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Results for “Thermodynamic assessment”

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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Apparent Minimum Free Energy Requirements for Methanogenic Archaea and Sulfate-Reducing Bacteria in an Anoxic Marine Sediment

Among the most fundamental constraints governing the distribution of microorganisms in the environment is the availability of chemical energy at biologically useful levels. To assess the minimum free energy yield that can support microbial metabolism in situ, we examined the thermodynamics of H2-consuming processes in anoxic sediments from Cape Lookout Bight, NC, USA. Depth distributions of H2 partial pressure, along with a suite of relevant concentration data, were determined in sediment cores collected in November (at 14.5 C) and August (at 27 C) and used to calculate free energy yields for methanogenesis and sulfate reduction. At both times of year, and for both processes, free energy yields gradually decreased (became less negative) with depth before reaching an apparent asymptote. Sulfate reducing bacteria exhibited an asymptote of -19.1 +/- 1.7 kj(mol SO4(2-)(sup -1) while methanogenic archaea were apparently supported by energy yields as small as -10.6 +/- 0.7 kj(mol CH4)(sup -1).

Hoehler, Tori M.↗
DOE OSTI2021

Vapor–liquid equilibrium of water with the MB-pol many-body potential

Among the many existing molecular models of water, the MB-pol many-body potential has emerged as a remarkably accurate model, capable of reproducing thermodynamic, structural, and dynamic properties across water's solid, liquid, and vapor phases. In this work, we assessed the performance of MB-pol with respect to an important set of properties related to vapor-liquid coexistence and interfacial behavior. Through direct coexistence classical molecular dynamics simulations at temperatures of 400 K < T < 600 K, we calculated properties such as equilibrium coexistence densities, vapor-liquid interfacial tension, vapor pressure, and enthalpy of vaporization and compared the MB-pol results to experimental data. We also compared rigid vs fully flexible variants of the MB-pol model and evaluated system size effects for the properties studied. We found that the MB-pol model predictions are in good agreement with experimental data, even for temperatures approaching the vapor-liquid critical point; this agreement was largely insensitive to system sizes or the rigid vs flexible treatment of the intramolecular degrees of freedom. Furthermore, these results attest to the chemical accuracy of MB-pol and its high degree of transferability, thus enabling MB-pol's application across a large swath of water's phase diagram.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Experimental Investigation of Thermodynamic Stabilization in Boron Imidazolate Frameworks (BIFs) Synthesized by Mechanochemistry

This study experimentally explores the energetics for the formation of boron–imidazolate frameworks (BIFs), which are synthesized by mechanochemistry. The topologically similar frameworks employ the same tetratopic linker based on tetrakis(imidazolyl)boric acid but differ in the monovalent cation metal nodes. This permits assessment of the stabilizing effect of metal nodes in frameworks with sodalite (SOD) and diamondoid (dia) topologies. The enthalpy of formation from endmembers (metal oxide and linker), which define thermodynamic stability of the structures, has been determined by use of acid solution calorimetry. The results show that heavier metal atoms in the node promote greater energetic stabilization of denser structures. Overall, in BIFs the relation between cation descriptors (ionic radius and electronegativity) and thermodynamic stability depends on framework topology. Thermodynamic stability increases with the metallic character of the cation employed as the metal node, independent of the framework topology. In conclusion, the results suggest unifying aspects for thermodynamic stabilization across MOF systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Thermodynamic Cycle Analysis of Magnetohydrodynamic-Bypass Airbreathing Hypersonic Engines

Established analyses of conventional ramjet/scramjet performance characteristics indicate that a considerable decrease in efficiency can be expected at off-design flight conditions. This can be explained, in large part, by the deterioration of intake mass flow and limited inlet compression at low flight speeds and by the onset of thrust degradation effects associated with increased burner entry temperature at high flight speeds. In combination, these effects tend to impose lower and upper Mach number limits for practical flight. It has been noted, however, that Magnetohydrodynamic (MHD) energy management techniques represent a possible means for extending the flight Mach number envelope of conventional engines. By transferring enthalpy between different stages of the engine cycle, it appears that the onset of thrust degradation may be delayed to higher flight speeds. Obviously, the introduction of additional process inefficiencies is inevitable with this approach, but it is believed that these losses are more than compensated through optimization of the combustion process. The fundamental idea is to use MHD energy conversion processes to extract and bypass a portion of the intake kinetic energy around the burner. We refer to this general class of propulsion system as an MHD-bypass engine. In this paper, we quantitatively assess the performance potential and scientific feasibility of MHD-bypass airbreathing hypersonic engines using ideal gasdynamics and fundamental thermodynamic principles.

