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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Radiation-induced reaction kinetics of Zn 2+ with e S - and Cl 2 ˙ - in Molten LiCl–KCl eutectic at 400–600 °C

We report molten chloride salts are currently under consideration as combined coolant and liquid fuel for next-generation molten salt nuclear reactors. Unlike complementary light-water reactor technologies, the radiation science underpinning molten salts is in its infancy, and thus requires a fundamental mechanistic investigation to elucidate the radiation-driven chemistry within molten salt reactors. Here we present an electron pulse radiolysis kinetics study into the behaviour of the primary radiolytic species generated in molten chloride systems, i.e., the solvated electron (e S - ) and di-chlorine radical anion (Cl 2 ˙- ). We examine the reaction of e S - with Zn 2+ from 400–600 °C (E a = 30.31 ± 0.09 kJ mol -1 ), and the kinetics and decay mechanisms of Cl 2 ˙- in molten lithium chloride-potassium chloride (LiCl–KCl) eutectic. In the absence of Zn 2+ , the lifetime of e S - was found to be dictated by residual impurities in ostensibly “pure” salts, and thus the observed decay is dependent on sample history rather than being an intrinsic property of the salt. The decay of Cl 2 ˙- is complex, owing to the competition of Cl 2 ˙- disproportionation with several other chemical pathways, one of which involves reduction by radiolytically-produced Zn + species. Overall, the reported findings demonstrate the richness and complexity of chemistry involving the interactions of ionizing radiation with molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Computing Reaction Kinetics with MC-PDFT–OPESf: Combining Multireference Electronic Structure Theory and Enhanced Sampling

Accurate rate constants are crucial for understanding and optimizing catalytic reactions mediated by enzymes, metalloproteins, and heterogeneous catalysts. These systems frequently present a dual computational challenge. Multiconfigurational reaction sites require multireference techniques for the accurate treatment of the electronic structure, and high activation barriers prevent efficient sampling of unbiased reactive transitions. In this work, we combine multiconfiguration pair-density functional theory (MC-PDFT) as an accurate and efficient multireference electronic structure method with on-the-fly probability-enhanced sampling flooding (OPESf) as an enhanced sampling method capable of accelerating reactive transitions. We demonstrate the approach on the Diels–Alder [4+2] cycloaddition between cis-butadiene and ethene as a reaction characterized by a large activation barrier and multireference character. MC-PDFT–OPESf provides reaction rates in agreement with experiments at a fraction of the computational cost required by conventional unbiased ab initio calculations. Here, we propose MC-PDFT–OPESf as an efficient approach for computing kinetics in strongly correlated molecular systems.

Chemical calculations↗
DOE OSTI2020

Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis

Microkinetic modeling based on density functional theory (DFT) derived energetics is important for addressing fundamental questions in catalysis. The quantitative fidelity of microkinetic models (MKMs), however, is often insufficient to conclusively infer the mechanistic details of a specific catalytic system. Here, this can be attributed to a number of factors such as an incorrect model of the active site for which DFT calculations are performed, deficiencies in the hypothesized reaction mechanism, inadequate consideration of the surface environment under reaction conditions, and intrinsic errors in the DFT exchange-correlation functional. Despite these limitations, we aim at developing a rigorous understanding of the reaction mechanism and of the nature of the active site for heterogeneous catalytic chemistries under reaction conditions. By achieving parity between experimental and modeling outcomes through robust parameter estimation and by ensuring coverage-consistency between DFT calculations and MKM predictions, it is possible to systematically refine the mechanistic model and, thereby, our understanding of the catalytic active site in situ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Experimental studies on the reaction kinetics of 1,1-dimethylhydrazine and oxygen

Measurements behind shock waves in highly diluted 1,1 dimethylhydrazine-O2-Ar mixtures clearly showed a two-stage reaction. In the first stage, UDMH decomposes via a unimolecular step; in the second stage, clearly separated from the first one, the decay products react further with O2. Values for the rate constant of unimolecular decomposition were obtained.

Just, T.↗
NASA NTRS1990

Characterization of reaction kinetics in a porous electrode

A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters.

