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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Chemical Kinetic Modeling of Ignition in HRRST

In the high repetition rate miniature shock tube, HRRST, the temperature and pressure change during the test time, complicating interpretation of ignition delay times. In order to evaluate the use of the HRRST as a reliable means of high throughput- high temperature ignition delay testing and make better use of the acquired data for kinetic validation, several methods of modeling were employed in order to account for the changing thermodynamic states in the HRRST. One line of approach was based on direct chemical modeling using the pressure profile and detailed or simplified kinetic mechanism, and the other was based on a Livengood-Wu type approach using modeled constant volume or constant pressure ignition delay times. Additionally, the modeling approaches evaluated the distinction between results based on thermodynamic trajectories either assuming non-reactive adiabatic conditions or measured from actual ignition delay experiments. Several n-heptane/iso-octane primary reference fuel and toluene/n-heptane/iso-octane toluene primary reference fuel blends were experimentally evaluated and compared with both experimental results and chemical kinetic mechanisms.

Tao, Mingyuan↗
DOE OSTI2025

Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique

Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique The Temporal Analysis of Products (TAP) pulse response methodology1 is a transient technique offering the time scale needed to deconvolve many reaction steps from the complex network typical to industrial catalytic processes. The traditional TAP measurement observes the gas phase dynamic response but, hereto now, has been devoid of any direct measurement of change in the catalyst itself. The development of an operando technique that couples gas phase transient kinetics to dynamic metal centers and surface species is presented. Significance Unification of the TAP methodology with time-resolved spectroscopic measurement can offer unprecedented insight into the complex kinetic phenomena regulated by the solid catalyst.

03 - NATURAL GAS↗
DOE OSTI2026

Effect of NO on DME-Methanol HCCI Combustion Using a Reduced Chemical Kinetics Mechanism

Methanol is an attractive fuel for the maritime sector due to its wide availability. Its direct use as a fuel, however, is accompanied by challenges such as high latent heat of vaporization and low cetane number. A potential solution to overcome the ignition properties of methanol could be through on-board generation of dimethyl ether (DME) via catalytic dehydration of methanol. The resulting mixture from dehydration can be mixed in with the intake air to generate a homogenous charge compression ignition (HCCI) preburn for subsequent direct injection (DI) mixing controlled compression ignition (MCCI) of neat methanol. Within that context, complementary experimental work found that the influence of combustion residuals on the heat release rate (HRR) was significant, specifically for residual NO. This finding motivated the present computational and kinetic evaluation of the effects of NO on the low (LTHR) and high (HTHR) temperature heat release rates. The strong influence of small quantities of NO on the combustion process of a DME/methanol/H2O mixture (low catalyst or reactor efficiency) necessitated a kinetics-based investigation into this phenomenon. A mechanism sourced from the existing literature with NO had 172 species and 1375 reactions, making it computationally expensive for use. Hence, a mechanism reduction effort was implemented, and a rate constant (k) tuning effort based on sensitivity analysis was needed to validate experimental results using a zero-dimensional engine model in Cantera. The reduced mechanism was able to successfully capture the negligible influence of NO addition on DME HCCI combustion, whereas an advancement in LTHR and HTHR for a DME/methanol/H2O mixture was kinetically confirmed. Reaction pathway analysis showed that addition of NO chemically counteracted the OH sink created by alcohols like methanol, increasing the effectiveness of DME ignition.

