quantum yields revealed a significant difference (around 20%) between the (S,S)- and (R,S)- diastereomers. In addition, the quantum yields of exciplexes differed by a factor of 2 regardless of solvent polarity. This allows us to suggest a similar influence of the chiral centers on the local charge transfer resulting in exciplex and full charge separation that leads to ion-biradicals. A simplified scheme is proposed to estimate a set of rate constant values (k1-k5) for the elementary stages in each solvent system.

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

System and method for treatment of a flue gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spiry, Irina Pavlovna; Wood, Benjamin Rue; Singh, Surinder Prabhjot

A method for treatment of a flue gas involves feeding the flue gas and a lean solvent to an absorber. The method further involves reacting the flue gas with the lean solvent within the absorber to generate a clean flue gas and a rich solvent. The method also involves feeding the clean flue gas from the absorber and water from a source, to a wash tower to separate a stripped portion of the lean solvent from the clean flue gas to generate a washed clean flue gas and a mixture of the water and the stripped portion of the leanmore » solvent. The method further involves treating at least a portion of the mixture of the water and the stripped portion of the lean solvent via a separation system to separate the water from the stripped portion of the lean solvent.« less

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Chiral nematic porous germania and germanium/carbon films

NASA Astrophysics Data System (ADS)

Xu, Jing; Nguyen, Thanh-Dinh; Xie, Kai; Hamad, Wadood Y.; MacLachlan, Mark J.

2015-07-01

We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering.We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering. Electronic supplementary information (ESI) available: TGA, IR, Raman, TEM, SEM, BET. See DOI: 10.1039/c5nr02520f

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Escape of anions from geminate recombination in THF due to charge delocalization

DOE PAGES

Chen, Hung -Cheng; Cook, Andrew R.; Asaoka, Sadayuki; ...

2017-11-24

Geminate recombination of 24 radical anions (M˙ –) with solvated protons (RH 2 +) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M˙ – and RH 2 + together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH 2 + to M˙ –. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (<0.2 ns) to measure, except for the anion ofmore » TCNE which did not undergo proton transfer. PT to C atoms was as slow as 70 ns and was always slow enough to be observable. A possible effect of charge delocalization on the PT rates could not be clearly separated from other factors. For 21 of the 24 molecules studied here, a free ion yield (71.6 ± 6.2 nmol J –1) comprising ~29% of the total, was formed. This yield of “Type I” free ions is independent of the PT rate because it arises entirely by escape from the initial distribution of ion pair distances without forming intimate ion pairs. Furthermore, three anions of oligo(9,9-dihexyl)fluorenes, F n˙ – (n = 2–4) were able to escape from intimate ion-pairs to form additional yields of “Type II” free ions with escape rate constants near 3 × 10 6 s –1. These experiments find no evidence for an inverted region for proton transfer.« less

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

Comparative study on Ce (III) and La (III) solvent extraction and separation from a nitric acid medium by D2EHPA and Cyanex272

NASA Astrophysics Data System (ADS)

Habibpour, R.; Dargahi, M.; Kashi, E.; Bagherpour, M.

2018-01-01

The solvent extraction of Cerium(III) and Lanthanum(III) from nitric acid solution using the organophosphorous extractants Di-(2-ethyl hexyl) phosphate (D2EHPA) and di-2,4,4- trimethylpentyl phosphoric acid (Cyanex272) in kerosene was investigated. In this study, the magnitude of the extraction of Ce(III) was found to be more significant with Cyanex272 than D2EHPA. D2EHPA was found to be a better extractant for La(III). Among the two extractants, Cyanex272 was used for the separation of Ce from La in three stages with an extraction efficiency of 90.2% for Ce. A 556 mg/L Ce solution was used for the scrubbing of La with an efficiency of ≈34%, which required multi stage scrubbing. The study of thermodynamic parameters such as enthalpy, entropy, and Gibbs free energy impart the exothermic and non-spontaneous process. The chemical speciation curves for lanthanum and cerium in the aqueous phase as a function of pH showed that the free La(III) and Ce(III) metal ion species were largely predominate between a pH = 0 and pH = 7.

Separation of Pr and Nd from La in chloride solution by extraction with a mixture of Cyanex 272 and Alamine 336

NASA Astrophysics Data System (ADS)

Liu, Yang; Jeon, Ho Seok; Lee, Man Seung

2015-09-01

The possibility of separation of Pr and Nd from La in a chloride leaching solution of monazite sand has been investigated by using a binary mixture of Cyanex 272 (bis(2,4,4-trimethylpentyl) phosphinic acid) and Alamine 336 (tri-octyl/decyl amine). The binary mixture showed synergism on the extraction of the three metals and led to an increase in the separation factor between Pr/Nd and La compared to Cyanex 272 alone. Although the addition of chloride ion into aqueous increased the extraction of the metals, this addition had negative effect on the separation of Nd/Pr and La. McCabe-Thiele diagrams for the extraction of Pr and Nd with the binary mixture were constructed. Stripping of metals from the loaded organic phase was achieved with 0.7 M HCl. The difference in the solvent extraction of the rare earth elements from chloride solution between the binary mixture and saponified extractants was also discussed.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

Active Solvent Modulation: A Valve-Based Approach To Improve Separation Compatibility in Two-Dimensional Liquid Chromatography.

PubMed

Stoll, Dwight R; Shoykhet, Konstantin; Petersson, Patrik; Buckenmaier, Stephan

2017-09-05

Two-dimensional liquid chromatography (2D-LC) is increasingly being viewed as a viable tool for solving difficult separation problems, ranging from targeted separations of structurally similar molecules to untargeted separations of highly complex mixtures. In spite of this performance potential, though, many users find method development challenging and most frequently cite the "incompatibility" between the solvent systems used in the first and second dimensions as a major obstacle. This solvent strength related incompatibility can lead to severe peak distortion and loss of resolution and sensitivity in the second dimension. In this paper, we describe a novel approach to address the incompatibility problem, which we refer to as Active Solvent Modulation (ASM). This valve-based approach enables dilution of 1 D effluent with weak solvent prior to transfer to the 2 D column but without the need for additional instrument hardware. ASM is related to the concept we refer to as Fixed Solvent Modulation (FSM), with the important difference being that ASM allows toggling of the diluent stream during each 2 D separation cycle. In this work, we show that ASM eliminates the major drawbacks of FSM including complex elution solvent profiles, baseline disturbances, and slow 2 D re-equilibration and demonstrate improvements in 2 D separation quality using both simple small molecule probes and degradants of heat-treated bovine insulin as case studies. We believe that ASM will significantly ease method development for 2D-LC, providing a path to practical methods that involve both highly complementary 1 D and 2 D separations and sensitive detection.

Removal of ion-implanted photoresists on GaAs using two organic solvents in sequence

NASA Astrophysics Data System (ADS)

Oh, Eunseok; Na, Jihoon; Lee, Seunghyo; Lim, Sangwoo

2016-07-01

Organic solvents can effectively remove photoresists on III-V channels without damage or etching of the channel material during the process. In this study, a two-step sequential photoresist removal process using two different organic solvents was developed to remove implanted ArF and KrF photoresists at room temperature. The effects of organic solvents with either low molar volumes or high affinities for photoresists were evaluated to find a proper combination that can effectively remove high-dose implanted photoresists without damaging GaAs surfaces. The performance of formamide, acetonitrile, nitromethane, and monoethanolamine for the removal of ion-implanted ArF and KrF photoresists were compared using a two-step sequential photoresist removal process followed by treatment in dimethyl sulfoxide (DMSO). Among the various combinations, the acetonitrile + DMSO two-step sequence exhibited the best removal of photoresists that underwent ion implantation at doses of 5 × 1013-5 × 1015 atoms/cm2 on both flat and trench-structured GaAs surfaces. The ability of the two-step process using organic solvents to remove the photoresists can be explained by considering the affinities of solvents for a polymer and its permeability through the photoresist.

Separation and preconcentration of Ag(I) in aqueous samples by flotation as an ion-associate using iodide and ferroin followed the determination by flame atomic absorption spectrometry.

PubMed

Hosseini, Mohammad Saeid; Hashemi-Moghaddam, Hamid; Kardan-Moghaddam, Gholamreza

2007-01-01

A simple method for separation/preconcentration and determination of Ag(I) in aqueous samples is described. The method is based on formation of an ion-associate between Ag(I)-iodide complex and ferroin, which can be floated at the interface of the aqueous/n-heptane phases. The flotation process was carried out using 500-ml aliquot of the aqueous solution and the floated layer was dissolved in 5 ml of 1 M HNO3 containing methanol (50% v/v) as the solvent. The Ag(I) content was then determined by flame atomic absorption spectrometry (FAAS). The method so could be considered as an enrichment process, was achieved to a quantitative feature, when the pH of the solution was adjusted to 4 and the concentrations of iodide and ferroin were about 3.2 x 10(-4) M and 6.25 x 10(-5) M, respectively. The LOD and RSD (n = 7) were obtained 1.0 x 10(-8) M and 2.4%, respectively. It was found that a large number of cations and anions even at high considerably foreign ion/Ag(I) ratios were not interfered. The method was applied satisfactorily to recovery of Ag(I) from different aqueous samples.

Optimized Carbonate and Ester-Based Li-Ion Electrolytes

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2008-01-01

To maintain high conductivity in low temperatures, electrolyte co-solvents have been designed to have a high dielectric constant, low viscosity, adequate coordination behavior, and appropriate liquid ranges and salt solubilities. Electrolytes that contain ester-based co-solvents in large proportion (greater than 50 percent) and ethylene carbonate (EC) in small proportion (less than 20 percent) improve low-temperature performance in MCMB carbon-LiNiCoO2 lithium-ion cells. These co-solvents have been demonstrated to enhance performance, especially at temperatures down to 70 C. Low-viscosity, ester-based co-solvents were incorporated into multi-component electrolytes of the following composition: 1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (1:1:8 volume percent) [where X = methyl butyrate (MB), ethyl butyrate EB, methyl propionate (MP), or ethyl valerate (EV)]. These electrolyte formulations result in improved low-temperature performance of lithium-ion cells, with dramatic results at temperatures below 40 C.

The fluorescent property of 3-[(2-hydroxy-1-naphthyl) methylideneamino]benzoic acid and its application as fluorescent chemosensor for Hg2 + and Al3 + ions

NASA Astrophysics Data System (ADS)

Sun, Changyan; Sun, Jiayi; Qiu, Fazheng; Li, Wenjun; Chang, Zhidong; Zhang, Lijun

2018-01-01

This manuscript studies the fluorescent property of 3-[(2-hydroxy-1-naphthyl)methylideneamino]benzoic acid (H2L). Fluorescent spectra show that in different solvents, H2L displays different fluorescent properties, which can be attributed to the interaction between the solvents and H2L. Further study indicates that H2L exhibits a highly selective and sensitive recognition for Hg2 + ions in dimethylsulfoxide (DMSO), Al3 + ions in methanol and N,N‧-dimethylformamide/water (DMF/H2O, 1/1, v/v). The bonding modes and bonding ratio of H2L and metal ions in different solvents are explored by Job's plot, 1H NMR titration, and electrospray ionization mass spectrometry (ESI-MS). The probable mechanisms were discussed.

Stability of coordination compounds of Ni2+ and Co2+ ions with succinic acid anion in water-ethanol solvents

NASA Astrophysics Data System (ADS)

Tukumova, N. V.; Dieu Thuan, Tran Thi; Usacheva, T. R.; Koryshev, N. E.; Sharnin, V. A.

2017-04-01

Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water-ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution ( X EtOH = 0-0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water-ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y2-).

Fundamental Chemical Kinetic And Thermodynamic Data For Purex Process Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, R.J.; Fox, O.D.; Sarsfield, M.J.

2007-07-01

To support either the continued operations of current reprocessing plants or the development of future fuel processing using hydrometallurgical processes, such as Advanced Purex or UREX type flowsheets, the accurate simulation of Purex solvent extraction is required. In recent years we have developed advanced process modeling capabilities that utilize modern software platforms such as Aspen Custom Modeler and can be run in steady state and dynamic simulations. However, such advanced models of the Purex process require a wide range of fundamental data including all relevant basic chemical kinetic and thermodynamic data for the major species present in the process. Thismore » paper will summarize some of these recent process chemistry studies that underpin our simulation, design and testing of Purex solvent extraction flowsheets. Whilst much kinetic data for actinide redox reactions in nitric acid exists in the literature, the data on reactions in the diluted TBP solvent phase is much rarer. This inhibits the accurate modelization of the Purex process particularly when species show a significant extractability in to the solvent phase or when cycling between solvent and aqueous phases occurs, for example in the reductive stripping of Pu(IV) by ferrous sulfamate in the Magnox reprocessing plant. To support current oxide reprocessing, we have investigated a range of solvent phase reactions: - U(IV)+HNO{sub 3}; - U(IV)+HNO{sub 2}; - U(IV)+HNO{sub 3} (Pu catalysis); - U(IV)+HNO{sub 3} (Tc catalysis); - U(IV)+ Np(VI); - U(IV)+Np(V); - Np(IV)+HNO{sub 3}; - Np(V)+Np(V); Rate equations have been determined for all these reactions and kinetic rate constants and activation energies are now available. Specific features of these reactions in the TBP phase include the roles of water and hydrolyzed intermediates in the reaction mechanisms. In reactions involving Np(V), cation-cation complex formation, which is much more favourable in TBP than in HNO{sub 3}, also occurs and complicates the redox chemistry. Whilst some features of the redox chemistry in TBP appear similar to the corresponding reactions in aqueous HNO{sub 3}, there are notable differences in rates, the forms of the rate equations and mechanisms. Secondly, to underpin the development of advanced single cycle flowsheets using the complexant aceto-hydroxamic acid, we have also characterised in some detail its redox chemistry and solvent extraction behaviour with both Np and Pu ions. We find that simple hydroxamic acids are remarkably rapid reducing agents for Np(VI). They also reduce Pu(VI) and cause a much slower reduction of Pu(IV) through a complex mechanism involving acid hydrolysis of the ligand. AHA is a strong hydrophilic and selective complexant for the tetravalent actinide ions as evidenced by stability constant and solvent extraction data for An(IV), M(III) and U(VI) ions. This has allowed the successful design of U/Pu+Np separation flowsheets suitable for advanced fuel cycles. (authors)« less

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

NASA Astrophysics Data System (ADS)

Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

2014-10-01

The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

A multiphase ion-transport analysis of the electrostatic disjoining pressure: implications for binary droplet coalescence

NASA Astrophysics Data System (ADS)

Mason, Lachlan; Gebauer, Felix; Bart, Hans-Jörg; Stevens, Geoffrey; Harvie, Dalton

2016-11-01

Understanding the physics of emulsion coalescence is critical for the robust simulation of industrial solvent extraction processes, in which loaded organic and raffinate phases are separated via the coalescence of dispersed droplets. At the droplet scale, predictive collision-outcome models require an accurate description of the repulsive surface forces arising from electrical-double-layer interactions. The conventional disjoining-pressure treatment of double-layer forces, however, relies on assumptions which do not hold generally for deformable droplet collisions: namely, low interfacial curvature and negligible advection of ion species. This study investigates the validity bounds of the disjoining pressure approximation for low-inertia droplet interactions. A multiphase ion-transport model, based on a coupling of droplet-scale Nernst-Planck and Navier-Stokes equations, predicts ion-concentration fields that are consistent with the equilibrium Boltzmann distribution; indicating that the disjoining-pressure approach is valid for both static and dynamic interactions in low-Reynolds-number settings. The present findings support the development of coalescence kernels for application in macro-scale population balance modelling.

Determination of adrenaline, noradrenaline and corticosterone in rodent blood by ion pair reversed phase UHPLC-MS/MS.

PubMed

Bergh, Marianne Skov-Skov; Bogen, Inger Lise; Andersen, Jannike Mørch; Øiestad, Åse Marit Leere; Berg, Thomas

2018-01-01

A novel ion pair reversed phase ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of the stress hormones adrenaline, noradrenaline and corticosterone in rodent blood was developed and fully validated. Separations were performed on an Acquity HSS T3 column (2.1mm i.d.×100mm, 1.8μm) with gradient elution and a runtime of 5.5min. The retention of adrenaline and noradrenaline was substantially increased by employing the ion pair reagent heptafluorobutyric acid (HFBA). Ion pair reagents are usually added to the mobile phase only, but we demonstrate for the first time that including HFBA to the sample reconstitution solvent as well, has a major impact on the chromatography of these compounds. The stability of adrenaline and corticosterone in rodent blood was investigated using the surrogate analytes adrenaline-d 3 and corticosterone-d 8 . The applicability of the described method was demonstrated by measuring the concentration of stress hormones in rodent blood samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of direct and alternating current vacuum ultraviolet lamps in atmospheric pressure photoionization.

PubMed

Vaikkinen, Anu; Haapala, Markus; Kersten, Hendrik; Benter, Thorsten; Kostiainen, Risto; Kauppila, Tiina J

2012-02-07

A direct current induced vacuum ultraviolet (dc-VUV) krypton discharge lamp and an alternating current, radio frequency (rf) induced VUV lamp that are essentially similar to lamps in commercial atmospheric pressure photoionization (APPI) ion sources were compared. The emission distributions along the diameter of the lamp exit window were measured, and they showed that the beam of the rf lamp is much wider than that of the dc lamp. Thus, the rf lamp has larger efficient ionization area, and it also emits more photons than the dc lamp. The ionization efficiencies of the lamps were compared using identical spray geometries with both lamps in microchip APPI mass spectrometry (μAPPI-MS) and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). A comprehensive view on the ionization was gained by studying six different μAPPI solvent compositions, five DAPPI spray solvents, and completely solvent-free DAPPI. The observed reactant ions for each solvent composition were very similar with both lamps except for toluene, which showed a higher amount of solvent originating oxidation products with the rf lamp than with the dc lamp in μAPPI. Moreover, the same analyte ions were detected with both lamps, and thus, the ionization mechanisms with both lamps are similar. The rf lamp showed a higher ionization efficiency than the dc lamp in all experiments. The difference between the lamp ionization efficiencies was greatest when high ionization energy (IE) solvent compositions (IEs above 10 eV), i.e., hexane, methanol, and methanol/water, (1:1 v:v) were used. The higher ionization efficiency of the rf lamp is likely due to the larger area of high intensity light emission, and the resulting larger efficient ionization area and higher amount of photons emitted. These result in higher solvent reactant ion production, which in turn enables more efficient analyte ion production. © 2012 American Chemical Society

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

PubMed

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.

Integrating a post-column makeup pump into preparative supercritical fluid chromatography systems to address stability and recovery issues during purifications.

PubMed

Bajpai, Lakshmikant; Naidu, Harshavardhan; Asokan, Kathiravan; Shaik, Khaja Mohiddin; Kaspady, Mahammed; Arunachalam, Piramanayagam; Wu, Dauh-Rurng; Mathur, Arvind; Sarabu, Ramakanth

2017-08-18

Purification of many pharmaceutical compounds by supercritical fluid chromatography (SFC) has always been challenging because of degradation of compound during the isolation step in the presence of acidic or basic modifiers in the mobile phase. Stability of such acid or base-sensitive compounds could be improved by post-column addition of a solvent containing base or acid modifier as counter ion through a make-up pump respectively to neutralize the compound fraction without affecting the resolution. One such case study has been presented in this work where the stability of a base-sensitive compound was addressed by the addition of acidic co-solvent through the make-up pump. Details of this setup and the investigation of degradation of the in-house base-sensitive compound are discussed in this paper. In addition, poor retentivity and low recovery of many non-polar compounds in SFC eluting under low co-solvent percentage is another major concern. Even though the desired separation could be achieved with low percentage of co-solvent, it's difficult to get the proper recovery after purification due to precipitation of the sample and significant aerosol formation inside the cyclone. We have demonstrated the first-time use of a post-column make-up pump on SFC 350 system to introduce additional solvent prior to cyclone to avoid the precipitation, reduce the aerosol formation and thus improve the recovery of non-polar compounds eluting under less than 10% of co-solvent. Copyright © 2017 Elsevier B.V. All rights reserved.

Adsorption of gold ions from industrial wastewater using activated carbon derived from hard shell of apricot stones - an agricultural waste.

PubMed

Soleimani, Mansooreh; Kaghazchi, Tahereh

2008-09-01

In this study, hard shell of apricot stones was selected from agricultural solid wastes to prepare effective and low cost adsorbent for the gold separation from gold-plating wastewater. Different adsorption parameters like adsorbent dose, particle size of activated carbon, pH and agitation speed of mixing on the gold adsorption were studied. The results showed that under the optimum operating conditions, more than 98% of gold was adsorbed onto activated carbon after only 3h. The equilibrium adsorption data were well described by the Freundlich and Langmuir isotherms. Isotherms have been used to obtain thermodynamic parameters. Gold desorption studies were performed with aqueous solution mixture of sodium hydroxide and organic solvents at ambient temperatures. Quantitative recovery of gold ions is possible by this method. As hard shell of apricot stones is a discarded as waste from agricultural and food industries, the prepared activated carbon is expected to be an economical product for gold ion recovery from wastewater.

Microfluidic chip for peptide analysis with an integrated HPLC column, sample enrichment column, and nanoelectrospray tip.

PubMed

Yin, Hongfeng; Killeen, Kevin; Brennen, Reid; Sobek, Dan; Werlich, Mark; van de Goor, Tom

2005-01-15

Current nano-LC/MS systems require the use of an enrichment column, a separation column, a nanospray tip, and the fittings needed to connect these parts together. In this paper, we present a microfabricated approach to nano-LC, which integrates these components on a single LC chip, eliminating the need for conventional LC connections. The chip was fabricated by laminating polyimide films with laser-ablated channels, ports, and frit structures. The enrichment and separation columns were packed using conventional reversed-phase chromatography particles. A face-seal rotary valve provided a means for switching between sample loading and separation configurations with minimum dead and delay volumes while allowing high-pressure operation. The LC chip and valve assembly were mounted within a custom electrospray source on an ion-trap mass spectrometer. The overall system performance was demonstrated through reversed-phase gradient separations of tryptic protein digests at flow rates between 100 and 400 nL/min. Microfluidic integration of the nano-LC components enabled separations with subfemtomole detection sensitivity, minimal carryover, and robust and stable electrospray throughout the LC solvent gradient.

Nature-Inspired Strategy toward Superhydrophobic Fabrics for Versatile Oil/Water Separation.

PubMed

Zhou, Cailong; Chen, Zhaodan; Yang, Hao; Hou, Kun; Zeng, Xinjuan; Zheng, Yanfen; Cheng, Jiang

2017-03-15

Phytic acid, which is a naturally occurring component that is widely found in many plants, can strongly bond toxic mineral elements in the human body, because of its six phosphate groups. Some of the metal ions present the property of bonding with phytic acid to form insoluble coordination complexes aggregations, even at room temperature. Herein, a superhydrophobic cotton fabric was prepared using a novel and facile nature-inspired strategy that introduced phytic acid metal complex aggregations to generate rough hierarchical structures on a fabric surface, followed by PDMS modification. This superhydrophobic surface can be constructed not only on cotton fabric, but also on filter paper, polyethylene terephthalate (PET) fabric, and sponge. Ag I , Fe III , Ce III , Zr IV , and Sn IV are very commendatory ions in our study. Taking phytic acid-Fe III -based superhydrophobic fabric as an example, it showed excellent resistance to ultraviolet (UV) irradiation, high temperature, and organic solvent immersion, and it has good resistance to mechanical wear and abrasion. The superhydrophobic/superoleophilic fabric was successfully used to separate oil/water mixtures with separation efficiencies as high as 99.5%. We envision that these superantiwetting fabrics, modified with phytic acid-metal complexes and PDMS, are environmentally friendly, low cost, sustainable, and easy to scale up, and thereby exhibit great potentials in practical applications.

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

PubMed

Zhu, Xiaobo; Li, Wang; Tang, Sen; Zeng, Majian; Bai, Pengyuan; Chen, Lunjian

2017-05-01

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V 2 O 5 and Sc 2 O 3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development and validation of a fast static headspace GC method for determination of residual solvents in permethrin.

PubMed

Tian, Jingzhi; Rustum, Abu

2016-09-05

A fast static headspace gas chromatography (HS-GC) method was developed to separate all residual solvents present in commercial active pharmaceutical ingredient (API) batches of permethrin. A total of six residual solvents namely 2-methylpentane, 3-methylpentane, methylcyclopentane, n-hexane, cyclohexane and toluene were found in typical commercial batches of permethrin; and three of them are not in the list of ICH solvents. All six residual solvents were baseline separated in five minutes by the new method presented in this paper. The method was successfully validated as per International Conference on Harmonisation (ICH) guidelines. Evaluation of this method was conducted to separate 26 commonly used solvents in the manufacturing of various APIs, key intermediates of APIs and pharmaceutical excipients. The results of the evaluation demonstrated that this method can also be used as a general method to determine residual solvents in various APIs, intermediates and excipients that are used in pharmaceutical products. Copyright © 2016 Elsevier B.V. All rights reserved.

Separation of polysaccharides from rice husk and wheat bran using solvent system consisting of BMIMOAc and DMI.

PubMed

Hou, Qidong; Li, Weizun; Ju, Meiting; Liu, Le; Chen, Yu; Yang, Qian; Wang, Jingyu

2015-11-20

A solvent system consisting of 1,3-dimethyl-2-imidazolidinone (DMI), and ionic liquid 1-butyl-3-methylimidazolium acetate (BMIMOAc) was used to separate polysaccharides from rice husk and wheat bran. The effects of the DMI/BMIMOAc ratios, temperature, and time on the dissolution of rice husk and wheat bran were investigated, and the influence of anti-solvents on the regeneration of polysaccharides-rich material was evaluated. We found that the solvent system is more powerful to dissolve rice husk and wheat bran than pure BMIMOAc, and that polysaccharides-rich material can be effectively separated from the biomass solution. The polysaccharides content of regenerated material from wheat bran can reach as high as 94.4% when ethanol was used as anti-solvents. Under optimized conditions, the extraction rate of polysaccharides for wheat bran can reach as high as 71.8% at merely 50°C. The recycled solvent system exhibited constant ability to separate polysaccharides from rice husk and wheat bran. Copyright © 2015 Elsevier Ltd. All rights reserved.