Fedkiw, Peter S.↗
DOE OSTI2022

Rate Controlling in Low-Temperature Standard NH 3 -SCR: Implications from Operando EPR Spectroscopy and Reaction Kinetics

Here, a series of seven Cu/SSZ-13 catalysts with Si/Al = 6.7 are used to elucidate key rate-controlling factors during low-temperature standard ammonia-selective catalytic reduction (NH 3 -SCR), via a combination of SCR kinetics and operando electron paramagnetic resonance (EPR) spectroscopy. Strong Cu-loading-dependent kinetics, with Cu atomic efficiency increasing nearly by an order of magnitude, is found when per chabazite cage occupancy for Cu ion increases from ~0.04 to ~0.3. This is due mainly to the release of intercage Cu transfer constraints that facilitates the redox chemistry, as evidenced from detailed Arrhenius analysis. Operando EPR spectroscopy studies reveal strong connectivity between Cu-ion dynamics and SCR kinetics, based on which it is concluded that under low-temperature steady-state SCR, kinetically most relevant Cu species are those with the highest intercage mobility. Transient binuclear Cu species are mechanistically relevant species, but their splitting and cohabitation are indispensable for low-temperature kinetics.

catalytic reactions↗
NASA NTRS1975

Static-kinetic reactions of man under conditions of brief weightlessness

Physical characteristics of human responses to weightlessness simulation during parabolic flights establish body immobilization and visual illusions as the most manifest causes of sensory distrubances. Repeated brief weightlessness exposures gradually decreased expressions of static-kinetic disorders.

Kolosov, I. A.↗
DOE OSTI2022

CaMn 0.9 Ti 0.1 O 3 based redox catalysts for chemical looping – Oxidative dehydrogenation of ethane: Effects of Na 2 MoO 4 promoter and degree of reduction on the reaction kinetics

Reduction kinetics and stability of 20 wt% Na 2 MoO 4 -promoted CaMn 0.9 Ti 0.1 O 3 were investigated for its applications in Chemical Looping – Oxidative Dehydrogenation (CL-ODH) of ethane, a potential alternative for ethylene production with higher efficiency and lower emissions. Here, the present work reports a kinetics model and parameters for a Na 2 MoO 4 -promoted, Ti-doped CaMnO 3 (CaMn 0.9 Ti 0.1 O 3 ) redox catalyst under H 2 and C 2 H 4 . A first-order reaction model provides the best fit for the reduction of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 , while the C 2 H 4 reduction is well described by an Avrami–Erofe’ev model. The activation energy for C 2 H 4 oxidation is approximately three times higher than that for H 2 conversion, showing that the activation of C 2 H 4 is significantly more difficult on the surface of the redox catalyst. The reduction rate of Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 under H 2 at 750 °C is more than two orders of magnitude greater than that under C 2 H 4 , while the reduction rate of unpromoted CaMn 0.9 Ti 0.1 O 3 is comparable under H 2 and C 2 H 4 , showing that the addition of Na 2 MoO 4 effectively suppresses C 2 H 4 combustion relative to H 2 oxidation. The kinetics results for Na 2 MoO 4 /CaMn 0.9 Ti 0.1 O 3 confirm its excellent selectivity towards hydrogen combustion, making it a promising candidate under CL-ODH. Additionally, the stability of the CaMn 0.9 Ti 0.1 O 3 @ Na 2 MoO 4 core-shell structure, which was the underlying reason for the excellent selectivity, was examined under both shallow and deep reductions. It was determined that deep reduction of the redox catalyst, e.g. higher than 80% solid conversion, would lead to loss of sodium and hence to decreased selectivity for hydrogen combustion. In contrast, the core-shell structure was well-maintained, exhibiting excellent performance after 50 redox cycles when deep reduction of the redox catalyst was avoided. This study offers a basis for both the CL-ODH reactor design and redox catalyst optimizations.

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

Mineral reaction kinetics constrain the length scale of rock matrix diffusion

Mass transport by aqueous fluids is a dynamic process in shallow crustal systems, redistributing nutrients as well as contaminants. Rock matrix diffusion into fractures (void space) within crystalline rock has been postulated to play an important role in the transient storage of solutes. The reacted volume of host rock involved, however, will be controlled by fluid-rock reactions. Here we present the results of a study which focusses on defining the length scale over which rock matrix diffusion operates within crystalline rock over timescales that are relevant to safety assessment of radioactive and other long-lived wastes. Through detailed chemical and structural analysis of natural specimens sampled at depth from an active system (Toki Granite, Japan), we show that, contrary to commonly proposed models, the length scale of rock matrix diffusion may be extremely small, on the order of centimetres, even over timescales of millions of years. This implies that in many cases the importance of rock matrix diffusion will be minimal. Additional analyses of a contrasting crystalline rock system (Carnmenellis Granite, UK) corroborate these results.

