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Results for “Chemical reaction progress”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Simulation of flame acceleration and deflagration-to-detonation transition with heat transfer in HE product and fractured HE

A simple heat transfer model has been developed for high explosives. For the gaseous high explosive (HE) product, the Smargorinsky eddy viscosity model has been adopted for estimating the turbulent thermal conductivity. Convective heat transfer in the fractured solid HE is modeled as the effective thermal conduction in the porous media, which is equivalent to the enthalpy flux carried by the velocity determined by Darcy’s law with Forchheimer term.Other features of the model include a multi-reaction chain, equation-of-state for each species involved, and a two-phase hotspot model. Test calculations are performed with various initial disturbances. Onset and progress of flame acceleration (FA) and chemical reactions are strongly affected by the heat transfer and initial disturbance. Staged development of FA also affirms the necessity of modeling based on a multi-reaction chain. When conditions warrant,e.g., stronger initial disturbance, FA evolves to deflagration-to-detonation transition (DDT),demonstrating automatic capture of the DDT.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2026

Exploding Bridgewire (EBW) Detonators: An Example of Synergistic Multiphysics

Exploding bridgewire (EBW) detonators are highly temporally reproducible explosive devices that require the rapid discharge of a high‐voltage capacitance to operate and so are immune to most of the accidental hazards associated with traditional electric detonators. They have been demonstrated to be safe enough for use in high‐consequence explosive applications. Despite continued use for over 82 years, understanding the exact mechanism of operation has remained elusive. Various researchers have ascribed either deflagration‐to‐detonation (DDT) or shock‐to‐detonation (SDT) phenomena observed in other explosive events to explain the science behind the successful engineering; however, a rigorous justification has been absent. Previously, we have demonstrated a complex interaction in EBW detonators between large electrical currents, non‐equilibrium thermodynamic material states, plasma physics, powder compaction phenomena, shock physics, photochemistry, and rapid conventional explosive chemical reaction processes. Specifically, we have made progress in understanding the complex multiphysics that operates in these detonators and demonstrating that it is a serendipitous synergy between UV light emitted from the arc formed as the bridge is electrically exploded and the accompanying short‐duration shock transmitted into the explosive powder bed that allows these devices to function at practical capacitor sizes and charge voltages. This insight not only places the topic on a firmer scientific footing but potentially enables new approaches to safe detonator design.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Shining light on the microscopic resonant mechanism responsible for cavity-mediated chemical reactivity

Strong light–matter interaction in cavity environments is emerging as a promising approach to control chemical reactions in a non-intrusive and efficient manner. The underlying mechanism that distinguishes between steering, accelerating, or decelerating a chemical reaction has, however, remained unclear, hampering progress in this frontier area of research. We leverage quantum-electrodynamical density-functional theory to unveil the microscopic mechanism behind the experimentally observed reduced reaction rate under cavity induced resonant vibrational strong light-matter coupling. We observe multiple resonances and obtain the thus far theoretically elusive but experimentally critical resonant feature for a single strongly coupled molecule undergoing the reaction. While we describe only a single mode and do not explicitly account for collective coupling or intermolecular interactions, the qualitative agreement with experimental measurements suggests that our conclusions can be largely abstracted towards the experimental realization. Specifically, we find that the cavity mode acts as mediator between different vibrational modes. In effect, vibrational energy localized in single bonds that are critical for the reaction is redistributed differently which ultimately inhibits the reaction.

