Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Zero liquid discharge”

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.

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

51 records · Page 3

Harnessing dimethyl ether with ultra-low-grade heat for scaling-resistant brine concentration and fractional crystallization

Solvent-driven separations may enable scalable concentration of hypersaline brines, supporting a circular resource economy from the extraction of lithium and rare earth elements from spent battery and magnet leachates. This work analyses a novel solvent-driven water extraction (SDWE) system employing dimethyl ether (DME) and ultra-low-grade heat for brine concentration and fractional crystallization. SDWE exploits DME’s unique properties: (1) a low dielectric constant that promotes water solubility over charged solutes by a factor of 10 3 , and (2) a high volatility that facilitate efficient DME reconcentration with ultra-low-grade heat. The techno-economic viability of SDWE is assessed with a computational framework that encompasses a liquid–liquid separator and a solvent concentrator. We integrate the extended universal quasichemical model with the virial equation of state to predict the compositions of the complex three-phase DME-water mixture at vapor–liquid and liquid–liquid equilibrium. Subsequently, we optimize the thermodynamic and economic performance of SDWE, by controlling the interstage flash pressure, heat source temperature, and the number of concentrating stages. DME-based SDWE concentrates an input saline feed to 5.5 M and regenerates over 99 % of the DME using ultra-low-grade heat below 50 °C, with a DME/water selectivity ratio of 125. Here our calculations reveal that optimal performance is achieved at interstage flash pressures of 0.4 – 0.5 bar for heat source temperatures between 323–373 K, with improved exergetic efficiencies at lower temperatures. At a heat source temperature of 323 K and an interstage pressure of 0.489 bar, DME-driven SDWE achieves an optimal thermodynamic efficiency of 20.5 % and a projected specific cost of US$ 1.93 m -3 . These specific costs suggest that SDWE is competitive with commercialized thermal distillation technologies, while mitigating the traditional risks associated with scaling in heat and mass exchangers with hypersaline brines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A novel approach for produced water treatment: Supercritical water oxidation and desalination

Produced water generated from oil and gas operations contains significant quantities of environmentally hazardous hydrocarbons, organic chemicals, and inorganic salts. Environmental regulations with impaired water disposal mandates produced water treatment and desalination. Industry standard desalination technologies are energy-intensive and mandate extensive produced water pre-treatment including removal of hydrocarbons constituents for efficient operations. Herein this study investigates a novel process intensification approach integrating supercritical water oxidation (SCWO) unit operation with a supercritical water desalination (SCWD) process for energy efficient produced water treatment and desalination. The coupled SCWD-SCWO process is found to be very energy-efficient and cost effective than existing industry standard desalination technologies. For energy efficient operation, the heat generated from the SCWO of hydrocarbons present in the produced water is used for power generation using a high efficiency and low-cost re-heat Rankine cycle process. The cost of treating produced water with proposed SCWO-SCWD process is independent of the salt concentration. The proposed process has the potential to offer step-change improvements over conventional processes in both the efficiency and cost of produced water treatment: for example, a cost and energy saving of 70% and 100% is calculated for the treatment of produced water containing 250 g/l salt and 10.6 g/l hydrocarbon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fouling characterization and treatment of water reuse concentrate with membrane distillation: Do organics really matter

Membrane distillation (MD) for the treatment of concentrated brines has been limited in part by membrane fouling, resulting in subsequent flux decline and membrane wetting. This study provides new insight into the identification of fouling and scaling mechanisms and pretreatment strategies for mitigating flux decline with MD treatment of water reuse reverse osmosis concentrate (ROC). Bench-scale direct contact MD experiments were performed with untreated and pretreated ROC. Biological activated carbon (BAC), chemical water softening, or fluidized bed crystallization reactor coupled with ion exchange (FBCR-IX) were selected as pretreatment strategies to isolate the effects of organic fouling and calcium scaling. Organic and inorganic compounds were analyzed by high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS). Calcium ions were found to be the major contributor to flux decline despite the high organic content in the ROC. Minimal organic fouling is likely because the organic matter in the ROC is hydrophilic, limiting hydrophobic-hydrophobic interactions between the organics and the membrane. Furthermore, the water flux declined by 63 % after removing organic compounds by BAC pretreatment, with 60 % of the calcium mass precipitating from the solution. Whereas, the water flux remained constant after removing multivalent ions with fluidized bed crystallization. Cleaning the membrane by acid washing and temperature reversal recovered 73 % and 12 % of the water flux, respectively. The analyses outlined in this study can assist in selecting appropriate fouling and scaling mitigation strategies for water reuse ROC and a wide range of feed solutions used in MD applications.

