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At least 685 records · Page 38

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO 2 Revealed by In Situ X‐Ray Spectroscopy

Abstract Advanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO 2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distributed Acoustic Sensing (DAS) Seismic Monitoring of CO 2 Injected for Enhanced Oil Recovery in Northern Michigan (Volume II.C)

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. This report describes the monitoring study conducted to assess the effectiveness of DAS (Distributed Acoustic Sensing) -based VSP (Vertical Seismic Profiling) technology for delineating CO 2 injected into the Silurian-age pinnacle reefs in northern Michigan, the host rocks for the MRCSP Phase III demonstration project. The DAS VSP study was conducted in the Chester 16 reef, one of several reefs in Otsego County Michigan that is operated by Core Energy, LLC of Traverse City, Michigan. Time-lapse DAS VSP was implemented at the Chester 16 reef to attempt to detect approximately 85,000 tonnes of CO 2 injected into the A-1 Carbonate and Brown Niagaran Formations. A baseline survey was conducted in February 2017 prior to injecting CO 2 and a repeat survey was conducted in August 2018. During the interim period between the baseline and repeat surveys, CO 2 was injected into the Chester 16 reef via the 6-16 injection well without production (withdrawal) of fluids from the reef. A grid of 181 source positions consisting of 44 vibrator positions, plus 137 dynamite shot locations, was used to give approximately continuous spatial coverage of the injection zone (A-1 Carbonate and upper Brown Niagaran) in the area between the two wells.

01 COAL, LIGNITE, AND PEAT↗

Preparation and Characterization of Inclusion Complexes of β-Cyclodextrin and Phenolics from Wheat Bran by Combination of Experimental and Computational Techniques

Bitterness often associated with whole wheat products may be related to phenolics in the bran. Cyclodextrins (CDs) are known to form inclusion complexes. The objective was to form inclusion complexes between β-CD and wheat phenolics. Pure phenolic acids (trans-ferulic acid (FA), caffeic acid (CA), and p-coumaric acid (CO)) and phenolic acids from wheat bran were used to investigate complex formation potential. Complexes were characterized by spectroscopy techniques, and a computational and molecular modeling study was carried out. The relative amount of complex formation between β-CD and wheat bran extract was CA > CO > FA. The phenolic compounds formed inclusion complexes with β-CDs by non-covalent bonds. The quantum-mechanical calculations supported the experimental results. The most stable complex was CO/β-CD complex. The ΔH value for CO/β-CD complex was -11.72 kcal/mol and was about 3 kcal/mol more stable than the other complexes. The QSPR model showed good correlation between binding energy and 1H NMR shift for the H5 signal. This research shows that phenolics and β-CD inclusion complexes could be utilized to improve the perception of whole meal food products since inclusion complexes have the potential to mask the bitter flavor and enhance the stability of the phenolics in wheat bran.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cobalt(II) Phthalocyanine Substituents Tune the Electrocatalytic CO 2 Conversion to Methanol

Cobalt phthalocyanine (Co(II)Pc) and its derivatives are promising molecular electrocatalysts for the electrochemical reduction of CO 2 to CO and methanol (CH 3 OH). Despite increasing interest, a detailed mechanistic understanding of how ligand substituents influence catalytic activity, selectivity, and efficiency remains limited. In this study, we employ density functional theory (DFT) to systematically investigate the influence of electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the electronic structure and redox properties of the Co(II)Pc electrocatalyst, and to elucidate CO 2 RR mechanistic pathways. Our results reveal that EWGs cause a positive shift in the reduction potentials, favor CO 2 binding over protonation of the Co metal center and promote downstream methanol formation at mild potentials. EDGs show opposite trends including favorable protonation steps, promoting a negative shift in the reduction potential, and facilitating the hydrogen evolution reaction (HER), which competes with the desired CO 2 RR pathway. Notably, CO dissociation is thermodynamically and kinetically unfavorable across all systems, positioning the redox potential versus CO dissociation energy as a key factor for methanol selectivity. Furthermore, these insights provide a predictive framework for rational catalyst design and underscore the critical role of electronic tuning in advancing molecular electrocatalysts for sustainable CO 2 conversion.