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

Synchrotron based transient x-ray absorption spectroscopy for emerging solid-state energy materials

The rational design of cutting-edge materials for an efficient solar energy conversion process is a challenging task, which demands a fundamental understanding of the mechanisms operative during the photoinduced physical and chemical reactions. In response to these issues, progress in the field has steered attention toward the use of time-resolved spectroscopic techniques to resolve the multiple intermediate species involved in these photoinduced reactions. Thanks to the advent of pump–probe technique, which leads to the development of various time-resolved spectroscopic methods, significant progress has been made in understanding the photophysical and photochemical properties (e.g., excited state dynamics, charge transfer mechanism, charge separation dynamics, etc.) of energy materials. Synchrotron-based x-ray transient absorption (XTA) spectroscopy is one of the most important time-resolved techniques to unravel the direct correlation of the material structure with their photophysical properties owing to its unique capability in directly observing electronic and structural evolution simultaneously. As a result, the aim of this work is to provide a systematic overview of the recent progress in using XTA for capturing the structural dynamics associated with excited state and charge separation dynamics in emerging solid-state energy materials.

14 SOLAR ENERGY↗
DOE OSTI2021

A Deep Learning Modeling Framework to Capture Mixing Patterns in Reactive-Transport Systems

Prediction and control of chemical mixing are vital for many scientific areas such as subsurface reactive transport, climate modeling, combustion, epidemiology, and pharmacology. Due to the complex nature of mixing in heterogeneous and anisotropic media, the mathematical models related to this phenomenon are not analytically tractable. Numerical simulations often provide a viable route to predict chemical mixing accurately. However, contemporary modeling approaches for mixing cannot utilize available spatial-temporal data to improve the accuracy of the future prediction and can be compute-intensive, especially when the spatial domain is large and for long-term temporal predictions. To address this knowledge gap, in this work we will present in this paper a deep learning (DL) modeling framework applied to predict the progress of chemical mixing under fast bimolecular reactions. This framework uses convolutional neural networks (CNN) for capturing spatial patterns and long short-term memory (LSTM) networks for forecasting temporal variations in mixing. By careful design of the framework—placement of non-negative constraint on the weights of the CNN and the selection of activation function, the framework ensures non-negativity of the chemical species at all spatial points and for all times. Our DL-based framework is fast, accurate, and requires minimal data for training. The time needed to obtain a forecast using the model is a fraction (≈ O(-6)) of the time needed to obtain the result using a high-fidelity simulation. To achieve an error of 10% (measured using the infinity norm) for capturing local-scale mixing features such as interfacial mixing, only 24% to 32% of the sequence data for model training is required. To achieve the same level of accuracy for capturing global-scale mixing features, the sequence data required for model training is 64% to 70% of the total spatial-temporal data. Hence, the proposed approach—a fast and accurate way to forecast long-time spatial-temporal mixing patterns in heterogeneous and anisotropic media—will be a valuable tool for modeling reactive-transport in a wide range of applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1991

Combustion of liquid fuel droplets in supercritical conditions

A comprehensive analysis of liquid-fuel droplet combustion in both sub- and super-critical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates finite-rate chemical kinetics and a full treatment of liquid-vapor phase equilibrium at the droplet surface. The governing equations and the associated interface boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to the supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influences on the fluid transport, gas/liquid interface thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibits a significant variation near the critical burning pressure, mainly as a result of reduced mass-diffusion rate and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

Shuen, J. S.↗
NASA NTRS1992

Combustion of liquid-fuel droplets in supercritical conditions

A comprehensive analysis of liquid-fuel droplet combustion in both subcritical and supercritical environments has been conducted. The formulation is based on the complete conservation equations for both gas and liquid phases, and accommodates variable thermophysical properties, finite-rate chemical kinetics, and a full treatment of liquid-vapor phase equilibrium at the drop surface. The governing equations and associated interfacial boundary conditions are solved numerically using a fully coupled, implicit scheme with the dual time-stepping integration technique. The model is capable of treating the entire droplet history, including the transition from the subcritical to supercritical state. As a specific example, the combustion of n-pentane fuel droplets in air is studied for pressures in the range of 5-140 atm. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the critical pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure.

