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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Reduced Equations for Calculating the Combustion Rates of Jet-A and Methane Fuel

Simplified kinetic schemes for Jet-A and methane fuels were developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) that is being developed at Glenn. These kinetic schemes presented here result in a correlation that gives the chemical kinetic time as a function of initial overall cell fuel/air ratio, pressure, and temperature. The correlations would then be used with the turbulent mixing times to determine the limiting properties and progress of the reaction. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentration of carbon monoxide as a function of fuel air ratio, pressure, and temperature. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates and the values obtained from the equilibrium correlations were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide, and NOx were obtained for both Jet-A fuel and methane.

Molnar, Melissa↗
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↗
NASA NTRS1993

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Montgomery, Christopher J.↗
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 NTRS2009

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

Balasubramaniam, R↗
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↗
NASA NTRS1973

Rate of reaction between molecular hydrogen and molecular oxygen

The shock tube data of Jachimowski and Houghton were rigorously analyzed to obtain rate constants for the candidate initiation reactions H2 + O2 yields H + HO2, H2 + O2 yields H2O + O, and H2 + O2 yields OH + OH. Reaction (01) is probably not the initiation process because the activation energy obtained is less than the endothermicity and because the derived rates greatly exceed values inferred in the literature from the reverse of reaction (01). Reactions (02) and (03) remain as possibilities, with reaction (02) slightly favored on the basis of steric and statistical considerations. The solution of the differential equations is presented in detail to show how the kinetics of other ignition systems may be solved.

Brokaw, R. S.↗
NASA NTRS2004

New Reduced Two-Time Step Method for Calculating Combustion and Emission Rates of Jet-A and Methane Fuel With and Without Water Injection

A simplified kinetic scheme for Jet-A, and methane fuels with water injection was developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) or even simple FORTRAN codes that are being developed at Glenn. The two time step method is either an initial time averaged value (step one) or an instantaneous value (step two). The switch is based on the water concentration in moles/cc of 1x10(exp -20). The results presented here results in a correlation that gives the chemical kinetic time as two separate functions. This two step method is used as opposed to a one step time averaged method previously developed to determine the chemical kinetic time with increased accuracy. The first time averaged step is used at the initial times for smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, initial water to fuel mass ratio, temperature, and pressure. The second instantaneous step, to be used with higher water concentrations, gives the chemical kinetic time as a function of instantaneous fuel and water mole concentration, pressure and temperature (T4). The simple correlations would then be compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide and NOx were obtained for Jet-A fuel and methane with and without water injection to water mass loadings of 2/1 water to fuel. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentrations of carbon monoxide and nitrogen oxide as functions of overall equivalence ratio, water to fuel mass ratio, pressure and temperature (T3). The temperature of the gas entering the turbine (T4) was also correlated as a function of the initial combustor temperature (T3), equivalence ratio, water to fuel mass ratio, and pressure.

Molnar, Melissa↗
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↗
NASA NTRS1993

Isolation of new ribozymes from a large pool of random sequences

An iterative in vitro selection procedure was used to isolate a new class of catalytic RNAs (ribozymes) from a large pool of random-sequence RNA molecules. These ribozymes ligate two RNA molecules that are aligned on a template by catalyzing the attack of a 3'-hydroxyl on an adjacent 5'-triphosphate - a reaction similar to that employed by the familiar protein enzymes that synthesize RNA. The corresponding uncatalyzed reaction also yields a 3',5'-phosphodiester bond. In vitro evolution of the population of new ribozymes led to improvement of the average ligation activity and the emergence of ribozymes with reaction rates 7 million times faster than the uncatalyzed reaction rate.

Bartel, David P.↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