42 ENGINEERING↗

Co-treating flue gas desulfurized effluent and produced water enables novel waste management and recovery of critical minerals

Herein this study reports a novel approach of resource recovery from co-managing two geographically co-located and chemically complementary wastewaters using a pilot-scale treatment process. Designed to treat flue gas desulfurized (FGD) effluent from combustion powerplants and produced water (PW) from energy industries, the process consists of soda-ash softening, nanofiltration (NF), and reverse osmosis (RO). Recovered products are barite, calcite, and low-salinity water. Using field-collected waters, the results show that softening at pH 8.5 produces calcite (yield: 30 kg/m 3 treated water), a chemical used as SO ₂(g) scrubbers. NF treatment under an applied pressure of 3.5 MPa yields a permeate stream laden with monovalent ions (water recovery 60%) and a concentrate stream with a sulfate concentration 1.8 times of the feedwater concentration. Mixing the NF concentrate and PW at a volumetric ratio of 1.0 precipitates a high-density barite material (4.1 g/cm 3 , yield: ~7.5 kg/m 3 mixture) – a critical mineral commonly used as a weighting agent in drilling. The RO treatment recovers >64% water as the permeate, which can be readily used as cooling make-up water at the powerplants. The RO concentrate stream can be further processed in a thermal evaporative system for additional water recovery and brine production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fouling mechanism in airblast atomizers and its suppression for water desalination

A detailed experimental study is presented on fouling behavior of the anti-clogging perforated plate atomizer designed for high salinity applications, and compared with a conventional (plain-jet) airblast atomizer. Low-pressure regions around fast moving air in the outer layer of spray (as in conventional atomizers: plain-jet and prefilming) due to Venturi suction were identified as the root cause of atomizer clogging, as they facilitate salt accumulation on the atomizer surface from spray. Accordingly, severe atomizer fouling, and fluctuations in spray cone angle were observed in the conventional airblast atomizer over 2 h at 100°C air and 50°C saline (44° to 76° at 35,000 ppm, and 44° to 91° at 100,000 ppm). In this regard, the perforated plate atomizer provides a novel liquid-film airblast atomization by maintaining a liquid-annulus film (around the air outlet) as the outer layer of spray. Doing so we achieved nearly complete suppression of fouling, and spray cone angle fluctuations (28° ± 1° at 35,000 ppm, and 30° ± 1° at 100,000 ppm). Later, novel liquid-film atomization was adopted in the conventional airblast atomizer. While, the conventional airblast atomization needed atomizer cleaning/maintenance after 35 min for 175°C air and 65°C saline at 100,000 ppm, the liquid-film atomization showed no sign of fouling over 14 h. Hence, current work establishes a benchmark liquid-film airblast atomization mechanism in the anti-clogging perforated plate atomizer for complete suppression of fouling in airblast atomization. Furthermore, this extends the application of airblast atomizers from high evaporation jet engines to ZLD-HDH desalination systems, spraying, powder metallurgy, pharmaceuticals and hospitals, and spray drying and cooling.

42 ENGINEERING↗

WaterTAP3 Model Results for NAWI's Baseline Analyses

Description: This folder contains the results for the WaterTAP3 model that was used for the eight NAWI (National Alliance for Water Innovation) baseline studies published in the Environmental Science and Technology special issue: Technology Baselines and Innovation Priorities for Water Treatment and Supply. The data structure and content are described in a README.txt file. For more details on how to use the data and interpret the results please refer to the model documentation and GitHub site linked in the submission.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Studies on the Encapsulation of Brine Generated from a Process Using Selective Electrodialysis Reversal

