Thermodynamics and kinetics of heterogeneous reactions
Thermodynamics and kinetics of sublimation, catalytic, and oxidation reactions
Batty, J. C.↗
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Learning heterogeneous reaction kinetics from X-ray videos pixel by pixel
Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries and electrocatalysts. Experimental characterizations of such materials by operando microscopy produce rich image datasets, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.
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Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel
Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries 1 and electrocatalysts 2. Experimental characterizations of such materials by operando microscopy produce rich image datasets 3–6, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation 7. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.
Chueh, William↗
Solid Fuel Burning in Steady, Strained, Premixed Flow Fields: The Graphite/Air/Methane System
A detailed numerical investigation was conducted on the simultaneous burning of laminar premixed CH4/air flames and solid graphite in a stagnation flow configuration. The graphite and methane were chosen for this model, given that they are practical fuels and their chemical kinetics are considered as the most reliable ones among solid and hydrocarbon fuels, respectively. The simulation was performed by solving the quasi-one-dimensional equations of mass, momentum, energy, and species. The GRI 2.1 scheme was used for the gas-phase kinetics, while the heterogeneous kinetics were described by a six-step mechanism including stable and radical species. The effects of the graphite surface temperature, the gas-phase equivalence ratio, and the aerodynamic strain rate on the graphite burning rate and NO, production and destruction mechanisms were assessed. Results indicate that as the graphite temperature increases, its burning rate as well as the NO, concentration increase. Furthermore, it was found that by increasing the strain rate, the graphite burning rate increases as a result of the augmented supply of the gas-phase reactants towards the surface, while the NO, concentration decreases as a result of the reduced residence time. The effect of the equivalence ratio on both the graphite burning rate and NO, concentration was found to be non-monotonic and strongly dependent on the graphite temperature. Comparisons between results obtained for a graphite and a chemically inert surface revealed that the chemical activity of the graphite surface can result to the reduction of NO through reactions of the CH3, CH2, CH, and N radicals with NO.
Egolfopoulos, Fokion N.↗
Symposium (International) on Combustion, 23rd, Universite d'Orleans, France, July 22-27, 1990, Proceedings
The present symposium on combustion discusses reaction kinetics, NO(x) kinetics, premixed, diffusion, and nonsteady flames, turbulent combustion, hazardous waste, fluidized bed combustion, coal boilers and furnaces, engines, heterogeneous kinetics, heterogeneous, droplet, and microgravity combustion, and high-temperature synthesis. Attention is given to reactions of biphenyl, methylnaphthalenes, and phenanthrene with atomic oxygen in the gas phase, the oxidation of ortho-xylene, the effects of water on combustion kinetics at high pressure, and the formation and measurement of N2O in combustion systems. Topics addressed include large ions in premixed benzene-oxygen flames, the structure and kinetics of CH4/N2O flames, the propagation of unsteady hydrogen premixed flames near flammability limits, and the basic structure of lean propane flames. Also considered are OH measurements of piloted diffusion flames of nitrogen-diluted methane near extinction, waste combustion, preferential oxidation of carbon surfaces, and reburning mechanisms in a pulverized coal combustor.
Source record↗
Spatio-Kinetic Electronic Heterogeneity in MoS 2 Revealed by Ultrafast Electron Microscopy: Implications for Optoelectronics
There is broad interest in layered, two-dimensional (2D) semiconductors owing to their high optical absorption and ability to heterogeneously integrate with various substrates. In such layered semiconductors, mesoscopic imperfections, such as surface step edges, may affect charge carrier kinetics and device performance, but studying their effects on carrier transport with sufficient spatial and temporal resolution is a challenge. Using scanning ultrafast electron microscopy, we image the near-surface charge carrier kinetics with μm/ps spatiotemporal resolution in single-crystal MoS 2 samples with surface steps tens of nanometers in height. We find an approximately 3-fold increase in surface trap density near such surface steps compared to the uniform, flat surface regions. Despite the difference in trap state density, filling of the traps occurs over the same time scale (∼100 ps), but carrier recovery is much slower near the step compared to the uniform regions of the material. Furthermore, these results provide an approach to measure ultrafast dynamics and determine the required uniformity of layered materials depending on the speed limit constraints for specific applications.
SEM↗
The Conundrum of “Pair Sites” in Langmuir–Hinshelwood Reaction Kinetics in Heterogeneous Catalysis
Not Available
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An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron
The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of these materials has been studied, also, in the present program.
Shanabarger, Mickey R.↗
An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron
The goal of this program was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of degradation. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.
Shanabarger, Mickey R.↗
An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron
The goal of this program has been to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. During the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak. Weak in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of several of these materials was studied. More recently, preliminary hydrogen permeation studies were completed for three high temperature alloys, Incoloy 909, Mo-47.5Re (wt. %), and this past year, Haynes 188.
