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At least 73 records · Page 4

Two Ligands of Interest in Recovering Uranium from the Oceans: The Correct Formation Constants of the Uranyl(VI) Cation with 2,2'-Bipyridyl-6,6'-dicarboxylic Acid and 1,10-Phenanthroline-2,9-dicarboxylic Acid

The ligands BDA (2,2'-bipyridyl-6,6'-dicarboxylic acid) and PDA (1,10-phenanthroline-2,9-dicarboxylic acid) are of interest as functional group types for ion-exchange materials for extracting uranium from the oceans, reported in a previous paper for PDA Lashley, M. A. ( Inorg. Chem. 2016 55 10818 10829). Yang, Y. ( Inorg. Chem. 2019, 58, 6064 6074) have published what they claim to be a more accurate result for the formation of the UO 2 2+ /PDA complex of log K 1 = 22.84 compared with our reported value of log K 1 = 16.5, as well as log K 1 = 21.52 for the BDA complex. The determination of log K 1 for the PDA and BDA complexes with the UO 2 2+ cation was carried out by Yang et al. using a competition reaction between DTPA (diethylenetriamine pentaacetic acid) and BDA or PDA, monitoring the absorbance due to the BDA and PDA ligands. This competition method using absorbance versus pH titrations was developed for determining the formation constants of the complexes of several polypyridyl ligands plus PDA complexes of metal ions, which were too stable for log K determination by competition with protons. A key feature of such titrations is that in the competition reaction, the displacement of the pyridyl donor ligand (e.g., PDA) by the competing ligand (e.g., DTPA), the absorbance spectrum of the displaced pyridyl donor ligand should be observed. Competing ligands used to date have been EDTA (ethylenediamine tetraacetic acid), DTPA, or the hydroxide ion. In the study of Yang et al., no such displaced PDA or BDA was apparent in the absorbance spectra in their titrations so that their reported log K 1 values have no validity. Their log K 1 values are so much higher than log K 1 for the uranyl DTPA complex (~13.6) that DTPA could not possibly displace BDA or PDA from the uranyl cation, and a competition reaction could not possibly occur. Here, we report the correct value of log K 1 = 15.4 (ionic strength = zero) for the uranyl BDA complex, to illustrate the correct determination of such a constant by a competition reaction between BDA and hydroxide, showing how the characteristic absorbance spectrum for a BDA complex, here the UO 2 2+ complex, disappears, and the distinctive absorbance spectrum of the free nonprotonated BDA ligand appears as the pH is increased, and BDA is displaced by the hydroxide ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of nitrogen nutrition management on biomass partitioning and nitrogen use efficiency indices in hydroponically grown potato

The National Aeronautics and Space Administration (NASA) has been conducting controlled environment research with potatoes (Solanum tuberosum L.) in recirculating nutrient film technique (NFT)-hydroponic systems as a human life support component during long-duration spaceflight. Standard nutrient solution management approaches include constant pH regulation with nitric acid (HNO3) and daily adjustment of electrical conductivity (EC) equivalent to half-strength modified Hoagland's solution, where nitrate (NO3-) is the sole nitrogen (N) source. Although tuber yields have been excellent with such an approach, N use efficiency indices are expected to be low relative to tuber biomass production. Furthermore, the high amount of N used in NFT-hydroponics, typically results in high inedible biomass, which conflicts with the need to minimize system mass, volume, and expenditure of resources for long-duration missions. More effective strategies of N fertilization need to be developed to more closely match N supply with demand of the crop. Hence, the primary objective of this study was to identify the optimal N management regime and plant N requirement to achieve high yields and to avoid inefficient use of N and excess inedible biomass production. In separate 84-day cropping experiments, three N management protocols were tested. Treatments which decreased NO3(-)-N supply indirectly through lowering nutrient solution EC (Expt. I), or disabling pH control, and/or supplying NH4(+)-N (Expt. III) did not significantly benefit tuber yield, but did influence N use efficiency indices. When supplied with an external 7.5 mM NO3(-)-N for the first 42 days after planting (DAP), lowered to 1.0 mM NO3(-)-N during the final 42 days (Expt. II), plants were able to achieve yields on par with plants which received constant 7.5 mM NO3(-)-N (control). By abruptly decreasing N supply at tuber initiation in Expt. II, less N was taken up and accumulated by plants compared to those which received high constant N (control). However, proportionately more plant accumulated N was used (N use efficiency) to produce tuber biomass when N supply was abruptly lowered at tuber initiation in Expt. II. Hence, a hydroponic nutrient solution N management system may be modified to elicit greater plant N-use while maintaining overall high tuber yield as opposed to achieving high tuber yields through excess N supply and shoot growth.