This topical report summarizes the laboratory testing, geochemical modeling, and mineralogical testing conducted to examine the efficacy of wastewater encapsulation for the brine generated from the Saltworks Flex electrodialysis reversal technology. Within the laboratory testing, the short- and long-term physical properties of seven separate mix designs were examined along with the leaching of each mix design. Additionally, geochemical thermodynamic modeling was used along with mineralogical analyses to help gain a fundamental understanding of the chemistry involved in the encapsulation process. Encapsulation is a process that results in the immobilization of constituents of interest by creating an engineered material that contains the waste within its matrix, both physically and chemically, in such a manner that the receiving environment is protected from adverse effects. Within the context of this study, encapsulation mix designs involved mixing the Saltworks brine with fly ash and various additives, principally lime (calcium oxide) and cement, to form a paste that eventually sets and hardens into a monolith upon placement in a landfill. Moisture conditioning fly ash with wastewater sources for on-site landfill disposal is a process that is in use at some sites and has been presented as a viable option to dispose of liquid wastes. However, because chemical reactions that can lead to sequestration of constituents of interest are not optimized, leaching can occur. Therefore, in this study, mixes were created to mimic moisture conditioning, as well as engineered pastes of varying mix designs. The study found that engineered encapsulation mixes provide significant resistance to leaching compared to moisture conditioning alone. The best performing encapsulation mix used lime as the additive, which proved superior to the use of cement. After 90 days of curing, this encapsulated mix was 5.5 times stronger than the moisture conditioned mix. Additionally, this mix exhibited an approximate 2.5 order of magnitude drop in hydraulic conductivity compared to the moisture conditioned mix. When comparing leaching, nearly all the chloride was found to evolve from the moisture conditioned mix, whereas only 6.7% of the chlorine contained in the best performing encapsulated mix leached out. Mineralogical analysis via X-ray diffraction (XRD) showed a significant concentration of the chloride sequestering mineral, Friedel’s salt, in the best performing encapsulation mix, whereas none was observed in the moisture conditioned mix, pointing to it being the primary chemical mechanism for chloride retention, along with the physical impermeability of the material. With respect to the modeling study, the model was successful in predicting the presence of most mineral phases observed in the XRD analysis.

01 COAL, LIGNITE, AND PEAT↗

System for Manipulating Drops and Bubbles Using Acoustic Radiation Pressure

The manipulation and control of drops of liquid and gas bubbles is achieved using high intensity acoustics in the form of and/or acoustic radiation pressure and acoustic streaming. generated by a controlled wave emission from a transducer. Acoustic radiation pressure is used to deploy or dispense drops into a liquid or a gas or bubbles into a liquid at zero or near zero velocity from the discharge end of a needle such as a syringe needle. Acoustic streaming is useful in manipulating the drop or bubble during or after deployment. Deployment and discharge is achieved by focusing the acoustic radiation pressure on the discharge end of the needle, and passing the acoustic waves through the fluid in the needle. through the needle will itself, or coaxially through the fluid medium surrounding the needle. Alternatively, the acoustic waves can be counter-deployed by focusing on the discharge end of the needle from a transducer axially aligned with the needle, but at a position opposite the needle, to prevent premature deployment of the drop or bubble. The acoustic radiation pressure can also be used for detecting the presence or absence of a drop or a bubble at the tip of a needle or for sensing various physical characteristics of the drop or bubble such as size or density.

Oeftering, Richard C.↗

CRADA Final Report: CRADA Number NFE-22-09311 with Agriwater Tech

Livestock wastewater management is a critical concern in the United States, with an annual production of approximately 1.37 billion tons of waste, surpassing human waste by three to twenty times. The mismanagement of manure wastewater poses significant threats to freshwater sources, ecosystems, and public health. Through this project, we proposed an innovative solution using electrocoagulation (EC) treatment. The EC technique is an electrochemical process involving the intentional corrosion of aluminum and iron electrodes to introduce trivalent ions into the solution, facilitating the co-precipitation and coagulation of contaminants and making the removal of water from sludge easier. The project's primary objective is to use EC to convert liquid animal manure into clean water for farm irrigation, drinking, and maintenance. This solution is vital for various farms including those facing drought, pursuing zero-discharge, and seeking Environmental Protection Agency (EPA) permits for livestock farm manure discharge into rivers. Preliminary research shows EC's potential to significantly reduce turbidity and phosphate levels in livestock wastewater, forming the basis for scalable onsite treatment. The goal of this proposed project is to develop an innovative farm-wastewater-treatment process to achieve clean water, fertilizer, and reduced greenhouse gases through electrification of current processes such as coagulation, dewatering, inactivation of viruses and bacteria, and filtration for recycling surface water from farm lagoons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CRADA Final Report: CRADA Number NFE-22-09311 with Agriwater Tech