58 GEOSCIENCES↗
DOE OSTI2026

Continuity of reaction kinetics across the pressure and materials gaps in CO oxidation on FeO–Pt interfaces

Translating atomic-scale insights from surface science studies of model catalysts to practical powder catalysts remains a persistent challenge in heterogeneous catalysis. Here, in this study, we demonstrate mechanistic continuity across the pressure and materials gaps during CO oxidation at the FeO-Pt interface using in situ microscopy, spectroscopy and computational modelling. Under reaction conditions, coordinatively unsaturated Fe (Fe cus ) sites at the interface enable selective O 2 activation on CO-saturated surfaces, circumventing the CO-poisoning limitation of platinum-group metals. We identify parallel reaction pathways involving the *O 2 -*CO intermediate. Remarkably, activation energies remain consistent at 12-15 kJ mol −1 (0.12-0.16 eV) from ultrahigh vacuum to atmospheric pressures and from FeO/Pt(111) model catalysts to FeO/Pt powder catalysts, validating mechanistic insights derived from surface science studies. Our findings show an example of bridging the long-standing divide between model and practical catalyst systems, establishing an effective approach to capture catalytic behaviours under operational conditions and advancing mechanism-driven catalyst design.

03 NATURAL GAS↗
DOE OSTI2024

From Fundamental Interfacial Reaction Kinetics to Macroscopic Current–Voltage Characteristics: Case Study of Solid Acid Fuel Cell Limitations and Possibilities

The unique properties of solid acid electrolytes, in particular CsH 2 PO 4 , are in many ways ideal for fuel cell operation. However, the technology is constrained by high cathode overpotentials. Here a simplified cathode geometry is employed to obtain the fundamental electrochemical parameters (exchange current density and charge transfer coefficient) describing the oxygen reduction reaction (ORR) at the CsH 2 PO 4 -Pt-gas interface. The parameters are incorporated into a 1D model of the voltage–current characteristics of realistic SAFC cathodes, which reproduced the measured polarization behavior of such cathodes without recourse to fitting adjustable parameters. Following this validation, the model is utilized to evaluate the impact of changes to cathode properties, microstructure, and operating conditions. Of these, the charge transfer coefficient, measured to have a value of ≈0.6 for ORR on Pt in the SAFC cathode environment, is found to have the greatest impact on power output. Nevertheless, even without material modifications, a combination of microstructural and operational modifications are identified with projected performance metrics meeting Department of Energy targets (0.8 V at 300 mA cm –2 , and peak power density of 1 W cm –2 ), albeit at high Pt loadings. However, the analysis indicates that truly meaningful advances will likely necessitate the discovery of alternative ORR catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Revisiting the Impact of Anion Selection on Sulfur Redox Reaction Kinetics for High Sulfur Loading Lithium–Sulfur Batteries

Lithium bis(trifluoromethane)sulfonimide (LiTFSI) is widely used in lithium–sulfur (Li–S) battery electrolytes due to its stability with lithium polysulfides (LiPSs) and moderate compatibility with lithium metal anodes. However, LiTFSI presents environmental concerns due to its association with per- and polyfluoroalkyl substances (PFAS), which are environmentally persistent and potentially toxic, raises sustainability concerns. This research also reveals that LiTFSI limits sulfur redox reactions (SRRs), making it less effective than other lithium salts. Additionally, some salts previously considered incompatible with Li-S systems due to their reactivity with LiPSs are demonstrated to perform effectively. For the first time, a protective, porous cathode electrolyte interphase (CEI) formed in situ through reactions between salt anions and LiPS is reported. The cells delivered a high specific capacity of 1230.8 mAh g −1 at 0.05 C with a sulfur loading of ≈6 mg cm −2 , limited lithium anode, maintaining a capacity retention of 76.2% after 100 cycles at 0.1 C. Under harsh conditions, such as high sulfur loading, lean electrolyte conditions (3 µL mg −1 ), and in anode-free cells, the cells continued to deliver outstanding capacity. This work provides valuable guidelines for understanding and selecting lithium salts to advance electrolyte design for Li–S batteries.

high loading batteries↗
DOE OSTI2023

Predicting encapsulant delamination in photovoltaic modules bridging photochemical reaction kinetics and fracture mechanics

Abstract Photovoltaic (PV) modules are subjected to environmental stressors (UV exposure, temperature, and humidity) that cause degradation within the encapsulant and its interfaces with adjacent glass and cell substrates. To save experimental time and to enable long‐term assessment with intensive degradation only taking place after many years, the development of predictive models is indispensable. Previous works have modeled the delamination of the ethylene vinyl acetate (EVA) encapsulant/glass and encapsulant/cell interfaces under field aging conditions with fundamental photochemical degradation reactions that lead to molecular scission and loss of interfacial adhesion, characterized by the fracture resistance, G c . However, these models were fundamentally limited in that the following aspects were not incorporated: (i) molecular crosslinking in the field, (ii) synergistic autocatalytic interactions of degradation mechanisms, (iii) connection between degraded encapsulant structure and its mechanical properties, and (iv) rigorous treatment of the plasticity contribution to G c with finite element models. Here, we present a time‐dependent multiscale model that addresses these limitations and is applicable to a wide range of encapsulants and interfaces. For the reference EVA encapsulant and its interfaces with the glass and cell, the presented model predicts an initial rise in G c in the first 3 years of field aging from crosslinking, then a subsequent sharp decline from degradation mechanisms. We used nanoindentation to measure the changes in EVA mechanical properties over exposure time to tune the model parameters. The model predictions of G c and mechanical properties match with experimental data and show an improvement compared to previous models. The model can even predict switches in failure interfaces, such as the observed EVA/cell to EVA/glass transition. We also conducted a sensitivity analysis study by varying the degradation and crosslinking kinetic parameters to demonstrate their effects on G c . Model extensions to polyolefin elastomer‐ and silicone‐encapsulants and their interfaces are also demonstrated.

