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At least 253 records · Page 14

Kinetic effects on the velocity-shear-driven instability

A comparison is made between the properties of the low-frequency long-wavelength velocity-shear-driven instability in kinetic theory and magnetohydrodynamics (MHD). The results show that the removal of adiabaticity along the magnetic field line in kinetic theory leads to modifications in the nature of the instability. Although the threshold for the instability in the two formalisms is the same, the kinetic growth rate and the unstable range in wave-number space can be larger or smaller than the MHD values depending on the ratio between the thermal speed, Alfven speed, and flow speed. When the thermal speed is much larger than the flow speed and the flow speed is larger than the Alfven speed, the kinetic formalism gives a larger maximum growth rate and broader unstable range in wave-number space. In this regime, the normalized wave number for instability can be larger than unity, while in MHD it is always less than unity. The normal mode profile in the kinetic case has a wider spatial extent across the shear layer.

Wang, Z.↗

Temperature dependence of protein solubility-determination, application to crystallization, and growth kinetics studies

A scintillation method was developed for determinations of the temperature dependence of the solubility, and of nucleation induction times of proteins, in 50-100 mu(l) volumes of solution. Solubility data for lysozyme and horse serum albumin were obtained for various combinations of pH and precipitant concentrations. These data and the nucleation induction information were used for dynamic crystallization control, that is, for the controlled separation of nucleation and growth stages. Individual lysozyme and horse serum albumin crystals were grown in 15-20 mu(l) solution volumes contained in x-ray capillaries. The morphology and kinetics of the growth and dissolution of lysozyme in aqueous solutions with 2.5 percent NaCl and at pH = 4.5 was studied in situ with a depth resolution of 300 A (4 unit cells) by high resolution optical microscopy and digital image processing. The bulk super- or under saturation, sigma, of the solution inside a closed growth cell was controlled by temperature. The growth habit was bound by (110) and (101) faces that grew through layer spreading, although with different growth rate dependencies on supersaturation/temperature. At sigma less than 10 (obtained at higher temperatures) growth was purely kinetic ally controlled, with impurity effects (macrostep formation and kinetic hindrance) becoming significant for sigma less than 2. At sigma greater than 10 (lower temperatures), anisotropies in the interfacial kinetics were more pronounced, with interfacial kinetics and bulk transport becoming equally important to the growth morphology. Growth rates were growth history dependent. The formation of striations (layers of irregularly incorporated solution) was unambiguously correlated with growth temperature variations. Etching exposed dislocations and various high-index faces whose growth morphologies were studied during return to the steady state growth form. Growth steps were observed to originate from two-dimensional nuclei or from outcrops of growth striations, and from dislocations that preferentially formed in growth sector boundaries.

Rosenberger, Franz↗

Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

Bhatt, R. T.↗

On the Linearly-Balanced Kinetic Energy Spectrum

It is well known that the earth's atmospheric motion can generally be characterized by the two dimensional quasi-geostrophic approximation, in which the constraints on global integrals of kinetic energy, entrophy and potential vorticity play very important roles in redistributing the wave energy among different scales of motion. Assuming the hypothesis of Kolmogrov's local isotropy, derived a -3 power law of the equilibrium two-dimensional kinetic energy spectrum that entails constant vorticity and zero energy flows from the energy-containing wave number up to the viscous cutoff. In his three dimensional quasi-geostrophic theory, showed that the spectrum function of the vertical scale turbulence - expressible in terms of the available potential energy - possesses the same power law as the two dimensional kinetic energy spectrum. As the slope of kinetic energy spectrum in the inertial range is theoretically related to the predictability of the synoptic scales (Lorenz, 1969), many general circulation models includes a horizontal diffusion to provide reasonable kinetic energy spectra, although the actual power law exhibited in the atmospheric general circulation is controversial. Note that in either the atmospheric modeling or the observational analyses, the proper choice of wave number Index to represent the turbulence scale Is the degree of the Legendre polynomial.