NASA Discipline Life Support Systems↗

Rate constants measured for hydrated electron reactions with peptides and proteins

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Braams, R.↗

Impact of Sn Lewis Acid Sites on the Dehydration of Cyclohexanol

The impact of Sn on the concentration and strength of acid sites in Al containing zeolites with MFI topology and their catalytic activity for the dehydration of cyclohexanol in the aqueous phase has been investigated. The materials maintain constant Al concentrations and consequently Bro̷nsted acid site (BAS) concentrations, while exhibiting an increasing concentration of Sn Lewis acid sites (LAS). The presence of water alters LAS (Sn) , leading to weak BAS (Sn) that increases the concentration of water in the zeolite micropore, while leaving the rate of dehydration of cyclohexanol unchanged. The TOF increases with the concentration of BAS (Al) in close contact with framework LAS (Sn) , referred to as BAS (Pair) . The increase in the Arrhenius pre-exponential factor, without affecting the activation barrier (E a ), leads to the hypothesis that the proximity of both sites allows for a later transition state induced by the polarization of the C–O bond, leading in turn to a higher transition entropy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature dependence of the formation of sulfate aerosols in the stratosphere

Classical nucleation theory is used in calculations of the temperature dependence of the characteristics and nucleation rates of sulfate aerosols in the binary H2SO4-H2O vapor mixture, in order to assess the influence of temperature on the formation of sulfate aerosols in the stratosphere, and to explore the possibility of new particle formation through homogeneous nucleation processes at regions where temperature is as low as -75 C, rather than the often-assumed -50 or -55 C. Calculation results indicate that the number of particles formed at a lower temperature is larger by several orders of magnitude than at higher temperatures, when water and sulfuric acid vapor concentrations are kept constant, and that large quantities of ultrafine particles which cannot be detected by conventional methods may exist at low-temperature stratospheric regions.

Yue, G. K.↗

Surface topographical changes measured by phase-locked interferometry

An electronic optical laser interferometer capable of resolving depth differences of as low as 30 A and planar displacements of 6000 A was constructed to examine surface profiles of bearing surfaces without physical contact. Topological chemical reactivity was determined by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. Scuffed bearing surfaces reacted much faster than virgin ones but that bearing surfaces exposed to lubricants containing an organic chloride reacted much more slowly. The reactivity of stainless steel plates, heated in a nitrogen atmosphere to different temperatures, were examined later at ambient temperature. The change of surface contour as a result of the probe reaction followed Arrhenius-type relation with respect to heat treatment temperature. The contact area of the plate of a ball/plate sliding elastohydrodynamic contact run on trimethylopropane triheptanoate with or without additives was optically profiled periodically. As scuffing was approached, the change of profile within the contact region changed much more rapidly by the acid probe and assumed a constant high value after scuffing. A nonetching metallurgical phase was found in the scuff mark, which was apparently responsible for the high reactivity.

