Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Reaction Rates”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Impact of Pycnonuclear Fusion Uncertainties on the Cooling of Accreting Neutron Star Crusts

Abstract The observation of X-rays during quiescence from transiently accreting neutron stars provides unique clues about the nature of dense matter. This, however, requires extensive modeling of the crusts and matching the results to observations. The pycnonuclear fusion reaction rates implemented in these models are theoretically calculated by extending phenomenological expressions and have large uncertainties spanning many orders of magnitude. We present the first sensitivity studies of these pycnonuclear fusion reactions in realistic network calculations. We also couple the reaction network with the thermal evolution code dStar to further study their impact on the neutron star cooling curves in quiescence. Varying the pycnonuclear fusion reaction rates alters the depth at which nuclear heat is deposited although the total heating remains constant. The enhancement of the pycnonuclear fusion reaction rates leads to an overall shallower deposition of nuclear heat. The impurity factors are also altered depending on the type of ashes deposited on the crust. These total changes correspond to a variation of up to 9 eV in the modeled cooling curves. While this is not sufficient to explain the shallow heat source, it is comparable to the observational uncertainties and can still be important for modeling the neutron star crust.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

CO 2 hydrogenation over rhodium cluster catalyst nucleated within a manganese oxide framework

Rhodium-based manganese oxide frameworks were explored as a prototype for carbon dioxide reactive capture and conversion. Three-dimensional frameworks of MnOx were utilized as support structures to isolate Rh metal centers. V, Na, and Zn were introduced as counterions to stabilize the structure and for their beneficial effect as promoters. Here, with this multicomponent catalyst, Rh active centers with MnOxs and varied counterions, we were able to selectively tune the catalytic performance of the material via the choice of counterion and structure of the host material. With cryptomelane-type tunnel manganese oxides octahedral molecular sieve (OMS2), we found that Rh-V-OMS2 was highly stable even after 48 hours on stream with a reaction rate of around 1.5x10 -4 mol CO 2 /g Rh /s, surpassing the net reactivity of other initially more active combinations. Furthermore, during CO 2 hydrogenation, in situ XAFS showed that single Rh atoms nucleated into nanoparticles/ sub-nanometer clusters with a coordination number of 5.5 or less. Our finding of the correlation between the reaction rate and particle size offers the potential for enhanced control over the reaction rate by tuning particle size. Our activity study with control experiments demonstrates that the activities of the catalysts are proved due to the unique metal support interaction offered by the Rh-X-MnO.

10 SYNTHETIC FUELS↗
DOE OSTI2021

Oxidation and Associated Pore Structure Modification During Experimental Alteration of Granite

Weathering plays a crucial role in a number of environmental processes, and the microstructure and evolution of multi-scale pore space is a critically important factor in the weathering of geological formations. In igneous rocks the infiltration of meteoric water into initially relatively dry material can cause the rock to begin to disaggregate, increasing porosity and surface area, and allowing further disaggregation and weathering to occur. These processes, in turn, allow biota to colonize the rock, further enhancing the weathering rate. In some igneous rocks this may be driven by oxidation of primary minerals. One such mineral, biotite, has been repeatedly mentioned as a cause of cracking during oxidation. However, the scale-dependence of the processes by which this occurs are poorly understood. We cannot, therefore, accurately extrapolate laboratory reaction rates to the field in predictive numerical models. In order to better understand the effects of oxidation and test the hypothesis that fracture and disaggregation are initiated by swelling of oxidizing biotites, we reacted granite cores in a selenic acid-rich aqueous solution at 200°C for up to 438 days. Elevated temperatures and selenic acid were used to provide relatively fast reaction rates and highly oxidizing conditions in sealed reaction vessels. These experiments were analyzed using a combination of imaging, X-ray diffraction, Mössbauer spectroscopy, and small- and ultra-small angle neutron scattering to interrogate porosity and microfracture formation. The experimental results show little observable biotite swelling, but significant transport and growth of iron oxides and/or clays along grain boundaries throughout the sample. Significant increases in porosity were also observed at the sample rim, likely associated with feldspar alteration. Fractures and transport were observed throughout the core, suggesting that stresses due to crystallization pressures caused by the growing iron phases may be the initiating factors in granite weathering, possibly followed by biotite swelling after sufficient permeability is achieved.