Lu, Huei,-Iin↗

Kinetic Energy Corrections for Slip-Stick Behavior in Brittle Adhesives

Fracture mechanics is the study of the failure of a body that contains a flaw. In the energy balance approach to fracture mechanics, contributions from the external work and elastic strain energy are accounted for but rarely are corrections for the kinetic energy given. Under slip-stick conditions, part of the external work is expended as kinetic energy. The magnitude of this kinetic energy depends upon the shape of the crack. A specimen with a blunt crack will fail at a high load and the crack will catastrophically travel through the material until the kinetic energy is dissipated. Material with a sharp crack will fail at a lower load but will still be catastrophic in nature. A kinetic term is incorporated into the energy balance approach. This term accounts for the velocity of the crack after failure and how far the crack travels before arresting. This correction makes the shape of the initiation crack irrelevant. When applied to data generated by tapered double cantilever beam specimens under slip-stick conditions, the scatter in the measured critical strain energy release rate is significantly reduced.

Macon, David J.↗

Core Physics and Kinetics Calculations for the Fissioning Plasma Core Reactor

Highly efficient, compact nuclear reactors would provide high specific impulse spacecraft propulsion. This analysis and numerical simulation effort has focused on the technical feasibility issues related to the nuclear design characteristics of a novel reactor design. The Fissioning Plasma Core Reactor (FPCR) is a shockwave-driven gaseous-core nuclear reactor, which uses Magneto Hydrodynamic effects to generate electric power to be used for propulsion. The nuclear design of the system depends on two major calculations: core physics calculations and kinetics calculations. Presently, core physics calculations have concentrated on the use of the MCNP4C code. However, initial results from other codes such as COMBINE/VENTURE and SCALE4a. are also shown. Several significant modifications were made to the ISR-developed QCALC1 kinetics analysis code. These modifications include testing the state of the core materials, an improvement to the calculation of the material properties of the core, the addition of an adiabatic core temperature model and improvement of the first order reactivity correction model. The accuracy of these modifications has been verified, and the accuracy of the point-core kinetics model used by the QCALC1 code has also been validated. Previously calculated kinetics results for the FPCR were described in the ISR report, "QCALC1: A code for FPCR Kinetics Model Feasibility Analysis" dated June 1, 2002.

Butler, C.↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj, S. V.↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 +/- 9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj. Sai V.↗

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al: Oxidation Kinetics - Part 1

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Raj. Sai V.↗

Constraints on triple oxygen isotope kinetics

The general assumption that systems are in equilibrium is convenient, but imperfect. Instead, the partial or full expression of kinetic reaction steps may need to be determined. Using an isotope fractionation Monte-Carlo model under the harmonic approximation (Figure 1 envelopes), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects. For the 16O-17O-18O system, accessible kinetic isotope effects can yield Δ′17O variations as large 0.8‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products, such as a gas and solid generated from the thermal decomposition of an initial solid. For example, previously published experiments on the thermal decomposition of calcite (CaCO3) and dehydroxylation of brucite (Mg(OH)2) are matched by density functional theory models of each kinetic isotope effect, thus revealing their origin in mass-dependent reaction. Beyond oxygen, our approach applies to any system with more than two isotopes.

