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All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Reactive collision terms for fluid transport theory

A modified Bhatnagar-Gross-Krook (BGK) collision method is used for the derivation of reactive collision terms to allow for complete higher-moment approximations in fluid transport theory. The general reactive collision terms for the 8-, 10- and 13-moment approximation for binary reactions are derived. Then, reactive collision terms for specific chemistry are derived with the assumptions: (1) all reactants and products have 13-moment distribution functions; (2) simple, classical assumptions provide sufficient models for reaction dynamics; and (3) the reaction rate is energy-independent. The derived specific formulas reflect two extremes in reactive collision dynamics: direct and indirect reaction mechanisms. Finally, considerations for correct use of the reactive collision terms are discussed in the context of space plasma environments.

Eccles, J. V.↗
NASA NTRS2005

Incorporation of a Chemical Equilibrium Equation of State into LOCI-Chem

Renewed interest in development of advanced high-speed transport, reentry vehicles and propulsion systems has led to a resurgence of research into high speed aerodynamics. As this flow regime is typically dominated by hot reacting gaseous flow, efficient models for the characteristic chemical activity are necessary for accurate and cost effective analysis and design of aerodynamic vehicles that transit this regime. The LOCI-Chem code recently developed by Ed Luke at Mississippi State University for NASA/MSFC and used by NASA/MSFC and SSC represents an important step in providing an accurate, efficient computational tool for the simulation of reacting flows through the use of finite-rate kinetics [3]. Finite rate chemistry however, requires the solution of an additional N-1 species mass conservation equations with source terms involving reaction kinetics that are not fully understood. In the equilibrium limit, where the reaction rates approach infinity, these equations become very stiff. Through the use of the assumption of local chemical equilibrium the set of governing equations is reduced back to the usual gas dynamic equations, and thus requires less computation, while still allowing for the inclusion of reacting flow phenomenology. The incorporation of a chemical equilibrium equation of state module into the LOCI-Chem code was the primary objective of the current research. The major goals of the project were: (1) the development of a chemical equilibrium composition solver, and (2) the incorporation of chemical equilibrium solver into LOCI-Chem. Due to time and resource constraints, code optimization was not considered unless it was important to the proper functioning of the code.

Cox, Carey F.↗
DOE OSTI2025

Isomerization kinetics of azobenzene crosslinked to a liquid crystal polymer network

Azobenzene is an important chromophore having numerous applications that are a direct implication of its ability to change shape upon irradiation with a suitable wavelength. Here, in this study, photoisomerization kinetics of a diacrylate azobenzene molecule (A3MA) cross-linked to a liquid crystal polymer network (LCN) is investigated. Isomerization experiments were conducted on planar LCN thin films with varying cross-linking densities for a fixed azobenzene concentration. The experiments were conducted at approximately 26 °C, which is significantly below each film’s glass transition temperature. The forward trans-cis and reverse cis-trans isomerization slows down in crosslinked azobenzene liquid crystal polymer networks (ALCNs) as compared to a solution and an uncrosslinked polymer mixture. The observed slowdown is due to the reduction in the free volume and increased steric hindrances with an increase in crosslinking. A single-term first-order kinetics rate equation is known to describe the isomerization kinetics in solutions or uncrosslinked mixtures while the same form fails to represent the reaction kinetics in moderate to highly cross-linked ALCNs. Our results for the first time indicate that a two-term first-order reaction rate is an accurate way to describe the forward trans-cis and reverse thermal cis-trans isomerization in crosslinked azobenzene liquid crystal polymer networks. In addition, the effect of film thickness and incident intensities on the reaction kinetics is investigated. Finally, the two-term isomerization kinetics is incorporated into a finite element photo-chemo-mechanical model to reveal the consequent slowdown in the actuation response of ALCN films. The current findings will be of particular interest to theoreticians and experimentalists alike, for it will help predict and understand accurately the responses of azobenzene-based coatings, and actuators and may have potential applications in underwater soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Isothermal oxidation of zirconium using steam

