SEARCH · Engineering Papers

Results for “Burn control”

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.

SourceResearch connectionFrom yearThrough year

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

At least 271 records · Page 15

All sources NASA NTRS DOE OSTI

DOE OSTI2022

Effect of zeolite type, temperature, and pH on Stage III glass alteration behavior for two nuclear waste glasses

We report long-term laboratory scale static alteration tests (up to 1500 d) were conducted on two low-activity waste glasses (LAWA44 and IDF18-A161) at S/V = 2000 m –1 . Tests were seeded with either analcime, clinoptilolite, zeolite P1, or zeolite P2 to induce Stage III glass alteration behavior. The effect of several parameters on glass Stage III behavior was studied with consideration of several variables, including temperature (22 °C – 90 °C) and pH (floating or initially set using KOH at values from 9.5 to 11.5). Temporal solution data and solids characterization at the end of the experiments are reported. Solution data demonstrated the occurrence of a sustained rate acceleration at temperatures down to 40 °C and the activation energy for these Stage III rates was determined for both glasses. Three major secondary phases were identified at the end of the experiments for both glasses: zeolite P1, zeolite P2, and/or analcime (along with minor phases: zeolites, clays, carbonates). The identification of the crystalline phases at the end of the experiment often differed from the zeolite seed phase. In addition, the use of the Avrami equation showed unimpeded zeolite growth (3-dimensional) in certain conditions, suggesting that in certain conditions the glass dissolution rate is controlled by zeolite formation kinetics whereas in other conditions the glass corrosion process impeded zeolite formation kinetics. The morphological evolution of the samples revealed the growth of the zeolites which completely fill the intergranular space in the powder bed. These results are discussed with regards to previous seeded and unseeded Stage III dissolution rate experiments performed on low- and high-activity nuclear waste glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2025

Quantum physics of stars

Stars are slowly developing objects; the lifetimes of the different burning phases are determined by the strength of nuclear reactions, which in turn are defined by the quantum structure of the associated nuclei at the threshold and the respective reaction mechanisms. Stars, from the nuclear physics perspective, are cold environments where only a few of the key nuclear reactions have been measured at the actual stellar plasma temperatures. This is also the case for more dynamic astrophysical phenomena from the big bang to stellar explosions. Most of the nuclear reaction rates are therefore based on theoretical extrapolations. A number of discrepancies between these predictions and the associated stellar signatures have been observed, and many may be due to low-energy or near-threshold quantum effects. These effects need to be understood in order to reliably model nuclear reaction processes, not only for stars but also for low-temperature plasma environments such as controlled magnetic or inertial confinement fusion systems, which operate in similar temperature regimes. This review summarizes the various theoretical techniques presently used for deriving reaction rates and discusses possible quantum effects that may impact the reaction cross section near the reaction threshold. These resemble enhanced single-particle and cluster structures near threshold and associated interference effects. New experimental techniques such as deep-underground accelerators or the study of transfer reactions to mimic the quantum-mechanical transition strength, the so-called Trojan horse method, provide ways to directly or indirectly probe the reaction features that determine the reaction rates at stellar energies. Furthermore, this is demonstrated on a number of key nuclear reactions for different nucleosynthesis environments. Finally, current inconsistencies between experimental predictions and observations are discussed.

