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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Modeling delayed thermal runaway in nitric acid-soaked cat litter mixed with radioactive waste

Thermal ignition of radioactive waste within a 55-gallon drum was simulated by using a pressure-dependent waste decomposition model (Hobbs et al. in Process Saf Environ Prot https://doi.org/10.1016/j.psep.2022.09.047, 2022) calibrated with data from full-scale drum experiments (Parker et al. in The thermolytic response of a surrogate RNS waste mixture at the drum scale. Los Alamos National Laboratory Report LA-UR-16-21760, 2016) and validated with experiments from multiple laboratories (Hobbs et al. in Thermal analysis of aged nitric acid-soaked kitty litter in TRU waste drums-23370.WM2023 Conference, Phoenix, AZ, 2023). The acceleration of nitric acid chemistry reacting with an organic cat litter leading to thermal ignition was likely triggered by a restricted vent in the drum. Here, we address whether the form of the rate equation in (Hobbs et al. in Process Saf Environ Prot https://doi.org/10.1016/j.psep.2022.09.047, 2022) is sufficient to extrapolate thermal ignition within aged drums of similar content that have been stored in Texas for over nine years by investigating four different reaction rate forms for waste decomposition. A critical reaction rate reduction analysis is performed on each of these models to determine if delayed thermal runaway within vented aged waste is possible after nine years. We found that a pressure-dependent first-order rate expression not only predicted the accidental ignition of the waste drum, but the form also matches multiple experiments from different laboratories. Even though the waste composition decreases over time, the model predicts that acceleration leading to thermal runaway is possible if the waste is confined, even after 9 years. In conclusion, waste containing oxidizers such as nitric acid should not be mixed with organic adsorbents, especially if the waste is confined.

cookoff↗
DOE OSTI2016

Design principles for high–pressure force fields: Aqueous TMAO solutions from ambient to kilobar pressures

Accurate force fields are one of the major pillars on which successful molecular dynamics simulations of complex biomolecular processes rest. They have been optimized for ambient conditions, whereas high-pressure simulations become increasingly important in pressure perturbation studies, using pressure as an independent thermodynamic variable. Here, we explore the design of non-polarizable force fields tailored to work well in the realm of kilobar pressures – while avoiding complete reparameterization. Our key is to first compute the pressure-induced electronic and structural response of a solute by combining an integral equation approach to include pressure effects on solvent structure with a quantum-chemical treatment of the solute within the embedded cluster reference interaction site model (EC-RISM) framework. Next, the solute’s response to compression is taken into account by introducing pressure-dependence into selected parameters of a well-established force field. In our proof-of-principle study, the full machinery is applied to N,N,N-trimethylamine-N-oxide (TMAO) in water being a potent osmolyte that counteracts pressure denaturation. EC-RISM theory is shown to describe well the charge redistribution upon compression of TMAO(aq) to 10 kbar, which is then embodied in force field molecular dynamics by pressure-dependent partial charges. The performance of the high pressure force field is assessed by comparing to experimental and ab initio molecular dynamics data. Beyond its broad usefulness for designing non-polarizable force fields for extreme thermodynamic conditions, a good description of the pressure-response of solutions is highly recommended when constructing and validating polarizable force fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Observations of height-dependent pressure-perturbation structure of a strong mesoscale gravity wave

Airborne observations using a downward-looking, dual-frequency, near-infrared, differential absorption lidar system provide the first measurements of the height-dependent pressure-perturbation field associated with a strong mesoscale gravity wave. A pressure-perturbation amplitude of 3.5 mb was measured within the lowest 1.6 km of the atmosphere over a 52-km flight line. Corresponding vertical displacements of 250-500 m were inferred from lidar-observed displacement of aerosol layers. Accounting for probable wave orientation, a horizontal wavelength of about 40 km was estimated. Satellite observations reveal wave structure of a comparable scale in concurrent cirrus cloud fields over an extended area. Smaller-scale waves were also observed. Local meteorological soundings are analyzed to confirm the existence of a suitable wave duct. Potential wave-generation mechanisms are examined and discussed. The large pressure-perturbation wave is attributed to rapid amplification or possible wave breaking of a gravity wave as it propagated offshore and interacted with a very stable marine boundary layer capped by a strong shear layer.