Oxidation of zirconium and its alloys under any atmosphere is generally characterised by a protective and non-protective stage. During the protective stage, the kinetics of oxidation are quasi-parabolic, while the oxide scale formed on the surface of the metal is black, compact, and protective in nature. For the non-protective stage, the oxidation rate becomes linear, while the protective oxide film turns into a deteriorated white scale. Breakaway is known as the transition point from protective to non-protective stage. The actual mechanism leading to breakaway of zirconium is still a matter of controversy, however some of the most common factors affecting breakaway are the following: - Impurities on the metal (Carbon, Oxygen, Nitrogen); - Oxidizing atmosphere (Presence of H{sub 2}O (g) or N{sub 2} (g)); - Sample preparation (Chemically etched or polished); - Temperature (LWR, LOCA). This research investigates the effect of temperature on 'breakaway' when zirconium is oxidized isothermally in steam for 60 min at 800 and 900 deg. C using thermogravimetric and optical microscopic imaging techniques. 1. Steam isothermal oxidations were performed on zirconium at 800 and 900 deg. C using a Thermogravimetric Analyzer (TGA). 2. Log-log plots of mass gain vs time were obtained from thermogravimetric results to calculate the reaction orders (n) and reaction rate constants (K) during oxidation. 3. Results of the kinetics of reaction were correlated with optical microscopic images form Light Microscope (LM) and Scanning Electron Microscope (SEM). Breakaway depends very strongly on temperature. At 800 deg. C, the weight gain followed a cubic-parabolic behaviour with evidence of a protective oxide film. On the other hand, oxidation at 900 deg. C showed signs of breakaway since the oxide film was cracked and oxidation rate was almost linear throughout the reaction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1973

The development and preliminary application of an invariant coupled diffusion and chemistry model

In many real-world pollution chemical reaction problems, the rate of reaction problems, the rate of reaction may be greatly affected by unmixedness. An approximate closure scheme for a chemical kinetic submodel which conforms to the principles of invariant modeling and which accounts for the effects of inhomogeneous mixing over a wide range of conditions has been developed. This submodel has been coupled successfully with invariant turbulence and diffusion models, permitting calculation of two-dimensional diffusion of two reacting (isothermally) chemical species. The initial calculations indicate the ozone reactions in the wake of stratospheric aircraft will be substantially affected by the rate of diffusion of ozone into the wake, and in the early wake, by unmixedness.

Hilst, G. R.↗
DOE OSTI2022

Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH 3 OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. Here, the experimental results show that the onset temperature of CH 3 OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH 3 OH oxidation from the literature and added some new low-temperature reaction pathways such as CH 2 O + HO 2 = HOCH 2 O 2 (RO 2 ), RO 2 + RO 2 = HOCH 2 O (RO) + HOCH 2 O (RO) + O 2 , and CH 3 OH + RO 2 = CH 2 OH + HOCH 2 O 2 H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO 2 chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO 2 chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO 2 formation.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2022

Metal Halide Perovskites Demonstrate Radiation Hardness and Defect Healing in Vacuum

Herein, we subject formamidinium lead iodide films to oxygen-containing gases (flowing O 2 or free diffusion of lab atmosphere), inert gases (flowing He, Ar, or N 2 ), and vacuum. Our films are irradiated by Cu Ka X-rays and held at 75 °C while X-ray diffraction is recorded. Under all gas conditions, we observe a reproducible 1.1 ± 0.5 A 3 perovskite lattice contraction from an initial unit cell volume of 256.5 ± 0.8 A 3 concurrent with continuous perovskite loss and lead iodide growth. Oxygen-containing gases increase the reaction rates without materially altering perovskite structural changes. Under the same temperature and irradiation conditions in vacuo, a self-healing reaction is observed, exhibited by a reproducible (0.9 ± 0.3 A 3 ) lattice expansion and stabilization of the perovskite. Furthermore, interactions between the perovskite, defects, and minority phases are simulated by generalized gradient approximation Perdew-Burke-Ernzerhof (GGA-PBE) density functional theory. Lattice contraction indicates an increase in the concentration of Schottky defects-pairs of formamidinium and iodine vacancies. Under irradiation in every atmospheric condition, a solid solution of Schottky defects with a concentration of several percent diffuses and precipitates forming lead iodide and consuming the defects. In the presence of ionized gases, this framework is modified to include the continual loss of formamidinium and iodine ions from the perovskite forming Schottky defects.