Liu, Kuan↗
NASA NTRS1991

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗
DOE OSTI2026

Fluid‐Driven Cohesive Strengthening: Critical Role of Reaction Kinetics as the Determinant for Frictional Stability

After an earthquake, faults in the Earth's crust lock up and slowly regain strength. This process, called fault healing, plays a key role in determining how often earthquakes happen and how large they can be. While scientists know that healing involves both mechanical friction and chemical changes in rocks, it has been unclear how these processes work together, especially over shorter timescales in laboratory settings. In our study, we ran controlled experiments on the mineral anhydrite under different fluid conditions. We found that the presence and pressure of water speeds up fault healing by triggering a chemical reaction that strengthens the fault over time. This strengthening makes the fault more resistant to sliding, which could delay future earthquakes—but also sets the stage for larger ones when they do occur. We propose a model that combines frictional and chemical processes to explain this water‐activated, time‐dependent healing. Importantly, our results show that even faults typically considered stable could still produce earthquakes if they undergo sufficient chemical healing. This has broad implications for understanding where and when earthquakes might strike, especially in fluid‐rich environments such as subduction zones and geoenergy settings.

Affinito, R [Pennsylvania State Univ., University ↗
DOE OSTI2025

Resolving the Coverage Dependence of Surface Reaction Kinetics with Machine Learning and Automated Quantum Chemistry Workflows

Microkinetic models for catalytic systems require estimation of many thermodynamic and kinetic parameters that can be calculated for isolated species and transition states using ab initio methods. However, the presence of nearby coadsorbates on the surface can dramatically alter these thermodynamic and kinetic parameters causing them to be dependent on species coverage fractions. As there are combinatorially many coadsorbed configurations on the surface, computing the coverage dependence of these parameters is far less straightforward. We present a framework for generating and applying machine learning models to predict coverage-dependent parameters for microkinetic models. Our toolkit enables automatic calculation and evaluation of coadsorbed configurations allowing us to sample 2,000 coadsorbed adsorbates and transition states (TSs) for a diverse set of 9 reactions on Cu(111), a challenging surface, with four possible coadsorbates. This dataset was then used to train subgraph isomorphic decision trees (SIDTs) to predict the stability and association energy of configurations. We were able to achieve mean absolute errors (MAEs) of 0.106 eV on adsorbates, 0.172 eV on TSs, and due to natural error cancellation in SIDTs for relative properties, 0.130 eV on reaction energies and 0.180 eV on activation barriers. In conclusion, we describe how to use these models to predict coverage-dependent corrections for adsorbates and TSs and demonstrate on H*, HO*, and O* comparing the generated SIDT model with an iteratively refined version.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Construction of MoS 2 /NiS 2 heterostructure with fast interfacial reaction kinetics for ultrafast sodium storage

Constructing heterostructure is a valid method to reinforcing sodium storage performance of transition metal chalcogenides materials. Herein, a simple, safe and controllable one step hydrothermal method is proposed to synthesize MoS 2 /NiS 2 heterostructure. Due to the difference in band gaps and work functions of MoS 2 and NiS 2 , the charges are redistributed at the MoS 2 /NiS 2 heterointerfaces, thereby accelerating the migration of electrons and Na + . The heterointerfaces provide extra active sites for storing Na + , thus increasing the sodium storage capacity of the heterostructure. Furthermore, the distinct redox potentials of NiS 2 and MoS 2 promote the structural stability of MoS 2 /NiS 2 heterostructure during the electrochemical reaction processes. Consequently, the obtained MoS 2 /NiS 2 heterostructure exhibits superior rate properties (339.4 mAh g –1 at 10 A g –1 ) and ultra-stable cycling stability (480.5 mAh g –1 after 350 cycles at 1 A g –1 ). Finally, this paper presents a valid strategy for creating heterostructure anodes with excellent sodium storage properties.

25 ENERGY STORAGE↗