Litchford, Ron J.↗
DOE OSTI2021

Bayesian automated weighting of aggregated DFT, MD, and experimental data for candidate thermodynamic models of aluminum with uncertainty quantification

Atomic-scale modeling methods such as density functional theory (DFT) and molecular dynamics (MD) can predict the thermodynamic properties of materials at a lower cost than experimental measurements. However, their regular usage in thermodynamic model construction is hampered by the lack of quantitative agreement with experimental measurements and the lack of uncertainty estimates on the data. To make regular usage of this atomistic simulation data, it is important to assess whether the atomistic simulation datasets, by themselves or in combination with experimental measurements, result in the same physics-informed models best supported by experimental measurements alone. Here, models of aluminum thermodynamic properties are discussed using three data sources: atomistic calculations (DFT and MD), experiments, and a combination of atomistic calculations and experiments. The study shows that, after ensuring self-consistency in predicting key invariant points, both experimental measurements and atomistic calculations can significantly contribute to an optimal model.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Alloying Effects on the Transport Properties of Refractory High-entropy Alloys

Additive Manufacturing (AM) has opened new frontiers for the design of refractory high-entropy alloys (HEAs) for high-temperature applications. The thermal conductivity of the AM feedstock is among the most important thermo-physical properties that control the melting and solidification process. Despite its significance, there remains a notable gap in both computational and experimental research concerning the thermal conductivity of HEAs. Here, we use density functional theory (DFT) to systematically investigate the alloying effects on the transport properties of Ti-Cr-Mo-W-V-Nb-Ta RHEAs, including electrical and thermal conductivities and Seebeck coefficient. The relaxation time of charge carriers is a key underlying parameter determining thermal conductivity that is exceedingly challenging to predict from first principles alone, and we thus follow the approach by Mukherjee, Satsangi, and Singh [Chem Mater 32, 6507 (2022)] to optimize the relaxation time for RHEAs. Here we validated thermal conductivity predictions on elemental solids, binary and ternary alloys, and RHEAs and compared them against thermodynamic (CALPHAD) predictions and our experiments with good correlations. To understand observed trends in thermal conductivity, we assessed the phase stability, electronic structure, phonon, and intrinsic- and tensile strength of down-selected RHEAs. Our electronic structure and phonon results connect well with the observed compositional trends for thermal transport in RHEAs. Our DFT assessment and CALPHAD predictions provide a unique design guide for RHEAs with tailored thermal conductivity, a critical consideration for AM and thermal-management applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations

In this paper, we present a perspective on the computational determination of entropy and its effects and consequences on heterogeneous catalysis. Special attention is paid to the role of anharmonicity and the deviations from the standard harmonic oscillator approximations which can fail to provide a reliable assessment of entropy. To address these challenges, advanced methodologies are needed that can explicitly account for these thermodynamic drivers through the appropriate statistical sampling of reactive free energy surfaces. We discuss where anharmonicity should be expected, where it has been observed from a theoretical perspective, and the methods currently employed to address it. We concentrate on three types of systems where we have observed major, nonnegligible anharmonic effects: (1) supported nanoparticles, where the migration of metal atoms, complexes, and entire clusters exhibit anharmonic behavior in their dynamic motion; (2) porous solids where confinement effects distort potential energy surfaces and hinder molecular motions resulting in large entropic terms; and (3) solid/liquid interfaces, where interactions between solvent molecules and adsorbed species can result in large solvent organization free energy and unique reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Ejector Enhanced Pulsejet Based Pressure Gain Combustors: An Old Idea With a New Twist

An experimental investigation of pressure-gain combustion for gas turbine application is described. The test article consists of an off-the-shelf valved pulsejet, and an optimized ejector, both housed within a shroud. The combination forms an effective can combustor across which there is a modest total pressure rise rather than the usual loss found in conventional combustors. Although the concept of using a pulsejet to affect semi-constant volume (i.e., pressure-gain) combustion is not new, that of combining it with a well designed ejector to efficiently mix the bypass flow is. The result is a device which to date has demonstrated an overall pressure rise of approximately 3.5 percent at an overall temperature ratio commensurate with modern gas turbines. This pressure ratio is substantially higher than what has been previously reported in pulsejet-based combustion experiments. Flow non-uniformities in the downstream portion of the device are also shown to be substantially reduced compared to those within the pulsejet itself. The standard deviation of total pressure fluctuations, measured just downstream of the ejector was only 5.0 percent of the mean. This smoothing aspect of the device is critical to turbomachinery applications since turbine performance is, in general, negatively affected by flow non-uniformities and unsteadiness. The experimental rig will be described and details of the performance measurements will be presented. Analyses showing the thermodynamic benefits from this level of pressure-gain performance in a gas turbine will also be assessed for several engine types. Issues regarding practical development of such a device are discussed, as are potential emissions reductions resulting from the rich burning nature of the pulsejet and the rapid mixing (quenching) associated with unsteady ejectors.