Oxygen isotopes↗

Constraints on Triple Oxygen Isotope Kinetics

Triple oxygen isotope methods (e.g., using δ 18 O, and Δ′ 17 O) have been used to classify meteorites, to constrain atmospheric chemistry, and to estimate primary productivity, among other uses. Such utility relies on the mass dependency of most chemical reactions: δ 17 O is proportional to δ 18 O by roughly a factor of 0.5. However, in detail, mass-dependency factors vary. While constraints on mass dependency are well established for equilibrium isotope effects, similar constraints for kinetic isotope effects are lacking. Using an ab initio Monte Carlo approach (see envelopes in Figure 1), we find the range of kinetic isotope effects (i.e., resulting from unidirectional chemical reactions) contains and exceeds the range of accessible equilibrium isotope effects for the 16 O 17 O 18 O system (Hayles and Killingsworth, 2022). Accessible kinetic isotope effects can yield Δ′ 17 O variations as large 0.8 ‰ from a single kinetic fractionation step. Reactions that yield the largest deviations from equilibrium are those with the largest molecular mass difference between decomposition fragments, typically the two products such as a gas and solid generated from the thermal decomposition of an initial solid. Comparison of DFT transition state model results against previously published experiments on the thermal decomposition of calcite (CaCO 3 ) (Miller et al., 2002) and dehydroxylation of brucite (Mg(OH) 2 ) (Clayton and Mayeda, 2009) show they are matched with mass-dependent kinetic isotope effects. This approach can be applied to any system with more than two isotopes.

Oxygen isotopes↗

State-Specific Kinetic Modeling for Predictions of Radiative Heating in H 2 /He Entry Flows

A 23-species State-to-State (StS) thermochemical model for H 2 /He mixtures is developed and used to simulate 1-D shocks at conditions relevant for ice and gas giant entry flows. To implement this StS model, a literature review of the state-specific excitation and ionization rates of atomic H is first performed. While electron impact rates from various sources are found to be in relatively good agreement, large discrepancies are found in the limited data available on heavy particle impact rates. To investigate the impact of these discrepancies on the predicted shock and radiance profiles, simulations are performed for three different versions of the kinetic model, each with a different set of heavy particle impact rates from the literature. Of these three models, two are found to over-predict and one is found to under-predict the radiance values seen in corresponding experimental data from the NASA Ames Electric Arc Shock Tube (EAST) facility. A sensitivity analysis to the electron and heavy particle impact rates is then performed, from which an improved kinetic model with modified rates is proposed. This modified kinetic model is found to reproduce the total integrated radiance seen in the EAST experiments accurately. This suggests that the associated radiative heating that would be encountered by an entry probe in these environments would be well predicted by this kinetic model. However, some discrepancies are still found i the relative contributions to the total radiance from different spectral features, suggesting that additional improvements to the kinetic model still need to be made.

Outer Planet↗

Kinetic modeling of microbial growth, enzyme activity, and gene deletions: An integrated model of β-glucosidase function in Cellvibrio japonicus

Understanding the complex growth and metabolic dynamics in microorganisms requires advanced kinetic models containing both metabolic reactions and enzymatic regulation to predict phenotypic behaviors under different conditions and perturbations. Most current kinetic models lack gene expression dynamics and are separately calibrated to distinct media, which consequently makes them unable to account for genetic perturbations or multiple substrates. This challenge limits our ability to gain a comprehensive understanding of microbial processes towards advanced metabolic optimizations that are desired for many biotechnology applications. Here, we present an integrated computational and experimental approach for the development and optimization of mechanistic kinetic models for microbial growth and metabolic and enzymatic dynamics. Our approach integrates growth dynamics, gene expression, protein secretion, and gene-deletion phenotypes. We applied this methodology to build a dynamic model of the growth kinetics in batch culture of the bacterium Cellvibrio japonicus grown using either cellobiose or glucose media. The model parameters were inferred from an experimental data set using an evolutionary computation method. The resulting model was able to explain the growth dynamics of C. japonicus using either cellobiose or glucose media and was also able to accurately predict the metabolite concentrations in the wild-type strain as well as in β-glucosidase gene deletion mutant strains. We validated the model by correctly predicting the non-diauxic growth and metabolite consumptions of the wild-type strain in a mixed medium containing both cellobiose and glucose, made further predictions of mutant strains growth phenotypes when using cellobiose and glucose media, and demonstrated the utility of the model for designing industrially-useful strains. Importantly, the model is able to explain the role of the different β-glucosidases and their behavior under genetic perturbations. Here, this integrated approach can be extended to other metabolic pathways to produce mechanistic models for the comprehensive understanding of enzymatic functions in multiple substrates.

