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Transient thermodynamic analyses have been made for the Kennedy Space Center (KSC) LOX loading system proposed for the space shuttle. The primary objective of these analyses is to predict the sensitivity of system performance to operating procedures, flow rate, temperature, and quality at the orbiter (ORB)/ground service equipment (GSE) interface. A further objective is to establish required system chill-down times. These analyses also include the prediction of transient thermodynamic conditions for the facility vent line, shuttle main engine (SSME) feed line entrance, ORB/ET interface, and the ET entrance (tank bottom).
Abstract Optical Bloch equations (OBE) describe the coherent exchange of energy between a quantum bit (qubit) and a quasi-resonant driving field in the presence of a thermal bath. Despite it being an ubiquitous process in quantum technologies, a sound thermodynamic analysis is still missing. We hereby provide such an analysis, by deriving the relevant framework from first principles. We start from a complete microscopic description of the qubit-bath system where definitions of heat, work and entropy production are unambiguous. We trace out the bath and coarse-grain the resulting expressions in time, using a methodology similar to the derivation of the dynamical master equation, to derive closed expressions for the first and second law in terms of system properties. Long coarse graining times yield the Floquet Master equation and its already known thermodynamic description. Short coarse-graining times yield instead the OBE and a novel thermodynamic framework which explicitly depends on quantum coherences in the qubit’s energy basis which produce quantum signatures in the heat and entropy production flows. This allows us to characterize a genuinely quantum non-equilibrium situation, where the coherences created by the driving field are continuously erased by the bath. Our findings can be readily extended to larger open quantum systems. They carry the seeds for future thermodynamic analyses of quantum gates and the design of quantum engines in the strong coherent driving regime.
This manuscript reports a CO2 hydrogenation process in a catalytic laboratory-scale packed-bed reactor using an Fe/BZY15 (BaZr0.8Y0.15O3-d) catalyst to form hydrocarbons (e.g., CH4, C2+) at elevated pressure of 30 bar and temperatures in the range 270 = T = 375 degrees C. The effects of temperature, feed composition (i.e., CO2/H2 ratio, and residence time (i.e., Weight Hourly Space Velocity (WHSV) are studied to understand the relationship between CO2 conversion and carbon selectivity. Catalyst characterization elucidates the relationships between the catalyst structure, surface adsorbates, and reaction pathways. Thermodynamic analyses guide the experimental conditions and assist interpreting results. While the feed composition and temperature influence the product distribution, the results suggest that the higher-carbon (C2+) selectivity and yield depend strongly on residence time. The results suggest that the CO2 hydrogenation reaction pathway is similar to Fischer-Tropsch (FT) synthesis. The reaction begins with CO2 activation to form CO, followed by chain-growth reactions similar to the FT process. The CO2 activation depends on the redox activity of the catalyst. However, the carbon chain growth depends primarily on the residence time. as is the case for the FT synthesis, high residence time (on the orders of hours) is required to achieve high C2+ yield. For such high residence times, catalyst-fouling carbon deposition can be problematic. The coke-resistant BZY15 catalyst support contributes to the catalytic activity and enables a coke-free operation for more than 100 h time-on-stream.
Aluminum alloys are being explored as lightweight structural materials for use in hydrogen-containing environments. In this paper, to understand hydrogen effects on deformation, we perform molecular statics studies of the hydrogen Cottrell atmosphere around edge dislocations in aluminum. First, we calculate the hydrogen binding energies at all interstitial sites in a periodic aluminum crystal containing an edge dislocation dipole. This allows us to use the Boltzmann equation to quantify the hydrogen Cottrell atmosphere. Based on these binding energies, we then construct a continuum model to study the kinetics of the hydrogen Cottrell atmosphere formation. Finally, we compare our results with existing theories and discuss the effects of hydrogen on deformation of aluminum-based alloys.
All-solid-state batteries with a lithium metal anode, enabled by lithium garnet solid electrolytes such as Li 7 La 3 Zr 2 O 12 (LLZO), are a promising next-generation energy-storage technology. The further development of all-solid-state battery requires the integration of high-energy cathodes such as LiNi 1-x-y Mn x Co y O 2 (NMC) with the garnet solid electrolyte with stable and low-resistance interfaces, which requires a coating layer to stabilize the interface during high-temperature sintering and electrochemical cycling. In order to guide the future development of interfacial coatings, we perform high-throughput thermodynamic analyses based on first-principles computation to investigate the stability of LLZO garnet and high-energy NMC cathodes with a wide range of materials chemistries. Here our study reveals the factors governing the materials stability with LLZO garnet and NMC cathodes, and identifies the mechanisms of good coating layers stable with LLZO and NMC. In addition to classifying known coating layers, our study provides detailed guiding charts and multiple new materials systems as promising coatings for stabilizing LLZO—NMC interfaces to enable high-energy-density garnet-based all-solid-state batteries. Our demonstrated computation scheme and high-throughput analyses are generally applicable to investigate and screen coating materials for stabilizing interfaces in energy-related applications.