Models & methods for nuclear reactions↗

DOE OSTI2023

Long-Term Persistence of Three Microbial Wildfire Biomarkers in Forest Soils

Long-term monitoring of microbial communities in the rhizosphere of post-fire forests is currently one of the key knowledge gaps. Knowing the time scale of the effects is indispensable to aiding post-fire recovery in vulnerable woodlands, including holm oak forests, that are subjected to a Mediterranean climate, as is the case with forests that are found in protected areas such as the Sierra Nevada National and Natural Park in southeastern Spain. We took rhizosphere soil samples from burned and unburned holm oak trees approximately 3, 6, and 9 years after the 2005 fire that devastated almost 3500 ha in southeastern Spain. We observed that the prokaryotic communities are recovering but have not yet reached the conditions observed in the unburned forest. A common denominator between this fire and other fires is the long-term persistence of three ecosystem recovery biomarkers—specifically, higher proportions of the genera Arthrobacter, Blastococcus, and Massilia in soil microbial communities after a forest fire. These pyrophilous microbes possess remarkable resilience against adverse conditions, exhibiting traits such as xerotolerance, nitrogen mineralization, degradation of aromatic compounds, and copiotrophy in favorable conditions. Furthermore, these biomarkers thrive in alkaline environments, which persist over the long term following forest fires. The relative abundance of these biomarkers showed a decreasing trend over time, but they were still far from the values of the control condition. In conclusion, a decade does not seem to be enough for the complete recovery of the prokaryotic communities in this Mediterranean ecosystem.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Spatially Precise Light‐Activated Dedoping in Wafer‐Scale MoS 2 Films

2D materials, particularly transition metal dichalcogenides (TMDCs), have shown great potential for microelectronics and optoelectronics. However, a major challenge in commercializing these materials is the inability to control their doping at a wafer scale with high spatial fidelity. Interface chemistry is used with the underlying substrate oxide and concomitant exposure to visible light in ambient conditions for photo-dedoping wafer scale MoS 2 . It is hypothesized that the oxide layer traps photoexcited holes, leaving behind long-lived electrons that become available for surface reactions with ambient air at sulfur vacancies (defect sites) resulting in dedoping. Additionally, high fidelity spatial control is showcased over the dedoping process, by laser writing, and fine control achieved over the degree of doping by modulating the illumination time and power density. This localized change in MoS 2 doping density is very stable (at least 7 days) and robust to processing conditions like high temperature and vacuum. The scalability and ease of implementation of this approach can address one of the major issues preventing the “Lab to Fab” transition of 2D materials and facilitate its seamless integration for commercial applications in multi-logic devices, inverters, and other optoelectronic devices.

14 SOLAR ENERGY↗

DOE OSTI2025

60 years of science in ICF: from conception to scientific breakeven on the National Ignition Facility

The recent achievements of a burning plasma, fusion ignition, and scientific energy gain with deuterium-tritium (DT) fuel at Lawrence Livermore National Laboratory’s National Ignition Facility (NIF) represents a major milestone in the development of inertial confinement fusion (ICF) and all of fusion research. In these experiments, fuel pressures well in excess of hundreds of GBars were achieved in the compressed fuel, and robust alpha heating of the fuel, far in excess of the energy provided by the implosion, were demonstrated for the first time. These achievements occurred 60 years after the inception of ICF and the first laser demonstration, and were made possible by more than five decades of research at laser facilities around the world. Advances in laser technology both in wavelength and precision, motivated by improved understanding of laser-plasma interaction physics and the demands of targets; improvements in target fabrication inspired by the need to control and minimize hydrodynamic instabilities in the implosion; and multi-dimensional simulations and diagnostics have been critical to this achievement. This paper will summarize the scientific and technical advances, the surprises, and the challenges that had to be overcome to achieve these goals.

fusion↗

DOE OSTI2024

Development and Testing of an Advanced Cascaded Thermoelectric Residential Heat Pump

Electricity-driven heat pumps using vapor compression cycle are an energy-efficient solution to replace fossil fuel burning and reduce greenhouse gas emissions for space heating in residential buildings. However, heating capacity and Coefficient of Performance (COP) of heat pumps degrade significantly with increasing temperature difference between ambient and indoor environments. Residents and building owners are hence reluctant to fully embrace electric heat pumps. The use of conventional all-electric heat pumps also causes concern for electric utilities due to an increased winter peak demand arising from the use of supplemental electric resistance heaters. Our research is an attempt to alleviate these concerns by designing and laboratory testing a thermoelectric (TE) heat pump cascaded with a vapor compression cycle to enhance heating capacity and COP. TE modules increase the subcooling in the refrigerant liquid of the vapor compression cycle to enlarge the evaporating capacity and works at an efficiency greater than a conventional electric resistance strip. This results in a simple, affordable, efficient and highly controllable solution to adequately meet space heating needs in dwellings. The laboratory testing of the 3-stage cascaded TE heat pump performed in this research has exhibited a higher heating capacity by above 15%, while maintaining a heating COP of 2.0-3.6 in the ambient temperature range of -18˚C to 8˚C (0˚F to 47 ˚F), which represents more than 60% of winter temperatures observed in US. If successfully commercialized, this technology can advance space-heating electrification by overcoming consumer cost barrier of heat pumps.