Anovitz, Lawrence M.↗
DOE OSTI2020

Accuracy of High Explosive Data used for Reactive Burn Model Calibration

Reactive burn models for a high explosive (HE) have three components: an equation of state (EOS) for the products, an EOS for the reactants and a reaction rate. For the products, we discuss the uncertainty in data for the planar detonation state and its release isentrope. For the reactants, the uncertainty in the principal shock locus data is discussed. For the reaction rate, we discuss uncertainties in shock initiation data (distance-of-run to detonation as a function of shock pressure), and curvature effect data (detonation speed as a function of front curvature). An important source of uncertainty for calibrating the reaction rate for a plastic-bonded explosive (PBX) results from variations in heterogeneities; that is the mesoscale structure of HE grains, binder and porosity. This shows up in the scatter of both shock initiation data and curvature effect data with small changes in initial density and initial temperature, and systematic changes with PBX lot. As illustrative examples, we use data for the conventional HMX based PBX 9501 and the insensitive TATB based PBX 9502 since these explosives have been extensively studied and high quality data are readily available in the literature.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2022

Estimation of the NiCu Cycle Strength and Its Impact on Type I X-Ray Bursts

Abstract Type I X-ray bursts (XRBs) are powered by thermonuclear burning on proton-rich unstable nuclides. The construction of burst models with accurate knowledge of nuclear physics is required to properly interpret burst observations. Numerous studies that have investigated the sensitivities of burst models to nuclear inputs have commonly extracted the strength of the NiCu cycle in the rp process, determined by the 59 Cu( p , α ) 56 Ni and 59 Cu( p , γ ) 60 Zn thermonuclear reaction rates, as critical in the determination of reaction flow in the burst. In this study, the strength of the cycle at the XRB temperature range was estimated based on published experimental data. The nuclear properties of the compound nucleus 60 Zn were evaluated for the 59 Cu( p , α ) 56 Ni and 59 Cu( p , γ ) 60 Zn reaction rate calculations. Monte Carlo rate calculations were conducted to include the large uncertainties of nuclear properties in the calculations. In the current work, a weak NiCu cycle is expected, whereas the rates adopted by the previous studies suggest a strong NiCu cycle. Model simulations were performed with the new rates to assess the impact on Type I XRBs. The results show that the estimated cycle strength does not strongly influence the model predictions of the burst light curve or synthesized abundances.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Marcus–Hush–Chidsey kinetics at electrode–electrolyte interfaces

Electrochemical kinetics at electrode–electrolyte interfaces limit the performance of devices including fuel cells and batteries. While the importance of moving beyond Butler–Volmer kinetics and incorporating the effect of electronic density of states of the electrode has been recognized, a unified framework that incorporates these aspects directly into electrochemical performance models is still lacking. In this work, we explicitly account for the density functional theory-calculated density of states numerically in calculating electrochemical reaction rates for a variety of electrode–electrolyte interfaces. We first show the utility of this for two cases related to Li metal electrodeposition and stripping on a Li surface and a Cu surface (anode-free configuration). The deviation in reaction rates is minor for cases with flat densities of states such as Li, but is significant for Cu due to nondispersive d-bands creating large variation. Finally, we consider a semiconducting case of a solid-electrolyte interphase consisting of LiF and Li2CO3 and note the importance of the Fermi level at the interface pinned by the redox reaction occurring there. We identify the asymmetry in reaction rates as a function of discharge/charge naturally within this approach.

Kurchin, Rachel (ORCID:0000000221474809)↗
DOE OSTI2024

Electrically driven proton transfer promotes Brønsted acid catalysis by orders of magnitude

Electric fields play a key role in enzymatic catalysis and can enhance reaction rates by 100,000-fold, but the same rate enhancements have yet to be achieved in thermochemical heterogeneous catalysis. In this work, we probe the influence of catalyst potential and interfacial electric fields on heterogeneous Brønsted acid catalysis. We observed that variations in applied potential of ~380 mV led to a 100,000-fold rate enhancement for 1-methylcyclopentanol dehydration, which was catalyzed by carbon-supported phosphotungstic acid. Mechanistic studies support a model in which the interfacial electrostatic potential drop drives quasi-equilibrated proton transfer to the adsorbed substrate prior to rate-limiting C–O bond cleavage. Large increases in rate with potential were also observed for the same reaction catalyzed by Ti/TiO y H x and for the Friedel Crafts acylation of anisole with acetic anhydride by carbon-supported phosphotungstic acid.