Two-Step Adsorption of PtCl 6 2– Complexes at a Charged Langmuir Monolayer: Role of Hydration and Ion Correlations

DOE PAGES

Uysal, Ahmet; Rock, William; Qiao, Baofu; ...

2017-11-03

Anion exchange at positively charged interfaces plays an important role in a variety of physical and chemical processes. However, the molecular-scale details of these processes, especially with heavy and large anionic complexes, are not well-understood. Here, we studied the adsorption of PtCl 6 2– anionic complexes to floating DPTAP monolayers in the presence of excess Cl– as a function of the bulk chlorometalate concentration. This system aims to simulate the industrial conditions for heavy metal separations with solvent extraction. In situ X-ray scattering and fluorescence measurements, which are element and depth sensitive, show that the chlorometalate ions only adsorb inmore » the diffuse layer at lower concentrations, while they adsorb predominantly in the Stern layer at higher concentrations. The response of DPTAP molecules to the adsorbed ions is determined independently by grazing incidence X-ray diffraction and supports this picture. Molecular dynamics simulations further elucidate the nanoscale structure of the interfacial complexes. The results suggest that ion hydration and ion–ion correlations play a key role in the competitive adsorption process.« less

Enhanced fluidity liquid chromatography of inulin fructans using ternary solvent strength and selectivity gradients.

PubMed

Bennett, Raffeal; Olesik, Susan V

2018-01-25

The value of exploring selectivity and solvent strength ternary gradients in enhanced fluidity liquid chromatography (EFLC) is demonstrated for the separation of inulin-type fructans from chicory. Commercial binary pump systems for supercritical fluid chromatography only allow for the implementation of ternary solvent strength gradients which can be restrictive for the separation of polar polymeric analytes. In this work, a custom system was designed to extend the capability of EFLC to allow tuning of selectivity or solvent strength in ternary gradients. Gradient profiles were evaluated using the Berridge function (RF 1 ), normalized resolution product (NRP), and gradient peak capacity (P c ). Selectivity gradients provided the separation of more analytes over time. The RF 1 function showed favor to selectivity gradients with comparable P c to that of solvent strength gradients. NRP did not strongly correlate with P c or RF 1 score. EFLC with the hydrophilic interaction chromatography, HILIC, separation mode was successfully employed to separate up to 47 fructan analytes in less than 25 min using a selectivity gradient. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of solvent polarity levels on separation of xanthone and coumarin from Calophyllum inophyllum leaves extract

NASA Astrophysics Data System (ADS)

Susanto, D. F.; Hapsari, S.; Trilutfiani, Z.; Borhet, A.; Aparamarta, H. W.; Widjaja, A.; Gunawan, S.

2018-03-01

Calophyllum inophyllum has various benefits that can be utilized from root, stem, leaf, until seed. C. inophyllum leaves contain many bioactive compounds, such as xanthone and coumarin which are useful as antioxidant, and inhibitors of enzyme activity from HIV virus. The aim of this research was to investigate the effect of solvent polarity levels on the separation of xanthone and coumarin compounds contained in the crude extract of C. inophyllum leaves. Crude leaves extract was obtained by percolation method. Moreover, Liquid Liquid Extraction (LLE) was used for separating xanthone and coumarin compounds. It was performed by methanol (polar solvent) and hexane (non-polar solvent) with solvent ratio of 1. Methanol concentration in water used were 20%, 50%, 80%, and 100%. Each fraction obtained was tested qualitatively using Thin Layer Chromatography (TLC) and quantitatively using Gas Chromatography (GC) to analyze xanthone and coumarin. The best separation result was obtained by using 50% methanol. In this results, coumarin and xanthones were separated in methanol fraction (81.18% recovery) and in hexane fraction (81.91% recovery), respectively.

Operator care and eco-concerned development of a fast, facile and economical assay for basic nitrogenous drugs based on simplified ion-pair mini-scale extraction using safer solvent combined with drop-based spectrophotometry.

PubMed

Plianwong, Samarwadee; Sripattanaporn, Areerut; Waewsa-nga, Kwanrutai; Buacheen, Parin; Opanasopit, Praneet; Ngawhirunpat, Tanasait; Rojanarata, Theerasak

2012-08-30

A fast, facile, and economical assay for basic nitrogenous drugs has been developed based on the mini-scale extraction of the drug-dye ion pair complex combined with the use of safe-for-analyst and eco-friendlier organic extractant and drop-based micro-spectrophotometry. Instead of using large volume devices, the extraction was simply carried out in typical 1.5 mL microcentrifuge tubes along with the use of micropipettes for accurate transfer of liquids, vortex mixer for efficient partitioning of solutes and benchtop centrifuge for rapid phase separation. In the last step, back-extraction was performed by using the microvolume of acidic solution in order to concentrate the colored species into a confined aqueous microdrop and to keep the analyst away from unwanted contact and inhalation of organic solvents during the quantitation step which was achieved by using cuvetteless UV-vis micro-spectrophotometry without any prior dilutions. Using chlorpheniramine maleate as a representative analyte and n-butyl acetate as a less toxic and non-ozone depleting extractant, the miniaturized method was less laborious and much faster. It was accurate, precise and insensitive to the interferences from common excipients. Notably, it gave the assay results of drug in tablets and oral solution comparable to the large-scale pharmacopeial method while the consumption of organic solvents and the release of wastes were lowered by 200-400 folds. Copyright © 2012 Elsevier B.V. All rights reserved.

Method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.

1982-01-19

Spent nuclear fuels, including actinide fuels, volatile and nonvolatile fission products, are reprocessed and separated in a molten metal solvent housed in a separation vessel made of a carbon-containing material. A first catalyst, which promotes the solubility and permeability of carbon in the metal solvent, is included. By increasing the solubility and permeability of the carbon in the solvent, the rate at which actinide oxides are reduced (carbothermic reduction) is greatly increased. A second catalyst, included to increase the affinity for nitrogen in the metal solvent, is added to increase the rate at which actinide nitrides form after carbothermic reduction is complete.

Computer-aided solvent selection for multiple scenarios operation of limited-known properties solute

NASA Astrophysics Data System (ADS)

Anantpinijwatna, Amata

2017-12-01

Solvents have been applied for both production and separation of the complex chemical substance such as the pyrrolidine-2-carbonyl chloride (C5H8ClNO). Since the properties of the target substance itself are largely unknown, the selection of the solvent is limited by experiment only. However, the reaction carried out in conventional solvents are either afforded low yields or obtained slow reaction rates. Moreover, the solvents are also highly toxic and environmental unfriendly. Alternative solvents are required to enhance the production and lessen the harmful effect toward both organism and environment. A costly, time-consuming, and laborious experiments are required for acquiring a better solvent suite for production and separation of these complex compounds; whereas, a limited improvement can be obtained. On the other hand, the combination of the state-of-the-art thermodynamic models can provide faster and more robust solutions to this solvent selection problem. In this work, a framework for solvents selection in complex chemical production process is presented. The framework combines a group-contribution thermodynamic model and a segment activity coefficient model for predicting chemical properties and solubilities of the target chemical in newly formulated solvents. A guideline for solvent selection is also included. The potential of the selected solvents is then analysed and verified. The improvement toward the production yield, production rate, and product separation is then discussed.

Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, Patrick Allen

2005-12-17

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity ofmore » the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5%-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.« less

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

PubMed

Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi

2015-12-01

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide

PubMed Central

Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.

2008-01-01

The division of thermodynamic solvation free energies of electrolytes into ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of −263.5, −260.2, and −273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the above solvents. PMID:17214493

Organic Lecture Demonstrations of Common-Ion Effect, Ionizing Power of Solvents, and First-Order Reaction Kinetics.

ERIC Educational Resources Information Center

Danen, Wayne C.; Blecha, M. Therese, Sr.

1982-01-01

Background information and experimental procedures are provided for three lecture-demonstrations (involving hydrolysis of tetra-butyl chloride) illustrating: (1) common-ion or mass law effect; (2) effect of changing ionizing power of a solvent on a solvolysis reaction; and (3) collecting/plotting data to illustrate a first-order reaction.…

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Electrolytes for lithium ion batteries

DOEpatents

Vaughey, John; Jansen, Andrew N.; Dees, Dennis W.

2014-08-05

A family of electrolytes for use in a lithium ion battery. The genus of electrolytes includes ketone-based solvents, such as, 2,4-dimethyl-3-pentanone; 3,3-dimethyl 2-butanone(pinacolone) and 2-butanone. These solvents can be used in combination with non-Lewis Acid salts, such as Li.sub.2[B.sub.12F.sub.12] and LiBOB.

Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.

PubMed

Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T

2014-07-16

The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

Development of solvent systems with room temperature ionic liquids for the countercurrent chromatographic separation of very nonpolar lipid compounds.

PubMed

Müller, Marco; Englert, Michael; Earle, Martyn J; Vetter, Walter

2017-03-10

Solvent systems are not readily available for the separation of very nonpolar compounds by countercurrent chromatography (CCC). In this study we therefore evaluated the suitability of room temperature ionic liquids (IL) in organic solvents for the CCC separation of the extremely nonpolar lipid compounds tripalmitin (PPP) and cholesteryl stearate (CS). The four IL tested were [C 10 mim][OTf], [C 2 mim][NTf 2 ], [P66614][NTf 2 ], and [P66614][Cl]. Search for a CCC-suited solvent system started with solubility studies with fourteen organic solvents. Following this, combinations were made with one organic solvent miscible and one organic solvent immiscible with IL (147 combinations). Twenty-four initially monophasic mixtures of two organic solvents became biphasic by adding IL. Several unexpected results could be observed. For instance, n-hexane and n-heptane became biphasic with [P66614][Cl]. Further nine systems became biphasic although the IL was not miscible in any of the two components. These 33 solvent systems were investigated with regard to phase ratio, settling time, share of IL in the upper phase and last not least the K U/L values of PPP and CS, which were 8.1 and 7.7 respectively. The most promising system, n-heptane/chloroform/[C 10 mim][OTf] (3:3:1, v/v/v) allowed a partial separation of PPP and CS by CCC which was not achieved beforehand. Copyright © 2017 Elsevier B.V. All rights reserved.

Nanostructured Block Polymer Membranes as High Capacity Adsorbers for the Capture of Metal Ions from Water

NASA Astrophysics Data System (ADS)

Boudouris, Bryan; Weidman, Jacob; Mulvenna, Ryan; Phillip, William

The efficient removal of metal ions from aqueous streams is of significant import in applications ranging from industrial waste treatment to the purification of drinking water. An emerging paradigm associated with this separation is one that utilizes membrane adsorbers as a means by which to bind metal salt contaminants. Here, we demonstrate that the casting of an A-B-C triblock polymer using the self-assembly and non-solvent induced phase separation (SNIPS) methodology results in a nanoporous membrane geometry. The nature of the triblock polymer affords an extremely high density of binding sites within the membrane. As such, we demonstrate that the membranes with binding capacities equal to that of state-of-the-art packed bed columns. Moreover, because the affinity of the C moiety can be tuned, highly selective binding events can occur based solely on the chemistry of the block polymer and the metal ions in solution (i.e., in a manner that is independent of the size of the metal ions). Due to these combined facts, these membranes efficiently remove heavy metal (e.g., lead- and cadmium-based) salts from contaminated water streams with greater than 95% efficiency. Finally, we show that the membranes can be regenerated through a simple treatment in order to provide long-lasting adsorber systems as well. Thus, it is anticipated that these nanostructured triblock polymer membranes are a platform by which to obtain next-generation water purification processes.

Ion-pairing in aqueous CaCl 2 and RbBr solutions. Simultaneous structural refinement of XAFS and XRD data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Thai V.; Fulton, John L.

2013-01-22

We present a new methodology involving the simultaneous refinement of both x-ray absorption and x-ray diffraction spectra (X-ray Absorption/Diffraction Structural Refinement,XADSR), to study hydration and ion pair structure of CaCl 2 and RbBr salts in concentrated aqueous solutions. The XADSR analysis includes the XAFS spectra analysis of both the cation and anion as a probe of their short-range structure with an XRD spectral analysis as a probe of the global structural. Together they deliver a comprehensive picture of the cation and anion hydration, the contact ion pair (CIP) structure and the solvent-separated ion pair (SSIP) structure. XADSR analysis of 6.0more » m aqueous CaCl 2 reveals that there are an insignificant number of Ca 2+-Cl- CIP’s, but there are approximately 3.4 SSIP’s separated by about 4.99 Å. In contrast XADSR analysis of aqueous RbBr yields about 0.7 pair CIP at a bond length 3.51 Å. The present work demonstrates a new approach for a direct co-refinement of XRD and XAFS spectra in a simple and reliable fashion, opening new opportunities for analysis in various disordered and crystalline systems. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the U.S. Department of Energy by Battelle.« less

Molecular dynamics studies of interpenetrating polymer networks for actuator devices

NASA Astrophysics Data System (ADS)

Brandell, Daniel; Kasemägi, Heiki; Citérin, Johann; Vidal, Frédéric; Chevrot, Claude; Aabloo, Alvo

2008-03-01

Molecular Dynamics (MD) techniques have been used to study the structure and dynamics of a model system of an interpenetrating polymer (IPN) network for actuator devices. The systems simulated were generated using a Monte Carlo-approach, and consisted of poly(ethylene oxide) (PEO) and poly(butadiene) (PB) in a 80-20 percent weight ratio immersed into propylene carbonate (PC) solutions of LiClO 4. The total polymer content was 32%, in order to model experimental conditions. The dependence of LiClO 4 concentration in PC has been studied by studying five different concentrations: 0.25, 0.5, 0.75, 1.0 and 1.25 M. After equilibration, local structural properties and dynamical features such as phase separation, coordination, cluster stability and ion conductivity were studied. In an effort to study the conduction processes more carefully, external electric fields of 1×10 6 V/m and 5×10 6 V/m has been applied to the simulation boxes. A clear relationship between the degree of local phase separation and ion mobility is established. It is also shown that although the ion pairing increases with concentration, there are still significantly more potential charge carriers in the higher concentrated systems, while concentrations around 0.5-0.75 M of LiClO 4 in PC seem to be favorable in terms of ion mobility. Furthermore, the anions exhibit higher conductivity than the cations, and there are tendencies to solvent drag from the PC molecules.

Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gloe, Karsten; Tasker, Peter A; Oshima, Tatsuya

Preface The theme of supramolecular chemistry (SC), entailing the organization of multiple species through noncovalent interactions, has permeated virtually all aspects of chemical endeavor over the past several decades. Given that the observed behavior of discrete molecular species depends upon their weak interactions with one another and with matrix components, one would have to conclude that SC must indeed form part of the fabric of chemistry itself. A vast literature now serves to categorize SC phenomena within a body of consistent terminology. The word supramolecular itself appears in the titles of dozens of books, several journals, and a dedicated encyclopedia.more » Not surprisingly, the theme of SC also permeates the field of solvent extraction (SX), inspiring the framework for this volume of Ion Exchange and Solvent Extraction. It is attempted in the six chapters of this volume to identify both how supramolecular behavior occurs and is studied in the context of SX and how SC is influencing the current direction of SX. Researchers and practitioners have long dealt with supramolecular interactions in SX. Indeed, the use of polar extractant molecules in nonpolar media virtually assures that aggregative interactions will dominate the solution behavior of SX. Analytical chemists working in the 1930s to the 1950s with simple mono- and bidentate chelating ligands as extractants noted that extraction of metal ions obeyed complicated mass-action equilibria involving complex stoichiometries. As chemists and engineers developed processes for nuclear and hydrometallurgical applications in the 1950s and 1960s, the preference for aliphatic diluents only enhanced the complexity and supramolecular nature of extraction chemistry. Use of physical techniques such as light scattering and vapor-pressure measurements together with various spectroscopic methods revealed organic-phase aggregates from well-defined dimers to small aggregates containing a few extractant molecules to large inverse micelles swollen with water molecules. Extraction systems involving long-chain cations such as alkylammonium species or long-chain anions such as sulfonates or carboxylates proved especially prone to extensive aggregate formation. The related phenomenon of third-phase formation in SX systems, long misunderstood, is now yielding to spectroscopic and scattering techniques showing extensive long-range organization. Over the last 50 years, tools for studying the structure and thermodynamics of aggregation have grown increasingly sophisticated, leading to a rich and detailed understanding of what we can now recognize as SC phenomena in SX. In the 1970s and 1980s, the rapid growth of SC elicited a paradigm shift in SX. The influence of SC principles had two major effects on the course of SX research. First, it provided a framework for understanding the supramolecular behavior that was already well appreciated in the field of SX, though earlier without the SC terminology. Second, it provided the conceptual tools to control supramolecular behavior in SX, direct it for intended functionality, and to simplify it. Extraction by designed reagents has been steadily progressing ever since, with commercial applications emerging to successfully validate this approach. With the discovery of crown ethers in the late 1960s, the advancement of extractant design has fruitfully employed the concept of inclusion. While considerable initial progress occurred with such molecules, especially because of their affinity and selectivity for alkali and alkaline earth metals, other molecular platforms such as calixarenes have proven more versatile. Multidentate receptors for partial to full inclusion of cations, anions, ion pairs, as well as neutral species, have now become commonplace for selective extraction. This volume of Ion Exchange and Solvent Extraction examines how the principles of SC are being employed both in advancing the design of new highly selective SX systems and in understanding aggregation phenomena in SX systems. Chapter 1 discusses the nature and definition of SC and how it is used generally in design of novel SX reagents. Major approaches using SC principles are outlined and illustrated. Chapter 2 expands upon the theme of ion-pair recognition and introduces outer-sphere recognition of metal complexes, a novel idea with the potential for structural control of solvation, casting a new light on solvent modifiers. Chapter 3 reviews the large literature of calixarenes as extraction reagents for metal ions, where the synthetic versatility of this family of compounds has produced vast possibilities for inclusion and selective separations. Chapter 4 extends such chemistry to extraction of biomolecules, where the potential for selective separations is only beginning to be explored through site recognition in macromolecules. In Chapter 5, a detailed examination of the liquid-liquid interface as an expression of supramolecular phenomena i...« less

Communication: Potentials of mean force study of ionic liquid ion pair aggregation in polar covalent molecule solvents

NASA Astrophysics Data System (ADS)

Bandlamudi, Santosh Rathan Paul; Benjamin, Kenneth M.

2018-05-01

Molecular dynamics (MD) simulations were conducted for 1-ethyl-3-methylimidazolium methylsulfate [EMIM][MeSO4] dissolved in six polar covalent molecules [acetic acid, acetone, chloroform, dimethyl sulfoxide (DMSO), isopropyl alcohol, and methanol] to understand the free energies of ionic liquid (IL) ion pairing/aggregation in the limit of infinite dilution. Free energy landscapes or potentials of mean force (PMF) were computed using umbrella sampling and the weighted histogram analysis method. The PMF studies showed the strongest IL ion pairing in chloroform, and the strength of IL ion pairing decreases in the order of chloroform, acetone, propanol, acetic acid, DMSO, and methanol. In the limit of infinite dilution, the free energy curves for IL ion aggregation in co-solvents were characterized by two distinct minima [global (˜3.6 Å) and local (˜5.7 Å)], while free energy values at these minima differed significantly for IL in each co-solvent. The PMF studies were extended for determining the free energy of IL ion aggregation as a function of concentration of methanol. Studies showed that as the concentration of methanol increased, the free energy of ion aggregation decreased, suggesting greater ion pair stability, in agreement with previously reported MD clustering and radial distribution function data.

Multisite Ion Model in Concentrated Solutions of Divalent Cations (MgCl2 and CaCl2): Osmotic Pressure Calculations

PubMed Central

2015-01-01

Accurate force field parameters for ions are essential for meaningful simulation studies of proteins and nucleic acids. Currently accepted models of ions, especially for divalent ions, do not necessarily reproduce the right physiological behavior of Ca2+ and Mg2+ ions. Saxena and Sept (J. Chem. Theor. Comput.2013, 9, 3538–3542) described a model, called the multisite-ion model, where instead of treating the ions as an isolated sphere, the charge was split into multiple sites with partial charge. This model provided accurate inner shell coordination of the ion with biomolecules and predicted better free energies for proteins and nucleic acids. Here, we expand and refine the multisite model to describe the behavior of divalent ions in concentrated MgCl2 and CaCl2 electrolyte solutions, eliminating the unusual ion–ion pairing and clustering of ions which occurred in the original model. We calibrate and improve the parameters of the multisite model by matching the osmotic pressure of concentrated solutions of MgCl2 to the experimental values and then use these parameters to test the behavior of CaCl2 solutions. We find that the concentrated solutions of both divalent ions exhibit the experimentally observed behavior with correct osmotic pressure, the presence of solvent separated ion pairs instead of direct ion pairs, and no aggregation of ions. The improved multisite model for (Mg2+ and Ca2+) can be used in classical simulations of biomolecules at physiologically relevant salt concentrations. PMID:25482831

Ion imprinted polymeric nanoparticles for selective separation and sensitive determination of zinc ions in different matrices

NASA Astrophysics Data System (ADS)

Shamsipur, Mojtaba; Rajabi, Hamid Reza; Pourmortazavi, Seied Mahdi; Roushani, Mahmoud

2014-01-01

Preparation of Zn2+ ion-imprinted polymer (Zn-IIP) nanoparticles is presented in this report. The Zn-IIP nanoparticles are prepared by dissolving stoichiometric amounts of zinc nitrate and selected chelating ligand, 3,5,7,20,40-pentahydroxyflavone, in 15 mL ethanol-acetonitrile (2:1; v/v) mixture as a porogen solvent in the presence of ethylene glycol-dimethacrylate (EGDMA) as cross-linking, methacrylic acid (MAA) as functional monomer, and 2,2-azobisisobutyronitrile (AIBN) as initiator. After polymerization, Cavities in the polymer particles corresponding to the Zn2+ ions were created by leaching the polymer in HCl aqueous solution. The synthesized IIPs were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal analysis techniques. Also, the pH range for rebinding of Zn2+ ion on the IIP and equilibrium binding time were optimized, using flame atomic absorption spectrometry. In selectivity study, it was found that imprinting results increased affinity of the material toward Zn2+ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for six times without any significant decrease in polymer binding affinities. Finally, the prepared sorbent was successfully applied to the selective recognition and determination of zinc ion in different real samples.

Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

NASA Astrophysics Data System (ADS)

Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

2017-12-01

Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

Study on the effects of electrolytes and solvents in the determination of quaternary ammonium ions by nonaqueous capillary electrophoresis with contactless conductivity detection.

PubMed

Buglione, Lucia; See, Hong Heng; Hauser, Peter C

2013-01-01

A study on the separation of lipophilic quaternary ammonium cations in NACE coupled with contactless conductivity detection (NACE-C(4)D) is presented. The suitability of different salts dissolved in various organic solvents as running electrolytes in NACE-C(4)D was investigated. A solvent mixture of methanol/acetonitrile at a ratio of 90%:10% v/v showed the best results. Deoxycholic acid sodium salt as BGE was found to provide exceptional high stability with low baseline noise that leads to highest S/N ratios for the target analytes among all BGEs tested. Under the optimum conditions, capillaries with different internal diameters were examined and an id of 50 μm was found to give best detection sensitivity. The proposed method was validated and showed good linearity in the range from 2.5 to 200 μM, low limits of detection (0.1-0.7 μM) and acceptable reproducibility of peak area (intraday RSD 0.1-0.7%, n = 3; interday RSD 5.9-9.4%, n = 3). © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Experimental and Computational Investigation into the Gas-Phase Acidities of Tyrosine and Phenylalanine: Three Structures for Deprotonated Tyrosine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bokatzian, Samantha S.; Stover, Michele L.; Plummer, Chelsea E.

Using mass spectrometry and correlated molecular orbital theory, three deprotonated structures were revealed for the amino acid tyrosine. The structures were distinguished experimentally by ion/molecule reactions involving proton transfer and trimethylsilyl azide. Gas-phase acidities from proton transfer reactions and from G3(MP2) calculations generally agree well. The lowest energy structure, which was only observed experimentally using electrospray ionization from aprotic solvents, is deprotonated at the carboxylic acid group and is predicted to be highly folded. A second unfolded carboxylate structure is several kcal/mol higher in energy and primarily forms from protic solvents. Protic solvents also yield a structure deprotonated at themore » phenolic side chain, which experiments find to be intermediate in energy to the two carboxylate forms. G3(MP2) calculations indicate that the three structures differ in energy by only 2.5 kcal/mol, yet they are readily distinguished experimentally. Structural abundance ratios are dependent upon experimental conditions, including the solvent and accumulation time of ions in a hexapole. Under some conditions, carboxylate ions may convert to phenolate ions. For phenylalanine, which lacks a phenolic group, only one deprotonated structure was observed experimentally when electrosprayed from protic solvent. This agrees with G3(MP2) calculations that find the folded and unfolded carboxylate forms to differ by 0.3 kcal/mol.« less

Biogas upgrading by chemical absorption using ammonia rich absorbents derived from wastewater.

PubMed

McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

2014-12-15

The use of ammonia (NH3) rich wastewaters as an ecological chemical absorption solvent for the selective extraction of carbon dioxide (CO2) during biogas upgrading to 'biomethane' has been studied. Aqueous ammonia absorbents of up to 10,000 gNH3 m(-3) demonstrated CO2 absorption rates higher than recorded in the literature for packed columns using 20,000-80,000 g NH3 m(-3) which can be ascribed to the process intensification provided by the hollow fibre membrane contactor used in this study to support absorption. Centrifuge return liquors (2325 g m(-3) ionised ammonium, NH4(+)) and a regenerant (477 gNH4(+) m(-3)) produced from a cationic ion exchanger used to harvest NH4(+) from crude wastewater were also tested. Carbon dioxide fluxes measured for both wastewaters compared reasonably with analogue ammonia absorption solvents of equivalent NH3 concentration. Importantly, this demonstrates that ammonia rich wastewaters can facilitate chemically enhanced CO2 separation which eliminates the need for costly exogenic chemicals or complex chemical handling which are critical barriers to implementation of chemical absorption. When testing NH3 analogues, the potential to recover the reaction product ammonium bicarbonate (NH4HCO3) in crystalline form was also illustrated. This is significant as it suggests a new pathway for ammonia separation which avoids biological nitrification and produces ammonia stabilised into a commercially viable fertiliser (NH4HCO3). However, in real ammonia rich wastewaters, sodium bicarbonate and calcium carbonate were preferentially formed over NH4HCO3 although it is proposed that NH4HCO3 can be preferentially formed by manipulating both ion exchange and absorbent chemistry. Copyright © 2014. Published by Elsevier Ltd.