Paxson, Daniel E.↗
NASA NTRSDate not supplied

Pre-Tropical Cyclone Squall Lines and the Connection to the Diurnal Cycle during Hurricane Laura (2020)

Previous studies on the tropical cyclone (TC) diurnal cycle have shown in observations and modeling the presence of outward propagating squall lines. These squall lines were observed in several TCs during the 2020 Atlantic hurricane season. Of these squall lines, one observed in Hurricane Laura made landfall over 14 hours prior to the hurricane’s eye. This squall was responsible for numerous tornado warnings, which disrupted preparations and evacuations ahead of the storm’s landfall. This study seeks to characterize these squall lines and their environmental and thermodynamic characteristics, determine whether they behave more like midlatitude squall lines or tropical cyclone rain bands, and assess the performance of the convection-allowing High Resolution Rapid Refresh model in forecasting them over the ocean and over land. By using a combination of operational radar data, a network of surface weather observations from land and sea, satellite data, and HRRR model output, this case will undergo an extensive evaluation based on criteria from past literature in order to better understand these features as a whole and in relation to the diurnal cycle.

Vivian L Brasfield↗
NASA NTRS2017

Constraints on Climate and Habitability for Earth-like Exoplanets Determined from a General Circulation Model

Conventional definitions of habitability require abundant liquid surface water to exist continuously over geologic timescales. Water in each of its thermodynamic phases interacts with solar and thermal radiation and is the cause for strong climatic feedbacks. Thus, assessments of the habitable zone require models to include a complete treatment of the hydrological cycle over geologic time. Here, we use the Community Atmosphere Model from the National Center for Atmospheric Research to study the evolution of climate for an Earth-like planet at constant CO2, under a wide range of stellar fluxes from F-, G-, and K-dwarf main sequence stars. Around each star we find four stable climate states defined by mutually exclusive global mean surface temperatures (Ts); snowball (Ts ≤ 235 K), waterbelt (235 K ≤ Ts ≤ 250 K), temperate (275 K ≤ Ts ≤ 315 K), and moist greenhouse (Ts ≥ 330 K). Each is separated by abrupt climatic transitions. Waterbelt, temperate, and cooler moist greenhouse climates can maintain open-ocean against both sea ice albedo and hydrogen escape processes respectively, and thus constitute habitable worlds. We consider the warmest possible habitable planet as having Ts ∼ 355 K, at which point diffusion limited water-loss could remove an Earth ocean in ∼1 Gyr. Without long timescale regulation of non-condensable greenhouse species at Earth-like temperatures and pressures, such as CO2, habitability can be maintained for an upper limit of ∼2.2, ∼2.4, and ∼4.7 Gyr around F-, G-, and K-dwarf stars respectively, due to main sequence brightening.

Eric T Wolf↗
NASA NTRSDate not supplied

Pre-Tropical Cyclone Squall Lines and the Connection to the Diurnal Cycle in Hurricane Laura (2020)

Previous studies on the tropical cyclone (TC) diurnal cycle have shown in observations and modeling the presence of outward propagating squall lines. These squall lines were observed in several TCs during the 2020 Atlantic hurricane season. Of these squall lines, one observed in Hurricane Laura made landfall over 13 hours prior to the hurricane’s eye. This squall was responsible for numerous tornado warnings, which disrupted preparations and evacuations ahead of the storm’s landfall. This study seeks to characterize these squall lines and their environmental and thermodynamic characteristics, determine whether they behave more like midlatitude squall lines or tropical cyclone rain bands, and assess the performance of the convection-allowing High Resolution Rapid Refresh model in forecasting them over the ocean and over land. By using a combination of operational radar data, a network of surface weather observations from land and sea, satellite data, and HRRR model output, this case will undergo an extensive evaluation based on criteria from past literature in order to better understand these features as a whole and in relation to the diurnal cycle.

