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Results for “Reaction Kinetics”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,045 records · Page 58
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Association of Cl with C 2 H 2 by unified variable-reaction-coordinate and reaction-path variational transition-state theory

Significance A key issue in chemical kinetics is advancing the theoretical framework to handle reactions beyond the domain of textbook transition-state theory by including––for example––anharmonicity, barrierless transition states, transition states in series, and the effect of conformational flexibility on equilibrium constants. Other key issues are validating affordable electronic structure methods for direct dynamics and the direct calculation of high-pressure limiting rate constants, which are often obtainable experimentally only by extrapolation. The present article addresses all these issues for a prototype radical–molecule association reaction and thereby demonstrates how to combine improved theoretical methods to provide rate constants in cases where experimental data are uncertain or missing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Studying Cloud and Radiative Impacts Through an Improved Physically Based Representation of Organic Aerosol in a Large-Scale Model (WRF-Chem) (Final Report)

The work performed under this award resulted in the development of a computationally-efficient kinetic model to simulate the chemistry, thermodynamics, and microphysics of organic aerosol. Versions of the kinetic model were used to study a suite of aerosol processes including, multigenerational gas-phase chemistry, phase-state influenced gas/particle partitioning, heterogeneous oxidation, oligomerization reactions, and experimental artifacts. The kinetic model has now been implemented into a regional chemistry-climate model (WRF-Chem) to further study the formation, evolution, properties, and spatiotemporal distribution of organic aerosol at urban, regional, and global scales.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

O 2 -Oxidation of Individual Graphite and Graphene Nanoparticles in the 1200 – 2200 K Range: Particle-to-Particle Variations and the Evolution of the Reaction Rates and Optical Properties

The kinetics for O 2 oxidation of individual graphite and graphene platelet nanoparticles (NPs) were studied as a function of temperature (1200 to 2200 K) at varying oxygen partial pressures, using a single nanoparticle mass spectrometry method. NP temperature (TNP) was measured by measuring the NP thermal emission spectra during the kinetics studies. The initial oxidation efficiency is found to peak in the 1200 to 1500 K range, dropping by an order of magnitude as TNP was increased above 2000 K. There were large NP-to-NP variations in the oxidation rates, attributed to variations in the NP surface structure. In addition, the oxidation efficiencies evolved, non-monotonically, as the NPs reacted, decreasing by factors of between 10 and 300. This evolution of reactivity is attributed to changes in the NP surface structure due to the combination of oxidation and annealing. In conclusion, the optical properties, including wavelength dependence of the emissivity and the absorption cross section for the 532 nm heating laser, also tended to evolve as the NPs oxidized, but differently for each individual NP, presumably reflecting differences in the initial structures and their evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Two-dimensional ring polymer molecular dynamics determination of the MnO + + H 2 /D 2 reaction rates on a Δ-machine learned potential energy surface

In this work, we investigate the impact of nuclear quantum effects in the kinetics of the MnO + + H 2 reaction, a prototypical system for gas-phase H 2 activation by transition metal oxide ions. The DFT based potential energy surfaces (PESs) for the lowest-lying quintet and septet spin states reported in our previous work are improved by 2953 newly calculated CCSD(T)/AVDZ points using a delta-machine learning (Δ-ML) method. To examine nuclear quantum effects, the rate coefficients are computed using ring-polymer molecular dynamics (RPMD). Due to the mechanistic complexity of the reaction, two reaction coordinates are necessary to map out the free-energy surface and an extended RPMD rate theory is developed. The calculated RPMD rate coefficients on the new PES are in better agreement with experimental data. The calculated kinetic isotope effects (KIEs) range from 1.6 to 1.8, also in good agreement with the experimental values. Additionally, the converged RPMD rate coefficients are 2.3 to 3.1 times higher than their classical counterparts across the studied temperature range, suggesting the presence of moderate nuclear quantum effects in this reaction.

