Connections between the Speciation and Solubility of Ni(II) and Co(II) in Molten ZnCl2
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99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “Solubility”
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Effects of gas relative permeability hysteresis and solubility on associated CO 2 storage performance
Not provided.
Energy & Fuels↗
Serial femtosecond crystallography of soluble proteins in lipidic cubic phase
Serial femtosecond crystallography (SFX) at X-ray free-electron lasers (XFELs) enables high-resolution protein structure determination using micrometre-sized crystals at room temperature with minimal effects from radiation damage. SFX requires a steady supply of microcrystals intersecting the XFEL beam at random orientations. An LCP–SFX method has recently been introduced in which microcrystals of membrane proteins are grown and delivered for SFX data collection inside a gel-like membrane-mimetic matrix, known as lipidic cubic phase (LCP), using a special LCP microextrusion injector. Here, it is demonstrated that LCP can also be used as a suitable carrier medium for microcrystals of soluble proteins, enabling a dramatic reduction in the amount of crystallized protein required for data collection compared with crystals delivered by liquid injectors. High-quality LCP–SFX data sets were collected for two soluble proteins, lysozyme and phycocyanin, using less than 0.1 mg of each protein.
59 BASIC BIOLOGICAL SCIENCES↗
Experimental determination of lead carbonate solubility at high ionic strengths: A Pitzer model description
In this article, solubility measurements of lead carbonate, PbCO 3 (cr), cerussite, as a function of total ionic strengths are conducted in the mixtures of NaCl and NaHCO 3 up to I = 1.2 mol•kg –1 and in the mixtures of NaHCO 3 and Na 2 CO 3 up to I = 5.2 mol•kg –1 , at room temperature (22.5 ± 0.5 °C). The solubility constant (log K sp ) for cerussite, PbCO 3 (cr) = Pb 2+ + CO 3 2- was determined as –13.76 ± 0.15 (2σ) with a set of Pitzer parameters describing the specific interactions of PbCO 3 (aq), Pb(CO 3 ) 2 2- , and Pb(CO 3 )Cl – with the bulk-supporting electrolytes, based on the Pitzer model. The model developed in this work can reproduce the experimental results including model-independent solubility values from the literature over a wide range of ionic strengths with satisfactory accuracy. The model is expected to find applications in numerous fields, including the accurate description of chemical behavior of lead in geological repositories, the modeling of formation of oxidized Pb–Zn ore deposits, and the environmental remediation of lead contamination.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrochemical Stability and Reversibility of Aqueous Polysulfide Electrodes Cycled Beyond the Solubility Limit
Batteries which use dissolved redox-active species, such as redox flow batteries (RFBs), are often considered to be constrained in their operation and energy density by the solubility limit of the redox species. Here, we show that soluble redox active electrolytes can be reversibly cycled deeply into the precipitation regime, permitting higher effective concentrations, energy densities, and lower costs. Using aqueous sodium polysulfide negative electrolytes cycled in the nominal Na 2 S 2 to Na 2 S 4 capacity range as an example, we show that the effective solubility can be increased from 5 M in the fully-dissolved state to as much as 10 M using the precipitation strategy. Stable cycling was observed at 8 M concentration over more than 1600h at room temperature. We also analyze the range of polysulfide electrochemical stability, and characterize the precipitate composition. This enhanced effective concentration approach may be generalized to other redox chemistries that utilize solubilized reactants, and may be especially useful for long-duration storage applications where slow charge-discharge rates allow equilibration of precipitated species with the redox-active solution.
