THE CONTRIBUTIONS OF NORMAL AND ANOMALOUS OSMOSIS TO THE OSMOTIC EFFECTS ARISING ACROSS CHARGED MEMBRANES WITH SOLUTIONS OF ELECTROLYTES

PubMed Central

Grim, Eugene; Sollner, Karl

1957-01-01

The osmotic effect arising across a porous membrane separating the solution of an electrolyte from water (or a more dilute solution) is ordinarily due to both normal osmosis, as it occurs also with non-electrolytes, and to "anomalous" osmosis. It is shown that the normal osmotic component cannot be measured quantitatively by the conventional comparison with a non-electrolytic reference solute. Anomalous osmosis does not occur with electroneutral membranes. Accordingly, with membranes which can be charged and discharged reversibly (without changes in geometrical structure), such as many proteinized membranes, the osmotic effects caused by an electrolyte can be measured both when only normal osmosis arises (with the membrane in the electroneutral state) and when normal as well as anomalous osmosis occurs (with the membrane in a charged state). The difference between these two effects is the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, with solutions of a variety of electrolytes using a concentration ratio of 2:1 over a wide range of concentrations. The rates of the movement of liquid across the membrane against an inconsequentially small hydrostatic head are recorded instead of, as conventional, the physiologically less significant pressure rises after a standard time. PMID:13439166

Electrochemical characterisation of a lithium-ion battery electrolyte based on mixtures of carbonates with a ferrocene-functionalised imidazolium electroactive ionic liquid.

PubMed

Forgie, John C; El Khakani, Soumia; MacNeil, Dean D; Rochefort, Dominic

2013-05-28

Electrolytic solutions of lithium-ion batteries can be modified with additives to improve their stability and safety. Electroactive molecules can be used as such additives to act as an electron (redox) shuttle between the two electrodes to prevent overcharging. The electroactive ionic liquid, 1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (TFSI), was synthesised and its electrochemical properties were investigated when diluted with ethylene carbonate-diethyl carbonate solvent at various concentrations. Cyclic voltammetry data were gathered to determine the redox potential, diffusion coefficient and heterogeneous rate constants of the electroactive imidazolium TFSI ionic liquid in the carbonate solution. The properties of this molecule as an additive in lithium battery electrolytes were studied in standard coin cells with a metallic Li anode and a Li4Ti5O12 cathode.

Fluctuation-enhanced electric conductivity in electrolyte solutions

DOE PAGES

Péraud, Jean-Philippe; Nonaka, Andrew J.; Bell, John B.; ...

2017-09-26

In this work, we analyze the effects of an externally applied electric field on thermal fluctuations for a binary electrolyte fluid. We show that the fluctuating Poisson–Nernst–Planck (PNP) equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation result in enhanced charge transport via a mechanism distinct from the well-known enhancement of mass transport that accompanies giant fluctuations. Although the mass and charge transport occurs by advection by thermal velocity fluctuations, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity and a nonzero cation–anion diffusion coefficient. Specifically, we predict a nonzero cation–anion Maxwell– Stefan coefficient proportionalmore » to the square root of the salt concentration, a prediction that agrees quantitatively with experimental measurements. The renormalized or effective macroscopic equations are different from the starting PNP equations, which contain no cross-diffusion terms, even for rather dilute binary electrolytes. At the same time, for infinitely dilute solutions the renormalized electric conductivity and renormalized diffusion coefficients are consistent and the classical PNP equations with renormalized coefficients are recovered, demonstrating the self-consistency of the fluctuating hydrodynamics equations. Our calculations show that the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye–Huckel–Onsager theory, while elucidating the physical origins of these corrections and generalizing straightforwardly to more complex multispecies electrolytes. Lastly, we show that strong applied electric fields result in anisotropically enhanced “giant” velocity fluctuations and reduced fluctuations of salt concentration.« less

Fluctuation-enhanced electric conductivity in electrolyte solutions

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

Péraud, Jean-Philippe; Nonaka, Andrew J.; Bell, John B.

In this work, we analyze the effects of an externally applied electric field on thermal fluctuations for a binary electrolyte fluid. We show that the fluctuating Poisson–Nernst–Planck (PNP) equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation result in enhanced charge transport via a mechanism distinct from the well-known enhancement of mass transport that accompanies giant fluctuations. Although the mass and charge transport occurs by advection by thermal velocity fluctuations, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity and a nonzero cation–anion diffusion coefficient. Specifically, we predict a nonzero cation–anion Maxwell– Stefan coefficient proportionalmore » to the square root of the salt concentration, a prediction that agrees quantitatively with experimental measurements. The renormalized or effective macroscopic equations are different from the starting PNP equations, which contain no cross-diffusion terms, even for rather dilute binary electrolytes. At the same time, for infinitely dilute solutions the renormalized electric conductivity and renormalized diffusion coefficients are consistent and the classical PNP equations with renormalized coefficients are recovered, demonstrating the self-consistency of the fluctuating hydrodynamics equations. Our calculations show that the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye–Huckel–Onsager theory, while elucidating the physical origins of these corrections and generalizing straightforwardly to more complex multispecies electrolytes. Lastly, we show that strong applied electric fields result in anisotropically enhanced “giant” velocity fluctuations and reduced fluctuations of salt concentration.« less

Calcium sulphate in ammonium sulphate solution

USGS Publications Warehouse

Sullivan, E.C.

1905-01-01

Calcium sulphate, at 25?? C., is two-thirds as soluble in dilute (o.i mol per liter) and twice as soluble in concentrated (3 mois per liter) ammonium sulphate solution as in water. The specific electric conductivity of concentrated ammonium sulphate solutions is lessened by saturating with calcium sulphate. Assuming that dissociation of ammonium sulphate takes place into 2NH4?? and SO4" and of calcium sulphate into Ca and SO4" only, and that the conductivity is a measure of such dissociation, the solubility of calcium sulphate in dilute ammonium sulphate solutions is greater than required by the mass-law. The conductivity of the dilute mixtures may be accurately calculated by means of Arrhenius' principle of isohydric solutions. In the data obtained in these calculations, the concentration of non-dissociated calcium sulphate decreases with increasing ammonium sulphate. The work as a whole is additional evidence of the fact that we are not yet in possession of all the factors necessary for reconciling the mass-law to the behavior of electrolytes. The measurements above described were made in the chemical laboratory of the University of Michigan.

Workman-Reynolds freezing potential measurements between ice and dilute salt solutions for single ice crystal faces.

PubMed

Wilson, P W; Haymet, A D J

2008-09-18

Workman-Reynolds freezing potentials have been measured for the first time across the interface between single crystals of ice 1h and dilute electrolyte solutions. The measured electric potential is a strictly nonequilibrium phenomenon and a function of the concentration of salt, freezing rate, orientation of the ice crystal, and time. When all these factors are controlled, the voltage is reproducible to the extent expected with ice growth experiments. Zero voltage is obtained with no growth or melting. For rapidly grown ice 1h basal plane in contact with a solution of 10 (-4) M NaCl the maximum voltage exceeds 30 V and decreases to zero at both high and low salt concentrations. These single-crystal experiments explain much of the data captured on this remarkable phenomenon since 1948.

Effects of fluid, electrolyte and substrate ingestion on endurance capacity.

PubMed

Maughan, R J; Fenn, C E; Leiper, J B

1989-01-01

The availability of carbohydrate (CHO) as a substrate for the exercising muscles is known to be a limiting factor in the performance of prolonged cycle exercise, and provision of exogenous CHO in the form of glucose can increase endurance capacity. The present study examined the effects of ingestion of fluids and of CHO in different forms on exercise performance. Six male volunteers exercised to exhaustion on a cycle ergometer at a workload which required approximately 70% of Vo2max. After one preliminary trial, subjects performed this exercise test on six occasions, one week apart. Immediately before exercise, and at 10-min intervals throughout, subjects ingested 100 ml of one of the following: control (no drink), water, glucose syrup, fructose syrup, glucose-fructose syrup or a dilute glucose-electrolyte solution. Each of the syrup solutions contained approximately 36 g CHO per 100 ml; the isotonic glucose-electrolyte solution contained 4 g glucose per 100 ml. A randomised Latin square order of administration of trials was employed. Expired air samples for determination of Vo2, respiratory exchange ratio and rate of CHO oxidation were collected at 15-min intervals. Venous blood samples were obtained before and after exercise. Subjects drinking the isotonic glucose-electrolyte solution exercised longer (90.8 (12.4) min, mean (SEM] than on the control test (70.2 (8.3) min; p less than 0.05).(ABSTRACT TRUNCATED AT 250 WORDS)

Electrostatics of polymer translocation events in electrolyte solutions.

PubMed

Buyukdagli, Sahin; Ala-Nissila, T

2016-07-07

We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.

An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range.

PubMed

Dutcher, Cari S; Ge, Xinlei; Wexler, Anthony S; Clegg, Simon L

2013-04-18

In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).

Focus Article: Oscillatory and long-range monotonic exponential decays of electrostatic interactions in ionic liquids and other electrolytes: The significance of dielectric permittivity and renormalized charges

NASA Astrophysics Data System (ADS)

Kjellander, Roland

2018-05-01

A unified treatment of oscillatory and monotonic exponential decays of interactions in electrolytes is displayed, which highlights the role of dielectric response of the fluid in terms of renormalized (effective) dielectric permittivity and charges. An exact, but physically transparent statistical mechanical formalism is thereby used, which is presented in a systematic, pedagogical manner. Both the oscillatory and monotonic behaviors are given by an equation for the decay length of screened electrostatic interactions that is very similar to the classical expression for the Debye length. The renormalized dielectric permittivities, which have similar roles for electrolytes as the dielectric constant has for pure polar fluids, consist in general of several entities with different physical meanings. They are connected to dielectric response of the fluid on the same length scale as the decay length of the screened interactions. Only in cases where the decay length is very long, these permittivities correspond approximately to a dielectric response in the long-wavelength limit, like the dielectric constant for polar fluids. Experimentally observed long-range exponentially decaying surface forces are analyzed as well as the oscillatory forces observed for short to intermediate surface separations. Both occur in some ionic liquids and in concentrated as well as very dilute electrolyte solutions. The coexisting modes of decay are in general determined by the bulk properties of the fluid and not by the solvation of the surfaces; in the present cases, they are given by the behavior of the screened Coulomb interaction of the bulk fluid. The surface-fluid interactions influence the amplitudes and signs or phases of the different modes of the decay, but not their decay lengths and wavelengths. The similarities between some ionic liquids and very dilute electrolyte solutions as regards both the long-range monotonic and the oscillatory decays are analyzed.

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.

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Order of wetting transitions in electrolyte solutions.

PubMed

Ibagon, Ingrid; Bier, Markus; Dietrich, S

2014-05-07

For wetting films in dilute electrolyte solutions close to charged walls we present analytic expressions for their effective interface potentials. The analysis of these expressions renders the conditions under which corresponding wetting transitions can be first- or second-order. Within mean field theory we consider two models, one with short- and one with long-ranged solvent-solvent and solvent-wall interactions. The analytic results reveal in a transparent way that wetting transitions in electrolyte solutions, which occur far away from their critical point (i.e., the bulk correlation length is less than half of the Debye length) are always first-order if the solvent-solvent and solvent-wall interactions are short-ranged. In contrast, wetting transitions close to the bulk critical point of the solvent (i.e., the bulk correlation length is larger than the Debye length) exhibit the same wetting behavior as the pure, i.e., salt-free, solvent. If the salt-free solvent is governed by long-ranged solvent-solvent as well as long-ranged solvent-wall interactions and exhibits critical wetting, adding salt can cause the occurrence of an ion-induced first-order thin-thick transition which precedes the subsequent continuous wetting as for the salt-free solvent.

Nuclear magnetic resonance studies of the solvation structures of a high-performance nonaqueous redox flow electrolyte

NASA Astrophysics Data System (ADS)

Deng, Xuchu; Hu, Mary; Wei, Xiaoliang; Wang, Wei; Mueller, Karl T.; Chen, Zhong; Hu, Jian Zhi

2016-03-01

Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and for understanding the detailed solvation structures. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. At dilute solute concentrations, most Fc1N112+ and TFSI- are fully disassociated with their own solvation shells formed by solvent molecules. At saturated concentration, Fc1N112+-TFSI- contact ion pairs are formed and the solvent molecules are preferentially interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

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.

Biocompatibility of hydroxyapatite coatings deposited by pulse electrodeposition technique on the Nitinol superelastic alloy.

PubMed

Marashi-Najafi, F; Khalil-Allafi, J; Etminanfar, M R

2017-07-01

The present study deals with pulse electrochemical deposition of HA on NiTi alloy and in vitro evaluation of coatings. At first step, a thermo-chemical surface modification process was applied to control the Ni release of the alloy. The electrochemical deposition of CaP coatings was examined at both dilute and concentrated solutions. The morphology and the composition of coatings were studied using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Plate like and needle like morphologies were formed for dilute and concentrated solution respectively and HA phase was formed by increasing the pulse current density for both electrolyte. The thickness of the samples was measured using cross sectioning technique. Fibroblast cell culture test on the coated samples revealed that the HA coating obtained by dilute solution shows the best biocompatibility. Also, MTT assay showed the highest cell density and cell proliferation after 5days for the HA coating of dilute solution. The contact angle of samples was measured and the coated samples showed a hydrophilic surface. Soaking the sample in SBF revealed that the crystallization rate of calcium-phosphate compounds is higher on the plate like HA coating as compared to the needle like morphology. The P release of the HA coated samples was measured in a physiological saline solution and the results show that the ions releasing in the plate like coating are less than the needle like coating. It seems that the stability of the plate like coating in biological environments is responsible for the better biocompatibility of the coating. Copyright © 2017 Elsevier B.V. All rights reserved.

4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl as a model organic redox active compound for nonaqueous flow batteries

NASA Astrophysics Data System (ADS)

Milshtein, Jarrod D.; Barton, John L.; Darling, Robert M.; Brushett, Fikile R.

2016-09-01

Nonaqueous redox flow batteries (NAqRFBs) that utilize redox active organic molecules are an emerging energy storage concept with the possibility of meeting grid storage requirements. Sporadic and uneven advances in molecular discovery and development, however, have stymied efforts to quantify the performance characteristics of nonaqueous redox electrolytes and flow cells. A need exists for archetypal redox couples, with well-defined electrochemical properties, high solubility in relevant electrolytes, and broad availability, to serve as probe molecules. This work investigates the 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl (AcNH-TEMPO) redox pair for such an application. We report the physicochemical and electrochemical properties of the reduced and oxidized compounds at dilute concentrations for electroanalysis, as well as moderate-to-high concentrations for RFB applications. Changes in conductivity, viscosity, and UV-vis absorbance as a function of state-of-charge are quantified. Cyclic voltammetry investigates the redox potential, reversibility, and diffusion coefficients of dilute solutions, while symmetric flow cell cycling determines the stability of the AcNH-TEMPO redox pair over long experiment times. Finally, single electrolyte flow cell studies demonstrate the utility of this redox couple as a platform chemistry for benchmarking NAqRFB performance.

Long-range electrostatic screening in ionic liquids

PubMed Central

Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

2015-01-01

Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 2. The systems H(+)-HSO4(-)-SO4(2-)-H2O from 0 to 3 mol kg(-1) as a function of temperature and H(+)-NH4(+)-HSO4(-)-SO4)2-)-H2O from 0 to 6 mol kg(-1) at 25 °C using a Pitzer ion interaction model, and NH4HSO4-H2O and (NH4)3H(SO4)2-H2O over the entire concentration range.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

A Pitzer ion interaction model has been applied to the systems H(2)SO(4)-H(2)O (0-3 mol kg(-1), 0-55 °C) and H(2)SO(4)-(NH(4))(2)SO(4)-H(2)O (0-6 mol kg(-1), 25 °C) for the calculation of apparent molar volume and density. The dissociation reaction HSO(4)(-)((aq)) ↔ H(+)((aq)) + SO(4)(2-)((aq)) is treated explicitly. Apparent molar volumes of the SO(4)(2-) ion at infinite dilution were obtained from part 1 of this work, (1) and the value for the bisulfate ion was determined in this study from 0 to 55 °C. In dilute solutions of both systems, the change in the degree of dissociation of the HSO(4)(-) ion with concentration results in much larger variations of the apparent molar volumes of the solutes than for conventional strong (fully dissociated) electrolytes. Densities and apparent molar volumes are tabulated. Apparent molar volumes calculated using the model are combined with other data for the solutes NH(4)HSO(4) and (NH(4))(3)H(SO(4))(2) at 25 °C to obtain apparent molar volumes and densities over the entire concentration range (including solutions supersaturated with respect to the salts).

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

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

Oral rehydration therapy in a rural area, northern Thailand.

PubMed

Varavithya, W; Sangshaisirisak, S; Ramaboot, S; Ruangkanchanasetr, S; Vivatwongkasem, C

1989-01-01

A cross-sectional sampling survey of mothers' practice of ORT in Amphoe Bunpotphesai in the northern part of Thailand included 1,619 children under five. Two hundred and six children were reported to have 223 diarrheal episodes. The incidence of diarrhea in children under five was 3.4 episodes per child per year. When children had diarrhea 65.5 per cent of mothers sought help from health providers, 25.2 per cent treated their children with drugs bought from stores, 2.3 per cent used herbal medicine and 6.1 per cent did not treat their children. 50.7 per cent of diarrheal episodes mother gave ORT, using ORS 19.7, commercial electrolytes mixture 16.6 and home available fluid 14.4 per cent. The accuracy of dilution of electrolytes powder from the packets was checked in 80 incidences. 31.8 and 27.8 per cent of mothers made correct dilution of ORS and commercial electrolytes products respectively. Health providers carried both ORS and commercial electrolytes packets. ORS added to a glass of water was found in 13.6 per cent which was 3 times concentrated. Commercial electrolytes products were too dilute in 72.2 per cent. 17.5 per cent of mothers divided electrolytes powder to add in one spoon of water to treat their children as one drug dose. Data showed that the ORT use rate was 50.7 per cent. Home available fluid was used by 14.4 per cent. ORT should be further promoted to control diarrheal diseases and health providers should give instructions to every mother or child minder on how to dispense ORS or electrolytes packets for appropriate dilution and use.

Demulsification of dilute oil/water emulsions with organic electrolytes

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

Jansson, M.; Pes, M.A.

1994-03-15

Tetraalkylammonium and tetraalkylphosphonium ions induce oil droplet coalescence in dilute oil/water emulsions stabilized by sodium dodecanoate. This was shown by dynamic light-scattering, monitoring oil droplet sizes, and kinetic measurements of oil droplet aggregation. A large ion size, a symmetrical ion geometry and a strongly interacting counterion were found to be important criteria for organic electrolytes to be efficient demulsifiers.

Bias due to Preanalytical Dilution of Rodent Serum for Biochemical Analysis on the Siemens Dimension Xpand Plus

PubMed Central

Johns, Jennifer L.; Moorhead, Kaitlin A.; Hu, Jing; Moorhead, Roberta C.

2018-01-01

Clinical pathology testing of rodents is often challenging due to insufficient sample volume. One solution in clinical veterinary and exploratory research environments is dilution of samples prior to analysis. However, published information on the impact of preanalytical sample dilution on rodent biochemical data is incomplete. The objective of this study was to evaluate the effects of preanalytical sample dilution on biochemical analysis of mouse and rat serum samples utilizing the Siemens Dimension Xpand Plus. Rats were obtained from end of study research projects. Mice were obtained from sentinel testing programs. For both, whole blood was collected via terminal cardiocentesis into empty tubes and serum was harvested. Biochemical parameters were measured on fresh and thawed frozen samples run straight and at dilution factors 2–10. Dilutions were performed manually, utilizing either ultrapure water or enzyme diluent per manufacturer recommendations. All diluted samples were generated directly from the undiluted sample. Preanalytical dilution caused clinically unacceptable bias in most analytes at dilution factors four and above. Dilution-induced bias in total calcium, creatinine, total bilirubin, and uric acid was considered unacceptable with any degree of dilution, based on the more conservative of two definitions of acceptability. Dilution often caused electrolyte values to fall below assay range precluding evaluation of bias. Dilution-induced bias occurred in most biochemical parameters to varying degrees and may render dilution unacceptable in the exploratory research and clinical veterinary environments. Additionally, differences between results obtained at different dilution factors may confound statistical comparisons in research settings. Comparison of data obtained at a single dilution factor is highly recommended. PMID:29497614

Ion Speciation and Transport Properties of LiTFSI in 1,3-Dioxolane Solutions: A Case Study for Li-S Battery Applications.

PubMed

Raccichini, Rinaldo; Dibden, James W; Brew, Ashley; Owen, John R; García-Aráez, Nuria

2018-01-11

Lithium-sulfur battery is considered to be one of the main candidates for "post-lithium-ion" battery generation because of its high theoretical specific capacity and inherently low cost. The role of electrolyte is particularly important in this system, and remarkable battery performances have been reported by tuning the amount of salt in the electrolyte. To further understand the reasons for such improvements, we chose the lithium bis(trifluoromethanesulfonyl)imide in 1,3-dioxolane electrolyte as a model salt-solvent system for a systematic study of conductivity and viscosity over a wide range of concentration from 10 -5 up to 5 m. The experimental results, discussed and interpreted with reference to the theory of electrolyte conductance, lead to the conclusion that triple ion formation is responsible for the highest molal conductivity values before reaching the maximum at 1.25 m. At higher concentrations, the molal conductivity drops quickly because of a rapid increase in viscosity and the salt-solvent system can be treated as a diluted form of molten salt.

Ion Transport in Confined Geometries below the Nanoscale: Access Resistance Dominates Protein Channel Conductance in Diluted Solutions.

PubMed

Alcaraz, Antonio; López, M Lidón; Queralt-Martín, María; Aguilella, Vicente M

2017-10-24

Synthetic nanopores and mesoscopic protein channels have common traits like the importance of electrostatic interactions between the permeating ions and the nanochannel. Ion transport at the nanoscale occurs under confinement conditions so that the usual assumptions made in microfluidics are challenged, among others, by interfacial effects such as access resistance (AR). Here, we show that a sound interpretation of electrophysiological measurements in terms of channel ion selective properties requires the consideration of interfacial effects, up to the point that they dominate protein channel conductance in diluted solutions. We measure AR in a large ion channel, the bacterial porin OmpF, by means of single-channel conductance measurements in electrolyte solutions containing varying concentrations of high molecular weight PEG, sterically excluded from the pore. Comparison of experiments performed in charged and neutral planar membranes shows that lipid surface charges modify the ion distribution and determine the value of AR, indicating that lipid molecules are more than passive scaffolds even in the case of large transmembrane proteins. We also found that AR may reach up to 80% of the total channel conductance in diluted solutions, where electrophysiological recordings register essentially the AR of the system and depend marginally on the pore characteristics. These findings may have implications for several low aspect ratio biological channels that perform their physiological function in a low ionic strength and macromolecule crowded environment, just the two conditions enhancing the AR contribution.

From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory.

PubMed

Gavish, Nir; Elad, Doron; Yochelis, Arik

2018-01-04

The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time relaxation, and underscreening, which all impact the emergence of fluid/solid interfaces, and the transport in these systems. Because these phenomena are not captured by existing mean-field models of electrolytes, there is a paramount need for a continuum framework for highly concentrated electrolytes and ionic liquid mixtures. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing a free energy that consists of short- and long-range interactions, along with an energy dissipation mechanism obtained by Onsager's relations. We show that the model can describe multiple bulk and interfacial morphologies at steady-state. Thus, the dynamic processes in the emergence of distinct morphologies become equally as important as the interactions that are specified by the free energy. The model equations not only provide insights into transport mechanisms beyond the Stokes-Einstein-Smoluchowski relations but also enable qualitative recovery of three distinct regions in the full range of the nonmonotonic electrical screening length that has been recently observed in experiments in which organic solvent is used to dilute ionic liquids.

[Massive transfusion of washed red blood cells: acid-base and electrolyth changes for different wash solutions].

PubMed

Sümpelmann, R; Schürholz, T; Marx, G; Ahrenshop, O; Zander, R

2003-09-01

The composition of normal saline (NaCl), the standard wash solution for cell saver autotransfusion, is considerably different from physiologic plasma values in small infants. Therefore, we investigated acid-base and electrolyte changes during massive cell saver autotransfusion with different wash solutions in young pigs. After approval by the animal protection authorities 15 young pigs (weight 10.6 +/- 1.1 kg, blood volume 848 +/- 88 ml, mean+/-SD) underwent 15 cycles of cell saver autotransfusion (Haemolite 2plus, Haemonetics). For each cycle, 100 ml arterial blood was withdrawn, washed with NaCl, physiologic multielectrolyte solution (PME, V Infusionslösung 296 mval Elektrolyte, Baxter) or physiologic erythrocyte protection solution (PEP, 3.2 % gelatine, pH 7.40, cHCO3 24 mmol/l), and then retransfused. Analyses of acid-base, electrolyte, and hematologic parameters were performed for systemic and washed blood samples. For NaCl there was a progressive decrease in systemic pH, HCO3 and base excess (BE) and an increase in chloride values (Cl) (p < 0.05). Use of PME slightly decreased pH (n. s.), whereas HCO3, BE and Cl remained stable. PEP slightly increased pH, HCO3 and BE, and decreased Cl (n. s.). Free hemoglobin increased in NaCl and PME (p < 0.05) and was below baseline in PEP (n. s.). Lactic acid course was comparable in all groups. The use of NaCl as wash solution for massive autotransfusion resulted in metabolic acidosis caused by dilution of HCO3 and increased Cl values. Fewer systemic acid-base and electrolyte changes were observed, when blood was washed with PME or PEP. The decreased hemoglobin release with PEP is possibly due to a gelatine specific electrostatic surface coating of erythrocyte membranes. For massive transfusion of washed red blood cells, physiologic multielectrolyte solution and physiologic erythrocyte protection solution should be preferred to NaCl, especially for small infants.

Ionic liquids behave as dilute electrolyte solutions

PubMed Central

Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

2013-01-01

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

Portable electrochemical system using screen-printed electrodes for monitoring corrosion inhibitors.

PubMed

Squissato, André L; Silva, Weberson P; Del Claro, Augusto T S; Rocha, Diego P; Dornellas, Rafael M; Richter, Eduardo M; Foster, Christopher W; Banks, Craig E; Munoz, Rodrigo A A

2017-11-01

This work presents a portable electrochemical system for the continuous monitoring of corrosion inhibitors in a wide range of matrices including ethanol, seawater and mineral oil following simple dilution of the samples. Proof-of-concept is demonstrated for the sensing of 2,5-dimercapto-1,3,5-thiadiazole (DMCT), an important corrosion inhibitor. Disposable screen-printed graphitic electrodes (SPGEs) associated with a portable batch-injection cell are proposed for the amperometric determination of DMCT following sample dilution with electrolyte (95% v/v ethanol + 5% v/v 0.1molL -1 H 2 SO 4 solution). This electrolyte was compatible with all samples and the organic-resistant SPGE could be used continuously for more than 200 injections (100µL injected at 193µLs -1 ) free from effects of adsorption of DMCT, which have a great affinity for metallic surfaces, and dissolution of the other reported SPGE inks which has hampered prior research efforts. Fast (180h -1 ) and precise responses (RSD < 3% n = 10) with a detection limit of 0.3µmolL -1 was obtained. The accuracy of the proposed method was attested through recovery tests (93-106%) and the reasonable agreement of results of DMCT concentrations in samples analyzed by both proposed and spectrophotometric (comparative) methods. Copyright © 2017 Elsevier B.V. All rights reserved.

Method and apparatus for adding electrolyte to a fuel cell stack

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

Congdon, J.V.; English, J.G.

1986-06-24

A process is described for adding electrolyte to a fuel cell stack, the stack comprising sheet-like elements defining a plurality of fuel cell units disposed one atop the other in abutting relationship, the units defining a substantially flat, vertically extending face, each unit including a cell comprising a pair of sheet-like spaced apart gas porous electrodes with a porous matrix layer sandwiched therebetween for retaining electrolyte during cell operation, each unit also including a sheet-like substantially non-porous separator, the separator being sandwiched between the cells of adjacent units. The improvement described here consists of: extending at least one of themore » sheet-like elements of each of a plurality of the fuel cell units outwardly from the stack face to define horizontal tabs disposed one above the other; depositing dilute electrolyte directly from electrolyte supply means upon substantially the full length, parallel to the stack face, of at least the uppermost tab, the tabs being constructed and arranged such that at least a portion of the deposited electrolyte cascades from tab to tab and down the face of the stack, the deposited electrolyte being absorbed by capillary action into the elements of the stack, the step of depositing continuing until all of the electrodes and matrix layers of the stack are fully saturated with the dilute electrolyte; and thereafter evaporating liquid from the saturated elements under controlled conditions of humidity and temperature until the stack has a desired electrolyte volume and electrolyte concentration therein.« less

Does Marcus-Hush theory really work Optical studies of intervalence transfer in acetylene-bridged biferrocene monocation at infinite dilution and at finite ionic strengths

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

Blackbourn, R.L.; Hupp, J.T.

1990-03-08

Intervalence charge-transfer data for acetylene-bridged biferrocene monocation (Bf{sup +}) have been collected in five solvents in the presence and absence of excess electrolyte and in the limit of infinite chromophore dilution. The study was motivated by earlier work which demonstrated that the intervalence absorption maximum for Bf{sup +} in methylene chloride could vary substantially with both chromophore concentration and added electrolyte concentration. In the present study similar (but smaller) variations are found in other solvents.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Specific Anion Effects on Na+ Adsorption at the Aqueous Solution-Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments.

PubMed

Olivieri, Giorgia; Parry, Krista M; D'Auria, Raffaella; Tobias, Douglas J; Brown, Matthew A

2018-01-18

Specific ion effects of the large halide anions have been shown to moderate anion adsorption to the air-water interface (AWI), but little quantitative attention has been paid to the behavior of alkali cations. Here we investigate the concentration and local distribution of sodium (Na + ) at the AWI in dilute (<1 M) aqueous solutions of NaCl, NaBr, and NaI using a combination of molecular dynamics (MD) and SESSA simulations, and liquid jet ambient pressure photoelectron spectroscopy measurements. We use SESSA to simulate Na 2p photoelectron intensities on the basis of the atom density profiles obtained from MD simulations, and we compare the simulation results with photoelectron spectroscopy experiments to evaluate the performance of a nonpolarizable force field model versus that of an induced dipole polarizable one. Our results show that the nonpolarizable force model developed by Horinek and co-workers (Chem. Phys. Lett. 2009, 479, 173-183) accurately predicts the local concentration and distribution of Na + near the AWI for all three electrolytes, whereas the polarizable model does not. To our knowledge, this is the first interface-specific spectroscopic validation of a MD force field. The molecular origins of the unique Na + distributions for the three electrolytes are analyzed on the basis of electrostatic arguments, and shown to arise from an indirect anion effect wherein the identity of the anion affects the strength of the attractive Na + -H 2 O electrostatic interaction. Finally, we use the photoelectron spectroscopy results to constrain the range of inelastic mean free paths (IMFPs) for the three electrolyte solutions used in the SESSA simulations that are able to reproduce the experimental intensities. Our results suggest that earlier estimates of IMFPs for aqueous solutions are likely too high.

Electrolyte chemistry control in electrodialysis processing

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

Hayes, Thomas D.; Severin, Blaine F.

Methods for controlling electrolyte chemistry in electrodialysis units having an anode and a cathode each in an electrolyte of a selected concentration and a membrane stack disposed therebetween. The membrane stack includes pairs of cationic selective and anionic membranes to segregate increasingly dilute salts streams from concentrated salts stream. Electrolyte chemistry control is via use of at least one of following techniques: a single calcium exclusionary cationic selective membrane at a cathode cell boundary, an exclusionary membrane configured as a hydraulically isolated scavenger cell, a multivalent scavenger co-electrolyte and combinations thereof.

Rapid recovery of dilute copper from a simulated Cu-SDS solution with low-cost steel wool cathode reactor.

PubMed

Chang, Shih-Hsien; Wang, Kai-Sung; Hu, Pei-I; Lui, I-Chun

2009-04-30

Copper-surfactant wastewaters are often encountered in electroplating, printed circuit boards manufacturing, and metal finishing industries, as well as in retentates from micellar-enhanced ultrafiltration process. A low-cost three-dimensional steel wool cathode reactor was evaluated for electrolytic recovery of Cu ion from dilute copper solution (0.2mM) in the presence of sodium dodecyl sulfate (SDS), octylphenol poly (ethyleneglycol) 9.5 ether (TX), nonylphenol poly (oxyethylene) 9 ether (NP9) and polyoxyethylene (20) sorbitan monooleate (TW) and also mixed surfactants (anionic/nonionic). The reactor showed excellent copper recovery ability in comparison to a parallel-plate reactor. The reactor rapidly recovered copper with a reasonable current efficiency. 93% of copper was recovered at current density of 1 A m(-2) and pH 4 in the presence of 8.5mM SDS. Initial solution pH, cathodic current density, solution mixing condition, SDS concentration, and initial copper concentrations significantly influenced copper recovery. The copper recovery rate increased with an increase in aqueous SDS concentrations between 5 and 8.5mM. The influences of nonionic surfactants on Cu recovery from SDS-Cu solution depended not only on the type of surfactants used, but also on applied concentrations. From the copper recovery perspective, TX at 0.1mM or NP should be selected rather than TW, because they did not inhibit copper recovery from SDS-Cu solution.

Impact of multicomponent ionic transport on pH fronts propagation in saturated porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Rolle, Massimo

2016-04-01

Multicomponent ionic interactions have been increasingly recognized as important factors for the displacement of charged species in porous media under both diffusion- [1,2] and advection-dominated flow regimes [3,4]. In this study we investigate the propagation of pH fronts during multicomponent ionic transport in saturated porous media under flow-through conditions. By performing laboratory bench-scale experiments combined with numerical modeling we show the important influence of Coulombic effects on proton transport in the presence of ionic admixtures. The experiments were performed in a quasi two-dimensional flow-through setup under steady-state flow and transport conditions. Dilute solutions of hydrochloric acid with MgCl2 (1:2 strong electrolyte) were used as tracer solutions to experimentally test the effect of electrochemical cross-coupling on the migration of diffusive/dispersive pH fronts. We focus on two experimental scenarios, with different composition of tracer solutions, causing remarkably different effects on the propagation of the acidic fronts with relative differences in the penetration depth of pH fronts of 36% between the two scenarios and of 25% and 15% for each scenario with respect to the transport of ions at liberated state (i.e., without considering the charge effects). Also significant differences in the dilution of the distinct ionic plumes, quantified using the flux-related dilution index at the laboratory bench scale [5], were measured at the outflow of the flow-through system. The dilution of the pH plumes also changed considerably (26% relative difference) in the two flow-through experiments only due to the different composition of the pore water solution and to the electrostatic coupling of the ions in the flow-through setups. Numerical transport simulations were performed to interpret the laboratory experiments. The simulations were based on a multicomponent ionic formulation accurately capturing the Coulombic interactions between the transported ions in the flow-through system. The results of purely forward simulations show a very good agreement with the high-resolution measurements performed at the outlet of the flow-through setup and illustrate the importance of charge effects on pH fronts propagation in porous media. [1] Giambalvo, E. R., C. I. Steefel, A. T. Fisher, N. D. Rosenberg, and C. G. Wheat (2002), Effect of fluid-sediment reaction on hydrothermal fluxes of major elements, eastern flank of the Juan de Fuca Ridge, Geochim. Cosmochim. Acta, 66, 1739-1757. [2] Appelo, C. A. J., and P. Wersin (2007), Multicomponent diffusion modeling in clay systems with application to the diffusion of tritium, iodide, and sodium in opalinus clay, Environ. Sci. Technol., 41, 5002-5007. [3] Rolle, M., M. Muniruzzaman, C. M. Haberer, and P. Grathwohl (2013), Coulombic effects in advection-dominated transport of electrolytes in porous media: Multicomponent ionic dispersion, Geochim. Cosmochim. Acta, 120, 195-205. [4] Muniruzzaman, M., C. M. Haberer, P. Grathwohl, and M. Rolle (2014), Multicomponent ionic dispersion during transport of electrolytes in heterogeneous porous media: Experiments and model-based interpretation, Geochim. Cosmochim. Acta, 141, 656-669. [5] Rolle, M., G. Chiogna, D. L. Hochstetler, and P. K. Kitanidis (2013), On the importance of diffusion and compound-specific mixing for groundwater transport: An investigation from pore to field scale, J. Contam. Hydrol., 153, 51-68.

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

One-step large-scale synthesis of micrometer-sized silver nanosheets by a template-free electrochemical method

NASA Astrophysics Data System (ADS)

Park, Sun Hwa; Son, Jin Gyeong; Lee, Tae Geol; Park, Hyun Min; Song, Jae Yong

2013-05-01

We have synthesized micrometer-sized Ag nanosheets via a facile, one-step, template-free electrochemical deposition in an ultra-dilute silver nitrate aqueous electrolyte. The nanosheet growth was revealed to occur in three stages: (1) formation of polygonal Ag nuclei on a substrate, (2) growth of {112}-faceted nanowire from the nuclei, and (3) anisotropic growth of (111)-planar nanosheets, approximately 20 to 50 nm in thickness and 10 μm in width, in the <112>-direction. The vertical growth of the facet nanowire was induced by the strong interface anisotropy between the deposit and electrolyte due to the ultra-dilute concentration of electrolyte and high reduction potential. The thickness of Ag nanosheets was controllable by the adjustment of the reduction/oxidation potential and frequency of the reverse-pulse potentiodynamic mode.

High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1998-10-20

This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

The thermodynamic characteristics of solutions of Bu4NI in dimethylsulfoxide over a wide concentration range

NASA Astrophysics Data System (ADS)

Safonova, L. P.; Shmukler, L. E.; Kolker, A. M.

2008-05-01

The integral heats of solution of Bu4NI in dimethylsulfoxide (DMSO) were measured at 298.15, 313.15, and 328.15 K and concentrations from dilute to saturation. The standard enthalpies and heat capacities of solution and solvation of Bu4NI in DMSO at various temperatures and the bar C_p^o (Bu_4 N^ + ) value at 298.15 K were calculated. The obtained and literature data were used to consider the influence of the nature of solvents on Δsol H m (Bu4NI) and of the electrolyte on Δsol H m in dimethylsulfoxide at 298.15 K. The dynamic viscosity and density of the Bu4NI-DMSO system were determined at various concentrations and temperatures. The Eyring equation was used to calculate the activation energy of viscous flow at all the concentrations studied.

A high-temperature high-pressure calorimeter for determining heats of solution up to 623 K.

PubMed

Djamali, Essmaiil; Turner, Peter J; Murray, Richard C; Cobble, James W

2010-07-01

A high-temperature high-pressure isoperibol calorimeter for determining the heats of solution and reaction of very dilute substances in water (10(-4) m) at temperatures up to 623 K is described. The energies of vaporization of water at steam saturation pressure were measured as a function of temperature and the results agree with the corresponding values from steam tables to better than 0.08+/-0.18%. The novelties of the present instrument relative to flow type heat capacity calorimeters are that measurements can be made at orders of magnitude lower concentrations and that measurement of heat of reaction involving solids or gases or in the presence of high concentrations of supporting electrolytes, acids, and bases is possible. Furthermore, the advantage of using enthalpy data over heat capacity data for calculations of the standard state Gibbs free energies of electrolytes is that the experimental heat data of this research need only be integrated once to derive higher temperature free energy data from lower temperatures. The derived heat capacities can be used mathematically to obtain free energies by double integration. However, the resulting errors are much smaller than if experimental aqueous heat capacities were used for the integrations.

Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents

DOEpatents

Angell, Charles Austen; Zhang, Sheng-Shui; Xu, Kang

1998-01-01

The present invention relates to electrolyte solvents for use in liquid or rubbery electrolyte solutions. Specifically, this invention is directed to boron-containing electrolyte solvents and boron-containing electrolyte solutions.

Thermodynamics of Dilute Solutions.

ERIC Educational Resources Information Center

Jancso, Gabor; Fenby, David V.

1983-01-01

Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H(2)SO(4) in 0-3 mol kg(-1) aqueous solutions of the pure acid and to represent directly the effect of the HSO(4)(-) ↔ H(+) + SO(4)(2-) reaction. The results are incorporated into the treatment of aqueous H(2)SO(4) density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

ELECTROLYTIC SEPARATION PROCESS AND APPARATUS

DOEpatents

McLain, M.E. Jr.; Roberts, M.W.

1962-03-01

A method is given for dissolving stainless steel-c lad fuel elements in dilute acids such as half normal sulfuric acid. The fuel element is made the anode in a Y-shaped electrolytic cell which has a flowing mercury cathode; the stainless steel elements are entrained in the mercury and stripped therefrom by a continuous process. (AEC)

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

High-pressure nuclear magnetic resonance studies of fuel cell membranes

NASA Astrophysics Data System (ADS)

Mananga, Eugene Stephane

This thesis focuses on the use of high pressure NMR to study transport properties in electrolyte membranes used for fuel cells. The main concern is in studying the self-diffusion coefficients of ions and molecules in membranes and solutions, which can be used to characterize electrolytes in fuel cells. For this purpose, a high-pressure fringe field NMR method to study transport properties in material systems useful for fuel cell and battery electrolytes, was designed, developed, and implemented. In this investigation, pressure is the thermodynamic variable to obtain additional information about the ionic transport process, which could yield the crucial parameter, activation volume. Most of the work involves proton NMR, with additional investigations of others nuclei, such as fluorine, phosphorus and lithium. Using the FFG method, two fuel cell membrane types (NAFION-117, SPTES), and different dilutions of phosphoric acid were investigated, as was LiTf salt in Diglyme solution, which is used as a lithium battery electrolyte. In addition to high-pressure NMR diffusion measurements carried out in the fringe field gradient for the investigation of SPTES, pulse field gradient spin echo NMR was also used to characterize the water diffusion, in addition to measuring diffusion rates as a function of temperature. This second method allows us to measure distinct diffusion coefficients in cases where the different nuclear (proton) environments can be resolved in the NMR spectrum. Polymer electrolyte systems, in which the mobility of both cations and anions is probed by NMR self-diffusion measurements using standard pulsed field gradient methods and static gradient measurements as a function of applied hydrostatic pressure, were also investigated. The material investigated is the low molecular weight liquid diglyme/LiCF3SO3 (LiTf) complexes which can be used as electrolytes in lithium batteries. Finally, high-pressure diffusion coefficient measurements of phosphoric acid in water at different concentrations: proton (1H) and phosphorus (31P) nuclei have been performed using the static field gradient spin-echo nuclear magnetic resonance. This study is expected to be helpful in improving the understanding of phosphoric acid fuel cell technology.

Spectrophotometric studies and applications for the determination of Ni2+ in zinc-nickel alloy electrolyte

NASA Astrophysics Data System (ADS)

Qiao, Xiaoping; Li, Helin; Zhao, Wenzhen; Li, Dejun

The absorption properties of zinc-nickel alloy electrolyte were studied by visible spectrophotometer. The results show that the relationship between the absorbance of the zinc-nickel alloy electrolyte and Ni2+ concentration in the electrolyte obeys Beer's law at 660 nm. In addition, other components except Ni2+ in the zinc-nickel alloy electrolyte such as zinc chloride, ammonium chloride, potassium chloride and boric acid have no obvious effect on the absorbance of zinc-nickel alloy electrolyte. Based on these properties, a new method is developed to determine Ni2+ concentration in zinc-nickel alloy electrolyte. Comparing with other methods, this method is simple, direct and accurate. Moreover, the whole testing process does not consume any reagent and dilution, and after testing, the electrolyte samples can be reused without any pollution to the environment.

Carbonic acid ionization and the stability of sodium bicarbonate and carbonate ion pairs to 200 °C - A potentiometric and spectrophotometric study

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Bénézeth, Pascale; Schott, Jacques

2013-11-01

Carbonic acid ionization and sodium bicarbonate and carbonate ion pair formation constants have been experimentally determined in dilute hydrothermal solutions to 200 °C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 °C and spectrophotometric pH measurements using the pH indicators, 2-napthol and 4-nitrophenol, at 25-200 °C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for NaHCO(aq)(K) and NaCO3-(aq)(K) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The NaHCO(aq) and NaCO3-(aq) ion pair formation constants vary between 25 and 200 °C having values of logK=-0.18 to 0.58 and logK=1.01 to 2.21, respectively. These ion pairs are weak at low-temperatures but become increasingly important with increasing temperature under neutral to alkaline conditions in moderately dilute to concentrated NaCl solutions, with NaCO3-(aq) predominating over CO32-(aq) in ⩾0.1 M NaCl solution at temperatures above 100 °C. The results demonstrate that NaCl cannot be considered as an inert (non-complexing) electrolyte in aqueous carbon dioxide containing solutions at elevated temperatures.

Does fluid resuscitation with balanced solutions induce electrolyte and metabolic abnormalities? An in vitro assessment.

PubMed

Krzych, Łukasz J; Czempik, Piotr F

2017-01-01

Popular intravenous fluids in clinical use may have an impact on electrolyte concentration and metabolic balance and should be considered as powerful pharmacological agents. There is a growing body of evidence that fluid therapy should be more individualised and preferably based on balanced solutions. We sought to investigate the impact of three commonly used balanced fluids on electrolytes and metabolic equilibrium in an in vitro setting. Study group comprised 32 healthy male volunteers (without history of any acute/chronic disorder or known metabolic abnormality), aged 21-35 (29 ± 4) years, weight 59-103 (81.2 ± 9.8) kg, from whom blood samples were withdrawn. The whole blood was diluted in 4:1 ratio with the study solutions to make an end-concentration of 20 vol.% of each solution. The test solutions included balanced crystalloid (Plasmalyte®, Baxter, Poland [PL]), succinylated gelatin (Geloplasma®, Fresenius Kabi, Poland [GEL]) and 6% HES 130/0.4 (Volulyte®, Fresenius Kabi, Poland [HES]). All fluids caused comparable degree of haemodilution. PL and GEL decreased (104 mmol/L, interquartile range [IQR] 103-105; and 106 mmol/L, IQR 105-107.5, respectively), whereas HES increased the concentration of Cl- to 109 (IQR 108-110) mmol/L. PL and HES decreased (136, IQR 136-137 mmol/L; and 138 mmol/L, IQR 137-139, respectively), whereas GEL increased the Na+ level to 140.5 (IQR 140-141) mmol/L. PL and HES decreased osmolality (277.2 mOsm/kg, IQR 275.7-278.4; and 280.9 mOsm/kg, IQR 279.3-282.0, respectively). GEL increased it to 285.7 (IQR 283.7-286.8) mOsm/kg. All test solutions caused a similar statistically significant (p < 0.05) drop in base excess and bicarbonate concentration, and these fell outside the reference values. Due to its composition, GEL caused a significant increase in lactate concentration. HES and GEL caused a statistically significant drop in strong ion difference value. Due to high lactate level, the effect of GEL was most pronounced. Balanced intravenous solutions should be safe in terms of their impact on human plasma electrolyte and meta-bolic equilibrium when administered to replace up to 20% of blood volume. In metabolic acidosis, balanced succinylated gelatin should be used with caution. Therefore, arterial blood gas analysis should be performed in patients in whom significant amounts of fluid are administrated, preferably with assessment of Cl-, Na+, lactate concentrations as well as pH, osmolality, and strong ion difference.

An electrochemical quartz crystal microbalance study of magnesium dissolution

NASA Astrophysics Data System (ADS)

Ralston, K. D.; Thomas, S.; Williams, G.; Birbilis, N.

2016-01-01

A quartz crystal microbalance (QCM) was used in conjunction with electrochemical measurements to study dissolution of pure magnesium (Mg) sensors in dilute NaCl electrolytes. Open circuit potential and potentiodynamic polarisation experiments were conducted in 0.01 M NaCl, having pH values 3 (buffered) and 6 (unbuffered). In the pH 3 solution, the Mg sensor showed a net mass-loss during the electrochemical tests, whereas, in the unbuffered pH 6 solution Mg showed a net mass-gain, corresponding to the growth of an Mg(OH)2 film on its surface. The loss in the electrochemical efficiency of Mg dissolution due to such direct parasitic Mg(OH)2 growth has been estimated to be around 17-34%. This loss relates to the low capacities and voltage fluctuations reported during discharge of primary Mg batteries.

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation

NASA Astrophysics Data System (ADS)

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-01

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ˜ cs-0.5 as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Flexible polyelectrolyte chain in a strong electrolyte solution: Insight into equilibrium properties and force-extension behavior from mesoscale simulation.

PubMed

Malekzadeh Moghani, Mahdy; Khomami, Bamin

2016-01-14

Macromolecules with ionizable groups are ubiquitous in biological and synthetic systems. Due to the complex interaction between chain and electrostatic decorrelation lengths, both equilibrium properties and micro-mechanical response of dilute solutions of polyelectrolytes (PEs) are more complex than their neutral counterparts. In this work, the bead-rod micromechanical description of a chain is used to perform hi-fidelity Brownian dynamics simulation of dilute PE solutions to ascertain the self-similar equilibrium behavior of PE chains with various linear charge densities, scaling of the Kuhn step length (lE) with salt concentration cs and the force-extension behavior of the PE chain. In accord with earlier theoretical predictions, our results indicate that for a chain with n Kuhn segments, lE ∼ cs (-0.5) as linear charge density approaches 1/n. Moreover, the constant force ensemble simulation results accurately predict the initial non-linear force-extension region of PE chain recently measured via single chain experiments. Finally, inspired by Cohen's extraction of Warner's force law from the inverse Langevin force law, a novel numerical scheme is developed to extract a new elastic force law for real chains from our discrete set of force-extension data similar to Padè expansion, which accurately depicts the initial non-linear region where the total Kuhn length is less than the thermal screening length.

Utilization of hydrolysate from lignocellulosic biomass pretreatment to generate electricity by enzymatic fuel cell system.

PubMed

Kim, Sung Bong; Kim, Dong Sup; Yang, Ji Hyun; Lee, Junyoung; Kim, Seung Wook

2016-04-01

The waste hydrolysate after dilute acid pretreatment (DAP) of lignocellulosic biomass was utilized to generate electricity using an enzymatic fuel cell (EFC) system. During DAP, the components of biomass containing hemicellulose and other compounds are hydrolyzed, and glucose is solubilized into the dilute acid solution, called as the hydrolysate liquid. Glucose oxidase (GOD) and laccase (Lac) were assembled on the electrode of the anode and cathode, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were measured, and the maximum power density was found to be 1.254×10(3) μW/cm(2). The results indicate that the hydrolysate from DAP is a reliable electrolyte containing the fuel of EFC. Moreover, the impurities in the hydrolysate such as phenols and furans slightly affected the charge transfer on the surface of the electrode, but did not affect the power generation of the EFC system in principal. Copyright © 2016 Elsevier Inc. All rights reserved.

An induced current method for measuring zeta potential of electrolyte solution-air interface.

PubMed

Song, Yongxin; Zhao, Kai; Wang, Junsheng; Wu, Xudong; Pan, Xinxiang; Sun, Yeqing; Li, Dongqing

2014-02-15

This paper reports a novel and very simple method for measuring the zeta potential of electrolyte solution-air interface. When a measuring electrode contacts the electrolyte solution-air interface, an electrical current will be generated due to the potential difference between the electrode-air surface and the electrolyte solution-air interface. The amplitude of the measured electric signal is linearly proportional to this potential difference; and depends only on the zeta potential at the electrolyte solution-air interface, regardless of the types and concentrations of the electrolyte. A correlation between the zeta potential and the measured voltage signal is obtained based on the experimental data. Using this equation, the zeta potential of any electrolyte solution-air interface can be evaluated quickly and easily by inserting an electrode through the electrolyte solution-air interface and measuring the electrical signal amplitude. This method was verified by comparing the obtained results of NaCl, MgCl2 and CaCl2 solutions of different pH values and concentrations with the zeta potential data reported in the published journal papers. Copyright © 2013 Elsevier Inc. All rights reserved.