Liu, Yang [University of New Mexico, Albuquerque, ↗
DOE OSTI2024

Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Criegee intermediates are reactive intermediates that are implicated in transforming the composition of Earth’s troposphere and in the formation of secondary organic aerosol, impacting Earth’s radiation balance, air quality and human health. Yet, direct identification of their signatures in the field remains elusive. Here, from particulate and gas-phase mass-spectrometric measurements in the Amazon rainforest, we identify sequences of masses consistent with the expected signatures of oligomerization of the CH 2 OO Criegee intermediate, a process implicated in ozonolysis-driven aerosol formation. In this study, we assess the potential contributions of oligomerization through laboratory ozonolysis experiments, direct kinetic studies of Criegee intermediate reactions, and high-level theoretical calculations. Global atmospheric models built on these kinetics results indicate that Criegee intermediate chemistry may play a larger role in altering the composition of Earth’s troposphere than is captured in current atmospheric models, especially in areas of high humidity. However, the models still capture only a relatively small fraction of the observed signatures, suggesting considerable underestimates of Criegee intermediate concentrations and reactivity and/or the dominance of other, presently uncharacterized, oxidation mechanisms. Resolving the remaining uncertainties in emission inventories and the effects of atmospheric water vapour on key chemical reactions will be required to definitively assess the role of Criegee intermediate oligomerization reactions.

58 GEOSCIENCES↗
DOE OSTI2021

Reactions of atomic thorium and uranium cations with CF 4 studied by guided ion beam tandem mass spectrometry

The fundamental chemistry of the actinides continues to be an area of interest because of their use in nuclear fuel cycles. Here, the kinetic energy dependences of the reactions of thorium and uranium cations with CF 4 were studied using guided ion beam tandem mass spectrometry. The products observed include AnF x + (An = Th or U, x = 1-3) and CF y + (y = 1-3). Although most reactions are exothermic according to literature thermochemistry, all cross sections display strong endothermic features indicating a restriction in the reactivity at low energies. For both actinides, only the AnF + + CF 3 product channel is observed at low energies; however, its formation proceeds very inefficiently. Furthermore, these results indicate that the reactions of Th + and U + with CF 4 are not thermodynamically driven and suggest that the low-energy reactivity results from precise alignment of the reactants.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

An Efficient Bifunctional Air Electrode for Reversible Protonic Ceramic Electrochemical Cells

One of the main bottlenecks that limits the performance of reversible protonic ceramic electrochemical cells (R-PCECs) is the sluggish kinetics of the oxygen reduction and evolution reactions (ORR and OER). Here, the significantly enhanced ORR and OER kinetics and stability of a conventional La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) air electrode by an efficient catalyst coating of barium cobaltite (BCO) is reported. The polarization resistance of a BCO-coated LSCF air electrode at 600 oC is 0.16 Ω cm 2 , about 30% of that of the bare LSCF air electrode under the same conditions. Further, a R-PCEC with the BCO-coated LSCF air electrode shows exceptional performance in both fuel cell (maximum power density of 1.16 W cm -2 at 600 ºC) and electrolysis (current density of 1.80 A cm -2 at 600 ºC at 1.3 V) modes. Finally, the performance enhancement is attributed mainly to the facilitated rate of oxygen surface exchange.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Mechanistic manifold in a hemoprotein-catalyzed cyclopropanation reaction with diazoketone

Abstract Hemoproteins have recently emerged as promising biocatalysts for new-to-nature carbene transfer reactions. However, mechanistic understanding of the interplay between productive and unproductive pathways in these processes is limited. Using spectroscopic, structural, and computational methods, we investigate the mechanism of a myoglobin-catalyzed cyclopropanation reaction with diazoketones. These studies shed light on the nature and kinetics of key catalytic steps in this reaction, including the formation of an early heme-bound diazo complex intermediate, the rate-determining nature of carbene formation, and the cyclopropanation mechanism. Our analyses further reveal the existence of a complex mechanistic manifold for this reaction that includes a competing pathway resulting in the formation of an N-bound carbene adduct of the heme cofactor, which was isolated and characterized by X-ray crystallography, UV-Vis, and Mössbauer spectroscopy. This species can regenerate the active biocatalyst, constituting a non-productive, yet non-destructive detour from the main catalytic cycle. These findings offer a valuable framework for both mechanistic analysis and design of hemoprotein-catalyzed carbene transfer reactions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