59 BASIC BIOLOGICAL SCIENCES↗

Non-equilibrium low-temperature plasma-assisted combustion of iso-octane: Perturbing pyrolysis and oxidation kinetics

Here, in this study, a plasma-coupled flow reactor facility is used to examine the effects of non-equilibrium low-temperature plasmas on perturbing the pyrolysis and oxidation kinetics of iso-octane. Experiments were performed in highly dilute reactive mixtures of nitrogen, at near isothermal conditions for temperatures ranging from 523 K to 1203 K. Experiments cumulatively demonstrated enhanced chemical reactivity with the plasma for temperatures below 900 K, and a lowering of the hot-ignition temperature. Detailed kinetic insight was derived from a 0D plasma-coupled kinetic model, utilizing a constructed mechanism that combined both plasma-specific chemistry and the neutral combustion chemistry. For pyrolysis conditions, the model displayed relatively good agreement with fuel consumption and the formation of most intermediates compared to the experimental data, demonstrating the model is able to accurately predict primary radical formation from the plasma directly interacting with the fuel. Enhanced reactivity was attributed to collisional quenching of excited-states of N 2 with fuel, which led to efficient fuel fragmentation and enhancement of the H-radical flux. For oxidation conditions, the model displayed satisfactory agreement with the experiments. Model predictions were able to accurately predict fuel consumption and most intermediate speciation data for T > 800 K, but most discrepancies were towards T < 800 K in particular with oxygenated intermediates. In the presence of oxygen, plasma effects were predominantly spent on efficient enhancement of O- and H-radical fluxes, leading to further fuel fragmentation and initiation of both the OH- and HO 2 -radical pools. Subsequent reactivity of iso-octane was then dictated by the response of the temperature-dependent neutral chemistry. At low-temperatures (T = 643 K), enhanced fuel radicals and O 2 -additon chemistry lead to the formation of oxygenated species, while at intermediate temperatures (T = 843 K) net decrease in OH-radical reactivity led to an increase in hydrocarbon speciation. Near the self-ignition threshold (T = 1163 K), radicals generated by high-temperature branching reactions dominate the oxidation process and effectively ignition. This study ultimately demonstrated that the enhancement of radicals afforded by the plasma causes a deviation in known understanding of iso-octane kinetics in some regards and warrants future studies to reconcile these discrepancies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Distinguishing Surface and Bulk Reactivity: Concentration-Dependent Kinetics of Iodide Oxidation by Ozone in Microdroplets

Iodine oxidation reactions play an important role in environmental, biological, and industrial contexts. The multiphase reaction between aqueous iodide and ozone is of particular interest due to its prevalence in the marine atmosphere and unique reactivity at the air–water interface. Here, we explore the concentration dependence of the I – + O 3 reaction in levitated microdroplets under both acidic and basic conditions. To interpret the experimental kinetics, molecular simulations are used to benchmark a kinetic model, which enables insight into the reactivity of the interface, the nanometer-scale subsurface region, and the bulk interior of the droplet. For all experiments, a kinetic description of gas- and liquid-phase diffusion is critical to interpreting the results. We find that the surface dominates the iodide oxidation kinetics under concentrated and acidic conditions, with the reactive uptake coefficient approaching an upper limit of 10 –2 at pH 3. In contrast, reactions in the subsurface dominate under more dilute and alkaline conditions, with inhibition of the surface reaction at pH 12 and an uptake coefficient that is 10× smaller. In conclusion, the origin of a changing surface mechanism with pH is explored and compared to previous ozone-dependent measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic Isotope Effects: Interpretation and Prediction Using Degrees of Rate Control