The Electrochemical Performance of Silicon Nanoparticles in Concentrated Electrolyte.

PubMed

Chang, Zeng-Hua; Wang, Jian-Tao; Wu, Zhao-Hui; Gao, Min; Wu, Shuai-Jin; Lu, Shi-Gang

2018-06-11

Silicon is a promising material for anodes in energy-storage devices. However, excessive growth of a solid-electrolyte interphase (SEI) caused by the severe volume change during the (de)lithiation processes leads to dramatic capacity fading. Here, we report a super-concentrated electrolyte composed of lithium bis(fluorosulfonyl)imide (LiFSI) and propylene carbonate (PC) with a molar ratio of 1:2 to improve the cycling performance of silicon nanoparticles (SiNPs). The SiNP electrode shows a remarkably improved cycling performance with an initial delithiation capacity of approximately 3000 mAh g -1 and a capacity of approximately 2000 mAh g -1 after 100 cycles, exhibiting about 6.8 times higher capacity than the cells with dilute electrolyte LiFSI-(PC) 8 . Raman spectra reveal that most of the PC solvent and FSI anions are complexed by Li + to form a specific solution structure like a fluid polymeric network. The reduction of FSI anions starts to play an important role owing to the increased concentration of contact ion pairs (CIPs) or aggregates (AGGs), which contribute to the formation of a more mechanically robust and chemically stable complex SEI layer. The complex SEI layer can effectively suppress the morphology evolution of silicon particles and self-limit the excessive growth, which mitigates the crack propagation of the silicon electrode and the deterioration of the kinetics. This study will provide a new direction for screening cycling-stable electrolytes for silicon-based electrodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of electrical double-layer interaction on coal flotation.

PubMed

Harvey, Paul A; Nguyen, Anh V; Evans, Geoffrey M

2002-06-15

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.

Ultra-fast AC electro-osmotic micropump with arrays of asymmetric ring electrode pairs in 3D cylindrical microchannel

NASA Astrophysics Data System (ADS)

Gao, Xiaobo; Li, Yu Xiao

2018-04-01

AC electro-osmotic (ACEO) micropumps presently involve the planar or nonplanar electrode pair array in the rectangular microchannel. However, this paper presented a theoretical model of an ultra-fast 3D ring ACEO micropump with arrays of asymmetric ring electrode pairs in the cylindrical microchannel. The theory is on the basis of the interaction between the nonuniform electric field and ions of an electric double layer (EDL) on the surface of ring electrodes. Therefore, we first established the equivalent hollow cylinder capacitance of EDL for ring ACEO micropumps. Then, the 3D Poisson-Boltzmann model by solving the electric field and fluidic flow field with the charge conservation and the slip velocity boundary conditions was numerically calculated. For a dilute strong electrolyte solution, the conductivity as a function of the electrolyte concentration can be obtained by the modified Kohlrausch's dilution empirical equation with the molar conductivity. The results revealed that the flow rate of ring ACEO was higher than the planar ACEO, which agreed well with the experiment. The dependences of the time-averaged pumping velocity on the frequency and concentration have similar bell profiles with a maximal value. Moreover, the optimal velocity with proper geometric parameters was obtained at a given frequency, voltage, concentration, and radius. The high-speed ring ACEO micropump will be significant for the experimental studies to further improve the flow rate and be hopeful for applications of microfluidic mixing, particle manipulation, and so on.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

PubMed

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-02-12

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

PubMed Central

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-01-01

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514

25 Mg NMR and computational modeling studies of the solvation structures and molecular dynamics in magnesium based liquid electrolytes

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

Hu, Jian Zhi; Rajput, Nav Nidhi; Wan, Chuan

There is increasing evidence that the solvation structure of the active components in a liquid electrolyte solution strongly impacts the performance in electrochemical applications. In this work, the nanoscale solvation structures and dynamics of Mg(BH4)2 and Mg(TFSI)2 dissolved in diglyme (DGM) at various concentrations and ratios of Mg(BH4)2/Mg(TFSI)2 were investigated using a combination of natural abundance 25Mg NMR, quantum chemistry calculations of 25Mg NMR chemical shifts, classical molecular dynamics (MD) calculations, and electrochemical performance tests. By mixing two competing Mg salts, we were able to reduce the strong covalent interactions between Mg2+ and BH4– anions. A small increase is observedmore » in the coordination number of Mg-TFSI and a significant increase in the interaction of Mg2+ ions with glymes. Through a combination of NMR, DFT and MD simulations, various stable species around 1 nm in size were detected in the mixed salt solution, which play key roles in the enhanced electrochemical performance of the mixed electrolyte. It is established that for the neat Mg(TFSI)2 in DGM electrolyte at dilute concentrations the TFSI- is fully dissociated from Mg2+. At higher concentrations, Mg2+ and TFSI- are only partially dissociated as contact ion pairs are formed. In contrast, at 0.01 M Mg(BH4)2 (saturated concentration) in DGM, the first solvation shell of a Mg2+ ion contains two BH4- anions and one DGM molecule, while the second solvation shell consists of five to six DGM molecules. An exchange mechanism between the solvation structures in the combined electrolyte containing both Mg(BH4)2 and Mg(TFSI)2 in DGM was found to result in the observation of a single 25Mg NMR peak. This exchange is responsible for an increase in uncoordinated anions, as well as improved stability and ionic conductivity as compared to single anion solution. Solvent molecule rearrangement and direct Mg-ion exchange between the basic solvation structures are hypothesized as likely reasons for the exchange. We elucidate that the solvent rearrangement is energetically much more favorable than direct Mg-ion hopping and is thus suggested as the dominant exchange mechanism.« less

25Mg NMR and Computational Modeling Studies of the Solvation Structures and Molecular Dynamics in Magnesium Based Liquid Electrolytes

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

Hu, Jian Z.; Rajput, Nav Nidhi; Wan, Chuan

There is increasing evidence that the solvation structure of the active components in a liquid electrolyte solution strongly impacts the performance in electrochemical applications. In this work, the nanoscale solvation structures and dynamics of Mg(BH4)2 and Mg(TFSI)2 dissolved in diglyme (DGM) at various concentrations and ratios of Mg(BH4)2/Mg(TFSI)2 were investigated using a combination of natural abundance 25Mg NMR, quantum chemistry calculations of 25Mg NMR chemical shifts, classical molecular dynamics (MD) calculations, and electrochemical performance tests. By mixing two competing Mg salts, we were able to reduce the strong covalent interactions between Mg2+ and BH4– anions. A small increase is observedmore » in the coordination number of Mg-TFSI and a significant increase in the interaction of Mg2+ ions with glymes. Through a combination of NMR, DFT and MD simulations, various stable species around 1 nm in size were detected in the mixed salt solution, which play key roles in the enhanced electrochemical performance of the mixed electrolyte. It is established that for the neat Mg(TFSI)2 in DGM electrolyte at dilute concentrations the TFSI- is fully dissociated from Mg2+. At higher concentrations, Mg2+ and TFSI- are only partially dissociated as contact ion pairs are formed. In contrast, at 0.01 M Mg(BH4)2 (saturated concentration) in DGM, the first solvation shell of a Mg2+ ion contains two BH4- anions and one DGM molecule, while the second solvation shell consists of five to six DGM molecules. An exchange mechanism between the solvation structures in the combined electrolyte containing both Mg(BH4)2 and Mg(TFSI)2 in DGM was found to result in the observation of a single 25Mg NMR peak. This exchange is responsible for an increase in uncoordinated anions, as well as improved stability and ionic conductivity as compared to single anion solution. Solvent molecule rearrangement and direct Mg-ion exchange between the basic solvation structures are hypothesized as likely reasons for the exchange. We elucidate that the solvent rearrangement is energetically much more favorable than direct Mg-ion hopping and is thus suggested as the dominant exchange mechanism.« less

Dilution Confusion: Conventions for Defining a Dilution

ERIC Educational Resources Information Center

Fishel, Laurence A.

2010-01-01

Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

Nickel recovery from electronic waste II electrodeposition of Ni and Ni-Fe alloys from diluted sulfate solutions.

PubMed

Robotin, B; Ispas, A; Coman, V; Bund, A; Ilea, P

2013-11-01

This study focuses on the electrodeposition of Ni and Ni-Fe alloys from synthetic solutions similar to those obtained by the dissolution of electron gun (an electrical component of cathode ray tubes) waste. The influence of various parameters (pH, electrolyte composition, Ni(2+)/Fe(2+) ratio, current density) on the electrodeposition process was investigated. Scanning electron microscopy (SEM) and X-ray fluorescence analysis (XRFA) were used to provide information about the obtained deposits' thickness, morphology, and elemental composition. By controlling the experimental parameters, the composition of the Ni-Fe alloys can be tailored towards specific applications. Complementarily, the differences in the nucleation mechanisms for Ni, Fe and Ni-Fe deposition from sulfate solutions have been evaluated and discussed using cyclic voltammetry and potential step chronoamperometry. The obtained results suggest a progressive nucleation mechanism for Ni, while for Fe and Ni-Fe, the obtained data points are best fitted to an instantaneous nucleation model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-12-01

The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

Strongly nonlinear dynamics of electrolytes in large ac voltages.

PubMed

Højgaard Olesen, Laurits; Bazant, Martin Z; Bruus, Henrik

2010-07-01

We study the response of a model microelectrochemical cell to a large ac voltage of frequency comparable to the inverse cell relaxation time. To bring out the basic physics, we consider the simplest possible model of a symmetric binary electrolyte confined between parallel-plate blocking electrodes, ignoring any transverse instability or fluid flow. We analyze the resulting one-dimensional problem by matched asymptotic expansions in the limit of thin double layers and extend previous work into the strongly nonlinear regime, which is characterized by two features--significant salt depletion in the electrolyte near the electrodes and, at very large voltage, the breakdown of the quasiequilibrium structure of the double layers. The former leads to the prediction of "ac capacitive desalination" since there is a time-averaged transfer of salt from the bulk to the double layers, via oscillating diffusion layers. The latter is associated with transient diffusion limitation, which drives the formation and collapse of space-charge layers, even in the absence of any net Faradaic current through the cell. We also predict that steric effects of finite ion sizes (going beyond dilute-solution theory) act to suppress the strongly nonlinear regime in the limit of concentrated electrolytes, ionic liquids, and molten salts. Beyond the model problem, our reduced equations for thin double layers, based on uniformly valid matched asymptotic expansions, provide a useful mathematical framework to describe additional nonlinear responses to large ac voltages, such as Faradaic reactions, electro-osmotic instabilities, and induced-charge electrokinetic phenomena.

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

NASA Technical Reports Server (NTRS)

Myerson, Allan S.; Izmailov, Alexander F.; Na, Han-Soo

1996-01-01

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

Dynamics of osmosis in a porous medium.

PubMed

Cardoso, Silvana S S; Cartwright, Julyan H E

2014-11-01

We derive from kinetic theory, fluid mechanics and thermodynamics the minimal continuum-level equations governing the flow of a binary, non-electrolytic mixture in an isotropic porous medium with osmotic effects. For dilute mixtures, these equations are linear and in this limit provide a theoretical basis for the widely used semi-empirical relations of Kedem & Katchalsky (Kedem & Katchalsky 1958 Biochim. Biophys. Acta 27, 229-246 (doi:10.1016/0006-3002(58)90330-5), which have hitherto been validated experimentally but not theoretically. The above linearity between the fluxes and the driving forces breaks down for concentrated or non-ideal mixtures, for which our equations go beyond the Kedem-Katchalsky formulation. We show that the heretofore empirical solute permeability coefficient reflects the momentum transfer between the solute molecules that are rejected at a pore entrance and the solvent molecules entering the pore space; it can be related to the inefficiency of a Maxwellian demi-demon.

The effect of ingested lactulose on absorption of L-rhamnose, D-xylose, and 3-O-methyl-D-glucose in subjects with ileostomies.

PubMed

Jenkins, A P; Menzies, I S; Nukajam, W S; Creamer, B

1994-09-01

We have previously shown that small oral doses of poorly absorbed solute can significantly reduce absorption of test sugars in normal volunteers. To confirm these results and investigate the underlying mechanism, the effects of lactulose on absorption of three test sugars in subjects with ileostomies were studied. Ten fasted subjects with ileostomies ingested an isosmolar test solution containing 2.5 g 3-O-methyl-D-glucose, 5.0 g D-xylose, 1.0 g L-rhamnose, and 50 microCi 51Cr-labelled ethylenediaminetetraacetic acid together with a blue dye transit marker. Urine was collected for time periods of 0-5 h and 5-24 h, to measure excretion of absorbed sugars, and ileostomy effluent was saved from 0-5 h and from 5 h until blue dye transit marker was no longer present, to measure small-bowel output of unabsorbed sugars. After 1 week the test was repeated, including 5 g lactulose in the test solution. Inclusion of lactulose in the test solution significantly reduced the 5 h and 24 h urine excretion of L-rhamnose and D-xylose but not that of 3-O-methyl-D-glucose and increased 0- to 5-h and total ileostomy output of L-rhamnose and D-xylose but not of 3-O-methyl-D-glucose. The presence of lactulose also reduced the time for first appearance of the blue dye transit marker in the effluent and increased effluent volume together with output of electrolyte. Poorly absorbed solute reduces intestinal absorption by retention of fluid and electrolyte, with subsequent intraluminal dilution and acceleration of transit.

Modeling the controllable pH-responsive swelling and pore size of networked alginate based biomaterials.

PubMed

Chan, Ariel W; Neufeld, Ronald J

2009-10-01

Semisynthetic network alginate polymer (SNAP), synthesized by acetalization of linear alginate with di-aldehyde, is a pH-responsive tetrafunctionally linked 3D gel network, and has potential application in oral delivery of protein therapeutics and active biologicals, and as tissue bioscaffold for regenerative medicine. A constitutive polyelectrolyte gel model based on non-Gaussian polymer elasticity, Flory-Huggins liquid lattice theory, and non-ideal Donnan membrane equilibria was derived, to describe SNAP gel swelling in dilute and ionic solutions containing uni-univalent, uni-bivalent, bi-univalent or bi-bi-valent electrolyte solutions. Flory-Huggins interaction parameters as a function of ionic strength and characteristic ratio of alginates of various molecular weights were determined experimentally to numerically predict SNAP hydrogel swelling. SNAP hydrogel swells pronouncedly to 1000 times in dilute solution, compared to its compact polymer volume, while behaving as a neutral polymer with limited swelling in high ionic strength or low pH solutions. The derived model accurately describes the pH-responsive swelling of SNAP hydrogel in acid and alkaline solutions of wide range of ionic strength. The pore sizes of the synthesized SNAP hydrogels of various crosslink densities were estimated from the derived model to be in the range of 30-450 nm which were comparable to that measured by thermoporometry, and diffusion of bovine serum albumin. The derived equilibrium swelling model can characterize hydrogel structure such as molecular weight between crosslinks and crosslinking density, or can be used as predictive model for swelling, pore size and mechanical properties if gel structural information is known, and can potentially be applied to other point-link network polyelectrolytes such as hyaluronic acid gel.

Modifications in structure and interaction of nanoparticle-protein-surfactant complexes in electrolyte solution

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.

2016-05-01

SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.

Electrosynthesis of cerium hexaboride by the molten salt technique

NASA Astrophysics Data System (ADS)

Amalajyothi, K.; Berchmans, L. John; Angappan, S.; Visuvasam, A.

2008-07-01

Molten salts are well thought-out as the incredibly promising medium for chemical and electrochemical synthesis of compounds. Hence a stab has been made on the electrochemical synthesis of CeB 6 using molten salt technique. The electrolyte consisted of lithium fluoride (LiF), boron trioxide (B 2O 3) and cerium chloride (CeCl 3). Electrochemical experiments were carried out in an inconal reactor in an argon atmosphere. Electrolysis was executed in a high-density graphite crucible, which doles out as the electrolyte clutching vessel as well as the anode. The cathode was made up of a molybdenum rod. The electrolysis was carried out at 900 °C at different current densities intended for the synthesis of CeB 6 crystals. After the electrolysis, the cathode product was removed and cleaned using dilute HCl solution. The crystals were scrutinized by X-ray diffraction (XRD) to make out the phase and the purity. It has been observed that CeB 6 crystals are synthesized at all current densities and the product has traces of impurities.

Novel integrated electrodialysis/electro-oxidation process for the efficient degradation of 2,4-dichlorophenoxyacetic acid.

PubMed

Raschitor, A; Llanos, J; Cañizares, P; Rodrigo, M A

2017-09-01

This work presents a novel approach of wastewater treatment technology that consists of a combined electrodialysis/electro-oxidation process, specially designed to allow increasing the efficiency in the oxidation of ionic organic pollutants contained in diluted waste. Respect to conventional electrolysis, the pollutant is simultaneously concentrated and oxidized, enhancing the performance of the cell due to the higher concentration achieved in the nearness of the anode. A proof of concept is tested with the ionic pesticide 2,4-D (2,4-dichlorophenoxyacetic acid) and results show that the efficiency of this new technology overcomes that electrolysis by more than double, regardless the supporting electrolyte used (either NaCl or Na 2 SO 4 ). Moreover, the removal rate of 2,4-D when using NaCl was found to be more efficient, due to the best performance of the electrode material selected (DSA ® ) towards the formation of oxidants in chloride supporting electrolyte. These results open the way for overcoming the efficiency limitations of electrochemical treatment processes for the treatment of solutions with low concentrated ionic pollutants. Copyright © 2017 Elsevier Ltd. All rights reserved.

A molecular Debye-Hückel theory and its applications to electrolyte solutions: The size asymmetric case

DOE PAGES

Xiao, Tiejun; Song, Xueyu

2017-03-28

We developed a molecular Debye-Hückel theory for electrolyte solutions with size asymmetry, where the dielectric response of an electrolyte solution is described by a linear combination of Debye-Hückel-like response modes. Furthermore, as the size asymmetry of an electrolyte solution leads to a charge imbalanced border zone around a solute, the dielectric response to the solute is characterized by two types of charge sources, namely, a bare solute charge and a charge distribution due to size asymmetry. These two kinds of charge sources are screened by the solvent differently, our theory presents a method to calculate the mean electric potential asmore » well as the electrostatic contributions to thermodynamic properties. Finally, the theory was successfully applied to binary as well as multi-component primitive models of electrolyte solutions.« less

Kidney function in the Spinifex hopping mouse, Notomys alexis.

PubMed

Gordge, L; Roberts, J R

2008-06-01

Notomys alexis (Spinifex hopping mouse) is found in the arid zone of Australia. The structure and function of the kidneys allow this species to conserve water. This study investigated the rate at which N. alexis can reduce urine volume and increase the concentration of electrolytes and solutes when water deprived. It also looked at the response to rehydration, following a period of water deprivation. The laboratory mouse, Mus musculus domesticus, was used for comparison. N. alexis is able to reduce urine volume and increase urine concentration more rapidly than M. m. domesticus when water deprived. This appears to occur prior to any measurable changes in plasma electrolyte concentrations and is not due to reductions in glomerular filtration rate. Gradual water deprivation over a period of 10 days allowed N. alexis to adjust so that urine composition was similar in many ways to animals that had ad libitum access to water, whereas M. m. domesticus required significant water supplementation to maintain body weight at 85% of initial body weight. Ability to concentrate urine rapidly is characteristic of a well-insulated renal medulla [Bankir, L., DeRouffignac, C., 1985. Urinary concentrating ability: insights from comparative anatomy. Am. J. Physiol. 249, R643-666]. However, a well-insulated medulla is normally associated with slow dilution of urine when animals are rehydrated. N. alexis was able to produce dilute urine very rapidly following rehydration of water deprived animals. Physiological control of renal function appears to be complex. Although M. m. domesticus is able to produce concentrated urine, it is unable to survive without free water and responds more slowly to water deprivation.

Developing New Electrolytes for Advanced Li-ion Batteries

NASA Astrophysics Data System (ADS)

McOwen, Dennis Wayne

The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were synthesized for this investigation: dilithium 1,2,5-thiadiazolidine-3,4-dione-1,1-dioxide (Li2TDD), lithium ethyl N-trifluoroacetylcarbamate (LiETAC), lithium hexafluoroisopropoxide (LiHFI), lithium pentafluorophenolate (LiPFPO), and lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI). Using crystalline solvate structure analysis and electrolyte solvation numbers, each of these lithium salts were compared to more well-characterized lithium salts, such as LiPF6 and LiBF4. From this study, links between anion structural characteristics and the anion...Li+ cation interactions (i.e., ionic association strength) were made. From the screening of the five lithium salts that were synthesized, LiTDI was determined to be a promising candidate for Li-ion battery electrolytes. Further characterization of carbonate- and mixed carbonate-LiTDI electrolytes (e.g., ionic conductivity) confirmed this to be the case. Coin cells containing LiTDI or LiPF6 electrolytes showed that cells with either electrolyte could deliver nearly identical power density at 25 °C. Additionally, thermogravimetric analysis (TGA) and NMR suggested that the LiTDI salt and carbonate-LiTDI electrolytes are thermally stable up to at least 60 °C. Further supporting this finding, coin cells cycled at 60 °C with LiPF6 lost significantly more capacity than those with LiTDI. Therefore, LiTDI is a prime candidate for the complete replacement of LiPF6 to significantly increase Li-ion battery tolerance to heat, improving the safety characteristics. In addition to searching for new lithium salts, the effect of lithium salt concentration on electrolyte physicochemical properties was investigated. This radically different approach to modifying electrolyte properties determined that amorphous, highly concentrated carbonate-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolytes have drastically different behavior than more dilute electrolytes. For example, the thermal stability and anodic stability vs. a Pt electrode of the concentrated electrolytes are significantly higher. Most striking, however, was the suppression of Al corrosion by the concentrated carbonate-LiTFSI electrolytes, despite the fact that Al corrosion of more dilute carbonate-LiTFSI electrolytes has consistently been attributed to the TFSI- anion in the literature. These results, explained by crystalline solvate analysis, Raman spectroscopy, and molecular dynamics simulations, could change the way Li-ion battery electrolytes are designed.

The role of long-range forces in the formation of thin liquid films on metals

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

Gyory, J.R.; Muller, R.H.

1987-06-01

White-light multiple beam interference is used to study the drainage of aqueous electrolytes from vertically optically smooth platinum and gold plates. Bulk liquid is in contact with the bottom of the metal plate. For short times following the lowering of the bulk liquid level, the change in the film profile agrees with that expected from viscous drainage. However, at long times, the film profile deviates from that expected and eventually becomes independent of time at a thickness between 0.08 and 0.25 micrometers. These profiles are best represented by a function dependent on the inverse cube root of height. The thicknessmore » of the equilibrium film profiles with increasing electrolyte concentration. A model based on long range van der Waals interactions resulting in a repulsive force between the interfaces of the film is shown to predict the correct profile shape, and for dilute electrolytes, the correct film thickness. This model also predicts increasing film thickness for increasing electrolyte concentration. The strength of this interaction is characterized by the Hamaker constant which can be calculated from the dielectric functions evaluated at imaginary frequencies of the film and substrate. For metals, this function is generated from spectral absorption data, limiting behavior for low and high frequencies, and by use of the Kramers-Kronig transformation. Hamaker constants calculated from the dielectric functions generated in this manner agree well with those derived from film profiles for dilute electrolytes.« less

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

PubMed

Daniele, Salvatore; Baldo, M Antonietta; Bragato, Carlo; Abdelsalam, Mamdouh Elsayed; Denuault, Guy

2002-07-15

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

Controlling turbulent drag across electrolytes using electric fields.

PubMed

Ostilla-Mónico, Rodolfo; Lee, Alpha A

2017-07-01

Reversible in operando control of friction is an unsolved challenge that is crucial to industrial tribology. Recent studies show that at low sliding velocities, this control can be achieved by applying an electric field across electrolyte lubricants. However, the phenomenology at high sliding velocities is yet unknown. In this paper, we investigate the hydrodynamic friction across electrolytes under shear beyond the transition to turbulence. We develop a novel, highly parallelised numerical method for solving the coupled Navier-Stokes Poisson-Nernst-Planck equation. Our results show that turbulent drag cannot be controlled across dilute electrolytes using static electric fields alone. The limitations of the Poisson-Nernst-Planck formalism hint at ways in which turbulent drag could be controlled using electric fields.

Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

NASA Astrophysics Data System (ADS)

Buyukkilic, Salih

Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations with charge-balancing oxygen vacancies. At higher temperatures near 700 °C, maximum enthalpy of formation shifts toward higher dopant concentrations, as a result of defect disordering. This concentration coincides with that of maximum ionic conductivity, extending the correlation seen previously near room temperature. It is also possible to co-dope these systems with Sm and Nd to further enhance ionic conductivity. For doubly doped ceria electrolytes, the solid solution phase of Ce1-xSm0.5xNd0.5xO2-0.5x (0 ≤ x ≤ 0.30) was investigated. It has been shown that for doubly doped ceria, the maximum enthalpy of formation occurs towards higher dopant concentration than that of singly doped counterparts, with less exothermic association enthalpies. These studies provide insight into the structure-composition-property-stability relations and aid in the rational design of the future SOFCs electrolytes.

Radiotracer Dilution Method for Mercury Inventory Study in Electrolytic Cells

NASA Astrophysics Data System (ADS)

Sugiharto, Su'ud, Zaki; Kurniadi, Rizal; Waris, Abdul; Santoso, Sigit Budi; Abidin, Zainal; Santoso, Gatot Budi

2010-06-01

Purpose of the experiment is to demonstrate feasibility the use of radiotracer to measure weight of mercury in electrolytic cells of soda industry. The weight of mercury in each cell of the plant is designed approximately 1700 kg. Radiotracer is prepared by mixing 203 Hg radioactive mercury with 2400 g of inactive mercury in a bath. The respective precisely weighted mercury aliquots to be injected into the cells are prepared by pouring approximately 130 g of radioactive mercury taken from the bath into 13 standard vials, in accordance with the number of the cells tested. Four standard references prepared by further dilution of ±2 g active mercury taken from the bath to obtain the dilution factors range of 12,000 to 20,000 from which the calibration graph is constructed. The injection process is conducting by pouring the radioactive mercury from aliquots into the flowing mercury at the inlet side of the cell and allows them to mix thoroughly. It is assumed that the mass of the radiotracer injected into a closed system remains constant, at least during the period of the test. From this experiment it was observed that the mixing time is two days after injection of radioactive mercury. The inactive mercury in each electrolytic cell calculated by the radiotracer method is of the range 1351.529 kg to 1966.354 kg with maximum error (95% confidence) is 1.52 %. The accuracy of measurement of the present method is better than gravimetric one which accounts 4 % of error on average.

[A mathematic analysis of different manners of replacement fluid infusion in continuous veno-venous hemofiltration].

PubMed

Wu, Yunzhen; Wang, Chunting

2015-05-01

To establish a mathematical formula for choosing the manner of replacement fluid infusion in continuous renal replacement therapy (CRRT), so as to provide the basis for improving the treatment effect. A mathematical formula for choosing the manner of replacement fluid infusion with continuous veno-venous hemofiltration (CVVH) was taken as an example, and it was compared with the result of standard replacement fluid in order to analyze the effect of different manners of infusion. (1) Comparison parameters: the plasma volume ("Vreturn") and some electrolyte concentration ("Creturn") in back way of CRRT ( if other thing was solute, filter coefficient should be 1.0). (2) Research objects: the actual replacement fluid (for example, the most complex should be sorted into A and B type) mode (pre or post) was compared with the standard replacement fluid (the A and B in one). (3) Based on the formula of standard replacement, four equations in different conditions were derived: pre-dilution and post-dilution mode; same direction and same ratio; same direction and different ratio; different direction and same ratio; different direction and different ratio. The calculated results of "Vreturn" (except hematocrit) and "Creturn" were same to the standard only following the rule of same direction and ratio for A and B no matter pre-dilution mode or post-dilution mode, and it was different from the standard in others. In pre-dilution mode and post-dilution mode, it showed: (1) A and B in same direction and different ratio: "Vreturn" and "Creturn" were different from the standard for the alterative ratio of B. (2) A and B in different direction and same ratio: "Vreturn" was same to the standard, but "Creturn" was different from the standard for the completely different and more complex computational formula. (3) A and B in different direction and different ratio: both "Vreturn" and "Creturn" were different from the standard. The different "Vreturn" was due to the different ratio of B. The different "Creturn" was caused by different ratio of B and the completely different computational formula. (1) For parts of replacement fluid which must be separated (for example, bicarbonate formula), the result is same to the standard, and is predicted and mastered only following the rule of same direction and ratio. Otherwise, we need to calculate the two parameters over and over again. The result will run out of our judgment. The wrongness of losing water and electrolyte disorders maybe come out. (2) Accordingly,the formula could be used to analyze the same case like the separated replacement infusion, for example, a large number of citrates as regional anticoagulation were infused only in the front of filter, while the replacement fluid can be done in varied forms.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

DOEpatents

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Processing of irradiated, enriched uranium fuels at the Savannah River Plant

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

Hyder, M L; Perkins, W C; Thompson, M C

Uranium fuels containing /sup 235/U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction withmore » dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of /sup 238/Pu is high enough to make its recovery desirable. Most of the /sup 238/Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, /sup 239/Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse.« less

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1991-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1988-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1989-01-01

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg.sub.2 Cl.sub.2 employing as the electrolyte solution a mixture of HCl and H.sub.2 O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H.sub.2 O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds.

A prospective randomized trial of two solutions for intrapartum amnioinfusion: effects on fetal electrolytes, osmolality, and acid-base status.

PubMed

Pressman, E K; Blakemore, K J

1996-10-01

Our purpose was to compare the effects of intrapartum amnioinfusion with normal saline solution versus lactated Ringer's solution plus physiologic glucose on neonatal electrolytes and acid-base balance. Patients undergoing amnioinfusion for obstetric indications were randomized to receive normal saline solution or lactated Ringer's solution plus physiologic glucose at standardized amnioinfusion rates. Data were collected prospectively on maternal demographics, course of labor, and maternal and neonatal outcome. Arterial cord blood was obtained for analysis of electrolytes, glucose, osmolality, lactic acid, and blood gases. Control subjects with normal fetal heart rate patterns, and clear amniotic fluid not receiving amnioinfusion were studied concurrently. Data were collected on 59 patients (21 normal saline solution, 18 lactated Ringer's solution plus physiologic glucose, and 20 controls). Maternal demographics, course of labor, and neonatal outcome were similar in all three groups. Cesarean sections were performed more often in the amnioinfusion groups (33.3% for normal saline solution, 38.9% for lactated Ringer's solution plus physiologic glucose) than in the control group (5.0%), p < 0.05. Cord arterial electrolytes, glucose, osmolality, lactic acid, and blood gases were not altered by amnioinfusion with either solution. Intrapartum amnioinfusion with normal saline solution or lactated Ringer's solution plus physiologic glucose has no effect on neonatal electrolytes or acid-base balance.

Separation and/or sequestration apparatus and methods

DOEpatents

Rieke, Peter C; Towne, Silas A; Coffey, Greg W; Appel, Aaron M

2015-02-03

Apparatus for separating CO.sub.2 from an electrolyte solution are provided. Example apparatus can include: a vessel defining an interior volume and configured to house an electrolyte solution; an input conduit in fluid communication with the interior volume; an output conduit in fluid communication with the interior volume; an exhaust conduit in fluid communication with the interior volume; and an anode located within the interior volume. Other example apparatus can include: an elongated vessel having two regions; an input conduit extending outwardly from the one region; an output conduit extending outwardly from the other region; an exhaust conduit in fluid communication with the one region; and an anode located within the one region. Methods for separating CO.sub.2 from an electrolyte solution are provided. Example methods can include: providing a CO.sub.2 rich electrolyte solution to a vessel containing an anode; and distributing hydrogen from the anode to acidify the electrolyte solution.

A Simple Method for Decreasing the Liquid Junction Potential in a Flow-through-Type Differential pH Sensor Probe Consisting of pH-FETs by Exerting Spatiotemporal Control of the Liquid Junction

PubMed Central

Yamada, Akira; Mohri, Satoshi; Nakamura, Michihiro; Naruse, Keiji

2015-01-01

The liquid junction potential (LJP), the phenomenon that occurs when two electrolyte solutions of different composition come into contact, prevents accurate measurements in potentiometry. The effect of the LJP is usually remarkable in measurements of diluted solutions with low buffering capacities or low ion concentrations. Our group has constructed a simple method to eliminate the LJP by exerting spatiotemporal control of a liquid junction (LJ) formed between two solutions, a sample solution and a baseline solution (BLS), in a flow-through-type differential pH sensor probe. The method was contrived based on microfluidics. The sensor probe is a differential measurement system composed of two ion-sensitive field-effect transistors (ISFETs) and one Ag/AgCl electrode. With our new method, the border region of the sample solution and BLS is vibrated in order to mix solutions and suppress the overshoot after the sample solution is suctioned into the sensor probe. Compared to the conventional method without vibration, our method shortened the settling time from over two min to 15 s and reduced the measurement error by 86% to within 0.060 pH. This new method will be useful for improving the response characteristics and decreasing the measurement error of many apparatuses that use LJs. PMID:25835300

Single polymer dynamics in semi-dilute unentangled and entangled solutions: from molecular conformation to normal stress

NASA Astrophysics Data System (ADS)

Schroeder, Charles

Semi-dilute polymer solutions are encountered in a wide array of applications such as advanced 3D printing technologies. Semi-dilute solutions are characterized by large fluctuations in concentration, such that hydrodynamic interactions, excluded volume interactions, and transient chain entanglements may be important, which greatly complicates analytical modeling and theoretical treatment. Despite recent progress, we still lack a complete molecular-level understanding of polymer dynamics in these systems. In this talk, I will discuss three recent projects in my group to study semi-dilute solutions that focus on single molecule studies of linear and ring polymers and a new method to measure normal stresses in microfluidic devices based on the Stokes trap. In the first effort, we use single polymer techniques to investigate the dynamics of semi-dilute unentangled and semi-dilute entangled DNA solutions in extensional flow, including polymer relaxation from high stretch, transient stretching dynamics in step-strain experiments, and steady-state stretching in flow. In the semi-dilute unentangled regime, our results show a power-law scaling of the longest polymer relaxation time that is consistent with scaling arguments based on the double cross-over regime. Upon increasing concentration, we observe a transition region in dynamics to the entangled regime. We also studied the transient and steady-state stretching dynamics in extensional flow using the Stokes trap, and our results show a decrease in transient polymer stretch and a milder coil-to-stretch transition for semi-dilute polymer solutions compared to dilute solutions, which is interpreted in the context of a critical Weissenberg number Wi at the coil-to-stretch transition. Interestingly, we observe a unique set of polymer conformations in semi-dilute unentangled solutions that are highly suggestive of transient topological entanglements in solutions that are nominally unentangled at equilibrium. Taken together, these results suggest that the transient stretching pathways in semi-dilute solution extensional flows are qualitatively different than for both dilute solutions and for semi-dilute solutions in shear flow. In a second effort, we studied the dynamics of ring polymers in background solutions of semi-dilute linear polymers. Interestingly, we observe strikingly large fluctuations in steady-state polymer extension for ring polymers in flow, which occurs due to the interplay between polymer topology and concentration leading to chain `threading' in flow. In a third effort, we developed a new microfluidic method to measure normal stress and extensional viscosity that can be loosely described as passive yet non-linear microrheology. In particular, we incorporated 3-D particle imaging velocimetry (PIV) with the Stokes trap to study extensional flow-induced particle migration in semi-dilute polymer solutions. Experimental results are analyzed using the framework of a second-order-fluid model, which allows for measurement of normal stress and extensional viscosity in semi-dilute polymer solutions, all of which is a first-of-its-kind demonstration. Microfluidic measurements of extensional viscosity are directly compared to the dripping-onto-substrate or DOS method, and good agreement is generally observed. Overall, our work aims to provide a molecular-level understanding of the role of polymer topology and concentration on bulk rheological properties by using single polymer techniques.

Studies of thermochemical water-splitting cycles

NASA Technical Reports Server (NTRS)

Remick, R. J.; Foh, S. E.

1980-01-01

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

Electrochemical performance of microporous and mesoporous activated carbons in neat and diluted 1-ethyl-3-methylimidazolium tetrafluoroborate

NASA Astrophysics Data System (ADS)

Kumagai, Seiji; Hatomi, Masaki; Tashima, Daisuke

2017-03-01

1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIm·BF4), neat and diluted with propylene carbonate to 1 mol L-1, have been employed as electrolytes of electrical double-layer capacitors (EDLCs). The effects of microporosity and mesoporosity in activated carbon (AC) electrodes on the capacitive and resistive performances upon the use of neat and diluted EMIm·BF4 have been explored. In addition to cyclic voltammetry and galvanostatic charge-discharge tests, electrochemical impedance spectroscopy has been performed employing Kang's equivalent circuit model consisting of three resistances, three constant phase elements, and one bounded Warburg impedance. The overall impedance of the EDLC cell was separated into components of intrinsic resistance, bulk electrolyte, diffusion layer, and Helmholtz layer. The specific capacitance and the equivalent series resistance (ESR) of mesoporous AC were found to be highly dependent on the rate of ionic transfer. Lower cell voltage was identified as being responsible for lower specific capacitance and larger ESR of mesoporous AC, which was similarly seen in the neat and diluted EMIm·BF4, and could be alleviated by increasing the cell voltage. The inferior rate performance and the cell-voltage-dependent performance of mesoporous AC, which were more distinctly observed in the neat EMIm·BF4, could be attributed to the lower mobility of EMIm+ and BF4- in mesopores.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Size and Charge Dependence of Ion Transport in Human Nail Plate

PubMed Central

Baswan, Sudhir M.; Li, S. Kevin; LaCount, Terri D.; Kasting, Gerald B.

2016-01-01

The electrical properties of human nail plate are poorly characterized, yet are a key determinate of the potential to treat nail diseases such as onychomycosis using iontophoresis. In order to address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of −1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were three-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upwards of 5 Å (approximately MW ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. PMID:26886342

Effect of cationic contaminants on polymer electrolyte fuel cell performance

NASA Astrophysics Data System (ADS)

Qi, Jing; Wang, Xiaofeng; Ozdemir, M. Ozan; Uddin, Md. Aman; Bonville, Leonard; Pasaogullari, Ugur; Molter, Trent

2015-07-01

The effect of cationic contaminants on polymer electrolyte fuel cell (PEFC) performance is investigated via in-situ injection of dilute cationic salt solutions. Four foreign cations (K+, Ba2+, Ca2+, Al3+) are chosen as contaminants in this study due to their prevalence and chemical structure (e.g. valence), however contaminants that have already received extensive coverage in the literature like sodium and iron are excluded. It is found that the cells with Ba(ClO4)2 and Ca(ClO4)2 injection exhibit little cell performance change during the current hold test, and the cells with Al(ClO4)3 and KClO4 injection show larger cell performance changes, i.e. decreasing cell voltage and increasing cell resistance. These cells with in-situ contaminant injection have a tendency to recover a portion of the lost performance after the recovery test when switched back to supersaturated air. The degradation in cell performance with the presence of cationic contaminants is mainly due, in addition to the membrane resistance increase associated with replacing protons on the sulfonate groups, to the increase in mass transport resistance and decrease in electrochemical surface area.

Charge regulation at semiconductor-electrolyte interfaces.

PubMed

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2015-07-01

The interface between a semiconductor material and an electrolyte solution has interesting and complex electrostatic properties. Its behavior will depend on the density of mobile charge carriers that are present in both phases as well as on the surface chemistry at the interface through local charge regulation. The latter is driven by chemical equilibria involving the immobile surface groups and the potential determining ions in the electrolyte solution. All these lead to an electrostatic potential distribution that propagate such that the electrolyte and the semiconductor are dependent on each other. Hence, any variation in the charge density in one phase will lead to a response in the other. This has significant implications on the physical properties of single semiconductor-electrolyte interfaces and on the electrostatic interactions between semiconductor particles suspended in electrolyte solutions. The present paper expands on our previous publication (Fleharty et al., 2014) and offers new results on the electrostatics of single semiconductor interfaces as well as on the interaction of charged semiconductor colloids suspended in electrolyte solution. Copyright © 2014 Elsevier Inc. All rights reserved.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2016-06-14

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

Iron-sulfide redox flow batteries

DOEpatents

Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

2013-12-17

Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1991-06-18

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figures.

Recovery of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1989-11-07

A process for electrolytically recovering mercury from mercury compounds is provided. In one embodiment, Hg is recovered from Hg[sub 2]Cl[sub 2] employing as the electrolyte solution a mixture of HCl and H[sub 2]O. In another embodiment, Hg is electrolytically recovered from HgO wherein the electrolyte solution is comprised of glacial acetic acid and H[sub 2]O. Also provided is an apparatus for producing isotopically enriched mercury compounds in a reactor and then transporting the dissolved compounds into an electrolytic cell where mercury ions are electrolytically reduced and elemental mercury recovered from the mercury compounds. 3 figs.

Polymer relaxation and stretching dynamics in semi-dilute DNA solutions: a single molecule study

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Brockman, Christopher; Schroeder, Charles

2015-03-01

In this work, we study polymer relaxation and stretching dynamics in semi-dilute DNA solutions using single molecule techniques. Using this approach, we uncover a unique scaling relation for longest polymer relaxation time that falls in the crossover regime described by semi-flexible polymer solutions, which is distinct from truly flexible polymer chains. In addition, we performed a series of step-strain experiments on single polymers in semi-dilute solutions in planar extensional flow using an automated microfluidic trap. In this way, we are able to precisely control the flow strength and the amount of strain applied to single polymer chains, thereby enabling direct observation of the full stretching and relaxation process in semi-dilute solutions during transient start-up and flow cessation. Interestingly, we observe polymer individualism in the conformation of single chains in semi-dilute solutions, which to our knowledge has not yet been observed. In addition, we observe the relaxation data can be explained by a multi-exponential decay process after flow cessation in semi-dilute solutions. Overall, our work reports key advance in non-dilute polymer systems from a molecular perspective via direct observation of dynamics in strong flows. DOW fellowship.

Achieving surface chemical and morphologic alterations on tantalum by plasma electrolytic oxidation.

PubMed

Goularte, Marcelo Augusto Pinto Cardoso; Barbosa, Gustavo Frainer; da Cruz, Nilson Cristino; Hirakata, Luciana Mayumi

2016-12-01

Search for materials that may either replace titanium dental implants or constitute an alternative as a new dental implant material has been widely studied. As well, the search for optimum biocompatible metal surfaces remains crucial. So, the aim of this work is to develop an oxidized surface layer on tantalum using plasma electrolytic oxidation (PEO) similar to those existing on oral implants been marketed today. Cleaned tantalum samples were divided into group 1 (control) and groups 2, 3, and 4 (treated by PEO for 1, 3, and 5 min, respectively). An electrolytic solution diluted in 1-L deionized water was used for the anodizing process. Then, samples were washed with anhydrous ethyl alcohol and dried in the open air. For complete anodic treatment disposal, the samples were immersed in acetone altogether, taken to the ultrasonic tank for 10 min, washed again in distilled water, and finally air-dried. For the scanning electron microscopy (SEM) analysis, all samples were previously coated with gold; the salt deposition analysis was conducted with an energy-dispersive X-ray spectroscopy (EDS) system integrated with the SEM unit. SEM images confirmed the changes on tantalum strips surface according to different exposure times while EDS analysis confirmed increased salt deposition as exposure time to the anodizing process also increased. PEO was able to produce both surface alteration and salt deposition on tantalum strips similar to those existing on oral implants been marketed today.

Supersaturated Electrolyte Solutions: Theory and Experiment

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.; Na, Han-Soo

1995-01-01

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

ELECTROCHEMICAL DECONTAMINATION AND RECOVERY OF URANIUM VALUES

DOEpatents

McLaren, J.A.; Goode, J.H.

1958-05-13

An electrochemical process is described for separating uranium from fission products. The method comprises subjecting the mass of uranium to anodic dissolution in an electrolytic cell containing aqueous alkali bicarbonate solution as its electrolyte, thereby promoting a settling from the solution of a solid sludge from about the electrodes and separating the resulting electrolyte solution containing the anodically dissolved uranium from the sludge which contains the rare earth fission products.

Methods and electrolytes for electrodeposition of smooth films

DOEpatents

Zhang, Jiguang; Xu, Wu; Graff, Gordon L; Chen, Xilin; Ding, Fei; Shao, Yuyan

2015-03-17

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

40 CFR 797.1400 - Fish acute toxicity test.

Code of Federal Regulations, 2011 CFR

2011-07-01

... construction materials, test chambers, and testing apparatus to dilution water or to test solutions prior to... or the leaching of substances from the test facilities into the dilution water or test solution. (5... intermittent passage of test solution or dilution water through a test chamber, or a holding or acclimation...

Electrolyte Solutions and Specific Ion Effects on Interfaces

ERIC Educational Resources Information Center

Friedman, Ran

2013-01-01

Introductory general and physical chemistry courses often deal with colligative properties of solutions and do not discuss nonideal solutions in detail. Yet, a growing body of evidence reveals that even at physiological concentrations electrolyte solutions cannot be treated as ideal when a charged or partially charged solute (such as a protein) is…

Charge-discharge characteristics of nickel/zinc battery with polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Iwakura, Chiaki; Murakami, Hiroki; Nohara, Shinji; Furukawa, Naoji; Inoue, Hiroshi

A new nickel/zinc (Ni/Zn) battery was assembled by using polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) and KOH aqueous solution, and its charge-discharge characteristics were investigated. The experimental Ni/Zn cell with the polymer hydrogel electrolyte exhibited well-defined charge-discharge curves and remarkably improved charge-discharge cycle performance, compared to that with a KOH aqueous solution. Moreover, it was found that dendritic growth hardly occurred on the zinc electrode surface during charge-discharge cycles in the polymer hydrogel electrolyte. These results indicate that the polymer hydrogel electrolyte can successfully be used in Ni/Zn batteries as an electrolyte with excellent performance.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte

NASA Astrophysics Data System (ADS)

Maizelis, Antonina; Bairachniy, Boris

2017-02-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated. The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte. The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte.

PubMed

Maizelis, Antonina; Bairachniy, Boris

2017-12-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated.The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte.The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

Electrolytic Polishing and Etching Techniques for Preparing Specimens of Bismuth and Antimony and Their Alloys: Materials and Structures.

DTIC Science & Technology

Electrolytic polishing was performed in a solution of methyl alcohol, sulphuric acid , hydrocloric acid and ethylene glycol. Etching was done...electrolytically in a 5 percent chromic acid solution. Use of these techniques has permitted detailed studies of the microstructures of bismuth-antimony single

A modified Lowry protein test for dilute protein solutions

Treesearch

Garold F. Gregory; Keith F. Jensen

1971-01-01

A modified Lowry protein test for dilute protein solutions modified Lowry protein test was compared with the standard Lowry protein test. The modified test was found to give estimates of protein concentration that were as good as the standard test and has the advange that proteins can be measured in very dilute solutions.

Nanometric Surface Oscillation Spectroscopy of Water-Poor Microemulsions.

PubMed

Corti, Mario; Raudino, Antonio; Cantù, Laura; Theisen, Johannes; Pleines, Maximilian; Zemb, Thomas N

2018-06-18

Selectively exchanging metal complexes between emulsified water-poor microemulsions and concentrated solutions of mixed electrolytes is the core technology for strategic metal recycling. Nanostructuration triggered by solutes present in the organic phase is understood, but little is known about fluctuations of the microemulsion-water interface. We use here a modified version of an opto-electric device initially designed for air bubbles, in order to evidence resonant electrically induced surface waves of an oily droplet suspended in an aqueous phase. Resonant waves of nanometer amplitude of a millimeter-sized microemulsion droplet containing a common ion-specific extractant diluted by dodecane and suspended in a solution of rare earth nitrate are evidenced for the first time with low excitation fields (5 V/cm). From variation of the surface wave spectrum with rare earth concentration, we evidence up-take of rare-earth ions at the interface and at higher concentration the formation of a thin "crust" of liquid crystal forming at unusually low concentration, indicative of a surface induced phase transition. The effect of the liquid crystal structure on the resonance spectrum is backed up by a model, which is used to estimate crust thickness.

Science Notes: Dilution of a Weak Acid

ERIC Educational Resources Information Center

Talbot, Christopher; Wai, Chooi Khee

2014-01-01

This "Science note" arose out of practical work involving the dilution of ethanoic acid, the measurement of the pH of the diluted solutions and calculation of the acid dissociation constant, K[subscript a], for each diluted solution. The students expected the calculated values of K[subscript a] to be constant but they found that the…

Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents.

PubMed

Bozym, David J; Uralcan, Betül; Limmer, David T; Pope, Michael A; Szamreta, Nicholas J; Debenedetti, Pablo G; Aksay, Ilhan A

2015-07-02

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon-electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5-10 mol% (i.e., ∼1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low-dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

The Effect of Structural Modifications on Ionic Conductivity in Newly-Designed Polyester Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Jung, Yuki; Coates, Geoff; Balsara, Nitash

2015-03-01

Gaining a fundamental understanding of the relationship between molecular structure and ionic conductivity of polymer electrolytes is an essential step toward designing next generation materials for battery applications. In this study, we use a systematic set of newly-designed polyesters with varying side-chain lengths and oxygen functional groups to elucidate the effects of structural modifications on the conductive properties of the corresponding electrolytes. Mixtures of polyesters and lithium bis(trifluromethanesulfonyl)imide (LiTFSI) were characterized using ac impedance spectroscopy to measure the ionic conductivity at various temperatures and salt concentrations. The relative conductivities of these electrolytes in the dilute limit are directly comparable to results of molecular dynamics simulations performed using the same polymers. The simulations correspond well with the experimental results, and provide molecular level insight about the solvation environment of the lithium ions and how the ions transport through these polyesters.

Fabrication of vertically aligned Pd nanowire array in AAO template by electrodeposition using neutral electrolyte.

PubMed

Taşaltın, Nevin; Oztürk, Sadullah; Kılınç, Necmettin; Yüzer, Hayrettin; Oztürk, Zaferziya

2010-05-01

A vertically aligned Pd nanowire array was successfully fabricated on an Au/Ti substrate using an anodic aluminum oxide (AAO) template by a direct voltage electrodeposition method at room temperature using diluted neutral electrolyte. The fabrication of Pd nanowires was controlled by analyzing the current-time transient during electrodeposition using potentiostat. The AAO template and the Pd nanowires were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) methods and X-Ray diffraction (XRD). It was observed that the Pd nanowire array was standing freely on an Au-coated Ti substrate after removing the AAO template in a relatively large area of about 5 cm2, approximately 50 nm in diameter and 2.5 μm in length with a high aspect ratio. The nucleation rate and the number of atoms in the critical nucleus were determined from the analysis of current transients. Pd nuclei density was calculated as 3.55 × 108 cm-2. Usage of diluted neutral electrolyte enables slower growing of Pd nanowires owing to increase in the electrodeposition potential and thus obtained Pd nanowires have higher crystallinity with lower dislocations. In fact, this high crystallinity of Pd nanowires provides them positive effect for sensor performances especially.