Vivian L Brasfield↗
NASA NTRSDate not supplied

Observational Analysis of Atlantic Basin Tropical Cyclone Squall Lines and Relationship to the Diurnal Cycle

Previous studies on the tropical cyclone (TC) diurnal cycle have shown in observations and modeling the presence of outward propagating squall lines. These squall lines were observed in several TCs during recent Atlantic hurricane seasons. Of these squall lines, one observed in Hurricane Laura made landfall over 14 hours prior to the hurricane’s eye. This squall was responsible for 40 tornado warnings, which disrupted preparations and evacuations ahead of the storm’s landfall. This study seeks to characterize these squall lines and their environmental and thermodynamic characteristics, determine whether they behave more like midlatitude squall lines or tropical cyclone rain bands, and assess the performance of the convection-allowing High Resolution Rapid Refresh model in forecasting them over the ocean and over land. By using a combination of operational radar data, a network of surface weather observations from land and sea, satellite data, and HRRR model output, this case will undergo an extensive evaluation based on criteria from past literature in order to better understand these features as a whole and in relation to the diurnal cycle.

Vivian Brasfield↗
NASA NTRS2017

Constraints on Climate and Habitability for Earth-like Exoplanets Determined from a General Circulation Model

Conventional definitions of habitability require abundant liquid surface water to exist continuously over geologic timescales. Water in each of its thermodynamic phases interacts with solar and thermal radiation and is the cause for strong climatic feedbacks. Thus, assessments of the habitable zone require models to include a complete treatment of the hydrological cycle over geologic time. Here, we use the Community Atmosphere Model from the National Center for Atmospheric Research to study the evolution of climate for an Earth-like planet at constant CO2, under a wide range of stellar fluxes from F-, G-, and K-dwarf main sequence stars. Around each star we find four stable climate states defined by mutually exclusive global mean surface temperatures (T(sub s)); snowball (T(sub s) ≼ 235 K), waterbelt (235 K ≼ T(sub s) ≼ 250 K), temperate (275 K ≼ T(sub s) ≼ 315 K), and moist greenhouse (T(sub s) ≽ 330 K). Each is separated by abrupt climatic transitions. Waterbelt, temperate, and cooler moist greenhouse climates can maintain open-ocean against both sea ice albedo and hydrogen escape processes respectively, and thus constitute habitable worlds. We consider the warmest possible habitable planet as having T(sub s) ∼ 355 K, at which point diffusion limited water-loss could remove an Earth ocean in ∼1 Gyr. Without long timescale regulation of non-condensable greenhouse species at Earth-like temperatures and pressures, such as CO2, habitability can be maintained for an upper limit of ∼2.2, ∼2.4, and ∼4.7 Gyr around F-, G-, and K-dwarf stars respectively, due to main sequence brightening.

Astrobiology↗
NASA NTRS2000

Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard properties of organic sulfur gases. However, a number of the properties for aqueous organic sulfur compounds have not been experimentally determined. Furthermore, most of thermodynamic data that are available are for 25 C and 1 bar. In order to determine reaction properties to temperatures and pressures appropriate to the hydrothermal conditions in which thermophilic organisms actually live, we use equations of state developed by Helgeson and co-workers (Helgeson et al., 1981, AJS 281, 1249). A key piece of information needed to go up in temperature is the partial molal heat capacity, which is one of the properties for which experimental data are unavailable for nearly all organic sulfur compounds. We have used correlation methods to determine the partial molal heat capacities and volumes of many organic solutes. These estimates allow us to asses the role of organic sulfur compounds during the reduction of carbon in hydrothermal settings. We will present these data, along with examples of the thermodynamic properties of reactions involving aqueous organic sulfur compounds.

Schulte, Mitchell↗
DOE OSTI2021

Atomistic Assessment of Solute-Solute Interactions during Grain Boundary Segregation

Grain boundary solute segregation is becoming increasingly common as a means of stabilizing nanocrystalline alloys. Thermodynamic models for grain boundary segregation have recently revealed the need for spectral information, i.e., the full distribution of environments available at the grain boundary during segregation, in order to capture the essential physics of the problem for complex systems like nanocrystalline materials. However, there has been only one proposed method of extending spectral segregation models beyond the dilute limit, and it is based on simple, fitted parameters that are not atomistically informed. In this work, we present a physically motived atomistic method to measure the full distribution of solute-solute interaction energies at the grain boundaries in a polycrystalline environment. We then cast the results into a simple thermodynamic model, analyze the Al(Mg) system as a case study, and demonstrate strong agreement with physically rigorous hybrid Monte Carlo/molecular statics simulations. This approach provides a means of rapidly measuring key interactions for non-dilute grain boundary segregation for any system with an interatomic potential.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Molten‐Salt‐Mediated Chemical Looping Oxidative Dehydrogenation of Ethane with In‐Situ Carbon Capture and Utilization