Alcohols↗

In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO 2 . The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol –1 . Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH 4 is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH 3 –O–Fe, to a bridging bidentate formate b-HCOO–Fe, to a monodentate formate m-HCOO–Fe, before CO 2 is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. Finally, the elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH 4 in gas-phase heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Over-Potential Tailored Thin and Dense Lithium Carbonate Growth in Solid Electrolyte Interphase for Advanced Lithium Ion Batteries

A stable solid electrolyte interphase (SEI) is highly desired to prevent parasitic reactions during normal operation of lithium-ion batteries (LIBs). Lithium carbonate (Li 2 CO 3 ) is one of the most significant components for smooth SEI passivation layers; while the formation mechanism and special distribution of the Li 2 CO 3 layer has not yet been illustrated. In this study, an over-potential tailored Li 2 CO 3 growth mechanism based on the typical hard carbon anode is demonstrated. With an increase in the over-potential, the size of Li 2 CO 3 decreases gradually as the amount increases. When the over-potential is large (potential at 0.01 V), a Li 2 CO 3 -rich thin and dense inorganic layer with the average thickness of 4.4 nm in the SEI is constructed. The special SEI the completely wraps the boundaries of the anode enables a larger Li-ion de-solvation energy barrier and a lower Li-ion diffusion energy barrier, which supports low self-discharge behavior and a fast kinetic rate at the anode. More generally, this Li 2 CO 3 growth mechanism is also applicable to commercialized graphite anodes and similar results are also obtained. Therefore, this work provides a new insight into the Li 2 CO 3 growth mechanism in SEIs, as well as a guideline for the design of stable artificial SEIs.

25 ENERGY STORAGE↗

Sequential Ammonia and Carbon Dioxide Adsorption on Pyrolyzed Biomass to Recover Waste Stream Nutrients

Untreated fecal waste in unsewered communities and reactive nitrogen (N) loading from wastewater and urine disposal are important environmental challenges. Through pyrolysis, untreated fecal waste can be converted into amine-rich carbon dioxide (CO 2 ) sorbents, the chemisorption of which tunes the surface chemistry toward ammonia (NH 3 ) uptake. We compared the N-loading potential within amine-rich pyrolyzed human solid waste through exposure to CO 2 followed by NH 3 with the N-loading potential on carboxyl-rich, pyrolyzed oxidized wood using sequential adsorption of isotopically labeled CO 2 and NH 3 . The total N content of pyrolyzed oxidized wood exposed once to NH3 was similar to native, pyrolyzed human solid waste (3.7% compared to 4.6%). However, sorption kinetics and spectroscopic evidence revealed distinct N forms between the two materials affecting subsequent CO 2 and NH 3 uptake. Tertiary amines comprised 70% of N in pyrolyzed waste, compared to only 53% in pyrolyzed oxidized wood. The high heat of adsorption of CO 2 on pyrolyzed human solid waste (50 kJ mol-1) at low concentrations (0.05 mmol CO 2 g -1 ) was indicative of CO 2 reactivity with tertiary amines, consistent with the formation of carbamic acid (Figure S1). Conversely, after exposure to NH 3 , pyrolyzed oxidized wood chemisorbed CO 2 at much higher concentrations (0.7 mmol CO 2 g-1), pointing to primary amines as the active functional moieties. Adsorption kinetics of pyrolyzed oxidized wood revealed continued, albeit diminishing NH 3 uptake with each consecutive CO 2 treatment, averaging 5.9 mmol NH 3 g -1 for the first NH 3 exposure event, and still 3.5 and 2.9 mmol NH 3 g -1 for the second and third. Penetration of 15 NH 3 and 13 CO 2 measured by NanoSIMS reached over 7 µm deep into both materials, explaining the large NH 3 capture. The significantly lower NH 3 adsorption compared to pyrolyzed oxidized wood may be a result of potassium (K) carbonate precipitation precluding a Lewis base interaction between NH 3 and chemisorbed CO 2 , suggested by a 2-fold increase in surface K concentrations after exposure of pyrolyzed human solid waste to CO 2 +NH 3 detected by XPS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chapter 8. Hybrid Biological–Inorganic Systems for CO 2 Conversion to Fuels

The biological reduction of CO 2 into organic carbon is integral to the formation and maintenance of all life on earth. An urgent need to mitigate the effects of CO 2 on our atmosphere has provided an imperative to exploit biological CO 2 fixation for the conversion of CO2 into valuable and energy rich fuels. Photosynthesis uses only sunlight, water, and CO2 as starting materials to form all biomass.