Astrophysical evaluation of Venus observations from Mariner II radiometer data, and thermodynamic analyses of planetary atmospheres
Transient thermodynamic analyses were made of the LOX loading system proposed for the space shuttle main propulsion test article (MPTA). This system is made up of a LOX replenish system and a main LOX line which include the barge tank, the lines, pumps, and valves between the barge and the orbiter (ORB) ground service equipment (GSE) interface, the MPTA fill system, the space shuttle main engine (SSME) chilldown bleed system, and the GSE vent system. System analyses include predictions of system performance sensitivity to operating sequence and LOX flowrate, temperature, and quality at the ORB/GSE interface. The transient thermodynamic conditions at the SSME feed line entrance, ET entrance (tank bottom), and the SSME bleed/GSE vent TEE are also included. The analyses are based on continuous SSME bleed flow during GSE facility chilldown.
Metalloenzyme superfamilies are typically defined by their protein scaffolds and active sites. Owing to the high tunability of protein structures, members of a single superfamily can catalyze diverse reactions with the same metallocofactor. Some superfamilies, such as amidohydrolase-related dinuclear oxygenases (AROs), display further versatility by utilizing multiple metallocofactors. We have shown that certain AROs catalyze monooxygenation reactions with diiron, dimanganese, and/or mixed manganese−iron cofactors, but the molecular factors governing the selection of a particular cofactor remain unknown, and the extent of this superfamily in biology is unclear. Here, we report bioinformatic analyses that expand the ARO superfamily to approximately 17,000 unique UniProt sequences, far exceeding the number of previously characterized enzymes. Through the integration of structural, spectroscopic, and thermodynamic analyses of representative proteins with a bioinformatic pipeline that identifies key secondary- and tertiary-sphere residues, we can predict in silico the metal preference for the majority of reported ARO sequences. These annotations were validated via the characterization of multiple new AROs, including ones implicated in key oxidative steps of natural product biosyntheses. This study establishes the key structure−function relationships governing metal preferences in AROs and highlights their vastly underappreciated role in myriad biological processes.
A mixing-line boundary-layer model is used to retrieve cloud-top height from satellite-derived cloud-top temperatures, using 700-hPa National Meteorological Center (NMC) analyses and the Comprehensive Ocean and Atmosphere Data Set (COADS) surface data as supporting datasets. Results are compared with the fixed-lapse-rate method of retrieving boundary-layer depth from sea surface temperatures (SST) and cloud-top temperatures. A radiative-convective equilibrium boundary-layer model is used to retrieve boundary-layer structure given SST and surface wind, satellite cloud-top temperatures and cloud fraction, and the 700-hPa NMC thermodynamic analyses. Good agreement is found between the COADS data and the model solutions for low-level temperature and moisture. This suggests that equilibrium boundary-layer models may be of use over remote oceans in the retrieval of boundary-layer structure.
The Optical Communications Group intends to experiment with a 2 by 2 meter Fresnel lens to determine its likelihood as an alternative to focusing mirrors for optical communications. The lens was delivered in four sections. A support structure was required for the lens in order to hold the four sections in a single flat plane with an adjustable degree angle. In order to use the 200-in. Hale telescope for optical communications purposes, an optical filter membrane must used to pass the communications wavelength while blocking sunlight wavelengths. This filter must withstand wind gusts of up to 50 miles per hour. Stress analysis predicts that the membrane will survive with a safety factor greater than two. The methods used were verified by pressure testing the material. Mechanical and thermodynamic analyses were performed on a simple Golay cell in order to optimize its dimensions for best performance. Flexures are examined as an inexpensive alternative to traditional methods for kinematically constraining a 1.5-meter spherical mirror.
Graphene-based single-atom catalysts are promising alternatives to platinum-based catalysts for fuel cell applications. Different transition metals have been screened using electronic structure methods by estimating onset potentials from the most endergonic elementary reaction step. Here, we calculate onset potentials for the oxygen reduction reaction on metal atoms embedded in N-substituted graphene di-vacancies by virtue of first-principles-informed microkinetic analysis. We find that for more oxophilic metals (Cr, Fe, Mn, and Ru), purely thermodynamic models systematically underestimate onset potentials. Furthermore, the oxophilic metals (Cr, Fe, Mn, and Ru) are oxidized under reaction conditions, leading to an increase in activity compared to their reduced state. Importantly, coadsorbed O m H n species actively participate in the reaction, which requires a dynamic treatment of spectator species. These findings highlight the limitations of thermodynamic analyses for electrocatalytic processes, which commonly assume the same oxidation state for each metal, and show that deviations between computational and experimental onset potentials cannot be solely attributed to the shortcomings of the electronic structure methods.