Tyrewala, Daanish [ORNL] (ORCID:0000000208599324)↗
DOE OSTI2018

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Manganese Removal

In the earlier study, a dynamic model for the BOF process based on the multizone reaction kinetics has been developed. In the preceding part, the mechanism of manganese transfer in three reactive zones of the converter has been analyzed. The study predicts that temperature at the slag–metal reaction interface plays a major role in the Mn reaction kinetics. Further, mathematical treatments to simulate the transient rate parameters associated with each reaction interface have been developed. The model calculations of Mn removal rate obtained from different zones of the converter predicts that the first stage of the blow is dominated by the oxidation of Mn at the jet impact zone, albeit some additional Mn refining has been observed as a result of the oxidation of metal droplets in emulsion phase. The simulation result shows that the reversion of Mn from slag to metal primarily takes place at the metal droplet in the emulsion due to an increase in slag–metal interface temperature during the middle stage of blowing. In the final stage of the blow, the competition between simultaneous reactions in jet impact and emulsion zone controls the direction of mass flow of manganese. Further, the model prediction shows that the Mn refining in the emulsion is a strong function of droplet diameter and the residence time. Smaller sized droplets approach equilibrium quickly and thus contribute to a significant Mn conversion between slag and metal compared to the larger sized ones. The overall model prediction for Mn in the hot metal has been found to be in good agreement with two data sets obtained from different size converters reported in the literature.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evaluating the benefits of kinetic Monte Carlo and microkinetic modeling for catalyst design studies in the presence of lateral interactions

Popular computational catalyst design strategies rely on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends. The main benefit of this approach is related to the inherent dimensionality reduction of the large material space to just a few catalyst descriptors. Conversely, it is well documented that a small set of descriptors is insufficient to capture the intricacies and complexities of a real catalytic system. The inclusion of coverage effects through lateral adsorbate-adsorbate interactions can narrow the gap between simplified descriptor predictions and real systems, but mean-field MKMs cannot properly account for local coverage effects. This shortcoming of the mean-field approximation can be rectified by switching to a lattice-based kinetic Monte Carlo (kMC) method using cluster expansion representation of adsorbate–adsorbate lateral interactions. Using the prototypical CO oxidation reaction as an example, we critically evaluate the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. Here, the mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, the MKM approach does provide a better entry point for computational catalyst design.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rate expressions and kinetic parameters for metal ferrites in relation to applications of fossil fuel conversion to hydrogen: Part 1 of 2

Here, the goal of the present work was to provide the necessary reaction emulation information to enable detailed process simulation of a chemical looping H 2 production system from fossil fuels using CaFe 2 O 4 . This specifically pertained to the necessary kinetic data, reaction model development, and model rate parameters required for reaction emulation in both reducing and oxidizing environments. A logical methodology was defined, which included discretization of the reaction network, establishing a core model for reaction emulation that could be adapted based on the system phenomena, and development of a rate parameter regression tool designed around the core model. An extensive array of data sets was acquired by which parametric regressions were performed. The work presented and tabulated a comprehensive set of rate parameters for the reduction and oxidation reactions of CaFe 2 O 4 and descendent phases of Ca 2 Fe 2 O 5 , FeO, Fe 3 O 4 , Fe, and CaO to emulate reaction behavior in a looping-based process environment. This included direct reduction using CH 4 , H 2 , and CO, and direct oxidation reactions with steam, CO 2 and O 2 . Dynamic equilibrium was quantified for reactions that could utilize H 2 O and CO 2 as soft oxidants to re-saturate lattice oxygen in the depleted structure/phases. The kinetics associated with the oxidative mechanisms with the soft oxidants were quantified and compared to those of the reducing counterparts. The analysis provided critical insight to emulate reactions for a process that seeks to use natural gas (NG) or other fossil fuels as a direct reductant for the end goal of H 2 production.

calcium ferrite oxygen carriers↗
DOE OSTI2010

An experimental and kinetic modeling study of the autoignition of {alpha}-methylnaphthalene/air and {alpha}-methylnaphthalene/n-decane/air mixtures at elevated pressures