CO2 Conversion to Fuels↗

Observations of the CO J=6-5 transition in starburst galaxies

Over the past several years, short-submillimeter observations of carbon monoxide's (CO) mid-J rotational levels have revealed the presence of a large amount of excited molecular gas in luminous giant molecular clouds in our Galaxy. Submillimeter lines are specific probes of excited material: collisional excitation of the level energy of 116 K above ground, and 6-5 transition's critical density is approximately 10(exp 6) cm(exp -3) in optically thin gas. Radiative trapping effects reduce the excitation requirements to some extent, but detection of the CO J=6-5 line is nearly indisputable proof of the existence of gas that is both warm and dense. The excitation conditions also imply that cool (T less than 20 K) molecular clouds within the beam neither emit nor absorb in the short-submillimeter lines; in our Galaxy, clouds with active massive star formation emit the strongest short-submillimeter CO rotational lines. We used these properties to explore the distribution of excited molecular material and physical conditions within the star formation regions of several classical starburst nuclei: NGC253, M82, and IC342. We have used the 6-5 transition as a thermometer of warm molecular gas in starburst nuclei, unambiguously finding that the nuclear molecular gas in starburst galaxies is substantially warmer than in typical disk clouds.

Harris, A. I.↗

Phase evolution during conventional and reactive flash sintering of (Mg,Ni,Co,Cu,Zn)O via in situ X-ray diffraction

Reactive flash sintering (RFS) enables the simultaneous synthesis and sintering of ceramics and has been shown to affect the reaction pathway of different materials. Herein, in situ synchrotron X-ray diffraction (XRD) is used to investigate the (Mg,Ni,Co,Cu,Zn)O entropy-stabilized oxide formation during: (i) conventional heating and (ii) RFS under current rate-controlled mode. The same reaction pathway is verified in both instances: the starting rock-salt (RS), spinel (Co 3 O 4 ), tenorite (CuO), and wurtzite (ZnO) phases transform into a single RS phase with a (1 1 1) to (2 0 0) intensity ratio of 0.67, consistent with a random distribution of the cations into the structure. Pt lattice peak shift from the XRD patterns is used as standard to monitor the sample surface temperature, revealing a strong endothermic reaction during the RS single-phase formation (Pt peaks shift toward higher angles while increasing sample temperature/current density). Furthermore, in RFS, the single-phase RS structure is formed in just 60 s at a furnace temperature of 600°C and a current rate of 220 mA mm -2 /min. Therefore, RFS greatly accelerates the synthesis of (Mg,Ni,Co,Cu,Zn)O, however, it does not play a role in the reaction pathway for this material formation.

36 MATERIALS SCIENCE↗

Surpassing the Performance of Phenolate-derived Ionic Liquids in CO 2 Chemisorption by Harnessing the Robust Nature of Pyrazolonates

Superbase-derived ionic liquids (SILs) are promising sorbents to tackle the carbon challenge featured by tunable interaction strength with CO 2 via structural engineering, particularly the oxygenate-derived counterparts (e. g., phenolate). However, for the widely deployed phenolate-derived SILs, unsolved stability issues severely limited their applications leading to unfavorable and diminished CO 2 chemisorption performance caused by ylide formation-involved side reactions and the phenolate-quinone transformation via auto-oxidation. Here, in this work, robust pyrazolonate-derived SILs possessing anti-oxidation nature were developed by introducing aza-fused rings in the oxygenate-derived anions, which delivered promising and tunable CO 2 uptake capacity surpassing the phenolate-based SIL via a carbonate formation pathway (O-C bond formation), as illustrated by detailed spectroscopy studies. Further theoretical calculations and experimental comparisons demonstrated the more favorable reaction enthalpy and improved anti-oxidation properties of the pyrazolonate-derived SILs compared with phenolate anions. The achievements being made in this work provides a promising approach to achieve efficient carbon capture by combining the benefits of strong interaction strength of oxygenate species with CO 2 and the stability improvement enabled by aza-fused rings introduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Star-formation rates, molecular clouds, and the origin of the far-infrared luminosity of isolated and interacting galaxies