Magnetic nanoparticles and high-speed countercurrent chromatography coupled in-line and using the same solvent system for separation of quercetin-3-O-rutinoside, luteoloside and astragalin from a Mikania micrantha extract.

PubMed

Wang, Juanqiang; Geng, Shan; Wang, Binghai; Shao, Qian; Fang, Yingtong; Wei, Yun

2017-07-28

A new in-line method of magnetic nanoparticles (MNPs) coupled with high-speed countercurrent chromatography (HSCCC) using a same solvent system during the whole separation process was established to achieve the rapid separation of flavonoids from Mikania micrantha. The adsorption and desorption capacities of five different MNPs for flavonoid standards and Mikania micrantha crude extract were compared and the most suitable magnetic nanoparticle Fe 3 O 4 @SiO 2 @DIH@EMIMLpro was selected as the in-line MNP column. An in-line separation system was established by combining this MNP column with HSCCC through a six-way valve. The comparison between two solvent systems n-hexane-ethyl acetate-methanol-water (3:5:3:5, v/v) and ethyl acetate-methanol-water (25:1:25, v/v) showed that the latter solvent system was more suitable for simultaneously in-line separating three flavonoids quercetin-3-O-rutinoside, luteoloside and astragalin from Mikania micrantha. The purities of these three compounds with the ethyl acetate-methanol-water solvent system were 95.13%, 98.54% and 98.19% respectively. Results showed the established in-line separation system of MNP-HSCCC was efficient, recyclable and served to isolate potential flavonoids with similar polarities from natural complex mixtures. The in-line combination of magnetic nanoparticles with high-speed countercurrent chromatography eluting with the same solvent system during the whole separation process was established for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

Ionic Asymmetry and Solvent Excluded Volume Effects on Spherical Electric Double Layers: A Density Functional Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medasani, Bharat; Ovanesyan, Zaven; Thomas, Dennis G.

In this article we present a classical density functional theory for electrical double layers of spherical macroions that extends the capabilities of conventional approaches by accounting for electrostatic ion correlations, size asymmetry and excluded volume effects. The approach is based on a recent approximation introduced by Hansen-Goos and Roth for the hard sphere excess free energy of inhomogeneous fluids (J. Chem. Phys. 124, 154506). It accounts for the proper and efficient description of the effects of ionic asymmetry and solvent excluded volume, especially at high ion concentrations and size asymmetry ratios including those observed in experimental studies. Additionally, we utilizemore » a leading functional Taylor expansion approximation of the ion density profiles. In addition, we use the Mean Spherical Approximation for multi-component charged hard sphere fluids to account for the electrostatic ion correlation effects. These approximations are implemented in our theoretical formulation into a suitable decomposition of the excess free energy which plays a key role in capturing the complex interplay between charge correlations and excluded volume effects. We perform Monte Carlo simulations in various scenarios to validate the proposed approach, obtaining a good compromise between accuracy and computational cost. We use the proposed computational approach to study the effects of ion size, ion size asymmetry and solvent excluded volume on the ion profiles, integrated charge, mean electrostatic potential, and ionic coordination number around spherical macroions in various electrolyte mixtures. Our results show that both solvent hard sphere diameter and density play a dominant role in the distribution of ions around spherical macroions, mainly for experimental water molarity and size values where the counterion distribution is characterized by a tight binding to the macroion, similar to that predicted by the Stern model.« less

On the Deficiencies of the Ferricinium-Ferrocene Redox Couple for Estimating Transfer Energies of Single Ions.

DTIC Science & Technology

1980-08-15

breakdown of the "ferrocene assumption" for estimating the transfer thermodynamics of single ions. I 4 Experimental Most solvents were Aldrich " Gold ...solvent "donor number" DN1 6 (Table I). A similar finding has been noted previously for monoatomic cations. 1 5 The small negative value of - Sc+) in water

Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

PubMed

Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

2017-08-03

The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

Molecular dynamics of acetamide based ionic deep eutectic solvents

NASA Astrophysics Data System (ADS)

Srinivasan, H.; Dubey, P. S.; Sharma, V. K.; Biswas, R.; Mitra, S.; Mukhopadhyay, R.

2018-04-01

Deep eutectic solvents are multi-component mixtures that have freezing point lower than their individual components. Mixture of acetamide+ lithium nitrate in the molar ratio 78:22 and acetamide+ lithium perchlorate in the molar ratio 81:19 are found to form deep eutectic solvents with melting point lower than the room temperature. It is known that the depression in freezing point is due to the hydrogen bond breaking ability of anions in the system. Quasielastic neutron scattering experiments on these systems were carried out to study the dynamics of acetamide molecules which may be influenced by this hydrogen bond breaking phenomena. The motion of acetamide molecules is modeled using jump diffusion mechanism to demonstrate continuous breaking and reforming hydrogen bonds in the solvent. Using the jump diffusion model, it is inferred that the jump lengths of acetamide molecules are better approximated by a Gaussian distribution. The shorter residence time of acetamide in presence of perchlorate ions suggest that the perchlorate ions have a higher hydrogen bond breaking ability compared to nitrate ions.

Effect on de-greasing solvents on conductive separable connector shields and semiconductive cable shields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perry, D.D.; Bolcar, J.P.

1990-04-01

A study has been conducted to determine the effects of commercial degreasing solvents on the conductivity of an EPDM separable connector shield and two types of cable shields based on EPR and XLPE, respectively. Solvents tested included a chlorinated solvent based on 1,1,1-trichloroethane and several so-called citrus solvents consisting of the natural terpene, limonene, or blends of limonene with other hydrocarbons. All the solvents significantly degraded the conductivity of the EPR and EPDM materials, but had little effect on the XLPE cable shield. The solvents differed, however, in the extent of their effects, the rate of recovery of conductivity aftermore » removal of the solvent, and the degree to which the original conductivity of the material was restored. The consequences of these results in terms of appropriate field use of these types of solvents by utility personnel are discussed.« less

Large-scale dialysis of sample lipids

USGS Publications Warehouse

Meadows, Jill; Tillitt, Donald E.; Huckins, James; Schroeder, D.

1993-01-01

The use of a semipermeable membrane device (SPMD) for dialysis in an organic solvent phase is an efficient alternative approach to separation of contaminants from large amounts of lipid (up to 50 grams or more) prior to organic chemical analysis. Passive separation of contaminants can be accomplished with a minimum of equipment and a comparatively small volume of solvent. This study examines the effects of factors such as dialytic solvent, lipid type, dialytic solvent:lipid volume ratio, dialysis time, and temperature on the performance of polyethylene SPMDs during lipid-contaminant separations. The experimental conditions for maximal recoveries of organochlorine pesticides and polychlorinated biphenyls with minimal lipid carryover are determined for the examined variables. When the dialytic procedure is optimized, very satisfactory and highly reproducible analyte recoveries can be obtained in a few days while separating > 90% of the lipid material in a single operation.

The Biodegradation of TNT in Enhanced Soil and Compost Systems

DTIC Science & Technology

1978-01-01

dimethylsulfoxide ( DMSO ) Is substituted for EDA because EDA tends to clog the sprayei . Dr. Chandler’s solvent system No. 1 is used for non-polar separa...material was converted to non- solvent -extractable, water-soluble materials of unknown Identity. These materials may represent the contents of dead... solvent system No. 1 54 2A TLC separation of TNT and derivatives using ChandlerIs solvent system No. 2 55 3A TLC separation of TNT and derivatives using

Method for removing contaminants from plastic resin

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2008-12-09

A resin recycling method that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The method includes receiving the resin in container form. The containers are then ground into resin particles. The particles are exposed to a solvent, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. After separating the particles and the resin, a solvent removing agent is used to remove any residual solvent remaining on the resin particles after separation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spiegel, G.W.

The kinetic solvent isotope effect, KSIE, (k/sub H/sub 2/O//k/sub D/sub 2/O/), at 25.0/sup 0/C and ionic strength, I, equal to 0.20 +- 0.02 M was measured for the nucleophilic displacement of iodine ion from iodomethane, iodoacetamide, and iodoacetate ion, thiophene from S-Methylthiophenium ion, and tosylate ion from methyl tosylate by bromide ion, chloride ion, acetate ion, hydroxide ion, water, ammonia, ethylenediamine, n-butylamine, piperazine, piperidine, quinuclidine, and 1,4-Diazabicyclo(2.2.2)octane (DABCO), and the monoprotonated cations of ethylenediamine, piperazine, and DABCO. By means of solvent partition measurements at 25.0/sup 0/C and I = 0.02 M between H/sub 2/O and D/sub 2/O and a commonmore » immiscible organic solvent, the ground state activity coefficients in D/sub 2/O, the solution in H/sub 2/O being chosen as the reference state, were determined for the nitrogen-containing nucleophiles (except ammonia) and the substrates methyl tosylate, iodoacetamide, and iodoacetic acid. The solubilities at 25.0/sup 0/C of the picrate and tetraphenylborate salts of the monoprotonated cationic forms of ethylenediamine, piperazine, and DABCO were measured to determine the activity coefficients in D/sub 2/O of these ions relative to an H/sub 2/O reference state. Applying the Eyring equation, the activity coefficients of the transition states in D/sub 2/O, reference state H/sub 2/O, were calculated.« less

SISGR: Linking Ion Solvation and Lithium Battery Electrolyte Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trulove, Paul C.; Foley, Matthew P.

2012-09-30

The solvation and phase behavior of the model battery electrolyte salt lithium trifluoromethanesulfonate (LiCF 3SO 3) in commonly used organic solvents; ethylene carbonate (EC), gamma-butyrolactone (GBL), and propylene carbonate (PC) was explored. Data from differential scanning calorimetry (DSC), Raman spectroscopy, and X-ray diffraction were correlated to provide insight into the solvation states present within a sample mixture. Data from DSC analyses allowed the construction of phase diagrams for each solvent system. Raman spectroscopy enabled the determination of specific solvation states present within a solvent-salt mixture, and X-ray diffraction data provided exact information concerning the structure of a solvates that couldmore » be isolated Thermal analysis of the various solvent-salt mixtures revealed the phase behavior of the model electrolytes was strongly dependent on solvent symmetry. The point groups of the solvents were (in order from high to low symmetry): C2V for EC, CS for GBL, and C1 for PC(R). The low symmetry solvents exhibited a crystallinity gap that increased as solvent symmetry decreased; no gap was observed for EC-LiTf, while a crystallinity gap was observed spanning 0.15 to 0.3 mole fraction for GBL-LiTf, and 0.1 to 0.33 mole fraction for PC(R)-LiTf mixtures. Raman analysis demonstrated the dominance of aggregated species in almost all solvent compositions. The AGG and CIP solvates represent the majority of the species in solutions for the more concentrated mixtures, and only in very dilute compositions does the SSIP solvate exist in significant amounts. Thus, the poor charge transport characteristics of CIP and AGG account for the low conductivity and transport properties of LiTf and explain why is a poor choice as a source of Li + ions in a Li-ion battery.« less

Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault

2016-01-28

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the timemore » evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.« less

Exploring Solute-Solvent Interactions of -Amino Acids in Aqueous [] Arrangements by Volumetric, Viscometric, Refractometric, and Acoustic Approach

NASA Astrophysics Data System (ADS)

Roy, Mahendra Nath; Roy, Milan Chandra; Basak, Saptarshi

2014-05-01

Qualitative and quantitative analysis of molecular interaction prevailing in glycine, l-alanine, l-valine, and aqueous solution of ionic liquid (IL) [1-ethylpyridinium tetrafluoroborate (] have been investigated by thermophysical properties. The apparent molar volume (), viscosity -coefficient, molal refraction (), and adiabatic compressibility ( of glycine, l-alanine, and l-valine have been studied in 0.001 mol , 0.003 mol , and 0.005 mol aqueous 1-ethylpyridinium tetrafluoroborate [] solutions at 298.15 K from the values of densities , viscosities (), refractive index (, and speed of sound , respectively. The extent of interaction, i.e., the solute-solvent interaction is expressed in terms of the limiting apparent molar volume (, viscosity -coefficient, and limiting apparent molar adiabatic compressibility (. The limiting apparent molar volumes (, experimental slopes ( derived from the Masson equation, and viscosity - and -coefficients using the Jones-Dole equation have been interpreted in terms of ion-ion and ion-solvent interactions, respectively. Molal refractions ( have been calculated with the help of the Lorentz-Lorenz equation. The role of the solvent (aqueous IL solution) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.

Descriptors for ions and ion-pairs for use in linear free energy relationships.

PubMed

Abraham, Michael H; Acree, William E

2016-01-22

The determination of Abraham descriptors for single ions is reviewed, and equations are given for the partition of single ions from water to a number of solvents. These ions include permanent anions and cations and ionic species such as carboxylic acid anions, phenoxide anions and protonated base cations. Descriptors for a large number of ions and ionic species are listed, and equations for the prediction of Abraham descriptors for ionic species are given. The application of descriptors for ions and ionic species to physicochemical processes is given; these are to water-solvent partitions, HPLC retention data, immobilised artificial membranes, the Finkelstein reaction and diffusion in water. Applications to biological processes include brain permeation, microsomal degradation of drugs, skin permeation and human intestinal absorption. The review concludes with a section on the determination of descriptors for ion-pairs. Copyright © 2015 Elsevier B.V. All rights reserved.

Preferential Solvation of Silver (I) Bromate in Methanol-Dimethylsulfoxide Mixtures

NASA Astrophysics Data System (ADS)

Janardhanan, S.; Kalidas, C.

1984-06-01

The solubiltiy of silver bromate, the Gibbs transfer energy of Ag+ and BrO3- and the solvent transport number in methanol-dimethyl sulfoxide mixtures are reported. The solubility of silver bromate increases with addition of DMSO. The Gibbs energy of transfer of the silver ion (based on the ferrocene reference method) decreases, while that of the bromate ion becomes slightly negative with the addition of DMSO. The solvent transport number A passes through a maximum (⊿ = 1.0 at XDMSO = 0.65. From these results, it is concluded that the silver ion is preferentially solvated by DMSO whereas the bromate ion shows no preferential solvation.

Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis.

PubMed

Yonetani, Yoshiteru

2015-07-28

Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl < kNaCl < kKCl < kCsCl. Analysis of the free-energy landscape with a solvent reaction coordinate and subsequent rate component analysis showed that the differences in these rate constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

Potential of mean force between two hydrophobic solutes in water.

PubMed

Southall, Noel T; Dill, Ken A

2002-12-10

We study the potential of mean force between two nonpolar solutes in the Mercedes Benz model of water. Using NPT Monte Carlo simulations, we find that the solute size determines the relative preference of two solute molecules to come into contact ('contact minimum') or to be separated by a single layer of water ('solvent-separated minimum'). Larger solutes more strongly prefer the contacting state, while smaller solutes have more tendency to become solvent-separated, particularly in cold water. The thermal driving forces oscillate with solute separation. Contacts are stabilized by entropy, whereas solvent-separated solute pairing is stabilized by enthalpy. The free energy of interaction for small solutes is well-approximated by scaled-particle theory. Copyright 2002 Elsevier Science B.V.

Argon direct analysis in real time mass spectrometry in conjunction with makeup solvents: a method for analysis of labile compounds.

PubMed

Yang, Hongmei; Wan, Debin; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

2013-02-05

Helium direct analysis in real time (He-DART) mass spectrometry (MS) analysis of labile compounds usually tends to be challenging because of the occurrence of prominent fragmentation, which obscures the assigning of an ion to an independent species or merely a fragment in a mixture. In the present work, argon DART (Ar-DART) MS in conjunction with makeup solvents has been demonstrated to analyze a variety of labile compounds including nucleosides, alkaloids, glucose, and other small molecules. The results presented here confirm that Ar-DART can generate significantly less energetic ions than conventional He-DART and is able to produce the intact molecular ions with little or no fragmentation in both positive and negative ion modes. Adding a makeup solvent (absolute ethyl alcohol, methanol, fluorobenzene, or acetone) to the argon gas stream at the exit of the DART ion source can result in 1-2 orders of magnitude increase in detection signals. The sensitivity attainable by Ar-DART was found to be comparable to that by He-DART. The investigation of influence of solvents improves our understanding of the fundamental desorption and ionization processes in DART. The practical application of this rapid and high throughput method is demonstrated by the successful analysis of a natural product (Crude Kusnezoff Monkshood) extract, demonstrating the great potential in mixture research.

Interfacial solvation thermodynamics

NASA Astrophysics Data System (ADS)

Ben-Amotz, Dor

2016-10-01

Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Generation of accurate peptide retention data for targeted and data independent quantitative LC-MS analysis: Chromatographic lessons in proteomics.

PubMed

Krokhin, Oleg V; Spicer, Vic

2016-12-01

The emergence of data-independent quantitative LC-MS/MS analysis protocols further highlights the importance of high-quality reproducible chromatographic procedures. Knowing, controlling and being able to predict the effect of multiple factors that alter peptide RP-HPLC separation selectivity is critical for successful data collection for the construction of ion libraries. Proteomic researchers have often regarded RP-HPLC as a "black box", while vast amount of research on peptide separation is readily available. In addition to obvious parameters, such as the type of ion-pairing modifier, stationary phase and column temperature, we describe the "mysterious" effects of gradient slope, column size and flow rate on peptide separation selectivity. Retention time variations due to these parameters are governed by the linear solvent strength (LSS) theory on a peptide level by the value of its slope S in the basic LSS equation-a parameter that can be accurately predicted. Thus, the application of shallower gradients, higher flow rates, or smaller columns will each increases the relative retention of peptides with higher S-values (long species with multiple positively charged groups). Simultaneous changes to these parameters that each drive shifts in separation selectivity in the same direction should be avoided. The unification of terminology represents another pressing issue in this field of applied proteomics that should be addressed to facilitate further progress. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free energetics of carbon nanotube association in aqueous inorganic NaI salt solutions: Temperature effects using all-atom molecular dynamics simulations.

PubMed

Ou, Shu-Ching; Cui, Di; Wezowicz, Matthew; Taufer, Michela; Patel, Sandeep

2015-06-15

In this study, we examine the temperature dependence of free energetics of nanotube association using graphical processing unit-enabled all-atom molecular dynamics simulations (FEN ZI) with two (10,10) single-walled carbon nanotubes in 3 m NaI aqueous salt solution. Results suggest that the free energy, enthalpy and entropy changes for the association process are all reduced at the high temperature, in agreement with previous investigations using other hydrophobes. Via the decomposition of free energy into individual components, we found that solvent contribution (including water, anion, and cation contributions) is correlated with the spatial distribution of the corresponding species and is influenced distinctly by the temperature. We studied the spatial distribution and the structure of the solvent in different regions: intertube, intratube and the bulk solvent. By calculating the fluctuation of coarse-grained tube-solvent surfaces, we found that tube-water interfacial fluctuation exhibits the strongest temperature dependence. By taking ions to be a solvent-like medium in the absence of water, tube-anion interfacial fluctuation shows similar but weaker dependence on temperature, while tube-cation interfacial fluctuation shows no dependence in general. These characteristics are discussed via the malleability of their corresponding solvation shells relative to the nanotube surface. Hydrogen bonding profiles and tetrahedrality of water arrangement are also computed to compare the structure of solvent in the solvent bulk and intertube region. The hydrophobic confinement induces a relatively lower concentration environment in the intertube region, therefore causing different intertube solvent structures which depend on the tube separation. This study is relevant in the continuing discourse on hydrophobic interactions (as they impact generally a broad class of phenomena in biology, biochemistry, and materials science and soft condensed matter research), and interpretations of hydrophobicity in terms of alternative but parallel signatures such as interfacial fluctuations, dewetting transitions, and enhanced fluctuation probabilities at interfaces. © 2015 Wiley Periodicals, Inc.

Method for preparing membranes with adjustable separation performance

DOEpatents

Peterson, E.S.; Orme, C.J.; Stone, M.L.

1995-01-31

Methods for adjustable separation of solutes and solvents involve the combination of the use of a maximally swollen membrane and subsequent vacuum depressurization exerted on the permeate side of that membrane. By adjusting the extent of depressurization it is possible to separate solvent from solutes and solutes from each other. Improved control of separation parameters as well as improved flux rates characterize the present invention. 2 figs.

Method for preparing membranes with adjustable separation performance

DOEpatents

Peterson, Eric S.; Orme, Christopher J.; Stone, Mark L.

1995-01-01

Methods for adjustable separation of solutes and solvents involve the combination of the use of a maximally swollen membrane and subsequent vacuum depressurization exerted on the permeate side of that membrane. By adjusting the extent of depressurization it is possible to separate solvent from solutes and solutes from each other. Improved control of separation parameters as well as improved flux rates characterize the present invention.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, S.K.; Hames, B.R.; Myers, M.D.

1998-03-24

A method is described for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, Stuart K.; Hames, Bonnie R.; Myers, Michele D.

1998-01-01

A method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide as a co-solvent in Li-ion batteries

NASA Astrophysics Data System (ADS)

Kim, Ketack; Cho, Young-Hyun; Shin, Heon-Cheol

2013-03-01

1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide (EMP-TFSI) is an ionic liquid with a melting temperature of 85 °C. Although it is a solid salt, it shows good miscibility with carbonate solvents, which allows EMP-TFSI to be used as a co-solvent in these systems. Ethylene carbonate is another solid co-solvent used in Li-ion batteries. Due to its smaller cationic size, EMP-TFSI provides better conductivity as a co-solvent than 1-methyl-1-propyl piperidinium bis(trifluoromethanesulfonyl)imide (MPP-TFSI), which is the smallest room-temperature piperidinium liquid salt known. In cells with 50 wt% IL and 50 wt% carbonate electrolyte, an EMP-TFSI mixed electrolyte performs better than an MPP-TFSI mixed electrolyte. Additionally, the discharge capacity values obtained from rate capability tests carried out with mixed EMP-TFSI are as good as those conducted with a pure carbonate electrolyte.

CONTINUOUS CHELATION-EXTRACTION PROCESS FOR THE SEPARATION AND PURIFICATION OF METALS

DOEpatents

Thomas, J.R.; Hicks, T.E.; Rubin, B.; Crandall, H.W.

1959-12-01

A continuous process is presented for separating metal values and groups of metal values from each other. A complex mixture. e.g., neutron-irradiated uranium, can be resolved into component parts. In the present process the values are dissolved in an acidic solution and adjusted to the proper oxidation state. Thenceforth the solution is contacted with an extractant phase comprising a fluorinated beta -diketone in an organic solvent under centain pH conditions whereupon plutonium and zirconium are extracted. Plutonium is extracted from the foregoing extract with reducing aqueous solutions or under specified acidic conditions and can be recovered from the aqueous solution. Zirconium is then removed with an oxalic acid aqueous phase. The uranium is recovered from the residual original solution using hexone and hexone-diketone extractants leaving residual fission products in the original solution. The uranium is extracted from the hexone solution with dilute nitric acid. Improved separations and purifications are achieved using recycled scrub solutions and the "self-salting" effect of uranyl ions.

An approach to beneficiation of spent lithium-ion batteries for recovery of materials

NASA Astrophysics Data System (ADS)

Marinos, Danai

Lithium ion batteries are one of the most commonly used batteries. A large amount of these have been used over the past 25 years and the use is expected to rise more due to their use in automotive batteries. Lithium ion batteries cannot be disposed into landfill due to safety reasons and cost. Thus, over the last years, there has been a lot of effort to find ways to recycle lithium ion batteries. A lot of valuable materials are present in a lithium ion battery making their recycling favorable. Many attempts, including pyrometallurgical and hydrometallurgical methods, have been researched and some of them are already used by the industry. However, further improvements are needed to the already existing processes, to win more valuable materials, use less energy and be more environmentally benign. The goal of this thesis is to find a low-temperature, low-energy method of recovering lithium from the electrolyte and to develop pathways for complete recycling of the battery. The research consists of the following parts: Pure LiPF6 powder, which is the electrolyte material, was characterized using x- ray diffraction analysis and DSC/TGA analysis. The LiPF6 powder was titrated using acid (HCl, HNO3, H2SO4), bases (NH4 OH) and distilled water. It was concluded that distilled water was the best solvent to selectively leach lithium from lithium-ion batteries. Leaching conditions were optimized including time, temperature, solid/liquid ratio and stirring velocity. All the samples were tested using ICP for chemical composition. Because leaching could be performed at room temperature, leaching was conducted in a flotation machine that was able to separate plastics by creating bubbles with no excess reagents use. The solution that contained lithium had to be concentrated more in order for lithium to be able to precipitate and it was shown that the solution could be concentrated by using the same solution over and over again. The next set of experiments was composed of battery shredding, steel separation by hand magnet, leaching with distilled water and sizing using wet sieving. Every fraction was sent to rare-earth rolls separation and eddy current separation. A size distribution analysis was conducted and the fractions were analyzed using ICP.

