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MFIX-Exa: CFD-DEM Simulations of Thermodynamics and Chemical Reactions in Multiphase Flows
For presentation at the AIChE Annual Meeting, Orlando, FL, November 5-10, 2023.
Zero diffusivity invariance for turbulent chemical reaction
Turbulent chemical reactions invariance preservation for zero diffusivity
Graph characterization of higher-order structure in atmospheric chemical reaction mechanisms
Atmospheric chemical reactions play an important role in air quality and climate change. While the structure and dynamics of individual chemical reactions are fairly well understood, the emergent properties of the entire atmospheric chemical system, which can involve many different species that participate in many different reactions, are not well described. In this work, we leverage graph-theoretic techniques to characterize patterns of interaction (“motifs”) in three different representations of gas-phase atmospheric chemistry, termed “chemical mechanisms.” These widely used mechanisms, the master chemical mechanism, the GEOS-Chem mechanism, and the Super-Fast mechanism, vary dramatically in scale and application, but they all generally aim to simulate the abundance and variability of chemical species in the atmosphere. This motif analysis quantifies the fundamental patterns of interaction within the mechanisms, which are directly related to their construction. For example, the gas-phase chemistry in the very small Super-Fast mechanism is entirely composed of bimolecular reactions, and its motif distribution matches that of an individual bimolecular reaction well. The larger and more complex mechanisms show emergent motif distributions that differ strongly from any specific reaction type, consistent with their complexity. The proposed motif analysis demonstrates that while these mechanisms all have a similar design goal, their higher-order structure of interactions differs strongly and thus provides a novel set of tools for exploring differences across chemical mechanisms.
Modeling downdraft biomass gasification process by restricting chemical reaction equilibrium with Aspen Plus
Not Available
Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces
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The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies
Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.
High accuracy barrier heights, enthalpies, and rate coefficients for chemical reactions
Abstract Quantitative chemical reaction data, including activation energies and reaction rates, are crucial for developing detailed kinetic mechanisms and accurately predicting reaction outcomes. However, such data are often difficult to find, and high-quality datasets are especially rare. Here, we use CCSD(T)-F12a/cc-pVDZ-F12// ω B97X-D3/def2-TZVP to obtain high-quality single point calculations for nearly 22,000 unique stable species and transition states. We report the results from these quantum chemistry calculations and extract the barrier heights and reaction enthalpies to create a kinetics dataset of nearly 12,000 gas-phase reactions. These reactions involve H, C, N, and O, contain up to seven heavy atoms, and have cleaned atom-mapped SMILES. Our higher-accuracy coupled-cluster barrier heights differ significantly (RMSE of ∼5 kcal mol −1 ) relative to those calculated at ω B97X-D3/def2-TZVP. We also report accurate transition state theory rate coefficients $${k}_{\infty }(T)$$ k ∞ ( T ) between 300 K and 2000 K and the corresponding Arrhenius parameters for a subset of rigid reactions. We believe this data will accelerate development of automated and reliable methods for quantitative reaction prediction.
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.
The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces
Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.
Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories
This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.
Optical spectroscopy system and method for monitoring liquid phase chemical reactions
A system for monitoring a chemical reaction in a liquid reactor system includes a sample liquid conduit in communication with the liquid reactor system for receiving sample liquid and directing the sample liquid to an optical spectroscopy device, and a laser beam source. The optical spectroscopy device receives the laser beam from the laser source, and guides the laser beam to the sample liquid to generate an optical spectroscopy signal. A detector detects the optical spectroscopy signal and creates a detection signal responsive to the optical spectroscopy signal. A processor processes the detection signal to determine the identity and amount of at least one chemical species in the liquid. A system for continuously sampling a chemical reaction and a method for continuously monitoring and controlling a chemical reaction are also disclosed.
Evaluation of a self-regulated in vitro hypoxic system by using chemical reactions
Highlights: • A self-regulated in vitro hypoxic system has been established using chemical reactions. • The chemical reaction was able to sustain the basic requirements of CO{sub 2} and pH levels of cell culture. • The hypoxia box design may provide countless applications for the study of hypoxia. In this study, we established an in vitro hypoxic system driven by a self-regulated chemical reaction that proved effective for cell culture. The hypoxic device was modified from a 1.5 L polypropylene preservation box normally employed for food storage. Pyrogallic acid, sodium hydroxide, and sodium carbonate were dissolved in water and injected into the box. Sodium dihydrogen phosphate solution was injected into the box after 15 min. We measured the concentrations of oxygen and carbon dioxide in the box to determine viability of the hypoxic system. It maintained low levels of oxygen less than 0.2% and stabilizing levels of carbon dioxide at 5% for at least 96 h. Therefore, this device sustained a stable hypoxic environment that may be applicable for cell culture and in vitro studies of hypoxia.
Nonadiabatically Driven Quantum Interference Effects in the Ultracold K + KRb → Rb + K 2 Chemical Reaction
The K + KRb → Rb + K 2 chemical reaction is the first ultracold atom–diatom chemical reaction for which experimental results have been reported for temperatures below 1 μK more than a decade ago. The reaction occurs through coupling with an excited electronic state that is accessible even in the ultracold limit. A previous quantum dynamics study, excluding nonadiabatic effects, has reported a rate coefficient that is about 35% below the experimental value. Here, we report the first nonadiabatic quantum dynamics study of this reaction and obtain rate coefficients in better agreement with experiments. Our results show that short-range dynamics mediated by coupling with the excited electronic state introduces quantum interference effects that influence both the state-to-state rate coefficients and the overall reaction rates.
Mixing and non-equilibrium chemical reaction in a compressible mixing layer
The effects of compressibility, chemical reaction exothermicity, and non-equilibrium chemical modeling in a reacting plane mixing layer were investigated by means of two dimensional direct numerical simulations. The chemical reaction was irreversible and second order of the type A + B yields Products + Heat. The general governing fluid equations of a compressible reacting flow field were solved by means of high order finite difference methods. Physical effects were then determined by examining the response of the mixing layer to variation of the relevant non-dimensionalized parameters. The simulations show that increased compressibility generally results in a suppressed mixing, and consequently a reduced chemical reaction conversion rate. Reaction heat release was found to enhance mixing at the initial stages of the layer growth, but had a stabilizing effect at later times. The increased stability manifested itself in the suppression or delay of the formation of large coherent structures within the flow. Calculations were performed for a constant rate chemical kinetics model and an Arrhenius type kinetic prototype. The choice of the model was shown to have an effect on the development of the flow. The Arrhenius model caused a greater temperature increase due to reaction than the constant kinetic model. This had the same effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.
Apparent activation energy of chemical reactions at high temperature.
Chemical reactions activation energy at high temperature, noting cross section shape role for deducing activation energy from rate data
CHEMICAL REACTIONS IN SUPERSONIC NOZZLE FLOWS
Chemical reactions in supersonic nozzle flows - vibrational relaxation - electron-ion recombination - sudden freezing analysis