Shuen, J. S.↗
NASA NTRS1993

Supercritical droplet combustion and related transport phenomena

An overview of recent advances in theoretical analyses of supercritical droplet vaporization and combustion is conducted. Both hydrocarbon and cryogenic liquid droplets over a wide range of thermodynamic states are considered. Various important high-pressure effects on droplet behavior, such as thermodynamic non-ideality, transport anomaly, and property variation, are reviewed. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the criticl pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

Yang, Vigor↗
DOE OSTI2022

Single-Molecule Chemical Reactions Unveiled in Molecular Junctions

Understanding chemical processes at the single-molecule scale represents the ultimate limit of analytical chemistry. Single-molecule detection techniques allow one to reveal the detailed dynamics and kinetics of a chemical reaction with unprecedented accuracy. It has also enabled the discoveries of new reaction pathways or intermediates/transition states that are inaccessible in conventional ensemble experiments, which is critical to elucidating their intrinsic mechanisms. Thanks to the rapid development of single-molecule junction (SMJ) techniques, detecting chemical reactions via monitoring the electrical current through single molecules has received an increasing amount of attention and has witnessed tremendous advances in recent years. Research efforts in this direction have opened a new route for probing chemical and physical processes with single-molecule precision. This review presents detailed advancements in probing single-molecule chemical reactions using SMJ techniques. We specifically highlight recent progress in investigating electric-field-driven reactions, reaction dynamics and kinetics, host–guest interactions, and redox reactions of different molecular systems. Finally, we discuss the potential of single-molecule detection using SMJs across various future applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Molecular Properties and Chemical Transformations Near Interfaces

The properties of bulk water and aqueous solutions are known to change in the vicinity of an interface and/or in a confined environment, including the thermodynamics of ion selectivity at interfaces, transition states and pathways of chemical reactions, and nucleation events and phase growth. Here we describe joint progress in identifying unifying concepts about how air, liquid, and solid interfaces can alter molecular properties and chemical reactivity compared to bulk water and multicomponent solutions. Furthermore, we also discuss progress made in interfacial chemistry through advancements in new theory, molecular simulation, and experiments.

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

Theoretical studies of chemical reactions related to the formation and growth of polycyclic aromatic hydrocarbons (PAH) and molecular properties of their key intermediates (Final Progress Report)

The formation mechanisms of polycyclic aromatic hydrocarbons, (PAHs) – organic molecules carrying fused benzene rings – are of great interest to scientists and engineers due to their importance in combustion chemistry and astrochemistry. On Earth, PAHs are largely produced in incomplete combustion of fossil fuel and are considered as critical precursors to unwanted soot particles leading to combustion inefficiency and causing air pollution along with detrimental health effects. Simple PAH molecules initially formed in the gas phase, are further involved in a build-up process in combustion flames leading to larger PAH, bowl-shaped nanostructures, fullerenes, and solid-phase species including carbonaceous dust, graphene particles, and soot. In deep space, PAH and their derivatives are potential key intermediates and nucleation sites leading eventually to carbonaceous nanoparticles (“interstellar grains”). Therefore, the understanding of the key processes in the synthesis of PAHs along with their precursors and their degradation mechanisms in combustion systems and in interstellar, circumstellar, and planetary atmospheric environments will provide critical insights into how complex aromatic structures, carbonaceous nanoparticles, and fullerenes are formed and destroyed. Achieving this understanding is an important step in the development of the efficient combustion processes and of the ecofriendly devices with reduced environmental pollution as well as technological strategies for the production of hydrogen and solid carbon through thermal or plasma-assisted pyrolysis of natural gas and biomass. Also, the understanding of the key processes of PAH and soot growth will help in our comprehension of chemical evolution in the universe. Detailed information on the mechanisms and reliable rate constants of the key elementary chemical reactions involved in PAH formation and destruction processes and in inception of soot particles is often missing, with the main deficiencies being the absence of temperature- and pressure-dependent rate constants for the broad range of conditions occurring in various terrestrial and interstellar processes and the lack of data on the reaction products and their branching ratios. Complementary to experimental studies, these gaps in knowledge can be filled by using quantum chemical calculations of reaction potential energy surfaces providing us with accurate energies of reaction products, intermediates, and transition states, revealing the reaction mechanism, and giving the molecular properties required to compute rate constants for relevant reaction steps and product branching ratios using the RRKM-Master Equation (ME) method. Molecular dynamics (MD) simulations can be used in cases when a reaction rate cannot be properly described by statistical theories. During the terminal renewal project period we employed these ab initio/RRKM-ME and MD approaches to complete our studies on several key reactions relevant to the formation/growth of PAH and inception of soot particles including (1) the reaction mechanism and kinetics of the resonance stabilized fulvenallenyl radical with propargyl and C 3 H 4 isomers; (2) the reaction mechanism and kinetics for the C + indene and C 2 + styrene reactions producing naphthyl or azulenyl radicals in low-temperature environments; (3) the MD study of non-equilibrium dimerization of acepyrene and coronene and its radical. The information derived from our theoretical calculations contributed to a better fundamental understanding of the reaction mechanisms and provide missing critical kinetic data to improve combustion models of hydrocarbon fuels and astrochemical models of the growth of carbonaceous molecules and particles in cold molecular clouds, circumstellar envelopes, and planetary atmospheres.