Shen, Bo↗

DOE OSTI2023

Phosphorus chemistry in plant charcoal: interplay between biomass composition and thermal condition

Background Vegetation fire may change Phosphorus (P) cycling in terrestrial ecosystems through converting biomass into fire residues. Aim The aim of this study was to understand the chemistry and mobility of P in fire residues to help reveal P thermochemistry during biomass burning and post-fire P cycling. Methods A combination of sequential extraction, liquid 31P NMR and P K-edge XANES was used to obtain quantitative P speciation and explain P solubilisation behaviours of charcoal. Key results Despite varying diverse P species existing in raw biomass, only two P structural moieties – orthophosphate and pyrophosphate – were identified in charcoal. However, relative abundance of pyrophosphate differs greatly among charcoal samples from different biomass types, ranging between 0 and 40% of total extractable P. Although P K-edge XANES data indicates abundant soluble phosphate minerals, most P (70–90%) is likely occluded physically in the charcoal. The bicarbonate-extractable P (the Olsen-P) varies significantly and cannot be explained by surface P concentration or elemental stoichiometry alone. Conclusion and implications The results suggest the importance of starting biomass P speciation (i.e. molecular structure and complexation environment) and thermal conditions in controlling P speciation and availability in charcoal. The different P chemistry between charcoal and ash suggests the importance of fire types and severity in disturbing the P cycle.

Forestry↗

DOE OSTI2021

Chapter 22: Compressed Air Evaluation Protocol. The Uniform Methods Project: Methods for Determining Energy Efficiency Savings for Specific Measures (September 2011 - August 2020)

Compressed-air systems are used widely throughout industry for many operations, including pneumatic tools, packaging and automation equipment, conveyors, and other industrial process operations. Compressed-air systems are defined as a group of subsystems composed of air compressors, air treatment equipment, controls, piping, pneumatic tools, pneumatically powered machinery, and process applications using compressed air. A compressed-air system has three primary functional subsystems: supply, distribution, and demand. Air compressors are the primary energy consumers in a compressed-air system and are the primary focus of this protocol. The two compressed-air energy efficiency measures specifically addressed in this protocol are: high-efficiency/variable speed drive (VSD) compressor replacing modulating, load/unload, or constant-speed compressor; compressed-air leak survey and repairs. This protocol provides direction on how to reliably verify savings from these two measures using a consistent approach for each.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

The crucial role of diagnostics in achieving ignition on the National Ignition Facility (NIF)

Well over 100 diagnostics can operate on the National Ignition Facility (NIF) as a result of several decades of development on NIF, and before that on Nova, OMEGA, and earlier LLNL lasers. A subset of these have guided the approach to achieving ignition on the NIF in 2022 [H. Abu-Shawareb et al. (Indirect Drive ICF Collaboration), Phys. Rev. Lett. 129(7), 075001 (2022)]. Achieving ignition on NIF has required many types of experiments with this core set of diagnostics, some constraining known unknowns and some revealing surprises—arguably unknown unknowns. Early design work realized that the extreme precision required for ignition on NIF would require fine-tuning by experiment, that is, measuring and adjusting known unknowns. Many examples are given where the use of the core set of ignition diagnostics in experimental arrangements called platforms demonstrated control of the key theoretical parameters defined as shape, adiabat, velocity, and mix. The direction of the adjustments to input conditions is found either by trend analysis or, in many cases, by observing from the diagnostic data the direction to make an adjustment. In addition, diagnostics have revealed some unexpected or neglected known issues, which degrade performance, or unexpected issues, unknown unknowns. Some of these factors had been previously considered, but underestimated or difficult to calculate at the time. The overall methodology can be described as a variant of Popper's falsifiability philosophy [K. Popper, The Logic of Scientific Discovery (Hutchinson, 1974)]. This paper summarizes the role of ignition diagnostics in terms of falsification or validation of theory or experimental setup as well as uncovering unexpected issues. The journey to ignition started in the seventies with a 1-µm wavelength laser producing disastrous results. Diagnostics have guided us to the recent multi-decadal goal of demonstrating ignition and burn in the laboratory.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2025