Trivalent Ions under Charged Langmuir Monolayers: Nanoscale Mechanisms for Charge Inversion and Liquid-Liquid Extraction

NASA Astrophysics Data System (ADS)

Miller, Mitchell

Ions dissolved in solution are known to interact in remarkable ways with charged Langmuir monolayers. The organic monolayer can be used as a molecular template for ordered nucleation of inorganic crystals (biomineralization) and functional nanoparticles. However, the clear majority of experiments demonstrating these behaviors have been performed with divalent ions. Trivalent ions are present in several important processes that are unique from previously studied divalent systems. We will demonstrate that trivalent ions under floating monolayers can model two important systems: charge inversion and liquid-liquid solvent extraction. Using in situ synchrotron x-ray scattering and emission methods, we can make direct, nanoscale observations of the interactions between ion and monolayer. Charge inversion is a fascinating phenomenon in which small ions of an opposite charge to some large object (colloidal particle, DNA molecule, etc.) will attach to and reverse the object's charge, rather than simply neutralizing it. There are many experimental systems demonstrating this behavior and an enormous body of theoretical work to explain it. Two classes of explanation exist for how charge inversion may occur, "chemical" and "physical" mechanism. Using grazing incidence diffraction (GID), we have found that ions can form an ordered lattice which is incommensurate to a floating, charged monolayer. Because the ions are incommensurate, they cannot be specifically attached to molecules in the monolayer and must be, therefore, held in place by "physical" means. Solvent extraction can be an extremely complex procedure, so our approach to studying it is to simplify the system into a basic model. Ordinarily, two immiscible liquids--an aqueous phase containing some desired species and other impurities and an organic phase, which sometimes contains extractant molecules that improve efficiency--are mixed together and allowed to separate again. While the liquids are being mixed together, the target species from the aqueous phase is pulled across the interface into the organic phase. The mechanism by which the transfer occurs is very poorly understood and very difficult to study directly since it is a very dynamic process and obscured by the bulk of the liquids. Here we propose that the air-water interface is a model of the liquid-liquid interface; in our model, the hydrophobic "organic" phase is the air above the water. This lets us make direct observations of the interactions between ions dissolved in the aqueous phase and the extractant molecules in the organic phase with x-rays, something which would be impossible in an ordinary solvent extraction experiment. We observed a sharp transition in ordering as the atomic weight of the ion dissolved in solution is increased. One would expect a continuous variation, since the size of the ions varies continuously. Second, using x-ray fluorescence, we find that heavier lanthanides are much more strongly attracted to the monolayer than light ones. The unexpected nature of our results emphasizes the need for bottom-up approaches to understanding these systems rather than the top-down method used for the last century. In addition, our results demonstrate that it is, indeed, possible to overcome the experimental difficulties and make the types of measurements necessary for this approach.

Aliphatic long chain quaternary ammonium compounds analysis by ion-pair chromatography coupled with suppressed conductivity and UV detection in lysing reagents for blood cell analysers.

PubMed

Giovannelli, D; Abballe, F

2005-08-26

A method has been developed which allows simultaneous determination of three linear alkyl trimethylammonium salts. Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride are widely used as main active ingredients of lysing reagents for blood cell analyzers which perform white blood cells differential determination into two or more sub-populations by impedance analysis. The ion-pair on styrene-divinyl benzene chromatographic phase looks like a suitable, reliable and long term stable tool for separation of such quaternary compounds. The detection based on suppressed conductivity was chosen because of the lack of significance chromophores. A micromembrane suppressor device compatible with high solvent concentration (up to 80%) was used in order to minimize the conductivity background before the detection. In the present work we show how the chemical post column derivatization makes the alkyl chain detectable also by UV direct detection at 210 nm.

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes

DOE PAGES

Baskin, Artem; Prendergast, David

2016-02-05

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baskin, Artem; Prendergast, David

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Protein separation through preliminary experiments concerning pH and salt concentration by tube radial distribution chromatography based on phase separation multiphase flow using a polytetrafluoroethylene capillary tube.

PubMed

Kan, Hyo; Tsukagoshi, Kazuhiko

2017-07-01

Protein mixtures were separated using tube radial distribution chromatography (TRDC) in a polytetrafluoroethylene (PTFE) capillary (internal diameter=100µm) separation tube. Separation by TRDC is based on the annular flow in phase separation multiphase flow and features an open-tube capillary without the use of specific packing agents or application of high voltages. Preliminary experiments were conducted to examine the effects of pH and salt concentration on the phase diagram of the ternary mixed solvent solution of water-acetonitrile-ethyl acetate (8:2:1 volume ratio) and on the TRDC system using the ternary mixed solvent solution. A model protein mixture containing peroxidase, lysozyme, and bovine serum albumin was analyzed via TRDC with the ternary mixed solvent solution at various pH values, i.e., buffer-acetonitrile-ethyl acetate (8:2:1 volume ratio). Protein was separated on the chromatograms by the TRDC system, where the elution order was determined by the relation between the isoelectric points of protein and the pH values of the solvent solution. Copyright © 2017 Elsevier B.V. All rights reserved.

Membrane augmented distillation to separate solvents from water

DOEpatents

Huang, Yu; Baker, Richard W.; Daniels, Rami; Aldajani, Tiem; Ly, Jennifer H.; Alvarez, Franklin R.; Vane, Leland M.

2012-09-11

Processes for removing water from organic solvents, such as ethanol. The processes include distillation to form a rectified overhead vapor, compression of the rectified vapor, and treatment of the compressed vapor by two sequential membrane separation steps.

Global Profiling of Various Metabolites in Platycodon grandiflorum by UPLC-QTOF/MS.

PubMed

Lee, Jae Won; Ji, Seung-Heon; Kim, Geum-Soog; Song, Kyung-Sik; Um, Yurry; Kim, Ok Tae; Lee, Yi; Hong, Chang Pyo; Shin, Dong-Ho; Kim, Chang-Kug; Lee, Seung-Eun; Ahn, Young-Sup; Lee, Dae-Young

2015-11-09

In this study, a method of metabolite profiling based on UPLC-QTOF/MS was developed to analyze Platycodon grandiflorum. In the optimal UPLC, various metabolites, including major platycosides, were separated well in 15 min. The metabolite extraction protocols were also optimized by selecting a solvent for use in the study, the ratio of solvent to sample and sonication time. This method was used to profile two different parts of P. grandiflorum, i.e., the roots of P. grandiflorum (PR) and the stems and leaves of P. grandiflorum (PS), in the positive and negative ion modes. As a result, PR and PS showed qualitatively and quantitatively different metabolite profiles. Furthermore, their metabolite compositions differed according to individual plant samples. These results indicate that the UPLC-QTOF/MS-based profiling method is a good tool to analyze various metabolites in P. grandiflorum. This metabolomics approach can also be applied to evaluate the overall quality of P. grandiflorum, as well as to discriminate the cultivars for the medicinal plant industry.

Direct analysis of terpenes from biological buffer systems using SESI and IR-MALDESI.

PubMed

Nazari, Milad; Malico, Alexandra A; Ekelöf, Måns; Lund, Sean; Williams, Gavin J; Muddiman, David C

2018-01-01

Terpenes are the largest class of natural products with a wide range of applications including use as pharmaceuticals, fragrances, flavorings, and agricultural products. Terpenes are biosynthesized by the condensation of a variable number of isoprene units resulting in linear polyisoprene diphosphate units, which can then be cyclized by terpene synthases into a range of complex structures. While these cyclic structures have immense diversity and potential in different applications, their direct analysis in biological buffer systems requires intensive sample preparation steps such as salt cleanup, extraction with organic solvents, and chromatographic separations. Electrospray post-ionization can be used to circumvent many sample cleanup and desalting steps. SESI and IR-MALDESI are two examples of ionization methods that employ electrospray post-ionization at atmospheric pressure and temperature. By coupling the two techniques and doping the electrospray solvent with silver ions, olefinic terpenes of different classes and varying degrees of volatility were directly analyzed from a biological buffer system with no sample workup steps.

Global Profiling of Various Metabolites in Platycodon grandiflorum by UPLC-QTOF/MS

PubMed Central

Lee, Jae Won; Ji, Seung-Heon; Kim, Geum-Soog; Song, Kyung-Sik; Um, Yurry; Kim, Ok Tae; Lee, Yi; Hong, Chang Pyo; Shin, Dong-Ho; Kim, Chang-Kug; Lee, Seung-Eun; Ahn, Young-Sup; Lee, Dae-Young

2015-01-01

In this study, a method of metabolite profiling based on UPLC-QTOF/MS was developed to analyze Platycodon grandiflorum. In the optimal UPLC, various metabolites, including major platycosides, were separated well in 15 min. The metabolite extraction protocols were also optimized by selecting a solvent for use in the study, the ratio of solvent to sample and sonication time. This method was used to profile two different parts of P. grandiflorum, i.e., the roots of P. grandiflorum (PR) and the stems and leaves of P. grandiflorum (PS), in the positive and negative ion modes. As a result, PR and PS showed qualitatively and quantitatively different metabolite profiles. Furthermore, their metabolite compositions differed according to individual plant samples. These results indicate that the UPLC-QTOF/MS-based profiling method is a good tool to analyze various metabolites in P. grandiflorum. This metabolomics approach can also be applied to evaluate the overall quality of P. grandiflorum, as well as to discriminate the cultivars for the medicinal plant industry. PMID:26569219

Pressurized liquid extraction coupled with countercurrent chromatography for systematic isolation of chemical constituents by preprogrammed automatic control.

PubMed

Zhang, Yuchi; Guo, Liping; Liu, Chunming; Fu, Zi' ao; Cong, Lei; Qi, Yanjuan; Li, Dongping; Li, Sainan; Wang, Jing

2013-09-15

Pressurized liquid extraction (PLE) coupled with high-speed countercurrent chromatography (HSCCC) via an automated procedure was firstly developed to extract and isolate ginsenosides from Panax quinquefolium. The experiments were designed under the guidance of mathematical model. The partition coefficient (K) values of the target compounds and resolutions of peak profiles were employed as the research indicators, and exponential function and binomial formulas were used to optimizing the solvent systems and flow rates of the mobile phases in a three-stage separation. In the first stage, ethyl acetate, n-butanol, and water were simultaneously pumped into the solvent separator at the flow rates 11.0, 10.0, and 23.0mL/min, respectively. The upper phase of the solvent system in the solvent separator was used as both the PLE solvent and the HSCCC stationary phase, followed by elution with the lower phase of the corresponding solvent system to separate the common ginsenosides. In the second and third stages, rare ginsenosides were first separated by elution with ethyl acetate, n-butanol, methanol, and water (flow rates: 20.0, 3.0, 5.0, and 11.0mL/min, respectively), then with n-heptane, n-butanol, methanol, and water (flow rates: 17.5, 6.0, 5.0, and 22.5mL/min, respectively). Nine target compounds, with purities exceeding 95.0%, and three non-target compounds, with purities above 84.48%, were successfully separated at the semipreparative scale in 450min. The separation results prove that the PLE/HSCCC parameters calculated via mathematical model and formulas were accurately and scientifically. This research has opened up great prospects for industrial automation application. Copyright © 2013 Elsevier B.V. All rights reserved.

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1995-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1995-10-03

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1996-02-13

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1996-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Coal liquefaction process with enhanced process solvent

DOEpatents

Givens, Edwin N.; Kang, Dohee

1984-01-01

In an improved coal liquefaction process, including a critical solvent deashing stage, high value product recovery is improved and enhanced process-derived solvent is provided by recycling second separator underflow in the critical solvent deashing stage to the coal slurry mix, for inclusion in the process solvent pool.

Density functional theory and conductivity studies of boron-based anion receptors

DOE PAGES

Leung, Kevin; Chaudhari, Mangesh I.; Rempe, Susan B.; ...

2015-07-10

Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of cathode surfaces and improving ion conductivity. The receptors are also potentially beneficial to rechargeable lithium ion and lithium air batteries. We apply Density Functional Theory (DFT) to show that an oxalate-based pentafluorophenyl-boron anion receptor binds as strongly, or more strongly, to fluoride anions than many phenyl-boron anion receptors proposed in the literature. Experimental data shows marked improvement in electrolyte conductivity when this oxalate anion receptor is present. The receptor ismore » sufficiently electrophilic that organic solvent molecules compete with F – for boron-site binding, and specific solvent effects must be considered when predicting its F – affinity. To further illustrate the last point, we also perform computational studies on a geometrically constrained boron ester that exhibits much stronger gas-phase affinity for both F – and organic solvent molecules. After accounting for specific solvent effects, however, its net F – affinity is about the same as the simple oxalate-based anion receptor. Lastly, we propose that LiF dissolution in cyclic carbonate organic solvents, in the absence of anion receptors, is due mostly to the formation of ionic aggregates, not isolated F – ions.« less

Transport equations of electrodiffusion processes in the laboratory reference frame.

PubMed

Garrido, Javier

2006-02-23

The transport equations of electrodiffusion processes use three reference frames for defining the fluxes: Fick's reference in diffusion, solvent-fixed reference in transference numbers, and laboratory fluxes in electric conductivity. The convenience of using only one reference frame is analyzed here from the point of view of the thermodynamics of irreversible processes. A relation between the fluxes of ions and solvent and the electric current density is deduced first from a mass and volume balance. This is then used to show that (i) the laboratory and Fick's diffusion coefficients are identical and (ii) the transference numbers of both the solvent and the ion in the laboratory reference frame are related. Finally, four experimental methods for the measurement of ion transference numbers are analyzed critically. New expressions for evaluating transference numbers for the moving boundary method and the chronopotentiometry technique are deduced. It is concluded that the ion transport equation in the laboratory reference frame plays a key role in the description of electrodiffusion processes.

Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

PubMed

Winter, Gregory T; Wilhide, Joshua A; LaCourse, William R

2016-02-01

Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

NASA Astrophysics Data System (ADS)

Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

2016-02-01

Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

Process for producing fuel grade ethanol by continuous fermentation, solvent extraction and alcohol separation

DOEpatents

Tedder, Daniel W.

1985-05-14

Alcohol substantially free of water is prepared by continuously fermenting a fermentable biomass feedstock in a fermentation unit, thereby forming an aqueous fermentation liquor containing alcohol and microorganisms. Continuously extracting a portion of alcohol from said fermentation liquor with an organic solvent system containing an extractant for said alcohol, thereby forming an alcohol-organic solvent extract phase and an aqueous raffinate. Said alcohol is separated from said alcohol-organic solvent phase. A raffinate comprising microorganisms and unextracted alcohol is returned to the fermentation unit.

Stable colloids in molten inorganic salts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hao; Dasbiswas, Kinjal; Ludwig, Nicholas B.

2017-02-15

A colloidal solution is a homogeneous dispersion of particles or droplets of one phase (solute) in a second, typically liquid, phase (solvent). Colloids are ubiquitous in biological, chemical and technological processes1, 2, homogenizing highly dissimilar constituents. To stabilize a colloidal system against coalescence and aggregation, the surface of each solute particle is engineered to impose repulsive forces strong enough to overpower van der Waals attraction and keep the particles separated from each other2. Electrostatic stabilization3, 4 of charged solutes works well in solvents with high dielectric constants, such as water (dielectric constant of 80). In contrast, colloidal stabilization in solventsmore » with low polarity, such as hexane (dielectric constant of about 2), can be achieved by decorating the surface of each particle of the solute with molecules (surfactants) containing flexible, brush-like chains2, 5. Here we report a class of colloidal systems in which solute particles (including metals, semiconductors and magnetic materials) form stable colloids in various molten inorganic salts. The stability of such colloids cannot be explained by traditional electrostatic and steric mechanisms. Screening of many solute–solvent combinations shows that colloidal stability can be traced to the strength of chemical bonding at the solute–solvent interface. Theoretical analysis and molecular dynamics modelling suggest that a layer of surface-bound solvent ions produces long-ranged charge-density oscillations in the molten salt around solute particles, preventing their aggregation. Colloids composed of inorganic particles in inorganic melts offer opportunities for introducing colloidal techniques to solid-state science and engineering applications.« less

Unfolding of a model protein on ion exchange and mixed mode chromatography surfaces.

PubMed

Gospodarek, Adrian M; Hiser, Diana E; O'Connell, John P; Fernandez, Erik J

2014-08-15

Recent studies with proteins indicate that conformational changes and aggregation can occur during ion exchange chromatography (IEC). Such behavior is not usually expected, but could lead to decreased yield and product degradation from both IEC and multi mode chromatography (MMC) that has ligands of both hydrophobic and charged functionalities. In this study, we used hydrogen exchange mass spectrometry to investigate unfolding of the model protein BSA on IEC and MMC surfaces under different solution conditions at 25°C. Increased solvent exposure, indicating greater unfolding relative to that in solution, was found for protein adsorbed on cationic IEC and MMC surfaces in the pH range of 3.0 to 4.5, where BSA has decreased stability in solution. There was no effect of anionic surfaces at pH values in the range from 6.0 to 9.0. Differences of solvent exposure of whole molecules when adsorbed and in solution suggest that adsorbed BSA unfolds at lower pH values and may show aggregation, depending upon pH and the surface type. Measurements on digested peptides showed that classifications of stability can be made for various regions; these are generally retained as pH is changed. When salt was added to MMC systems, where electrostatic interactions would be minimized, less solvent exposure was seen, implying that it is the cationic moieties, rather than the hydrophobic ligands, which cause greater surface unfolding at low salt concentrations. These results suggest that proteins of lower stability may exhibit unfolding and aggregation during IEC and MMC separations, as they can with hydrophobic interaction chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

Stereoselective quantitation of mecoprop and dichlorprop in natural waters by supramolecular solvent-based microextraction, chiral liquid chromatography and tandem mass spectrometry.

PubMed

Caballo, C; Sicilia, M D; Rubio, S

2013-01-25

Liquid chromatography (LC)/tandem mass spectrometry (MS/MS) after supramolecular solvent-based microextraction (SUSME) was firstly used in this work for the enantioselective determination of chiral pesticides in natural waters. The method developed for the quantitation of the R- and S-enantiomers of mecoprop (MCPP) and dichlorprop (DCPP) involved the extraction of the herbicides in a supramolecular solvent (SUPRAS) made up of reverse aggregates of dodecanoic acid (DoA), analyte re-extraction in acetate buffer (pH = 5.0), separation of the target enantiomers on a chiral column of permethylated α-cyclodextrin under isocratic conditions, and detection of the daughter ions (m/z = 140.9 and 160.6 for MCPP and DCPP, respectively) using a hybrid triple quadrupole mass spectrometer equipped with an electrospray source operating in the negative ion mode. Similar recoveries (ca. 75%) and actual concentration factors (ca. 94) were obtained for both phenoxypropanoic acids (PPAs). The quantitation limits were 1 ng L(-1) for R- and S-MCPP, and 4 ng L(-1) for R- and S-DCPP, and the precision, expressed as relative standard deviation (n = 6) was in the ranges 2.4-2.7% ([R-MCPP] = [S-MCPP] = 5 ng L(-1) and [R-DCPP] = [S-DCPP] = 15 ng L(-1)) and 1.6-1.8% (100 ng L(-1) of each enantiomer). The SUSME-LC-MS/MS method was successfully applied to the determination of the enantiomers of MCPP and DCPP in river and underground waters, fortified at concentrations between 15 and 180 ng L(-1) at variable enantiomeric ratios (ER = 1-9). Copyright © 2012 Elsevier B.V. All rights reserved.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Safe battery solvents

DOEpatents

Harrup, Mason K.; Delmastro, Joseph R.; Stewart, Frederick F.; Luther, Thomas A.

2007-10-23

An ion transporting solvent maintains very low vapor pressure, contains flame retarding elements, and is nontoxic. The solvent in combination with common battery electrolyte salts can be used to replace the current carbonate electrolyte solution, creating a safer battery. It can also be used in combination with polymer gels or solid polymer electrolytes to produce polymer batteries with enhanced conductivity characteristics. The solvents may comprise a class of cyclic and acyclic low molecular weight phosphazenes compounds, comprising repeating phosphorus and nitrogen units forming a core backbone and ion-carrying pendent groups bound to the phosphorus. In preferred embodiments, the cyclic phosphazene comprises at least 3 phosphorus and nitrogen units, and the pendent groups are polyethers, polythioethers, polyether/polythioethers or any combination thereof, and/or other groups preferably comprising other atoms from Group 6B of the periodic table of elements.

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

PubMed

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Metal retention in human transferrin: consequences of solvent composition in analytical sample preparation methods.

PubMed

Quarles, C Derrick; Randunu, K Manoj; Brumaghim, Julia L; Marcus, R Kenneth

2011-10-01

The analysis of metal-binding proteins requires careful sample manipulation to ensure that the metal-protein complex remains in its native state and the metal retention is preserved during sample preparation or analysis. Chemical analysis for the metal content in proteins typically involves some type of liquid chromatography/electrophoresis separation step coupled with an atomic (i.e., inductively coupled plasma-optical emission spectroscopy or -mass spectrometry) or molecular (i.e., electrospray ionization-mass spectrometry) analysis step that requires altered-solvent introduction techniques. UV-VIS absorbance is employed here to monitor the iron content in human holo-transferrin (Tf) under various solvent conditions, changing polarity, pH, ionic strength, and the ionic and hydrophobic environment of the protein. Iron loading percentages (i.e. 100% loading equates to 2 Fe(3+):1 Tf) were quantitatively determined to evaluate the effect of solvent composition on the retention of Fe(3+) in Tf. Maximum retention of Fe(3+) was found in buffered (20 mM Tris) solutions (96 ± 1%). Exposure to organic solvents and deionized H(2)O caused release of ~23-36% of the Fe(3+) from the binding pocket(s) at physiological pH (7.4). Salt concentrations similar to separation conditions used for ion exchange had little to no effect on Fe(3+) retention in holo-Tf. Unsurprisingly, changes in ionic strength caused by additions of guanidine HCl (0-10 M) to holo-Tf resulted in unfolding of the protein and loss of Fe(3+) from Tf; however, denaturing and metal loss was found not to be an instantaneous process for additions of 1-5 M guanidinium to Tf. In contrast, complete denaturing and loss of Fe(3+) was instantaneous with ≥6 M additions of guanidinium, and denaturing and loss of iron from Tf occurred in parallel proportions. Changes to the hydrophobicity of Tf (via addition of 0-14 M urea) had less effect on denaturing and release of Fe(3+) from the Tf binding pocket compared to changes in ionic strength. This journal is © The Royal Society of Chemistry 2011

Citropin 1.1 Trifluoroacetate to Chloride Counter-Ion Exchange in HCl-Saturated Organic Solutions: An Alternative Approach.

PubMed

Sikora, Karol; Neubauer, Damian; Jaśkiewicz, Maciej; Kamysz, Wojciech

2018-01-01

In view of the increasing interest in peptides in various market sectors, a stronger emphasis on topics related to their production has been seen. Fmoc-based solid phase peptide synthesis, although being fast and efficient, provides final products with significant amounts of trifluoroacetate ions in the form of either a counter-ion or an unbound impurity. Because of the proven toxicity towards cells and peptide activity inhibition, ion exchange to more biocompatible one is purposeful. Additionally, as most of the currently used counter-ion exchange techniques are time-consuming and burdened by peptide yield reduction risk, development of a new approach is still a sensible solution. In this study, we examined the potential of peptide counter-ion exchange using non-aqueous organic solvents saturated with HCl. Counter-ion exchange of a model peptide, citropin 1.1 (GLFDVIKKVASVIGGL-NH 2 ), for each solvent was conducted through incubation with subsequent evaporation under reduced pressure, dissolution in water and lyophilization. Each exchange was performed four times and compared to a reference method-lyophilization of the peptide from an 0.1 M HCl solution. The results showed superior counter-ion exchange efficiency for most of the organic solutions in relation to the reference method. Moreover, HCl-saturated acetonitrile and tert -butanol provided a satisfying exchange level after just one repetition. Thus, those two organic solvents can be potentially introduced into routine peptide counter-ion exchange.

Potential of mean force for ion pairs in non-aqueous solvents. Comparison of polarizable and non-polarizable MD simulations

NASA Astrophysics Data System (ADS)

Odinokov, A. V.; Leontyev, I. V.; Basilevsky, M. V.; Petrov, N. Ch.

2011-01-01

Potentials of mean force (PMF) are calculated for two model ion pairs in two non-aqueous solvents. Standard non-polarizable molecular dynamics simulation (NPMD) and approximate polarizable simulation (PMD) are implemented and compared as tools for monitoring PMF profiles. For the polar solvent (dimethylsulfoxide, DMSO) the PMF generated in terms of the NPMD reproduces fairly well the refined PMD-PMF profile. For the non-polar solvent (benzene) the conventional NPMD computation proves to be deficient. The validity of the correction found in terms of the approximate PMD approach is verified by its comparison with the result of the explicit PMD computation in benzene. The shapes of the PMF profiles in DMSO and in benzene are quite different. In DMSO, owing to dielectric screening, the PMF presents a flat plot with a shallow minimum positioned in the vicinity of the van der Waals contact of the ion pair. For the benzene case, the observed minimum proves to be unexpectedly deep, which manifests the formation of a tightly-binded contact ion pair. This remarkable effect arises owing to the strong electrostatic interaction that is incompletely screened by a non-polar medium. The PMFs for the binary benzene/DMSO mixtures display intermediate behaviour depending on the DMSO content.

[CuCl(n)](2-n) ion-pair species in 1-ethyl-3-methylimidazolium chloride ionic liquid-water mixtures: ultraviolet-visible, X-ray absorption fine structure, and density functional theory characterization.

PubMed

Li, Guosheng; Camaioni, Donald M; Amonette, James E; Zhang, Z Conrad; Johnson, Timothy J; Fulton, John L

2010-10-07

We studied the coordination environment about Cu(II) in a pure ionic liquid, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), and in binary mixtures of this compound with water across the entire range of compositions, using a combination of X-ray absorption fine structure (XAFS), ultraviolet-visible (UV-vis) spectroscopy, and electronic structure calculations. Our results show a series of stages in the ion pairing of the divalent cation, Cu(II), including the contact ion pairing of Cu(2+) with multiple Cl(-) ligands to form various CuCl(n)((2-n)) polyanions, as well as the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM(+) cation. Ion-pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen-bond network in [EMIM]Cl-water mixtures. The CuCl(4)(2-) species dominates in the [EMIM]Cl solvent, and calculations along with spectroscopy show that its geometry distorts to C(2) symmetry compared to D(2d) in the gas phase. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.

Process for enhancing the value of hydrocabonaceous natural recources

DOEpatents

Bunger, James W.; Cogswell, Donald E.

2005-04-05

A process for upgrading hydrocarbonaceous oil containing heteroatom-containing compounds where the hydrocarbonaceous oil is contacted with a solvent system that is a mixture of a major portion of a polar solvent having a dipole moment greater than about 1 debye and a minor portion of water to selectively separate the constituents of the carbonaceous oil into a heteroatom-depleted raffinate fraction and heteroatom-enriched extract fraction. The polar solvent and the water-in-solvent system are formulated at a ratio where the water is an antisolvent in an amount to inhibit solubility of heteroatom-containing compounds and the polar solvent in the raffinate, and to inhibit solubility of non-heteroatom-containing compounds in the extract. The ratio of the hydrocarbonaceous oil to the solvent system is such that a coefficient of separation is at least 50%. The coefficient of separation is the mole percent of heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction minus the mole percent of non-heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction. The solvent-free extract and the raffinate concentrates may be used directly or processed to make valuable petroleum, chemical or industrial products.

