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Results for “Decomposition 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 OSTI2021

Differential effects of redox conditions on the decomposition of litter and soil organic matter

Soil redox conditions exert substantial influence on biogeochemical processes in terrestrial ecosystems. Humid tropical forests are often characterized by fluctuating redox dynamics, yet how redox fluctuations affect patterns in soil versus litter decomposition and associated CO2 fluxes are not well understood in these ecosystems. We used a 13C-labeled litter addition to explicitly follow the decomposition of litter-derived vs. native soil-derived organic matter in response to four different soil redox regimes—static oxic or anoxic, and two oscillating treatments—in soil from the Luquillo Experimental Forest, Puerto Rico. We coupled this incubation experiment with high-resolution mass spectrometry analysis to characterize the preferential decomposition of specific classes of organic molecules. CO2 production from litter and soil organic matter (SOM) showed distinctly different responses to redox manipulation. The cumulative production of SOM-derived CO2 was positively correlated with the length of soil exposure to an oxic headspace (r = 0.89, n = 20), whereas cumulative 13C-litter-derived CO2 production was not linked to oxygen availability. The CO2 production rate from litter was highest under static anoxic conditions in the first half of the incubation period, and later dropped to the lowest among all redox treatments. In the consistently anoxic soils, we observed the depletion of more oxidized water-extractable organic matter (especially amino sugars, carbohydrates, and proteins) over time, suggesting that under anaerobic conditions, microbes preferentially used more oxidized litter-derived compounds during the early stages of decomposition. Results from kinetic modeling showed that more frequent anoxic exposure limited the decomposition of a slow-cycling C pool, but not a fast-cycling pool. Overall, our results demonstrate that substrate source—freshly added litter vs. native organic matter—plays an important role in the redox sensitivity of organic matter decomposition. In soil environments that regularly experience redox fluctuations, anaerobic heterotrophs can be surprisingly effective in degrading fresh plant litter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

Kinetics Thermal Decomposition Biomolecul↗
DOE OSTI2023

Spatio–Temporal Coarse–Graining Decomposition of the Global Ocean Geostrophic Kinetic Energy

We expand on a recent determination of the first global energy spectrum of the ocean’s surface geostrophic circulation using a coarse-graining (CG) method. We compare spectra from CG to those from spherical harmonics by treating land in a manner consistent with the boundary conditions. While the two methods yield qualitatively consistent domain-averaged results, spherical harmonics spectra are too noisy at gyre-scales (> 1000 km). More importantly, spherical harmonics are inherently global and cannot provide local information connecting scales with currents geographically. CG shows that the extra-tropics mesoscales (100–500 km) have a root-mean-square (rms) velocity of ~15 cm/s, which increases to ~30–40 cm/s locally in the Gulf Stream and Kuroshio and to ~16–28 cm/s in the ACC. There is notable hemispheric asymmetry in mesoscale energy-per-area, which is higher in the north due to continental boundaries. We estimate that ≈25–50% of total geostrophic energy is at scales smaller than 100 km, and is un(der)-resolved by pre-SWOT satellite products. Spectra of the time-mean circulation show that most of its energy (up to 70%) resides in stationary eddies with characteristic scales smaller than (< 500 km). This highlights the preponderance of ‘standing’ small-scale structures in the global ocean due to the temporally coherent forcing by boundaries. By coarse-graining in space and time, we compute the first spatio-temporal global spectrum of geostrophic circulation from AVISO and NEMO. These spectra show that every length-scale evolves over a wide range of time-scales with a consistent peak at ≈200 km and ≈2–3 weeks.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Nitromethane Decomposition via Automated Reaction Discovery and an Ab Initio Corrected Kinetic Model

In the explore the systematic construction of kinetic models from in silico reaction data for the decomposition of nitromethane. Our models are constructed in a computationally affordable manner by using reactions discovered through accelerated molecular dynamics simulations using the ReaxFF reactive force field. The reaction paths are then optimized to determine reaction rate parameters. We introduce a reaction barrier correction scheme that combines accurate thermochemical data from density functional theory with ReaxFF minimal energy paths. We validate our models across different thermodynamic regimes, showing predictions of gas phase CO and NO concentrations and high-pressure induction times that are similar to experimental data. The kinetic models are analyzed to find fundamental decomposition reactions in different thermodynamic regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Interactions of Hydrazine and Blowby Gases