Multiphysics Running-In Simulations for Pebble-Bed Reactors with Griffin

Griffin, a Multiphysics Object-Oriented Simulation Environment (MOOSE)–based application targeting transient modeling of advanced reactors, has been used recently to model pebble-bed reactors (PBRs). The modeling effort has focused thus far on equilibrium core calculations. A new capability to simulate the running-in phase of PBR operation has been added to Griffin. This work demonstrates the new capability with a coupled multiphysics running-in simulation. Griffin computes power densities in the core at each time step of the running-in simulation and passes these to Pronghorn, which models fluid flow and heat transfer to calculate pebble surface temperatures. These surface temperatures are used along with the power densities in a heat conduction model to compute average fuel and moderator temperatures, which are passed back to Griffin and accounted for with temperature-dependent cross sections. This work also describes a novel methodology for determining appropriate pebble feed rates and control rod positioning during the running-in simulation. Furthermore, the RZ-geometry model used in this work requires minimal computational resources and can be used for optimization and uncertainty studies in future works.

Griffin↗

DOE OSTI2023

Exploratory analysis of machine learning techniques in the Nevada geothermal play fairway analysis

Play fairway analysis (PFA) is commonly used to generate geothermal potential maps and guide exploration studies, with a particular focus on locating and characterizing blind geothermal systems. This study evaluates the application of machine learning techniques to PFA in the Great Basin region of Nevada. Following the evaluation of various techniques, we identified two approaches to PFA that produced promising results, 1) supervised Bayesian probabilistic neural networks to generate geothermal potential maps with confidence intervals, and 2) unsupervised principal component analysis paired with k-means clustering to generate both cluster maps to help identify spatial patterns, as well as new combined feature inputs. We applied these techniques to perform a comparative analysis between two principal sets of geological and geophysical features related to permeability and heat and a set of positive (known geothermal resources) and negative training sites (known drill sites with unsuitable geothermal conditions). We found that these methods constrain previously unrecognized feature controls on geothermal favorability, many of which are spatially organized within the extent of cluster groups and the major structural-hydrologic domains of the study area. Furthermore, we utilized exploratory unsupervised modeling to highlight spatial relationships between input data and predictive output results of our supervised modeling. As a result, we demonstrate how our models compare to the previous Nevada PFA and how the rapid insights these machine learning techniques offer may support future assessments of both known and undiscovered blind geothermal systems in the Great Basin region of Nevada and beyond.

15 GEOTHERMAL ENERGY↗

DOE OSTI2026

Variations of Alloying Site Density in Pd 1 Cu Single‐Atom Alloy Catalysts Lead to Shifted Product Yields in Electrochemical CO Reduction

Single-atom alloy (SAA) catalysis research often reports that a SAA catalyst, in the general formulation of a single-atom metal M1 alloyed on the surface of the host metal M2, facilitates a probe reaction. However, for catalytic reactions that present decoupled rate- and selectivity-limiting steps, the alloying site density may significantly manipulate these independent steps, but it has rarely been explicitly examined for any SAA systems. Herein, using the electrocatalytic CO reduction as a probe reaction, we report that the nominal Pd 1 Cu cube SAA catalysts exhibit distinctive high reactivity toward ethylene or ethanol, respectively, depending on whether the Pd atoms are in dilute or crowded forms. Although the presence of single-atom Pd embedded on Cu uniformly promotes CHO* formation and C─C coupling, the dilute-Pd 1 Cu favors ethylene formation by enabling low-barrier C─O cleavage from a flat CH 2 CH 2 OH* intermediate, whereas the crowded-Pd 1 Cu promotes ethanol formation by stabilizing an upright hydrogenation transition state of the same intermediate. Furthermore, we present evidence that the catalytic chemistry of crowded Pd 1 species differs from that of the Pd 2 -dimer; the latter, albeit unstable, steers reaction selectivity to acetate instead. In conclusion, these results uncovered the underappreciated importance of controlling SAA catalytic chemistry from the perspective of single-atom site densities.