Lauer, J. L.↗

Unnatural selection in chemical systems

The theory of evolution through natural selection was proposed by Darwin and Wallace to explain how the characteristics of populations of animals change with time. An examination of their assumptions shows that the theory has much broader application than they originally envisaged. We now know that in appropriate environments RNA molecules or computer viruses, for example, can evolve. The adventure with which we are concerned is the quest for chemical systems that undergo processes analogous to Darwinian selection in the test tube. The search is not restricted to systems that are closely related to nucleic acids, although most of the available experimental evidence concerns such systems. A population of molecules satisfies all the requirements of the theory is there are different kinds of molecules in the population and if each individual molecule can direct the formation of copies of itself, then a population of molecules will adapt to a varying environment by changing its composition so as to maintain as high as possible a rate of replication. Sol Spiegelman is the inventor of 'unnatural selection'. He showed clearly that populations of RNA molecules evolve when replicated repeatedly by Q beta RNA polymerase under a chosen set of adverse reaction conditions. In the systems that he studied, the initial population was fairly homogeneous and much of the variation was created during the course of the experiment by mutation, that is, error of replication. The term 'unnatural selection' will be used loosely to describe evolution of nucleic acids or other replicatable polymers in vitro. The term 'Natural Selection' will be reserved for the evolution of living organisms and their viruses. Natural Section usually involves the coevolution of nucleic acids and proteins, while 'unnatural selection', as practiced so far, allows replicating nucleic acids to evolve but hold constant the enzymes that catalyze replication. It is widely believed that biology based on DNA, RNA, and proteins was preceded by the biology of an 'RNA world' in which enzymes were composed of RNA alone. The origin of RNA replication is thus the central puzzle of the origins of life. Consequently, RNA-catalyzed RNA replication is presently one of the main goals of experimental work on unnatural selection. However, there is also a more distant goal, namely, to achieve replication and selection in systems unrelated to RNA. These different systems are discussed in this article.

Orgel, Leslie E.↗

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗

The Stability of SiO{sub 2} Fe{sub 3}O{sub 4} Nanoparticles for Uranium Extraction in Acidic Media - 20189

This comprehensive study has shown that the proposed strategy of SiO{sub 2} coating of Fe{sub 3}O{sub 4} nanoparticles (NPs) for the use of uranium (U) extraction in acidic media was successful. The breakdown of Fe{sub 3}O{sub 4} in acidic media has proven to be a challenge when applying to a nuclear waste removal scenario, leading to the dissolution of Fe{sub 3}O{sub 4} and preventing uptake of U ions in the waste. To overcome this a SiO{sub 2} passivating layer was grafted to the Fe{sub 3}O{sub 4} NPs, to which an acid stability test was conducted between pH 3 and pH 4. It has been shown via Transmission Electron Microscopy (TEM) and zeta potential measurements that the uncoated Fe{sub 3}O{sub 4} NPs exhibit rapid coagulation when exposed to acidic conditions, moving from a stable zeta potential of -44 mV to an unstable zeta potential of +6 mV. SiO{sub 2} coated Fe{sub 3}O{sub 4} on the other hand can remain stable for several hours and continue to be stable beyond that. Throughout acid exposure the zeta potential of these NPs remained at ∼ -38 mV, showing great stability. As a functionality is needed on the surface of the NPs for separation and extraction, the phosphate complex used was also tested for its acid stability. It was determined that with a constant zeta potential of ∼ -20 mV, the phosphate functionality was able to remain stable in the acidic conditions simulating the environment of certain nuclear wastes. Overall SiO{sub 2} coated (PO)x-Fe{sub 3}O{sub 4} NPs show great promise for application in separation and removal of U in acid media. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Force Field X: A computational microscope to study genetic variation and organic crystals using theory and experiment

Force Field X (FFX) is an open-source software package for atomic resolution modeling of genetic variants and organic crystals that leverages advanced potential energy functions and experimental data. FFX currently consists of nine modular packages with novel algorithms that include global optimization via a many-body expansion, acid–base chemistry using polarizable constant-pH molecular dynamics, estimation of free energy differences, generalized Kirkwood implicit solvent models, and many more. Applications of FFX focus on the use and development of a crystal structure prediction pipeline, biomolecular structure refinement against experimental datasets, and estimation of the thermodynamic effects of genetic variants on both proteins and nucleic acids. The use of Parallel Java and OpenMM combines to offer shared memory, message passing, and graphics processing unit parallelization for high performance simulations. Overall, the FFX platform serves as a computational microscope to study systems ranging from organic crystals to solvated biomolecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and modeling studies of PR and ND oxalate solubility to high ionic strengths: Insight into actinide(III) oxalates