The interactions between hydrazine and blowby gases from pyrovalves was explored in this research project. Investigating the decomposition chemistry of hydrazine through detailed chemical kinetic modeling is a project started last summer while participating in the Summer Faculty Fellowship program. During the 1999-2000 academic year, the chemical kinetic mechanism for hydrazine decomposition developed while a SFF at NASA's White Sands Test Facility was further revised and validated against the limited experimental data in the literature. This mechanism was then used in assessing the effects of blowby gas species on hydrazine decomposition. The combustion products introduced into the fuel line by pyrovalve actuation consist primarily of hydrogen gas. Hydrogen is also a product of the decomposition of hydrazine. Additional gaseous chemical species are introduced into the fuel, as well as metals and metal salts that deposit onto the walls of the fuel line. The deposition process is undoubtedly very rapid, and exothermic. Therefore, the major focus of this summer's work was examining the effects of hydrogen presence on hydrazine decomposition, with some representative calculations including the remaining gaseous species found to exist in blowby gases. Since hydrogen is a product of hydrazine decomposition, all reactions necessary to evaluate its effect on hydrazine decomposition chemistry were in the original mechanism developed. However, the mechanism needed to be considerably expanded to include the reactions of the other gaseous blowby species with hydrazine, all the intermediate species formed in its decomposition, and each other. The expanded mechanism consists of 70 species interacting via a network of 452 reactions. Calculations with molecular hydrogen introduced into hydrazine gas in an inert bath gas indicate that H2 presence as an initial reactant in substantial amounts can dramatically impact the decomposition process for hydrazine. The other gaseous blowby species (CO, CO2, H2O, CH4, O2, and N2) were found to have little effect compared to the inclusion of hydrogen itself as an initial reagent. This result is undoubtedly due, in part, to the fact that the blowby gas used in these calculations consisted of 94.6% H2. A more rigorous examination of the behavior of the full detailed mechanism under a variety of conditions was not performed.

Meagher, Nancy E.↗
NASA NTRS1992

Recovery and separation of precious metals from space

During the past year a viable procedure centered around centrifugal partition chromatography (CPC), a multistage liquid-liquid partitioning technique for the separation of precious metals (Pt, Pd, Rh, Ir, Os, Ru), was developed. Stable and inexpensive ligands that can be readily recycled to achieve the separations of the precious metals were identified. The separation methods developed so far yield three separate fractions: Pt, Pd, and Rh-Ir. The Rh-Ir pair can be separated in a subsequent run. The total amount of precious metals separated in a single experiment varied from 1 to 50 mg. The factors affecting the efficiencies of these separations were studied. The kinetics of the decomposition of the complex and the ion pair have a major bearing on these efficiencies, with slow kinetics resulting in poor efficiencies. The methods for the improvement of the efficiencies were also investigated. For example, significant improvement in the efficiencies and separation times for Pt and Pd were achieved by the use of chloride gradient in the mobile phase. Two papers were published and talks were presented on our work at the FACSS meeting in Anaheim, Oct. 1991, and at the Pittsburgh Conference in New Orleans, Mar. 1992.

Freiser, H.↗
NASA NTRS1995

The rate of pyrite decomposition on the surface of Venus

We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in the plains of Venus (approximately 740 K). These lifetimes are very short on a geological time scale and show that pyrite cannot exist on the surface of Venus for any appreciable length of time.

Fegley, B., Jr.↗
NASA NTRS1978

Production and analysis of thermal decomposition products from polymeric materials

A description is presented of a strategy for analyzing the combustion process and the degradation products which are formed. One of three primary objectives in the study of polymer degradation is related to the characterization of the material to be studied and the investigation of the thermal behavior of the material. Another objective is concerned with the definition of the nature of the decomposition process by identification and quantitation of the degradation products. The third objective involves the determination of the mechanism and kinetics of the decomposition process. The methods of sample degradation include pyrolysis, oxidative degradation, flaming combustion, and the use of large-scale combustion chambers. Methods of chemical separation and identification are considered, taking into account low-boiling volatiles, high-boiling volatiles, and ancillary techniques.

Chatfield, D. A.↗
DOE OSTI2024

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Homogeneous nucleation kinetics

Homogeneous nucleation kinetics are rederived in a manner fundamentally similar to the approach of classical nucleation theory with the following modifications and improvements. First, the cluster is a parent phase cluster and does not require energization to the parent state. Second, the thermodynamic potential used to describe phase stability is a continuous function along the pathway of phase decomposition. Third, the kinetics of clustering corresponds directly to the diffusional flux of monomers through the cluster distribution and are formally similar to classical theory with the resulting kinetic equation modified by two terms in the preexponential factor. These terms correct for the influence of a supersaturation dependent clustering within the parent phase and for the influence of an asymmetrical cluster concentration as a function of cluster size at the critical cluster size. Fourth, the supersaturation dependence of the nucleation rate is of the same form as that given by classical nucleation theory. This supersaturation dependence must however be interpreted in terms of a size dependent surface tension. Finally, there are two scaling laws which describe supersaturation to either constant nucleation rate or to the thermodynamically determined physical spinodal.