Science & Technology - Other Topics↗
DOE OSTI2020

Dissolution of Fluoride Salts in Hanford Tank Waste

The Direct Feed High-Level Waste (DFHLW) strategy seeks to bypass the Hanford Waste Treatment and Immobilization Plant Pretreatment Facility while retaining some processing functions to maximize waste feed loading and minimize high-level waste (HLW) waste volume. The DFHLW flowsheet needs leaching, washing, and solids concentration operations either in new or existing tanks. The effectiveness and efficiency of sludge washing has a substantial impact on DST space, mission duration, and the evaporation and low-activity waste (LAW) treatment operations required by these large wash-water additions. One target species requiring washing is fluoride. The HLW glass composition limits for fluorine drive operations to dissolve fluoride-bearing salts into the LAW fraction and thereby maximize waste loading in HLW glass. The fluoride in many high-level wastes at Hanford is predominantly in the form of fluoride-salt precipitates: villiaumite (NaF), kogarkoite (Na 3 FSO 4 ), and natrophosphate (Na 7 F(PO 4 ) 2 ·19H 2 O). Fluoride produces melter off-gas that creates corrosion risk in the off-gas system piping, while the sulfate and phosphate in the fluoride double salts kogarkoite and natrophosphate can be detrimental to glass waste loading. Fluoride salts are sparingly soluble, with solubilities ranging from approximately 40 to 130 kg per kL of pure water, and the dissolution kinetics of the three fluoride salts are not well known. Unexpected delays in a tank dissolution process could be encountered as a result of the lack of information about dissolution rates. In addition, if the double salts show transient non-stoichiometric dissolution of fluoride versus phosphate or sulfate, unexpectedly high concentrations of one of these other constituents could be produced. Washington River Protection Solutions authorized Pacific Northwest National Laboratory to collect the available data for fluoride salt dissolution rate, provide a scoping estimate of dissolution time if possible, and identify gaps in the understanding and predictive capability for estimating dissolution time. Open literature and Hanford reports were reviewed to document, understand, and (where possible) evaluate limitations on fluoride salt equilibria and dissolution kinetics, including both mass transport and surface reaction rate. Scoping estimates of dissolution time were made for mass-transfer-controlled dissolution of spherical particles of fluoride salts suspended in liquid. This is not the only potential governing mechanism; dissolution could be substantially slower if the surface reaction rate (the rate of release of ions from the surface) is the controlling mechanism. When the minimum amount of water for complete dissolution is used and the slip velocity between the liquid and suspended particles is less than or equal to the terminal settling velocity, the estimated mass-transfer rates allow 0.1 mm particles of fluoride salt to dissolve in minutes at 25 °C in water containing no other dissolved salts. Much larger solids, such as the 6-mm chunks that have been seen in heels, could take a few hours to more than a week to dissolve. The actual dissolution times will depend strongly on the actual slip velocity, the extent of particle suspension, constraint by surface reaction rates, the ratio of solvent to solid, and the presence of common ions that shift the solubility equilibria to restrict dissolution of fluoride salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Evidence against the Efimov effect in 12 C from spectroscopy and astrophysics

Background: The Efimov effect is a universal phenomenon in physics whereby three-body systems are stabilized via the interaction of an unbound two-body subsystems. A hypothetical state in 12 C at 7.458-MeV excitation energy, comprising a loose structure of three α particles in mutual two-body resonance, has been suggested in the literature to correspond to an Efimov state in nuclear physics. The existence of such a state has not been demonstrated experimentally. Purpose: Using a combination of γ spectroscopy, charged-particle spectroscopy, and astrophysical rate calculations allowing for strict limits on the existence of such a state to been established here. Method: Using the combined data sets from two recent experiments, one with the TexAT (Texas Active Target) TPC (Time Projection Chamber) to measure α decay and the other with Gammasphere to measure γ decay of states in 12 C populated by 12 N and 12 B β decay, respectively, we achieve high sensitivity to states in close proximity to the α threshold in 12 C. Results: No evidence of a state at 7.458 MeV is seen in either data set. Using a likelihood method, the 95% confidence limit γ -decay branching ratio is determined as a function of the β-decay feeding strength relative to the Hoyle state. In parallel, calculations of the 3α reaction rate show the inclusion of the Efimov corresponds to a large increase in the reaction rate around 5 × 10 7 K. Conclusion: From decay spectroscopy—at the 95% confidence limit, the Efimov state cannot exist at 7.458 MeV with any γ-decay branching ratio unless the β strength is less than 0.7% of the Hoyle state. This limit is evaluated for a range of different excitation energies and the results are not favorable for existence of the hypothetical Efimov state in 12 C . Furthermore, the 3α reaction rate with the inclusion of a state between 7.43 and 7.53 MeV exceeds the rate required for stars to undergo the red giant phase.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media