Starr, David O'C.↗
DOE OSTI2015

Anomalous breakdown of Bloch's rule in the Mott-Hubbard insulator MnTe 2

Here, we reinvestigate the pressure dependence of the crystal structure and antiferromagnetic phase transition in MnTe 2 using the rigorous and reliable tool of high-pressure neutron powder diffraction. First-principles density functional theory calculations are carried out in order to gain microscopic insight. The measured N eel temperature of MnTe 2 is found to show unusually large pressure dependence of 12 K GPa –1 . This gives rise to a large violation of Bloch s rule given by α = d log T N /d log V = –10/3 ≈ –3.3, to an value of –6.0 ± 0.1 for MnTe 2 . The ab initio calculation of the electronic structure and the magnetic exchange interactions in MnTe 2 for the measured crystal structures at different pressures indicates the pressure dependence of the Neel temperature α is –5.61, in close agreement with experimental findings. The microscopic origin of this behavior turns out to be dictated by the distance dependence of the cation-anion hopping interaction strength.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Characterization of the pressure coefficient of manganin and temperature evolution of pressure in piston-cylinder cells

Here, we report measurements of the temperature- and pressure-dependent resistance, R ( T , p ), of a manganin manometer in a 4 He-gas pressure setup from room temperature down to the solidification temperature of 4 He ( T solid ~ 50 K at 0.8 GPa) for pressures, p , between 0 GPa and ~0.8 GPa. The same manganin wire manometer was also measured in a piston-cylinder cell (PCC) from 300 K down to 1.8 K and for pressures between 0 GPa and ~2 GPa. From these data, we infer the temperature and pressure dependence of the pressure coefficient of manganin, α ( T , p ), defined by the equation R p = (1 + αp ) R 0 , where R 0 and R p are the resistances of manganin at ambient pressure and finite pressure, respectively. Our results indicate that upon cooling, α first decreases, then goes through a broad minimum at ~120 K, and increases again toward lower temperatures. In addition, we find that α is almost pressure-independent at T ≳ 60 K up to p ~ 2 GPa, but shows a pronounced p dependence at T ≲ 60 K. Using this manganin manometer, we demonstrate that p overall decreases with decreasing temperature in the PCC for the full pressure range and that the size of the pressure difference between room temperature and low temperatures ( T = 1.8 K), Δ p , decreases with increasing pressure. We also compare the pressure values inferred from the manganin manometer with the low-temperature pressure, determined from the superconducting transition temperature of elemental lead (Pb). As a result of these data and analysis, we propose a practical algorithm to infer the evolution of pressure with temperature in a PCC.

47 OTHER INSTRUMENTATION↗
DOE OSTI2016

High-pressure phase transition makes B 4.3 C boron carbide a wide-gap semiconductor

Single-crystal B4.3C boron carbide is investigated concerning the pressure-dependence of optical properties and of Raman-active phonons up to ~70 GPa. The high concentration of structural defects determining the electronic properties of boron carbide at ambient conditions initially decrease and finally vanish with pressure increasing. We obtain this immediately from transparency photos, allowing to estimate the pressure-dependent variation of the absorption edge rapidly increasing around 55 GPa. Glass-like transparency at pressures exceeding 60 GPa indicate that the width of the band exceeds ~3.1 eV thus making boron carbide a wide-gap semiconductor. Furthermore, the spectra of Raman–active phonons indicate a pressure-dependent phase transition in single-crystal natB4.3C boron carbide near 35 GPa., particularly related to structural changes in connection with the C-B-C chains, while the basic icosahedral structure remains largely unaffected.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Saturation curve of SiO{sub 2} component in rutile-type GeO{sub 2}: A recoverable high-temperature pressure standard from 3 GPa to 10 GPa