The PFLOTRAN Reaction Sandbox

Abstract. As modern reactive transport simulators evolve to accommodate the demands of a user community, researchers need a platform for prototyping new biogeochemical processes, many of which are niche and specific to laboratory or field experiments. The PFLOTRAN Reaction Sandbox leverages modern, object-oriented Fortran in an attempt to provide such an environment within an existing reactive transport simulator. This work describes the PFLOTRAN Reaction Sandbox concept and implementation through several illustrative examples. Reaction Sandbox Biodegradation Hill customizes the existing microbially mediated biodegradation reaction formulation within PFLOTRAN to better match empirical data. Reaction Sandbox Simple provides an isolated environment for testing numerous preconfigured kinetic rate expressions and developing user intuition. Reaction Sandbox Example serves as a template for creating new sandboxes within PFLOTRAN.

58 GEOSCIENCES↗
DOE OSTI2020

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl,sec-butyl, iso-butyl, andtert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. The mass spectra confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a minor channel (<7.7%) through HNO loss and formation of an aldehyde. These high pressure experiments were also used to determine the disproportionation/recombination ratio for iso-butyl radicals as 0.3. Reanalysis of the lower-temperature literature and the present data yielded rate constants for the disproportionation reaction, iso-butyl + iso-butyl = iso-butene + iso-butane. A chemical kinetics model was developed for the reactions of the butyl isomers that included new paths for highly energized adducts. These adducts are formed by the addition of H, CH 3 or C 2 H 5 to the butyl radicals. Accompanying theoretical investigations show that chemically activated pathways are competitive with stabilization of the adduct by collision under the conditions of the laser schlieren experiments. These calculations also show that at 10 bar and T< 1000 K stabilization is the only important reaction, but at higher temperatures, even at 10 bar, chemically activated product channels should also be considered. Branching fractions and rate coefficients are presented for these reactions. Furthermore, this study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. Overall, the results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.

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

Rate Equations for Reversible Disproportionation Reactions and Fitting to Time-Course Data

Integrated rate equations are straightforward to fit to experimental data to verify a proposed mechanism and to extract kinetic parameters. Such equations are derived for reversible disproportionation/comproportionation reactions with any set of initial concentrations. Extraction of forward and reverse rate constants from experimental data by fitting the rate law to the data is demonstrated for the disproportionation of 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO) under acidic conditions where the approach to equilibrium is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Phase-Dependent Structure Sensitivity of Pt/TiO 2 for CO Oxidation Reactions

Here, in this study, we investigated the effect of the support (rutile vs anatase titania) and of the Pt size of Pt nanoparticles and supports (rutile vs anatase) in the CO oxidation reaction. The steady-state specific activity of Pt/Rutile gradually increases with Pt dispersion, while that of Pt/Anatase is invariant with respect to Pt dispersion and is lower than the activity of Pt/Rutile. Our kinetic studies demonstrated that the reaction order for CO based on steady state is positive for sub-nm Pt clusters stabilized on rutile titania and it gradually changes to zero for large Pt clusters (>1 nm), as known in agreement with other studies for for supported Pt catalysts. In contrast, Pt/Anatase catalysts always show zero order dependence irrespective of Pt the size of Pt nanoparticles. Scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS) and CO chemisorption results confirm that the notable sintering of sub-nm Pt clusters supported on anatase occurs with time-on-stream, which we correlate with might be related with the change of the CO reaction order from positive (order initially) tobut zero order for larger particles after sintered states. On the contrary, Pt/Rutile does not show serious sintering during the reaction, and it shows positive reaction order even during the steady state. Thus Pt/Rutile shows positive order at steady state and higher specific activity. Our study reveals the origin of profound catalytic differences between Pt nanoparticles supported on anatase and rutile titania and highlights better stability and activity of Pt/Rutile catalysts. than Pt/Anatase due to its better stability.