Kinetic isotope effects (KIEs) have been used for decades in catalysis research as a tool for clarifying reaction mechanisms. Significant primary kinetic isotope effects have usually been interpreted as being a result of isotope substitution at a site of bond breaking (or forming) in the rate-determining step in the reaction mechanism. However, quantitative analysis of the magnitude of the KIE in complex multistep reaction mechanisms is seldom reported. We prove here that the logarithm of the rate ratio for two isotopes is the weighted average over all species in the mechanism of their standard-state free energy difference between the two isotopes, divided by RT. The weighting factor is the degree of rate control (DRC) for that species (e.g., transition state, intermediate, reactant) when the rate is measured separately for each isotope. It is instead the degree of selectivity ratio control (DSRC) when the KIE is measured as the product selectivity in a parallel competition between two isotopes within the same reactant molecule. Since only a few species have non-zero DRCs (or DSRCs) for most reactions, only these few contribute to this weighted average and the KIE. We show that this provides a simple way to interpret and quantitatively predict kinetic isotope effects that is powerful in the insights it provides, allowing one to evaluate directly which species contribute most to the KIE. By applying it to H/D KIEs in several example mechanisms, we further show that the traditional way of interpreting KIEs that focuses only on the rate-determining step can easily lead to misunderstanding of KIE and the reaction mechanism. Finally, this highlights the importance to consider the effect of isotope substitution on the energies of all species with large DRCs (i.e, those whose energies are kinetically relevant). This method also offers opportunities for quantitative validation of mechanism-based microkinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics Measurements in Resistive Electrolytes Using Ring-Disk Electrode: Ring as Current “Shield” Enables Uniform Disk Current Distribution

Rotating disk electrodes are commonly used for electrochemical kinetics measurements. A major disadvantage of these types of electrodes is their nonuniform secondary current distribution, especially when performing electroanalytical measurements in resistive electrolytes. Such nonuniform current distribution can render the values of kinetics constants extracted from the disk electrode to be highly inaccurate. Furthermore, one emerging class of electrolytes that suffer from low ionic conductivities is deep eutectic solvents (DES). DES are a promising class of electrolytes for various emerging applications; however, due to their resistive nature, the secondary current distribution when using them is typically highly nonuniform. For example, the Wagner number when measuring Cu²⁺/Cu⁺ kinetics in choline chloride–ethylene glycol DES (1:4 molar ratio of ChCl:EG) is very low (<0.1), indicating highly nonuniform current distribution over the disk electrode. We show here that the Cu²⁺/Cu⁺ exchange current density measured using disk electrodes is very inaccurate due to the aforementioned nonuniform current distribution. To obtain uniform disk current distribution, we employ here a coplanar concentric rotating ring-disk electrode (RRDE), where the ring serves the function of a current “shield.” Specifically, we show using modeling that the ring minimizes the current distribution nonuniformity at the disk by effectively shielding the disk against current spikes near the disk edge. This enables improved precision in electrode kinetics measurements for the Cu²⁺/Cu⁺ couple in resistive DES. To enable broad applicability of this technique, an analytical expression based on the Wagner number is integrated into an iterative algorithm to help users identify ring conditions to achieve uniform current distribution and thus improved electroanalytics at the disk.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Putting multipoint kinetics to the test: preliminary analysis of the MUSE-4 experiment with APOLLO3

Modeling neutron kinetics is a challenging task and over the years, several approaches have been developed offering different tradeoffs between precision and cost. Probably the most popular one is point kinetics (PK), which, despite being very cheap, provides good results for many applications. One of the limitations of PK is that it is not able to model effects that happen before the prompt jump time scale. In practice, applications, where those time scales are interesting, are rare and those for which experimental data are available are even rarer. One of those cases is the MUSE-4 experiment for which the focus is on the very fast behavior and where we have no thermal feedback. As we have shown in a recent paper, a simple extension of PK, known as multipoint kinetics (MPK), can overcome this limitation. In this paper, which is intended as a preliminary study, we show how a simple MPK model can qualitatively reproduce the fast behavior that we cannot model with PK. Moreover, we will show how to exploit its low cost and compact form to model also slow effects as the precursors built up, behaviours that are not affordable to model with more expensive techniques, such as kinetic Monte Carlo simulations. For the periodic pulse transients with no feedbacks we will also provide an analytical solution in closed form. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