The accuracy and precision of pressure measurements and the pursuit of reliable and readily available pressure scales at simultaneous high temperatures and pressures are still topics in development in high pressure research despite many years of work. In situ pressure scales based on x-ray diffraction are widely used but require x-ray access, which is lacking outside of x-ray beam lines. Other methods such as fixed points require several experiments to bracket a pressure calibration point. In this study, a recoverable high-temperature pressure gauge for pressures ranging from 3 GPa to 10 GPa is presented. The gauge is based on the pressure-dependent solubility of an SiO{sub 2} component in the rutile-structured phase of GeO{sub 2} (argutite), and is valid when the argutite solid solution coexists with coesite. The solid solution varies strongly in composition, mainly in pressure but also somewhat in temperature, and the compositional variations are easily detected by x-ray diffraction of the recovered products because of significant changes in the lattice parameters. The solid solution is measured here on two isotherms, one at 1200 °C and the other at 1500 °C, and is developed as a pressure gauge by calibrating it against three fixed points for each temperature and against the lattice parameter of MgO measured in situ at a total of three additional points. A somewhat detailed thermodynamic analysis is then presented that allows the pressure gauge to be used at other temperatures. This provides a way to accurately and reproducibly evaluate the pressure in high pressure experiments and applications in this pressure-temperature range, and could potentially be used as a benchmark to compare various other pressure scales under high temperature conditions. - Graphical abstract: The saturation curve of SiO{sub 2} in TiO{sub 2} shows a strong pressure dependence and a strong dependence of unit cell volume on composition. This provides an opportunity to use this saturation curve as a measurement of pressure during a high-pressure experiment. The curve is a sensitive measure of pressure from 3 GPa to 10 GPa at high temperatures. The pressure is derived from lattice parameter measurements on the recovered solid solution, meaning that in-situ measurements are not necessary to evaluate the pressure of the experiment. - Highlights: • The unit cell of a saturated GeO{sub 2}–SiO{sub 2} solid solution is used as a pressure sensor. • We measure nine bracketed pressure points on the GeO{sub 2}–SiO{sub 2} saturation surface. • We provide a pressure calibrant from 3 GPa to 10 GPa at two temperatures. • Four points are measured at 1200 °C and five points at 1500 °C. • A thermodynamic model is developed for use of the calibrant at other temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Origin of the Bandgap Bowing in ZNSe(1-x)Te(x) Alloys

Photomodulated reflection and optical absorption spectroscopies were used to measure the composition and hydrostatic pressure dependencies of interband optical transitions in ZnSe(1-x)Te(x) alloys. On the Te-rich side, the bandgap reduction and the reduction in the pressure dependence of the bandgap are well explained by the band anticrossing interaction between the ZnTe conduction band states and the Se localized state located at 2.85 eV above the valence band top of ZnTe. On the Se-rich side, an interaction between the degenerate Gamma valence bands of ZnSe and the localized Te state located at 0.1 eV above the valence band top of ZnSe is proposed to generate the bandgap reduction and the rapid increase of the spin-orbit splitting with increasing Te concentration. A linear interpolation between these two models accounts for the composition and pressure dependencies of the bandgap in the entire composition range.

Walukiewicz, W.↗
DOE OSTI2020

Strength of porous α-SiO 2 in a shock loaded environment: Calibration via Richtmyer–Meshkov instability and validation via Mach lens

The strength of brittle porous media is of concern in numerous applications, for example, earth penetration, crater formation, and blast loading. Thus, it is of importance to possess techniques that allow for constitutive model calibration within the laboratory setting. The goal of the current work is to demonstrate an experimental technique allowing for strength assessment of porous media subjected to shock loading, which can be implemented into pressure-dependent yield surfaces within numerical simulation schemes. As a case study, the deviatoric response of distended α-SiO 2 has been captured in a tamped Richtmyer–Meshkov instability (RMI) environment at a pressure regime of 4–10 GPa. Hydrocode simulations were used to interpret RMI experimental data, and a resulting pressure-dependent yield surface akin to the often employed modified Drucker–Prager model was calibrated. Simulations indicate that the resulting jet length generated by the RMI is sensitive to the porous media strength, thereby providing a feasible experimental platform capable of capturing the pressurized granular deviatoric response. Furthermore, in efforts to validate the RMI-calibrated strength model, a set of Mach-lens experiments was performed and simulated with the calibrated pressure-dependent yield surface. Excellent agreement between the resulting Mach-lens length in experiment and simulation provides additional confidence to the RMI yield-surface calibration scheme.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Strength of porous α-SiO 2 in a shock loaded environment