Kim, Haneul [Ulsan National Institute of Science a↗
DOE OSTI2021

Microstructure-dependent rate theory model of defect segregation and phase stability in irradiated polycrystalline LiAlO 2

We report gamma lithium aluminate (LiAlO 2 ) is a breeder material for tritium and is one of key components in a tritium-producing burnable absorber rod (TPBAR). Dissolution and precipitation of second phases such as LiAl 5 O 8 and voids are observed in irradiated LiAlO 2 . Such microstructure changes cause the degradation of thermomechanical properties of LiAlO 2 and affect tritium retention and release kinetics, and hence, the TPBAR performance. In this work, a microstructure-dependent model of radiation-induced segregation (RIS) has been developed for investigating the accumulation of species and phase stability in polycrystalline LiAlO 2 structures under irradiation. Three sublattices (i.e. [Li, Al, V] I [O, V o ] II [Li i , Al i , O i , V i ] III ), and concentrations of six diffusive species (i.e. Li; vacancy of Li or Al at [Li, Al, V] I sublattice, O vacancy at [O, V o ] II sublattice, and Li, Al and O interstitials at [Li i , Al i , O i , V i ] III interstitial sublattices; are used to describe spatial and temporal distributions of defects and chemistry. Microstructure-dependent thermodynamic and kinetic properties including the generation, reaction, and chemical potentials of defects and defect mobility are taken into account in the model. The parametric studies demonstrated the capability of the developed RIS model to assess the effect of thermodynamic and kinetic properties of defects on the segregation and depletion of species in polycrystalline structures and to explain the phase stability observed in irradiated LiAlO 2 samples. The developed RIS model will be extended to study the precipitation of LiAl 5 O 8 and voids and tritium retention by integrating the phase-field method.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Atomic Layer Deposition (ALD) of Metal and Metal Oxide Films: A Surface Science Study (Final Report)

This is the final report for this project. The long-term objective of our project is to develop a general molecular-level picture of the surface chemistry associated with ALD processes. Our central hypothesis is that the chemistry of ALD precursors can differ significantly from that seen in solution. Awareness of such differences should provide general guidelines on what to watch for when synthesizing new ALD precursors and designing and optimizing new ALD processes, especially in terms of minimizing the incorporation of impurities in the growing films and of carrying out depositions under mild pressure and temperature conditions. The main objective of our research project has been to advance the fundamental knowledge of the surface chemistry of ALD precursors needed for the design and optimization of film deposition processes. A modern surface-science approach has been implemented to both elucidate the mechanism of the reactions of the precursors on the surface and characterize the composition and morphology of the growing films. In general, emphasis is being placed on: • Identifying the primary reactions that may lead to the deposition of clean films; •Identifying the secondary reactions that may help the ALD process, by, for instance, helping with the reduction (or oxidation) of the metal atom; • Identifying the secondary reactions that may lead to the deposition of undesirable impurities in the growing films; • Determining the kinetic parameters of the relevant surface reactions in order to define the optimum conditions for film deposition and to minimize impurity deposition. • Characterizing the nature of the resulting films, with focus on their stoichiometry and on the final oxidation states of the constituent elements; and • Using the information obtained to propose better precursors for given ALD processes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Degradation and Accelerated Recovery of Surface Passivation in n+, p+, and Intrinsic Poly-Si/SiOx Passivating Contacts for Silicon Solar Cells

We report on the degradation and recovery of surface passivation of fired poly-Si/SiOx passivating contacts with hydrogen containing Al2O3 during annealing in the dark and under illumination. Upon firing to a peak temperature of 670 degrees C, the iVoc for symmetric test structures with n+, p+, and intrinsic poly-Si/SiOx contacts decreases due to a loss of surface passivation. Upon further annealing over the temperature range of 200-350 degrees C in the dark, depending on the type of doping, the surface passivation either shows further degradation followed by recovery, or direct recovery to the initial iVoc. Annealing at higher temperatures and/or higher illumination intensities accelerates the kinetics for both degradation and recovery processes. We show that the degradation and recovery processes are thermally activated and proceed identically in subsequent firing and annealing steps showing their cyclic nature. We present a series reaction model to explain the kinetics of degradation and recovery processes for n+ and intrinsic poly-Si/SiOx contacts. By fitting the model's rate expressions to the data, the determined effective activation energy barriers for degradation and recovery for n+ poly-Si/SiOx contacts in the dark are 1.24 and 1.51 eV, which are lowered under 7.5 Suns illumination to 0.76 and 1.15 eV, respectively.

14 SOLAR ENERGY↗
DOE OSTI2024

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↗