Fabrication of vertically aligned Pd nanowire array in AAO template by electrodeposition using neutral electrolyte

PubMed Central

2010-01-01

A vertically aligned Pd nanowire array was successfully fabricated on an Au/Ti substrate using an anodic aluminum oxide (AAO) template by a direct voltage electrodeposition method at room temperature using diluted neutral electrolyte. The fabrication of Pd nanowires was controlled by analyzing the current–time transient during electrodeposition using potentiostat. The AAO template and the Pd nanowires were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) methods and X-Ray diffraction (XRD). It was observed that the Pd nanowire array was standing freely on an Au-coated Ti substrate after removing the AAO template in a relatively large area of about 5 cm2, approximately 50 nm in diameter and 2.5 μm in length with a high aspect ratio. The nucleation rate and the number of atoms in the critical nucleus were determined from the analysis of current transients. Pd nuclei density was calculated as 3.55 × 108 cm−2. Usage of diluted neutral electrolyte enables slower growing of Pd nanowires owing to increase in the electrodeposition potential and thus obtained Pd nanowires have higher crystallinity with lower dislocations. In fact, this high crystallinity of Pd nanowires provides them positive effect for sensor performances especially. PMID:20596417

ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

NASA Astrophysics Data System (ADS)

Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

Multi-electrolyte-step anodic aluminum oxide method for the fabrication of self-organized nanochannel arrays

PubMed Central

2012-01-01

Nanochannel arrays were fabricated by the self-organized multi-electrolyte-step anodic aluminum oxide [AAO] method in this study. The anodization conditions used in the multi-electrolyte-step AAO method included a phosphoric acid solution as the electrolyte and an applied high voltage. There was a change in the phosphoric acid by the oxalic acid solution as the electrolyte and the applied low voltage. This method was used to produce self-organized nanochannel arrays with good regularity and circularity, meaning less power loss and processing time than with the multi-step AAO method. PMID:22333268

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes

NASA Astrophysics Data System (ADS)

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-01

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Halogen-free boron based electrolyte solution for rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinjie; Guo, Yongsheng; Yang, Jun; Nuli, Yanna; Zhang, Fan; Wang, Jiulin; Hirano, Shin-ichi

2014-02-01

All halogen containing electrolytes for Mg battery are apt to corrode conventional metal current collectors. In this paper, a new type of halogen-free boron based electrolyte (Mg[Mes3BPh]2/THF) is designed and prepared. Electrochemical tests show that this electrolyte system possesses high ion conductivity (1.5 × 10-3 S cm-1) and good Mg deposition-dissolution reversibility. More importantly, the same electrochemical window (2.6 V vs. Mg RE) of the electrolyte on Pt and stainless steel electrodes indicates that halogen-free electrolyte indeed lessens the corrosion to conventional metal current collectors. The surface morphologies of stainless steel, aluminum and copper are further observed after their anodic potentiostatic polarization in 0.25 mol L-1 Mg[Mes3BPh]2/THF electrolyte solution for 2 days. A comparison with halogen containing electrolytes proves that the presence of halogen in electrolyte is the reason for corrosion. This work provides a stepping stone for developing new halogen-free electrolyte systems for rechargeable Mg batteries.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-06-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed Central

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-01-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy. PMID:1624155

[Formation of oxalate in oxaliplatin injection diluted with infusion solutions].

PubMed

Eto, Seiji; Yamamoto, Kie; Shimazu, Kounosuke; Sugiura, Toshimune; Baba, Kaori; Sato, Ayaka; Goromaru, Takeshi; Hagiwara, Yoshiaki; Hara, Keiko; Shinohara, Yoshitake; Takahashi, Kojiro

2014-01-01

Oxaliplatin use can cause acute peripheral neuropathy characterized by sensory paresthesias, which are markedly exacerbated by exposure to cold temperatures, and is a dose-limiting factor in the treatment of colorectal cancer.Oxalate is eliminated in a series of nonenzymatic conversions of oxaliplatin in infusion solutions or biological fluids.Elimination of oxalate from oxaliplatin has been suggested as one of the reasons for the development of acute neuropathy.In this study, we developed a high-performance liquid chromatography(HPLC)-based method to detect oxalate formation, and investigated the time dependent formation of oxalate in oxaliplatin diluted with infusion solutions.The results obtained showed that the amount of oxalate in the solution corresponded to 1.6% of oxaliplatin 8 h after oxaliplatin dilution with a 5% glucose solution. On the other hand, oxalate formation from oxaliplatin diluted with a saline solution was ten-fold higher than that from oxaliplatin diluted with the 5% glucose solution.Most patients who were intravenously injected with oxaliplatin experienced venous pain.As a preventive measure against venous pain, dexamethasone was added to the oxaliplatin injection.We measured the amount of oxalate formed in the dexamethasone-containing oxaliplatin injection diluted with a 5% glucose solution.The amount of oxalate formed when dexamethasone was added did not differ significantly from that formed when dexamethasone was not added.Thus, there are no clinical problems associated with the stability of oxaliplatin solutions.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Whole-bowel irrigation for mechanical colon cleansing.

PubMed

Michael, K A; DiPiro, J T; Bowden, T A; Tedesco, F J

1985-01-01

The physiology, solution composition, indications, efficacy, and safety of whole-bowel irrigation (WBI) for mechanical bowel cleansing are reviewed. WBI with isotonic electrolyte solutions produces diarrhea when the infusion rate exceeds the capacity of the intestine to distend and absorb the solution. A number of solutions are used for WBI, including 0.9% sodium chloride, balanced electrolyte solutions, lactated Ringer's, mannitol, and electrolyte solutions containing polyethylene glycol 3350 (PEG). WBI solution administration rates vary from 15-90 mL/min, by oral ingestion or nasogastric tube, with total volumes ranging from 1 to 20 L. The onset of diarrhea occurs as soon as 20 minutes with clearing of the effluent as early as 90 minutes. Faster administration rates appear to shorten overall cleansing time. Two PEG-electrolyte lavage solutions (ELSs) have recently gained FDA approval. The recommended dosage rate is 1.2-1.8 L/hr orally or by nasogastric tube until rectal effluent is clear. In most patients, this requires a maximum of 4-6 L. Initial data indicate that PEG-ELSs are safe for elderly patients and for patients who have an increased risk of fluid overload, but these solutions have not been evaluated in children, pregnant women, or patients with inflammatory bowel disease. WBI is an effective alternative to other regimens for removing fecal material and reducing bowel lumen bacterial counts before colonoscopy and colorectal surgery. Retention of bacterial counts before colonoscopy and colorectal surgery. Retention of excess WBI solution may interfere with the quality of barium enema radiographs; this can be minimized by completing the irrigation the evening before the examination. Gastrointestinal side effects occur in about one third of the patients following WBI, but do not generally require discontinuing the irrigation. Solutions containing PEG with sodium sulfate as the primary electrolyte result in the least net water and electrolyte movement and are preferred over other solutions.

[Rice water with and without electrolytes in diarrhea with a high stool output].

PubMed

Mota-Hernández, F; Posadas-Tello, N M; Rodríguez-Leyva, G

1993-12-01

The objective of the study was to determine the efficacy and safety of two rice-based oral rehydration solutions, with and without added electrolyte in children presenting acute diarrheal dehydration with high stool output (> 10 mL/kg/h) during a two-hour rehydration period. Twenty-two patients of one to 18 months old were recruited and randomly distributed into two groups: group A received the rice-based solution without electrolytes, and group B received the rice-based solution with electrolytes. A stool output diminishing was observed in both groups and rehydration was achieved in 4.0 +/- 0.9 hours in 21 patients from group A and in 4.6 +/- 0.9 hours in 13 patients group group B. There was not a statistically significant difference between the groups regarding the laboratory results. The rice-based oral rehydration solution without added electrolytes was useful for rehydration of children presenting high stool output, after administering the WHO/ORS recommended formula during a two-hour period.

Evaluation of Adsorbed Arsenic and Potential Contribution to Shallow Groundwater in Tulare Lake Bed Area, Tulare Basin, California

USGS Publications Warehouse

Gao, S.; Fujii, R.; Chalmers, A.T.; Tanji, K.K.

2004-01-01

Elevated As concentrations in shallow groundwater in parts of the Tulare Basin, California, are a concern because of potential migration into deeper aquifers that could serve as a source of future drinking water. The objectives of this study were to evaluate adsorbed As and the potential contribution to groundwater using (i) isotopic dilution, (ii) successive extraction with an electrolyte solution resembling the pore-water chemical composition, and (iii) PO4 exchange for As. Sediment samples collected from 2 to 4 m below land surface in the Tulare Lake bed area contained a total As concentration of 24 mg As kg-1. Pore water extracted under hydraulic pressure contained a total As concentration of 590 ??g As L-1, which predominantly contained As as arsenate [As(V), 97%], a minor amount of arsenite [As(III), 3%], and non-detectable organic As. The isotopic dilution method [73As(V)] estimated that the concentration of adsorbed As(V) on the sediment was 5.7 mg As kg-1 at pH 8.5 and 6.7 mg As kg-1 at pH 7.5, respectively. Fourteen successive 24-h extractions with the artificial pore water released up to 57 to 61% of the adsorbed As(V) that was determined by isotopic dilution, indicating that only a portion of the adsorbed As could be released to groundwater. The phosphate-exchangeable As (0.1 M PO4, pH 8.5 or 7.5) was 63% of the isotopically exchangeable As(V). Thus, extraction of As by 0.1 M PO4 at ambient pHs is recommended as a method to determine the potential amount of As(V) on sediments that could be released to the solution phase. The overall results indicated that adsorbed As could be a significant source of As to groundwater. However, other factors that affect As transport such as the leaching rate need to be considered.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-12-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-11-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Nonlocal Electrostatics in Spherical Geometries Using Eigenfunction Expansions of Boundary-Integral Operators.

PubMed

Bardhan, Jaydeep P; Knepley, Matthew G; Brune, Peter

2015-01-01

In this paper, we present an exact, infinite-series solution to Lorentz nonlocal continuum electrostatics for an arbitrary charge distribution in a spherical solute. Our approach relies on two key steps: (1) re-formulating the PDE problem using boundary-integral equations, and (2) diagonalizing the boundary-integral operators using the fact that their eigenfunctions are the surface spherical harmonics. To introduce this uncommon approach for calculations in separable geometries, we first re-derive Kirkwood's classic results for a protein surrounded concentrically by a pure-water ion-exclusion (Stern) layer and then a dilute electrolyte, which is modeled with the linearized Poisson-Boltzmann equation. The eigenfunction-expansion approach provides a computationally efficient way to test some implications of nonlocal models, including estimating the reasonable range of the nonlocal length-scale parameter λ. Our results suggest that nonlocal solvent response may help to reduce the need for very high dielectric constants in calculating pH-dependent protein behavior, though more sophisticated nonlocal models are needed to resolve this question in full. An open-source MATLAB implementation of our approach is freely available online.

Nonlocal Electrostatics in Spherical Geometries Using Eigenfunction Expansions of Boundary-Integral Operators

PubMed Central

Bardhan, Jaydeep P.; Knepley, Matthew G.; Brune, Peter

2015-01-01

In this paper, we present an exact, infinite-series solution to Lorentz nonlocal continuum electrostatics for an arbitrary charge distribution in a spherical solute. Our approach relies on two key steps: (1) re-formulating the PDE problem using boundary-integral equations, and (2) diagonalizing the boundary-integral operators using the fact that their eigenfunctions are the surface spherical harmonics. To introduce this uncommon approach for calculations in separable geometries, we first re-derive Kirkwood’s classic results for a protein surrounded concentrically by a pure-water ion-exclusion (Stern) layer and then a dilute electrolyte, which is modeled with the linearized Poisson–Boltzmann equation. The eigenfunction-expansion approach provides a computationally efficient way to test some implications of nonlocal models, including estimating the reasonable range of the nonlocal length-scale parameter λ. Our results suggest that nonlocal solvent response may help to reduce the need for very high dielectric constants in calculating pH-dependent protein behavior, though more sophisticated nonlocal models are needed to resolve this question in full. An open-source MATLAB implementation of our approach is freely available online. PMID:26273581

A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media.

PubMed

de Barros, F P J; Fiori, A; Boso, F; Bellin, A

2015-01-01

Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data. Copyright © 2015 Elsevier B.V. All rights reserved.

A sealed optical cell for the study of lithium-electrode|electrolyte interfaces

NASA Astrophysics Data System (ADS)

Howlett, P. C.; MacFarlane, D. R.; Hollenkamp, A. F.

A sealed, symmetrical, lithium optical cell, which enables optical images of lithium surface deposits and in situ Raman spectra to be obtained simply and conveniently during charge-discharge cycling of lithium metal electrodes, has been designed and tested. A conventional aprotic liquid, 1 M lithium hexafluorophosphate in propylene carbonate, and an experimental ionic liquid, 20 mol% lithium bis(trifluoromethanesulfonyl)amide in 1-ethyl 3-methyl imidazolium bis(trifluoromethanesulfonyl)amide, are investigated as electrolyte solutions. Images obtained from the cell with the former electrolyte solution demonstrate the problems associated with cycling lithium metal electrodes. Images obtained with the latter electrolyte solution provide clear evidence that continued investigation of ionic liquids for use with lithium metal electrodes is warranted. Operation of the cell with the conventional electrolyte yields Raman spectra of good quality. The spectra display vibrational modes which arise from the electrolyte, as well as several additional modes which are associated with the deposits formed during cycling.

Multi-dimensional multi-species modeling of transient electrodeposition in LIGA microfabrication.

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

Evans, Gregory Herbert; Chen, Ken Shuang

2004-06-01

This report documents the efforts and accomplishments of the LIGA electrodeposition modeling project which was headed by the ASCI Materials and Physics Modeling Program. A multi-dimensional framework based on GOMA was developed for modeling time-dependent diffusion and migration of multiple charged species in a dilute electrolyte solution with reduction electro-chemical reactions on moving deposition surfaces. By combining the species mass conservation equations with the electroneutrality constraint, a Poisson equation that explicitly describes the electrolyte potential was derived. The set of coupled, nonlinear equations governing species transport, electric potential, velocity, hydrodynamic pressure, and mesh motion were solved in GOMA, using themore » finite-element method and a fully-coupled implicit solution scheme via Newton's method. By treating the finite-element mesh as a pseudo solid with an arbitrary Lagrangian-Eulerian formulation and by repeatedly performing re-meshing with CUBIT and re-mapping with MAPVAR, the moving deposition surfaces were tracked explicitly from start of deposition until the trenches were filled with metal, thus enabling the computation of local current densities that potentially influence the microstructure and frictional/mechanical properties of the deposit. The multi-dimensional, multi-species, transient computational framework was demonstrated in case studies of two-dimensional nickel electrodeposition in single and multiple trenches, without and with bath stirring or forced flow. Effects of buoyancy-induced convection on deposition were also investigated. To further illustrate its utility, the framework was employed to simulate deposition in microscreen-based LIGA molds. Lastly, future needs for modeling LIGA electrodeposition are discussed.« less

Case report: intraoperative anaphylactoid reaction and hydroxyethyl starch in balanced electrolyte solution (Hextend).

PubMed

Hall, Brian A; Frigas, Evangelo; Matesic, Damir; Gillett, Michael D; Sprung, Juraj

2006-10-01

To report a first case of probable anaphylactoid reaction to 6% hydroxyethyl starch reconstituted in balanced electrolyte and glucose solution (Hextend). A 22-yr-old man was admitted for a partial nephrectomy. Near the end of the four-hour operation, an infusion of Hextend was initiated. Shortly thereafter, mechanical ventilation became difficult, peak inspiratory pressure increased to 55 cm H2O with audible wheezing over the patient's lungs. Blood pressure suddenly decreased to 68/46 mmHg. Multiple doses of phenylephrine, ephedrine and epinephrine were required to restore the patient's blood pressure. Postoperatively, a diffuse urticarial rash was apparent on his upper torso. The patient recovered uneventfully. His postoperative serum tryptase was 26.3 ng x mL(-1) (reference range, < 11.5 ng x mL(-1)) and the urine N-methyl-histamine was 2448 microg x g(-1) creatinine (reference range, 30-200 microg x g(-1) creatinine). Two months after the event, skin testing was conducted to test for possible allergy to latex, lidocaine, propofol, cisatracurium, succinylcholine, vecuronium, midazolam, fentanyl, ondansetron, neostigmine, and cephazolin, and all were negative. Hextend was also tested, starting with a 1:100,000 dilution and the results were negative. The temporal relationship of severe hypotension, bronchospasm and skin rash within ten minutes from administration of Hextend in this patient suggests an immediate hypersensitivity reaction to hetastarch. The elevated levels of serum tryptase and urinary N-methyl-histamine suggest that this hypersensitivity was mediated from mast cell degranulation. Negative skin testing suggests that the reaction was anaphylactoid.

In Situ Raman Spectroscopic Studies on Concentration of Electrolyte Salt in Lithium-Ion Batteries by Using Ultrafine Multifiber Probes.

PubMed

Yamanaka, Toshiro; Nakagawa, Hiroe; Tsubouchi, Shigetaka; Domi, Yasuhiro; Doi, Takayuki; Abe, Takeshi; Ogumi, Zempachi

2017-03-09

Lithium-ion batteries have attracted considerable attention due to their high power density. The change in concentration of salt in the electrolyte solution in lithium-ion batteries during operation causes serious degradation of battery performance. Herein, a new method of in situ Raman spectroscopy with ultrafine multifiber probes was developed to simultaneously study the concentrations of ions at several different positions in the electrolyte solution in deep narrow spaces between the electrodes in batteries. The total amount of ions in the electrolyte solution clearly changed during operation due to the low permeability of the solid-electrolyte interphase (SEI) at the anode for Li + permeation. The permeability, which is a key factor to achieve high battery performance, was improved (enhanced) by adding film-forming additives to the electrolyte solution to modify the properties of the SEI. The results provide important information for understanding and predicting phenomena occurring in a battery and for designing a superior battery. The present method is useful for analysis in deep narrow spaces in other electrochemical devices, such as capacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size and Charge Dependence of Ion Transport in Human Nail Plate.

PubMed

Baswan, Sudhir M; Li, S Kevin; LaCount, Terri D; Kasting, Gerald B

2016-03-01

The electrical properties of human nail plate are poorly characterized yet are a key determinate of the potential to treat nail diseases, such as onychomycosis, using iontophoresis. To address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of -1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were 3-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upward of 5 Å (molecular weight, ca. ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes-A Review.

PubMed

Rajput, Nav Nidhi; Seguin, Trevor J; Wood, Brandon M; Qu, Xiaohui; Persson, Kristin A

2018-04-26

Fundamental molecular-level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applications. In particular, exhaustive knowledge of solvation structure, stability, and transport properties is critical for developing stable electrolytes for fast-charging and high-energy-density next-generation energy storage systems. Accordingly, there is growing interest in the rational design of electrolytes for beyond lithium-ion systems by tuning the molecular-level interactions of solvate species present in the electrolytes. Here we present a review of the solvation structure of multivalent electrolytes and its impact on the electrochemical performance of these batteries. A direct correlation between solvate species present in the solution and macroscopic properties of electrolytes is sparse for multivalent electrolytes and contradictory results have been reported in the literature. This review aims to illustrate the current understanding, compare results, and highlight future needs and directions to enable the deep understanding needed for the rational design of improved multivalent electrolytes.

Solubility of non-polar gases in electrolyte solutions

NASA Technical Reports Server (NTRS)

Walker, R. L., Jr.

1970-01-01

Solubility theory describes the effects of both concentration and temperature on solute activity coefficients. It predicts the salting-out effect and the decrease in solubility of non-polar gases with increased electrolyte concentration, and can be used to calculate heats of solution, entropies, and partial molal volumes of dissolved gases

NREL Establishes World Record for Solar Hydrogen Production | News | News |

Science.gov Websites

acid/water solution (electrolyte) where the water-splitting reaction occurs to form hydrogen and oxygen efficiency and to partially protect the critical underlying layers from the corrosive electrolyte solution

Drude-jellium model for the microwave conductivity of electrolyte solutions

NASA Astrophysics Data System (ADS)

Nhan, Tran Thi; Theu, Luong Thi; Tuan, Le; Viet, Nguyen Ai

2018-05-01

The microwave conductivity characteristics of electrolyte solutions have attracted much interest of researchers because a good understanding of their properties plays a key role to study fundamental processes in biology and chemistry. In this work, we consider the solution of sodium chloride as a plasma consisting of ions with water background. Its plasmon frequency is calculated by the jellium theory. The linear dependence of the microwave conductivity on the ion concentration of the electrolyte solutions is explained by a microscopic approach and described by a combination of this plasmon relationship and the simplified Drude formula for dielectric constant. Furthermore, the dependence of the microwave conductivity on the frequency of the salt solution is also examined. We suggest that it obeys the logistic distribution. We found a good agreement between theoretical calculations and experimental data. The values of the damping coefficient γ for the conductive solutions at low frequencies and the cutting frequency are estimated. The linear dependence of the diffusion coefficient on the temperature of the salt solution is also shown, in similarity with the result in the other model. The application of the Drude-jellium model could be done for the other electrolyte solutions in order to study theirs electro-dynamic properties.

Electrodeposition of magnesium and magnesium/aluminum alloys

DOEpatents

Mayer, Anton

1988-01-01

Electrolytes and plating solutions for use in processes for electroplating and electroforming pure magnesium and alloys of aluminum and magnesium and also electrodeposition processes. An electrolyte of this invention is comprised of an alkali metal fluoride or a quaternary ammonium halide, dimethyl magnesium and/or diethyl magnesium, and triethyl aluminum and/or triisobutyl aluminum. An electrolyte may be dissolved in an aromatic hydrocarbon solvent to form a plating solution. The proportions of the component compounds in the electrolyte are varied to produce essentially pure magnesium or magnesium/aluminum alloys having varying selected compositions.

Electrodeposition of magnesium and magnesium/aluminum alloys

DOEpatents

Mayer, A.

1988-01-21

Electrolytes and plating solutions for use in processes for electroplating and electroforming pure magnesium and alloys of aluminum and magnesium and also electrodeposition processes. An electrolyte of this invention is comprised of an alkali metal fluoride or a quaternary ammonium halide, dimethyl magnesium and/or diethyl magnesium, and triethyl aluminum and/or triisobutyl aluminum. An electrolyte may be dissolved in an aromatic hydrocarbon solvent to form a plating solution. The proportions of the component compounds in the electrolyte are varied to produce essentially pure magnesium or magnesium/aluminum alloys having varying selected compositions.

A Modified Robinson-Stokes equation for describing the thermodynamic properties of aqueous solutions of 1-1 electrolytes

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2008-05-01

Equations relating osmotic, mean ionic activity, and water activity coefficients to electrolyte concentrations in binary aqueous solutions were substantiated within the framework of cluster concepts. The model includes the contribution to solution nonideality of electrostatic interactions in terms of the Debye-Hückel theory along with hydration and association of salts via relations containing hydration and association numbers in the standard states. According to the description of data on 54 aqueous solutions of 1-1 electrolytes, this model should be given preference compared with the most extensively used NRTL, NRTL-NRF, Wilson, and Pitzer models.

Electrolyte solutions including a phosphoranimine compound, and energy storage devices including same

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

Klaehn, John R.; Dufek, Eric J.; Rollins, Harry W.

An electrolyte solution comprising at least one phosphoranimine compound and a metal salt. The at least one phosphoranimine compound comprises a compound of the chemical structure ##STR00001## where X is an organosilyl group or a tert-butyl group and each of R.sup.1, R.sup.2, and R.sup.3 is independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. An energy storage device including the electrolyte solution is also disclosed.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

Autonomous colloidal crystallization in a galvanic microreactor

NASA Astrophysics Data System (ADS)

Punckt, Christian; Jan, Linda; Jiang, Peng; Frewen, Thomas A.; Saville, Dudley A.; Kevrekidis, Ioannis G.; Aksay, Ilhan A.

2012-10-01

We report on a technique that utilizes an array of galvanic microreactors to guide the assembly of two-dimensional colloidal crystals with spatial and orientational order. Our system is comprised of an array of copper and gold electrodes in a coplanar arrangement, immersed in a dilute hydrochloric acid solution in which colloidal micro-spheres of polystyrene and silica are suspended. Under optimized conditions, two-dimensional colloidal crystals form at the anodic copper with patterns and crystal orientation governed by the electrode geometry. After the aggregation process, the colloidal particles are cemented to the substrate by co-deposition of reaction products. As we vary the electrode geometry, the dissolution rate of the copper electrodes is altered. This way, we control the colloidal motion as well as the degree of reaction product formation. We show that particle motion is governed by a combination of electrokinetic effects acting directly on the colloidal particles and bulk electrolyte flow generated at the copper-gold interface.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

PubMed

Song, Jinsuk; Kim, Mahn Won

2010-03-11

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

Method of quantitating dsDNA

DOEpatents

Stark, Peter C.; Kuske, Cheryl R.; Mullen, Kenneth I.

2002-01-01

A method for quantitating dsDNA in an aqueous sample solution containing an unknown amount of dsDNA. A first aqueous test solution containing a known amount of a fluorescent dye-dsDNA complex and at least one fluorescence-attenutating contaminant is prepared. The fluorescence intensity of the test solution is measured. The first test solution is diluted by a known amount to provide a second test solution having a known concentration of dsDNA. The fluorescence intensity of the second test solution is measured. Additional diluted test solutions are similarly prepared until a sufficiently dilute test solution having a known amount of dsDNA is prepared that has a fluorescence intensity that is not attenuated upon further dilution. The value of the maximum absorbance of this solution between 200-900 nanometers (nm), referred to herein as the threshold absorbance, is measured. A sample solution having an unknown amount of dsDNA and an absorbance identical to that of the sufficiently dilute test solution at the same chosen wavelength is prepared. Dye is then added to the sample solution to form the fluorescent dye-dsDNA-complex, after which the fluorescence intensity of the sample solution is measured and the quantity of dsDNA in the sample solution is determined. Once the threshold absorbance of a sample solution obtained from a particular environment has been determined, any similarly prepared sample solution taken from a similar environment and having the same value for the threshold absorbance can be quantified for dsDNA by adding a large excess of dye to the sample solution and measuring its fluorescence intensity.

Ficts and facts of epinephrine and norepinephrine stability in injectable solutions.

PubMed

Hoellein, Ludwig; Holzgrabe, Ulrike

2012-09-15

Epinephrine (EPI) and norepinephrine (NE) play an important role in emergency medicine and acute treatment of hypotension and shocks in the intensive care unit. Injectable solutions can either be provided as proprietary medicinal products or as individually prepared dilutions. Due to the chemical structure of EPI and NE, the stability of the corresponding solutions is limited. Thus, most manufacturers of EPI and NE injectable solutions use sulfites and nitrogen for stabilization, Nevertheless, storage conditions such as temperature and light have to be considered, but are often neglected in the daily hospital routine. In addition, hospital pharmacies prepare EPI and NE solutions and dilute commercially available solutions for individual therapy, especially on ICUs. Since the influence of dilution and the presence of excipients and other preservatives are not systematically explored, we collected published data and investigations on stability on the potency of EPI and NE injectable solutions in order to deduce storage recommendations for diluted EPI and NE solutions of different concentration. Copyright © 2012 Elsevier B.V. All rights reserved.

Isotonicity of liver and of kidney tissue in solutions of electrolytes.

PubMed

OPIE, E L

1959-07-01

Solutions of a wide variety of electrolytes, isotonic with liver or with kidney tissue, have approximately the same osmotic pressure as solutions of sodium chloride isotonic with tissues of the two organs respectively; that is, with solutions approximately twice as concentrated as the sodium chloride of mammalian blood plasma. The molar concentration of various electrolytes isotonic with liver or with kidney tissue immediately after its removal from the body is determined by the molecular weight, valency, and ion-dissociation of these electrolytes in accordance with the well known conditions of osmosis. The plasma membranes of liver and of kidney cells are imperfectly semipermeable to electrolytes, and those that enter the cell, though retarded in so doing, bring about injury which increases permeability to water. The osmotic activity of cells of mammalian liver and kidney immediately after their removal from the body resembles that of plant cells, egg cells of marine invertebrates, and mammalian red blood corpuscles and presumably represents a basic property of living cells by which osmotic pressure may be adjusted to functional need.

ISOTONICITY OF LIVER AND OF KIDNEY TISSUE IN SOLUTIONS OF ELECTROLYTES

PubMed Central

Opie, Eugene L.

1959-01-01

Solutions of a wide variety of electrolytes, isotonic with liver or with kidney tissue, have approximately the same osmotic pressure as solutions of sodium chloride isotonic with tissues of the two organs respectively; that is, with solutions approximately twice as concentrated as the sodium chloride of mammalian blood plasma. The molar concentration of various electrolytes isotonic with liver or with kidney tissue immediately after its removal from the body is determined by the molecular weight, valency, and ion-dissociation of these electrolytes in accordance with the well known conditions of osmosis. The plasma membranes of liver and of kidney cells are imperfectly semipermeable to electrolytes, and those that enter the cell, though retarded in so doing, bring about injury which increases permeability to water. The osmotic activity of cells of mammalian liver and kidney immediately after their removal from the body resembles that of plant cells, egg cells of marine invertebrates, and mammalian red blood corpuscles and presumably represents a basic property of living cells by which osmotic pressure may be adjusted to functional need. PMID:13664872

Sensitive bridge circuit measures conductance of low-conductivity electrolyte solutions

NASA Technical Reports Server (NTRS)

Schmidt, K.

1967-01-01

Compact bridge circuit measures sensitive and accurate conductance of low-conductivity electrolyte solutions. The bridge utilizes a phase sensitive detector to obtain a linear deflection of the null indicator relative to the measured conductance.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Contrasting the Influence of Cationic Amino Acids on the Viscosity and Stability of a Highly Concentrated Monoclonal Antibody.

PubMed

Dear, Barton J; Hung, Jessica J; Truskett, Thomas M; Johnston, Keith P

2017-01-01

To explain the effects of cationic amino acids and other co-solutes on the viscosity, stability and protein-protein interactions (PPI) of highly concentrated (≥200 mg/ml) monoclonal antibody (mAb) solutions to advance subcutaneous injection. The viscosities of ≥200 mg/ml mAb1 solutions with various co-solutes and pH were measured by capillary rheometry in some cases up to 70,000 s -1 . The viscosities are analyzed in terms of dilute PPI characterized by diffusion interaction parameters (k D ) from dynamic light scattering (DLS). MAb stability was measured by turbidity and size exclusion chromatography (SEC) after 4 weeks of 40°C storage. Viscosity reductions were achieved by reducing the pH, or adding histidine, arginine, imidazole or camphorsulfonic acid, each of which contains a hydrophobic moiety. The addition of inorganic electrolytes or neutral osmolytes only weakly affected viscosity. Systems with reduced viscosities also tended to be Newtonian, while more viscous systems were shear thinning. Viscosity reduction down to 20 cP at 220 mg/ml mAb1 was achieved with co-solutes that are both charged and contain a hydrophobic interaction domain for sufficient binding to the protein surface. These reductions are related to the DLS diffusion interaction parameter, k D , only after normalization to remove the effect of charge screening. Shear rate profiles demonstrate that select co-solutes reduce protein network formation.

Coulombic interactions during advection-dominated transport of ions in porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Stolze, Lucien; Rolle, Massimo

2017-04-01

Solute transport of charged species in porous media is significantly affected by the electrochemical migration term resulting from the charge-induced interactions among dissolved ions and with solid surfaces. Therefore, the characterization of such Coulombic interactions and their effect on multicomponent ionic transport is of critical importance for assessing the fate of charged solutes in porous media. In this work we present a detailed investigation of the electrochemical effects during conservative multicomponent ionic transport in homogeneous and heterogeneous domains by means of laboratory bench-scale experiments and numerical simulations. The investigation aims at quantifying the key role of small-scale electrostatic interactions in flow-through systems, especially when advection is the dominant mass-transfer process. Considering dilute solutions of strong electrolytes (e.g., MgCl2 and NaBr) we report results showing the important role of Coulombic interactions in the lateral displacement of the different ionic species for steady-state transport scenarios in which the solutions are continuously injected through different portions of the flow-through chamber [1, 2]. Successively, we focus our attention on transient transport and pulse injection of the electrolytes. In these experiments high-resolution spatial and temporal monitoring of the ions' concentrations (600 samples; 1800 concentration measurements), at closely spaced outlet ports (5 mm), allowed us resolving the effects of charge interactions on the temporal breakthrough and spatial profiles of the cations and anions [3]. The interpretation of the experimental results requires a multicomponent modeling approach with an accurate description of local hydrodynamic dispersion, as well as the explicit quantification of the dispersive fluxes' cross-coupling due to the Coulombic interactions between the charged species. A new 2-D simulator [4], coupling the solution of the multicomponent ionic transport problem with the geochemical code PHREEQC has been developed and used to quantitatively interpret the experimental results. References [1] Rolle M., Muniruzzaman M., Haberer C.M. and P. Grathwohl (2013). Geochim. Cosmochim. Acta 120, 195-205. [2] Muniruzzaman M., Haberer C.M., Grathwohl P. and M. Rolle (2014). Geochim. Cosmochim. Acta 141, 656-669. [3] Muniruzzaman M. and M. Rolle (2017). Water Resour. Res. (in press). [4] Muniruzzaman M. and M. Rolle (2016). Adv. Water Resour. 98, 1-15.

Electrochemical performance of solid oxide fuel cells having electrolytes made by suspension and solution precursor plasma spraying

NASA Astrophysics Data System (ADS)

Marr, M.; Kuhn, J.; Metcalfe, C.; Harris, J.; Kesler, O.

2014-01-01

Yttria-stabilized zirconia (YSZ) electrolytes were deposited by suspension plasma spraying (SPS) and solution precursor plasma spraying (SPPS). The electrolytes were evaluated for permeability, microstructure, and electrochemical performance. With SPS, three different suspensions were tested to explore the influence of powder size distribution and liquid properties. Electrolytes made from suspensions of a powder with d50 = 2.6 μm were more gas-tight than those made from suspensions of a powder with d50 = 0.6 μm. A peak open circuit voltage of 1.00 V was measured at 750 °C with a cell with an electrolyte made from a suspension of d50 = 2.6 μm powder. The use of a flammable suspension liquid was beneficial for improving electrolyte conductivity when using lower energy plasmas, but the choice of liquid was less important when using higher energy plasmas. With SPPS, peak electrolyte conductivities were comparable to the peak conductivities of the SPS electrolytes. However, leak rates through the SPPS electrolytes were higher than those through the electrolytes made from suspensions of d50 = 2.6 μm powder. The electrochemical test data on SPPS electrolytes are the first reported in the literature.

Liquid electrode

DOEpatents

Ekechukwu, Amy A.

1994-01-01

A dropping electrolyte electrode for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions.

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

Su, Liang; Ferrandon, Magali; Barton, John L.

The identification and development of conductive electrolytes with high concentrations of redox active species is key to realizing energy-dense nonaqueous flow batteries. Herein, we explore the use of ether solvents (1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (DEGDME), and tetraethylene glycol dimethyl ether (TEGDME)) as the basis for redox electrolytes containing a lithium ion supporting salt (LiBF4 or LiTFSI) and 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) as an active material. An automated high-throughput platform is employed to screen various electrolyte compositions by measuring solution conductivity and solute solubility as a function of solvent and salt type, component concentration, and temperature. Subsequently, the electrochemicalmore » and transport properties of select redox electrolytes are characterized by cyclic voltammetry using glassy carbon disk electrodes and by linear sweep voltammetry using carbon fiber ultramicroelectrodes. In general, improvements in electrolyte conductivity and solute solubility are observed with ether-based formulations as compared to previously reported propylene carbonate (PC)-based formulations. In particular, the addition of DOL to a DME-based electrolyte increases the conductivity and decreases the temperature for solubilization at high LiTFSI and DBBB concentrations. The redox behavior of DBBB remains consistent across the range of concentrations tested while the diffusion coefficient scales with changes in solution viscosity.« less

Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

PubMed

Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

2016-09-13

For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

Plasma Electrolytic Oxidation Coatings on Pure Ti Substrate: Effects of Na3PO4 Concentration on Morphology and Corrosion Behavior of Coatings in Ringer's Physiological Solution

NASA Astrophysics Data System (ADS)

Roknian, Masoud; Fattah-alhosseini, Arash; Gashti, Seyed Omid

2018-03-01

Plasma electrolytic oxidation has been used as a relatively new method for applying ceramic coatings having different features. In the present study, commercially pure titanium is used as substrate, and effects of trisodium phosphate electrolyte concentration on the microstructure, as well as corrosion behavior of the coating in Ringer's physiological solution are investigated. The morphology and phase compositions of coatings were analyzed by using scanning electron microscopy (SEM) and x-ray diffraction patterns. The study on the corrosion behavior of samples in a Ringer's physiological solution was carried out using open-circuit potential potentiodynamic polarization and electrochemical impedance spectroscopy. The results of electrochemical analysis proved that higher concentration of phosphate electrolyte leads to increase in the corrosion resistance of applied coatings. Accordingly, obtained results revealed that the optimum electrolyte concentration for the best corrosion behavior was 20 g L-1. Furthermore, SEM images and reduction in the dielectric breakdown potential indicated that increase in the electrolyte concentration leads to morphological improvement and smoothening of the surface.

Isotherm-Based Thermodynamic Model for Solute Activities of Asymmetric Electrolyte Aqueous Solutions.

PubMed

Nandy, Lucy; Dutcher, Cari S

2017-09-21

Adsorption isotherm-based statistical thermodynamic models can be used to determine solute concentration and solute and solvent activities in aqueous solutions. Recently, the number of adjustable parameters in the isotherm model of Dutcher et al. J. Phys. Chem. A/C 2011, 2012, 2013 were reduced for neutral solutes as well as symmetric 1:1 electrolytes by using a Coulombic model to describe the solute-solvent energy interactions (Ohm et al. J. Phys. Chem. A 2015, Nandy et al. J. Phys. Chem. A 2016). Here, the Coulombic treatment for symmetric electrolytes is extended to establish improved isotherm model equations for asymmetric 1-2 and 1-3 electrolyte systems. The Coulombic model developed here results in prediction of activities and other thermodynamic properties in multicomponent systems containing ions of arbitrary charge. The model is found to accurately calculate the osmotic coefficient over the entire solute concentration range with two model parameters, related to intermolecular solute-solute and solute-solvent spacing. The inorganic salts and acids treated here are generally considered to be fully dissociated. However, there are certain weak acids that do not dissociate completely, such as the bisulfate ion. In this work, partial dissociation of the bisulfate ion from sulfuric acid is treated as a mixture, with an additional model parameter that accounts for the dissociation ratio of the dissociated ions to nondissociated ions.

Apparent Ionic Charge in Electrolyte and Polyelectrolyte Solutions

ERIC Educational Resources Information Center

Magdelenat, H.; And Others

1978-01-01

Compares average displacements of charged particles under thermal motion alone with those obtained by the action of an external electric field to develop a concept of "apparent charge" to approximate actual structural charge in an electrolyte solution. (SL)

Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries

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

Wan, Chuan; Xu, Suochang; Hu, Mary Y.

The composition of the solid electrolyte interphase (SEI) layers associated with a high performance Cu|Li cell using lithium bis(fluorosulfonyi)imide (LiFSI) in 1,2-dimethoxyethane (DME) as electrolyte is determined by a multinuclear (6Li, 19F, 13C and 1H) solid-state MAS NMR study at high magnetic field (850 MHz). This cell can be cycled at high rates (4 mA•cm-2) for more than 1000 cycles with no increase in the cell impedance at high Columbic efficiency (average of 98.4%) in a highly concentrated LiFSI-DME electrolyte (4 M). LiFSI, LiF, Li2O2 (and/or CH3OLi), LiOH, Li2S and Li2O are observed in the SEI and validated by comparingmore » with the spectra acquired on standard compounds and literature reports. To gain further insight into the role of the solute and its concentration dependence on the formation of SEIs while keeping the solvent of DME unchanged, the SEIs from different concentrations of LiFSI-DME and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-DME electrolyte are also investigated. It is found that LiF, a lithiated compound with superior mechanical strength and good Li+ ionic conductivity, is observed in the concentrated 4.0 M LiFSI-DME and the 3.0 M LiTFSI-DME systems but not in the diluted 1.0 M LiFSI-DME system. Li2O exists in both low and high concentration of LiFSI-DME while no Li2O is observed in the LiTFSI system. Furthermore, the dead metallic Li is reduced in the 4 M LiFSI-DME system compared with that in the 1 M LiFSI-DME system. Quantitative 6Li MAS results indicate that the SEI associated with the 4 M LiFSI-DEME is denser or thicker than that of the 1 M LiFSI-DME and the 3 M LiTFSI-DME systems. These findings are likely the reasons for explaining the high electrochemical performance associated with the high concentration LiFSI-DME system.« less

Comparison of the in vitro effects of saline, hypertonic hydroxyethyl starch, hypertonic saline, and two forms of hydroxyethyl starch on whole blood coagulation and platelet function in dogs.

PubMed

Wurlod, Virginie A; Howard, Judith; Francey, Thierry; Schweighauser, Ariane; Adamik, Katja N

2015-01-01

To compare the in vitro effects of hypertonic solutions and colloids to saline on coagulation in dogs. In vitro experimental study. Veterinary teaching hospital. Twenty-one adult dogs. Blood samples were diluted with saline, 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH), 7.2% hypertonic saline (HTS), hydroxyethyl starch (HES) 130/0.4 or hydroxyethyl starch 600/0.75 at ratios of 1:22 and 1:9, and with saline and HES at a ratio of 1:3. Whole blood coagulation was analyzed using rotational thromboelastometry (extrinsic thromboelastometry-cloting time (ExTEM-CT), maximal clot firmness (MCF) and clot formation time (CFT) and fibrinogen function TEM-CT (FibTEM-CT) and MCF) and platelet function was analyzed using a platelet function analyzer (closure time, CTPFA ). All parameters measured were impaired by saline dilution. The CTPFA was prolonged by 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH) and HTS but not by HES solutions. At clinical dilutions equivalent to those generally administered for shock (saline 1:3, HES 1:9, and hypertonic solutions 1:22), CTPFA was more prolonged by HH and HTS than other solutions but more by saline than HES. No difference was found between the HES solutions or the hypertonic solutions. ExTEM-CFT and MCF were impaired by HH and HTS but only mildly by HES solutions. At clinically relevant dilutions, no difference was found in ExTEM-CFT between HTS and saline or in ExTEM-MCF between HH and saline. No consistent difference was found between the 2 HES solutions but HH impaired ExTEM-CFT and MCF more than HTS. At high dilutions, FibTEM-CT and -MCF and ExTEM-CT were impaired by HES. Hypertonic solutions affect platelet function and whole blood coagulation to a greater extent than saline and HES. At clinically relevant dilutions, only CTPFA was markedly more affected by hypertonic solutions than by saline. At high dilutions, HES significantly affects coagulation but to no greater extent than saline at clinically relevant dilutions. © Veterinary Emergency and Critical Care Society 2015.

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.

Process for electrolytic deposition of metals on zirconium materials

DOEpatents

Donaghy, Robert E.

1979-01-30

A process for the electrolytic deposition of a metal layer on an article comprised of zirconium or a zirconium alloy is disclosed. The article is activated in an aged aqueous solution comprising from about 10 to about 20 grams per liter ammonium bifluoride and from about 0.75 to about 2 grams per liter of sulfuric acid. The solution is aged by immersion of pickled zirconium in the solution for at least about 10 minutes. The loosely adhering film formed on the article in the activating step is removed and the article is contacted with an electrolytic plating solution containing the metal to be deposited on the article in the presence of an electrode receiving current.

High-Performance Cells Containing Lithium Metal Anodes, LiNi0.6Co0.2Mn0.2O2 (NCM 622) Cathodes, and Fluoroethylene Carbonate-Based Electrolyte Solution with Practical Loading.

PubMed

Salitra, Gregory; Markevich, Elena; Afri, Michal; Talyosef, Yosef; Hartmann, Pascal; Kulisch, Joern; Sun, Yang-Kook; Aurbach, Doron

2018-06-13

We report on the highly stable lithium metal|LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) cells with practical electrodes' loading of 3.3 mA h g -1 , which can undergo many hundreds of stable cycles, demonstrating high rate capability. A key issue was the use of fluoroethylene carbonate (FEC)-based electrolyte solutions (1 M LiPF 6 in FEC/dimethyl carbonate). Li|NCM 622 cells can be cycled at 1.5 mA cm -2 for more than 600 cycles, whereas symmetric Li|Li cells demonstrate stable performance for more than 1000 cycles even at higher areal capacity and current density. We attribute the excellent performance of both Li|NCM and Li|Li cells to the formation of a stable and efficient solid electrolyte interphase (SEI) on the surface of the Li metal electrodes cycled in FEC-based electrolyte solutions. The composition of the SEI on the Li and the NCM electrodes is analyzed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. A drastic capacity fading of Li|NCM cells is observed, followed by spontaneous capacity recovery during prolonged cycling. This phenomenon depends on the current density and the amount of the electrolyte solution and relates to kinetic limitations because of SEI formation on the Li anodes in the FEC-based electrolyte solution.

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Selection of new Kynar-based electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Christie, Alasdair M.; Christie, Lynn; Vincent, Colin A.

New electrolyte solution compositions have been identified for use in lithium-ion batteries after gelling with an appropriate quantity of Kynar polymer. Since the Li + conducting medium is largely the liquid electrolyte component, the assessment of these solutions as suitable lithium-ion cell candidates were investigated before adding the polymer. Selected electrolyte solutions were then used in the preparation of polymer gels. The specific conductivities of Kynar-based gels were determined as a function of salt concentration and polymer concentration. Optimised self-supporting polymer films, based on mixtures of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and lithium hexafluorophosphate (LiPF 6) or lithium tetrafluoroborate (LiBF 4), showed good high current density cycling performance when used as separators in coke and Li 1- xMn 2O 4 (spinel) half-cells.

Effects of sulfate and nitrate anions on aluminum corrosion in slightly alkaline solution

NASA Astrophysics Data System (ADS)

Li, Shengyi; Church, Benjamin C.

2018-05-01

The corrosion mechanisms and kinetics of AA1085 in Li2SO4 and LiNO3 aqueous rechargeable lithium-ion battery electrolytes were investigated at pH 11 using chronoamperometry. The corrosion kinetics of AA1085 is controlled by the electrolyte concentration level and the anodic potentials. AA1085 is susceptible to crystallographic pitting corrosion in Li2SO4 electrolytes. The rates of pit nucleation and pit growth both decreased at higher Li2SO4 concentrations or at lower anodic potentials. AA1085 passivates against pitting corrosion in LiNO3 electrolytes due to the formation of a thick, uniform corrosion product layer. The growth rate of the passive film was slightly enhanced by increasing the electrolyte concentration and anodic potentials. X-ray photoelectron spectroscopy spectra showed the formation of a thin sulfate-incorporated passive film on the electrode, which comprises Al2(SO)418H2O, Al(OH)SO4 and Al(OH)3, before the occurrence of pitting growth in 2 M Li2SO4 electrolyte. The thick corrosion product layer formed in 5 M LiNO3 electrolyte was composed of Al(OH)3 and AlOOH. Raman spectroscopy on deionized water, LiOH solution, Li2SO4 and LiNO3 electrolytes depicted changes of solution structure with increasing electrolyte concentration. The influence of extrinsic and intrinsic factors on the corrosion kinetics of AA1085 in Li2SO4 and LiNO3 electrolytes at pH 11 are discussed in detail.

Electrode effects on temporal changes in electrolyte pH and redox potential for water treatment

PubMed Central

Ciblak, Ali; Mao, Xuhui; Padilla, Ingrid; Vesper, Dorothy; Alshawabkeh, Iyad; Alshawabkeh, Akram N.

2012-01-01

The performance of electrochemical remediation methods could be optimized by controlling the physicochemical conditions of the electrochemical redox system. The effects of anode type (reactive or inert), current density and electrolyte composition on the temporal changes in pH and redox potential of the electrolyte were evaluated in divided and mixed electrolytes. Two types of electrodes were used: iron as a reactive electrode and mixed metal oxide coated titanium (MMO) as an inert electrode. Electric currents of 15, 30, 45 and 60 mA (37.5 mA L−1, 75 mA L−1, 112.5 mA L−1 and 150 mA L−1) were applied. Solutions of NaCl, Na2SO4 and NaHCO3 were selected to mimic different wastewater or groundwater composition. Iron anodes resulted in highly reducing electrolyte conditions compared to inert anodes. Electrolyte pH was dependent on electrode type, electrolyte composition and current density. The pH of mixed-electrolyte was stable when MMO electrodes were used. When iron electrodes were used, the pH of electrolyte with relatively low current density (37.5 mA L−1) did not show significant changes but the pH increased sharply for relatively high current density (150 mA L−1). Sulfate solution showed more basic and relatively more reducing electrolyte condition compared to bicarbonate and chloride solution. The study shows that a highly reducing environment could be achieved using iron anodes in divided or mixed electrolytes and the pH and redox potential could be optimized by using appropriate current and polarity reversal. PMID:22416866

Liquid electrode

DOEpatents

Ekechukwu, A.A.

1994-07-05

A dropping electrolyte electrode is described for use in electrochemical analysis of non-polar sample solutions, such as benzene or cyclohexane. The liquid electrode, preferably an aqueous salt solution immiscible in the sample solution, is introduced into the solution in dropwise fashion from a capillary. The electrolyte is introduced at a known rate, thus, the droplets each have the same volume and surface area. The electrode is used in making standard electrochemical measurements in order to determine properties of non-polar sample solutions. 2 figures.

True Anomalous Osmosis in Multi-Solute Model Membrane Systems

PubMed Central

Grim, Eugene; Sollner, Karl

1960-01-01

The transport of liquid across charged porous membranes separating two electrolytic solutions of different composition consists of both a normal and an anomalous osmotic component. Anomalous osmosis does not occur with electroneutral membranes. Thus, with membranes which can be charged and discharged reversibly, normal osmosis can be measured with the membrane in the electroneutral state, and normal together with anomalous osmosis with the membrane in a charged state, the difference between these two effects being the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, in multi-solute systems with 0.2 and 0.4 osmolar solutions of a variety of electrolytes and of glucose against solutions of other solutes of the same, one-half, and twice these osmolarities. In the simpler systems the magnitude of the true anomalous osmosis can be predicted semiquantitatively by reference to appropriate single-solute systems. In isoosmolar systems with two electrolytic solutions the anomalous osmotic flow rates may reach 300 µl./cm.2 hr. and more; systems with electrolytic solutions against solutions of glucose can produce twice this rate. These fluxes are of the same order of magnitude as the liquid transport rates across such living structures as the mucosa of dog gall bladder, ileum, and urinary bladder. PMID:13708691

Separations by supported liquid membrane cascades

DOEpatents

Danesi, P.R.

1983-09-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solution and the supported liquid membranes are arranged to provide a continuous process.

Permanent physico-chemical properties of extremely diluted aqueous solutions of homeopathic medicines.