14 SOLAR ENERGY↗
DOE OSTI2025

Cosmological parameter estimation with a joint-likelihood analysis of the cosmic microwave background and big bang nucleosynthesis

Here, we present a joint-likelihood analysis of big bang nucleosynthesis (BBN) and cosmic microwave background (CMB) data, consistently combining likelihoods and taking into account uncertainties in nuclear reaction rates for the first time. Bayesian inference is performed on the baryon abundance and the effective number of neutrino species, 𝑁 eff , using a CMB Boltzmann solver in combination with LINX , a new flexible and efficient BBN code. We marginalize over Planck nuisance parameters and nuclear rates to find 𝑁 eff =3.0⁢8$^{+0.15}_{−0.14}$, 2.9⁢4$^{+0.16}_{−0.15}$, or 2.96$^{+0.13}_{−0.14}$, for three separate reaction networks. This framework enables robust testing of the lambda cold dark matter paradigm and its variants with CMB and BBN data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Dataset for scientific paper "Simulated plant‑mediated oxygen input has strong impacts on fine‑scale porewater biogeochemistry and weak impacts on integrated methane fluxes in coastal wetlands", a modeling study based on field observation at the tidal salt marshes of the Parker River Estuary, Massachusetts, United States

This dataset is the raw and processed data for the paper "Simulated plant ‑ mediated oxygen input has strong impacts on fine ‑ scale porewater biogeochemistry and weak impacts on integrated methane fluxes in coastal wetlands". This study investigated how plant-mediated oxygen input affects subsurface biogeochemical reactions of organic carbon degradation and the resulting methane emissions of coastal wetlands by model simulation. We used the subsurface geochemical simulator PFLOTRAN for the modeling, which produced the simulated changes in porewater chemical substances and methane emissions over 10 days under different scenarios of plant-mediated oxygen input.Specifically, this dataset contains: 1) the input files for PFLOTRAN of all simulation runs conducted in this study. Those files are with an extension of ".in", containing information of the biogeochemical reaction network (stoichiometry, reaction rate, Monod constants, etc), fluid flow rate and oxygen concentration in the fluid which together simulated the plant-mediated oxygen input, the configuration of artificial reactions that simulated the methane fluxes, etc. The PFLOTRAN input files are text files, which can be opened by NotePad, but running these input files will require proper installation of PFLOTRAN (instruction: https://documentation.pflotran.org/user_guide/how_to/installation/installation.html). 2) the raw and processed model output from PFLOTRAN of all simulation runs, and 3) the python scripts used to process the raw model output, including random allocation of root cells, converting raw data into organized formats, calculating the methane fluxes based on the model output, data visualization, etc. The raw and processed model output from PFLOTRAN are in .spydata format, which can be viewed with Python. and 3) the python scripts for data processing and analysis are programming scripts, which can be opened with Python.This modeling work, in particular the model parameterization of root density and initial conditions of porewater concentrations of biogeochemical substances, was based on field measurements at the salt marsh of the Upper Parker River Estuary, Massachusetts, United States.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1976

Effect of magnetic field on reduction of nickel oxide

Results of observations recorded during constant temperature reduction of NiO, a paramagnetic substance, to Ni, a ferromagnetic element, are presented. The application of a large magnetic field (4,200 oersted) does not result in an acceleration of the reduction rate. To explain earlier observations that 500- and 1,400-oersted magnetic fields increase the reduction rate of iron ore which contains hematite (Fe2O3), Peters (1973) had suggested that thermodynamics theory could predict the acceleration in reaction rate when product and reactant species differ widely in their magnetic properties.

Rowe, M. W.↗
NASA NTRS1982

Charge exchange in the Io torus and exosphere

Charge-exchange cross sections and their velocity dependence have been estimated for the most important reactions in the Io torus and exosphere. The methods used for calculating the cross sections are given and discussed in some detail. For symmetric-resonant single and double charge exchange, the cross sections are slowly varying functions of velocity. For inelastic charge-exchange collisions, the transition probabilities into a given final state can depend critically on velocity. Models are described which can be used to estimate both the most rapid charge-exchange processes and those states which play an important role. Calculated cross sections are used to obtain reaction rates as a function of radial position, demonstrating the importance of charge exchange in the inner torus. Charge-exchange reactions of torus ions with molecular species in Io's exosphere may yield a net supply of neutrals and plasma to the torus.