25 ENERGY STORAGE↗
Nanomineralogy as a new dimension in understanding elusive geochemical processes in soils: The case of low-solubility-index elements
Nanomineralogical studies of mineral surface coatings in soils reveal insights into biogeochemical processes that heretofore were not known to exist. This is a new dimension in understanding past and present biogeochemical processes in soils, and in this study it is a way to better understand the behavior of low-solubility-index elements such as Al, Ti, and Zr. Soils were sampled from selected sites in Sudbury (Ontario, Canada) that have been affected by acidification and particulate matter emissions from base-metal smelters with subsequent remediation within the past century. These anthropogenic processes have affected an entire landscape, but are now recorded in assemblages of nano-size phases that can be only studied using a combination of focused ion beam technology (for sample preparation) and high-resolution analytical transmission electron microscopy (for phase identification). A first generation of clay minerals (pre-acidification phase), their partial replacement by nano-size hematite and amorphous silica (anthropogenic acidification), and a second generation of clay minerals (post-acidification, including soil remediation) are products of changes in soil biogeochemical processes during these natural and anthropogenic-induced weathering stages. Furthermore, complex assemblages of nanophases formed prior to the second generation of clay minerals depict underlying mechanisms for the mobilization and sequestration of the low-solubility-index elements Zr and Ti under acidic conditions. The occurrence of baddeleyite (ZrO 2 ), anatase (TiO 2 ), and the Magneli phases Ti 4 O 7 and Ti 5 O 9 (all present at the nanoscale) suggest an influx of nanocolloidal Zr and Ti oxides during weathering of smelter-derived particulate matter. Kelyshite {NaZr[Si 2 O 6 (OH)]}, authigenic zircon (ZrSiO 4 ), and kleberite [Fe 3+ Ti 6 O 11 (OH) 5 ] are most likely products of the sequestration of the Zr- and Ti-bearing nanocolloids.
58 GEOSCIENCES↗
Synthesis of highly water soluble tetrabenzoporphyrins and their application toward photodynamic therapy
Novel tetraaryl-(pyridinium-4-yl)-tetrabenzoporphyrins have been successfully synthesized via a Heck-based sequence reaction. These tetrabenzoporphyrins were substituted with eight pyridyl groups at the fused benzene rings. Methylation of the pyridyl groups with methyl iodide afforded highly water soluble tetrabenzoporphyrins carrying eight ionic groups. The extended π-conjugation broadened and red-shifted the absorption band of these porphyrins to 650–750 nm. Furthermore, these cationic tetrabenzoporphyrins showed non-toxicity in the dark up to 100 uM. High phototoxicity with IC 50 values lower than 18 μM were obtained for these tetrabenzoporphyrins.
DFT calculation photosensitizer↗
Solubility of iron, nickel, and cobalt in liquid potassium and effect of oxygen gettering agents on iron solubility
Iron, nickel, and cobalt solubility in liquid potassium, and effect of oxygen gettering agents on iron solubility
LIQUID POTASSIUM↗
Trans-signaling of interleukin-6 (IL-6) is mediated by the soluble IL-6 receptor, but not by soluble CD5
IL-6 exerts its pleiotropic activities on its target cells via the IL-6 alpha-receptor (IL-6R), which is expressed on a limited number of cell types. IL-6 can further signal via soluble forms of its receptor (sIL-6R), a process that has been termed trans-signaling. Recently, CD5 was described as an alternative alpha-receptor for IL-6 on B cells leading to the phosphorylation of the transcription factor STAT3 via the signal-transducing β-receptor gp130 in a Jak2-dependent manner. In this study, we sought to investigate whether IL-6 was also able to signal via soluble CD5 (sCD5) analogous to IL-6 trans-signaling. We show that IL-6 indeed binds to sCD5, but that this does not lead to the activation of signal transduction or cell proliferation. Furthermore, sCD5 did also not interfere with IL-6 classic signaling, suggesting that the affinity between the two proteins was too weak to provoke a biological effect. Thus, trans-signaling of IL-6 can only occur via sIL-6R, but not sCD5. - Highlights: • IL-6 binds to sCD5, albeit with less affinity compared to sIL-6R. • IL-6/sCD5 is not able to perform IL-6 trans-signaling. • sCD5 does not act as an inhibitory decoy receptor for IL-6.
60 APPLIED LIFE SCIENCES↗
Comparing measurements of limiting current of electrolytes with theoretical predictions up to the solubility limit
Imposing a steady ionic current through an electrolyte results in the formation of salt concentration gradients that compromise battery performance. The limiting current is usually defined as the current at which the salt concentration at the cathode approaches zero. Higher currents cannot be imposed on the cell as larger concentration gradients are unsustainable. We study the limiting current in electrolytes comprising a perfluorinated oligomer, C8-DMC, and lithium bis-(fluorosulfonyl)imide salt in symmetric lithium cells. The time-dependence of the potential, which increases as salt concentration gradients develop, was also measured. Both steady-state and transient behaviors are modeled using Newman's concentrated solution theory; transport and thermodynamic parameters needed to perform the calculations were measured independently. The limiting current is a nonmonotonic function of salt concentration in both theory and experiment. The model shows that at low salt concentrations (below 0.88 mol/kg solvent), the concentration at the cathode approaches zero at limiting current. In contrast, at high salt concentrations (above 0.88 mol/kg solvent), the concentration at the anode approaches the solubility limit (2.03 mol/kg solvent). The experimentally determined salt concentration at which the limiting current is maximized is in excellent agreement with theoretical predictions made without resorting to any adjustable parameters.