PubMed

Elia, V; Baiano, S; Duro, I; Napoli, E; Niccoli, M; Nonatelli, L

2004-07-01

The purpose of this study was to obtain information about the influence of successive dilutions and succussions on the water structure. 'Extremely diluted solutions' (EDS) are solutions obtained through the iteration of two processes: dilution in stages of 1:100 and succussion, typically used in homeopathic medicine. The iteration is repeated until extreme dilutions are reached, so that the chemical composition of the solution is identical to that of the solvent. Nine different preparations, were studied from the 3cH to 30cH (Hahnemannian Centesimal Dilution). Four of those were without the active principle (potentized water). Two different active principles were used: Arsenicum sulphuratum rubrum (ASR), As4S4, 2,4-dichlorophenoxyacetic acid (2,4D). The solvents were: a solution of sodium bicarbonate and of silicic acid at 5 x 10(-5) M (mol/l) each, and solutions of sodium bicarbonate 5 x 10(-5), 7.5 x 10(-5) and 10 x 10(-5) M (mol/l) in double-distilled water. The containers were Pyrex glass to avoid the release of alkaline oxide and silica from the walls. Conductivity measurements of the solutions were carried out as a function of the age of the potencies. We found increases of electrical conductivity compared to untreated solvent. Successive dilution and succussion can permanently alter the physico-chemical properties of the aqueous solvent. But we also detected changes in physio-chemical parameters with time. This has not previously been reported. The modification of the solvent could provide an important support to the validity of homeopathic medicine, that employs 'medicines without molecules'. The nature of the phenomena here described remains still unexplained, nevertheless some significant experimental results were obtained.

Ionic Liquid as an Effective Additive for Rechargeable Magnesium Batteries

DOE PAGES

Pan, Baofei; Lau, Ka -Cheong; Vaughey, John T.; ...

2017-03-02

Here, the effect of the addition of an ionic liquid DEME•TFSI to an electrolyte solution of Mg(HMDS) 2-MgCl 2 in THF was studied electrochemically and spectroscopically. Reversible magnesium deposition/dissolution was achieved with the DEME•TFSI-modified electrolyte. This electrolyte shows higher ionic conductivity, and a linear relationship was observed between the ionic conductivity and the concentration of DEME•TFSI in THF solution of Mg(HMDS) 2-MgCl 2. Mg-Mo 6S 8 coin cells have also been successfully cycled using Mg(HMDS) 2-MgCl 2 electrolyte with the addition of DEME•TFSI. Raman and NMR spectroscopy suggest that DEME•TFSI facilitates magnesium deposition/dissolution by improving ionic conductivity of the electrolyte.

Fecal electrolyte testing for evaluation of unexplained diarrhea: Validation of body fluid test accuracy in the absence of a reference method.

PubMed

Voskoboev, Nikolay V; Cambern, Sarah J; Hanley, Matthew M; Giesen, Callen D; Schilling, Jason J; Jannetto, Paul J; Lieske, John C; Block, Darci R

2015-11-01

Validation of tests performed on body fluids other than blood or urine can be challenging due to the lack of a reference method to confirm accuracy. The aim of this study was to evaluate alternate assessments of accuracy that laboratories can rely on to validate body fluid tests in the absence of a reference method using the example of sodium (Na(+)), potassium (K(+)), and magnesium (Mg(2+)) testing in stool fluid. Validations of fecal Na(+), K(+), and Mg(2+) were performed on the Roche cobas 6000 c501 (Roche Diagnostics) using residual stool specimens submitted for clinical testing. Spiked recovery, mixing studies, and serial dilutions were performed and % recovery of each analyte was calculated to assess accuracy. Results were confirmed by comparison to a reference method (ICP-OES, PerkinElmer). Mean recoveries for fecal electrolytes were Na(+) upon spiking=92%, mixing=104%, and dilution=105%; K(+) upon spiking=94%, mixing=96%, and dilution=100%; and Mg(2+) upon spiking=93%, mixing=98%, and dilution=100%. When autoanalyzer results were compared to reference ICP-OES results, Na(+) had a slope=0.94, intercept=4.1, and R(2)=0.99; K(+) had a slope=0.99, intercept=0.7, and R(2)=0.99; and Mg(2+) had a slope=0.91, intercept=-4.6, and R(2)=0.91. Calculated osmotic gap using both methods were highly correlated with slope=0.95, intercept=4.5, and R(2)=0.97. Acid pretreatment increased magnesium recovery from a subset of clinical specimens. A combination of mixing, spiking, and dilution recovery experiments are an acceptable surrogate for assessing accuracy in body fluid validations in the absence of a reference method. Copyright © 2015 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Obtaining accurate amounts of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, Mark W.; George, William A.

1987-01-01

A process for obtaining pre-determined, accurate rate amounts of mercury. In one embodiment, predetermined, precise amounts of Hg are separated from HgO and plated onto a cathode wire. The method for doing this involves dissolving a precise amount of HgO which corresponds to a pre-determined amount of Hg desired in an electrolyte solution comprised of glacial acetic acid and H.sub.2 O. The mercuric ions are then electrolytically reduced and plated onto a cathode producing the required pre-determined quantity of Hg. In another embodiment, pre-determined, precise amounts of Hg are obtained from Hg.sub.2 Cl.sub.2. The method for doing this involves dissolving a precise amount of Hg.sub.2 Cl.sub.2 in an electrolyte solution comprised of concentrated HCl and H.sub.2 O. The mercurous ions in solution are then electrolytically reduced and plated onto a cathode wire producing the required, pre-determined quantity of Hg.

Unusual effect of the magnetic field component of the microwave radiation on aqueous electrolyte solutions.

PubMed

Horikoshi, Satoshi; Sumi, Takuya; Serpone, Nick

2012-01-01

The heating characteristics of aqueous electrolyte solutions (NaCl, KCl, CaCl2, NaBF4, and NaBr) of varying concentrations in ultrapure water by 2.45 GHz microwave radiation from a single-mode resonance microwave device and a semiconductor microwave generator were examined under conditions where the electric field (E-field) was dominant and where the magnetic field (H-field) dominated. Although magnetic field heating is not generally used in microwave chemistry, the electrolyte solutions were heated almost entirely by the microwaves' H-field. The heating rates under H-field irradiation at the higher concentrations of electrolytes (0.125 M to 0.50 M) exceeded the rates under E-field irradiation. This inversion phenomenon in heating is described in terms of the penetration depth of the microwaves. On the other hand, the action of the microwave radiation on ethylene glycol containing an electrolyte differed from that observed for water under E-field and H-field conditions.

Obtaining accurate amounts of mercury from mercury compounds via electrolytic methods

DOEpatents

Grossman, M.W.; George, W.A.

1987-07-07

A process is described for obtaining pre-determined, accurate rate amounts of mercury. In one embodiment, predetermined, precise amounts of Hg are separated from HgO and plated onto a cathode wire. The method for doing this involves dissolving a precise amount of HgO which corresponds to a pre-determined amount of Hg desired in an electrolyte solution comprised of glacial acetic acid and H[sub 2]O. The mercuric ions are then electrolytically reduced and plated onto a cathode producing the required pre-determined quantity of Hg. In another embodiment, pre-determined, precise amounts of Hg are obtained from Hg[sub 2]Cl[sub 2]. The method for doing this involves dissolving a precise amount of Hg[sub 2]Cl[sub 2] in an electrolyte solution comprised of concentrated HCl and H[sub 2]O. The mercurous ions in solution are then electrolytically reduced and plated onto a cathode wire producing the required, pre-determined quantity of Hg. 1 fig.

Investigation of electrolyte measurement in diluted whole blood using spectroscopic and chemometric methods

NASA Technical Reports Server (NTRS)

Soller, Babs R.; Favreau, Janice; Idwasi, Patrick O.

2003-01-01

The feasibility of using near-infrared (NIR) spectroscopy in combination with partial least-squares (PLS) regression was explored to measure electrolyte concentration in whole blood samples. Spectra were collected from diluted blood samples containing randomized, clinically relevant concentrations of Na+, K+, and Ca2+. Sodium was also studied in lysed blood. Reference measurements were made from the same samples using a standard clinical chemistry instrument. Partial least squares (PLS) was used to develop calibration models for each ion with acceptable results (Na+, R2 = 0.86, CVSEP = 9.5 mmol/L; K+, R2 = 0.54, CVSEP = 1.4 mmol/L; Ca2+, R2 = 0.56, CVSEP = 0.18 mmol/L). Slightly improved results were obtained using a narrower wavelength region (470-925 nm) where hemoglobin, but not water, absorbed indicating that ionic interaction with hemoglobin is as effective as water in causing measurable spectral variation. Good models were also achieved for sodium in lysed blood, illustrating that cell swelling, which is correlated with sodium concentration, is not required for calibration model development.

Sensitive determination of anions in saliva using capillary electrophoresis after transient isotachophoretic preconcentration.

PubMed

Xu, Zhongqi; Doi, Takayuki; Timerbaev, Andrei R; Hirokawa, Takeshi

2008-10-19

A transient isotachophoresis-capillary electrophoresis (tITP-CE) system for the determination of minor inorganic anions in saliva is described. The complete separation and quantification of bromide, iodide, nitrate, nitrite, and thiocyanate has been achieved with only centrifugation and dilution of the saliva sample. In-line tITP preconcentration conditions, created by introduction of the plugs of 5 mM dithionic acid (leading electrolyte) and 10 mM formic acid (terminating electrolyte) before and after the sample zone, respectively, allowed the limits of direct UV absorption detection (at 200 nm) to be up to 50-fold improved as compared with CE without tITP. As a result, nitrate and thiocyanate were still detectable at 4.6 and 3.8 microgl(-1), respectively, in 1000 times diluted saliva. The daily variations of anionic concentrations in saliva samples taken from a smoking health volunteer were discussed based on the results of tITP-CE analysis. It was confirmed that the thiocyanate concentration in saliva noticeably increased after smoking. This is apparently the first report on simultaneous quantification of more than four anionic salivary constituents using CE.

Effects of carbohydrate-hydration strategies on glucose metabolism, sprint performance and hydration during a soccer match simulation in recreational players.

PubMed

Kingsley, Michael; Penas-Ruiz, Carlos; Terry, Chris; Russell, Mark

2014-03-01

This study compared the effects of three carbohydrate-hydration strategies on blood glucose concentration, exercise performance and hydration status throughout simulated soccer match-play. A randomized, double-blind and cross-over study design was employed. After familiarization, 14 recreational soccer players completed the soccer match simulation on three separate occasions. Participants consumed equal volumes of 9.6% carbohydrate-caffeine-electrolyte (∼ 6 mg/kg BW caffeine) solution with carbohydrate-electrolyte gels (H-CHO), 5.6% carbohydrate-electrolyte solution with electrolyte gels (CHO) or electrolyte solution and electrolyte gels (PL). Blood samples were taken at rest, immediately before exercise and every 15 min during exercise (first half: 15, 30, 45 min; second half: 60, 75, 90 min). Supplementation influenced blood glucose concentration (time × treatment interaction: p<0.001); however, none of the supplementation regimes were effective in preventing a drop in blood glucose at 60 min. Mean sprint speed was 3 ± 1% faster in H-CHO when compared with PL (treatment: p=0.047). Supplementation caused a 2.3 ± 0.5% increase in plasma osmolality in H-CHO (p<0.001) without change in CHO or PL. Similarly, mean sodium concentrations were 2.1 ± 0.4% higher in H-CHO when compared with PL (p=0.006). Combining high carbohydrate availability with caffeine resulted in improved sprint performance and elevated blood glucose concentrations throughout the first half and at 90 min of exercise; however, this supplementation strategy negatively influenced hydration status when compared with 5.6% carbohydrate-electrolyte and electrolyte solutions. Copyright © 2013 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Modeling mass transfer and reaction of dilute solutes in a ternary phase system by the lattice Boltzmann method

NASA Astrophysics Data System (ADS)

Fu, Yu-Hang; Bai, Lin; Luo, Kai-Hong; Jin, Yong; Cheng, Yi

2017-04-01

In this work, we propose a general approach for modeling mass transfer and reaction of dilute solute(s) in incompressible three-phase flows by introducing a collision operator in lattice Boltzmann (LB) method. An LB equation was used to simulate the solute dynamics among three different fluids, in which the newly expanded collision operator was used to depict the interface behavior of dilute solute(s). The multiscale analysis showed that the presented model can recover the macroscopic transport equations derived from the Maxwell-Stefan equation for dilute solutes in three-phase systems. Compared with the analytical equation of state of solute and dynamic behavior, these results are proven to constitute a generalized framework to simulate solute distributions in three-phase flows, including compound soluble in one phase, compound adsorbed on single-interface, compound in two phases, and solute soluble in three phases. Moreover, numerical simulations of benchmark cases, such as phase decomposition, multilayered planar interfaces, and liquid lens, were performed to test the stability and efficiency of the model. Finally, the multiphase mass transfer and reaction in Janus droplet transport in a straight microchannel were well reproduced.

Are electrostatic potentials between regions of different chemical composition measurable? The Gibbs-Guggenheim Principle reconsidered, extended and its consequences revisited.

PubMed

Pethica, Brian A

2007-12-21

As indicated by Gibbs and made explicit by Guggenheim, the electrical potential difference between two regions of different chemical composition cannot be measured. The Gibbs-Guggenheim Principle restricts the use of classical electrostatics in electrochemical theories as thermodynamically unsound with some few approximate exceptions, notably for dilute electrolyte solutions and concomitant low potentials where the linear limit for the exponential of the relevant Boltzmann distribution applies. The Principle invalidates the widespread use of forms of the Poisson-Boltzmann equation which do not include the non-electrostatic components of the chemical potentials of the ions. From a thermodynamic analysis of the parallel plate electrical condenser, employing only measurable electrical quantities and taking into account the chemical potentials of the components of the dielectric and their adsorption at the surfaces of the condenser plates, an experimental procedure to provide exceptions to the Principle has been proposed. This procedure is now reconsidered and rejected. No other related experimental procedures circumvent the Principle. Widely-used theoretical descriptions of electrolyte solutions, charged surfaces and colloid dispersions which neglect the Principle are briefly discussed. MD methods avoid the limitations of the Poisson-Bolzmann equation. Theoretical models which include the non-electrostatic components of the inter-ion and ion-surface interactions in solutions and colloid systems assume the additivity of dispersion and electrostatic forces. An experimental procedure to test this assumption is identified from the thermodynamics of condensers at microscopic plate separations. The available experimental data from Kelvin probe studies are preliminary, but tend against additivity. A corollary to the Gibbs-Guggenheim Principle is enunciated, and the Principle is restated that for any charged species, neither the difference in electrostatic potential nor the sum of the differences in the non-electrostatic components of the thermodynamic potential difference between regions of different chemical compositions can be measured.

Ultraconcentrated Sodium Bis(fluorosulfonyl)imide-Based Electrolytes for High-Performance Sodium Metal Batteries.

PubMed

Lee, Jaegi; Lee, Yongwon; Lee, Jeongmin; Lee, Sang-Min; Choi, Jeong-Hee; Kim, Hyungsub; Kwon, Mi-Sook; Kang, Kisuk; Lee, Kyu Tae; Choi, Nam-Soon

2017-02-01

We present an ultraconcentrated electrolyte composed of 5 M sodium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane for Na metal anodes coupled with high-voltage cathodes. Using this electrolyte, a very high Coulombic efficiency of 99.3% at the 120th cycle for Na plating/stripping is obtained in Na/stainless steel (SS) cells with highly reduced corrosivity toward Na metal and high oxidation durability (over 4.9 V versus Na/Na + ) without corrosion of the aluminum cathode current collector. Importantly, the use of this ultraconcentrated electrolyte results in substantially improved rate capability in Na/SS cells and excellent cycling performance in Na/Na symmetric cells without the increase of polarization. Moreover, this ultraconcentrated electrolyte exhibits good compatibility with high-voltage Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) and Na 0.7 (Fe 0.5 Mn 0.5 )O 2 cathodes charged to high voltages (>4.2 V versus Na/Na + ), resulting in outstanding cycling stability (high reversible capacity of 109 mAh g -1 over 300 cycles for the Na/Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) cell) compared with the conventional dilute electrolyte, 1 M NaPF 6 in ethylene carbonate/propylene carbonate (5/5, v/v).

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

Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

PubMed

Ohba, Tomonori

2014-02-24

An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Submicroporous/microporous and compatible/incompatible multi-functional dual-layer polymer electrolytes and their interfacial characteristics with lithium metal anode

NASA Astrophysics Data System (ADS)

Lee, Young-Gi; Kyhm, Kwangseuk; Choi, Nam-Soon; Ryu, Kwang Sun

A novel multi-functional dual-layer polymer electrolyte was prepared by impregnating the interconnected pores with an ethylene carbonate (EC)/dimethyl carbonate (DMC)/lithium hexafluorophosphate (LiPF 6) solution. An incompatible layer is based on a microporous polyethylene (PE) and a compatible layer, based on a poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) is sub-microporous and compatible with an electrolyte solution. The Li electrode/the dual-layer polymer electrolyte/Li[Ni 0.15Li 0.23M n0.62]O 2 cell showed stable cycle performance under prolonged cycle number. This behavior is due to the enhanced compatibility between the matrix polymer and the liquid electrolytes within the submicroporous compatible layer, which could lead to a controlled Li + deposition on the Li anode surface by forming homegeneous electrolyte zone near the anode.

Ion Pairing and Diffusion in Magnesium Electrolytes Based on Magnesium Borohydride.

PubMed

Samuel, Devon; Steinhauser, Carl; Smith, Jeffrey G; Kaufman, Aaron; Radin, Maxwell D; Naruse, Junichi; Hiramatsu, Hidehiko; Siegel, Donald J

2017-12-20

One obstacle to realizing a practical, rechargeable magnesium-ion battery is the development of efficient Mg electrolytes. Electrolytes based on simple Mg(BH 4 ) 2 salts suffer from poor salt solubility and/or low conductivity, presumably due to strong ion pairing. Understanding the molecular-scale processes occurring in these electrolytes would aid in overcoming these performance limitations. Toward this goal, the present study examines the solvation, agglomeration, and transport properties of a family of Mg electrolytes based on the Mg(BH 4 ) 2 salt using classical molecular dynamics. These properties were examined across five different solvents (tetrahydrofuran and the glymes G1-G4) and at four salt concentrations ranging from the dilute limit up to 0.4 M. Significant and irreversible salt agglomeration was observed in all solvents at all nondilute Mg(BH 4 ) 2 concentrations. The degree of clustering observed in these divalent Mg systems is much larger than that reported for electrolytes containing monovalent cations, such as Li. The salt agglomeration rate and diffusivity of Mg 2+ were both observed to correlate with solvent self-diffusivity: electrolytes using longer- (shorter-) chain solvents had the lowest (highest) Mg 2+ diffusivity and agglomeration rates. Incorporation of Mg 2+ into Mg 2+ -BH 4 - clusters significantly reduces the diffusivity of Mg 2+ by restricting displacements to localized motion within largely immobile agglomerates. Consequently, diffusion is increasingly impeded with increasing Mg(BH 4 ) 2 concentration. These data are consistent with the solubility limitations observed experimentally for Mg(BH 4 ) 2 -based electrolytes and highlight the need for strategies that minimize salt agglomeration in electrolytes containing divalent cations.

The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions

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

See, Kimberly A.; Chapman, Karena W.; Zhu, Lingyang

2016-01-13

Mg batteries are an attractive alternative to Li-based energy storage due to the possibility of higher volumetric capacities with the added advantage of using sustainable materials. A promising emerging electrolyte for Mg batteries is the magnesium aluminum chloride complex (MACC) which shows high Mg electrodeposition and stripping efficiencies and relatively high anodic stabilities. As prepared, MACC is inactive with respect to Mg deposition; however, efficient Mg electrodeposition can be achieved following an electrolytic conditioning process. Through the use of Raman spectroscopy, surface enhanced Raman spectroscopy, 27Al and 35Cl nuclear magnetic resonance spectroscopy, and pair distribution function analysis, we explore themore » active vs inactive complexes in the MACC electrolyte and demonstrate the codependence of Al and Mg speciation. These techniques report on significant changes occurring in the bulk speciation of the conditioned electrolyte relative to the as-prepared solution. Analysis shows that the active Mg complex in conditioned MACC is very likely the [Mg2(μ–Cl)3·6THF]+ complex that is observed in the solid state structure. Additionally, conditioning creates free Cl– in the electrolyte solution, and we suggest the free Cl– adsorbs at the electrode surface to enhance Mg electrodeposition.« less

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

Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

PubMed

Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

2018-04-04

Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

PubMed

See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

2017-10-18

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest to the Mg electrolyte community.

Sonic wave separation of invertase from a dilute solution to generated droplets.

PubMed

Tanner, R D; Ko, S; Loha, V; Prokop, A

2000-01-01

It has previously been shown that a droplet fractionation process, simulated by shaking a separatory funnel containing a dilute protein solution, can generate droplets richer in protein than present in the original dilute solution. In this article, we describe an alternative method that can increase the amount of protein transferred to the droplets. The new method uses ultrasonic waves, enhanced by a bubble gas stream to create the droplets. The amount of protein in these droplets increases by about 50%. In this method, the top layer of the dilute protein solution (of the solution-air interface) becomes enriched in protein when air is bubbled into the solution. This concentrating procedure is called bubble fractionation. Once the protein has passed through the initial buildup, this enriched protein layer is transferred into droplets with the aid of a vacuum above the solution at the same time that ultrasonic waves are introduced. The droplets are then carried over to a condenser and coalesced. We found that this new method provides an easier way to remove the protein-enriched top layer of the dilute solution and generates more droplets within a shorter period than the separatory funnel droplet generation method. The added air creates the bubbles and carries the droplets, and the vacuum helps remove the effluent airstream from the condenser. The maximum partition coefficient, the ratio of the protein concentration in the droplets to that in the residual solution (approx 8.5), occurred at pH 5.0.

Cation profiling of passive films on stainless steel formed in sulphuric and acetic acid by deconvolution of angle-resolved X-ray photoelectron spectra

NASA Astrophysics Data System (ADS)

Högström, Jonas; Fredriksson, Wendy; Edstrom, Kristina; Björefors, Fredrik; Nyholm, Leif; Olsson, Claes-Olof A.

2013-11-01

An approach for determining depth gradients of metal-ion concentrations in passive films on stainless steel using angle-resolved X-ray photoelectron spectroscopy (ARXPS) is described. The iterative method, which is based on analyses of the oxidised metal peaks, provides increased precision and hence allows faster ARXPS measurements to be carried out. The method was used to determine the concentration depth profiles for molybdenum, iron and chromium in passive films on 316L/EN 1.4432 stainless steel samples oxidised in 0.5 M H2SO4 and acetic acid diluted with 0.02 M Na2B4O7 · 10H2O and 1 M H2O, respectively. The molybdenum concentration in the film is pin-pointed to the oxide/metal interface and the films also contained an iron-ion-enriched surface layer and a chromium-ion-dominated middle layer. Although films of similar composition and thickness (i.e., about 2 nm) were formed in the two electrolytes, the corrosion currents were found to be three orders of magnitude larger in the acetic acid solution. The differences in the layer composition, found for the two electrolytes as well as different oxidation conditions, can be explained based on the oxidation potentials of the metals and the dissolution rates of the different metal ions.

Conductance of solutions of lithium tris(trifluoromethanesulfonyl) methide in water, acetonitrile, propylene carbonate, N,N-dimethylformamide, and nitromethane at 25 C

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

Croce, F.; D`Aprano, A.; Nanjundiah, C.

1996-01-01

In order to determine the solution properties of lithium tris(trifluoromethanesulfonyl) methide (LiMe) in water and the aprotic solvents acetonitrile (AN), propylene carbonate (PC), N,N-dimethylformamide (DMF), and nitromethane (MeNO{sub 2}), conductance measurements have been carried out at 25 C. Molar conductivities at infinite dilution ({Lambda}{degree}) and ion pair association constants (K{sub a}) were obtained analyzing the experimental data with the Fuoss-Hsia conductance equation using the expansion of Fernandez-Prini and Justice with and without inclusion of the Chen effect. The results show that according to the ability of the solvents to solvate lithium ion, ion-pair formation is small or nonexistent in solventsmore » with high donor number (water, PC, DMF, and AN) but fairly moderate in nitromethane. Single-ion molar conductivities at infinite dilution for ClO{sub 4}{sup {minus}}, AsF{sub 6}{sup {minus}}, PF{sub 6}{sup {minus}} CF{sub 3}SO{sub 3}{sup {minus}}, N(CF{sub 3}SO{sub 2}){sub 2}{sup {minus}}, and C(CF{sub 3}SO{sub 2}){sub 3}{sup {minus}} anions, obtained by combining these results with literature data, decrease as expected as the ionic radius increases, and with one exception are always greater than that of the lithium ion. This general trend does not, however, apply in water where the limiting ionic conductance of the lithium cation is greater than that of the methide anion. This anomalous behavior is attributed to significant solvation of the methide ion in water. Voltammetric measurements indicate high electrochemical stability of methide anion. Such anodic stability and the increase in the transference number of lithium ion in LiMe solutions strongly support the use of this electrolyte in high energy, high voltage lithium batteries.« less

Four-electron transfer tandem tetracyanoquinodimethane for cathode-active material in lithium secondary battery

NASA Astrophysics Data System (ADS)

Kurimoto, Naoya; Omoda, Ryo; Mizumo, Tomonobu; Ito, Seitaro; Aihara, Yuichi; Itoh, Takahito

2018-02-01

Quinoid compounds are important candidates of organic active materials for lithium-ion batteries. However, its high solubility to organic electrolyte solutions and low redox potential are known as their major drawbacks. To circumvent these issues, we have designed and synthesized a tandem-tetracyanoquinonedimethane type cathode-active material, 11,11,12,12,13,13,14,14-octacyano-1,4,5,8-anthradiquinotetramethane (OCNAQ), that has four redox sites per molecule, high redox potential and suppressed solubility to electrolyte solution. Synthesized OCNAQ has been found to have two-step redox reactions by cyclic voltammetry, and each step consists of two-electron reactions. During charge-discharge tests using selected organic cathode-active materials with a lithium metal anode, the cell voltages obtained from OCNAQ are higher than those for 11,11-dicyanoanthraquinone methide (AQM) as expected, due to the strong electron-withdrawing effect of the cyano groups. Unfortunately, even with the use of the organic active material, the issue of dissolution to the electrolyte solution cannot be suppressed completely; however, appropriate choice of the electrolyte solutions, glyme-based electrolyte solutions in this study, give considerable improvement of the cycle retention (98% and 56% at 10 and 100 cycles at 0.5C, respectively). The specific capacity and energy density obtained in this study are 206 mAh g-1 and 554 mWh g-1 with respect to the cathode active material.

First-principles molecular dynamics simulation study on electrolytes for use in redox flow battery

NASA Astrophysics Data System (ADS)

Choe, Yoong-Kee; Tsuchida, Eiji; Tokuda, Kazuya; Ootsuka, Jun; Saito, Yoshihiro; Masuno, Atsunobu; Inoue, Hiroyuki

2017-11-01

Results of first-principles molecular dynamics simulations carried out to investigate structural aspects of electrolytes for use in a redox flow battery are reported. The electrolytes studied here are aqueous sulfuric acid solutions where its property is of importance for dissolving redox couples in redox flow battery. The simulation results indicate that structural features of the acid solutions depend on the concentration of sulfuric acid. Such dependency arises from increase of proton dissociation from sulfuric acid.

Ion-rejection, electrokinetic and electrochemical properties of a nanoporous track-etched membrane and their interpretation by means of space charge model.

PubMed

Yaroshchuk, Andriy; Boiko, Yuriy; Makovetskiy, Alexandre

2009-08-18

Due to their straight cylindrical pores, nanoporous track-etched membranes are suitable materials for studies of the fundamentals of nanofluidics. In contrast to single nanochannels, the nano/micro interface, in this case, can be quantitatively considered within the scope of macroscopically 1D models. The pressure-induced changes in the concentration of dilute KCl solutions (salt rejection phenomenon) have been studied experimentally with a commercially available nanoporous track-etched membrane of poly (ethylene terephthalate) (pore diameter ca. 21 nm). Besides that, we have also studied the concomitant stationary transmembrane electrical phenomenon (filtration potential) and carried out time-resolved measurements of the electrical response to a rapid pressure switch-off (within 5-10 ms). The latter has enabled us to split the filtration potential into the streaming potential and membrane potential components. In this way, we could also confirm that the observed nonlinearity of filtration potential, as a function of the transmembrane volume flow, was primarily caused by the salt rejection. The results of experimental measurements have been interpreted by means of a space charge model with the surface charge density being a single fitting parameter (the pore size was estimated from the membrane hydraulic permeability). By using the surface charge density fitted to the salt rejection data, the results of electrical measurements could be reproduced theoretically with a typical accuracy of 10% or better. Taking into account the simplifications made in the modeling, this accuracy appears to be good and confirms the quantitative applicability of the basic concept of space charge model to the description of transport properties of dilute electrolyte solutions in nanochannels of ca. 20 nm.

Removal of lead from aqueous solutions using Cassia grandis seed gum-graft-poly(methylmethacrylate).

PubMed

Singh, Vandana; Tiwari, Stuti; Sharma, Ajit Kumar; Sanghi, Rashmi

2007-12-15

Using persulfate/ascorbic acid redox system, a series of Cassia grandis seed gum-graft-poly(methylmethacrylate) samples were synthesized. The copolymer samples were evaluated for lead(II) removal from the aqueous solutions where the sorption capacities were found proportional to the grafting extent. The conditions for the sorption were optimized using copolymer sample of highest percent grafting. The sorption was found pH and concentration dependent, pH 2.0 being the optimum value. Adsorption of lead by the grafted seed gum followed a pseudo-second-order kinetics with a rate constant of 4.64 x 10(-5) g/mg/min. The equilibrium data followed the Langmuir isotherm model with maximum sorption capacity of 126.58 mg/g. The influence of electrolytes NaCl, Na(2)SO(4) on lead uptake was also studied. Desorption with 2 N HCl could elute 76% of the lead ions from the lead-loaded copolymer. The regeneration experiments revealed that the copolymer could be successfully reused for at least four cycles though there was a successive loss in lead sorption capacity with every cycle. The adsorbent was also evaluated for Pb(II) removal from battery waste-water containing 2166 mg/L Pb(II). From 1000 times diluted waste water, 86.1% Pb(II) could be removed using 0.05 g/20 ml adsorbent dose, while 0.5 g/20 ml adsorbent dose was capable of removing 60.29% Pb from 10 times diluted waste water. Optimum Pb(II) binding under highly acidic conditions indicated that there was a significant contribution of nonelectrostatic interactions in the adsorption process. A possible mechanism for the adsorption has been discussed.

Electrolytic dissolver

DOEpatents

Wheelwright, E.J.; Fox, R.D.

1975-08-26

This patent related to an electrolytic dissolver wherein dissolution occurs by solution contact including a vessel of electrically insulative material, a fixed first electrode, a movable second electrode, means for insulating the electrodes from the material to be dissolved while permitting a free flow of electrolyte therebetween, means for passing a direct current between the electrodes and means for circulating electrolyte through the dissolver. (auth)

An Alternative Approach for Preparing and Standardizing Some Common Aqueous Reagents Used in an Undergraduate Laboratory

ERIC Educational Resources Information Center

Melaku, Samuel; Dabke, Rajeev B.

2014-01-01

A guide for instructors and laboratory assistants to prepare some common aqueous reagents used in an undergraduate laboratory is presented. Dilute reagents consisting of H[superscript +](aq), I[subscript 3][superscript-](aq), Ce[superscript 4+](aq), and Ag[superscript+](aq) were prepared by electrolytic oxidation of respective precursors.…

Monolithic solid electrolyte oxygen pump

DOEpatents

Fee, Darrell C.; Poeppel, Roger B.; Easler, Timothy E.; Dees, Dennis W.

1989-01-01

A multi-layer oxygen pump having a one-piece, monolithic ceramic structure affords high oxygen production per unit weight and volume and is thus particularly adapted for use as a portable oxygen supply. The oxygen pump is comprised of a large number of small cells on the order of 1-2 millimeters in diameter which form the walls of the pump and which are comprised of thin, i.e., 25-50 micrometers, ceramic layers of cell components. The cell components include an air electrode, an oxygen electrode, an electrolyte and interconnection materials. The cell walls form the passages for input air and for exhausting the oxygen which is transferred from a relatively dilute gaseous mixture to a higher concentration by applying a DC voltage across the electrodes so as to ionize the oxygen at the air electrode, whereupon the ionized oxygen travels through the electrolyte and is converted to oxygen gas at the oxygen electrode.

Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation

DOE PAGES

Sun, Zhe; Tian, Ye; Hom, Wendy L.; ...

2016-12-28

The thermal response of semi-dilute solutions (5 w/w%) of two amphiphilic thermoresponsive poly(ethylene oxide)-b-poly(N,N-diethylacrylamide)-b-poly(N,N-dibutylacrylamide) (PEO 45-PDEAm x-PDBAm 12) triblock copolymers, which differ only in the size of the central responsive block, in water was examined in this paper. Aqueous PEO45-PDEAm41-PDBAm12 solutions, which undergo a thermally induced sphere-to-worm transition in dilute solution, were found to reversibly form soft (G'≈10 Pa) free-standing physical gels after 10 min at 55 °C. PEO 45-PDEAm 89-PDBAm 12 copolymer solutions, which undergo a thermally induced transition from spheres to large compound micelles (LCM) in dilute solution, underwent phase separation after heating at 55 °C for 10more » min owing to sedimentation of LCMs. The reversibility of LCM formation was investigated as a non-specific method for removal of a water-soluble dye from aqueous solution. Finally, the composition and size of the central responsive block in these polymers dictate the microscopic and macroscopic response of the polymer solutions as well as the rates of transition between assemblies.« less

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Greenbaum, S.; Surampudi, S.

2000-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (< -20C). However, in some cases the presence of such co-solvents does not directly translate into improved low temperature cell performance, presumably due to the formation of ionically resistive surface films on carbonaceous anodes. In order to understand this behavior, a number of lithium-graphite cells have been studied containing electrolytes with various ester co-solvents, including methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), and ethyl butyrate (EB). The charge/discharge characterization of these cells indicates that the higher molecular weight esters result in electrolytes which possess superior low temperature performance in contrast to the lower molecular weight ester-containing solutions, even though these solutions display lower conductivity values.

Can oral rehydration solution be safely flavored at home?

PubMed

Nijssen-Jordan, C

1997-12-01

To determine the concentration of sodium, potassium, glucose, and osmolality of oral rehydration solutions (ORS) which have been flavored with varying amounts of unsweetened Kool-Aid powder, Jell-O powder, apple juice, or orange juice. Descriptive. Alberta Children's Hospital Chemistry Laboratory. None. Addition of varying amounts of flavoring easily available in all households to commercially available unsweetened ORS. Concentrations of electrolytes, glucose, and osmolality. Addition of fruit juices or flavor powders to commercially produced ORS does alter the electrolyte content and osmolality. When limited amounts of flavoring or juice is added, the osmolality of the solution approaches iso-osmolality. Small amounts of unsweetened Kool-Aid powder, Jell-O powder, and apple or orange juice can be added to oral rehydration solutions without significantly altering electrolyte composition and osmolality.

Use of vitamin B12 in joint lavage for determination of dilution factors of canine synovial fluid.

PubMed

de Bruin, Tanya; de Rooster, Hilde; van Bree, Henri; Cox, Eric

2005-11-01

To test a modified saline (0.9% NaCl) solution joint washing (lavage) technique that includes the use of vitamin B12 as an internal marker for the evaluation of synovial fluid dilution in lavage samples from canine joints. 9 plasma samples obtained from blood samples of 9 healthy dogs and 9 synovial fluid samples aspirated from stifle joints of 9 cadaveric dogs. Photometric absorbances of 25% vitamin B12 solution, canine synovial fluid, and canine plasma were measured in a spectrophotometer to establish an optimal wavelength for analysis. Canine synovial fluid and plasma samples were mixed with the 25% vitamin B12 solution to obtain 1%, 3%, 5%, 10%, 20%, and 50% solutions of synovial fluid or plasma. Diluted synovial fluid and plasma samples were used to simulate joint lavage samples and to examine the possible interference of these substances (synovial fluid or plasma) with the absorbance of the 25% vitamin B12 solution in photometric analysis. The optimal wavelength was found to be at 550 nm. Canine synovial fluid and plasma samples did not interfere with the absorbance measurements of the 25% vitamin B12 solution up to a 50% dilution of plasma or synovial fluid. The modified saline solution joint lavage method with the use of a 25% vitamin B12 solution as an internal standard provides an accurate and reliable technique for the evaluation of synovial fluid dilution in lavage samples from canine joints.

Potential of Zero Charge and Its Temperature Derivative for Au(111) Electrode|Alkanethiol SAM|1.0 M Aqueous Electrolyte Solution Interfaces: Impact of Electrolyte Solution Ionic Strength and Its Effect on the Structure of the Modified Electrode|Electrolyte Solution Interface

DOE PAGES

Smalley, John F.

2017-04-06

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less

Large-current-controllable carbon nanotube field-effect transistor in electrolyte solution

NASA Astrophysics Data System (ADS)

Myodo, Miho; Inaba, Masafumi; Ohara, Kazuyoshi; Kato, Ryogo; Kobayashi, Mikinori; Hirano, Yu; Suzuki, Kazuma; Kawarada, Hiroshi

2015-05-01

Large-current-controllable carbon nanotube field-effect transistors (CNT-FETs) were fabricated with mm-long CNT sheets. The sheets, synthesized by remote-plasma-enhanced CVD, contained both single- and double-walled CNTs. Titanium was deposited on the sheet as source and drain electrodes, and an electrolyte solution was used as a gate electrode (solution gate) to apply a gate voltage to the CNTs through electric double layers formed around the CNTs. The drain current came to be well modulated as electrolyte solution penetrated into the sheets, and one of the solution gate CNT-FETs was able to control a large current of over 2.5 A. In addition, we determined the transconductance parameter per tube and compared it with values for other CNT-FETs. The potential of CNT sheets for applications requiring the control of large current is exhibited in this study.

Utilization of aloe vera extract as electrolyte for an accumulator

NASA Astrophysics Data System (ADS)

Azmi, F.; Sispriatna, D.; Ikhsan, K.; Masrura, M.; Azzahra, S. S.; Mahidin; Supardan, M. D.

2018-03-01

Aloe vera contains acid, which has the potential to generate electric current. The objective of this research is to study the potency of aloe vera extract as electrolyte for an accumulator. Experimental results showed that aloe vera extract has no a stable value of voltage and currency. The voltage and currency of aloe vera extract were reduced more than 50% for 60 minutes. Then, aloe vera extract was mixed with accu zuur to produce electrolyte solution. The mixture composition of aloe vera extract to accu zuur of 50:50 (v/v) generated stable voltage and currency. The experimental results showed the potential use of aloe vera extract to reduce the chemicals used in a conventional electrolyte solution.

Colloidal Electrolytes and the Critical Micelle Concentration

ERIC Educational Resources Information Center

Knowlton, L. G.

1970-01-01

Describes methods for determining the Critical Micelle Concentration of Colloidal Electrolytes; methods described are: (1) methods based on Colligative Properties, (2) methods based on the Electrical Conductivity of Colloidal Electrolytic Solutions, (3) Dye Method, (4) Dye Solubilization Method, and (5) Surface Tension Method. (BR)

Evaluation of an intravenous preparation information system for improving the reconstitution and dilution process.

PubMed

Jo, Yun Hee; Shin, Wan Gyoon; Lee, Ju-Yeun; Yang, Bo Ram; Yu, Yun Mi; Jung, Sun Hoi; Kim, Hyang Sook

2016-10-01

There are very few studies reporting the impact of providing intravenous (IV) preparation information on quality use of antimicrobials, particularly regarding their reconstitution and dilution. Therefore, to improve these processes in IV antimicrobial administration, an IV preparation information system (IPIS) was implemented in a hospital. We aimed to evaluate the effect of improving reconstitution and dilution by implementing an IPIS in the electronic medical record (EMR) system. Prescriptions and activity records of nurses for injectable antimicrobials that required reconstitution and dilution for IV preparation from January 2008 to December 2013 were retrieved from EMR, and assessed based on packaging label information for reconstituting and diluting solutions. We defined proper reconstitution and dilution as occurring when the reconstitution and dilution solutions prescribed were consistent with the nurses' acting records. The types of intervention in the IPIS were as follows: a pop-up alert for proper reconstitution and passive guidance for proper dilution. We calculated the monthly proper reconstitution rate (PRR) and proper dilution rate (PDR) and evaluated the changes in these rates and trends using interrupted time series analyses. Prior to the initiation of the reconstitution alert and dilution information, the PRR and PDR were 12.7 and 46.1%, respectively. The reconstitution alert of the IPIS rapidly increased the PRR by 41% (p<0.001), after which the PRR decreased by 0.9% (p=0.013) per month after several months. However, there was no significant change in the rate or trend of the PDR during the study period. This study demonstrated that the provision of reconstitution alerts by the IPIS contributed to improving the reconstitution process of IV antimicrobial injection administration. However, providing passive information on dilution solutions was ineffective. Furthermore, solutions to ensure the continuous effectiveness of alert systems are warranted and should be actively sought. Copyright © 2016. Published by Elsevier Ireland Ltd.

Effect of glycine and glucose on sodium and water absorption in patients with cholera

PubMed Central

Nalin, D. R.; Cash, R. A.; Rahman, M.; Yunus, Md.

1970-01-01

Electrolyte solutions containing glucose, glycine, or a combination of the two were absorbed sufficiently well from the intestine to supply maintenance fluid and the electrolytes required by cholera patients. Data on net absorption and duration and volume of diarrhoea show that a solution containing both glucose and glycine provides more effective therapy than solutions containing either glucose or glycine alone. PMID:5473608

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

Scanning drop sensor

DOEpatents

Jin, Jian; Xiang, Chengxiang; Gregoire, John

2017-05-09

Electrochemical experiments are performed on a collection of samples by suspending a drop of electrolyte solution between an electrochemical experiment probe and one of the samples that serves as a test sample. During the electrochemical experiment, the electrolyte solution is added to the drop and an output solution is removed from the drop. The probe and collection of samples can be moved relative to one another so the probe can be scanned across the samples.

On the Consequences of Clausius-Duhem Inequality for Electrolyte Solutions

NASA Astrophysics Data System (ADS)

Reis, Martina; Bassi, Adalberto Bono Maurizio Sacchi

2014-03-01

Based on the fundamentals of thermo-statics, non-equilibrium thermodynamics theories frequently employ an entropy inequality, where the entropy flux is collinear to the heat flux, and the entropy supply is proportional to the energy supply. Although this assumption is suitable for many material bodies, e.g. heat-conducting viscous fluids, there is a class of materials for which these assumptions are not valid. By assuming that the entropy flux and the entropy supply are constitutive quantities, in this work it is demonstrated that the entropy flux for a reacting ionic mixture of non-volatile solutes presents a non-collinear term due to the diffusive fluxes. The consequences of the collinearity between the entropy flux and the heat flux, as well as the proportionality of the entropy supply and the energy supply on the stability of chemical systems are also investigated. Furthermore, by considering an electrolyte solution of non-volatile solutes in phase equilibrium with water vapor, and the constitutive nature of the entropy flux, the stability of a vapor-electrolyte solution interface is studied. Despite this work only deals with electrolyte solutions, the results presented can be easily extended to more complex chemical reacting systems. The first author acknowledges financial support from CNPq (National Counsel of Technological and Scientific Development).

Method of preparing electrolyte for use in fuel cells

DOEpatents

Kinoshita, Kimio; Ackerman, John P.

1978-01-01

An electrolyte compact for fuel cells includes a particulate support material of lithium aluminate that contains a mixture of alkali metal compounds, such as carbonates or hydroxides, as the active electrolyte material. The porous lithium aluminate support structure is formed by mixing alumina particles with a solution of lithium hydroxide and another alkali metal hydroxide, evaporating the solvent from the solution and heating to a temperature sufficient to react the lithium hydroxide with alumina to form lithium aluminate. Carbonates are formed by reacting the alkali metal hydroxides with carbon dioxide gas in an exothermic reaction which may proceed simultaneously with the formation with the lithium aluminate. The mixture of lithium aluminate and alkali metal in an electrolyte active material is pressed or otherwise processed to form the electrolyte structure for assembly into a fuel cell.

Extremely Stable Sodium Metal Batteries Enabled by Localized High-Concentration Electrolytes

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

Zheng, Jianming; Chen, Shuru; Zhao, Wengao

Sodium (Na) metal is a promising anode for Na ion batteries. However, the high reactivity of Na metal with electrolytes and the low Na metal cycling efficiency have limited its practical application in rechargeable Na metal batteries. High concentration electrolytes (HCE, ≥4 M) consisting of sodium bis(fluorosulfonyl)imide (NaFSI) and ether solvent could ensure the stable cycling of Na metal with high coulombic efficiency, but suffer from high viscosity, poor wetting ability, and high salt cost. Here, we report that the salt concentration could be significantly reduced (≤ 1.5 M) by diluting with a hydrofluoroether (HFE) as ‘inert’ diluent, which maintainsmore » the solvation structures of HCE, thereby forming a localized high concentration electrolyte (LHCE). A LHCE (2.1 M NaFSI/DME-BTFE (solvent molar ratio 1:2)) has been demonstrated to enable the dendrite-free Na deposition with high coulombic efficiency of > 99%, fast-charging (20C) and stable cycling (90.8% retention after 40,000 cycles) of Na||Na3V2(PO4)3 batteries.« less

Systematic Experimental and Computational Investigation of Ion Transport in Novel Polyether Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Webb, Michael; Jung, Yukyung; Zheng, Qi; Miller, Thomas, III; Coates, Geoffrey; Balsara, Nitash

Polyethers, such as poly(ethylene oxide) (PEO), are considered to be the most promising polymer electrolyte materials due to their high ionic conductivity and electrochemical stability, both essential for battery applications. To gain a fundamental understanding of the transport properties of polyether systems, we design a systematic set of linear PEO-like polymers to explore the effect of adding carbon spacers to the backbone of the chain. Ac impedance spectroscopy is employed to measure the ionic conductivity of polyether/lithium salt electrolytes; the results elucidate tradeoffs between lowering the glass transition temperature and diluting the polar groups on the polymer chain. Molecular-level insight is provided by molecular dynamics simulations of the polyether electrolytes. We define the useful and intuitive metric of ``connectivity'', a parameter calculated from simulations which describes the physical arrangements of solvation sites in a polymer melt. Direct comparison of experiment and theory allows us to determine the relationship between connectivity and conductivity. The comparison provides insight regarding the factors that control conductivity, and highlights considerations that must be taken when designing new ion-conducting polymers.

Bubble coalescence suppression driven carbon monoxide (CO)-water mass transfer increase by electrolyte addition in a hollow fiber membrane bioreactor (HFMBR) for microbial CO conversion to ethanol.

PubMed

Jang, Nulee; Yasin, Muhammad; Kang, Hyunsoo; Lee, Yeubin; Park, Gwon Woo; Park, Shinyoung; Chang, In Seop

2018-05-04

This study investigated the effects of electrolytes (CaCl 2 , K 2 HPO 4 , MgSO 4 , NaCl, and NH 4 Cl) on CO mass transfer and ethanol production in a HFMBR. The hollow fiber membranes (HFM) were found to generate tiny gas bubbles; the bubble coalescence was significantly suppressed in electrolyte solution. The volumetric gas-liquid mass transfer coefficients (k L a) increased up to 414% compared to the control. Saturated CO (C ∗ ) decreased as electrolyte concentrations increased. Overall, the maximum mass transfer rate (R max ) in electrolyte solution ranged from 106% to 339% of the value obtained in water. The electrolyte toxicity on cell growth was tested using Clostridium autoethanogenum. Most electrolytes, except for MgSO 4 , inhibited cell growth. The HFMBR operation using a medium containing 1% MgSO 4 achieved 119% ethanol production compared to that without electrolytes. Finally, a kinetic simulation using the parameters got from the 1% MgSO 4 medium predicted a higher ethanol production compared to the control. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigations on Mg-borate kinetics and mechanisms during evaporation, dilution and crystallization by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Jiaoyu; Chen, Jing; Dong, Yaping; Li, Wu

2018-06-01

Raman spectra of boron-concentrated, diluted, and corresponding mother solutions of brine were recorded at 298.15 K. The main polyborate anions present and their interactions in brine during evaporation and dilution were proposed according to the Raman spectra. The polyborate anions B(OH)3, B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- were found to be the main forms in boron-concentrated brine with B3O3(OH)4- ion being the principal form. Diluting brines with water accelerated depolymerization of B5O6(OH)4- and B6O7(OH)62- anions into B(OH)3 and B3O3(OH)4- ions and generated OH- ions, causing the pH of the solutions to increase from 4.2 to almost 8.0. Mg-borates precipitated from all diluted solutions could be classified as either hexaborates or triborates. A mechanism of solid phase transformation was also proposed and discussed based on Raman spectra analysis and solid species and solution pH data.

Osmotic Transport across Cell Membranes in Nondilute Solutions: A New Nondilute Solute Transport Equation

PubMed Central

Elmoazzen, Heidi Y.; Elliott, Janet A.W.; McGann, Locksley E.

2009-01-01

The fundamental physical mechanisms of water and solute transport across cell membranes have long been studied in the field of cell membrane biophysics. Cryobiology is a discipline that requires an understanding of osmotic transport across cell membranes under nondilute solution conditions, yet many of the currently-used transport formalisms make limiting dilute solution assumptions. While dilute solution assumptions are often appropriate under physiological conditions, they are rarely appropriate in cryobiology. The first objective of this article is to review commonly-used transport equations, and the explicit and implicit assumptions made when using the two-parameter and the Kedem-Katchalsky formalisms. The second objective of this article is to describe a set of transport equations that do not make the previous dilute solution or near-equilibrium assumptions. Specifically, a new nondilute solute transport equation is presented. Such nondilute equations are applicable to many fields including cryobiology where dilute solution conditions are not often met. An illustrative example is provided. Utilizing suitable transport equations that fit for two permeability coefficients, fits were as good as with the previous three-parameter model (which includes the reflection coefficient, σ). There is less unexpected concentration dependence with the nondilute transport equations, suggesting that some of the unexpected concentration dependence of permeability is due to the use of inappropriate transport equations. PMID:19348741

Bridging Redox Species-Coated Graphene Oxide Sheets to Electrode for Extending Battery Life Using Nanocomposite Electrolyte.

PubMed

Huang, Yi Fu; Ruan, Wen Hong; Lin, Dong Ling; Zhang, Ming Qiu

2017-01-11

Substituting conventional electrolyte for redox electrolyte has provided a new intriguing method for extending battery life. The efficiency of utilizing the contained redox species (RS) in the redox electrolyte can benefit from increasing the specific surface area of battery electrodes from the electrode side of the electrode-electrolyte interface, but is not limited to that. Herein, a new strategy using nanocomposite electrolyte is proposed to enlarge the interface with the aid of nanoinclusions from the electrolyte side. To do this, graphene oxide (GO) sheets are first dispersed in the electrolyte solution of tungstosilicic salt/lithium sulfate/poly(vinyl alcohol) (SiWLi/Li 2 SO 4 /PVA), and then the sheets are bridged to electrode, after casting and evaporating the solution on the electrode surface. By applying in situ conductive atomic force microscopy and Raman spectra, it is confirmed that the GO sheets doped with RS of SiWLi/Li 2 SO 4 can be bridged and electrically reduced as an extended electrode-electrolyte interface. As a result, the RS-coated GO sheets bridged to LiTi 2 (PO 4 ) 3 //LiMn 2 O 4 battery electrodes are found to deliver extra energy capacity (∼30 mAh/g) with excellent electrochemical cycling stability, which successfully extends the battery life by over 50%.

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

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

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

Stresses due to Relative Sliding between Particles Surrounded by an Electrolyte Solution with Application to Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Cong; Conlisk, A. T.