Rasmussen, D. H.↗
DOE OSTI2026

Metastable formation and disordering kinetics of body-centered orthorhombic CrNi 2 laths in a Cr-Ni binary alloy

Chromium (Cr) alloys combine low density with high-temperature strength but suffer from brittleness and rapid softening. Body-centered orthorhombic (BCO) CrNi 2 laths have been shown to improve Cr-alloy high-temperature strength retention, yet their thermal stability and transformation behavior remain unclear. CrNi 2 conventionally forms through long-range ordering from a face-centered cubic (FCC) phase. Using multiscale microscopy and neutron diffraction, we show that CrNi 2 instead nucleates from a body-centered cubic (BCC) matrix, in a binary Cr 85 Ni 15 alloy. Despite aging above the equilibrium ordering temperature, CrNi 2 persists for ∼220 h at 760 °C before fully disordering, indicating sluggish transformation kinetics. The formation and decomposition follow differing transformation pathways (BCC → CrNi 2 → FCC), revealing kinetic asymmetry not captured by equilibrium Cr-Ni phase diagrams. In conclusion, these findings redefine the transformation behavior of CrNi 2 , establish its metastable kinetic window, and suggest alloying strategies to stabilize CrNi 2 for precipitation strengthening of high-temperature Cr-alloys.

CrNi2 transformation kinetics↗
DOE OSTI2021

Evolution of the role of molybdenum in duplex stainless steels during thermal aging: From enhancing spinodal decomposition to forming heterogeneous precipitates

Thermal aging of ferrite in duplex stainless steels leads to a complex microstructural evolution that can give way to large deleterious changes in mechanical properties. The microstructural evolution mechanisms that happen concurrently are strongly linked to minor changes in composition. By characterizing duplex stainless steels with various compositions over a range of aging conditions, it was revealed that adding a modest amount of Mo to cast austenitic stainless steel (such as changing from grade CF3 to grade CF3M) not only increases the kinetics of spinodal decomposition and Ni-Si-Mn-rich G-phase precipitation, but it also forms a separate Mo-rich phase. At shorter equivalent aging times, Mo segregates from Fe and towards Cr accelerating spinodal decomposition. At longer aging times, Mo enriches in the Ni-Si-Mn clusters before phase separating into an adjoined Mo-rich cluster. We found that these phase changes and precipitation events result in a rather steep drop in fracture and impact toughness. These results will inform the design of similar alloys for use at high temperatures.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Viscosity Relaxation in Molten HgZnTe

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with zinc mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790 C increases by a factor of two, while the viscosity at 810 C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n-mers, we propose a scheme, which contains formation reactions with second order kinetics that increase the molecular weight, and decomposition reactions with first order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n-mer formation is much smaller than the rate constant for n-mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady state toward which the melt relaxes occurs as the rate of formation of an n-mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an (n+1)-mer.

Su, Ching-Hua↗
DOE OSTI2025

First-Principles Insights into the Thermocatalytic Cracking of Ammonia-Hydrogen Blends on Fe(110). 2. Kinetics

Ammonia (NH 3 ) is an energy-rich molecule that is routinely synthesized from nitrogen (N 2 ) and hydrogen (H 2 ). NH 3 ’s more favorable physical properties compared to H 2 suggests it may offer a way to more conveniently store, transport, and, when needed, extract H 2 via thermal decomposition. However, the high kinetic barrier and endoergicity to decompose to H 2 and N 2 require high temperatures. The standard reaction free energy indicates nearly 100% thermodynamic conversion to the diatomic molecules only at ~673 K and higher. However, even at these temperatures, a catalyst, e.g., iron (Fe), is needed for favorable kinetic conversion. Here, in this study, we explore via density functional theory the kinetics of NH 3 decomposition on the most stable facet of body-centered cubic Fe, namely, (110), under typical high-temperature and finite-pressure operando conditions. We predict coverage-dependent energetics of elementary surface reactions, often neglected in atomic-scale modeling. From these models, we find the recombinative desorption of adsorbed N as N 2 is rate-determining at 573.15–773.15 K and even at an extreme case of 1173.15 K. From microkinetic modeling, we find that the steady-state turnover frequencies (TOFs) for N 2 and H 2 generation rates (r$_{H_2}$) depend exponentially on temperature. The catalyst achieves a steady-state TOF of 36.4 s –1 and an r$_{H_2}$ of 0.107 μmol cm –2 s –1 for a feed of 1.8 bar NH 3 with 0.2 bar H 2 at 1173.15 K. However, at 773.15 K, with the same feed composition and velocity, the steady-state TOF and r$_{H_2}$ decrease to 0.14 s –1 and 4.10 × 10 –4 μmol cm –2 s –1 , respectively, as the process is significantly hindered by slow N 2 desorption. Although at first glance counterintuitive, our simulations suggest that surface modifications that reduce Fe’s reactivity toward NH x species should enhance its overall NH 3 decomposition activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