Johnson, R. E.↗
DOE OSTI2024

Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H 2 followed by O 2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate determining. Electronic structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from that involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H 2 and, alternatively, with D 2 on the cluster incorporating the dioxygen ligands, and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H 2 with D 2 to give HD. Here, we posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

02 PETROLEUM↗
DOE OSTI2020

On the competition between mixing rate and uniformity in a coaxial hydrodynamic focusing mixer

Fast microfluidic mixers for use with line-of-sight integrating detection schemes pose unique challenges. Such detectors typically cannot discriminate signal from slow moving (e.g. near internal walls) and fast-moving portions of the fluid stream. This convolves reaction rate dynamics with fluid flow residence time dynamics. Further, the small cross sections of typical three-dimensional hydrodynamic focusing devices lead to lower detection signals. The current study focuses on achieving both small time scales of mixing and homogenous residence times. This is achieved by injecting sample through a center capillary and hydrodynamically focusing using a sheath flow within a tapered second capillary. The current design also features a third, larger coaxial capillary. The mixed stream flows into the large cross-section of this third capillary to decelerate and expand the stream by up to 14-fold to improve line-of-sight signal strength of reaction products. Hydrodynamic focusing, mixing, and expansion are studied using analytical and numerical models and also studied experimentally using a fluorescein-iodide quenching reaction. The experimentally validated models are used to explore trade-offs between mixing rate and uniformity. For the first time, this work presents detailed analysis of the Lagrangian time history of species transport during mixing inside coaxial capillaries to measure mixing nonuniformity. The mixing region enables order 100 μs mixing times and residence time widths of the same order (140 μs).

42 ENGINEERING↗
DOE OSTI2023

Revising the dynamic energy budget theory with a new reserve mobilization rule and three example applications to bacterial growth

Dynamic energy budget (DEB) theory has been applied to model a wide range of organisms, including microbes. In the standard DEB model, biomass is partitioned into reserve and structural compartments, where reserve biomass is mobilized in a pseudolinear manner (while the reserve biomass density, defined as the ratio between reserve and structural biomass, decays linearly) to drive maintenance and the growth of structural biomass (and extracellular enzyme production if it is considered). However, the linear dynamics of the reserve biomass density makes the standard DEB model incapable of explaining the slowdown of microbial growth at high reserve density that is caused by macromolecular crowding effect which reduces biochemical reaction rates (a typical situation occurs when microbes are experiencing severe moisture stress) and is inconsistent with the observation that intracellular enzymatic reactions generally follow non-linear kinetics. By partitioning biomass into reserve, kinetic, and structural compartments, we show here that the Equilibrium Chemistry Approximation (ECA) kinetics can be used to represent enzymatically catalyzed reserve biomass mobilization that can then drive the kinetic and structural biomass synthesis. This revised DEB model better represents the tradeoff in ribosome allocation for structural growth and internal enzyme production, is structurally compatible with metabolic models of cell individuals, and includes the standard DEB model and the popular compromise model as special cases for representing population growth. We then applied the revised DEB model to interpret components of bacterial respiration, their dependence on substrate availability, and emergent microbial carbon use efficiency dynamics for an exponentially growing population. We found that the revised DEB model enables a better understanding of bacterial substrates use (carbon in our examples) than that can be derived from a few other models in the literature. In particular, the revised DEB model explains why carbon use efficiency may first increase, then plateau, and finally decrease with growth rate (and substrate uptake rate), as a function of proteomics. Additionally, the revised DEB model explains why the kinetic biomass compartment needs to be divided to reasonably incorporate proteomic control of microbial growth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Uncertainty Quantification and Error Propagation in the Enthalpy and Entropy of Surface Reactions Arising from a Single DFT Functional

Accounting for parametric uncertainty in models is essential for quantifying the models’ predictive ability. Recently, approaches have been introduced to estimate parametric uncertainty in kinetic models while accounting for correlations among energy parameters. However, correlations have been estimated indirectly and correlations in entropies have not been accounted for. For surface-catalyzed microkinetic models of >C2 (more than two carbon-containing) molecules, which consist of thousands of reaction steps and intermediate surface species, first-principles density functional theory (DFT) is costly, and thus, estimation of thermochemistry and reaction barriers requires surrogate methods of DFT, such as group additivity and Brønsted–Evans–Polanyi relationships, respectively. For such parametrization, model uncertainty is unclear. This work develops a framework to overcome these gaps using group additivity and a single DFT functional. We estimate correlations in parameters of kinetic models and quantify uncertainty for thermochemistry, reaction barriers, reaction paths, and ultimately reaction rates, accounting also for the contribution of entropic uncertainty. Furthermore, the approach is illustrated on propane combustion and ethane oxidative dehydrogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)

Abstract The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO 3 ) of different microstructures and solid impurity contents using FeCl 2 . Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1–2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO 3 ) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO 3 grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