The autoignition of {alpha}-methylnaphthalene (AMN), the bicyclic aromatic reference compound for the cetane number (CN), and AMN/n-decane blends, potential diesel surrogate mixtures, was studied at elevated pressures for fuel/air mixtures in a heated high-pressure shock tube. Additionally, a comprehensive kinetic mechanism was developed to describe the oxidation of AMN and AMN/n-decane blends. Ignition delay times were measured in reflected shock experiments for {phi} = 0.5, 1.0, and 1.5 AMN/air mixtures (CN = 0) for 1032-1445 K and 8-45 bar and for {phi} = 1.0 30%-molar AMN/70%-molar n-decane/air (CN = 58) and 70%-molar AMN/30%-molar n-decane/air mixtures (CN = 28) for 848-1349 K and 14-62 bar. Kinetic simulations, based on the comprehensive AMN/n-decane mechanism, are in good agreement with measured ignition times, illustrating the emerging capability of comprehensive mechanisms for describing high molecular weight transportation fuels. Sensitivity and reaction flux analysis indicate the importance of reactions involving resonance stabilized phenylbenzyl radicals, the formation of which by H-atom abstractions with OH radicals has an important inhibiting effect on ignition. (author)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Theoretical kinetics predictions for NH 2 + HO 2

Recent modeling studies of NH 3 oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies between existing literature mechanisms. In this study high level theoretical kinetics predictions have been obtained for the reaction of NH 2 with HO 2 , which has previously been highlighted as an important reaction with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations including large basis sets and high-level corrections to yield high accuracy (~0.2 kcal/mol) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature and pressure dependent kinetics. For the radical-radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constant as well as the branching to the NH 3 + O 2 , H 2 NO + OH, and HNO + H 2 O channels. Rate constants are also reported for the H 2 NO + OH reaction as they arise naturally from the analysis. The rate constant and branching fraction determined in this work for the NH 2 + HO 2 reaction deviate significantly from values used in most previous modeling studies. The fact that the main product channel is chain terminating, rather than propagating, has strong implications for modeling NH 3 ignition and oxidation, in particular at intermediate temperatures and elevated pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Flame Chemistry Workshop: a perspective on challenges and strategic actions in combustion experiments and chemical kinetics modeling

Continued progress in the development of predictive models for combustion chemistry—including ignition and flame behavior, species evolution, and combustion system performance—relies on overcoming enduring and emerging challenges in experimental measurements, theoretical formulations, and chemical kinetics mechanism construction. As combustion science continues to coincide with advances in sustainable fuels development, plasma technologies, and automated modeling capabilities, the need for coordinated, community-driven strategies is essential. The Flame Chemistry Workshop (FCWS), held biennially before the International Symposium on Combustion, serves as a dedicated platform to identify, consolidate, and address these challenges in a structured and collaborative manner. This perspective arises from discussions at the 7th FCWS in Milan, Italy (2024), and presents a collective view of the critical barriers currently limiting progress. Across the five technical domains discussed during the 7th FCWS – sustainable fuels combustion, advanced diagnostics for combustion measurements, experiments and modeling in plasma combustion, artificial intelligence and automated methods for theory and mechanisms generation, and chemical kinetic models—a series of persistent and emerging scientific challenges were identified, highlighting the need for deeper integration between three areas: theory, experiments, and modeling. In conclusion, the present article concisely describes present challenges that were identified in each of the technical domains in an effort to streamline and coordinate solutions to accelerate progress in combustion science.