2013-11-01

Mechanical stresses in the solid phase of the electrodes within lithium-ion batteries have been the subject of much work recently with the emphasis on the stresses induced by lithium insertion to or extraction from the active solid material. The particles within lithium-ion battery electrodes can undergo relative motion with relative velocities of different magnitudes and directions. One mode of the relative motion, resembling the slider bearing motion, manifests itself as two particles sliding relative to each other within an electrolyte solution. The electrolyte solution within the narrow pores between the particles is the medium through which the particles interact with each other. The effect of the electrolyte solution is not conventionally considered. The relative motion of the particles induces significant pressures. The primary objective of this work is to develop a model based on the lubrication approximation to investigate the magnitude and direction of the stresses induced by this sliding motion. Other applications in the biomedical field are also discussed. Supported by DOE Graduate Automotive Technology Education (GATE) and OSU Center for Automotive Research.

The Use of Redox Mediators for Enhancing Utilization of Li2S Cathodes for Advanced Li-S Battery Systems.

PubMed

Meini, Stefano; Elazari, Ran; Rosenman, Ariel; Garsuch, Arnd; Aurbach, Doron

2014-03-06

The development of Li2S electrodes is a crucial step toward industrial manufacturing of Li-S batteries, a promising alternative to Li-ion batteries due to their projected two times higher specific capacity. However, the high voltages needed to activate Li2S electrodes, and the consequent electrolyte solution degradation, represent the main challenge. We present a novel concept that could make feasible the widespread application of Li2S electrodes for Li-S cell assembly. In this concept, the addition of redox mediators as additives to the standard electrolyte solution allows us to recover most of Li2S theoretical capacity in the activation cycle at potentials as low as 2.9 VLi, substantially lower than the typical potentials >4 VLi needed with standard electrolyte solution. Those novel additives permit us to preserve the electrolyte solution from being degraded, allowing us to achieve capacity as high as 500 mAhg(-1)Li2S after 150 cycles with no major structural optimization of the electrodes.

Examination of an aloe vera galacturonate polysaccharide capable of in situ gelation for the controlled release of protein therapeutics

NASA Astrophysics Data System (ADS)

McConaughy, Shawn David

A therapeutic delivery platform has been investigated with the ultimate goal of designing a sustained protein release matrix utilizing an in-situ gelling, acidic polysaccharide derived from the Aloe vera plant. The Aloe vera polysaccharide (AvP) has been examined in order to determine how chemical composition, structure, molecular weight and solution behavior affect gelation and protein/peptide delivery. Correlations are drawn between structural characteristics and solution behavior in order to determine the impact of polymer conformation and solvation on gel formation under conditions designed to simulate nasal applications. Steady state and dynamic rheology, classic and dynamic light scattering, zeta potential, pulse field gradient nuclear magnetic resonance and fluorescence spectroscopy have been employed to gain insight into the effects of galacturonic acid content, degree of methylation, entanglement and ionic strength on both solution behavior and the hydrogel state which ultimately governs protein/peptide release. This dissertation is divided into two sections. In the first section, a series of Aloe vera polysaccharides (AvP), from the pectin family have been structurally characterized indicating high galacturonic acid (GalA) content, low degree of methylester substitution (DM), low numbers of rhamnose residues and high molecular weight with respect to pectins extracted from traditional sources. The behavior of AvP was examined utilizing dilute solution, low-shear rheological techniques for specific molecular weight samples at selected conditions of ionic strength. From these dilute aqueous solution studies, the Mark-Houwink-Sakurada (MHS) constants (K and alpha), persistence length (Lp) and inherent chain stiffness (B parameter) were determined, indicating an expanded random coil in aqueous salt solutions. The critical concentration for transition from dilute to concentrated solution, C e, was determined by measuring both the zero shear viscosity and fluorescence emission of the probe molecule 1,8-anilino-1-naphthalene sulphonic acid (1,8-ANS) as a function of polymer concentration. Correlations are drawn between viscosity experiments and measurement of zeta potential. Increased degrees of intermolecular interactions are responsible for a shift of Ce to lower polymer concentrations with increasing ionic strength. Additionally, dynamic rheology data are presented highlighting the ability of AvP to form gels at low polymer and calcium ion concentrations, exemplifying the technological potential of this polysaccharide for in-situ drug delivery. In the second section, properties of Aloe vera galacturonate hydrogels formed via Ca2+ crosslinking have been studied in regard to key parameters influencing gel formation including molecular weight, ionic strength and molar ratio of Ca2+ to COO- functionality. Dynamic oscillatory rheology and pulsed field gradient NMR (PFG-NMR) studies have been conducted on hydrogels formed at specified Ca2+ concentrations in the presence and absence of Na+ and K+ ions, in order to assess the feasibility of in situ gelation for controlled delivery of therapeutics. Aqueous Ca2+ concentrations similar to those present in nasal and subcutaneous fluids induce the formation of elastic Aloe vera polysaccharide (AvP) hydrogel networks. By altering the ratio of Ca2+ to COO- functionality, networks may be tailored to provide elastic modulus (G') values between 20 and 20,000 Pa. The Aloe vera polysaccharide exhibits time dependent phase separation in the presence of monovalent electrolytes. Thus the relative rates of calcium induced gelation and phase separation become major considerations when designing a system for in situ delivery applications where both monovalent (Na+, K+) and divalent (Ca2+) ions are present. PFG-NMR and fluorescence microscopy confirm that distinctly different morphologies are present in gels formed in the presence and absence 0.15 M NaCl. Curve fitting of theoretical models to experimental release profiles of fluorescein labeled dextrans indicate diffusion rates are related to hydrogel morphology. These studies suggest that for efficient in situ release of therapeutic agents, polymer concentrations should be maintained above the critical entanglement concentration (Ce, 0.60 wt%) when [Ca2+]/[COO -] ratios are less than 1. Additionally, the monovalent electrolyte concentration in AvP solutions should not exceed 0.10 M prior to Ca 2+ crosslinking.

Treating Vomiting

MedlinePlus

... those descibed below. Estimated Oral Fluid and Electrolyte Requirements by Body Weight Body Weight (in pounds) Minimum Daily Fluid Requirements (in ounces)* Electrolyte Solution Requirements for Mild Diarrhea ( ...

Gas nanobubbles and aqueous nanostructures: the crucial role of dynamization.

PubMed

Demangeat, Jean-Louis

2015-04-01

Nanobubbles (NBs) have been a subject of intensive research over the past decade. Their peculiar characteristics, including extremely low buoyancy, longevity, enhanced solubility of oxygen in water, zeta potentials and burst during collapse, have led to many applications in the industrial, biological and medical fields. NBs may form spontaneously from dissolved gas but the process is greatly enhanced by gas supersaturation and mechanical actions such as dynamization. Therefore, the formation of NBs during the preparation of homeopathic dilutions under atmospheric pressure cannot be ignored. I suggested in 2009 the involvement of NBs in nanometric superstructures revealed in high dilutions using NMR relaxation. These superstructures seemed to increase in size with dilution, well into the ultramolecular range (>12c). I report here new experiments that confirm the involvement of NBs and prove the crucial role of dynamization to create superstructures specific to the solute. A second dynamization was shown to enhance or regenerate these superstructures. I postulate that superstructures result from a nucleation process of NBs around the solute, with shells of highly organized water (with ions and silicates if any) which protect the solute against out-diffusion and behave as nucleation centres for further dilution steps. The sampling tip may play an active role by catching the superstructures and thus carry the encaged solute across the dilution range, possibly up to the ultramolecular range. The superstructures were not observed at low dilution, probably because of a destructuring of the solvent by the solute and/or of an inadequate gas/solute ratio. Copyright © 2015 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

Non-aqueous electrolytes for lithium ion batteries

DOEpatents

Chen, Zonghai; Amine, Khalil

2015-11-12

The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

New methods allowing the detection of protein aggregates

PubMed Central

Demeule, Barthélemy; Palais, Caroline; Machaidze, Gia; Gurny, Robert

2009-01-01

Aggregation compromises the safety and efficacy of therapeutic proteins. According to the manufacturer, the therapeutic immunoglobulin trastuzumab (Herceptin®) should be diluted in 0.9% sodium chloride before administration. Dilution in 5% dextrose solutions is prohibited. The reason for the interdiction is not mentioned in the Food and Drug Administration (FDA) documentation, but the European Medicines Agency (EMEA) Summary of Product Characteristics states that dilution of trastuzumab in dextrose solutions results in protein aggregation. In this paper, asymmetrical flow field-flow fractionation (FFF), fluorescence spectroscopy, fluorescence microscopy and transmission electron microscopy (TEM) have been used to characterize trastuzumab samples diluted in 0.9% sodium chloride, a stable infusion solution, as well as in 5% dextrose (a solution prone to aggregation). When trastuzumab samples were injected in the FFF channel using a standard separation method, no difference could be seen between trastuzumab diluted in sodium chloride and trastuzumab diluted in dextrose. However, during FFF measurements made with appropriate protocols, aggregates were detected in 5% dextrose. The parameters enabling the detection of reversible trastuzumab aggregates are described. Aggregates could also be documented by fluorescence microscopy and TEM. Fluorescence spectroscopy data were indicative of conformational changes consistent with increased aggregation and adsorption to surfaces. The analytical methods presented in this study were able to detect and characterize trastuzumab aggregates. PMID:20061815

Sodium perxenate permits rapid oxidation of manganese for easy spectrophotometric determination

NASA Technical Reports Server (NTRS)

Bane, R. W.

1967-01-01

Sodium perxenate oxidizes manganese to permanganate almost instantaneously in dilute acid solution and without a catalyst. A solution is prepared by dissolving 200 mg of sodium perxenate in distilled water and diluting to 100 ml.

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Reddy, V. Prakash; Prakash, G. K. Syria; Hu, Jinbo; Yan, Ping; Smart, Marshall; Bugga, ratnakumar; Chin, Keith; Surampudi, Subarao

2008-01-01

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Scanning drop sensor

DOEpatents

Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Shinde, Aniketa A.; Guevarra, Dan W.; Jones, Ryan J.; Marcin, Martin R.; Mitrovic, Slobodan

2017-05-09

Electrochemical or electrochemical and photochemical experiments are performed on a collection of samples by suspending a drop of electrolyte solution between an electrochemical experiment probe and one of the samples that serves as a test sample. During the electrochemical experiment, the electrolyte solution is added to the drop and an output solution is removed from the drop. The probe and collection of samples can be moved relative to one another so the probe can be scanned across the samples.

Modification of vortex ring formation using dilute polymer solution

NASA Astrophysics Data System (ADS)

Jordan, Daniel; Krane, Michael; Peltier, Joel; Patterson, Eric; Fontaine, Arnold

2006-11-01

This talk will present the results of an experimental study to determine the effect of dilute polymer solution on the formation of a vortex ring. Experiments were conducted in a large, glass tank, filled with water. Vortex rings were produced by injecting a slug of dilute polymer solution into the tank through a nozzle. The injection was controlled by a prescribed piston motion in the nozzle. For the same piston motion, vortex rings were produced for 3 concentrations of the polymer solution, including one with no polymer. The vortex ring flowfield was measured using DPIV. Differences between the 3 cases of polymer concentration in vortex ring formation time, circulation, size, and convection speed are presented.

Photoelectrodialytic cell

DOEpatents

Murphy, George W.

1983-01-01

A multicompartment photoelectrodialytic demineralization cell is provided with a buffer compartment interposed between the product compartment and a compartment containing an electrolyte solution. Semipermeable membranes separate the buffer compartment from the product and electrolyte compartments. The buffer compartment is flushed to prevent leakage of the electrolyte compartment from entering the product compartment.

Microfluidics Meets Dilute Solution Viscometry: An Undergraduate Laboratory to Determine Polymer Molecular Weight Using a Microviscometer

ERIC Educational Resources Information Center

Pety, Stephen J.; Lu, Hang; Thio, Yonathan S.

2011-01-01

This paper describes a student laboratory experiment to determine the molecular weight of a polymer sample by measuring the viscosity of dilute polymer solutions in a PDMS microfluidic viscometer. Sample data are given for aqueous solutions of poly(ethylene oxide) (PEO). A demonstration of shear thinning behavior using the microviscometer is…

Stable dye-sensitized solar cells based on a gel electrolyte with ethyl cellulose as the gelator

NASA Astrophysics Data System (ADS)

Vasei, Maryam; Tajabadi, Fariba; Jabbari, Ali; Taghavinia, Nima

2015-09-01

A simple gelating process is developed for the conventional acetonitrile-based electrolyte of dye solar cells, based on ethyl cellulose as the gelator. The electrolyte becomes quasi-solid-state upon addition of an ethanolic solution of ethyl cellulose to the conventional acetonitrile-based liquid electrolyte. The photovoltaic conversion efficiency with the new gel electrolyte is only slightly lower than with the liquid electrolyte, e.g., 6.5 % for liquid electrolyte versus 5.9 % for gel electrolyte with 5.8 wt% added ethyl cellulose. Electrolyte gelation has small effect on the ionic diffusion coefficient of iodide, and the devices are remarkably stable for at least 550 h under irradiation at 55 °C.

Method of preparing mercury with an arbitrary isotopic distribution

DOEpatents

Grossman, Mark W.; George, William A.

1986-01-01

This invention provides for a process for preparing mercury with a predetermined, arbitrary, isotopic distribution. In one embodiment, different isotopic types of Hg.sub.2 Cl.sub.2, corresponding to the predetermined isotopic distribution of Hg desired, are placed in an electrolyte solution of HCl and H.sub.2 O. The resulting mercurous ions are then electrolytically plated onto a cathode wire producing mercury containing the predetermined isotopic distribution. In a similar fashion, Hg with a predetermined isotopic distribution is obtained from different isotopic types of HgO. In this embodiment, the HgO is dissolved in an electrolytic solution of glacial acetic acid and H.sub.2 O. The isotopic specific Hg is then electrolytically plated onto a cathode and then recovered.

Method of preparing mercury with an arbitrary isotopic distribution

DOEpatents

Grossman, M.W.; George, W.A.

1986-12-16

This invention provides for a process for preparing mercury with a predetermined, arbitrary, isotopic distribution. In one embodiment, different isotopic types of Hg[sub 2]Cl[sub 2], corresponding to the predetermined isotopic distribution of Hg desired, are placed in an electrolyte solution of HCl and H[sub 2]O. The resulting mercurous ions are then electrolytically plated onto a cathode wire producing mercury containing the predetermined isotopic distribution. In a similar fashion, Hg with a predetermined isotopic distribution is obtained from different isotopic types of HgO. In this embodiment, the HgO is dissolved in an electrolytic solution of glacial acetic acid and H[sub 2]O. The isotopic specific Hg is then electrolytically plated onto a cathode and then recovered. 1 fig.

Antibacterial activity of dilute povidone-iodine solutions used for ocular surface disinfection in dogs.

PubMed

Roberts, S M; Severin, G A; Lavach, J D

1986-06-01

Bacterial cultures of specimens from healthy canine eyelids and ocular surfaces were found to demonstrate bacterial growth in 69.7% (53/76) of the eyes sampled. Organisms most commonly isolated included: Staphylococcus aureus, alpha-hemolytic Streptococcus sp, S epidermidis, and Escherichia coli. Evaluation of dilute povidone-iodine solutions for effectiveness as ocular surface disinfectants was conducted. Bacterial growth initially detected in 32 of 46 eyes was not detected after disinfection with a 2-minute scrub and 2-minute soaking procedure, using 1:2, 1:10, or 1:50 dilutions of a povidone-iodine solution that contained 1% available iodine. The eyelid and ocular surfaces of 16 eyes were disinfected with 1:100 povidone-iodine solution. Bacterial growth initially present in 10 of 16 eyes was present in 1 eye after disinfection and consisted of a single colony of E coli. After eyes were disinfected with 1:10, 1:50, or 1:100 povidone-iodine solutions, there was no evidence of corneal epithelial edema or sloughing. In 15 eyes subjected to disinfection with the 1:2 dilution, one instance of epithelial corneal edema was noticed. A 1:50 dilution of povidone-iodine is recommended as an ocular surface disinfectant for use in presurgical situations.

Biochar-manure compost in conjunction with pyroligneous solution alleviated salt stress and improved leaf bioactivity of maize in a saline soil from central China: a 2-year field experiment.

PubMed

Lashari, Muhammad Siddique; Ye, Yingxin; Ji, Haishi; Li, Lianqing; Kibue, Grace Wanjiru; Lu, Haifei; Zheng, Jufeng; Pan, Genxing

2015-04-01

Salinity is a major stress threatening crop production in dry lands. A 2-year field experiment was conducted to assess the potential of a biochar product to alleviate salt-stress to a maize crop in a saline soil. The soil was amended with a compost at 12 t ha(-1) of wheat straw biochar and poultry manure compost (BPC), and a diluted pyroligneous solution (PS) at 0.15 t ha(-1) (BPC-PS). Changes in soil salinity and plant performance, leaf bioactivity were examined in the first (BPC-PS1) and second (BPC-PS2) year following a single amendment. While soil salinity significantly decreased, there were large increases in leaf area index, plant performance, and maize grain yield, with a considerable decrease in leaf electrolyte leakage when grown in amendments. Maize leaf sap nitrogen, phosphorus and potassium increased while sodium and chloride decreased, leaf bioactivity related to osmotic stress was significantly improved following the treatments. These effects were generally greater in the second than in the first year. A combined amendment of crop straw biochar with manure compost plus pyroligneous solution could help combat salinity stress to maize and improve productivity in saline croplands in arid/semi-arid regions threatened increasingly by global climate change. © 2014 Society of Chemical Industry.

Application of refractometry to quality assurance monitoring of parenteral nutrition solutions.

PubMed

Chang, Wei-Kuo; Chao, You-Chen; Yeh, Ming-Kung

2008-01-01

Parenteral nutrition (PN) solution contains various concentrations of dextrose, amino acids, lipids, vitamins, electrolytes, and trace elements. Incorrect preparation of PN solution could lead to patient death. In this study we used the refractive index as a quality assurance tool to monitor the preparation of PN solution. Refractive indices of single nutrient components and PN solutions consisting of various concentrations of dextrose, amino acids, electrolytes, and lipids were measured. A mathematical equation and its linear plot were generated then used to predict the refractive index of the PN solution. The best-fit refractive index for PN solution (i.e., the predicted refractive index)=0.9798x(% dextrose)+1.2889x(% amino acids)+1.1017x(% lipids)+0.9440x(% sum of the electrolytes)+0.5367 (r2=0.99). This equation was validated by comparing the measured refractive indices of 500 clinical PN solutions to their predicted refractive indices. We found that 2 of the 500 prepared samples (0.4%) had less than the predicted refractive index (<95%). Refractive index can be used as a reliable quality assurance tool for monitoring PN preparation. Such information can be obtained at the bedside and used to confirm the accuracy of the PN solution composition.

Durability of the Li 1+xTi 2–xAl x(PO 4) 3 Solid Electrolyte in Lithium–Sulfur Batteries

DOE PAGES

Wang, Shaofei; Ding, Yu; Zhou, Guangmin; ...

2016-10-31

Adoption of cells with a solid-state electrolyte is a promising solution for eliminating the polysulfide shuttle problem in Li-S batteries. Among the various known lithium-ion conducting solid electrolytes, the sodium superionic conductor (NASICON)-type Li 1+xTi 2-xAl x(PO 4) 3 offers the advantage of good stability under ambient conditions and in contact with air. Accordingly, we present here a comprehensive assessment of the durability of Li 1+xTi 2-xAl x(PO 4) 3 in contact with polysulfide solution and in Li-S cells. Because of its high reduction potential (2.5 V vs Li/Li +), Li 1+xTi 2-xAl x(PO 4) 3 gets lithiated in contactmore » with lithium polysulfide solution and Li 2CO 3 is formed on the particle surface, blocking the interfacial lithium-ion transport between the liquid and solid-state electrolytes. After the lithium insertion into the NASICON framework, the crystal expands in an anisotropic way, weakening the crystal bonds, causing fissures and resultant cracks in the ceramic, corroding the grain boundaries by polysulfide solution, and leaving unfavorable pores. The assembly of pores creates a gateway for polysulfide diffusion from the cathode side to the anode side, causing an abrupt decline in cell performance. Therefore, the solid-state electrolytes need to have good chemical compatibility with both the electrode and electrolyte, long-term stability under harsh chemical environment, and highly stable grain boundaries.« less

The Significance of the Origin of Physical Chemistry for Physical Chemistry Education: The Case of Electrolyte Solution Chemistry

ERIC Educational Resources Information Center

de Berg, Kevin Charles

2014-01-01

Physical Chemistry's birth was fraught with controversy, a controversy about electrolyte solution chemistry which has much to say about how scientific knowledge originates, matures, and responds to challenges. This has direct implications for the way our students are educated in physical chemistry in particular and science in general. The…

Liquid-Feed Methanol Fuel Cell With Membrane Electrolyte

NASA Technical Reports Server (NTRS)

Surampudi, Subbarao; Narayanan, S. R.; Halpert, Gerald; Frank, Harvey; Vamos, Eugene

1995-01-01

Fuel cell generates electricity from direct liquid feed stream of methanol/water solution circulated in contact with anode, plus direct gaseous feed stream of air or oxygen in contact with cathode. Advantages include relative simplicity and elimination of corrosive electrolytic solutions. Offers potential for reductions in size, weight, and complexity, and for increases in safety of fuel-cell systems.

DNA/RNA sequencing using a semiconducting nanopore

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

Fleharty, Mark; Petsev, Dimiter N.; Van Swol, Frank B.

The present disclosure provides novel apparatus including, though not necessarily limited to, biosensors utilizing semiconductor materials in electrolyte solutions and methods for using the same. The biosensors rely on a unique property wherein a charged body in the electrolyte solution produces a detectable change in the local conductivity of the semiconductor as the body approaches or travels near the semiconductor.

Liquid junction schottky barrier solar cell

DOEpatents

Williams, Richard

1980-01-01

A mixture of ceric ions (Ce.sup.+4) and cerous ions (Ce.sup.+3) in an aqueous electrolyte solution forms a Schottky barrier at the interface between an active region of silicon and the electrolyte solution. The barrier height obtained for hydrogenated amorphous silicon using the Ce.sup.+4 /Ce.sup.+3 redox couple is about 1.7 eV.

Enhancement in Diffusion of Electrolyte through Membrane Using Ultrasonic Dialysis Equipment with Plane Membrane

NASA Astrophysics Data System (ADS)

Li, Hui; Ohdaira, Etsuzo; Ide, Masao

1995-05-01

Application of ultrasound to accelerate the dialysis separation of electrolytes through a membrane was studied with ultrasonic dialysis equipment. The experiments were conducted with cellophane membrane and KCl solution, CH3COONa solution, and a mixture of KCl and saponin solutions. It was found that the diffusion velocity of electrolyte through a membrane with ultrasonic irradiation is faster than that without ultrasonic irradiation, and it increases with acoustic pressure. It has become clear that the reasons for enhancement caused by ultrasound are increase in liquid particle velocity and diffusion coefficient due to ultrasonic vibration. It was confirmed that the permeability of the membrane was not degraded by ultrasound in the ranges of acoustic pressure and irradiation time in this study.

Low temperature double-layer capacitors

NASA Technical Reports Server (NTRS)

Brandon, Erik J. (Inventor); West, William C. (Inventor); Smart, Marshall C. (Inventor)

2011-01-01

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -75.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. An optimized concentration (e.g., 0.10 M to 0.75 M) of salt, such as tetraethylammonium tetrafluoroborate, is dissolved into the electrolyte solution. In some cases (e.g., 1,3-dioxolane cosolvent) additives, such as 2% by volume triethylamine, may be included in the solvent mixture to prevent polymerization of the solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Electrochemical system and method for electropolishing superconductive radio frequency cavities

DOEpatents

Taylor, E. Jennings; Inman, Maria E.; Hall, Timothy

2015-04-14

An electrochemical finishing system for super conducting radio frequency (SCRF) cavities including a low viscosity electrolyte solution that is free of hydrofluoric acid, an electrode in contact with the electrolyte solution, the SCRF cavity being spaced apart from the electrode and in contact with the electrolyte solution and a power source including a first electrical lead electrically coupled to the electrode and a second electrical lead electrically coupled to the cavity, the power source being configured to pass an electric current between the electrode and the workpiece, wherein the electric current includes anodic pulses and cathodic pulses, and wherein the cathodic pulses are interposed between at least some of the anodic pulses. The SCRF cavity may be vertically oriented during the finishing process.

Photoelectrodialytic cell

DOEpatents

Murphy, G.W.

1983-09-13

A multicompartment photoelectrodialytic demineralization cell is provided with a buffer compartment interposed between the product compartment and a compartment containing an electrolyte solution. Semipermeable membranes separate the buffer compartment from the product and electrolyte compartments. The buffer compartment is flushed to prevent leakage of the electrolyte compartment from entering the product compartment. 3 figs.

Effects of two different strategies of fluid administration on inflammatory mediators, plasma electrolytes and acid/base disorders in patients undergoing major abdominal surgery: a randomized double blind study

PubMed Central

2013-01-01

Background Administration of normal saline might increase circulating levels of pro-inflammatory cytokines and may cause variation of plasmatic electrolytic and hyperchloremic acidosis, which in turn can impair renal function. Hence the use of balanced solutions could influence the inflammatory cascade triggered by the surgical procedures, the plasmatic electrolyte concentration, the acid–base equilibrium, and the renal function. Methods This is a double blind randomized trial. Forty patients undergoing major abdominal surgery (bowel cancer) were allocated in two groups, the balanced solution (BS) group in which the fluids administered were balanced solutions (colloids and crystalloids); and the unbalanced solution (UBS) group in which the fluids administered were unbalanced solutions (colloids and crystalloids). Measurements were performed after anaesthesia induction (T0), at the end of surgery (T1), within 2 h after surgery (T2) and 24 h after the beginning of surgery (T3). The following data were collected: 1) active matrix metalloproteinase 9 (MMP-9) and its tissue inhibitor (TIMP-1), IL-6, IL-8, IL-10; 2) blood gases variables; 3) electrolytes, albumin, total serum protein and the strong ion difference; 4) neutrophil gelatinase-associated lipocalin (NGAL) from urinary sample. Results The BS group exhibited higher circulating level of IL-10 and TIMP-1 and lower level of active MMP-9. The UBS group experienced hypercloremia, hypocalcemia, hypomagnesemia, worse acid–base equilibrium and higher level of NGAL. Conclusions The use of balanced solutions was responsible of less alteration of plasmatic electrolytes, acid–base equilibrium, kidney function and it might be associated with an early anti-inflammatory mechanisms triggering. Trial registration ClinicalTrials.gov (Ref: NCT01320891). PMID:24059479

Analytical calculation of electrolyte water content of a Proton Exchange Membrane Fuel Cell for on-board modelling applications

NASA Astrophysics Data System (ADS)

Ferrara, Alessandro; Polverino, Pierpaolo; Pianese, Cesare

2018-06-01

This paper proposes an analytical model of the water content of the electrolyte of a Proton Exchange Membrane Fuel Cell. The model is designed by accounting for several simplifying assumptions, which make the model suitable for on-board/online water management applications, while ensuring a good accuracy of the considered phenomena, with respect to advanced numerical solutions. The achieved analytical solution, expressing electrolyte water content, is compared with that obtained by means of a complex numerical approach, used to solve the same mathematical problem. The achieved results show that the mean error is below 5% for electrodes water content values ranging from 2 to 15 (given as boundary conditions), and it does not overcome 0.26% for electrodes water content above 5. These results prove the capability of the solution to correctly model electrolyte water content at any operating condition, aiming at embodiment into more complex frameworks (e.g., cell or stack models), related to fuel cell simulation, monitoring, control, diagnosis and prognosis.

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

PubMed

Ketenoglu, Didem; Spiekermann, Georg; Harder, Manuel; Oz, Erdinc; Koz, Cevriye; Yagci, Mehmet C; Yilmaz, Eda; Yin, Zhong; Sahle, Christoph J; Detlefs, Blanka; Yavaş, Hasan

2018-03-01

The effects of varying LiPF 6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li + ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF 4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

Use of Piggyback Electrolytes for Patients Receiving Individually Prescribed vs Premixed Parenteral Nutrition.

PubMed

Busch, Rebecca A; Curtis, Caitlin S; Leverson, Glen E; Kudsk, Kenneth A

2015-07-01

Parenteral nutrition (PN) is available as individualized prescriptions frequently prepared with an automated compounding device or as commercially prepared premixed solutions. Our institution exclusively used individualized PN until an amino acid shortage forced a temporary switch to premixed solutions. In general, premixed solutions contain lower electrolyte levels than individualized formulations prescribed for patients with normal organ function. We aimed to quantify supplemental intravenous piggyback (IVPB) electrolyte use in adult patients receiving individualized and premixed PN and to quantify any effect on difference in the cost of therapy. We compared use of supplemental IVPB electrolytes administered to patients receiving PN during consecutive periods prior to and during the amino acid shortage. Electrolyte IVPBs tabulated were potassium chloride, 10 and 20 mEq; magnesium sulfate, 2 g and 4 g; potassium phosphate, 7.5 and 15 mmol; and sodium phosphate, 7.5 and 15 mmol IVPB. There was no statistical difference in the number of PN formulations administered per day during each period (14.7 ± 3.9 vs 14.0 ± 2.6, individualized vs premixed, respectively). Total IVPB electrolytes prescribed per day increased significantly from the individualized PN period to the premixed PN period (7.03 ± 3.8 vs 13.8 ± 6.8; P < .0001). The additional IVPB electrolyte supplementation required in patients receiving premixed PN was associated with an additional $11,855.74 cost per 30 days of therapy compared with those who received individualized PN. Inpatient use of premixed PN results in a significant increase in IVPB electrolyte supplementation and cost compared with individualized PN use. © 2014 American Society for Parenteral and Enteral Nutrition.

The effect of calcium hydroxide, alkali dilution and calcium concentration in mitigating the alkali silica reaction using palm oil fuel ash

NASA Astrophysics Data System (ADS)

Asrah, Hidayati; Mirasa, Abdul Karim; Bolong, Nurmin

2018-02-01

This study investigated the mechanism of how POFA mitigated the ASR expansion. Two types of POFA; the UPOFA and GPOFA with different fineness were used to replace the cement at 20% and 40% and their effects on the mortar bar expansion, calcium hydroxide, alkali dilution, and calcium concentration were investigated. The results showed that UPOFA has a significant ability to mitigate the ASR, even at a lower level of replacement (20%) compared to GPOFA. The mechanism of UPOFA in mitigating the ASR expansion was through a reduction in the calcium hydroxide content, which produced low calcium concentration within the mortar pore solution. Low pore solution alkalinity signified that UPOFA had good alkali dilution effect. Meanwhile, a higher dosage of GPOFA was required to mitigate the ASR expansion. An increase in the pore solution alkalinity of GPOFA mortar indicated higher penetration of alkalis from the NaOH solution, which reduced the alkali dilution effect. However, this was compensated by the increase in the cement dilution effect at higher GPOFA replacement, which controlled the mortar bar expansion below the ASTM limit.

On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

PubMed

Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

2017-02-08

We demonstrate herein that Mn 3+ and not Mn 2+ , as commonly accepted, is the dominant dissolved manganese cation in LiPF 6 -based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn 3+ fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn 3+ in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn 3+ occurs at a very slow rate.

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

Small quaternary alkyl phosphonium bis(fluorosulfonyl)imide ionic liquid electrolytes for sodium-ion batteries with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode material

NASA Astrophysics Data System (ADS)

Hilder, Matthias; Howlett, Patrick C.; Saurel, Damien; Gonzalo, Elena; Armand, Michel; Rojo, Teófilo; Macfarlane, Douglas R.; Forsyth, Maria

2017-05-01

A saturated solution of 2.3 M sodium bis(fluorosulfonyl)imide in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide ionic liquid shows a high conductivity (0.94 mScm-1 at 50 °C), low ion association, and a wide operational temperature window (-71 °C-305 °C) making it a promising electrolyte for sodium battery applications. Cycling with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode display excellent performance at 50 °C outperforming conventional organic solvent based electrolytes in terms of capacities (at C/10) and long term cycle stability (at C/2). Post analysis of the electrolyte shows no measurable changes while the sodium metal anode and the cathode surface shows the presence of electrolyte specific elements after cycling, suggesting the formation of a stabilizing solid electrolyte interface. Additionally, cycling changes the topography and particle morphology of the cathode. Thus, the electrolyte properties and cell performance match or outperform previously reported results with the additional benefit of replacing the hazardous and flammable organic solvent solutions commonly employed.

Reusable chelating resins concentrate metal ions from highly dilute solutions

NASA Technical Reports Server (NTRS)

Bauman, A. J.; Weetal, H. H.; Weliky, N.

1966-01-01

Column chromatographic method uses new metal chelating resins for recovering heavy-metal ions from highly dilute solutions. The absorbed heavy-metal cations may be removed from the chelating resins by acid or base washes. The resins are reusable after the washes are completed.

Diluted povidone-iodine versus saline for dressing metal-skin interfaces in external fixation.

PubMed

Chan, C K; Saw, A; Kwan, M K; Karina, R

2009-04-01

To compare infection rates associated with 2 dressing solutions for metal-skin interfaces. 60 patients who underwent distraction osteogenesis with external fixators were equally randomised into 2 dressing solution groups (diluted povidone-iodine vs. saline). Fixations were attained using either rigid stainless steel 5-mm diameter half pins or smooth stainless steel 1.8-mm diameter wires. Half-pin fixation had one metal-skin interface, whereas wire fixation had 2 interfaces. Patients were followed up every 2 weeks for 6 months. Of all 788 metal-skin interfaces, 143 (18%) were infected: 72 (19%) of 371 in the diluted povidone-iodine group and 71 (17%) of 417 in the saline group. Dressing solution and patient age did not significantly affect infection rates. Half-pin fixation was more likely to become infected than wire fixation (25% vs 15%). Saline is as effective as diluted povidone-iodine as a dressing solution for metal-skin interfaces of external fixators. Saline is recommended in view of its easy availability and lower costs.

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

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

Pinch-off dynamics, extensional viscosity and relaxation time of dilute and ultradilute aqueous polymer solutions

NASA Astrophysics Data System (ADS)

Biagioli, Madeleine; Dinic, Jelena; Jimenez, Leidy Nallely; Sharma, Vivek

Free surface flows and drop formation processes present in printing, jetting, spraying, and coating involve the development of columnar necks that undergo spontaneous surface-tension driven instability, thinning, and pinch-off. Stream-wise velocity gradients that arise within the thinning neck create and extensional flow field, which induces micro-structural changes within complex fluids that contribute elastic stresses, changing the thinning and pinch-off dynamics. In this contribution, we use dripping-onto-substrate (DoS) extensional rheometry technique for visualization and analysis of the pinch-off dynamics of dilute and ultra-dilute aqueous polyethylene oxide (PEO) solutions. Using a range of molecular weights, we study the effect of both elasticity and finite extensibility. Both effective relaxation time and the transient extensional viscosity are found to be strongly concentration-dependent even for highly dilute solutions.

Development of taste sensing system using inorganic membrane

NASA Astrophysics Data System (ADS)

Kojima, Yohichiro; Hasegawa, Yuki

2011-09-01

We developed a novel taste sensor for liquid and verified its effectiveness using coffee. We fabricated an inorganic metal oxide membrane liquid sensor using the laser ablation method. The sensor shows a sufficient sensitivity for electrolyte solutions, while it shows a relatively low response for non-electrolyte solutions. We differentiated and identified five brands of commercially available coffee using the sensor.

[Adverse effects of drugs in intensive care units: analysis of the administration of electrolyte solutions and antibiotics].

PubMed

Manenti, S; Chaves, A B; Leopoldino, R S; Padilha, K G

1998-12-01

The aims of this study were: 1) to verify the incidence of adverse occurrences (AOs) with medication related to the time of electrolyte solutions infusion and the frequency of doses of antibiotics prescribed and administered to the patients; 2) to characterize the nature of those occurrences. The study was developed in two ICUs of a general hospital of São Paulo City. The population was composed by 51 patients that were in the ICUs in August of 1996. Sixty percent of the patients were older than 60 years, 58.8% were women, 49.1% remained in ICU from 1 to 4 days and 41.2% went to the Intermediate Care Units after ICU. Regarding the incidence of AOs related to the time of administration of the electrolyte solutions and the frequency of doses of antibiotics the non execution of the patient's medical prescriptions was verified in 76.3% and 38.8% respectively. The largest frequency of irregularities with the electrolyte solutions (60.2%) was the infusion faster than the prescribed time followed by the reduction of the number of doses of antibiotics administered. Taking these into consideration we have to invest in preventive measures to reduce those occurrences.

Hydrophobic, Porous Battery Boxes

NASA Technical Reports Server (NTRS)

Bragg, Bobby J.; Casey, John E., Jr.

1995-01-01

Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

Electrical conductivity of electrolytes applicable to natural waters from 0 to 100 degrees C

USGS Publications Warehouse

McCleskey, R. Blaine

2011-01-01

The electrical conductivities of 34 electrolyte solutions found in natural waters ranging from (10-4 to 1) mol•kg-1 in concentration and from (5 to 90) °C have been determined. High-quality electrical conductivity data for numerous electrolytes exist in the scientific literature, but the data do not span the concentration or temperature ranges of many electrolytes in natural waters. Methods for calculating the electrical conductivities of natural waters have incorporated these data from the literature, and as a result these methods cannot be used to reliably calculate the electrical conductivity over a large enough range of temperature and concentration. For the single-electrolyte solutions, empirical equations were developed that relate electrical conductivity to temperature and molality. For the 942 molar conductivity determinations for single electrolytes from this study, the mean relative difference between the calculated and measured values was 0.1 %. The calculated molar conductivity was compared to literature data, and the mean relative difference for 1978 measurements was 0.2 %. These data provide an improved basis for calculating electrical conductivity for most natural waters.

The influence of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions

NASA Astrophysics Data System (ADS)

Boehnstedt, W.

1980-09-01

The paper describes the effect of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions. The dissolution is accelerated by the addition of small quantities of gallium or indium ions to the electrolyte indicated by the shift of the zero current potential by about 250 mV on the current-potential curve. Scanning electron microscope studies showed that gallium ions produce many small cracks in the aluminum electrode and collect at the grain boundary areas, increasing the electrode surface; this enlargement, in combination with increased electrolyte agitation due to greater hydrogen evolution, provides higher current densities at the same potential. It is concluded that this process will widen the possibilities of using aluminum and its alloys in high-rate batteries.

ELECTROLYTIC PRODUCTION OF URANIUM TETRAFLUORIDE

DOEpatents

Lofthouse, E.

1954-08-31

This patent relates to electrolytic methods for the production of uranium tetrafluoride. According to the present invention a process for the production of uranium tetrafluoride comprises submitting to electrolysis an aqueous solution of uranyl fluoride containing free hydrofluoric acid. Advantageously the aqueous solution of uranyl fluoride is obtained by dissolving uranium hexafluoride in water. On electrolysis, the uranyl ions are reduced to uranous tons at the cathode and immediately combine with the fluoride ions in solution to form the insoluble uranium tetrafluoride which is precipitated.

Chemical modification of electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Afanas'ev, Vladimir N.; Grechin, Aleksandr G.

2002-09-01

Modern approaches to modifying chemically electrolytes for lithium batteries are analysed with the aim of optimising the charge-transfer processes in liquid-phase and solid (polymeric) media. The main regularities of transport properties of lithium electrolyte solutions containing complex (encapsulated) ions in aprotic solvents and polymers are discussed. The prospects for the development of electrolytic solvosystems with the chain (ionotropic) mechanism of conduction with respect to lithium ions are outlined. The bibliography includes 126 references.

Conversion of Carbon Dioxide into Ethanol by Electrochemical Synthesis Method Using Cu-Zn Electrode

NASA Astrophysics Data System (ADS)

Riyanto; Ramadan, S.; Fariduddin, S.; Aminudin, A. R.; Hayatri, A. K.

2018-01-01

Research on conversion of carbon dioxide into ethanol has been done. The conversion process is carried out in a sodium bicarbonate electrolyte solution in an electrochemical synthesis reactor. As cathode was used Cu-Zn, while as anode carbon was utilized. Variations of voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis were performed to determine the optimum conditions to convert carbon dioxide into ethanol. Sample of the electrochemical synthesis process was analyzed by gas chromatography. From the result, it is found that the optimum conditions of the electrochemical synthesis process of carbon dioxide conversion into ethanol are voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis are 3 volts, 0.4 M and 90 minutes with the ethanol concentration of 10.44%.

The CETAC ADX-500 Autodiluter System: A Study of Dilution Performance with the ELAN 6000 ICP-MS and ELAN Software

USGS Publications Warehouse

May, T.W.; Wiedmeyer, Ray H.

1998-01-01

The CETAC ADX-500 autodiluter system was tested with ELAN?? v 2.1 software and the ELAN 6000 ICP-MS instrument to determine on-line automated dilution performance during analysis of standard solutions containing nine analytes representative of the mass spectral range (mass 9 to mass 238). Two or more dilution schemes were tested for each of 5 test tube designs. Dilution performance was determined by comparison of analyte concentration means of diluted and non-diluted standards. Accurate dilutions resulted with one syringe pump addition of diluent in small diameter round-bottomed (13 mm OD) or conical-tipped (18 mm OD) tubes and one or more syringe pump additions in large diameter (28 mm OD) conical-tipped tubes. Inadequate dilution mixing which produced high analyte concentration means was observed for all dilutions conducted in flat-bottomed tubes, and for dilutions requiring multiple syringe additions of diluent in small diameter round-bottomed and conical tipped tubes. Effective mixing of diluted solutions was found to depend largely upon tube diameter and liquid depth: smaller tube diameters and greater liquid depth resulted in ineffective mixing, whereas greater tube diameter and shallower liquid depth facilitated effective mixing. Two design changes for the autodiluter were suggested that would allow effective mixing to occur using any dilution scheme and tube design.

Removal of contaminant gases from an electrolytic urine pretreatment process. [in spacecraft life support systems

NASA Technical Reports Server (NTRS)

Colombo, G. V.; Putnam, D. F.

1977-01-01

The effluent gas stream from an electrolytic urine pretreatment process was analyzed by gas chromatography-mass spectroscopy and wet chemical methods to determine its composition. The major constituents were identified as: hydrogen, carbon dioxide, oxygen, nitrogen, water vapor, and chlorine. The trace impurities were chlorinated light hydrocarbons, and a number of other organic impurities in the low ppm range. Several methods of removing all of the undesirable gases to levels acceptable for return to a space cabin atmosphere were investigated experimentally. A subsystem concept comprised of the following sequential unit processes and operations was successfully demonstrated: (1) raw urine scrubbing, (2) silica gel sorption, (3) dilution with cabin air, and (4) catalytic oxidation.

Efficacy and Safety of Combined Oral and Enema Therapy Using Polyethylene Glycol 3350-Electrolyte for Disimpaction in Pediatric Constipation

PubMed Central

Yoo, Taeyeon

2017-01-01

Purpose We evaluated the efficacy and safety of combined oral and enema therapy using polyethylene glycol (PEG) 3350 with electrolyte solution for disimpaction in hospitalized children. Methods We retrospectively studied 28 children having functional constipation who received inpatient treatment between 2008 and 2016. The amount of oral PEG 3350 electrolyte solution administered was 50–70 mL/kg/d (PEG 3350, 3–4.1 g/kg/d), and an enema solution was administered 1–2 times a day as a single dose of 15–25 mL/kg (PEG 3350, 0.975–1.625 g/kg/d). A colon transit time (CTT) test based on the Metcalf protocol was performed in some patients. Results Administration of oral and enema doses of PEG 3350 electrolyte solution showed 2.1±0.3 times and 2.9±0.4 times, respectively. After disimpaction, the frequency of defecation increased from 2.2±0.3 per week to once a day (1.1±0.1 per day). The number of patients who complained of abdominal pain was reduced from 15 (53.6%) to 4 (14.3%). Before hospitalization, nine patients underwent a CTT test, and 5 of 9 patients (55.6%) were classified as belonging to a group showing abnormalities. And in some patients, mild adverse effects were noted. We examined electrolytes and osmolality before and after disimpaction in 16 of 28 patients, and no abnormalities were noted. Conclusion In terms of therapeutic efficacy and safety, combined oral and enema therapy using high-dose PEG 3350 with electrolytes is considered superior to conventional oral monotherapy or combined oral and enema therapy on an outpatient basis. PMID:29302506

Efficacy and Safety of Combined Oral and Enema Therapy Using Polyethylene Glycol 3350-Electrolyte for Disimpaction in Pediatric Constipation.

PubMed

Yoo, Taeyeon; Bae, Sun Hwan

2017-12-01

We evaluated the efficacy and safety of combined oral and enema therapy using polyethylene glycol (PEG) 3350 with electrolyte solution for disimpaction in hospitalized children. We retrospectively studied 28 children having functional constipation who received inpatient treatment between 2008 and 2016. The amount of oral PEG 3350 electrolyte solution administered was 50-70 mL/kg/d (PEG 3350, 3-4.1 g/kg/d), and an enema solution was administered 1-2 times a day as a single dose of 15-25 mL/kg (PEG 3350, 0.975-1.625 g/kg/d). A colon transit time (CTT) test based on the Metcalf protocol was performed in some patients. Administration of oral and enema doses of PEG 3350 electrolyte solution showed 2.1±0.3 times and 2.9±0.4 times, respectively. After disimpaction, the frequency of defecation increased from 2.2±0.3 per week to once a day (1.1±0.1 per day). The number of patients who complained of abdominal pain was reduced from 15 (53.6%) to 4 (14.3%). Before hospitalization, nine patients underwent a CTT test, and 5 of 9 patients (55.6%) were classified as belonging to a group showing abnormalities. And in some patients, mild adverse effects were noted. We examined electrolytes and osmolality before and after disimpaction in 16 of 28 patients, and no abnormalities were noted. In terms of therapeutic efficacy and safety, combined oral and enema therapy using high-dose PEG 3350 with electrolytes is considered superior to conventional oral monotherapy or combined oral and enema therapy on an outpatient basis.

Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

DOEpatents

Bailey, James L.; Barnes, Laurel A.; Wiedmeyer, Stanley G.; Williamson, Mark A.; Willit, James L.

2014-07-08

An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies and an anode shroud for each of the anode assemblies. The anode shroud may be used to dilute, cool, and/or remove off-gas from the electrolytic oxide reduction system. The anode shroud may include a body portion having a tapered upper section that includes an apex. The body portion may have an inner wall that defines an off-gas collection cavity. A chimney structure may extend from the apex of the upper section and be connected to the off-gas collection cavity of the body portion. The chimney structure may include an inner tube within an outer tube. Accordingly, a sweep gas/cooling gas may be supplied down the annular space between the inner and outer tubes, while the off-gas may be removed through an exit path defined by the inner tube.

Non-Ideality in Solvent Extraction Systems: PNNL FY 2014 Status Report

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

Levitskaia, Tatiana G.; Chatterjee, Sayandev; Pence, Natasha K.

The overall objective of this project is to develop predictive modeling capabilities for advanced fuel cycle separation processes by gaining a fundamental quantitative understanding of non-ideality effects and speciation in relevant aqueous and organic solutions. Aqueous solutions containing actinides and lanthanides encountered during nuclear fuel reprocessing have high ionic strength and do not behave as ideal solutions. Activity coefficients must be calculated to take into account the deviation from ideality and predict their behavior. In FY 2012-2013, a convenient method for determining activity effects in aqueous electrolyte solutions was developed. Our initial experiments demonstrated that water activity and osmotic coefficientsmore » of the electrolyte solutions can be accurately measured by the combination of two techniques, a Water Activity Meter and Vapor Pressure Osmometry (VPO). The water activity measurements have been conducted for binary lanthanide solutions in wide concentration range for all lanthanides (La-Lu with the exception of Pm). The osmotic coefficients and Pitzer parameters for each binary system were obtained by the least squares fitting of the water activity data. However, application of Pitzer model for the quantitative evaluation of the activity effects in the multicomponent mixtures is difficult due to the large number of the required interaction parameters. In FY 2014, the applicability of the Bromley model for the determination of the Ln(NO 3) 3 activity coefficients was evaluated. The new Bromley parameters for the binary Ln(NO 3) 3 electrolytes were obtained based on the available literature and our experimental data. This allowed for the accurate prediction of the Ln(NO 3) 3 activity coefficients for the binary Ln(NO 3) 3 electrolytes. This model was then successfully implemented for the determination of the Ln(NO 3) 3 activity coefficients in the ternary Nd(NO 3) 3/HNO 3/H2O, Eu(NO 3) 3/HNO 3/H 2O, and Eu(NO 3) 3/NaNO 3/H 2O systems. The main achievement of this work is the verified pathway for the estimation of the activity coefficients in the multicomponent aqueous electrolyte systems. The accurate Bromley electrolytes contributions obtained in this work for the entire series of lanthanide(III) nitrates (except Pm) can be applied for predicting activity coefficients and non-ideality effects for multi-component systems containing these species. This work also provides the proof-of-principle of extending the model to more complex multicomponent systems. Moreover, this approach can also be applied to actinide-containing electrolyte systems, for determination of the activity coefficients in concentrated radioactive solutions.« less

Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

2018-04-01

Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

Biochemical composition of fluids for amnioinfusion during fetoscopy.

PubMed

Adama van Scheltema, P N; In't Anker, P S; Vereecken, A; Vandenbussche, F P H A; Deprest, J A; Devlieger, R

2008-01-01

To evaluate which of the commercially available solutions is best suited for amnioinfusion during fetoscopy, based on resemblance with the biochemical properties of amniotic fluid. Amniotic fluid samples from 10 pregnancies were studied. Specimens were obtained from 5 pathologic pregnancies (of which 3 were complicated by polyhydramnios) and 5 uncomplicated pregnancies. The concentrations of sodium, potassium, chloride, bicarbonate, calcium, glucose, osmolality, pH, total protein content and albumin were determined in each sample. A literature search (PubMed, Embase) was performed to identify commercially available fluids used for amnioinfusion in clinical practice. The composition of these infusion solutions was compared to the amniotic fluid samples mentioned above. We identified two different electrolyte solutions used in clinical practice for amnioinfusion. We identified four additional commercially available solutions that could potentially be used for amnioinfusion. Most of these infusion solutions differ considerably from midtrimester amniotic fluid samples both in electrolyte composition and pH, with the most striking difference in the latter. Lactated Ringer's solution approximates amniotic fluid the closest for both electrolyte composition and pH. This infusion solution seems to be the most suitable choice for amnioinfusion during fetoscopy. (c) 2008 S. Karger AG, Basel.

40 CFR 180.1196 - Peroxyacetic acid; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... antimicrobial treatment in solutions containing a diluted end use concentration of peroxyacetic acid up to 100... food commodities when used in sanitizing solutions containing a diluted end-use concentration of...

Sulfuric Acid and Water: Paradoxes of Dilution

ERIC Educational Resources Information Center

Leenson, I. A.

2004-01-01

On equilibrium properties of aqueous solutions of sulfuric acid, Julius Thomsen has marked that the heat evolved on diluting liquid sulfuric acid with water is a continuous function of the water used, and excluded absolutely the acceptance of definite hydrates as existing in the solution. Information about thermochemical measurement, a discussion…

Profound effects of cardiopulmonary bypass priming solutions on the fibrin part of clot formation: an ex vivo evaluation using rotation thromboelastometry.