Abstract Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.

58 GEOSCIENCES↗
DOE OSTI2020

Extracting meaningful standard enthalpies and entropies of activation for surface reactions from kinetic rates

While analyses based on the Arrhenius kinetic model have been successfully applied since its introduction, the Arrhenius model neglects to describe pre-exponential factor in a scientifically meaningful fashion. Since the 1930s, transition-state theory (TST), has met with success in interpreting the pre-exponential factor’s value, allowing a standard entropy of activation to be estimated. However, analyses based on TST’s assumptions have been applied inconsistently in the literature, particularly in corrosion science, leading to difficulty in comparison of standard entropy of activations from different studies. In this work, the foundational principles of TST and standard states are discussed and a standard method to apply TST in analyzing rates of surface reactions is recommended. When full details are not available, reacting species’ concentrations should be normalized to the concentration of active surface sites. For corrosion reactions, conversion relationships are given to convert from units of corrosion rate to surface reaction rate, consistent with TST. This method is dubbed a surface reactant equi-density approximation. Application of this standard to reported data results in adjustments of the standard entropy of activation between - 65 and +50 J/mol K and brings reported entropies into a narrower range of values.

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

A chemical kinetics theory for interpreting the non-monotonic temperature dependence of enzymatic reactions

Abstract. One notable observation of enzymatic chemical reactions is that, for a given abundance of enzymes and substrates, temperature increases cause reaction rates to first increase consistent with the Arrhenius relationship, then plateau, and finally fall off quickly to zero at high temperatures. While many mathematical functions have been used to describe this pattern, we here propose a chemical kinetics theory which successfully replicates this observation and provides insights into the processes responsible for these dynamics. The chemical kinetics theory combines the law of mass action, von Smoluchowski's diffusion-limited chemical reaction theory, and Eyring's transition state theory. This new theory reveals that the thermally reversible enzyme denaturation ensured by the ceaseless thermal motion of molecules and ions in an enzyme solution explains the plateau and subsequent decrease in chemical reaction rates with increasing temperature. The temperature-dependent affinity parameter (K) that relates enzymes and substrates through their binding also affects the shape of the emergent temperature response. We demonstrate that with an increase in substrate availability, K shifts the optimal temperature, where reaction rates plateau, towards higher values. Further, we show that the chemical kinetics theory accurately represents 12 sets of published enzyme assay data and includes the popular mechanistic model by Ratkowsky et al. (2005) as a special case. Given its good performance and solid theoretical underpinning, we believe this new theory will facilitate the construction of more mechanistic-based environmental biogeochemical models.