Abstract The molten‐salt‐mediated oxidative dehydrogenation (MM‐ODH) of ethane (C 2 H 6 ) via a chemical looping scheme represents an effective carbon capture and utilization (CCU) method for the valorization of ethane‐rich shale gas and concurrent mitigation of carbon dioxide (CO 2 ) emissions. Here, stepwise experimentation with Li 2 CO 3 ‐Na 2 CO 3 ‐K 2 CO 3 (LNK) ternary salts (i) assessed how each component of the LNK mixture impacted ethane MM‐ODH performance and (ii) explored physicochemical and thermodynamic mechanisms behind melt‐induced changes to ethylene (C 2 H 4 ) and carbon monoxide (CO) yields. Of fifteen screened LNK compositions, nine exhibited ethylene yields greater than 50 % at 800 °C while maintaining C 2 H 4 selectivities of 85 % or higher. LNK salts rich in Li 2 CO 3 content yielded more ethylene and CO on average than their counterparts, and net CO 2 capture per cycle reached a maximum of ~75 %. Extended MM‐ODH cycling also demonstrated long‐term stability of a high‐performing LNK medium. Density functional theory (DFT) calculations andab initiomolecular dynamics (AIMD) simulations suggested that the molten salt does not directly activate C 2 H 6 . Meanwhile, an empirical model informed by experimental data and reaction thermodynamics adequately predicted overall MM‐ODH performance from LNK composition and provided insights into the system′s primary drivers.

Chemistry↗
DOE OSTI2021

Progress and prospects of thermo-mechanical energy storage – A critical review

The share of electricity generated by intermittent renewable energy sources is increasing (now at 26% of global electricity generation) and the requirements of affordable, reliable and secure energy supply designate grid-scale storage as an imperative component of most energy transition pathways. The most widely deployed bulk energy storage solution is pumped-hydro energy storage (PHES), however, this technology is geographically constrained. Alternatively, flow batteries are location independent and have higher energy densities than PHES, but remain associated with high costs and low lifetimes, which highlights the importance of developing and utilizing additional larger-scale, longer-duration and long-lifetime energy storage alternatives. Here, we review a class of promising bulk energy storage technologies based on thermo-mechanical principles, which includes: compressed-air energy storage (CAES), liquid-air energy storage (LAES) and pumped-thermal electricity storage (PTES). The thermodynamic principles upon which these thermo-mechanical energy storage (TMES) technologies are based are discussed and a synopsis of recent progress in their development is presented, assessing their ability to provide reliable and cost-effective solutions. The current performance and future prospects of TMES systems are examined within a unified framework and a thermoeconomic analysis is conducted to explore their competitiveness relative to each other as well as when compared to PHES and flow battery systems. This includes carefully selected thermodynamic and economic methodologies for estimating the component costs of each configuration in order to provide a detailed and fair comparison at various system sizes. The analysis reveals that the technical and economic characteristics of TMES systems are such that, especially at higher discharge power ratings and longer discharge durations, they can offer promising performance (round-trip efficiencies higher than 60%) along with high lifetimes (> 30 years), low specific costs (often below 100 $/kWh), low ecological footprints and unique sector-coupling features compared to other storage options. TMES systems have significant potential for further progress and the thermoeconomic comparisons in this paper can be used as a benchmark for their future evolution.

25 ENERGY STORAGE↗
DOE OSTI2025

Future North Atlantic tropical cyclone intensities in thermodynamically modified historical environments

Tropical cyclones (TCs) have ranked as the deadliest and most financially crippling natural disasters in the United States. It is imperative to assess potential shifts in TC intensity within the paradigm of an evolving climate. In this study we apply a fixed-constraint storyline approach that holds storm tracks and initial conditions constant to probe future TC intensity in the North Atlantic Basin. First, we simulate 618 historical TC events using the Risk Analysis Framework for Tropical Cyclones (RAFT)'s deep-learning intensity model. Next, we apply warming signals derived from eight CMIP6 climate scenarios and rerun each event to explore how intensities respond across scenarios. Finally, we develop an interactive dashboard that allows users to explore individual storm simulations and the scenario-modified environmental drivers. Together, this dataset and tool provide a clear, illustrative way to investigate how TC intensity responds to changes in air-sea state.

Climate Change↗