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At least 109 records · Page 6

Scanning Electrochemical Microscopy for Kinetic Investigations in Viscous Deep Eutectic Solvents: Identifying Practical Approach Curves and Deviations from Electron Transfer Models

Determining heterogeneous electrochemical electron transfer (ET) kinetics in electrolytes with a wide range of physical properties is of great interest for achieving high-performance redox flow batteries. Among such electrolytes, concentrated hydrogen-bonded electrolytes (CoHBEs), including deep eutectic solvents (DESs), have recently garnered significant attention. Unfortunately, traditional Tafel analysis using macroelectrodes often encounters issues with mass transfer limitations in CoHBEs with high viscosities, thereby restricting kinetic analysis to a narrow potential window. Here, in this work, we introduce a methodology for evaluating ET kinetics in viscous DES using the scanning electrochemical microscopy (SECM). We first determined practical solutions to SECM tip positioning in ethaline DES, which yield pseudopositive feedback responses. Lattice Boltzmann method (LBM) simulations helped us rationalize the impact of the fluid and concentration fields, as well as tip geometry, tip approach velocity v, and the solvent viscosity ηs, on the shape of the approach curves. In addition to successfully recreating approach curves over a variety of conditions, we found that approaching a conductor ensured a practical point where the normalized tip response (Ni T = 2) converged at L = 0.7 within ∼10% error regardless of tip velocity. With positioning capabilities at hand, we investigated the kinetics of Fe 3+ /Fe 2+ redox couple in aqueous and the ethaline media. The experimental kinetic results were interpreted using the Butler–Volmer (BV) and Marcus–Hush–Chidsey (MHC) models. For ethaline, a nonideal kinetic behavior was observed, potentially attributed to solvent dynamics within DESs or to the interplay of chloride anions in the charge transfer process.

electrodes

Large deviations of ionic currents in dilute electrolytes

Here, we evaluate the exponentially rare fluctuations of the ionic current for a dilute electrolyte by means of macroscopic fluctuation theory. We consider the fluctuating hydrodynamics of a fluid electrolyte described by a stochastic Poisson–Nernst–Planck equation. We derive the Euler–Lagrange equations that dictate the optimal concentration profiles of ions conditioned on exhibiting a given current, whose form determines the likelihood of that current in the long-time limit. For a symmetric electrolyte under small applied voltages, number density fluctuations are small, and ionic current fluctuations are Gaussian with a variance determined by the Nernst–Einstein conductivity. Under large applied potentials, the ionic current distribution is generically non-Gaussian. Its structure is constrained thermodynamically by Gallavotti–Cohen symmetry and the thermodynamic uncertainty principle.

Farhadi, Jafar [University of California, Berkeley

Structural complexity in the f -block: small deviations of the complexation of lanthanides by O,Oʹ -diethylmonothiophosphate

Dithiophosphinic acids undergo radiolytic degradation during the extraction of actinides in used nuclear fuel. These will degrade into monothiophosphinic acids and then to phosphinic acids. To elucidate how the complexes that are formed during these radioactive separations change as the ligand degrades, the mixed donor ligand O,O′- diethylmonothiophosphate is chosen as an analog for the monothiophosphinic intermediate. Herein, the monothiophosphate complexes Ln 2 (OPS(OEt) 2 ) 6 (H 2 O) 8 (Ln = La) (La 2 L 6 H 2 O), Ln 2 (OPS(OEt) 2 ) 6 (EtOH) 4 (Ln = La) (La 2 L 6 EtOH), K 2 [Ln(OPS(OEt) 2 ) 5 (H 2 O) 2 ]·H 2 O·CH 2 Cl 2 , (Ln = Ce) (CeL 5 -α), K 2 [Ln(OPS(OEt) 2 ) 5 (H 2 O) 2 ]·H 2 O·CH 2 Cl 2 , (Ln = Pr) (PrL 5 -β), K[Ln(OPS(OEt) 2 ) 4 (H 2 O) 3 ], (Ln = Pr, Sm-Er) (ML 4 ), and K 3 [Ln(OPS(OEt) 2 ) 6 ], (Ln = Dy) (DyL 6 ) were synthesized and characterized using single-crystal X-ray diffraction and optical spectroscopy. Although the lanthanides contract in a nearly linear fashion, the structural changes observed as the f-block is traversed in these compounds are not necessarily a hard line but more so a blend of different structure types possible for each f-element. Furthermore, comparison of the Ln−O bond lengths shows a nearly linear contraction, but the Ln−S bond lengths do not monotonically decrease because of the hard Lewis acidity of the Ln 3+ cations.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C