Chemical kinetics↗
DOE OSTI2020

Pilgrim : A thermal rate constant calculator and a chemical kinetics simulator

Pilgrim is a program written in Python and designed to use direct dynamics in the calculation of thermal rate constants of chemical reactions by the variational transition state theory (VTST), based on electronic structure calculations for the potential energy surface. Pilgrim can also simulate reaction mechanisms using kinetic Monte Carlo (KMC). For reaction processes with many elementary steps, the rate constant of each of these steps can be calculated by means of conventional transition state theory (TST) or by using VTST. In the current version, Pilgrim can evaluate thermal rates using the canonical version of reaction-path VTST, which requires the calculation of the minimum energy path (MEP) associated with each elementary step or transition structure. Multi-dimensional quantum effects can be incorporated through the small-curvature tunneling (SCT) approximation. These methodologies are available both for reactions involving a single structure of the reactants and the transition state and also for reactions involving flexible molecules with multiple conformations of the reactant and/or of the transition state. For systems with many conformers, the program can evaluate each of the elementary reaction rate constants by multipath canonical VTST or multi-structural VTST. Moreover, the reactant can be unimolecular or bimolecular. Torsional anharmonicity can be incorporated through either the MSTor or the Q2DTor programs. Dual-level calculations are also available in Pilgrim: automatic high-level single-point energies can be used to correct the energy of reactants, transition states, products, and MEP points using the interpolated single-point energies (ISPE) algorithm. When the rate constants of all the chemical processes of interest are known, by means of their calculation using Pilgrim or alternatively through analytical fits to the rate constants as functions of temperature, it is possible to simulate a multistep mechanism under specified laboratory conditions using KMC. Finally, this algorithm allows performing a kinetic simulation to monitor the evolution of each chemical species with time and obtain the product yields.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2010

The kinetics of Al-Si spinel phase crystallization from calcined kaolin

The crystallization of Al-Si spinel from medium ordered kaolin with high content of kaolinite was investigated using the differential thermal analysis (DTA). The apparent activation energy of the process was evaluated from the dependence of exothermic peak of crystallization on heating rate. Within the applied interval of heating rate (1-40 K min{sup -1}) the temperature of peak maximum increases from initial value of 1220.5 K in about 54.2 K. The apparent activation energy of the process 856{+-}2 kJ mol{sup -1}was calculated using the Kissinger equation. The growth morphology of Al-Si spinel crystal was evaluated from the Avrami parameter. The average value of morphology parameter determined within the observed interval of heating rate is 3.08{+-}0.03. This value indicates that crystallization mechanism of Al-Si spinel phase proceeds by bulk nucleation of the new phase with constant number of nuclei and that the three-dimensional growth of crystals is controlled by the reaction rate on the phases interface. - Graphical abstract: Kinetics of crystallization of Al-Si spinel from calcined kaolin was investigated by the DTA using the Kissinger kinetic approach. The apparent activation energy and morphology parameter of the process is 856{+-}2 kJ mol{sup -1} and 3.08{+-}0.03, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Thermochemical and kinetic aspects of the sulfurization of Cu-Sb and Cu-Bi thin films

CuSbS{sub 2} and Cu{sub 3}BiS{sub 3} are being investigated as part of a search for new absorber materials for photovoltaic devices. Thin films of these chalcogenides were produced by conversion of stacked and co-electroplated metal precursor layers in the presence of elemental sulfur vapour. Ex-situ XRD and SEM/EDS analyses of the processed samples were employed to study the reaction sequence with the aim of achieving compact layer morphologies. A new 'Time-Temperature-Reaction' (TTR) diagram and modified Pilling-Bedworth coefficients have been introduced for the description and interpretation of the reaction kinetics. For equal processing times, the minimum temperature required for CuSbS{sub 2} to appear is substantially lower than for Cu{sub 3}BiS{sub 3}, suggesting that interdiffusion across the interfaces between the binary sulfides is a key step in the formation of the ternary compounds. The effects of the heating rate and sulfur partial pressure on the phase evolution as well as the potential losses of Sb and Bi during the processes have been investigated experimentally and the results related to the equilibrium pressure diagrams obtained via thermochemical computation. - Graphical Abstract: Example of 3D plot showing the equilibrium pressure surfaces of species potentially escaping from chalcogenide films as a function of temperature and sulfur partial pressure. Bi{sub (g)}, Bi{sub 2(g)}, and BiS{sub (g)} are the gaseous species in equilibrium with solid Bi{sub 2}S{sub 3(s)} considered in this specific example. The pressure threshold plane corresponds to the pressure limit above which the elemental losses from 1 {mu}m thick films exceeds 10% of the original content per cm{sup 2} area of film and dm{sup 3} capacity of sulfurization furnace under static atmosphere conditions. The sulfurization temperature/sulfur partial pressure boundaries required to minimise the elemental losses below a given value can be easily read from the 2D projection of the intersection curves into the T-p{sub S2} plane. Highlights: Black-Right-Pointing-Triangle Sulfurization of Sb-Cu and Bi-Cu metal precursors for thin film PV applications. Black-Right-Pointing-Triangle Kinetics shows the rate determining step to be the interdiffusion of binary sulfides. Black-Right-Pointing-Triangle Phase evolution is consistent with Pilling-Bedworth coefficients of Cu, Sb and Bi. Black-Right-Pointing-Triangle Elemental losses can be minimised via the use of equilibrium pressure diagrams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Parameter estimation for models of ligninolytic and cellulolytic enzyme kinetics