Shah, Deep B.↗
Enhancing the Solubility of Semiconducting Polymers in Eco-Friendly Solvents with Carbohydrate-Containing Side Chains
Semiconducting polymers are at the forefront of next-generation organic electronics due to their robust mechanical and optoelectronic properties. However, their extended π-conjugation often leads to materials with low solubilities in common organic solvents, thus requiring processing in high-boiling-point and toxic halogenated solvents to generate thin-film devices. To address this environmental concern, a natural product-inspired side-chain engineering approach was used to incorporate galactose-containing moieties into semiconducting polymers toward improved processability in greener solvents. Novel isoindigo-based polymers with different ratios of galactose-containing side chains were synthesized to improve the solubilities of the organic semiconductors in alcohol-based solvents. The addition of carbohydrate-containing side chains to π-conjugated polymers was found to considerably impact the intermolecular aggregation of the materials and their microstructures in the solid state as confirmed by atomic force microscopy and grazing-incidence wide-angle X-ray scattering. The charge transport characteristics of the new semiconductors were evaluated by the fabrication of organic field-effect transistors prepared from both toxic halogenated and greener alcohol-based solvents. Importantly, the incorporation of carbohydrate-containing side chains was shown to have very little detrimental impact on the electronic properties of the polymer when processed from green solvents.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High CO2 solubility, permeability and selectivity in ionic liquids with the tetracyanoborate anion
Five different ionic liquids containing the tetracyanoborate anion were synthesized and evaluated for CO2 separation performance. Measured CO2 solubility values were exceptionally high compared to analogous ionic liquids with different anions and ranged from 0.128 mol L-1 atm(-1) to 0.148 mol L-1 atm(-1). In addition, CO2 permeability and CO2/N-2 selectivity values were measured using a supported ionic liquid membrane architecture and the separations performance of the ionic liquid membranes exceeded the Robeson upper bound. These results establish the distinct potential of ionic liquids with the tetracyanoborate, [B(CN)(4)], anion for the separation of CO2.
Mahurin, SM↗
Efficient electrochemical synthesis of robust, densely functionalized water soluble quinones
Robust, highly water-soluble quinone derivatives are efficiently prepared by a scalable electrosynthetic protocol employing low-cost commercially available precursors.
Gerken, James B.↗
Influence of soluble oligomeric aluminum on precipitation in the Al-KOH-H2O system
The role of oligomeric aluminate (Al(OH)4-) species in the precipitation of aluminum phases such as gibbsite (a-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance to developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated Al species in solution to octahedrally coordinated Al in gibbsite. Here we report a quantitative study of dissolved Al in the Al-KOH-H2O system using a combination of molecular spectroscopies. We established a relationship between changes in 27Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al2O(OH)62 . A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH:Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of gibbsite; high concentrations of dimeric Al2O(OH)62-, yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role of the Al2O(OH)62- dimer in promoting gibbsite precipitation from solution, where the potassium ion-paired dimer possibly catalyzes a more rapid transformation of Al coordination from tetrahedral in solution to octahedral in gibbsite.
Dembowski, Mateusz↗
A crucible salt saturation method for determining sulfur solubility in glass melt
Experiments were conducted to determine sulfur solubility in Hanford low-activity waste (LAW) glass melts by a sulfur saturation method. Sulfur-incorporated glass melts were prepared by salt saturation and bubbling methods. The salt saturation method was performed by mixing crushed pre-melted baseline glasses with an excess amount of Na2SO4 prior to melting the mixture at 1150°C for one hour. The bubbling method involved bubbling the glass melt at 1150°C in a Pt crucible with an SO2/O2/N2 gas mix to equilibrate the melt at a known pressure of SO3. Preliminary results suggested that performing one cycle of mixing and melting was not sufficient to saturate the glass. The bubbling method successfully incorporated sulfur into the glass but caused significant losses of sodium from the melt. In order to saturate the glass melt with sulfate without causing noticeable sodium loss, a modified crucible salt saturation method was developed by repeating the mixing and melting of the glass and salt mixture. For all three representative LAW glasses tested in this study, it was found that after three mixing and melting cycles, the sulfur concentration reaches a plateau, indicating reasonable sulfur saturation.