Actinide oxalates are chemical compounds important to nuclear industry, ranging from actinide separation in waste reprocessing, to production of specialty actinides, and to disposal of high level nuclear waste (HLW) and spent nuclear fuel (SNF). In this study, the solubility constants for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O by performing solubility experiments in HNO 3 and mixtures of HNO 3 and H 2 C 2 O 4 at 23.0 ± 0.2 °C have been determined. The targeted starting materials, Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O, were successfully synthesized at room temperature using PrCl 3 , NdCl 3 and oxalic acid as the source metrials. Then, we utilized the targeted solubility-controlling phases to conduct solubility measurements. There was no phase change over the entire periods of experiments, demonstrating that Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O were the solubility-controlling phases in our respective experiments. Based on our experimental data, we have developed a thermodynamic model for Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O in the mixtures of HNO 3 and H 2 C 2 O 4 to high ionic strengths. The model for Pr 2 (C 2 O 4 ) 3 •10H 2 O reproduces well the reported experimental data for Pu 2 (C 2 O 4 ) 3 •10H 2 O, which are not utilized for the model development, demonstrating that Pr(III) is an excellent analog for Pu(III). Similarly, the model for Nd 2 (C 2 O 4 ) 3 •10H 2 O reproduces the solubility of Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The Pitzer model was used for the calculation of activity coefficients. Based on the published, well established model for dissociation constants for oxalic acid and stability constants for actinide-oxalate complexes [i.e., AmC 2 O 4 + , and Am(C 2 O 4 ) 2 - ] to high ionic strengths, we have obtained the solubility constants (log 10 K 0 ) for the following reactions at 25 °C, Pr 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Pr 3+ + 3C 2 O 4 2- + 10H 2 O(l). Nd 2 (C 2 O 4 ) 3 •10H 2 O ⇌ 2Nd 3+ + 3C 2 O 4 2- + 10H 2 O(l). to be -30.82 ± 0.30 (2σ), and - 31.14 ± 0.35 (2σ), respectively. These values for can be directly applied to Pu 2 (C 2 O 4 ) 3 •10H 2 O, Am 2 (C 2 O 4 ) 3 •10H 2 O and Cm 2 (C 2 O 4 ) 3 •10H 2 O. The model established for actinide oxalates by this study provides the needed knowledge with regard to solubilities of actinide/REE oxalates at various ionic strengths, and is expected to find applications in many fields, including the geological disposal of nuclear waste and the mobility of REE under the surface conditions, as Pr 2 (C 2 O 4 ) 3 •10H 2 O and Nd 2 (C 2 O 4 ) 3 •10H 2 O can be regarded as the pure Pr and Nd end-members of deveroite, a recently discovered natural REE oxalate with the following stoichiometry, (Ce 1.01 Nd 0.33 La 0.32 Pr 0.11 Y 0.11 Sm 0.01 Pb 0.04 U 0.03 Th 0.01 Ca 0.04 ) 2.01 (C 2 O 4 ) 2.99 •9.99H 2 O. Regarding its importance in the geological disposal of nuclear waste, Am 2 (C 2 O 4 ) 3 •10H 2 O/Pu 2 (C 2 O 4 ) 3 •10H 2 O/Cm 2 (C 2 O 4 ) 3 •10H 2 O can be the source-term phase for actinides, as demonstrated by the instance in the disposal in clay/shale formations. This is exemplified by the stability of Am 2 (C 2 O 4 ) 3 •10H 2 O in comparison with Am(OH) 3 (am), Am(OH) 3 (s) and AmCO 3 (OH)(s) under the relevant geological repository conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. A theoretical expression for the rotating ring-disk electrode technique; the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; oxygen reduction mechanism in trifluoromethanesulfonic acid (TFMSA), considered as an alternate electrolyte for the acid fuel cells; and transport properties of the phosphoric acid electrolyte at high concentrations and temperatures are covered.

Chin, D. T.↗

Observationally Constrained Modeling of the Reactive Uptake of Isoprene-Derived Epoxydiols under Elevated Relative Humidity and Varying Acidity of Seed Aerosol Conditions