PubMed

Brinkman, Arinda C M; Romijn, Johannes W A; van Barneveld, Lerau J M; Greuters, Sjoerd; Veerhoek, Dennis; Vonk, Alexander B A; Boer, Christa

2010-06-01

Dilutional coagulopathy as a consequence of cardiopulmonary bypass (CPB) system priming may also be affected by the composition of the priming solution. The direct effects of distinct priming solutions on fibrinogen, one of the foremost limiting factors during dilutional coagulopathy, have been minimally evaluated. Therefore, the authors investigated whether hemodilution with different priming solutions distinctly affects the fibrinogen-mediated step in whole blood clot formation. Prospective observational laboratory study. University hospital laboratory. Eight male healthy volunteers. Blood samples diluted with gelatin-, albumin-, or hydroxyethyl starch (HES)-based priming solutions were ex-vivo evaluated for clot formation by rotational thromboelastometry. The intrinsic pathway (INTEM) coagulation time increased from 186 +/- 19 seconds to 205 +/- 16, 220 +/- 17, and 223 +/- 18 seconds after dilution with gelatin-, albumin-, or HES-containing prime solutions (all p < 0.05 v baseline). The extrinsic pathway (EXTEM) coagulation time was only minimally affected by hemodilution. Moreover, all 3 priming solutions significantly reduced the INTEM and EXTEM maximum clot firmness. The HES-containing priming solution induced the largest decrease in the maximum clot firmness attributed to fibrinogen, from 13 +/- 1 mm (baseline) to 6 +/- 1 mm (p < 0.01 v baseline). All studied priming solutions prolonged coagulation time and decreased clot formation, but the fibrinogen-limiting effect was the most profound for the HES-containing priming solution. These results suggest that the composition of priming solutions may distinctly affect blood clot formation, in particular with respect to the fibrinogen component in hemostasis. Copyright 2010 Elsevier Inc. All rights reserved.

Electrolytic method for the production of lithium using a lithium-amalgam electrode

DOEpatents

Cooper, John F.; Krikorian, Oscar H.; Homsy, Robert V.

1979-01-01

A method for recovering lithium from its molten amalgam by electrolysis of the amalgam in an electrolytic cell containing as a molten electrolyte a fused-salt consisting essentially of a mixture of two or more alkali metal halides, preferably alkali metal halides selected from lithium iodide, lithium chloride, potassium iodide and potassium chloride. A particularly suitable molten electrolyte is a fused-salt consisting essentially of a mixture of at least three components obtained by modifying an eutectic mixture of LiI-KI by the addition of a minor amount of one or more alkali metal halides. The lithium-amalgam fused-salt cell may be used in an electrolytic system for recovering lithium from an aqueous solution of a lithium compound, wherein electrolysis of the aqueous solution in an aqueous cell in the presence of a mercury cathode produces a lithium amalgam. The present method is particularly useful for the regeneration of lithium from the aqueous reaction products of a lithium-water-air battery.

Fluid and Electrolyte Balance model (FEB)

NASA Technical Reports Server (NTRS)

Fitzjerrell, D. G.

1973-01-01

The effects of various oral input water loads on solute and water distribution throughout the body are presented in the form of a model. The model was a three compartment model; the three compartments being plasma, interstitial fluid and cellular fluid. Sodium, potassium, chloride and urea were the only major solutes considered explicitly. The control of body water and electrolyte distribution was affected via drinking and hormone levels.

Chromium recovery from exhausted baths generated in plating processes and its reuse in the tanning industry.

PubMed

Torras, Josep; Buj, Irene; Rovira, Miquel; de Pablo, Joan

2012-03-30

Chromium plating used for functional purposes provides an extremely hard, wear and corrosion resistant layer by means of electrolytic deposition. Typical layer thicknesses range between 2.5 and 500 μm. Chromium electroplating baths contain high concentrations of Cr(VI) with chromium trioxide (CrO(3)) as the chromium source. When because of technical or economic reasons a bath gets exhausted, a waste containing mainly chromium as dichromate as well as other heavy metals is generated. Chromium may then be purified for use in other industrial processes with different requirements. In this work, a sustainable system for using galvanic wastes as reagents in the leather tanning industry, thus reducing quantity of wastes to be treated, is presented. Metal cations present in the chromium exhausted bath were precipitated with NaOH. Then, the solution containing mainly soluble Cr(VI) was separated. By means of sodium sulphite in acidic conditions, Cr(VI) was reduced to Cr(III) as chromium (III) sulphate. From chromium (III) sulphate a basic Cr(III) sulphate may be obtained, which is one of most used compounds in the tanning industry. Cr(III) concentration in the final solution allows its reuse without concentration, but with a slight dilution. Copyright © 2012 Elsevier B.V. All rights reserved.

The Effect of Ionic Strength on the Solubility of an Electrolyte

ERIC Educational Resources Information Center

Willey, Joan D.

2004-01-01

A simple experiment was conducted for studying and demonstrating visually and dramatically the effect of ionic strength on the solubility of an electrolyte is described. It is seen that the experiment visually illustrates the effect of ionic strength on electrolyte solubility by the appearance of the two solutions and by the difference in the…

Preliminary study of application of Moringa oleifera resin as polymer electrolyte in DSSC solar cells

NASA Astrophysics Data System (ADS)

Saehana, Sahrul; Darsikin, Muslimin

2016-04-01

This study reports the preliminary study of application of Moringa oleifera resin as polymer electrolyte in dye-sensitized solar cell (DSSC). We found that polymer electrolyte membrane was formed by using solution casting methods. It is observed that polymer electrolyte was in elastic form and it is very potential to application as DSSC component. Performance of DSSC which employing Moringa oleifera resin was also observed and photovoltaic effect was found.

An aqueous electrolyte of the widest potential window and its superior capability for capacitors.

PubMed

Tomiyasu, Hiroshi; Shikata, Hirokazu; Takao, Koichiro; Asanuma, Noriko; Taruta, Seiichi; Park, Yoon-Yul

2017-03-21

A saturated aqueous solution of sodium perchlorate (SSPAS) was found to be electrochemically superior, because the potential window is remarkably wide to be approximately 3.2 V in terms of a cyclic voltammetry. Such a wide potential window has never been reported in any aqueous solutions, and this finding would be of historical significance for aqueous electrolyte to overcome its weak point that the potential window is narrow. In proof of this fact, the capability of SSPAS was examined for the electrolyte of capacitors. Galvanostatic charge-discharge measurements showed that a graphite-based capacitor containing SSPAS as an electrolyte was stable within 5% deviation for the 10,000 times repetition at the operating voltage of 3.2 V without generating any gas. The SSPAS worked also as a functional electrolyte in the presence of an activated carbon and metal oxides in order to increase an energy density. Indeed, in an asymmetric capacitor containing MnO 2 and Fe 3 O 4 mixtures in the positive and negative electrodes, respectively, the energy density enlarged to be 36.3 Whkg -1 , which belongs to the largest value in capacitors. Similar electrochemical behaviour was also confirmed in saturated aqueous solutions of other alkali and alkaline earth metal perchlorate salts.

How Does the Alkyl Chain Length of an Ionic Liquid Influence Solute Rotation in the Presence of an Electrolyte?

PubMed

Prabhu, Sugosh R; Dutt, G B

2016-12-29

Fluorescence anisotropies of a nonpolar solute, 9-phenylanthracene (9-PA), have been measured in 1-alkyl-3-methylimidazolium (alkyl = methyl, butyl, octyl, and dodecyl) bis(trifluoromethylsulfonyl)imides ([RMIM][Tf 2 N]) with varying amounts (0-0.3 mole fraction) of lithium bis(trifluoromethylsulfonyl)imide (LiTf 2 N). This study has been carried out to understand how the length of the alkyl chain and the concentration of the electrolyte influence the rotational diffusion of a nonpolar solute. It has been observed that the addition of an electrolyte to the ionic liquid increases the bulk viscosity of the system significantly, as the Li + cations strongly coordinate with the [Tf 2 N] anions in the polar domains. The reorientation times of 9-PA have been analyzed with the aid of Stokes-Einstein-Debye hydrodynamic (SED) theory, and they fall within the broad limits set by the hydrodynamic slip and stick boundary conditions. However, deviations from the SED theory have been noticed upon addition of LiTf 2 N, and the influence of the electrolyte is more pronounced in the case of ionic liquids with shorter alkyl chains. The observed trends have been rationalized in terms of electrolyte-induced structural changes in these ionic liquids.

An aqueous electrolyte of the widest potential window and its superior capability for capacitors

PubMed Central

Tomiyasu, Hiroshi; Shikata, Hirokazu; Takao, Koichiro; Asanuma, Noriko; Taruta, Seiichi; Park, Yoon-Yul

2017-01-01

A saturated aqueous solution of sodium perchlorate (SSPAS) was found to be electrochemically superior, because the potential window is remarkably wide to be approximately 3.2 V in terms of a cyclic voltammetry. Such a wide potential window has never been reported in any aqueous solutions, and this finding would be of historical significance for aqueous electrolyte to overcome its weak point that the potential window is narrow. In proof of this fact, the capability of SSPAS was examined for the electrolyte of capacitors. Galvanostatic charge-discharge measurements showed that a graphite-based capacitor containing SSPAS as an electrolyte was stable within 5% deviation for the 10,000 times repetition at the operating voltage of 3.2 V without generating any gas. The SSPAS worked also as a functional electrolyte in the presence of an activated carbon and metal oxides in order to increase an energy density. Indeed, in an asymmetric capacitor containing MnO2 and Fe3O4 mixtures in the positive and negative electrodes, respectively, the energy density enlarged to be 36.3 Whkg−1, which belongs to the largest value in capacitors. Similar electrochemical behaviour was also confirmed in saturated aqueous solutions of other alkali and alkaline earth metal perchlorate salts. PMID:28322349

Raising the Corrosion Resistance of Low-Carbon Steels by Electrolytic-Plasma Saturation with Nitrogen and Carbon

NASA Astrophysics Data System (ADS)

Kusmanov, S. A.; Grishina, E. P.; Belkin, P. N.; Kusmanova, Yu. V.; Kudryakova, N. O.

2017-05-01

Structural features of the external oxide layer and internal nitrided, carbonitrided and carburized layers in steels 10, 20 and St3 produced by the method of electrolytic plasma treatment are studied. Specimens of the steels are tested for corrosion in a naturally aerated 1-N solution of sodium chloride. The condition of the metal/sodium chloride solution interface is studied by the method of electrochemical impedance spectroscopy. It is shown that the corrosion resistance of low-carbon steels can be raised by anode electrolytic-plasma saturation with nitrogen and carbon. Recommendations are given on the choice of carbonitriding modes for structural steels.

Enhanced photoelectric performance in self-powered UV detectors based on ZnO nanowires with plasmonic Au nanoparticles scattered electrolyte

NASA Astrophysics Data System (ADS)

Zeng, Yiyu; Ye, Zhizhen; Lu, Bin; Dai, Wei; Pan, Xinhua

2016-04-01

Vertically aligned ZnO nanowires (NWs) were grown on a fluorine-doped tin-oxide-coated glass substrate by a hydrothermal method. Au nanoparticles were well dispersed in the mixed solution of ethanol and deionized water. A simple self-powered ultraviolet detector based on solid-liquid heterojunction was fabricated, utilizing ZnO NWs as active photoanode and such prepared mixed solution as electrolyte. The introduction of Au nanoparticles results in considerable improvements in the responsivity and sensitivity of the device compared with the one using deionized water as electrolyte, which is attributed to the enhanced light harvesting by Au nanoparticles.

Graphene quantum dots as the electrolyte for solid state supercapacitors

PubMed Central

Zhang, Su; Li, Yutong; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng; Hong, Song; Huang, Minglu

2016-01-01

We propose that graphene quantum dots (GQDs) with a sufficient number of acidic oxygen-bearing functional groups such as -COOH and -OH can serve as solution- and solid- type electrolytes for supercapacitors. Moreover, we found that the ionic conductivity and ion-donating ability of the GQDs could be markedly improved by simply neutralizing their acidic functional groups by using KOH. These neutralized GQDs as the solution- or solid-type electrolytes greatly enhanced the capacitive performance and rate capability of the supercapacitors. The reason for the enhancement can be ascribed to the fully ionization of the weak acidic oxygen-bearing functional groups after neutralization. PMID:26763275

Polyethylene glycol-electrolyte solution (PEG-ES)

MedlinePlus

... electrolytes to prevent dehydration and other serious side effects that may be caused by fluid loss as ... to your pharmacist or contact your local garbage/recycling department to learn about take-back programs in ...

Improving the Efficiency of 3-D Hydrogeological Mixers: Dilution Enhancement Via Coupled Engineering-Induced Transient Flows and Spatial Heterogeneity

NASA Astrophysics Data System (ADS)

Di Dato, Mariaines; de Barros, Felipe P. J.; Fiori, Aldo; Bellin, Alberto

2018-03-01

Natural attenuation and in situ oxidation are commonly considered as low-cost alternatives to ex situ remediation. The efficiency of such remediation techniques is hindered by difficulties in obtaining good dilution and mixing of the contaminant, in particular if the plume deformation is physically constrained by an array of wells, which serves as a containment system. In that case, dilution may be enhanced by inducing an engineered sequence of injections and extractions from such pumping system, which also works as a hydraulic barrier. This way, the aquifer acts as a natural mixer, in a manner similar to the industrialized engineered mixers. Improving the efficiency of hydrogeological mixers is a challenging task, owing to the need to use a 3-D setup while relieving the computational burden. Analytical solutions, though approximated, are a suitable and efficient tool to seek the optimum solution among all possible flow configurations. Here we develop a novel physically based model to demonstrate how the combined spatiotemporal fluctuations of the water fluxes control solute trajectories and residence time distributions and therefore, the effectiveness of contaminant plume dilution and mixing. Our results show how external forcing configurations are capable of inducing distinct time-varying groundwater flow patterns which will yield different solute dilution rates.

Rheological observation of glassy dynamics of dilute polymer solutions near the coil-stretch transition in elongational flows.

PubMed

Sridhar, T; Nguyen, D A; Prabhakar, R; Prakash, J Ravi

2007-04-20

It has long been conjectured that the macroscopic dynamics of dilute polymer solutions may exhibit a glasslike slowdown caused by ergodicity breaking, in the vicinity of the coil-stretch transition in elongational flows. We report experimental observations using a filament stretching rheometer that confirm the existence of such glassy states. It is observed that different time-dependent elongational strain-rate profiles lead to a pronounced history dependence and aging effects within a narrow range of strain rates. The results have a direct bearing on the analysis and design of processes employing dilute polymer solutions, such as ink-jet printing, surface coating, and turbulent-drag reduction.

Elucidating the Higher Stability of Vanadium (V) Cations in Mixed Acid Based Redox Flow Battery Electrolytes

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

Vijayakumar, M.; Wang, Wei; Nie, Zimin

2013-11-01

The Vanadium (V) cation structures in mixed acid based electrolyte solution were analysed by density functional theory (DFT) based computational modelling and 51V and 35Cl Nuclear Magnetic Resonance (NMR) spectroscopy. The Vanadium (V) cation exists as di-nuclear [V2O3Cl2.6H2O]2+ compound at higher vanadium concentrations (≥1.75M). In particular, at high temperatures (>295K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl2.6H2O]2+ compound. This chlorine bonded [V2O3Cl2.6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in Vanadium based electrolyte solutions. The combined theoretical and experimental approachmore » reveals that formation of chlorine bonded [V2O3Cl2.6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based Vanadium (V) electrolyte solutions.« less

"excess Heat" during Electrolysis in Platinium /K2CO3/ Nickel Light Water System

NASA Astrophysics Data System (ADS)

Tian, J.; Jin, L. H.; Weng, Z. K.; Song, B.; Zhao, X. L.; Xiao, Z. J.; Chen, G.; Du, B. Q.

2006-02-01

The characteristic variation of heating coefficients (k = ΔT/ΔP°C/W) of Pt(H)-Ni electrolytic system with K2CO3 and Na2CO3 solutions was studied in both situations of electric and electrolytic heating, respectively. The results in equilibrium revealed that there was an obvious difference of k in electrolytic-heating (Δk ≈ 30°C/W, kK2CO3 > kNa2CO3) between these two systems, whereas there was a little difference of k in electric heating (Δk ≈ 2°C/W, kK2CO3 < kNa2CO3 between them. "Excess heat" of about 2.5 × 104 J was produced during electrolysis of K2CO3 solution over 1 day of electrolysis. The differences of K2CO3 solution after electrolysis in the potential of hydrogen value (ΔpH = 0.15) and in absorbency (ΔA = 0.108) implied that some new Ca2+ might have formed in the electrolytic system.

Surface-charge-governed electrolyte transport in carbon nanotubes

NASA Astrophysics Data System (ADS)

Xue, Jian-Ming; Guo, Peng; Sheng, Qian

2015-08-01

The transport behavior of pressure-driven aqueous electrolyte solution through charged carbon nanotubes (CNTs) is studied by using molecular dynamics simulations. The results reveal that the presence of charges around the nanotube can remarkably reduce the flow velocity as well as the slip length of the aqueous solution, and the decreasing of magnitude depends on the number of surface charges and distribution. With 1-M KCl solution inside the carbon nanotube, the slip length decreases from 110 nm to only 14 nm when the number of surface charges increases from 0 to 12 e. This phenomenon is attributed to the increase of the solid-liquid friction force due to the electrostatic interaction between the charges and the electrolyte particles, which can impede the transports of water molecules and electrolyte ions. With the simulation results, we estimate the energy conversion efficiency of nanofluidic battery based on CNTs, and find that the highest efficiency is only around 30% but not 60% as expected in previous work. Project supported by the National Natural Science Foundation of China (Grant Nos. 11375031 and 11335003).

Determination of the structural properties of the aqueous electrolyte LiCl6H 2 O at the supercooled state using the Reverse Monte Carlo (RMC) simulation

NASA Astrophysics Data System (ADS)

ZIANE, M.; HABCHI, M.; DEROUICHE, A.; MESLI, S. M.; BENZOUINE, F.; KOTBI, M.

2017-03-01

A structural study of an aqueous electrolyte whose experimental results are available. It is a solution of A structural study of an aqueous electrolyte whose experimental results are available. It is a solution LiCl6H 2 O type at supercooled state (162K) contrasted with pure water at room temperature by means of Partial Distribution Functions (PDF) issue from neutron scattering technique. The aqueous electrolyte solution of the chloride lithium LiCl presents interesting properties which is studied by different methods at different concentration and thermodynamical states: This system possesses the property to become a glass through a metastable supercooled state when the temperature decreases. Based on these partial functions, the Reverse Monte Carlo method (RMC) computes radial correlation functions which allow exploring a number of structural features of the system. The purpose of the RMC is to produce a consistent configuration with the experimental data. They are usually the most important in the limit of systematic errors (of unknown distribution).

Fluid and electrolyte disturbances in critically ill patients.

PubMed

Lee, Jay Wook

2010-12-01

Disturbances in fluid and electrolytes are among the most common clinical problems encountered in the intensive care unit (ICU). Recent studies have reported that fluid and electrolyte imbalances are associated with increased morbidity and mortality among critically ill patients. To provide optimal care, health care providers should be familiar with the principles and practice of fluid and electrolyte physiology and pathophysiology. Fluid resuscitation should be aimed at restoration of normal hemodynamics and tissue perfusion. Early goal-directed therapy has been shown to be effective in patients with severe sepsis or septic shock. On the other hand, liberal fluid administration is associated with adverse outcomes such as prolonged stay in the ICU, higher cost of care, and increased mortality. Development of hyponatremia in critically ill patients is associated with disturbances in the renal mechanism of urinary dilution. Removal of nonosmotic stimuli for vasopressin secretion, judicious use of hypertonic saline, and close monitoring of plasma and urine electrolytes are essential components of therapy. Hypernatremia is associated with cellular dehydration and central nervous system damage. Water deficit should be corrected with hypotonic fluid, and ongoing water loss should be taken into account. Cardiac manifestations should be identified and treated before initiating stepwise diagnostic evaluation of dyskalemias. Divalent ion deficiencies such as hypocalcemia, hypomagnesemia and hypophosphatemia should be identified and corrected, since they are associated with increased adverse events among critically ill patients.

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.

Durable electrooptic devices comprising ionic liquids

DOEpatents

Burrell, Anthony K [Los Alamos, NM; Agrawal, Anoop [Tucson, AZ; Cronin,; John, P [Tucson, AZ; Tonazzi, Juan C. L. [Tucson, AZ; Warner, Benjamin P [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM

2009-12-15

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

Durable Electrooptic Devices Comprising Ionic Liquids

DOEpatents

Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

2008-11-11

Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

Factors contributing to inactivation of isolated thylakoid membranes during freezing in the presence of variable amounts of glucose and NaCl.

PubMed Central

Santarius, K A; Giersch, C

1984-01-01

During freezing of isolated spinach thylakoids in sugar/salt solutions, the two solutes affected membrane survival in opposite ways: membrane damage due to increased electrolyte concentration can be prevented by sugar. Calculation of the final concentrations of NaCl or glucose reached in the residual unfrozen portion of the system revealed that the effects of the solutes on membrane activity can be explained in part by colligative action. In addition, the fraction of the residual liquid in the frozen system contributes to membrane injury. During severe freezing in the presence of very low initial solute concentrations, membrane damage drastically increased with a decrease in the volume of the unfrozen solution. Freezing injury under these conditions is likely to be due to mechanical damage by the ice crystals that occupy a very high fraction of the frozen system. At higher starting concentrations of sugar plus salt, membrane damage increased with an increase in the amount of the residual unfrozen liquid. Thylakoid inactivation at these higher initial solute concentrations can be largely attributed to dilution of the membrane fraction, as freezing damage at a given sugar/salt ratio decreased with increasing the thylakoid concentration in the sample. Moreover, membrane survival in the absence of freezing decreased with lowering the temperature, indicating that the temperature affected membrane damage not only via alterations related to the ice formation. From the data it was evident that damage of thylakoid membranes was determined by various individual factors, such as the amount of ice formed, the final concentrations of solutes and membranes in the residual unfrozen solution, the final volume of this fraction, the temperature and the freezing time. The relative contribution of these factors depended on the experimental conditions, mainly the sugar/salt ratio, the initial solute concentrations, and the freezing temperature. PMID:6478028

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors

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

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

An effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic-liquid (IL) electrolytes is reported. Using model electrochemical cells based on two identical onion-like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Also, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

A low-temperature electrolyte for lithium and lithium-ion batteries

NASA Astrophysics Data System (ADS)

Plichta, E. J.; Behl, W. K.

An electrolyte consisting of 1 M solution of lithium hexafluorophosphate in 1:1:1 ethylene carbonate(EC)-dimethyl carbonate(DMC)-ethyl methyl carbonate(EMC) is proposed for low temperature applications of lithium and lithium-ion cells. The new electrolyte has good conductivity and electrochemical stability. Lithium and lithium-ion cells using the new electrolyte were found to be operable at temperatures down to -40°C. The paper also reports on the electrochemical stability of aluminum metal, which is used as a substrate for the positive electrodes in lithium-ion cells, in the new electrolyte.

21 CFR 175.270 - Poly(vinyl fluoride) resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

...(vinyl fluoride) basic resins have an intrinsic viscosity of not less than 0.75 deciliter per gram as determined by ASTM method D1243-79, “Standard Test Method for Dilute Solution Viscosity of Vinyl Chloride... (ASTM method D1243-79, “Standard Test Method for Dilute Solution Viscosity of Vinyl Chloride Polymers...

Aluminum reference electrode

DOEpatents

Sadoway, Donald R.

1988-01-01

A stable reference electrode for use in monitoring and controlling the process of electrolytic reduction of a metal. In the case of Hall cell reduction of aluminum, the reference electrode comprises a pool of molten aluminum and a solution of molten cryolite, Na.sub.3 AlF.sub.6, wherein the electrical connection to the molten aluminum does not contact the highly corrosive molten salt solution. This is accomplished by altering the density of either the aluminum (decreasing the density) or the electrolyte (increasing the density) so that the aluminum floats on top of the molten salt solution.

Behavior of highly diluted electrolytes in strong electric fields-prevention of alumina deposition on grading electrodes in HVDC transmission modules by CO2-induced pH-control.

PubMed

Weber, Immo; Mallick, Bert; Schild, Matthias; Kareth, Sabine; Puchta, Ralph; van Eldik, Rudi

2014-09-15

Alumina deposition on platinum grading electrodes in high voltage direct current (HVDC) transmission modules is an unsolved problem that has been around for more than three decades. This is due to the unavoidable corrosion of aluminum heat sinks that causes severe damage to electrical power plants and losses in the range of a million Euro range per day in power outage. Simple experiments in a representative HV test setup showed that aluminates at concentrations even below 10(-8) mol L(-1) can deposit on anodes through neutralization by protons produced in de-ionized water (κ≤0.15 μS cm(-1)) at 20-35 kV (8 mA) per electrode. In this otherwise electrolyte-poor aqueous environment, the depositions are formed three orders of magnitude below the critical precipitation concentration at pH 7! In the presence of an inert electrolyte such as TMAT (tetramethylammonium-p-toluenesulfonate), at a concentration level just above that of the total dissolved aluminum, no deposition was observed. Deposition can be also prevented by doping with CO2 gas at a concentration level that is magnitudes lower than that of the dissolved aluminum. From an overview of aqueous aluminum chemistry, the mystery of the alumina deposition process and its inhibition by CO2 is experimentally resolved and fully explained by field accumulation and repulsion models in synergism with acid-base equilibria. The extraordinary size of the alumina depositions is accounted for in terms of proton tunneling through "hydrated" alumina, which is supported by quantum chemical calculations. As a consequence, pulse-purging with pure CO2 gas is presented as a technical solution to prevent the deposition of alumina. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilayered composite proton exchange membrane and a process for manufacturing the same

DOEpatents

Santurri, Pasco R; Duvall, James H; Katona, Denise M; Mausar, Joseph T; Decker, Berryinne

2015-05-05

A multilayered membrane for use with fuel cells and related applications. The multilayered membrane includes a carrier film, at least one layer of an undoped conductive polymer electrolyte material applied onto the carrier film, and at least one layer of a conductive polymer electrolyte material applied onto the adjacent layer of polymer electrolyte material. Each layer of conductive polymer electrolyte material is doped with a plurality of nanoparticles. Each layer of undoped electrolyte material and doped electrolyte material may be applied in an alternating configuration, or alternatively, adjacent layers of doped conductive polymer electrolyte material is employed. The process for producing a multilayered composite membrane includes providing a carrier substrate and solution casting a layer of undoped conductive polymer electrolyte material and a layer of conductive polymer electrolyte material doped with nanoparticles in an alternating arrangement or in an arrangement where doped layers are adjacent to one another.

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

Water anomalous thermodynamics, attraction, repulsion, and hydrophobic hydration

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

Cerdeiriña, Claudio A., E-mail: calvarez@uvigo.es; Debenedetti, Pablo G., E-mail: pdebene@princeton.edu

A model composed of van der Waals-like and hydrogen bonding contributions that simulates the low-temperature anomalous thermodynamics of pure water while exhibiting a second, liquid-liquid critical point [P. H. Poole et al., Phys. Rev. Lett. 73, 1632 (1994)] is extended to dilute solutions of nonionic species. Critical lines emanating from such second critical point are calculated. While one infers that the smallness of the water molecule may be a relevant factor for those critical lines to move towards experimentally accessible regions, attention is mainly focused on the picture our model draws for the hydration thermodynamics of purely hydrophobic and amphiphilicmore » non-electrolyte solutes. We first focus on differentiating solvation at constant volume from the corresponding isobaric process. Both processes provide the same viewpoint for the low solubility of hydrophobic solutes: it originates from the combination of weak solute-solvent attractive interactions and the specific excluded-volume effects associated with the small molecular size of water. However, a sharp distinction is found when exploring the temperature dependence of hydration phenomena since, in contrast to the situation for the constant-V process, the properties of pure water play a crucial role at isobaric conditions. Specifically, the solubility minimum as well as enthalpy and entropy convergence phenomena, exclusively ascribed to isobaric solvation, are closely related to water’s density maximum. Furthermore, the behavior of the partial molecular volume and the partial molecular isobaric heat capacity highlights the interplay between water anomalies, attraction, and repulsion. The overall picture presented here is supported by experimental observations, simulations, and previous theoretical results.« less

Advanced Double Layer Capacitor

DTIC Science & Technology

1989-07-01

Membrane and Electrode Assemblies The Nafion electrolyte was introduced into the electrode by two different methods: 1) mixing of the Nafion solution with... electroosmotic transport of water, allows some liquid electrolyte to permeate into the structure, which causes partial flooding. On the basis of these...solution of Nafion 117) was mixed with the RuO x powder. The solvent was then allowed to evaporate and the resulting composite powder was crushed and

A simple model of fluid flow and electrolyte balance in the body

NASA Technical Reports Server (NTRS)

White, R. J.; Neal, L.

1973-01-01

The model is basically a three-compartment model, the three compartments being the plasma, interstitial fluid and cellular fluid. Sodium, potassium, chloride and urea are the only major solutes considered explicitly. The control of body water and electrolyte distribution is affected via drinking and hormone levels. Basically, the model follows the effect of various oral input water loads on solute and water distribution throughout the body.

New electrolyte may increase life of polarographic oxygen sensors

NASA Technical Reports Server (NTRS)

Albright, C. F.

1967-01-01

Electrolyte increases life on oxygen sensors in a polarograph used for measuring the partial pressure of oxygen in a gas mixture. It consists of a solution of lithium chloride, dimethyl acetamide and water.

Composition and particle size of electrolytic copper powders prepared in water-containing dimethyl sulfoxide electrolytes

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul'; Abzhalov, B. S.; Mamyrbekova, Aizhan

2017-07-01

The possibility of the electroprecipitation of copper powder via the cathodic reduction of an electrolyte solution containing copper(II) nitrate trihydrate and dimethyl sulfoxide (DMSO) is shown. The effect electrolysis conditions (current density, concentration and temperature of electrolyte) have on the dimensional characteristics of copper powder is studied. The size and shape of the particles of the powders were determined by means of electron microscopy; the qualitative composition of the powders, with X-ray diffraction.

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

Electrolyte solutions at curved electrodes. II. Microscopic approach

NASA Astrophysics Data System (ADS)

Reindl, Andreas; Bier, Markus; Dietrich, S.

2017-04-01

Density functional theory is used to describe electrolyte solutions in contact with electrodes of planar or spherical shape. For the electrolyte solutions, we consider the so-called civilized model, in which all species present are treated on equal footing. This allows us to discuss the features of the electric double layer in terms of the differential capacitance. The model provides insight into the microscopic structure of the electric double layer, which goes beyond the mesoscopic approach studied in Paper I. This enables us to judge the relevance of microscopic details, such as the radii of the particles forming the electrolyte solutions or the dipolar character of the solvent particles, and to compare the predictions of various models. Similar to Paper I, a general behavior is observed for small radii of the electrode in that in this limit the results become independent of the surface charge density and of the particle radii. However, for large electrode radii, non-trivial behaviors are observed. Especially the particle radii and the surface charge density strongly influence the capacitance. From the comparison with the Poisson-Boltzmann approach, it becomes apparent that the shape of the electrode determines whether the microscopic details of the full civilized model have to be taken into account or whether already simpler models yield acceptable predictions.

Electrolyte solutions at curved electrodes. II. Microscopic approach.

PubMed

Reindl, Andreas; Bier, Markus; Dietrich, S

2017-04-21

Density functional theory is used to describe electrolyte solutions in contact with electrodes of planar or spherical shape. For the electrolyte solutions, we consider the so-called civilized model, in which all species present are treated on equal footing. This allows us to discuss the features of the electric double layer in terms of the differential capacitance. The model provides insight into the microscopic structure of the electric double layer, which goes beyond the mesoscopic approach studied in Paper I. This enables us to judge the relevance of microscopic details, such as the radii of the particles forming the electrolyte solutions or the dipolar character of the solvent particles, and to compare the predictions of various models. Similar to Paper I, a general behavior is observed for small radii of the electrode in that in this limit the results become independent of the surface charge density and of the particle radii. However, for large electrode radii, non-trivial behaviors are observed. Especially the particle radii and the surface charge density strongly influence the capacitance. From the comparison with the Poisson-Boltzmann approach, it becomes apparent that the shape of the electrode determines whether the microscopic details of the full civilized model have to be taken into account or whether already simpler models yield acceptable predictions.

Characterization of stainless steel surface processed using electrolytic oxidation and titanium complex ion solution

NASA Astrophysics Data System (ADS)

Kang, Yubin; Choi, Jaeyoung; Park, Jinju; Kim, Woo-Byoung; Lee, Kun-Jae

2017-09-01

This study attempts to improve the physical and chemical adhesion between metals and ceramics by using electrolytic oxidation and a titanium organic/inorganic complex ion solution on the SS-304 plate. Surface analysis confirmed the existence of the Tisbnd Osbnd Mx bonds formed by the bonding between the metal ions and the Ti oxide at the surface of the pre-processed SS plate, and improved chemical adhesion during ceramic coating was expected by confirming the presence of the carboxylic group. The adhesion was evaluated by using the ceramic coating solution in order to assess the improved adhesion of the SS plate under conditions. The results showed that both the adhesion and durability were largely improved in the sample processed with all the pre-processing steps, thus confirming that the physical and chemical adhesion between metals and ceramics can be improved by enhancing the physical roughness via electrolytic oxidation and pre-processing using a Ti complex ion solution.

Transport and spectroscopic studies of liquid and polymer electrolytes

NASA Astrophysics Data System (ADS)

Bopege, Dharshani Nimali

Liquid and polymer electrolytes are interesting and important materials to study as they are used in Li rechargeable batteries and other electrochemical devices. It is essential to investigate the fundamental properties of electrolytes such as ionic conductivity, diffusion, and ionic association to enhance battery performance in different battery markets. This dissertation mainly focuses on the temperature-dependent charge and mass transport processes and ionic association of different electrolyte systems. Impedance spectroscopy and pulsed field gradient nuclear magnetic resonance spectroscopy were used to measure the ionic conductivity and diffusion coefficients of ketone and acetate based liquid electrolytes. In this study, charge and mass transport in non-aqueous liquid electrolytes have been viewed from an entirely different perspective by introducing the compensated Arrhenius formalism. Here, the conductivity and diffusion coefficient are written as an Arrhenius-like expression with a temperature-dependent static dielectric constant dependence in the exponential prefactor. The compensated Arrhenius formalism reported in this dissertation very accurately describes temperature-dependent conductivity data for acetate and ketone-based electrolytes as well as temperature-dependent diffusion data of pure solvents. We found that calculated average activation energies of ketone-based electrolytes are close to each other for both conductivity and diffusion data (in the range 24-26 kJ/mol). Also, this study shows that average activation energies of acetate-based electrolytes are higher than those for the ketone systems (in the range 33-37 kJ/mol). Further, we observed higher dielectric constants and ionic conductivities for both dilute and concentrated ketone solutions with temperature. Vibrational spectroscopy (Infrared and Raman) was used to probe intermolecular interactions in both polymer and liquid electrolytes, particularly those which contain lithium trifluoromethanesulfonate, LiCF3SO3, abbreviated here as lithium triflate(LiTf). The molar absorption coefficients of nus(SO3), deltas(CF3), and deltas(SO3) vibrational modes of triflate anion in the LiTf-2-pentanone system were found to be 6708+/-89, 5182+/-62, and 189+/-2 kg mol-1 cm-1, respectively using Beer-Lambert law. Our results show that there is strong absorption by nu s(SO3) mode and weak absorption by deltas(CF 3) mode. Also, the absorptivity of each mode is independent of the ionic association with Li ions. This work allows for the direct quantitative comparison of calculated concentrations in different samples and different experimental conditions. In addition, this dissertation reports the temperature-dependent vibrational spectroscopic studies of pure poly(ethylene oxide) and LiTf-poly(ethylene oxide) complexes. A significant portion of this dissertation focuses on crystallographic studies of ketone-salt (LiTf:2-pentanone and NaTf:2-hexanone) and amine-acid (diethyleneamine: H3PO4, N,N'-dimethylethylenediamine:H 3PO4, and piperazine:H3PO4) systems. Here, sodium trifluoromethanesulfonate, NaCF3SO3 is abbreviated as NaTf. As model compounds, these systems provide valuable information about ion-ion interactions, which are helpful for understanding complex polymer systems. During this study, five crystal structures were solved using single X-ray diffractometry, and their vibrational modes were studied in the mid-infrared region. In the secondary amine/phosphoric acid systems, the nature of hydrogen-bonding network was examined.

Influence of electrolytes (TEABF4 and TEMABF4) on electrochemical performance of graphite oxide derived from needle coke.

PubMed

Yang, Sunhye; Kim, Ick-Jun; Choi, In-Sik; Bae, Mi-Kyeong; Kim, Hyun-Soo

2013-05-01

The structure of needle coke was changed to graphite oxide structure after oxidation treatment with 70 wt.% of nitric acid and sodium chlorate (NaClO3), and the inter-layer distance of the oxidized needle coke was expanded to 6.9 angstroms. The first charge profile of the oxidized needle coke-cell with 1.2 M TEMABF4/acetonitrile solution displayed that the intercalation of electrolyte ions into the inter-layer occurred at 1.0 V, which value is lower than 1.3 V of the oxidized needle coke-cell with 1.2 M TEABF4/acetonitrile solution. After first charge/discharge, the cell using TEMABF4 electrolyte exhibited smaller electrode resistance of 0.05 omega, and larger specific volume capacitance of 25.5 F/ml at the two-electrode system in the potential range 0-2.5 V than those of the cell using TEABF4 electrolyte. Compared to the TEABF4 electrolyte, better electrochemical performance of the TEMABF4 electrolyte in the oxidized needle coke may be caused by the smaller cation (TEMA+) size and better ion mobility in the nanopores between inter-layers.

Moderately nonlinear diffuse-charge dynamics under an ac voltage.

PubMed

Stout, Robert F; Khair, Aditya S

2015-09-01

The response of a symmetric binary electrolyte between two parallel, blocking electrodes to a moderate amplitude ac voltage is quantified. The diffuse charge dynamics are modeled via the Poisson-Nernst-Planck equations for a dilute solution of point-like ions. The solution to these equations is expressed as a Fourier series with a voltage perturbation expansion for arbitrary Debye layer thickness and ac frequency. Here, the perturbation expansion in voltage proceeds in powers of V_{o}/(k_{B}T/e), where V_{o} is the amplitude of the driving voltage and k_{B}T/e is the thermal voltage with k_{B} as Boltzmann's constant, T as the temperature, and e as the fundamental charge. We show that the response of the electrolyte remains essentially linear in voltage amplitude at frequencies greater than the RC frequency of Debye layer charging, D/λ_{D}L, where D is the ion diffusivity, λ_{D} is the Debye layer thickness, and L is half the cell width. In contrast, nonlinear response is predicted at frequencies below the RC frequency. We find that the ion densities exhibit symmetric deviations from the (uniform) equilibrium density at even orders of the voltage amplitude. This leads to the voltage dependence of the current in the external circuit arising from the odd orders of voltage. For instance, the first nonlinear contribution to the current is O(V_{o}^{3}) which contains the expected third harmonic but also a component oscillating at the applied frequency. We use this to compute a generalized impedance for moderate voltages, the first nonlinear contribution to which is quadratic in V_{o}. This contribution predicts a decrease in the imaginary part of the impedance at low frequency, which is due to the increase in Debye layer capacitance with increasing V_{o}. In contrast, the real part of the impedance increases at low frequency, due to adsorption of neutral salt from the bulk to the Debye layer.

Separation and concentration of lower alcohols from dilute aqueous solutions

DOEpatents

Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

1991-01-01

A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

2014-06-01

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

Bidentate organophosphorus solvent extraction process for actinide recovery and partition

DOEpatents

Schulz, Wallace W.

1976-01-01

A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

High-throughput ab-initio dilute solute diffusion database.

PubMed

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-07-19

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.

Nonequilibrium mechanisms of weak electrolyte electrification under the action of constant voltage

NASA Astrophysics Data System (ADS)

Stishkov, Yu. K.; Chirkov, V. A.

2016-07-01

The formation of space charge in weak electrolytes, specifically in liquid dielectrics, has been considered. An analytical solution is given to a simplified set of Nernst-Planck equations that describe the formation of nonequilibrium recombination layers in weak electrolytes. This approximate analytical solution is compared with computer simulation data for a complete set of Poisson-Nernst-Planck equations. It has been shown that the current passage in weak electrolytes can be described by a single dimensionless parameter that equals the length of a near-electrode recombination layer divided by the width of the interelectrode gap. The formation mechanism and the structure of charged nonequilibrium near-electrode layers in the nonstationary regime have been analyzed for different injection-to-conduction current ratios. It has been found that almost all charge structures encountered in weak dielectrics can be accounted for by the nonequilibrium dissociation-recombination mechanism of space charge formation.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

PubMed

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface and capillary forces encountered by zinc sulfide microspheres in aqueous electrolyte.

PubMed

Gillies, Graeme; Kappl, Michael; Butt, Hans-Jürgen

2005-06-21

The colloid probe technique was used to investigate the interactions between individual zinc sulfide (ZnS) microspheres and an air bubble in electrolyte solution. Incorporation of zinc ions into the electrolyte solution overcomes the disproportionate zinc ion dissolution and mimics high-volume-fraction conditions common in flotation. Determined interaction forces revealed a distinct lack of long-ranged hydrophobic forces, indicated by the presence of a DLVO repulsion prior to particle engulfment. Single microsphere contact angles were determined from particle-bubble interactions. Contact angles increased with decreasing radii and with surface oxidation. Surface modification by the absorption of copper and subsequently potassium O-ethyldithiocarbonate (KED) reduced repulsive forces and strongly increased contact angles.

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

Solubilization of benomyl for xylem injection in vascular wilt disease control

Treesearch

Percy McWain; Garold F. Gregory; Garold F. Gregory

1971-01-01

Benomyl, in varying amounts, was solubilized in several solvents, thus allowing injection into trees for fungus disease prevention and therapy. A large amount of benomyl can be solubilized in diluted lactic acid. The resulting solution can be infinitely diluted with water without pre-cipitation. These characteristics make it the current solution of choice for our tree...

Dynamics of falling droplet and elongational properties of dilute nonionic surfactant solutions with drag-reducing ability

NASA Astrophysics Data System (ADS)

Tamano, Shinji; Ohashi, Yota; Morinishi, Yohei

2017-05-01

The dynamics of the falling droplet through a nozzle for dilute nonionic surfactant (oleyl-dimethylamine oxide, ODMAO) aqueous solutions with viscoelastic and drag-reducing properties were investigated at different concentrations of ODMAO solutions Cs = 500, 1000, and 1500 ppm by weight. The effects of the flow rate and tube outer diameter on the length of the filament, which was the distance between the tube exit and the lower end of a droplet at the instant when the droplet almost detached from the tube, were clarified by flow visualization measurements by a high-speed video camera. Two types of breaking-off processes near the base of the droplet and within the filament were classified by the Ohnesorge number Oh and the Weber number We. In the regime of the higher Oh and We, the length of the filament became drastically larger at Cs = 1000 and 1500 ppm, whose high spinnability represented the strong viscoelasticity of ODMAO solutions. In the case where the filament was broken up near the lower end of the neck and thinning in time, the thinning of the diameter of the filament was measured by a light-emitting diode micrometer. As for the elasto-capillary thinning of dilute nonionic surfactant solutions, the initial necking process was similar to that of Newtonian fluids and then followed the exponential thinning like polymer solutions. The apparent elongational viscosity of the dilute nonionic surfactant solution was evaluated in the elasto-capillary thinning regime, in which the elongation rate was almost constant. At Cs = 1000 and 1500 ppm, the Trouton ratio, which was the ratio of the apparent elongational viscosity to the shear viscosity, was found to be several orders of magnitude larger than that of Newtonian fluids, while the shear viscosity measured by the capillary viscometer was almost the same order of the Newtonian fluids. The higher elongational property would be closely related to the higher drag-reducing ability of dilute nonionic surfactant solutions.

Thermal Coefficient of Redox Potential of Alkali Metals

NASA Astrophysics Data System (ADS)

Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

2018-05-01

The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Effect of temperature and selected sugars on dilute solution properties of two hairless canary seed starches compared with wheat starch.

PubMed

Heydari, Ali; Razavi, Seyed Mohammad Ali; Irani, Mahdi

2018-03-01

In this paper, influence of temperature (25, 35, 45 and 55°C) and sugars (sucrose and lactose) at different concentrations (0, 5, 10 and 15%) on some molecular parameters of starches from two canary seed varieties (C05041 and CDC Maria) in the dilute regime were investigated in comparison to wheat starch (WS). The results indicated that the intrinsic viscosity ([η]) values of C05041, CDC Maria and WS samples were 1.42, 1.46 and 1.70dl/g at 25°C, respectively. Intrinsic viscosity of selected starches decreased with an increase in temperature, but the effect of high temperatures were somewhat unnoticeable. By increasing the sugar concentration, intrinsic viscosity of each starch solution significantly decreased in comparison with the value determined for sugar free solution. Lactose had more pronounced effect on the intrinsic viscosity reduction of CDC Maria starch and WS at 25°C and 35°C compared with sucrose (P<0.05). But at 55°C, the effect of increasing sucrose on decreasing of [η] of CDC Maria and WS samples were more considerable. The shape factor of starch samples at 25°C were spherical, but increasing temperature from 25°C to 55°C, CSSs and WS samples took an ellipsoidal shape. The interaction between starches and solvent/cosolutes is the predominant factors determining their functional properties in food systems. One of the aspects can help to understand the characteristic of biopolymers such as starches is determination of their dilute solution properties as a function of common additives which are used in food systems. As a matter of fact, dilute solution properties can help to understand the potential applications of biopolymers in food and non-food application. Attentively, dilute solution properties would give some priceless information about molecular properties, biopolymer behavior and its interaction with copolymers. For instance, intrinsic viscosity provides deep insight into fundamental properties of the solute and its interaction with the solvent and/or cosolutes, conformation of flexible chains. There are many studies which investigated the effect of different parameters such as temperature, salts and sugars on dilute solution properties of hydrocolloids, especially gums. Regrettably, few researches scrutinized the influence of various cosolutes on dilute solution properties of starch. Then in this paper, we studied the dilute solution properties of starches from two canary seed varieties (C05041 and CDC Maria), as a new potential source of starch, (CSSs), in comparison to wheat starch at different experimental conditions (temperatures and sugars at different concentrations) in order to shed light on its behavior in real system in comparison to wheat starch. Because of the unique properties of wheat starch, comparison of canary seed starch with wheat starch in dilute regime can help to having better vision of this new starch source. Overall, the intrinsic viscosity, coil dimensions (R coil and V coil ), swollen specific volume, shape function, and hydration parameter of selected starches were determined affected by temperature and sugars concentration treatments. The importance of these results will be cleared when taking into account the influence of crucial additives generally used in food systems, for instance, different sugars and/or frequent processing parameters such as temperature on rheological and functional properties. Copyright © 2017 Elsevier B.V. All rights reserved.

Ordered transport and identification of particles

DOEpatents

Shera, E.B.

1993-05-11

A method and apparatus are provided for application of electrical field gradients to induce particle velocities to enable particle sequence and identification information to be obtained. Particle sequence is maintained by providing electroosmotic flow for an electrolytic solution in a particle transport tube. The transport tube and electrolytic solution are selected to provide an electroosmotic radius of >100 so that a plug flow profile is obtained for the electrolytic solution in the transport tube. Thus, particles are maintained in the same order in which they are introduced in the transport tube. When the particles also have known electrophoretic velocities, the field gradients introduce an electrophoretic velocity component onto the electroosmotic velocity. The time that the particles pass selected locations along the transport tube may then be detected and the electrophoretic velocity component calculated for particle identification. One particular application is the ordered transport and identification of labeled nucleotides sequentially cleaved from a strand of DNA.

Chloride supporting electrolytes for all-vanadium redox flow batteries.

PubMed

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

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.

Nanoporous carbon tunable resistor/transistor and methods of production thereof

DOEpatents

Biener, Juergen; Baumann, Theodore F; Dasgupta, Subho; Hahn, Horst

2014-04-22

In one embodiment, a tunable resistor/transistor includes a porous material that is electrically coupled between a source electrode and a drain electrode, wherein the porous material acts as an active channel, an electrolyte solution saturating the active channel, the electrolyte solution being adapted for altering an electrical resistance of the active channel based on an applied electrochemical potential, wherein the active channel comprises nanoporous carbon arranged in a three-dimensional structure. In another embodiment, a method for forming the tunable resistor/transistor includes forming a source electrode, forming a drain electrode, and forming a monolithic nanoporous carbon material that acts as an active channel and selectively couples the source electrode to the drain electrode electrically. In any embodiment, the electrolyte solution saturating the nanoporous carbon active channel is adapted for altering an electrical resistance of the nanoporous carbon active channel based on an applied electrochemical potential.

Ordered transport and identification of particles

DOEpatents

Shera, E. Brooks

1993-01-01

A method and apparatus are provided for application of electrical field gradients to induce particle velocities to enable particle sequence and identification information to be obtained. Particle sequence is maintained by providing electroosmotic flow for an electrolytic solution in a particle transport tube. The transport tube and electrolytic solution are selected to provide an electroosmotic radius of >100 so that a plug flow profile is obtained for the electrolytic solution in the transport tube. Thus, particles are maintained in the same order in which they are introduced in the transport tube. When the particles also have known electrophoretic velocities, the field gradients introduce an electrophoretic velocity component onto the electroosmotic velocity. The time that the particles pass selected locations along the transport tube may then be detected and the electrophoretic velocity component calculated for particle identification. One particular application is the ordered transport and identification of labeled nucleotides sequentially cleaved from a strand of DNA.

Rate of Bubble Coalescence following Quasi-Static Approach: Screening and Neutralization of the Electric Double Layer

PubMed Central

Katsir, Yael; Marmur, Abraham

2014-01-01

Air-bubble coalescence in aqueous electrolytic solutions, following quasi-static approach, was studied in order to understand its slow rate in purified water and high rate in electrolytic solutions. The former is found to be due to surface charges, originating from the speciation of dissolved CO2, which sustain the electric double layer repulsion. Rapid coalescence in electrolytic solutions is shown to occur via two different mechanisms: (1) neutralization of the carbonaceous, charged species by acids; or (2) screening of the repulsive charge effects by salts and bases. The results do not indicate any ion specificity. They can be explained within the DLVO theory for the van der Waals and electric double layer interactions between particles, in contrast to observations of coalescence following dynamic approach. The present conclusions should serve as a reference point to understanding the dynamic behavior. PMID:24589528

Responsive Copolymers for Enhanced Petroleum Recovery

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

McCormick, C.; Hester, R.

The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

Thermal and electrochemical properties of nonflammable electrolyte solutions containing fluorinated alkylphosphates for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Todorov, Yanko Marinov; Aoki, Masahiro; Mimura, Hideyuki; Fujii, Kenta; Yoshimoto, Nobuko; Morita, Masayuki

2016-11-01

Nonflammable organic electrolyte solutions containing fluorinated alkylphosphates (FAP) have been examined as safer electrolytes for lithium-ion batteries (LIB). Although the ionic conductivity of LiPF6 in neat tris(2,2,2-trifluoroethyl)phosphate (TFEP) solvent is very low, it increases upon the addition of alkyl carbonates such as ethylene carbonate (EC) and fluoroethylene carbonate (4-fluoro-2-oxo-1,3-dioxolane, FEC). A specific conductivity of 1 mS cm-1 or higher was obtained at room temperature for the system containing proper amounts of the carbonates and 0.5 M (mol dm-3) LiPF6. A conventional mixed alkylcarbonate-based solution containing LiPF6 showed a sign of considerable exothermic reactions on the differential scanning calorimetry (DSC) response below 300 °C. However, the LiPF6/TFEP solution showed no significant exothermic response up to 400 °C, even in the presence of charged LiCoO2 (LCO) positive electrode. The addition of an alkylcarbonate to the LiPF6/TFEP solution produced an exothermic response as a result of the thermal decomposition of the carbonate over the charged LCO. However, the temperature at which the exothermic reaction starts was significantly higher in the system containing FEC than that containing EC. The thermal analysis results suggested that the LiPF6/FEC + TFEP combination could work as a safer electrolyte system in LIB under severe conditions.