The strength of brittle porous media is of concern in numerous applications, for example, earth penetration, crater formation, and blast loading; thus it is of importance to possess techniques that allow for constitutive model calibration within the laboratory setting. It is the goal of the immediate work to demonstrate an experimental technique allowing for strength assessment, which can be implemented into pressure dependent yield surfaces within numerical simulation schemes. As a case study, the deviatoric strength of distended α-SiO 2 has been captured in a tamped Richtmyer- Meshkov instability environment at a pressure regime of 4-10 GPa. In contrast to traditional RMI studies used to infer strength in solids, the described approach herein is implemented to probe the behavior of the porous tamp media backing the corrugated solid surface. Hydrocode simulation has been used to interpret the experiment, and a resulting pressure-dependent yield surface akin to the often employed Modified Drucker-Prager model has been calibrated via the coupled experiment and simulation. The simulations indicate that the resulting jet length generated by the RMI is highly sensitive to the porous media strength, thereby providing a feasible experimental platform capable of capturing pressurized granular deviatoric response. Additionally, a Mach lens loading environment has also been implemented as a validation case study, demonstrating good agreement between experiment and simulation within an alternative loading environment. Calibration and validation of the pressure-dependent yield surface gives confidence to the model form, thereby providing a framework for future porous media strength studies.

36 MATERIALS SCIENCE↗
DOE OSTI2013

High pressure melting curves of silver, gold and copper

In this work, based on the Lindemann's formula of melting and the pressure-dependent Grüneisen parameter, we have investigated the pressure effect on melting temperature of silver, gold and copper metals. The analytical expression of melting temperature as a function of volume compression has been derived. Our results are compared with available experimental data as well as with previous theoretical studies and the good and reasonable agreements are found. We also proposed the potential of this approach on predicting melting of copper at very high pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Heat capacity jump at T c and pressure derivatives of superconducting transition temperature in the Ba 1 - x Na x Fe 2 As 2 ( 0.1 ≤ x ≤ 0.9 ) series

We present the evolution of the initial (up to ~ 10 kbar) hydrostatic pressure dependencies of T c and of the ambient pressure, and the jump in the heat capacity associated with the superconducting transition as a function of Na doping in the Ba1-xNaxFe2As2 family of iron-based superconductors. For Na concentrations 0.15 ≤ x ≤ 0.9, the jump in specific heat at T c , ΔC p | T$_c$ , follows the ΔC p ∝ to T 3 (the so-called BNC scaling) found for most BaFe 2 As 2 based superconductors. This finding suggests that, unlike the related Ba 1-x K x Fe 2 As 2 series, there is no significant modification of the superconducting state (e. g., change in superconducting gap symmetry) in the Ba 1-x Na x Fe 2 As 2 series over the whole studied Na concentration range. Pressure dependencies are nonmonotonic for x = 0.2 and 0.24. For other Na concentrations, T c decreases under pressure in an almost linear fashion. The anomalous behavior of the x = 0.2 and 0.24 samples under pressure is possibly due to the crossing of the phase boundaries of the narrow antiferromagnetic tetragonal phase, unique for the Ba 1-x Na x Fe 2 As 2 series, with the application of pressure. The negative sign of the pressure derivatives of T c across the whole superconducting dome (except for x = 0.2) is a clear indication of the nonequivalence of substitution and pressure for the Ba 1-x Na x Fe 2 As 2 series.