While soil enzymes have been explicitly included in the soil organic carbon (SOC) decomposition models, there is a serious lack of suitable data for model parameterization. This study provides well-documented enzymatic parameters for application in enzyme-driven SOC decomposition models from a compilation and analysis of published measurements. In particular, we developed appropriate kinetic parameters for five typical ligninolytic and cellulolytic enzymes ( -glucosidase, cellobiohydrolase, endo-glucanase, peroxidase, and phenol oxidase). The kinetic parameters included the maximum specific enzyme activity (Vmax) and half-saturation constant (Km) in the Michaelis-Menten equation. The activation energy (Ea) and the pH optimum and sensitivity (pHopt and pHsen) were also analyzed. pHsen was estimated by fitting an exponential-quadratic function. The Vmax values, often presented in different units under various measurement conditions, were converted into the same units at a reference temperature (20 C) and pHopt. Major conclusions are: (i) Both Vmax and Km were log-normal distributed, with no significant difference in Vmax exhibited between enzymes originating from bacteria or fungi. (ii) No significant difference in Vmax was found between cellulases and ligninases; however, there was significant difference in Km between them. (iii) Ligninases had higher Ea values and lower pHopt than cellulases; average ratio of pHsen to pHopt ranged 0.3 0.4 for the five enzymes, which means that an increase or decrease of 1.1 1.7 pH units from pHopt would reduce Vmax by 50%. (iv) Our analysis indicated that the Vmax values from lab measurements with purified enzymes were 1 2 orders of magnitude higher than those for use in SOC decomposition models under field conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

Highlights: Black-Right-Pointing-Pointer Several tests were performed in DTA/TGA for understanding the thermal behavior of pure PVC. Black-Right-Pointing-Pointer We did a kinetic model for the de-chlorination of PVC molecule. Black-Right-Pointing-Pointer A temperature of 340 Degree-Sign C was defined as the optimum temperature for breaking the bond of chlorine in the PVC molecule. Black-Right-Pointing-Pointer The experimental validation of this temperature, led to a removal rate of 99.9% chlorine. - Abstract: Although PVC-containing wastes are an important potential source of energy they are frequently disposed in landfill. In thermal treatment processes such as pyrolysis and gasification, the presence of poly(vinyl chloride) (PVC), a compound with 56.7% of chlorine, may cause problems concerned with environmental protection, as consequence of the formation of hydrochloric acid, chlorine gas and dioxins, as well as corrosion phenomena of the reactor/equipment materials. Thus, a possible solution may involve a previous removal of the chlorine from PVC containing waste through a pyrolysis process at low temperatures before the material being submitted to a subsequent thermal treatment, for energetic valorization. In this work, a kinetic model for the thermal decomposition of PVC has been developed, in view of its de-chlorination. DTA/TGA testing at different temperatures indicated a first order reaction and an activation energy of 133,800 J/mol. An almost completed de-chlorination reaction was obtained at 340 Degree-Sign C under an inert atmosphere. The resulted material is a C{sub n}H{sub n} type polymer with potential to be used in an energy recovery process. Validation test performed at laboratory scale indicate that the temperature of 340 Degree-Sign C enables the removal of {approx}99.9% of the chlorine present in PVC. The chloride can be fixed in the form of an aqueous solution of HCl or calcium chloride, driving to an alternative full process with environmental benefits and reduction of the costs associated to the PCV - containing materials/wastes management.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to N 2 reduction

Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by cadmium sulfide (CdS) nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model, which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of the sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway that competes with N 2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N 2 reduction.