Jin, Tongan↗
Experimental Determination of Solubilities of Sodium Polyborates In MgCl 2 Solutions: Solubility Constant of Di-Sodium Hexaborate Tetrahydrate, and Implications For the Diagenetic Formation of Ameghinite
In this paper, solubility measurements were conducted for sodium polyborates in MgCl 2 solutions at 22.5 ± 0.5 °C. According to solution chemistry and XRD patterns, di-sodium tetraborate decahydrate (borax) dissolves congruently, and is the sole solubility-controlling phase, in a 0.01 mol/kg MgCl 2 solution: Na 2 B 4 O 7 •10H 2 O(cr) ⇌ 2Na + + 4B(OH) 4 + 2H + + H 2 O(l). However, in a 0.1 mol/kg MgCl 2 solution borax dissolves incongruently and is in equilibrium with di-sodium hexaborate tetrahydrate: 2Na 2 B 6 O 10 •4H 2 O(cr) + 2Na + + 23H 2 O(l) ⇌ 3Na 2 B 4 O 7 •10H 2 O(cr) + 2H + . In this study, the equilibrium constant (log K 0 ) for Reaction 2 at 25 °C and infinite dilution was determined to be –16.44 ± 0.13 (2σ) based on the experimental data and the Pitzer model for calculations of activity coefficients of aqueous species. In accordance with the log K 0 for Reaction 1 from a previous publication from this research group, and log K 0 for Reaction 2 from this study, the equilibrium constant for dissolution of di-sodium hexaborate tetrahydrate at 25 °C and at infinite dilution, Na 2 B 6 O 10 •4H 2 O(cr) + 10H 2 O(l) ⇌ 2Na + + 6B(OH) 4 - + 4H + was derived to be –45.42 ± 0.16 (2σ). The equilibrium constants determined in this study can find applications in many fields. For example, in the field of nuclear waste management, the formation of di-sodium hexaborate tetrahydrate in brines containing magnesium will decrease borate concentrations, making less borate available for interactions with Am(III). In the field of experimental investigations, based on the equilibrium constant for Reaction 2, the experimental systems can be controlled in terms of acidity around neutral pH by using the equilibrium assemblage of borax and di-sodium hexaborate tetrahydrate at 25 °C. As salt lakes and natural brines contain both borate and magnesium as well as sodium, the formation of sodium hexaborate tetrahydrate may influence the chemical evolution of salt lakes and natural brines. Di-sodium hexaborate tetrahydrate is a polymorph of the mineral ameghinite [chemical formula Na 2 B 6 O 10 •4H 2 O; structural formula NaB 3 O 3 (OH) 4 or Na 2 B 6 O 6 (OH) 8 ]. Finally, di-sodium hexaborate tetrahydrate could be a precursor of ameghinite and could be transformed when borate deposits are subject to diagenesis.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2 O at 298.15 K to high ionic strengths: Experimental validation and model applications]
In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3 (micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3 (micro cr), avoiding the possibility of phase change.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Rhenium Solubility in Borosilicate Nuclear Waste Glass: Implications for the Processing and Immobilization of Technetium-99
The immobilization of 99Tc in a suitable host matrix has proved to be an arduous task for the researchers in nuclear waste community around the world. At the Hanford site in Washington State, the total amount of 99Tc in low-activity waste (LAW) is ~1300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility/retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of the similarity between their ionic radii and other chemical aspects. The glasses containing Re (0 – 10,000 ppm by mass) were synthesized in vacuum-sealed quartz ampoules in order to minimize the loss of Re by volatilization during melting at 1000 °C. The rhenium was found to predominantly exist as Re (VII) in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) with inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of crystalline inclusions that were detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). The implications of these results on the immobilization of 99Tc from radioactive wastes in borosilicate glasses have been discussed.
borosilicate glass↗