Bud'ko, Sergey L.↗
DOE OSTI2019

An Analytical Model for Capturing the Decline of Fracture Conductivity in the Tuscaloosa Marine Shale Trend from Production Data

Fracture conductivity decline is a concern in the Tuscaloosa Marine Shale (TMS) wells due to the high content of clay in the shale. An analytical well productivity model was developed in this study considering the pressure-dependent conductivity of hydraulic fractures. The log-log diagnostic approach was used to identify the boundary-dominated flow regime rather than the linear flow regime. Case studies of seven TMS wells indicated that the proposed model allows approximation of the field data with good accuracy. Production data analyses with the model revealed that the pressure-dependent fracture conductivity in the TMS in the Mississippi section declines following a logarithmic mode, with dimensionless coefficient χ varying between 0.116 and 0.130. The pressure-dependent decline of fracture conductivity in the transient flow period is more significant than that in the boundary-dominated flow period.

58 GEOSCIENCES↗
DOE OSTI2012

O{sub 2}(a{sup 1}{Delta}{sub g}) + Mg, Fe, and Ca: Experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping

The first excited electronic state of molecular oxygen, O{sub 2}(a{sup 1}{Delta}{sub g}), is formed in the upper atmosphere by the photolysis of O{sub 3}. Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O{sub 3}. In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O{sub 2}(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O{sub 2}(a) was produced by bubbling a flow of Cl{sub 2} through chilled alkaline H{sub 2}O{sub 2}, and its absolute concentration determined from its optical emission at 1270 nm (O{sub 2}(a{sup 1}{Delta}{sub g}- X{sup 3}{Sigma}{sub g}{sup -}). The following results were obtained at 296 K: k(Mg + O{sub 2}(a) + N{sub 2}{yields} MgO{sub 2}+ N{sub 2}) = (1.8 {+-} 0.2) Multiplication-Sign 10{sup -30} cm{sup 6} molecule{sup -2} s{sup -1}; k(Fe + O{sub 2}(a) {yields} FeO + O) = (1.1 {+-} 0.1) Multiplication-Sign 10{sup -13} cm{sup 3} molecule{sup -1} s{sup -1}; k(Ca + O{sub 2}(a) + N{sub 2}{yields} CaO{sub 2}+ N{sub 2}) = (2.9 {+-} 0.2) Multiplication-Sign 10{sup -28} cm{sup 6} molecule{sup -2} s{sup -1}; and k(Ca + O{sub 2}(a) {yields} CaO + O) = (2.7 {+-} 1.0) Multiplication-Sign 10{sup -12} cm{sup 3} molecule{sup -1} s{sup -1}. The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O{sub 2}(a) concentration, is estimated to be {+-}40%. Mg + O{sub 2}(a) occurs exclusively by association on the singlet surface, producing MgO{sub 2}({sup 1}A{sub 1}), with a pressure dependent rate coefficient. Fe + O{sub 2}(a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only {approx}0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by near-resonant electronic energy transfer to Fe(a{sup 5}F) + O{sub 2}(X). The reaction of Ca + O{sub 2}(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO{sub 2}({sup 1}A{sub 1}), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O({sup 3}P). In order to interpret the Ca + O{sub 2}(a) results, we utilized density functional theory along with multireference and explicitly correlated CCSD(T)-F12 electronic structure calculations to examine the lowest lying singlet and triplet surfaces. In addition to mapping stationary points, we used a genetic algorithm to locate minimum energy crossing points between the two surfaces. Simulations of the Ca + O{sub 2}(a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice-Ramsperger-Kassel-Marcus (RRKM) theory implemented within a weak collision, multiwell master equation model. In terms of atmospheric significance, only in the case of Ca does reaction with O{sub 2}(a) compete with O{sub 3} during the daytime between 85 and 110 km.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Combined ultrasonic elastic wave velocity and microtomography measurements at high pressures