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

Biodegradable transient battery built on core-double-shell zinc microparticle networks

A transient or biodegradable battery is provided having a filament structure that limits the speed of reaction allowing for a longer duration of battery power with a controlled current limit. In one embodiment, the filament may be constructed of zinc microparticles or nanoparticles having a thin outer insulation whereby a chemical reaction at the center core results in the progressive disintegration of the insulation revealing more core material. In one embodiment, microparticles or nanoparticles are coated with outer layers of chitosan and Al2O3 nanofilms, respectively, with designable discharge current and battery lifespan by controlling the exposed cross-sectional area of the zinc microparticle center core and the length of the filament, respectively. This novel structure of biodegradable battery provides improved control of battery life and power output, providing a promising solution to power transient medical implants.

Wang, Xudong↗
NASA NTRS1992

Computed potential energy surfaces for chemical reactions

The work on the NH + NO system which was described in the last progress report was written up and a draft of the manuscript is included in the appendix. The appendix also contains a draft of a manuscript on an Ar + H + H surface. New work which was completed in the last six months includes the following: (1) calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction; (2) calculations for the NH2 + O reaction; (3) calculations for the CH3 + O2 reaction; and (4) calculations for CH3O and the two decomposition channels--CH2OH and H + H2CO. Detailed descriptions of this work will be given in manuscripts; however, brief descriptions of the CH3 + OH and CH3 + O2 projects are given.

Heinemann, K.↗
DOE OSTI2020

Catalytic N 2 -to-NH 3 (or -N 2 H 4 ) Conversion by Well-Defined Molecular Coordination Complexes

Nitrogen fixation, the six-electron/six-proton reduction of N 2 , to give NH 3 , is one of the most challenging and important chemical transformations. Notwithstanding the barriers associated with this reaction, significant progress has been made in developing molecular complexes that reduce N 2 into its bioavailable form, NH 3 . This progress is driven by the dual aims of better understanding biological nitrogenases and improving upon industrial nitrogen fixation. In this review, we highlight both mechanistic understanding of nitrogen fixation that has been developed, as well as advances in yields, efficiencies, and rates that make molecular alternatives to nitrogen fixation increasingly appealing. We begin with a historical discussion of N 2 functionalization chemistry that traverses a timeline of events leading up to the discovery of the first bona fide molecular catalyst system and follow with a comprehensive overview of d-block compounds that have been targeted as catalysts up to and including 2019. Furthermore, we end with a summary of lessons learned from this significant research effort and last offer a discussion of key remaining challenges in the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Improved General Chemical-Kinetics Program

New general chemical-kinetics code, GCKP84, developed to compute progress of many types of complex gas-phase chemical reactions. Replaces original GCKP code and offers greatly improved efficiency, additional capabilities, and greater convenience. New code written in FORTRAN IV.

Bittker, David A.↗