Excited state intramolecular charge transfer reaction in nonaqueous electrolyte solutions: Temperature dependence

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

Pradhan, Tuhin; Gazi, Harun Al Rasid; Biswas, Ranjit

2009-08-07

Temperature dependence of the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in ethyl acetate (EA), acetonitrile (ACN), and ethanol at several concentrations of lithium perchlorate (LiClO{sub 4}) has been investigated by using the steady state and time resolved fluorescence spectroscopic techniques. The temperature range considered is 267-343 K. The temperature dependent spectral peak shifts and reaction driving force (-{Delta}G{sub r}) in electrolyte solutions of these solvents can be explained qualitatively in terms of interaction between the reactant molecule and ion-atmosphere. Time resolved studies indicate that the decay kinetics of P4C is biexponential, regardless of solvents, LiClO{sub 4} concentrations,more » and temperatures considered. Except at higher electrolyte concentrations in EA, reaction rates in solutions follow the Arrhenius-type temperature dependence where the estimated activation energy exhibits substantial electrolyte concentration dependence. The average of the experimentally measured activation energies in these three neat solvents is found to be in very good agreement with the predicted value based on data in room temperature solvents. While the rate constant in EA shows a electrolyte concentration induced parabolic dependence on reaction driving force (-{Delta}G{sub r}), the former in ethanol and ACN increases only linearly with the increase in driving force (-{Delta}G{sub r}). The data presented here also indicate that the step-wise increase in solvent reorganization energy via sequential addition of electrolyte induces the ICT reaction in weakly polar solvents to crossover from the Marcus inverted region to the normal region.« less

Nanosized solvent superstructures in ultramolecular aqueous dilutions: twenty years' research using water proton NMR relaxation.

PubMed

Demangeat, Jean-Louis

2013-04-01

proton nuclear magnetic resonance (NMR) relaxation times T1, T2, T1/T2 are sensitive to motion and organization of water molecules. Especially, increase in T1/T2 reflects a higher degree of structuring. My purpose was to look at physical changes in water in ultrahigh aqueous dilutions. Samples were prepared by iterative centesimal (c) dilution with vigorous agitation, ranging between 3c and 24c (Avogadro limit 12c). Solutes were silica-lactose, histamine, manganese-lactose. Solvents were water, NaCl 0.15 M or LiCl 0.15 M. Solvents underwent strictly similar, simultaneous dilution/agitation, for each level of dilution, as controls. NMR relaxation was studied within 0.02-20 MHz. No changes were observed in controls. Increasing T1 and T1/T2 were found in dilutions, which persisted beyond 9c (manganese-lactose), 10c (histamine) and 12c (silica-lactose). For silica-lactose in LiCl, continuous decrease in T2 with increase in T1/T2 within the 12c-24c range indicated growing structuring of water despite absence of the initial solute. All changes vanished after heating/cooling. These findings were interpreted in terms of nanosized (>4-nm) supramolecular structures involving water, nanobubbles and ions, if any. Additional study of low dilutions of silica-lactose revealed increased T2 and decreased T1/T2 compared to solvent, within the 10(-3)-10(-6) range, reflecting transient solvent destructuring. This could explain findings at high dilution. Proton NMR relaxation demonstrated modifications of the solvent throughout the low to ultramolecular range of dilution. The findings suggested the existence of superstructures that originate stereospecifically around the solute after an initial destructuring of the solvent, developing more upon dilution and persisting beyond 12c. Copyright © 2013 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

Olfactory Impact of Higher Alcohols on Red Wine Fruity Ester Aroma Expression in Model Solution.

PubMed

Cameleyre, Margaux; Lytra, Georgia; Tempere, Sophie; Barbe, Jean-Christophe

2015-11-11

This study focused on the impact of five higher alcohols on the perception of fruity aroma in red wines. Various aromatic reconstitutions were prepared, consisting of 13 ethyl esters and acetates and 5 higher alcohols, all at the average concentrations found in red wine. These aromatic reconstitutions were prepared in several matrices. Sensory analysis revealed the interesting behavior of certain compounds among the five higher alcohols following their individual addition or omission. The "olfactory threshold" of the fruity pool was evaluated in several matrices: dilute alcohol solution, dilute alcohol solution containing 3-methylbutan-1-ol or butan-1-ol individually, and dilute alcohol solution containing the mixture of five higher alcohols, blended together at various concentrations. The presence of 3-methylbutan-1-ol or butan-1-ol alone led to a significant decrease in the "olfactory threshold" of the fruity reconstitution, whereas the mixture of alcohols raised the olfactory threshold. Sensory profiles highlighted changes in the perception of fruity nuances in the presence of the mixture of higher alcohols, with specific perceptive interactions, including a relevant masking effect on fresh- and jammy-fruit notes of the fruity mixture in both dilute alcohol solution and dearomatized red wine matrices. When either 3-methylbutan-1-ol or butan-1-ol was added to the fruity reconstitution in dilute alcohol solution, an enhancement of butyric notes was reported with 3-methylbutan-1-ol and fresh- and jammy-fruit with butan-1-ol. This study, the first to focus on the impact of higher alcohols on fruity aromatic expression, revealed that these compounds participate, both quantitatively and qualitatively, in masking fruity aroma perception in a model fruity wine mixture.

Paper-based microfluidic system for tear electrolyte analysis† †We declare no competing financial interests. ‡ ‡Electronic supplementary information (ESI) available: Microscopic images of G1 paper and G41 paper under brightfield; optimization of CO2 laser radiation fluence and beam speed for ablating filter paper-G1; photographs of DI water diffusion in microfluidic channels with different lengths, different widths, different viscosities of fluid and different numbers of channels; fluorescence intensity readouts of Na+ and K+ ions with varied concentrations of fluorescent probes; effect of variations in temperature on fluorescence intensity; photographs of DMSO on G1 paper dried in the air; calibration curves of electrolyte sensing on G1 paper using microplate reader measurement; calculation of sensitivity of the fluorescent sensors based on International Union of Pure and Applied Chemistry (IUPAC) guidelines; quantification of ion interference in buffer solution and artificial tear fluid; light attenuation of LED lights using different optical filters; the design of the sample collection device and its potential clinical use; calibration curves of electrolyte sensors using the paper-based microfluidic system; quantifications of evaporation effect on sampling process; design of the sample collection device and its potential clinical use; batch-to-batch variation experiments; equation for background subtraction; movies of sample collection and measurements. See DOI: 10.1039/c6lc01450j Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.

PubMed Central

Jiang, Nan; Tamayol, Ali; Ruiz-Esparza, Guillermo U.; Zhang, Yu Shrike; Medina-Pando, Sofía; Gupta, Aditi; Wolffsohn, James S.; Butt, Haider; Khademhosseini, Ali

2017-01-01

The analysis of tear constituents at point-of-care settings has a potential for early diagnosis of ocular disorders such as dry eye disease, low-cost screening, and surveillance of at-risk subjects. However, current minimally-invasive rapid tear analysis systems for point-of-care settings have been limited to assessment of osmolarity or inflammatory markers and cannot differentiate between dry eye subclassifications. Here, we demonstrate a portable microfluidic system that allows quantitative analysis of electrolytes in the tear fluid that is suited for point-of-care settings. The microfluidic system consists of a capillary tube for sample collection, a reservoir for sample dilution, and a paper-based microfluidic device for electrolyte analysis. The sensing regions are functionalized with fluorescent crown ethers, o-acetanisidide, and seminaphtorhodafluor that are sensitive to mono- and divalent electrolytes, and their fluorescence outputs are measured with a smartphone readout device. The measured sensitivity values of Na+, K+, Ca2+ ions and pH in artificial tear fluid were matched with the known ion concentrations within the physiological range. The microfluidic system was tested with samples having different ionic concentrations, demonstrating the feasibility for the detection of early-stage dry eye, differential diagnosis of dry eye sub-types, and their severity staging. PMID:28207920

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M.; Ratnakumar, B.; Greenbaum, S.; Surampudi, S.

1998-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (<-20 degrees Celcius).

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, Terje A.

1985-01-01

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Method of synthesizing polymers from a solid electrolyte

DOEpatents

Skotheim, T.A.

1984-10-19

A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

Opalescence in monoclonal antibody solutions and its correlation with intermolecular interactions in dilute and concentrated solutions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2015-04-01

Opalescence indicates physical instability of a formulation because of the presence of aggregates or liquid-liquid phase separation in solution and has been reported for monoclonal antibody (mAb) formulations. Increased solution opalescence can be attributed to attractive protein-protein interactions (PPIs). Techniques including light scattering, AUC, or membrane osmometry are routinely employed to measure PPIs in dilute solutions, whereas opalescence is seen at relatively higher concentrations, where both long- and short-range forces contribute to overall PPIs. The mAb molecule studied here shows a unique property of high opalescence because of liquid-liquid phase separation. In this study, opalescence measurements are correlated to PPIs measured in diluted and concentrated solutions using light scattering (kD ) and high-frequency rheology (G'), respectively. Charges on the molecules were calculated using zeta potential measurements. Results indicate that high opalescence and phase separation are a result of the attractive interactions in solution; however, the presence of attractive interactions do not always imply phase separation. Temperature dependence of opalescence suggests that thermodynamic contribution to opalescence is significant and Tcloud can be utilized as a potential tool to assess attractive interactions in solution. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Light emission from organic single crystals operated by electrolyte doping

NASA Astrophysics Data System (ADS)

Matsuki, Keiichiro; Sakanoue, Tomo; Yomogida, Yohei; Hotta, Shu; Takenobu, Taishi

2018-03-01

Light-emitting devices based on electrolytes, such as light-emitting electrochemical cells (LECs) and electric double-layer transistors (EDLTs), are solution-processable devices with a very simple structure. Therefore, it is necessary to apply this device structure into highly fluorescent organic materials for future printed applications. However, owing to compatibility problems between electrolytes and organic crystals, electrolyte-based single-crystal light-emitting devices have not yet been demonstrated. Here, we report on light-emitting devices based on organic single crystals and electrolytes. As the fluorescent materials, α,ω-bis(biphenylyl)terthiophene (BP3T) and 5,6,11,12-tetraphenylnaphthacene (rubrene) single crystals were selected. Using ionic liquids as electrolytes, we observed clear light emission from BP3T LECs and rubrene EDLTs.

Study on Latent Heat of Fusion of Ice in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Kumano, Hiroyuki; Asaoka, Tatsunori; Saito, Akio; Okawa, Seiji

In this study, latent heat of fusion of ice in aqueous solutions was measured to understand latent heat of fusion of ice slurries. Propylene glycol, ethylene glycol, ethanol, NaCl and NaNO3 solutions were examined as the aqueous solutions. In the measurement, pure ice was put into the solution, and the temperature variation of the solution due to the melting of the ice was measured. Then, the effective latent heat of fusion was calculated from energy balance equation. When ice melts in solution, the concentration of the solution varies due to the melting of the ice, and dilution heat must be considered. Therefore, the latent heat of fusion of ice in aqueous solutions was predicted by considering the effects of dilution and freezing-point depression. The latent heat of fusion was also measured by differential scanning calorimetry(DSC) to compare the results obtained from the experiments with that obtained by DSC. As the result, it was found that the effective latent heat of fusion of ice decreased with the increase of the concentration of solution, and the effective latent heat of fusion was calculated from latent heat of fusion of pure ice and the effects of freezing-point depression and the dilution heat.

Effects of environment factors on initiation of sperm motility in sea cucumber Apostichopus japonicus (Selenka)

NASA Astrophysics Data System (ADS)

Yu, Li; Shao, Mingyu; Bao, Zhenmin; Hu, Jingjie; Zhang, Zhifeng

2011-06-01

Sperm of sea cucumber Apostichopus japonicus (Selenka) were quiescent in electrolyte NaCl solution and artificial seawater (ASW) and nonelectrolyte glucose and mannitol solutions when the osmolality was less than 200 mOsm kg-1. The sperm started to be motile as a result of increased osmolality, indicating an osmolality-dependent initiation of sperm motility in sea cucumber. After a brief incubation in hypotonic NaCl and glucose solutions with osmolalities of 200 and 400 mOsm kg-1, sperm lost partial motile ability. Sperm became immobilized when pH was 6.0 in NaCl, glucose and mannitol solutions, suggesting that an H+ release is involved in sperm activation. The decreased pH had no effect on the percentage of motile sperm in ASW, whereas it delayed the time period to reach the maximum motility (motilitymax). Extracellular Ca2+ in electrolyte solutions was not essential for motility stimulation but shortened the time of reaching motilitymax. When Ca2+ was mixed in nonelectrolyte solutions the sperm motility was completely suppressed. The K+ channel blocker, quinine, suppressed the sperm motility in electrolyte solution, showing a possible involvement of K+ transport in the process. High K+ concentration did not affect the sperm motility in NaCl solution, but decreased it in ASW and almost entirely suppressed it in nonelectrolyte solutions. The different effects of pH and K+ in ASW and NaCl solution indicate that external ions may also regulate sperm motility.

Aluminum reference electrode

DOEpatents

Sadoway, D.R.

1988-08-16

A stable reference electrode is described for use in monitoring and controlling the process of electrolytic reduction of a metal. In the case of Hall cell reduction of aluminum, the reference electrode comprises a pool of molten aluminum and a solution of molten cryolite, Na[sub 3]AlF[sub 6], wherein the electrical connection to the molten aluminum does not contact the highly corrosive molten salt solution. This is accomplished by altering the density of either the aluminum (decreasing the density) or the electrolyte (increasing the density) so that the aluminum floats on top of the molten salt solution. 1 fig.

A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

PubMed Central

Feng, Yan; Liu, Hui; Yang, Jun

2017-01-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

Stability of parallel electroosmotic flow subject to an axial modulated electric field

NASA Astrophysics Data System (ADS)

Suresh, Vinod; Homsy, George

2001-11-01

The stability of parallel electroosmotic flow in a micro-channel subjected to an AC electric field is studied. A spatially uniform time harmonic electric field is applied along the length of a two-dimensional micro-channel containing a dilute electrolytic solution, resulting in a time periodic parallel flow. The top and bottom walls of the channel are maintained at constant potential. The base state ion concentrations and double layer potential are determined using the Poisson-Boltzmann equation in the Debye-Hückel approximation. Experiments by other workers (Santiago et. al., unpublished) have shown that such a system can exhibit instabilities that take the form of mixing motion occurring in the bulk flow outside the double layer. It is shown that such instabilities can potentially result from the coupling of disturbances in the ion concentrations or electric potential to the base state velocity or ion concentrations, respectively. The stability boundary of the system is determined using Floquet theory and its dependence on the modulation frequency and amplitude of the axial electric field is studied.

A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

PubMed

Feng, Yan; Liu, Hui; Yang, Jun

2017-06-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

Anodic stripping voltammetry with carbon paste electrodes for rapid Ag(I) and Cu(II) determinations.

PubMed

Labar, C; Lamberts, L

1997-05-01

The simultaneous determination of silver(I) and copper(II) is realized for the routine analysis of trace levels of these elements by anodic stripping voltammetry (ASV) at the carbon paste electrode (CPE). The electrochemical response is studied in 14 different supporting electrolytes, ranging from acidic solutions (pH 0.1) to neutral and basic (pH 9.7) media, and the parameters governing electrodeposition and stripping steps are characterized for each medium by the use of pseudo-voltammograms. Comparison between different modes of matter transport mechanisms is also given. The dynamic range of the method is 0.05 to 150 mug 1(-1) Ag(I) in the majority of the media studied and can be extended to 400 mug l(-1) in selected media, with a general reproducibility in the +/- 2% range for five replicate measurements. The total analysis time lies between approximately 30 s and 10 min. Activation of the CPE surface has been studied, but this pretreatment is demonstrated to be unfavourable and is replaced by a simpler unique 'cleaning' procedure of dipping the CPE in diluted nitric acid.

Photocatalytic effect of anodic titanium oxide nanotubes on various cell culture media

NASA Astrophysics Data System (ADS)

Yu, Chun-Kang; Hu, Kan-Hung; Wang, Shing-Hoa; Hsu, Todd; Tsai, Huei-Ting; Chen, Chien-Chon; Liu, Shiu-Mei; Lin, Tai-Yuan; Chen, Chin-Hsing

2011-02-01

The use of titanium dioxide (TiO2) in photodynamic therapy for the treatment of cancer cells has been proposed following studies of cultured cancer cells. In this work, an ordered channel array of anodic titanium oxide (ATO) was fabricated by anodizing titanium foil. The ATO layer of nanotubes with diameters of 100 nm was made in NH4F electrolyte by anodization. The photocatalytic effect of ATO was examined on various culture media by ultraviolet A (UV-A) (366 nm) irradiation. After UV-A irradiation of the ATO layer, redox potential of Tris-HCl buffer (pH 7.5) and dilute acrylamide solution increased instantaneously. The redox potential of the serum-containing RPMI1640 medium also increased dramatically, while that of serum-containing MEM and DMEM media increased slightly. The UVA-induced high redox potential was correlated with the greater ability to break down plasmid DNA strands. These phenomena suggest that a culture medium, such as RPMI1640, with a greater ability to produce free radical may be associated with a stronger photocatalytic effect of ATO on cultured cancer cells reported previously.

Triple-Label β Liquid Scintillation Counting

PubMed Central

Bukowski, Thomas R.; Moffett, Tyler C.; Revkin, James H.; Ploger, James D.; Bassingthwaighte, James B.

2010-01-01

The detection of radioactive compounds by liquid scintillation has revolutionized modern biology, yet few investigators make full use of the power of this technique. Even though multiple isotope counting is considerably more difficult than single isotope counting, many experimental designs would benefit from using more than one isotope. The development of accurate isotope counting techniques enabling the simultaneous use of three β-emitting tracers has facilitated studies in our laboratory using the multiple tracer indicator dilution technique for assessing rates of transmembrane transport and cellular metabolism. The details of sample preparation, and of stabilizing the liquid scintillation spectra of the tracers, are critical to obtaining good accuracy. Reproducibility is enhanced by obtaining detailed efficiency/quench curves for each particular set of tracers and solvent media. The numerical methods for multiple-isotope quantitation depend on avoiding error propagation (inherent to successive subtraction techniques) by using matrix inversion. Experimental data obtained from triple-label β counting illustrate reproducibility and good accuracy even when the relative amounts of different tracers in samples of protein/electrolyte solutions, plasma, and blood are changed. PMID:1514684

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

DOE PAGES

Liu, Yiqun; Li, Chen; Liu, Cong; ...

2018-04-24

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

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

Liu, Yiqun; Li, Chen; Liu, Cong

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Cathodic Corrosion of a Bulk Wire to Nonaggregated Functional Nanocrystals and Nanoalloys

PubMed Central

2018-01-01

A key enabling step in leveraging the properties of nanoparticles (NPs) is to explore new, simple, controllable, and scalable nanotechnologies for their syntheses. Among “wet” methods, cathodic corrosion has been used to synthesize catalytic aggregates with some control over their size and preferential faceting. Here, we report on a modification of the cathodic corrosion method for producing a range of nonaggregated nanocrystals (Pt, Pd, Au, Ag, Cu, Rh, Ir, and Ni) and nanoalloys (Pt50Au50, Pd50Au50, and AgxAu100–x) with potential for scaling up the production rate. The method employs poly(vinylpyrrolidone) (PVP) as a stabilizer in an electrolyte solution containing nonreducible cations (Na+, Ca2+), and cathodic corrosion of the corresponding wires takes place in the electrolyte under ultrasonication. The ultrasonication not only promotes particle–PVP interactions (enhancing NP dispersion and diluting locally high NP concentration) but also increases the production rate by a factor of ca. 5. Further increase in the production rate can be achieved through parallelization of electrodes to construct comb electrodes. With respect to applications, carbon-supported Pt NPs prepared by the new method exhibit catalytic activity and durability for methanol oxidation comparable or better than the commercial benchmark catalyst. A variety of AgxAu100–x nanoalloys are characterized by ultraviolet–visible absorption spectroscopy and high-resolution transmission electron microscopy. The protocol for NP synthesis by cathodic corrosion should be a step toward its further use in academic research as well as in its practical upscaling. PMID:29446912

Electrochemical performance of C4O6H4KNa aqueous electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Jianqiang; Song, Senyang; Chen, Yanzheng; Huang, Siyun; Li, Ping; Luo, Heming

2018-06-01

The paper is devoted in the study of the simple method to study the performance of aqueous electrolytes, whereas the custom-made FBNC-700 (FB represents FAC-brown, N represents "nitrogen-self-doped," C represents mesoporous-carbon materials, and 700 represents carbonization temperature.) was utilized as the electrode material, where the C4O6H4KNa solution was utilized as an aqueous electrolyte. The polarization curves was be used in the three-electrode system to conduct the voltage window preliminary selection of the C4O6H4KNa solution, the voltage window was 1.3 V (-0.8 V to 0.5 V). The concentration had minimal effects on the voltage window. The method is faster and more efficient way to study the performance of aqueous electrolytes for supercapacitors. In the 2 M C4O6H4KNa solution, the FBNC-700 displayed a 97 F g-1 specific capacitance at the current density of 0.5 A g-1 in the two-electrodes tests. Also, following 5000 cycles at a current density of 1 A g-1, the FBNC-700 had good stability with 76.22% capacitance retention.

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films

NASA Astrophysics Data System (ADS)

Ren, Jianjun; Zuo, Yu

2012-11-01

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films were studied. The voltage-time response for galvanostatic anodization of aluminum in malonic acid solution exhibits a conventional three-stage feature but the formation voltage is much higher. With the increase of electrolyte concentration, the electrolyte viscosity increases simultaneously and the high viscosity decreases the film growth rate. With the concentration increase of the malonic acid electrolyte, the critical current density that initiates local "burning" on the sample surface decreases. For malonic acid anodization, the field-assisted dissolution on the oxide surface is relatively weak and the nucleation of pores is more difficult, which results in greater barrier layer thickness and larger cell dimension. The embryo of the porous structure of anodic film has been created within the linear region of the first transient stage, and the definite porous structure has been established before the end of the first transient stage. The self-ordering behavior of the porous film is influenced by the electrolyte concentration, film thickness and the applied current density. Great current density not only improves the cell arrangement order but also brings about larger cell dimension.

Motor-mediated microtubule self-organization in dilute and semi-dilute filament solutions.

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

Swaminathan, S.; Ziebert, F.; Aranson, I. S.

We study molecular motor-induced microtubule self-organization in dilute and semi-dilute filament solutions. In the dilute case, we use a probabilistic model of microtubule interaction via molecular motors to investigate microtubule bundle dynamics. Microtubules are modeled as polar rods interacting through fully inelastic, binary collisions. Our model indicates that initially disordered systems of interacting rods exhibit an orientational instability resulting in spontaneous ordering. We study the existence and dynamic interaction of microtubule bundles analytically and numerically. Our results reveal a long term attraction and coalescing of bundles indicating a clear coarsening in the system; microtubule bundles concentrate into fewer orientations onmore » a slow logarithmic time scale. In semi-dilute filament solutions, multiple motors can bind a filament to several others and, for a critical motor density, induce a transition to an ordered phase with a nonzero mean orientation. Motors attach to a pair of filaments and walk along the pair bringing them into closer alignment. We develop a spatially homogenous, mean-field theory that explicitly accounts for a force-dependent detachment rate of motors, which in turn affects the mean and the fluctuations of the net force acting on a filament. We show that the transition to the oriented state can be both continuous and discontinuous when the force-dependent detachment of motors is important.« less

Investigation of Possible Maillard Reaction Between Acyclovir and Dextrose upon Dilution Prior to Parenteral Administration.

PubMed

Siahi Shadbad, Mohammad Reza; Ghaderi, Faranak; Hatami, Leila; Monajjemzadeh, Farnaz

2016-12-01

In this study the stability of parenteral acyclovir (ACV) when diluted in dextrose (DEX) as large volume intravenous fluid preparation (LVIF) was evaluated and the possible Maillard reaction adducts were monitored in the recommended infusion time. Different physicochemical methods were used to evaluate the Maillard reaction of dextrose with ACV to track the reaction in real infusion condition. Other large volume intravenous fluids were checked regarding the diluted drug stability profile. Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and mass data proved the reaction of glucose with dextrose. A Maillard-specific high performance liquid chromatography (HPLC) method was used to track the reaction in real infusion condition in vitro. The nucleophilic reaction occurred in diluted parenteral preparations of acyclovir in 5% dextrose solutions. The best diluent solution was also selected as sodium chloride and introduced based on drug stability and also its adsorption onto different infusion sets (PVC or non PVC) to provide an acceptable administration protocol in clinical practices. Although, the Maillard reaction was proved and successfully tracked in diluted solutions, and the level of drug loss when diluted in dextrose was reported to be between 0.27 up to 1.03% of the initial content. There was no drug adsorption to common infusion sets. The best diluent for parenteral acyclovir is sodium chloride large volume intravenous fluid.

High-throughput ab-initio dilute solute diffusion database

PubMed Central

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-01-01

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

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

Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

2015-12-08

An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

Long-term stability study of clofarabine injection concentrate and diluted clofarabine infusion solutions.

PubMed

Kaiser, Jeanette; Krämer, Irene

2012-06-01

The aim of this study was to investigate the physicochemical stability of clofarabine (CAFdA) injection concentrate and ready-to-use CAFdA infusion solutions over a prolonged period of 28 days. To determine the stability of CAFdA infusion solutions, the injection concentrate (Evoltra®, 1 mg/mL, Genzyme) was diluted either with 0.9% sodium chloride or 5% glucose infusion solution. The resulting concentrations of 0.2 mg/mL or 0.6 mg/mL, respectively, were chosen to represent the lower and upper limit of the ordinary concentration range. Test solutions were stored under refrigeration (2-8°C) or at room temperature either light protected or exposed to light. CAFdA concentrations and pH values were determined at different time intervals throughout a 28-day storage period. Compatibility of diluted CAFdA infusion solutions (0.1-0.4 mg/mL) with different container materials (polyvinyl chloride (PVC), glass, and polypropylene/polyethylene (PP/PE)) was tested over a 48-h storage period. CAFdA concentrations were measured by a stability-indicating reversed phase high-performance liquid chromatography (HPLC) assay with ultraviolet detection. CAFdA injection concentrate and CAFdA infusion solutions remained physicochemically stable (>90% CAFdA) for 4 weeks. Results are independent of storage conditions, drug concentrations (0.2, 0.6, and 1.0 mg/mL) and diluents (0.9% sodium chloride, 5% glucose infusion solution). Adsorption of CAFdA to container material can be excluded. CAFdA injection concentrate and diluted infusion solutions in commonly used vehicles are stable for at least 28 days either refrigerated or at room temperature. Physicochemical stability favors pharmacy-based centralized preparation. Due to microbiological reasons, strict aseptic handling and storage of the products under refrigeration is recommended.

Engineered Osmosis for Energy Efficient Separations: Optimizing Waste Heat Utilization FINAL SCIENTIFIC REPORT DOE F 241.3

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

NATHAN HANCOCK

2013-01-13

The purpose of this study is to design (i) a stripper system where heat is used to strip ammonia (NH{sub 3}) and carbon dioxide (CO{sub 2}) from a diluted draw solution; and (ii) a condensation or absorption system where the stripped NH{sub 3} and CO{sub 2} are captured in condensed water to form a re-concentrated draw solution. This study supports the Industrial Technologies Program of the DOE Office of Energy Efficiency and Renewable Energy and their Industrial Energy Efficiency Grand Challenge award solicitation. Results from this study show that stimulated Oasys draw solutions composed of a complex electrolyte solution associatedmore » with the dissolution of NH{sub 3} and CO{sub 2} gas in water can successfully be stripped and fully condensed under standard atmospheric pressure. Stripper bottoms NH{sub 3} concentration can reliably be reduced to < 1 mg/L, even when starting with liquids that have an NH{sub 3} mass fraction exceeding 6% to stimulate diluted draw solution from the forward osmosis membrane component of the process. Concentrated draw solution produced by fully condensing the stripper tops was show to exceed 6 M-C with nitrogen-to-carbon (N:C) molar ratios on the order of two. Reducing the operating pressure of the stripper column serves to reduce the partial vapor pressure of both NH{sub 3} and CO{sub 2} in solution and enables lower temperature operation towards integration of industrial low-grade of waste heat. Effective stripping of solutes was observed with operating pressures as low as 100 mbar (3-inHg). Systems operating at reduced pressure and temperature require additional design considerations to fully condense and absorb these constituents for reuse within the Oasys EO system context. Comparing empirical data with process stimulation models confirmed that several key parameters related to vapor-liquid equilibrium and intrinsic material properties were not accurate. Additional experiments and refinement of material property databases within the chosen process stimulation software was required to improve the reliability of process simulations for engineering design support. Data from experiments was also employed to calculate critical mass transfer and system design parameters (such as the height equivalent to a theoretical plate (HETP)) to aid in process design. When measured in a less than optimal design state for the stripping of NH{sub 3} and CO{sub 2} from a simulated dilute draw solution the HETP for one type of commercial stripper packing material was 1.88 ft/stage. During this study it was observed that the heat duty required to vaporize the draw solution solutes is substantially affected by the amount of water boilup also produced to achieve a low NH{sub 3} stripper bottoms concentration specification. Additionally, fluid loading of the stripper packing media is a critical performance parameter that affects all facets of optimum stripper column performance. Condensation of the draw solution tops vapor requires additional process considerations if being conducted in sub-atmospheric conditions and low temperature. Future work will focus on the commercialization of the Oasys EO technology platform for numerous applications in water and wastewater treatment as well as harvesting low enthalpy energy with our proprietary osmotic heat engine. Engineering design related to thermal integration of Oasys EO technology for both low and hig-grade heat applications is underway. Novel thermal recovery processes are also being investigated in addition to the conventional approaches described in this report. Oasys Water plans to deploy commercial scale systems into the energy and zero liquid discharge markets in 2013. Additional process refinement will lead to integration of low enthalpy renewable heat sources for municipal desalination applications.« less

Compatibility of electrolytically produced sodium hypochlorite solutions on long- term implanted dialysis catheters.

PubMed

Mishkin, G J

2007-01-01

More than 20% of the world's population use a catheter for dialysis, despite guidelines limiting their use. Although the structure and design of the catheters differ by manufacturer, the material used in central venous catheters and peritoneal dialysis catheters are the same across manufacturers. Given the long-term use of these catheters in the dialysis population, the good compatibility of the antiseptics and disinfectants used on the catheters is imperative to prevent failure and cracking of the catheter material. Tensile strengths of commercially available catheters were measured after exposure to commonly used disinfectants. The tensile strength was then compared between the catheters by analyzing the displacement vs. force (N) curves produced during the evaluation. A total of 44 catheter lumens were evaluated. The electrolytically produced sodium hypochlorite solution, Alcavis 50/ExSept Plus, was the only solution shown to be compatible with all three catheter materials resulting in a deviation of less than 10% for each of the different catheter types. Electrolytically produced sodium hypochlorite solutions were the only solutions in this study that did not alter the physical properties of any of the catheters after long-term exposure.

Separations by supported liquid membrane cascades

DOEpatents

Danesi, Pier R.

1986-01-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid membranes. The membranes contain alternatively a liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solutions and the supported liquid membranes are arranged in such a way to provide a continuous process which leads to the continuous enrichment of the species which show the highest permeability coefficients. By virtue of the very high number of stages which can be arranged, even chemical species having very similar chemical behavior (and consequently very similar permeability coefficients) can be completely separated. The invention also provide a way to concentrate the separated species.

Process of concentrating ethanol from dilute aqueous solutions thereof

DOEpatents

Oulman, C.S.; Chriswell, C.D.

1981-07-07

Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%. 5 figs.

Process of concentrating ethanol from dilute aqueous solutions thereof

DOEpatents

Oulman, Charles S. [Ames, IA; Chriswell, Colin D. [Slater, IA

1981-07-07

Relatively dilute aqueous solutions of ethanol are concentrated by passage through a bed of a crystalline silica polymorph, such as silicalite, to adsorb the ethanol with residual dilute feed in contact with the bed, which is displaced by passing concentrated aqueous ethanol through the bed without displacing the adsorbed ethanol. A product concentrate is then obtained by removing the adsorbed ethanol from the bed together with at least a portion of the concentrated aqueous ethanol used as the displacer liquid. This process permits ethanol to be concentrated from dilute fermentation beers, which may contain from 6 to 10% ethanol, to obtain a concentrate product at very low energy cost having an ethanol concentration in excess of 95%, such as a concentration of from 98 to 99.5%.

Thermal and volumetric properties of complex aqueous electrolyte solutions using the Pitzer formalism - The PhreeSCALE code

NASA Astrophysics Data System (ADS)

Lach, Adeline; Boulahya, Faïza; André, Laurent; Lassin, Arnault; Azaroual, Mohamed; Serin, Jean-Paul; Cézac, Pierre

2016-07-01

The thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (Lϕ) and the apparent molar heat capacity (Cp,ϕ). The volumetric property is the apparent molar volume (Vϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (∆HD), the heat capacity (cp) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (Cp0) and volume (V0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations.

Excessive Counterion Condensation on Immobilized ssDNA in Solutions of High Ionic Strength

PubMed Central

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-01-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (ηrel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, ηrel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations. PMID:14645075

Excessive counterion condensation on immobilized ssDNA in solutions of high ionic strength.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-12-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (etarel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, etarel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations.

SEPARATION OF THORIUM FROM URANIUM

DOEpatents

Bane, R.W.

1959-09-01

A description is given for the separation of thorium from uranium by forming an aqueous acidic solution containing ionic species of thorium, uranyl uranium, and hydroxylamine, flowing the solution through a column containing the phenol-formaldehyde type cation exchange resin to selectively adsorb substantially all the thorium values and a portion of the uranium values, flowing a dilute solution of hydrochloric acid through the column to desorb the uranium values, and then flowing a dilute aqueous acidic solution containing an ion, such as bisulfate, which has a complexing effect upon thortum through the column to desorb substantially all of the thorium.

Low Temperature Double-Layer Capacitors Using Asymmetric and Spiro-Type Quaternary Ammonium Salts

NASA Technical Reports Server (NTRS)

Smart, Marshall C. (Inventor); Brandon, Erik J. (Inventor); West, William C. (Inventor)

2014-01-01

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -80.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. A quaternary ammonium salt including at least one of triethylmethylammonium tetrafluoroborate (TEMATFB) and spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF.sub.4), is used in an optimized concentration (e.g., 0.10 M to 0.75 M), dissolved into the electrolyte solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Humic acids as pseudocapacitive electrolyte additive for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Wasiński, Krzysztof; Walkowiak, Mariusz; Lota, Grzegorz

2014-06-01

Novel electrolyte additive for electrochemical capacitors has been reported. It has been demonstrated for the first time that addition of humic acids (HA) to KOH-based electrolyte significantly increases capacitance of symmetrical capacitors with electrodes made of activated carbon. Specific capacitances determined by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy consistently showed increases for HA concentrations ranging from 2% w/w up to saturated solution with maximum positive effect observed for 5% w/w of the additive. The capacitance increase has been attributed to complex faradaic processes involving oxygen-containing groups of HA molecules. Due to abundant resources, low cost and easy processability the reported solution can find application in electrochemical capacitor technologies.

The solvation structure of Mg ions in dichloro complex solutions from first-principles molecular dynamics and simulated X-ray absorption spectra.

PubMed

Wan, Liwen F; Prendergast, David

2014-10-15

The knowledge of Mg solvation structure in the electrolyte is requisite to understand the transport behavior of Mg ions and their dissolution/deposition mechanism at electrolyte/electrode interfaces. In the first established rechargeable Mg-ion battery system [D. Aurbach et al. Nature 2000, 407, 724], the electrolyte is of the dichloro complex (DCC) solution family, Mg(AlCl2BuEt)2/THF, resulting from the reaction of Bu2Mg and EtAlCl2 with a molar ratio of 1:2. There is disagreement in the literature regarding the exact solvation structure of Mg ions in such solutions, i.e., whether Mg(2+) is tetra- or hexacoordinated by a combination of Cl(-) and THF. In this work, theoretical insight into the solvation complexes present is provided based on first-principles molecular dynamics simulations (FPMD). Both Mg monomer and dimer structures are considered in both neutral and positively charged states. We found that, at room temperature, the Mg(2+) ion tends to be tetracoordinated in the THF solution phase instead of hexacoordinated, which is the predominant solid-phase coordination. Simulating the X-ray absorption spectra (XAS) at the Mg K-edge by sampling our FPMD trajectories, our predicted solvation structure can be readily compared with experimental measurements. It is found that when changing from tetra- to hexacoordination, the onset of X-ray absorption should exhibit at least a 1 eV blue shift. We propose that this energy shift can be used to monitor changes in the Mg solvation sphere as it migrates through the electrolyte to electrolyte/electrode interfaces and to elucidate the mechanism of Mg dissolution/deposition.

Reaction of Cl- ions in electrolyte solution induced electrical discharge plasma in the presence of argon fine bubbles

NASA Astrophysics Data System (ADS)

Hayashi, Yui; Takada, Noriharu; Wahyudiono, Kanda, Hideki; Goto, Motonobu

2017-05-01

Active chlorine species such as chlorine molecules and hypochlorous acid have been known as high performance sanitizers. They would act more reactive on chemical and biological substances when an electrical discharge was introduced in water containing an electrolyte substance. Here, the reaction of chloride (Cl-) ions were examined by introducing of a pulsed discharge plasma in sodium chloride (NaCl) solution as an electrolyte solution at room temperature. The results show that a large electrical current generated by the pulsed discharge plasma affected the reaction of Cl- ions to result available chlorine. The reaction pathway for available chlorine production was assumed similar with the reaction pathway as electrolysis. A pulsed discharge plasma in NaCl solution in the presence of argon (Ar) fine bubbles exhibited intense emissions and high electron density compared to when no Ar fine bubbles were introduced. At these conditions, the dissociation reaction rate of water increased drastically leads to the formation of 0 atoms. As a result, the reaction of Cl- ions and the available chlorine generation were also increased.

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

NASA Astrophysics Data System (ADS)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially in mixed-phase cloud regime, of ammonium sulfate coated mineral dust particles in the condensation mode when the coating dilutes during cloud droplet activation.

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, Encarnación; Putnis, Christine V.; Wang, Lijun; Putnis, Andrew

2011-07-01

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li +, F - and SO42-, and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.

Electrochemical cell with calcium anode

DOEpatents

Cooper, John F.; Hosmer, Pamela K.; Kelly, Benjamin E.

1979-01-01

An electrochemical cell comprising a calcium anode and a suitable cathode in an alkaline electrolyte consisting essentially of an aqueous solution of an hydroxide and a chloride. Specifically disclosed is a mechanically rechargeable calcium/air fuel cell with an aqueous NaOH/NaCl electrolyte.

Water and solute absorption from carbohydrate-electrolyte solutions in the human proximal small intestine: a review and statistical analysis.

PubMed

Shi, Xiaocai; Passe, Dennis H

2010-10-01

The purpose of this study is to summarize water, carbohydrate (CHO), and electrolyte absorption from carbohydrate-electrolyte (CHO-E) solutions based on all of the triple-lumen-perfusion studies in humans since the early 1960s. The current statistical analysis included 30 reports from which were obtained information on water absorption, CHO absorption, total solute absorption, CHO concentration, CHO type, osmolality, sodium concentration, and sodium absorption in the different gut segments during exercise and at rest. Mean differences were assessed using independent-samples t tests. Exploratory multiple-regression analyses were conducted to create prediction models for intestinal water absorption. The factors influencing water and solute absorption are carefully evaluated and extensively discussed. The authors suggest that in the human proximal small intestine, water absorption is related to both total solute and CHO absorption; osmolality exerts various impacts on water absorption in the different segments; the multiple types of CHO in the ingested CHO-E solutions play a critical role in stimulating CHO, sodium, total solute, and water absorption; CHO concentration is negatively related to water absorption; and exercise may result in greater water absorption than rest. A potential regression model for predicting water absorption is also proposed for future research and practical application. In conclusion, water absorption in the human small intestine is influenced by osmolality, solute absorption, and the anatomical structures of gut segments. Multiple types of CHO in a CHO-E solution facilitate water absorption by stimulating CHO and solute absorption and lowering osmolality in the intestinal lumen.

Process for strontium-82 separation

DOEpatents

Heaton, Richard C.; Jamriska, Sr., David J.; Taylor, Wayne A.

1992-01-01

A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets comprises dissolving the molybdenum target in a hydrogen peroxide solution to form a first solution containing ions selected from a group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium, rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, and yttrium; passing the solution through a first cationic resin whereby ions selected from a group consisting of zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium a portion of zirconium and a portion of rubidium are selectively absorbed by the first resin; contacting the first resin with an acid solution to strip and remove the absorbed ions from the first cationic exchange resin to form a second solution; evaporating the second solution for a time sufficient to remove substantially all of the acid and water from the solution whereby a residue remains; dissolving the residue in a dilute acid to form a third solution; passing the third solution through a second cationic resin whereby the ions are absorbed by the second resin; contacting the second resin with a dilute sulfuric acid solution whereby the absorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium and zirconium are selectively removed from the second resin; and contacting the second resin with a dilute acid solution whereby the absorbed strontium ions are selectively removed.

Process for strontium-82 separation

DOEpatents

Heaton, R.C.; Jamriska, D.J. Sr.; Taylor, W.A.

1992-12-01

A process for selective separation of strontium-82 and strontium-85 from proton irradiated molybdenum targets comprises dissolving the molybdenum target in a hydrogen peroxide solution to form a first solution containing ions selected from a group consisting of molybdenum, niobium, technetium, selenium, vanadium, arsenic, germanium, zirconium, rubidium, zinc, beryllium, cobalt, iron, manganese, chromium, strontium, and yttrium; passing the solution through a first cationic resin whereby ions selected from a group consisting of zinc, beryllium, cobalt, iron, manganese, chromium, strontium, yttrium a portion of zirconium and a portion of rubidium are selectively absorbed by the first resin; contacting the first resin with an acid solution to strip and remove the absorbed ions from the first cationic exchange resin to form a second solution; evaporating the second solution for a time sufficient to remove substantially all of the acid and water from the solution whereby a residue remains; dissolving the residue in a dilute acid to form a third solution; passing the third solution through a second cationic resin whereby the ions are absorbed by the second resin; contacting the second resin with a dilute sulfuric acid solution whereby the absorbed ions selected from the group consisting of rubidium, zinc, beryllium, cobalt, iron, manganese, chromium and zirconium are selectively removed from the second resin; and contacting the second resin with a dilute acid solution whereby the absorbed strontium ions are selectively removed. 1 fig.

Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery

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

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S 3 - radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S 3 -. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfurmore » inventory from the cathode to the electrolyte.« less

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Lee, Kuang-Tsin; Wu, Nae-Lih

An aqueous gel electrolyte has for the first time been successfully applied to the MnO 2· nH 2O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H 2O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10 -1 S cm -1. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg).

Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery

DOE PAGES

McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R.; ...

2018-03-23

In situ Raman microscopy was used to study polysulfide speciation in the bulk ether electrolyte during the discharge and charge of a Li-S electrochemical cell to assess the complex interplay between chemical and electrochemical reactions in solution. During discharge, long chain polysulfides and the S 3 - radical appear in the electrolyte at 2.4 V indicating a rapid equilibrium of the dissociation reaction to form S 3 -. When charging, however, an increase in the concentration of all polysulfide species was observed. This highlights the importance of the electrolyte to sulfur ratio and suggests a loss in the useful sulfurmore » inventory from the cathode to the electrolyte.« less

Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates

DOE PAGES

Godinho, Jose R. A.; Stack, Andrew G.

2015-03-30

Here we investigate the growth kinetics and morphology of barite (BaSO 4) crystals by measuring the growth rates of the (001), (210), (010), and (100) surfaces using vertical scanning interferometry. Solutions with saturation indices 1.1, 2.1, and 3.0 without additional electrolyte, in 0.7 M NaCl, or in 1.3 mM SrCl2 are investigated. Face-specific growth rates are inhibited in the SrCl 2 solution relative to a solution without electrolyte, except for (100). Contrarily, growth of all faces is promoted in the NaCl solution. The variation of face-specific rates is solution-specific, which leads to a. change of the crystal morphology and overallmore » growth rate of crystals. The measured face-specific growth rates are used to model the growth of single crystals. Modeled crystals have a morphology and size similar to those grown from solution. Based on the model the time dependence of surface area and growth rates is analyzed. Growth rates change with time due to surface area normalization for small crystals and large growth intervals. By extrapolating rates to crystals with large surfaces areas, time-independent growth rates are 0.783, 2.96, and 0.513 mmol∙m -2∙h -1, for saturation index 2.1 solutions without additional electrolyte, NaCl, and SrCl 2, respectively.« less

Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates

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

Godinho, Jose R. A.; Stack, Andrew G.

Here we investigate the growth kinetics and morphology of barite (BaSO 4) crystals by measuring the growth rates of the (001), (210), (010), and (100) surfaces using vertical scanning interferometry. Solutions with saturation indices 1.1, 2.1, and 3.0 without additional electrolyte, in 0.7 M NaCl, or in 1.3 mM SrCl2 are investigated. Face-specific growth rates are inhibited in the SrCl 2 solution relative to a solution without electrolyte, except for (100). Contrarily, growth of all faces is promoted in the NaCl solution. The variation of face-specific rates is solution-specific, which leads to a. change of the crystal morphology and overallmore » growth rate of crystals. The measured face-specific growth rates are used to model the growth of single crystals. Modeled crystals have a morphology and size similar to those grown from solution. Based on the model the time dependence of surface area and growth rates is analyzed. Growth rates change with time due to surface area normalization for small crystals and large growth intervals. By extrapolating rates to crystals with large surfaces areas, time-independent growth rates are 0.783, 2.96, and 0.513 mmol∙m -2∙h -1, for saturation index 2.1 solutions without additional electrolyte, NaCl, and SrCl 2, respectively.« less

On the thermal behavior of model Li-Li xCoO 2 systems containing ionic liquids in standard electrolyte solutions

NASA Astrophysics Data System (ADS)

Larush, L.; Borgel, V.; Markevich, E.; Haik, O.; Zinigrad, E.; Aurbach, D.; Semrau, G.; Schmidt, M.

We report herein on the possibility of using ionic liquids (ILs) as additives to conventional electrolyte solutions, based on alkyl carbonates and LiPF 6 for attenuating thermal reactions in Li battery systems. As a model, a Li-Li 0.5CoO 2 system was used. The ionic liquids chosen included cations based on derivatives of pyrrolidinium and imidazolium, and the anions bioxalato borate (C 4O 8B -, BOB), (CH 3SO 2) 2N - (TFSI), and PF 3(C 2S 5) 3 - (FAP). The thermal behavior of solutions alone, solutions with Li metal, Li 0.5CoO 2 and Li metal + Li 0.5CoO 2 was studied. It was found that the presence of 10% of ILs, with derivatives of pyrrolidinium cations and FAP or TFSI anions in standard EC-DMC/LiPF 6 solutions, improves considerably the thermal stability of Li 0.5CoO 2 in electrolyte solutions. The onset temperatures of the thermal reactions of Li 0.5CoO 2 with solution species are higher and their heat evolution is considerably lower, when they contain these ionic liquids as additives. This finding opens the door for further studies and optimization of the use of selected ILs as additives that may improve the safety features of Li-ion batteries.

On the nature of liquid junction and membrane potentials.

PubMed

Perram, John W; Stiles, Peter J

2006-09-28

Whenever a spatially inhomogeneous electrolyte, composed of ions with different mobilities, is allowed to diffuse, charge separation and an electric potential difference is created. Such potential differences across very thin membranes (e.g. biomembranes) are often interpreted using the steady state Goldman equation, which is usually derived by assuming a spatially constant electric field. Through the fundamental Poisson equation of electrostatics, this implies the absence of free charge density that must provide the source of any such field. A similarly paradoxical situation is encountered for thick membranes (e.g. in ion-selective electrodes) for which the diffusion potential is normally interpreted using the Henderson equation. Standard derivations of the Henderson equation appeal to local electroneutrality, which is also incompatible with sources of electric fields, as these require separated charges. We analyse self-consistent solutions of the Nernst-Planck-Poisson equations for a 1 : 1-univalent electrolyte to show that the Goldman and Henderson steady-state membrane potentials are artefacts of extraneous charges created in the reservoirs of electrolyte solution on either side of the membrane, due to the unphysical nature of the usual (Dirichlet) boundary conditions assumed to apply at the membrane-electrolyte interfaces. We also show, with the aid of numerical simulations, that a transient electric potential difference develops in any confined, but initially non-uniform, electrolyte solution. This potential difference ultimately decays to zero in the real steady state of the electrolyte, which corresponds to thermodynamic equilibrium. We explain the surprising fact that such transient potential differences are well described by the Henderson equation by using a computer algebra system to extend previous steady-state singular perturbation theories to the time-dependent case. Our work therefore accounts for the success of the Henderson equation in analysing experimental liquid-junction potentials.

Nonlocal electrostatics in ionic liquids: The key to an understanding of the screening decay length and screened interactions.

PubMed

Kjellander, Roland

2016-09-28

Screened electrostatic interactions in ionic liquids are investigated by means of exact statistical mechanical analysis combined with physical arguments that enhance the transparency and conceptual accessibility of the analysis and results. The constituent ions and immersed particles in the liquid can have arbitrary shapes and any internal charge distributions. The decay of the screened electrostatic potential and the free energy of interaction in ionic liquids can be exponentially damped oscillatory (like in molten simple salts) as well as plain exponential and long-ranged (like in dilute electrolyte solutions). Both behaviors are in agreement with the exact statistical mechanical analysis and reasons for their appearances are investigated. Exact but surprisingly simple expressions for the decay parameter κ of the screened electrostatics are obtained, which replace the classical expression for the Debye-Hückel parameter κ DH (the reciprocal Debye length). The expressions are applicable both for cases with plain exponential and oscillatory behaviors. The key importance of nonlocal electrostatics is thereby demonstrated explicitly. Dielectric properties of ionic liquids and other electrolytes are investigated, in particular the static dielectric function ϵ̃(k) and some effective relative permittivities (E r eff and E r ∗ ), which take roles that the dielectric constant ε r has for polar liquids consisting of electroneutral molecules. The dielectric constant in the latter case, which is the limit of ϵ̃(k) when the wave number k → 0, can be expressed solely in terms of dipolar features of the molecules. In contrast to this, the effective dielectric permittivities of ionic liquids have contributions also from quadrupolar, octupolar, and higher multipolar features of the constituent ions. The "dielectric constant" of electrolytes does not exist since ϵ̃(k)→∞ when k → 0, a well-known effect of perfect screening. The effective relative permittivities, E r eff , and E r ∗ of ionic liquids are obtained from the non-diverging part of ϵ̃(k), but not as a k → 0 limit. Influences of ion associations, especially pairing, are investigated for screened electrostatics and these permittivities. A general, multipolar expansion of ϵ̃(k) is derived and used to analyze dielectric properties of ionic liquids and other electrolytes.