Jin, Zehua [Clemson University, SC (United States)↗

DOE OSTI2022

Intercomparison of airborne and surface-based measurements during the CLARIFY, ORACLES and LASIC field experiments

Data are presented from intercomparisons between two research aircraft, the FAAM BAe-146 and the NASA Lockheed P3, and between the BAe-146 and the surface-based DOE (Department of Energy) ARM (Atmospheric Radiation Monitoring) Mobile Facility at Ascension Island (8 S, 14.5W, a remote island in the mid-Atlantic). These took place from 17 August to 5 September 2017, during the African biomass burning season. The primary motivation was to give confidence in the use of data from multiple platforms with which to evaluate numerical climate models. The three platforms were involved in the CLouds-Aerosol-Radiation Interaction and Forcing for Year 2017 (CLARIFY-2017), ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES), and Layered Atlantic Smoke and Interactions with Clouds (LASIC) field experiments. Comparisons from flight segments on six days where the BAe-146 flew alongside the ARM facility on Ascension Island are presented, along with comparisons from wing-tip to wing-tip flight of the P3 and BAe-146 on 18 th August 2017. The intercomparison flight sampled a relatively clean atmosphere overlying a moderately polluted boundary layer, while the 6 fly-bys of the ARM site sampled both clean and polluted conditions 2–4 km upwind. We compare and validate characterisations of aerosol physical, chemical, and optical properties, atmospheric radiation, and cloud microphysics between platforms. We assess the performance of measurement instrumentation in the field, under conditions where sampling conditions are not tightly controlled as in laboratory measurements where calibrations are performed. Solar radiation measurements compared well between airborne platforms. Optical absorption coefficient measurements compared well across all three platforms, even though absolute magnitudes were often low (< 10 Mm -1 ) and close to the sensitivity limits of measurement instrumentation thereby confounding assessments of the comparability of absorption Ångström exponent characterisations. Aerosol absorption measurements from airborne platforms were more comparable than aircraft-to-ground observations. Scattering coefficient observations compared well between airborne platforms, but agreement with ground-based measurements was worse, potentially caused by small differences in sampling conditions or actual aerosol population differences. Chemical composition measurements followed a similar pattern, with better comparisons between the airborne platforms. Thermodynamics, aerosol, and cloud microphysical properties generally compared well.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Integrating continuous atmospheric boundary layer and tower-based flux measurements to advance understanding of land-atmosphere interactions

The atmospheric boundary layer mediates the exchange of energy, matter, and momentum between the land surface and the free troposphere, integrating a range of physical, chemical, and biological processes and is defined as the lowest layer of the atmosphere (ranging from a few meters to 3 km). In this review, we investigate how continuous, automated observations of the atmospheric boundary layer can enhance the scientific value of co-located eddy covariance measurements of land-atmosphere fluxes of carbon, water, and energy, as are being made at FLUXNET sites worldwide. We highlight four key opportunities to integrate tower-based flux measurements with continuous, long-term atmospheric boundary layer measurements: (1) to interpret surface flux and atmospheric boundary layer exchange dynamics and feedbacks at flux tower sites, (2) to support flux footprint modelling, the interpretation of surface fluxes in heterogeneous terrain, and quality control of eddy covariance flux measurements, (3) to support regional-scale modeling and upscaling of surface fluxes to continental scales, and (4) to quantify land-atmosphere coupling and validate its representation in Earth system models. Adding a suite of atmospheric boundary layer measurements to eddy covariance flux tower sites, and supporting the sharing of these data to tower networks, would allow the Earth science community to address new emerging research questions, better interpret ongoing flux tower measurements, and would present novel opportunities for collaborations between FLUXNET scientists and atmospheric and remote sensing scientists.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