It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before approximately 2.2 billion years (Gyr) ago. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.
The synthesis of fully epitaxial ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb 2 Ir 2 O 7 (PIO) and Bi 2 Ru 2 O 7 (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Furthermore, thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.
Mechanistic investigation of the catalytic conversion of model compounds for plastic pyrolysis oil (1-octene, octadiene, octane, and toluene) over ZSM-5 in a fixed-bed reactor was studied. 1-Octene breaks down into smaller olefins, which undergo further cracking, oligomerization, cyclization, and hydrogen transfer to eventually produce benzene, toluene, xylene (BTX), coke, and hydrogen. The effect of contact time on 1-octene conversion was further investigated and compared with thermodynamics analyses to elucidate the reaction network. Under the reaction conditions (500 oC, 1 atm), octadiene undergoes thermal coking, significantly contributing to reactor fouling. The products from octane cracking are similar to the products from 1-octene conversion whereas toluene undergoes disproportionation, dealkylation and coking. The analysis of spent catalyst showed long-chain hydrocarbons created by oligomerization reactions filled the pores and covered the surface of the catalyst. As a result, when mesoporous ZSM-5 is used instead of conventional, product selectivity is maintained for 70 hours in time-on-stream experiments.
Ti-silicates activate H 2 O 2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H 2 O 2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH 3 OH) or acetonitrile (CH 3 CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH 3 CN than CH 3 OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH 3 CN and CH 3 OH. Specifically, apparent activation free energy values ($ΔG^{‡}_{App}$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH 3 CN on Ti-BEA and in CH 3 OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($ΔG^{‡}_{App}$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.
Aromatics, including benzene, toluene, and xylenes (BTX), are essential chemical building blocks and are widely used as solvents, fuel additives, and polymers. With the recent development in CO 2 capture technologies and the progress made in producing H 2 using renewable energy, direct hydrogenation of CO 2 to aromatics via heterogeneous catalysis has emerged as a promising pathway to accomplish the production of aromatics with simultaneous utilization of waste CO 2 . In this review, we focus on recent advances in the nascent field of direct CO 2 aromatization, whereby tandem catalysts composed of CO 2 hydrogenation and aromatization functionalities are designed and deployed. We review two categories of tandem catalysts: catalysts integrating Fe-based/H-ZSM-5 components following RWGS (reverse water-gas shift of CO 2 to CO)-FT (Fischer-Tropsch synthesis of lower olefins)-aromatization pathways, and catalysts combining metal oxide/H-ZSM-5 domains following CO 2 to methanolaromatization pathways. The key parameters that determine the catalytic performance, such as the composition and structure of the Fe-based or metal oxide-based CO 2 conversion catalysts, the properties of H-ZSM-5, and the synergy between the two components, are analyzed to provide insights for the design of efficient tandem catalysts for CO 2 aromatization. In parallel, thermodynamic analyses, mechanistic studies, and density functional theory (DFT) computations for the relevant reaction routes and pathways are discussed to offer improved understanding of CO 2 activation, reaction intermediates, and product formation. In closing, the challenges and prospects for these tandem reactions are addressed to provide suggested paths forward for future research.
Silicon carbide (SiC) components are being considered for a wide range of nuclear applications due to their high-temperature strength retention, low neutron absorption, chemical inertness, and dimensional stability under neutron irradiation. However, machining and joining of SiC components have traditionally limited its application to relatively simple geometries. Recent work has demonstrated additive manufacturing of complex, high-purity, crystalline SiC components using a combination of binder jet printing and densification via chemical vapor infiltration (CVI). The process lends itself to embedding of fuel, absorbers, moderators, and sensors at strategic locations within a component. The latter could allow for enhanced in situ performance monitoring of limiting fuel temperatures, self-shielded neutron flux, and potentially spatially distributed strain within complex SiC components if sensors can be successfully embedded during CVI. This work describes (1) methods for embedding sensors; (2) thermodynamic analyses and material compatibility testing for identifying sensors capable of surviving high temperatures and exposure to hydrogen and hydrogen chloride during CVI; and (3) nuclear applications for embedded sensors, including potential failure modes during fabrication and during reactor operation. Molybdenum-sheathed thermocouples were successfully embedded in a complex SiC component, whereas niobium-sheathed high-temperature irradiation-resistant thermocouples started to drift as soon as the reactant gases were introduced and ultimately failed during CVI due to severe constrained expansion, potentially resulting from niobium hydride formation in the low-temperature region of the CVI system. Optical fibers were successfully embedded in SiC, but further work is needed to protect the fragile fiber leads after their protective coatings are removed during CVI.