Livestock wastewater management is a critical concern in the United States, with an annual production of approximately 1.37 billion tons of waste, surpassing human waste by three to twenty times. The mismanagement of manure wastewater poses significant threats to freshwater sources, ecosystems, and public health. Through this project, we proposed an innovative solution using electrocoagulation (EC) treatment. The EC technique is an electrochemical process involving the intentional corrosion of aluminum and iron electrodes to introduce trivalent ions into the solution, facilitating the co-precipitation and coagulation of contaminants and making the removal of water from sludge easier. The project's primary objective is to use EC to convert liquid animal manure into clean water for farm irrigation, drinking, and maintenance. This solution is vital for various farms including those facing drought, pursuing zero-discharge, and seeking Environmental Protection Agency (EPA) permits for livestock farm manure discharge into rivers. Preliminary research shows EC's potential to significantly reduce turbidity and phosphate levels in livestock wastewater, forming the basis for scalable onsite treatment. The goal of this proposed project is to develop an innovative farm-wastewater-treatment process to achieve clean water, fertilizer, and reduced greenhouse gases through electrification of current processes such as coagulation, dewatering, inactivation of viruses and bacteria, and filtration for recycling surface water from farm lagoons.

54 ENVIRONMENTAL SCIENCES↗

Tool Chain for Simulations of Bi-Filar Coil Winding for Fast Quench Protection

The advancement of high-field magnets utilizing high-temperature superconductors (HTS) brings about complex challenges, especially in quench detection and protection. Traditional methods often fall short due to the inherently slow quench propagation in HTS materials. One promising approach to overcome this involves using a bifilar winding configuration, where two conductors are placed side by side. Under normal operation, they function in series, but during a quench event, they switch to an anti-parallel mode. This shift reduces the differential inductance of the coil to near zero, enabling rapid current oscillations through a capacitor discharge. The resulting high-frequency current flow leads to swift, uniform heating, triggering a full-coil quench within microseconds. Moreover, the strong mutual coupling between the two windings significantly reduces electrical noise in voltage measurements. In this work, we explore the viability of this concept by designing, constructing, and testing a REBCO bifilar racetrack coil in liquid nitrogen. We also present a validated simulation model that closely mirrors the coil's dynamic behavior under these conditions, aligning well with experimental observations.

Jayathilaka, Rehan [Northern Illinois U.]↗

Microchannel-based Membrane-less Extraction of Li from Unconventional Lithium Sources & the Separation of REE