Shanabarger, Mickey R.↗
An Investigation of the Effect of Surface Impurities on the Adsorption Kinetics of Hydrogen Chemisorbed onto Iron
The original goal of this program was to investigate the effect surface impurities have on the heterogeneous kinetic processes of those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. However, shortly after the initiation of the original program, the program's NASA Technical Monitor, Dr. Howard Nelson, requested that the effort supported by this Co-operative Agreement be redirected to study more pressing materials issues associated to the development of the National Aero-Space Plane (NASP). The results of these efforts are outlined in this report. Detailed discussions of specific work, including experimental techniques and procedures, will be found in the publications listed with the subsection discussing that specific work as well and in Section 5. No inventions were generated or disclosed within this Agreement.
Shanabarger, M. R.↗
An Investigation of the Effect of Surface Impurities on the Adsorption Kinetics of Hydrogen Chemisorbed onto Iron
The original goal of this program was to investigate the effect surface impurities have on the heterogeneous kinetic processes of those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. However, shortly after the initiation of the original program, the program's NASA Technical Monitor, Dr. Howard Nelson, requested that the effort supported by this Co-operative Agreement be redirected to study more pressing materials issues associated to the development of the National Aero-Space Plane (NASP). The results of these efforts are outlined in this report. Detailed discussions of specific work, including experimental techniques and procedures, will be found in the publications listed with the subsection discussing that specific work as well and in Section 5. No inventions were generated or disclosed within this Agreement.
Shanabarger, R. M.↗
Kinetics of the Heterogeneous Reaction HNO3(g) + NaBr(s)<->HBr(g) +NaNO3(s)
The kinetics of the heterogeneous reaction HNO3(g) + NaBr(s)<->HBr(g)+NaNO3(s)has been investigated at 296K using a fast-flow reactor coupled to an electron-impact ionization mass spectrometer.
Heterogeneous Reactions HNO2 salts↗
Fundamental combustion experiments in microgravity
Technical bases for microgravity combustion experimentation are identified for important areas of study. The analyses which underlie the need for microgravity experiments of single and two-phase autoignitions, explosions, thermokinetic oscillations, and kinetic oscillations are emphasized. It is shown that turbulent combustion experiments at microgravity are needed and that heterogeneous kinetics are a centrally important process in a number of classic experiments.
Berlad, A. L.↗
Multiphase combustion experimentation in microgravity
This paper examines the need for and implementation of microgravity combustion studies of two phase media. Experimental and analytical aspects of several heterogeneous kinetic systems are discussed. These include: flame propagation and extinction for quiescent clouds of uniformly premixed fuel particulates in an oxidizing atmosphere; autoignition of clouds of uniformly premixed fuel particulates in a quiescent oxidizing atmosphere; and the roles of catalytically significant surfaces in gaseous autoignition processes.
Berlad, A. L.↗
Density functional theory-based surrogate kinetic models for heterogeneous reactions of hydrocarbon intermediates on silicon carbide
The increasing demand for high-performance materials in advanced technologies highlights the importance of achieving a fundamental understanding and potential control of silicon carbide (SiC) deposition processes. However, existing models often lack sufficient theoretical detail, relying heavily on empirical data and offering limited predictive capability. In particular, the complex surface chemistry governing SiC growth remains poorly understood. This study addresses these challenges by employing density functional theory (DFT) to investigate key heterogeneous reactions involving hydrocarbon intermediates on SiC surfaces, including dehydrogenation, hydrogenation, and carbon deposition. Transition state searches were conducted to identify reaction pathways and energy barriers. While first-principles calculations offer high accuracy, they are computationally intensive. To extend the utility of these first-principles results, vibrational analyses were performed using phonon-based statistical thermochemistry to compute temperature-dependent reaction rates which were used to develop Arrhenius-type surrogate kinetic models. Furthermore, the resulting framework provides a more rigorous, physically grounded basis for integrating atomistic insights into continuum-scale modeling, ultimately enabling improved prediction and optimization of SiC film growth in high-performance material systems.
Density Functional Theory↗
Kinetics of the Heterogeneous Reaction CO + O = CO(sub 2) on Inorganic Oxide and Water Ice Surfaces: Implications for the Martian Atmosphere
The heterogeneous reaction CO + O - CO(sub 2) on water ice and varios inorganic oxide surfaces has been investigated in order to evaluate the proposition that this heterogeneous reaction may contribute to the CO(sub 2) stability in the Martian atmosphere.
heterogeneous reaction inorganic oxide martian atm↗
Magnetic resonance insights into the heterogeneous, fractal-like kinetics of chemically recyclable polymers
Moving toward a circular plastics economy is a vital aspect of global resource management. Chemical recycling of plastics ensures that high-value monomers can be recovered from depolymerized plastic waste, thus enabling circular manufacturing. However, to increase chemical recycling throughput in materials recovery facilities, the present understanding of polymer transport, diffusion, swelling, and heterogeneous deconstruction kinetics must be systematized to allow industrial-scale process design, spanning molecular to macroscopic regimes. To develop a framework for designing depolymerization processes, we examined acidolysis of circular polydiketoenamine elastomers. We used magnetic resonance to monitor spatially resolved observables in situ and then evaluated these data with a fractal method that treats nonlinear depolymerization kinetics. This approach delineated the roles played by network architecture and reaction medium on depolymerization outcomes, yielding parameters that facilitate comparisons between bulk processes. These streamlined methods to investigate polymer hydrolysis kinetics portend a general strategy for implementing chemical recycling on an industrial scale.
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