Computational solvent system screening for the separation of tocopherols with centrifugal partition chromatography using deep eutectic solvent-based biphasic systems.

PubMed

Bezold, Franziska; Weinberger, Maria E; Minceva, Mirjana

2017-03-31

Tocopherols are a class of molecules with vitamin E activity. Among those, α-tocopherol is the most important vitamin E source in the human diet. The purification of tocopherols involving biphasic liquid systems can be challenging since these vitamins are poorly soluble in water. Deep eutectic solvents (DES) can be used to form water-free biphasic systems and have already proven applicable for centrifugal partition chromatography separations. In this work, a computational solvent system screening was performed using the predictive thermodynamic model COSMO-RS. Liquid-liquid equilibria of solvent systems composed of alkanes, alcohols and DES, as well as partition coefficients of α-tocopherol, β-tocopherol, γ-tocopherol, and σ-tocopherol in these biphasic solvent systems were calculated. From the results the best suited biphasic solvent system, namely heptane/ethanol/choline chloride-1,4-butanediol, was chosen and a batch injection of a tocopherol mixture, mainly consisting of α- and γ-tocopherol, was performed using a centrifugal partition chromatography set up (SCPE 250-BIO). A separation factor of 1.74 was achieved for α- and γ-tocopherol. Copyright © 2017 Elsevier B.V. All rights reserved.

Kinetics of Polymer-Fullerene Phase Separation during Solvent Annealing Studied by Table-Top X-ray Scattering.

PubMed

Vegso, Karol; Siffalovic, Peter; Jergel, Matej; Nadazdy, Peter; Nadazdy, Vojtech; Majkova, Eva

2017-03-08

Solvent annealing is an efficient way of phase separation in polymer-fullerene blends to optimize bulk heterojunction morphology of active layer in polymer solar cells. To track the process in real time across all relevant stages of solvent evaporation, laboratory-based in situ small- and wide-angle X-ray scattering measurements were applied simultaneously to a model P3HT:PCBM blend dissolved in dichlorobenzene. The PCBM molecule agglomeration starts at ∼7 wt % concentration of solid content of the blend in solvent. Although PCBM agglomeration is slowed-down at ∼10 wt % of solid content, the rate constant of phase separation is not changed, suggesting agglomeration and reordering of P3HT molecular chains. Having the longest duration, this stage most affects BHJ morphology. Phase separation is accelerated rapidly at concentration of ∼25 wt %, having the same rate constant as the growth of P3HT crystals. P3HT crystallization is driving force for phase separation at final stages before a complete solvent evaporation, having no visible temporal overlap with PCBM agglomeration. For the first time, such a study was done in laboratory demonstrating potential of the latest generation table-top high-brilliance X-ray source as a viable alternative before more sophisticated X-ray scattering experiments at synchrotron facilities are performed.

Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries

NASA Astrophysics Data System (ADS)

Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

2016-03-01

Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution.

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

PubMed Central

Athanassiadis, Basil

2017-01-01

Calcium hydroxide pastes have been used in endodontics since 1947. Most current calcium hydroxide endodontic pastes use water as the vehicle, which limits the dissolution of calcium hydroxide that can be achieved and, thereby, the maximum pH that can be achieved within the root canal system. Using polyethylene glycol as a solvent, rather than water, can achieve an increase in hydroxyl ions release compared to water or saline. By adopting non-aqueous solvents such as the polyethylene glycols (PEG), greater dissolution and faster hydroxyl ion release can be achieved, leading to enhanced antimicrobial actions, and other improvements in performance and biocompatibility. PMID:29065542

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Properties of cupric ions in benzylamine oxidase from pig plasma as studied by magnetic-resonance and kinetic methods.

PubMed Central

Barker, R; Boden, N; Cayley, G; Charlton, S C; Henson, R; Holmes, M C; Kelly, I D; Knowles, P F

1979-01-01

Benzylamine oxidase from pig plasma has been studied by a variety of chemical and physical techniques. 1. Analytical ultracentrifugation, gel electrophoresis and isoelectric-focusing studies suggest that the enzyme is composed of two subunits with closely similar primary structures. 2. E.s.r. and n.m.r. measurements show that the enzyme contains two well-separated (greater than 0.6 nm) Cu2+ ions at chemically distinct sites. Each Cu2+ ion is coordinated by two water molecules, one 'axial' and the other 'equatorial'. Both water molecules undergo fast exchange (10(5)--10(8) s-1) with solvent and are deprotonated in the pH range 8--9, but only the equatorial water molecule is displaced by the inhibitors N3- and CN-. 3. Kinetic and e.s.r. measurements show that azide and cyanide compete against O2 binding and also make the two Cu2+ sites identical. It is concluded that Cu2+ must participate in the re-oxidation of reduced enzyme by molecular O2. PMID:218560

Anisotropic solvent model of the lipid bilayer. 1. Parameterization of long-range electrostatics and first solvation shell effects.

PubMed

Lomize, Andrei L; Pogozheva, Irina D; Mosberg, Henry I

2011-04-25

A new implicit solvation model was developed for calculating free energies of transfer of molecules from water to any solvent with defined bulk properties. The transfer energy was calculated as a sum of the first solvation shell energy and the long-range electrostatic contribution. The first term was proportional to solvent accessible surface area and solvation parameters (σ(i)) for different atom types. The electrostatic term was computed as a product of group dipole moments and dipolar solvation parameter (η) for neutral molecules or using a modified Born equation for ions. The regression coefficients in linear dependencies of solvation parameters σ(i) and η on dielectric constant, solvatochromic polarizability parameter π*, and hydrogen-bonding donor and acceptor capacities of solvents were optimized using 1269 experimental transfer energies from 19 organic solvents to water. The root-mean-square errors for neutral compounds and ions were 0.82 and 1.61 kcal/mol, respectively. Quantification of energy components demonstrates the dominant roles of hydrophobic effect for nonpolar atoms and of hydrogen-bonding for polar atoms. The estimated first solvation shell energy outweighs the long-range electrostatics for most compounds including ions. The simplicity and computational efficiency of the model allows its application for modeling of macromolecules in anisotropic environments, such as biological membranes.

Ionization Suppression and Recovery in Direct Biofluid Analysis Using Paper Spray Mass Spectrometry

NASA Astrophysics Data System (ADS)

Vega, Carolina; Spence, Corina; Zhang, Chengsen; Bills, Brandon J.; Manicke, Nicholas E.

2016-04-01

Paper spray mass spectrometry is a method for the direct analysis of biofluid samples in which extraction of analytes from dried biofluid spots and electrospray ionization occur from the paper on which the dried sample is stored. We examined matrix effects in the analysis of small molecule drugs from urine, plasma, and whole blood. The general method was to spike stable isotope labeled analogs of each analyte into the spray solvent, while the analyte itself was in the dried biofluid. Intensity of the labeled analog is proportional to ionization efficiency, whereas the ratio of the analyte intensity to the labeled analog in the spray solvent is proportional to recovery. Ion suppression and recovery were found to be compound- and matrix-dependent. Highest levels of ion suppression were obtained for poor ionizers (e.g., analytes lacking basic aliphatic amine groups) in urine and approached -90%. Ion suppression was much lower or even absent for good ionizers (analytes with aliphatic amines) in dried blood spots. Recovery was generally highest in urine and lowest in blood. We also examined the effect of two experimental parameters on ion suppression and recovery: the spray solvent and the sample position (how far away from the paper tip the dried sample was spotted). Finally, the change in ion suppression and analyte elution as a function of time was examined by carrying out a paper spray analysis of dried plasma spots for 5 min by continually replenishing the spray solvent.

A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

PubMed Central

Krakowiak, Joanna; Lundberg, Daniel

2012-01-01

The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands. PMID:22950803

Rapid characterization of lithium ion battery electrolytes and thermal aging products by low-temperature plasma ambient ionization high-resolution mass spectrometry.

PubMed

Vortmann, Britta; Nowak, Sascha; Engelhard, Carsten

2013-03-19

Lithium ion batteries (LIBs) are key components for portable electronic devices that are used around the world. However, thermal decomposition products in the battery reduce its lifetime, and decomposition processes are still not understood. In this study, a rapid method for in situ analysis and reaction monitoring in LIB electrolytes is presented based on high-resolution mass spectrometry (HR-MS) with low-temperature plasma probe (LTP) ambient desorption/ionization for the first time. This proof-of-principle study demonstrates the capabilities of ambient mass spectrometry in battery research. LTP-HR-MS is ideally suited for qualitative analysis in the ambient environment because it allows direct sample analysis independent of the sample size, geometry, and structure. Further, it is environmental friendly because it eliminates the need of organic solvents that are typically used in separation techniques coupled to mass spectrometry. Accurate mass measurements were used to identify the time-/condition-dependent formation of electrolyte decomposition compounds. A LIB model electrolyte containing ethylene carbonate and dimethyl carbonate was analyzed before and after controlled thermal stress and over the course of several weeks. Major decomposition products identified include difluorophosphoric acid, monofluorophosphoric acid methyl ester, monofluorophosphoric acid dimethyl ester, and hexafluorophosphate. Solvents (i.e., dimethyl carbonate) were partly consumed via an esterification pathway. LTP-HR-MS is considered to be an attractive method for fundamental LIB studies.

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang, Liem X.; Chang, Tsun-Mei

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li +(aq) and the kinetics of ion pairings in lithium-ion batteries (LIB). We report one of the first computer simulations of the exchange dynamics around hydrated Li + in acetonitrile (ACN), which is common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li +-[BF 4] and Li +-[PF 6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells aroundmore » Li +(aq). We calculate exchange rates using transition state theory and weighted them with transmission coefficients determined by the reactive flux and Impey, Madden, and McDonald approaches and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li +-[BF 4] and Li +-[PF 6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.« less

Differential Cationization of Fatty Acids with Monovalent Cations Studied by ESI-MS/MS and Computational Approach.

PubMed

Sudarshana Reddy, B; Pavankumar, P; Sridhar, L; Saha, Soumen; Narahari Sastry, G; Prabhakar, S

2018-04-24

The intercellular and intracellular transport of charged species (Na + /K + ) entail interaction of the ions with neutral organic molecules and formation of adduct ions. The rate of transport of the ions across the cell membrane(s) may depend on the stability of the adduct ions, which in turn rely on structural aspects of the organic molecules that interact with the ions. Positive ion ESI mass spectra were recorded for the solutions containing fatty acids (FAs) and monovalent cations (X=Li + , Na + , K + , Rb + and Cs + ). Product ion spectra of the [FA+X] + ions were recorded at different collision energies. Theoretical studies were exploited under both gas phase and solvent phase to investigate the structural effects of the fatty acids during cationization. Stability of [FA+X] + adduct ions were further estimated by means of AIM topological analyses and interaction energy (IE) values. Positive ion ESI-MS analyses of the solution of FAs and X + ions showed preferential binding of the K + ions to FAs. The K + ion binding increased with the increase in number of double bonds of FAs, while decreased with increase in the number of carbons of FAs. Dissociation curves of [FA+X] + ions indicated the relative stability order of the [FA+X] + ions and it was in line with the observed trends in ESI-MS. The solvent phase computational studies divulged the mode of binding and the binding efficiencies of different FAs with monovalent cations. Among the studied monovalent cations, the cationization of FAs follow the order K + >Na + >Li + >Rb + >Cs + . The docosahexaenoic acid showed high efficiency in binding with K + ion. The K + ion binding efficiency of FAs depends on the number of double bonds in unsaturated FAs and the carbon chain length in saturated FAs. The cationization trends of FAs obtained from the ESI-MS, ESI-MS/MS analyses were in good agreement with solvent phase computational studies. This article is protected by copyright. All rights reserved.

Pervaporation and Vapor Permeation Tutorial: Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

EPA Science Inventory

Pervaporation and vapor permeation are membrane-based processes proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol or butanol recovery from fermentation broths, solvent/biofuel dehydration to meet ...

Pervaporation & Vapor Permeation Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

EPA Science Inventory

Pervaporation and vapor permeation are membrane-based processes which have been proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol or butanol recovery from dilute fermentation broths, solvent/biofu...

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Performance of thermally-chargeable supercapacitors in different solvents.

PubMed

Lim, Hyuck; Zhao, Cang; Qiao, Yu

2014-07-07

The influence of solvent on the temperature sensitivity of the electrode potential of thermally-chargeable supercapacitors (TCSs) is investigated. For large electrodes, the output voltage is positively correlated with the dielectric constant of solvent. When nanoporous carbon electrodes are used, different characteristics of system performance are observed, suggesting that possible size effects must be taken into consideration when the solvent molecules and solvated ions are confined in a nanoenvironment.

Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

DOEpatents

Turner, Terry D.; Beller, Laurence S.; Clark, Michael L.; Klingler, Kerry M.

1997-01-01

A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus are also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container.

Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

DOEpatents

Turner, T.D.; Beller, L.S.; Clark, M.L.; Klingler, K.M.

1997-10-14

A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: (a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; (b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; (c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and (d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus is also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container. 8 figs.

Qualitative and quantitative evaluation of solvent systems for countercurrent separation.

PubMed

Friesen, J Brent; Ahmed, Sana; Pauli, Guido F

2015-01-16

Rational solvent system selection for countercurrent chromatography and centrifugal partition chromatography technology (collectively known as countercurrent separation) studies continues to be a scientific challenge as the fundamental questions of comparing polarity range and selectivity within a solvent system family and between putative orthogonal solvent systems remain unanswered. The current emphasis on metabolomic investigations and analysis of complex mixtures necessitates the use of successive orthogonal countercurrent separation (CS) steps as part of complex fractionation protocols. Addressing the broad range of metabolite polarities demands development of new CS solvent systems with appropriate composition, polarity (π), selectivity (σ), and suitability. In this study, a mixture of twenty commercially available natural products, called the GUESSmix, was utilized to evaluate both solvent system polarity and selectively characteristics. Comparisons of GUESSmix analyte partition coefficient (K) values give rise to a measure of solvent system polarity range called the GUESSmix polarity index (GUPI). Solvatochromic dye and electrical permittivity measurements were also evaluated in quantitatively assessing solvent system polarity. The relative selectivity of solvent systems were evaluated with the GUESSmix by calculating the pairwise resolution (αip), the number of analytes found in the sweet spot (Nsw), and the pairwise resolution of those sweet spot analytes (αsw). The combination of these parameters allowed for both intra- and inter-family comparison of solvent system selectivity. Finally, 2-dimensional reciprocal shifted symmetry plots (ReSS(2)) were created to visually compare both the polarities and selectivities of solvent system pairs. This study helps to pave the way to the development of new solvent systems that are amenable to successive orthogonal CS protocols employed in metabolomic studies. Copyright © 2014 Elsevier B.V. All rights reserved.

Simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma by liquid chromatography-tandem mass spectrometry with positive/negative ion-switching electrospray ionization and its application in pharmacokinetic study.

PubMed

Zhu, He; Ding, Li; Shakya, Shailendra; Qi, Xiemin; Hu, Linlin; Yang, Xiaolin; Yang, Zhonglin

2011-11-15

A new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method operated in the positive/negative electrospray ionization (ESI) switching mode has been developed and validated for the simultaneous determination of asperosaponin VI and its active metabolite hederagenin in rat plasma. After addition of internal standards diazepam (for asperosaponin VI) and glycyrrhetic acid (for hederagenin), the plasma sample was deproteinized with acetonitrile, and separated on a reversed phase C18 column with a mobile phase of methanol (solvent A)-0.05% glacial acetic acid containing 10 mM ammonium acetate and 30 μM sodium acetate (solvent B) using gradient elution. The detection of target compounds was done in multiple reaction monitoring (MRM) mode using a tandem mass spectrometry equipped with positive/negative ion-switching ESI source. At the first segment, the MRM detection was operated in the positive ESI mode using the transitions of m/z 951.5 ([M+Na](+))→347.1 for asperosaponin VI and m/z 285.1 ([M+H](+))→193.1 for diazepam for 4 min, then switched to the negative ESI mode using the transitions of m/z 471.3 ([M-H](-))→471.3 for hederagenin and m/z 469.4 ([M-H](-))→425.4 for glycyrrhetic acid, respectively. The sodiated molecular ion [M+Na](+) at m/z 951.5 was selected as the precursor ion for asperosaponin VI, since it provided better sensitivity compared to the deprotonated and protonated molecular ions. Sodium acetate was added to the mobile phase to make sure that abundant amount of the sodiated molecular ion of asperosaponin VI could be produced, and more stable and intensive mass response of the product ion could be obtained. For the detection of hederagenin, since all of the mass responses of the fragment ions were very weak, the deprotonated molecular ion [M-H](-)m/z 471.3 was employed as both the precursor ion and the product ion. But the collision energy was still used for the MRM, in order to eliminate the influences induced by the interference substances from the rat plasma. The validated method was successfully applied to study the pharmacokinetics of asperosaponin VI and its active metabolite hederagenin in rat plasma after oral administration of asperosaponin VI at a dose of 90 mg/kg. Copyright © 2011 Elsevier B.V. All rights reserved.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

Anomalous Protein-Protein Interactions in Multivalent Salt Solution.

PubMed

Pasquier, Coralie; Vazdar, Mario; Forsman, Jan; Jungwirth, Pavel; Lund, Mikael

2017-04-13

The stability of aqueous protein solutions is strongly affected by multivalent ions, which induce ion-ion correlations beyond the scope of classical mean-field theory. Using all-atom molecular dynamics (MD) and coarse grained Monte Carlo (MC) simulations, we investigate the interaction between a pair of protein molecules in 3:1 electrolyte solution. In agreement with available experimental findings of "reentrant protein condensation", we observe an anomalous trend in the protein-protein potential of mean force with increasing electrolyte concentration in the order: (i) double-layer repulsion, (ii) ion-ion correlation attraction, (iii) overcharge repulsion, and in excess of 1:1 salt, (iv) non Coulombic attraction. To efficiently sample configurational space we explore hybrid continuum solvent models, applicable to many-protein systems, where weakly coupled ions are treated implicitly, while strongly coupled ones are treated explicitly. Good agreement is found with the primitive model of electrolytes, as well as with atomic models of protein and solvent.

Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.

2015-01-28

Random copolymers of isoprene and 4-vinylbenzyl chloride (VBCl) with varying compositions were synthesized via nitroxide-mediated polymerization. Subsequent quaternization afforded solvent processable and cross-linkable ionomers with a wide range of ion exchange capacities (IECs). Solution cast membranes were thermally cross-linked to form anion exchange membranes. Cross-linking was achieved by taking advantage of the unsaturations on the polyisoprene backbone, without added cross-linkers. A strong correlation was found between water uptake and ion conductivity of the membranes: conductivities of the membranes with IECs beyond a critical value were found to be constant related to their high water absorption. Environmentally controlled small-angle X-ray scatteringmore » experiments revealed a correlation between the average distance between ionic clusters and the ion conductivity, indicating that a well-connected network of ion clusters is necessary for efficient ion conduction and high ion conductivity.« less

Diffusional Motion of Redox Centers in Carbonate Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Kee Sung; Rajput, Nav Nidhi; Wei, Xiaoliang

2014-09-14

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self diffusion coefficents (D) of solutes and solvents were measured by 1H and 19F pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC) and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0-50 °C and for various concentrations (0.25 - 1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increasedmore » in all solvents. Since the peaks for the two ions (Fc1N212 and TFSI) are separated in one-dimensional NMR spectra, separate diffusion coefficients could be measured and DTFSI is larger than DFc1N112 in all samples measured. The EC, PC and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC and EMC. A difference in D (DPC < DEC < DEMC), and both a higher Ea for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112+, which is a relatively stronger interaction than that between Fc1N112+ and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that DPC = DEC = DEMC and Fc1N112+ and all components of the EC/PC/EMC solution have the same Ea for translational motion, while the ratio DEC/PC/EMC/DFc1N112+ is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112+ transference numbers lie around 0.4 and increases slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.« less

Use of once-through treat gas to remove the heat of reaction in solvent hydrogenation processes

DOEpatents

Nizamoff, Alan J.

1980-01-01

In a coal liquefaction process wherein feed coal is contacted with molecular hydrogen and a hydrogen-donor solvent in a liquefaction zone to form coal liquids and vapors and coal liquids in the solvent boiling range are thereafter hydrogenated to produce recycle solvent and liquid products, the improvement which comprises separating the effluent from the liquefaction zone into a hot vapor stream and a liquid stream; cooling the entire hot vapor stream sufficiently to condense vaporized liquid hydrocarbons; separating condensed liquid hydrocarbons from the cooled vapor; fractionating the liquid stream to produce coal liquids in the solvent boiling range; dividing the cooled vapor into at least two streams; passing the cooling vapors from one of the streams, the coal liquids in the solvent boiling range, and makeup hydrogen to a solvent hydrogenation zone, catalytically hydrogenating the coal liquids in the solvent boiling range and quenching the hydrogenation zone with cooled vapors from the other cooled vapor stream.

A dispersive liquid--liquid microextraction methodology for copper (II) in environmental samples prior to determination using microsample injection flame atomic absorption spectrometry.

PubMed

Alothman, Zeid A; Habila, Mohamed; Yilmaz, Erkan; Soylak, Mustafa

2013-01-01

A simple, environmentally friendly, and efficient dispersive liquid-liquid microextraction method combined with microsample injection flame atomic absorption spectrometry was developed for the separation and preconcentration of Cu(II). 2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-PADAP) was used to form a hydrophobic complex of Cu(II) ions in the aqueous phase before extraction. To extract the Cu(II)-5-Br-PADAP complex from the aqueous phase to the organic phase, 2.0 mL of acetone as a disperser solvent and 200 microL of chloroform as an extraction solvent were used. The influences of important analytical parameters, such as the pH, types and volumes of the extraction and disperser solvents, amount of chelating agent, sample volume, and matrix effects, on the microextraction procedure were evaluated and optimized. Using the optimal conditions, the LOD, LOQ, preconcentration factor, and RSD were determined to be 1.4 microg/L, 4.7 microg/L, 120, and 6.5%, respectively. The accuracy of the proposed method was investigated using standard addition/recovery tests. The analysis of certified reference materials produced satisfactory analytical results. The developed method was applied for the determination of Cu in real samples.

Electrostatic Solvation Energy for Two Oppositely Charged Ions in a Solvated Protein System: Salt Bridges Can Stabilize Proteins

PubMed Central

Gong, Haipeng; Freed, Karl F.

2010-01-01

Abstract Born-type electrostatic continuum methods have been an indispensable ingredient in a variety of implicit-solvent methods that reduce computational effort by orders of magnitude compared to explicit-solvent MD simulations and thus enable treatment using larger systems and/or longer times. An analysis of the limitations and failures of the Born approaches serves as a guide for fundamental improvements without diminishing the importance of prior works. One of the major limitations of the Born theory is the lack of a liquidlike description of the response of solvent dipoles to the electrostatic field of the solute and the changes therein, a feature contained in the continuum Langevin-Debye (LD) model applied here to investigate how Coulombic interactions depend on the location of charges relative to the protein/water boundary. This physically more realistic LD model is applied to study the stability of salt bridges. When compared head to head using the same (independently measurable) physical parameters (radii, dielectric constants, etc.), the LD model is in good agreement with observations, whereas the Born model is grossly in error. Our calculations also suggest that a salt bridge on the protein's surface can be stabilizing when the charge separation is ≤4 Å. PMID:20141761

Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

PubMed

Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

2009-05-07

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G, M05-2X/6-31+G, M05-2X/cc-pVTZ, B3LYP/6-31G, and HF/6-31G. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marenich, Aleksandr; Cramer, Christopher J; Truhlar, Donald G

2009-04-30

We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the “D” stands for “density” to denote that the full solute electron density is used without defining partial atomic charges. “Continuum” denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where “universal” denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which amore » few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous organic solvents and water), and 143 transfer free energies for 93 neutral solutes between water and 15 organic solvents. The elements present in the solutes are H, C, N, O, F, Si, P, S, Cl, and Br. The SMD model employs a single set of parameters (intrinsic atomic Coulomb radii and atomic surface tension coefficients) optimized over six electronic structure methods: M05-2X/MIDI!6D, M05-2X/6-31G*, M05-2X/6-31+G**, M05-2X/cc-pVTZ, B3LYP/6-31G*, and HF/6-31G*. Although the SMD model has been parametrized using the IEF-PCM protocol for bulk electrostatics, it may also be employed with other algorithms for solving the nonhomogeneous Poisson equation for continuum solvation calculations in which the solute is represented by its electron density in real space. This includes, for example, the conductor-like screening algorithm. With the 6-31G* basis set, the SMD model achieves mean unsigned errors of 0.6-1.0 kcal/mol in the solvation free energies of tested neutrals and mean unsigned errors of 4 kcal/mol on average for ions with either Gaussian03 or GAMESS.« less

Electrode-Electrolyte Interfaces in Lithium-Sulfur Batteries with Liquid or Inorganic Solid Electrolytes.