Combined ultrasonic and microtomographic measurements were conducted for simultaneous determination of elastic property and density of noncrystalline materials at high pressures. A Paris-Edinburgh anvil cell was placed in a rotation apparatus, which enabled us to take a series of x-ray radiography images under pressure over a 180{sup o} angle range and construct accurately the three-dimensional sample volume using microtomography. In addition, ultrasonic elastic wave velocity measurements were carried out simultaneously using the pulse reflection method with a 10{sup o} Y-cut LiNbO{sub 3} transducer attached to the end of the lower anvil. Combined ultrasonic and microtomographic measurements were carried out for SiO{sub 2} glass up to 2.6 GPa and room temperature. A decrease in elastic wave velocities of the SiO{sub 2} glass was observed with increasing pressure, in agreement with previous studies. The simultaneous measurements on elastic wave velocities and density allowed us to derive bulk (K{sub s}) and shear (G) moduli as a function of pressure. K{sub s} and G of the SiO{sub 2} glass also decreased with increasing pressure. The negative pressure dependence of K{sub s} is stronger than that of G, and as a result the value of K{sub s} became similar to G at 2.0-2.6 GPa. There is no reason why we cannot apply this new technique to high temperatures as well. Hence the results demonstrate that the combined ultrasonic and microtomography technique is a powerful tool to derive advanced (accurate) P-V-Ks-G-(T) equations of state for noncrystalline materials.

47 OTHER INSTRUMENTATION↗
DOE OSTI2015

Yttrium aluminium garnet under pressure: Structural, elastic, and vibrational properties from ab initio studies

The structural, elastic, and vibrational properties of yttrium aluminum garnet Y{sub 3}Al{sub 5}O{sub 12} are studied under high pressure by ab initio calculations in the framework of the density functional theory. The calculated ground state properties are in good agreement with the available experimental data. Pressure dependences of bond length and bulk moduli of the constituent polyhedra are reported. The evolution of the elastic constants and the major elastic properties, Young and shear modulus, Poisson's ratios, and Zener anisotropy ratio, are described. The mechanical stability is analyzed, on the light of “Born generalized stability criteria,” showing that the garnet is mechanically unstable above 116 GPa. Symmetries, frequencies, and pressure coefficients of the Raman-active modes are discussed on the basis of the calculated total and partial phonon density of states, which reflect the dynamical contribution of each atom. The relations between the phonon modes of Y{sub 3}Al{sub 5}O{sub 12} and the internal and external molecular modes of the different polyhedra are discussed. Infrared-active modes, as well as the silent modes, and their pressure dependence are also investigated. No dynamical instabilities were found below 116 GPa.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

High-pressure behavior and thermoelastic properties of niobium studied by in situ x-ray diffraction

In situ synchrotron energy dispersive x-ray diffraction (XRD) experiments on Nb have been conducted at pressures up to 6.4 GPa and temperatures up to 1073 K. From the pressure-volume-temperature measurements, thermoelastic parameters were derived for the first time for Nb based on the thermal pressure (ΔP{sub th}) equation of state (EOS), modified high-T Birch-Murnaghan EOS, and Mie-Grüneisen-Debye EOS. With the pressure derivative of the bulk modulus K{sub T}{sup ´} fixed at 4.0, we obtained the ambient isothermal bulk modulus K{sub T0}=174(5) GPa, the temperature derivative of bulk modulus at constant pressure (∂K{sub T}/∂T){sub P}=-0.060(8) GPa K⁻¹ and at constant volume (∂K{sub T}/∂T){sub V}=-0.046(8) GPa K⁻¹, the volumetric thermal expansivity α{sub T}(T)=2.3(3)×10⁻⁵+0.3(2)×10⁻⁸T (K⁻¹), as well as the pressure dependence of thermal expansion (∂α/∂P){sub T}=(₋2.0±0.4)×10⁻⁶ K⁻¹ GPa⁻¹. Fitting the present data to the Mie-Grüneisen-Debye EOS with Debye temperature Θ₀=276.6 K gives γ₀=1.27(8) and K{sub T0}=171(3) GPa at a fixed value of q=3.0. The ambient isothermal bulk modulus and Grüneisen parameter derived from this work are comparable to previously reported values from both experimental and theoretical studies. An in situ high-resolution, angle dispersive XRD study on Nb did not indicate any anomalous behavior related to pressure-induced electronic topological transitions at ~5 GPa as has been reported previously.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1997

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

Hynes, A. J.↗