An evaluation of air quality in major urban areas of India

Rapid economic growth and burgeoning population have contributed to enhanced levels of PM 2.5 concentrations in urban regions of India. Evaluation of ambient air quality facilitates the assessment of effectiveness of emission control measures and early identification of new sources. This study provides a comprehensive statistical analysis of PM 2.5 concentrations in key urban areas across India, including Delhi, Kolkata, Mumbai, Chennai, Hyderabad, and several regional centers. Data from 2017 to 2023 was analyzed using trend analysis, cluster analysis, principal component analysis, and geostatistical interpolation to understand spatiotemporal variations and sources. The analysis reveals significant differences in spatial distribution of PM 2.5 concentrations with high annual averages in urban regions in Indo-Gangetic plain (82–123 μg m −3 ) and relatively lower concentrations (29–46 μg m −3 ) in southern urban areas of Kerala, Tamil Nadu and Andhra Pradesh. Delhi state had the highest 24-averaged PM 2.5 concentrations (112 μg m −3 ) followed by urban regions in Uttar Pradesh, Bihar and West Bengal (94 μg m −3 ). Trend analysis from 2017 to 2023 revealed an overall 2.5% decline in site-wide PM2.5 concentrations, with the exception of Ludhiana, which exhibited a consistent annual increase of 10%. Principal component analysis (PCA) attributes 30% of the variance to wintertime emissions, 13% to biomass burning, and 18% to the regional haze in the northern Indo-Gangetic Plain. Different analyses clearly demonstrates the contribution of biomass burning to pollution in Delhi and surrounding cities. Transboundary pollution to Kolkata is likely from the highly polluted region in Indo-Gangetic Plain. Coastal cities of Mumbai and Chennai has relatively lower pollution attributed to the influence of sea breeze dilution, with mostly local contribution and some potential transport from upwind industry clusters. Hyderabad also has local contribution due to high density of vehicular traffic and local small industries. This study shows that mitigation efforts targeting clusters of regions should be undertaken to curb the high PM2.5 pollution. Policy measures should be implemented both at local and the intra-state level to address shared sources and transport of pollution.

Hysplitbacktrajectories↗

DOE OSTI2024

A Prefire Approach for Probabilistic Assessments of Postfire Debris‐Flow Inundation

Increases in wildfire activity and rainfall intensification are driving more postfire debris flows (PFDF) in many regions around the world. PFDFs are most common in the first postfire year and may even occur before a fire is fully controlled. This underscores the importance of assessing postfire hazards before a fire starts. Evaluation of PFDF hazards prior to fire can help strategize interventions lessening the negative effects of future fires. However, debris-flow runout and inundation analyses are not routine in PFDF hazard assessments, partially due to time constraints and substantial uncertainties in boundary conditions. Here, we propose a prefire PFDF inundation assessment framework using a debris-flow runout model based on the Herschel-Bulkley (HB) rheology (HEC-RAS v6.1). We constrain model inputs and parameters using Bayesian posterior analysis, rainfall-runoff simulations, and a debris-flow volume model. We use observations from recent PFDF incidents in northern Arizona, USA, to calibrate model components and then apply our prefire inundation assessment framework in a nearby unburned area. Specifically, we (a) identify yield stress as the most influential factor on inundation extent and arrival time in a HB model, (b) establish posterior distributions for model parameters suitable for forward modeling by leveraging uncertainties in field observations, and (c) implement a predictive forward analysis in an area that has not burned recently to evaluate PFDF inundation under several future fire scenarios. This study improves our ability to assess postfire debris-flow hazards before a fire begins and provides guidance for future applications of single-phase rheological models when assessing PFDF hazards.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

A Prefire Approach for Probabilistic Assessments of Postfire Debris-Flow Inundation

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li–U 24 , Li–U 28 , K–U 28 , Li/K–U 60 , Mo 132 , and Mo 154 , in terms of three components: enthalpy of dissolution (ΔH diss ), enthalpy of formation of aqueous POMs (ΔH f,(aq) ), and enthalpy of formation of POM crystals (ΔH f,(c) ). ΔH diss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔH f,(aq) and are more stable than those containing only peroxide bridges. Here, in general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔH f,(aq) can be accurately estimated using only ΔH f,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