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

The Role of Evolving Interfacial Substrate Properties on Heterogeneous Cellulose Hydrolysis Kinetics

Interfacial enzyme reactions require formation of an enzyme–substrate complex at the surface of a heterogeneous substrate, but often multiple modes of enzyme binding and types of binding sites complicate analysis of their kinetics. Excess heterogeneous substrate is often used as a justification to model the substrate as unchanging, but using the study of the enzymatic hydrolysis of insoluble cellulose as an example, we argue that reaction rates are dependent on evolving substrate interfacial properties. We hypothesize that the relative abundance of binding sites on cellulose where hydrolysis can occur (productive binding sites) and binding sites where hydrolysis cannot be initiated or is inhibited (nonproductive binding sites) contribute to rate limitations. We show that the initial total number of productive binding sites (the productive binding capacity) determines the magnitude of the initial burst phase of cellulose hydrolysis, while productive binding site depletion explains overall hydrolysis kinetics. Furthermore, we show that irreversibly bound surface enzymes contribute to the depletion of productive binding sites. Our model shows that increasing the ratio of productive to nonproductive binding sites promotes hydrolysis, while maintaining an elevated productive binding capacity throughout conversion is key to preventing hydrolysis slowdown.

09 BIOMASS FUELS↗
DOE OSTI2011

Reaction Kinetics of CO2 Carbonation with Mg-Rich Minerals

Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO{sub 2}. Direct carbonation of CO{sub 2} with Mg-rich minerals reported in this research for the first time could be considerably superior to conventional liquid extraction processes from an energy consumption perspective due to its avoidance of the use of a large amount of water with high specific heat capacity and latent heat of vaporization. Kinetic models of the reactions of the direct CO{sub 2} carbonation with Mg-rich minerals and within simulated flue gas environments are important to the scale-up of reactor designs. Unfortunately, such models have not been made available thus far. This research was initiated to fill that gap. Magnesium silicate (Mg{sub 2}SiO{sub 4}), a representative compound in Mg-rich minerals, was used to study CO{sub 2} carbonation reaction kinetics under given simulated flue gas conditions. It was found that the chosen sorbent deactivation model fits well the experimental data collected under given conditions. A reaction order of 1 with respect to CO{sub 2} is obtained from experimental data. The Arrhenius form of CO{sub 2} carbonation with Mg{sub 2}SiO{sub 4} is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Automatic computer procedure for generating exact and analytical kinetic energy operators based on the polyspherical approach: General formulation and removal of singularities

We present new techniques for an automatic computation of the kinetic energy operator in analytical form. These techniques are based on the use of the polyspherical approach and are extended to take into account Cartesian coordinates as well. An automatic procedure is developed where analytical expressions are obtained by symbolic calculations. This procedure is a full generalization of the one presented in Ndong et al., [J. Chem. Phys. 136, 034107 (2012)]. The correctness of the new implementation is analyzed by comparison with results obtained from the TNUM program. We give several illustrations that could be useful for users of the code. In particular, we discuss some cyclic compounds which are important in photochemistry. Among others, we show that choosing a well-adapted parameterization and decomposition into subsystems can allow one to avoid singularities in the kinetic energy operator. We also discuss a relation between polyspherical and Z-matrix coordinates: this comparison could be helpful for building an interface between the new code and a quantum chemistry package.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