PubMed

Yu, Xingwen; Manthiram, Arumugam

2017-11-21

Electrode-electrolyte interfacial properties play a vital role in the cycling performance of lithium-sulfur (Li-S) batteries. The issues at an electrode-electrolyte interface include electrochemical and chemical reactions occurring at the interface, formation mechanism of interfacial layers, compositional/structural characteristics of the interfacial layers, ionic transport across the interface, and thermodynamic and kinetic behaviors at the interface. Understanding the above critical issues is paramount for the development of strategies to enhance the overall performance of Li-S batteries. Liquid electrolytes commonly used in Li-S batteries bear resemblance to those employed in traditional lithium-ion batteries, which are generally composed of a lithium salt dissolved in a solvent matrix. However, due to a series of unique features associated with sulfur or polysulfides, ether-based solvents are generally employed in Li-S batteries rather than simply adopting the carbonate-type solvents that are generally used in the traditional Li + -ion batteries. In addition, the electrolytes of Li-S batteries usually comprise an important additive, LiNO 3 . The unique electrolyte components of Li-S batteries do not allow us to directly take the interfacial theories of the traditional Li + -ion batteries and apply them to Li-S batteries. On the other hand, during charging/discharging a Li-S battery, the dissolved polysulfide species migrate through the battery separator and react with the Li anode, which magnifies the complexity of the interfacial problems of Li-S batteries. However, current Li-S battery development paths have primarily been energized by advances in sulfur cathodes. Insight into the electrode-electrolyte interfacial behaviors has relatively been overshadowed. In this Account, we first examine the state-of-the-art contributions in understanding the solid-electrolyte interphase (SEI) formed on the Li-metal anode and sulfur cathode in conventional liquid-electrolyte Li-S batteries and how the resulting chemical and physical properties of the SEI affect the overall battery performance. A few strategies recently proposed for improving the stability of SEI are briefly summarized. Solid Li + -ion conductive electrolytes have been attempted for the development of Li-S batteries to eliminate the polysulfide shuttle issues. One approach is based on a concept of "all-solid-state Li-S battery," in which all the cell components are in the solid state. Another approach is based on a "hybrid-electrolyte Li-S battery" concept, in which the solid electrolyte plays roles both as a Li + -ion conductor for the electrochemical reaction and as a separator to prevent polysulfide shuttle. However, these endeavors with the solid electrolyte are not able to provide an overall satisfactory cell performance. In addition to the low ionic conductivity of solid-state electrolytes, a critical issue lies in the poor interfacial properties between the electrode and the solid electrolyte. This Account provides a survey of the relevant research progress in understanding and manipulating the interfaces of electrode and solid electrolytes in both the "all-solid-state Li-S batteries" and the "hybrid-electrolyte Li-S batteries". A recently proposed "semi-solid-state Li-S battery" concept is also briefly discussed. Finally, future research and development directions in all the above areas are suggested.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

Effect of HEH[EHP] impurities on the ALSEP solvent extraction process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holfeltz, Vanessa E.; Campbell, Emily L.; Peterman, Dean R.

In solvent extraction processes, organic phase impurities can negatively impact separation factors, hydrolytic performance, and overall system robustness. This affects the process-level viability of a separation concept and necessitates knowledge of the behavior and mechanisms to control impurities in the solvent. The most widespread way through which impurities are introduced into a system is through impure extractants and/or diluents used to prepare the solvent, and often development of new purification schemes to achieve the desired level of purity is needed. In this work, the acidic extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])—proposed for application in extractive processes aimed at separating trivalentmore » minor actinides from lanthanides and other fission products—is characterized with respect to its common impurities and their impact on Am(III) stripping in the Actinide Lanthanide SEParation (ALSEP) system. To control impurities in HEH[EHP], existing purification technologies commonly applied for the acidic organophosphorus reagents are reviewed, and a new method specific to HEH[EHP] purification is presented.« less

Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

McIntosh, Lucas D.

Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the disordered structure observed in diblock polymer melts near the order-disorder transition. In the resulting solid PEMs, the conductivity and modulus are both high, exceeding the 1 mS/cm and approaching the 1 GPa metrics, respectively, often cited for lithium-metal batteries. In the final chapter, an alternative synthetic route to generate nanostructured PEMs is presented. This strategy relies on the formation of a thermodynamically stable network morphology exhibited by a triblock terpolymer prepared with crosslinking moieties along the backbone. Although the mechanical properties of the resulting PEM are excellent, the conductivity is found to be somewhat limited by network defects that result from the solvent-casting procedure.

Dielectric Studies on Binary Mixtures of Diethyl Ether (DEE) in Polar Solvents

NASA Astrophysics Data System (ADS)

Pradhan, S. K.; Dash, S. K.; Swain, M. D.; Swain, B. B.

2011-11-01

Dielectric constant (ɛ) of diethylether (DEE) in binary mixtures with four polar solvents such as n-butanl, i-butanol, t-butanol and tolune has been measured at 455 kHz and at a temperature 303.15 K. The refractive indices were measured at a regulated temperature by Pulfrich refractometer at sodium D-line. The data is used to evaluate mutual correlation factor gab, excess molar polarization and excess free energy of mixing ΔGab by using Winkelmann-Quitzsch equation for binary mixtures to asses the suitability of the polar solvents as modifiers. The trend of variation for these parameters exhibit marked dependence on the nature of alcohols. Diethylether is one of the solvent extractant used for the extraction and separation of zirconium and hafnium in reactor technology. The extractant is blended with appropriate polar modifiers for greater dispersal and more rapid phase disengagement. This facilitates in the elimination of the third organo-aqueous phase containing some of the metal ions. As such the study of molecular interaction among the component molecules has been undertaken in these binary mixtures using the dielectric route. The interaction parameters such as mutual correlation factor gab is found to be less than one in all alcohols, while it is negative in toluene upto 0.7 DEE molefraction and thereafter becoming positive. The nature of variation of the excess miolar polarization ΔP and excess free energy of mixing Gab tends to support the assessment of gab to choose a suitable polar modifier.

Role of solvent in metal-on-metal surface diffusion: A case for rational solvent selection for materials synthesis

NASA Astrophysics Data System (ADS)

Imandi, Venkataramana; Jagannath, Mantha Sai Pavan; Chatterjee, Abhijit

2018-09-01

The effect of solvent on diffusion at metal surfaces is poorly understood despite its importance to morphological evolution during materials processing, corrosion and catalysis. In this article, we probe the metal-solvent interfacial structure, effective nature of interactions and dynamics when a solvent is in contact with a metal using a novel accelerated molecular dynamics simulation technique called temperature programmed molecular dynamics (TPMD). TPMD simulations reveal that surface diffusion of metal-on-metal can be made to vary over orders-of-magnitude by tuning the metal-solvent interaction. Ultimately, the solvent can have an indirect effect on diffusion. As the solvent tugs at the metal surface the separation between the adsorbed metal atom (adatom) and the surface layer can be modulated via metal-solvent interactions. The resulting adatom-surface separation can cause stronger/weaker binding of the adatom to the metal surface, which in turn results in the observed slower/enhanced diffusion in the presence of solvent. We believe this effect is ubiquitous in pure metal and metal alloys and in principle one could rationally select solvent to control the material structural evolution. Implications on materials synthesis are discussed in the context of formation of nanoporous materials.

Advanced dielectric continuum model of preferential solvation

NASA Astrophysics Data System (ADS)

Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

2009-01-01

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

Diamond, titanium dioxide, titanium silicon oxide, and barium strontium titanium oxide nanoparticles as matrixes for direct matrix-assisted laser desorption/ionization mass spectrometry analysis of carbohydrates in plant tissues.

PubMed

Gholipour, Yousef; Giudicessi, Silvana L; Nonami, Hiroshi; Erra-Balsells, Rosa

2010-07-01

Nanoparticles (NPs) of diamond, titanium dioxide, titanium silicon oxide, barium strontium titanium oxide, and silver (Ag) were examined for their potential as MALDI matrixes for direct laser desorption/ionization of carbohydrates, especially fructans, from plant tissue. Two sample preparation methods including solvent-assisted and solvent-free (dry) NPs deposition were performed and compared. All examined NPs except for Ag could desorb/ionize standard sucrose and fructans in positive and in negative ion mode. Ag NPs yielded good signals only for nonsalt-doped samples that were measured in the negative ion mode. In the case of in vivo studies, except for Ag, all NPs studied could desorb/ionize carbohydrates from tissue in both the positive and negative ion modes. Furthermore, compared to the results obtained with soluble sugars extracted from plant tissues, fructans with higher molecular weight intact molecular ions could be detected when the plant tissues were directly profiled. The limit of detection (LOD) of fructans and the ratios between signal intensities and fructan concentrations were analyzed. NPs had similar LODs for standard fructan triose (1-kestose) in the positive ion mode and better LODs in the negative ion mode when compared with the common crystalline organic MALDI matrixes used for carbohydrates (2,5-dihydroxybenzoic acid and nor-harmane) or carbon nanotubes. Solvent-free NP deposition on tissues partially improves the signal acquisition. Although lower signal-to-noise ratio sugar signals were acquired from the tissues when compared to the solvent-assisted method, the reproducibility averaged over all sample was more uniform.

Ultracapacitor electroyte

DOEpatents

Wei, Chang; LeBlanc, Jr., Oliver Harris; Jerabek, Elihu Calvin

2001-07-03

The invention relates to an ultracapacitor and to a method of making an ultracapacitor. The ultracapacitor of the invention includes two solid, nonporous current collectors, two porous electrodes separating the collectors, a porous separator between the electrodes and an electrolyte occupying the pores in the electrodes and separator. The electrolyte includes a cyclic carbonate solvent, a cyclic ester solvent and an electrolyte salt. The invention also relates to a stack of ultracapacitor cells.

The separation of lanthanides and actinides in supercritical fluid carbon dioxide

DOE PAGES

Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; ...

2015-10-28

Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aines, Roger D; Spadaccini, Christopher M; Stolaroff, Joshuah K

Method and apparatus for separating a target substance from a fluid or mixture. Capsules having a coating and stripping solvents encapsulated in the capsules are provided. The coating is permeable to the target substance. The capsules having a coating and stripping solvents encapsulated in the capsules are exposed to the fluid or mixture. The target substance migrates through the coating and is taken up by the stripping solvents. The target substance is separated from the fluid or mixture by driving off the target substance from the capsules.

Bimodal dielectric relaxation of electrolyte solutions in weakly polar solvents.

PubMed

Yamaguchi, Tsuyoshi; Koda, Shinobu

2014-12-28

The dielectric relaxation spectra of dilute electrolyte solutions in solvents of small dielectric constants are investigated both theoretically and experimentally. The theoretical calculation in our previous work [T. Yamaguchi, T. Matsuoka, and S. Koda, J. Chem. Phys. 135, 164511 (2011)] is reanalyzed, and it is shown that the dielectric relaxation spectra are composed of three components, namely, the relaxation of ionic atmosphere, the reorientational relaxation of ion pairs, and the collision between ions. The relaxation frequency of the slowest one increases with increasing the concentration, and the slower two relaxations, those of ionic atmosphere and ion pairs, merge into one at the concentration where the Debye length is comparable to the size of ions. Experimentally, the dielectric relaxation spectra of some electrolytes in two solvents, tetrahydrofuran and tetraglyme, are determined at frequencies from 300 kHz to 200 MHz, and the presence of the slower two relaxations was confirmed. The concentration dependence of the relaxation frequency is also in harmony with the theoretical calculation. The relationship between the dielectric relaxation spectra and the concentration dependence of the ionic conductivity is discussed.

Bimodal dielectric relaxation of electrolyte solutions in weakly polar solvents

NASA Astrophysics Data System (ADS)

Yamaguchi, Tsuyoshi; Koda, Shinobu

2014-12-01

The dielectric relaxation spectra of dilute electrolyte solutions in solvents of small dielectric constants are investigated both theoretically and experimentally. The theoretical calculation in our previous work [T. Yamaguchi, T. Matsuoka, and S. Koda, J. Chem. Phys. 135, 164511 (2011)] is reanalyzed, and it is shown that the dielectric relaxation spectra are composed of three components, namely, the relaxation of ionic atmosphere, the reorientational relaxation of ion pairs, and the collision between ions. The relaxation frequency of the slowest one increases with increasing the concentration, and the slower two relaxations, those of ionic atmosphere and ion pairs, merge into one at the concentration where the Debye length is comparable to the size of ions. Experimentally, the dielectric relaxation spectra of some electrolytes in two solvents, tetrahydrofuran and tetraglyme, are determined at frequencies from 300 kHz to 200 MHz, and the presence of the slower two relaxations was confirmed. The concentration dependence of the relaxation frequency is also in harmony with the theoretical calculation. The relationship between the dielectric relaxation spectra and the concentration dependence of the ionic conductivity is discussed.

Characteristics of Lithium Ions and Superoxide Anions in EMI-TFSI and Dimethyl Sulfoxide.

PubMed

Jung, Sun-ho; Federici Canova, Filippo; Akagi, Kazuto

2016-01-28

To clarify the microscopic effects of solvents on the formation of the Li(+)-O2(–) process of a Li–O2 battery, we studied the kinetics and thermodynamics of these ions in dimethyl sulfoxide (DMSO) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI) using classical molecular dynamics simulation. The force field for ions–solvents interactions was parametrized by force matching first-principles calculations. Despite the solvation energies of the ions are similar in both solvents, their mobility is much higher in DMSO. The free-energy profiles also confirm that the formation and decomposition rates of Li(+)-O2(–) pairs are greater in DMSO than in EMI-TFSI. Our atomistic simulations point out that the strong structuring of EMI-TFSI around the ions is responsible for these differences, and it explains why the LiO2 clusters formed in DMSO during the battery discharge are larger than those in EMI-TFSI. Understanding the origin of such properties is crucial to aid the optimization of electrolytes for Li–O2 batteries.

Ion pair-based liquid-phase microextraction combined with cuvetteless UV-vis micro-spectrophotometry as a miniaturized assay for monitoring ammonia in waters.

PubMed

Senra-Ferreiro, Sonia; Pena-Pereira, Francisco; Costas-Mora, Isabel; Romero, Vanesa; Lavilla, Isela; Bendicho, Carlos

2011-09-15

A miniaturized method based on liquid-phase microextraction (LPME) in combination with microvolume UV-vis spectrophotometry for monitoring ammonia in waters is proposed. The methodology is based on the extraction of the ion pair formed between the blue indophenol obtained according to the Berthelot reaction and a quaternary ammonium salt into a microvolume of organic solvent. Experimental parameters affecting the LPME performance such as type and concentration of the quaternary ammonium ion salt required to form the ion pair, type and volume of extractant solvent, effect of disperser solvent, ionic strength and extraction time, were optimized. A detection limit of 5.0 μg L(-1) ammonia and an enrichment factor of 30 can be attained after a microextraction time of 4 min. The repeatability, expressed as relative standard deviation, was 7.6% (n=7). The proposed method can be successfully applied to the determination of trace amounts of ammonia in several environmental water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Review of chemical separation techniques applicable to alpha spectrometric measurements

NASA Astrophysics Data System (ADS)

de Regge, P.; Boden, R.

1984-06-01

Prior to alpha-spectrometric measurements several chemical manipulations are usually required to obtain alpha-radiating sources with the desired radiochemical and chemical purity. These include sampling, dissolution or leaching of the elements of interest, conditioning of the solution, chemical separation and preparation of the alpha-emitting source. The choice of a particular method is dependent on different criteria but always involves aspects of the selectivity or the quantitative nature of the separations. The availability of suitable tracers or spikes and modern high resolution instruments resulted in the wide-spread application of isotopic dilution techniques to the problems associated with quantitative chemical separations. This enhanced the development of highly elective methods and reagents which led to important simplifications in the separation schemes. The chemical separation methods commonly used in connection with alpha-spectrometric measurements involve precipitation with selected scavenger elements, solvent extraction, ion exchange and electrodeposition techniques or any combination of them. Depending on the purpose of the final measurement and the type of sample available the chemical separation methods have to be adapted to the particular needs of environment monitoring, nuclear chemistry and metrology, safeguards and safety, waste management and requirements in the nuclear fuel cycle. Against the background of separation methods available in the literature the present paper highlights the current developments and trends in the chemical techniques applicable to alpha spectrometry.

Integration of electrochemistry with ultra-performance liquid chromatography/mass spectrometry.

PubMed

Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A; Chen, Hao

2015-01-01

This study presents the development of ultra-performance liquid chromatography (UPLC) mass spectrometry (MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of proteins/peptides that contain disulfide bonds. In our approach, a protein/peptide mixture sample undergoes a fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and tandem mass spectrometry (MS/MS) analyses. The electrochemical cell is coupled to the mass spectrometer using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, peptides that contain disulfide bonds can be differentiated from those without disulfide bonds, as the former are electroactive and reducible. MS/MS analysis of the disulfide-reduced peptide ions provides increased information on the sequence and disulfide-linkage pattern. In a reactive DESI- MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which will be useful in top- down protein structure MS analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1(~)2 orders of magnitude by using UPLC for the liquid chromatography (LC)/EC/MS platform, in comparison to the previously used high- performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion, and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis.

Integration of Electrochemistry with Ultra Performance Liquid Chromatography/Mass Spectrometry (UPLC/MS)

PubMed Central

Cai, Yi; Zheng, Qiuling; Liu, Yong; Helmy, Roy; Loo, Joseph A.; Chen, Hao

2015-01-01

This study presents the development of ultra-performance liquid chromatography/mass spectrometry (UPLC/MS) combined with electrochemistry (EC) for the first time and its application for the structural analysis of disulfide bond-containing proteins/peptides. In our approach, a protein/peptide mixture sample undergoes fast UPLC separation and subsequent electrochemical reduction in an electrochemical flow cell followed by online MS and MS/MS analyses. The electrochemical cell is coupled to MS using our recently developed desorption electrospray ionization (DESI) interface. Using this UPLC/EC/DESI-MS method, disulfide bond-containing peptides can be differentiated from those without disulfide bonds as the former are electroactive and reducible. Tandem MS analysis of the disulfide-reduced peptide ions provides increased sequence and disulfide linkage pattern information. In a reactive DESI-MS detection experiment in which a supercharging reagent was used to dope the DESI spray solvent, increased charging was obtained for the UPLC-separated proteins. Strikingly, upon online electrolytic reduction, supercharged proteins (e.g., α-lactalbumin) showed even higher charging, which would be useful in top-down protein structure analysis as increased charges are known to promote protein ion dissociation. Also, the separation speed and sensitivity are enhanced by approximately 1~2 orders of magnitude by using UPLC for the LC/EC/MS platform, in comparison to the previously used high performance liquid chromatography (HPLC). This UPLC/EC/DESI-MS method combines the power of fast UPLC separation, fast electrochemical conversion and online MS structural analysis for a potentially valuable tool for proteomics research and bioanalysis. PMID:26307715

Influence of Ionization Source Conditions on the Gas-Phase Protomer Distribution of Anilinium and Related Cations

NASA Astrophysics Data System (ADS)

Attygalle, Athula B.; Xia, Hanxue; Pavlov, Julius

2017-08-01

The gas-phase-ion generation technique and specific ion-source settings of a mass spectrometer influence heavily the protonation processes of molecules and the abundance ratio of the generated protomers. Hitherto that has been attributed primarily to the nature of the solvent and the pH. By utilizing electrospray ionization and ion-mobility mass spectrometry (IM-MS), we demonstrate, even in the seemingly trivial case of protonated aniline, that the protomer ratio strongly depends on the source conditions. Under low in-source ion activation, nearly 100% of the N-protomer of aniline is produced, and it can be subsequently converted to the C-protomer by collisional activation effected by increasing the electrical potential difference between the entrance and exit orifices of the first vacuum region. This activation and transformation process takes place even before the ion is mass-selected and subjected to IM separation. Despite the apparent simplicity of the problem, the preferred protonation site of aniline in the gas phase—the amino group or the aromatic ring—has been a topic of controversy. Our results not only provide unambiguous evidence that ring- and nitrogen-protonated aniline can coexist and be interconverted in the gas phase, but also that the ratio of the protomers depends on the internal energy of the original ion. There are many dynamic ion-transformation and fragmentation processes that take place in the different physical compartments of a Synapt G2 HDMS instrument. Such processes can dramatically change the very identity even of small ions, and therefore should be taken into account when interpreting product-ion mass spectra.

Studies on polar high-speed counter-current chromatographic systems in separation of amaranthine-type betacyanins from Celosia species.

PubMed

Spórna-Kucab, Aneta; Milo, Angelika; Kumorkiewicz, Agnieszka; Wybraniec, Sławomir

2018-01-15

Betacyanins, natural plant pigments exhibiting antioxidant and chemopreventive properties, were extracted from Celosia spicata (Thouars) Spreng. inflorescences and separated by high-speed counter-current chromatography (HSCCC) in two polar solvent systems composed of: TBME - 1-BuOH - ACN - H 2 O (0.7% HFBA, 2:2:1:5, v/v/v/v) (system I) and EtOH - ACN - 1-PrOH - (NH 4 ) 2 SO 4satd.soln - H 2 O (0.5:0.5:0.5:1.2:1, v/v/v/v/v) (system II). The systems were used in the head-to-tail (system I) and tail-to-head (system II) mode. The flow rate of the mobile phase was 2.0 ml/min and the column rotation speed was 860 rpm. The retention of the stationary phase was 73.5% (system I) and 80.0% (system II). For the identification of separated betacyanins in the crude extract as well as in the HSCCC fractions, LC-DAD-ESI-MS/MS analyses were performed. Depending on the target compounds, each of the systems exhibit meaningfully different selectivity and applicability. For the pairs of amaranthines (1/1') and betanins (2/2'), the best choice is the system II, but the acylated amaranthine pairs (3/3' and 4/4') can be resolved only in the ion-pair system I. For the indication of the most suitable solvent system for Celosia plumosa hort., Celosia cristata L. and Celosia spicata (Thouars) Spreng. species, the profiles of betacyanins in different plant parts were studied. Copyright © 2017. Published by Elsevier B.V.

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

Kim, Yu Seung; Lee, Kwan-Soo; Rockward, Tommy Q. T.

2013-03-12

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

Kim, Yu Seung [Los Alamos, NM; Lee, Kwan-Soo [Blacksburg, VA; Rockward, Tommy Q. T. [Rio Rancho, NM

2011-07-19

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Experimental evidence for the participation of deep eutectic solvents in silver chloride crystal formation at low temperature

NASA Astrophysics Data System (ADS)

Bhatt, Jitkumar; Mondal, Dibyendu; Prasad, Kamalesh

2016-05-01

Deep eutectic solvents (DESs) obtained by the complexation of choline chloride (ChoCl) as hydrogen bond acceptor and hydrogen bond donors such as ethylene glycol (ChoCl-EG 1:2) and glycerol (ChoCl-Gly 1:2) were used as media for the formation of AgCl crystals. Although formation of AgCl crystals was observed in both the solvents but the rate of formation of crystals was faster in ChoCl-EG 1:2 at low temperature (4-5 °C). In the crystals, cholinium cations were found to be present with chloride ions bridged with Ag ions resulting generation of 1D network of AgCl2 anions.

Synthesis and the luminescent properties of the Nd3+ ions doped three kinds of fluoride nanocrystals in organic solvents

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Changyong; Bo, Shuhui; Liu, Xinhou; Zhen, Zhen

2015-10-01

Oleic acid (OA)-modified LaF3:Nd, NaYF4:Nd and CaF2:Nd nanocrystals (NCs) with the different Nd3+ ion concentration (2% and 5%) have been prepared. The structure and morphology of NCs were identified by XRD, TEM, FT-IR and TGA. The size of OA-modified NC is a mean diameter of 5-10 nm and can be dispersed in common organic solvents to form a transparent solution. The optical loss of NCs in organic solvent is the first time to discuss in this work. The luminescence properties of NCs were also characterized and studied by fluorescence spectrometer. The nanoparticles in solid and in the solution all exhibited the strong emission at the 1060 nm when the materials were excited around 800 nm. Compared with the LaF3 and CaF2 matrix, NaYF4 as the host can protect the Nd3+ ions more efficiently away from the nonradiative transitions. The longest luminescent lifetime of the solid NaYF4:2%Nd NCs was up to 136 μs, and the little difference of the fluorescence lifetime existed between the NCs in solid state and in solution. The low optical loss in organic solvent indicated that the Nd3+ ions-doped fluoride NCs are promising materials for optical amplification fields.

Solvent-shared pairs of densely charged ions induce intense but short-range supra-additive slowdown of water rotation.

PubMed

Vila Verde, Ana; Santer, Mark; Lipowsky, Reinhard

2016-01-21

The question "Can ions exert supra-additive effects on water dynamics?" has had several opposing answers from both simulation and experiment. We address this ongoing controversy by investigating water reorientation in aqueous solutions of two salts with large (magnesium sulfate) and small (cesium chloride) effects on water dynamics using molecular dynamics simulations and classical, polarizable models. The salt models are reparameterized to reproduce properties of both dilute and concentrated solutions. We demonstrate that water rotation in concentrated MgSO4 solutions is unexpectedly slow, in agreement with experiment, and that the slowdown is supra-additive: the observed slowdown is larger than that predicted by assuming that the resultant of the extra forces induced by the ions on the rotating water molecules tilts the free energy landscape associated with water rotation. Supra-additive slow down is very intense but short-range, and is strongly ion-specific: in contrast to the long-range picture initially proposed based on experiment, we find that intense supra-additivity is limited to water molecules directly bridging two ions in solvent-shared ion pair configuration; in contrast to a non-ion-specific origin to supra-additive effects proposed from simulations, we find that the magnitude of supra-additive slowdown strongly depends on the identity of the cations and anions. Supra-additive slowdown of water dynamics requires long-lived solvent-shared ion pairs; long-lived ion pairs should be typical for salts of multivalent ions. We discuss the origin of the apparent disagreement between the various studies on this topic and show that the short-range cooperative slowdown scenario proposed here resolves the existing controversy.

Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols.

PubMed

Zhou, Xibin; Zhang, Yahe; Zhao, Suoqi; Hsu, Chang Samuel; Shi, Quan

2013-12-15

Monohydric alcohols are common in natural products, bio-oils, and medicine. We have found that monohydric alcohols can form O3 (ions containing three oxygen atoms) and O4 adduct ions in negative electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which would significantly affect the composition analysis of alcohols, especially in a complex mixture. It is necessary to study the reaction pathways and the method to eliminate or reduce the 'artifact' adducts. Octadecanol, cholesterol, squalanol and two complex monohydric alcohol mixtures were selected as model compounds. These samples were subjected to negative ion ESI FT-ICR MS analysis. The composition and formation mechanism of adducts were studied by the ultrahigh-resolution accurate mass measurement for elemental composition, along with the MS(2) isolation and collision-induced dissociation (CID) experiments for structural determination. The reaction pathway of O3 adduct formation is the coupling of a monohydric alcohol ion with a CO2 to form a stable O3 ionic species by likely a covalent bond (source of CO2 is not clear). The O4 species are formed by O3 ionic species adducted with an alcohol molecule of the solvent, such as methanol or ethanol, by likely a hydrogen bond. These adduct ions could be eliminated or reduced by increasing collision energy. However, excessive collision energy would fragment monohydric alcohol ions. The formation mechanisms of O3 and O4 adducts from monohydric alcohols in negative ion ESI FT-ICR MS were proposed. The solvent adduction effects can be eliminated or reduced by optimizing the collision energy of CID in FT-ICR MS. Copyright © 2013 John Wiley & Sons, Ltd.