The CO luminosities of 93 galaxies have been determined and are compared with their IRAS FIR luminosities. Strongly interacting/merging galaxies have L(FIR)/L(CO) substantially higher than that of isolated galaxies or galactic giant molecular clouds (GMCs). Galaxies with tidal tails/bridges are the most extreme type with L(FIR)/L(CO) nine times as high as isolated galaxies. Interactions between close pairs of galaxies do not have much effect on the molecular content and global star-formation rate. If the high ratio L(FIR)/L(CO) in strongly interacting galaxies is due to star formation then the efficiency of this process is higher than that of any galactic GMC. Isolated galaxies, distant pairs, and close pairs have an FIR/CO luminosity ratio which is within a factor of two of galactic GMCs with H II regions. The CO luminosities of FIR-luminous galaxies are among the highest observed for any spiral galaxies.

Solomon, P. M.↗

Stacked Greenfield and Brownfield ROZ Fairways in the Illinois Basin Geo-Laboratory: Co-Optimization of EOR and Associated CO 2 Storage

Residual oil zones (ROZs) are economically viable targets for carbon dioxide enhanced oil recovery (CO 2 -EOR); thick, carbonate ROZs in the San Andres Formation in the Wasson Field of the Permian Basin are an example. Incremental oil produced from CO 2 -EOR can be carbon negative via associated storage of injected CO 2 . Given the regional extent of ROZ fairways and generally higher net utilization of CO 2 (compared to conventional CO 2 -EOR), ROZs provide the opportunity for significant carbon neutral to carbon negative oil production with associated CO 2 storage, and therefore should be a priority target for exploration. However, ROZs have not been widely recognized or identified due to poor or no conventional oil production. Hence, in places like the Illinois Basin (ILB), exploratory analyses are required to recognize the existence of an ROZ. As part of this study, four formations were selected for detailed regional characterization and analysis: Carper Sandstone (part of the Borden Siltstone), Tar Springs Sandstone, Cypress Sandstone, and Middle Devonian (Geneva Dolomite and associated Dutch Creek Sandstone). The four formations underwent regional geological characterization to develop a regional geologic framework for the ROZs and their overlying seals. Findings of this study are supported by data from two field laboratory sites, one with stacked greenfield ROZs and the other with a stacked complex that includes a brownfield ROZ and depleted conventional reservoirs. The field laboratory sites were used to collect data and conduct tests to validate ROZ detection methodologies and identify economic field-deployable strategies to co-optimize CO 2 -EOR and associated storage in stacked ROZs. Findings from these field sites were extrapolated to characterize the basin-wide stacked ROZ fairway resource.

01 COAL, LIGNITE, AND PEAT↗

Impact of aquifer properties on the extent and timeline of CO 2 trapping

Abstract Geologic CO 2 sequestration in porous saline aquifers is a promising approach to reducing atmospheric concentrations of CO 2 . Reactive transport simulations provide the opportunity to analyze which factors influence geochemical reactivity in the reservoir, understand those most important for promoting CO 2 trapping, and assess individual sites. Field‐scale aquifer characterization is time and resource intensive such that here, reactive transport simulations are leveraged to enhance understanding of selected aquifer properties including porosity, permeability, depth of storage, and carbonate mineralogy on the overall CO 2 trapping potential to better select sites promoting geochemical reactivity for CO 2 trapping. There are different mechanisms for sequestrating CO 2 . Once injected, CO 2 will dissolve into the brine to create an acidic environment, resulting in the dissolution of pre‐injection formation minerals. Released ions can reprecipitate as secondary minerals. The dissolved CO 2 and mineralized CO 2 are considered as a more secure form of CO 2 trapping in this study compared to the free supercritical CO 2 . Here, a framework leveraging a controlled set of field scale simulations is developed to facilitate rapid, optimized site selection. Simulations vary aquifer properties to understand the impact of each unique property on CO 2 trapping, tracking, and comparing the amount of supercritical, aqueous, and mineralized CO 2 . The rate at which the CO 2 injected into the aquifer is converted to aqueous or mineralized CO 2 is newly defined here as the sequestration efficiency and used to compare simulation results. The reservoir depth and fraction of carbonate minerals in the formation are shown to be more important factors than reservoir porosity and permeability in affecting CO 2 trapping. However, the impact of aquifer properties on the evolution of injected CO 2 depends on the stage of the sequestration project. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.