Isoprene is the non-methane volatile organic compound (VOC) emitted in largest amounts to the atmosphere, and it is a significant source of secondary organic aerosol (SOA) mass. The uptake of isoprene oxidation products followed by multiphase chemistry in fine particles is the key pathway to form isoprene epoxydiol-derived SOA (IEPOX-SOA). However, many parameters that relate to diffusion and reaction of IEPOX in the particle phase remain uncertain, since reaction kinetics previously measured in bulk aqueous phase solutions might be different from atmospheric aerosols. Here, we use simultaneous environmental chamber measurements of multiple parameters governing IEPOX-SOA formation at timescales of ~hours: particle size distribution, composition, and volatility of IEPOX-SOA to constrain the key parameters governing IE-POX-SOA formation under humid (i.e., 50% relative humidity, RH) and varying seed aerosol acidity conditions. Reducing the 2-methyltetrol (tetrol) reaction rate constants by a factor of 4 brings the model predictions in agreement with the IEPOX-SOA measurements with acidified ammonium bisulfate seed aerosols. For less acidic ammonium sulfate aerosols both the organo-sulfate (OS) and tetrol reaction rate constants need to be reduced to bring model predictions closer to chamber observations. Using the measured non-volatile content of IEPOX-SOA we constrain the oligomerization timescale of 2-methyltetrols. We find that the oligomerization timescale is 4 hours with acidified seed aerosols, but a much longer time scale of 24 hours is needed for non-acidified seed aerosols, indicating that the aerosol acidity greatly affects the oligomerization rate of tetrols. Here we show that the actual kinetics of IEPOX-SOA formation rate on aerosol seeds consisting of both ammonium bisulfate and ammonium sulfate are a factor of 4~5 slower under 50-60% RH conditions compared to their application in previous models, which were based on bulk aqueous solution measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous photo-Fenton-like degradation of emerging pharmaceutical contaminants in wastewater using Cu-doped MgO nanoparticles

In this study, a facile thermal decomposition method was utilized to synthesize Cu-doped MgO nanoparticles possessing mesoporosity. These mesoporous Cu doped MgO nanoparticles were shown to be efficient photo-Fenton-like catalysts for the degradation of emerging pharmaceutical contaminants in wastewater and were able to completely oxidize salicylic acid within 1 hour under optimized conditions. Tetracycline was shown to be converted to other intermediates with a large portion of it undergoing full mineralization. Batch experiments were conducted to demonstrate the effects of Cu loading on MgO, overall catalyst loading, and H 2 O 2 concentration on the salicylic acid and tetracycline conversion and rate constants. Quenching experiments revealed that both •OH radicals or HO 2 •/•O 2 - radicals were involved in the reaction, with the latter showing a higher contribution. The surface dissolution of MgO was shown to facilitate a high pH environment which completely prevented Cu from leaching out of the catalyst while retaining high activity. The catalyst reusability was shown to be satisfactory with high activity and conversion being preserved over five cycles.

04 OIL SHALES AND TAR SANDS↗

Surface Functionalized Barium Titanate Nanoparticles: A Combined Experimental and Computational Study

Barium titanate (BTO) nanoparticles show great potential for use in electrostatic capacitors with high energy density. This includes both polymer composite and sintered capacitors. However, questions about the nanoparticles' size distribution, amount of agglomeration, and surface ligand effect on performance properties remain. Reducing particle agglomeration is a crucial step to understanding the properties of nanoscale particles, as agglomeration has significant effects on the composite dielectric constant. BTO surface functionalization using phosphonic acids is known reduce BTO nanoparticle agglomeration. We explore solution synthesized 10 nm BTO particles with tert-butylphosphonic acid ligands. Recent methods to quantifying agglomeration using an epoxy matrix before imaging shows that tert-butylphosphonic acid ligands reduce BTO agglomeration by 33%. Thermometric, spectroscopic, and computational methods provide confirmation of ligand binding and provide evidence of multiple ligand binding modes on the BTO particle surface.

36 MATERIALS SCIENCE↗

Additives Lower Dielectric Constants Of Polyimides

Dielectric constants as low as 2.43 make polyimides more attractive for electronic applications. Process makes aromatic condensation polyimide films and coatings with dielectric constants lowered by incorporation of diamic acid additives. Materials provide better electrical insulation without sacrificing temperature stability of polyimide binders. Applicable whenever high temperature, low absorption of moisture, and high electrical-insulation properties needed. Applications include semiconductors and printed-circuit boards for computer industry and possibly automotive industry.

Stoakely, Diane M.↗

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. The areas covered were: (1) development of a theoretical expression for the rotating ring disk electrode technique; (2) determination of the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; (3) determination of oxygen reduction mechanism in trifluoreomethanesulfonic acid (TFMSA) which was considered as an alternate electrolyte for the acid fuel cells; and (4) the measurement of transport properties of the phosphoric acid electrolyte at high concentrations and temperatures.

Chin, D. T.↗