The rapid and direct determination of ATP-ase activity by ion exchange chromatography and the application to the activity of heat shock protein-90

PubMed Central

Bartolini, Manuela; Wainer, Irving W.; Bertucci, Carlo; Andrisano, Vincenza

2012-01-01

Adenosine nucleotides are involved as substrates or co-factors in several biochemical reactions, catalyzed by enzymes, which modulate energy production, signal transduction and cell proliferation. We here report the development and optimization of an ion exchange liquid chromatography (LC) method for the determination of ATP, ADP and AMP. This method is specifically aimed at the determination of the ATP-ase activity of human heat shock protein 90 (Hsp90), a molecular chaperone that has emerged as target enzyme in cancer therapy. Separation of the three nucleotides was achieved in a 15-min run by using a disk shaped monolithic ethylene diamine stationary phase of small dimensions (2×6 mm i.d.), under a three-solvent gradient elution mode and UV detection at 256 nm. The described direct LC method resulted highly specific as a consequence of the baseline separation of the three adenosine nucleotides and could be applied to the determination of the enzymatic activity of ADP/ATP generating or consuming enzymes (such as kinases). Furthermore, comparison of the LOD and LOQ values of the LC method with those obtained with the malachite green assay, which is one of the most used indirect screening methodologies for ATP-ase activity, showed that the LC method has a similar range of application without presenting the drawbacks related to contamination by inorganic phosphate ions and glycerol, which are present in Hsp90 commercial samples. PMID:22497853

Negative corona discharge-ion mobility spectrometry as a detection system for low density extraction solvent-based dispersive liquid-liquid microextraction.

PubMed

Ebrahimi, Amir; Jafari, Mohammad T

2015-03-01

This paper deals with a method based on negative corona discharge ionization ion mobility spectrometry (NCD-IMS) for the analysis of ethion (as an organophosphorus pesticide). The negative ions such as O2(-) and NO(x)(-) were eliminated from the background spectrum to increase the instrument sensitivity. The method was used to specify the sample extracted via dispersive liquid-liquid microextraction (DLLME) based on low density extraction solvent. The ion mobility spectrum of ethion in the negative mode and the reduced mobility value for its ion peak are firstly reported and compared with those of the positive mode. In order to combine the low density solvent DLLME directly with NCD-IMS, cyclohexane was selected as the extraction solvent, helping us to have a direct injection up to 20 µL solution, without any signal interference. The method was exhaustively validated in terms of sensitivity, enrichment factor, relative recovery, and repeatability. The linear dynamic range of 0.2-100.0 µg L(-1), detection limit of 0.075 µg L(-1), and the relative standard deviation (RSD) of about 5% were obtained for the analysis of ethion through this method. The average recoveries were calculated about 68% and 92% for the grape juice and underground water, respectively. Finally, some real samples were analyzed and the feasibility of the proposed method was successfully verified by the efficient extraction of the analyte using DLLME before the analysis by NCD-IMS. Copyright © 2014 Elsevier B.V. All rights reserved.

Microsolvation of the potassium ion with aromatic rings: comparison between hexafluorobenzene and benzene.

PubMed

Marques, J M C; Llanio-Trujillo, J L; Albertí, M; Aguilar, A; Pirani, F

2013-08-22

We employ a recently developed methodology to study structural and energetic properties of the first solvation shells of the potassium ion in nonpolar environments due to aromatic rings, which is important to understand the selectivity of several biochemical phenomena. Our evolutionary algorithm is used in the global optimization study of clusters formed of K(+) solvated with hexafluorobenzene (HFBz) molecules. The global intermolecular interaction for these clusters has been decomposed in HFBz-HFBz and in K(+)-HFBz contributions, using a potential model based on different decompositions of the molecular polarizability of hexafluorobenzene. Putative global minimum structures of microsolvation clusters up to 21 hexafluorobenzene molecules were obtained and compared with the analogous K(+)-benzene clusters reported in our previous work (J. Phys. Chem. A 2012, 116, 4947-4956). We have found that both K(+)-(Bz)n and K(+)-(HFBz)n clusters show a strong magic number around the closure of the first solvation shell. Nonetheless, all K(+)-benzene clusters have essentially the same first solvation shell geometry with four solvent molecules around the ion, whereas the corresponding one for K(+)-(HFBz)n is completed with nine HFBz species, and its structural motif varies as n increases. This is attributed to the ion-solvent interaction that has a larger magnitude for K(+)-Bz than in the case of K(+)-HFBz. In addition, the ability of having more HFBz than Bz molecules around K(+) in the first solvation shell is intimately related to the inversion in the sign of the quadrupole moment of the two solvent species, which leads to a distinct ion-solvent geometry of approach.

Super-hydrophobic fluorine containing aerogels

DOEpatents

Coronado, Paul R [Livermore, CA; Poco, John F [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2007-05-01

An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.

Automated process for solvent separation of organic/inorganic substance

DOEpatents

Schweighardt, F.K.

1986-07-29

There is described an automated process for the solvent separation of organic/inorganic substances that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In the process, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control apparatus. The mixture in the filter is agitated by ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process. 4 figs.

Automated process for solvent separation of organic/inorganic substance

DOEpatents

Schweighardt, Frank K.

1986-01-01

There is described an automated process for the solvent separation of organic/inorganic substances that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In the process, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control apparatus. The mixture in the filter is agitated by ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process.

Automated apparatus for solvent separation of a coal liquefaction product stream

DOEpatents

Schweighardt, Frank K.

1985-01-01

An automated apparatus for the solvent separation of a coal liquefaction product stream that operates continuously and unattended and eliminates potential errors resulting from subjectivity and the aging of the sample during analysis. In use of the apparatus, metered amounts of one or more solvents are passed sequentially through a filter containing the sample under the direction of a microprocessor control means. The mixture in the filter is agitated by means of ultrasonic cavitation for a timed period and the filtrate is collected. The filtrate of each solvent extraction is collected individually and the residue on the filter element is collected to complete the extraction process.

Solvent screening for a hard-to-dissolve molecular crystal.

PubMed

Maiti, A; Pagoria, P F; Gash, A E; Han, T Y; Orme, C A; Gee, R H; Fried, L E

2008-09-01

Materials with a high-degree of inter- and intra-molecular hydrogen bonding generally have limited solubility in conventional organic solvents. This presents a problem for the dissolution, manipulation and purification of these materials. Using a state-of-the-art density-functional-theory based quantum chemical solvation model we systematically evaluated solvents for a known hydrogen-bonded molecular crystal. This, coupled with direct solubility measurements, uncovered a class of ionic liquids involving fluoride anions that possess more than two orders of magnitude higher solvation power as compared with the best conventional solvents. The crystal structure of one such ionic liquid, determined by X-ray diffraction spectroscopy, indicates that F- ions are stabilized through H-bonded chains with water. The presence of coordinating water in such ionic liquids seems to facilitate the dissolution process by keeping the chemical activity of the F- ions in check.

Structure and dynamics of phosphate ion in aqueous solution: an ab initio QMCF MD study.

PubMed

Pribil, Andreas B; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M

2008-11-15

A simulation of phosphate in aqueous solution was carried out employing the new QMCF MD approach which offers the possibility to investigate composite systems with the accuracy of a QMMM method but without the time consuming creation of solute-solvent potential functions. The data of the simulations give a clear picture of the hydration shells of the phosphate anion. The first shell consists of 13 water molecules and each oxygen of the phosphate forms in average three hydrogens bonds to different solvent molecules. Several structural parameters such as radial distribution functions and coordination number distributions allow to fully characterize the embedding of the highly charged phosphate ion in the solvent water. The dynamics of the hydration structure of phosphate are described by mean residence times of the solvent molecules in the first hydration shell and the water exchange rate. 2008 Wiley Periodicals, Inc.

SEPARATION OF PLUTONIUM FROM ELEMENTS HAVING AN ATOMIC NUMBER NOT LESS THAN 92

DOEpatents

Fitch, F.T.; Russell, D.S.

1958-09-16

other elements having atomic numbers nnt less than 92, It has been proposed in the past to so separate plutonium by solvent extraction iato an organic solvent using triglycoldichlcride as the organic solvent. The improvement lies in the discovery that triglycoldichloride performs far more efflciently as an extractant, wher certain second organie compounds are added to it. Mentioned as satisfactory additive compounds are benzaldehyde, saturated aliphatic aldehydes containtng at least twc carbon atoms, and certain polyhydric phenols.

Energy impact of cathode drying and solvent recovery during lithium-ion battery manufacturing

NASA Astrophysics Data System (ADS)

Ahmed, Shabbir; Nelson, Paul A.; Gallagher, Kevin G.; Dees, Dennis W.

2016-08-01

Successful deployment of electric vehicles requires maturity of the manufacturing process to reduce the cost of the lithium ion battery (LIB) pack. Drying the coated cathode layer and subsequent recovery of the solvent for recycle is a vital step in the lithium ion battery manufacturing plant and offers significant potential for cost reduction. A spreadsheet model of the drying and recovery of the solvent, is used to study the energy demand of this step and its contribution towards the cost of the battery pack. The base case scenario indicates that the drying and recovery process imposes an energy demand of ∼10 kWh per kg of the solvent n-methyl pyrrolidone (NMP), and is almost 45 times the heat needed to vaporize the NMP. For a plant producing 100 K battery packs per year for 10 kWh plug-in hybrid vehicles (PHEV), the energy demand is ∼5900 kW and the process contributes 107 or 3.4% to the cost of the battery pack. The cost of drying and recovery is equivalent to 1.12 per kg of NMP recovered, saving 2.08 per kg in replacement purchase.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process.

PubMed

Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V

2011-12-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. © The Author(s) 2011. Published by Oxford University Press.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process

PubMed Central

Reshetnikov, Roman V.; Sponer, Jiri; Rassokhina, Olga I.; Kopylov, Alexei M.; Tsvetkov, Philipp O.; Makarov, Alexander A.; Golovin, Andrey V.

2011-01-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. PMID:21893589

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A

Solvent extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs. cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent extraction system, either with chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride thanmore » for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a very polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion-pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.« less

Towards a comprehensive model for the electronic and vibrational structure of the Creutz-Taube ion.

PubMed

Reimers, Jeffrey R; Wallace, Brett B; Hush, Noel S

2008-01-13

Since the synthesis of the Creutz-Taube ion, the nature of its charge localization has been of immense scientific interest, this molecule providing a model system for the understanding of the operation of biological photosynthetic and electron-transfer processes. However, recent work has shown that its nature remains an open question. Many systems of this type, including photosynthetic reaction centres, are of current research interest, and thereby the Creutz-Taube ion provides an important chemical paradigm: the key point of interest is the details of how such molecules behave. We lay the groundwork for the construction of a comprehensive model for its chemical and spectroscopic properties. Advances are described in some of the required areas including: simulation of electronic absorption spectra; quantitative depiction of the large interaction of the ion's electronic description with solvent motions; and the physics of Ru-NH3 spectator-mode vibrations. We show that details of the solvent electron-phonon coupling are critical in the interpretation of the spectator-mode vibrations, as these strongly mix with solvent motions when 0.75<2J/lambda<1. In this regime, a double-well potential exists which does not support localized zero-point vibration, and many observed properties of the Creutz-Taube ion are shown to be consistent with the hypothesis that the ion has this character.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang, Liem X.; Chang, Tsun-Mei

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li{sup +} and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li{sup +} in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li{sup +}-[BF{sub 4}] and Li{sup +}-[PF{sub 6}] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shellsmore » around Li{sup +}. We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li{sup +}-[BF{sub 4}] and Li{sup +}-[PF{sub 6}] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.« less

Extraction of benzene and cyclohexane using [BMIM][N(CN)2] and their equilibrium modeling

NASA Astrophysics Data System (ADS)

Ismail, Marhaina; Bustam, M. Azmi; Man, Zakaria

2017-12-01

The separation of aromatic compound from aliphatic mixture is one of the essential industrial processes for an economically green process. In order to determine the separation efficiency of ionic liquid (IL) as a solvent in the separation, the ternary diagram of liquid-liquid extraction (LLE) 1-butyl-3-methylimidazolium dicyanamide [BMIM][N(CN)2] with benzene and cyclohexane was studied at T=298.15 K and atmospheric pressure. The solute distribution coefficient and solvent selectivity derived from the equilibrium data were used to evaluate if the selected ionic liquid can be considered as potential solvent for the separation of benzene from cyclohexane. The experimental tie line data was correlated using non-random two liquid model (NRTL) and Margules model. It was found that the solute distribution coefficient is (0.4430-0.0776) and selectivity of [BMIM][N(CN)2] for benzene is (53.6-13.9). The ternary diagram showed that the selected IL can perform the separation of benzene and cyclohexane as it has extractive capacity and selectivity. Therefore, [BMIM][N(CN)2] can be considered as a potential extracting solvent for the LLE of benzene and cyclohexane.

Overview of reductants utilized in nuclear fuel reprocessing/recycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patricia Paviet-Hartmann; Catherine Riddle; Keri Campbell

2013-10-01

Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but itmore » is also a non-metallic chemical that is readily decomposed to innocuous products by heating. However, it has been observed that the presence of high nitric acid concentrations or impurities (such as metal ions) in hydroxylamine solutions increase the likelihood of the initiation of an autocatalytic reaction. Recently there has been some interest in the application of simple hydrophilic hydroxamic ligands such as acetohydroxamic acid (AHA) for the stripping of tetravalent actinides in the UREX process flowsheet. This approach is based on the high coordinating ability of hydroxamic acids with tetravalent actinides (Np and Pu) compared with hexavalent uranium. Thus, the use of AHA offers a route for controlling neptunium and plutonium in the UREX process by complexant based stripping of Np(IV) and Pu(IV) from the TBP solvent phase, while U(VI) ions are not affected by AHA and remain solvated in the TBP phase. In the European GANEX process, AHA is also used to form hydrophilic complexes with actinides and strip them from the organic phase into nitric acid. However, AHA does not decompose completely when treated with nitric acid and hampers nitric acid recycling. In lieu of using AHA in the UREX + process, formohydroxamic acid (FHA), although not commercially available, hold promises as a replacement for AHA. FHA undergoes hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. Unfortunately, FHA powder was not stable in the experiments we ran in our laboratory. In addition, AHA and FHA also decompose to hydroxylamine which may undergo an autocatalytic reaction. Other reductants are available and could be extremely useful for actinides separation. The review presents the current plutonium reductants used in used nuclear fuel reprocessing and will introduce innovative and novel reductants that could become reducers for future research on UNF separation.« less

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

Non-aqueous liquid compositions comprising ion exchange polymers reference to related application

DOEpatents

Kim,; Yu Seung, Lee [Los Alamos, NM; Kwan-Soo, Rockward [Los Alamos, NM; T, Tommy Q [Rio Rancho, NM

2012-08-07

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Solute-Solvent Charge-Transfer Excitations and Optical Absorption of Hydrated Hydroxide from Time-Dependent Density-Functional Theory.

PubMed

Opalka, Daniel; Sprik, Michiel

2014-06-10

The electronic structure of simple hydrated ions represents one of the most challenging problems in electronic-structure theory. Spectroscopic experiments identified the lowest excited state of the solvated hydroxide as a charge-transfer-to-solvent (CTTS) state. In the present work we report computations of the absorption spectrum of the solvated hydroxide ion, treating both solvent and solute strictly at the same level of theory. The average absorption spectrum up to 25 eV has been computed for samples taken from periodic ab initio molecular dynamics simulations. The experimentally observed CTTS state near the onset of the absorption threshold has been analyzed at the generalized-gradient approximation (GGA) and with a hybrid density-functional. Based on results for the lowest excitation energies computed with the HSE hybrid functional and a Davidson diagonalization scheme, the CTTS transition has been found 0.6 eV below the first absorption band of liquid water. The transfer of an electron to the solvent can be assigned to an excitation from the solute 2pπ orbitals, which are subject to a small energetic splitting due to the asymmetric solvent environment, to the significantly delocalized lowest unoccupied orbital of the solvent. The distribution of the centers of the excited state shows that CTTS along the OH(-) axis of the hydroxide ion is avoided. Furthermore, our simulations indicate that the systematic error arising in the calculated spectrum at the GGA originates from a poor description of the valence band energies in the solution.

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directlymore » involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.« less

Molten carbonate fuel cell cathode with mixed oxide coating

DOEpatents

Hilmi, Abdelkader; Yuh, Chao-Yi

2013-05-07

A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

Separation and characterization of polycyclic aromatic hydrocarbons and alkylphenols in coal derived solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hurtubise, R.J.; Allen, T.W.; Hussain, A.

1981-03-29

Dry-column chromatography with an aluminum oxide stationary phase and a n-hexane-ether (19:1) mobile phase was used to separate polycyclic aromatic hydrocarbons (PAH) by ring size. Prior to the dry-column chromatography step, the coal derived solvents were added to an acid treated silica gel column and eluted with chloroform. This step removed pyridine-type nitrogen heterocycles. After separation of the individual ring fractions, the fractions were further separated by either thin layer chromatography (TLC) or high performance liquid chromatography (HPLC). If TLC was used, then after separation fluorescence profiles of each PAH ring fraction distributed on 30%-acetylated cellulose chromatoplates were obtained withmore » a spectrodensitometer. Measurement of fluorescence peak heights gave an approximate measure of the amount of the 3-, 4-, 5-, and 6- ring PAH. For HPLC separation, the 3- and 4- ring PAH fractions obtained from the dry-column chromatography step were separated with a ..mu..-Bondapak C/sub 18/ column and methanol:water (65:35) mobile phase. The HPLC separated PAH were characterized by chromatographic correlation factors and corrected fluorescence excitation spectra. Alkylphenols were identified in coal recycle solvent sample following separation by HPLC.« less

Hydrometallurgical Separation of Niobium and Tantalum: A Fundamental Approach

NASA Astrophysics Data System (ADS)

Nete, Motlalepula; Purcell, Walter; Nel, Johann T.

2016-02-01

A mixture of pure Ta2O5 and Nb2O5 was dissolved using two different fluxes, namely NH4F·HF and Na2HPO4/NaH2PO4·H2O. Selective precipitation and ion exchange were used as separation techniques. Selective precipitation using p-phenylediamine in a fluoride matrix resulted in the isolation of 73(3)% tantalum accompanied by 23(5)% niobium. A separation factor of 11(4) was obtained. A single solvent extraction step using methyl-isobutyl ketone at a 4 M H2SO4 yielded excellent Ta and Nb separation in the fluoride solution with 80% of the Ta and only 2% Nb recovered in the organic layer. A two-step extraction recovered 100% Ta at 0.5-4 M H2SO4 with a separation factor of ~2000. A study of the extraction mechanism indicated that the stability of the protonated compounds such as H2TaF7/H2NbOF5 is in the extraction and separation determining steps in this process. A K' (double de-protonated constant) of approximately 0.2 was calculated for H2TaF7. Only 91.7% Nb and 73.4% Ta were recovered from anion separation using strong Amberlite resin and 96.1% Nb and 52.3% using the weak Dowex Marathon resin from fluoride dissolution.

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

Stimuli responsive ion gels based on polysaccharides and other polymers prepared using ionic liquids and deep eutectic solvents.

PubMed

Prasad, Kamalesh; Mondal, Dibyendu; Sharma, Mukesh; Freire, Mara G; Mukesh, Chandrakant; Bhatt, Jitkumar

2018-01-15

Ion gels and self-healing gels prepared using ionic liquids (ILs) and deep eutectic solvents (DESs) have been largely investigated in the past years due to their remarkable applications in different research areas. Herewith we provide an overview on the ILs and DESs used for the preparation of ion gels, highlight the preparation and physicochemical characteristics of stimuli responsive gel materials based on co-polymers and biopolymers, with special emphasis on polysaccharides and discuss their applications. Overall, this review summarizes the fundamentals and advances in ion gels with switchable properties prepared using ILs or DESs, as well as their potential applications in electrochemistry, in sensing devices and as drug delivery vehicles. Copyright © 2017 Elsevier Ltd. All rights reserved.

SLTCAP: A Simple Method for Calculating the Number of Ions Needed for MD Simulation.

PubMed

Schmit, Jeremy D; Kariyawasam, Nilusha L; Needham, Vince; Smith, Paul E

2018-04-10

An accurate depiction of electrostatic interactions in molecular dynamics requires the correct number of ions in the simulation box to capture screening effects. However, the number of ions that should be added to the box is seldom given by the bulk salt concentration because a charged biomolecule solute will perturb the local solvent environment. We present a simple method for calculating the number of ions that requires only the total solute charge, solvent volume, and bulk salt concentration as inputs. We show that the most commonly used method for adding salt to a simulation results in an effective salt concentration that is too high. These findings are confirmed using simulations of lysozyme. We have established a web server where these calculations can be readily performed to aid simulation setup.

Recent advances in f-element separations based on a new method for the production of pentavalent americium in acidic solution

DOE PAGES

Mincher, Bruce J.; Schmitt, Nicholas C.; Schuetz, Brian K.; ...

2015-03-11

The peroxydisulfate anion has long been used for the preparation of hexavalent americium (Am VI) from the normally stable Am III valence state in mildly acidic solutions. However, there has been no satisfactory means to directly prepare the pentavalent state (Am V) in that medium. Some early literature reports indicated that the peroxydisulfate oxidation was incomplete, and silver ion catalysis in conjunction with peroxydisulfate became accepted as the means to ensure quantitative generation of Am VI. Incomplete oxidation would be expected to leave residual Am III, or to produce Am V in treated solutions. However, until recently, the use ofmore » peroxydisulfate as an Am V reagent has not been reported. Here, parameters influencing the oxidation were investigated, including peroxydisulfate and acid concentration, temperature, duration of oxidative treatment, and the presence of higher concentrations of other redox active metals such as plutonium. Using optimized conditions determined here, quantitative Am V was prepared in an acidic solution and the UV/Vis extinction coefficients of the Am V 513 nm peak were measured over a range of nitric acid concentrations. Furthermore, the utility of Am V for separations from the lanthanides and curium by solvent extraction, organic column chromatography and inorganic ion exchangers was also investigated.« less

Microporous plastic member such as a battery separator and process for making same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundberg, E.G.; Campbell, G.A.; Doucette, E.I.

A process for producing a microporous plastic member useful as a battery separator comprises the following operations: forming a coherent dough by mixing a vinyl chloride resin with a plasticizing amount of a first solvent and with finely divided particles of a filler which contains volatilizable releasable constituent by heating and which shrinks substantially and irreversibly upon release of the volatilizable constituent, an example of which is hydrated silica; forming the solvent-containing dough into a shaped member; extracting the first solvent from the member before any substantial evaporation of solvent occurs by contacting it with a second solvent in amore » liquid bath at a temperature substantially below the boiling point of any liquid present, the second solvent being one which is capable of dissolving the first solvent without dissolving the resin and the filler, thereby deplasticizing the member by extractively removing the first solvent from the member; and thereafter heating the member at an elevated temperature but below the softening point of the resin until the filler is shrunk within the member by release of its volatilizable content. 10 claims.« less

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

DOE PAGES

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

2018-04-16

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics.

PubMed

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution.

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics

PubMed Central

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution. PMID:25962096

Thermodynamics and kinetics of Na+/K+-formate ion pairs association in polarizable water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Nguyen, Phuong T. M.; Nguyen, Van T.; Annapureddy, Harsha V. R.; Dang, Liem X.; Do, D. D.

2012-12-01

To enhance our understanding of ion specific activity in biological systems, the potential of mean force approach was utilized to study solvent effects on the interactions between two alkali cations (Na+ and K+) with a formate anion in water. A very complex free energy landscape was observed, much more so than alkali-halide ion pairs. Furthermore, a stronger binding between the Na+-formate pair was found in comparison to the K+-formate pair in water, which is in agreement with experimental and theoretical studies [1-4]. The kinetics of ion-pair inter-conversions was studied using the transition rate theory, along with a number of theoretical approaches such as the Kramers and Grote-Hynes theories. These kinetic results were used to predict solvent effects on dynamical features of ion-pair association, in which we have found that the dynamics of K+-formate pairs is faster than Na+-formate pairs.

Ion-neutral Clustering of Bile Acids in Electrospray Ionization Across UPLC Flow Regimes

NASA Astrophysics Data System (ADS)

Brophy, Patrick; Broeckling, Corey D.; Murphy, James; Prenni, Jessica E.

2018-02-01

Bile acid authentic standards were used as model compounds to quantitatively evaluate complex in-source phenomenon on a UPLC-ESI-TOF-MS operated in the negative mode. Three different diameter columns and a ceramic-based microfluidic separation device were utilized, allowing for detailed descriptions of bile acid behavior across a wide range of flow regimes and instantaneous concentrations. A custom processing algorithm based on correlation analysis was developed to group together all ion signals arising from a single compound; these grouped signals produce verified compound spectra for each bile acid at each on-column mass loading. Significant adduction was observed for all bile acids investigated under all flow regimes and across a wide range of bile acid concentrations. The distribution of bile acid containing clusters was found to depend on the specific bile acid species, solvent flow rate, and bile acid concentration. Relative abundancies of each cluster changed non-linearly with concentration. It was found that summing all MS level (low collisional energy) ions and ion-neutral adducts arising from a single compound improves linearity across the concentration range (0.125-5 ng on column) and increases the sensitivity of MS level quantification. The behavior of each cluster roughly follows simple equilibrium processes consistent with our understanding of electrospray ionization mechanisms and ion transport processes occurring in atmospheric pressure interfaces. [Figure not available: see fulltext.