Tang, Jinyun↗
DOE OSTI2020

Level Structure of {sup 31}S Via {sup 32}S({ital p,d}) {sup 31}S

Background: Properties of proton-unbound S-31 states determine the P-30(p, gamma) S-31 reaction rate, which has a significant impact on explosive hydrogen burning in classical novae and type-I x-ray bursts. Despite several previous studies, uncertainties still remain with respect to the nuclear structure of S-31 near the proton threshold. Purpose: The level structure of S-31 has been presently investigated via a charged-particle spectroscopy experiment using the S-32(p, d) S-31 reaction. Method: Deuterons corresponding to S-31 excited states with 3.285 <= E-x <= 10.8 MeV were momentum analyzed via an Enge split-pole spectrograph at six laboratory angles between 10 degrees and 62 degrees. Differential cross sections of the S-32(p, d)S-31 reaction were measured at E-p = 34.5 MeV. Distorted-wave Born approximation calculations were performed to constrain the spin-parity assignments of several of the observed levels. Results: We have detected 72 excited states of S-31, out of which 17 are within the astrophysical region of interest corresponding to the temperature range of 0.1-1.5 GK. We have resolved the discrepancy in the spin and parity of an excited state with E-x = 6542 keV, showing that is it not J(pi) = 3/2(-), and therefore the contribution of this state to the P-30(p, gamma) reaction rate is likely much less significant than previously thought owing to the larger angular-momentum transfer required to populate this excited state. Moreover, our measurement results help consolidate the spin-parity assignments for the 6377 and 6636 keV states in S-31. Conclusions: This work presents the most comprehensive spin-parity assignments to date from a single-neutron transfer reaction on S-32 to S-31 excited states in the region between 6 to 7 MeV excitation energy. This region is significant for the determination of the P-30(p, gamma)S-30 reaction rate over the temperatures characteristic of explosive hydrogen burning in novae.

Setoodehnia, K.↗
DOE OSTI2021

An uncertainty quantification method relevant to material test reactors

Within material test reactor calculations, energy dependent flux and reaction rate uncertainties are typically not quantified when performing as-run analyses to determine the neutron field experienced by the experiment. When high fidelity Monte-Carlo codes are used in such analyses, straight forward methods to calculate output uncertainties are not available, instead expert opinion is used to postulate computational uncertainties. New methods to propagate uncertainties through these high fidelity simulations are available when sufficient computational power is available. A tool is developed here for sampling any part of an MCNP input from random distributions to determine output uncertainties based on those inputs. Another tool is developed to sample nuclear data cross-section in ACE format using multi-group nuclear data covariances. The Total Monte-Carlo Method and Gesellschaft für Anlagen-und Reaktorsicherheit method (GRS) are implemented and compared to one another as well as MCNP sensitivity and uncertainty calculations. The methods were applied to the Godiva critical sphere k-eigenvalue, the UAM pin-cell benchmark energy dependent flux and reaction rates, and the Advanced Test Reactor energy dependent flux within an experimental location. Furthermore, the two methods agree well, with GRS allowing for an order of magnitude speedup for reaction rate uncertainty calculations and several orders of magnitude for eigenvalue uncertainty calculations.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Reactivity of the Hydrated Electron

Hydrated electrons are created in virtually every radiation environment and in many photochemical or electrochemical environments where liquid water is present, so their reaction products and reaction rate constants are naturally important in applications. Thanks to the strong optical absorbance of (e - ) aq , these rate constants are easy to measure, and a large database has been accumulated. It is not generally appreciated that no working theory of hydrated electron reaction rates presently exists. We discuss key experimental observations of hydrated electron reactions in the context of recent progress in theoretical and simulation developments toward understanding them, made possible by ever increasing computational power.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Efficient and Selective Chemical Transformations in Highly Charged and Confined Nanodroplets

The acceleration of chemical reaction rates and the increased product selectivity in microdroplets compared to that in bulk solutions has become a topic of increasing interest that has been extensively characterized by electrospray ionization mass spectrometry (ESI-MS). However, the sources of this acceleration and the detailed relationships between droplet properties and resulting reaction rate acceleration are still under debate. Moreover, droplet properties are governed by multiple interrelated experimental parameters, i.e., electrospray voltage, solution flow rate, etc., which makes it difficult and time-consuming to explore this diverse parameter space using traditional manual experimental or computational approaches. In this work, we developed an automated experimental platform integrating reactions in controlled charged microdroplet environments with ESI-MS characterization and sequential hybrid Bayesian modeling, as well as an optimal experimental design framework, to achieve multidimensional parameter optimization for higher reaction turnover rates, based on a model reaction of tetraethylenepentamine (TEPA) with carbon dioxide. With the current platform, we have achieved automated scans with a range of electrospray voltages and solution flow rates, and determined and optimized parameter settings to achieve increased reaction turnovers. We have also linked this platform to the underlying properties of droplets via a hybrid model incorporating physics, high-level theoretical calculations, and machine learning (ML) approaches. The autonomous platform is broadly applicable to a range of chemical reactions relevant to DOE’s mission in chemical separations, catalysis, and materials synthesis.

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

Steam‐Induced Coarsening of Single‐Unit‐Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Abstract Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.

Guefrachi, Yasmine↗