This final report provides an overview of the Project's entire duration, covering July 1, 2021 to December 31, 2023. It primarily focuses on the achievements, technological developments, and unique challenges the team faced while working on separating and extracting Lithium from produced waters. The project's primary aim was to create an integrated, high-throughput, membrane-less, and modular microfluidic platform that could extract Lithium from unconventional sources. We have successfully met all goals and milestones envisioned in the SOPO document. The most critical primary milestones, including the Go-No-Go milestone (refer to the Gantt chart in the Appendices), were successfully accomplished. We demonstrated phase separation (>90%) and extraction (>85%) performance in the MPSE using synthetic, and representative produced water composition feed at 50 ml/min total flow through MPSE 36. We have also performed a parametric study of the MPSE operations, beyond the scope of SOPO, exploring operating conditions of current and broader interest. The extended investigation of operational parameters is concurrent with our efforts to seek further development of the MPSE technology beyond the scope of the Project. Along these lines of development, we have made efforts to be responsive to DOE calls for technological developments of other types of resources (beyond PW) for the recovery of Critical Materials and higher TRL development (beyond TRL 4). During the work on this Project, we developed and implemented three innovative technical approaches that emerged from our efforts to successfully meet the Project milestones. The innovative & original technical approaches developed and implemented in this Project are now the contributions to process engineering that could be clearly credited to the Project. First, Convergent Design Approach is a comprehensive feedforward & feedback loop of four design phases: i) design for functionality, ii) design for manufacturing, iii) design for sustainability, and iv) design for market. Next was Process Intensification. A major aim of this Project was to create an innovative phase separation & extraction microscale-based technology for Li separation – thus the words microchannel-based in the Project title. A microscale-based technology is intrinsically in the center of the Process Intensification domain as defined by its unique principles. Therefore, Process Intensification was implicitly envisioned in the Project’s SOPO. Lastly, Time Scale Analysis is a novel tool for discovering the needs and directions of Process Intensification implementations in any process technology. This Project is fully credited for developing and implementing the three novel technical approaches mentioned above. These are general contributions to process engineering that emerged from this Project. Beyond the original SOPO scope, the OSU-U.Pitt research group utilized a Convergent Design methodology, integrating first-principles mathematical modeling with experimental validation on the Minimum Development Vehicle. By creating these Digital Twins, the team rapidly assessed manufacturing iterations to support TEA analysis. This framework further enabled the development of advanced Surface Modification Techniques, where hydrophobic and oleophobic coating strategies were optimized via Digital Twin tools and validated through rigorous 100-hour longevity testing. TEA Analysis: The closing efforts of this Project were focused on the TEA analysis. TEA analysis had two primary functions: i) enabling critical assessments of design variations withing 10 the Concurrent Design Approach, thus enabling evolution of the MPSE design to reach faster- better-cheaper alternatives; and ii) to create a bridge between the accomplishments of this Project and future projects of higher TRL, beyond TRL 6 level. It is important to note that the TEA model created in the Project stirred the technological solutions for the recovery of critical materials toward a vision of a very profitable modular plant that has unique zero-waste water discharge signature. More importantly, thanks to our experimental performance data and conservative assumptions, the TEA model predicts minimal technological and investment risks. Low cost of a modular unit of a nominal capacity of [1000 tons of Li 2 CO 3 /year] positions the MPSE based technology within the reach of community investors, thus offering a paradigm shift in the development of critical technologies. The project successfully navigated two primary challenges: solvent selection and manufacturing adaptation. Restricted by the SOPO to existing literature for lithium recovery, the team identified a critical need for a "material excellence program" to develop next-generation solvents, eventually concluding with a preliminary investigation into promising Ionic Liquids (ILs). Simultaneously, COVID-19 supply chain disruptions forced a pivot from traditional manufacturing to advanced additive methods at ATAMI-OSU. By transitioning from stainless steel to 3D-printed polymer substrates, the team achieved a transformative three-order-of- magnitude reduction in manufacturing costs and compressed prototyping timelines from several months to just two days. The MPSE technology offers significant energy, environmental, and economic advantages by overcoming the traditional bottlenecks of phase-separation hardware and contactor size. Unlike conventional mixer-settlers or membrane-based systems, MPSE operates without moving parts or fouling-prone membranes, achieving robust performance even with challenging, viscous, or particulate-heavy feeds. Key performance metrics include an energy intensity reduction of 5–50x (3–40 kJ/m 3 ) compared to incumbent technologies and a dramatic reduction of processing time to under 60 seconds, which drastically reduces the physical plant footprint. These technical efficiencies translate into superior economic outcomes; for a 100 t/year Li 2 CO 3 facility, implementing MPSE is projected to nearly halve contactor CAPEX (from $\$$6.08M to $\$$3.01M) and significantly increase the project's Net Present Value (NPV), derisking new investment and enabling distributed critical-mineral processing configurations. The commercialization of MPSE technology is being spearheaded by Vigsur Dynamics Inc., which has adopted a structured, parallel approach to technical and business development since its formation in January 2026. Following extensive customer discovery and engagement with the Oregon State University accelerator, Vigsur Dynamics is working to establish a business model that transitions from pilot demonstrations to modular hardware sales, ultimately aiming for a "build-own-operate" service strategy. Current technical milestones—including 100 hours of continuous operation, superior energy efficiency, and successful 6-unit modular scale-up— provide a foundation for this transition. Backed by ongoing IP licensing and a growing network of industrial and venture advisors, the company is actively de-risking the platform to replace conventional mixer-settler systems in the critical minerals market.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the Design and Test of a Liquid Injection Electric Thruster

A liquid injection electric thruster (LINJET) was designed and tested. The results of the tests were very encouraging with thruster performance levels well in excess of design goals. Supporting activities to the engine design and test included a five-million pulse life test on the main capacitor, a 46-million pulse test on the trigger electronics, design and fabrication of a zero resistance torque connector for use with the torsional pendulum thrust stand, design and fabrication of a logic box for control of engine firing, and a physical and chemical properties characterization of the perfluorocarbon propellant. While the results were encouraging, testing was limited, as many problems existed with the design. The most significant problem was involved with excessive propellant flow which contributed to false triggering and shorting. Low power active thermal control of the propellant storage cavity, coupled with a re-evaluation of the injection ring pore size and area exposed to the main capacitor discharge are areas that should be investigated should this design be carried forward.