Energy & Fuels↗

Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H 2 Syngas Production from Electrochemical CO 2 Reduction

The electrochemical carbon dioxide reduction reaction (CO 2 RR) to produce synthesis gas (syngas) with tunable CO/H 2 ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd-modified niobium nitride (Pd/NbN) is found to generate much higher CO and H 2 partial current densities and greater CO Faradaic efficiency than Pd-modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In-situ X-ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO 2 RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO 2 RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO 2 to syngas with a potential reduction in precious metal loading.

25 ENERGY STORAGE↗

Coupled Hydromechanical Modeling of Induced Seismicity From CO 2 Injection in the Illinois Basin

Injection of CO 2 for geologic carbon sequestration into deep sedimentary formations involves fluid pressure increases that engage hydromechanical processes that can cause seismicity by activation of existing faults. In this work, we use a coupled multiphase fluid flow and geomechanical simulator to model spatiotemporal fluid pressure and stress changes in order to study the poroelastic effect of CO 2 injection on faults in crystalline basement rock below the injection zone. The seismicity rate along features interpreted to be basement faults is modeled using Dieterich's rate-and-state earthquake nucleation model. The methodology is applied to microseismicity detected during CO 2 injection into the Mount Simon formation during the Illinois Basin—Decatur Project. The modeling accurately captures an observed reduction in seismicity rate when the injection in the second well was into a slightly shallower zone above the base of the Mount Simon formation. Moreover, the modeling shows that it is important to consider poroelastic stress changes, in addition to fluid pressure changes for accurately modeling of the observed seismicity rate.

58 GEOSCIENCES↗

Effects of Surface Roughness on the Electrochemical Reduction of CO 2 over Cu

We have investigated the role of surface roughening on the CO 2 reduction reaction (CO 2 RR) over Cu. The activity and product selectivity of Cu surfaces roughened by plasma pretreatment in Ar, O 2 , or N 2 were compared with that of electrochemically polished Cu samples. Differences in total and product current densities, the ratio of current densities for HER (the hydrogen evolution reaction) to CO 2 RR, and the ratio of current densities for C 2+ to C 1 products depend on the electrochemically active surface and are nearly independent of plasma composition. Theoretical analysis of an electropolished and roughened Cu surface reveals a higher fraction of undercoordinated Cu sites on the roughened surface, sites that bind CO preferentially. Roughened surfaces also contain square sites similar to those on a Cu(100) surface but with neighboring step sites, which adsorb OC-COH, a precursor to C 2+ products. Here, these findings explain the increases in the formation of oxygenates and hydrocarbons relative to CO and the ratio of oxygenates to hydrocarbons observed with increasing surface roughness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Star formation and the distribution of HI and infrared emission in M51

H I, infrared, CO, H alpha and beta band observations of M51, the prototypical grand-design spiral galaxy, are used to study the consequences of star formation for the distribution of H I and dust. Using the H I and CO data sets new tests of the idea that the H I is largely a dissociation product in star-forming regions were performed. It was confirmed that the H I spiral arms are generally coincident with the H II region arms, and offset downstream from the CO arms. The radial distributions of total gas, H alpha and H I surface density have a simple explanation in the dissociation picture. The distributions also demonstrate how the surface density of H I might be related to the star formation efficiency in molecule-rich galaxies. The large width of the H I regions along the arms compared to that of the H II regions can be understood in terms of a simple Stroemgren sphere calculation. The longer lifetime of the stars producing dissociating radiation vs. those producing ionizing radiation will also contribute to the greater width of the H I arms if stars are continuously forming on the arms. The lack of detailed coincidence of the H I and H II regions along the inner arms has a variety of possible explanations within the dissociation scenario. Two simple tests to probe the origin of the IRAS emission in M51 were performed.

Rand, Richard J.↗