Femtosecond-picosecond laser photolysis studies on the dynamics of excited charge-transfer complexes: Aromatic hydrocarbon-acid anhydride, -tetracyanoethylene, and -tetracyanoquinodimethane systems in acetonitrile solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asahi, Tsuyoshi; Mataga, Noboru

1991-03-07

Formation processes of contact ion pairs (CIP) from the excited Franck-Condon (FC) state of charge-transfer (CT) complexes of aromatic hydrocarbons with acid anhydride as well as cyano compound acceptors in acetonitrile solution and charge recombination (CR) rates (k{sub CR}{sup CIP}) of produced CIP states have been investigated by femtosecond and picosecond laser phototlysis and time-resolved absorption spectral measurements covering a wide range of free energy gap-{Delta}G{degree}{sub ip} between the ion pair and the ground state. It has been confirmed that the CIP formation becomes faster and k{sub CR}{sup CIP} of the produced CIP increases with increase of the strengths ofmore » the electron donor (D) and acceptor (A) in the complex, i.e., with decrease of the {minus}{Delta}G{degree}{sub ip} value. This peculiar energy gap dependence of k{sub CR}{sup CIP}, quite different from the bell-shaped one observed in the case of the solvent-separated ion pairs (SSIP) or loose ion pairs (LIP) formed by encounter between fluorescer and quencher in the fluoresence quenching reaction, has been interpreted by assuming the change of electronic and geometrical structures of CIP depending on the strengths of D and A.« less

Separating effective high density polyethylene segments from olefin block copolymers using high temperature liquid chromatography with a preloaded discrete adsorption promoting solvent barrier.

PubMed

Chatterjee, Tirtha; Rickard, Mark A; Pearce, Eric; Pangburn, Todd O; Li, Yongfu; Lyons, John W; Cong, Rongjuan; deGroot, A Willem; Meunier, David M

2016-09-23

Recent advances in catalyst technology have enabled the synthesis of olefin block copolymers (OBC). One type is a "hard-soft" OBC with a high density polyethylene (HDPE) block and a relatively low density polyethylene (VLDPE) block targeted as thermoplastic elastomers. Presently, one of the major challenges is to fractionate HDPE segments from the other components in an experimental OBC sample (block copolymers and VLDPE segments). Interactive high temperature liquid chromatography (HTLC) is ineffective for OBC separation as the HDPE segments and block copolymer chains experience nearly identical enthalpic interactions with the stationary phase and co-elute. In this work we have overcome this challenge by using liquid chromatography under the limiting conditions of desorption (LC LCD). A solvent plug (discrete barrier) is introduced in front of the sample which specifically promotes the adsorption of HDPE segments on the stationary phase (porous graphitic carbon). Under selected thermodynamic conditions, VLDPE segments and block copolymer chains crossed the barrier while HDPE segments followed the pore-included barrier solvent and thus enabled separation. The barrier solvent composition was optimized and the chemical composition of fractionated polymer chains was investigated as a function of barrier solvent strength using an online Fourier-transform infrared (FTIR) detector. Our study revealed that both the HDPE segments as well as asymmetric block copolymer chains (HDPE block length≫VLDPE block length) are retained in the separation and the barrier strength can be tailored to retain a particular composition. At the optimum barrier solvent composition, this method can be applied to separate effective HDPE segments from the other components, which has been demonstrated using an experimental OBC sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Triticonazole enantiomers: Separation by supercritical fluid chromatography and the effect of the chromatographic conditions.

PubMed

He, Jianfeng; Fan, Jun; Yan, Yilun; Chen, Xiaodong; Wang, Tai; Zhang, Yaomou; Zhang, Weiguang

2016-11-01

Enantiomeric pairs of triticonazole have been successfully separated by supercritical fluid chromatography coupled with a tris(3,5-dimethylphenylcarbamoyl) cellulose-coated chiral stationary phase in this work. The effects of co-solvent, dissolution solvent, flow rate, backpressure, and column temperature have been studied in detail with respect to retention, selectivity, and resolution of triticonazole. As indicated, the co-solvents mostly affected the retention factors and resolution, due to the different molecular structure and polarity. In addition, the dissolution solvents, namely, chloromethanes and alcohols, have been also important for enantioseparation because of the different interaction with stationary phase. Higher flow rate and backpressure led to faster elution of the triticonazole molecules, and the change of column temperature showed slight effect on the resolution of triticonazole racemate. Moreover, a comparative separation experiment between supercritical fluid chromatography and high performance liquid chromatography revealed that chiral supercritical fluid chromatography gave the 3.5 times value of R s /t R2 than high performance liquid chromatography, which demonstrated that supercritical fluid chromatography had much higher separation efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, self-assembly, and properties of Mn doped ZnO nanoparticles.

PubMed

Barick, K C; Bahadur, D

2007-06-01

We report here a novel process to prepare Mn doped ZnO nanoparticles by a soft chemical route at low temperature. The synthesis process is based on the hydrolysis of zinc acetate dihydrate and manganese acetate tetrahydrate heated under reflux to 160-175 degrees C using diethylene glycol as a solvent. X-ray diffraction analysis reveals that the Mn doped ZnO crystallizes in a wurtzite structure with crystal size of 15-25 nm. These nano size crystallites of Mn doped ZnO self-organize into polydisperse spheres in size ranging from 100-400 nm. Transmission Electron Microscopy image also shows that each sphere is made up of numerous nanocrystals of average diameter 15-25 nm. By means of X-ray photoelectron spectroscopy and electron spin resonance spectroscopy, we determined the valence state of Mn ions as 2+. These nanoparticles were found to be ferromagnetic at room temperature. Monodisperse porous spheres (approximately 250 nm) were obtained by size selective separation technique and then self-assembled in a closed pack periodic array through sedimentation with slow solvent evaporation, which gives strong opalescence in visible region.

[Na5(THF)10Ce(mnt)4]infinity: a honeycomb network polymer that yields homoleptic cerium(III) tetrakis(dithiolene) complexes in donor solvents.

PubMed

Weis, Eric M; Barnes, Charles L; Duval, Paul B

2006-12-11

The first example of a lanthanide tetrakis(dithiolene) complex, [Na5(THF)10Ce(mnt)4] (1) (mnt = 1,2-maleonitrile-1,2-dithiolate), has been synthesized and characterized by X-ray crystallography and spectroscopic methods. In the solid state, 1 exists as a 2-D corrugated honeycomb network polymer in which the monomeric units comprising the trigonal nodes are knitted together by interlocking dative Na-N bonds extended from nitrile groups of bifunctional mnt ligands coordinated through the sulfur atoms to adjacent cerium centers. Individual honeycomb sheets are separated by 14.8 A. Compound 1 dissolves in donor solvents such as THF and acetonitrile to give soluble [Ce(mnt)4]5- units that exhibit spectroscopic features (i.e., NMR, luminescence, UV-vis) that are consistent with the 4f1 Ce(III) ion. In the first examination of the redox chemistry of a lanthanide dithiolene complex, cyclic voltammetry measurements conducted on 1 reveal a single irreversible oxidation wave that is likely attributable to ligand-centered oxidation.

Tunable solvation effects on the size-selective fractionation of metal nanoparticles in CO2 gas-expanded solvents.

PubMed

Anand, Madhu; McLeod, M Chandler; Bell, Philip W; Roberts, Christopher B

2005-12-08

This paper presents an environmentally friendly, inexpensive, rapid, and efficient process for size-selective fractionation of polydisperse metal nanoparticle dispersions into multiple narrow size populations. The dispersibility of ligand-stabilized silver and gold nanoparticles is controlled by altering the ligand tails-solvent interaction (solvation) by the addition of carbon dioxide (CO2) gas as an antisolvent, thereby tailoring the bulk solvent strength. This is accomplished by adjusting the CO2 pressure over the liquid, resulting in a simple means to tune the nanoparticle precipitation by size. This study also details the influence of various factors on the size-separation process, such as the types of metal, ligand, and solvent, as well as the use of recursive fractionation and the time allowed for settling during each fractionation step. The pressure range required for the precipitation process is the same for both the silver and gold particles capped with dodecanethiol ligands. A change in ligand or solvent length has an effect on the interaction between the solvent and the ligand tails and therefore the pressure range required for precipitation. Stronger interactions between solvent and ligand tails require greater CO2 pressure to precipitate the particles. Temperature is another variable that impacts the dispersibility of the nanoparticles through changes in the density and the mole fraction of CO2 in the gas-expanded liquids. Recursive fractionation for a given system within a particular pressure range (solvent strength) further reduces the polydispersity of the fraction obtained within that pressure range. Specifically, this work utilizes the highly tunable solvent properties of organic/CO2 solvent mixtures to selectively size-separate dispersions of polydisperse nanoparticles (2 to 12 nm) into more monodisperse fractions (+/-2 nm). In addition to providing efficient separation of the particles, this process also allows all of the solvent and antisolvent to be recovered, thereby rendering it a green solvent process.

SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF

DOEpatents

Crandall, H.W.; Thomas, J.R.

1959-06-30

The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.

Racemization of (S)-profen thioesters by strong neutral bases in nonpolar organic solvents: implication for ion-pair kinetic basicity.

PubMed

Chen, Chia-Yin; Chang, Yu-Shang; Lin, Shun-An; Wen, Hui-I; Cheng, Yu-Chi; Tsai, Shau-Wei

2002-05-17

The racemization of (S)-profen 2,2,2-trifluoroethyl thioesters in isooctane with trioctylamine as base was carried out, in which the Hammett equation log(k(int)) = 3.584sigma - 3.745 was successfully applied to describe the electron-withdrawing effect of the substituents to the alpha-phenyl moiety of the thioesters. A combination of neutral strong organic bases with different nonpolar solvents was employed to determine the second-order interconversion constants for the racemization of (S)-naproxen 2,2,2-trifluoroethyl thioester, in which solvent hydrophobicity was found to have less effect on the racemization. Implication for ion-pair kinetic basicity scale for the neutral strong bases in isooctane was further discussed.

Hexaacetato calix(6)arene as the novel extractant for palladium.

PubMed

Mathew, V J; Khopkar, S M

1997-10-01

A novel method is proposed for the solvent extraction of palladium. A superamolecular compound, hexaacetato calix(6)arene in low concentration in toluene quantitatively extracts microgram concentration of palladium at pH 7.5. It can be stripped from the organic phase with 2 M nitric acid and determined spectrophotometrically as its stannous chloride complex at 635 nm. The probable composition of the extracted species is Pd(HR)(2)Cl. As low as 1x10(-3) M of extractant is adequate for quantitative extraction. Toluene was the best diluent. With nitric and perchloric acid (1.5-3 M) the stripping was complete. Palladium was separated in large ratios from alkali and alkaline earths (1:50). The main group elements were tolerated in higher ratios (1:25), but ions like zinc, cadmium, iron, nickel, platinium, thorium, vanadium and molydenum were tolerated at low concentrations (1:1). The ions showing strong interference were copper, chromium. The relative standard deviation is +/-1.1%.

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

DOE PAGES

Hartnett, Patrick E.; Dyar, Scott M.; Margulies, Eric A.; ...

2015-07-31

The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ~6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, uponmore » CH₂Cl₂ vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ~4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.« less

SEPARATION PROCESS FOR TRANSURANIC ELEMENT AND COMPOUNDS THEREOF

DOEpatents

Magnusson, L.B.

1958-04-01

A process is described for the separation of neptunium, from aqueous solutions of neptunium, plutonium, uraniunn, and fission prcducts. This separation from an acidic aqueous solution of a tetravalent neptuniunn can be made by contacting the solution with a certain type of chelating,; agent, preferably dissolved in an organic solvent, to form a neptunium chelate compound. When the organic solvent is present, the neptunium chelate compound is extracted; otherwise, it precipitates from the aqueous solution and is separated by any suitable means. The chelating agent is a fluorinated BETA -diketone. such as trifluoroacetyl acetone.

Does Harcus-Hush theory really work The solvent dependence of intervalence charge-transfer energetics in (NH[sub 3])[sub 5]Ru[sup II]-4,4'-bipyridine-Ru[sup III](NH[sub 3] )[sub 5][sup 5+] in the limit of infinite dilution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hupp, J.T.; Dong, Y.; Blackbourn, R.L.

1993-04-01

Because of concern about ion-pairing artifacts, the solvent dependence of the intervalence charge-transfer absorption energy for a prototypical mixed-valence system, (NH[sub 3])[sub 5]Ru[sup III]-4,4'-bipyridine-Ru[sup II](NH[sub 3])[sub 5][sup 5+], has been reexamined in the limit of infinite dilution. New data are reported for 14 solvents. While one of these (hexamethylphosphoramide) yields anomalous energetics, the absorption energies for the remaining 13 solvents agree qualitatively with the predictions of the Marcus-Hush theory (i.e., two-sphere dielectric continuum theory). On a quantitative basis, however, there is substantial disagreement with theory, at least when the charge-transfer distance is equated with the metal-to-metal separation distance (as conventionallymore » done). Replacement of this distance with a much shorter distance inferred from by electronic Stark-effect spectroscopy leads to a 3-fold decrease in the magnitude of calculated solvent reorganizational contributions to the overall intervalence energy (and therefore, very good agreement with experiment). Unfortunately, the use of such a short charge-transfer distance (d = 5.1 [+-] 0.7 A) also leads to a violation of one of the boundary conditions for use of the two-sphere model. Reformulation of the problem in terms of a generalized dipole-inversion, dielectric cavity problem, however, leads to nearly perfect agreement between theory and experiment. Additional analysis shows that experiment now also agrees reasonably well with theory regarding the magnitude of solvent-independent energy contributions. Finally, it is noted that downward revision in the estimated charge-transfer distance (from 11.3 to 5.1 A) leads to a substantial upward revision in the experimental (i.e., oscillator-strength based) estimate of the electronic coupling element, H[sub if], for intervalence transfer. 33 refs., 3 figs., 2 tabs.« less

SOLVENT EXTRACTION PROCESS FOR URANIUM FROM CHLORIDE SOLUTIONS

DOEpatents

Blake, C.A. Jr.; Brown, K.B.; Horner, D.E.

1960-05-24

An improvement was made in a uranium extraction process wherein the organic extractant is a phosphine oxide. An aqueous solution containing phosphate ions or sulfate ions together with uranium is provided with a source of chloride ions during the extraction step. The presence of the chloride ions enables a phosphine oxide to extract uranium in the presence of strong uranium- complexing ions such as phosphate or sulfate ions.

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

PubMed

Wu, Qinming; Meng, Xiangju; Gao, Xionghou; Xiao, Feng-Shou

2018-05-08

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of zeolites have been proposed and verified. In addition to a significant reduction in liquid wastes and a remarkable increase in zeolite yields, the solvent-free synthesis of zeolites exhibits more unprecedented benefits, including (i) the formation of hierarchical micro-, meso-, and macrostructures, which benefit the mass transfer in the reactions, (ii) rapid synthesis at higher temperatures, which greatly improve the space-time yields of zeolites, and (iii) construction of a novel catalytic system for encapsulation of metal nanoparticles and metal oxide particles within zeolite crystals synergistically combining the advantages of catalytic metal nanoparticles and metal oxide particles (high activity) and zeolites (shape selectivity). We believe that the concept of "solvent-free synthesis of zeolites" would open a door for deep understanding of zeolite crystallization and the design of efficient zeolitic catalysts.

Coordination polymer gels with important environmental and biological applications.

PubMed

Jung, Jong Hwa; Lee, Ji Ha; Silverman, Julian R; John, George

2013-02-07

Coordination Polymer Gels (CPGs) constitute a subset of solid-like metal ion and bridging organic ligand structures (similar to metal-organic frameworks) that form multi-dimensional networks through a trapped solvent as a result of non-covalent interactions. While physical properties of these gels are similar to conventional high molecular weight organic polymer gels, coordination polymer gel systems are often fully reversible and can be assembled and disassembled in the presence of additional energy (heat, sonication, shaking) to give a solution of solvated gelators. Compared to gels resulting from purely organic self-assembled low molecular weight gelators, metal ions incorporated into the fibrilar networks spanning the bulk solvent can impart CPGs with added functionalities. The solid/liquid nature of the gels allows for species to migrate through the gel system and interact with metals, ligands, and the solvent. Chemosensing, catalysis, fluorescence, and drug-delivery applications are some of the many potential uses for these dynamic systems, taking advantage of the metal ion's coordination, the organic polydentate ligand's orientation and functionality, or a combination of these properties. By fine tuning these systems through metal ion and ligand selection and by directing self-assembly with external stimuli the rational synthesis of practical systems can be envisaged.

COORDINATION COMPOUND-SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Reas, W.H.

1959-03-10

A method is presented for the separation of uranium from aqueous solutions containing a uranyl salt and thorium. Thc separation is effected by adding to such solutions an organic complexing agent, and then contacting the solution with an organic solvent in which the organic complexing agent is soluble. By use of the proper complexing agent in the proper concentrations uranium will be complexed and subsequently removed in the organic solvent phase, while the thorium remains in the aqueous phase. Mentioned as suitable organic complexing agents are antipyrine, bromoantipyrine, and pyramidon.

SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS

DOEpatents

Cowan, G.A.

1959-08-25

The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.

Isolation and purification of series bioactive components from Hypericum perforatum L. by counter-current chromatography.

PubMed

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Xu, Chunming; Ito, Yoichiro

2011-03-01

Counter-current chromatography (CCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate-water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, ¹HNMR and ¹³CNMR. Copyright © 2011 Elsevier B.V. All rights reserved.

Isolation and purification of series bioactive components from Hypericum Perforatum L. by high-speed counter-current chromatography

PubMed Central

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Ito, Yiochiro

2011-01-01

High-speed counter-current chromatography (HSCCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate–water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, 1HNMR and 13CNMR. PMID:21306961

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Molten-Salt-Based Growth of Group III Nitrides

DOEpatents

Waldrip, Karen E.; Tsao, Jeffrey Y.; Kerley, Thomas M.

2008-10-14

A method for growing Group III nitride materials using a molten halide salt as a solvent to solubilize the Group-III ions and nitride ions that react to form the Group III nitride material. The concentration of at least one of the nitride ion or Group III cation is determined by electrochemical generation of the ions.

STABILITY OF A CYLINDRICAL SOLUTE-SOLVENT INTERFACE: EFFECT OF GEOMETRY, ELECTROSTATICS, AND HYDRODYNAMICS.

PubMed

Li, B O; Sun, Hui; Zhou, Shenggao

The solute-solvent interface that separates biological molecules from their surrounding aqueous solvent characterizes the conformation and dynamics of such molecules. In this work, we construct a solvent fluid dielectric boundary model for the solvation of charged molecules and apply it to study the stability of a model cylindrical solute-solvent interface. The motion of the solute-solvent interface is defined to be the same as that of solvent fluid at the interface. The solvent fluid is assumed to be incompressible and is described by the Stokes equation. The solute is modeled simply by the ideal-gas law. All the viscous force, hydrostatic pressure, solute-solvent van der Waals interaction, surface tension, and electrostatic force are balanced at the solute-solvent interface. We model the electrostatics by Poisson's equation in which the solute-solvent interface is treated as a dielectric boundary that separates the low-dielectric solute from the high-dielectric solvent. For a cylindrical geometry, we find multiple cylindrically shaped equilibrium interfaces that describe polymodal (e.g., dry and wet) states of hydration of an underlying molecular system. These steady-state solutions exhibit bifurcation behavior with respect to the charge density. For their linearized systems, we use the projection method to solve the fluid equation and find the dispersion relation. Our asymptotic analysis shows that, for large wavenumbers, the decay rate is proportional to wavenumber with the proportionality half of the ratio of surface tension to solvent viscosity, indicating that the solvent viscosity does affect the stability of a solute-solvent interface. Consequences of our analysis in the context of biomolecular interactions are discussed.

Ion concentrations and velocity profiles in nanochannel electroosmotic flows

NASA Astrophysics Data System (ADS)

Qiao, R.; Aluru, N. R.

2003-03-01

Ion distributions and velocity profiles for electroosmotic flow in nanochannels of different widths are studied in this paper using molecular dynamics and continuum theory. For the various channel widths studied in this paper, the ion distribution near the channel wall is strongly influenced by the finite size of the ions and the discreteness of the solvent molecules. The classical Poisson-Boltzmann equation fails to predict the ion distribution near the channel wall as it does not account for the molecular aspects of the ion-wall and ion-solvent interactions. A modified Poisson-Boltzmann equation based on electrochemical potential correction is introduced to account for ion-wall and ion-solvent interactions. The electrochemical potential correction term is extracted from the ion distribution in a smaller channel using molecular dynamics. Using the electrochemical potential correction term extracted from molecular dynamics (MD) simulation of electroosmotic flow in a 2.22 nm channel, the modified Poisson-Boltzmann equation predicts the ion distribution in larger channel widths (e.g., 3.49 and 10.00 nm) with good accuracy. Detailed studies on the velocity profile in electro-osmotic flow indicate that the continuum flow theory can be used to predict bulk fluid flow in channels as small as 2.22 nm provided that the viscosity variation near the channel wall is taken into account. We propose a technique to embed the velocity near the channel wall obtained from MD simulation of electroosmotic flow in a narrow channel (e.g., 2.22 nm wide channel) into simulation of electroosmotic flow in larger channels. Simulation results indicate that such an approach can predict the velocity profile in larger channels (e.g., 3.49 and 10.00 nm) very well. Finally, simulation of electroosmotic flow in a 0.95 nm channel indicates that viscosity cannot be described by a local, linear constitutive relationship that the continuum flow theory is built upon and thus the continuum flow theory is not applicable for electroosmotic flow in such small channels.

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li xMn 2O 4 (100) Surfaces [First principles modeling of Mn(II) migration to and dissolution from Li xMn 2O 4 (100) surfaces

DOE PAGES

Leung, Kevin

2012-04-13

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (100) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is necessary but far from sufficient. Key steps that facilitate Mn(II) ion migration include concerted liquid/solid-state motions, proton-induced weakening of Mn-O bonds forming mobile OH - surface groups; andmore » chemical reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI component facilitates electrochemical reduction and decomposition of LEDC. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Separation of betacyanins from purple flowers of Gomphrena globosa L. by ion-pair high-speed counter-current chromatography.

PubMed

Spórna-Kucab, Aneta; Jagodzińska, Joanna; Wybraniec, Sławomir

2017-03-17

Betacyanins, known as antioxidants and chemopreventive natural compounds with colourful properties, were extracted from purple flowers of Gomphrena globosa L. belonging to the Amaranthaceae family and separated for the first time by ion-pair high-speed counter-current chromatography (HSCCC). The pigments were detected by LC-DAD-ESI-MS/MS technique. Separation of betacyanins (300mg) by HSCCC was accomplished in four solvent systems: tert-butyl methyl ether - butanol - acetonitrile - water (0.7% and 1.0% HFBA - heptafluorobutyric acid - system I and III) and tert-butyl methyl ether - butanol - methanol - water (0.7% and 1.0% HFBA - system II and IV) (2:2:1:5, v/v/v/v) in the head-to-tail mode. The mobile phase (aqueous phase) was run at 2.0ml/min and the column rotation speed was 860rpm. The applied systems enabled to study the influence of HFBA concentration as well as systems polarity on betacyanins separation. Comparison of the systems containing 0.7% HFBA (systems I-II) demonstrates that the replacement of acetonitrile by methanol increases the resolution (R s ) between all betacyanins and does not influence the retention of the stationary phase (S f =76%). Higher concentration of the acid in systems III-IV slightly decreases S f to 71% in the systems with 1.0% HFBA. Comparison of the resolution values for betacyanins in the systems with 0.7% and 1.0% HFBA demonstrates that higher concentration of the acid improves the separation effectiveness for all betacyanins as a result of increasing of the chemical affinity of the pigments to the organic stationary phase in HSCCC. The systems III-IV with 1% HFBA are the most effective for the separation of all the studied betacyanins. Copyright © 2017 Elsevier B.V. All rights reserved.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

Nanoporous thermosetting polymers.

PubMed

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

Solvent-mediated nonelectrostatic ion-ion interactions predicting anomalies in electrophoresis.

PubMed

Goswami, Prakash; Dhar, Jayabrata; Ghosh, Uddipta; Chakraborty, Suman

2017-03-01

We study the effects of solvent-mediated nonelectrostatic ion-ion interactions on electrophoretic mobility of a charged spherical particle. To this end, we consider the case of low surface electrostatic potential resulting in the linearization of the governing equations, which enables us to deduce a closed-form analytical solution to the electrophoretic mobility. We subsequently compare our results to the standard model using Henry's approach and report the changes brought about by the nonelectrostatic potential. The classical approach to determine the electrophoretic mobility underpredicts the particle velocity when compared with experiments. We show that this issue can be resolved by taking into account nonelectrostatic interactions. Our analysis further reveals the phenomenon of electrophoretic mobility reversal that has been experimentally observed in numerous previous studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fully automated methods for the determination of hydrochlorothiazide in human plasma and urine.

PubMed

Hsieh, J Y; Lin, C; Matuszewski, B K; Dobrinska, M R

1994-12-01

LC assays utilizing fully automated sample preparation procedures on Zymark PyTechnology Robot and BenchMate Workstation for the quantification of hydrochlorothiazide (HCTZ) in human plasma and urine have been developed. After aliquoting plasma and urine samples, and adding internal standard (IS) manually, the robot executed buffer and organic solvent addition, liquid-liquid extraction, solvent evaporation and on-line LC injection steps for plasma samples, whereas, BenchMate performed buffer and organic solvent addition, liquid-liquid and solid-phase extractions, and on-line LC injection steps for urine samples. Chromatographic separations were carried out on Beckman Octyl Ultrasphere column using the mobile phase composed of 12% (v/v) acetonitrile and 88% of either an ion-pairing reagent (plasma) or 0.1% trifluoroacetic acid (urine). The eluent from the column was monitored with UV detector (271 nm). Peak heights for HCTZ and IS were automatically processed using a PE-Nelson ACCESS*CHROM laboratory automation system. The assays have been validated in the concentration range of 2-100 ng ml-1 in plasma and 0.1-20 micrograms ml-1 in urine. Both plasma and urine assays have the sensitivity and specificity necessary to determine plasma and urine concentrations of HCTZ from low dose (6.25/12.5 mg) administration of HCTZ to human subjects in the presence or absence of losartan.