Jones, T. A.↗

Effect of Propellant Feed System Coupling and Hydraulic Parameters on Analysis of Chugging

A digital distributed parameter model was used to study the effects of propellant-feed- system coupling and various hydraulic parameters on the analytical prediction of chugging instabilities. Coupling between the combustion chamber and feed system was controlled by varying the compliance of the injector-dome region. The coupling with the feed system above the pump was varied by changing the amount of cavitation compliance at the pump inlet. The stability limits and chugging frequencies proved to be strongly dependent on the degree of feed-system coupling. The maximum stability condition occurred with intermediate coupling. Under conditions of a high degree of feed-system-combustor coupling, the stability limits and chugging frequencies were primarily dependent on the feed-system characteristics; the responses were characterized by beating patterns. For the system analyzed, the pump suction line had little effect on the stability limits or chugging frequencies. Beating, present under the condition of near zero injector -dome compliance, was eliminated when the suction line was decoupled by employing a sufficiently high value of pump-inlet compliance. Under conditions of maximum feed-system coupling, the magnitude and distribution of line losses in the discharge line had a significant effect on the stability limits but had negligible effect on the chugging frequency and beating characteristics. Also, the length of the discharge line greatly affected the stability limits, chugging frequency, and beating characteristics. The length of the suction line, however, had little effect on the stability limits and chugging frequency but did influence the beating pattern. A resistive-shunt device attached to the pump discharge line to suppress chugging was investigated. The analysis showed that the device was effective under conditions of high feed-system coupling.

CHUGGING↗

High-resolution infrared spectroscopy of jet cooled cyclobutyl in the α-CH stretch region: large-amplitude puckering dynamics in a 4-membered ring radical

We report gas-phase cyclobutyl radical (c-C 4 H 7 ) is generated at a rotational temperature of T rot = 26(1) K in a slit-jet discharge mixture of 70% Ne/30% He and 0.5–0.6% cyclobromobutane (c-C 4 H 7 Br). A fully rovibrationally resolved absorption spectrum of the α-CH stretch fundamental band between 3062.9 cm −1 to 3075.7 cm −1 is obtained and analyzed, yielding first precision structural and dynamical information for this novel radical species. The α-CH stretch band origin is determined to be 3068.7887(4) cm −1 , which implies only a modest (≈0.8 cm −1 ) blue shift from rotationally unresolved infrared spectroscopic studies of cyclobutyl radicals in liquid He droplets [ A. R. Brown, P. R. Franke and G. E. Douberly, J. Phys. Chem. A , 2017, 121 , 7576–7587]. Of particular dynamical interest, a one-dimensional potential energy surface with respect to the ring puckering coordinate is computed at CCSD(T)/ANO2 level of theory and reveals a double minimum C s puckered geometry, separated by an exceedingly shallow planar C 2v transition state barrier (E barr ≈ 1 cm −1 ). Numerical solutions on this double minimum potential yield a zero-point energy for the ground state (E zero-point ≈ 27 cm −1 ) greatly in excess of the interconversion barrier. This is indicative of highly delocalized, large amplitude motion of the four-membered ring structure, for which proper vibrationally averaging of the moment of inertia tensor reproduces the experimentally determined inertial defect remarkably well. Finally, intensity alternation in the experimental spectrum due to nuclear spin statistics upon exchange of three indistinguishable H atom pairs (IH = ½) matches K a + K c = even : odd = 36 : 28 predictions, implying that the unpaired electron in the radical center lies in an out-of-plane p π orbital. Thus, high-resolution infrared spectroscopy provides first experimental confirmation of a shallow double minimum ring puckering potential with a highly delocalized ground state wave function peaked at a planar C 2v transition state geometry consistent with a cyclobutyl π radical.

Chemistry↗