Nonlocal electrostatics in ionic liquids: The key to an understanding of the screening decay length and screened interactions

NASA Astrophysics Data System (ADS)

Kjellander, Roland

2016-09-01

Screened electrostatic interactions in ionic liquids are investigated by means of exact statistical mechanical analysis combined with physical arguments that enhance the transparency and conceptual accessibility of the analysis and results. The constituent ions and immersed particles in the liquid can have arbitrary shapes and any internal charge distributions. The decay of the screened electrostatic potential and the free energy of interaction in ionic liquids can be exponentially damped oscillatory (like in molten simple salts) as well as plain exponential and long-ranged (like in dilute electrolyte solutions). Both behaviors are in agreement with the exact statistical mechanical analysis and reasons for their appearances are investigated. Exact but surprisingly simple expressions for the decay parameter κ of the screened electrostatics are obtained, which replace the classical expression for the Debye-Hückel parameter κDH (the reciprocal Debye length). The expressions are applicable both for cases with plain exponential and oscillatory behaviors. The key importance of nonlocal electrostatics is thereby demonstrated explicitly. Dielectric properties of ionic liquids and other electrolytes are investigated, in particular the static dielectric function ɛ ˜ ( k ) and some effective relative permittivities ( Er eff and Er ∗ ), which take roles that the dielectric constant ɛr has for polar liquids consisting of electroneutral molecules. The dielectric constant in the latter case, which is the limit of ɛ ˜ ( k ) when the wave number k → 0, can be expressed solely in terms of dipolar features of the molecules. In contrast to this, the effective dielectric permittivities of ionic liquids have contributions also from quadrupolar, octupolar, and higher multipolar features of the constituent ions. The "dielectric constant" of electrolytes does not exist since ɛ ˜ ( k ) → ∞ when k → 0, a well-known effect of perfect screening. The effective relative permittivities, Er eff , and Er ∗ of ionic liquids are obtained from the non-diverging part of ɛ ˜ ( k ) , but not as a k → 0 limit. Influences of ion associations, especially pairing, are investigated for screened electrostatics and these permittivities. A general, multipolar expansion of ɛ ˜ ( k ) is derived and used to analyze dielectric properties of ionic liquids and other electrolytes.

Fuel cell anode configuration for CO tolerance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas A.

2004-11-16

A polymer electrolyte fuel cell (PEFC) is designed to operate on a reformate fuel stream containing oxygen and diluted hydrogen fuel with CO impurities. A polymer electrolyte membrane has an electrocatalytic surface formed from an electrocatalyst mixed with the polymer and bonded on an anode side of the membrane. An anode backing is formed of a porous electrically conductive material and has a first surface abutting the electrocatalytic surface and a second surface facing away from the membrane. The second surface has an oxidation catalyst layer effective to catalyze the oxidation of CO by oxygen present in the fuel stream where at least the layer of oxidation catalyst is formed of a non-precious metal oxidation catalyst selected from the group consisting of Cu, Fe, Co, Tb, W, Mo, Sn, and oxides thereof, and other metals having at least two low oxidation states.

Electrodeionization method

DOEpatents

Lin, YuPo J.; Hestekin, Jamie; Arora, Michelle; St. Martin, Edward J.

2004-09-28

An electrodeionization method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit.

Dilute acid pretreatment of corncob for efficient sugar production

Treesearch

G.S. Wang; Jae-Won Lee; Junyong Zhu; Thomas W. Jeffries

2011-01-01

Aqueous dilute acid pretreatments of corncob were conducted using cylindrical pressure vessels in an oil bath. Pretreatments were conducted in a temperature range of 160–190 °C with acid-solution-to-solid-corncob ratio of 2. The acid concentration (v/v) in the pretreatment solution was varied from 0% to 0.7%, depending on temperature. This gives acid charge on ovendry-...

Concentration fluctuations and dilution in aquifers

NASA Astrophysics Data System (ADS)

Kapoor, Vivek; Kitanidis, Peter K.

1998-05-01

The concentration of solute undergoing advection and local dispersion in a random hydraulic conductivity field is analyzed to quantify its variability and dilution. Detailed numerical evaluations of the concentration variance σc2 are compared to an approximate analytical description, which is based on a characteristic variance residence time (VRT), over which local dispersion destroys concentration fluctuations, and effective dispersion coefficients that quantify solute spreading rates. Key features of the analytical description for a finite size impulse input of solute are (1) initially, the concentration fields become more irregular with time, i.e., coefficient of variation, CV=σc/, increases with time ( being the mean concentration); (2) owing to the action of local dispersion, at large times (t > VRT), σc2 is a linear combination of 2 and (∂/∂xi)2, and the CV decreases with time (at the center, CV ≅ (N)1/2 VRT/t, N being the macroscopic dimensionality of the plume); (3) at early time, dilution and spreading can be severely disconnected; however, at large time the volume occupied by solute approaches that apparent from its spatial second moments; and (4) in contrast to the advection-local dispersion case, under advection alone, the CV grows unboundedly with time (at the center, CV ∝ tN/4), and spatial second moment is increasingly disconnected from dilution, as time progresses. The predicted large time evolution of dilution and concentration fluctuation measures is observed in the numerical simulations.

Nonflammable gel electrolyte containing alkyl phosphate for rechargeable lithium batteries

NASA Astrophysics Data System (ADS)

Yoshimoto, Nobuko; Niida, Yoshihiro; Egashira, Minato; Morita, Masayuki

A nonflammable polymeric gel electrolyte has been developed for rechargeable lithium battery systems. The gel film consists of poly(vinylidenefluoride- co-hexafluoropropylene) (PVdF-HFP) swollen with lithium hexafluorophosphate (LiPF 6) solution in ternary solvent containing trimethyl phosphate (TMP). High ionic conductivity of 6.2 mS cm -1 at 20 °C was obtained for the gel electrolyte consisting of 0.8 M LiPF 6/EC + DEC + TMP (55:25:20) with PVdF-HFP, which is comparable to that of the liquid electrolyte containing the same electrolytic salt. Addition of a small amount of vinylene carbonate (VC) in the gel electrolyte improved the rechargeability of a graphite electrode. The rechargeable capacity of the graphite in the gel containing VC was ca. 300 mAh g -1, which is almost the same as that in a conventional liquid electrolyte system.

Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

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

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systemsmore » that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less

Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries

DOE PAGES

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; ...

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systemsmore » that fundamentally decouple electrolyte volume from reaction mechanism. Furthermore, this perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity.

PubMed

Burke, Colin M; Pande, Vikram; Khetan, Abhishek; Viswanathan, Venkatasubramanian; McCloskey, Bryan D

2015-07-28

Among the "beyond Li-ion" battery chemistries, nonaqueous Li-O2 batteries have the highest theoretical specific energy and, as a result, have attracted significant research attention over the past decade. A critical scientific challenge facing nonaqueous Li-O2 batteries is the electronically insulating nature of the primary discharge product, lithium peroxide, which passivates the battery cathode as it is formed, leading to low ultimate cell capacities. Recently, strategies to enhance solubility to circumvent this issue have been reported, but rely upon electrolyte formulations that further decrease the overall electrochemical stability of the system, thereby deleteriously affecting battery rechargeability. In this study, we report that a significant enhancement (greater than fourfold) in Li-O2 cell capacity is possible by appropriately selecting the salt anion in the electrolyte solution. Using (7)Li NMR and modeling, we confirm that this improvement is a result of enhanced Li(+) stability in solution, which, in turn, induces solubility of the intermediate to Li2O2 formation. Using this strategy, the challenging task of identifying an electrolyte solvent that possesses the anticorrelated properties of high intermediate solubility and solvent stability is alleviated, potentially providing a pathway to develop an electrolyte that affords both high capacity and rechargeability. We believe the model and strategy presented here will be generally useful to enhance Coulombic efficiency in many electrochemical systems (e.g., Li-S batteries) where improving intermediate stability in solution could induce desired mechanisms of product formation.

Recent results on aqueous electrolyte cells

NASA Astrophysics Data System (ADS)

Wessells, Colin; Huggins, Robert A.; Cui, Yi

2011-03-01

The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi2(PO4)3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO3 and Li2SO4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm-2 between two platinum electrodes in 5 M LiNO3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm-2 it can reach 2.3 V. LiTi2(PO4)3 was synthesized using a Pechini method and cycled in pH-neutral Li2SO4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g-1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi2(PO4)3 anode with cell voltages of 2 V and above.

Process for cobalt separation and recovery in the presence of nickel from sulphate solutions by Cyanex 272

NASA Astrophysics Data System (ADS)

Park, Kyung-Ho; Mohapatra, Debasish

2006-10-01

The present paper deals with the extraction of cobalt from a solution containing cobalt and nickel in a sulphate medium similar to the leach liquor obtained by the dilute sulphuric acid pressure leaching of the Pacific Ocean nodules matte followed by copper extraction. The commercial extractant Cyanex 272 (bis (2, 4, 4-trimethylpentyl) phosphinic acid) is used for this purpose. The leach liquor used for the present study contains Co =1.78 g/L and Ni=16.78 g/L. Before cobalt extraction, impurities, such as copper and iron, are removed from the leach liquor by the precipitation method. Increasing the concentration of Cyanex 272 increased the extraction percentage of cobalt due to the increase of equilibrium pH. Cobalt extraction efficiency of >99.9 % is achieved with 0.20 M Cyanex 272 in two counter-current stages at an aqueous: organic (A:O) phase ratio of 1.5∶1. Complete stripping of cobalt from the loaded organic containing 2.73 g/L Co was carried out at pH 1.4 by a synthetic cobalt spent electrolyte in two stages at an A:O ratio of 1∶2. The enrichment of cobalt during extraction and stripping operations was about 3.5 times. A complete process flowsheet for the separation and recovery of cobalt is presented.

Improved fabrication of electrolytic capacitors

NASA Technical Reports Server (NTRS)

Gamari, F. J.; Moresi, J. L.

1975-01-01

After processing parts for assembly, insulative cup is fitted to bottom of can, then electrolytic solution consisting of white sulfuric acid gel is inserted into can. Pellet is put in can and is fitted tightly into cup. Finally, bead weld is formed between can and header plug.

Sieving of electrolytes at capillary wall of cat skeletal muscle by osmotic water flow.

PubMed

Watson, P D

1993-12-01

To test the hypothesis that a significant proportion of transcapillary water flow occurs through solute-restricting channels, we investigated the effects of transcapillary water movement on plasma electrolytes in isolated perfused cat skeletal muscle. The lower hindlimbs of anesthetized cats were perfused with a plasma-albumin solution and were weighed to determine transcapillary water movement. Osmolality was increased 60-70 mosmol/kgH2O with sucrose, creating water fluxes of 8-10 ml.min-1.100 g-1, and the changes in the venous concentrations of sodium, potassium, and chloride were determined. The ion concentrations were all reduced by 6-7% with no significant difference between them. The amount of reduction was quantitatively explained by the flow of ion-free water from the interstitial space into plasma and the diffusion of electrolyte in the same direction. These findings support the hypothesis that important water-only transcapillary channels exist in mammalian skeletal muscle. The observations may also explain some of the electrolyte changes seen in intense exercise.

Surface layer formation of LiCoO2 thin film electrodes in non-aqueous electrolyte containing lithium bis(oxalate)borate

NASA Astrophysics Data System (ADS)

Matsui, Masaki; Dokko, Kaoru; Akita, Yasuhiro; Munakata, Hirokazu; Kanamura, Kiyoshi

2012-07-01

Surface layer formation processes on a LiCoO2 thin film electrode in a non-aqueous electrolyte containing lithium bis(oxalate)borate (LiBOB) were investigated using in situ FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The in situ FTIR spectra of the electrolyte solution containing LiBOB showed that the adsorption of BOB anions on the electrode surface occurred during the charge process of the LiCoO2 thin film electrode above 4.0 V. XPS analysis for the LiCoO2 thin film electrode charged in an electrolyte containing LiBOB suggested that the adsorbed BOB anions on the electrode surface prevent the continuous decomposition of hexafluorophosphate (PF6) anions resulting in the formation of a very thin surface layer containing organic species, while the LiCoO2 charged in a LiPF6 solution had a relatively thick surface layer containing organic species and inorganic species.

Thermodynamic properties of gases dissolved in electrolyte solutions.

NASA Technical Reports Server (NTRS)

Tiepel, E. W.; Gubbins, K. E.

1973-01-01

A method based on perturbation theory for mixtures is applied to the prediction of thermodynamic properties of gases dissolved in electrolyte solutions. The theory is compared with experimental data for the dependence of the solute activity coefficient on concentration, temperature, and pressure; calculations are included for partial molal enthalpy and volume of the dissolved gas. The theory is also compared with previous theories for salt effects and found to be superior. The calculations are best for salting-out systems. The qualitative feature of salting-in is predicted by the theory, but quantitative predictions are not satisfactory for such systems; this is attributed to approximations made in evaluating the perturbation terms.

Formulation of ionic liquid electrolyte to expand the voltage window of supercapacitors

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

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

We report an effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic liquid (IL) electrolytes. Moreover, using model electrochemical cells based on two identical onion like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte’s cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Additionally, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Formulation of ionic liquid electrolyte to expand the voltage window of supercapacitors

DOE PAGES

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

2015-03-18

We report an effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic liquid (IL) electrolytes. Moreover, using model electrochemical cells based on two identical onion like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte’s cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Additionally, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride- co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Zhao, Xiaohui; Shin, Chorong; Baek, Dong-Ho; Choi, Jae-Won; Manuel, James; Heo, Min-Yeong; Ahn, Jou-Hyeon; Nah, Changwoon

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride- co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10 -3 S cm -1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.

A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction

PubMed Central

Kim, Young-Soo; Cho, Yoon-Gyo; Odkhuu, Dorj; Park, Noejung; Song, Hyun-Kon

2013-01-01

Electrolytes are characterized by their ionic conductivity (σi). It is desirable that overall σi results from the dominant contribution of the ions of interest (e.g. Li+ in lithium ion batteries or LIB). However, high values of cationic transference number (t+) achieved by solid or gel electrolytes have resulted in low σi leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level σi (~101 mS cm−1) with high t+ of Li+ (>0.8) for LIB. A conventional liquid electrolyte in presence of a cyano resin was physically and irreversibly gelated at 60°C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, σi of the electrolyte followed a typical Arrhenius-type temperature dependency, even if its viscosity increased dramatically with temperature. Based on the Li+-driven ion conduction, LIB using the organogel electrolyte delivered significantly enhanced cyclability and thermal stability. PMID:23715177

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life.

PubMed

He, Mingfu; Lau, Kah Chun; Ren, Xiaodi; Xiao, Neng; McCulloch, William D; Curtiss, Larry A; Wu, Yiying

2016-12-05

Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Herein we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3 mol kg -1 ). Raman spectra of NaTFSI/DMSO electrolytes and ab initio molecular dynamics simulation reveal the Na + solvation number in DMSO and the formation of Na(DMSO) 3 (TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2 ) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relevant Features of a Triethylene Glycol Dimethyl Ether-Based Electrolyte for Application in Lithium Battery.

PubMed

Carbone, Lorenzo; Di Lecce, Daniele; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steve; Hassoun, Jusef

2017-05-24

Triethylene glycol dimethyl ether (TREGDME) dissolving lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is studied as a suitable electrolyte medium for lithium battery. Thermal and rheological characteristics, transport properties of the dissolved species, and the electrochemical behavior in lithium cell represent the most relevant investigated properties of the new electrolyte. The self-diffusion coefficients, the lithium transference numbers, the ionic conductivity, and the ion association degree of the solution are determined by pulse field gradient nuclear magnetic resonance and electrochemical impedance spectroscopy. The study sheds light on the determinant role of the lithium nitrate (LiNO 3 ) addition for allowing cell operation by improving the electrode/electrolyte interfaces and widening the voltage stability window. Accordingly, an electrochemical activation procedure of the Li/LiFePO 4 cell using the upgraded electrolyte leads to the formation of stable interfaces at the electrodes surface as clearly evidenced by cyclic voltammetry, impedance spectroscopy, and ex situ scanning electron microscopy. Therefore, the lithium battery employing the TREGDME-LiCF 3 SO 3 -LiNO 3 solution shows a stable galvanostatic cycling, a high efficiency, and a notable rate capability upon the electrochemical conditions adopted herein.

Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life

DOE PAGES

He, Mingfu; Lau, Kah Chun; Ren, Xiaodi; ...

2016-11-03

Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Here in this paper, we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3molkg -1). Raman spectra of NaTFSI/DMSO electrolytes and abinitio molecular dynamics simulation reveal the Na + solvation number in DMSO and themore » formation of Na(DMSO) 3(TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.« less

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

NASA Astrophysics Data System (ADS)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li-air battery. Towards this end, using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of properties, we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA +, O2 reduction is a highly reversible one-electron process involving the O2/O2- couple in all of the electrolytes examined with little effect on the nature of the solvent. On the other hand, in Li+-containing electrolytes relevant to the Li-air battery, O2 reduction proceeds in a stepwise fashion to form O2-, O22- and O2- as products. These reactions in presence of Li+ are irreversible or quasi-reversible electrochemical processes and the solvents have significant influence on the kinetics, and reversibility or lack thereof, of the different reduction products. Reversible reduction of O2 to long-lived superoxide in a Li+-conducting electrolyte in DMSO has been shown for the first time here. Chapter 5 is the culmination of the thesis where the practical application of the work is demonstrated. We designed electrolytes that facilitate Li-Air rechargeability, by applying the knowledge gained from chapters 2-4. A rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF6 in tetraethylene glycol dimethyl ether, CH3O(CH2CH 2O)4CH3 was designed, built and its performance studied. It was shown that the cell yields high capacity and can be recharged in spite the absence of catalyst in the carbon cathode. The application of X-ray diffraction to identify these products formed in a porous carbon electrode is shown here for the first time. The rechargeability of the cell was investigated by repeated charge/discharge cycling of the cell, and the factors limiting the cycle life of the cell were studied using AC impedance spectra of the cells as a function of cycle number. In conclusion, the work carried out in this research has shown that the O2 electrochemistry in organic electrolytes is substantially different from that in aqueous electrolytes. Our work has uncovered the key roles the ion conducting salts and the organic solvents play in determining the nature of the reduction products and their reversibility. The results presented here for the first time provide a rational approach to the design and selection of organic electrolyte solutions for use in the rechargeable Li-air battery. (Abstract shortened by UMI.)

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, Jr., Henry D.

1993-01-01

A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Independence of the effective dielectric constant of an electrolytic solution on the ionic distribution in the linear Poisson-Nernst-Planck model.

PubMed

Alexe-Ionescu, A L; Barbero, G; Lelidis, I

2014-08-28

We consider the influence of the spatial dependence of the ions distribution on the effective dielectric constant of an electrolytic solution. We show that in the linear version of the Poisson-Nernst-Planck model, the effective dielectric constant of the solution has to be considered independent of any ionic distribution induced by the external field. This result follows from the fact that, in the linear approximation of the Poisson-Nernst-Planck model, the redistribution of the ions in the solvent due to the external field gives rise to a variation of the dielectric constant that is of the first order in the effective potential, and therefore it has to be neglected in the Poisson's equation that relates the actual electric potential across the electrolytic cell to the bulk density of ions. The analysis is performed in the case where the electrodes are perfectly blocking and the adsorption at the electrodes is negligible, and in the absence of any ion dissociation-recombination effect.

Bio-sorbable, liquid electrolyte gated thin-film transistor based on a solution-processed zinc oxide layer.

PubMed

Singh, Mandeep; Palazzo, Gerardo; Romanazzi, Giuseppe; Suranna, Gian Paolo; Ditaranto, Nicoletta; Di Franco, Cinzia; Santacroce, Maria Vittoria; Mulla, Mohammad Yusuf; Magliulo, Maria; Manoli, Kyriaki; Torsi, Luisa

2014-01-01

Among the metal oxide semiconductors, ZnO has been widely investigated as a channel material in thin-film transistors (TFTs) due to its excellent electrical properties, optical transparency and simple fabrication via solution-processed techniques. Herein, we report a solution-processable ZnO-based thin-film transistor gated through a liquid electrolyte with an ionic strength comparable to that of a physiological fluid. The surface morphology and chemical composition of the ZnO films upon exposure to water and phosphate-buffered saline (PBS) are discussed in terms of the operation stability and electrical performance of the ZnO TFT devices. The improved device characteristics upon exposure to PBS are associated with the enhancement of the oxygen vacancies in the ZnO lattice due to Na(+) doping. Moreover, the dissolution kinetics of the ZnO thin film in a liquid electrolyte opens the possible applicability of these devices as an active element in "transient" implantable systems.

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy.

PubMed

Kumar, Bharat; Crittenden, Scott R

2013-11-01

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson-Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length.

THE INACTIVATION OF DILUTE SOLUTIONS OF CRYSTALLINE TRYPSIN BY X-RADIATION

PubMed Central

McDonald, Margaret R.

1954-01-01

The activity of dilute solutions of crystalline trypsin is destroyed by x-rays. The inactivation is an exponential function of the radiation dose. The reaction yield of inactivation is independent of the intensity at which the radiation is delivered or the quality of the x-rays. The reaction yield increases with increasing concentration of trypsin, varying from 0.06 to 0.7 micromoles per liter per 1000 r for trypsin solutions ranging from 1 x 10–7 to 2 x 10–4 M. PMID:13192318

Antimicrobial and other properties of a new stabilized alkaline glutaraldehyde disinfectant/sterilizer.

PubMed

Miner, N A; McDowell, J W; Willcockson, G W; Bruckner, N I; Stark, R L; Whitmore, E J

1977-04-01

The properties of stabilized alkaline 2% glutaraldehyde solution (SGS) are discussed. SGS is discussed with regard to its chemistry, antimicrobial properties, organic soil resistance, toxicity, corrosivity and chemical stability. SGS retains the maximum antimicrobial activity of alkaline glutaraldehyde solutions and the chemical stability heretofore observed only with acidic glutaraldehyde solutions. These improvements, along with the inherent resistance of glutaraldehyde to neutralization by organic soil, allow SGS to be continuously used for 14 days in situations of high dilution, or 28 days in situations of low dilution.

The Effects of Micromixing Two Solutions of Two Concentrations in a Two Tier PDMS Micromixer

NASA Astrophysics Data System (ADS)

Sundra, Sargunan; Fhong Soon, Chin; Zainal, Nurfarina; Sek Tee, Kian; Ahmad, Nornabihah; Gan, Siew Hua

2017-08-01

Micromixing technology has drastically advanced in the past few decades. Micromixers are one of the elements in integrated microfluidic systems for chemical, analytical chemistry, pharmaceutical, and biological applications. In this study, two tier micromixer was used to mix and dilute two solutions of similar and different concentration in order to investigate performance of micromixer’s mixing. This paper presents the fabrication of a designed micromixer using polydimethylsiloxane (PDMS) and vinyl tape methods which reduce time, cost and complexity of prototyping. The serpentine structure of the microchannels was designed to enhance both mixing and dilution. Two types of food dyes and distilled water were used to investigate the mixing performance of the micromixer followed by spectrophotometry analysis. It is observed that the single dye solution and distilled water shows better mixing performance compared to the micromixing of two dye solutions which was supported by the diffusion theory. 2.00 ml/min was the optimum flow rate that allow optimum mixing and dilution between two different concentrated liquids.

Thiocyanates as attractive redox-active electrolytes for high-energy and environmentally-friendly electrochemical capacitors.

PubMed

Gorska, Barbara; Bujewska, Paulina; Fic, Krzysztof

2017-03-15

This manuscript reports on the novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH 4 SCN). The effect of salt concentration, electrode porosity and current collectors on the capacitance value, system stability, and power performance has been investigated. Therefore, thiocyanate-based electrolytes were recognized as cheap and highly conductive electrolytic solutions (up to 401 mS cm -1 for NH 4 SCN at RT) allowing a cell voltage of 1.6 V in a symmetric carbon/carbon system to be achieved. At the same time, they display an attractive redox activity, enhancing the energy of the device with a good performance during cycling.

THE PREPARATION AND PROPERTIES OF HIGHLY PURIFIED ASCORBIC ACID OXIDASE

PubMed Central

Powers, Wendell H.; Lewis, Stanley; Dawson, Charles R.

1944-01-01

1. A method is described for the preparation of a highly purified ascorbic acid oxidase containing 0.24 per cent copper. 2. Using comparable activity measurements, this oxidase is about one and a half times as active on a dry weight basis as the hitherto most highly purified preparation described by Lovett-Janison and Nelson. The latter contained 0.15 per cent copper. 3. The oxidase activity is proportional to the copper content and the proportionality factor is the same as that reported by Lovett-Janison and Nelson. 4. When dialyzed free of salt, the blue concentrated oxidase solutions precipitate a dark green-blue protein which carries the activity. This may be prevented by keeping the concentrated solutions about 0.1 M in Na2HPO4. 5. When highly diluted for activity measurements the oxidase rapidly loses activity (irreversibly) previous to the measurement, unless the dilution is made with a dilute inert protein (gelatin) solution. Therefore activity values obtained using such gelatin-stabilized dilute solutions of the oxidase run considerably higher than values obtained by the Lovett-Janison and Nelson technique. 6. The effect of pH and substrate concentration on the activity of the purified oxidase in the presence and absence of inert protein was studied. PMID:19873382

Stabilization of Silicon Carbide (SiC) micro- and nanoparticle dispersions in the presence of concentrated electrolyte.

PubMed

Vilinska, Annamaria; Ponnurangam, Sathish; Chernyshova, Irina; Somasundaran, Ponisseril; Eroglu, Damla; Martinez, Jose; West, Alan C

2014-06-01

Achieving a stable and robust dispersion of ultrafine particles in concentrated electrolytes is challenging due to the shielding of electrostatic repulsion. Stable dispersion of ultrafine particles in concentrated electrolytes is critical for several applications, including electro-codeposition of ceramic particles in protective metal coatings. We achieved the steric stabilization of SiC micro- and nano-particles in highly concentrated electroplating Watts solutions using their controlled coating with linear and branched polyethyleneimines (PEI) as dispersants. Branched polyethyleneimine of 60,000 MW effectively disperses both microparticles and nanoparticles at a concentration of 1000 ppm. However, lower polymer dosages and smaller polymers fail to disperse, presumably due to insufficient coverage and bridging flocculation. Dispersion stability correlates well with the adsorption density of PEI on microparticles. We discuss the results in the framework of DLVO theory and suggest possible dispersion mechanisms. However, though the dispersion is enhanced with extended adsorption time, the residual PEI in solution adversely affects electroplating. We overcome this drawback by precoating the particles with the polymer and resuspending them in Watts solution. With this novel approach, we obtained robust dispersions. These results offer new possibilities to control dispersion at high electrolyte concentration, as well as bring new insights into the dispersion phenomenon. Copyright © 2014 Elsevier Inc. All rights reserved.

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

Computer Simulation Study of Graphene Oxide Supercapacitors: Charge Screening Mechanism.

PubMed

Park, Sang-Won; DeYoung, Andrew D; Dhumal, Nilesh R; Shim, Youngseon; Kim, Hyung J; Jung, YounJoon

2016-04-07

Graphene oxide supercapacitors in the parallel plate configuration are studied via molecular dynamics (MD) simulations. The full range of electrode oxidation from 0 to 100% is examined by oxidizing the graphene surface with hydroxyl groups. Two different electrolytes, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI(+)BF4(-)) as an ionic liquid and its 1.3 M solution in acetonitrile as an organic electrolyte, are considered. While the area-specific capacitance tends to decrease with increasing electrode oxidation for both electrolytes, its details show interesting differences between the organic electrolyte and ionic liquid, including the extent of decrease. For detailed insight into these differences, the screening mechanisms of electrode charges by electrolytes and their variations with electrode oxidation are analyzed with special attention paid to the aspects shared by and the contrasts between the organic electrolyte and ionic liquid.

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

Padmaraj, O.; Satyanarayana, N., E-mail: nallanis2011@gmail.com; Venkateswarlu, M.

A novel fibrous polymer blend [(100-x) % P(VdF-co-HFP)/x % PMMA, x = 10, 20, 30, 40, 50] electrolyte membranes were prepared by electrospinning technique. Structural, thermal and surface morphology of all the compositions of electrospun polymer blend membranes were studied by using XRD, DSC & SEM. The newly developed five different compositions of polymer blend fibrous electrolyte membranes were obtained by soaking in an electrolyte solution contains 1M LiPF{sub 6} in EC: DEC (1:1,v/v). The wet-ability and conductivity of all the compositions of polymer blend electrolyte membranes are evaluated through electrolyte uptake and impedance measurements. The polymer blend [90% P(VdF-co-HFP)/10%more » PMMA] electrolyte membrane showed good wet-ability and high conductivity (1.788 × 10{sup −3} Scm{sup −1}) at room temperature.« less

Electrolytic conductivity at 0.5 S m-1 and 5 mS m-1

NASA Astrophysics Data System (ADS)

Seitz, S.; Sander, B.; Snedden, A.; DeLeeBeeck, L.; Canaza, G. T.; Asakai, T.; Maksimov, I.; Song, X.; Wang, H.; Kozlowski, W.; Dumanska, J.; Jakusovszky, B.; Szilágyi, Z. N.; Gavrilkin, V.; Stennik, O.; Ovchinnikov, Y.; Gonzaga, F. B.; da Cruz Cunha, K.; Ferraz, S. F.; Hanková, Z.; Máriássy, M.; Vicarova, M.; Vospelova, A.; Ortiz-Aparicio, J. L.; Lara-Manzano, J. V.; Uribe-Godínez, J.; Stoica, D.; Fisicaro, P.; Suvorov, V. I.; Konopelko, L. A.; Smirnov, A. M.; Amaya, R. C.; Quezada, H. T.

2017-01-01

Key Comparison CCQM-K36.2016 was a follow-up comparison for K36 and provided updated support for the corresponding calibration and measurement capability (CMC) entries in the BIPM CMC database. It aimed to demonstrate the capabilities of the participating NMIs to measure electrolytic conductivity of aqueous electrolyte solutions in the conductivity range 0.15 S m-1 to 1.5 S m-1 and in the conductivity range 1.5 mS m-1 to 15 mS m-1. To this end electrolytic conductivity of a potassium chloride solution (nominal conductivity 0.5 S m-1) and of a HCl solution (nominal conductivity 5 mS m-1) had to be measured. 17 NMIs participated in the comparison. The key comparison reference value (KCRV) of the KCl solution was (0.50999 +/-0.00032) S m-1 and the KCRV of the HCl solution was (4.9877 +/-0.012) mS m-1. Both values were estimated from the medians of the results considered eligible for KCRV calculation. They were given with their expanded uncertainties (95% coverage). The majority of the 0.5 S m-1 results were consistent with the KCRV. Two institutes showed a small inconsistency, one outlier was observed. The conductivity of the HCl solution showed a small, but steady linear drift of 0.00006843 mS m-1 per day during the measurement period and was corrected for KCRV calculation. Some institutes reported unstable measurement conditions for this solution. The results of seven participants have been inconsistent with the KCRV. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Battery using a metal particle bed electrode

DOEpatents

Evans, James V.; Savaskan, Gultekin

1991-01-01

A zinc-air battery in a case including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit.

Gex-Model Using Local Area Fraction for Binary Electrolyte Systems

NASA Astrophysics Data System (ADS)

Haghtalab, Ali; Joda, Marzieh

2007-06-01

The correlation and prediction of phase equilibria of electrolyte systems are essential in the design and operation of many industrial processes such as downstream processing in biotechnology, desalination, hydrometallurgy, etc. In this research, the local composition non-random two liquid-nonrandom factor (NRTL-NRF) model of Haghtalab and Vera was extended for uni-univalent aqueous electrolyte solutions. Based on the assumptions of the NRTL-NRF model, excess Gibbs free energy ( g E) functions were derived for binary electrolyte systems. In this work, the local area fraction was applied and the modified model of NRTL-NRF was developed with either an equal or unequal surface area of an anion to the surface area of a cation. The modified NRTL-NRF models consist of two contributions, one due to long-range forces represented by the Debye-Hückel theory, and the other due to short-range forces, represented by local area fractions of species through nonrandom factors. Each model contains only two adjustable parameters per electrolyte. In addition, the model with unequal surface area of ionic species gives better results in comparison with the second new model with equal surface area of ions. The results for the mean activity coefficients for aqueous solutions of uni-univalent electrolytes at 298.15 K showed that the present model is more accurate than the original NRTL-NRF model.

Colloid osmotic pressure and extravasation of plasma proteins following infusion of Ringer's acetate and hydroxyethyl starch 130/0.4.

PubMed

Zdolsek, J H; Bergek, C; Lindahl, T L; Hahn, R G

2015-11-01

During fluid infusion therapy, plasma proteins are diluted and leak from the intravascular space, which alters the colloid osmotic pressure (COP) and potentially affects coagulation. We hypothesised that acetated Ringer's and starch solution, alone or in combination, influence these mechanisms differently. On different occasions, 10 male volunteers were infused with 20 ml/kg acetated Ringer's and 10 ml/kg 6% hyroxyethyl starch 130/0.4 (Voluven(®) ) alone or in combination (first with starch solution followed by Ringer's solution). Blood samples were collected every 30-min for measurements of COP, blood haemoglobin, platelets, and plasma concentrations of albumin, immunoglobulins (IgG and IgM), coagulation factor VII (FVII), fibrinogen, cystatin C, activated partial thromboplastin time (APTT) and prothrombin international normalised ratio (PT-INR). Changes were compared with the haemoglobin-derived plasma dilution. The COP increased by 8.4% (SD 3) with starch and decreased by 26.2% (7.9) with Ringer's. These infusions diluted the plasma by 23.4% (5.3) and 18.7% (4.9) respectively. The COP changes in the combined experiment followed the same pattern as the individual infusions. Albumin and IgG changes in excess of the plasma dilution were very subtle. The intravascular contents of the IgM and platelets decreased, whereas FVII, fibrinogen and cystatin C increased. PT-INR increased by 1/3 of the plasma dilution, whereas changes in APTT did not correlate with the plasma dilution. The starch increased COP and only minor capillary leak occurred in healthy volunteers. The fluid-induced plasma dilution correlated with mild impairment of the extrinsic coagulation pathway but not of the intrinsic pathway. © 2015 The Acta Anaesthesiologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Ionic interactions in biological and physical systems: a variational treatment.

PubMed

Eisenberg, Bob

2013-01-01

Chemistry is about chemical reactions. Chemistry is about electrons changing their configurations as atoms and molecules react. Chemistry has for more than a century studied reactions as if they occurred in ideal conditions of infinitely dilute solutions. But most reactions occur in salt solutions that are not ideal. In those solutions everything (charged) interacts with everything else (charged) through the electric field, which is short and long range extending to the boundaries of the system. Mathematics has recently been developed to deal with interacting systems of this sort. The variational theory of complex fluids has spawned the theory of liquid crystals (or vice versa). In my view, ionic solutions should be viewed as complex fluids, particularly in the biological and engineering context. In both biology and electrochemistry ionic solutions are mixtures highly concentrated (to approximately 10 M) where they are most important, near electrodes, nucleic ids, proteins, active sites of enzymes, and ionic channels. Ca2+ is always involved in biological solutions because the concentration (really free energy per mole) of Ca2+ in a particular location is the signal that controls many biological functions. Such interacting systems are not simple fluids, and it is no wonder that analysis of interactions, such as the Hofmeister series, rooted in that tradition has not succeeded as one would hope. Here, we present a variational treatment of ard spheres in a frictional dielectric with the hope that such a treatment of an lectrolyte as a complex fluid will be productive. The theory automatically extends to spatially nonuniform boundary conditions and the nonequilibrium systems and flows they produce. The theory is unavoidably self-consistent since differential equations are derived (not assumed) from models of (Helmholtz free) nergy and dissipation of the electrolyte. The origin of the Hofmeister series is (in my view) an inverse problem that becomes well posed when enough data from disjoint experimental traditions are interpreted with a self-consistent theory.

Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl.sub.4) to promote electrolyte wetting

DOEpatents

Eberhart, James G.; Battles, James E.

1980-01-01

Electrochemical cell components such as interelectrode separators, retaining screens and current collectors are contacted with lithium tetrachloroaluminate prior to contact with molten electrolytic salt to improve electrolyte wetting. The LiAlCl.sub.4 can be applied in powdered, molten or solution form but, since this material has a lower melting point than the electrolytic salt used in high-temperature cells, the powdered LiAlCl.sub.4 forms a molten flux prior to contact by the molten electrolyte when both materials are initially provided in solid form. Components of materials such as boron nitride and other materials which are difficult to wet with molten salts are advantageously treated by this process.

Boiling characteristics of dilute polymer solutions and implications for the suppression of vapor explosions

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

Bang, K.H.; Kim, M.H.

Quenching experiments of hot solid spheres in dilute aqueous solutions of polyethylene oxide polymer have been conducted for the purpose of investigating the physical mechanisms of the suppression of vapor explosions in this polymer solutions. Two spheres of 22.2mm and 9.5mm-diameter were tested in the polymer solutions of various concentrations at 30{degrees}C. Minimum film boiling temperature ({Delta}T{sub MFB}) in this highly-subcooled liquid rapidly decreased from over 700{degrees}c for pure water to about 150{degrees}C as the polymer concentration was increased up to 300ppm for 22.2mm sphere, and it decreased to 350{degrees}C for 9.5mm sphere. This rapid reduction of minimum film boilingmore » temperature in the PEO aqueous solutions can explain its ability of the suppression of spontaneous vapor explosions. The ability of suppression of vapor explosions by dilute polyethylene oxide solutions against an external trigger pressure was tested by dropping molten tin into the polymer solutions at 25{degrees}C. It was observed that in 50ppm solutions more mass fragmented than in pure water, but produced weaker explosion pressures. The explosion was completely suppressed in 300ppm solutions with the external trigger. The debris size distributions of fine fragments smaller than 0.7mm were shown almost identical regardless of the polymer concentrations.« less

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, H.D. Jr.

1993-04-20

A process is described for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

An empirical model for parameters affecting energy consumption in boron removal from boron-containing wastewaters by electrocoagulation.

PubMed

Yilmaz, A Erdem; Boncukcuoğlu, Recep; Kocakerim, M Muhtar

2007-06-01

In this study, it was investigated parameters affecting energy consumption in boron removal from boron containing wastewaters prepared synthetically, via electrocoagulation method. The solution pH, initial boron concentration, dose of supporting electrolyte, current density and temperature of solution were selected as experimental parameters affecting energy consumption. The obtained experimental results showed that boron removal efficiency reached up to 99% under optimum conditions, in which solution pH was 8.0, current density 6.0 mA/cm(2), initial boron concentration 100mg/L and solution temperature 293 K. The current density was an important parameter affecting energy consumption too. High current density applied to electrocoagulation cell increased energy consumption. Increasing solution temperature caused to decrease energy consumption that high temperature decreased potential applied under constant current density. That increasing initial boron concentration and dose of supporting electrolyte caused to increase specific conductivity of solution decreased energy consumption. As a result, it was seen that energy consumption for boron removal via electrocoagulation method could be minimized at optimum conditions. An empirical model was predicted by statistically. Experimentally obtained values were fitted with values predicted from empirical model being as following; [formula in text]. Unfortunately, the conditions obtained for optimum boron removal were not the conditions obtained for minimum energy consumption. It was determined that support electrolyte must be used for increase boron removal and decrease electrical energy consumption.

Enzyme stabilization by glass-derived silicates in glass-exposed aqueous solutions

USGS Publications Warehouse

Ives, J.A.; Moffett, J.R.; Arun, P.; Lam, D.; Todorov, T.I.; Brothers, A.B.; Anick, D.J.; Centeno, J.; Namboodiri, M.A.A.; Jonas, W.B.

2010-01-01

Objectives: To analyze the solutes leaching from glass containers into aqueous solutions, and to show that these solutes have enzyme activity stabilizing effects in very dilute solutions. Methods: Enzyme assays with acetylcholine esterase were used to analyze serially succussed and diluted (SSD) solutions prepared in glass and plastic containers. Aqueous SSD preparations starting with various solutes, or water alone, were prepared under several conditions, and tested for their solute content and their ability to affect enzyme stability in dilute solution. Results: We confirm that water acts to dissolve constituents from glass vials, and show that the solutes derived from the glass have effects on enzymes in the resultant solutions. Enzyme assays demonstrated that enzyme stability in purified and deionized water was enhanced in SSD solutions that were prepared in glass containers, but not those prepared in plastic. The increased enzyme stability could be mimicked in a dose-dependent manner by the addition of silicates to the purified, deionized water that enzymes were dissolved in. Elemental analyses of SSD water preparations made in glass vials showed that boron, silicon, and sodium were present at micromolar concentrations. Conclusions: These results show that silicates and other solutes are present at micromolar levels in all glass-exposed solutions, whether pharmaceutical or homeopathic in nature. Even though silicates are known to have biological activity at higher concentrations, the silicate concentrations we measured in homeopathic preparations were too low to account for any purported in vivo efficacy, but could potentially influence in vitro biological assays reporting homeopathic effects. ?? 2009 The Faculty of Homeopathy.

Sulfonated polysulfone battery membrane for use in corrosive environments

DOEpatents

Arnold, Jr., Charles; Assink, Roger

1987-01-01

For batteries containing strong oxidizing electrolyte and a membrane separating two electrolyte solutions, e.g., a zinc ferricyanide battery, an improved membrane is provided comprising an oxidative resistant, conductive, ion-selective membrane fabricated from a catenated aromatic polymer having an absence of tertiary hydrogens, e.g., a sulfonated polysulfone.

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2011 CFR

2011-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2014 CFR

2014-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2013 CFR

2013-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2010 CFR

2010-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

40 CFR Appendix C to Part 438 - Metal-Bearing Operations Definitions

Code of Federal Regulations, 2012 CFR

2012-07-01

... chromium. (1) In phosphate conversion, coatings are applied for one or more of the following reasons: to... electrolysis. The part is one of the electrodes and the electrolyte is usually alkaline. Electrolytic alkaline... during salt bath descaling includes spent process solutions, quenches, and rinses. Shot Tower—Lead Shot...

Electrochemical behavior of high performance on-chip porous carbon films for micro-supercapacitors applications in organic electrolytes

NASA Astrophysics Data System (ADS)

Brousse, K.; Huang, P.; Pinaud, S.; Respaud, M.; Daffos, B.; Chaudret, B.; Lethien, C.; Taberna, P. L.; Simon, P.

2016-10-01

Carbide derived carbons (CDCs) are promising materials for preparing integrated micro-supercapacitors, as on-chip CDC films are prepared via a process fully compatible with current silicon-based device technology. These films show good adherence on the substrate and high capacitance thanks to their unique nanoporous structure which can be fine-tuned by adjusting the synthesis parameters during chlorination of the metallic carbide precursor. The carbon porosity is mostly related to the synthesis temperature whereas the thickness of the films depends on the chlorination duration. Increasing the pore size allows the adsorption of large solvated ions from organic electrolytes and leads to higher energy densities. Here, we investigated the electrochemical behavior and performance of on-chip TiC-CDC in ionic liquid solvent mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) diluted in either acetonitrile or propylene carbonate via cyclic voltammetry and electrochemical impedance spectroscopy. Thin CDC films exhibited typical capacitive signature and achieved 169 F cm-3 in both electrolytes; 65% of the capacitance was still delivered at 1 V s-1. While increasing the thickness of the films, EMI+ transport limitation was observed in more viscous PC-based electrolyte. Nevertheless, the energy density reached 90 μW h cm-2 in 2M EMIBF4/ACN, confirming the interest of these CDC films for micro-supercapacitors applications.

Dilution and Mixing in transient velocity fields: a first-order analysis

NASA Astrophysics Data System (ADS)

Di Dato, Mariaines; de Barros, Felipe, P. J.; Fiori, Aldo; Bellin, Alberto

2017-04-01

An appealing remediation technique is in situ oxidation, which effectiveness is hampered by difficulties in obtaining good mixing of the injected oxidant with the contaminant, particularly when the contaminant plume is contained and therefore its deformation is physically constrained. Under such conditions (i.e. containment), mixing may be augmented by inducing temporal fluctuations of the velocity field. The temporal variability of the flow field may increase the deformation of the plume such that diffusive mass flux becomes more effective. A transient periodic velocity field can be obtained by an engineered sequence of injections and extractions from wells, which may serve also as a hydraulic barrier to confine the plume. Assessing the effectiveness of periodic flows to maximize solute mixing is a difficult task given the need to use a 3D setup and the large number of possible flow configurations that should be analyzed in order to identify the optimal one. This is the typical situation in which analytical solutions, though approximated, may assist modelers in screening possible alternative flow configurations such that solute dilution is maximized. To quantify dilution (i.e. a precondition that enables reactive mixing) we utilize the concept of the dilution index [1]. In this presentation, the periodic flow takes place in an aquifer with spatially variable hydraulic conductivity field which is modeled as a Stationary Spatial Random Function. We developed a novel first-order analytical solution of the dilution index under the hypothesis that the flow can be approximated as a sequence of steady state configurations with the mean velocity changing with time in intensity and direction. This is equivalent to assume that the characteristic time of the transient behavior is small compared to the period characterizing the change in time of the mean velocity. A few closed paths have been analyzed quantifying their effectiveness in enhancing dilution and thereby mixing between the resident contaminant and an oxidant. In particular, we considered three different flow configurations: (1) a "circular" pattern, in which the vector of the mean velocity rotates at a constant celerity; (2) a "shake" pattern, in which the velocity has a constant magnitude and changes direction alternatively leading to a "back and forth" type of movement and finally (3) a more general "shake and rotate" pattern, which combines the previous two configurations. The new analytical solution shows that dilution is affected by the configuration of the periodic mean flow. Results show that the dilution index increases when the rotation-shake configuration is adopted. In addition, the dilution index is augmented with the oscillation amplitude of the shake component. This analysis is useful to identify optimal flow configurations that may be approximately reproduced in the field and which efficiency may be checked more accurately by numerical simulations, thereby alleviating the computational burden by efficiently screening among alternative configurations. References [1] Kitanidis, P. K. (1994), The concept of the Dilution Index, Water Resour. Res., 30(7), 2011-2026, doi:10.1029/94WR00762.

ELECTROLYTIC SOLUTIONS. Annual Progress Report, May 1, 1962-June 1, 1963

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

Braunstein, J.

Results of investigations of the thermodynamics of association in molten salts and in concentrated aqueous electrolyte solutions are reported. Association constants of Pb(II) with chloride or bromide and of Cd(II) with chloride or bromide in molten mixtures of LiNC/sub 3/ and KNO/sub 3/ were measured potentiometrically at several temperatures and compared with previous results in mixtures of NaNO/sub 3/ and KNO/sub 3/. The anomalous'' solvent effect of lithium ion, reported previously for the association of Cd(II) with bromide was observed aiso for the other associations and a tentative explanation is suggested. The temperature dependence of the association constants was foundmore » to be in agreement with the quasi-lattice model. The association constant of Ag(I) with iodide in molten mixtures of NaNO/sub 3/ and KNO/sub 3/ was measured and compared with previous results in pure KNO/sub 3/. The solvent effect was consistent with the reciprocal coulomb effect.'' Techniques were developed, and preliminary results obtained for measuring association constants in the solvent system KNO/sub 3/--Ca(NO/sub 3/)/sub 2/ in order to investigate the effect of charge as well as size of solvent cation on association constants in molten salt solutions. The measurement of association constants in concentrated aqueous electrolyte solutions was continued. The association of Cd(II) with bromide in aqueous LiNC/sub 3/ was measured as part of a program to find a system that would lend itself to investigation over the range between anhydrous molten salt and aqueous electrolyte solution. Cells and electrodes were developed for investigating association constants in equimolar LiNO/sub 3/ -KNO/sub 3/ with controlled small water contents, and preliminary results are reported. (auth)« less

A SERS characterization of the stability of polythionates at the gold-electrolyte interface

NASA Astrophysics Data System (ADS)

Mirza, Jeff; Smith, Scott R.; Baron, Janet Y.; Choi, Yeonuk; Lipkowski, Jacek

2015-01-01

A gold nanorod (AuNR) array electrode was employed to record SERS spectra as a function of immersion time in electrolyte solutions of tetrathionate, trithionate, the [Au(S2O3)2]3- complex, sulfide and thiosulfate. The generalized two-dimensional correlation spectroscopy was employed to deconvolute broad bands in the SERS spectra. The results show that the polythionates, tetrathionate and trithionate, sulfide, and the [Au(S2O3)2]3- complex decompose to form cyclo-S8, polymeric and monoatomic sulfur at the gold surface. The relative amount of these different forms of sulfur in the film formed at the surface depends on the nature of the electrolyte species. The decomposition of tetrathionate leads predominantly to the formation of cyclo-S8. Comparable amounts of all three forms of sulfur are formed in the solution of the [Au(S2O3)2]3- complex. Monoatomic sulfur is formed predominantly at the gold surface in solutions of trithionate and thiosulfate. In contrast to the previous suggestions, the results of this study demonstrate that polythionates are not present in the passive layer during gold leaching from thiosulfate solutions at a prolonged leaching times.

Experimental Investigations of the Weathering of Suspended Sediment by Alpine Glacial Meltwater

NASA Astrophysics Data System (ADS)

Brown, Giles H.; Tranter, M.; Sharp, M. J.

1996-04-01

The magnitude and processes of solute acquisition by dilute meltwater in contact with suspended sediment in the channelized component of the hydroglacial system have been investigated through a suite of controlled laboratory experiments. Constrained by field data from Haut Glacier d'Arolla, Valais, Switzerland the effects of the water to rock ratio, particle size, crushing, repeated wetting and the availability of protons on the rate of solute acquisition are demonstrated. These free-drift experiments suggest that the rock flour is extremely geochemically reactive and that dilute quickflow waters are certain to acquire solute from suspended sediment. These data have important implications for hydrological interpretations based on the solute content of glacial meltwater, mixing model calculations, geochemical denudation rates and solute provenance studies.

Microstructure, thickness and sheet resistivity of Cu/Ni thin film produced by electroplating technique on the variation of electrolyte temperature

NASA Astrophysics Data System (ADS)

Toifur, M.; Yuningsih, Y.; Khusnani, A.

2018-03-01

In this research, it has been made Cu/Ni thin film produced with electroplating technique. The deposition process was done in the plating bath using Cu and Ni as cathode and anode respectively. The electrolyte solution was made from the mixture of HBrO3 (7.5g), NiSO4 (100g), NiCl2 (15g), and aquadest (250 ml). Electrolyte temperature was varied from 40°C up to 80°C, to make the Ni ions in the solution easy to move to Cu cathode. The deposition was done during 2 minutes on the potential of 1.5 volt. Many characterizations were done including the thickness of Ni film, microstructure, and sheet resistivity. The results showed that at all samples Ni had attacked on the Cu substrate to form Cu/Ni. The raising of electrolyte temperature affected the increasing of Ni thickness that is the Ni thickness increase with the increasing electrolyte temperature. From the EDS spectrum, it can be informed that samples already contain Ni and Cu elements and NiO and CuO compounds. Addition element and compound are found for sample Cu/Ni resulted from 70° electrolyte temperature of Ni deposition, that are Pt and PtO2. From XRD pattern, there are several phases which have crystal structure i.e. Cu, Ni, and NiO, while CuO and PtO2 have amorphous structure. The sheet resistivity linearly decreases with the increasing electrolyte temperature.