Connecting In Situ Stress and Wellbore Deviation to Near-Well Fracture Complexity Using Phase-Field Simulations

The interactions among in situ stress, rock fabric, wellbore geometry, natural fractures, and other natural or man-made defects create highly complex fracture trajectories in the near-wellbore region, far more intricate than those in the far-field. These near-wellbore complexities are critical for the Utah FORGE project and Enhanced Geothermal Systems (EGS) in general. Frictional pressure loss in the near-wellbore region during stimulation can significantly influence the growth of far-field fractures, while pressure losses during circulation serve as a major source of energy dissipation. Near-wellbore fracture complexities are often observable through image logs, offering valuable insights into in situ stress characteristics. However, leveraging this information requires a high-fidelity model capable of capturing the interplay among the diverse factors influencing fracture behavior.

58 GEOSCIENCES

The State of Electric Vehicle Adoption in Colorado for Multifamily versus Single-Family Dwellings: A Methodology for Quantifying Deviation from Parity

Given that electric vehicle adoption is well underway, the spatial distribution of electric vehicle owners by housing type—single-family or multifamily— shows whether parity (equal adoption rates) is being achieved or to what extent adoption by housing type is over or undersaturated (i.e., over- or under-adoption). We use a proprietary dataset of vehicle registrations with modeled housing type to analyze saturation ratios in Colorado in 2022. We found significant single-family oversaturation and multifamily undersaturation in 14% and 23% of ZIP codes, respectively, suggesting Colorado can still mitigate disparities in electric vehicle adoption by housing type through accessible vehicles and charging.

29 ENERGY PLANNING, POLICY, AND ECONOMY

Radial rib antenna surface deviation analysis program

A digital computer program was developed which analyzes any radial rib antenna with ribs radiating from a central hub. The program has the capability for calculating the antenna surface contour (reversed pillowing effect), the optimum rib shape for minimizing the rms surface error, and the actual rms surface error. Rib deflection due to mesh tension and catenary cable tension can also be compensated for, and the pattern from which the mesh gores are cut can be determined.

Coyner, J. V., Jr.

An estimator for the standard deviation of a natural frequency. II.

A method has been presented for estimating the variability of a system's natural frequencies arising from the variability of the system's parameters. The only information required to obtain the estimates is the member variability, in the form of second-order properties, and the natural frequencies and mode shapes of the mean system. It has also been established for the systems studied by means of Monte Carlo estimates that the specification of second-order properties is an adequate description of member variability.

Schiff, A. J.

Standard deviation of vertical two-point longitudinal velocity differences in the atmospheric boundary layer.

Statistical estimates of wind shear in the planetary boundary layer are important in the design of V/STOL aircraft, and for the design of the Space Shuttle. The data analyzed in this study consist of eleven sets of longitudinal turbulent velocity fluctuation time histories digitized at 0.2 sec intervals with approximately 18,000 data points per time history. The longitudinal velocity fluctuations were calculated with horizontal wind and direction data collected at the 18-, 30-, 60-, 90-, 120-, and 150-m levels. The data obtained confirm the result that Eulerian time spectra transformed to wave-number spectra with Taylor's frozen eddy hypothesis possess inertial-like behavior at wave-numbers well out of the inertial subrange.

Fichtl, G. H.

Properties of white light flares. I - Association with H-alpha flares and sudden frequency deviations.

All four large EUV bursts for which there were available concurrent white light observations of at least fair quality, were detected as white light flares. The rise times and maxima of the white light emissions coincided with rise times and maxima of the EUV bursts. The frequency of strong EUV bursts suggests that white light flares may occur at the rate of five or six per year near sunspot maximum. All of the white light flare areas coincided with intense bright areas of the H-alpha flares. These small areas appeared to be sources of high velocity ejecta in H-alpha. The white light flares occurred as several knots or patches of 2 to 15 arc-sec diameter, with bright cores perhaps less than 2 arc-sec diameter (1500 km). They preferred the outer penumbral borders of strong sunspots within 10 arc-sec of a longitudinal neutral line in the magnetic field.

Mcintosh, P. S.

Wide deviation phase modulator

Modulator produces phase-modulated waveform having high modulating linearity. Technique is inherently wideband with respect to carrier frequency and can operate over decade carrier frequency range without adjustments. Circuit performance is both mathematically predictable and highly reproducible.

Couch, R. H.